Journal of Analytical and Applied Pyrolysis 93 (2012) 153159

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Journal of Analytical and Applied Pyrolysis

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Study on structure and pyrolysis behavior of lignin derived from corncob acid
hydrolysis residue
Yanqin Huang a , Zhiguo Wei a,b , Zejing Qiu a,b , Xiuli Yin a, , Chuangzhi Wu a
a
Key Laboratory of Renewable Energy and Gas Hydrate, Guangzhou Institute of Energy Conversion, Chinese Academy of Sciences, No. 2, Nengyuan Rd, Wushan Tianhe District,
Guangzhou 510640, China
b
Graduate University of Chinese Academy of Sciences, Beijing 100049, China

a r t i c l e i n f o a b s t r a c t

Article history: The structure and pyrolysis charateristics of lignin isolated from corncob acid hydrolysis residue (CAHL)
Received 30 August 2011 were studied. Characteritic bands corresponding to guaiacyl and syringyl groups were detected by FTIR,
Accepted 30 October 2011 and CAHL particle was polygonal in shape with multiple conchoidal fracture surface. Result of TGA showed
Available online 7 November 2011
that CAHL underwent thermo-degradation at a wide temperature range of 180850 C, and two mass
loss peaks were observed at 237 C and 340 C. Evolution of methanol and phenols were mainly detected
Keywords:
at 150420 C, while CO2 , CO and CH4 appeared to be the main gaseous products at temperature above
CAHL
400 C. Py-GC/MS analysis showed that phenolic compounds, mainly consisting of guaiacol- and syringol-
Structure
Pyrolysis
type, were generated from cracking of arylglycerol--ether (-O-4) linkage in CAHL. SEM analysis showed
TG-FTIR that portoins of CAHL char appeared brittle with conchoidal fractures at 550750 C, and vesicle was
Py-GC/MS observed due to plastic formation above 850 C.
2011 Elsevier B.V. All rights reserved.

1. Introduction syrigyl, and p-hydroxyphenyl unit [1416]. A number of studies

Biofuels such as bio-ethanol and bio-butanol, produced from
lingocellulosic biomass by hydrolysis-and-fermentation technique,
are considered as effective alternatives for gasoline and transport
needs [15]. During hydrolysis, most of hemicellulose and part
of cellulose are hydrolyzed, and a great amount of solid residue
(4050 wt% of feedstock) rich-in-lignin are then concentrated [6].
If the hydrolysis residue (HR) can be effectively utilized, the pro-
duction of biofuels from lingocellulosic biomass could be cheaper;
meanwhile environmental pollution resulting from discharge of
the HR could be also prevented.
Thermal chemical process provides a promising method for uti-
lization of the HR [79]. On one hand, bio-oil can be produced from
HR through fast pyrolysis [7]. On the other hand, gasication also
provides a benecial and realistic way to convert the HR to gaseous
fuels from which electricity, liquid fuels and chemicals can be pro-
duced [8,9]. It is known that biomass has been changed during
hydrolysis process in both component and structure [1013], and
that the lignin is the main component of the HR (about 50 wt%)
[6]. Lignin is the most abundant polymeric aromatic organic sub-
stance in the plant world. Generally, lignin is mainly formed by the
polymerization of three phenyl propane monomers, i.e. guaiacyl,
have been reported in the literature on pyrolysis of lignin [1722].
However, the thermal decomposition behavior of lignin derived
from HR (i.e. residue lignin) has rarely been reported. Therefore,
study on pyrolysis of residue lignin, the major component of HR,
is of practical importance for better understanding of pyrolytic
behavior of the HR.
The main purpose of this study was to investigate structure
and pyrolysis characteristics of lignin isolated from corncob acid
hydrolysis residue (CAHL). The structure of CAHL was rstly charac-
terized by Fourier transform infra-red (FTIR) and scanning electron
microscopy (SEM); then thermal decomposition behavior of CAHL
and evolution characteristic of pyrolysis products were exam-
ined by thermogravimetric analyzer coupled with FTIR (TG-FTIR);
pyrolysis-gas chromatography-mass spectrometry analysis (Py-
GC/MS) was also employed to further explain pyrolysis behavior of
CAHL; moreover, surface morphology of CAHL char was character-
ized by SEM to investigate transformation during CAHL pyrolysis.
2. Material and methods
2.1. Materials

Corncob acid hydrolysis residues (CAHR) were collected from a

continous acid hydrolysis process of Corncob-to-butanol. There-
Corresponding author. Tel.: +86 02087057731; fax: +86 02087057737. into, corncob was selected from Liaoning province (China), and
E-mail address: xlyin@ms.giec.ac.cn (X. Yin). hydrolysis conditions used were 2% H2 SO4 , 20 min at 180 C. Before

0165-2370/$ see front matter 2011 Elsevier B.V. All rights reserved.
doi:10.1016/j.jaap.2011.10.011
154 Y. Huang et al. / Journal of Analytical and Applied Pyrolysis 93 (2012) 153159

Table 1
Component, ultimate and proximate analyses of CAHR and corncob.

Material Component Ultimate Proximate

wad % wdaf % wad %

Cc HCc Lignin C H Ob N S Mc Ash Vc FCc

a
CAHR 28.18 8.83 47.84 53.66 5.34 40.80 0.04 0.16 8.19 1.25 61.64 28.92
Corncob 36.47 39.85 13.52 46.43 5.78 47.69 0.08 0.02 4.43 1.36 76.84 17.37
a
Corncob acid hydrolysis residue.
b
By difference.
c
C cellulose; HC hemicellulose; M moisture; V volatile matters; FC xed carbon.

Table 2
Ultimate and proximate analyses of CAHL.

Material Ultimate wdaf % Proximate wad %

C H O N S H/C O/C Ash Va FCa

CAHL 60.95 5.25 33.69 0.03 0.08 1.03 0.41 0.26 65.01 34.73
a
V volatile matters; FC xed carbon.

experiment, the CAHR was rstly washed to remove the remained
sulfuric acid, then was dried, crushed, sieved and the size frac-
tion of (150250 m) was chosen as sample. Corncobs, as raw
materials, were treated in the same way as CAHR except for wash-
ing treatment. The proximate, ultimate and chemical component
analyses of corncob and CAHR are listed in Table 1. Thereinto, cel-
lulose, content was analyzed by nitric acidethanol method [23].
The contents of lignin and holocellulose were analyzed on the basis
of Chinese National Standards Methods of GB/T2677.8-1994 and
GB/T2677.10-1995, respectively. The hemicellulose content was
calculated by difference between holocellulose and cellulose. It is
found that the CAHR has higher lignin content (50 wt%), lower
oxygen content, and higher ratio of C:H compared with corncob.
2.2. Isolation of CAHL
It has been reported that lignin can be effectively isolated from
non-woody biomass using enzymatic acid hydrolysis lignin (EMAL)
isolating method [24,25]. Generally, EMAL process mainly includes
two steps as fully described in [25]: (1) cellulase enzymatic hydrol-
ysis, and (2) mild acidolysis. For CAHR, due to most of cellulose
and hemicellose had been hydrolyzed during process of corncob-
to-butanol, the cellulase enymatic hydrolysis process can be left
out [24,26]. CAHL was isolated using the modied EMAL method as
previously described in [24], and Table 2 shows the ultimate and
proximate analyses of CAHL.
2.3. Structure analysis of CAHL using FTIR
Functional groups and chemical bonds of the CAHL were ana-
lyzed by Fourier transform infra-red (FTIR) spectrometry (Nexus
series, Thermo Nicolet Co., America). Samples were prepared with
the potassium bromide (KBr) pellet technique. The FTIR spectrum
was recorded at the range of wave numbers from 400 to 4000 cm1
with a resolution of 4 cm1 and each spectrum was based on the
average of 36 scans.
2.4. TG-FTIR experiment
A thermogravimetric analyzer (TGA, NETZSCH STA409C/PC) is
coupled to the FTIR spectrophotometer to investigate pyrolysis
bahavoiur of CAHL. In the TGA experiment, the samples were
heated from 30 to 900 C at a heating rate of 20 K/min under N2
atmosphere. In each case, the mass of sample is less than 10 mg to
avoid the possible temperature gradient in the sample and ensure
kinetic control of the process.
The FTIR is connected to TGA through a ow cell which
is preheated to an internal temperature of 180 C to prevent
condensation of the produced gas on the cell wall. The FTIR
spectrometer was set to collect 32 interferograms in the range
of 4004000 cm1 with a resolution of 4 cm1 . During pyroly-
sis all the interferograms were collected and post-processed to
obtain the absorption spectra and the corresponding gas formation
proles.
2.5. Pyrolysis-GC/MS analysis
The pyrolysis of CAHL were performed with a pyrolysis unit
(Chemical Data Systems, CDS Proprobe 5000, USA) coupled online
with a Shimadzu QP2010 GC/MS using a capillary column Rxi-
1MS (30 m 0.25 mm i.d., 0.25 m lm thickness). Approximately
500 g of the sample was deposited on a ferromagnetic wire and
then inserted into the glass liner and placed immediately in the
pyrolyzer. Pyrolysis was performed at 420 C, 520 C, 600 C, and
780 C for 10 s at a heating rate of 10 C/ms. The chromatograph
was programmed from 50 C (holding for 5 min) to 250 C (holding
for 10 min) at a rate of 10 C/min. The carrier gas of Helium and split
ratio was set 1.0 mL/min and 70:1, respectively. The injector tem-
perature was kept at 250 C while the GC/MS interface was kept at
280 C. The mass spectrometer operated under EI conditions (70 eV)
in the range from 45 to 600 m/z. Pyrolysis products were identied
by interpretation of mass spectra and by comparison with NIST and
Wiley libraries.
2.6. CAHL pyrolysis
2.6.1. Char preparation
Pyrolysis of CAHL was carried out under N2 atmosphere in
a tubular reactor which was described in detail previously [27].
Briey, it was comprised of an electric heating furnace, a tem-
perature control system, a 600 mm (L) 35 mm (I.D.) quartz tube
reactor, and a porcelain boat containing samples. About 0.5 g of
the CAHL, spread as a thin layer in the porcelain boat, was loaded
into a quartz glass container and then placed at cold side of the
quartz tube. The gas temperature in the heated zone of the reac-
tor was then increased and continuously monitored using K-type
thermocouples. Once the reactor had stabilized at the desired tem-
perature of 550950 C, the sample container was put into the
heated zone and kept for about 12 min to ensure complete con-
version. Then the product char was allowed to cool to ambient
temperature, and char yield was calculated from the amount of char
based on the initial mass of the unpyrolyzed CAHL. During each
 Y. Huang et al. / Journal of Analytical and Applied Pyrolysis 93 (2012) 153159 155

1.00 100 6
o
340 C
0.98
Transmittance (100%)

The mass loss / wt%

621

)
80

833

o -1
0.96 o
237 C 4

Mass loss rate / (wt%C

2937
0.94

1039
60

1380
1460
1705
0.92

1508

1128
1163
1260
1604
0.90 2
40
0.88
3429

0.86 20
4000 3500 3000 2500 2000 1500 1000 500 0
-1
Wave numbers /cm 0 200 400 600 800
Temperature /C
Fig. 1. FTIR spectra of CAHL.

Fig. 2. TG/DTG curves of CAHL under 20 K/min.

Table 3
FTIR analysis of CAHL microstructure.
Therefore, the CAHL has the typical function groups of lignin as
Wavenumbers/cm1 Assignment (bond) described [17,29].
3429 OH stretching vibration
1380, 2937 CH stretching vibration 3.2. Thermal analysis of CAHL
1705 C O stretching vibration
1460, 1604 Aromatic ring C C stretching vibration
1508 Aromatic ring skeleton vibration
The TG and DTG curves for CAHL under nitrogen at 20 K/min are
1260 Guaiacyl ring breathing with CO stretching shown in Fig. 2. The mass loss stage is observed within a wide tem-
1163 Aliphatic ether COH asymmetric vibration perature range from 180 to 850 C, which can be explained by the
1128 CH in plane deformation vibration of syringyl units fact that lignin contains many aromatic rings with various branches
1039 Aromatic ring CH in plane bending vibration
(as shown in Section 3.1), and activity of the chemical bonds and
833 CH stretching vibration of syringyl units
functional groups in lignin covers an extremely wide temperature
range [30]. The pyrolysis temperature zone of CAHL is similar to that
of CAHR [31]. It was reported that thermo-degradation of corncob
lignin was also within the wide temperature zone [32]. However, a
test, the yield of char was used as an index for the reproducibil- sharp mass loss stage for corncob was observed within a narrow
ity of experiments. Chars pyrolyzed under the same conditions temperature zone of 260420 C [31]. Furthermore, char residue is
are considered to be identical only if the difference in yield is less one of the main products from CAHL pyrolysis, accounting for about
than 2%. 30 wt% of the feedstock, which is similar to char yield from CAHR
pyrolysis, but much higher than that from both corncob (about
2.6.2. Char characterization by SEM analysis 20 wt%) and corncob lignin [31,32].
The surface morphology of CAHL char was characterized by DTG curve of CAHL shows that a shoulder peak, which is
scanning electron microscopy (SEM) analyzer (ESEM XL-30, Fhilips relatively inert and overlapped by the second pyrolysis stage,
Co., Netherlands). For SEM analysis, the point resolution was set to is observed at 237 C at the rst major pyrolysis stage, while
2.5 nm with an accelerating voltage of 130 kV and a magnication a notable mass loss peak appears at 340 C. It was found
of 25300,000. that although thermal decomposition of corncob lignin could
be also divided into two pyrolysis stages, however, it should
be noted that the characteristic mass loss peaks from corncob
3. Results and discussion
lignin pyrolysis appeared at elevated temperatures under the
same heating rate [32]. Similar result was also reported in by
3.1. Structure of CAHL by FTIR analysis

The FTIR spectra of CAHL are presented in Fig. 1 and the

typical bands are listed in Table 3. Fig. 1 shows that absorp-
tion bands appeared in 7501600 cm1 are superimposed, while
pure absorption bands are observed in 16004000 cm1 . The
major absorption bands representing typical structure of lignin
appears in the ngerprint region between 800 and 1800 cm1 .
The appearance of the band locating at 1260 cm1 shows the exis-
tence of guaiacyl groups, and that locating at 1128 and 833 cm1
indicates the existence of syringyl groups. The characteristic
bands locating in 1460, 1508 and 1604 cm1 indicate the exis-
tence of aromatic rings. The appearance of carbonyl groups at
1705 cm1 not in 16601675 cm1 indicated that C O bands is
not in conjugation with the aromatic rings [28]. The absorption
at 1380 cm1 and 2937 cm1 corresponds to the CH stretching
vibration of alkyl groups. Furthermore, OH stretching vibra-
tion in phenol hydroxyl groups, representing another typical
function group of lignin, is reected in the band of 3429 cm1 . Fig. 3. FTIR spectra of pyrolysis products from CAHL at characteristic temperatures.
156 Y. Huang et al. / Journal of Analytical and Applied Pyrolysis 93 (2012) 153159
Fig. 4. the evolution of main volatile products from CAHL pyrolysis characterized by DTG-FTIR.
shen et al. [20], indicating that the shoulder peak and notable
mass loss peak appeared at 270 C and at 376 C, respec-
tively. This may be explained that the CAHL chemical structure
had taken a change during acid hydrolysis process of corncob-
to-butanol, which promoted the evolution of volatiles during
pyrolysis.
3.3. Evolution characteristics of CAHL pyrolysis
The evolution of volatiles from CAHL pyrolysis can be detected
according to the absorption bands through 3D-FTIR spectrogram
(absorbance-wavenumber-minute). The composition of volatile
products can be determined by the characteristic wavenumber
bands, while the yield history of the products can be found by
the absorbance against minutes. Fig. 3 shows the FTIR spectra
of gaseous products at the temperature of 237 C and 340 C
corresponding to the shoulder peak and the sharp peak,
respectively. The characteristic bands of water at 35003900 cm1
is generated from the cracking of aliphatic hydroxyl groups in
the lateral chains [17]. The absorption bands at 28003200 cm1
showed the existence of hydrocarbons, of which methane is the
most abundant according to the absorbance peak at 3016 cm1 .
The bands at 22262398 cm1 and 21482195 cm1 indicate
the formation of CO2 and CO generated from cracking of lateral
CC bond. Formaldehyde, appearing at 1745 cm1 , may form
by fragmentation of the hydroxymethylene groups (CH2 OH)
present in the phenyl propane side chains [21]. The absorption
bands of hydroxyl groups (OH) at 13001400 cm1 indicate
the evolution of phenols and alcohols, of the alcohols methanol
is most abundant according to the absorbance peak at 1057 cm1 .
Comparatively, the stronger absorbance at 1220 cm1 indicates
that phenols are important characteristic products of CAHL
pyrolysis.
It is known that the absorbance at a specic wavenumber
is linearly dependent on gas concentration according to the
LambertBeer Law. Thus the variation of absorbance in the whole
 Y. Huang et al. / Journal of Analytical and Applied Pyrolysis 93 (2012) 153159 157

Table 4
Identication and relative molar abundance of the compounds from Py-GC/MS of CAHL.

Retention time (min) Compounds Relative content (mol%)

420 C 520 C 600 C 780 C

1.55 2,2-Dimethoxy-1,3-propanediol 6.82

1.606 Cyclobutanol 19.83
1.622 Acetone 3.11
1.828 Acetic acid 1.02 1.17 2.41
1.97 1,3-Dioxolane 1.1 3.2 1.84 3.37
2.148 1-Hydroxy-2-propanone 2.38
2.292 Benzene 2.42
3.198 Formyl-ethylene glycol-ester 1.34 2.59 1.4 0.68
8.794 Phenol 0.83 0.41 2.35 2.07
10.788 2-Methoxy-phenol 0.95 0.95 3.57 1.15
13.05 2,3-Dihydrobenzofuran 2.51 2.91 6.74 5.12
13.219 3,3-Dimethoxy-2-pentanol 1.88 3.27 2.00
13.383 2-(4-Acetylphenolic)-acetic ester 5.6
13.608 2-(4-Methylphenolic)-acetic ester 4.85
13.867 2-(2-(2-Acetoxyl-oxethyl)-phenolic)-acetic ester 20.24 8.31 15.41 3.68
13.985 4-Ethyl-2-methoxy-3-phenol 13.1 0.68
14.072 Glycyl-d-Hreonine 8.39
14.092 2,3,4-Trimethoxy-3-pentanol 7.59
14.459 4-Ethylene-2-methoxy-phenol 1.64 3.45 5.97 2.48
14.517 2,4-Dimethyl-3-pentanol 4.28
14.753 2,6-Dimethoxy-3-phenol-propanoic acid 1.58
14.856 2,6-Dimethoxy-phenol 0.49 2.58 2.55 1.07
15.408 4-hydroxy-3-methoxy-phenylaldehyde 0.65 0.95 0.44 0.56
15.672 3,7,11-trimethoxy-3-dodecanol 2.17
16.086 1,2,3-Trimethoxy-benzene 1.15 0.85
17.599 3,5-Dimethoxy-acetophenone 2.43
19.201 2,6-Dimethoxy-4-(2-propenyl)-phenol 1.16

process can reect the tendency of product yield of the gas species.
The detailed evolution of typical products (water, CO2 , CO, CH4 ,
methanol, phenols) from the CAHL pyrolysis can be explained
using FTIR spectra in Fig. 4 together with the corresponding DTG
curve.
Fig. 4 shows that the main volatile is water in the initial pyrol-
ysis stage below 150 C. With the increase of temperature over
200 C, the evolution of CO2 and CO are observed due to the crack-
ing and reforming of thermolabile carboxyl, carbonyl and ether
groups in the phenylpropane side chains. Furthermore, the for-
mation of CO at high temperature range (500800 C) is probably
ascribed to breaking of diaryl ether groups and secondary pyrol-
ysis volatiles. Two absorbance peaks are observed in absorbance
curve of CH4 . The rst one appearing at 420 C is mainly ascribed
to breakage of weak bonded methoxy group (OCH3 ) and methy-
lene group (CH2 ) of higher bond energy [33]. The second shoulder
peak appearing at 540 C can be attributed to the profound rupture
of aromatic rings [21]. The evolution of CH4 OH, due to cracking
of aromatic methoxy groups and aliphatic CH2 OH group in
position of the alkyl side chains, is observed at 150420 C and
reaches a maximum at 370 C. The formation of phenols, occur-
ring at 200420 C with a maximum at 370 C, was attributed to
dehydration of OH groups in the alkyl side chain of the lignin
basic units, followed by the cleavage of ether bonds between these
units.
3.4. The Py-GC/MS analysis
According to TG-DTG analysis of CAHL, pyrolysis of CAHL
was carried out with Py-GC/MS at 420, 520, 600 and 780 C.
The identication and relative molar abundance of the released
compounds from CAHL pyrolysis are shown in Table 4. No
carbohydrate-derived compounds were present, while oxy-
gen compounds, containing acids, alcohols, aldehydes, ketones,
esters, furans and phenols, are identied in the pyrolysates of
the CAHL. It is notable that various phenolic compounds, due
to cleavage of arylglycerol--ether (-O-4) linkage existing in
CAHL, are predominant products in pyrolysis mixture [17]. Gen-
erally, it is found that the phenolic compounds can be divided
into two types: syringol-derivatives (2,6-dimethoxy-phenol,
2,6-dimethoxy-4-(2-propenyl)-phenol, etc.) and guaiacol-
derivatives (2-methoxy-phenol, 4-ethyl-2-methoxy-3-phenol,
etc.).
By comparison of pyrolysate contents obtained at different tem-
perature, it is found that relative contents of alcohols and ketones
are increasing at elevated temperature. In addition, phenol and
benzene are identied in pyrolysate at temperature up to 780 C.
This may be explained as the macromolecule compounds were
further broken into fragments besides multi-degradation at high
temperature [6].
3.5. SEM analysis of CAHL and its chars
Fig. 5 shows the SEM analysis of CAHL and its chars pyrolyzed
at 550950 C. It is found that the individual particles of CAHL
are polygonal in shape with multiple conchoidal fracture sur-
face (Fig. 5b), which is consistent with analysis results from
Ramesh et al. [34]. Moreover, some pores of different sizes were
also observed on portion surface of CAHL (Fig. 5a). During CAHL
pyrolyzing, portions of the matrix appeared brittle with conchoidal
fractures at temperature of 550750 C (Fig. 5ce), which can be
explained that the volatile matters are released rapidly and the
matrix are destroyed with formation of conchoidal fracture. Similar
results were reported during alkali lignin pyrolyzing at tempera-
ture over 550 C [34]. As temperature increases up to 850 C, vesicle
formation is observed on surface of the CAHL due to plastic for-
mation at high temperature. Furthermore, it should be noted that
carbon structure ordering was observed on surface of the CAHL
char pyrolyzed at high temperature over 850 C (Fig. 5gh), and
char from 950 C has a higher carbon structure ordering than that
from 850 C.
158 Y. Huang et al. / Journal of Analytical and Applied Pyrolysis 93 (2012) 153159
Fig. 5. SEM micrographs of CAHL and its chars prepared at different temperatures (a, b CAHL; c 550 C; d 650 C; e 750 C; f, g 850 C; h 950 C).
4. Conclusions
The CAHL particle is polygonal in shape with multiple con-
choidal fracture surface, and characteristic bands corresponding to
typical structure of lignin, such as guaiacyl and syringyl groups, are
observed in FTIR spectra of CAHL.
Thermal degradation of CAHL occurs at a wide temperature
range of 180850 C, and two mass loss peaks appeared at 237 C
and 340 C, respectively. Evolution of large molecular volatiles,
especially methanol and phenols were mainly detected at temper-
ature of 150420 C, while CO2 , CO and CH4 appear to be the main
gaseous products above 400 C.
Phenolic compounds, mainly consisting of guaiacol- and
syringol-type, may be mainly generated from the cracking of
arylglycerol--ether (-O-4) linkage of CAHL. In addition, phenol
and benzene are identied at temperature up to 780 C, which is
ascribed to further cleavage of macromolecule compounds into
fragments besides multi-degradation at high temperature.
During CAHL pyrolysis process, portions of the matrix appeared
brittle with conchoidal fractures at temperature of 550750 C, and
vesicle formation is observed due to plastic formation at tempera-
ture up to 850 C. Furthermore, CAHL char from 950 C has a higher
carbon structure ordering than that from 850 C.
Acknowledgements
The authors would like to acknowledge the nancial support
from the National Natural Science Foundation of China (50876109)
and the National Key Technology Research and Development Pro-
gram of China (2011BAD22B06).
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