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Catalytic Production of Levulinic Acid (LA) from Actual Biomass

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Catalytic Production of Levulinic Acid (LA) from Actual Biomass molecules Review Catalytic Production of LevulinicLevulinic AcidAcid (LA)(LA) fromfrom ActualActual BiomassBiomass Michela SignorettoSignoretto, Somayeh, Somayeh Taghavi, Taghavi, Elena Elena Ghedini Ghedini and and Federica Federica Menegazzo Menegazzo * * CATMAT Lab,Lab, DepartmentDepartment ofof MolecularMolecular SciencesSciences andand Nanosystems,Nanosystems, Ca’ Foscari University of Venice and Ca’ Foscari University of Venice and INSTM RUVe, via Torino 155, 30172 Venezia Mestre, Italy INSTM RUVe, via Torino 155, 30172 Venezia Mestre, Italy * Correspondence: [email protected] * Correspondence: [email protected] Received: 28 June 2019; Accepted: 26 Ju Julyly 2019; Published: 30 30 July July 2019 2019 Abstract: Catalytic conversion of actual biomass to valuable chemicals is a crucial issue in green chemistry. This review discusses on the recent approachapproach in the levulinic acid (LA) formation from three prominent generationsgenerations ofof biomasses.biomasses. Our paper highlights the impact of the nature of different different types of biomass and their complex structure and im impurities,purities, different different groups of catalyst, solvents, and reaction system, and condition andand allall relatedrelated prospros andand conscons forfor thisthis process.process. Keywords: threethree generationsgenerations of of biomasses; biomasses; actual actual biomass biomass transformation; transformation; hydrolysis; hydrolysis; levulinic levulinic acid; catalysts;acid; catalysts; biorefinery biorefinery 1. Introduction Among thethe challenging challenging issues issues that that humans humans are are struggling struggling with with in the in 21st the century, 21st century, Climate Climate change andchange Energy and securityEnergy aresecurity considered are considered as the most as important the most issuesimportant that needissues to that be addressed need to be [1 ].addressed With the rapid[1]. With depletion the rapid of fossil depletion fuels, of international fossil fuels, attempt international to raise attempt the use to of renewableraise the use energy of renewable such as biomass energy hassuch greatly as biomass increased has greatly [2–4]. Variousincreased approaches, [2–4]. Variou includings approaches, thermal, including biological, thermal, and chemo-catalytic biological, and processeschemo-catalytic have beenprocesses performed have inbeen order performed to produce in order fuels andto produce chemicals fuels from and biomass, chemicals owing from to environmentalbiomass, owing and to environmental economic needs and [5]. economic Two diff erentneeds types [5]. Two of processes different are types used of forprocesses this application. are used Thefor this first application. type is thermochemical The first type process is thermochemical in which the entire process biomass in which could the be entire considered biomass asfeedstock. could be Theseconsidered processes as feedstock. mainly include These gasification,processes mainly liquefaction, include pyrolysis, gasification, and liquefaction, high-pressure pyrolysis, supercritical and extraction.high-pressure On supercritical the other hand, extraction. individual On the fractions other hand, of biomass, individual including fractions starch, of biomass, sugars, including cellulose, andstarch, fatty sugars, acids couldcellulose, be separated and fatty and acids transformed could be separated by a hydrolysis and transformed step (catalyzed by bya hydrolysis acids or bases), step after(catalyzed which by there acids are or severalbases), after processes which for there transforming are several each processes one [ 6for]. Acid-catalyzedtransforming each hydrolysis one [6]. hasAcid-catalyzed been considered hydrolysis to be ahas crucial been stepconsidered for chemicals to be a production crucial step at for a relatively chemicals mild production temperature at a (100–250relatively◦ C).mild Furfural, temperature glucose, (100–250 5-hydroxymethylfurfural °C). Furfural, glucose, (5-HMF), 5-hydroxymethylfurfural and levulinic acid (LA) (5-HMF), are regarded and aslevulinic the key acid intermediate (LA) are regarded platform as chemicals the key intermediate [7]. platform chemicals [7]. LA is a linear C5-alkyl carbon chain that is knownknown as 4-oxopentanoic acid or gamma ketovaleric acid and also also 3-acetylpropionic 3-acetylpropionic acid. acid. It Itis isa short a short chain chain fatty fatty acid acid with with molecular molecular formula formula C5H C8O5H3 (see8O3 (seeFigure Figure 1) [8].1)[ The8]. TheBiomass Biomass Program Program of the of the US US Depa Departmentrtment of ofEnergy Energy in in 2004 2004 regarded regarded LA LA as as one of the top 12 most promisingpromising bio-basedbio-based platformplatform chemicalschemicals [[2].2]. Figure 1. The molecular structure of levulinic acid. Molecules 2019, 24, x; doi: FOR PEER REVIEW www.mdpi.com/journal/molecules Molecules 2019, 24, 2760; doi:10.3390/molecules24152760 www.mdpi.com/journal/molecules Molecules 2019, 24, 2760 2 of 20 Molecules 2019, 24, x FOR PEER REVIEW 2 of 20 LA acts asLA a acts viable as a chemicalviable chemical bridge bridge between between biomass biomass and and petroleum petroleum processing. processing. Multiple MultipleLA LA derivatives have been suggested for fuel applications, such as γ-valerolactone (GVL), ethyl levulinate derivatives(EL), have and been methyl suggested tetrahydrofuran for fuel (MTHF). applications, One of the most such important as γ-valerolactone processes is the (GVL), hydrogenation ethyl levulinate (EL), and methylof LA to tetrahydrofuran γ-valerolactone, and (MTHF). further to Oneliquid of alkenes the most with importanteight or more processes carbons. In is addition, the hydrogenation LA of LA to γ-valerolactone,can be used as a as and gasoline further and to biodiesel liquid additives alkenes by with conversion eight or to morea family carbons. of valerate In esters addition, [9– LA can 17]. Besides renewable biofuels, LA is also a promising basic chemical for other applications. As be used as a as gasoline and biodiesel additives by conversion to a family of valerate esters [9–17]. shown in Figure 2, LA can be converted to a range of multiple derivatives that have various market Besides renewableapplications. biofuels, The chemicals LA is that also are a produced promising from basic LA are chemical currentlyfor used other in several applications. industries, such As shown in Figure2, LAas can solvents, be converted resins, chemical to a intermediates, range of multiple polyme derivativesrs, electronics, thatbatteries, have adsorbents, various photography, market applications. The chemicalsplasticizers that are rubber, produced cosmetic, from drug LAdelivery are systems, currently textiles, used and in pharmaceutical several industries, products such [7,8,18– as solvents, 29]. resins, chemical intermediates, polymers, electronics, batteries, adsorbents, photography, plasticizers rubber, cosmetic, drug delivery systems, textiles, and pharmaceutical products [7,8,18–29]. Figure 2. Levulinic acid (LA) derivatives [1,17]. Figure 2. Levulinic acid (LA) derivatives [1,17]. There are several different feedstocks for synthesis of LA, including raw materials and precursors, such as polysaccharides,There are several monosaccharides, different feedstocks furfural, for 5-hydroxymethylsynthesis of LA, includ furfuraling raw (5-HMF), materials and and renewable resources,precursors, such as such the as most polysaccharides, types of monosaccharid biomasses.es, Polysaccharides, furfural, 5-hydroxymethyl including furfural starch,(5-HMF), cellulose, and renewable resources, such as the most types of biomasses. Polysaccharides, including starch, hemicellulose, and chitin, are the main components of biomass. Their hydrolysis could lead to cellulose, hemicellulose, and chitin, are the main components of biomass. Their hydrolysis could lead the formationto the of formation monosaccharides, of monosaccharides, such as such glucose as glucose and and fructose fructose [[30].30]. As can beAs seen can inbe Figureseen in Figure3, there 3, there are threeare three di differentfferent genera generationstions of biomasses: of biomasses: (i) First generation of biomass comes from food crops such as sugar, starchy crops, vegetable oil, or (i) First generationanimal fat. of biomass comes from food crops such as sugar, starchy crops, vegetable oil, or animal(ii) Second fat. generation of biomass is non-food crops such as wood, organic waste, food crop waste, (ii) Second generationand specific ofbiomass biomass crops. is Most non-food of biomasse cropss insuch this generation as wood, are organic considered waste, as the food crop waste, andlignocellulosic specific biomass biomass. crops. Most of biomasses in this generation are considered as the lignocellulosic biomass. (iii) Third generation of biomass comes from algae. Therefore, the reaction of LA production from three different generations of biomass is consecutive and usually includes three general steps (see Figure3): (i) pretreatment of biomass to extract polysaccharides, (ii) hydrolysis of polysaccharides into monosaccharides such as hexoses and pentoses, and pentoses, (iii) conversion of monosaccharides to LA during several steps [31]. Molecules 2019, 24, x FOR PEER REVIEW 3 of 20 (iii) Third generation of biomass comes from algae. Therefore, the reaction of LA production from three different generations of biomass is consecutive and usually includes three general steps (see Figure 3): (i) pretreatment of biomass to
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