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Energy xxx (2014) 1e6

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Energy
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The effect of hemicelluloses and lignin on acid hydrolysis of cellulose


S.-Y. Yoon a, S.-H. Han b, S.-J. Shin a, *
a
b

Department of Wood and Paper Science, Chungbuk National University, Cheongju 361-763, South Korea
Department of Forest Genetic Resources, Korea Forest Research Institute, Suwon 441-350, South Korea

a r t i c l e i n f o

a b s t r a c t

Article history:
Received 13 September 2013
Received in revised form
10 January 2014
Accepted 29 January 2014
Available online xxx

In acid hydrolysis of plant biomass, polysaccharides are converted to monosaccharides, which is basic
raw material for biorenery for fermentation based process. These monosaccharides, however, are not
stable in acidic reaction medium, and are converted to organic acids via furans. Impact of hemicelluloses
and lignin on acid hydrolysis of cellulose was investigated to focus on monosaccharide production with
different degrees of cellulose purity. Two-step concentrated sulphuric acid process was applied to
biomass for monosaccharide conversion. Kinetics of cellulose hydrolysis was analysed using 1H NMR
spectroscopy. Higher reaction temperature in secondary hydrolysis caused severe degradation of the
monosaccharides. In pure and holocellulose, further reaction of glucose in acidic reaction medium
produced formic acid and levulinic acid. However, lignocellulosic biomass generated much less formic
acid and levulinic acid under the same reaction condition. Humin (or pseudo-lignin) was also formed by
the condensation of lignin and furans from monosaccharides in acidic reaction condition. Thus, the
fermentation inhibitors, furans and formic acid, were generated in low quantities by lignocellulosic
biomass than by delignied biomass such as pure cellulose or holocellulose.
2014 Elsevier Ltd. All rights reserved.

Keywords:
Acid hydrolysis
Cellulose
Xylan
Lignin
Formic acid
1
H NMR

1. Introduction
More than 400 thousand years, re has been used as energy
with lignocellulosic biomass as raw material. Lignocellulosic
biomass is formed by glucose, which is converted from carbon dioxide and water at chlorophyll in plant leaf with sunlight energy.
Since civilization, cooking and heating have used wood as solid
fuels until replaced by coal and petroleum-based products. However, global warming and depleting of crude oils lead to more
attraction on renewable energy.
Although renewable energy is an important energy resource in
many countries, less than 15% of primary energy is supplied by
renewable resources [1e3]. Technological progress and global
warming have led to increased application of renewable energies in
modern world. Energy which does not increase the carbon dioxide
in the atmosphere and can be produced by continuously is called as
renewable energy. Geo-thermal, wind, tidal, photovoltalic and
biomass energy is classied as renewable energy category.
Biomass is an important renewable resource that can replace
petroleum-based energy and chemicals [4e6]. Cellulose is the most
abundant organic material and is produced by dehydration and

* Corresponding author. Tel.: 82 432612542; fax: 82 432732241.


E-mail address: soojshin@cbnu.ac.kr (S.-J. Shin).

condensation reaction of glucose generated by photosynthesis.


Lignocellulosic biomass composed of cellulose, hemicelluloses and
lignin as major components with small amount of extractives as
minor components. Cellulose and hemicelluloses are formed by
polymerization of monosaccharides with dehydration and
condensation reaction from glucose or other monosaccharides.
Cellulose is homopolymer, composed of glucose with b-1,4glucosidic linkages. But, hemicelluloses are composed with
different monosaccharides. In softwood, main hemicellulose is
glucomannan, which backbone is glucose and mannose with
galactose or acetic acid as side chains. In hardwood, xylan is main
hemicellulose, main back is composed with xylose with b-1,4xylosici linkage with acetic acid and 4-O-methyglucuronic acid as
side chains. Lignin is totally different chemical structure with
phenypropanoid repeating unit with three dimensional amorphous
network structures.
Cellulose in plant biomass is a strength-enforcing bre in the
composite structure of cell wall along with the other main cell wall
components, hemicelluloses and lignin. Cellulose is depolymerized
by cellulases, which are produced by wood rot fungi and wood rot
bacteria. In addition, acids can catalyse the depolymerization by
hydrolysis reaction. Hemicelluloses, the heterogeneous polysaccharides in plants, are depolymerized to galactose, glucose, and
mannose from (galacto)glucomannan, and xylose from glucuronoxylan. Lignin, other main component in plant biomass, is

http://dx.doi.org/10.1016/j.energy.2014.01.104
0360-5442/ 2014 Elsevier Ltd. All rights reserved.

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composed of phenylpropanoid units, which cannot produce


monosaccharides by hydrolysis.
Conversion of lignocellulosic biomass to monosaccharides is the
key step for liquid fuel production via biochemical process.
Monosaccharides hydrolysed by enzymes or acids are fermented to
alcohol, which can be used as transportation fuel, replacing gasoline or diesel depending on further process.
For enzymatic saccharication of plant biomass, proper
pre-treatment is an essential step for higher conversion of polysaccharides to monosaccharides. Due to complex structural properties of plant biomass, only 10e20% of polysaccharides are
converted to monosaccharides by commercial cellulases without
pre-treatment [7]. Physical and/or chemical pre-treatments
breakdown the complex biomass structure, which enables cellulases to access the substrate to hydrolyse. Xylan removal [8,9],
lignin removal [10,11], or cellulose decrystallisation [12,13] are the
methods for breaking down the complex plant biomass structure.
At higher temperature, diluted sulphuric or hydrochloric acid
can hydrolyse the polysaccharides to monosaccharides. Diluted
acid hydrolysis process needs only few percent of acid, which
resulted in easier process for acid treatment. At low pH and high
temperature, produced monosaccharides are not stable, which
resulted in the further reaction to formic acid via furan
intermediates.
Concentrated acid hydrolysis process is a two-step process;
concentrated acid decrystallises cellulose to less crystallized oligosaccharides followed by less concentrated and higher reaction
temperature for converting decrystallised oligosaccharides to
monosaccharides [14,15]. Historically, concentrated acid hydrolysis
of polysaccharides started in 1883 with the invention of the method
to dissolve and hydrolyse cotton cellulose with concentrated sulphuric acid. Concentrated sulphuric acid disrupts the crystalline
structure of cellulose by interfering with hydrogen bonds, breaking
it down to oligosaccharides.
Advantages of concentrated acid hydrolysis process are higher
conversion from polysaccharides to monosaccharides with minimum formation of reaction by-products with careful control of
reaction conditions, no limitations of biomass resources, and long
history of commercial trials. Main disadvantages of this process are
higher usages of acids than dilute acid hydrolysis process and
sensitivity to moisture content of biomass raw materials. Concentrated sulphuric acid hydrolysis was applied at the Northern
Regional Research Laboratory in Peoria, Illinois in the USA, in Bozen
in Italy, and in Hokkaido in Japan during or after the Second World
War. The key factor in these processes is effective mixing of plant
biomass and sulphuric acid to keep the sulphuric acid usage minimum. To use monosaccharides as industrial raw materials, removal
of sulphuric acid is essential [16]. To separate sulphuric acid from
monosaccharide solution, neutralization with calcium hydroxide
was applied in the USA and Italy. In the method used in Hokkaido,
sulphuric acid was removed by diffusion dialysis.
Separation of acid from acid hydrolysates is the one of the big
obstacle in applying the acid hydrolysis technology into ethanol
mass production based on lignocellulosic biomass. Formation of
insoluble salts [5], chromatographic removal or dialysis techniques
can be applied [17,18]. Sulphate anion can form insoluble salt with
calcium cation as gypsum. During formation of gypsum, parts of
monosaccharides are adsorbed the surface of gypsum, which
caused the loss of monosacharides after recovered sugar solution.
Ion-exchange chromatography can be applied for sulphuric acid
removal from acid hydrolysates. Column packing materials are selective for binding anions or cations in the eluent depending on
their chemical structure. Sulphuric acid in acid hydrolysates can be
separated by anion exchange or cation exchange resins. Commercial or pilot-plant application of ion-exchange chromatography for

sulphuric acid removal from acid hydrolysates was applied by


BlueFire Renewables and Masada Resource Group.
Monosaccharide produced from lignocellulosic biomass can be
converted to bioalcohol, ethanol or butanol based on fermentation
microorganisms. By Saccharomyces cerevisiae or Scheffersomyces
stipitis (former known as Pichia stipitis) can convert monosaccharides to ethanol. Butanol can be formed by acetonee
butanoleethanol fermentation by Clostridium acetobutylicum or
Clostridium beijerinckii. Simultaneous saccharication and cofermentation process showed the best results for energy consumption
point with water recycling for bioethanol production from lignocellulosic raw material [19]. In bioethanol production from
switchgrass, required energy as the use of natural resources, electricity, fossil fuels, and human-derived serves and goods was a
quarter of the produced ethanol [20].
Produced bioalcohol can replace the gasoline for transportation
fuel. Due to better antiknock characteristics, ethanol has advantage
over gasoline. Because of ethanol can be mixed with water, blend
with ethanol in gasoline resulted in corrosions on the mechanical
components made by copper, brass or aluminium containing parts
[21]. The other problem from ethanol is that ethanol can react with
most rubber and this cause a jam in the fuel line [22]. Technical
resolutions for previous mentions are needed for replacement from
gasoline to ethanol. For biobutanol, miscibility with water is very
limited and no reaction with metal lead to better fuel properties
than ethanol. With replacement gasoline to butanol, there is no
trouble in engine with not high enough octane value [23,24].
Careful control of reaction conditions is a key step for concentrated acid hydrolysis based biorenery process. The focus of this
work is the conversion of cellulose to glucose by concentrated
sulphuric acid hydrolysis with maximum glucose yield and minimum formation of glucose degradation products focused on the
second acid hydrolysis. Additionally, the impact of xylan and lignin
on cellulose acid hydrolysis was investigated.
2. Materials and methods
2.1. Materials
Cotton cellulose was purchased as sheet form, and cut and
milled to 40e60 mesh size. Avicel cellulose was purchase from
SigmaeAldrich. Willow biomass (Salix caprea) was supplied by
Korea Forest Research Institute, Department of Forest Genetic Resources, Suwon, South Korea as air-dried biomass. Preparation of
willow biomass was detailed describes by Han et al. [4]. Supplied
willow biomass was cut and milled to less than 20-mesh by Willy
mill.
2.2. Methods
2.2.1. Compositional analysis of willow biomass and avicel cellulose
Organic solvent soluble extractives and hot-water soluble extractives contents were analysed based on the United States National Renewable Energy Laboratory (NREL) Procedure except
acetone was used instead of ethanol-benzene solvents (http://
www.nrel.gov/biomass/analytical_procedures.html). Acetone and
hot-water extracted goat willow were used for Klason lignin
determination and carbohydrate compositional analysis. Klason
lignin content was analysed by NREL procedure but carbohydrate
composition was analysed by acid hydrolysis followed by 1H NMR
spectroscopy [25].
2.2.2. Acid hydrolysis
Cellulose containing samples (70 mg, oven-dried) were hydrolysed with 72% sulphuric acid (0.8 ml) for 1 h at 30  C for rst

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hydrolysis and those hydrolysed were diluted to 4% acid with 3.2 ml


of deuterium oxide (D2O) for second hydrolysis at different reaction
temperatures and times. The hydrolysis solutions were cooled,
ltered through a lter paper, and the liquid fraction was used for
determination of glucose, 5-hydroxymethylfurfural (5-HMF), and
formic acid by 1H NMR spectroscopy. Prepared ltered hydrolysates
were put into NMR tubes without any neutralization or
derivatization.
2.2.3. Quantitative analysis using 1H NMR spectroscopy
Acidic ltrates were analysed by Bruker AVANCE NMR Spectrometer (500 MHz for proton). The NMR data were processed by
Topspin software to resolve and integrate the NMR peaks.
Anomeric hydrogen peak regions (4.4e5.4 ppm) in NMR spectra
were integrated for carbohydrate compositional analysis. NMR
operation conditions followed as described in literature [25]. Due to
the hydrogen exchange with hydroxyl groups in monosaccharides,
HDO (water replaced by one hydrogen to deuterium) was formed
that could interfere with anomeric hydrogen peak assignment,
which was solved by adjusting the acidity of analysis solution by
adding sulphuric acid. Formic acid and 5-HMF were analysed by
integration of aromatic hydrogen peak region [26,27].
Spectra of protons in monosaccharides are very complicated
with similar chemical shift values in 1H NMR spectrophic analysis.
However, anomeric hydrogens show relatively downeld chemical
shifts and separate at different chemical shifts in different monosaccharides, which allows the quantitative analysis of monosaccharide composition by 1H NMR spectroscopy. In Fig. 1, NMR
spectrum of anomeric hydrogen of glucose was shown as alpha and
beta forms. L-Rhamnose was used as internal standard for the
quantitative analysis of residual glucose in acidic medium. In Fig. 2,
NMR spectra of formic acid and 5-HMF appear in aromatic
hydrogen region. Hydrogen peak integration of 5-HMF, formic acid,
anomeric peaks of glucose can quantitatively analyse the conversion from cellulose to glucose and glucose degradation.
3. Results and discussion
3.1. Quantitative analysis of acid hydrolysis by 1H NMR
spectroscopy
In concentrated acid hydrolysis, cellulose was converted to
oligomers at rst stage of hydrolysis, and oligomers were converted
to glucose at second stage of hydrolysis. First stage of hydrolysis
was run at mild temperature with high acid concentration, and

Fig 2. 1H NMR spectrum of glucose degraded products at downeld hydrogen region.

higher temperature with mild acid concentration was used at


second stage of acid hydrolysis. During the second stage of hydrolysis, part of glucose was converted to levulinic acid and formic acid
via 5-HMF.
The liberated monosaccharides and their further reaction
products can be separated and quantitatively analysed by highperformance liquid chromatography (HPLC) or ion chromatography (IC) without derivatization. With derivatisation to alditol
acetate form, gas chromatography (GC) can be used for separation
and quantitative analysis. Disadvantages of chromatographic
analysis are long analysis time, purging the column, adjusting pH
for column packing materials, and quantitative analysis with
standard sample runs, or lengthy works for derivatization (for GC).
NMR methods have been used for chemical composition, stereochemistry, and mutarotation kinetics of monosaccharides in
solution state for many years [28]. NMR spectra of monosaccharides developed for compositional characterization of polysaccharides [29]. During polysaccharide to monosaccharide
conversion, parts of monosaccharides further react to generate
formic acid and levulinic acid via furan compounds [30].
Chemical shifts of levulinic acid protons are between 2.0 and
2.8 ppm [30], which is quite separated from anomeric and aromatic
hydrogen regions. Since 5-HMF converts to formic acid and levulinic acid in equal amounts, formic acid was quantitatively analysed
to evaluate 5-HMF conversion in this work.
With this quantitative analysis method, conversion of fructose
to 5-HMF was successfully analysed [31]. In this work, cellulose to
glucose conversion with side reaction of formation of formic and
levulinic acid, furans were quantitatively analysed by 1H NMR
spectroscopic method.
3.2. Compositional analysis of willow and alpha-cellulose

Fig 1. 1H NMR spectrum of glucose at anomeric hydrogen region.

Plant lignocellulosic biomass is photosynthesised by carbon


dioxide and water with energy from sunlight. Original form of
product is glucose, which polymerises to cellulose or is converted
to other monosaccharides such as mannose, galactose, arabinose,
and xylose by epimerization and decarboxylation reactions, which
form hemicelluloses. Phenylpropanoid compounds, which are the
building blocks of lignin, are formed from erythrose and phosphoeneolpyruvate. Softwood biomass has glucomannan and lignin

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as main components, compared with hardwood or annual plants


that have cellulose, xylan, and lignin as major constituents. During
acid hydrolysis of plant biomass, cellulose, glucomannan, xylan,
and lignin reacted by acid. Main reaction of polysaccharides is hydrolysis but lignin is condensed by acid, which can be separated by
ltration process.
Due to complexity in the chemistry of wood biomass component, chemical compositions vary not only among different tree
species but also depend on the morphological elements involved.
The hydrophobic extractives consist mainly of fats, waxes, terpenoids, and long aliphatic alcohols. Terpenoids, resin acids, and
sterols are located in the resin canals present in the cork cells and in
the pathological exudates of wounded part. The main hemicellulose in the hardwood is O-acetyl-4-O-methyl-glucuronoxylan,
varying within the range 15e30% depending on the wood species.
This xylan consists of a b-D-xylopyronose backbone with 1 2 4
linkages. Approximately seven acetyl groups are attached at the C-2
or C-3 positions per ten xylopyranose units. Additionally, one 4-Omethylglucuronic acid group is linked per 8e20 xylopyranose
backbone units by an alpha-1 2 2-linkage [32]. Acetyl groups on
the xylopyranose backbone are hydrolysed to acetic acid in acidic or
alkaline media, and are the main acetic acid source in acidic hydrolysates [32].
Lignins in woody biomass are polymerized mainly from three
monomers called monolignols, namely, p-coumaryl alcohol, coniferyl alcohol, and sinapyl alcohol. The difference between these
three monomers is the number of methoxy groups in the phenylpropanoid structure. Coniferyl alcohol has one methoxy group at
the C-5 position, which is main lignin component in softwood.
Sinapyl alcohol has two methoxy groups at the C-3 and C-5 positions, part of main components in hardwood with conifer alcohol.
P-coumaryl alcohol contains no methoxy groups, which mainly
located in grass. In the lignin biosynthesis process, the position of
the methoxy group is not the active site in the lignin polymerization. Hence, when there are less methoxy groups contained in
softwood lignin, it is more condensed and has a higher molecular
weight than that of hardwood.
In this work, impact of xylan and lignin on cellulose hydrolysis
was investigated for higher yield of monosaccharides and less
formation of fermentation inhibitors. Based on chemical composition analysis, Avicel cellulose consisted of cellulose and xylan as
shown in Table 1. Chemical composition of goat willow is also listed
in Table 1. Like other plant biomass, goat willow has cellulose,
hemicelluloses, and lignin as main components with other extractives as minor components (Table 1). With these results, Avicel
cellulose is the model for holocellulose (which is a cellulosee
hemicelluloses complex) and goat willow is the model for hardwood biomass, which contains cellulose, hemicelluloses, and
lignin. Main hemicellulose in goat willow is xylan, which is a
common constituent of hardwood biomass, compared with glucomannan as the main hemicellulose in softwood biomass.

trend leads to formation of crystalline regions in cellulose chains.


Part of cellulose is not highly ordered region, which called as
amorphous regions. Amorphous cellulose near the surface is
hydrolysed readily by acid hydrolysis [33]. Crystalline structure of
microbril bundles cannot penetrate by acid in mild acid hydrolysis
at elevated temperature, which resulted in cellulose nanocrystal.
Holocellulose (cellulose with hemicelluloses) or goat willow
(hardwood) has more complex structure than pure cotton cellulose,
which makes more complex reaction in concentrated sulphuric
acid hydrolysis of polysaccharides. With structural complexity
(crystalline and amorphous regions within cellulose) and complex
structure of lignocellulosic (cellulose, hemicelluloses and lignin),
hydrolysis of cellulose to glucose is not simple and clear reaction
pathway. Unstability of monosaccharides formed by acid hydrolysis
in reaction medium makes the reaction more complicated.
During acid hydrolysis, most of cellulose is converted to glucose
by acid-catalysed hydrolysis in this work. However, the glucose
formed is not stable in acidic medium and degrades to levulinic acid
and formic acid via 5-HMF. Reaction time, temperature, and acid
concentration control the degradation of glucose to organic acids.
Reaction temperature of second hydrolysis is the main variable
for stability of formed glucose. In Fig. 3, most of glucose was stable
at 100  C but part of glucose was converted to formic acid and
levulinic acid via 5-HMF at 120  C (in Fig. 4). Formed formic acid
can inhibit the acetoneebutanoleethanol fermentation by C. acetobutylicum [34].
With different cellulose raw materials, especially goat willow
biomass, cellulose hydrolysis to glucose had a different pattern.
Complex cell wall structure with xylan and lignin hinders cellulose
to oligosaccharide conversion, leading to more glucose formation
with increasing reaction time (in Fig. 5) as in goat willow, which has
cellulose, xylan, and lignin as major biomass components. At higher
reaction temperature of second hydrolysis, glucose was converted
to other products (formic acid, levulinic acid, and 5-HMF). Xylan
reaction products may facilitate glucose degradation (in Fig. 6).
Due to instability of glucose in acidic medium, part of glucose is
degraded to formic acid and levulinic acid via 5-HMF pathway. At
mild second hydrolysis reaction temperature, formation of levulinic
and formic acids was less than 4% of glucose. Glucose from goat
willow formed less formic acid than pure cellulose or holocellulose
(in Fig. 7 and Fig. 8). In acid hydrolysis, xylan hydrolysed to xylose
faster than the hydrolysis of cellulose to glucose [26]. This trend
was more obvious at higher reaction temperature of second hydrolysis reaction (in Fig. 8). More formic acid was formed from
avicellulose (cellulose and xylan) than pure cellulose, which might
come from accelerating the glucose degradation from xylan hydrolysis products.

3.3. Cellulose to glucose hydrolysis


Due to their chemical structure and spatial conformation, the
cellulose chains tend to aggregate to high order structure. This

Table 1
Chemical composition of avicell cellulose and goat willow (unit: %).

Avicell cellulose
Goat willow

Acetone
soluble
extractives

Hot-water
soluble
extractives

Lignin

Celluose

Xylan

e
0.8

e
11.4

e
18.3

85.0
51.0

15.0
18.5

Fig 3. Conversion from cellulose to glucose with different second hydrolysis reaction
temperature.

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S.-Y. Yoon et al. / Energy xxx (2014) 1e6

Fig 4. Conversion from cellulose to formic acid with different second hydrolysis reaction temperature.

Fig 5. Different respond to acid hydrolysis with different cellulose raw material (reaction temperature of second hydrolysis with 100  C).

Impact of lignin on acid hydrolysis of cellulose was investigated.


Presence of lignin in goat willow slowed down the acid hydrolysis
of cellulose by the acid content (in Fig. 5). In cellulose and holocellulose, increased second hydrolysis reaction time led to more
degradation of produced glucose. However, in goat willow biomass,
incomplete conversion of cellulose to oligosaccharides led to
increased glucose concentration with increasing second hydrolysis
reaction time in second hydrolysis. Part of incompletely converted
oligosaccharides was converted to glucose on increasing reaction
time at second hydrolysis stage. When the reaction temperature of

Fig 6. Different respond to acid hydrolysis with different cellulose raw material (reaction temperature of second hydrolysis with 120  C).

Fig 7. Conversion from cellulose to formic acid with different cellulose raw material
(reaction temperature of second hydrolysis with 100  C).

second hydrolysis was increased to 120  C, increasing reaction time


led to more degradation of glucose from cellulose, holocellulose,
and goat willow biomass.
Conversions from glucose to formic acid and levulinic acid via 5HMF or from xylose to formic acid via furfural occur in aqueous
acidic medium. Careful control of reaction condition can minimize
these conversion reactions. Formation of formic acid was less than
4% at 100  C second hydrolysis temperature. However, at second
reaction temperature of 120  C, formation of formic acid was signicant and quite different with different cellulose purity (in Fig. 8).
More glucose was degraded in holocellulose and goat willow than
pure cellulose (in Fig. 6). Formation of formic acid was not proportional to degraded glucose. More than 25% of glucose was
converted to formic acid in holocellulose, which was quite higher
than the 15% conversion of glucose to formic acid in pure cellulose
(in Fig 8). However, lignin in goat willow prevented the formation
of levulinic acid and formic acid. As shown in Fig 9, part of glucose
or 5-HMF can be converted to humins and these reactions are
facilitated by the presence of lignin [35,36].
4. Conclusions
The effect of second hydrolysis reaction condition on concentrated sulphuric acid to cellulose to glucose conversion was investigated to focus on reaction temperature and time. Also, the effect
of hemicelluloses and lignin on acid hydrolysis of cellulose was
investigated to focus on the monosaccharide production with

Fig 8. Conversion from cellulose to formic acid with different cellulose raw material
(reaction temperature of second hydrolysis with 120  C).

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Fig 9. Degradation of glucose to levulinic and formic acid.

different degrees of cellulose purity and formation of possible


fermentation inhibitors.
Higher reaction temperature in second hydrolysis caused the
severe degradation of formed monosaccharides at the range of
100e120  C range. For maximum glucose yield, reaction temperature of second hydrolysis should keep at 100  C for hindering
glucose degradation to organic acids via furans.
In pure and holocellulose (cellulose and xylan), more formic acid
was formed by further reaction of glucose in acidic reaction medium to formic acid and levulinic acid at 120  C. However, lignocellulosic biomass (goat willow, which contained cellulose, xylan
and lignin) formed much less formic acid and levulinic acid at the
same reaction condition. So, fermentation inhibitors, furans and
formic acid, were generated less by lignocellulosic biomass than
delignied biomass (avicell cellulose) or pure cellulose.
Acknowledgements
This research was supported by Basic Science Research Program
through the National Research Foundation of Korea (NRF) funded
by the Ministry of Education (2013R1A1A2004658).
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Please cite this article in press as: Yoon S-Y, et al., The effect of hemicelluloses and lignin on acid hydrolysis of cellulose, Energy (2014), http://
dx.doi.org/10.1016/j.energy.2014.01.104

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