Renewable and Sustainable Energy Reviews 94 (2018) 340–362

Contents lists available at ScienceDirect

Renewable and Sustainable Energy Reviews

journal homepage: www.elsevier.com/locate/rser

From lignocellulosic biomass to levulinic acid: A review on acid-catalyzed T

hydrolysis
⁎
Shimin Kanga, Jinxia Fub, Gang Zhanga,
a
Guangdong Provincial Key Laboratory of Distributed Energy Systems, Dongguan University of Technology, Dongguan, Guangdong, China
b
Hawaii Natural Energy Institute, University of Hawaii, Honolulu, HI, USA

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

Keywords: Catalytic conversion of renewable biomass to “green” chemicals and fuel additives has been extensively in-
Levulinic acid vestigated in the past few decades. Interests on two top platform intermediates for biofuel production, i.e.
5-hydroxymethylfurfural levulinic acid (LA) and 5-hydroxymethylfurfural (HMF), have increased significantly. These two chemicals are
Biomass generally produced from biomass through acid hydrolysis. This review summarizes the discoveries of the most
Hydrolysis
recent studies on acid-catalyzed hydrolysis, including (i) biomass pretreatment, (ii) glucose production from
Humins
cellulose hydrolysis, (iii) fructose formation from glucose isomerization, (iv) HMF formation from glucose/
Bioenergy
fructose dehydration and (v) LA production from HMF rehydration. Humins, the main byproducts, are also
discussed in the aspect of their influence on the hydrolysis process, structure, formation mechanism, and ap-
plications.

1. Introduction
With the depletion of fossil fuels and the growth of concerns over
climate change, bioenergy and green chemicals derived from biomass
have attracted significant attention in recent years. Thermochemical
processes initially developed for fossil fuel conversion have been em-
ployed for producing value-added chemicals and biofuels from biomass.
These processes include pyrolysis [1–3], hydrolysis/alcoholysis [4–8],
hydrothermal liquefaction [9–13], gasification [14–16] and carboni-
zation [17–19]. Acid-catalyzed hydrolysis, a process generally con-
ducted at a relatively mild temperature (100–250 °C), has been re-
garded as an essential step for bioenergy production, and furfural,
glucose, 5-hydroxymethylfurfural (HMF) and levulinic acid (LA) are
regarded as key intermediate platform chemicals [7,20–24]. The
roadmap for acid catalytic hydrolysis of lignocellulosic biomass to
bioenergy is shown in Fig. 1 [25–34]. The hemicellulose can be con-
verted to xylose and furfural, while cellulose can be hydrolyzed to
glucose, HMF, and LA. The lignin and humins are solid residues left
from hydrolysis of biomass. The furfural, glucose, HMF and LA obtained
can be further upgraded to biofuels and biofuel additives, and the solid
residues can be used for heat generation and aromatic bio-oil produc-
tion [34–36]. For instance, furfural has become a platform for special
biofuel production, including methyltetrahydrofuran and methylfuran,
ethylfurfuryl and ethyltetrahydrofurfuryl ethers, valerate esters, and
various C10–C15 oil products [25,26]. In addition, the furfural upgraded
products can be used as gasoline replacement or blends for diesel
[25,26]. Glucose is a good material for production of bioethanol, an
important component of oxygenated gasoline [27]. HMF can be up-
graded to C9-C11 low oxygenate diesel range fuels (e.g., 1-ethox-
ynonane) [28], and C13–C15 hydrocarbons [29]. LA, a chemical bridge
connecting biomass and petroleum processing, has also been regarded a
desirable feedstock for liquid fuel production [30]. One well-estab-
lished way is hydrogenation of LA to γ-valerolactone and further to
liquid alkenes with eight or more carbons [31]. Alternatively, LA can be
converted to a family of valerate esters (e.g., methyl, ethyl, and propyl
valerate) using as gasoline additive [30,32,33]. In addition to the up-
grading as renewable biofuels, HMF and LA are also promising basic
chemicals for other applications (see Fig. 2) [7,20,37–54]. Both LA and
HMF can be converted to resins, solvents, polymers and chemical in-
termediates. LA is also an important source for spice, cosmetic, phar-
maceutical, pesticide, and fungicide production. The biomass hydro-
lysis process also produces formic acid byproduct [55–58], which has
been utilized for synthesizing formaldehyde, plasticizers, rubber, tex-
tiles and pharmaceutical products. [7,44]. Formic acid can also be used
as a hydrogen donor for LA hydrogenation to produce fuel additive,
such as γ-valerolactone. [59].
To produce the intermediate platform chemicals (e.g., glucose,
HMF, LA), acid catalytic hydrolysis has become a conventional

Abbreviations: LA, levulinic acid; HMF, 5-hydroxymethylfurfural

⁎
Corresponding author.
E-mail address: zhanggang@dgut.edu.cn (G. Zhang).

https://doi.org/10.1016/j.rser.2018.06.016
Received 29 March 2017; Received in revised form 7 June 2018; Accepted 7 June 2018
1364-0321/ © 2018 Elsevier Ltd. All rights reserved.
S. Kang et al. Renewable and Sustainable Energy Reviews 94 (2018) 340–362

Fig. 1. Roadmap for acid catalytic hydrolysis of lignocellulosic biomass for production of bioenergy.

Fig. 2. The potential applications of HMF and LA.

technology promoting the production of biofuel in a more sustainable
way. Thus, studies on the acid catalytic hydrolysis process, especially
for production of HMF and LA, have become a research hotspot. The
earliest paper published on HMF production was in 1875, in which acid
catalyst was employed for conversion of sugar [60]. HMF derived from
biomass, however, didn’t gain much attention until 1980s. Teong et al.
[61] reviewed the history of HMF production process and summarized
that the development of HMF production process have three main
stages, i.e.(i) early stage before 1980, (ii) developing stage from 1980 to
2000 and (iii) active stage after 2000. LA was brought to attention by
Mulder in the 1840 [62] and characterized as a platform chemical with
high potential in 1956 [63]. LA was first synthesized by heating fruc-
tose with hydrochloric acid [62]. In 2004, LA and HMF were both
regarded as one of the top 12 bio-based platform chemicals by the
United States Department of Energy (DOE) [23]. Interest on the ap-
plications of HMF and LA has led to an extensive study on tailored acid-
catalyzed hydrolysis of biomass, and this interest continues to increase
in the recent years. A few review papers have also been published fo-
cusing on the preparation and application of LA and HMF. Chang et al.
[64] summarized the development of solid catalysts for LA and deri-
vative alkyl levulinates production from biomass. Zheng et al. [65],
Zakrzewska et al. [66] and Teong et al. [61] reviewed the production
pathways of HMF and LA in terms of reaction mediums (e.g. aqueous,
solvents, ionic liquids). Hu et al. [67], Tang et al. [68] and Zhang et al.
[69] outlined the recent advances in catalytic transformation of HMF
and LA to the fuels and chemicals. In addition, Mood et al. [70] and

Rferences are very important

341
S. Kang et al.
Fig. 3. The hydrolysis mechanism from cellulose to LA.
Verardi et al. [71] reviewed the biomass hydrolysis pretreatment
methods focusing on bioethanol production.
It has been widely accepted that the reaction pathways for LA and
HMF production are quite similar, and HMF is a key intermediate for LA
formation in the biomass hydrolysis process (shown in Fig. 3). This
reaction is consecutive and usually includes 5 steps: (i) pretreatment of
lignocellulose biomass, (ii) hydrolysis of cellulose into glucose, (iii)
isomerization of glucose to fructose, (iv) dehydration of hexoses (glu-
cose and fructose) to HMF, and (v) rehydration of HMF to LA
[22,72,73]. Humins, a class of unavoidable byproducts in the acid-
catalyzed hydrolysis process, can significantly affect the yield of bio-
mass [23,74–77]. Therefore, it is also essential to discover reaction
pathways and optimize reaction conditions to prevent the formation of
humins. The goal of this article is to provide a critical review on HMF
and LA production, focusing on the acid catalyzed hydrolysis of lig-
nocellulosic biomass. This paper is organized as follows: (1) a brief
overview of this paper, (2) the influence of lignocellulosic biomass
342
Renewable and Sustainable Energy Reviews 94 (2018) 340–362
composition, (3) the impact of lignocellulosic biomass pretreatment
techniques, (4) the cellulose acid hydrolysis process to produce glucose,
(5) the reaction pathways and conditions on HMF production from
glucose, (6) the reaction process and condition on LA formation, (7) the
characteristics, formation routes and application of humins byproduct
and (8) summary of the key findings and future prospects of research.
2. Influence of lignocellulosic biomass composition
Lignocellulosic biomass has been recognized as an attractive feed-
stock for large scale production of LA and HMF due to its sustainable
characteristics and comparable low costs [58]. The lignocellulosic
biomass is mainly composed of cellulose, hemicellulose, lignin and a
small amount of inorganic salts [9]. The composition of biomass de-
pends on the species, e.g., the cellulose, hemicellulose and lignin con-
tents are 40–55 wt%, 24–40 wt%, and 18–25 wt% in the hardwood
stems, while 45–50 wt%, 25–35 wt%, and 25–35 wt% in the softwood
S. Kang et al.
stems, respectively [8,9,78,79]. These major components also have
different fates in the acid-catalyzed hydrolysis process [58]. Hexoses,
usually derived from cellulose and a small part of hemicellulose, can be
converted directly to HMF and LA, whereas lignin, inorganic salts and
majority parts of hemicellulose cannot directly contribute to the HMF
and LA production. Lignin, xylan and inorganic salts even have negative
impacts on the LA and HMF formation, which is discussed below.
2.1. Surface accessibility
The surface accessibility is a critical factor for cellulose hydrolysis
[80]. The three major organic components of lignocelluloses, i.e. cel-
lulose, hemicellulose and lignin, are generally linked by hydrogen
bonding, chemical bonding, and covalent linkages. Hydrogen bonding
exists between all these substances, while chemical bonding and
covalent linkages only exist between hemicellulose and lignin [81] and
between cellulose and lignin [82–85]. The hydrogen bonding and
possible chemical linkages result in the cellulose and hemicellulose
densely packed by layers of lignin [85]. Therefore, the surface of cel-
lulose is blocked by hemicellulose and lignin, which prevents hydrolysis
process of cellulose through acid catalysts.
2.2. Low concentration
The concentration of raw biomass for LA production in aqueous
solution is usually in a range of 100–200 g/L (listed in Table 1). The
initial concentration of hexoses derived from cellulose, however, is low
in the reaction solution, 50–100 g/L, owing to the existence of lignin
and hemicellulose. As one LA molecule (molecular weight: 116 g/mol)
is formed by one hexose molecule (molecular weight: 180 g/mol), the
theoretical yield of LA from hexoses is 64.4 wt%. The high LA yield
from raw biomass is usually limited to 50–60% of the theoretical yield
[42,56,103,105]. The LA concentration after reaction, therefore, is
roughly 16–40 g/L disregard of the solvent volume change. Actually, it
has been reported that a maximum LA concentration, 16.14 g/L, was
obtained through the FeCl3 catalytic conversion of corn stalk [118]. The
low LA concentration results in relative higher cost in the LA down-
stream processing, indicating that direct hydrolysis of raw biomass is
not desirable. Similar issues were also observed in HMF production,
which is discussed in Section 5.3.
2.3. Humins formation
Different from cellulose and hemicellulose, lignin, a phenolic
polymer, requires much severer conditions for decomposition in acid-
assisted hydrothermal process. Most of lignin remains in solid state
during LA production [56,58], and only a small portion of lignin dis-
solves in the reaction solution as acid soluble lignin [109,124]. How-
ever, it has been reported that the presence of lignin facilitates the
humins formation and results in a lower LA yield [125]. In addition, the
existence of chemical reactions and/or physical interactions between
lignin and LA also induces a lower LA yield in the hydrolysis process
[58].
2.4. Decomposition of hemicellulose-derived monosaccharides
Hemicellulose is easier to be hydrolyzed and form monosaccharides
(e.g., xylose) in comparison with cellulose owing to its branched and
amorphous structure [126,127]. Under dilute acidic hydrolysis condi-
tions, the rate of the monosaccharides decomposition has the following
order: xylose > arabinose > mannose > galactose > glucose [128].
Therefore, the formation of furfural derived from xylose decomposition
is inevitable in the lignocellulosic biomass hydrolysis process. Furfural
is often very unstable in the acidic solution and can react with sugars to
form humins [129–131]. Runge and Zhang reported that the direct
hydrolysis of hemicellulose and cellulose reduces the LA yield owing to
343
Renewable and Sustainable Energy Reviews 94 (2018) 340–362
reactions between furfural and C5 sugars in a one-pot batch reaction
system [132]. The hemicellulose (or C5 sugars), however, can be used
for LA production through a three-step reaction: (i) acid-catalyzed de-
hydration of hemicellulose (or C5 sugars) to produce furfural, (ii) fur-
furyl alcohol formation through hydrogenation of furfural, and (iii) LA
production through acid-catalyzed hydrolysis of furfuryl alcohol
[49,133]. Although ~ 70–80 wt% of the biomass constitutes (cellulose
and hemicellulose) can be used for LA production, it is still impossible
to co-process cellulose and hemicellulose considering the difference of
their reaction pathways.
2.5. Catalyst deactivation
Inorganic metal salts (e.g., K salts, Ca salts, Mg salts) present in
natural biomass can be leached into aqueous solution [134,135]. The
existence of these leached metal ions in the biomass hydrolysis process
results in catalyst deactivation, as the protons on the solid acid catalysts
can be replaced by these metal ions [136,137]. The Ca salts in raw
biomass also have negative impacts on homogeneous catalyst H2SO4
[74], one of the most widely used homogeneous catalysts for biomass
hydrolysis [42,138], as insoluble calcium sulfate can precipitate even in
dilute H2SO4 and result in reactor clogging in the biomass hydrolysis
process [42].
In summary, the presence of lignin, xylan and inorganic salts in
lignocellulosic biomass has destructive impacts on HMF and LA pro-
duction from cellulose and it is crucial to develop a process that could
convert the major components of lignocellulosic biomass to value-
added chemicals and/or fuels in order to reduce the production cost and
waste generation.
3. Impact of pretreatment
One of the methods to increase the LA and HMF production yield is
to isolate cellulose from biomass before the hydrolysis. This has been
widely employed for enzymatic hydrolysis of biomass in bio-ethanol
production [80,139–142]. Various pretreatment methods have been
developed, including mechanical communication, steam explosion, CO2
explosion, ozonolysis, acid hydrolysis, alkaline hydrolysis, pyrolysis,
organosolv and biological pretreatment processes [80,139–142].
For LA and HMF production from lignocellulosic materials, effective
pretreatment methods have to meet the following requirements: (i)
removal of soluble inorganic salts, xylan and/or lignin and recovery of
products derived from xylan or lignin; (ii) improvement on surface
accessibility of cellulose as well as avoiding the degradation or loss of
hexoses; (iii) direct utilization of the pretreated solids for subsequent
acid hydrolysis processes and (iv) minimizing the amount of reagents
used in pretreatment and subsequent neutralization process to reduce
the overall production cost.
Among all the above mentioned pretreatment methods, the dilute
acid pretreatment is one of the most widely used methods for bio-
ethanol production [143–145]. Although the removal of lignin by the
dilute acid treatment is insignificant and most lignin remains in solids
phase after the pretreatment [145], the dilute acid pretreatment is still
regarded as a potential technology for the LA and HMF production for
following reasons:
(1) Most of the sugars in hemicellulose can be released as sugar
monomers by the dilute acid pretreatment, and these sugar mono-
mers are usually recoverable [143,146–149], whereas most of the
glucan (glucose) remains in the pretreated solids [58,143]. A small
fraction of the glucose can be removed due to the release of the
glucose in hemicellulose and the hydrolysis of the amorphous cel-
lulose. The acid pretreatment of the raw biomass results in the
formation of acid salts (e.g., potassium sulfate, sodium bisulfate,
and magnesium bisulfate in sulfuric acid as the acid reagent), which
makes the removal of metal ions from the biomass body to aqueous
S. Kang et al. Renewable and Sustainable Energy Reviews 94 (2018) 340–362

Table 1
LA production from acid catalyzed hydrolysis of biomass derived feedstocks.
Feedstocks Catalyst Reaction conditions LA yield Reference

0.1 M glucose 1 M H2SO4 140 °C, 2 h 60 mol% [57]

73 g/L olive tree pruning 37% HCl, 11.5 meq 200 °C, 1 h 20.1 wt% [74]
73 g/L poplar sawdust 37% HCl, 11.5 meq 200 °C, 1 h 29.3 wt%
73 g/L paper sludge 98% H2SO4, 8.3 meq 200 °C, 1 h 15.4 wt%
73 g/L paper sludge 37% HCl, 11.5 meq 200 °C, 1 h 31.4 wt%
0.1 M HMF 1 M H2SO4 98 °C, 180 min 94 mol% [86]
0.1 M fructose 1 M H2SO4 140 °C 74 mol% [87]
1 M D-glucose 0.01 M H2SO4 180 °C, 6 h 27 mol% [88]
1 M D-fructose 0.055 M H2SO4 180 °C, 6 h 31 mol% [88]
5% fructose 1.5 g/L InCl3 180 °C, 45 min 45 mol% [89]
5% fructose 6.7% Amberlyst 15 140 °C, 8 h 56 mol% [90]
10 wt% fructose 0.1 M HCl + 0.9 wt% CrCl3 140 °C, 250 min 46 mol% [91]
20 g/L glucose 20 g/L Fe/HY 180 °C, 3 h 62.0 mol% [92,93]
33.3 g/L glucose GaHPMo/glucose= 1/5 150 °C, 10 h 56 wt% [94]
0.35 M glucose 5.8 M H2SO4 98 °C, 12 h 38 mol% [95]
0.35 M glucose 7.2 M HCl 98 °C, 6 h 35 mol%
1% glucose CrCl3 and HY zeolite (1:1) 160 °C, 180 min 62 mol% [96]
0.0556 mol/L glucose H3PO4 (0.02 M) - CrCl3 (0.02 M) mixture 170 °C, 4.5 h 49.8 mol% [97]
1% glucose 0.75% MFI-type zeolite 180 °C, 8 h 35.8 mol% [98]
30 g/L glucose 2 g/L S2O82-/ZrO2-TiO2-Fe3O4 190 °C, 2 h 70.2 mol% [99]
0.0556 mol/L glucose 0.015 M In(CF3SO3)3 180 °C, 5 h 15.8 mol% [100]
0.0556 mol/L glucose 0.015 M C7H8O3S 180 °C, 5 h 32.0 mol%
0.0556 mol/L glucose 0.015 M In(CF3SO3)3 and H2C2O4 180 °C, 5 h 41.6 mol%
3.2% cellulose 0.045 g/ml SO2 210 °C, 45 min 45 mol% [101]
2% cellulose 0.02 M CrCl3 200 °C, 3 h, 300 rpm shaking 67 mol% [102]
99.6 mM cellulose 0.927 M HCl 180–200 °C 60% of theoretical [103]
1.7 wt% cellulose 1 M H2SO4 150 °C, 2 h 60 mol% [104]
2% cellulose 2% ZrO2 180 °C, 3 h, 600 rpm stirring 53.9 mol% [105]
5% cellulose 4% aluminium-modified mesoporous 180 °C, 24 h 52.9 mol% [106]
niobium phosphate
10% sugar cane bagasse (with 69% of sugar 0.55 M H2SO4 150 °C, 8 h 63 mol%, [107]
ploymer)
9.1% pretreated rice husks 4.5% (v/v) HCl 160 °C, 56 bar and 70 min 54.5% in terms of cellulose [108]
conversion
9.1% pretreated rice husks 4% (v/v) H2SO4 170 °C, 60 min 45.7% in terms of cellulose
conversion
1 wt% water hyacinth (C6-sugars is 26.3 wt 1 M H2SO4 175 °C, 30 min 53 mol% based on the amount of [109]
%) C6-sugars
9% Miscanthus (40.7% glucan) 0.10–0.53 M H2SO4 160–200 °C 58–72 mol% based on the [110]
amount of glucan
10% sorghum flour 8% H2SO4 200 °C, 30 min 32.6 wt% [111]
6% wheat straw 3% H2SO4 210 °C, 42 min 41 wt% based on cellulose [112]
content
5% cotton 1 M HCl 150 °C, 2 h 44 mol% [113]
120 g/L glucosamine 4% H2SO4 188 °C, 49 min 25.3 wt% [114]
2.5% chitosan 0.06 M SnCl4·5H2O microwave irradiation 200 °C, 23.9 wt% [115]
30 min, 17–19 bar
corn stalk 0.05 mol/L FeCl3 230 °C, 10 min 48.73 mol% [116]
62.5 kg/m3H. tuberosus L. H2SO4 (2 kg/m3) 160–200 °C, 10–35 min 32.3 wt% [117]
10 wt% corn stalk 0.5 M FeCl3 180 °C, 40 min 48.89 mol% [118]
14 wt% pennisetum alopecuroides 8% H2SO4 190 °C, 60 min 50.49% theoretical [119]
100 g/L furfural residue 2% H2SO4 180 °C, 2 h 66.6 mol% [120]
6.25% wheat straw 3% H2SO4 210–230 °C, 30 min 19.2 wt% [121]
0.056 M glucose 32.3 mol% Fe-NbP 180 °C, 3 h 64.2 mol% [122]
50 g/L cellulose 20 g/L cellulase-mimetic solid acid 180 °C, 12 h 51 mol% [123]
10 g/L glucose 20 g/L cellulase-mimetic solid acid 180 °C, 12 h 61 mol%

solution easier [149]. T − 100 ⎞

(2) The dilute acid pretreatment assists to increase the cellulose per-
centage in the feedstocks. For example, after the pretreatment of
eucalyptus by 0.1 M H2SO4 at 150 °C, the pretreated wood has a
glucan content of 63.8 wt%, about 1.4 times increase than that in
original eucalyptus [59], indicating that pretreatment is essential
for improving the LA yields.
(3) The pretreated solids can be directly used for HMF or LA production
without neutralization, as the pretreatment and subsequent hy-
drolysis processes both use acid catalysts.
(4) The reaction condition for the dilute acid pretreatment is mild in
comparison with that of cellulose acid hydrolysis, which can be
reflected by the severity factor shown in Eq. (1) [150],
Severity factor = log ⎛t × exp ⎛ ⎞ − pH
⎝ ⎝ 14.75 ⎠ ⎠ (1)
where T is temperature, t is time, and pH is the solution acidity. The
severity factor has been widely used for biomass hydrolysis evaluation
[151–153]. In the dilute acid pretreatment of corn stover process, the
severity factor is in a range of 1–2, which is much lower than that for LA
production, severity factor > 3 [56,149,154,155], indicating that the
pretreatment can be conducted in the hydrolysis reaction system
without further investment.
Regarding to the overall production cost, it is more desirable to
develop a method that (i) requires less investment, (ii) has lower en-
vironmental impacts and (iii) can utilize all cellulose, hemicellulose and
lignin for chemical and fuel production [156]. Fig. 4 shows the process

344
S. Kang et al.
Fig. 4. Acid pretreatment and hydrolysis of lignocellulosic biomass.
of dilute acid pretreatment followed by acid hydrolysis for LA and/or
HMF production. In this process, hemicellulose is decomposed to xy-
lose, furfural etc., while cellulose is used to produce HMF, LA and
formic acid. The remaining solid residues (humins and lignin) can be
used for combustion [58]. Similarly, Jeong et al. proposed a two-step
acid-catalyzed treatment of Quercus mongolica to obtain C5 sugars and
LA [157]. The C5 sugars were released from hemicellulosic through
acid-catalyzed pre-treatment, and the LA was produced through acid-
catalyzed hydrolysis of cellulose in solid residue under more severe
conditions. Ji et al. developed a process to produce furfural and LA from
corncob in a batch reaction incorporating distillation using step tem-
perature profiling. The distillation not only reduced furfural loss to
humins, but also resulted in a fairly pure and concentrated furfural
solution [158]. Giuliano et al. also developed an integrated process to
produce LA, succinic acid, and ethanol from hardwood biomass [159].
4. Hydrolysis of cellulose to produce glucose
Although cellulose is a hygroscopic material and is able to absorb
8–14% water under atmospheric conditions, it is insoluble in water
[78]. The initial stage of cellulose hydrolysis under mild conditions is a
heterogeneous reaction, and homogenous proton catalysts (e.g., H2SO4
and HCl) are usually effectively enough, as they can penetrate into the
heterogeneous matrix of cellulose. The catalytic hydrolysis of cellulose
by heterogeneous catalyst is, however, preferred owing to its green
characteristics [160].
Acid-catalyzed hydrolysis of cellulose to produce glucose generally
has three steps: (i) protonation of glycosidic oxygen, (ii) scission of
glycosidic linkage and (iii) nucleophilic attack of water (path (A) in
Fig. 3) [161,162]. After protonation of the glycosidic oxygen, the
neighboring anhydroglucose unit connected to the glycosidic oxygen on
the C1 position undergoes a half-chair rotational conformation change.
The half-chair rotational conformation change is hindered by both
intra- and inter-chain hydrogen bonds [161,162]. Although the clea-
vage of β-1,4-glycosidic bonds of cellulose is a rate-determining step
[163], the degree of crystallinity is the critical factor that affects the
reaction rate. With higher crystallinity, the accessibility of the β-1,4-
glycosidic bonds is restricted, which results in a slow hydrolysis rate.
For example, the reaction rate of ball-milled cellulose with low crys-
tallinity index is faster than that of commercial cellulose substrates with
higher crystallinity [163]. In addition, a steam explosion combined
with superfine grinding can also effectively enhance the accessibility of
cellulose and result in increased LA yield [163].
5. From glucose to HMF
The hydrolysis of cellulose to glucose and decomposition of glucose
usually occurs simultaneously, but the reaction rates are highly affected
by the reaction conditions. Sasaki et al. reported that the glucose de-
composition rate was much faster than its formation rate in hydrolysis
process at a relative low temperature (290–350 °C), whereas the cel-
lulose hydrolysis rate was faster than that of glucose decomposition
when the temperature is > 350 °C [164,165]. The yield of HMF,
however, is low (~ 11%), and few LA were obtained when operating at
high temperature (> 350 °C) without acid catalyst [165]. Thus, acid
345
Renewable and Sustainable Energy Reviews 94 (2018) 340–362
catalysts play a critical role in the process of converting glucose to HMF
and LA. Plenty types of catalysts have been developed in the past 15
years. It has been reported that approximately 100 inorganic and or-
ganic chemicals are identified as catalysts for the HMF synthesis [166],
and these chemicals can be classified to five types, i.e. organic acids
(e.g., oxalic acid, p-TsOH), inorganic acids (e.g., H2SO4, HCl), salts
(e.g., (NH4)2SO4/SO3), lewis acids (e.g., AlCl3, ZnCl2) and the others
(e.g., ion-exchange resins) [167]. Ionic liquids and ionic liquid metal
salts were mainly employed for solvent reaction systems except for
aqueous solution [168–171]. Organic acids, such as formic, acetic and
lactic acids, can be used for dehydration of fructose to produce HMF,
but cannot be used for glucose conversion [172], illustrating that the
isomerization of glucose to fructose or direct catalytic dehydration of
glucose to HMF is much more difficult in comparison with the catalytic
dehydration of fructose to HMF under the weak organic acid conditions.
5.1. Reaction pathways
Two reaction pathways were identified for HMF production from
glucose depending on whether the fructose is formed as intermediate
(see pathway B and F, and E in Fig. 3). For reaction with the HCl cat-
alyst but without an isomerization catalyst, HMF was directly formed
from glucose without forming the fructose intermediate [20,173,174].
Pedersen et al. demonstrated that the rate of HMF formation during
glucose dehydration with HCl catalyst cannot be explained by a
pathway with the formation of fructose intermediate [174]. It has also
been reported that HMF was formed from glucose dehydration by a
carbocation involved reaction [20,175]. In this reaction, the open-chain
structure of glucose is dehydrated at the C2 position by forming a C2
carbocation. The C2 carbocation then reacts with the C5 hydroxyl
group to form tetrahydro-3,4-dihydroxy-5-(hydroxymethyl)-2-fur-
aldehyde, which further dehydrates to HMF (path E in Fig. 3).
The HMF yield from direct conversion of glucose is usually low
owing to the glucose's stable pyranoside ring structure [176], whereas
the dehydration of fructose (step F in Fig. 3) usually results in higher
HMF yield and faster reaction rate [177–181]. Thus, a potential
pathway to improve the HMF production is to replace the glucose based
raw material with fructose-containing polysaccharides, such as inulin, a
natural polysaccharide consisting of linear chains of fructose units with
the polymer chains terminated by a glucose unit [182]. It is, however,
challenging to realize large-scale production of inulin due to the feed-
stock limitation [183,184]. For example, inulin is often rich in edible
stalks or roots competing with food production.
5.2. Glucose/fructose isomerization
As fructose usually has better performance for HMF production in
comparison with glucose, glucose/fructose isomerization is more de-
sirable for the hydrolysis process. In this process, glucose is first con-
verted to fructose and the HMF is formed through fructose dehydration
(path B and F in Fig. 3). The reaction mechanism of fructose dehydra-
tion has been investigated, and two main pathways were identified, i.e.
(i) acyclic pathway via the intermediate of enol and (ii) cyclic pathway
via the intermediate of frutofuranosyl (path G and H in Fig. 3, respec-
tively) [185,186]. The isomerization reaction becomes a rate de-
termining step for the HMF formation, when Lewis acid salts are used in
catalytic conversion of glucose [187]. The isomerization process of
glucose to fructose can be accelerated by three types of catalysts, i.e.,
enzyme, base and Lewis acid.
5.2.1. Enzymatic isomerization
Immobilized enzymes were employed for the isomerization reaction
in industrial scale processes [188,189], even though the fructose pro-
duction cost is relatively high [190–192]. Enzymatic isomerization is
attractive owing to its high selectivity and mild reaction conditions
(e.g., 60 °C, pH = 8.2) [179]. Glucose/fructose solutions containing
S. Kang et al. Renewable and Sustainable Energy Reviews 94 (2018) 340–362

Table 2
Production of HMF from glucose and fructose.
Hexoses Concentration Catalyst Temperature Reaction time Yield Measured /estimated HMF Reference
concentration

Fructose 1%wt HCl (pH=1) 150 °C 2h 27% ∽0.3 g/L2 [172]

5 wt% NbOH 180 °C 18% ∽0.2 g/L2
100 g/L 0.1 M H3PO4, 1 wt% CaP2O6, 1 wt% a-Sr 200 °C 5 min 22–39% 22-39 g/L [178]
(PO3)2.
2 wt.% TiO2 (half of the substrate) 200 °C 1 min 17.8% on C basis ∽0.2 g/L2 [180]
3 min 34.8% on C basis ∽0.5 g/L2
5 min 38.1% on C basis ∽0.5 g/L2
ZrO2 (half of the substrate) 1 min 6.10% on C basis ∽0.1 g/L2
3 min 19.6% on C basis ∽0.3 g/L2
5 min 30.6% on C basis ∽0.4 g/L2
none 5 min 13.2% on C basis ∽0.2 g/L2
NaOH (half of the substrate) 2.75% on C basis < 0.1 g/L2
H2SO4 (half of the substrate) 47.0% on C basis ∽0.7 g/L2
100 g/L 0.1 g/mL TiO2 200 °C 5 min ∽22% on C basis ∽15.4 g/L2 [181]
0.1 g/mL ZrO2 ∽14% on C basis ∽9.8 g/L2
10 g/L 0.1 g/ml Nb0.2–WO3 120 °C 1-3 h 27-30% 2.7-3 g/L2 [203]
30 wt% 0.25 M HCl 180 °C 2.5-3 min 25.5 mol%1 60 g/L [219]
50 wt% 14.3 mol%1 64 g/L
0.05 mol/L - 350-400 °C 0.14-0.78 s 0.6-7.7% < 0.7 g/L2 [220]
0.5% HCl (pH=1.5-1.8) 210-270 °C 0.5-300 s - - [221]
10 g/L 10 g/L titanate nanotube 120 °C 0.5 h 16% ∽1.6 g/L2 [222]
6 wt% VOPO4·H2O/TiO2 80 °C 1h 35.0 mol% ∽1.5 g/L2 [223]
VOPO4·H2O 41.9 mol% ∽1.8 g/L2
Cr-VOPO4·2H2O 48.5 mol% ∽2.0 g/L2
Fe-VOPO4·2H2O 37.0 mol% ∽1.6 g/L2
10 wt% niobium phosphate (NP4) (substrate to 85 °C 1h 24.6 mol%1 ∽1.7 g/L2 [224]
catalyst=0.8)
6 wt% niobium phosphate (NP2) (substrate to 33.0 mol%1
∽1.4 g/L 2

catalyst=1.6)
0.05 M HCl (PH=1.5-5) 240 °C 120 s 9.0-44.7 mol% 0.6-2.8 g/L2 [225]
H2SO4 (PH=1.5-5) 14.9 −40.6 mol 0.9-2.6 g/L2
%
H3PO4 (PH=1.5-5) 7.2 −65.3 mol% 0.5-4.1 g/L2
citric acid (PH=1.5-5) 0.5 −49.3 mol% 0.03-3.1 g/2
maleic acid (PH=1.5-5) 1.5-60.0 mol% 0.09-3.8 g/L2
PTSA (PH=1.5-5) 2.0-37.0 mol% 0.1-2.3 g/L2
oxalic acid (PH=1.5-5) 0.70-18.2 mol% 0.04-1.1 g/L2
none 18.08 mol% ∽1.1 g/L2
6 wt% 33 g/L (α-ZrP)HF 100 °C 2h 9.4 mol%1 ∽0.4 g/L2 [226]
33 g/Lγ-ZrP 26.4 mol%1 ∽1.1 g/L2
33 g/L α-L-ZrP2O7 19.3 mol%1 ∽0.8 g/L2
33 g/Lγ-L-ZrP2O7 22.3 mol%1 ∽0.9 g/L2
33 g/L C-ZrP2O7 43.0 mol%1 ∽1.8 g/L2
H3PO4 treated niobic acid (catalyst/ 2h 21.6 mol%1 ∽0.9 g/L2 [227]
glucose=1.4)
niobium phosphate (catalyst/glucose=1.4) 3h 32.4 mol%1 ∽1.4 g/L2
1 wt % various ZrPs (catalyst/glucose=1:1 − 1:4) 240 °C 120 s 18.6-50.2 mol% ∽0.1 g/L2 [228]
10 g/L 10 mmol/L H2SO4 180 °C 600 s 28 mol%1 2 g/L [229]
(continued on next page)

346
S. Kang et al. Renewable and Sustainable Energy Reviews 94 (2018) 340–362

Table 2 (continued)

Hexoses Concentration Catalyst Temperature Reaction time Yield Measured /estimated HMF Reference
concentration

Glucose 1%wt HCl (pH=1) 220 °C 2h 26% ∽0.3 g/L2 [172]

1%wt 5 wt% NbOH 200 °C 16% ∽0.2 g/L2
100 g/L 0.1 M H3PO4, 1 wt% CaP2O6, 1 wt% a-Sr 200-230 °C 5 min 4–21% 4-21 g/L2 [178]
(PO3)2.
2 wt.% TiO2 (half of the substrate) 200 °C 1 min 6.1% on C basis ∽0.1 g/L2
[180]
3 min 14.1% on C basis ∽0.2 g/L2
5 min 18.6% on C basis ∽0.3 g/L2
ZrO2 (half of the substrate) 1 min 2.1% on C basis < 0.1 g/L2
3 min 7.1% on C basis ∽0.1 g/L2
5 min 10.0% on C basis ∽0.1 g/L2
none 3 min 3.4% on C basis < 0.1 g/L2
NaOH (half of the substrate) 4.9% on C basis ∽0.1 g/L2
H2SO4 (half of the substrate) 2.4% on C basis < 0.1 g/L2
100 g/L 100 g/L TiO2 200 °C 5 min 20% on C basis ∽14 g/L2 [181]
100 g/L ZrO2 6% on C basis ∽4.2 g/L2
10-100 g/L 0.1 g/ml Nb0.2–WO3 120 °C 3h 12-34% 3.4-12 g/L2 [203]
10 g/L 0.1 g/ml Nb0.2–WO3 1-6 h 16-36% 1.6-3.6 g/L2
0.055 M 100 g/L Nb2O5·nH2O 120 °C 3h 12.1 mol%1 ∽0.8 g/L2 [211]
100 g/L Na+/Nb2O5·nH2O 12.4 mol%1 ∽0.9 g/L2
100 g/L H3PO4/Nb2O5·nH2O 47.9 mol%1 ∽3.3 g/L2
0.05 mol/L none 350-400 °C 0.2-1.7 s 0.1-6.1% < 0.6 g/L2 [220]
10 g/L 10 g/L titanate nanotube 120 °C 3h 14 wt% ∽1.4 g/L2 [224]
1 wt % amorphous ZrP (catalyst/glucose=1:1 − 1:4) 240 °C 60-240 s 3.2-23.5 mol% < 0.1 g/L2 [228]
10% 1% AlCl3 130 °C 360 min 11.2 wt% ∽1.1 g/L2 [230]
10% 1% CrCl3·6H2O 130 °C 360 min 13.0 wt% ∽1.3 g/L2

1
The yield is calculated based on the conversion ratio and selectivity.
2
The HMF concentration is estimated based on the initial hexoses concentration and the HMF yield, with a hypothesis that the volume of the solvent is not changed.

53–60% of fructose can be obtained with the presence of immobilized
enzymatic isomerases [193–195]. Alipour and Omidvarborna reported
an enzymatic and catalytic integrated approach for high yield LA pro-
duction from saccharified biomass hydrolysate [196]. In this approach,
the glucose in the hydrolysate was first isomerize to fructose by the GXI
enzymes, and then the fructose was transferred to an acidic ionic liquid
and aqueous mixture reaction medium for LA production. The con-
version process of fructose to produce HMF and LA usually conducts in
strong acidic solutions under elevated temperature conditions (see
Tables 1 and 2). The difference in operation conditions require the
enzymes to be separated from the glucose/fructose solution before
starting the dehydration process, as the enzymes can be deactivated at
the high temperature under acid conditions. The enzymatic iso-
merization process also has some disadvantages, such as low turnover
rates, high cost for large loading of enzymes and difficulty in catalyst
separation from aqueous solution [162]. High production cost, there-
fore, is expected for the enzymatic isomerization followed by acid-
catalyzed reaction. A challenge on future work is to develop a con-
secutive and effective process integrating the enzymatic isomerization
with acid-catalyzed thermal conversion.
and acids would be needed to neutralize the alkaline catalysts dissolved
in the glucose/fructose solution. Heterogeneous catalysts with solid
bases are a potential choice [195,201,202]. Lima et al. [203] reported
that the fructose yield and selectivity in glucose isomerization was
20–39% and 62–84%, respectively, with the presence of metallosilicate
solid bases. Similar results were obtained by Moreau et al. that the
glucose conversion ratio and fructose selectivity were 7–42%, and
60–86%, respectively, with the existence of cation-exchanged zeolites
and hydrotalcites [195]. Moreau et al. concluded that the high se-
lectivity to fructose can only be achieved, when the glucose conversion
rate is lower than 25% [195].
Amphoteric heterogeneous catalysts containing both the base sites
and acid sites were also employed for isomerization [183]. The glucose
can be isomerized with the presence of base sites and the fructose
formed can be further dehydrated with the existence of acid sites. The
synthesis of the heterogeneous amphoteric catalyst has to prohibit the
mutual interaction between the acid and base sites. Amphoteric cata-
lyst, therefore, has a limitation that both base sites and acid sites are
weak, or hard to dissociate. The weak acid sites have negative effects on
the fructose dehydration, for which stronger Brønsted acidity is pre-
ferred [203].

5.2.2. Alkali catalyzed isomerization

The alkali catalyzed isomerization of glucose to produce fructose
was first developed in the 1890s [197], also known as Lobry de Bruy-
n–Alberda–van Ekenstein transformation (path C in Fig. 3). In this
process, the aldose–ketose isomerization occurs by proton transfer with
the presence of a base. The aldose is deprotonated and forms a series of
enolate intermediates, followed by re-protonation of the enolate inter-
mediates [198,199]. Mannose is also formed in the fructose iso-
merization process. Thus, the product is a mixture of glucose, fructose,
and mannose after the isomerization of glucose, and saccharinic acids
and oligomeric acids are also produced in this process [193].
Furthermore, it has been reported that weak base sites were more
important than strong base sites [200], and only a small amount of
weak/neutral base sites were needed for the isomerization process
[195]. Homogeneous alkaline catalysts, such as NaOH, are not pre-
ferred, as the conversion process of hexoses usually uses acid catalysts
5.2.3. Lewis acid catalyzed isomerization
Lewis acid is one of the most widely used catalysts for isomerization
reaction, in which intramolecular hydride shift transforms from the
open form of glucose to the open form of fructose (path D in Fig. 3)
[20,175,204,205]. Unlike the base and enzyme catalysts, the advantage
of the Lewis acids is that their catalytic activity stays constant even with
the presence of strong Brønsted acids.
The widely used Lewis acidic metal chlorides (e.g., AlCl3, CrCl3,
etc.) are classified as either “water-compatible” or “water-sensitive,”
depending on their hydrolysis constant [174]. According to Eq. (2), the
water-sensitive Lewis acidic metal chlorides (e.g., AlCl3) can produce
both Lewis and Bronsted acidity in aqueous solution [187],
xM3 + +yH2 O = Mx (OH) y (3x − y) ++yH+ (2)
where “M 3+
” is the trivalent Lewis acid metal ions, such as Al 3+
and

347
S. Kang et al.
Cr3+. The water-sensitive metal chlorides improve both the glucose/
fructose isomerization and the hexoses dehydration. The loss of the
water-sensitive metal chlorides, however, is unavoidable. Thus, metal
chlorides are preferred in ionic liquids or organic solvents [206–210].
High ratio of Lewis acid catalysts (mass ratio of catalyst to glucose
reached 10) are also needed to perform effective glucose isomerization
[210,211], which is usually not desirable for large scale environment-
friendly processes. Thus, the water-compatible metal chlorides are
preferred for accelerating the isomerization process considering the
recyclability and environmental impacts. These metal chlorides, how-
ever, could result in lower HMF selectivity in the fructose dehydration
process [187].
Beside the metal chlorides, solid Lewis acids, such as zeolities (e.g.,
Fe-ZSM-5, Cu-ZSM-5, Al-ZSM-5, zeolite Y, and mordenite), were also
employed for the catalytic dehydration of glucose to produce HMF
[91,195,212,213]. The hydrothermal instability, however, is a dis-
advantage in zeolities application, as dealumination and collapse of
framework occur at high temperature under water vapor environment
and result in quick deactivation of the zeolites [91,214,215]. Gardner
et al. also reported that salts naturally existed in biomass can sig-
nificantly affect the hydrothermal stability of zeolite catalysts, even
when highly diluted [91].
Interestingly, the presence of Brønsted acid can facilitate the Lewis
acid catalyzed isomerization and improve the reaction selectivity [216].
Thus, the design and application of bifunctional catalysts with appro-
priate amount of stable Lewis acid and Brønsted acid sites were also
explored. Yue et al. suggested a strategy that combines Lewis acidic
transition metal oxides with weak Brønsted acid sites for the catalytic
isomerization of glucose to fructose and dehydration of fructose to a
partially dehydrated intermediate with subsequent rapid dehydration
of intermediate to HMF utilizing mineral acid HCl [203]. They found
that glucose can be isomerized in water on the Lewis acid surface sites
with WO3. Nb substitution on the WO3 surface facilitates the sugar
deprotonation and results in an overall lower activation barrier for
isomerization [203]. Su et al. developed a bifunctional catalyst MIL-
101(Cr)-SO3H to improve glucose conversion for HMF production, and
found that the best catalytic activity occurs when the molar ratio of
Brönsted acid site to Lewis acid site on the bifunctional catalyst is 1.1
[217].
5.3. Problems of HMF yield and isolation
Table 2 summarizes the reactions for HMF production from glucose
and fructose in aqueous phase. The reactions in ionic liquids, organic
solvents and biphasic systems are not included here. Apart from the
fructose and glucose, acid-catalyzed conversions of raw biomass or
polysaccharides for HMF production were also investigated
[20,33,117,218]. HMF yields, however, were generally low regardless
of the type of acid catalysts used in the water solution [21]. The HMF
yields from glucose in most of the study are < 30 mol% or 30% on
carbon basis, and only one study reaches 47.9 mol% [211]. The HMF
yield from fructose is slightly higher than that from glucose, but the
yields are still < 50 mol% in most of the work listed in Table 2. It is
worth noting that the HMF yield is also affected by the glucose/fructose
dosage, e.g. high initial glucose concentration can induce low HMF
yield [203]. To improve the efficiency of biomass conversion and in-
crease the yield of HMF, new methods need to be developed to over-
come the technical difficulties, such as the further rehydration reaction
of HMF to LA and the formation of large molecular weight humins. The
formation of humins in the aqueous phase is inevitable [74,231]. The
recent studies on humins formation, methods to prevent humins for-
mation and application of humins were discussed in Section 7.
The HMF concentrations through the conversion of glucose and
fructose are both very low based on measurement or estimation listed in
Table 2, and this could result in high cost of HMF separation and
purification in the downstream processing. The poor stability and high
348
Renewable and Sustainable Energy Reviews 94 (2018) 340–362
solubility of HMF in acid aqueous solutions could also lead to low HMF
selectivity and difficulties in HMF isolation. This has become a limita-
tion for the application of simple aqueous phase system [61]. It has
been reported that the separation cost could account for 50% or more of
the whole process [232,233], which become the main impediment for
large scale HMF production. In fact, the industry scale production of
HMF directly from raw biomass has not been realized yet. The recent
HMF application mainly focuses on the production of downstream bulk
chemicals, such as adipic acid [234,235], 2,5-furandicarboxylic acid
[236–238], 2,5-Dimethylfuran. [239]. Interestingly, Gao et al. [237]
and Wang et al. [238] found that the pure HMF can be directly oxidized
to 2,5-furandicarboxylic acid with the presence of catalysts in the
aqueous solution. Direct conversion of the raw HMF from biomass hy-
drolysis to the furandicarboxylic acid is, therefore, a potential way to
solve the HMF isolation and purification problem. Systematic works on
related research area are still needed in the future.
5.4. Technics for increase the HMF yield
Two types of technics have been developed to improve the HMF
yield by preventing the side reactions: (i) adjusting the process para-
meters, such as pH (or acidity), temperature, pressure, reaction time
and (ii) conducting in situ extraction.
5.4.1. Reaction temperature and pressure
As shown in Table 2, the reaction condition for the HMF production
varies. The reaction temperature is usually 80–240 °C with the reaction
time from seconds to hours and the hexose dosage spans in a range of
1–50 wt%. In comparison with reaction conditions for LA formation,
relative higher temperature and shorter reaction time are preferred for
HMF production [240]. Supercritical water is regarded as a good re-
action medium in order to decrease the reaction time and inhibit the
HMF side-reactions [225,241], although unsatisfying yields of HMF
from dehydration of D-fructose was also observed [229]. The influences
of water density, and reaction temperature and pressure on HMF pro-
duction were investigated. Aida et al. reported that high reaction
temperatures and water densities, and short residence times can im-
prove the 5-HMF selectivity by kinetically preventing the formation of
1,2,4-benzenetriol byproduct [242]. They also found that the dehy-
dration reaction and the hydrolysis of 5-HMF were both accelerated due
to the increase of water density at 400 °C, when the pressure was in-
creased from 40 to 70 MPa and at 80 MPa [220,242]. The reaction
pressure, however, would not affect the glucose decomposition reac-
tions under relative low pressure conditions (4–15 MPa) [211]. It
should be noted that the retro-aldol, dehydration and hydration reac-
tions can be accelerated under high temperature and pressure condi-
tions and result in the formation of water soluble byproducts, such as
furfural, formaldehyde, erythrose, glycolaldehyde, glyceraldehyde,
pyruvaldehyde, lactic acid, dihydroxyacetone, 1,2,4-benzenetriol, LA,
formic acid and soluble polymers, which could reduce the HMF yields
[210,211,242]. Another obstacle to industrialize the supercritical water
technology is the relative high cost of equipment and operation [172].
5.4.2. Effects of catalyst
Acid is usually required for the catalytic dehydration of glucose/
fructose, and lower acidity or acid concentration can increase HMF
yield [87,243]. Takeuchi, et al. studied the impacts of three mineral
acids (i.e. HCl, H2SO4, and H3PO4) on catalytic dehydration of glucose,
and identified that low acidity improves the HMF formation, while
increased acidity boosts the LA formation [243]. The pH range for HMF
formation was also investigated. Kuster and Temmink found that no
HMF was formed when pH is > 3.9 and no LA was formed when pH
is > 2.7 at 175 °C [244]. de Souza et al. found that relative high 5-HMF
yields can be obtained when the pH is in a range of 1.5–1.9. New cat-
alysts have also been developed to inhibit the rehydration of HMF (e.g.
the lanthanide (III) (La3+–Lu3+)). It has been reported that the
S. Kang et al.
lanthanide(III) (La3+–Lu3+) can effectively accelerate the dehydration
of hexose to produce HMF and prevent the subsequent hydrolysis re-
action to form LA [245]. In addition, Gupta et al. found that potash-
alum is an effectively catalyst for HMF production from mono-sugars
[246]. The potash-alum was also regarded as a promising catalyst for
dehydration of C6 sugars owing to its low-cost and relatively non-cor-
rosive characteristics [247].
5.4.3. In situ extraction of 5-HMF
The in situ extraction of 5-HMF from the aqueous phase is a desir-
able pathway to prevent the rehydration and oligomerization of HMF.
Dumesic's group has made big contributions by developing a series of
water-organic solvent biphasic systems for the HMF production through
carbohydrate dehydration in order to inhibit the humins formation and
increase HMF yield [177,219,248–250]. High yield of HMF (62%) was
achieved from catalytic conversion of glucose in the water/2-sec-bu-
tylphenol biphasic systems [177], and high selectivity of HMF (80%)
was also obtained when converting fructose in the water/methyliso-
butylketone biphasic system [219]. In addition, 2-sec-butylphenol,
methylisobutylketone and other water immiscible solvents (e.g., tetra-
hydrofuran, alkylphenols, valerolactone) were also employed in the
biphasic systems for HMF extraction [251–254]. Owing to the high
aqueous solubility of HMF, large volumes of organic solvent are often
needed for the in situ extraction, which would result in cost, separation
and environmental issues. In fact, the extraction of HMF from the
aqueous phase is the major factor that affects the final yield of HMF and
is regarded as a barrier for industrializing the HMF production [255].
6. LA formation
LA is regarded as the final product during the biomass hydrolysis
process in dilute acid solution. Although LA can be converted to uni-
dentified chemicals, the reaction rate is over 500 times lower than that
of HMF conversion [256]. LA is generally protonated and can form a
very stable protonated dihydro-5-hydroxy-5-methyl-2(3H)-furanone
according to results obtained from quantum chemistry calculations
using GAMESS [256]. LA can also be converted to other byproducts in
more severe reaction conditions, such as higher catalyst concentration
and temperature, and longer reaction time [103,110,116,257–259]. For
example, during the conversion of Pennisetum alopecuroides, the de-
composition rate of LA is faster than its formation rate when a sulfuric
acid concentration is > 10 wt%.[119] High acid concentration can also
convert LA to gas products, such as H2, CH4, CO [260].
In the rehydration process, water is added to the furan ring C2-C3
bond of HMF with the presence of acid catalyst, and LA and formic acid
are formed as final products (path I in Fig. 3) [261]. It has been re-
ported, however, that acids with a pKa > 2 (such as LA and formic
acid) are poor catalysts for the rehydration reaction, indicating that
HMF rehydration is not an auto-catalytic reaction [262]. Yang et al.
found that the essential step for LA production from glucose is the
dehydration process of protonated glucose [263]. Assary et al. also
reported that the dehydration steps are highly endothermic and the
whole process from glucose to LA is dominated by the dehydration steps
[264]. Garcés et al. identified a general trend that higher selectivity to
LA are achieved when fructose is used as reactant. [265] In contrast,
glucose dehydration leads to the formation of byproducts, such as an-
hydroglucose and glucose oligomers [265]. Thus, a process combining
isomerization of glucose to fructose and dehydration is preferred for LA
production. Girisuta et al. reported that the LA yields from D-fructose
are substantially higher, approximately 10 mol%, than that from D-
glucose when sulfuric acid was employed as catalyst [109]. The iso-
merization of glucose to fructose with the existence of Bronsed acid,
however, appears to have negligible contribution to the glucose con-
sumption [266].
Theoretically, the molar yield of formic acid should be equivalent to
that of LA. The yield of formic acid, however, is often lower than that of
349
Renewable and Sustainable Energy Reviews 94 (2018) 340–362
LA owing to the side reactions of formic acid [55,58,257]. Carbon di-
oxide, carbon monoxide, hydrogen and water were even formed
through the thermal degradation of formic acid at high temperature
(> 180 °C) [55]. Interestingly, Yang et al. reported that excess formic
acid can be obtained from glucose at high temperatures through ret-
roaldol reaction on the C6 of glucose [266].
6.1. Influence of reaction conditions
According to the data listed in Table 1 and Table 2, the LA pro-
duction requires higher temperature and acid concentration, and longer
reaction time in comparison with the HMF production, and the reaction
condition varies with biomass. For instance, the reaction temperature
and catalyst concentration have more impacts on LA production than
reaction time when Helianthus tuberosus L. is employed as feedstock
[104], whereas the influence of substrate concentration, temperature
and time is more crucial than that of catalyst concentration in the
conversion process of glucosamine [114].
6.1.1. Catalysts
HMF conversion rates and LA yield are correlated to the H+ con-
centration in mineral acid catalyzed reaction, while the influences of
anion is negligible [262]. A high concentration of acid catalyst is usu-
sally preferred for the conversion of D-fructose [87], corn stalk [118]
and Gelidium amansii [267], and increased HCl concentration can also
improve the LA selectivity in fructose dehydration process [265]. Acid
concentration, however, does not have significant impacts on the LA
selectivity in glucose dehydration, and glucose dimers and anhy-
droglucose is usually formed when glucose serves as reactant. [265]
6.1.1.1. Homogeneous catalyst. Strong Brønsted homogeneous acid
catalysts are often used in biomass hydrolysis to produce LA, and
H2SO4 and HCl are two of the most widely used and most effective
catalysts [86]. It is hard to state which catalyst is more efficient, as their
efficiency depends on reaction condition and biomass type
[95,101,243]. For example, HCl is more desirable in the catalytic
conversion of biomass with high concentration of calcium salts, such as
paper-mill cellulose and tobacco chops [74]. Calcium sulfate (CaSO4) is
formed when H2SO4 is employed to convert paper-mill cellulose and
tobacco chops, and the precipitation of calcium sulfate can result in
reactor clogging. In addition, the activation energy of H2SO4 in the
dehydration process of D-fructose is slightly lower than that of HCl
[268], indicating that the dehydration of D-fructose catalyzed by H2SO4
is relative easier than that catalyzed by HCl.
Since Lewis acid accelerates the isomerisation of glucose to fructose
and Brønsted acid improves the reaction of fructose to LA, combination
of Lewis acid and Brønsted acid for the conversion of glucose to LA is
preferred. Choudhary et al. reported that a high yield of LA (~46%)
was obtained in a reaction catalyzed by both CrCl3 and HCl, and
identified the complex interaction between the two catalysts, i.e.
Brønsted acid inhibits the aldose-to-ketose isomerization, while Lewis
acid increases the conversion rate of fructose and HMF by accelerating
the side reactions [91]. Yang et al. developed a mixed-acid system with
Lewis acids and Brønsted acids to produce LA from glucose, and the
CrCl3 −H3PO4 system developed was proven to have a strong synergic
catalytic activity for converting glucose to LA [97]. The mixed-acid
system exhibited the highest synergic catalytic activity when the con-
centration of CrCl3 in the CrCl3 −H3PO4 system was 0.4–0.5 [97]. In
addition, it was also reported that the activation energy of LA formation
from glucose dehydration catalyzed by the CrCl3 −H3PO4 mixed-acid
system was lower than those reactions catalyzed by homogeneous
Brønsted acid or Lewis acid [269], indicating that the mixed-acid cat-
alyst system may be able to lower the reaction temperature. The
chromium salt, however, is not a desirable catalyst considering its
toxicity and cost. Besides Brønsted acids and Lewis acids, homogeneous
transition metal salts were also employed. Cao et al. found that Cu2+
S. Kang et al.
and Fe3+ can accelerate the hydrolysis reaction of cellulose to glucose
at 200 °C, and high efficiency of converting cellulose to LA can be
reached [270].
6.1.1.2. Heterogeneous catalyst. The development of environmental-
friendly heterogeneous acid catalysts for LA production has attracted
much attention recently. Many types of heterogeneous catalysts,
including solid catalyst consisted of both the Bronsted acid and Lewis
acids sites, have been developed. For example, Fe/HY zeolite and Fe-
NbP (Fe-doped niobiumphosphate) was employed as catalyst for
converting glucose to LA [112,271]. It is worth noting that catalyst
with excess Lewis acidity can also convert glucose into humins, and
consequently decrease LA yields [260].
The efficiency of solid acid catalysts is also affected by many factors.
The primary factor is the limited contact between the solid acid with
the solid feedstocks (e.g., cellulose and raw biomass). As hydrogen ions
mainly locate on surface of solid catalyst, only a small portion of them
can be dispersed into the solution [272]. The key to solve this issue is to
improve the mass transfer between the solid catalyst active sites and
feedstocks. It has been reported that NaCl can be added into the reac-
tion solution to improve the LA yield, as NaCl interrupts the hydrogen
bonding of cellulose and increases the cellulous solubility under hy-
drothermal conditions [273].
Another major factor is the deactivation of solid catalysts caused by
inhibition and/or leaching of active sites on the surface of the catalyst
[136,274–276]. Depending on the characteristics of the deactivated
catalysts, several regenerating methods have been developed. For ex-
ample, dilute acid soaking treatment can be employed to recover the
hydrogen ion through ion exchange with metal cations, or to release the
hydrogen ion through ester formation (e.g., sulfonic esters)
[136,276,277]. When the catalyst is covered by solid byproducts, cal-
cination at high temperatures (e.g., 500 °C) can also be utilized to re-
move the organic deposits [105,278]. Many acid catalysts (e.g., acidic
resin catalysts), however, can only be treated at a relative low tem-
perature (e.g., < 200 °C). To remove the deposits on these solid acid
catalysts, organic solvent washing is preferred. Organic solvents, e.g.
ethanol, methylene chloride, methanol and acetone, have been em-
ployed for this process [56,279–281]. In addition, H2O2 solution was
also used to regenerate the deactivated solid acid catalysts for LA
production, as H2O2 solution can effectively remove humins from solid
acids. [123,282,283]. As most of the above treatments cannot recover
the catalyst caused by leaching of the active sites, it is also essential to
improve the catalyst stability by developing solid acid catalysts with
locked-in active sites. As the LA yield is influence by both surface area
and accessibility of acid sites on solid acids [284,285], designing het-
erogeneous catalysts containing higher surface area and more acces-
sible acidic moieties are crucial for future catalyst preparation.
6.1.2. Temperature and reaction time
Due to the inter- and intra-molecular hydrogen bonding, cellulose is
insoluble in water when the temperature is below 320 °C [286]. The
increase of temperature can improve the cellulose hydrolysis process,
but also result in side reactions. Chen et al. reported that the formation
of insoluble humins is significantly accelerated with the increase of
temperature when converting vegetable waste, and lead to decreased
yield of the total soluble products [287]. The impact of reaction tem-
perature also varies with biomass. Yuan et al. reported that the pre-
ferred reaction temperature is 190 °C for the acid-catalyzed conversion
of Pennisetum alopecuroides [119]. Zhi et al. found that high tem-
perature can reduce the reaction time in FeCl3 catalyzed conversion of
corn stalk, but the maximum LA yield (reached with 0.5 mol/L FeCl3
solution) does not change with temperature, indicating that tempera-
ture increase accelerates the reaction rate without affecting the che-
mical equilibrium [116]. In addition, Zheng et al. identified that LA
yields highly relies on the reaction temperature and acid concentration,
and high reaction temperature and acid concentration are preferred to
350
Renewable and Sustainable Energy Reviews 94 (2018) 340–362
increase the LA yield according to their study on catalytic conversion of
corn stalks [118]. Similarly, Jeong and Park reported that elevated
temperature is crucial for LA production from Gelidium amansii [267].
Fachri et al., however, found that low temperature, high acid con-
centration and low initial D-fructose concentration are preferred for the
conversion of D-fructose [268]. Hydrolysis time also plays an essential
role for LA production in the acid-catalyzed conversion process of
Pennisetum alopecuroides, and the yield of LA increases linearly with
reaction time at the first stage of the reaction [119]. Similar phenomena
were also observed in the acid-catalyzed hydrolysis of Gelidium amansii
[267].
The integrated impacts of reaction time, temperature and catalyst
concentration can be reflected by the severity factor. Relative high se-
verity factors can improve the LA production until the yield reaches a
maximum [56,114,115]. Kang et al. identified that the LA yield can
reach 50 mol% in the hydrolysis process of cellulose when the severity
factor is above 3.9 [56]. Further increase of the severity factor (e.g.
from 3.9 to 4.5), however, cannot increase the LA yield due to the
formation of humins and other byproducts [56]. Gwitaek reported that
the highest LA yield was achieved when the integrated severity factor
was 3.28, and the LA yield stayed almost constant at higher factors in
the conversion process of Helianthus tuberosus L. [117]. The highest 5-
HMF yield was achieved when the factor was in a range of 2.1–2.4, and
the HMF yield decreased linearly with the increase of severity factor
when the value was > 2.4 [117]. Similarly, the total reducing sugar
yield in the conversion of Helianthus tuberosus L. decreases linearly
with the increase of severity factor when the value is above 2.1 [117]. It
is worth noting that LA production generally requires a higher severity
factor in comparison with that of HMF production.
6.1.3. Other parameters
The reactor type also affects the LA production. It has been reported
that the LA yield obtained in a continuous reactor was greater than that
in a batch reactor [43]. Fachri et al. even demonstrated that continuous
ideal-stirred tank reactor is the most desirable sysetem for LA produc-
tion from fructose [87].
Concentration (or solid-liquid ratio) is also an essential factor that
affects the LA yield. High solid-liquid ratio usually causes swelling and
agglomeration problem [119]. In general, a high ratio of biomass
loading inhibits the formation of LA [57,104]. For example, when the
solid-liquid ratio is > 1:6, the LA yield decreases in the acid-catalyzed
conversion of Pennisetum alopecuroides [119].
Polarity of the solvent usually affects the distribution of sugars and
products in the sugar conversion process. Hu et al. reported that LA
yields varied significantly in different solvents, e.g. water > THF with
wet Amberlyst 70 > THF with dried Amberlyst 70 in toluene [272].
They also found that the molecular size of sugars does not affect the
formation of insoluble polymer and LA [272].
6.2. LA separation and recovery
Although many investigations have been done in order to increase
the LA yield, LA separation from the acidic aqueous solution is still
challenging. Downstream processing is even regarded as an obstacle for
the large-scale production of LA through hydrolysis, as approximately
50–70% of the total cost for LA production was generated by down-
stream processing [288]. The yields shown in Table 1 are usually
measured directly by HPLC or GC after reaction, regardless of the loss in
the isolation process. Therefore, the actual yields obtained in the pro-
cess are even lower [289].
Efficient isolation methods are needed to increase the recovery rate
and purity of the product. The cost of the downstream processing for LA
isolation highly relates to the reaction condition. High LA yield are
usually obtained in a solution with low concentration of feedstocks, but
low LA concentration results in high isolation cost. Thus, it is essential
to consider both LA yield and concentration when developing an
S. Kang et al.
integrated process. Kang and Yu developed an intensified reaction
process that can achieve high LA concentrations from lignocellulosic
biomass with a decreased isolation cost [58]. In this process, eucalyptus
was first pretreated in a mild condition to hydrolyze hemicellulose and
recover xylose and furfural. The pretreated wood with a high content of
cellulose was then treated under relatively severe conditions to produce
LA and formic acid. The reaction solution was then reused for proces-
sing the pretreated wood, and high concentrations of LA (105 g/L) and
formic acid (39 g/L) was obtained [58].
Methods have also been developed for the LA separation and pur-
ification based on the characteristics of LA and acid catalysts. The key
for these methods is to achieve a high recovery rate of LA with high
purity and to recycle the acid catalysts simultaneously. Solid acid cat-
alysts are preferred in the separation process. As LA is a stable organic
acid with a boiling point of 245 °C, LA can be easily recovered through
distillation of the solution to achieve a simple solid (heterogeneous
catalyst)-liquid (LA solution) separation. The separation process is,
however, more complex when homogeneous inorganic acids are used.
For instance, flash separation is required to separate volatile HCl from
LA [44], and organic solvent extraction is used to separate H2SO4 (an
acid with high boiling point, 337 °C) from LA and the remaining H2SO4
was left in water solution [290]. The candidate extraction solvent in-
cludes methyl isobutyl ketone [291], 2-methyltetrahydrofuran [292],
furfural [293] and 1-octanol [294]. To improve the extraction effi-
ciency, reactive extraction, an improved solvent extraction process, was
also developed to recover LA, in which both extractants and organic
solvent diluents are required. Various new reactive extractants were
also developed, e.g. aliquat 336, alamine 308, trioctylamine, tripropy-
lamine, and amberlite LA-2 [295–299]. Generally, large volumes of
extraction solvents are required owing to the high solubility of LA in the
water solution, and this would result in high manufacturing cost and
increased energy input. Other challenges associated with the solvent
extraction process include the extraction of byproducts along with LA
and the toxicity and vapor pressure characteristics of the solvents used.
Other methods developed for LA separation include membrane se-
paration [300], chromatographic separation [293,301] and adsorption
[288,302,303]. Adsorption is the simplest and most widely applied
method. Various adsorbents have been employed for LA separation,
such as active carbon and special adsorption resins (including ion-ex-
change resins) [302,304,305]. Lin et al. investigated the recovery rate
of LA from actual biomass hydrolysate by a microporous hyper-cross-
linked polymer, SY-01 [306]. The SY-01 resin exhibited good properties
for LA recovery, including quick adsorption, ease of desorption and
regeneration, as well as relatively stable capacity. Datta and Uslu found
that the maximum adsorption capacity of LA on commercial adsorbent
amberlite XAD-4 at 318 K was 35.98 mg g−1 [307]. The low absorbent
capacity, however, usually limits its application in industry scale pro-
duction of LA [43]. The use of activated carbon as the adsorbent also
has low LA selectivity. For ion exchange resin, the pretreatment and
regeneration process restrict its application, as this process produces
wastewaters with acid and alkali [288].
6.3. LA production industry
The LA consumption is estimated to be increasing in the next few
years and the amount may reach 3820 t in 2020 [308]. Nowadays, LA is
mainly produced from maleic anhydride and furfural, and the price of it
is a relative high, 5–8 $/kg in 2013 [73,308]. The use of biomass is
considered as a potential way to decrease the LA price. It has been
reported that a low price, 0.09–0.22 $/kg, can be realized through
Biofine process [309], one of the most recommended technologies for
LA production from biomass [22]. This process generally involves two
major steps: (i) depolymerization of biomass to HMF and mono-
saccharides at a temperature of 210–220 °C with ~ 12 s reaction time,
and (ii) production of LA at a temperature of 190–200 °C with a reac-
tion time of 15–30 mins.
351
Renewable and Sustainable Energy Reviews 94 (2018) 340–362
Several commercial-scale plants have been developed for the LA
production. Biobased chemical company GFBiochemicals (Caserta,
Italy) is the first company that produces LA directly from biomass using
the Biofine two-step hydrolysis process at commercial scale [22,310].
Segetis, Inc. (Minnesota, USA) developed a system for LA production
from corn syrup and cellulosic sugars [311,312], and announced that
they have successfully started a pilot scale plant with a capacity of 80
metric tons/year [311,313]. Incitor (New Mexico, USA), a bio-based
chemical and fuel company, produces energy-dense fuels, fuel additives
and commodity, and specialty chemicals from various biomass [314].
Incitor is working on a plant with a capacity of processing
160,000–240,000 metric tons of biomass per year to produce com-
modity chemicals, such as ethyl levulinate, ethyl formate, LA, lactones
and the Alestron fuel [314].
7. Humins
7.1. Impacts of humins
The formation of humis is inevitable in LA and/or HMF production
[74,231], due to thermodynamics characteristics of the acid-catalyzed
reaction [263]. The formation of humins is more severely affected by
the initial concentration of feedstock than that of the targeted products.
This can be reflected by the reaction orders, as a higher reaction order
ususally indicates greater impacts of feedstock concentration on the
reaction rate. For instance, in cellulose conversion process, the reaction
order of glucose and HMF in the main reaction is 1.09 and 0.88, re-
spectively, which are both lower than their value in the undesired side
reactions, 1.30 and 1.23, respectively [104]. Similarly, in a glucose
reaction, the reaction order for humins production (1.30) was higher
than that for HMF production (1.09) [57]. Tarabanko et al. found that
the humins formation is a second order reaction and is related to the
initial concentration of carbohydrate [315]. Although the reaction
order of humins formation varies with reaction systems, it is generally
accepted that a high initial concentration of feedstock results in a high
yield of humins [56,244,315–319].
In general, humins are regarded as undesired products owing to the
following reasons.
(1) Cellulosic carbon is wasted in the form of humins and causes low
efficiency of valuable platform chemical production in bior-
efineries. Table 3 summarized the yields and characteristics of hu-
mins under different types of reaction. The humins yield is usually
20–50% with a carbon content of 55–65%, indicating that ~
30–80% of the glucose carbon (40%) is not used for targeted che-
micals production. The relative high yield of humins, however, can
not be avoided in pilot or industrialized scale plants. Approximately
25–30 wt% of carbohydrate materials ends up as humins byproduct
in the Biofine process [325]. About 20 mol% of fructose forms hu-
mins through oxalic acid-catalyzed reactions in the pilot scale
production of HMF [326]. It should be noted that the humins yield
are highly affected by the types of feedstocks, and it was reported
that the humins yields is fructose > xylose > glucose [88].
(2) Humins can deposit on the inner wall of the continuous tube re-
actor, and result in reactor clogging, increase of pressure and de-
crease of the heat transfer efficiency. To avoid the safety problem
caused by increase of pressure, better materials are needed for the
reactor manufacturing.
(3) The formation of humins decreases the efficiency of solid acid
catalyst, as solid acid catalysts can be deactivated by humins
through blocking acidic active sites [284].
(4) LA, HMF and carbohydrates can be absorbed by humins [315,327].
Hoang et al. reported that these active products (e.g., LA, formic
acid and sugar intermediates) graft to humin matrix through con-
densation [327]. Homogeneous catalyst, such as H2SO4, can also be
absorbed by the humins. It was reported that only ~ 90.5% of the
S. Kang et al. Renewable and Sustainable Energy Reviews 94 (2018) 340–362

Table 3
The yield (selectivity) and elemental analysis of humins.
Feedstock Catalyst Temperature Time Yield (%) Selectivity (C%) Elemental analysis Reference

C wt% H wt% O wt%

0.1 M HMF 1 M H2SO4 98 °C < 4h 61.2 4.5 [86]

7.7 wt% cellulose 0.05 M H2SO4 150–200 °C 0–1000 min – 55.2 4.9 [104]
0–1 M fructose 0.1 M H3PO4 240 °C 120 s 65.5 4.4 [318]
~5% of D-glucose 0.5% H2SO4 175–180 °C 2h 21 wt% 66.4a 4.7a 28.9a [319]
1% glucose – 100–200 °C 0–240 min – 48.65 5.78 45.57 [320]
200 g/L glucose 0.05 M H2SO4 170 °C 6h 58.2 4.5 37.3 [321]
33.3 mM glucose butyric acid and H3PO4 (pH 4.0) 190 °C 20 min 10 C% [322]
33.3 mM glucose butyric acid and H3PO4 (pH 2.0) 190 °C 70 min 7 C%
100 g/L cellulose 0.2 M H2SO4 170 °C 240 min 25 wt% [57]
200 g/L glucose 0.2 M H2SO4 170 °C 5h 21.0 wt% [58]
100 g/L HMF 0.2 M H2SO4 170 °C 5h 11.1 wt%
0.1 M glucose 0.1 M H2SO4 125 °C 5h 29 wt% [75]
0.1 M fructose 0.1 M H2SO4 125 °C 2h 24 wt%
0.1 M HMF 0.1 M H2SO4 125 °C 2h 18 wt%
10 wt% glucose Amberlyst 70 (0.1 M total acid sites) 150–180 °C 10–240 min 35–55 C% [77]
29 wt%. cellulose none 220 °C 30 min 35.3 C%
10 wt% glucose Amberlyst 70 (0.1 M total acid sites) 150–180 °C 10–240 min 35–55 C%
1.5 M glucose 0.055 M H2SO4 180 °C 6h 36 wt% [88]
2 M glucose 0.01 M H2SO4 220 °C 6h 35 wt%
10% glucose none 180 °C 5–150 min 54–65 C% [240]
0.25–0.5 M HMF 0.5–2 M HCl 95 °C 0.25–24 h 0–23 wt% [317]
0.25–1 M fructose 0.5–2 M HCl 95 °C 0.25–24 h 0–52 wt%
0.05 M HMF – 350 °C 400 s about 23 wt% [323]
50 g/L glucose 0.05 g/L ZrPO4 135 °C 6.5 h 29 wt% [324]

a
acetone-insoluble fraction of humins.

H2SO4 catalyst was left in the aqueous solution after removing
humins by filtration [58]. Washing with water is, therefore, re-
quired to achieve the complete recovery of targeted chemicals, such
as LA and H2SO4 catalyst. Otherwise, part of the final products and
catalysts would be lost due to the adsorption effects of humins.
7.2. Structure of humins
Methods, such as FT-IR/ATR-IR, C13 NMR, H1 NMR, SEM, element
analyzer, pyrolysis GC-MS and Raman spectrum, have been utilized to
analyze the morphology and structure of solid humins
[140,319,323,328–330]. These methods were first developed for ana-
lyzing hydrocarbons produced from biomass hydrothermal treatment
[18,331–333]. The solid humins, in fact, are special hydrocarbons
formed through acid-catalyzed hydrolysis of biomass. Recently, dy-
namic light scattering (DLS) was employed for investigating the acti-
vation energy of humins formation, and the value is 18–55 kJ/mol
[334], which is lower than the activation barriers of humins formation,
90–120 kJ/mol [76,86,335]. Orella et al., demonstrated that this dif-
ference was mainly caused by disturbance of the humins formation
during the DLS measurement, which significantly limits the light scat-
tering [334].
Water soluble humins were also identified in the reaction solution,
which can continuously grow and precipitate [88,336]. These soluble
humins derived from the C6 sugars had molecular weights of
300–500 g/mol [88], about 2–3 times higher than that of C6 sugars
(180 g/mol) and about 2–5 times higher than that of the intermediate
HMF (126 g/mol). These soluble humins are, therefore, oligomers
containing 16–27 carbon atoms assuming that they had a carbon con-
tent of 65 wt%. Approximately 20 wt% of the precipitated humins can
be isolated by acetone [231]. The structure of acetone soluble fraction,
however, is similar to that of the insoluble humins, indicating that this
soluble fraction may be regarded as shorter and less dense oligomers of
insoluble humins.
The recent studies have found the preliminarily structure of solid
humins, and humins generally have a conjugated network structure and
contain furan rings with functional groups, such as ketones, aldehydes,
and aromatic alcohols [75,76]. These furan rings are connected by
ether and acetal bonds, and humins usually consist of 60% of furan
rings and 20% of aliphatic linkages [319]. According to the 1D 13 C
solid-state NMR, IR and pyrolysis analysis, the furan rings in the humins
are, however, connected by ethylene and methyl linkages with ketone
groups [337]. As 2-acetyl furan or 2-acetyl, 5-methyl furan usually
exists in humins pyrolysis product, it was proposed that furan rings are
also linked by an acetyl group via αC, and αC connects with βC of other
furan ring by CH2 linkages [337]. The structure of humins was also
analyzed and reported (shown in Fig. 5A) [337]. van Zandvoort et al.
demonstrated that humins are mainly composed of furanic rings with
linkages of aliphatic groups [88]. With the help of 2D 13 C solid-state
NMR analysis, they identified four types of linkages, i.e. Cα–Cα,
Caliphatic–Cα, C–O–C, and Cβ–Cβ linkages, and found that Cα–Cα and
Caliphatic–Cα are the main linkages [338]. They further reported the
molecular structure of glucose-derived humins (shown in Fig. 5).
Most of the humins used for morphology and structure analysis
derive from pure raw materials, such as HMF, glucose, fructose and
cellulose. Although the yields of humins are highly affected by the re-
action conditions and feedstocks, it is generally accepted that humins
are furan-rich polymers comprised of various oxygen functional groups
[75,76,88,319,323,339–341]. The only difference is that a FTIR peak at
1670 cm−1 exists in humins derived from HMF, and this peak dis-
appears in humins derived from glucose and fructose. This peak is as-
cribed to the C˭O stretching of the aldehyde group in HMF-type units,
and the difference results from the low concentration of HMF in mixture
or reaction conditions designated to convert glucose or fructose [336].
Interestingly, the humins characteristics can also be affected by
phenolics. It was reported that adding 1,2,4-trihydroxybenzene (TB) to
the reaction solution increases the particle size of isolated humins, and
spherical particles are formed when the ratio of TB in the feedstock
reaches 20 mol% [88]. When lignocellulosic biomass was used in the
hydrolysis reaction, the humins formed have a more complex structure
and morphology due to the existence of unconverted lignin and mixing
of humins derived from cellulose and hemicellulose hydrolysis. In the
conversion process of pretreated eucalyptus wood, the humins in-
corporated with the unconverted lignin and formed a solid residue with

352
S. Kang et al.
Fig. 5. The proposed humins structures (A and B), and the proposed structure of hydrothermal alkaline catalyzed humins (C).
high carbon content, 63.8–67.6 wt%, and relatively high heating value,
25–27 MJ/kg [58].
7.3. Mechanism of humins formation
Dehydration occurs during the formation of humins, as oxygen and
hydrogen were lost during the conversion of hexoses to humins [88].
The polymerization via aldol addition/condensation is a possible
pathway for humins formation based on the Gibbs free energy changes
of intermediates formation in the conversion of HMF to LA and humins
[328]. Self-condensation of HMF for humins formation is impossible, as
there is no α H-atom on HMF [342]. Several reaction pathways on
condensation reactions between hexoses, HMF, and intermediates were
proposed, such as humins formation from fructose through inter-
molecular condensation [250,317,343,344] and acetalization reaction
between hydroxyl groups of fructose and aldehyde group of HMF
[219,317,344]. It has also been reported that the humins formation
could result from side reactions between all intermediates [345]. The
mechanisms of HMF as an essential precursor for humins formation are
summarized below.
As the stretching vibration of C˭C bonds of furanic rings exists in all
the HMF-, glucose- and fructose-derived humins, humins can be mainly
formed through HMF (or another furanic components) as an inter-
mediate [336]. Patil et al. concluded that the humins formation in-
volves an aldol condensation reaction of HMF with 2,5-dioxo-6-hy-
droxyhexanal (DHH) [75,76]. Theoretically, like LA, DHH is an
intermediate derived from HMF through 4, 5 acid-catalyzed addition of
water, even though it was not detected in the reaction mixtures
(Fig. 6A) [261]. Thus, the rehydration of HMF on C˭C position is a key
factor affecting the selectivity of humins and LA.
Another identified key intermediate for humins formation from
HMF is 1,2,4-benzenetriol, which is generated by opening of the furan
ring of HMF, followed by other steps as shown in Fig. 6B
[323,346,347]. The 1,2,4-benzenetriol is very reactive and can con-
tinue to react with the reactive intermediate from the dehydration of
glucose or HMF and form large molecular weight compounds or humins
[323,346].
Sumerskii et al. suggested that methylol and/or carbonyl groups on
353
Renewable and Sustainable Energy Reviews 94 (2018) 340–362
the HMF can be protonated and form a carbocation, which can attack
the methylol group of other HMF and form ether and/or acetal inter-
mediates [319]. The intermediates containing carbonyl groups can in-
duce polycondensation reactions and form humins with branched
structure (see Fig. 6C) [319]. According to this reaction mechanism
investigation, Sumerskii et al. further concluded that adding a small
amount of mercaptan HMF can prevent formation of humins [319], but
no experimental data were provided. Tsilomelekis et al. demonstrated
that the humins formation mechanism involves nucleophilic attack of a
HMF carbonyl group on the α- or β-position of the furanic ring [336].
The nucleophilic attack can be suppressed with the presence of di-
methyl sulfoxide (DMSO), which is reflected by the small humin par-
ticles observed in SEM images [336]. Aldol addition/condensation also
occurred owing to the C˭O stretching of humins [336].
In general, LA is considered as a relative stable compound in acidic
hydrolysis solution and does not form humins through polymerization.
Kang and Yu [58] and Tarabanko et al. [315], however, found that
adding LA in the reaction solution at the beginning of the test can
significantly increase the humins formation and decrease the LA yield.
Tarabanko et al. also proposed that LA behaves like proton acceptor in
the reaction and forms the corresponding carbocation, which further
reacted with target product and results in the increase of product mo-
lecular weight, oligomerization and humins formation [315].
7.4. Inhibition of humins formation
Many methods have been developed to prevent the formation of
humins. One of the desirable ways is to adjust the reaction parameters.
Low biomass concentrations, high acid concentrations and low reaction
temperatures usually can inhibit the formation of humins
[76,86,104,109,211,307,317]. For example, a high acid concentration
(e.g., 0.2 M H2SO4) can increase the selectivity of LA formation from
HMF in the acid-catalyzed rehydration process [76]. The influence of
lowered reaction temperature can be reflected by the activation energy,
as the activation energy for humins formation is much higher than the
other activation energies for the formation of target products in the
acid-catalyzed conversion from glucose to LA [57].
Replacing the reaction water solution with other special mediums is
S. Kang et al. Renewable and Sustainable Energy Reviews 94 (2018) 340–362

Fig. 6. Proposed mechanisms of humins formation.

also an option. The special mediums include organic solvents, ionic 7.5. Application
liquids and biphasic systems (e.g., aqueous/organic solvent, ionic li-
quids/organic solvent) [20,41,47,175,250,278,346–351]. The utiliza- As the formation of humins is unavoidable in the acid water solu-
tion of these special medium, however, can cause other issues, such as tion, value added applications of humins by economic- and environ-
high production cost and potential environmental risks when large ment-friendly methods are essential for the biomass hydrolysis in-
amount of ionic liquids or organic solvents are used. dustry. Currently, humins are mainly used as fuel for heat generation
The humins formation can also be prohibited by protecting the ac- owing to its carbon rich characteristics. The possible applications of
tive functional groups of the main intermediates (i.e., glucose and humins to produce value-added products have been investigated, in-
HMF). Alcohols are regarded as one of the most efficient agents. The cluding thermochemical decomposition of humins to obtain oils and
presence of a large amount of methanol causes the reaction to generate synthesis gas. The thermochemical methods include hydrothermal de-
mainly methyl glucosides and methoxymethyl-2-furaldehyde inter- gradation [330], pyrolysis [358], wet oxidation [311], gasification and
mediates, and results in a very low yield of humins but high yields of steam reforming [344,345].
levulinates (LA and methyl levulinate) [56,331,352–355]. Although
methanol is essential to protect glucose from quick conversion to me-
7.5.1. Catalytic hydrothermal degradation/pretreatment
thyl glucosides, it cannot inhibit the humins formation from HMF [56].
Alkaline catalyzed hydrothermal degradation was preferred, as it
The use of methanol is also challenging, as methanol can be consumed
can completely dissolve humins in aqueous solution [321,340]. High
by side reactions. For example, approximately 61.4 mol% of methanol
temperature (e.g., 200–240 °C), long reaction time (e.g., 6–2 h) and
was consumed when glucose reacted in a solution with 90 vol% me-
high alkali concentration (e.g., 0.5–2 M NaOH) accelerate the de-
thanol at 170 °C for 2 h [56].
gradation of humins to low-molecular-weight products [321,340]. The
Furthermore, concentrated hydrochloric acid/ dichloromethane
combination of reduction in humins molecular weight and formation of
systems can convert cellulose and sugars to (chloromethyl)furfural in-
polar functional groups increases the solubility of humins. In addition,
stead of HMF [356,357]. The hydroxyl group of HMF was protected by
the alkali-treated humins have increased contents of aromatic and
the formation of chloromethyl group that inhibited the humins for-
carboxylic acid groups, by sacrificing the furan groups [340]. Fig. 5C
mation and resulted in a total high yield of (chloromethyl)furfural
shows the molecular structure of alkali-treated, glucose-derived humins
(70–90%) and LA (5–9%) [357]. The (chloromethyl)furfural can also be
[340]. New application of humins was also explored based on their
efficiently converted into HMF and LA through further hydrolysis
solubility in alkali solution. Kang et al. found that humins can be
[356,357]. However, the utilization of concentrated hydrochloric acid
converted to acetic acid through wet oxidation after completely dis-
and dichloromethane can cause environmental and operation issues,
solved through alkaline catalyzed hydrothermal treatment [321]. Fur-
and increase production cost. In summary, humins formation is a cru-
thermore, the alkaline pretreatment improves the oil production from
cial factor that affects the acid-catalyzed conversion of carbohydrates. It
humins by aqueous reforming, and approximately 8 wt% of humins-oils
is essential to develop efficient and simple technologies to prevent the
can be obtained by reformation of the alkali-treated humins [231]. In
formation of humins in biorefineries.
the heating process to reach the reforming temperature, de-volatilisa-
tion and aromatization/graphitisation of humins also occurs [327]. The

354
S. Kang et al.
humins oils formed usually consisted of phenolics, aromatic ketones,
aliphatic carboxylic acid, and paraffins [231]. Only 3 wt% of oil was
formed, however, through the direct aqueous reforming of humins
without prior alkaline pretreatment [231]. Supported ruthenium cata-
lysts were also employed for catalytic hydrothermal conversion of hu-
mins in mixtures of formic acid/2-propanol at 400 °C [313]. The con-
version ratio can reach 69% with the existence of Ru/C and formic acid,
and the obtained humins oils were mainly alkyl phenolics and oligo-
mers [359].
7.5.2. Pyrolysis, gasification and steam reforming
The pyrolysis process can also be used for humins-oils production.
Rasrendra et al. reported that 30 wt% of the humins can be converted to
low molecular weight products, including gas and liquid products
[358]. The liquid products include furanics and organic acids, but the
concentration of these compounds is very low (< 1%). Bubbling flui-
dized bed was also employed for humins pyrolysis and gasification
[360]. Humin pyrolysis yields predominantly to aqueous liquid (20 wt
%), whereas the subsequent steam gasification of the pyrolysis char
(35 wt%) can be used to generate hydrogen, which can serve as reactant
for other processes [360].
As coal and biomass, humins are also potential material for syngas
production owing to its high carbon content [361]. Gasification at high
temperature and steam reforming process were developed for syngas
production from humins [325,339,362]. Dry reforming of humins
without catalyst, however, is very difficult, as the graphitic type
structure was formed prior to the gasification [88,339,362]. A high
gasification temperature (above 1000 °C) is, therefore, required due to
the low reactivity of graphitic humins towards steam/CO2 reforming
[88]. Adding alkali metal carbonates (e.g., sodium carbonate) can im-
prove the conversion of humins by lowering the gasification tempera-
tures (e.g., to 700 °C), but the loss of sodium carbonate catalyst was
observed due to its decomposition [362].
7.5.3. Composites or materials
Humins can be modified to produce valuable composites or mate-
rials. Mija et al. reported that humins can be used as a reactive semi-
ductile thermoset matrix to impregnate cellulosic fibers [363]. They
further found that humins can be employed to enhance the modulus
and tensile strength of pure polyfurfurylalcohol resins [363]. Pin et al.
implanted large quantities (55–75 wt% of the initial feedstocks) of
humins to a polyfuranic thermosetting network to form a thermosetting
furanic composite [364,365]. The humins-based matrix exhibits a two-
fold higher tensile strength in comparison with other composites tested,
but the incorporation of humins decreases the brittleness of the furanic
composites [364]. Kang et al. [366] employed humins as a phenol re-
placement for synthesis of modified phenol-formaldehyde adhesives
through a two-step process. In this process, humins were firstly hy-
drothermal treated to obtain alkaline soluble products, which were
further reacted with phenol and formaldehyde to produce humin-
phenol-formaldehyde adhesive. The properties of the adhesive were
measured, and the key indexes (dynamic viscosity, bonding strength,
pH value, free formaldehyde level, free phenol level and solid content)
of the humin-phenol-formaldehyde adhesive meets the Chinese Na-
tional Standard of phenolic adhesive. These results exhibit an en-
couraging application direction of humins, i.e. production of green and
valuable composites from humins. In addition, LA and sulfonated
carbon were obtained with a total carbon utilization ratio of 70% in a
reaction that p-toluenesulfonic acid catalyzed the conversion of glucose
with limited water [277]. In this reaction, the humins were converted
to solid catalytic material (sulfonated carbon), which has good catalytic
activity in the esterification reaction. Based on the above discussion, the
recent applications of humins are summarized in Fig. 7.
7.5.4. Other applications
Though works have been done on the application of humins, more
355
Renewable and Sustainable Energy Reviews 94 (2018) 340–362
Fig. 7. Recent studies on humins application.
research is still needed. The application of humins may be similar to
that of lignin, as they are also carbon-hydrogen-oxygen based polymers.
For lignin, studies have been done with a focus on investigating its
structure and chemical properties [367–369], pretreatment and de-
composition process [4,11,19,124,370–372], and modification and
applications [367,372–376]. Therefore, several potential applications
of humins may be expected, such as for soil amendment [377,378],
utilizing as substitute or precursor in carbon sequestration [379–382],
adsorbents [14,383,384], container nurseries [385], carbon black [386]
and for other special carbon-based material production [374]. It is
worth noting that lignin is a phenolic high polymer, whereas humins is
mainly comprised of furans. The difference in molecular structure of
lignin and humins may result in difference in their conversion and
application. For example, under similar pyrolysis conditions, the ga-
s–liquid yields of humins are lower than that of kraft lignin [358].
8. Conclusion and future prospects
LA and HMF are valuable platform chemicals that can be used for
producing numerous value-added chemicals and fuels. Lignocellulosic
biomass is a desirable feedstock for large scale production of LA and
HMF through acid-catalyzed hydrolysis. Acid catalyst participates in
the whole reaction, including (i) initial pretreatment, (ii) hydrolysis of
cellulose to glucose, (iii) isomerization of glucose to fructose, (iv) de-
hydration of glucose/fructose to HMF and (v) rehydration of HMF to
LA. Humins, an unavoidable byproduct formed in acid-catalyzed reac-
tions, are the crucial factor that affects the hydrolysis efficiency. Based
on the discussion of this review, five summarized viewpoints are listed
below.
(1) The initial dilute acid pretreatment of lignocellulosic biomass is
essential, as it increases the efficiency of biomass utilization and
improves hydrolysis process of cellulose.
(2) Isomerization of glucose to fructose is desirable for HMF production
through hydrolysis, and Lewis acid may be the most promising
isomerization catalyst owing to its high stability in acidic aqueous
solution.
(3) The conversion of cellulosic biomass to produce HMF in aqueous
solution in an industrial scale has two major challenges: (i) low
HMF yield, and (ii) difficulties for isolation due to its high boiling
point, low concentration, instability and high solubility in acidic
water.
(4) In comparison with glucose and HMF production, the LA produc-
tion requires much severer reaction conditions. The good stability
of LA in the acidic aqueous solution, however, is an advantage in
comparison with that of HMF, and it keeps an acceptable LA yield
in the reaction and makes the commercial-scale production devi-
sable.
(5) Humins formation is inevitable in the biomass hydrolysis for HMF
and LA production. Humins, however, have the potentiality to be
S. Kang et al.
converted to oils and syngas through thermochemical processes, or
be modified to valuable composites/ materials. The value-added
application of humins is more desirable.
In addition, four brief viewpoints for future research are proposed
and listed below.
(1) Replacing homogeneous acid catalyst with green and efficient
heterogeneous catalysts is the trend for future biomass hydrolysis
process. Development of heterogeneous catalysts would aim to
produce locked-in active sites, high surface area and accessible
acidic moieties.
(2) Although HMF is mainly used as an intermediate for preparing
downstream valuable chemicals (e.g., adipic acid, fur-
andicarboxylic acid, 2,5-Dimethylfuran) [222–226], isolation and
purification of HMF from the acidic aqueous solution is still a
bottleneck for reducing the HMF application cost. One potential
way to solve the problem is the direct conversion of the raw HMF
produced from carbohydrates to target chemicals in the acidic
aqueous solution, without a pre-isolation and purification process.
However, works on this research area is still needed.
(3) Production of LA through cellulosic biomass hydrolysis is a pro-
mising pathway. Improvements, however, are still needed to
achieve LA production in a commercial scale. These improvements
include (i) developing economical- and environmental-friendly
process to achieve both higher yield and concentration, and (ii)
developing efficient and low-cost separation and purification tech-
nics.
(4) Although preliminary investigations on humins structure and for-
mation mechanism have been conducted, more studies are still re-
quired to achieve the maximum inhibition of humins formation or
further utilization of humins. Considering the carbon rich char-
acteristics of humins, future work on converting humins to value-
added new carbon materials are suggested.
Acknowledgments
This work was supported by the National Natural Science
Foundation of China (21606045), Natural Science Foundation of
Guangdong Province of China (2017A030313084, 2017A030313261),
Social Science and Technology Development Project of Dongguan
(2014108101036), Young Innovative Talents Program from
Department of Education of Guangdong Province (2015KQNCX163),
and Guangdong Innovation Research Team for Higher Education
(2017KCXTD030).
References
[1] Collard FX, Blin J. A review on pyrolysis of biomass constituents: mechanisms and
composition of the products obtained from the conversion of cellulose, hemi-
celluloses and lignin. Renew Sustain Energy Rev 2014;38(5):594–608.
[2] Sharma A, Pareek V, Zhang D. Biomass pyrolysis – a review of modelling, process
parameters and catalytic studies. Renew Sustain Energy Rev 2015;50:1081–96.
[3] Doassanscarrère N, Ferrasse JH, Boutin O, Mauviel G, Lédé J. Comparative study of
biomass fast pyrolysis and direct liquefaction for bio-oils production: products
yield and characterizations. Energy Fuels 2014;28(8):5103–11.
[4] Kang S, Li X, Li B, Fan J, Chang J. Effects of lignins on antioxidant biodiesel
production in supercritical methanol. Energy Fuels 2011;25(6):2746–8.
[5] Zou X, Qin T, Huang L, Zhang X, Yang Z, Wang Y. Mechanisms and main regula-
rities of biomass liquefaction with alcoholic solvents. Energy Fuels
2009;23(10):5213–8.
[6] Yun Y, Long Y, Wu H. Near-Complete recovery of sugar monomers from cellulose
and lignocellulosic biomass via a two-step process combining mechanochemical
hydrolysis and dilute acid hydrolysis. Energy Fuels 2015;30(3):1571–8.
[7] Pileidis FD, Titirici MM. Levulinic acid biorefineries: new challenges for efficient
utilization of biomass. ChemSusChem 2016;9(21):562–82.
[8] Ye S, Cheng J. Hydrolysis of lignocellulosic materials for ethanol production: a
review. Bioresour Technol 2002;83(1):1–11.
[9] Kumar S, Gupta RB. Biocrude production from switchgrass using subcritical water.
Energy Fuels 2009;23(10):5151–9.
[10] Kang S, Yu J. Hydrophobic organic compounds from hydrothermal liquefaction of
356
Renewable and Sustainable Energy Reviews 94 (2018) 340–362
bacterial biomass. Biomass Bioenergy 2015;74(5):92–5.
[11] Kang S, Li X, Fan J, Chang J. Classified separation of lignin hydrothermal liquefied
products. Ind Eng Chem Res 2011;50(19):11288–96.
[12] Kang S, Li B, Chang J, Fan J. Antioxidant abilities comparison of lignins with their
hydrothermal liquefaction products. BioResources 2011;6(1):243–52.
[13] Ruiz HA, Rodríguez-Jasso RM, Fernandes BD, Vicente AA, Teixeira JA.
Hydrothermal processing, as an alternative for upgrading agriculture residues and
marine biomass according to the biorefinery concept: a review. Renew Sustain
Energy Rev 2013;21(4):35–51.
[14] Kumar S, Loganathan VA, Gupta RB, Barnett MO. An assessment of U(VI) removal
from groundwater using biochar produced from hydrothermal carbonization. J
Environ Manag 2011;92(10):2504–12.
[15] Nilsson S, Gómezbarea A, Fuentescano D, Haro P, Pinnahernández G. Gasification
of olive tree pruning in fluidized bed: experiments in a laboratory-scale plant and
scale-up to industrial operation. Energy Fuels 2017;31(1):542–54.
[16] Ruiz JA, Juárez MC, Morales MP, Muñoz P, Mendívil MA. Biomass gasification for
electricity generation: review of current technology barriers. Renew Sustain
Energy Rev 2013;18(2):174–83.
[17] Funke A, Ziegler F. Hydrothermal carbonization of biomass: a summary and dis-
cussion of chemical mechanisms for process engineering. Biofuels, Bioprod Bioref
2010;4(2):160–77.
[18] Kang S, Li X, Fan J, Chang J. Characterization of hydrochars produced by hy-
drothermal carbonization of lignin, cellulose, D-xylose, and wood meal. Ind Eng
Chem Res 2012;51(26):9023–31.
[19] Kang S, Li X, Fan J, Chang J. Solid fuel production by hydrothermal carbonization
of black liquor. Bioresour Technol 2012;110(110):715–8.
[20] Saha B, Abu-Omar MM. Advances in 5-hydroxymethylfurfural production from
biomass in biphasic solvents. Green Chem 2014;45(16):24–38.
[21] Wang TF, Nolte MW, Shanks BH. Catalytic dehydration of C6 carbohydrates for the
production of hydroxymethylfurfural (HMF) as a versatile platform chemical.
Green Chem 2014;45(13):548–72.
[22] Hayes DJ, Steve F, Hayes MHB, Ross JRH. The Biofine process – production of
levulinic acid, furfural, and formic acid from lignocellulosic feedstocks. In: Kamm
B, Gruber PR, Kamm M, editors. Biorefineries-industrial processes and products:
status quo and future directions. Germany: Wiley-VCH Verlag GmbH Weinheim;
2008. p. 139–64.
[23] Werpy TA, Holladay JE, White JF. Top value added chemicals from biomass: i.
results of screening for potential candidates from sugars and synthesis gas.
Richland, WA, USA: Pacific Northwest National Laboratory; 2004.
[24] Alvira P, Tomáspejó E, Ballesteros M, Negro MJ. Pretreatment technologies for an
efficient bioethanol production process based on enzymatic hydrolysis: a review.
Bioresour Technol 2010;101(13):4851–61.
[25] Lange JP, van der Heide E, van Buijtenen J, Price R. Furfural—A promising plat-
form for lignocellulosic biofuels. Chemsuschem 2012;5:150–66.
[26] Zeitsch KJ. The chemistry and technology of furfural and its many by-products.
Amsterdam: Elsevier; 2000.
[27] Morales M, Quintero J, Conejeros R, Aroca G. Life cycle assessment of lig-
nocellulosic bioethanol: environmental impacts and energy balance. Renew
Sustain Energy Rev 2015;42:1349–61.
[28] Bohre A, Saha B, Abuomar MM. Catalytic upgrading of 5-hydroxymethylfurfural to
drop-in biofuels by solid base and bifunctional metal-acid catalysts. Chemsuschem
2015;8:4022–9.
[29] Huber GW, Chheda JN, Barrett CJ, Dumesic JA. Production of liquid alkanes by
aqueous-phase processing of biomass-derived. Science 2005;308:1446–50.
[30] Bozell JJ. Connecting biomass and petroleum processing with a chemical bridge.
Science 2010;329:522.
[31] Bond JQ, Alonso DM, Wang D, West RM, Dumesic JA. Integrated catalytic con-
version of gamma-valerolactone to liquid alkenes for transportation fuels. Science
2010;327:1110–4.
[32] Lange JP, Price R, Ayoub PM, Louis J, Petrus L, Clarke L, Gosselink H. Valeric
biofuels: a platform of cellulosic transportation fuels. Angew Chem Int Ed
2010;49:4479–83.
[33] Pan T, Deng J, Xu Q, Xu Y, Guo QX, Fu Y. Catalytic conversion of biomass-derived
levulinic acid to valerate esters as oxygenated fuels using supported ruthenium
catalysts. Green Chem 2013;15:2967–74.
[34] Wettstein SG, Alonso DM, Gürbüz EI, Dumesic JA. A roadmap for conversion of
lignocellulosic biomass to chemicals and fuels. Curr Opin Chem Eng
2012;1:218–24.
[35] Liu G, Bao J. Evaluation of electricity generation from lignin residue and biogas in
cellulosic ethanol production. Bioresour Technol 2017;243:1232–6.
[36] Cheng F, Brewer CE. Producing jet fuel from biomass lignin: potential pathways to
alkyl benzenes and cycloalkanes. Renew Sustain Energy Rev 2017;72:673–722.
[37] Dwivedi AD, Gupta K, Tyagi D, Rai RK, Mobin SM, Singh SK. Ruthenium and
formic acid based tandem catalytic transformation of bioderived furans to levulinic
acid and diketones in water. ChemCatChem 2015;7(24):4050–8.
[38] Yan Z, Lin L, Liu S. Synthesis of γ-valerolactone by hydrogenation of biomass-
derived levulinic acid over ru/C catalyst. Energy Fuels 2009;23(8):3853–8.
[39] Windom BC, Lovestead TM, Mascal M, Nikitin EB, Bruno TJ. Advanced distillation
curve analysis on ethyl levulinate as a diesel fuel oxygenate and a hybrid biodiesel
fuel. Energy Fuels 2011;25(4):1878–90.
[40] Baslyman W. Microwave-assisted dehydration of fructose into 5-hydro-
xymethylfurfural (5-HMF) over acidic porous catalysts. Ottawa, Ontario:
University of Ottawa; 2015.
[41] Chidambaram M, Bell AT. A two-step approach for the catalytic conversion of
glucose to 2,5-dimethylfuran in ionic liquids. Green Chem 2010;7(12):1253–62.
[42] Girisuta B. Levulinic acid from lignocellulosic biomass [Doctoral Dissertation].
S. Kang et al.
Groningen, Netherlands: University of Groningen; 2007.
[43] Morone A, Apte M, Pandey RA. Levulinic acid production from renewable waste
resources: bottlenecks, potential remedies, advancements and applications. Renew
Sustain Energy Rev 2015;51:548–65.
[44] Rackemann DW, Doherty WO. The conversion of lignocellulosics to levulinic acid.
Biofuels Bioprod Bioref 2011;5(2):198–214.
[45] Rout PK, Nannaware AD, Prakash O, Kalra A, Rajasekharan R. Synthesis of hy-
droxymethylfurfural from cellulose using green processes: a promising biochem-
ical and biofuel feedstock. Chem Eng Sci 2016;142:318–46.
[46] Shrestha RG, Marie‐Josée D, Vijaya R. Starch to value added biochemicals. Starch -
Starke 2015;68(3–4):274–86.
[47] Ståhlberg T, Rodriguez-Rodriguez S, Fristrup P, Riisager A. Metal-free dehydration
of glucose to 5-(hydroxymethyl)furfural in ionic liquids with boric acid as a pro-
moter. Chem-A Eur J 2011;17(5):1456–64.
[48] Thombal RS, Jadhav VH. Efficient conversion of carbohydrates to 5-hydro-
xymethylfurfural (HMF) using ZrCl4 catalyst in nitromethane. Biofuel Res J
2014;3(2):81–4.
[49] Yan K, Jarvis C, Gu J, Yan Y. Production and catalytic transformation of levulinic
acid: a platform for speciality chemicals and fuels. Renew Sustain Energy Rev
2015;51:986–97.
[50] Zhu SL, Li JD, Jiang XX, Yang B, Jiang JC, Zhang AL. Process of conversion of 5-
hydroxymethylfurfural and levulinic acid to biomass-based chemicals. Biomass-
Chem Eng 2016;50(4):53–9.
[51] Martínez JJ, Silva L, Rojas HA, Romanelli GP, Santos LA, Ramalho TC, Brijaldo
MH, Passos FB. Reductive amination of levulinic acid to different pyrrolidones on
ir/sio2-so3h: elucidation of reaction mechanism. Catal Today 2017;296:118–26.
[52] Yoshida R, Sun D, Yamada Y, Sato S, Hutchings GJ. Vapor-phase hydrogenation of
levulinic acid to γ-valerolactone over Cu-Ni bimetallic catalysts. Catal Commun
2017;97:79–82.
[53] He D, Horváth IT. Application of silica-supported Shvo's catalysts for transfer
hydrogenation of levulinic acid with formic acid. J Organomet Chem
2017;847(1):263–9.
[54] Song S, Yao S, Cao J, Di L, Wu G, Guan N, Li L. Heterostructured Ni/NiO composite
as a robust catalyst for the hydrogenation of levulinic acid to γ-valerolactone.
Applied. Catal B Environ 2017;217(15):115–24.
[55] Ahlkvist J, Wärnå J, Salmi T, Mikkola JP. Heterogeneously catalyzed conversion of
nordic pulp to levulinic and formic acids. React Kinet Mech Catal
2016;119(2):1–13.
[56] Kang S, Yu J. Effect of methanol on formation of levulinates from cellulosic bio-
mass. Ind Eng Chem Res 2015;54(46):11552–9.
[57] Girisuta B, Janssen LPBM, Heeres HJ. Green chemicals: a kinetic study on the
conversion of glucose to levulinic acid. Chem Eng Res Des 2006;84(5):339–49.
[58] Kang S, Yu J. An intensified reaction technology for high levulinic acid con-
centration from lignocellulosic biomass. Biomass- Bioenergy 2016;95:214–20.
[59] Heeres H, Handana R, Chunai D, Rasrendra CR, Girisuta B, Heeres HJ. Combined
dehydration/(transfer)-hydrogenation of c6-sugars (D-glucose and D-fructose) to γ-
valerolactone using ruthenium catalysts. Green Chem 2009;11:1247–55.
[60] Grote AFV, Tollens B. Untersuchungen über Kohlenhydrate. I. Ueber die bei
Einwirkung von Schwefelsäure auf Zucker entstehende Säure (Levulinsäure).
Justus Liebigs Ann Chem 1875;175:181–204.
[61] Teong S, Yi GS, Zhang YG. Hydroxymethylfurfural production from bioresources:
past, present and future. Green Chem 2014;16(4):2015–26.
[62] Mulder GJ. "Untersuchungen über die Humussubstanzen" [Investigations on humic
substances]. J Prakt Chem ( Ger) 1840;21(1):203–40.
[63] Leonard RH. Levulinic acid as a basic chemical raw material. Ind Eng Chem
1956;48(8):1330–41.
[64] Chang C, Deng L, Qi X, Bai J, Fang S. Progress of application of solid catalysts in
levulinic acid and alkyl levulinates produced from biomass. Chem Ind For Prod
2017;37:11–21.
[65] Zheng X, Gu X, Ren Y, Zhi Z, Lu X. Production of 5‐hydroxymethyl furfural and
levulinic acid from lignocellulose in aqueous solution and different solvents.
Biofuels Bioprod Bioref 2016;10(6):917–31.
[66] Zakrzewska ME, Bogel-Łukasik E, Bogel-Łukasik R. Ionic liquid-mediated forma-
tion of 5-Hydroxymethylfurfural-a promising biomass-derived building block.
Chem Rev 2011;42(20):397–417.
[67] Hu L, Lin L, Wu Z, Zhou S, Liu S. Recent advances in catalytic transformation of
biomass-derived 5-hydroxymethylfurfural into the innovative fuels and chemicals.
Renew Sustain Energy Rev 2017;74:230–57.
[68] Tang X, Wei J, Ding N, Sun Y, Zeng X, Hu L, Liu S, Lei T, Lin L. Chemoselective
hydrogenation of biomass derived 5-hydroxymethylfurfural to diols: key inter-
mediates for sustainable chemicals, materials and fuels. Renew Sustain Energy Rev
2017;77:287–96.
[69] Zhang J, Wu SB, Li B, Zhang HD. Advances in the catalytic production of valuable
levulinic acid derivatives. ChemCatChem 2012;4:1230–7.
[70] Mood SH, Golfeshan AH, Tabatabaei M, Jouzani GS, Najafi GH, Gholami M,
Ardjmand M. Lignocellulosic biomass to bioethanol, a comprehensive review with
a focus on pretreatment. Biomass Bull 2013;27(6):77–93.
[71] Verardi A, De Bari I, Ricca E, Calabrò V. Hydrolysis of lignocellulosic biomass:
current status of processes and technologies and future perspectives. In Bioethanol.
London, United Kingdom: InTech; 2012. http://dx.doi.org/10.5772/23987.
[72] Deng W, Zhang Q, Wang Y. Catalytic transformations of cellulose and its derived
carbohydrates into 5-hydroxymethylfurfural, levulinic acid, and lactic acid. Sci Sin
Chim 2015;58(1):29–46.
[73] Mukherjee A, Dumont MJ, Raghavan V. Review: sustainable production of hy-
droxymethylfurfural and levulinic acid: challenges and opportunities. Biomass
Bioenergy 2015;72:143–83.
357
Renewable and Sustainable Energy Reviews 94 (2018) 340–362
[74] Galletti AMR, Antonetti C, Luise VD, Licursi D, Nassi D. Levulinic acid production
from waste biomass. BioResources 2012;7(2):1824–35.
[75] Patil SKR, Heltzel J, Lund CRF. Comparison of structural features of humins
formed catalytically from glucose, fructose, and 5-hydroxymethylfurfuraldehyde.
Energy Fuels 2012;26(8):5281–93.
[76] Patil SKR, Lund CRF. Formation and growth of humins via aldol addition and
condensation during acid-catalyzed conversion of 5-hydroxymethylfurfural.
Energy Fuels 2011;25(10):4745–55.
[77] Weingarten R, Conner WC, Huber GW. Production of levulinic acid from cellulose
by hydrothermal decomposition combined with aqueous phase dehydration with a
solid acid catalyst. Energy Environ Sci 2012;5(6):7559–74.
[78] Harmsen PFH, Huijgen W, Bermudez L, Bakker R. Literature review of physical and
chemical pretreatment processes for lignocellulosic biomass. Wagening UR, Food
Biobased Res 2010.
[79] Jørgensen H, Kristensen JB, Felby C. Enzymatic conversion of lignocellulose into
fermentable sugars: challenges and opportunities. Biofuels Bioprod Bioref
2007;1(2):119–34.
[80] Mcmillan JD. In Pretreatment of lignocellulosic biomass. ACS Symp Ser (USA)
1994:292–324.
[81] Chen H. Chemical composition and structure of natural lignocellulose.
Biotechnology of Lignocellulose. Netherlands: Springer; 2014. p. 25–71.
[82] Eriksson Ö, Goring DAI, Lindgren BO. Structural studies on the chemical bonds
between lignins and carbohydrates in spruce wood. Wood Sci Technol
1980;14(4):267–79.
[83] Jin Z, Katsumata KS, Lam TB, Iiyama K. Covalent linkages between cellulose and
lignin in cell walls of coniferous and nonconiferous woods. Biopolymers
2006;83(2):103–10.
[84] Košíková B, Ebringerová A. Lignin-carbohydrate bonds in a residual soda spruce
pulp lignin. Wood Sci Technol 1994;28(4):291–6.
[85] Deutsch. Sharma A, Kar SK, editors. Energy sustainability through green energy. In
Green Energy and Technology. Berlin, Germany: Springer; 2015.
[86] Girisuta B, Janssen LPBM, Heeres HJ. A kinetic study on the decomposition of 5-
hydroxymethylfurfural into levulinic acid. Green Chem 2006;8(8):701–9.
[87] Fachri BA, Abdilla R, Bovenkamp H, Rasrendra C, Heeres HJ. Experimental and
kinetic modeling studies on the sulphuric acid catalyzed conversion of D-fructose to
5-hydroxymethylfurfural and levulinic acid in water. ACS Sustain Chem Eng
2015;3(2):3024–34.
[88] van Zandvoort I, Wang Y, Rasrendra CB, van Eck ER, Bruijnincx PC, Heeres HJ,
Weckhuysen BM. Formation, molecular structure, and morphology of humins in
biomass conversion: influence of feedstock and processing conditions.
ChemSusChem 2013;6(9):1745–58.
[89] Shen Y, Xu Y, Sun J, Wang B, Xu F, Sun R. Efficient conversion of monosaccharides
into 5-hydroxymethylfurfural and levulinic acid in InCl3–H2O medium. Catal
Commun 2014;50(14):17–20.
[90] Son PA, Nishimura S, Ebitani K. Synthesis of levulinic acid from fructose using
Amberlyst-15 as a solid acid catalyst. React Kinet Mech Catal 2012;106(1):185–92.
[91] Choudhary V, Mushrif SH, Ho C, Anderko A, Nikolakis V, Marinkovic NS, Frenkel
AI, Sandler SI, Vlachos DG. Insights into the interplay of Lewis and Brønsted acid
catalysts in glucose and fructose conversion to 5-(hydroxymethyl)furfural and le-
vulinic acid in aqueous media. J Am Chem Soc 2013;135(10):3997–4006.
[92] Ramli NAS, Amin NAS. Fe/HY zeolite as an effective catalyst for levulinic acid
production from glucose: characterization and catalytic performance. Appl Catal B
Environ 2015;163:487–98.
[93] Ramli NAS, Amin NAS. Optimization of renewable levulinic acid production from
glucose conversion catalyzed by Fe/HY zeolite catalyst in aqueous medium.
Energy Convers Manag 2015;95:10–9.
[94] Kumar VB, Pulidindi IN, Mishra RK, Gedanken A. Development of Ga salt of mo-
lybdophosphoric acid for biomass conversion to levulinic acid. Energy Fuels
2016;30(12):10583–91.
[95] Tarabanko VE, Chernyak MY, Aralova SV. Kinetics of levulinic acid formation from
carbohydrates at moderate temperatures. React Kinet, Mech Catal
2002;75(1):117–26.
[96] Ya’Aini N, Amin NAS, Endud S. Characterization and performance of hybrid cat-
alysts for levulinic acid production from glucose. Microporous Mesoporous Mater
2013;171(171):14–23.
[97] Yang F, Fu J, Mo J, Lu X. Synergy of lewis and brønsted acids on catalytic hy-
drothermal decomposition of hexose to levulinic acid. Energy Fuels
2013;27(11):6973–8.
[98] Zeng W, Cheng DG, Zhang H. Dehydration of glucose to levulinic acid over MFI-
type zeolite in subcritical water at moderate conditions. React Kinet Mech Catal
2010;100(2):377–84.
[99] Wang Y, Nie X. Preparation of magnetic solid acid catalyst S2O82-/ZrO2-TiO2-Fe3O4
and its application to synthesis of levulinic acid. J Cent South Univ Technol)
2016;47(1):26–32.
[100] Fu J, Yang F, Mo J, Zhuang J, Lu X. Catalytic decomposition of glucose to levulinic
acid by synergy of organic Lewis acid and Brønsted acid in water. BioResources
2015;10(1):1346–56.
[101] Liu W, Hou Y, Wu W, Liu Z, Liu Q, Tian S, Marsh KN. Efficient conversion of
cellulose to glucose, levulinic acid, and other products in hot water using SO2 as a
recoverable catalyst. Ind Eng Chem Res 2012;51(47):15503–8.
[102] Peng L, Lin L, Zhang J, Zhuang J, Zhang B, Gong Y. Catalytic conversion of cel-
lulose to levulinic acid by metal chlorides. Molecules 2010;15(8):5258–72.
[103] Shen J, Wyman CE. Hydrochloric acid-catalyzed levulinic acid formation from
cellulose: data and kinetic model to maximize yields. AIChE J 2012;58(1):236–46.
[104] Girisuta B, Janssen LPBM, Heeres HJ. Kinetic study on the acid-catalyzed hydro-
lysis of cellulose to levulinic acid. Ind Eng Chem Res 2007;46(6):1696–708.
S. Kang et al.
[105] Joshi SS, Zodge AD, Pandare KV, Kulkarni BD. Efficient conversion of cellulose to
levulinic acid by hydrothermal treatment using zirconium dioxide as a recyclable
solid acid catalyst. Ind Eng Chem Res 2014;53(49):18796–805.
[106] Ding D, Wang J, Xi J, Liu X, Lu G, Wang Y. High-yield production of levulinic acid
from cellulose and its upgrading to γ-valerolactone. Green Chem
2014;16(8):685–93.
[107] Girisuta B, Dussan K, Haverty D, Leahy JJ, Hayes MHB. A kinetic study of acid
catalysed hydrolysis of sugar cane bagasse to levulinic acid. Chem Eng J
2013;217(2):61–70.
[108] Bevilaqua DB, Rambo MKD, Rizzetti TM, Cardoso AL, Martins AF. Cleaner pro-
duction: levulinic acid from rice husks. J Clean Prod 2013;47(5):96–101.
[109] Girisuta B, Danon B, Manurung R, Janssen LPBM, Heeres HJ. Experimental and
kinetic modelling studies on the acid-catalysed hydrolysis of the water hyacinth
plant to levulinic acid. Bioresour Technol 2008;99(17):8367–75.
[110] Dussan K, Girisuta B, Haverty D, Leahy JJ, Hayes MH. Kinetics of levulinic acid
and furfural production from Miscanthus × giganteus. Bioresour Technol
2013;149C:216–24.
[111] Fang Q, Hanna MA. Experimental studies for levulinic acid production from whole
kernel grain sorghum. Bioresour Technol 2002;81(3):187–92.
[112] Chang C, Xiaojian MA, Cen P. Kinetic studies on wheat straw hydrolysis to levu-
linic acid. Chin J Chem Eng 2009;17(5):835–9.
[113] Victor A, Pulidindi IN, Gedanken A. Levulinic acid production from Cicer ar-
ietinum, cotton, Pinus radiata and sugarcane bagasse. RSC Adv
2014;4(84):44706–11.
[114] Jeong GT. Production of levulinic acid from glucosamine by dilute-acid catalyzed
hydrothermal process. Ind Crops Prod 2014;62:77–83.
[115] Omari KW, Besaw JE, Kerton FM. Hydrolysis of chitosan to yield levulinic acid and
5-hydroxymethylfurfural in water under microwave irradiation. Green Chem
2012;14(5):1480–7.
[116] Zhi Z, Li N, Qiao Y, Zheng X, Wang H, Lu X. Kinetic study of levulinic acid pro-
duction from corn stalk at relatively high temperature using FeCl3 as catalyst: a
simplified model evaluated. Ind Crops Prod 2015;76(7):672–80.
[117] Gwitaek J. Catalytic conversion of Helianthus tuberosus L. to sugars, 5-hydro-
xymethylfurfural and levulinic acid using hydrothermal reaction. Biomass-
Bioenergy 2015;74:113–21.
[118] Zheng X, Zhi Z, Gu X, Li X, Zhang R, Lu X. Kinetic study of levulinic acid pro-
duction from corn stalk at mild temperature using FeCl3 as catalyst. Fuel
2017;187:261–7.
[119] Yuan Z, Long J, Xia Y, Zhang X, Wang T, Ma L. Production of levulinic acid from
Pennisetum alopecuroides in the presence of an acid catalyst. BioResources
2016;11(2):3511–23.
[120] Xu X, Lu X, Fu J, Lu X. Catalytic decomposition of furfural residue with dilute
sulfuric acid to produce levulinic acid in high temperature liquid water. J Chem
Eng Chin Univ 2015;29(6):1377–82.
[121] Chang C, Ma X, Cen P. Technology for production of levulinic acid as new platform
chemical from wheat straw. Trans Chin Soc Agric Eng 2006;22(6):161–4.
[122] Liu Y, Li H, He J, Zhao W, Yang T, Yang S. Catalytic conversion of carbohydrates to
levulinic acid with mesoporous niobium-containing oxides. Catal Commun
2017;93:20–4.
[123] Shen F, Jr RL S, Li L, Yan L, Qi X. Eco-friendly method for efficient conversion of
cellulose into levulinic acid in pure water with cellulase-mimetic solid acid cata-
lyst. ACS Sustain Chem Eng 2017;5(3):2421–7.
[124] Kang S, Li X, Fan J, Chang J. Hydrothermal conversion of lignin: a review. Renew
Sustain Energy Rev 2013;27(6):546–58.
[125] Yoon SY, Han SH, Shin SJ. The effect of hemicelluloses and lignin on acid hy-
drolysis of cellulose. Energy 2014;77:19–24.
[126] Hamelinck CN, Hooijdonk GV, Faaij AP. Ethanol from lignocellulosic biomass:
techno-economic performance in short-, middle- and long-term. Biomass
Bioenergy 2005;28(4):384–410.
[127] Kim ES, Liu S, Abuomar MM, Mosier NS. Selective conversion of biomass hemi-
cellulose to furfural using maleic acid with microwave heating. Energy Fuels
2012;26(2):1298–304.
[128] Xiang Q, Lee YY, Torget RW. Kinetics of glucose decomposition during dilute-acid
hydrolysis of lignocellulosic biomass. Appl Biochem Biotechnol
2004;113–116(1):1127–38.
[129] Foody B, Tolan JS, Rahme Z, Anand V. Recovery of inorganic salt during pro-
cessing of lignocellulosic feedstocks. US8247203, 2012.
[130] Hu X, Wang S, Wu L, Dong D, Hasan MM, Li CZ. Acid-treatment of C5 and C6 sugar
monomers/oligomers: insight into their interactions. Fuel Process Technol
2014;126(10):315–23.
[131] Rackemann DW, Bartley JP, Doherty WOS. Methanesulfonic acid-catalyzed con-
version of glucose and xylose mixtures to levulinic acid and furfural. Ind Crops
Prod 2014;52(1):46–57.
[132] Runge T, Zhang C. Two-stage acid-catalyzed conversion of carbohydrates into
levulinic acid. Ind Eng Chem Res 2012;51(8):3265–70.
[133] Lange JP, van de Graaf WD, Haan RJ. Conversion of furfuryl alcohol into ethyl
levulinate using solid acid catalysts. ChemSusChem 2009;2(5):437–41.
[134] Vassilev SV, Baxter D, Andersen LK, Vassileva CG. An overview of the chemical
composition of biomass. Fuel 2010;89(5):913–33.
[135] Masiá AAT, Buhre BJP, Gupta RP, Wall TF. Characterising ash of biomass and
waste. Fuel Process Technol 2007;88(11–12):1071–81.
[136] Tang P, Jian Y. Kinetic analysis on deactivation of a solid brønsted acid catalyst in
conversion of sucrose to levulinic acid. Ind Eng Chem Res 2014;53(29):11629–37.
[137] Hu X, Lievens C, Mourant D, Wang Y, Wu L, Gunawan R, Song Y, Li CZ.
Investigation of deactivation mechanisms of a solid acid catalyst during ester-
ification of the bio-oils from mallee biomass. Appl Energy 2013;111(4):94–103.
358
Renewable and Sustainable Energy Reviews 94 (2018) 340–362
[138] Carvalheiro F, Duarte LC, Girio FM. Hemicellulose biorefineries: a review on
biomass pretreatments. J Sci Ind Res 2008;67(11):849–64.
[139] Jönsson LJ, Martín C. Pretreatment of lignocellulose: formation of inhibitory by-
products and strategies for minimizing their effects. Bioresour Technol
2015;199:103–12.
[140] Kumar P, Barrett DM, Delwiche MJ, Stroeve P. Methods for pretreatment of lig-
nocellulosic biomass for efficient hydrolysis and biofuel production. Ind Eng Chem
Res 2009;48(8):3713–29.
[141] Nguyen MT, Choi SP, Lee J, Lee JH, Sim SJ. Hydrothermal acid pretreatment of
Chlamydomonas reinhardtii biomass for ethanol production. J Microbiol
Biotechnol 2009;19(2):161–6.
[142] Sindhu R, Kuttiraja M, Binod P, Janu KU, Sukumaran RK, Pandey A. Dilute acid
pretreatment and enzymatic saccharification of sugarcane tops for bioethanol
production. Bioresour Technol 2011;102(23):10915–21.
[143] Yang B, Wyman CE. Pretreatment: the key to unlocking low‐cost cellulosic
ethanol. Biofuels Bioprod Biorefin 2008;2(2):26–4026.
[144] Zheng Y, Pan Z, Zhang R, Wang D. Enzymatic saccharification of dilute acid
pretreated saline crops for fermentable sugar production. Appl Energy
2009;86(11):2459–65.
[145] Zhu Y. Overview of biomass pretreatment technologies. Novozymes
2011;18610:1–10.
[146] Gorhmann K, Torget RW, Himmel ME. Optimization of dilute acid pretreatment of
biomass. In: Proceedings of the Biotechnology and Bioengineering Symposium; 15
(15), 1986. 59–80.
[147] Grohmann K, Himmel M, Rivard C, Tucker M, Baker J, Torget R, Graboski M.
Chemical-mechanical methods for the enhanced utilization of straw. In:
Proceedings of the Biotechnology & Bioengineering Symposium. 14 (14), 1984.
137–157.
[148] Grohmann K, Torget R, Himmel M. In Dilute acid pretreatment of biomass at high
acid concentrations, In: Proceedings of the Biotechnology & Bioengineering
Symposium (United States), Gatlinburg, TN, USA, Gatlinburg, TN, USA.1986.
[149] Lloyd TA, Wyman CE. Combined sugar yields for dilute sulfuric acid pretreatment
of corn stover followed by enzymatic hydrolysis of the remaining solids. Bioresour
Technol 2005;96(18):1967–77.
[150] Chum HL, Johnson DK, Black SK. Organosolv pretreatment for enzymic hydrolysis
of poplars. 2. Catal Eff Comb Sev Parameter Ind Eng Chem Res
1990;29(2):156–62.
[151] Bower S, Wickramasinghe R, Nagle NJ, Schell DJ. Modeling sucrose hydrolysis in
dilute sulfuric acid solutions at pretreatment conditions for lignocellulosic bio-
mass. Bioresour Technol 2008;99(15):7354–62.
[152] Lee JW, Jeffries TW. Efficiencies of acid catalysts in the hydrolysis of lig-
nocellulosic biomass over a range of combined severity factors. Bioresour Technol
2011;102(10):5884–90.
[153] Söderström J, Pilcher L, Galbe M, Zacchi G. Two step steam pretreatment of
softwood by dilute H2SO4 impregnation for ethanol production. Biomass
Bioenergy. 24: 475-486. Biomass- Bioenergy 2003;24(6):475–86.
[154] Paniagua-García AI, Díez-Antolínez R, Hijosa-Valsero M, Sánchez ME, Coca M.
Response surface optimization of dilute sulfuric acid pretreatment of switchgrass
(Panicum virgatum L.) for fermentable sugars production. Chem Eng Trans
2016;49:223–8.
[155] Kim DH, Lee SB, Kim SK, Park DH, Jeong GT. Optimization and evaluation of
sugars and chemicals production from green macro-algae Enteromorpha in-
testinalis. Bioenergy Res 2016;9(4):1155–66.
[156] Poliakoff M, Licence P. Sustainable technology - green chemistry. Nature
2007;450(7171):810–2.
[157] Jeong H, Jang SK, Hong CY, Kim SH, Lee SY, Lee SM, Choi JW, Choi IG. Levulinic
acid production by two-step acid-catalyzed treatment of Quercus mongolica using
dilute sulfuric acid. Bioresour Technol 2016:225.
[158] Ji H, Zhu JY, Gleisner R. Integrated production of furfural and levulinic acid from
corncob in a one-pot batch reaction incorporating distillation using step tem-
perature profiling. RSC Adv 2017;7(73):46208–14.
[159] Giuliano A, Cerulli R, Poletto M, Raiconi G, Barletta D. Process pathways opti-
mization for a lignocellulosic biorefinery producing levulinc acid, succinic acid
and ethanol. Ind Eng Chem Res 2016;55(40):10699–717.
[160] Chen H, Yu B, Jin S. Production of levulinic acid from steam exploded rice straw
via solid superacid, S2O82-/ZrO2-SiO2-Sm2O3. Bioresour Technol
2011;102(3):3568–70.
[161] Dornath PJ. Rational development of carbon-based materials for adsorption-en-
hanced conversion of cellulose to value-added chemicals.
Amherst,Massachusetts,USA: University of Massachusetts Amherst; 2016.
[162] Rinaldi R, Schüth F. Acid hydrolysis of cellulose as the entry point into biorefinery
schemes. ChemSusChem 2009;2(12):1096–107.
[163] Vyver SVD, Thomas J, Geboers J, Keyze S, Smet M, Dehaen W, Jacobs PA, Sels BF.
Catalytic production of levulinic acid from cellulose and other biomass-derived
carbohydrates with sulfonated hyperbranched poly(arylene oxindole)s. Energy
Environ Sci 2011;4(9):3601–10.
[164] Sasaki M, Kabyemela B, Malaluan R, Hirose S, Takeda N, Adschiri T, Arai K.
Cellulose hydrolysis in subcritical and supercritical water. J Supercrit Fluids the
1998;13(1):261–8.
[165] Sasaki M, Fang Z, Fukushima Y, Adschiri TA, Arai K. Dissolution and hydrolysis of
cellulose in subcritical and supercritical water. Ind Eng Chem Res
2000;39(8):2883–90.
[166] Lewkowski J. Synthesis, chemistry and applications of 5-hydroxymethylfurfural
and its derivatives. ARKIVOC 2001;34(2):17–54.
[167] Cottier L, Descotes G. 5-(hydroxymethyl)furfural syntheses and chemical trans-
formations. Trends Heterocycl Chem 1991;2:233–48.
S. Kang et al.
[168] Melo FCD, Souza RFD, Coutinho PLA, Souza MOD. Synthesis of 5-hydro-
xymethylfurfural from dehydration of fructose and glucose using ionic liquids. J
Braz Chem Soc 2014;25(12):2378–84.
[169] Moreau C, Finiels A, Vanoye L. Dehydration of fructose and sucrose into 5-hy-
droxymethylfurfural in the presence of 1-H-3-methyl imidazolium chloride acting
both as solvent and catalyst. J Mol Catal A Chem 2006;253(1–2):165–9.
[170] Chen JY, Zhong JW, Li KG, Xing H. Catalytic conversion of glucose to 5-hydro-
xymethylfurfural by 1,3-disulfonic acid imidazolium tetrachloroaluminate. Adv
New Renew Energy 2014;3:239–44.
[171] Li J, Jing Y, Liu C, Zhang D. A theoretical elucidation: why does a SO3H-func-
tionalized imidazolium-based ionic liquid catalyze the conversion of 5-hydro-
xymethylfurfural to levulinic acid? New J Chem 2017;4(1):8714–20.
[172] Souza RLD, Yu H, Rataboul F, Essayem N. 5-hydroxymethylfurfural (5-HMF)
production from hexoses: limits of heterogeneous catalysis in hydrothermal con-
ditions and potential of concentrated aqueous organic acids as reactive solvent
system. Challenges 2012;3(2):212–32.
[173] Robyt F. Essentials of catbohydrates chemsitry. New York: Springer; 1998. p.
48–74.
[174] Pedersen AT, Ringborg R, Grotkjær T, Pedersen S, Woodley JM. Synthesis of 5-
hydroxymethylfurfural (HMF) by acid catalyzed dehydration of glucose–fructose
mixtures. Chem Eng J 2015;273:455–64.
[175] Pagántorres YJ, Wang T, Gallo JMR, Shanks BH, Dumesic JA. Production of 5-
hydroxymethylfurfural from glucose using a combination of Lewis and Brønsted
acid catalysts in water in a biphasic reactor with an alkylphenol solvent. ACS
Catalysis 2. 2012. p. 930–4.
[176] Hu L, Zhao G, Hao W, Tang X, Sun Y, Lin L, Liu S. Catalytic conversion of bio-
mass‐derived carbohydrates into fuels and chemicals via furanic aldehydes. RSC
Adv 2012;44(2):11184–206.
[177] Chheda JN, Románleshkov Y, Dumesic JA. Production of 5-hydroxymethylfurfural
and furfural by dehydration of biomass-derived mono- and poly-saccharides.
Green Chem 2007;9(4):342–50.
[178] Daorattanachai P, Khemthong P, Viriya-Empikul N, Laosiripojana N,
Faungnawakij K. Conversion of fructose, glucose, and cellulose to 5-hydro-
xymethylfurfural by alkaline earth phosphate catalysts in hot compressed water.
Carbohydr Res 2012;363C(12):58–61.
[179] Grande PM, Bergs C. Chemo-enzymatic conversion of glucose into 5-hydro-
xymethylfurfural in seawater. ChemSusChem 2012;5(7):1203–6.
[180] Qi X, Watanabe M, Aida TM, Smith RL. Catalytical conversion of fructose and
glucose into 5-hydroxymethylfurfural in hot compressed water by microwave
heating. Catal Commun 2008;9(13):2244–9.
[181] Watanabe M, Aizawa Y, Iida T, Nishimura R, Inomata H. Catalytic glucose and
fructose conversions with TiO2 and ZrO2 in water at 473 K: relationship between
reactivity and acid–base property determined by TPD measurement. Appl Catal A
General 2005;295(2):150–6.
[182] Kang S, Ye J, Zhang Y, Chang J. Preparation of biomass hydrochar derived sul-
fonated catalysts and their catalytic effects for 5-hydroxymethylfurfural produc-
tion. RSC Adv 2013;3(20):7360–6.
[183] Chi ZM, Zhang T, Cao TS, Liu XY, Cui W, Zhao CH. Biotechnological potential of
inulin for bioprocesses. Bioresour Technol 2011;102(6):4295–303.
[184] Laere AV, Ende WVD. Inulin metabolism in dicots: chicory as a model system.
Plant Cell Environ 2002;25(6):803–13.
[185] Tong X, Ma Y, Li Y. Biomass into chemicals: conversion of sugars to furan deri-
vatives by catalytic processes. Appl Catal A Gen 2010;385(1):1–13.
[186] Ma J, Yu W, Wang M, Jia X, Lu F, Xu J. Advances in selective catalytic transfor-
mation of ployols to value-added chemicals. Chin J Catal 2013;34(3):492–507.
[187] Wang T, Glasper JA, Shanks BH. Kinetics of glucose dehydration catalyzed by
homogeneous Lewis acidic metal salts in water. Appl Catal A Gen
2015;498(6):214–21.
[188] Jensen VJ, Rugh S. Industrial-scale production and application of immobilized
glucose isomerase. Methods Enzymol 1987;136C:356–70.
[189] Buchholz K, Seibel J. Industrial carbohydrate biotransformations. Carbohydr Res
2008;343(12):1966–79.
[190] Chen KC, Chang CM. Operational stability of immobilized d -glucose isomerase in
a continuous feed stirred tank reactor. Enzym Microb Technol 1984;6(8):359–64.
[191] Rohrbach RP, Maliarik MJ. Increasing the stability of amyloglucosidase. US
4415656 A. 1983.
[192] Suga KI, Chen KC, Taguchi H. Optimal operation and replacement policies for a
reactor with immobilized enzymes subject to deactivation. J Ferment Technol
1981;59(2):137–47.
[193] Bock K, Meldal M, Meyer B, Wiebe L. Isomerization of D-glucose with glucose-
isomerase. A mechanistic study. Acta Chem Scand 1983;37(38):101–8.
[194] Lloyd NE, Horwath RO. Glucose isomerase process. US, US4410627, 1983.
[195] Moreau C, Durand R, Roux A, Tichit D. Isomerization of glucose into fructose in
the presence of cation-exchanged zeolites and hydrotalcites. Appl Catal A Gen
2000;193(1–2):257–64.
[196] Alipour S, Omidvarborna H. Enzymatic and catalytic hybrid method for levulinic
acid synthesis from biomass sugars. J Clean Prod 2017;143:490–6.
[197] de Bruyn LCA, van Ekenstein AW. Action of alkalis on the sugars. Reciprocal
transformation of glucose, fructose, and mannose. Recl Des Trav Chim Des Pays-
Bas 1895;14:201–16.
[198] Románleshkov Y, Moliner M, Labinger JA, Davis ME. Mechanism of glucose iso-
merization using a solid Lewis acid catalyst in water. Angew Chem Int Ed
2010;49(47):8954–7.
[199] Takagaki A, Ohara M, Nishimura S, Ebitani K. A one-pot reaction for biorefinery:
combination of solid acid and base catalysts for direct production of 5-hydro-
xymethylfurfural from saccharides. Chem Commun 2010;41(10):6276–8.
359
Renewable and Sustainable Energy Reviews 94 (2018) 340–362
[200] Siqueira BG, Silva MAP, Moraes C. Synthesis of HMF from glucose in aqueous
medium using niobium and titaniium oxides. Braz J Pet Gas 2013;7(2):71–82.
[201] Lima S, Dias AS, Lin Z, Brandão P, Ferreira P, Pillinger M, Rocha J, Calvino-Casilda
V, Valente AA. Isomerization of D-glucose to D-fructose over metallosilicate solid
bases. Appl Catal A Gen 2008;339(1):21–7.
[202] Souza ROL, Fabiano DP, Feche C, Rataboul F, Cardoso D, Essayem N.
Glucose–fructose isomerisation promoted by basic hybrid catalysts. Catal Today
2012;195(1):114–9.
[203] Yue C, Li G, Pidko EA, Wiesfeld JJ, Rigutto M, Hensen EJ. Dehydration of glucose
to 5-hydroxymethylfurfural using Nb-doped tungstite. ChemSusChem
2016;9(17):2421–9.
[204] Li J, Ma Y, Wang L, Song Z, Li H, Wang T, Li H, Eli W. Catalytic conversion of
glucose into 5-hydroxymethylfurfural by Hf(OTf)4 Lewis acid in water. Catalysts
2016;6(1):1.
[205] Yang G, Pidko EA, Hensen EJ. The mechanism of glucose isomerization to fructose
over Sn-BEA zeolite: a periodic density functional theory study. ChemSusChem
2013;6(9):1688–96.
[206] Binder JB, Raines RT. Simple chemical transformation of lignocellulosic biomass
into furans for fuels and chemicals. J Am Chem Soc 2009;131(5):1979–85.
[207] Qi X, Watanabe M, Aida TM, Smith RL. Catalytic conversion of cellulose into 5-
hydroxymethylfurfural in high yields via a two-step process. Cellulose
2011;18(5):1327–33.
[208] Su Y, Brown HM, Huang X, Zhou XD, Amonette JE, Zhang ZC. Single-step con-
version of cellulose to 5-hydroxymethylfurfural (HMF), a versatile platform che-
mical. Applied. Catal A Gen 2009;361(1–2):117–22.
[209] Gu Z, Lu X, Gao W, Li W. Degradation of cellulose into 5-hydroxylmethylfurfuran
catalyzed by metallic Lewis acids. Chem Bull 2013;76(2):144–9.
[210] Wang P, Li B, Ren L, Chong Y. The preparation of 5-hydroxymethylfurfural base on
the catalysis of glucose by using solid acid and metallic oxide. J Green Sci Technol
2015;3:266–9.
[211] Nakajima K, Baba Y, Noma R, Kitano M, Kondo JN, Hayashi S, Hara M.
Nb2O5·nH2O as a heterogeneous catalyst with water-tolerant Lewis acid sites. J Am
Chem Soc 2011;133(12):4224–7.
[212] Moreno-Recio M, Santamaría-González J, Maireles-Torres P. Brönsted and Lewis
acid ZSM-5 zeolites for the catalytic dehydration of glucose into 5-hydro-
xymethylfurfural. Chem Eng J 2016;303:22–30.
[213] Saravanamurugan S, Paniagua M, Melero JA, Riisager A. Efficient isomerization of
glucose to fructose over zeolites in consecutive reactions in alcohol and aqueous
media. J Am Chem Soc 2013;135(14):5246–9.
[214] Li Y, Zhu J, Liu H, Wang P, Tian H. Increase in the hydrothermal stability of the La-
modified ZSM-5 zeolite. Acta Phys-Chim Sin 2011;27(1):52–8.
[215] Sanchez-Castillo MA, Madon RJ, Dumesic JA. Role of rare earth cations in Y
zeolite for hydrocarbon cracking. J Phys Chem B 2005;109(6):2164–75.
[216] Bohn CM. Transformation of biomass carbohydrates by transition metal catalysts.
Dissertations & theses - gradworks. West Lafayette, USA: Purdue University; 2014.
[217] Su Y, Bao Z, Zhang Z, Xing H, Yang Q, Su B, Yang Y, Su Y, Bao Z, Zhang Z, Xing H,
Yang Q, Su B, Yang Y, Ren Q. Sulfonic acid functionalized MIL-101(Cr) catalysts
with tunable Lewis acid and Bronsted acid sites for glucose dehydration to 5-HMF.
J Chem Ind Eng (China) 2016;67(7):2799–807.
[218] HMF from plant biomass in one step. Tce the Chemical Engineer.
[219] Román-Leshkov Y, Chheda JN, Dumesic JA. Phase modifiers promote efficient
production of hydroxymethylfurfural from fructose. Science
2006;312(5782):1933–7.
[220] Aida TM, Tajima K, Watanabe M, Saito Y, Kuroda K, Nonaka T, Hattori H, Smith
RL, Arai K. Reactions of D-fructose in water at temperatures up to 400 °C and
pressures up to 100 MPa. J Supercrit Fluids 2007;42(1):110–9.
[221] Asghari FS, Yoshida H. Kinetics of the decomposition of fructose catalyzed by
hydrochloric acid in subcritical water: formation of 5-hydroxymethylfurfural, le-
vulinic, and formic acids. Ind Eng Chem Res 2007;46(23):7703–10.
[222] Kitano M, Nakajima K, Kondo JN, Hayashi S, Hara M. Protonated titanate nano-
tubes as solid acid catalyst. J Am Chem Soc 2010;132(31):6622–3.
[223] Moreau C, Durand R, Razigade S, Duhamet J, Faugeras P, Rivalier P, Ros P,
Avignon G. Dehydration of fructose to 5-hydroxymethylfurfural over H-morde-
nites. Appl Catal A Gen 1996;145(1–2):211–24.
[224] Carlini C, Giuttari M, Galletti AMR, Sbrana G, Armaroli T, Busca G. Selective
saccharides dehydration to 5-hydroxymethyl-2-furaldehyde by heterogeneous
niobium catalysts. Appl Catal A Gen 1999;183(2):295–302.
[225] Asghari S, Yoshida F, Hiroyuki. Acid-catalyzed production of 5-hydroxymethyl
furfural from D-fructose in subcritical water. Ind Eng Chem Res
2006;45(7):2163–73.
[226] Benvenuti F, Carlini C, Patrono P, Galletti AMR, Sbrana G, Massucci MA, Galli P.
Heterogeneous zirconium and titanium catalysts for the selective synthesis of 5-
hydroxymethyl-2-furaldehyde from carbohydrates. Appl Catal A Gen
2000;193(193):147–53.
[227] Armaroli T, Busca G, Carlini C, Giuttari M, Galletti AMR, Sbrana G. Acid sites
characterization of niobium phosphate catalysts and their activity in fructose de-
hydration to 5-hydroxymethyl-2-furaldehyde. J Mol Catal A Chem
2000;151(1–2):233–43.
[228] Asghari FS, Yoshida H. Dehydration of fructose to 5-hydroxymethylfurfural in sub-
critical water over heterogeneous zirconium phosphate catalysts. Carbohydr Res
2006;341(14):2379–87.
[229] Bicker M, Kaiser D, Ott L, Vogel H. Dehydration of d -fructose to hydro-
xymethylfurfural in sub- and supercritical fluids. J Supercrit Fluids
2005;36(2):118–26.
[230] Zhou C, Zhao J, Yagoub EGA, Ma H, Yu X, Hu J, Bao X, Liu S. Conversion of
glucose into 5-hydroxymethylfurfural in different solvents and catalysts: reaction
S. Kang et al.
kinetics and mechanism. Egypt J Pet 2016. http://dx.doi.org/10.1016/j.ejpe.
2016.07.005.
[231] van Zandvoort I. Towards the valorization of humin by-products: characterization,
solubilization and catalysis [Doctoral Dissertation]. Utrecht, the Netherlands:
Utrecht University; 2015.
[232] Kunasundari B. Isolation and recovery of microbial polyhydroxyalkanoates.
Express Polym Lett 2011;5(7):620–34.
[233] Wu R, Xu Y, Liu D. Progress in down-stream processing of biologically produced
1,3-propanediol. Chin J Biotechnol 2011;27(3):493–501.
[234] Zhang S, Lan J, Chen Z, Yin G, Li G. Catalytic synthesis of 2,5-furandicarboxylic
acid from furoic acid: transformation from C5 platform to C6 derivatives in bio-
mass utilizations. Acs Sustain Chem Eng 2017;5:9360–9.
[235] Vyver SVD, Románleshkov Y. Emerging catalytic processes for the production of
adipic acid. Catal Sci Technol 2013;3(6):1465–79.
[236] Han X, Li C, Liu X, Xia Q, Wang Y. Selective oxidation of 5-hydroxymethylfurfural
to 2,5-furandicarboxylic acid over MnOx–CeO2 composite catalysts. Green Chem
2016;19(4):996–1004.
[237] Gao T, Gao T, Fang W, Cao Q. Base-free aerobic oxidation of 5-hydro-
xymethylfurfural to 2,5-furandicarboxylic acid in water by hydrotalcite-activated
carbon composite supported gold catalyst. Mol Catal 2017;439:171–9.
[238] Wang Q, Hou W, Li S, Xie J, Li J, Zhou Y, Wang J. Hydrophilic mesoporous Poly
(ionic liquid) supported Au-Pd alloy nanoparticles towards aerobic oxidation of 5-
hydroxymethylfurfural to 2,5-furandicarboxylic acid under mild condition. Green
Chem 2017;19:3820–30.
[239] Hu L, Tang X, Xu J, Wu Z, Lin L, Liu S. Selective transformation of 5-
Hydroxymethylfurfural into the liquid fuel 2,5-Dimethylfuran over carbon-sup-
ported Ruthenium. Ind Eng Chem Res 2014;53(8):3056–64.
[240] Weingarten R, Cho J, Xing R, Conner WC, Huber GW. Kinetics and reaction en-
gineering of levulinic acid production from aqueous glucose solutions.
ChemSusChem 2012;5(7):1280–90.
[241] Jadhav AH, Kim H, Hwang IT. An efficient and heterogeneous recyclable silico-
tungstic acid with modified acid sites as a catalyst for conversion of fructose and
sucrose into 5-hydroxymethylfurfural in superheated water. Bioresour Technol
2013;132(132):342–50.
[242] Aida TM, Sato Y, Watanabe M, Tajima K, Nonaka T, Hattori H, Arai K. Dehydration
of D -glucose in high temperature water at pressures up to 80 MPa. J Supercrit
Fluids 2007;40(3):381–8.
[243] Takeuchi Y, Jin F, Tohji K. Acid catalytic hydrothermal conversion of carbohy-
drate biomass into useful substances. J Mater Sci 2008;43(7):2472–5.
[244] Kuster BFM, Temmink HMG. The influence of pH and weak-acid anions on the
dehydration of d -fructose. Carbohydr Res 1977;54(2):185–91.
[245] Kei-Ichi S, Inoue Y, Ishida H. Catalytic activity of lanthanide(III) ions for the de-
hydration of hexose to 5hydroxymethyl 2-furaldehyde in water. Bull Chem Soc
Jpn 2001;32(42):1145–50.
[246] Gupta D, Ahmad E, Pant KK, Saha B. Efficient utilization of potash alum as a green
catalyst for production of furfural, 5-hydroxymethylfurfural and levulinic acid
from mono-sugars. RSC Adv 2017;7(67):41973–9.
[247] Shunmugadhas G, Kumar S, Kumaresan S. Potash alum [KAl(SO4)2·12H2O] cata-
lysed esterification of formylphenoxyaliphatic acids. J Chem Sci
2012;124:857–63.
[248] Chheda JN, Dumesic JA. Dehydration, aldol condensation and hydrogenation
processes for the production of liquid alkanes from biomass-derived carbohy-
drates. Catal Today 2007;38(39):59–70.
[249] Crisci AJ, Tucker MH, Dumesic JA, Scott SL. Bifunctional solid catalysts for the
selective conversion of fructose to 5-Hydroxymethylfurfural. Top Catal
2010;53(15–18):1185–92.
[250] Román-Leshkov Y, Dumesic JA. Solvent effects on fructose dehydration to 5-
Hydroxymethylfurfural in biphasic systems saturated with inorganic salts. Top
Catal 2009;52(3):297–303.
[251] Azadi P, Carrasquilloflores R, Pagántorres YJ, Gürbüz EI, Farnood R, Dumesic JA.
Catalytic conversion of biomass using solvents derived from lignin. Green Chem
2012;14(6):1573–6.
[252] Li W, Xu Z, Zhang T, Li G, Jameel H, Chang HM, Ma L. Catalytic conversion of
biomass-derived carbohydrates into 5-hydroxymethylfurfural using a strong solid
acid catalyst in aqueous γ-valerolactone. BioResources 2016;11(3):5839–53.
[253] Tucker MH, Crisci AJ, Wigington BN, Phadke N, Alamillo R, Zhang J, Scott SL,
Dumesic JA. Acid-functionalized SBA-15-type periodic mesoporous organosilicas
and their use in the continuous production of 5-hydroxymethylfurfural. ACS
Catalysis 2. 2012. p. 1865–76.
[254] Yang Y, Hu CW, Abuomar MM. Synthesis of furfural from xylose, xylan, and
biomass using AlCl3·6H2O in biphasic media via xylose isomerization to xylulose.
ChemSusChem 2012;5(2):405–10.
[255] Kazi FK, Patel AD, Serrano-Ruiz JC, Dumesic JA, Anex RP. Techno-economic
analysis of dimethylfuran (DMF) and hydroxymethylfurfural (HMF) production
from pure fructose in catalytic processes. Chem Eng J 2011;169(1–3):329–38.
[256] Karwa S, Gajiwala VM, Heltzel J, Patil SKR, Lund CRF. Reactivity of levulinic acid
during aqueous, acid-catalyzed HMF hydration. Catal Today 2015;263:16–21.
[257] Liu Q, Yang F, Yin H, Du Y. Conversion of saccharides into levulinic acid and 5-
hydroxymethylfurfural over WO3–Ta2O5 catalysts. RSC Adv 2016;6(55):49760–3.
[258] Yan L, Greenwood AA, Hossain A, Yang B. A comprehensive mechanistic kinetic
model for dilute acid hydrolysis of switchgrass cellulose to glucose, 5-HMF and
levulinic acid. RSC Adv 2014;4(45):23492–504.
[259] Jing Q, LÜ X. Kinetics of non-catalyzed decomposition of glucose in high-tem-
perature liquid water. Chin J Chem Eng 2008;16(6):890–4.
[260] Akin O, Yuksel A. Novel hybrid process for the conversion of microcrystalline
cellulose to value-added chemicals: part 1: process optimization. Cellulose
360
Renewable and Sustainable Energy Reviews 94 (2018) 340–362
2016;23(6):1–19.
[261] Horvat J, Klaić B, Metelko B, Šunjić V. Mechanism of levulinic acid formation.
Tetrahedron Lett 1985;26(17):2111–4.
[262] Purushothaman RKP, Haveren JV. Exploratory catalyst screening studies on the
base free conversion of glycerol to lactic acid and glyceric acid in water using
bimetallic Au–Pt banoparticles on acidic zeolites. Top Catal 2014;57(17):1445–53.
[263] Yang G, Pidko EA, Hensen EJM. Mechanism of Brønsted acid-catalyzed conversion
of carbohydrates. J Catal 2012;295:122–32.
[264] Assary RS, Redfern PC, Hammond JR, Greeley J, Curtiss LA. Computational studies
of the thermochemistry for conversion of glucose to levulinic acid. J Phys Chem B
2010;114(27):9002–9.
[265] Garcés D, Díaz E, Ordóñez S. Aqueous phase conversion of hexoses into 5-
Hydroxymethylfurfural and levulinic acid in the presence of hydrochloric acid:
mechanism and kinetics. Ind Eng Chem Res 2017;56(18).
[266] Yang L, Tsilomelekis G, Caratzoulas S, Vlachos DG. Mechanism of brønsted acid-
catalyzed glucose dehydration. ChemSusChem 2015;8(8):1334–41.
[267] Jeong GT, Park DH. Production of sugars and levulinic acid from marine biomass
Gelidium amansii. Appl Biochem Biotechnol 2010;161(1):41–52.
[268] Fachri BA, Abdilla R, Bovenkamp H, Rasrendra C, Heeres HJ. Experimental and
kinetic modeling studies on the sulphuric acid catalyzed conversion of D-Fructose
to 5-Hydroxymethylfurfural and levulinic acid in water. ACS Sustain Chem Eng
2015;3(2):3024–34.
[269] Wei W, Wu S. Experimental and kinetic study of glucose conversion to levulinic
acid catalyzed by synergy of Lewis and Brønsted acids. Chem Eng J
2016;307:389–98.
[270] Cao X, Peng X, Sun S, Zhong L, Chen W, Wang S, Sun RC. Hydrothermal con-
version of xylose, glucose, and cellulose under the catalysis of transition metal
sulfates. Carbohydr Polym 2015;118:44–51.
[271] Ramli NAS, Amin NAS. Kinetic study of glucose conversion to levulinic acid over
Fe/HY zeolite catalyst. Chem Eng J 2016;283:150–9.
[272] Xun H, Shuai W, Westerhof RJM, Wu L, Yao S, Dong D, Li CZ. Acid-catalyzed
conversion of C6 sugar monomer/oligomers to levulinic acid in water, tetra-
hydrofuran and toluene: importance of the solvent polarity. Fuel 2015;141:56–63.
[273] Potvin J, Sorlien E, Hegner J, Deboef B, Lucht BL. Effect of NaCl on the conversion
of cellulose to glucose and levulinic acid via solid supported acid catalysis.
Tetrahedron Lett 2011;52(44):5891–3.
[274] Kang S, Yu J. A gasoline-grade biofuel formed from renewable poly-
hydroxybutyrate on solid phosphoric acid. Fuel 2015;160:282–90.
[275] Vilcocq L, Castilho PC, Carvalheiro F, Duarte LC. Hydrolysis of oligosaccharides
over solid acid catalysts: a Review. ChemSusChem 2014;7(4):1010–9.
[276] Kang S, Chang J, Fan J. One step preparation of sulfonated solid catalyst and its
effect in esterification reaction. Chin J Chem Eng 2014;22(4):392–7.
[277] Kang S, Zhang G, Yang X, Yin HY, Fu XF, Liao J, Tu J, Huang X, Qin FGF, Xu Y.
Effects of p-toluenesulfonic acid in the conversion of glucose for levulinic acid and
sulfonated carbon production. Energy Fuels 2017;31(3):2847–54.
[278] Son J, Wilson J. Mesoporous niobium phosphate: an excellent solid acid for the
dehydration of fructose to 5-hydroxymethylfurfural in water. Catal Sci Technol
2012;2(12):2485–91.
[279] Heguaburu V, Franco J, Reina L, Tabarez C, Moyna G, Moyna P. Dehydration of
carbohydrates to 2-furaldehydes in ionic liquids by catalysis with ion exchange
resins. Catal Commun 2012;27(27):88–91.
[280] Sidhpuria KB, Daniel-Da-Silva AL, Trindade T, Coutinho JAP. Supported ionic li-
quid silica nanoparticles (SILnPs) as an efficient and recyclable heterogeneous
catalyst for the dehydration of fructose to 5-hydroxymethylfurfural. Green Chem
2011;13(2):340–9.
[281] Tian C, Oyola Y, Nelson K, Chai SH, Zhu X, Bauer JC, Janke C, Brown S, Guo Y, Dai
S. A renewable HSO3/H2PO3-grafted polyethylene fiber catalyst: an efficient het-
erogeneous catalyst for the synthesis of 5-hydroxymethylfurfural from fructose in
water. RSC Adv 2013;3(44):21242–6.
[282] Zuo Y, Zhang Y, Fu Y. Catalytic conversion of cellulose into levulinic acid by a
sulfonated chloromethyl polystyrene solid acid catalyst. Chemcatchem
2014;6(3):753–7.
[283] Alonso DM, Gallo JMR, Mellmer MA, Wettstein SG, Dumesic JA. Direct conversion
of cellulose to levulinic acid and gamma-valerolactone using solid acid catalysts.
Catal Sci Technol 2013;3(4):927–31.
[284] Thapa I, Mullen B, Saleem A, Leibig C, Baker RT, Giorgi JB. Efficient green cat-
alysis for the conversion of fructose to levulinic acid. Appl Catal A Gen 2017.
[285] Xiang M, Liu J, Fu W, Tang T, Wu D. Improved activity for cellulose conversion to
levulinic acid through hierarchization of ETS-10 zeolite. Acs Sustain Chem Eng
2017;5(7).
[286] Deguchi S, Tsujii K, Horikoshi K. Cooking cellulose in hot and compressed water.
Chem Commun 2006;31(31):3293–5.
[287] Chen SS. Valorization of cellulosic food waste into levulinic acid catalyzed by
heterogeneous Brønsted acids: temperature and solvent effects. Chem Eng J
2017;327:328–35.
[288] Lin X, Huang Q, Qi G, Shi S, Xiong L, Huang C, Chen X, Li H, Chen X. Estimation of
fixed-bed column parameters and mathematical modeling of breakthrough beha-
viors for adsorption of levulinic acid from aqueous solution using SY-01 resin. Sep
Purif Technol 2017;174:222–31.
[289] Rosatella AA, Simeonov SP, Frade RFM, Afonso CAM. 5-Hydroxymethylfurfural
(HMF) as a building block platform: biological properties, synthesis and synthetic
applications. Green Chem 2011;13(32):754–93.
[290] Ayoub PM. Process for the reactive extractive extraction of levulinic acid.
US7378549, 2008.
[291] Sadhukhan J, Ng KS, Martinez-Hernandez E. Novel integrated mechanical biolo-
gical chemical treatment (MBCT) systems for the production of levulinic acid from
S. Kang et al.
fraction of municipal solid waste: a comprehensive techno-economic analysis.
Bioresour Technol 2016;215:131–43.
[292] Laitinen AT, Penttilä KJT, Kaunisto JM. Physical solvent extraction of levulinic
acid from dilute aqueous solution with 2-methyltetrahydrofuran. Sep Sci Technol
2016;3:1–9.
[293] Farone WA, Cuzens JE. Method for the production of levulinic acid. US5892107,
1999.
[294] Brouwer T, Blahusiak M, Babic K, et al. Reactive extraction and recovery of le-
vulinic acid, formic acid and furfural from aqueous solutions containing sulphuric
acid. Sep Purif Technol 2017;185(12):186–95.
[295] Uslu H, Kirbaslar SI. Investigation of levulinic acid distribution from aqueous
phase to organic phase with TOA extractant. Ind Eng Chem Res
2008;47:4598–606.
[296] Uslu H, Kirbaslar SI. Equilibrium studies of extraction of levulinic acid by
(Trioctylamine (TOA) + Ester) solvents. J Chem Eng Data 2008;53:1557–63.
[297] Uslu H. Reactive extraction of levulinic acid using TPA in Toluene solution: lser
modeling, kinetic and equilibrium studies. Sep Sci Technol 2008;43:1535–48.
[298] Uslu H, Kirbaslar SI, Wasewar KL. Reactive extraction of levulinic acid by
Amberlite LA-2 Extractant. J Chem Eng Data 2009;54:712–8.
[299] Datta D, Marti ME, Pal D, et al. Equilibrium study on the extraction of levulinic
acid from aqueous solution with aliquat 336 dissolved in different diluents: sol-
vent's polarity effect and column design. J Chem Eng Data 2016;62(1):3–10.
[300] Kim JH, Na JG, Yang JW, Chang YK. Separation of galactose, 5-hydro-
xymethylfurfural and levulinic acid in acid hydrolysate of agarose by nanofiltra-
tion and electrodialysis. Bioresour Technol 2013;140(7):64–72.
[301] Valentin E, Nam HG, Kim PH, Joo HW, Shim HJ, Chang YK, Mun S. Application of
a Dowex-50WX8 chromatographic process to the preparative-scale separation of
galactose, levulinic acid, and 5-hydroxymethylfurfural in acid hydrolysate of
agarose. Sep Purif Technol 2014;133:297–302.
[302] Liu BJ, Liu SW, Liu TB, Mao JW. A Novel granular activated carbon adsorption
method for separation of levulinic acid from formic acid. Adv Mater Res
2012;550–553:1691–5.
[303] Liu B, Liu S. Adsorption of levulinic acid from aqueous solution onto basic poly-
meric adsorbent: experimental and modeling studies. Sep Sci Technol
2011;46(15):2391–9.
[304] Liu BJ, Ren QL. Sorption of levulinic acid onto weakly basic anion exchangers:
equilibrium and kinetic studies. J Colloid Interface Sci 2006;294(2):281–7.
[305] Liu BJ, Hu ZJ, Ren QL. Single-component and competitive adsorption of levulinic/
formic acids on basic polymeric adsorbents. Colloids Surf A Physicochem Eng Asp
2009;339(1–3):185–91.
[306] Lin X, Huang Q, Qi G, Xiong L, Huang C, Chen X, Li H. Adsorption behavior of
levulinic acid onto microporous hyper-cross-linked polymers in aqueous solution:
equilibrium, thermodynamic, kinetic simulation and fixed-bed column studies.
Chemosphere 2017;171:231.
[307] Datta D, Uslu H. Adsorption of levulinic acid from aqueous solution by Amberlite
XAD-4. J Mol Liq 2017;234:330–4.
[308] Global levulinic acid market expected to reach 3,820 t by 2020. 〈http://www.
grandviewresearch.com/industry-analysis/levulinic-acid-market〉 [Accessed
March 2015].
[309] Bozell JJ, Moens L, Elliott DC, Wang Y, Neuenscwander GG, Fitzpatrick SW, Bilski
RJ, Jarnefeld JL. Production of levulinic acid and use as a platform chemical for
derived products. Resour Conserv Recycl 2000;28(3–4):227–39.
[310] GFBiochemicals starts production of levulinic acid. 〈http://biomassmagazine.
com/articles/12205/gfbiochemicals-starts-production-of-levulinic-acid〉
[Accessed 22 July 2015].
[311] Segetis starts levulinic acid pilot production. 〈http://greenchemicalsblog.com/
2013/10/10/segetis-starts-levulinic-acid-pilot-production/〉 [Accessed 10 October
2013].
[312] Mullen BD, Leibig CM, Kapicak LA, Bunning DL, Strand SM, Joseph BD, Marc RD,
Page SR, Louwagie AJ, Janine YD. Process to prepare levulinc acid. US2012/
066368，2013.
313] Segetis successfully starts pilot plant facility to produce levulinic acid from biomass
in Minnesota. 〈http://www.specialchem4bio.com/news/2013/10/18/segetis-
successfully-starts-pilot-plant-facility-to-produce-levulinic-acid-from-biomass-in-
minnesot〉 [Accessed 18 October 2013].
[314] Incitor’s high performance fuel from algae biomass. 〈http://www.
algaeindustrymagazine.com/incitors-jacob-berman-and-troy-lapsys/〉 [Accessed
11 November 2012].
[315] Tarabanko VE, Smirnova MA, Chernyak MY, Kondrasenko AA, Tarabanko NV. The
nature and mechanism of selectivity decrease of the acid-catalyzed fructose con-
version with increasing the carbohydrate concentration. J Sib Fed Univ Chem
2015;8(1):6–18.
[316] Kuster BFM. The influence of water concentration on the dehydration of D-fruc-
tose. Carbohydr Res 1977;54(2):177–83.
[317] Kuster BFM, Baan HSVD. The influence of the initial and catalyst concentrations
on the dehydration of d -fructose. Carbohydr Res 1977;54(2):165–76.
[318] Yoshida H, Asghari FS. In Acid-catalyzed production of 5-hydroxymethyl furfural
from D-fructose in subcritical water, In: Proceedings of the a combination of the
China/USA joint chemical engineering conference and the China/japan joint
chemical engineering symposium; 2005; pp 2163–2173.
[319] Sumerskii IV, Krutov SM, Zarubin MY. Humin-like substances formed under the
conditions of industrial hydrolysis of wood. Russ J Appl Chem 2010;83(2):320–7.
[320] Lin H, Sun W, Ru B, Chen J, Wang S. Kinetic study on conversion of glucose to 5-
hydroxymethylfurfural in different solvents. Trans Chin Soc Agric Mach
2015;46(11):201–7.
[321] Kang S, Zhang G, Yang Q, Tu J, Guo X, Qin FGF, Xu Y. A new technology for
361
Renewable and Sustainable Energy Reviews 94 (2018) 340–362
utilization of biomass hydrolysis residual humins for acetic acid production.
BioResources 2016;11:9496–505.
[322] Baugh KD, Mccarty PL. Thermochemical pretreatment of lignocellulose to enhance
methane fermentation: i. Monosaccharide and furfurals hydrothermal decom-
position and product formation rates. Biotechnol Bioeng 1988;31(1):62–70.
[323] Chuntanapum A, Matsumura Y. Formation of tarry material from 5-HMF in sub-
critical and supercritical water. Ind Eng Chem Res 2009;48(22):9837–46.
[324] Ordomsky VV, Sushkevich VL, Schouten JC, Schaaf JVD, Nijhuis TA. Glucose
dehydration to 5-hydroxymethylfurfural over phosphate catalysts. J Catal
2013;300(3):37–46.
[325] Kamm B, Gruber PR, Kamm M. Biorefineries - industrial processes and products.
Chem Int – Newsmag IUPAC 2008;29(3). [25-25].
[326] Rapp KM. Process for preparing pure 5-hydroxymethylfurfuraldehyde.
US4740605, 1988.
[327] Hoàng TMC. Catalytic gasification of humin based by-product from biomass pro-
cessing - a sustainable route for hydrogen. The Netherlands: Gildeprint, Enschede;
2014.
[328] Heltzel J, Patil SKR, Lund CRF. Humin formation pathways. In reaction pathways
and mechanisms in thermocatalytic biomass conversion II. Singapore: Springer;
2016. p. 105–18.
[329] Herzfeld J, Rand D, Matsuki Y, Daviso E, Makjurkauskas M, Mamajanov I.
Molecular structure of humin and melanoidin via solid state NMR. J Phys Chem B
2011;115(19):5741–5.
[330] Kang S, Li X, Fan J, Chang J. A direct synthesis of adsorbable hydrochar by hy-
drothermal conversion of lignin. Energy Sources Part A Recovery Util Environ Eff
2016;38(9):1255–61.
[331] Sevilla M, Fuertes AB. Chemical and structural properties of carbonaceous pro-
ducts obtained by hydrothermal carbonization of saccharides. Aust J Soil Res
2010;15(16):4195–203.
[332] Sevilla M, Fuertes AB. The production of carbon materials by hydrothermal car-
bonization of cellulose. Carbon 2009;47(9):2281–9.
[333] Dayton DC, Carpenter J, Farmer J, Turk B, Gupta R. Biomass hydropyrolysis in a
pressurized fluidized bed reactor. Energy Fuels 2013;27(7):3778–85.
[334] Orella M. Understanding humins: molecular characterization and growth rates.
Newark, DE, USA: Undergraduate Senior Theses University of Delaware; 2014.
[335] Swift TD, Bagia C, Nikolakis V, Vlachos DG, Peklaris G, Dornath P, Wei F. Reactive
adsorption for the selective dehydration of sugars to furans: modeling and ex-
periments. AIChE J 2013;59(9):3378–90.
[336] Tsilomelekis G, Orella MJ, Lin Z, Cheng Z, Zheng W, Nikolakis V, Vlachos D.
Molecular structure, morphology and growth mechanisms and rates of 5-hydro-
xymethyl furfural (HMF) derived humins. Green Chem 2015;18(7):1983–93.
[337] Hoang TMC. Humin based by-products from biomass processing as a potential
carbonaceous source for synthesis gas production. Green Chem
2015;17(2):959–72.
[338] van Zandvoort I, Koers EJ, Weingarth M, Bruijnincx PCA, Baldus M, Weckhuysen
BM. Structural characterization of C-enriched humins and alkali-treated C humins
by 2D solid-state NMR. Green Chem 2015;17(8):4383–92.
[339] Hoang TMC, Eck ERHV, Bula WP, Gardeniers JGE, Lefferts L, Seshan K. Humin
based by-products from biomass processing as a potential carbonaceous source for
synthesis gas production. Green Chem 2014;17(2):959–72.
[340] van Zandvoort I, Eck ERHV, Peinder PD, Heeres HJ, Bruijnincx PCA, Weckhuysen
BM. Full, reactive solubilization of humin byproducts by alkaline treatment and
characterization of the alkali-treated humins formed. ACS Sustain Chem Eng
2015;3(3):533–43.
[341] Reiche S, Kowalew N. Influence of synthesis pH and oxidative strength of the
catalyzing acid on the morphology and chemical structure of hydrothermal
carbon. ChemPhysChem 2014;16(3):579–87.
[342] Huber GW, Dumesic JA. An overview of aqueous-phase catalytic processes for
production of hydrogen and alkanes in a biorefinery. Catal Today
2006;111(1):119–32.
[343] Chu YD, Berglund KA. Kinetics of difructose dianhydrides formation under fruc-
tose crystallization conditions. Starch - Starke 1990;42(3):112–7.
[344] Vinke P, Bekkum HV. The dehydration of fructose towards 5-hydro-
xymethylfurfural using activated carbon as adsorbent. Starch - Starke
1992;44(3):90–6.
[345] Kuster BFM. 5-Hydroxymethylfurfural (HMF). A review focussing on its manu-
facture. Starch - Starke 1990;42(8):314–21.
[346] Hu X, Lievens C, Larcher A, Li CZ. Reaction pathways of glucose during ester-
ification: effects of reaction parameters on the formation of humin type polymers.
Bioresour Technol 2011;102(21):10104–13.
[347] Luijkx GCA. Hydrothermal formation of 1,2,4-benzenetriol from 5-hydro-
xymethyl-2-furaldehyde and D-fructose. Carbohydr Res 1993;242(15):131–9.
[348] Wagh VK, Badgujar KC, Patil NM, Bhanage BM. Recent trends of ionic liquids for
the synthesis of 5-hydroxymethylfurfural. Curr Org Chem 2016;20(7):736–51.
[349] Shi N, Liu Q, Zhang Q, Wang T, Ma L. High yield production of 5-hydro-
xymethylfurfural from cellulose by high concentration of sulfates in biphasic
system. Green Chem 2013;15(7):1967–74.
[350] Yang Y, Hu C, Abuomar MM. Conversion of carbohydrates and lignocellulosic
biomass into 5-hydroxymethylfurfural using AlCl3·6H2O catalyst in a biphasic
solvent system. Green Chem 2012;14(2):509–13.
[351] Farrán A, Chao C, Sandoval M, Xu Y, Jian L, Hernáiz MJ, Linhardt RJ. Green
solvents in carbohydrate chemistry: from raw materials to fine chemicals. Chem
Rev 2015;115(14):6811–53.
[352] Démolis A, Essayem N, Rataboul F. Synthesis and applications of alkyl levulinates.
ACS Sustain Chem Eng 2014;2(6):1338–52.
[353] Hu X, Li CZ. Levulinic esters from the acid-catalysed reactions of sugars and
S. Kang et al.
alcohols as part of a bio-refinery. Green Chem 2011;13(7):1676–9.
[354] Peng L, Lin L, Li H, Yang Q. Conversion of carbohydrates biomass into levulinate
esters using heterogeneous catalysts. Appl Energy 2011;88(12):4590–6.
[355] Wu X, Fu J, Lu X. One-pot preparation of methyl levulinate from catalytic alco-
holysis of cellulose in near-critical methanol. Carbohydr Res 2012;358(9):37–9.
[356] Mascal M, Nikitin EB. Direct, high‐yield conversion of cellulose into biofuel.
Angew Chem Int Ed 2008;47(41):7924–6.
[357] Mascal M, Nikitin E. High-yield conversion of plant biomass into the key value-
added feedstocks 5-(hydroxymethyl)furfural, levulinic acid, and levulinic esters
via 5-(chloromethyl)furfural. Green Chem 2010;12(3):370–3.
[358] Rasrendra CB, Windt M, Wang Y, Adisasmito S. Makertihartha IGBN, Eck ERHV,
Meier D, Heeres HJ. Experimental studies on the pyrolysis of humins from the
acid-catalysed dehydration of C6-sugars. J Anal Appl Pyrolysis
2013;104(10):299–307.
[359] Wang Y, Agarwal S, Kloekhorst A, Heeres HJ. Catalytic hydrotreatment of humins
in mixtures of formic acid/2‐propanol with supported ruthenium catalysts.
ChemSusChem 2016;9(9):951–61.
[360] Wild PD. Two-stage thermochemical valorisation of sugar-derived humins. In:
Proceedings of the 5th international congress on process engineering (GPE 2016);
2016.
[361] Kopyscinski J, Schildhauer TJ, Biollaz SMA. Production of synthetic natural gas
(SNG) from coal and dry biomass – A technology review from 1950 to 2009. Fuel
2010;89:1763–83.
[362] Hoang TM, Lefferts L, Seshan K. Valorization of humin-based byproducts from
biomass processing-a route to sustainable hydrogen. ChemSusChem
2013;6(9):1651–8.
[363] Mija A, Waal JCVD, Pin JM, Guigo N, Jong ED. Humins as promising material for
producing sustainable carbohydrate-derived building materials. Constr Build
Mater 2016. http://dx.doi.org/10.1016/j.conbuildmat.2016.11.019.
[364] Pin JM, Guigo N, Mija A, Vincent L, Sbirrazzuoli N, Waal JCVD, Jong ED.
Valorization of biorefinery side-stream products: combination of humins with
polyfurfuryl alcohol for composite elaboration. ACS Sustain Chem Eng
2014;2(2):2182–90.
[365] De Jong E, Cornelis VDWJ, Pin JMBL, Guigo NDC. Composition comprising fur-
furyl alcohol. WO/2015/088341; 2015.
[366] Kang S, Fu J, Zhang G, Zhang W, Yin H, Xu Y. Synthesis of humin-phenol-for-
maldehyde adhesive. Polymers 2017;9(8):373.
[367] Feofilova EP, Mysyakina IS. Lignin: chemical structure, biodegradation, and
practical application (a review). Appl Biochem Microbiol 2016;52(6):573–81.
[368] Li M, Pu Y, Ragauskas AJ. Current understanding of the correlation of lignin
structure with biomass recalcitrance. Front Chem 2016;4(45):1–8.
[369] Wang C, Kelley SS, Venditti RA. Lignin-based thermoplastic materials.
ChemSusChem 2016;9(8):770–83.
[370] Cannatelli MD, Ragauskas AJ. Conversion of lignin into value-added materials and
chemicals via laccase-assisted copolymerization. Appl Microbiol Biotechnol
362
Renewable and Sustainable Energy Reviews 94 (2018) 340–362
2016;100(20):8685–91.
[371] Kang S, Chang J, Fan J. Phenolic antioxidant production by hydrothermal lique-
faction of lignin. Energy Sources Part A Recovery Util Environ Eff
2015;37(5):494–500.
[372] Jin YQ, Cheng XS, Zheng ZB. Preparation and characterization of phenol-for-
maldehyde adhesives modified with enzymatic hydrolysis lignin. Bioresour
Technol 2010;101(6):2046–8.
[373] Mahmood N, Yuan Z, Schmidt J, Xu C. Depolymerization of lignins and their
applications for the preparation of polyols and rigid polyurethane foams. A re-
view. Renew Sustain Energy Rev 2016;60:317–29.
[374] Kang S, Ye J, Chang J. Recent advances in carbon-based sulfonated catalyst:
preparation and application. Int Rev Chem Eng 2013;5:133–44.
[375] Guo Z, Liu Z, Ye L, Ge K, Zhao T. The production of lignin-phenol-formaldehyde
resin derived carbon fibers stabilized by BN preceramic polymer. Mater Lett
2015;142:49–51.
[376] Kang S, Ye J, Chang J. One step preparation of sulfonated solid catalyst and its
effect in esterification reaction. Chin J Chem Eng 2014;22(4):392–7.
[377] Mumme J, Eckervogt L, Pielert J, Diakité M, Rupp F, Kern J. Hydrothermal car-
bonization of anaerobically digested maize silage. Bioresour Technol
2011;102(19):9255–60.
[378] Ro KS, Cantrell KB, Hunt PG. High-temperature pyrolysis of blended animal
manures for producing renewable energy and value-added biochar. Ind Eng Chem
Res 2010;49(20):10125–31.
[379] Galinato SP, Yoder JK, Granatstein D. The economic value of biochar in crop
production and carbon sequestration. Energy Policy 2010;39(10):6344–50.
[380] Lehmann J. A handful of carbon. Nature 2007;447(7141):143.
[381] Sevilla M, Maciá-Agulló JA, Fuertes AB. Hydrothermal carbonization of biomass as
a route for the sequestration of CO2: chemical and structural properties of the
carbonized products. Biomass- Bioenergy 2011;35(7):3152–9.
[382] Vaccari FP, Baronti S, Lugato E, Genesio L, Castaldi S, Fornasier F, Miglietta F.
Biochar as a strategy to sequester carbon and increase yield in durum wheat. Eur J
Agron 2011;34(4):231–8.
[383] Liu Z, Zhang FS. Removal of copper (II) and phenol from aqueous solution using
porous carbons derived from hydrothermal chars. Desalination
2011;267(1):101–6.
[384] Sun K, Ro K, Guo M, Novak J, Mashayekhi H, Xing B. Sorption of bisphenol A, 17α-
ethinyl estradiol and phenanthrene on thermally and hydrothermally produced
biochars. Bioresour Technol 2011;102(10):5757–63.
[385] Dumroese RK, Heiskanen J, Englund K, Tervahauta A. Pelleted biochar: chemical
and physical properties show potential use as a substrate in container nurseries.
Biomass- Bioenergy 2011;35(5):2018–27.
[386] Wang LL, Wang XF, Zou B, Ma XY, Qu YN, Rong CG, Li Y, Su Y, Wang ZC.
Preparation of carbon black from rice husk by hydrolysis, carbonization and
pyrolysis. Bioresour Technol 2011;102(17):8220–4.