Fuel Processing Technology 197 (2020) 106213

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Fuel Processing Technology

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A review on catalytic synthesis of energy rich fuel additive levulinate T

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 LE I N FO A B S T R A C T

Keywords: Levulinate esters are unique potential value added energy-chemicals which has significantly attracted remark-
Levulinate able attention of global researchers due to its potential importance as a fuel-blending chemical. Conversely,
Fuel-additive competent synthesis of levulinate compounds is in initial phase of research which mostly involves the chal-
Catalysis lenging catalytic synthesis. The existing literature showed that, the role of acid-functionalized catalyst is very
Biomass derived
important for the synthesis of levulinate esters whereas, various kinds of the catalyst are widely used in last few
Value added chemicals
years to synthesize these value added chemicals. Moreover, applications of levulinate compounds as energy
products are in emergent phase which requisites the extensive research efforts to improve engine performance
and process efficiency. Looking to this view, the present article execute critical evaluation of progressing re-
search linked to (i) potential applications of the levulinate compounds, (ii) market scenario of levulinate
synthesis, (iii) different catalytic pathways of levulinate synthesis (iv) mechanistic approach to synthesize le-
vulinate (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 opportu-
nities and challenges associated with the development of representative levulinate synthesis biorefinary.

1. Introduction
The use of daily non-renewable petroleum/diesel/natural gases/
coal (fossil-fuels) based energy resources are insufficient to execute the
expected global future energy demands due to increase in the world-
wide population, improved standard of living, infrastructural develop-
ment and modernization [1,2]. The cost of these fossil-fuels is con-
tinuously 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 de-
mand 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 de-
velop 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 ap-
plications [11,12]. Moreover, this biomass is exclusive source of re-
newable 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
Available online 16 September 2019
0378-3820/ © 2019 Elsevier B.V. All rights reserved.
K.C. Badgujar, et al.
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 lig-
nocellulosic material or waste which is in the development stage of
growing lignocellulosic or waste biorefinery [14–18]. At present the
concept of biorefinary 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), Pacific
Northwest National Laboratory (PNNL), and Office of Energy Efficiency
and Renewable Energy (OEERE) identified 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, γ-valerolactone, and Δ-amino
levulinic acid [20,21]. Among all these value added chemicals, levuli-
nate compounds are identified 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 de-
mands [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 pro-
duction 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) different
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 le-
vulinate as a fuel blend. Moreover, the present article also summarizes
the future opportunities and challenges associated with the develop-
ment of representative levulinate biorefinary.
20
16
Number of articals
12
8
4
0
Before 2011 2013 2015 2017 2019
2009 Year
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 (esterification) AND (LIMIT-
TO (DOCTYPE, “ar”)).
2
Fuel Processing Technology 197 (2020) 106213
2. 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], refining of mineral oils [25], chemicals
synthesis/synthetic reagent [26], polymer precursor [27], foam com-
prising material [28], resin precursors [29], green solvents [30], plas-
ticizer [31], food-flavour 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.
3. 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
profitability and productivity for the synthesis of levulinate compounds
which needs to be overcome in near future along with the growth of
biorefinary. 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].
4. 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 offers 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 offers 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 esterification 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, hetero-
polyacids, mixed metal oxide, resins, nano-structured solid acid
K.C. Badgujar, et al.
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 scientific literature which focusing the basic catalytic pathways
(its processing, advantages and challenges) to obtain levulinate esters
from levulinic acid.
5. Catalytic synthesis of levulinate esters
In field of organic catalysis, various heterogeneous recyclable cat-
alysts (solid-acid, nano-catalyst, bio-catalyst etc.) have received mas-
sive consideration due to their typical features like robustness to cata-
lytic 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-struc-
tured, etc. Each type of this catalyst has its own advantages and lim-
itations [46–50].
5.1. Silica based catalyst
Silica is the inorganic porous low-cost material which has globally
attracted the significant 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 offers better mechanical stability. Pas-
quale et al., [51] carried out catalytic tests for the production of ethyl
levulinate via esterification of levulinic acid with ethanol (Table 1,
entry 1). They showed that, silica-included catalyst offered three con-
secutive reaction cycles. Yang and Tang [52] carried out esterification
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 re-
generation (Table 1, entry 13). Ramli et al., [55] performed production
3
Fuel Processing Technology 197 (2020) 106213
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 significant 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).
Esterification 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 offer simultaneous homogenous and hetero-
geneous 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 dy-
namic acidic catalytic sites of tungsten oxide over larger surface area of
SBA-16 [53]. Sulfonic acid mesostructured silica offers more benefits
over various homogenous sulphonic acid catalysts (H2SO4, PTSA, pro-
pylsulfonic acid) due to higher surface area, higher hydrophobicity and
heterogeneity which offer recyclability. However, these silica functio-
nalised catalysts may have leaching problem. In conclusion, the func-
tionalized modified 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 func-
tionalization is the skilful tedious process [47–49].
5.2. Resins
Resins are organo-polymeric material which possesses the high
surface area, high ion-exchange capacities and a typical functionality
K.C. Badgujar, et al. Fuel Processing Technology 197 (2020) 106213

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 5h 99 5 52
3 BL HClO4/SiO2 nanoporous solid-acid (10% w/w) 1:86 100 °C 5h 90 – 52
4 ISPL HClO4/SiO2 nanoporous solid-acid (10% w/w) 1:86 100 °C 6h 85 – 52
5 ISAL HClO4/SiO2 nanoporous solid-acid (10% w/w) 1:86 100 °C 6h 70 – 52
6 TBL HClO4/SiO2 nanoporous solid-acid (10% w/w) 1:86 100 °C 5h 68 – 52
7 BENL HClO4/SiO2 nanoporous solid-acid (10% w/w) 1:86 100 °C 10 h 45 – 52
8 ML Tungsten oxide incorporated SBA-16 catalyst (0.5 g), flow: 30 mL min−1, liquid feed flow: 1 mL h−1 1:7 250 °C – 96 – 53
9 EL Tungsten oxide incorporated SBA-16 catalyst (0.5 g), flow: 30 mL min−1, liquid feed flow: 1 mL h−1 1:7 250 °C – 95 – 53
10 PL Tungsten oxide incorporated SBA-16 catalyst (0.5 g), flow: 30 mL min−1, liquid feed flow: 1 mL h−1 1:7 250 °C – 94 – 53
11 BL Tungsten oxide incorporated SBA-16 catalyst (0.5 g), flow: 30 mL min−1, liquid feed flow:1 mL h−1 1:7 250 °C – 94 – 53
12 ISBL Tungsten oxide incorporated SBA-16 catalyst (0.5 g), flow: 30 mL min−1, liquid feed flow:1 mL h−1 1:7 250 °C – ~65 – 53
13 EL Sulfonic mesostructured silica (7 wt%) 1:4.86 117 °C 2h 100 3 54
14 ML Sulphated silica (30%) 1:20 64 °C 4h 69 3 55
15 BL Aluminum-containing MCM-41 (1%) 1:5 120 °C 8h 90 10 56
16 ISBL Aluminum-containing MCM-41 (3%) 1:5 110 °C 8h 98 – 56
17 EL Silica supported sulfonic acid catalyst (1 mol%) 1:1 75 °C 2h 94 6 57

Resin catalyst
18 PENL Aquivion mP98 (10 mol%) 1:10 90 °C 24 h 92 5 58
19 ML Amberlyst-15 (30%) 1:20 64.7 °C 5h 82 – 59
20 EL Amberlyst-15 (30%) 1:20 78.4 °C 5h 71 – 59
21 BL Amberlyst-15 (30%) 1:20 117.74 °C 5h 55 5 59
22 EL Amberlyst-15 (2.5 wt%) 1:5 343 K 5h ~54 4 60
23 BL Amberlyst-15 (20 wt%) 1:4 397 K 75 min 97.03 – 61
24 BL Dowex 50Wx2, gel-type resin (0.8%) 1:3 80 °C 8h 94 – 62

Heteropolyacid catalyst
25 EL 3D Graphene aerogel anchored tungstophosphoric acid (45 wt%) 1:10 80 °C 9h 89.1 5 63
26 EL Dodecatungstophosphoric acid supported on desilicated H-ZSM-5 as catalyst (0.25 wt% to LVA), speed of 1:8 351 K 4h 94 4 64
agitation: 250 rpm
27 BL Ammonium co-doped phosphotungstic acid (1.5%) 1:2 120 °C 2h 99 4 65
28 BL Silver co-doped phosphotungstic acid (1.5%) 1:2 120 °C 2h 92 – 65
29 HL Dodecatungstophosphoric acid anchored to Al-MCM-41 (25 wt%) 1:5 100 °C 10 h 100 6 66
30 EL Zirconia supported phosphotungstic acid (1 g) 1:17 150 °C 3h 97.3 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 Reflux 5h 98.6 – 70
34 ML Organic-salt of H4SiW12O40 (4 mol%) 1:5 Reflux 5h 100 – 70
35 ISBL Organic-salt of H4SiW12O40 (4 mol%) 1:5 Reflux 5h 87.8 5 70
36 BL Dodecatungston phosphoric acid supported on K10 (10 mol%) 1:6 120 °C 4h 97 3 71
37 EL H4SiW12O40 (8 mol%) 1:18 25 °C 8h ~90 3 72
38 ML H4SiW12O40 (8 mol%) 1:18 25 °C 8h 92 – 72
39 PL H4SiW12O40 (8 mol%) 1:18 25 °C 8h 90 – 72
40 BL H4SiW12O40 (8 mol%) 1:18 25 °C 8h 91 – 72
41 SBL H4SiW12O40 (8 mol%) 1:18 25 °C 8h 72 – 72
42 TBL H4SiW12O40 (8 mol%) 1:18 25 °C 8h 14 – 72
43 PL Heteropoly acid supported on silicalite-1 (100 mg) 1:5 100 °C 5h 90 4 73
44 BL Heteropoly acid supported on silicalite-1 (100 mg) 1:5 100 °C 5h 93 – 73
45 HEL Heteropoly acid supported on silicalite-1 (100 mg) 1:5 100 °C 5h 76 – 73
46 EL Hetero poly acid supported STA-AlSBA-15 (20 wt%) 1:10 75 °C 5h 87.4 3 74
47 ML Tungstosilicic acid (104 mg), LVA: 205 mg, AL:2 mL, cyclohexane 5 mL, Temp 65 °C, Time 6 h. – 65 °C 6h 73 4 75
48 EL Tungstosilicic acid (104 mg), LVA: 205 mg, AL:2 mL, cyclohexane 5 mL, Temp 75 °C, Time 6 h. – 75 °C 6h 67 4 75

Zeolite catalyst
49 ML Micro/Meso-HZ-5 catalyst (20 wt%) 1:8 393 K 5h 91 – 76
50 EL Micro/Meso-HZ-5 catalyst (20 wt%) 1:8 393 K 5h 95 – 76
51 BL Micro/Meso-HZ-5 catalyst (20 wt%) 1:8 393 K 5h 96 – 76
52 OL Micro/Meso-HZ-5 catalyst (20 wt%) 1:8 393 K 5h 98 6 76
53 EL Bimodal micro–mesoporous H/BEA zeolites catalyst (20 wt%) 1:6 78 °C 5h 40 4 77
54 BL Desilicated H-ZSM-5 catalyst (20% to LVA) 1:6 393 K 5h 95 6 78
55 BL H-BEA catalyst (10 wt%) 1:7 120 °C 4h 82.2 5 79
56 BL H-MOR catalyst (10 wt%) 1:7 120 °C 4h 29.5 – 79
57 BL H-Y catalyst (10 wt%) 1:7 120 °C 4h 32.2 – 79
58 BL H-SM-5 catalyst (10 wt%) 1:7 120 °C 4h 30.6 – 79
59 EL Modified H-ZSM-5 catalyst (20 wt%) 1:8 393 K 5h 98 7 80
60 HL Hierarchical H-ZSM-5 catalyst (24 wt%) 1:9 401 °C 5h 97.2 5 81
61 OL Modified H-ZSM-5 catalyst (25.4 wt%) 1:7.56 393 K 4h 99 7 82

Carbonaceous catalyst
62 EL Sulphonic carbon (Bagasse carbonized) based catalyst (0.3 g) 1:5 120 °C 9h 88.2 5 83
63 EL Sulfonated hydrothermal carbons catalyst (5 wt%) 1:5 60 °C 1h 91.5 – 84
64 EL Loofah sponge-derived carbon (5 wt%) 1:5 80 °C 10 h 91 4 85
65 EL Starbon (0.1 g) 1:30 80 °C ~6 h 85 – 86
66 EL Calcined carbon cryogel crystal (25 wt%) 1:15 150 °C 4h 86.5 – 87
(continued on next page)

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K.C. Badgujar, et al. Fuel Processing Technology 197 (2020) 106213

Table 1 (continued)

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 – 87

68 EL Craboncryogel crystal (25 wt%) 1:15 150 °C 4h 86.5 – 88

Zirconia catalyst
69 ML Mesoporous H3PW12O40/ZrO2–Si(Ph)Si hybrid catalyst (2 wt%) 1:7 65 °C 3h ~100 3 89
70 EL Sulphated mesoporous zircon-silicates (5 wt%), 700 rpm 1:10 70 °C 24 h 79 5 90
71 EL Sulphated Si-doped ZrO2 solid (5 wt%), 700 rpm 1:10 70 °C 10 h 65.6 5 91
72 ML Mesoporous H3PW12O40/ZrO2–Si(Ph)Si 1.0 hybrid catalyst (2 wt%) 1:7 Reflux 3h 99.9 3 92
73 EL Mesoporous H3PW12O40/ZrO2–Si(Ph)Si 1.0 hybrid catalyst (2 wt%) 1:7 Reflux 3h 91.5 – 92
74 BL Mesoporous H3PW12O40/ZrO2–Si(Ph)Si 1.0 hybrid catalyst (2 wt%) 1:7 Reflux 3h 82.8 – 92
75 EL Sulphated zirconia coated hydroxyethyl cellulose catalytic membrane (8 g/L) 1:3 70 °C 7h 95 – 93
76 EL Powder sulphated zirconia catalyst (8 g/L) 1:3 70 °C 7h 39.92 5 93
77 ML Mesoporous super acidic zirconia catalyst UDCaT-5 (catalyst loading 0.01 g/cm3), speed of agitation: 1:20 160 °C 3h 100 6 94
1000 rpm
78 EL Mesoporous super acidic zirconia catalyst UDCaT-5 (catalyst loading 0.01 g/cm3), speed of agitation: – 160 °C 3h 100 – 94
1000 rpm
79 PL Mesoporous super acidic zirconia catalyst UDCaT-5 (catalyst loading 0.01 g/cm3), speed of agitation: – 160 °C 3h 95 – 94
1000 rpm
80 BL Mesoporous super acidic zirconia catalyst UDCaT-5 (catalyst loading 0.01 g/cm3), speed of agitation: – 160 °C 3h 98 – 94
1000 rpm
81 PENL Mesoporous super acidic zirconia catalyst UDCaT-5 (catalyst loading 0.01 g/cm3), speed of agitation: 160 °C 3h 94 – 94
1000 rpm

Acid catalyst
82 EL Bio-glycerol derived carbon–sulfonic-acid (50 mg) 1:5 Reflux 3h 99 5 95
83 ML Bio-glycerol derived carbon–sulfonic-acid (50 mg) 1:5 Reflux 3h 99 – 95
84 PL Bio-glycerol derived carbon–sulfonic-acid (50 mg) 1:5 Reflux 3h 95 – 95
85 BL Bio-glycerol derived carbon–sulfonic-acid (50 mg) 1:5 Reflux 3h 44 – 95
86 EL PTSA (2.5 mol%) 1:10 120 °C 5 min 100 – 96

Metal salt catalyst

87 ML Al2(SO4)3 (20 mmol%), LVA: 1 mmol, AL 14 mL, microwave 400 W – 110 °C 0.5 h 99.4 5 97
88 ML CrCl3 (20 mmol%), LVA: 1 mmol, AL 14 mL, microwave 400 W – 110 °C 0.5 h 91.5 – 97
89 ML SnCl4 (20 mmol%), LVA: 1 mmol, AL 14 mL, microwave 400 W – 110 °C 0.5 h 96.8 – 97
90 ML SnSO4 (20 mmol%), LVA: 1 mmol, AL 14 mL, microwave 400 W – 110 °C 0.5 h 15.7 – 97
91 ML FeCl3 (20 mmol%), LVA: 1 mmol, AL 14 mL, microwave 400 W – 110 °C 0.5 h 89.6 – 97
92 ML CuSO4 (20 mmol%), LVA: 1 mmol, AL 14 mL, microwave 400 W – 110 °C 0.5 h 49.5 – 97
93 ML CuCl2 (20 mmol%), LVA: 1 mmol, AL 14 mL, microwave 400 W – 110 °C 0.5 h 66.1 – 97
94 ML AlCl3 (20 mmol%), LVA: 1 mmol, AL 14 mL, microwave 400 W – 110 °C 0.5 h 83.9 – 97
95 ML ZnCl2 (20 mmol%), LVA: 1 mmol, AL 14 mL, microwave 400 W – 110 °C 0.5 h 8.1 – 97
96 EL Fe2(SO4)3 (3 mol%) 1:6 333 K 4h ~94 4 98
97 ML Fe2(SO4)3 (3 mol%) 1:6 333 K 4h ~94 – 98
98 BL Fe2(SO4)3 (3 mol%) 1:6 333 K 4h ~90 – 98
99 PL Fe2(SO4)3 (3 mol%) 1:6 333 K 4h ~88 – 98
100 EL FeCl3 (3 mol%) 1:3 333 K 4h ~85 – 98
101 EL CuSO4 (3 mol%) 1:3 333 K 4h 15 – 98
102 EL FeSO4(3 mol%) 1:3 333 K 4h 12 – 98
103 EL ZnSO4(3 mol%) 1:3 333 K 4h 10 – 98
104 EL NiSO4(3 mol%) 1:3 333 K 4h 2 – 98
105 EL MnSO4(3 mol%) 1:3 333 K 4h 2 – 98

Metal organic framework catalyst

106 EL MOF supported ployoxometalates Cu BTC [HPM] (40 mg) – 120 °C 4h 100 3 99
LVA: 0.5 mmol, AL: 10 mL
107 ML Sulphonic acid functionalized hafnium based MOF (0.8 mol%), LVA: 1 mmol, AL: 20 mL – 120 °C 2.5 h 94 4 100
108 EL Sulphonic acid functionalized hafnium based MOF (0.8 mol%), LVA: 1 mmol, AL: 20 mL – 120 °C 2h 90 – 100
109 PL Sulphonic acid functionalized hafnium based MOF (0.8 mol%), LVA: 1 mmol, AL: 20 mL – 120 °C 2h 87 – 100
110 ISPL Sulphonic acid functionalized hafnium based MOF (0.8 mol%), LVA: 1 mmol, AL: 20 mL – 120 °C 2h 88 – 100
111 BL Zirconia containing MOF UIO-66 (1.8 mol%) 1:6 120 °C 5h 99 3 101
112 BL Zirconia containing MOF UIO-66-NH2 (1.8 mol%) 1:6 120 °C 5h 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, – 105 °C 3h 90.4 5 102
117 EL Sulphated TiO2 nano-rods (2 wt%), LVA:LA 1: 1 by weight – 105 °C 3h 75 – 102
118 EL Nanosized tin oxide (2.5 wt%) 1:5 70 °C 7.5 h 77 – 103
119 BL Organo-sulfonic acid modified titanate nanotube hybrid nanostructures (15 wt%) 1:6.65 120 °C 8h 82.7 5 104
120 EL Sulphated zirconia nano particles (2.5 wt%) 1:5 70 °C 8h 80 – 105
121 EL Organo-silica nanotube (2 wt%) 9.85:68.9 78 °C 3h 94.4 4 106
122 EL Sulphonated carbon nano tubes (2.5 wt%) 1:5 343 K 5h 55 – 107

Ionic liquid catalyst

123 EL Sulphonic acid-functionalized benzimidazolium based poly ionic liquid (15 wt%) 1:10 70 °C 9h 99.5 5 108
124 PL [MIM][HSO4] (ratio of IL to LVA:0.25), rpm 700. 1:2 90 °C 1.5 h 91 – 109
125 HL [MIM][HSO4] (ratio of IL to LVA:0.25), rpm 700. 1:2 90 °C 1.5 h 90 – 109
126 IBL [MIM][HSO4] (ratio of IL to LVA:0.25), rpm 700. 1:2 90 °C 1.5 h 92 6 109

(continued on next page)

5
K.C. Badgujar, et al. Fuel Processing Technology 197 (2020) 106213

Table 1 (continued)

Entry LVA Catalyst and other reaction conditions Mole ratio Temp Time Yield Reuse Ref.

Biocatalyst
127 ML Surface functionalized SBA-15 immobilized lipase (150 mg), solvent methyl tert-butyl ether: 15 ml, speed 1:2 50 °C 2.5 h 71 4 110
of agitation 300 rpm
128 EL Surface functionalized SBA-15 immobilized lipase (150 mg), solvent methyl tert-butyl ether: 15 ml, speed 1:2 50 °C 2.5 h 73 – 110
of agitation 300 rpm
129 BL Lipase immobilized on meso-molding 3-dimensional macroporous organosilica (10 mg) 1:10 40 °C 12 h 74.59 9 111
130 OL Lipase immobilized on meso-molding 3-dimensional macroporous organosilica (10 mg) 1:10 40 °C 10 h 84.51 – 111
131 LL Lipase immobilized on meso-molding 3-dimensional macroporous organosilica (10 mg) 1:10 40 °C 10 h 91.14 – 111
132 BL CAL B lipase (35 mg), solvent methyl tert-butyl ether: 15 ml, speed of agitation 500 rpm 1:2 50 °C 2h 88 3 112
133 EL CAL B lipase (35 mg) 1:1.1 51.4 °C 42 min 96.2 – 113
134 ML CAL B lipase (120 mg), solvent: methyl tert-butyl ether 2 mL 4:7 45 °C 8h 94 – 114
135 EL CAL B lipase (120 mg), solvent: methyl tert-butyl ether 2 mL 4:7 45 °C 8h 96 – 114
136 PL CAL B lipase (120 mg), solvent: methyl tert-butyl ether 2 mL 4:7 45 °C 8h 98 – 114
137 BL CAL B lipase (120 mg), solvent: methyl tert-butyl ether 2 mL 4:7 45 °C 8h 99 – 114
138 HL CAL B lipase (120 mg), solvent: methyl tert-butyl ether 2 mL 4:7 45 °C 8h 96 – 114
139 HL T. Lanuginosus lipase (130 mg), solvent: methyl tert-butyl ether 2.5 mL 4:7 45 °C 8h 40 – 114
140 HL M. Miehei lipase (130 mg), solvent: methyl tert-butyl ether 2.5 mL 4:7 45 °C 8h 30 – 114
141 HL Steapsin lipase (130 mg), solvent: methyl tert-butyl ether 2.5 mL 4:7 45 °C 8h 18 – 114
142 HL A. Niger lipase (130 mg), solvent: methyl tert-butyl ether 2.5 mL 4:7 45 °C 8h 10 – 114
143 ML CAL B lipase (230 mg), co-solvent: ethyl methyl ketone 1.8 mL, supercritical carbon dioxide pressure: 14:10 321 K 5h 98 – 115
8.8 MPa
144 EL CAL B lipase (230 mg), co-solvent: ethyl methyl ketone 1.8 mL, supercritical carbon dioxide pressure: 14:10 321 K 5h 99 – 115
8.8 MPa
145 PL CAL B lipase (230 mg), co-solvent: ethyl methyl ketone 1.8 mL, supercritical carbon dioxide pressure: 14:10 321 K 5h 99 – 115
8.8 MPa
146 BL CAL B lipase (230 mg), co-solvent: ethyl methyl ketone 1.8 mL, supercritical carbon dioxide pressure: 14:10 321 K 5h 99 – 115
8.8 MPa
147 BL M. javanicus lipase (250 mg), co-solvent: ethyl methyl ketone 2.4 mL, supercritical carbon dioxide 16:10 318 K 6h 16 – 115
pressure: 9 MPa
148 BL R. oryzae lipase (250 mg), co-solvent: ethyl methyl ketone 2.4 mL, supercritical carbon dioxide pressure: 16:10 318 K 6h 20 – 115
9 MPa
149 BL C. cylindracea lipase (250 mg), co-solvent: ethyl methyl ketone 2.4 mL, supercritical carbon dioxide 16:10 318 K 6h 28 – 115
pressure: 9 MPa
150 BL P. cepacia lipase (250 mg), co-solvent: ethyl methyl ketone 2.4 mL, supercritical carbon dioxide pressure: 16:10 318 K 6h 36 – 115
9 MPa

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 im-
portant 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
esterification 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-to-
luensulfonic acid and Aquivion mp98 (micronized pellets of per-
fluorosulfonic 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 cat-
alyst 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 com-
pounds. Also, Amberlyst-70 is offering good yield of the product levu-
linate which having exceptional thermal stability and flexibility 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 specifically more in polar reaction
media. Swellings property of resin is co-related with the flexibility and
stiffness 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 stiffness 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 flexibility and swelling as compared to conventional resins.
Functionalization is another important factor which is accounted for
swelling and flexibility property of resin. In general surface functiona-
lization and over-sulphonation reasons for higher stiffness of resins.
Hence, Amberlyst 46 and Purolite CT224 are less active for the ester-
ification reactions which are surface-sulphonated and over-sulphonated
respectively [62]. However, Amberlyst 70 offered excellent yield due to
exceptional thermal stability and non-stiffness [62].
It is observed that, gel type resin base catalyst having greater
swelling ability and offers excellent yield of the levulinate compounds.
Thus, gel-type resin such as Dowex 50Xx2 offers 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.

6
K.C. Badgujar, et al.
Thus in conclusion, uses of resins are offering advantages like easy
product/reaction mass separation, reusability of resin-catalyst and non-
corrosiveness to reactor [59–62]. Also it maintains the appropriate
hydrophobicity, flexibility 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 sol-
vents, stiffness, 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.
5.3. Heteropoly acid
A heteropolyacid is a special type of acid, designed by a specific
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-cat-
alyst in the synthesis of fine 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] ap-
plying dodeca-tungsto-phosphoric acid tethered on desilicated H-ZSM-5
catalyst (Table 1, entry 26) while Zhou et al., [65] used silver or am-
monium 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 fixed 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, me-
thyl 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 efficient 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 sup-
ported catalyst furnishes well acidity and offers 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 offers a higher reaction rate than silver co-doped hetero-
polyacid. 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 sub-
sequent leaching, several authors have anchored hydrophobic graphene
based compound on the heteropolyacid which displayed reduction in
leaching of catalyst.
The heteropolyacid supported catalyst offers 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 re-
ported to be the most feasible catalyst. These results attributed to, ex-
cess 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/
7
Fuel Processing Technology 197 (2020) 106213
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, effective mass transfer influ-
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].
5.4. Zeolites
Zeolites are the naturally occurring crystalline three dimensional
aluminosilicate microporous system which is interlinked by oxygen
atom and possess specific 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-refining plants, water purification,
effluent treatment and waste water treatment plants [76–78]. Zeolites
can be designed with appropriate variation according to their func-
tional 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], modified H-ZSM-5 (Table 1, en-
tries 54) [78], hierarchical H-ZSM-5catalyst [81] for esterification of
levulinic acid into various renewable alkyl levulinates (Table 1, entry
60). All these used catalysts offer 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 levu-
linate 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 modified H-ZSM-5 catalyzed synthesis of octyl levulinate (Table 1,
entry 61).
The zeolites H-BEA offers better yield due to presence of tri-direc-
tional 12-member-ring whereas, H-MOR, H-SM-5 are mono-directional
and bi-directional zeolites respectively which possess the diffusion
limitations for the reactant molecules. The excellent synthesis of levu-
linate compounds can be achieved by modified 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 effective surface area, generation of meso-porosity
and improvement of mass transfer at active catalytic sites. [64,79,80].
Effect of various structural features such as different 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 pre-
sence 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 diffusion limitations should be elimi-
nated for effective catalysis. During modification, uniform dispersion of
the metals or heteropolyacid and size of pores/cavities/channels is task
of skill-full hand.
5.5. Carbonaceous material
Carbonaceous material is the novel type of acid catalyst which is
generally prepared by the partial pyrolysis of carbon based material at
K.C. Badgujar, et al.
specified temperature followed by sulphonation in the presence of mi-
neral 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 le-
vulininc 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-de-
rived 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 sufficiently
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 cat-
alytic 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 offers the promising catalyst as well as
levulinate synthesis [87,88]. Calcined material offers 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 en-
vironment as lethal pollutants, uniform catalytic activity and re-
generation of catalyst is always challenging issue to work out with these
types of catalysts.
5.6. Zirconia
Zirconia is the solid-acid zirconium metal-oxide catalyst which is
receiving enormous attention in the scientific communities due to its
characteristic features of porosity, thermal stability and catalytic ac-
tivity [89–94]. The sufficient pore size always evades the diffusion
constrains and facilitates the easy mass transport phenomenon for
bulky and long chain molecules [90–92]. Su et al., [89] very well de-
signed a mesoporous H3PW12O40-ZrO–Si(Ph)Si hybrid catalyst to pro-
duce methyl levulinate (Table 1, entry 69). Kuwahara et al. [90,91]
performed synthesis of ethyl levulinate by applying sulphated meso-
porous 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 levuli-
nate esters (for example, methyl levulinate, ethyl levulinate, butyl le-
vulinate) (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 offers excellent
8
Fuel Processing Technology 197 (2020) 106213
yield of the product ethyl levulinate than simple powder sulphated
zirconia catalyst (Table 1, entries 75,76). Yadav and Yadav [94] syn-
thesized 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 cat-
alyst 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 cata-
lysts which adsorb various polar molecules onto catalyst surface and
make it unavailable for catalysis, restricts the effective mass diffusion
and hence deactivate dynamic sites of catalyst. Furthermore, adsorbed
water molecules on the catalyst surface cause reversible esterification
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 diffusion restriction which needed frequent regeneration of the
catalyst.
5.7. 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 ad-
dition of the native reaction solvent or water or acid [95,96]. Varkolu
et al., [95] (Table 1, entries 82–85) performed esterification using re-
cyclable catalyst bio-glycerol derived carbon–sulfonic-acid to synthe-
size 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
difficult to use as well as reuse in the reaction. Some authors have taken
efforts 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 esterification reac-
tion. Homogeneous catalysis with mineral acid always has higher re-
action 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 se-
paration of catalyst from reaction media etc. These practical difficulties
discourage the use of mineral acid catalysts in synthetic organic reac-
tion.
5.8. Metal salt
Metal salts involve simple metal halides in which metal possessing
K.C. Badgujar, et al.
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 modifications and are sufficiently 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 offers 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 offers 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 offers binding site and higher reaction rate for the es-
terification reaction. Higher acidity is attributed to higher charge pre-
sent on the central metal atom. Al2(SO4)3 and Fe2(SO4)3 are having
trivalent central metal atom which offers better yield and higher cata-
lytic 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, neu-
tralization of catalyst, reuse of catalyst and purification of product).
Furthermore, higher activation energy, harsh reaction temperature,
catalyst disposal and reusability are also unavoidable challenges.
5.9. 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 com-
binations of metal ion, oxo-cluster and organic linker can lead to pro-
duce the bank of MOFs which will offer high variability and mod-
ifications 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
different alkyl-levulinate compounds via use of sulfonic acid-functio-
nalized 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 tem-
perature 120 °C, while Zr-MOF is possessing the higher reaction rate at
comparatively lower temperature 80 °C. The alkaline organic func-
tionality 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 le-
vulinic 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 offer respective metal coordina-
tion bond valency; also they possess the good stability (chemical/
thermal) and uniform size nano-pores or channels [99,100]. The chal-
lenges associated with the designing of MOF is a skill-full task, and
having high risk of loss of active chemical sites during designing
9
Fuel Processing Technology 197 (2020) 106213
[46–49]. The major concern is the severe toxicity of certain metals
present in MOF which limits their practical scope and applications.
5.10. 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 levu-
linate using sulphated tin oxides nano particles and sulphated zirconia
oxides nano particles in their different studies (Table 1, entry 118, 120).
Zhou et al., [104] used covalently attached organo-sulfonic acid de-
rived 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 func-
tional group arene-sulfonic-acid for efficient synthesis of ethyl levuli-
nate (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 ap-
plied for the synthesis of levulinate compounds. It was observed that,
nano-catalyst which are hydrophobic in nature were offering good yield
of the levulinate compounds. This is attributed to phenomenon of sur-
face hydrophobicity which increases the rate of esterification reaction.
Hydrophobic surface catalyst hampers polar molecules adsorption on
the catalyst surface and making it available easily for the transforma-
tion. Thus organo-silica nanotube catalyst is offering 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-struc-
tures are offering better mass transport phenomenon to active catalytic
sites, to evade the diffusion restrictions and to afford 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 affect the reaction rate and
selectivity of the desired product [46–49]. Moreover, functionalization
and modification of the surface of nano-structures is the tedious and
skill full task in order to incorporate the proper dynamic functionality
of nano-catalyst.
5.11. 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-flammability, 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
K.C. Badgujar, et al. Fuel Processing Technology 197 (2020) 106213

Table 2 Nature's catalyst [110–115]. Several advantages are associated with the
Effect of catalyst loading for the synthesis of levulinate compounds. Nature's catalysts such as biodegradability, waste-free synthesis and
Entry Catalyst loading Yield Reference easily disposability after their successful use [115–120]. Moreover,
these biocatalysts are often offer excellent stereo-chemo-and regio-se-
Catalyst loading in %, catalyst: 3 M-SiO2, reflux temperature, time: 4 h, mole ratio LVA lectivity [120–127]. These biocatalysts work at mild reaction tem-
to ethanol: 1:20
perature and can be easily incorporated in greener reaction media
1 10 44 55
2 20 52 55
[112–118]. They are non-hazardous to environment, energy saving,
3 30 55 55 obtained from natural resources and safe to use, hence they are con-
4 40 51 55 sidered as a green sustainable catalyst [122–127].
5 50 47 55 Salvi and Yadav [110] used surface functionalization of SBA-15 for
Catalyst loading: mol%, catalyst: SiO2-(CH2)3-SO3H, temperature: 75 °C, time: 2 h, mole immobilization of lipase Candida Antarctica B (CAL B) which was fur-
ratio LVA to butanol 1:1 ther used for the catalytic test to carry out synthesis of alkyl levulinates
6 0.01 15 57
(Table 1, entries 127,128). Zhou et al., [111] performed synthesis of
7 0.1 36 57
8 1 95 57 long chain alkyl levulinates using CAL B immobilized on meso-molding
9 5 95 57 three-dimensional macro-porous organo-silica as a biocatalyst (Table 1,
Catalyst loading: % LVA, catalyst: 15% (w/w) DTPA/DH-ZSM-5, temperature: 351 K,
entries 129–131). Yadav and Borkar [112] proposed kinetic model of
mole ratio LVA to butanol 1:6, time: 4 h, agitation speed: 250 rpm, synthesis of n-butyl levulinate for the immobilized CAL B lipase cata-
10 0.10 72 64 lyzed reaction (Table 1, entry 132). Lee et al., [113] performed bio-
11 0.15 76 64 catalyzed synthesis of ethyl levulinate ester in a solvent-free system
12 0.20 82 64
(Table 1, entry 133). Badgujar and Bhanage [114] carried out thermo-
13 0.25 95 64
chemical energy assessment to synthesize levulinates using im-
Catalyst loading: wt%, catalyst: H-BEA catalyst, mole ratio LVA to butanol 1:7, time:
mobilized lipase biocatalyst CAL B (Table 1, entries 134–142). Badgujar
4 h, temperature: 120 °C; stirring speed: 400 rpm
14 7 70.2 79 and Bhanage [115] performed lipase catalyzed synthesis of alkyl le-
15 10 82.2 79 vulinates in supercritical carbon dioxide (Table 1, entries 143–150).
16 12 85.1 79 Various fungal and bacterial lipases are used for the present
17 14 62.1 79 synthesis. Among all studied lipases, CAL B showed excellent activity
Catalyst loading: wt%, mole ratio, catalyst: Loofah sponge-derived carbon, LVA to for this transformation. Lipase possesses the amino acid lid at the cat-
ethanol 1:5, temperature 80 °C, time 8 h. alytic active sites of lipase to pass reactants to active catalytic amino-
18 0 0 85
acid triad of enzyme. However, the superior activity of CAL B was re-
19 2.5 72 85
20 5.0 86 85 cognized due to lack of ‘flap or lid’ which facilitates quite easy diffusion
21 7.5 88 85 of the reacting molecules to the dynamic biocatalytic sites of lipase.
22 10.0 88 85 Moreover, most active, stable and bead immobilized form of the lipase
23 12.5 86 85 CAL B is easily available in market which is directly used in the reaction
Catalyst loading in mg, mole ratio hexanol to LVA 4:7 mmol, solvent: methyl tertiary system. Conversely, other lipases need modifications via immobiliza-
butyl ether: 2.5 mL; temperature 45 °C; rotation speed, 200 rpm, time 8 h. tion process or genetic engineering to employ in reaction media, which
24 40 33 114
is a task of skilful hands. Many times enzyme activity gets lost or de-
25 100 72 114
26 120 99 114 crease in immobilization or in genetic engineering process. However,
27 140 97 114 immobilization process offers easy recyclability and improves the sta-
28 150 97 114 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
performer of catalyst and solvent for the synthesis of levulinate esters compounds. In conclusion, the biocatalysts are non-hazardous and ab-
(Table 1, entries 124–126). solutely greener in nature. The major challenging issue related with
Only two research articles are reported direct synthesis of levulinate these biocatalysts is stability towards reaction media, organic sub-
compounds using levulinic acid and IL which involves imidazolium as a strates, operational condition, reusability and cost of production.
cation while hydrogen sulphate as an anionic counterpart. [MIM] Immobilization, rational designing, protein engineering and directed
[HSO4] was found to be the best suited ionic liquid among studied evaluation are expensive and time-consuming methodologies to im-
([MIM][HSO4], [BIM][HSO4], [HIM][HSO4], [OIM][HSO4]) ionic li- prove or to develop the biocatalyst for organic transformation. Further
quids. This is due to reason of increase of chain length from methyl to these biocatalyst developing methodologies do not offer any assurance
butyl to hexyl to octyl of cation counterpart which increases the steric for the success of designing of biocatalysts and its activity.
hindrance, viscosity of IL and decreases acidic functionality. Increase in
the steric hindrance causes diffusion constrain to reactant molecules at 6. Reaction engineering aspect
active catalytic sites whereas, increase of viscosity limited the mass
transportation rate of reacting molecules. Thus [MIM][HSO4] is the 6.1. Effect of catalyst loading
most suited IL catalyst for the levulinate ester synthesis. These ionic
liquids can offers binding sites and active side arms; moreover, ionic Catalyst loading plays an imperative role since, availability of cat-
liquid can provides active media to work out various metal salts/ions/ alytic sites and substrate mass transfer are vital parameters which affect
complexes etc. [108,109]. The major challenges associated with ionic the process yield as well as process efficiency [114,115]. Ramli et al.,
liquid is their fabrication cost, viscosity, disposable issue, separation [55] observed that, EL yield was increased as catalyst loading increased
techniques, poor reusability, non-regeneration of catalyst, corrosiveness from 10 wt% to 30 wt%. Further increase of catalyst loading from 30 to
and condition of specifically designed reactors. 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
5.12. Lipase reaction mixture viscosity and mass transfer limitation due to higher
catalyst loading. Maggi et al., [57] optimized reaction process for cat-
Biocatalysis is booming at present era for an organic synthesis re- alyst loading in the range of 0.01 to 5 mol% (Table 2, entries 6–9). They
search due to its unique features such as enzymes are recognized as showed that, 1 mol% catalyst loading is enough to achieve maximum

10
K.C. Badgujar, et al. Fuel Processing Technology 197 (2020) 106213

conversion of BL. Nandiwale et al., [64] proposed that, reaction rate Table 3
and yield was increased as catalyst loading increased from 0.10 to Effect of mole ratio of LVA: alcohol for the synthesis of levulinate compounds.
0.25%, hence higher yield of EL was obtained at 0.25% catalyst loading Entry Mole ratio Yield Reference
(Table 2, entries 10–13). Maheria et al., [79] depicted the influence of
catalyst loading which showed that, yield of butyl levulinate synthesis Catalyst: SiO2-(CH2)3-SO3H, catalyst loading: 1%, mole ratio: LVA: ethanol,
temperature: 100 °C, time: 2 h.
increase as the catalyst loading is increased from 7 to 12 wt%. Further
1 1:1 96 57
increase of catalyst loading from 12 to 14 wt% showed decrease in yield 2 1:2 95 57
(Table 2, entries 14–17). Similarly, Li et al., [85] also reported that, 3 1:5 96 57
catalyst loading increases the yield of EL synthesis. Further they also Catalyst: 15% (w/w) DTPA/DH-ZSM-5, catalyst to LA ratio: 0.25, mole ration: LVA:
showed that, the reaction of levulinate ester synthesis cannot be per- ethanol, temperature: 351 K, time: 4 h, agitation speed: 250 rpm
formed without catalyst (Table 2, entries 18–23). Badgujar and Bha- 4 1:6 90 64
nage [114] studied the influence of biocatalyst loading on hexyl levu- 5 1:8 95 64
6 1:10 89 64
linate synthesis which showed increment of hexyl levulinate yield at
7 1:12 85 64
higher biocatalytic loading (120 mg) (Table 2, entries 24–28). Further
Catalyst: Loofah sponge-derived carbon, mole ratio: LVA: ethanol catalyst dosage 5.0 wt
increase in the biocatalyst loading beyond 120 mg did not have sig-
%, temperature: 80 °C, time 8 h.
nificant impact on the yield of biocatalyst which was attributed to ex- 8 1:2.5 65 85
istence of additional catalytic sites than actual necessity. 9 1:5 86 85
In conclusion, lower catalyst loading required more reaction time to 10 1:7.5 82 85
get higher reaction yield. Several times it was observed that, reaction 11 1:10 79 85
12 1:12.5 77 85
yield increases as the catalyst loading increases which is attributed to
13 1:15 75 85
the involvement of active catalytic sites available at higher catalyst
Catalyst: UDCat-5, mole ratio: LVA:ethanol, catalyst loading: 0.01 g/cm3, agitation
loading. Sometimes, surplus available catalytic sites (due to excess
speeds: 1000 rpm, temperature: 160 °C, time 3 h
catalyst loading) do not actively participate in the reaction process and 14 1:15 80 94
hence does not improve the yield of product (levulinate synthesis). 15 1:20 99 94
However extreme catalyst loading may hamper the mass transport 16 1:25 99 94
phenomenon process due to overcrowding of catalyst sites, further they Catalyst: lipase immobilized on 3-dimensional macro-porous organo-silica, catalyst
may increase the viscosity of the reaction media. At higher catalyst loading: 10 mg, mole ratio: LVA:butanol, temperature: 40 °C, time 4 h.
loading, an active catalyst matter may be thrown out of reaction media 17 1:5 27 111
18 1:10 39 111
due to stirring or rotation speed of agitator. Moreover, higher catalyst
19 1:15 25 111
loading increases the process costing hence, it is vital aspect of reaction 20 1:20 18 111
engineering to optimize the biocatalyst loading. 21 1:30 10 111

6.2. Effect of reactant mole ratio

It is always essential to optimize the mole ratio of reactants to get
higher yield, process efficiency as well as to avoid progress of side re-
action 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, esterification efficiency 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 addi-
tion 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
esterification 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 tem-
perature always evaporates the ethanol fastly as compared to water,
which leads to make deficiency of one of the essential alcoholic reactant
to synthesize levulinate ester. This situation promotes the reverse re-
action (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.
6.3. Effect of solvent
The selection of reaction media for the organic reaction is a tricky
task as solvent display significant role in easy dissolution, dispersion of
reactants in reaction media, mass-diffusion 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 esterification
of levulinic acid with alcohols which specifically involves the use of
four types of solvents: alcohol itself as a solvent (excess alcoholic re-
actant), organic solvent, supercritical fluid 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 en-
dothermic esterification reaction which is carried out at relatively
higher temperature [57,64]. At higher reaction temperature alcohol
may get evaporate quickly which create deficiency of essential alco-
holic 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

11
K.C. Badgujar, et al. Fuel Processing Technology 197 (2020) 106213

Table 4 Table 5
Effect of various solvents for the synthesis of levulinate compounds. Effect of reaction temperature for the synthesis of levulinate compounds.
Entry Rpm Yield Reference Entry Temperature Yield Reference

Catalyst: Immobead immobilized CAL B, hexanol: LVA 4:7 mmol, solvent 2.5 mL; Mole ratio LVA: butanol 1:1, catalyst: SiO2-(CH2)3-SO3H, catalyst loading 1%, time:
biocatalyst: 120 mg; temperature 45 °C; orbital rotation speed, 200 rpm, time 8 h. 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
4 1,4 dioxane 75 114
Mole ratio LVA:ethanol 1:5, Catalyst: Loofah sponge-derived carbon, catalyst dosage
5 Dichloro methane 58 114
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
9 Toluene 90 115
Mole ratio: LVA: butanol 1:10, catalyst: immobilized lipase on meso-molding 3-
10 Diethyl ether 96 115
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-off (stripped down) in polar reaction sol-
vent which is essentially required for biocatalyst to remain active
[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 le-
vulinate 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 su-
percritical 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 offers 40% yield, whereas, use of
small amount of moderately polar co-solvents (ethyl methyl ketone,
diethyl ether) offers excellent yield (> 95%) of product levulinate
compound than non-polar (hexane, toluene) co-solvents (Table 4, en-
tries 6–10). Thus the use of these moderately polar co-solvents in su-
percritical carbon dioxide maintains sufficient 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 esterification 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 li-
quid 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 re-
action intermediates and better thermal stability than conventional
solvents [109]. Moreover, these ionic liquids can function to offer
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 pro-
duct pentyl levulinate esters. Thus, these ILs can be well separated from
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
the reaction mass and can be efficiently recycled upto 5 recycles
without significant loss in yield [108,109].
6.4. Effect 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 acti-
vation for the esterification reaction occurred at higher reaction tem-
perature [51–60]. Furthermore, esterification 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 influence of the reaction temperature has enormous im-
portance 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 tempera-
ture increases from 50 °C to 75 °C, further increment of temperature
beyond 75 °C has negligible effect 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 re-
action 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 effect of reaction temperature in the range of 25–45 °C
to verify the most suitable reaction temperature for enzymatic synth-
esis, since enzymes are very prone to degrade at higher reaction tem-
perature.
In conclusion, it is observed that, systematic increase of reaction

12
K.C. Badgujar, et al. Fuel Processing Technology 197 (2020) 106213

temperature causes enhancement of molecular collision in between
reacting molecules which linearly increases the reaction rate and sub-
sequent yield of corresponding levulinate compound. Most of the con-
ventional chemical catalysts are stable at elevated reaction temperature
and demands higher reaction temperature for the endothermic ester-
ification reaction. Contrary to this, biocatalytic reaction processes
under mild reaction conditions to avoid biocatalyst deactivation. Thus,
appropriate reaction temperature boosts up catalyst performance, re-
duces media viscosity, increases reactant solubility and increases the
mass-transport influence. Moreover in literature, temperature optimi-
zation study is correlated with the energy of activation study, which
demonstrating energy requirement for the given reaction system. Thus,
lower activation energy signifies superior catalytic efficiency, lesser
reaction processing time and advanced reaction rate.
alcoholic substrate. The effective agitation of the reaction media can
overcome the problem of reaction homogeneity and the mass transport
in viscous reaction media. Further effective 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 efficiency, further enormous amount of energy is required to
achieve the effective mass diffusion by rotation/agitation. In general
macro-porous catalytic material and media suspended (floating) cata-
lyst can sustain in poor mass transfer process however, biocatalyst, high
weighted and micro-porous catalyst needs effective agitation for the
reaction progress. Excess agitation may avoid actual catalyst surface
contact with reactants, since, catalyst may be thrown outside of reac-
tion system and stick to upper wall of reactor.
6.6. Effect of substrate structure

6.5. Effect of speed of agitation and mass transfer Substrate study has enormous importance in order to develop a
commercial protocol, hence it is essential to study synthesis of variety
It is essential to check the mass transfer influence for the hetero- of levulinate esters having carbon chain and branching from C1 to C8
geneous system like synthesis of levulinate ester using solid base cata- [53,72,100]. In literature study it is observed that, all primary alcohols
lysts in which both reactants are in the liquid phase while catalyst is in having carbon chain length C1 to C4 are easily converted into the re-
solid phase [94,114]. Effective mass transfer of the reactants to the spective levulinate compound [53,76,98]. Branched primary alcohol
active sites/pores of catalyst generally affects reaction in positive way (with carbon chain length C1 to C4) substrate also has more or less
[64,88]. This effective mass transfer of the catalyst can be achieved by same reaction rate [53,72]. However, secondary alcohols offer poor to
the appropriate rotation speed of agitator or baffles or rotating needle. sluggish levulinate yield due to steric obstruction at reactive catalytic
In various mass transfer analyses study, the mass transfer influence was sites which inhibits nucleophilic attack of hydroxyl group of alcohol. It
observed upto certain speed of rotation. For example, Nandiwale et al., is observed that, long-chain (carbon chain beyond C5) substrate mo-
[64] found increase of the reaction yield when speed of rotation is in- lecules offer sluggish reaction yield at prolonged reaction time
creased from 100 rpm to 200 rpm for use of heteropoly acid type of [100,114,115]. This may be attributed to diffusion restriction of long-
catalyst. Further increase of speed beyond 200 rpm did not have any chain substrate molecules to micro porous active catalytic sites. More-
mass transfer influence (Table 6, entries 1–4). Zainol et al., [88] as well over, long-chain molecules displayed hydrophobic-hydrophobic inter-
as Yadav and Yadav [94] did not observe any mass diffusion resistance action with catalyst like lipases and metal organic frameworks, which
for the specified reaction system for the carbon cryogel and zirconia reduces the rate of reaction [53,72,100].
based catalyst (Table 6, entries 5–10). Yadav and Borkar [112] ob-
served impact of mass diffusion limitation for immobilized lipase bio- 6.7. Reaction set up, product separation and recyclability
catalyst. The reaction yield was found to be increased when rotation per
minutes increases from 200 to 750 rpm (Table 6, entries 11–14). Fur- Esterification reaction is carried out by various ways of reaction set
ther increase of the rotation beyond 750 rpm has negative impact on up which involves the reactor round bottom flask with reflux con-
the yield of levulinate synthesis. denser, closed system stainless steel batch reactor, continuous flow
Thus in conclusion, external mass transfer affects the levulinate reactor, membrane reactor and supercritical fluid reactor
synthesis, since levulinic acid is the viscous reactant as compare to the [53,59,62,93,97]. The round bottom flask with reflux condenser needs
proper cooling condition to avoid the evaporation of reactants and
Table 6 products, since reaction temperature is too high [59]. A closed system
Effect of speed of agitation for the synthesis of levulinate compounds. stainless steel batch reactor involves the internal inert gas at a parti-
Entry Rpm Yield Reference cular pressure in order to maintain the liquid phase [62,76]. Con-
tinuous flow reactor system involves catalyst bed through which reac-
Catalyst: DTPA/DH-ZSM-5, catalyst loading: 15% (w/w), mole ratio LVA: ethanol 1:8, tion mixture (containing substrates) is allowed to pass with a particular
catalyst to LVA ratio: 0.25; temperature: 351 K; time 4 h.
flow rate using feed pump [53]. Pervaporation catalytic membrane
1 100 81 64
2 150 88 64 reactor can be used to obtain the levulinate compounds which will
3 200 95 64 offers reactive separation system [93]. A supercritical fluid more spe-
4 250 95 64 cifically supercritical carbon dioxide can be used as a reaction solvent
Catalyst: carbon cryogel, catalyst loading: 25 wt%, mole ratio LVA:ethanol 1:15, in static mode for the synthesis of levulinate esters [115].
temperature: 78 °C, time: 1 h In practice, reaction down-steam processing has great importance in
5 100 26 88 order to recycle catalyst, to separate product from reaction mass, to
6 200 26 88
purify product from by-products/impurities and to improve the process
7 300 26 88
efficiency [114,115]. Practically reaction is quenched by maintaining
Catalyst UDCaT, catalyst loading 0.01 g/cm3, LVA:ethanol 0.0375:0.75 mol,
the cooling condition. Homogenous reaction mass is directly subjected
temperature 160 °C.
8 800 99 94 for the solvent extraction process immediately after quenching of re-
9 1000 99 94 action to get pure levulinate compound. Heterogeneous reaction mass is
10 1200 99 94 separated from the catalyst by simple filtration or vacuum filtration or
Catalyst: CAL-B, catalyst loading 35 mg, mole ratio LVA;butanol 0.01:0.02 mol, solvent: centrifugation process to get catalyst-free crude reaction mixture. Se-
tetra-butyl methyl ether up to 15 mL, temperature 50 °C, and bio-catalyst 35 mg. parated catalyst is washed properly to remove traces of the reaction
11 200 55 112 mass. Further it is dried or stored or regenerated as per the need of next
12 500 78 112
subsequent reaction. In general, yield in catalyst recyclability may get
13 750 85 112
14 1000 78 112 reduced due to catalyst leaching or catalyst deactivation or due to
handling loss in previous reaction cycle.

13
K.C. Badgujar, et al.
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 ex-
traction 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 efficiency of product separation in which re-
action and separation of product (from reaction mass) is carried out
simultaneously during the progress of reaction [61].
7. Mechanism for synthesis of levulinate esters from biomass
derived levulinic acid
7.1. Acid catalyzed mechanism
In case of acid catalyzed mechanism, carbonyl oxygen gets co-
ordinated 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 at-
tacked by nucleophilic alcoholic group (oxygen) and eliminates the
protonated hydroxyl group of levulinic acid which tends to offer desired
product levulinate ester [55,60].
7.2. Metal salt catalyzed synthesis of levulinate esters
The central metal ion of these salts possesses the high Lewis-acidity
which offers binding site for the carbonyl oxygen atom of acidic func-
tionality 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.
7.3. 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
Scheme 3. Mechanism of metal salt catalyzed synthesis of levulinate esters.
14
Fuel Processing Technology 197 (2020) 106213
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 me-
tal‑carbonyl oxygen coordination which will offers levulinate com-
pound and catalyst MOF into its original state.
7.4. 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 offer desired levulinate ester.
7.5. 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 en-
zyme-acyl complex (4) [124–126]. In the next step, nucleophilic species
(any alcohol) quickly attacks on the electron deficient centre (carbonyl
carbon) of an enzyme-acyl covalent intermediate (5) and lead to offer
another intermediate having tetrahedral geometry (6) which finally
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 re-
action equilibrium towards right hand side for completion of reaction
[119, 122, 125, 126].
K.C. Badgujar, et al. Fuel Processing Technology 197 (2020) 106213

Scheme 4. Mechanism of acidic functionality MOF catalyzed synthesis of levulinate esters.

Scheme 5. Mechanism of basic functionality MOF catalyzed synthesis of levulinate esters.

8. 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 (specifically methyl-, ethyl-, butyl- levulinate) offers
marvellous characteristics to fuels (after blending in appropriate com-
position) such as flow-property, spark property, lubricity, flash 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 offer better engine and fuel efficiency
without engine modification 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 affected 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 efficiency are discussed herewith
[130–142].

Scheme 6. Mechanism of ionic liquid catalyzed synthesis of levulinate esters.

15
K.C. Badgujar, et al. Fuel Processing Technology 197 (2020) 106213

Scheme 7. Mechanism of biocatalyst (lipase) catalyzed synthesis of levulinate esters.

emission [135]. Tian et al., [136] observed superior anti-knock quality

Cold Flow
Properties
Heat
Safety
Values
Fuel
Anti- Blending
Spray
Corrosives Evaporation
Properties
Oxidation
Emission
Stability
Cleanliness
Fig. 2. General properties to access blended fuels.
Joshi et al., [130] found that, blending of ethyl levulinate (15%)
improves the cold-flow properties of fuel [130]. Moreover, they ob-
served that, the cloud-point, pour-point and cold-filter plugging-points
of biodiesel can be improved by blending an additive ethyl levulinate,
whereas, kinematic-viscosities and the flash-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 specifically offers 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-flash-point, kinematic-viscosity and lowering of CO
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 effect, while it improved density of fuel [137].
Zhi-Wei et al. [138], found that, distillation, cold-filter-plugging-
point, closed-cup flash-point and solidifying-point of levulinate blended
fuel is remarkably improved. Moreover, density, cetane-number and
kinematic-viscosity of fuel blends are modified 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-flow performance property of biodiesel
[139]. Along with this, Srikanth et al., observed modified values of
flash-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
above advantages and features, levulinate is found to be a superior fuel-
blender or fuel-additive agent.
9. Challenges and opportunities
Solid acid catalyst is offering robust catalytic system, recyclability,
isolation advantages and special co-ordination features for the ester-
ification 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 cat-
alysis 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 different types of reactors according to
catalyst characteristics. Further, various catalytic aspects such as acti-
vation energy, initial reaction rate, catalyst inhibition factor, kinetics

16
K.C. Badgujar, et al.
and turn over frequency (TOF) are essential to study for determination
of most robust catalytic system.
Various catalytic influencing parameters such as catalyst stability
(thermal and chemical), catalyst leaching, internal diffusion 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 efficient catalytic protocol for industrial organic
transformation. Green Chemistry principles and green metric para-
meters 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-effective protocols which may offer 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 efficiency and number of catalyst reusa-
bility.
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 chal-
lenging 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 en-
zyme) which may take time for the industrial scale-up development.
However it will completely offer 100% greener protocol to synthesize
renewable fuels from renewable biomass derived substrates using re-
newable 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
different compounds in fuel (Fuel blend selection) and different blend
compositions for example 5%, 10%, 15%, 20% etc. (Fuel blend opti-
mization) is needed to access by all means considering an engine effi-
ciency and emission performance with respect fuel standards. The en-
vironmental 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
find out more effective and potential fuel blending additives.
10. Conclusion and future viewpoint
In conclusion, levulinate compounds are essential energy com-
pounds 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 efficient
pathway. Since, levulinic acid offers excellent yield of levulinate com-
pounds 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 efforts 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
17
Fuel Processing Technology 197 (2020) 106213
efficiency. 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 influence of fuel-blending of these levulinates
should be on top priority of research to search most efficient bending
levulinate species.
References
[1] V. Dhyani, T. Bhaskar, A comprehensive review on the pyrolysis of lignocellulosic
biomass, Renew. Energy 129 (2018) 695–716.
[2] K.C. Badgujar, B.M. Bhanage, Factors governing dissolution process of lig-
nocellulosic biomass in ionic liquid: current status, overview and challenges,
Bioresour. Technol. 178 (2015) 2–18.
[3] Y. Sun, J. Cheng, Hydrolysis of lignocellulosic materials for ethanol production: a
review, Bioresour. Technol. 83 (2002) 1–11.
[4] K. V. Wagh, K. C. Badgujar, N. M. Patil, B. M. Bhanage, Recent trends of ionic
liquids for the synthesis of 5-hydroxymethylfurfural, Curr. Org. Chem. 20 (2016)
736–751.
[5] V.C. Badgujar, K.C. Badgujar, Enhanced biocatalytic activity of immobilized
steapsin lipase in supercritical carbon dioxide for production of biodiesel using
waste cooking oil, Bioprocess Biosyst. Eng. 42 (2019) 47–61.
[6] https://ec.europa.eu/energy/en/topics/renewable-energy.
[7] https://eur-lex.europa.eu/eli/dir/2018/2001/oj.
[8] https://www.eea.europa.eu/data-and-maps/indicators/use-of-cleaner-and-
alternative-fuels/use-of-cleaner-and-alternative-4.
[9] https://unctad.org/en/docs/ditcbcc20091_en.pdf.
[10] K. Tadele, S. Verma, M.A. Gonzalez, R.S. Varma, A sustainable approach to em-
power the bio-based future: upgrading of biomass via process intensification,
Green Chem. 19 (2017) 1624–1627.
[11] H. Zoebelin, Dictionary of Renewable Resources, Wiley VCH, Weinheim, 2001.
[12] D.W. Rackemann, W.O.S. Doherty, The conversion of lignocellulosics to levulinic
acid, Biofuels BioprodBioref 5 (2011) 198–214.
[13] K.C. Badgujar, B.M. Bhanage, Dedicated & Waste Feedstocks for Biorefinery: An
Approach to Develop a Sustainable Society in Waste Biorefinery Potential and
Perspective, Ed by Bhaskar T, Pandey A, Mohan SV, Lee D. Elsevier 2018, ISBN:
978-0-444-63992-9.
[14] M.O.S. Dias, T.L. Junqueira, O. Cavalett, L.G. Pavanello, M.P. Cunha, C.D.F. Jesus,
R.M. Filho, A. Bonomi, Biorefineries for the production of first and second gen-
eration ethanol and electricity from sugarcane, Appl. Energy 109 (2013) 72–78.
[15] M.O.S. Dias, O. Cavalett, R.M. Filhob, A. Bonomi, Integrated first and second
generation ethanol production from sugarcane, Chem. Eng. Trans. 37 (2014)
445–450.
[16] N.J. Glithero, P. Wilson, S.J. Ramsden, Straw use and availability for second
generation biofuels in England, Biomass Bioenergy 55 (2013) 311–321.
[17] S.K. Prajapati, P. Kumar, A. Malik, V.K. Vijay, Bioconversion of algae to methane
and subsequent utilization of digestate for algae cultivation: a closed loop bioe-
nergy generation process, Bioresour. Technol. 158 (2014) 174–180.
[18] K. Kohli, R. Prajapati, B. Sharma, Bio-based chemicals from renewable biomass for
integrated biorefineries, Energies 12 (2019) 233–273.
[19] Pacific Northwest National Laboratory, National Renewable Energy Laboratory
and Energy Efficiency and Renewable Energy (PNNL/NREL/EERE), Top Value
Added Chemicals from Biomass: Results of Screening for Potential Candidates
from Sugars and Synthesis Gas, Department of Energy, Oak Ridge, TN, 2004.
[20] S. Kang, J. Fu, G. Zhang, From lignocellulosic biomass to levulinic acid: a review
on acid-catalyzed hydrolysis, Renew Sust Energy Rev 94 (2018) 340–362.
[21] A. Mukherjee, M.J. Dumont, V. Raghavan, Review: Sustainable production of
hydroxymethylfurfural and levulinic acid: challenges and opportunities, Biomass
Bioenergy 72 (2015) 143–183.
[22] E. Christensen, A. Williams, S. Paul, S. Burton, R.L. McCormick, Properties and
performance of levulinate esters as diesel blend components, Energy Fuel 25
(2011) 5422–5428.
[23] A. Deemolis, N. Essayem, F. Rataboul, Synthesis and applications of alkyl levuli-
nates, ACS Sustain. Chem. Eng. 2 (2014) 1338–1352.
[24] https://www.scopus.com.
[25] F.X. Govers, Solvent Refining of Mineral Oils. U.S. Patent US2087473, 1937.
[26] B.D. Mullen, V. Badarinarayana, E.S. Hall, M.J. Tjossas, C.M. Leibig, Stabilized
Levulinic Ester Ketals, Patent WO2013055781A1, 2013.
[27] I. Alloaoua, et al., (Co) Polymerization of vinyl levulinate by cobalt-mediated
radical polymerization and functionalization by ketoxime click chemistry, Polym.
Chem. 5 (2014) 2923–2929.
[28] M.A. Harmer, V. Kapur, S.R. Williams, Closed-Cell Tannin Based Foams
Comprising Polymer and Blowing Agent. Patent WO2012162645A2, 2012.
[29] S. Cousinet, Biobased vinyl levulinate as styrene replacement for unsaturated
polyester resin, Polym. Chem. 52 (2014) 3356–3364.
[30] L. Lomba, B. Giner, I. Bandres, C. Lafuente, M.R. Pino, Physicochemical properties
of green solvents derived from biomass. Green Chem.. 13 (2011) 2062–2070.
[31] P. Bloom, Levulinic Acid Ester Derivatives As Reactive Plasticizers and Coalescent
Solvents. Patent WO2007094922A2, 2007.
[32] D.J. Yontz, Fabricating Fragrant Formulations from Essential Oils and Solvents as
Olfactory Flavorants for Food, Fragrances for Candles, Cosmetics, Soaps or Other
Uses. U.S. Patent US20110274643A1, 2011.
[33] https://www.avantium.com/yxy/products-applications/.
K.C. Badgujar, et al.
[34] L. R. Rieth, C.M. Leibig, J. Pratt, M. Jackson, Latex Coating Compositions
Including Carboxy Ester Ketal Coalescents, Coalescent Evaluation and Use of
Coalescents in Coatings. Patent WO2012021826A2, 2012.
[35] J. Tsucha, K. Yoshida, Skin cosmetics containing levulinates, glycyrrizates, and
resorcinol or isopropylmethylphenol. Japanese patent 05320023 to Kanebo, 1994.
[36] N.B Ferrer, L.G. Prats, Este vez Company, C.; Castells Boliart, J. Degreasing
Compositions Derived from Levulinic Acid Obtainable from Biomass and Process
for Degreasing Metal Surfaces. European Patent EP2540871A1, 2013.
[37] https://www.grandviewresearch.com/industry-analysis/ethyl-levulinate-market.
[38] https://www.prnewswire.com/news-releases/ethyl-levulinate-market-worth-118-
million-by-2022-grand-view-research-inc-571956931.html.
[39] https://www.gminsights.com/industry-analysis/ethyl-levulinate-market.
[40] C. Song, S. Liu, X. Peng, J. Long, W. Lou, X. Li, Catalytic conversion of carbohy-
drates to levulinate ester over heteropolyanion-based ionic liquids, ChemSusChem
9 (2016) 3307–3316.
[41] A.S. Amarasekara, B. Wiredu, Acidic Ionic Liquid Catalyzed One-Pot Conversion of
Cellulose to Ethyl Levulinate and Levulinic Acid in Ethanol-Water Solvent System,
Bioenerg Res 7 (2014) 1237–1243.
[42] Shen, et al., One-pot synthesis of levulinic acid from cellulose in ionic liquids,
Bioresour. Technol. 192 (2015) 812–816.
[43] L. Peng, H. Li, L. Xi, K. Chen, H. Chen, Facile and efficient conversion of furfuryl
alcohol into n-butyl levulinate catalyzed by extremely low acid concentration,
Bioresources 9 (2014) 3825–3834.
[44] P. Neves, Mesoporous zirconia-based mixed oxides as versatile acid catalysts for
producing bio-additives from furfuryl alcohol and glycerol, Appl. Catal. A Gen.
487 (2014) 148–157.
[45] Zhu, et al., One-pot conversion of furfural to alkyl levulinate over bifunctional Au-
H4SiW12O40/ZrO without external H2, Green Chem. 18 (2016) (2016) 5667.
[46] Princy Gupta, Satya Paul, Solid acids: green alternatives for acid catalysis, Catal.
Today 236 (2014) 153–170.
[47] A. Yamaguchi, M. Shirai, Catalytic production of sugar alcohols from lig-
nocellulosic biomass, Catal. Today 265 (2016) 199–202.
[48] Lei Hu, Lu Lin, Zhen Wu, Shouyong Zhou, Shijie Liu, Chemocatalytic hydrolysis of
cellulose into glucose over solid acid catalysts, Appl. Catal. B Environ. 174-175
(2015) 225–243.
[49] K. Tanabe, M. Misono, Y. Ono, H. Hattori, Studies in surface and science and
catalysis, New Solid Acids and Bases, The catalytic approach, Studies in Surface
Science and Catalysis Advisory Editors: B. Delmon and J. T. Yates, Elsevier
Publication.
[50] R.K. Sharma, R. Gaur, M. Yadav, A. Goswami, R. Zbořil, M.B. Gawande, An effi-
cient copper-based magnetic nanocatalyst for the fixation of carbon dioxide at
atmospheric pressure, Sci. Rep. 8 (2018) 1901.
[51] G. Pasquale, P. Vázquez, G. Romanelli, G. Baronetti, Catalytic upgrading of le-
vulinic acid to ethyl levulinate using reusable silica-included Wells-Dawson het-
eropolyacid as catalyst, Catal. Commun. 18 (2012) 115–120.
[52] F. Yang, J. Tang, Catalytic upgrading of renewable levulinic acid to levulinate
esters using perchloric acid decorated nanoporous silica gels, Chemistry Select 4
(2019) 1403–1409.
[53] S.S. Enumula, V.R.B. Gurram, R.R. Chada, D.R. Burri, S.R.R. Kamaraju, Clean
synthesis of alkyl levulinates from levulinic acid over one pot Synthesized WO3-
SBA-16 catalyst, J. Mol. Catal. A Chem. 426 (2017) 30–38.
[54] J.A. Melero, G. Morales, J. Iglesias, M. Paniagua, B. Hernández, S. Penedo,
Efficient conversion of levulinic acid into alkyl levulinates catalyzed by sulfonic
mesostructured silica, Appl. Catal. A Gen. 466 (2013) 116–122.
[55] N.A.S. Ramli, N.I. Hisham, A.S. Amin, Esterification of levulinic acid to levulinate
esters in the presence of sulfated silica catalyst, Sains Malaysiana 47 (2018)
1131–1138.
[56] A.N. Chermahini, M. Nazeri, Esterification of the levulinic acid with n-butyl and
isobutyl alcohols over aluminum-containing MCM-41, Fuel Process. Technol. 167
(2017) 442–450.
[57] R. Maggi, N.R. Shiju, V. Santacroce, G. Maestri, F. Bigi, G. Rothenberg, Silica-
supported sulfonic acids as recyclable catalyst for esterification of levulinic acid
with stoichiometric amounts of alcohols, Beilstein J. Org. Chem. 12 (2016)
2173–2180.
[58] V. Trombettoni, L. Bianchi, A. Zupanic, A. Porciello, M. Cuomo, O. Piermatti,
A. Marrocchi, L. Vaccaro, Efficient catalytic upgrading of levulinic acid into alkyl
levulinates by resin-supported acids and flow reactors, Catalysts 7 (2017)
235–248.
[59] N.A.S. Ramli, N.H. zaharuddin, N.A.S. Amin, Esterification of renewable levuininc
acid to levulinate ester using Amberlyst 15 as a solid acid catalyst, Jurnal
Teknologi (Sciences & Engineering) 79 (2017) 137–142.
[60] D.R. Fernandes, A.S. Rocha, E.F. Mai, Claudio J.A. Mota, V. Teixeira da Silva,
Levulinic acid esterification with ethanol to ethyl levulinate production over solid
acid catalysts, Appl. Catal. A Gen. 425 (2012) 199–204.
[61] M.B. Kokare, V. Rajani, C.S. Mathpati, Response surface optimization, kinetic
study and process design of n-butyl levulinate synthesis, Chem. Eng. Res. Des. 137
(2018) 577–588.
[62] M.A. Tejero, E. Ramírez, C. Fité, J. Tejero, F. Cunill, Esterification of levulinic acid
with butanol over ion exchange resins, Appl. Catal. A Gen. 517 (2016) 56–66.
[63] M. Wu, X. Zhang, X. Su, X. Li, X. Zheng, X. Guan, P. Liu, 3D graphene aerogel
anchored tungstophosphoric acid catalysts: Characterization and catalytic per-
formance for levulinicacid esterification with ethanol, Catal. Commun. 85 (2016)
66–69.
[64] K.Y. Nandiwale, S.K. Sonar, P.S. Niphadkar, P.N. Joshi, S. Deshpande, V.S. Patil, V.
V. Bokade, Catalytic upgrading of renewable levulinic acid to ethyl levulinate
biodiesel using dodecatungstophosphoric acid supported on desilicated H-ZSM-5
18
Fuel Processing Technology 197 (2020) 106213
as catalyst, Appl. Catal. A Gen. 460 (2013) 90–98.
[65] X. Zhou, et al., Efficient conversion of renewable levulinic acid to n-butyl levuli-
nate catalyzed by ammonium and silver co-doped phosphotungstic acid, J. Mol.
Catal. A Chem. 417 (2016) 71–75.
[66] M. Wu, et al., Esterification of levulinic acid into hexyl levulinate over dodeca-
tungstophosphoric acid anchored to Al-MCM-41, J. Exp. Nanosci. 11 (2016)
1331–1347.
[67] N.A.S. Ramli, N.A.S. Amin, D. Sivasubramaniam, Esterification of levulinic acid
using ZrO-supported phosphotungstic acid catalyst for ethyl levulinate production,
Bioenerg. Res. 10 (2017) 1–12, https://doi.org/10.1007/s12155-017-9872-1.
[68] X.-C. Zheng, X. Guan, N. Li, X.L. Zhang, M. Wu, Synthesis of biofuel via levulinic
acid esterification over porous solid acid consisting of tungstophosphoricacid and
reduced graphene oxide, Res. Chem. Intermed. 43 (2017) 6651–6664, https://doi.
org/10.1007/s11164-017-3012-6.
[69] M. Wu, Tungstophosphoric acid-based mesoporous materials anchored to MCM-
41: characterization and catalytic performance in esterification of levulinic acid
with ethanol, J. Porous. Mater. 23 (2016) 1329–1338, https://doi.org/10.1007/
s10934-016-0192-1 2016 1-10.
[70] Q.J. Liun, Clean efficient conversion of renewable levulinic acid to levulinate es-
ters catalyzed by an organic-salt of H4SiW12O40, Process Saf. Environ. Prot. 117
(2018) 341–349.
[71] S. Dharne, V.V. Bokade, Esterification of levulinic acid to n-butyl levulinate over
heteropolyacid supported on acid-treated clay, J. Nat. Gas Chem. 20 (2011)
18–24.
[72] C.B. Vilanculo, L.C.A. Leles, M.J. Silva, H4SiW12O40-catalyzed levulinic acid es-
terification at room temperature for production of fuel bioadditives, Waste and
Biomass Valorization (2018) 1–10, https://doi.org/10.1007/s12649-018-00549-x.
[73] K. Manikandan, K.K. Cheralathan, Heteropoly acid supported on silicalite–1 pos-
sesing intracrystalline nanovoids prepared using biomass – an efficient and re-
cyclable catalyst for esterification of levulinic acid, Appl. Catal. A Gen. 547 (2017)
237–247.
[74] N. Lucas, L. Gurrala, A. Athawale, Heteropolyacids supported on mesoporous
AlSBA-15 as efficient catalysts for esterification of levulinic acid Journal of Porous,
Materials 2019, 1–9. doi:https://doi.org/10.1007/s10934-019-00734-w1-10.
[75] K. Yan, G. Wu, J. Wen, A. Chen, One-step synthesis of mesoporous H4SiW12O40
catalysts for the production of methyl and ethyl levulinate biodiesel, Catal.
Commun. 34 (2013) 58–63.
[76] K.Y. Nandiwale, V.V. Bokade, environmentally benign catalytic process for es-
terification of renewable levulinic acid to various alkyl levulinates biodiesel,
Environ. Prog. Sustain. Energy 34 (2015) 795–801.
[77] C.R. Patil, P.S. Niphadkar, V.V. Bokade, P.N. Joshi, Esterification of levulinic acid
to ethyl levulinate over bimodal micro–mesoporous H/BEA zeolite derivatives,
Catal. Commun. 43 (2014) 188–191.
[78] K.Y. Nandiwale, V.V. Bokade, Esterification of renewable levulinic acid to n-butyl
levulinate over modified H-ZSM-5, Chem. Eng. Technol. 38 (2015) 1–8.
[79] K.C. Maheria, A. Dalai, J. Kozinski, Esterification of levulinic acid to n-butyl le-
vulinate over various acidic zeolites, Catal. Lett. 143 (2013) 1220–1225.
[80] K.Y. Nandiwale, P.S. Niphadkar, S.S. Deshpande, V.V. Bokade, Esterification of
renewable levulinic acid to ethyl levulinate biodiesel catalyzed by highly active
and reusable desilicated H-ZSM-5, J. Chem. Technol. Biotechnol. 89 (2014)
1507–1515.
[81] K.Y. Nandiwale, V.V. Bokade, Optimization by Box–Behnken experimental design
for synthesis of n-hexyl levulinate biolubricant over hierarchical H-ZSM-5: an ef-
fort towards agricultural waste minimization, Process Saf. Environ. Prot. 9 (2016)
159–166.
[82] K.Y. Nandiwale, S.K. yadava V.V. Bokade, Production of octyl levulinate biolu-
bricant over modified H-ZSM-5: optimization by response surface methodology,
Journal of Energy Chemistry 23 (2014) 535–541.
[83] C. Liu, K. Zhang, Y. Liu, S. Wu, Esterification of levulininc acid into ethyl levuli-
nate catalyzed by sulphonated bagasse-carbonized solid acid, Bioresourecs 14
(2019) 2186–2196.
[84] F.D. Pileidis, M. Tabassum, S. Coutts, M. Titirici, Esterification of Levulinic acid
into ethyl levulinate catalysed by sulfonated hydrothermal carbons, Chin. J. Catal.
35 (2014) 929–936.
[85] N. Li, S. Jiang, Z. Liu, X. Guan, X. Zheng, Preparation and catalytic performance of
loofah sponge-derived carbon sulfonic acid for the conversion of levulinic acid to
ethyl levulinate, Catal. Commun. 121 (2019) 11–14.
[86] V.L. Budarin, J.H. Clark, R. Luque, D.J. Macquarrie, Versatile mesoporous car-
bonaceous materials for acid catalysis, Chem. Commun. (2007) 634–636.
[87] M.M. Zainol, N.A.S. Amin, M. Asmadi, Effects of thermal treatment on carbon
cryogel preparation for catalytic esterification of levulinic acid to ethyl levulinate,
Fuel Process. Technol. 167 (2017) 431–441.
[88] M.M. Zainol, N.A.S. Amin, M. Asmadi, Kinetics and thermodynamic analysis of
levulinic acid esterification using lignin-furfural carbon cryogel catalyst, Renew.
Energy 130 (2019) 547–557.
[89] F. Su, L. Ma, D. Song, X. Zhang, Y. Guo, Design of a highly ordered mesoporous
H3PW12O40/ZrO–Si(Ph)Si hybrid catalyst for methyl levulinate synthesis, Green
Chem. 15 (2013) 885.
[90] Y. Kuwahara, T. Fujitani, H. Yamashita, Esterification of levulinic acid with
ethanol over sulfated mesoporous zirconosilicates: influences of the preparation
conditions on the structural properties and catalytic performances, Catal. Today
237 (2014) 18–28.
[91] Y. Kuwahara, W. Kaburagi, K. Nemoto, T. Fujitani, Esterification of Levulinic acid
with ethanol over sulfated Si-doped ZrO2 solid acid catalyst: Study of the struc-
ture–activity relationships, Appl. Catal. A Gen. 476 (2014) 186–196.
[92] F. Su, et al., Pore morphology-controlled preparation of ZrO-based hybrid catalysts
K.C. Badgujar, et al.
functionalized by both organosilica moieties and Keggin-type heteropoly acid for
the synthesis of levulinate esters, J. Mater. Chem. A 1 (2013) 13219–13221.
[93] D. Unlu, O. Ilgen, N.D. Hilmioglu, Reactive separation system for effective upgrade
of levulinic acid into ethyl levulinate, Chem. Eng. Res. Des. 118 (2017) 248–258.
[94] G.D. Yadav, A.R. Yadav, Synthesis of ethyl levulinate as fuel additives using het-
erogeneous solid superacidic catalysts: efficacy and kinetic modelling, Chem. Eng.
J. 243 (2014) 556–563.
[95] M. Varkolu, et al., Esterification of levulinic acid with ethanol over bio-glycerol
derived carbon–sulfonic-acid, Reac. Kinet. Mech. Cat. 120 (2017) 69–80, https://
doi.org/10.1007/s11144-016-1105-7 (1-16).
[96] M.P. Negus, A.C. Mansfield, N.E. Leadbeater, The preparation of ethyl levulinate
facilitated by flow processing: the catalyzed and uncatalyzed esterification of le-
vulinic acid, Journal of Flow Chemistry 5 (2015) 148–150.
[97] Y. Huang, T. Yang, B. Cai, X. Chang, H. Pan, Highly efficient metal salt catalyst for
the esterification of biomass derived levulinic acid under microwave irradiation,
RSC Adv. 6 (2016) 2106–2111.
[98] F.P. Martins, F.A. Rodrigues, M.J. Silva, Fe2(SO4)-catalyzed levulinic acid ester-
ification: production of fuel bioadditives, Energies 11 (2018) 1263.
[99] T. Guo, M. Qiu, X. Qi, Selective conversion of biomass-derived levulinic acid to
ethyl levulinate catalyzed by metal organic framework (MOF)-supported poly-
oxometalates, Appl. Catal. A Gen. 572 (2019) 168–175.
[100] S.S.R. Gupta, M.L. Kantam, Catalytic conversion of furfuryl alcohol or levulinic
acid into alkyl levulinates using a sulfonic acid-functionalized hafnium-based
MOF, Catal. Commun. 124 (2019) 62–66.
[101] F.G. Cirujano, A. Corma, F.X. Llabrés, I. Xamen, Conversion of levulinic acid into
chemicals: synthesis of biomass derived levulinate esters over Zr-containing MOFs,
Chem. Eng. Sci. 124 (2015) 52–60.
[102] Z. Li, R. Wnetrzak, W. Kwapinski, J.J. Leahy, Synthesis and characterization of
sulfated TiO2 nanorods and ZrO/TiO2 nanocomposites for the esterification of
biobased organic acid, ACS Applied Material and Interfaces 4 (2012) 4499–4505.
[103] M. Popova, Efficient solid acid catalysts based on sulfated tin oxides for liquid
phase esterification of levulinic acid with ethanol, Appl. Catal. A Gen. 560 (2018)
119–131.
[104] S. Zhou, et al., Covalently linked organo-sulfonic acid modified titanate nanotube
hybrid nanostructures for the catalytic esterification of levulinic acid with n-butyl
Alcohol, Chem. Eng. J. 361 (2019) 571–577.
[105] M. Popova, Influence of the preparation method of sulfated zirconia nanoparticles
for levulinic acid esterification, Reac Kinet Mech Cat 120 (2017) 55–67, https://
doi.org/10.1007/s11144-016-1088-4.
[106] D. Song, Ethane-bridged organosilica nanotubes functionalized with arenesulfonic
acid and phenyl groups for the efficient conversion of levulinic acid or furfuryl
alcohol to ethyl levulinate, ChemCatChem 8 (2016) 2037–2048.
[107] B.L. Oliveira, V. Teixeira da Silva, Sulfonated carbon nanotubes as catalysts for the
conversion of Levulinic acid into ethyl levulinate, Catal. Today 234 (2014)
257–263.
[108] A.G. Khiratkar, Sulphonic acid-functionalized benzimidazolium based poly ionic
liquid catalyzed esterification of levulinic acid, Catal. Lett. 148 (2018) 680–690,
https://doi.org/10.1007/s10562-017-2284-1.
[109] S.G. Kalghatgi, B.M. Bhanage, Green syntheses of levulinate esters using ionic li-
quid 1-methyl imidazolium hydrogen sulphate [MIM][HSO4] in solvent free
system, J. Mol. Liq. 281 (2019) 70–80.
[110] H.M. Salvi, G.D. Yadav, Surface functionalization of SBA-15 for immobilization of
lipase and its application in synthesis of alkyl levulinates: optimization and ki-
netics, Biocatalysis and Agricultural Biotechnology 18 (2019) 101038.
[111] L. Zhou, Conversion of levulinic acid into alkyl levulinates: using lipase im-
mobilized on meso-molding three-dimensional macroporous organosilica as cat-
alyst, Bioresour. Technol. 247 (2018) 568–575.
[112] G.D. Yadav, I.V. Borkar, Kinetic modeling of immobilized lipase catalysis in
synthesis of n-butyl levulinate, Ind. Eng. Chem. Res. 47 (2008) 3358–3363.
[113] A. Lee, N. Chaibakhsh, M.B.A. Rahman, M. Basri, B.A. Tejo, Optimized enzymatic
synthesis of levulinate ester in solvent-free system, Ind. Crop. Prod. 32 (2010)
246–251.
[114] K.C. Badgujar, B.M. Bhanage, Thermo-chemical energy assessment for production
of energy-rich fuel additive compounds by using levulinic acid and immobilized
lipase, Fuel Process. Technol. 138 (2015) 139–146.
[115] K.C. Badgujar, B.M. Bhanage, The green metric evaluation and synthesis of diesel-
blend compounds from biomass derived levulinic acid in supercritical carbon di-
oxide, Biomass Bioenergy 84 (2016) 12–21.
[116] K.C. Badgujar, B.M. Bhanage, Carbohydrate base co-polymers as an efficient im-
mobilization matrix to enhance lipase activity for potential biocatalytic applica-
tions, Carbohydr. Polym. 134 (2015) 709–717.
[117] K.C. Badgujar, B.M. Bhanage, Application of lipase immobilized on the bio-
compatible ternary blend polymer matrix for synthesis of citronellyl acetate in
non-aqueous media: kinetic modelling study, Enzym. Microb. Technol. 57 (2014)
16–25.
19
Fuel Processing Technology 197 (2020) 106213
[118] K.C. Badgujar, B.M. Bhanage, Immobilization of lipase on biocompatible co-
polymer of polyvinyl alcohol and chitosan for synthesis of laurate compounds in
supercritical carbon dioxide using response surface methodology, Process
Biochem. 50 (2015) 1224–1236.
[119] K.C. Badgujar, B.M. Bhanage, Enhanced biocatalytic activity of lipase immobilized
on biodegradable copolymer of chitosan and polyvinyl alcohol support for
synthesis of propionate ester: kinetic approach, Ind. Eng. Chem. Res. 53 (2014)
18806–18815.
[120] K.C. Badgujar, T. Sasaki, B.M. Bhanage, Synthesis of lipase nano-bio-conjugates as
an efficient biocatalyst: characterization and activity-stability studies with po-
tential biocatalytic applications, RSC Adv. 5 (2015) 55238–55251.
[121] K.C. Badgujar, B.M. Bhanage, Investigation of deactivation thermodynamics of
lipase immobilized on polymeric carrier, Bioprocess Biosyst. Eng. 40 (2017)
74–757.
[122] K.C. Badgujar, B.M. Bhanage, The solvent stability study with thermodynamic
analysis and superior biocatalytic activity of burkholderia cepacia lipase im-
mobilized on biocompatible hybrid matrix of polyvinyl alcohol and hypromellose,
J. Phys. Chem. B 118 (2014) 14808–14819.
[123] K.C. Badgujar, B.M. Bhanage, B.M. Bhanage, Enhanced biocatalytic activity of
immobilized Pseudomonas cepacia lipase under sonicated condition, Bioprocess
Biosyst. Eng. 39 (2016) (2016) 211–221.
[124] K.C. Badgujar, B.M. Bhanage, Lipase immobilization on hyroxypropyl methyl
cellulose support and its applications for chemo-selective synthesis of β-amino
ester compounds, Process Biochem. 51 (2016) 1420–1433.
[125] K.C. Badgujar, K.P. Dhake, B.M. Bhanage, Immobilization of Candida cylindracea
lipase on poly lactic acid, polyvinyl alcohol and chitosan based ternary blend film:
Characterization, activity, stability and its application for N-acylation reactions,
Process Biochem. 48 (2013) 1335–1347.
[126] K.C. Badgujar, K.P. Dhake, B.M. Bhanage, Synthesis of geranyl acetate in non-
aqueous media using immobilized Pseudomonas Cepacia lipase on biodegradable
polymer film: Kinetic modelling and chain length effect study, Process Biochem.
49 (2014) 1304–1313.
[127] V.C. Badgujar, K.C. Badgujar, P.M. Yeole, B.M. Bhanage, Immobilization of
Rhizomucor miehei lipase on a polymeric film for synthesis of important fatty acid
esters: kinetics and application studies, Bioprocess Biosyst. Eng. 40 (2017)
1463–1478.
[128] P.J. Fagan, E. Korovessi, L.E. Manzer, R. Mehta, S.M. Thomas, Levulinic and
Formic Acid Esters, as Gasoline and Diesel Fuel Oxygenate Additives, Prepared
from Biomass by Hydrolysis and Esterification with Olefins. Patent
WO2003085071, 2003.
[129] (Directive 2009/30/EC).
[130] H. Joshi, B.R. Moser, J. Toler, W.F. Smith, T. Walker, Ethyl levulinate: a potential
bio-based diluent for biodiesel which improves cold flow properties, Biomass
Bioenergy 35 (2011) 3262–3266.
[131] B.C. Windom, T.M. Lovestead, M. Mascal, E.B. Nikitin, T.J. Bruno, Advanced
distillation curve analysis on ethyl levulinate as a diesel fuel oxygenate and a
hybrid biodiesel fuel, Energy Fuel 25 (2011) 1878–1890.
[132] Lei, et al., Performance and emission characteristics of a diesel engine running on
optimized ethyl levulinate biodiesel diesel blends, Energy 95 (2016) 29–40.
[133] C.J. Chuck, J. Donnelly, The compatibility of potential bioderived fuels with jet A-
1 aviation kerosene, Appl. Energy 118 (2014) 83–91.
[134] A. Janssen, S. Pischinger, M. Muether, Potential of cellulose-derived biofuels for
soot free diesel combustion, SAE Int. J. Fuels Lubr. 3 (2010) 70–84.
[135] Wang et al., A comparison of the physical and chemical properties, performance
and emissions of ethyl levulinate- biodiesel-diesel and n-butanol-biodiesel-diesel
blends, Energy Fuel. 51 (2017) 5055–62.
[136] Tian, et al., Anti-knock quality of sugar derived levulinic esters and cyclic ethers,
Fuel 202 (2017) 414–425.
[137] Q. Tian, C. Guanyi, L. Tingzhou, Y. Beibei, W. Zhiwei, A comparison on physical
and chemical properties of several alternative fuel formulas, Journal of Biobased
Materials and Bioenergy 9 (2015) 74–77.
[138] Zhi-Wei, et al., A study on physical and chemical properties based on ethyl le-
vulinate as a diesel fuel addition, Journal of Biobased Materials and Bioenergy 9
(2015) 3–8.
[139] D. Unlu, N. Boz, O. Ilgen, N. Hilmioglu, Improvement of fuel properties of bio-
diesel with bioadditive ethyl levulinate, Open Chem 16 (2018) 647–652.
[140] H.V. Srikanth, V.J. Godiganur, S. Venkateswaran, B. Manne, Bio-based diluents
improve cold flow properties of dairy washed milk-scum biodiesel, Renew. Energy
111 (2017) 168–174.
[141] Ghosh, et al., The combustion kinetics of the lignocellulosic biofuel, ethyl levuli-
nate, Combustion and flame 193 (2018) 157–169.
[142] C.G. Chol, R. Dhabhai, A.K. Dalai, M. Reaney, Purification of crude glycerol de-
rived from biodiesel production process: experimental studies and techno-eco-
nomic analyses, Fuel Process. Technol. 178 (2018) 78–87.