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Alkyl Levulinates from Furfuryl Alcohol Using CT151 Purolite As Heterogenous Catalyst: Optimization, Purification, and Recycling

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Alkyl Levulinates from Furfuryl Alcohol Using CT151 Purolite As Heterogenous Catalyst: Optimization, Purification, and Recycling Article Alkyl Levulinates from Furfuryl Alcohol Using CT151 Purolite as Heterogenous Catalyst: Optimization, Purification, and Recycling Mattia Annatelli, Giacomo Trapasso, Lucrezia Lena and Fabio Aricò * Department of Environmental Sciences, Informatics and Statistics, Ca’ Foscari University of Venice, 30172 Venezia, Italy; [email protected] (M.A.); [email protected] (G.T.); [email protected] (L.L.) * Correspondence: [email protected] Abstract: Commercially available Purolite CT151 demonstrated to be an efficient acid catalyst for the synthesis of alkyl levulinates via alcoholysis of furfuryl alcohol (FA) at mild temperatures (80–120 ◦C) and short reaction time (5 h). Reaction conditions were first optimized for the synthesis of ethyl levulinate and then tested for the preparation of methyl-, propyl-, isopropyl-, butyl, sec-butyl- and allyl levulinate. Preliminary scale-up tests were carried out for most of the alkyl levulinates (starting from 5.0 g of FA) and the resulting products were isolated as pure by distillation in good yields (up to 63%). Furthermore, recycling experiments, conducted for the preparation of ethyl levulinate, showed that both the Purolite CT151 and the exceeding ethanol can be recovered and reused for four consecutive runs without any noticeable loss in the catalyst activity. Keywords: alkyl levulinate; furfuryl alcohol; alcoholysis; purolite resin; heterogenous catalyst; biobased platform chemicals; biorefinery Citation: Annatelli, M.; Trapasso, G.; Lena, L.; Aricò, F. Alkyl Levulinates from Furfuryl Alcohol Using CT151 Purolite as Heterogenous Catalyst: Optimization, Purification, and 1. Introduction Recycling. Sustain. Chem. 2021, 2, Alkyl levulinates (AlkLevs) are biobased chemicals that occupy a strategic role in 493–505. https://doi.org/10.3390/ biomass valorization as potential substitutes of several oil-based compounds [1,2]. Their suschem2030027 applications in the fields of biofuels (additives), plasticizers, lubricants, flavoring agents, fragrances, and green solvents have been extensively investigated [3,4]. Academic Editor: Matthew Jones In particular, short-chain (C1–C4) AlkLevs, i.e., methyl (MetLev), ethyl (EtLev) and butyl levulinate (BuLev), showed great potential as oxygenated fuel additives for gasoline Received: 24 May 2021 blends [5–7]. AlkLevs were also employed as green solvents either as such or as precursors Accepted: 4 August 2021 of γ-valerolactone (GVL), a cyclic ester that has found interesting applications in perfume Published: 13 August 2021 and food industries in addition to being exploited as solvent and fuel additive [8,9]. As depicted in Figure1, several synthetic routes to AlkLevs are reported in the Publisher’s Note: MDPI stays neutral literature; raw biomass or monomers derived from biomass can be both used as starting with regard to jurisdictional claims in materials. The related synthetic procedures are based on an alcoholysis reaction promoted published maps and institutional affil- by (Brønsted) acid catalyst where the product selectivity depends on the substrate used [4]. iations. In fact, direct conversion of biomass such as cellulose leads to AlkLevs with low or moderate yields due to a combination of solubility issues and drastic conditions required for the depolymerization step [10]. In this view, starting from simple C6 carbohydrates such as D-Glucose or D-Fructose is more convenient, although once again this acid-catalyzed Copyright: © 2021 by the authors. methodology suffers from some solubility issues and the need for relative high temperature Licensee MDPI, Basel, Switzerland. (120–200 ◦C) [11–21]. It should also be mentioned that, when D-Glucose is employed This article is an open access article as substrate, an isomerization step is required, and this negatively affects the AlkLev distributed under the terms and yield. Furthermore, using simple carbohydrates as starting materials often resulted in conditions of the Creative Commons the formation of a certain amount of humins due to the presence of 5-(hydroxymethyl) Attribution (CC BY) license (https:// creativecommons.org/licenses/by/ furfural (HMF) as reaction intermediate, a biobased platform chemical well known for its 4.0/). unstable nature. Sustain. Chem. 2021, 2, 493–505. https://doi.org/10.3390/suschem2030027 https://www.mdpi.com/journal/suschem Sustain. Chem. 2021, 2, FOR PEER REVIEW 2 Sustain. Chem. 2021, 2 494 (hydroxymethyl) furfuralIn contrast, (HMF) conversion as reaction of levulinic intermediate, acid (LA) into a alkyl biobased levulinates platform via esterification chemical is a high yielding process; however, since LA is derived from biomass, (poly)saccharides well known for its unstablewould be preferable nature. starting materials [22–24]. Figure 1. Hexoses and pentoses routed to alkyl levulinates. Figure 1. Hexoses and pentoses routed to alkyl levulinates. Taking into account these considerations, a pentose sugar would be a more suitable starting material for AlkLev preparation (Figure1). Pentose sugars such as D-xylose, In contrast, conversionobtained from of hemicellulose, levulinic areacid easily (LA) converted into intoalkyl furfural levulinates via acid-catalyzed via esterification dehydra- is a high yielding process;tion; furfural however, can then be since promptly LA reduced is derived to furfuryl from alcohol biomass, (FA) via hydrogenation. (poly)saccharides As would be preferablemore starting than 60% materials of the furfural [22–24]. produced worldwide is transformed into FA, this precursor is low cost and available in large amounts. Together with LA, FA provides the most promising Taking into accountsubstrate these for the preparationconsiderations, of AlkLevs a [pentose25]. sugar would be a more suitable starting material for AlkLevNumerous preparation acid catalysts were(Figure investigated 1). Pentose for alcoholysis sugars of FAsuch to alkyl as D-xylose, levulinates. ob- Initial studies focused on the use of homogeneous catalysts such as strong mineral acids or tained from hemicellulose,metal salts. are [26] However,easily conver the difficultted productinto furfural separation, via catalyst acid-catalyzed toxicity, and reaction dehydra- tion; furfural can thencontainer be promptly corrosion led reduced to the exploitation to furfuryl of heterogeneous alcohol (FA) catalysts, via including hydrogenation. acidic As more than 60% ionof exchangethe furfural resins [produced27–29], zeolites worldwide [30–32], (sulfated) is transformed zirconia-based into catalysts FA, [33 this–35], pre- (supported) heteropolyacids [36–39], activated carbon [40–42], functionalized organosil- cursor is low cost andica materialsavailable [43 –in48 ],large ionic amounts. liquids [49,50 Together], and several with sulfonic LA acid, FA functionalized provides the ma- most promising substrateterials for [the51–54 preparation]. Some studies of were AlkLevs also conducted [25]. employing continuous-flow appara- Numerous acidtus catalysts [32,44] or microwave-assisted were investigated procedures for alcoholysis [26,42]. Despite of this FA extensive to alkyl research levulinates. on the FA alcoholysis reaction, there are still some issues to be addressed in order to set Initial studies focusedup a on cost-effective the use andof homogeneous green procedure for catalysts its conversion such into as AlkLevs. strong In mineral fact, most acids or metal salts. [26] ofHowever, the abovementioned the difficult published product works focusedseparation, on the catalyticcatalyst system toxicity, highlighting and reac- its preparation, efficiency, and recycling. On the other hand, only limited attention was tion container corrosiondedicated led to to the the reaction exploitation scale since of experiments heterogeneous are typically catalysts, conducted including starting from acidic ion exchange resins1–10 [27–29], mmol of zeolites FA (ca. 0.1–1.0 [30–32], g). Furthermore, (sulfated) the zirconia-based purification of alkyl catalysts levulinates from[33–35], (supported) heteropolyacidsthe reaction mixture [36–39], is never activated addressed carbon in detail; [40–42], FA conversion functionalized and AlkLevs organosilica yields are primarily determined employing various analytical methods, i.e., gas chromatography, gas materials [43–48], ionicchromatography–mass liquids [49,50], spectrometry, and several or high-performance sulfonic acid liquid functionalized chromatography. materials [51–54]. Some studies wereIn this also prospect, conducted the work presentedemploying here encompassescontinuous-flow a systematic apparatus study on the[32,44] alcoholysis of FA to alkyl levulinates focusing on: or microwave-assisted procedures [26,42]. Despite this extensive research on the FA alco- holysis reaction, there are still some issues to be addressed in order to set up a cost-effec- tive and green procedure for its conversion into AlkLevs. In fact, most of the abovemen- tioned published works focused on the catalytic system highlighting its preparation, effi- ciency, and recycling. On the other hand, only limited attention was dedicated to the re- action scale since experiments are typically conducted starting from 1–10 mmol of FA (ca. 0.1–1.0 g). Furthermore, the purification of alkyl levulinates from the reaction mixture is never addressed in detail; FA conversion and AlkLevs yields are primarily determined employing various analytical methods, i.e., gas chromatography, gas chromatography– mass spectrometry, or high-performance liquid chromatography. In this prospect, the work presented here
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