Bioresource Technology 153 (2014) 379382

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Bioresource Technology
journal homepage: www.elsevier.com/locate/biortech

Short Communication

Thermogravimetric analysis of lignocellulosic biomass with ionic liquid

pretreatment
Jiafu Zhang b, Lu Feng b, Dan Wang a, Ruihong Zhang b,c, Guangqing Liu b,, Gang Cheng a,
a

Beijing Key Laboratory of Bioprocess, Beijing University of Chemical Technology, Beijing 100029, China
Biomass Energy and Environmental Engineering Research Center, Beijing University of Chemical Technology, Beijing 100029, China
c
Department of Biological and Agricultural Engineering, University of California, Davis, CA 95616, USA
b

h i g h l i g h t s
 Thermogravimetric analysis (TGA) of ionic liquid (IL) pretreated biomass performed.
 Insight into the IL pretreatment revealed by TGA discussed.
 Cleavage of side chains and degradation of backbone of xylan detected.

a r t i c l e

i n f o

Article history:
Received 5 September 2013
Received in revised form 30 November 2013
Accepted 2 December 2013
Available online 11 December 2013
Keywords:
Ionic liquid pretreatment
Biomass
TGA

a b s t r a c t
Thermogravimetry (TG) was employed to understand the interactions between ionic liquids (ILs) and biomass components. The thermal decomposition proles of several biomass samples with IL pretreatment
at different temperatures were studied by TG. Samples of Avicel (PH101), xylan from beechwood and
alkaline lignin as well as switchgrass and corn stover were pretreated using 1-butyl-3-methylimidazolium acetate ([C4mim][OAc]) at temperatures of 50130 C for 6 h. Analysis of TG data provided insight
into the mode of degradation of xylan and lignin in [C4mim][OAc]. Pretreated Avicel samples exhibited
higher decomposition temperatures due to transformation from cellulose I into cellulose II, while
samples of switchgrass and corn stover showed an improved thermal stability as a result of removal of
minerals by [C4mim][OAc]. More intensive pretreatment produced decreased thermal resistance due
to degradation of biomass components and decrystallization.
2013 Elsevier Ltd. All rights reserved.

1. Introduction
The conversion of lignocellulosic biomass into other valuable
forms of energy has become a global research focus (Menon and
Rao, 2012). A biological conversion process of lignocellulosic
biomass into advanced biofuels typically consists of three steps:
pretreatment, saccharication and fermentation. Plant cell walls
are composed of crystalline cellulose bers embedded in a solid
matrix of lignin and hemicelluloses that impedes enzyme and
microbial accessibility. Among various pretreatment methods
developed to mitigate biomass recalcitrance for enzymatic hydrolysis, the ionic liquid (IL) pretreatment receives special attentions
due to the ability of ILs to dissolve cellulose under relatively mild
conditions (Menon and Rao, 2012). IL pretreatment has been reported to increase the surface area, decrease cellulose crystallinity
Corresponding authors. Tel.: +86 13426369755 (G. Liu), +86 13693276690
(G. Cheng).
E-mail addresses: guangqing.liu@gmail.com (G. Liu), chenggang@mail.buct.
edu.cn (G. Cheng).
0960-8524/$ - see front matter 2013 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.biortech.2013.12.004

and lignin content, which all contribute positively to the improved

hydrolysis efciency (Singh et al., 2013). However, since plant cell
walls are of multi-components and spatially heterogeneous, the
interactions of ILs with plant cell walls are essentially heterogeneous reactions, which are not fully understood yet.
Thermogravimetry (TG) and differential thermogravimetry
(DTG) analysis of lignocellulosic biomass provide information on
the thermal decomposition proles of respective components
(Marcilla et al., 2013), which can be used to follow the physiochemical changes that occur during pretreatment processes
(Caballero et al., 1997; Chen et al., 2010). Analysis of the TGDTG
curves of olive stones samples treated by 72% sulphuric acid demonstrated that hemicellulose was separated from cellulose and
lignin without signicantly altering the structure of them
(Caballero et al., 1997). To date, however, there are only a few studies which utilized TGDTG data of biomass samples to investigate
the IL pretreatment process (Casas et al., 2013; Labb et al., 2012;
Moniruzzaman and Ono, 2013; Muhammad et al., 2012; Singh
et al., 2013; Wen et al., 2012). Decreased biomass thermal stability
was reported due to changes in cellulose crystal structure and

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J. Zhang et al. / Bioresource Technology 153 (2014) 379382

degradation of biomass components after IL pretreatment (Labb

et al., 2012; Singh et al., 2013). The decreased resistance to thermal
decomposition was also correlated to reduced biomass recalcitrance to enzymatic hydrolysis (Labb et al., 2012). However,
regenerated cellulose or biomass samples after IL pretreatment
usually consist of cellulose II lattice (Cheng et al., 2012b), which
was shown be thermally more stable than native cellulose I lattice
(Gao et al., 2011; Yue et al., 2012). Therefore, a closer look at the TG
data of IL-pretreated biomass is needed. In this work, a systematic
TG investigation of the impact of IL pretreatment on cellulose,
xylan and lignin as well as on switchgrass and Corn stover samples
were carried out. Our objective of this work was to assess the
impact of IL pretreatment on biomass samples by means of
thermogravimetric analysis.
2. Methods
2.1. Materials and preparation
Swithcgrass was harvested from a local farm of Tong Liao City of
inner Mongolia, China. Corn stover was harvested from a local farm
of Yan Qing City of Beijing, China. 1-Butyl-3-methylimidazolium
acetate ([C4mim][OAc]) was purchased from Lanzhou Institute of
Chemical Physics, China. Biomass samples were ground and sieved
( 40/+60 cut). Avicel PH101 (lot# BCBJ4592V), xylan from beechwood (lot#BCBH7762V), alkaline lignin (lot#MKBJ0452V) were
purchased from SigmaAldrich.
2.2. Ionic liquid pretreatment
Biomass samples were pretreated in [C4mim][OAc] at 5 wt.%. A
biomass solution was prepared by combining 0.5 g of biomass with
9.5 g [C4mim][OAc] in a 50 mL glass centrifuge tube. The mixture
was heated in an oil bath without stirring at different temperatures, varying from 50 to 130 C for 6 h. All experiments were conducted in triplicates. After 6 h incubation, 35 mL of tap water
(ethanol for precipitation of xylan) was added into the biomass/
[C4mim][OAc] slurry. The resultant slurry was centrifuged at
10,000g for 10 min. The supernatant containing IL was removed,
and the precipitate was washed at least four times with water.
The recovered solids were dried in an oven at 105 C for 24 h and
then stored in a sealed plastic bag at 5 C for analysis. The weight
loss percentage of lignin after pretreatment was 42 2 and it was
16 2 for xylan. The weight loss percentage of cellulose was 11 1
for pretreatment at 50 and 90 C and it was 51 3 for pretreatment
at 130 C. The weight loss percentage of switchgass was 25 5 for
pretreatment at 50 and 90 C and it was 60 10 for pretreatment at
130 C. The weight loss percentage of corn stover was 38 7.
2.3. XRD measurement
Pretreated and untreated samples of cellulose were analyzed by
XRD. Samples from three pretreatment trials were mixed together
for XRD analysis. The samples were scanned on a D8 ADVANCE
diffractometer equipped with a sealed tube Cu Ka source. Scans
were collected from 2h = 5 to 60 with step size of 0.03 at 4 s
per step.
2.4. TG measurement
Thermal analysis was performed by using a thermogravimetric
analyzer (DTG-60A, SHIMADZU). Samples of 510 mg placed in
alumina crucibles (70 lL) were heated from 50 to 800 C at a rate
of 10 C/min in the presence of nitrogen (30 ml/min).

3. Results and discussion

TG measures the instantaneous biomass weight at specic
temperatures as biomass temperature is increased. Assessment of
cellulose, hemicellulose and lignin individual components could
shed insights on the mechanisms contributing to IL pretreatment
of biomass. Cellulose thermal decomposition curves for untreated
and IL-pretreated samples are shown in Fig. 1a. DTG data of untreated cellulose show a single peak with a peak value (Tmax) of
335 C. The value of Tmax derived from TGA data represents the
temperature at which the maximum decomposition rate occurs.
It is used to evaluate the impact of IL pretreatment on the thermal
stability of biomass samples. The untreated celluose (Avicel
PH101) has a cellulose I structure with a crystallinity index (CrI)
of 0.72. Pretreatment of cellulose samples in [C4mim][OAc] at temperatures of 50, 90 and 130 C leads to two peaks on the thermolgrams. At a solid loading of 5 wt.%, cellulose samples are believed
to be fully dissolved in [C4mim][OAc] during pretreatment process,
suggested by visual observation of a clear solution. They transform
into a mixture of cellulose II and amorphous cellulose upon addition with water (Cheng et al., 2012b). The value of CrI of pretreated
cellulose samples is around 0.60 (Fig. S1). After pretreatment at
50 C, the low-temperature peak has a Tmax of 277 C, corresponding to the degradation of amorphous cellulose (Singh et al., 2013).
The high-temperature peak corresponds to degradation of cellulos
II lattice. It have a Tmax of 341 C, which is higher than that of unteated cellulose. The improved thermal stability of cellulose II was
reported before. A study of regenerated bacterial cellulose bers
prepared by the NMMO
H2O process showed an improved resistance to thermal degradation (Gao et al., 2011). The regenerated
bacterial cellulose had a cellulose II structure with a CrI of 0.61.
A comparative investigation of cellulose nano-crystals from native
and mercerized cotton bers also found that cellulose II had better
thermal stability (Yue et al., 2012). However, studies of regenerated celluose prepared from IL pretreatment usually reported decreased decompostion temperatures (Singh et al., 2013; Zhang
et al., 2010). In those work it is noticed that the regenerated cellulose either had a low CrI or was depolymerized signicantly. The
value of CrI of IL-treated cellulose in current study is higher than
those of previously reported. After pretreatment at 130 C, the Tmax
shifted to a lower temperature due to depolymerization of cellulose chains. It is also noted that the weight loss percentage of cellulose after pretreatment at 130 C was about 50, which offered
additional evidence of cellulose degradation. The IL pretreatment
usually changes biomass particle sizes, which may also impact
the thermal degradation behavior. However, it was shown that
the particle size did not change the Tmax of oil palm shell
(Luangkiattikhun et al., 2008) and olive stones (Marcilla et al.,
2013). It affected only the solid residue obtained. The particle size
of oil palm shell was in the range of 0.361.40 mm and of olive
stones was in the range of 0.213.5 mm in those studies.
Xylan is the major component of hemicellulose. Untreated xylan exhibits two peaks on the DTG curve (Fig. 1b). It was suggested
that the low-temperature peak corresponded to degradation of
side chains and the other one was due to degradation of the backbone (Sanchez-Silva et al., 2012). As shown in Fig. 1b, the low-temperature peak gradually disappears with increasing pretreatment
temperature, suggesting that IL pretreatment caused cleavage of
the side chains of xylan. A small shift to lower temperatures of
the high-temperature peak is also observed, indicating degradation
of the backbone. The observed degradation of xylan after IL pretreatment is consistent with literature reports (Labb et al.,
2012; Xu et al., 2012). Under mild pretreatment temperatures
(6080 C), [C2mim][OAc] was shown to deacetylate hemicelluose
of yellow poplar (Labb et al., 2012). At temperatures above 130 C,

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381

Fig. 1. DTG curves of (a) Avicel, (b) xylan and (c) alkaline lignin pretreated in [C4mim][OAc] at 50 C, 90 C, 130 C for 6 h. The solid loading was 5 wt.% for all the samples. The
insets in (a), (b) and (c) present low-temperature and high-temperature peaks positions (abbreviated as TmaxL and TmaxH, respectively).

Fig. 2. DTG curves of (a) switchgrass, (b) corn stover pretreated in [C4mim][OAc] at 50 C, 70 C, 90 C, 130 C for 6 h. (c) Tmax of pseudo cellulose and hemicelluloses as a
function of pretreatment temperature. (d) Relative percentage of pseudo hemicelluloses degraded as a function of pretreatment temperature.

signicant xylan degradation was reported for corn stover samples

preteated in [C2mim][OAc] (Xu et al., 2012).
Lignin decomposes in a wide temperature range (300500 C)
due to its heterogeneity and lack of a dened primary structure.
The recovery percentage of lignin after pretreatment was close to
60, which is essentially indepedent of temperature. Its weight loss
to IL/water mixture solvents was mainly due to degradation. After
IL pretreatment, the DTG curves of recovered lignin show two narrower peaks (Fig. 1c), which is consistent with a prior study (Singh
et al., 2013). The narrower peak width suggests a more uniform
chemical structure in comparison to untreated lignin. It seems that
the IL pretreatment breaks down lignin and separates them into
fractions with different chemical compositions. A previous small

angle neutron scattering study reported that [C2mim][OAc]treated Kraft lignin formed well-dened aggregates in DMSO while
for untreated lignin the size distribution was very broad (Cheng
et al., 2012a). Small angle neutron scattering data indicated that
degradation of lignin molecules generated nanometer-scale subunits (45 nm) with well-dened shapes (Cheng et al., 2012a). In
addition, the DTG data of lignin pretreated at different temperatures are essentially same, suggesting that increasing temperatures
above 50 C did not further alter the structures of recovered lignin.
Thermal decomposition of lignocellulosic biomass samples often presents two distinct peaks in the DTG due to the degradation
of hemicelluloses, followed by cellulose. Decomposition of lignin
occurs in a wide range that overlaps partially with that of hemicel-

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J. Zhang et al. / Bioresource Technology 153 (2014) 379382

luloses and cellulose. Thermal decomposition data of untreated

and IL-treated switchgrass and corn stover samples are presented
in Fig. 2a and b, respectively. The thermal decomposition peaks
shift to higher temperatures for samples pretreated at 50 C, and
they move back to lower temperatures with further increasing pretreatment temperatures. The DTG peak at 200400 C was mainly
deconvoluted into two pseudo-component peaks (Marcilla et al.,
2013), hemicellulose and cellulose, with their corresponding Tmax
determined. Fig. 2c demonstrates that the Tmax values of pseudohemicellulose (Tmax1) and cellulose peaks (Tmax2) increase after
6 h of pretreatment at 50 C, indicating an improved thermal
stability. They start decreasing with further increasing the temperature, and nally, both values of Tmax1 and Tmax2 become lower
than those of untreated biomass samples after being pretreated
at 130 C. The enhanced thermal stability of biomass samples after
IL pretreatment at lower temperatures is in contrast with literature
reports (Labb et al., 2012; Singh et al., 2013). XRD data of [C4mim][OAc]-treated switchgrass and corn stover samples showed a
decrease in CrI and there was no cellulose II structure formed before 90 C (Zhang et al., 2014). Analysis of IL pretreatment of
extractive free Yellow poplar at 6080 C (Labb et al., 2012) demonstrated that [C2mim][OAc] decreased crystallinity and lowered
both values of Tmax1 and Tmax2. An improved thermal stability
was however reported for cypress wood treated with
[C2mim][OAc] at 80 C for 1 h (Moniruzzaman and Ono, 2013). In
that study, an increase of crystallinity was observed as a result of
partially removing amorphous cellulose by [C2mim][OAc]. After
analyzing the literature data, it becomes apparent that a decrease
of CrI of cellulose I cannot lead to improved thermal stability. A further search into the literature leads to the conclusion that removing minerals in biomass samples by IL pretreatment play an import
role in changing their thermal properties. Biomasses contain mineral matter in various amounts. Removal of minerals in biomass by
washing with HCl or hot water led to a shift of Tmax to higher values
(Marcilla et al., 2013). Imidazolium-based ILs are known to dissolve minerals (Sarvaramini et al., 2013). Therefore, it is proposed
that IL-pretreatment removed minerals contained in biomass and
this led to an enhanced thermal stability. With further increasing
temperature, the changes in cellulose crystal structure and degradation of biomass play increasingly more important roles than loss
of minerals, which makes the Tmax shifting to lower temperatures.
XRD data (Zhang et al., 2014) showed the formation of cellulose II
after pretreatment at 130 C, and it is believed that at this temperature a severe degradation of biomass components already occurred. Delignication occurring at higher pretreatment
temperatures may also contribute to lowered thermal stability.
The decreased thermal stability can also be inferred from the
variation of the relative ratio between pseudo-hemicellulose and
cellulose peaks. The mass loss of pseudo-hemicellulose over total
mass loss of pseudo-hemicellulose and cellulose at a specic pretreatment temperature was calculated and plotted as a function
of temperature in Fig. 2d. As shown in Fig. 2d, more materials
decomposed at the low-temperature zone of pseudo-hemicellulose
with increasing pretreatment temperatures, suggesting decreased
biomass thermal stability.
4. Conclusion
Thermogravimetric analysis revealed different responses of
biomass components to [C4mim][OAc] pretreatment, which offered important insights on their interactions with [C4mim][OAc].
The side chains of xylan proved to be thermally less stable than
that of the backbone. Regenerated cellulose II lattice after IL
pretreatment without signicant depolymerization was more
resistant to thermal degradation than native cellulose. IL pretreatment broke down the structure of lignin and the recovered lignin

fractions contain more uniform compositions. Minerals in biomass

interfered with the interpretation of the observed thermal behavior of IL-pretreated biomass samples and degradation of biomass
at higher temperatures lowered its thermal stability.
Acknowledgements
This work was supported in part by the National High Technology Research and Development Program of China (863 Program,
No. 2012AA101803). Guangqing Liu acknowledges the nancial
support of this research from the National Natural Science Foundation of China (No. 51108016).
Appendix A. Supplementary data
Supplementary data associated with this article can be found, in
the online version, at http://dx.doi.org/10.1016/j.biortech.2013.
12.004.
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