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FuelProcessingTechnology197(2020)106213 A review on catalytic synthesis of energy

rich fuel additive levulinate compounds from biomass derived levulinic acid Kirtikumar
C. Badgujara,b, Vivek C. Badgujara,c, Bhalchandra M. Bhanagea,? a Department of
Chemistry, Institute of Chemical Technology, Matunga, Mumbai 400019, India b
Department of Chemistry, SIES College of Arts, Science & Commerce, Mumbai 400022,
India c Department of Chemistry, Pratap College of Arts, Science & Commerce, Amalner
425401, India
A R T I C L E I N F O Keywords: Levulinate Fuel-additive Catalysis Biomass derived Value
added chemicals A B S T R A C T Levulinate esters are unique potential value added
energy-chemicals which has signi?cantly attracted remark- able attention of global
researchers due to its potential importance as a fuel-blending chemical. Conversely,
competent synthesis of levulinate compounds is in initial phase of research which mostly
involves the challenging catalytic synthesis.
The existing literature showed that, the role of acid-functionalized catalyst is very
important for the synthesis of levulinate esters whereas, various kinds of the catalyst are
widely used in last few years to synthesize these value added chemicals. Moreover,
applications of levulinate compounds as energy products are in emergent phase which
requisites the extensive research e?orts to improve engine performance and process e?
ciency. Looking to this view, the present article execute critical evaluation of progressing
research linked to (i) potential applications of the levulinate compounds, (ii) market
scenario of levulinate synthesis, (iii) di?erent catalytic pathways of levulinate synthesis
(iv) mechanistic approach to synthesize levulinate (v) use of various catalysts to obtain
levulinates (vi) fuel blending properties of levulinates and (vii) advantages of levulinates
as a fuel blender.
Moreover, the present article also summarizes the future opportunities and challenges
associated with the development of representative levulinate synthesis biore?nary.
/
Introduction The use of daily non-renewable petroleum/diesel/natural gases/ coal
(fossil-fuels) based energy resources are insu?cient to execute the expected global
future energy demands due to increase in the world- wide population, improved
standard of living, infrastructural development and modernization [1,2].
The cost of these fossil-fuels is continuously increasing day-by-day due to their limited
existing natural resources, moreover burning of these fossil-fuels has several unavoid-
able environmental concerns such as emission of toxic-pollutants, acid- rain,
temperature-rising, smog-creation and global-warming [3,4]. At present, these fossil
based fuels do not have any promising alternative which is continuously alarming and
evoking global researchers to or- ganize alternative renewable energy resources for
future energy demand as well as security [5].
The European Union (EU) has already set a grand 2020 plan in which every EU member
state shall ensure the share of at least 10% renewable energy in all forms of transport by
2020 [6], whereas the European Parliament and the Council of European Union (EPCEU)
has set a target of minimum 27% share of renewable energy in order to secure future
energy demands by 2030 [7]. Most recent energy utilization survey showed that, in year
2015 and 2017, the share of energy obtained from renewable sources was 6.7% and
7.2% respectively [8]. In the EU, Sweden has contributed a share of 30% for use of
renewable resources in transportation fuels in 2016 [8].
According to Energy Independence and Security Act of 2007, The US needed almost 36
billions gallons of renewable fuels by the year 2022, which will be expected to have only
86% (31 billion gallons) of their actual need [9]. Looking to all above aspects there is
necessity to develop a bio-based technology for production of renewable fuels which
can satisfy and secure the need of transportation energy/fuel [1–9]. Biomass is any kind
of carbon based matter (forest/agricultural/ marine/plant/municipal residual) which is
renewable and available in fresh or waste form [10–13]. The quantity of biomass
produced is about 2.0
× 1011 tons per annum while an approximate 3.33% of this biomass is utilized by
human being or animals for the food and non-food applications [11,12]. Moreover, this
biomass is exclusive source of renewable energy which can produce carbon-based
fuels or speciality chemicals or value added chemicals for the Green and Sustainable Fu-
ture [13]. In the search of alternative renewable resources, the First
/ ? Corresponding author. E-mail address: bm.bhanage@ictmumbai.edu.in (B.M.
Bhanage). https://doi.org/10.1016/j.fuproc.2019.106213 Received 1 May 2019; Received
in revised form 4 September 2019; Accepted 5 September 2019 0378-
3820/©2019ElsevierB.V.Allrightsreserved.
Generation Biofuels are obtained from the classical food-crops via well- known
conventional technology which may create the harmful impact on the eco-system and
human/animal food-chain [14–18]. The advance Second Generation Biofuels are
obtained from the non-feed lignocellulosic material or waste which is in the
development stage of growing lignocellulosic or waste biore?nery [14–18]. At present
the concept of biore?nary is utilized broadly to obtain the value added chemicals and
liquid fuels from carbon based non-feed materials [14–18].
In 2004, the National Renewable Energy Laboratory (NREL), Paci?c Northwest National
Laboratory (PNNL), and O?ce of Energy E?ciency and Renewable Energy (OEERE) identi?
ed the levulinic acid (LVA) as one of the crucial specialty building-block chemical which
is ex- clusively generated from biomass [19]. This LVA has received massive importance
due to its broad substrate applicability to synthesize various value added chemicals such
as 1,4-pentanediol, 2-butanone, 2-methyl tetrahydrofuran, 3-hydroxy propanoic acid, 5-
nonanone, angelica lac- tone, diphenolic acid, glycerol ketal ester oligomer, levulinate
esters, succinic acid, valeric acid and valerate, ?-valerolactone, and ?-amino levulinic acid
[20,21].
Among all these value added chemicals, levulinate compounds are identi?ed as the
most vital value added energy chemicals due to their fuel-blending properties which can
assist to achieve the target of EU and EPCEU to secure the future energy demands [22].
These levulinate compounds can be synthesized by using various substrates and
respective chemical transformations [22]. In 2014, one excellent review article was
published for the production of levulinate compounds by Demolis et al. [23]. This
article was highlighting the levulinate esters synthesis and its applications [23].
However in last few years, number of research articles are continuously increasing for
the catalytic synthesis/production of the levulinate compounds which evoke us to
present a review article which can spotlight the recent advances in the catalytic synthesis
of the levulinate esters [24]. Research scenario about production of the levulinate esters
showed growing interest in the synthesis of levulinate compounds due to its potential
applications as a fuel-additive compounds [23,24]. (Fig. 1.) Looking to this view, the
present article execute critical evaluation of progressing research linked to (i) potential
applications of levulinate compounds, (ii) market scenario of levulinate synthesis, (iii) di?
erent catalytic pathways of levulinate synthesis (iv) mechanistic approach to synthesize
levulinate (v) use of various catalysts to obtain levulinates (vi) fuel blending properties of
levulinates and (vii) advantages of levulinate as a fuel blend.
Moreover, the present article also summarizes the future opportunities and challenges
associated with the development of representative levulinate biore?nary. Fig. 1. Scopus
survey for the synthesis of levulinate ester using biomass derived levulinic acid Scopus
search key: (TITLE-ABS-KEY (conversion AND of AND levulinic AND acid AND to AND
levulinate)) AND (esteri?cation) AND (LIMIT- TO (DOCTYPE, “ar”)). Potential applications
of levulinate esters Levulinate compounds possessing great commercial importance due
to the their potential applications as/in like fuel-blending components [23], bio-
lubricants [21], re?ning of mineral oils [25], chemicals synthesis/synthetic reagent [26],
polymer precursor [27], foam comprising material [28], resin precursors [29], green
solvents [30], plas- ticizer [31], food-?avour agent [32,33], coating composition [34],
pharmaceutical/cosmetics [35], degreasing surface agent/stain re- moval [36], building
blocks for polycarbonate and herbicides synthesis [33] etc. Global market scenario The
label for levulinate compounds as “Sustainable Fuel-Additives” has major positive
impact in grow of commercial market of levulinates.
According to grand view research market survey, the universal market demand of
levulinate compounds in year 2014 was 32.4 tons (valued as $ 8.8 Millions) which is likely
to reach almost 49.1 tons (valued as $ 11.8 Millions) by 2022 with compound annual
growth rate of 5.3%. [37]. Furthermore, use of levulinates as a super bio-solvent in
synthetic organic industries may widen the scope of levulinate synthesis in coming years
[37]. The major levulinate producing industries are Sigma Aldrich Pvt. Ltd., Alfa Aesar
Pvt. Ltd., Tokyo Chemical Industry Co. Ltd., Axxence Aromatic and Ventos Pvt. Ltd. etc.
[38].
According Gi- minsights analysis report, the ethyl levulinate market is at basic stage of
grow and showing steady rise along with exploration, applications and potential of ethyl
levulinate product [39]. However, the high cost of the primary raw material and its
processing is hampering the industrial pro?tability and productivity for the synthesis of
levulinate compounds which needs to be overcome in near future along with the growth
of biore?nary. Hence, sustainable and economically feasible synthetic routes of
levulinate can play important role in commercial production [39].
The long-standing and excessive exposure to ethyl levulinate may reasons to giddiness,
eye itching, lung ulcer, which limits the market expansion and corresponding
development [37]. Thus at present, the industrial scale-up and potential applications are
in primary phase of research and will have to expect for the new horizons in near future
[37]. Synthetic routes for the synthesis of levulinate ester compounds Basically there are
four pathways to synthesize the levulinate esters as shown in Scheme 1 [40–42], First
pathway is the direct one-pot synthesis of levulinate ester from cellulose via
isomerization, dehy- dration, rehydration and alcoholysis reaction in acidic media [41].
One- pot synthesis has few advantages like skipping of various reaction processing
however, this method has several drawbacks such as lower mass yield, lesser conversion,
sluggish selectivity, multiple products, humin formation etc. which limits the scope of
this route [41,42]. The second pathway involves the catalytic alcoholysis of furfuryl
alcohol which directly o?ers levulinate ester [43]. Advantage of this method is the
easiness of reaction, higher yield, moderate reaction conditions, and lesser by-product
formation [43,44].
Disadvantage of this protocol is production and availability of the furfuryl alcohol as

compared to sole biomass and levulinic acid feedstock [43,44]. The third pathway
involves reduction of furfural to furfuryl alcohol followed by catalytic alcoholysis which
directly o?ers levulinate ester [45]. Disadvantage of this method is the use of hazardous
hydrogen gas for reduction at the high reaction temperature and pressure [45]. Fourth
pathway is the direct esteri?cation of the levulinic acid using various acidic sites
possessing catalyst [23].
This is the simplest and sustainable pathway which is creating water as a side-product
[23]. Various kinds of solid acid catalysts (zeolites, silica based, heteropolyacids, mixed
metal oxide, resins, nano-structured solid acid
/ Scheme 1. Various pathways of synthesis of levulinate esters.
material etc.) are used to obtain the respective levulinate ester [23]. Moreover levulinic
acid is well commercialized product and available easily in the market. In the present
review, we have highlighted the recent scienti?c literature which focusing the basic
catalytic pathways (its processing, advantages and challenges) to obtain levulinate esters
from levulinic acid.
Catalytic synthesis of levulinate esters In ?eld of organic catalysis, various heterogeneous

recyclable catalysts (solid-acid, nano-catalyst, bio-catalyst etc.) have received massive
consideration due to their typical features like robustness to catalytic activity, stability
to reaction media, reusability and ease of applicability [46–50]. These solid acid catalysts
are of various types and can be used according to their practical applicability such as
silica- based, tungsten-based, metal-salt based, resin-based and nano-structured, etc.
Each type of this catalyst has its own advantages and limitations [46–50]. Silica based
catalyst Silica is the inorganic porous low-cost material which has globally attracted the
signi?cant attention of researchers due to its extra- ordinarily features such as proper
surface functionalization, higher surface area, catalytically active surface, chemical and
thermal stability [51–57]. Along with this, silica o?ers better mechanical stability. Pas-
quale et al.,
[51] carried out catalytic tests for the production of ethyl levulinate via esteri?cation of
levulinic acid with ethanol (Table 1, entry 1). They showed that, silica-included catalyst
o?ered three con- secutive reaction cycles. Yang and Tang [52] carried out esteri?cation
of levulinic acid with various alcohols using perchloric acid decorated nano-porous silica
(Table 1, entries 2–7). Similarly Enumula et al., [53] highlighted the use of tungsten oxide
incorporated solid acid silica- catalyst for the one-pot synthesis of alkyl levulinates
under continuous mode vapour phase conditions (Table 1, entries 8–12). Malero et al.,
[54] demonstrated sulfonic mesoporous silica as an outstanding catalyst for synthesis of

alkyl (ethyl) levulinates (Table 1, entry 13). Furthermore, they reused catalyst thrice
without its regeneration (Table 1, entry 13). Ramli et al., [55] performed production of
methyl levulinate with 69% yields using sulphated silica at mild process condition (Table
1, entry 14). Chermahini and Nazeri [56] used aluminum containing MCM-41 for the
synthesis of isobutyl and butyl levulinate, further they have used regenerated catalyst
for recycling without signi?cant loss in activity (Table 1, entries 15, 16). Maggi et al.,
[57] carried out synthesis of ethyl levulinate using silica supported sulfonic acid catalysts
which furnishes excellent conversion as well as selectivity with use of stoichiometric
quantity of alkanol (Table 1, entry 17). Esteri?cation of levulinic acid involves alcohol as a
reactant as well as solvents which is polar in nature. Silica based catalyst leads to form
the H– bonding in polar solvent, also there is possibility of dissolution of active
functionalized component of silica supported catalyst in polar solvent.
This leads to o?er simultaneous homogenous and heterogeneous catalysis and
reduces subsequent activity as well as reusability of catalyst [51]. This silica can be
functionalized into various acidic functionalities such as HClO4, H2SO4, PTSA, TFA in
which HClO4-SiO2 works as more active and robust catalyst due to higher surface area
and acidity [52]. Incorporation of the tungsten oxide into SBA-16 silica structure also
showed improvement in activity, acidity and subsequent yield of levulinate product.
This was attributed to dispersion of dynamic acidic catalytic sites of tungsten oxide
over larger surface area of SBA-16 [53]. Sulfonic acid mesostructured silica o?ers more
bene?ts over various homogenous sulphonic acid catalysts (H2SO4, PTSA, pro-
pylsulfonic acid) due to higher surface area, higher hydrophobicity and heterogeneity
which o?er recyclability. However, these silica functio- nalised catalysts may have
leaching problem. In conclusion, the functionalized modi?ed mesoporous silica
possesses the meso-porosity and strong acidity which may facilitate the acid catalyzed
reactions [53–56].
The challenges associated with the silica base catalysts are easy deactivation in the polar
solvents due to H-bonding between active silica-functionalized groups and polar
molecules [46–48]. Moreover, the cost of functionalization is a major concern while
multistage functionalization is the skilful tedious process [47–49]. Resins Resins are
organo-polymeric material which possesses the high surface area, high ion-exchange
capacities and a typical functionality
Table 1 Synthesis of fuel-additive levulinate compounds from biomass derived levulinic
acid using various catalytic systems. Entry LVA Catalyst and other reaction conditions
Mole ratio Temp Time Yield Reuse Ref.
Silica catalyst 1 EL Silica included Wells-Dawson heteropoly acid 1:64 78 °C 10 h 93

3 51 2 EL HClO4/SiO2 nanoporous solid-acid (10% w/w) 1:86 100 °C 5 h 99 5 52 3 BL
HClO4/SiO2 nanoporous solid-acid (10% w/w) 1:86 100 °C 5 h 90
g), ?ow: 30 mL min-1, liquid feed ?ow: 1 mL h-1 1:7 250 °C
g), ?ow: 30 mL min-1, liquid feed ?ow:1 mL h-1 1:7 250 °C
°C 5 h 82
4 67 31 EL Porous solid acid consisting of tungstophosphoric acid supported on
reduced graphene oxide (0.50 g) 1:7.5 80 °C 11 h 96.9 5 68 32 EL Tungstophosphoric
acid based mesoporous material anchored on MCM-41 (25 wt%) 1:5 80 °C 10 h 77.1 5
69 33 EL Organic-salt of H4SiW12O40 (4 mol%) 1:5 Re?ux 5 h 98.6
5 70 36 BL Dodecatungston phosphoric acid supported on K10 (10 mol%) 1:6 120 °C 4
h 97 3 71 37 EL H4SiW12O40 (8 mol%) 1:18 25 °C 8 h ~90 3 72 38 ML H4SiW12O40 (8
mol%) 1:18 25 °C 8 h 92
g) 1:30 80 °C ~6 h 85 Entry LVA Catalyst and other reaction conditions Mole ratio Temp
Time Yield Reuse Ref. 67 EL Carbonized carbon cryogel crystal (15 wt%) 1:19 78 °C 10 h
61.4
hybrid catalyst (2 wt%) 1:7 Re?ux 3 h 91.5
mol%) 1:10 120 °C 5 min 100
mmol, AL: 10 mL
mol%) 1:6 120 °C 5 h 99 3 101 113 LL Zirconia containing MOF UIO-66 (9 mol%) 1:1 80
°C 20 h ~90 3 101 114 CL Zirconia containing MOF UIO-66 (9 mol%) 1:1 80 °C 20 h ~82
3 101 115 OLL Zirconia containing MOF UIO-66 (9 mol%) 1:1 80 °C 20 h ~62 3 101
Nano-material catalyst 116 EL Sulphated TiO2/ZrO2 nano-composites (2 wt%), LVA:LA
1: 1 by weight,
h 77
1:2 90 °C 1.5 h 91 Entry LVA Catalyst and other reaction conditions Mole ratio Temp
Time Yield Reuse Ref. Biocatalyst ML: Methyl levulinate, EL: Ethyl levulinate, PL: Propyl
levulinate, BL: Butyl levulinate, ISPL: Isopropyl levulinate, ISAL: Isoamyl levulinate, TBL:
Tertiary butyl levulinate, BENL: Benzyl levulinate, ISBL: Isobutyl levulinate, PENL: Pentyl
levulinate, HL: Hexyl levulinate, SBL: Secondary butyl levulinate, TBL: Tertiary butyl
levulinate, HEL: Hexyl levulinate, OL: Octyl levulinate, LL: Lauryl levulinate, CL: Cetyl
levulinate, OLL: Oleyl levulinate, AL: Alcohol, LVA: Levulinic acid.
(depends on type of resin) [58–62]. The presence of the sulphonic-acid groups imparts
the acidic character in resins which initiates the acid catalyzed process [59–62].
Trombettoni et al., [58] used sulfonated cation exchange resins (Aquivion mP90) for the
synthesis of levulinate compounds using long chain aliphatic alcohols (Table 1, entries
18). Ramli et al., [59] employed ion-exchange resins (Amberlyst-15) as a solid acid
catalyst for alkyl levulinate synthesis (Table 1, entries 19–21). Fernandes et al.,
[60] showed that Amberlyst-15 played important role for the synthesis of levulinate
compound due to SO3H and SO4 functional groups (Table 1, entry 22). Kokare et al.,
[61] carried out response surface optimization for the synthesis of n-butyl levulinate
using Amberlyst-15 (Table 1, entry 23). Tejero et al., [62] executed esteri?cation of
levulinic acid with alkanol (butanol) by applying an ion exchange resins (Dowex 50Wx2,
gel-type resin) (Table 1, entry 24).
Various resin base catalysts are widely used such as Amberlyst-15, Amberlyst-16,
Amberlyst-35, Amberlyst-36, Amberlyst-39, Amberlyst- 46, Amberlyst-70, Purolite,
Dowex, polystyrene-supported p-toluensulfonic acid and Aquivion mp98 (micronized
pellets of per- ?uorosulfonic polymer etc.) for levulinate synthesis. The better yield of
levulinate compounds can be achieved using Aquivion mP98, since it hampers the
adsorption of by-product water molecules from its own surface [58]. This case is not
observed in Amberlyst and polystyrene- supported p-toluensulfonic acid.
Adsorption/residing of by-product water molecules on the catalyst surface/pores greatly
hamper the catalyst activity and respective reaction progress [55].
Amberlyst-15 is the sulfonated ion-exchange resins which are widely used instead of the
homogenous sulfonated catalyst for the synthesis of levulinate compounds. Also,
Amberlyst-70 is o?ering good yield of the product levulinate which having exceptional
thermal stability and ?exibility among all macro porous Amberlyst resins [62]. Use and
recovery of these Amberlyst-15 and Amberlyst-70 in reaction medium is very simple,
moreover it is less expensive than other resin based catalyst and hence used widely.
However, higher reaction temperature condition is greatly hampering the activity of

Amberlyst-15. In general resin shows the swelling property in all kinds of reaction media;
however extent of swelling is speci?cally more in polar reaction media. Swellings
property of resin is co-related with the ?exibility and sti?ness of resin which is depends
on the amount of divinylbenzene (cross-linker) used during fabrication of resin. Higher
the cross linking or divinylbenzene content more is the sti?ness and lesser is the swel-
ling. Enlargement of pore size occurred due to swelling property, which improves the
mass transport and consequent reaction rate.
The same is also accounted for the gel-type of resin which possessing the higher degree
of ?exibility and swelling as compared to conventional resins. Functionalization is
another important factor which is accounted for swelling and ?exibility property of resin.
In general surface functionalization and over-sulphonation reasons for higher sti?ness
of resins. Hence, Amberlyst 46 and Purolite CT224 are less active for the ester- i?cation
reactions which are surface-sulphonated and over-sulphonated respectively [62].
However, Amberlyst 70 o?ered excellent yield due to exceptional thermal stability and
non-sti?ness [62]. It is observed that, gel type resin base catalyst having greater swelling
ability and o?ers excellent yield of the levulinate compounds. Thus, gel-type resin such
as Dowex 50Xx2 o?ers better yield than macro-porous resins. The swelling of the gel
type resin in polar reaction media (reactants: levulinic acid and alcohol; by-product:
water) causes increment of parent pore size, recurrence of new pores due to swelling
and subsequent improvement in the surface area and mass transfer.
Thus in conclusion, uses of resins are o?ering advantages like easy product/reaction
mass separation, reusability of resin-catalyst and non- corrosiveness to reactor [59–62].
Also it maintains the appropriate hydrophobicity, ?exibility and porosity in the reaction
media [60–62]. The major challenges associated with the use of the resins are high
costing, sluggish thermo-stability, inability towards high boiling solvents, sti?ness,
disintegration of the basic functionality at elevated temperatures, formation of H-bonds
and destabilization of active groups [46–49]. Moreover, stirrer tank always
fractures/scratches the resins.
Heteropoly acid A heteropolyacid is a special type of acid, designed by a speci?c

combination of certain metals (tungsten, molybdenum or vanadium) and p-block non-
metals (silicon, phosphorus or arsenic) with acidic hydrogen and oxygen which is
frequently used as a reusable acid-catalyst in the synthesis of ?ne chemicals [63–75].
Several structural combinations can be prepared by changing the metal and non-metal
species [70–75]. Wu et al., [63] used 3D graphene aerogel anchored tungsto-phosphoric
acid catalyst which possessing the abundant porous structure for the synthesis of ethyl
levulinate (Table 1, entry 25). Si- milarly ethyl levulinate was synthesized by Nadiwale et
al.,
[64] applying dodeca-tungsto-phosphoric acid tethered on desilicated H-ZSM-5

catalyst (Table 1, entry 26) while Zhou et al., [65] used silver or ammonium co-doped
phosphotungstic acid for the synthesis of levulinate compound (Table 1, entry 27,28).
Wu et al., [66] and Ramli et al., [67] employed dodeca-tungsto-phosphoric acid ?xed to
Al-MCM-41 and zirconia supported phosphotungstic acid for the synthesis of hexyl le-
vulinate and ethyl levulinate respectively which further displaying the excellent
recyclability (Table 1, entries 29,30). Zheng et al., [68] and Wu et al., [69] synthesized
ethyl levulinate by using tungstophosphoric acid supported on graphene oxide and
MCM-41 respectively (Table 1, entries 31,32). Liun et al.,
[70] carried out the synthesis of ethyl, methyl and isobutyl levulinates using organic-
salt of H4SiW12O40 (Table 1, entries 33–35). Dharane and Bokade [71] proposed
synthesis of butyl levulinate using dodecatungsten phosphoric acid supported on acid-
treated clay (K-10) (Table 1, entry 36). Whereas Vilanculo et al., [72] used simple
H4SiW12O40 for synthesis of several levulinates (Table 1, entries 37–42). Manikandan,
and Cheralathan [73] used heteropoly acid supported silicalites for various alkyl
levulinate synthesis (Table 1, entries 43–45), while Lucas et al.,
[74] and Yan et al., [75] used hetero poly acid supported STA-AlSBA-15 and tungstisilicic
acid H4SiW12O40 - SiO2 for an e?cient synthesis of alkyl levulinates (Table 1, entries 46–
48). In a catalytic synthesis, fate of product formation is depends on the physico-
chemical characteristics of catalyst. The heteropolyacid supported catalyst furnishes
well acidity and o?ers better conversion of the levulinate compounds which may be
attributed to improved surface area and free dynamic catalytic sites for the processing
of reaction.
Ammonium co-doped heteropolyacid is having higher hydrophilicity, Keggin structure

with higher acidic strength as well as surface acidic sites which o?ers a higher reaction
rate than silver co-doped heteropolyacid. At the same time, higher hydrophilicity of
catalyst showed leaching of the active co-doped component of catalyst which shrinks
the reusability. To avoid the problem of higher hydrophilicity and subsequent leaching,
several authors have anchored hydrophobic graphene based compound on the
heteropolyacid which displayed reduction in leaching of catalyst.
The heteropolyacid supported catalyst o?ers better yield than sole support of AlSBA-15
or Silica or K10 or MCM-41 or Al-MCM-41 and desilicated H-ZSM-5. Among all,
desilicated H-ZSM-5 and K10 was reported to be the most feasible catalyst. These
results attributed to, excess acidic catalytic sites and surface area which enhancing the
reaction rate. However, excess heteropolyacid loading decreases the surface area due to
deposition of heteropolyacid species inside the pores/surface/ channels. Moreover, use
of the organic salts of heteropolyacid has problems like solubilization in the polar
reaction media, which subse- quently reduces the catalyst activity and recyclability.
In conclusion, heteropolyacids have several advantages since; these heteropolyacids

possess the very strong Brønsted acidity, e?ective mass transfer in?u- ence and can be
applicable as homogenous or heterogeneous catalyst based on their structural
composition and reaction synthesis solvent [66–69]. The major challenges associated
with the heteropolyacid is the lower thermal stability, lower surface area, unequal
dispersion of the positive charges, solubility in the polar solvent, catalyst reusability and
regeneration [46–48].
Zeolites Zeolites are the naturally occurring crystalline three dimensional aluminosilicate
microporous system which is interlinked by oxygen atom and possess speci?c molecular
pores, channels and cavities [76–82] (Table 1, entries 49–61). Hence, they are widely
used in/as an ion-exchangers, solid-acid catalysts and material adsorbents in various
sectors like petroleum industry, oil-re?ning plants, water puri?cation, e?uent treatment
and waste water treatment plants [76–78]. Zeolites can be designed with appropriate
variation according to their functional applications and textural properties [79–82].
Nandiwale and Bokade used various zeolites based catalyst such as micro/meso-HZ-5
zeolite (Table 1, entries 49–52) [76], modi?ed H-ZSM-5 (Table 1, entries 54) [78],
hierarchical H-ZSM-5catalyst [81] for esteri?cation of levulinic acid into various
renewable alkyl levulinates (Table 1, entry 60). All these used catalysts o?er excellent
yield and recyclability for levulinate ester synthesis. Patil, et al., [77] carried out synthesis
of ethyl levulinate by applying bimodal micro- mesoporous H/BEA-zeolite de- rivative
(Table 1, entry 53). Nandiwale et al.,
[80] as well as Maheria and Dalai [79] performed synthesis of ethyl levulinate and butyl
levulinate which was catalyzed through active and recyclable desilicated and acidic
zeolites respectively (Table 1, entries 55–59). Nandiwale et al., [82] performed
optimization via response surface methodology for modi?ed H-ZSM-5 catalyzed
synthesis of octyl levulinate (Table 1, entry 61). The zeolites H-BEA o?ers better yield due
to presence of tri-directional 12-member-ring whereas, H-MOR, H-SM-5 are mono-
directional and bi-directional zeolites respectively which possess the di?usion limitations
for the reactant molecules.
The excellent synthesis of levulinate compounds can be achieved by modi?ed

desilicated H-ZSM-5 as compared to original H-ZSM-5 due to the increase of surface
area. Desilication process involves selective extraction of silicon which causes increment
of e?ective surface area, generation of meso-porosity and improvement of mass transfer
at active catalytic sites. [64,79,80]. E?ect of various structural features such as di?erent
kinds of zeolites geometry (tri-directional 12-member-ring, mono-directional 12-
member-ring and bi-directional 10-member-ring) are useful to control the catalytic
process, zeolites acidity, surface area, channel size, pore size, Si/Al ratio and crystalanity
according to reaction system.
In conclusion, zeolites are highly selective in function, due to presence of the uniform
molecular pore/channels/cavities which allows entry of selective molecules depending
on the size of pore/channels/ cavities [77–81]. However, a major challenge associated
with the zeolite is the thermal stability and tedious designing according to their proper
applications which may hamper the acidic catalytic properties [47–49]. Internal mass
transfer di?usion limitations should be elimi- nated for e?ective catalysis. During modi?
cation, uniform dispersion of the metals or heteropolyacid and size of
pores/cavities/channels is task of skill-full hand.
Carbonaceous material Carbonaceous material is the novel type of acid catalyst which is
generally prepared by the partial pyrolysis of carbon based material at
speci?ed temperature followed by sulphonation in the presence of mineral acids like
sulphuric acid [83–88]. Major advantages include the inertness to reaction media,
improved metal adsorption, reusability, thermal stability and catalyst dispersion ability
[83–85]. Liu et al., [83] used sulphonated bagasse-carbonized solid acid for conversion
of levulininc acid into ethyl levulinate (Table 1, entry 62). Pileidis et al.,
[84] carried out transformation of levulinic acid with ethanol into ethyl levulinate
catalyzed through sulfonated hydrothermal carbon (Table 1, entry 63). Li et al., [85]
carried out preparation of loofah sponge-derived carbon sulfonic acid to carryout
catalytic process to synthesize levulinic acid into to ethyl levulinate (Table 1, entry 64).
Budarin et al., [86] carried out synthesis of versatile mesoporous carbonaceous ma-
terials (starbon) for the synthesis of ethyl levulinate (Table 1, entry 65). Zainol et al.
[87,88], used calcined carbon cryogel preparation for the catalytic synthesis of ethyl
levulinate which displayed su?ciently higher acidity than carbonized carbon cryogel
crystal (Table 1, entries 66–68) [87,88]. Various carbonaceous catalyst such as sulfonated
carbon catalyst, sponge derived carbon catalyst, starbon, calcined carbon cryogel crystal
and carbonized carbon cryogel crystal etc. have been used to carry out the synthesis of
levulinate compounds. In general, direct sulphonated carbon based catalyst displayed
excellent recyclability and higher catalytic activity (like pure sulphuric acid) due to
covalent bonding of the SO3H group to carbon based catalyst.
During fabrication of the catalyst, sulfonation temperature needs to control otherwise it

may cause poly- sulphonation and subsequent reduction of catalytic active sites [83–88].
Further calcination and carbonization are two important processes to synthesize other
carbonaceous material catalyst, in which calcined carbonaceous material o?ers the
promising catalyst as well as levulinate synthesis [87,88]. Calcined material o?ers
excellent thermal stability, acidic sites, microporosity and large total surface area as
compared to carbonized cryogel.
Moreover, the calcined material can be fabricated at lower temperature, whereas

carbonized material needed extreme higher temperature. Carbonized material
fabrication is time limiting process in which excess heating treatment for longer re-
action time may diminish the catalytic active sites and increases the process costing. In
conclusion, carbonaceous catalytic material is highly active robust catalyst. However,
major challenging issue is that, it is in developing phase, pyrolysis process is always a
non-green method which occurred at higher temperature [47–49].
Burning of carbon base material always creates the pollutants which are escaped in the
environment as lethal pollutants, uniform catalytic activity and regeneration of
catalyst is always challenging issue to work out with these types of catalysts. Zirconia
Zirconia is the solid-acid zirconium metal-oxide catalyst which is receiving enormous
attention in the scienti?c communities due to its characteristic features of porosity,
thermal stability and catalytic activity [89–94]. The su?cient pore size always evades the
di?usion constrains and facilitates the easy mass transport phenomenon for bulky and
long chain molecules [90–92]. Su et al.,
[89] very well designed a mesoporous H3PW12O40-ZrO–Si(Ph)Si hybrid catalyst to

produce methyl levulinate (Table 1, entry 69). Kuwahara et al. [90,91] performed
synthesis of ethyl levulinate by applying sulphated mesoporous zirconosilicates (Table
1, entry 70) [90] and sulphated Si-doped zirconium oxide catalyst (Table 1, entry 71) [91].
Su et al., [92] carried out pore morphology-controlled synthesis of zirconium oxide
based hybrid catalysts which was further applied for the synthesis of levulinate esters
(for example, methyl levulinate, ethyl levulinate, butyl levulinate) (Table 1, entries 72–
74). Unlu et al. [93] carried out synthesis of ethyl levulinate by using model catalyst
sulphated zirconia layered (coated) with hydroxyethyl cellulose catalytic membrane and
powder sulphated zirconia catalyst.
It was observed that, sulphated zirconia layered hydroxyethyl cellulose catalytic

membrane o?ers excellent yield of the product ethyl levulinate than simple powder
sulphated zirconia catalyst (Table 1, entries 75,76). Yadav and Yadav [94] synthesized
various alkyl levulinate compounds using heterogeneous super acidic zirconia catalysts
UDCAT-5 (Table 1, entries 77–81). Simple zirconia, silicon-doped zirconia, hybrid
zirconia, organo- hybrid zirconia has been employed for the levulinate ester synthesis.
It was observed that, introduction of the hydrophobic group in zirconia remarkably

improve the catalyst activity for levulinate synthesis. Thus among all studied zirconia
base catalysts, organo-hybrid zirconia catalyst displayed excellent reactivity towards
synthesis of levulinate compounds at mild reaction condition. The surface
hydrophobicity of hybrid catalyst can be maintained by introduction of various organic
compounds such as phenyl group or hydroxy ethyl cellulose group etc.
Introduction of the organic binder into zirconia increases the surface hydrophobicity
which increases the reaction rate. Hydrophobic zirconia catalyst inhibits adsorption of
polar molecules (ethanol, levulinic acid and water) on the catalyst surface and makes it
easily available for the transformation. The same is not true for the surface hydrophilic
catalysts which adsorb various polar molecules onto catalyst surface and make it
unavailable for catalysis, restricts the e?ective mass di?usion and hence deactivate
dynamic sites of catalyst.
Furthermore, adsorbed water molecules on the catalyst surface cause reversible esteri?
cation reaction and disturbs the equilibrium. Silicon can also be doped with zirconia
which showed improvement in acidity, meso-porosity, surface area and stability of
catalyst. However, such doped zirconia catalyst may tend to have sluggish recyclability
since; doped component can be easily leached out. Further these catalysts are non-
corrosive, easier to regenerate and mechanically stable [89–94].
Conversely, the major challenge associated with this catalyst is the leaching of sulphated
ions from the porous framework during reaction [46–49]. Moreover, some times, pores
are blocked due to trapping of larger size molecules and create di?usion restriction
which needed frequent regeneration of the catalyst. Acid catalyst Homogeneous
catalysis is simple and increases the reaction rate quite easily [95,96]. Various kinds of
simple mineral acids are generally used which are commercially easily available at low
cost.
Also, it is quite easy to modulate the acidic strength as per requirement by addition of
the native reaction solvent or water or acid [95,96]. Varkolu et al., [95] (Table 1, entries
82–85) performed esteri?cation using recyclable catalyst bio-glycerol derived carbon–
sulfonic-acid to synthesize various levulinates. Negus et al., [96] prepared ethyl
levulinate catalyzed by p-toluene sulphonic acid (PTSA) (Table 1, entries 86). Simple acid
catalysis includes acids like HCl, H2SO4, HNO3, PTSA etc. Among all these catalyst
H2SO4, and PTSA works better due to their higher acid strength.
However, all these represented catalysts are in liquid state which forms homogenous
reaction system and hence it is di?cult to use as well as reuse in the reaction. Some
authors have taken e?orts to modify these acid catalysts by developing bio-glycerol
derived carbon-sulfonic-acid to avoid post reaction challenges such as isolation,
neutralization, corrosion and recyclability. All these Bronsted acid type catalysts showed
excellent catalytic activity for the esteri?cation reaction. Homogeneous catalysis with
mineral acid always has higher reaction rate with lesser cost of catalyst.
However, a major concern is the handling issue, corrosiveness of reactor, high reaction
temperature, non-reusability, non-regeneration, hazardous aids, waste disposal, toxicity,
miscibility in hydrophobic media, down streaming and separation of catalyst from
reaction media etc. These practical di?culties discourage the use of mineral acid catalysts
in synthetic organic reaction. Metal salt Metal salts involve simple metal halides in
which metal possessing
vacant d-orbitals [97,98]. These metals are acted as site of Lewis acid and hence possess
the co-ordination features [97,98]. In general, these metal salts are activated only at the
higher reaction temperature [97,98].
They are inexpensive, easily available in the market, required no-tedious modi?cations
and are su?ciently stable [97,98]. Huang et al., [97] used various metal-salt catalysts for
synthesis of methyl levulinate ester using biomass derived levulinic acid in presence of
microwave irradiation (Table 1, entries 87–95). They have used various metal salts such
as Al2(SO4)3, CrCl3, SnCl4, SnSO4, FeCl3, CuSO4, CuCl2, AlCl3, ZnCl2, among which
Al2(SO4)3 o?ers excellent yield of methyl levulinate (Table 1, entries 87–95). Martins et
al.,
[98] carried out synthesis of various alkyl levulinates using Fe2(SO4)3 (Table 1, entry 96–
99). They have used various metal salts such as Fe2(SO4)3, FeCl3, CuSO4, FeSO4, ZnSO4,
NiSO4, MnSO4 for ethyl levulinate synthesis among which Fe2(SO4)3 o?ers excellent
yield of methyl levulinate (Table 1, entries 96, 100–105). Several metal salts are widely
used for the levulinate synthesis such as halide salts of Cr, Sn, Al, Zn, Fe, sulphate salts of
Sn, Cu, Fe, Zn, Ni and Mn etc.
The central metal ion of these salts possesses higher Lewis acidity which o?ers binding
site and higher reaction rate for the esteri?cation reaction. Higher acidity is attributed
to higher charge present on the central metal atom. Al2(SO4)3 and Fe2(SO4)3 are
having trivalent central metal atom which o?ers better yield and higher catalytic
activity than corresponding bivalent central metal atom. The central metal atom directly
coordinated to the carbonyl oxygen and increases the positivity of carbonyl carbon for
subsequent nucleophilic attack.
These meal salts may acted as homogeneous catalyst and hence requires lesser reaction
time or otherwise heterogeneous depending on reaction media or supported
appropriately in the medium [97,98]. The major challenging issues associated with these
metal salts are down- stream processing (isolation of product, isolation of metal salt,
neutralization of catalyst, reuse of catalyst and puri?cation of product). Furthermore,
higher activation energy, harsh reaction temperature, catalyst disposal and reusability
are also unavoidable challenges.
MOF Metal Organic Frameworks (MOF) are the three dimensional porous material which
are formed by linkage in between the metal-ions-oxo clusters and multidentate
hydrophobic linker [99–101]. Various combinations of metal ion, oxo-cluster and
organic linker can lead to produce the bank of MOFs which will o?er high variability
and mod- i?cations necessarily required for catalysis [100,101]. Guo et al., [99] used
copper organic framework (MOF)-supported polyoxometalates to perform selective
transformation of levulinic acid to ethyl levulinate (Table 1, entries 106).
Gupta and Kantam [100] carried out synthesis of di?erent alkyl-levulinate compounds via
use of sulfonic acid-functionalized hafnium-based MOF (Table 1, entries 107–110).
Cirujano et al., [101] performed synthesis of levulinate esters over zirconia containing
MOF as a catalyst (Table 1, entries 111–115). Among various reported MOF catalysts
(Cu-MOF, Hf-MOF and Zr- MOF), Hf-MOF is possessing the higher reaction rate at
higher temperature 120 °C, while Zr-MOF is possessing the higher reaction rate at
comparatively lower temperature 80 °C.
The alkaline organic functionality present in Zr-MOF will lead to abstract the alcoholic
proton from the alcohol, while acidic organic functionality present in Hf-MOF causes
protonation to the carbonyl group of carboxylic moiety of levulinic acid. Moreover,
MOFs possess the exceptional nano-sized pore channels and cavities [99,100]. The
Bronsted acidity in MOFs can be imported by launching sulfonated group bearing
legands which is the most dynamic approach to introduce -SO3H. Acidic MOFs possess
the Lewis acid character and hence easily o?er respective metal coordination bond
valency; also they possess the good stability (chemical/ thermal) and uniform size nano-
pores or channels [99,100].
The challenges associated with the designing of MOF is a skill-full task, and having
high risk of loss of active chemical sites during designing [46–49]. The major concern is
the severe toxicity of certain metals present in MOF which limits their practical scope
and applications. Nano-catalyst Nano-materials have received enormous importance in
last decade due to its excellent unique features such as high chemical stability, bulky
surface area, non-toxicity, and comparatively more hydrophobic surface [102–107]
(Table 1, entries 116–126).
Moreover, these nano- materials not only acts as catalyst but they also work as support
in the reaction media to tether the active catalyst, also these nano-materials can be
functionalized with active functionality depending on the type and requirement of
synthetic reaction [102–104]. Li et al., [102] carried out synthesis of ethyl levulinate
sulphated TiO2 nano-rods and ZrO2/TiO2 nano-composites (Table 1, entry 116,117).
Popova et al., [103,105] performed synthesis of ethyl levulinate using sulphated tin
oxides nano particles and sulphated zirconia oxides nano particles in their di?erent
studies (Table 1, entry 118, 120). Zhou et al.,
[104] used covalently attached organo-sulfonic acid derived titanate nano-tube hybrid
nano-structures for the synthesis of butyl levulinate (Table 1, entry 119). Song et al.,
[106] used ethane- bridged organo-silica nano-tubes which are functionalized with
functional group arene-sulfonic-acid for e?cient synthesis of ethyl levulinate (Table 1,
entry 121). Oliveira et al. [107] used sulphated carbon nano-tubes as catalysts for the
transformation of levulinic acid to ethyl levulinate (Table 1, entry 122).
Various nano-size catalyst in form of tubes (organo-silica nanotube), rods (sulphated

TiO2 nano-rods), particles (sulphated zirconia nano particles) and composites (sulphated
TiO2/ZrO2-composites) are applied for the synthesis of levulinate compounds. It was
observed that, nano-catalyst which are hydrophobic in nature were o?ering good yield
of the levulinate compounds. This is attributed to phenomenon of surface
hydrophobicity which increases the rate of esteri?cation reaction. Hydrophobic surface
catalyst hampers polar molecules adsorption on the catalyst surface and making it
available easily for the transformation.
Thus organo-silica nanotube catalyst is o?ering promising results among all reported
nano-catalyst due to their surface hydrophobicity. Furthermore, nano structure possess
higher catalytic surface to promote reaction rate. In conclusion, the notable
characteristics of nano-structures are o?ering better mass transport phenomenon to
active catalytic sites, to evade the di?usion restrictions and to a?ord grand active
catalytic surface [105–107]. The major challenges are associated with the preparation of
the nano-structures with similar chemical, physical and textural properties; otherwise it
may a?ect the reaction rate and selectivity of the desired product [46–49].
Moreover, functionalization and modi?cation of the surface of nano-structures is the

tedious and skill full task in order to incorporate the proper dynamic functionality of
nano-catalyst. Ionic liquid Simply, ionic liquids (IL) are the molten salts at room
temperature [108,109]. These ionic liquids can be prepared in vast numbers by several
permutation and combinations of IL cation and anion, in which IL cation is generally
organic while anion is inorganic or organic [108].
In last two decades, ionic liquid has received exceptional attention due to its bi-
functional role as a solvent and catalyst. Moreover, ionic liquid possess outstanding
physical and chemical qualities like broad liquid state range, better thermal stability,
non-volatility, better solvation ability, non-?ammability, wide electro-chemical range,
higher ionic- conductivity, better solubilization and stabilization ability to reactive
intermediates which make them robust medium for organic synthesis [108,109].
Khiratkar et al.,
[108] used sulphonic acid-functionalized benzimidazolium based poly-ionic-liquid as a

catalyst for the synthesis of ethyl levulinate (Table 1, entry 123), while Kalghatgi and
Bhanage [109] used 1-methyl imidazolium hydrogen sulphate as a dual
Table 2 E?ect of catalyst loading for the synthesis of levulinate compounds. Entry
Catalyst loading Yield Reference Nature's catalyst [110–115]. Several advantages are
associated with the Nature's catalysts such as biodegradability, waste-free synthesis and
easily disposability after their successful use [115–120].
Moreover,
these biocatalysts are often o?er excellent stereo-chemo-and regio-se-
Catalyst loading in %, catalyst: 3 M-SiO2, re?ux temperature, time: 4 h, mole ratio LVA to
ethanol: 1:20 1 10 44 55 2 20 52 55 3 30 55 55 4 40 51 55 5 50 47 55 Catalyst loading:
mol%, catalyst: SiO2-(CH2)3-SO3H, temperature: 75 °C, time: 2 h, mole ratio LVA to
butanol 1:1 6 0.01 15 57 7 0.1 36 57 8 1 95 57 9 5 95 57 Catalyst loading: % LVA,
catalyst: 15% (w/w) DTPA/DH-ZSM-5, temperature: 351 K, mole ratio LVA to butanol 1:6,
time: 4 h, agitation speed: 250 rpm, 10 0.10 72 64 11 0.15 76 64 12 0.20 82 64 13 0.25 95
64 Catalyst loading: wt%, catalyst: H-BEA catalyst, mole ratio LVA to butanol 1:7, time: 4
h, temperature: 120 °C; stirring speed: 400 rpm 14 7 70.2 79 15 10 82.2 79 16 12 85.1 79
17 14 62.1
79 Catalyst loading: wt%, mole ratio, catalyst: Loofah sponge-derived carbon, LVA to
ethanol 1:5, temperature 80 °C, time 8 h. 18 0 0 85 19 2.5 72 85 20 5.0 86 85 21 7.5 88 85
22 10.0 88 85 23 12.5 86 85 Catalyst loading in mg, mole ratio hexanol to LVA 4:7 mmol,
solvent: methyl tertiary butyl ether: 2.5 mL; temperature 45 °C; rotation speed, 200 rpm,
time 8 h. 24 40 33 114 25 100 72 114 26 120 99 114 27 140 97 114 28 150 97 114
performer of catalyst and solvent for the synthesis of levulinate esters (Table 1, entries
124–126).
Only two research articles are reported direct synthesis of levulinate compounds using
levulinic acid and IL which involves imidazolium as a cation while hydrogen sulphate as
an anionic counterpart. [MIM] [HSO4] was found to be the best suited ionic liquid
among studied ([MIM][HSO4], [BIM][HSO4], [HIM][HSO4], [OIM][HSO4]) ionic liquids.
This is due to reason of increase of chain length from methyl to butyl to hexyl to octyl of
cation counterpart which increases the steric hindrance, viscosity of IL and decreases
acidic functionality.
Increase in the steric hindrance causes di?usion constrain to reactant molecules at active
catalytic sites whereas, increase of viscosity limited the mass transportation rate of
reacting molecules. Thus [MIM][HSO4] is the most suited IL catalyst for the levulinate
ester synthesis. These ionic liquids can o?ers binding sites and active side arms;
moreover, ionic liquid can provides active media to work out various metal salts/ions/
complexes etc. [108,109]. The major challenges associated with ionic liquid is their
fabrication cost, viscosity, disposable issue, separation techniques, poor reusability, non-
regeneration of catalyst, corrosiveness and condition of speci?cally designed reactors.
Lipase Biocatalysis is booming at present era for an organic synthesis research due to
its unique features such as enzymes are recognized as lectivity [120–127]. These
biocatalysts work at mild reaction temperature and can be easily incorporated in
greener reaction media [112–118]. They are non-hazardous to environment, energy
saving, obtained from natural resources and safe to use, hence they are con- sidered as
a green sustainable catalyst [122–127].
Salvi and Yadav [110] used surface functionalization of SBA-15 for immobilization of
lipase Candida Antarctica B (CAL B) which was further used for the catalytic test to
carry out synthesis of alkyl levulinates (Table 1, entries 127,128). Zhou et al., [111]
performed synthesis of long chain alkyl levulinates using CAL B immobilized on meso-
molding three-dimensional macro-porous organo-silica as a biocatalyst (Table 1, entries
129–131). Yadav and Borkar [112] proposed kinetic model of synthesis of n-butyl
levulinate for the immobilized CAL B lipase catalyzed reaction (Table 1, entry 132). Lee
et al.,
[113] performed bio- catalyzed synthesis of ethyl levulinate ester in a solvent-free

system (Table 1, entry 133). Badgujar and Bhanage [114] carried out thermo- chemical
energy assessment to synthesize levulinates using immobilized lipase biocatalyst CAL B
(Table 1, entries 134–142). Badgujar and Bhanage [115] performed lipase catalyzed
synthesis of alkyl levulinates in supercritical carbon dioxide (Table 1, entries 143–150).
Various fungal and bacterial lipases are used for the present synthesis.
Among all studied lipases, CAL B showed excellent activity for this transformation. Lipase
possesses the amino acid lid at the catalytic active sites of lipase to pass reactants to
active catalytic amino- acid triad of enzyme. However, the superior activity of CAL B was
recognized due to lack of ‘?ap or lid’ which facilitates quite easy di?usion of the
reacting molecules to the dynamic biocatalytic sites of lipase. Moreover, most active,
stable and bead immobilized form of the lipase CAL B is easily available in market which
is directly used in the reaction system.
Conversely, other lipases need modi?cations via immobilization process or genetic
engineering to employ in reaction media, which is a task of skilful hands. Many times
enzyme activity gets lost or decrease in immobilization or in genetic engineering
process. However, immobilization process o?ers easy recyclability and improves the sta-
bility of enzymes towards reaction media. Thus commercially available immobilized CAL
B lipase is the most active and stable form of lipase which displayed excellent catalytic
activity for synthesis of levulinate compounds.
In conclusion, the biocatalysts are non-hazardous and ab- solutely greener in nature.
The major challenging issue related with these biocatalysts is stability towards reaction
media, organic substrates, operational condition, reusability and cost of production.
Immobilization, rational designing, protein engineering and directed evaluation are
expensive and time-consuming methodologies to improve or to develop the
biocatalyst for organic transformation.
Further these biocatalyst developing methodologies do not o?er any assurance for the
success of designing of biocatalysts and its activity. Reaction engineering aspect E?ect of
catalyst loading Catalyst loading plays an imperative role since, availability of catalytic
sites and substrate mass transfer are vital parameters which a?ect the process yield as
well as process e?ciency [114,115]. Ramli et al., [55] observed that, EL yield was increased
as catalyst loading increased from 10 wt% to 30 wt%. Further increase of catalyst
loading from 30 to 50 wt% showed decrease in yield of EL (Table 2, entries 1–5).
The lesser reaction yield at higher catalyst loading was attributed to increase of reaction
mixture viscosity and mass transfer limitation due to higher catalyst loading. Maggi et
al., [57] optimized reaction process for catalyst loading in the range of 0.01 to 5 mol%
(Table 2, entries 6–9). They showed that, 1 mol% catalyst loading is enough to achieve
maximum
conversion of BL. Nandiwale et al., [64] proposed that, reaction rate and yield was
increased as catalyst loading increased from 0.10 to 0.25%, hence higher yield of EL was
obtained at 0.25% catalyst loading Table 3 E?ect of mole ratio of LVA: alcohol for the
synthesis of levulinate compounds.
/ Entry Mole ratio Yield Reference

(Table 2, entries 10–13). Maheria et al., [79] depicted the in?uence of
catalyst loading which showed that, yield of butyl levulinate synthesis increase as the
catalyst loading is increased from 7 to 12 wt%. Further increase of catalyst loading from
12 to 14 wt% showed decrease in yield (Table 2, entries 14–17). Similarly, Li et al., [85]
also reported that, catalyst loading increases the yield of EL synthesis. Further they also
showed that, the reaction of levulinate ester synthesis cannot be performed without
catalyst (Table 2, entries 18–23).
Badgujar and Bha- nage [114] studied the in?uence of biocatalyst loading on hexyl levu-
linate synthesis which showed increment of hexyl levulinate yield at higher biocatalytic
loading (120 mg) (Table 2, entries 24–28). Further increase in the biocatalyst loading
beyond 120 mg did not have signi?cant impact on the yield of biocatalyst which was
attributed to ex- istence of additional catalytic sites than actual necessity. In conclusion,
lower catalyst loading required more reaction time to get higher reaction yield.
Several times it was observed that, reaction yield increases as the catalyst loading
increases which is attributed to the involvement of active catalytic sites available at
higher catalyst loading. Sometimes, surplus available catalytic sites (due to excess
catalyst loading) do not actively participate in the reaction process and Catalyst: SiO2-
(CH2)3-SO3H, catalyst loading: 1%, mole ratio: LVA: ethanol, temperature: 100 °C, time:
2 h. 1 1:1 96 57 2 1:2 95 57 3 1:5 96 57 Catalyst: 15% (w/w) DTPA/DH-ZSM-5, catalyst
to LA ratio: 0.25, mole ration: LVA: ethanol, temperature: 351 K, time: 4 h, agitation
speed: 250 rpm 4 1:6 90 64 5 1:8 95 64 6 1:10 89 64 7 1:12 85 64 Catalyst: Loofah
sponge-derived carbon, mole ratio: LVA: ethanol catalyst dosage 5.0
wt %, temperature: 80 °C, time 8 h. 8 1:2.5 65 85 9 1:5 86 85 10 1:7.5 82 85 11 1:10 79 85

12 1:12.5 77 85 13 1:15 75 85 Catalyst: UDCat-5, mole ratio: LVA:ethanol, catalyst
loading: 0.01 g/cm3, agitation speeds: 1000 rpm, temperature: 160 °C, time 3 h 14 1:15
80 94
E?ect of reactant mole ratio It is always essential to optimize the mole ratio of reactants
to get higher yield, process e?ciency as well as to avoid progress of side reaction and
the bi-product formation [114,115]. Maggi et al., [57] found that, 1:1 mole ratio of LVA:
ethanol was the best suitable mole ratio (Table 3, entries 1–3). Nandiwale et al.,
[64] observed that, reaction yield increased as the moles of alcohol (ethanol) increased
(upto 1:8), further increment in alcohol (1:10 or 1:12 mole ratio of LVA:ethanol) moles
cause decrease in the yield of levulinate ester synthesis (Table 3, entries 4–7). Li et al.,
[85] observed that, esteri?cation e?ciency was found to be highest for 1:5 mole ratio of
LVA to ethanol. Further change of mole ratio from 1:5 to 1:15 causes decreases in the
yield of the subsequent product (Table 3, entries 8–13). This is attributed to fact that,
additional ethanol quantity causes dilution of the reaction media.
Yadav and Yadav [94] proposed that, the initial reaction rate and yield increased as the
alcohol mole ratio changes from 1:15 to 1:20 which is required to attain the reaction
equilibrium quickly (Table 3, entries 14–16). Zhou [111] reported that, mole ratio 1:10
(LVA:butanol) is the best suitable mole ratio to obtain higher yield of butyl levulinate
(Table 3, entries 17–21). Further they also reported that, excess addition of butanol in
reaction media increases the dilution and reduces the mass transfer and subsequent
yield of the reaction.
In conclusion, synthesis of levulinate ester using levulinic acid is the esteri?cation

reaction which is reversible in nature. Inhibition of backward reaction or shifting of
equilibrium towards forward reaction always increases the yield of the product. The
boiling point of ethanol is 78 °C, which is lower than that of water. Hence, higher
reaction temperature always evaporates the ethanol fastly as compared to water,
which leads to make de?ciency of one of the essential alcoholic reactant to synthesize
levulinate ester.
This situation promotes the reverse reaction (back-hydrolysis) and shifted equilibrium
towards left hand side. To avoid this alcohol as a reactant is added in the execs quantity.
Thus, reaction rate is enhanced by addition of excess alcoholic component; however,
excess alcohol may cause dilution of active reacting species and reduces the mass
transfer and subsequent reaction rate. The use of the stoichiometric amount of both
reactants is not recommended, since by-product water occupies the actual dynamic
catalytic sites and di- minishes the catalyst activity.
This can be avoided by the use of excess alcohol which suppresses the role of water in
catalyst deactivation and in reverse hydrolysis. E?ect of solvent The selection of reaction
media for the organic reaction is a tricky task as solvent display signi?cant role in easy
dissolution, dispersion of reactants in reaction media, mass-di?usion of substrate to
dynamic catalytic sites and easy product recovery [44,58,69,109,114,115].
Synthesis of levulinate compounds can be carried out by esteri?cation of levulinic acid

with alcohols which speci?cally involves the use of four types of solvents: alcohol itself as
a solvent (excess alcoholic reactant), organic solvent, supercritical ?uid and ionic liquid
[108,110–115]. In literature, several reports presented use of alcohol as a reactants as
well as solvent for the synthesis of levulinate compounds [51–58]. Use of excess alcohol
reagent is essential for reversible endothermic esteri?cation reaction which is carried
out at relatively higher temperature [57,64].
At higher reaction temperature alcohol may get evaporate quickly which create de?
ciency of essential alcoholic reactant to synthesize levulinate compound [84,111].
Further evaporation of alcohol from the reaction solvent increases the fractional
concentration of by-product water molecules [85,94]. This in-situ condition causes
catalyst deactivation as well as shifting of reaction equilibrium towards left hand side
(reverse hydrolysis) which ulti- mately reduces the yield of levulinate compound.
To avoid this alcohol is used in excess quantity which acts as suppressant for back
hydrolysis. Organic solvent generally not used for levulinate ester synthesis via chemical
catalysis, as excess use of alcohol itself acts as a reactant as
Table 4 E?ect of various solvents for the synthesis of levulinate compounds. / Entry Rpm
Yield Reference / Catalyst: Immobead immobilized CAL B, hexanol: LVA 4:7 mmol,
solvent 2.5 mL; biocatalyst: 120 mg; temperature 45 °C; orbital rotation speed, 200 rpm,
time 8 h.
Table 5 E?ect of reaction temperature for the synthesis of levulinate compounds. / Entry
Temperature Yield Reference / Mole ratio LVA: butanol 1:1, catalyst: SiO2-(CH2)3-SO3H,
catalyst loading 1%, time: 2 h. (for entry 1: 7 h)
1 Methyl tert-butyl ether 97 114 1 50 79 57 2 Diethyl ether 89 114 2 75 95 57 3
Tetrahydrofuran 84 114 3 100 96 57 Mole ratio LVA:ethanol 1:5, Catalyst: Loofah
sponge-derived carbon, catalyst dosage 5.0 wt%, time: 8 h Catalyst: Acrylic resin
immobilized CAL B, LVA:butanol 0.014:0.010, co-solvent: 4 40 26 85 2.2 cm3; biocatalyst:
250 mg; supercritical carbon dioxide pressure: 9 MPa; 5 50 42 85 temperature: 323 K;
time 5 h.
6 60 64 85 6 Without co-solvent 40 115 7 70 72 85 7 Hexane 63 115 8 80 88 85 8 Ethyl
methyl ketone 99 115 9 90 83 85 Mole ratio: LVA: butanol 1:10, catalyst: immobilized
lipase on meso-molding 3- dimensional macroporous organosilica, time 4 h Catalyst:
[MIM][HSO4] (ration of IL to LVA:0.25), LVA: pentanol 1:2, temperature: 10 30 25 111 90
°C; time 1.5 h, rpm 700. 11 40 38 111 11 [MIM][HSO4] 91 109 12 50 32 111 / 13 60 23
111 well as solvent [55,87]. However, biocatalysis cannot perform well in alcoholic or
polar solvents since, vital trace amount of water present in biocatalyst vicinity is pulled-
o? (stripped down) in polar reaction solvent which is essentially required for biocatalyst
to remain active Mole ratio: hexanol:LVA 4:7, solvent: methyl tert-butyl ether, 2.5 mL;
biocatalyst: 120 mg; orbital rotation speed, 200 rpm, time 8 h 14 25 19 114 15 35 56 114
16 40 72 114 17 45 99 114
[114,115].
For the same reason, highly polar reaction solvents are also avoided for the biocatalytic
synthesis, whereas, various non-polar to
slightly polar solvents can be used for biocatalytic synthesis. However, use of highly
non-polar solvent is not feasible for levulinate synthesis, due to solubility problem of
levulinic acid in non-polar solvent. Bad- gujar and Bhanage [114] observed that,
moderately polar methyl tert- butyl ether was solvent of the best choice for the lipase
catalyzed levulinate synthesis reaction than polar solvents (such as di-ethyl ether,
tetrahydrofuran, methylene dichloride and 1,4 dioxane etc.) (Table 4, entries 1–5).
Another important choice of solvent for levulinate synthesis is supercritical carbon
dioxide which is recommended as sustainable green solvent [115].
This supercritical carbon dioxide can be used as a major solvent which has low viscosity
and low dielectric constant, whereas, alcohol/levulinic acid has dissimilar viscosity and
dielectric constant. To carry out levulinate synthesis, both alcohol and levulinic acid
should be get solubilised in supercritical carbon dioxide solvent which can be solved by
use of small amount of suitable co-solvent. Badgujar and Bhanage [115] reported sole
use of supercritical carbon dioxide solvent for butyl levulinate synthesis which o?ers 40%
yield, whereas, use of small amount of moderately polar co-solvents (ethyl methyl
ketone, diethyl ether) o?ers excellent yield (> 95%) of product levulinate compound than
non-polar (hexane, toluene) co-solvents (Table 4, entries 6–10).
Thus the use of these moderately polar co-solvents in supercritical carbon dioxide
maintains su?cient activity of biocatalyst and improves dissolution of reactants into
supercritical carbon dioxide to enhance the reaction rate of levulinate synthesis. Another
important alternative as a solvent for esteri?cation reaction is the use of ionic liquid in
reaction. Kalghatgi and Bhanage [109] used ionic liquid methyl imidazolium hydrogen
sulphate [MIM][HSO4] for the synthesis of pentyl levulinate (Table 4, entry 11).
Herein, ionic liquid plays as a bi-functional role of ‘Solvent’ as well as ‘Catalyst’, also
they possess the exceptional characteristics such as high solvation ability, wide liquid
range, high ionic conductivity, stabilization of reaction intermediates and better
thermal stability than conventional solvents [109]. Moreover, these ionic liquids can
function to o?er binding and active side arms for catalysis to synthesize levulinate
compounds at relatively moderate temperature 90 °C. The major out- come of the use
of IL in levulinate synthesis is insolubility of the product pentyl levulinate esters.
Thus, these ILs can be well separated from the reaction mass and can be e?ciently
recycled upto 5 recycles without signi?cant loss in yield [108,109]. E?ect of reaction
temperature Synthetic reaction temperature is a crucial parameter to consider the cost
and energy utilization of process and scale-up synthesis [114,115]. Experimentally it is
observed that, solid-acid catalyst activation for the esteri?cation reaction occurred at
higher reaction temperature [51–60].
Furthermore, esteri?cation reaction is endothermic reaction which endorse reaction
equilibrium to forward direction (right hand side) at higher reaction temperature
[57,64,85,945]. Thus the study of in?uence of the reaction temperature has enormous
importance in chemistry, since, increase of reaction temperature leads to promote the
molecular collision and subsequent reaction rate. How- ever, achievement of higher
reaction temperature is energy demanding process which raises the process costing.
Maggi et al.,
[57] showed increment of reaction yield as temperature increases from 50 °C to 75 °C,
further increment of temperature beyond 75 °C has negligible e?ect on reaction yield
(Table 5, entries 1–3). Li et al., [85] reported increase of reaction yield as temperature
increases from 40 °C to 80 °C, further increment of temperature beyond 80 °C showed
decrease in the reaction yield, since, ethanol itself is get evaporated at the temperature
beyond 80 °C (Table 5, entries 4–9). However, Zhou [111] found that highest yield of
levulinate compound can be obtained at 40 °C using catalyst lipase immobilized on
meso- molding 3-dimensional macroporous organosilica compound.
Further increase of temperature beyond 40 °C causes decrease in the yield of levulinate

compound due to high temperature sensitivity of biocatalyst immobilized lipase (Table
5, entries 10–13). Similarly, Badgujar and Bhanage [114] carried out levulinate ester
synthesis at very mild reaction condition (at 45 °C) using biocatalyst Candida
Antarctica B Li- pase, wherein they achieved highest 99% yield (Table 5, entries 14–17).
They studied the e?ect of reaction temperature in the range of 25–45 °C to verify the
most suitable reaction temperature for enzymatic synthesis, since enzymes are very
prone to degrade at higher reaction temperature.
In conclusion, it is observed that, systematic increase of reaction

temperature causes enhancement of molecular collision in between reacting molecules
which linearly increases the reaction rate and subsequent yield of corresponding
levulinate compound. Most of the conventional chemical catalysts are stable at
elevated reaction temperature and demands higher reaction temperature for the
endothermic ester- i?cation reaction. Contrary to this, biocatalytic reaction processes
under mild reaction conditions to avoid biocatalyst deactivation.
Thus, appropriate reaction temperature boosts up catalyst performance, reduces

media viscosity, increases reactant solubility and increases the mass-transport in?uence.
Moreover in literature, temperature optimization study is correlated with the energy of
activation study, which demonstrating energy requirement for the given reaction
system. Thus, lower activation energy signi?es superior catalytic e?ciency, lesser reaction
processing time and advanced reaction rate.
E?ect of speed of agitation and mass transfer It is essential to check the mass transfer
in?uence for the heterogeneous system like synthesis of levulinate ester using solid
base catalysts in which both reactants are in the liquid phase while catalyst is in solid
phase [94,114]. E?ective mass transfer of the reactants to the active sites/pores of
catalyst generally a?ects reaction in positive way [64,88]. This e?ective mass transfer of
the catalyst can be achieved by the appropriate rotation speed of agitator or ba?es or
rotating needle. In various mass transfer analyses study, the mass transfer in?uence was
observed upto certain speed of rotation.
For example, Nandiwale et al., [64] found increase of the reaction yield when speed of
rotation is increased from 100 rpm to 200 rpm for use of heteropoly acid type of
catalyst. Further increase of speed beyond 200 rpm did not have any mass transfer in?
uence (Table 6, entries 1–4). Zainol et al., [88] as well as Yadav and Yadav [94] did not
observe any mass di?usion resistance for the speci?ed reaction system for the carbon
cryogel and zirconia based catalyst (Table 6, entries 5–10).
Yadav and Borkar [112] observed impact of mass di?usion limitation for immobilized
lipase biocatalyst. The reaction yield was found to be increased when rotation per
minutes increases from 200 to 750 rpm (Table 6, entries 11–14). Fur- ther increase of the
rotation beyond 750 rpm has negative impact on the yield of levulinate synthesis. Thus
in conclusion, external mass transfer a?ects the levulinate synthesis, since levulinic acid is
the viscous reactant as compare to the Table 6 E?ect of speed of agitation for the
synthesis of levulinate compounds.
Entry Rpm Yield Reference Catalyst: DTPA/DH-ZSM-5, catalyst loading: 15% (w/w), mole
ratio LVA: ethanol 1:8, catalyst to LVA ratio: 0.25; temperature: 351 K; time 4 h. 1 100 81
64 2 150 88 64 3 200 95 64 4 250 95 64 Catalyst: carbon cryogel, catalyst loading: 25
wt%, mole ratio LVA:ethanol 1:15, temperature: 78 °C, time: 1 h 5 100 26 88 6 200 26
88 7 300 26 88 Catalyst UDCaT, catalyst loading 0.01 g/cm3, LVA:ethanol 0.0375:0.75
mol, temperature 160 °C. 8 800 99 94 9 1000 99 94 10 1200 99 94 Catalyst: CAL-B,
catalyst loading 35 mg, mole ratio LVA;butanol 0.01:0.02 mol, solvent: tetra-butyl methyl
ether up to 15 mL, temperature 50 °C, and bio-catalyst 35 mg. alcoholic substrate.
The e?ective agitation of the reaction media can overcome the problem of reaction
homogeneity and the mass transport in viscous reaction media. Further e?ective mass
transport avoided the accumulation of by-product like water inside the porous catalytic
media. Poor agitation and mass transfer hamper the reaction yield and process e?ciency,
further enormous amount of energy is required to achieve the e?ective mass di?usion by
rotation/agitation.
In general macro-porous catalytic material and media suspended (?oating) catalyst can
sustain in poor mass transfer process however, biocatalyst, high weighted and micro-
porous catalyst needs e?ective agitation for the reaction progress. Excess agitation may
avoid actual catalyst surface contact with reactants, since, catalyst may be thrown
outside of reaction system and stick to upper wall of reactor. E?ect of substrate
structure Substrate study has enormous importance in order to develop a commercial
protocol, hence it is essential to study synthesis of variety of levulinate esters having
carbon chain and branching from C1 to C8 [53,72,100].
In literature study it is observed that, all primary alcohols having carbon chain length C1
to C4 are easily converted into the respective levulinate compound [53,76,98].
Branched primary alcohol (with carbon chain length C1 to C4) substrate also has more
or less same reaction rate [53,72]. However, secondary alcohols o?er poor to sluggish
levulinate yield due to steric obstruction at reactive catalytic sites which inhibits
nucleophilic attack of hydroxyl group of alcohol.
It is observed that, long-chain (carbon chain beyond C5) substrate molecules o?er
sluggish reaction yield at prolonged reaction time [100,114,115]. This may be attributed
to di?usion restriction of long- chain substrate molecules to micro porous active
catalytic sites. More- over, long-chain molecules displayed hydrophobic-hydrophobic
inter- action with catalyst like lipases and metal organic frameworks, which reduces the
rate of reaction [53,72,100].
Reaction set up, product separation and recyclability Esteri?cation reaction is carried out
by various ways of reaction set up which involves the reactor round bottom ?ask with
re?ux condenser, closed system stainless steel batch reactor, continuous ?ow reactor,
membrane reactor and supercritical ?uid reactor [53,59,62,93,97]. The round bottom ?
ask with re?ux condenser needs proper cooling condition to avoid the evaporation of
reactants and products, since reaction temperature is too high [59]. A closed system
stainless steel batch reactor involves the internal inert gas at a particular pressure in
order to maintain the liquid phase [62,76].
Con- tinuous ?ow reactor system involves catalyst bed through which reaction mixture
(containing substrates) is allowed to pass with a particular ?ow rate using feed pump
[53]. Pervaporation catalytic membrane reactor can be used to obtain the levulinate
compounds which will o?ers reactive separation system [93]. A supercritical ?uid more
speci?cally supercritical carbon dioxide can be used as a reaction solvent in static
mode for the synthesis of levulinate esters [115].
In practice, reaction down-steam processing has great importance in order to recycle

catalyst, to separate product from reaction mass, to purify product from by-
products/impurities and to improve the process e?ciency [114,115]. Practically reaction
is quenched by maintaining the cooling condition. Homogenous reaction mass is
directly subjected for the solvent extraction process immediately after quenching of re-
action to get pure levulinate compound. Heterogeneous reaction mass is separated
from the catalyst by simple ?ltration or vacuum ?ltration or centrifugation process to get
catalyst-free crude reaction mixture. Se- parated catalyst is washed properly to remove
traces of the reaction mass.
Further it is dried or stored or regenerated as per the need of next subsequent reaction.
In general, yield in catalyst recyclability may get reduced due to catalyst leaching or
catalyst deactivation or due to
handling loss in previous reaction cycle.
/ Scheme 2. Mechanism of acid catalyzed synthesis of levulinate esters.
The desired levulinate product can be extracted using catalyst-free crude reaction
mixture by solvent extraction process. In solvent extraction process, levulinate
compound preferentially shifted in organic solvent through extraction process, while
both unreacted reactants are shifted in aqueous phase due to polar nature.
The extracted phase (organic solvent) can be evaporated by vacuum evaporation to get
pure levulinate compounds. Many times reactive distillation process is much useful to
achieve higher e?ciency of product separation in which reaction and separation of
product (from reaction mass) is carried out simultaneously during the progress of
reaction [61]. Mechanism for synthesis of levulinate esters from biomass derived
levulinic acid Acid catalyzed mechanism In case of acid catalyzed mechanism, carbonyl
oxygen gets coordinated with the active acid catalyzed site (Scheme 2) [51–53,55,60].
Due to this coordination, carbonyl carbon positivity increases which then leads to form
carbocation [51–53]. This carbocation is get attacked by nucleophilic alcoholic group
(oxygen) and eliminates the protonated hydroxyl group of levulinic acid which tends to
o?er desired product levulinate ester [55,60]. Metal salt catalyzed synthesis of levulinate
esters The central metal ion of these salts possesses the high Lewis-acidity which o?ers
binding site for the carbonyl oxygen atom of acidic functionality of levulinic acid
(Scheme 3).
The central metal atom of metal salt is directly coordinated to the carbonyl oxygen,
eliminates X- and leads to create carbocation. This carbocation is get attacked by the
nucleophilic oxygen of alcoholic group and tends to form sp3 carbon. This tetravalent
carbon converted into trivalent sp2 carbon of levulinate ester with elimination of water
molecule. This process continuously occurs in cyclic manner. MOF catalyzed synthesis of
levulinate esters The acidic functionality incorporated in the MOF causes protonation of
the carbonyl oxygen atom of levulinic acid (Scheme 4) which leads to form sp2
carbocation.
This carbocation is get attacked by alcoholic oxygen (nucleophile) and form sp3 carbon.
This tetravalent sp3 carbon is getting converted into trivalent sp2 carbon with an
elimination of water molecule to form levulinate ester. However in case of base cat-
alyzed MOF, nucleophile (alcoholic oxygen) directly attacks on the sp2 hybridized acidic
carbon of levulinic acid (Scheme 5). The carbonyl oxygen of levulinate leads to form
coordination with the metals of MOF and increases the positivity of carbonyl oxygen.
The nucleophilic attack of alcoholic oxygen is promoted with abstraction of alcoholic

proton by basic functionality incorporated in the MOF. Finally in this repetitive cycle
elimination of the water molecule occurs with breaking of metal-carbonyl oxygen
coordination which will o?ers levulinate compound and catalyst MOF into its original
state. Ionic liquid catalyzed synthesis of levsulinate esters In case of ionic liquid (IL)
catalyzed mechanism, carbonyl oxygen gets coordinated with the IL cation as an active
catalytic site of IL (Scheme 6).
Due to this coordination, hybridization of carbonyl carbon changes from sp3 to sp2 with
increase in positivity of carbonyl carbon and subsequent formation of carbocation. At
the same time, IL anion abstract alcohol proton while nucleophilic oxygen of alcoholic
group attacks on the carbocation and leads to form tetravalent sp3 moiety. This
tetravalent sp3 moiety eliminates water as well as and IL molecule to o?er desired
levulinate ester.
Biocatalytic mechanism of synthesis of levulinate esters The lipase catalyzed biocatalytic

mechanism consists of triad of catalytically active amino-acids (serine, aspartic acid and
the histidine) which basically reacts with the levulinic acid (1) (Scheme 7) [124–127].
Initially, glycine and serine residues form the Michaelis- Menten complex with the
levulinic acid functionality (2) which then converted into the intermediate having the
tetrahedral geometry (3) [126,127]. Afterwards, the serine hydroxyl attacks and causes
the dis- charge of aqua molecules as the by-product with formation of an enzyme-acyl
complex (4) [124–126].
In the next step, nucleophilic species (any alcohol) quickly attacks on the electron de?
cient centre (carbonyl carbon) of an enzyme-acyl covalent intermediate (5) and lead to
o?er another intermediate having tetrahedral geometry (6) which ?nally breaks into the
desired product levulinate (7) [124,125,127]. During this process, active amino-acids
present in the catalytic triad assist to abstract protons and to form H-bonds which
increase the positivity into the carbonyl carbon. This is essential for the further
processing of reaction equilibrium towards right hand side for completion of reaction
[119, 122, 125, 126].
/ Scheme 3. Mechanism of metal salt catalyzed synthesis of levulinate esters.
/ Scheme 4.
Mechanism of acidic functionality MOF catalyzed synthesis of levulinate esters. Scheme

5. Mechanism of basic functionality MOF catalyzed synthesis of levulinate esters.
Importance and fuel blending properties of levulinate compounds Levulinate esters are
very well known recognized as an essential energy-chemicals and fuel-additive agents
which are blended with the automobile fuel due to excellent fuelling properties (Fig. 2)
[128].
These levulinates (speci?cally methyl-, ethyl-, butyl- levulinate) o?ers marvellous

characteristics to fuels (after blending in appropriate composition) such as ?ow-
property, spark property, lubricity, ?ash point-, cloud-point- stability etc. [128].
Moreover, it also promotes the cleaner combustion process of the fuel with reduction of
harmful exhausting pollutants (for example CO, CO2, hydrocarbon, sulphur) [128]. Thus,
these levulinate blended fuels o?er better engine and fuel e?ciency without engine
modi?cation and hence European Union has directed the blending of these levulinate
additives in fuels which assisting to ensure the share of renewable energy in
transportation fuel [129]. Various fuel properties are a?ected by the addition of
levulinate in the fuel, some of the recent articles related to the performance of the le-
vulinate blended fuels and engine e?ciency are discussed herewith [130–142].
/ Scheme 6.
Mechanism of ionic liquid catalyzed synthesis of levulinate esters.

/ Scheme 7. Mechanism of biocatalyst (lipase) catalyzed synthesis of levulinate esters.
emission [135]. Tian et al., [136] observed superior anti-knock quality for ethyl levulinate
and methyl levulinate [136]. The better anti-knock property is attributed to the
molecular structure of ethyl levulinate and methyl levulinate which are producing stable
intermediates during the auto-ignition process and slow-down the reaction rate [136].
Tian et al.,
[137] proposed that, blending of levulinate do not have distinct phases and corrosive e?
ect, while it improved density of fuel [137]. Zhi-Wei et al. [138], found that, distillation,
cold-?lter-plugging- point, closed-cup ?ash-point and solidifying-point of levulinate
blended fuel is remarkably improved. Moreover, density, cetane-number and kinematic-
viscosity of fuel blends are modi?ed which is according to International Fuel Standard
criteria [138]. Unlu et al.,
[139] observed that, the levulinate blended biodiesel was less-viscous whereas, the acid-
number value and the pour-point were increased for levulinate blended biodiesel upto
some extent [139]. Besides this, the levulinate blending is improving the cold-?ow
performance property of biodiesel [139]. Along with this, Srikanth et al., observed modi?
ed values of ?ash-point, acid-value and viscosity for the levulinate blended fuel [140].
Ghosh et al., [141] proposed that, ethyl levulinate is the best additive which also function
like octane-booster. Thus, looking to the
Fig. 2. General properties to access blended fuels. Joshi et al.,
[130] found that, blending of ethyl levulinate (15%) improves the cold-?ow properties of
fuel [130]. Moreover, they observed that, the cloud-point, pour-point and cold-?lter
plugging-points of biodiesel can be improved by blending an additive ethyl levulinate,
whereas, kinematic-viscosities and the ?ash-point are get reduced with rising blend of
ethyl levulinate [130]. Similar kinds of results were also reported by Windom et al., [131].
The blend of 20% ethyl levulinate +79% petroleum diesel +1% co-additive increases
almost 7% oxygen content of fuel, while this blend is speci?cally o?ers the cleaner-
burning than pure diesel [131]. Besides this, levulinate blended fuel also possesses the
higher lubricity and lower sulphur content [131,132]. Chuck and Donnelly proposed that,
blending of the butyl levulinate increases the cleaner combustion with reduction of
particulate matter [133] as well as smoke emissions [134]. Wang et al.,
[135] reported several observations for levulinate blends such as levulinate fuel-blends
showed good miscibility, improvement in other fuel properties such as closed-cup-?ash-
point, kinematic-viscosity and lowering of CO above advantages and features, levulinate
is found to be a superior fuel- blender or fuel-additive agent. Challenges and
opportunities Solid acid catalyst is o?ering robust catalytic system, recyclability, isolation
advantages and special co-ordination features for the ester- i?cation reactions.
At present conventional solid acid catalyst are widely used in research laboratory and in
few industries. The uses of modern acid catalysts (MOF, resins, nano-catalyst, IL and
carbonaceous materials) are limited only upto invention and lab scale synthesis. Hence,
there is need to augment the development in modern acid catalysis which involves the
real practical applications for industrial scale- up synthesis. For this technological
advancement and renovation are essentially needed to employ new type of acid catalyst
(MOF, resins, nano-catalyst, IL and carbonaceous materials) which involves newly
designing of reactors according to use of catalyst features.
Since, dif- ferent types of catalyst needed di?erent types of reactors according to
catalyst characteristics. Further, various catalytic aspects such as activation energy,
initial reaction rate, catalyst inhibition factor, kinetics
and turn over frequency (TOF) are essential to study for determination of most robust
catalytic system. Various catalytic in?uencing parameters such as catalyst stability
(thermal and chemical), catalyst leaching, internal di?usion constrain, catalyst
regeneration and reusability need special attention to address before transferring the
process to industrial scale-up synthesis which may help to achieve an e?cient catalytic
protocol for industrial organic transformation. Green Chemistry principles and green
metric parameters should be get accessed for the catalytic organic synthesis to make
the process greener.
These green metric parameters assist to select waste-free and cost-e?ective protocols
which may o?er sustainable eco- friendly synthesis of desired levulinate compounds.
Green metric parameters evaluation is the best way to compare various catalytic system,
which includes the determination of mass intensity, E-factor, mass productivity, reaction
e?ciency and number of catalyst reusability. According to current literature survey, it is
apparently seen that, activation of solid-acid catalysis required an elevated temperature
which will ask for the high energy requirement. Thus it is a key challenging issue to
reduce the reaction temperature.
Further very harsh reaction conditions violet the green chemistry principles. To circum-
vent this green chemistry contravention, there is need to employ the sustainable
alternative such as biocatalytic protocols (microbes or enzyme) which may take time
for the industrial scale-up development. However it will completely o?er 100% greener
protocol to synthesize renewable fuels from renewable biomass derived substrates
using renewable bio-catalysts at mild reaction conditions.
Very few research articles are analyzing the blending fuel properties and engine
performance of levulinate blends. Impact of blending of di?erent compounds in fuel
(Fuel blend selection) and di?erent blend compositions for example 5%, 10%, 15%, 20%
etc. (Fuel blend optimization) is needed to access by all means considering an engine
e?- ciency and emission performance with respect fuel standards. The environmental
concern (Emission performance) is the most important parameter considering the
emission of various gases and global warming, which needs extra attention to address.
Thus the “Performance, Assessment and Comparison” aspect of fuel blend need a
comprehensive study to develop a potential “Blended Fuel”. Detail evaluation of various
fuel related parameters (as shown in Fig. 2) and overall techno-economical analysis
needs to evaluate for comparative account of engine performance with fuel additives.
Literature review showed that, engine performance study of methyl-, ethyl- and butyl-
levulinates are well studied and hence attention need to be paid to synthesize other
small, branched and long chain alkyl levulinates to ?nd out more e?ective and potential
fuel blending additives. Conclusion and future viewpoint In conclusion, levulinate
compounds are essential energy compounds which possesses the potential for fuel-
blending.
Moreover, these levulinate compounds are having the wide applications in day to day
life. Levulinate compounds are synthesized by four various pathways using substrates
such as dedicated biomass feedstock or levulinic acid or furfural or furfuryl alcohol.
Synthesis of levulinate compounds from biomass derived levulinic acid using acidic
catalyst is the most e?cient pathway. Since, levulinic acid o?ers excellent yield of
levulinate compounds and commercially easily available in market than other sub-
strates. Various catalytic systems are used to synthesize levulinates from the levulinic
acid.
Every catalytic system has its own advantages and disadvantages which are discussed in
details considering the future scale-up approach. However, use of the greener and bio-
based catalytic system is more recommended to build a bio-based sustainable society.
Extensive e?orts are needed for the successful technology transfer from lab scale to
industry scale for the synthesis of levulinates through robust catalytic system. Blending
of levulinate compounds (methyl levulinate, ethyl levulinate and butyl levulinate) in the
fuel boost-up the fuel e?ciency. Moreover, it improves the physico-chemical,
combustion and emission performance of the engine.
Exploration are still needed for the synthesis of other small, branched, long chain
levulinates. Further assessment of in?uence of fuel-blending of these levulinates should
be on top priority of research to search most e?cient bending levulinate species.
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Date: Senin, Juni 08, 2020

FuelProcessingTechnology197(2020)106213 A review on catalytic synthesis of energy

Disadvantage of this protocol is production and availability of the furfuryl alcohol as

Catalytic synthesis of levulinate esters In ?eld of organic catalysis, various heterogeneous

[54] demonstrated sulfonic mesoporous silica as an outstanding catalyst for synthesis of

Silica catalyst 1 EL Silica included Wells-Dawson heteropoly acid 1:64 78 °C 10 h 93

However, higher reaction temperature condition is greatly hampering the activity of

Heteropoly acid A heteropolyacid is a special type of acid, designed by a speci?c

[64] ap- plying dodeca-tungsto-phosphoric acid tethered on desilicated H-ZSM-5

Ammonium co-doped heteropolyacid is having higher hydrophilicity, Keggin structure

In conclusion, heteropolyacids have several advantages since; these heteropolyacids

The excellent synthesis of levu- linate compounds can be achieved by modi?ed

During fabrication of the catalyst, sulfonation temperature needs to control otherwise it

Moreover, the calcined material can be fabricated at lower temperature, whereas

[89] very well de- signed a mesoporous H3PW12O40-ZrO–Si(Ph)Si hybrid catalyst to

It was observed that, sulphated zirconia layered hydroxyethyl cellulose catalytic

It was observed that, introduction of the hydrophobic group in zirconia remarkably

Various nano-size catalyst in form of tubes (organo-silica nanotube), rods (sulphated

Moreover, functionalization and modi?cation of the surface of nano-structures is the

[108] used sulphonic acid-functionalized benzimidazolium based poly-ionic-liquid as a

[113] performed bio- catalyzed synthesis of ethyl levulinate ester in a solvent-free

/ Entry Mole ratio Yield Reference

wt %, temperature: 80 °C, time 8 h. 8 1:2.5 65 85 9 1:5 86 85 10 1:7.5 82 85 11 1:10 79 85

In conclusion, synthesis of levulinate ester using levulinic acid is the esteri?cation

Synthesis of levulinate compounds can be carried out by esteri?cation of levulinic acid

Further increase of temperature beyond 40 °C causes decrease in the yield of levulinate

In conclusion, it is observed that, systematic increase of reaction

Thus, appropriate reaction temperature boosts up catalyst performance, re- duces

In practice, reaction down-steam processing has great importance in order to recycle

The nucleophilic attack of alcoholic oxygen is promoted with abstraction of alcoholic

Biocatalytic mechanism of synthesis of levulinate esters The lipase catalyzed biocatalytic

Mechanism of acidic functionality MOF catalyzed synthesis of levulinate esters. Scheme

These levulinates (speci?cally methyl-, ethyl-, butyl- levulinate) o?ers marvellous

Mechanism of ionic liquid catalyzed synthesis of levulinate esters.

Cheng, Hydrolysis of lignocellulosic materials for ethanol production: a review,

Vijay, Bioconversion of algae to methane and subsequent utilization of digestate for

Raghavan, Review: Sustainable production of hydroxymethylfurfural and levulinic acid:

Patent WO2007094922A2, 2007. D.J. Yontz, Fabricating Fragrant Formulations from

Wiredu, Acidic Ionic Liquid Catalyzed One-Pot Conversion of Cellulose to Ethyl

Rothenberg, Silica- supported sulfonic acids as recyclable catalyst for esteri?cation of

Liu, 3D graphene aerogel anchored tungstophosphoric acid catalysts: Characterization

Wu, Tungstophosphoric acid-based mesoporous materials anchored to MCM- 41:

Silva, H4SiW12O40-catalyzed levulinic acid es- teri?cation at room temperature for

Chen, One-step synthesis of mesoporous H4SiW12O40 catalysts for the production of

Bokade, Optimization by Box–Behnken experimental design for synthesis of n-hexyl

Titirici, Esteri?cation of Levulinic acid into ethyl levulinate catalysed by sulfonated

Yamashita, Esteri?cation of levulinic acid with ethanol over sulfated mesoporous

Leadbeater, The preparation of ethyl levulinate facilitated by ?ow processing: the

Qi, Selective conversion of biomass-derived levulinic acid to ethyl levulinate catalyzed by

Leahy, Synthesis and characterization of sulfated TiO2 nanorods and ZrO/TiO2

Popova, In?uence of the preparation method of sulfated zirconia nanoparticles for

Khiratkar, Sulphonic acid-functionalized benzimidazolium based poly ionic liquid

Bhanage, Thermo-chemical energy assessment for production of energy-rich fuel

Bhanage, Application of lipase immobilized on the bio- compatible ternary blend

K.C. Badgujar, B.M. Bhanage, B.M. Bhanage, Enhanced biocatalytic activity of

Zhiwei, A comparison on physical and chemical properties of several alternative fuel

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