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Hydrogenative Cyclization of Levulinic Acid to Γ-Valerolactone with Methanol and Ni-Fe Bimetallic Catalysts

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Hydrogenative Cyclization of Levulinic Acid to Γ-Valerolactone with Methanol and Ni-Fe Bimetallic Catalysts catalysts Article Hydrogenative Cyclization of Levulinic Acid to γ-Valerolactone with Methanol and Ni-Fe Bimetallic Catalysts 1, , 1, 1,2 Ligang Luo * y, Xiao Han y and Qin Zeng 1 College of Life Science, Shanghai Normal University, 100 Guilin Rd, Shanghai 200241, China; [email protected] (X.H.); [email protected] (Q.Z.) 2 The Public Experiment Center, University of Shanghai for Science and Technology, Shanghai 200093, China * Correspondence: [email protected] Ligang Luo and Xiao Han Contributed equally to this work. y Received: 26 August 2020; Accepted: 14 September 2020; Published: 21 September 2020 Abstract: A series of Ni-Fe/SBA-15 catalysts was prepared and tested for the catalytic hydrogenation of levulinic acid to γ-valerolactone, adopting methanol as the only hydrogen donor, and investigating the synergism between Fe and Ni, both supported on SBA-15, towards this reaction. The characterization of the synthesized catalysts was carried out by XRD (X-ray powder diffraction), TEM (transmission electron microscopy), H2-TPD (hydrogen temperature-programmed desorption), XPS (X-ray photoelectron spectroscopy), and in situ FT-IR (Fourier transform–infrared spectroscopy) techniques. H2-TPD and XPS results have shown that electron transfer occurs from Fe to Ni, which is helpful both for the activation of the C=O bond and for the dissociative activation of H2 molecules, also in agreement with the results of the in situ FT-IR spectroscopy. The effect of temperature and reaction time on γ-valerolactone production was also investigated, identifying the best reaction conditions at 200 ◦C and 180 min, allowing for the complete conversion of levulinic acid and the complete selectivity to γ-valerolactone. Moreover, methanol was identified as an efficient hydrogen donor, if used in combination with the Ni-Fe/SBA-15 catalyst. The obtained results are promising, especially if compared with those obtained with the traditional and more expensive molecular hydrogen and noble-based catalysts. Keywords: biomass ester derivatives; solvothermal processing; levulinic acid; γ-valerolactone; Ni-Fe bimetallic catalysts 1. Introduction The world is highly dependent on the utilization of fossil resources to fulfill energy needs for the production of heat and power. Nevertheless, the surplus consumption of fossil fuels is escalating the concentration of atmospheric CO2, which causes serious global warming threats [1,2]. As a solution to the above primary challenges, considerable attention has been paid to the exploitation of renewable resources [1]. In this context, the conversion of the cellulose fraction of biomass into value-added platform chemicals, such as 5-hydroxymethylfurfural (5-HMF) and levulinic acid (LA), has been thoroughly investigated [2,3]. Moreover, the transformation of LA into more added-value bio-fuels and bio-chemicals is strategic, thanks to its reactive keto and carboxylic functional groups, which can be exploited for the synthesis of many valuable bio-chemicals, such as fuel additives, fragrances, solvents, pharmaceuticals, and plasticizers [4]. Among these high-value chemicals, γ-valerolactone (GVL) is receiving considerable attention to synthesize added-value bio-chemicals, such as food additives, solvents, and drug intermediates, as well as new bio-fuels [5,6]. Three pathways have been proposed Catalysts 2020, 10, 1096; doi:10.3390/catal10091096 www.mdpi.com/journal/catalysts Catalysts 2020, 10, 1096x FOR PEER REVIEW 22 of of 14 such as food additives, solvents, and drug intermediates, as well as new bio-fuels [5,6]. Three pathwaysfor GVL production, have been as proposed reported for in SchemeGVL production,1. The first requiresas reported the high-temperaturein Scheme 1. The LAfirst conversion requires the in high-temperaturethe gas phase, occurring LA conversion via its endothermic in the gas dehydrationphase, occurring to angelicalactone, via its endothermic which isdehydration subsequently to angelicalactone,hydrogenated to which GVL. is The subsequently second occurs hydrogenated in the liquid to phase,GVL. The at lower second temperatures, occurs in the where liquid thephase, LA atketo lower group temperatures, is reduced towhere 4-hydroxyvaleric the LA keto group acid, which is reduced is in turnto 4-hydroxyvaleric dehydrated to GVL.acid, Lastly,which is the in thirdturn possibilitydehydrated provides to GVL. Lastly, the esterification the third possibility of LA to theprovid lesses reactive the esterification alkyl levulinate, of LA to which the less undergoes reactive alkylhydrogenation levulinate, and which dehydration undergoes to hydrog GVL [6enation]. and dehydration to GVL [6]. SchemeScheme 1. 1.Di Differentfferent pathways pathways for for thethe hydrogenationhydrogenation of levulinic levulinic acid acid (LA) (LA) to to γ-valerolactoneγ-valerolactone (GVL). (GVL). According to the above mechanisms, dehydration is generally favored by the presence of acid catalysts, whereas the hydrogenationhydrogenation is catalyzedcatalyzed byby transitiontransition metals.metals. Many homogeneous and heterogeneous catalysts catalysts have have been been employed employed for for the the hydrogenation hydrogenation of LA of to LA GVL to GVLin the inliquid the liquidphase phase[7]. However, [7]. However, given the given well-known the well-known drawbacks drawbacks of the homogeneous of the homogeneous catalysts (the catalysts possible (the corrosion possible ofcorrosion the equipment, of the equipment, difficult direcycle/reuse,fficult recycle and/reuse, environmental and environmental concerns), concerns), heterogeneous heterogeneous ones have ones beenhave beencertainly certainly preferred preferred [8]. Many [8]. Many noble noble metal metal catalysts catalysts have have been been tested tested for forthis thisreaction, reaction, in particular,in particular, Pt, Pt, Au, Au, Pd, Pd, Rh, Rh, and and Ru, Ru, in in many many cases cases achieving achieving promising promising catalytic catalytic performances performances with respect to GVL [[9–12].9–12]. For For example, example, Son Son et al. ha haveve studied studied the the catalytic catalytic performances performances of of Ru/C, Ru/C, Ru/SBA, Au/ZrC, and Au/ZrO catalysts for the LA hydrogenation, highlighting the good catalytic Ru/SBA, Au/ZrC, and Au/ZrO22 catalysts for the LA hydrogenation, highlighting the good catalytic performances and stability of the Au/ZrO catalyst, which can be reused five times, achieving a high performances and stability of the Au/ZrO2 catalyst, which can be reused five times, achieving a high GVL yield (90 mol %) [10]. [10]. However, However, although although the noble noble metal metal catalysts catalysts show show excellent excellent performances for the hydrogenation of such carbonyl compounds, the high costs limit their further application in the industry. On this basis, non-noble metal catalysts remain the preferred choice for improving the sustainable catalyticcatalytic transformationtransformation ofof LA LA to to GVL GVL [13 [13,14].,14]. In In particular, particular, Ni-based Ni-based catalysts catalysts (Raney-Ni, (Raney- Ni/MoOx/C, Cu/ZrO , NiCu/Al O , and Mo C) are active in this reaction [13–15]. For example, Mohan Ni, Ni/MoOx/C, Cu/ZrO2 2, NiCu/Al2 3 2O3, and2 Mo2C) are active in this reaction [13–15]. For example, et al. have examined the influence of catalysts with Ni supported on SiO , Al O , ZnO, ZrO , TiO , Mohan et al. have examined the influence of catalysts with Ni supported 2on SiO2 23, Al2O3, ZnO,2 ZrO2, and MgO, highlighting the excellent catalytic performances of Ni/SiO towards the LA hydrogenation TiO2, and MgO, highlighting the excellent catalytic performances2 of Ni/SiO2 towards the LA 1 1 hydrogenationto GVL (0.8506 to kg GVL GVL (0.8506 kg catalyst kg GVL− h −kg atcatalyst 250 ◦C)−1 h [15−1 at]. 250 The °C) characterization [15]. The characterization of these catalysts of these by catalystsFT-IR spectroscopy by FT-IR spectroscopy has indicated has that indicated both Lewis that and both Brönsted Lewis acid and sites Brönsted play an acid important sites play role an in importantthe dehydration role in the of the dehydration intermediate of the 4-hydroxypentanoic intermediate 4-hydroxypentanoic acid [16], thus acid highlighting [16], thus highlighting that the use thatof tunable the use bifunctional of tunable bifunctional catalysts is catalysts preferred is forpreferred improving for improving the catalysis the catalysis of this reaction. of this reaction. In this Incontext, this context, the addition the addition of another of another metal metal could coul modifyd modify the electronic the electronic structure structure of Ni, of decreasingNi, decreasing the theinteraction interaction between between active active metal metal and supports, and supports, thus enhancing thus enhancing the reaction the reaction activity [activity17]. For [17]. example, For example,the Cu species the Cu hadspecies an importanthad an important effect oneffect the on chemical the chemical environment environment of Ni of species Ni species and and acted acted as an electronic promoter on Ni surface active sites in Ni-Cu/Al O bimetallic catalysts, achieving the as an electronic promoter on Ni surface active sites in Ni-Cu/Al2 2O33 bimetallic catalysts, achieving the highest GVL yield of 96 mol % (250(250 ◦°C,C, 6.56.5 MPa,MPa, andand 22 h)h) [[18].18]. Regarding the possible hydrogen sources, LA hydrogenation has been carried out mainly with molecular H (0.8–6.5 MPa), both in sources, LA hydrogenation has been carried out mainly
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