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

have been reported in the literature on pyrolysis of lignin [1722].
Biofuels such as bio-ethanol and bio-butanol, produced from However, the thermal decomposition behavior of lignin derived
lingocellulosic biomass by hydrolysis-and-fermentation technique, from HR (i.e. residue lignin) has rarely been reported. Therefore,
are considered as effective alternatives for gasoline and transport study on pyrolysis of residue lignin, the major component of HR,
needs [15]. During hydrolysis, most of hemicellulose and part is of practical importance for better understanding of pyrolytic
of cellulose are hydrolyzed, and a great amount of solid residue behavior of the HR.
(4050 wt% of feedstock) rich-in-lignin are then concentrated [6]. The main purpose of this study was to investigate structure
If the hydrolysis residue (HR) can be effectively utilized, the pro- and pyrolysis characteristics of lignin isolated from corncob acid
duction of biofuels from lingocellulosic biomass could be cheaper; hydrolysis residue (CAHL). The structure of CAHL was rstly charac-
meanwhile environmental pollution resulting from discharge of terized by Fourier transform infra-red (FTIR) and scanning electron
the HR could be also prevented. microscopy (SEM); then thermal decomposition behavior of CAHL
Thermal chemical process provides a promising method for uti- and evolution characteristic of pyrolysis products were exam-
lization of the HR [79]. On one hand, bio-oil can be produced from ined by thermogravimetric analyzer coupled with FTIR (TG-FTIR);
HR through fast pyrolysis [7]. On the other hand, gasication also pyrolysis-gas chromatography-mass spectrometry analysis (Py-
provides a benecial and realistic way to convert the HR to gaseous GC/MS) was also employed to further explain pyrolysis behavior of
fuels from which electricity, liquid fuels and chemicals can be pro- CAHL; moreover, surface morphology of CAHL char was character-
duced [8,9]. It is known that biomass has been changed during ized by SEM to investigate transformation during CAHL pyrolysis.
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- 2. Material and methods
stance in the plant world. Generally, lignin is mainly formed by the
polymerization of three phenyl propane monomers, i.e. guaiacyl, 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: [email protected] (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 The FTIR is connected to TGA through a ow cell which
sulfuric acid, then was dried, crushed, sieved and the size frac- is preheated to an internal temperature of 180 C to prevent
tion of (150250 m) was chosen as sample. Corncobs, as raw condensation of the produced gas on the cell wall. The FTIR
materials, were treated in the same way as CAHR except for wash- spectrometer was set to collect 32 interferograms in the range
ing treatment. The proximate, ultimate and chemical component of 4004000 cm1 with a resolution of 4 cm1 . During pyroly-
analyses of corncob and CAHR are listed in Table 1. Thereinto, cel- sis all the interferograms were collected and post-processed to
lulose, content was analyzed by nitric acidethanol method [23]. obtain the absorption spectra and the corresponding gas formation
The contents of lignin and holocellulose were analyzed on the basis proles.
of Chinese National Standards Methods of GB/T2677.8-1994 and
GB/T2677.10-1995, respectively. The hemicellulose content was 2.5. Pyrolysis-GC/MS analysis
calculated by difference between holocellulose and cellulose. It is
found that the CAHR has higher lignin content (50 wt%), lower The pyrolysis of CAHL were performed with a pyrolysis unit
oxygen content, and higher ratio of C:H compared with corncob. (Chemical Data Systems, CDS Proprobe 5000, USA) coupled online
with a Shimadzu QP2010 GC/MS using a capillary column Rxi-
2.2. Isolation of CAHL 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
It has been reported that lignin can be effectively isolated from then inserted into the glass liner and placed immediately in the
non-woody biomass using enzymatic acid hydrolysis lignin (EMAL) pyrolyzer. Pyrolysis was performed at 420 C, 520 C, 600 C, and
isolating method [24,25]. Generally, EMAL process mainly includes 780 C for 10 s at a heating rate of 10 C/ms. The chromatograph
two steps as fully described in [25]: (1) cellulase enzymatic hydrol- was programmed from 50 C (holding for 5 min) to 250 C (holding
ysis, and (2) mild acidolysis. For CAHR, due to most of cellulose for 10 min) at a rate of 10 C/min. The carrier gas of Helium and split
and hemicellose had been hydrolyzed during process of corncob- ratio was set 1.0 mL/min and 70:1, respectively. The injector tem-
to-butanol, the cellulase enymatic hydrolysis process can be left perature was kept at 250 C while the GC/MS interface was kept at
out [24,26]. CAHL was isolated using the modied EMAL method as 280 C. The mass spectrometer operated under EI conditions (70 eV)
previously described in [24], and Table 2 shows the ultimate and in the range from 45 to 600 m/z. Pyrolysis products were identied
proximate analyses of CAHL. by interpretation of mass spectra and by comparison with NIST and
Wiley libraries.
2.3. Structure analysis of CAHL using FTIR
2.6. CAHL pyrolysis
Functional groups and chemical bonds of the CAHL were ana-
lyzed by Fourier transform infra-red (FTIR) spectrometry (Nexus 2.6.1. Char preparation
series, Thermo Nicolet Co., America). Samples were prepared with Pyrolysis of CAHL was carried out under N2 atmosphere in
the potassium bromide (KBr) pellet technique. The FTIR spectrum a tubular reactor which was described in detail previously [27].
was recorded at the range of wave numbers from 400 to 4000 cm1 Briey, it was comprised of an electric heating furnace, a tem-
with a resolution of 4 cm1 and each spectrum was based on the perature control system, a 600 mm (L) 35 mm (I.D.) quartz tube
average of 36 scans. 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
2.4. TG-FTIR experiment 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-
A thermogravimetric analyzer (TGA, NETZSCH STA409C/PC) is tor was then increased and continuously monitored using K-type
coupled to the FTIR spectrophotometer to investigate pyrolysis thermocouples. Once the reactor had stabilized at the desired tem-
bahavoiur of CAHL. In the TGA experiment, the samples were perature of 550950 C, the sample container was put into the
heated from 30 to 900 C at a heating rate of 20 K/min under N2 heated zone and kept for about 12 min to ensure complete con-
atmosphere. In each case, the mass of sample is less than 10 mg to version. Then the product char was allowed to cool to ambient
avoid the possible temperature gradient in the sample and ensure temperature, and char yield was calculated from the amount of char
kinetic control of the process. 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 is generated from the cracking of aliphatic hydroxyl groups in
mass loss peak appeared at 270 C and at 376 C, respec- the lateral chains [17]. The absorption bands at 28003200 cm1
tively. This may be explained that the CAHL chemical structure showed the existence of hydrocarbons, of which methane is the
had taken a change during acid hydrolysis process of corncob- most abundant according to the absorbance peak at 3016 cm1 .
to-butanol, which promoted the evolution of volatiles during The bands at 22262398 cm1 and 21482195 cm1 indicate
pyrolysis. the formation of CO2 and CO generated from cracking of lateral
CC bond. Formaldehyde, appearing at 1745 cm1 , may form
3.3. Evolution characteristics of CAHL pyrolysis by fragmentation of the hydroxymethylene groups (CH2 OH)
present in the phenyl propane side chains [21]. The absorption
The evolution of volatiles from CAHL pyrolysis can be detected bands of hydroxyl groups (OH) at 13001400 cm1 indicate
according to the absorption bands through 3D-FTIR spectrogram the evolution of phenols and alcohols, of the alcohols methanol
(absorbance-wavenumber-minute). The composition of volatile is most abundant according to the absorbance peak at 1057 cm1 .
products can be determined by the characteristic wavenumber Comparatively, the stronger absorbance at 1220 cm1 indicates
bands, while the yield history of the products can be found by that phenols are important characteristic products of CAHL
the absorbance against minutes. Fig. 3 shows the FTIR spectra pyrolysis.
of gaseous products at the temperature of 237 C and 340 C It is known that the absorbance at a specic wavenumber
corresponding to the shoulder peak and the sharp peak, is linearly dependent on gas concentration according to the
respectively. The characteristic bands of water at 35003900 cm1 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. to cleavage of arylglycerol--ether (-O-4) linkage existing in
The detailed evolution of typical products (water, CO2 , CO, CH4 , CAHL, are predominant products in pyrolysis mixture [17]. Gen-
methanol, phenols) from the CAHL pyrolysis can be explained erally, it is found that the phenolic compounds can be divided
using FTIR spectra in Fig. 4 together with the corresponding DTG into two types: syringol-derivatives (2,6-dimethoxy-phenol,
curve. 2,6-dimethoxy-4-(2-propenyl)-phenol, etc.) and guaiacol-
Fig. 4 shows that the main volatile is water in the initial pyrol- derivatives (2-methoxy-phenol, 4-ethyl-2-methoxy-3-phenol,
ysis stage below 150 C. With the increase of temperature over etc.).
200 C, the evolution of CO2 and CO are observed due to the crack- By comparison of pyrolysate contents obtained at different tem-
ing and reforming of thermolabile carboxyl, carbonyl and ether perature, it is found that relative contents of alcohols and ketones
groups in the phenylpropane side chains. Furthermore, the for- are increasing at elevated temperature. In addition, phenol and
mation of CO at high temperature range (500800 C) is probably benzene are identied in pyrolysate at temperature up to 780 C.
ascribed to breaking of diaryl ether groups and secondary pyrol- This may be explained as the macromolecule compounds were
ysis volatiles. Two absorbance peaks are observed in absorbance further broken into fragments besides multi-degradation at high
curve of CH4 . The rst one appearing at 420 C is mainly ascribed temperature [6].
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 3.5. SEM analysis of CAHL and its chars
of aromatic rings [21]. The evolution of CH4 OH, due to cracking
of aromatic methoxy groups and aliphatic CH2 OH group in Fig. 5 shows the SEM analysis of CAHL and its chars pyrolyzed
position of the alkyl side chains, is observed at 150420 C and at 550950 C. It is found that the individual particles of CAHL
reaches a maximum at 370 C. The formation of phenols, occur- are polygonal in shape with multiple conchoidal fracture sur-
ring at 200420 C with a maximum at 370 C, was attributed to face (Fig. 5b), which is consistent with analysis results from
dehydration of OH groups in the alkyl side chain of the lignin Ramesh et al. [34]. Moreover, some pores of different sizes were
basic units, followed by the cleavage of ether bonds between these also observed on portion surface of CAHL (Fig. 5a). During CAHL
units. pyrolyzing, portions of the matrix appeared brittle with conchoidal
fractures at temperature of 550750 C (Fig. 5ce), which can be
3.4. The Py-GC/MS analysis explained that the volatile matters are released rapidly and the
matrix are destroyed with formation of conchoidal fracture. Similar
According to TG-DTG analysis of CAHL, pyrolysis of CAHL results were reported during alkali lignin pyrolyzing at tempera-
was carried out with Py-GC/MS at 420, 520, 600 and 780 C. ture over 550 C [34]. As temperature increases up to 850 C, vesicle
The identication and relative molar abundance of the released formation is observed on surface of the CAHL due to plastic for-
compounds from CAHL pyrolysis are shown in Table 4. No mation at high temperature. Furthermore, it should be noted that
carbohydrate-derived compounds were present, while oxy- carbon structure ordering was observed on surface of the CAHL
gen compounds, containing acids, alcohols, aldehydes, ketones, char pyrolyzed at high temperature over 850 C (Fig. 5gh), and
esters, furans and phenols, are identied in the pyrolysates of char from 950 C has a higher carbon structure ordering than that
the CAHL. It is notable that various phenolic compounds, due 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 and the National Key Technology Research and Development Pro-
gram of China (2011BAD22B06).
The CAHL particle is polygonal in shape with multiple con-
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