Synthesis Of Ethyl Levulinate Research Articles

Magnetically separable sulfated zirconia as highly active acidic catalysts for selective synthesis of ethyl levulinate from furfuryl alcohol

Magnetically separable sulfated zirconia catalysts were prepared by a two-step approach.

Insights into the metal salt catalyzed ethyl levulinate synthesis from biorenewable feedstocks

Ethyl levulinate (EL) synthesis from biorenewable feedstocks in the presence of metal salts and under non-microwave instant heating reaction environment has been studied. Initial screening suggested CuCl2 and FeCl3 as an efficient catalyst for EL synthesis from 5-hydroxymethylfurfural (HMF), thereby resulting into 47.5% and 43.3% EL yield respectively at 160°C in 5min. Interestingly, environmentally benign and widely available metal salt, AlCl3, was found to yield comparable EL (39.0%) when experiments were performed under identical reaction conditions. Therefore, further study was performed using AlCl3 to estimate the effect of operating parameters and catalyst concentration over EL yield and HMF conversion. Thereafter, a comparative study on the effect of microwave vs non-microwave instant heating reaction environment has been done to develop a sustainable process for EL synthesis. Consequently, mechanistic insights on reactant conversion and product yield have been attempted to understand various pathways followed. Thereafter, effect of reaction temperature, catalyst loading, ethanol concentration and heating rates were explored. EL synthesis from HMF under instant heating reaction conditions in the presence of metal salts is reported for the first time. We anticipate that present work would be helpful in providing insights on effects of instant heating method and operating conditions for EL synthesis from HMF.

3D graphene aerogel anchored tungstophosphoric acid catalysts: Characterization and catalytic performance for levulinic acid esterification with ethanol

3D graphene aerogel (GA) was synthesized from graphene oxide (GO) using a hydrothermal procedure combined with freeze-drying. Then, they were used to assemble the supported H3PW12O40 (HPW) catalysts. The optimization of the reaction parameters for levulinic acid esterification with ethanol was performed and the catalytic performance of the HPW/GA catalysts was comparatively investigated. The results showed that these catalysts had abundant porous structure. In particular, they were found to be efficient in the synthesis of ethyl levulinate, which is promising in reducing the consumption of petroleum-derived fossil fuels.

Ethane‐Bridged Organosilica Nanotubes Functionalized with Arenesulfonic Acid and Phenyl Groups for the Efficient Conversion of Levulinic Acid or Furfuryl Alcohol to Ethyl Levulinate

AbstractA 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, Brønsted 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 Brønsted 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.

Biodiesel additive ethyl levulinate synthesis by catalytic membrane: SO4−2/ZrO2 loaded hydroxyethyl cellulose

In this study, different catalytic membranes have been improved for use as heterogeneous acid catalyst to synthesize fuel bioadditive ethyl levulinate from levulinic acid and ethanol. Catalyst design was done by wet impregnation method. Catalytic membrane was prepared by solution casting method by loading of catalyst in hydroxyethyl cellulose polymer. Catalytic membranes including tungstosilicic acid hydrate, tungstosilicic acid supported on zirconium oxide and sulfated zirconium oxide were prepared and characterized. According to experimental results, sulfated zirconium oxide loaded catalytic membrane was found more effective when compared to the other catalytic membranes studied. Effects of reaction parameters such as reaction time, catalyst loading on membrane, reaction temperature, catalytic membrane amount, initial molar ratio on the conversion of levulinic acid were also investigated. Pseudo homogeneous second order kinetic model was applied to the experimental data. Activation energies and kinetic constants were determined. The theoretical conversion data were fitted well with the experimental data.

Synthesis of Ethyl Levulinate as a Fuel Bioadditive by a Novel Catalytically Active Pervaporation Membrane

The pervaporation catalytic membrane reactor (PVCMR) is an innovative process where the reactor is combined with a separation unit. The PVCMR consumes less energy than conventional processes and is an environmentally friendly process. The catalytic composite membrane is used in which catalysts are embedded onto the permselective membrane. The production process of ethyl levulinate is a progressive, green, energy-efficient technology by the PVCMR. In present paper, a catalytically active membrane is prepared and used in the synthesis of ethyl levulinate. Ethyl levulinate is one of the fuel bioadditives. A heterogeneous catalyst (silicotungstic acid) was embedded in the membrane. A hydrophilic hydroxyethyl cellulose membrane was prepared. Reaction parameters, such as the temperature, catalyst concentration in the membrane, and initial molar ratio of reactants, were investigated on the conversion of levulinic acid. The reaction performance of the PVCMR and batch reactor was compared, and it was found that th...

Catalytic and mechanistic insights into the production of ethyl levulinate from biorenewable feedstocks

Reaction mechanisms and properties of catalyst materials for the synthesis of ethyl levulinate.

Direct Conversion of Carbohydrates into Ethyl Levulinate with Potassium Phosphotungstate as an Efficient Catalyst

A series of metal-modified phosphotungstates were prepared and performed for direct synthesis of ethyl levulinate from fructose in ethanol. Considering the cost of catalysts, catalytic activity of catalysts, and easy separation of catalysts together, K-HPW-1 was chosen as the most suitable catalyst for synthesis of ethyl levulinate from fructose. A high ethyl levulinate yield of 64.6 mol% was obtained at 150 °C within 2 h in ethanol. The introduction of low polar toluene as a co-solvent improved the yield of ethyl levulinate to 68.7 mol%. The recovered catalyst remained high activity with the yield of ethyl levulinate converted from fructose above 50 mol% after being used five times. Moreover, the generality of the catalyst was further demonstrated by glucose, sucrose, inulin, and cellulose with ethyl levulinate yielding 14.5, 35.4, 52.3, and 14.8 mol%, respectively.

Synthesis of Ethyl Levulinate from Levulinic Acid over Solid Super Acid Catalyst

In this study, 40 % H3PW12O40/ZrO2 catalyst was synthesized, characterized and tested for conversion of levulinic acid (LA) and ethanol (EtOH) to ethyl levulinate (EL). The catalyst was prepared through wetimpregnation method. Catalyst characterization using BET and NH3-TPD revealed that the catalytic performance was dominantly influenced by the acid sites and surface area of the catalyst. The perfomance of the catalyst was tested based on reaction time (30 min to 4 h) and reaction temperature (120 °C to 160 °C) with 1:5 levulinic acid to ethanol ratio. The 40 % H3PW12O40/ZrO2 catalyst exhibited high catalytic performance at 150 °C with time taken 3 h for 99 % yield of ethyl levulinate.

Catalytic upgrading of renewable furfuryl alcohol to alkyl levulinates using AlCl3 as a facile, efficient, and reusable catalyst

The use of various aluminum salts as acid catalysts was compared in terms of catalytic upgrading of renewable furfuryl alcohol in hot ethanol medium. The commercially available AlCl3 was emerged as a simple, cheap, and efficient catalyst for the synthesis of ethyl levulinate. From this study, four significant parameters including AlCl3 dosage, furfuryl alcohol concentration, temperature, and time were evaluated and modeled to determine the optimal combination via response surface methodology with a central composite rotatable design. All parameters influenced the formation of ethyl levulinate—the maximum yield was 95.7% (100% furfuryl alcohol conversion). AlCl3 could be recovered efficiently and reused multiple times without substantial loss of its catalytic activity. Moreover, AlCl3 as the catalyst with optimized conditions was appropriate for the alcoholysis of furfuryl alcohol in other linear alcohols to afford equally high yields of the corresponding alkyl levulinates.

Arylsulfonic acid functionalized hollow mesoporous carbon spheres for efficient conversion of levulinic acid or furfuryl alcohol to ethyl levulinate

Abstract A series of arylsulfonic acid functionalized hollow mesoporous carbon spheres (ArSO 3 H-HMCSs) with controllable ArSO 3 H loadings (1.8 and 3.2 wt%) and inner diameters (120–260 nm) were successfully prepared by chemical bonding ArSO 3 H groups to furfuryl alcohol-derived hollow mesoporous carbon spheres via diazonium coupling. The morphology, textural properties and chemical structure of as-prepared ArSO 3 H-HMCSs were well characterized by TEM, FESEM, nitrogen gas porosimetry measurement, XRD measurement, Raman scattering and FT-IR spectroscopy as well as XPS surface probe technique. As the novel solid acid catalysts, the catalytic activity and stability of the ArSO 3 H-HMCSs were evaluated by synthesis of ethyl levulinate from biomass-derived platform molecules, levulinic acid or furfuryl alcohol. The obtained excellent acid catalytic activity in comparison of other carbon-based SO 3 H catalysts such as ArSO 3 H-functionalized ordered mesoporous carbon, sulfonated hollow mesoporous carbon spheres as well as sulfonated incompletely carbonized d -glucose and cellulose was explained in terms of their strong Bronsted acidity and perfect hollow nanospherical morphology with thin mesoporous shell.

Design of organosulfonic acid functionalized organosilica hollow nanospheres for efficient conversion of furfural alcohol to ethyl levulinate

One-step prepared organosulfonic acid-functionalized organosilica hollow nanospheres exhibited excellent catalytic activity and stability in direct synthesis of ethyl levulinate from ethanolysis of biomass-derived furfural alcohol.

Synthesis of ethyl levulinate as fuel additives using heterogeneous solid superacidic catalysts: Efficacy and kinetic modeling

Esters of levulinic acid, which is biomass derived, are used as oxygenated additives in fuels, flavoring and fragrance industry or as blending components in biodiesel. A series of sulphated metal oxide catalysts were prepared and their activities were tested in the synthesis of ethyl levulinate as the model compound, among which UDCaT-5 (mesoporous super acidic zirconia modified catalyst) was the most active and robust catalyst. The effects of various parameters were studied in a batch reactor to establish kinetics and mechanism of reaction under optimized conditions. The reaction follows Langmuir–Hinshelwood–Hougen–Watson mechanism involving weak adsorption of the reactants and products. The apparent energy of activation was found to be 9.00kcal/mol for ethyl levulinate. Several other alkyl levulinates were produced from esterification of levulinic acid with different alcohols using UDCaT-5. The use of solid acid catalyst made the process environmentally benign. The catalyst was reused up to four runs including the fresh one. A green and effective route for conversion of biobased levulinic acid into valuable esters is established.

Conformal sulfated zirconia monolayer catalysts for the one-pot synthesis of ethyl levulinate from glucose.

Here we describe a simple route to creating conformal sulphated zirconia monolayers throughout an SBA-15 architecture that confers efficient acid-catalysed one-pot conversion of glucose to ethyl levulinate.

Optimized enzymatic synthesis of levulinate ester in solvent-free system

Ethyl levulinate, produced through esterification of levulinic acid, is a ketoester with various applications. Synthesis of ethyl levulinate was carried out in solvent-free system using immobilized Candida antarctica lipase B (Novozym 435) as the biocatalyst for the reaction. Response surface methodology (RSM) with a four-factor-five-level central composite rotatable design (CCRD) was employed to study and optimize the reaction conditions in the synthesis of levulinate ester. The effect of four main reaction parameters including time, temperature, ethanol/levulinic acid molar ratio and amount of enzyme on the synthesis of ester were analyzed. A quadratic polynomial model was fitted to the data with an R 2 of 0.8993. Model validation experiments show good correspondence between actual and predicted values. A high conversion yield (96.2%) was obtained at the optimum conditions of 51.4 °C, 41.9 min, 292.3 mg enzyme amount and 1.1:1 alcohol:acid molar ratio.