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.]
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.
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.
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.
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.
Hydrothermal carbon enriched with sulfonic and carboxyl groups as an efficient solid acid catalyst for butanolysis of furfuryl alcohol
Yang, Jinfan,Zhang, Hongyu,Ao, Zhifeng,Zhang, Sufeng
, p. 109 - 113 (2019)
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.
Recognizing soft templates as stimulators in multivariate modulation of tin phosphate and its application in catalysis for alkyl levulinate synthesis
Manjunathan, Pandian,Shanbhag, Dhanush Y.,Vinu, Ajayan,Shanbhag, Ganapati V.
, p. 272 - 282 (2021)
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
Clean synthesis of alkyl levulinates from levulinic acid over one pot synthesized WO3-SBA-16 catalyst
Enumula, Siva Sankar,Gurram, Venkata Ramesh Babu,Chada, Raji Reddy,Burri, David Raju,Kamaraju, Seetha Rama Rao
, p. 30 - 38 (2017)
The present work highlights the application of solid acid catalyst to produce alkyl levulinate from levulinic acid in continuous mode under vapor phase conditions. In this context, tungsten oxide incorporated SBA-16 catalysts were prepared by one pot direct synthesis method and evaluated for the titled reaction. Under optimized reaction conditions, 3 wt% WO3-SBA-16 catalyst delivered complete conversion of levulinic acid with 95% selectivity towards ethyl levulinate. The synthesized catalysts were characterized to know the physico-chemical features by various techniques, namely, X-ray diffraction, N2 physisorption, temperature programmed reduction of hydrogen (H2-TPR), temperature programmed desorption of ammonia (NH3-TPD), DR-UV–vis spectroscopy, Fourier transform infrared (FTIR) spectroscopy, transmission electron microscopy (TEM) and scanning electron microscopy (SEM). The characterization results suggest that, the superior catalytic activity can be ascribed due to the enhanced acidity of SBA-16 obtained through incorporation of tungsten oxide and easy of accessibility for the dispersed active sites through uniform pore channels. The constant catalytic activity in 10 h time on study shows the sturdiness of the catalyst and the spent catalyst can be regenerated several times. Moreover, various alkyl levulinates (methyl, n-propyl, and n-butyl) were synthesized with more than 90% selectivity over this catalyst.
Efficient conversion of biomass-derived furfuryl alcohol to levulinate esters over commercial α-Fe2O3
Ren, Dezhang,Fu, Jun,Li, Lu,Liu, Yunjie,Jin, Fangming,Huo, Zhibao
, p. 22174 - 22178 (2016)
An efficient process for the production of levulinate esters from biomass-derived furfuryl alcohol in liquid alcohol over commercial α-Fe2O3 was firstly investigated. Among the catalysts we tested, α-Fe2O3, a cheap, commercially available and environmentally benign catalyst, exhibited a remarkable catalytic performance for the transformation and gives levulinate esters in good yield compared to the previous studies. The corresponding esters such as methyl levulinate, ethyl levulinate and butyl levulinate were obtained in high yields under optimized reaction conditions. Several influence factors for the formation of levulinate esters were also discussed. A plausible reaction mechanism for the formation of levulinate ester from furfuryl alcohol was proposed. From the viewpoint of practice and economy, the present study provides a potential application for the efficient synthesis of fine chemicals from biomass-derived compounds over cheap, commercially available and environmentally benign catalysts.
Efficient conversion of renewable levulinic acid to n-butyl levulinate catalyzed by ammonium and silver co-doped phosphotungstic acid
Zhou, Xi,Li, Ze Xian,Zhang, Chao,Gao, Xue Ping,Dai, You Zhi,Wang, Gong Ying
, p. 71 - 75 (2016)
Ammonium and silver co-doped phosphotungstic acid was developed as novel efficient catalyst for the synthesis of n-butyl levulinate. The catalyst was characterized by element analysis, FT-IR, XRD and Hammett indicator method. Among them, (NH4)0.5Ag0.5H2PW12O40 exhibited the highest catalytic activity, and the yield of n-butyl levulinate could reach up to 99.0% within 2 h. The results showed that the activity of (NH4)0.5Ag0.5H2PW12O40 was higher than that of single Ag+ or NH4+ doped H3PW and other representative catalysts reported by literatures. In addition, (NH4)0.5Ag0.5H2PW12O40 performed good reusability for this reaction.
Enhanced heterogeneous catalytic conversion of furfuryl alcohol into butyl levulinate
Demmacarà, Piera,Ciriminna, Rosaria,Shiju,Rothenberg, Gadi,Pagliaro, Mario
, p. 835 - 840 (2014)
We study the catalytic condensation of furfuryl alcohol with 1-butanol to butyl levulinate. A screening of several commercial and as-synthesized solid acid catalysts shows that propylsulfonic acid-functionalized mesoporous silica outperforms the state-of-the-art phosphotungstate acid catalysts. The catalyst is prepared via template-assisted sol-gel polycondensation of TEOS and MPTMS. It gives 96 % yield (and 100 % selectivity) of butyl levulinate in 4h at 110 °C. Reaction profiles before and after a hot filtration test confirm that the active catalytic species do not leach into the solution. The catalyst synthesis, characterization, and mode of operation are presented and discussed. Sour cat: Screening several commercial and as-synthesized solid acid catalysts in the condensation of furfuryl alcohol with 1-butanol to afford butyl levulinate shows that the best catalyst is a sulfonic acid-functionalized mesoporous silica, allowing a significant improvement over the state-of-the-art. The catalyst selectively affords n-butyl levulinate in relatively short time at 110 °C.
One pot synthesis of WOx/mesoporous-ZrO2 catalysts for the production of levulinic-acid esters
Ciptonugroho, Wirawan,Al-Shaal, Mohammad G.,Mensah, Joel B.,Palkovits, Regina
, p. 17 - 29 (2016)
WOx/mesoporous-ZrO2 (WmZr) has been successfully prepared by one-pot evaporation induced self-assembly. The resulting textural properties are highly affected by the additions of WO3 and calcination temperatures. XRD and Raman spectroscopy were used to investigate the crystalline structures and surface states of the materials. Surface acidity was studied employing NH3-TPD and DRIFT spectroscopy with pyridine adsorption. Catalysts loaded with 20-25 wt.% WO3 and calcined at 800 °C exhibited the highest surface acidity with the greatest amount of Br?nsted acid sites. The catalysts were tested in the esterification of levulinic acid (LA) with 1-butanol (1-BuOH). Pseudo- (p-BL) and normal-butyl levulinate (n-BL) were observed as the only products. The highest conversion of LA (64-67%) as well as a selectivity of n-BL of up to 97% could be achieved applying a catalyst with 20 wt.% WO3 loading calcined at 800 °C. A clear correlation between catalyst activity and the relative ratio of Br?nsted and Lewis acid sites could be confirmed.
Synthesis of n-Butyl Levulinate Using Mesoporous Zeolite H-BEA Catalysts with Different Catalytic Characteristics
Morawala, Dhara H.,Dalai, Ajay K.,Maheria, Kalpana C.
, p. 1049 - 1060 (2020)
Abstract: The present work focuses on the utilization of waste biomass for the improvement of key catalytic properties of conventional zeolite H-BEA. In the present endeavor, zeolite H-BEA has been modified using cetyltrimethyl ammonium bromide (CTAB) and rice husk (a waste biomass resource), via desilication post synthetic route, which is not reported so far. The synthesized mesoporous zeolite H-BEA catalysts have been characterized by various characterization techniques such as, SEM, 27Al and 29Si MAS-NMR, wide and low angle XRD, ICP-OES, FT-IR, TGA, NH3-TPD and BET surface area. The resultant mesoporous zeolite materials (MCCK and MCRK) exhibited bimodal porosity as well as improved physicochemical properties, and the utility of these modified zeolites as heterogeneous catalysts has been demonstrated in the production of n-butyl levulinate via levulinic acid (LA) esterification. The catalytic material, which has been modified using CTAB and rice husk, is found to exhibit better catalytic activity towards the synthesis of n-butyl levulinate (95.6%) as compared to other zeolite counterparts under the optimised reaction conditions, which is attributed to its enhanced surface area and lower Si/Al ratio as compared to other catalysts under study.
Esterification of levulinic acid over Sn(II) exchanged Keggin heteropolyacid salts: An efficient route to obtain bioaditives
Da Silva, Márcio José,Chaves, Diego Morais,Teixeira, Milena Galdino,Oliveira Bruziquesi, Carlos Giovani
, (2021/03/04)
In this paper, we describe a process to add value to the biomass derivatives (i.e., levulinic acid), converting it to bioadditives over solid Sn(II) exchanged Keggin heteropolyacid salts. These solid catalysts are an attractive alternative to the traditional soluble and corrosive Br?nsted acid catalysts. Among Sn(II) heteropoly salts, the Sn1.5PW12O40 was the most active and selective catalyst, achieving high conversions (ca. 90 %) and selectivity (90–97 %) for alkyl esters and angelica lactone, the main reaction products. The impacts of the main reaction parameters (i.e., catalyst load, temperature, and the molar ratio of alcohol to acid) were investigated. The use of renewable raw material, and an efficient and recyclable catalyst are the main positive features of this process. The Sn1.5PW12O40 catalyst was easily recovered and reused without loss activity.
Utilization of renewable resources: Investigation on role of active sites in zeolite catalyst for transformation of furfuryl alcohol into alkyl levulinate
Vaishnavi,Sujith,Kulal, Nagendra,Manjunathan, Pandian,Shanbhag, Ganapati V.
, (2021/01/18)
A bio-derived furfuryl alcohol transformation into various high-value chemicals is a growing field of interest among researchers. This study reports an exclusive investigation of the porosity and active sites responsible for the efficient alcoholysis of furfuryl alcohol to alkyl levulinate by the aid of zeolite catalyst. Alkyl levulinate is a promising platform chemical potentially used as a fuel additive and also for the production of chemicals. A detailed study using well-characterized HZSM-5 catalyst on the influence of acidity and post synthesis modification like desilication, dealumination, metal ion exchange and phosphate modification revealed the most desired type of acid sites required to catalyze this reaction. Among the HZSM-5 catalysts tested, HZSM-5 (SAR 95) showed the best performance of ≥ 99 % furfuryl alcohol conversion and 85 % butyl levulinate selectivity under optimum conditions. The catalyst exhibited good recyclability additionally addressing all the challenges reported in the previous literature fulfilling the green chemistry principles.
