Applied Energy 95 (2012) 2230

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Applied Energy
journal homepage: www.elsevier.com/locate/apenergy

Catalytic effects of NaOH and Na2CO3 additives on alkali lignin pyrolysis

and gasication
Da-liang Guo a, Shu-bin Wu a,, Bei Liu a, Xiu-li Yin b, Qing Yang b
a
b

State Key Laboratory of Pulp and Paper Engineering, South China University of Technology, Guangzhou 510640, PR China
The Renewable Energy and Gas Hydrate Key Laboratory of CAS, Guangzhou Institute of Energy Conversion, Chinese Academy of Sciences, Guangzhou 510640, PR China

a r t i c l e

i n f o

Article history:
Received 23 October 2011
Received in revised form 12 January 2012
Accepted 15 January 2012
Available online 17 March 2012
Keywords:
Lignin
Black liquor
Pyrolysis and gasication
NaOH and Na2CO3
TG-FTIR

a b s t r a c t
The interest in utilization of alkali lignin in black liquor by pyrolysis and gasication is increasing due to
the wish to produce bio-fuel and bio-chemical. Besides alkali lignin, the sodium salts are also the basic
component of black liquor; they exist in two main forms: as phenolic sodium (ACONa) and carboxylate
sodium (ACOONa) groups forming a part of alkali lignin or as dissolved salts (NaOH and Na2CO3). In this
paper, the inuences of these dissolved salts on the pyrolysis and gasication characteristics of alkali lignin were discussed. Five lignin samples, including pure acid precipitated lignin, 10% and 60% NaOHloaded lignin, 10% and 60% Na2CO3-loaded lignin, and black liquor solids were selected as the testing
samples. Following experimental research on the evolution patterns of volatile products were carried
out on a thermogravimetric analyzer coupled with Fourier transform infrared spectrometry. The experimental data indicated that the pyrolysis and gasication reaction of alkali lignin could be catalyzed by
NaOH and Na2CO3. In the pyrolysis stage, the maximum mass loss rate decreased with increasing amount
of NaOH and Na2CO3 additives, while in the gasication stage it increased. In the gasication stage, the
temperature of the maximum mass loss rate shifted to lower value with increasing amount of NaOH
and Na2CO3 additives, but did not signicantly change in the pyrolysis stage. FTIR analysis showed that
the inuences of NaOH and Na2CO3 additives on the pyrolysis and gasication products mainly varied in
amounts but not in species. FTIR results also suggested that the release time of the volatile was affected
by increasing NaOH and Na2CO3 additives amount. Moreover, NaOH and Na2CO3 markedly improved the
evolution of CO in the gasication stage.
2012 Elsevier Ltd. All rights reserved.

1. Introduction
In recent years more and more biomass-containing wastes such
as agricultural and industrial wastes have begun to supplement future energy needs in place of fossil fuel [19]. One of the potential
conversion methods for such wastes is via pyrolysis and gasication
processes [1]. Black liquor (BL), a major waste from chemical pulp
and paper production, contains, on a dry basis, about 40% of inorganic compounds and 60% of organic compounds [1,3]. The organic
compounds are composed mainly of degraded lignin (alkali lignin),
and the inorganic compounds are mostly recyclable pulping chemicals (alkali salts) [4,5]. In a conventional mill powerhouse, black liquor is red in a recovery boiler to produce combustion heat for
electrical generation, and more importantly to recover pulping
chemicals [6,7]. In the recent 20 years, the pyrolysis and gasication of black liquor has attracted great interest and been extensively
studied [17,1016]. Furthermore, it is considered as an alternative

Corresponding author. Tel./fax: +86 02022236808.

E-mail address: shubinwu@scut.edu.cn (S.-b. Wu).
0306-2619/$ - see front matter 2012 Elsevier Ltd. All rights reserved.
doi:10.1016/j.apenergy.2012.01.042

technology to replace conventional recovery boiler and convert this

waste into more valuable fuel products [7,10].
In the soda pulping process, sodium hydroxide is used as the
cooking chemical to dissolve lignin. Chemical action and solubilization make Na+ connect with phenolic hydroxyl groups (AOH)
and carboxyl acid groups (ACOOH) of lignin by chemical bonds,
forming phenolic sodium (ACONa) and carboxylate sodium
(ACOONa) groups (PCSG) [1719]. So, the sodium salts in black
liquor exist in two main forms: as organic bound Na salts (PCSG)
and as soluble salts (NaOH and Na2CO3). While the former form
of sodium salts can be considered as a part of the alkali lignin,
the latter form of sodium salts exist as ionic species associated
with the water. Upon drying, the soluble salts would tend to be
more concentrated in the abundant pore structures of alkali lignin,
weakly associated with the internal pore surface [4,20]. Thus, the
sodium salts species exist in black liquor in different chemical
and physical forms.
During the past decade, a number of studies have illustrated the
strong effects of different factors such as the reaction temperature
[11,12], pressure [13,14], and pretreatment [15] on the technical
performance. According to the previous works [17,21], the high

D.-l. Guo et al. / Applied Energy 95 (2012) 2230

23

Nomenclature
T 0i;i1;2

temperature ranges of un-catalyzed pyrolysis and

gasication
Ti,i = 1,2,3,4 temperature ranges of catalyzed pyrolysis and
gasication
T 0i max;i1;2 temperature at maximum mass loss rate in un-catalyzed pyrolysis and gasication
Timaxv,i = 1,2,3,4 temperature at maximum mass loss rate in
catalyzed pyrolysis and gasication

content of sodium salts in black liquor has a signicant effect on

the pyrolysis and gasication reaction of alkali lignin. Unfortunately, the inuence mechanisms of both the dissolved salts and
PCSG on the pyrolysis and gasication characteristic of alkali lignin
are not clearly understood. In our previous research [19], we have
investigated the effect of organic bound Na groups (PCSG) on pyrolysis and gasication behaviors of alkali lignin. In particular, we
have found that the pyrolysis and gasication characteristic of
alkali lignin depended on PCSG. Similarly, Raveendran et al. [22]
proposed the alkali and alkaline earth metallic species have a
strong inuence on both the pyrolysis characteristics and the product distribution. Teng et al. [23] suggested that de-ashing increases
the volatile yield, initial decomposition temperature and rate of
pyrolysis. Jensen et al. [24] concluded that the existence of inorganic salts inuences the property of volatiles, decreases the yield
of tar and promotes the formation of char. Based on these previous
studies, we believe that the dissolved salts in black liquor are some
of the important parameters to evaluate the pyrolysis and gasication characteristic of alkali lignin. Furthermore, fundamental pyrolysis and CO2-gasication characteristic of alkali lignin with and
without sodium salts catalysis have so far not been studied.
The objective of the present study was to investigate if NaOH
and Na2CO3 as soluble Na salts would have catalytic effects on
the pyrolysis and gasication reaction of alkali lignin. In addition,
basic data on the pyrolysis and CO2-gasication of alkali lignin
and black liquor solid (BLS) were obtained. A thermogravimetric
analyzer coupled with Fourier transform infrared spectrometry
(TG-FTIR) was used in this study. TGA was adopted to keep a detailed recording of the mass loss data, and FTIR was used to predict
the product evolution pattern and yield.
2. Materials and methods
2.1. Materials preparation
The black liquor sample, with solids content of 73.2%, was obtained from a sodaanthraquinone (AQ) wheat straw pulp mill in
Shandong Province, China. Samples were ltered through a 200mesh screen to remove any suspended matter.
Pure acid precipitated lignin (APL) sample, without NaOH and
Na2CO3, was separated from the black liquor by acid precipitation
with 1 N H2SO4 to pH 2.5. The acid precipitated solids were ltered
from the solution, washed thoroughly with distilled water, and
dried by freeze-drying. Subsequently, the dried solids were dissolved in 1,4-dioxane, ltered to remove any inorganic impurities,
and reclaimed by rotary evaporation of solvent under vacuum and
dried. Finally, the absolutely dry APL was used for this research
without further purication.
According to previous researches [2527], the acid precipitation
process of alkali lignin is relevant to precipitation pH. As the pH
value decreases, the organic bound Na on lignin structure will be
gradually replaced by hydrogen ions; as the pH value increases,
the hydrogen on lignin structure will be also replaced by sodium

Dm0i;i1;2 mass loss in un-catalyzed pyrolysis and gasication

Dmi,i = 1,2,3,4 mass loss in catalyzed pyrolysis and gasication
dm=dt 0i;i1;2 =m0  mf reactivity in un-catalyzed pyrolysis and
gasication
dm=dt 0i;i1;2;3;4 =m0  mf reactivity in catalyzed pyrolysis and
gasication

ions. Based on this principle, 10% NaOH- and 10% Na2CO3-loaded APL
samples were prepared by impregnating method [19,28,29]. A
known amount of APL solid was rst added into two beakers.
0.1 mol/L NaOH and Na2CO3 solution were then added into the beakers, respectively, until the APL samples just dissolved; the loading
amount of NaOH and Na2CO3 was 10% at this time. In order to avoid
loading excessive NaOH and Na2CO3, the process of addition needed
to be as gradual and slow as possible. 60% NaOH- and 60% Na2CO3loaded APL samples were also prepared by the same method; the
only difference is that, the adding amount of 0.1 mol/L NaOH and
Na2CO3 solution were 60%. Finally, the lignin solution was dried in
an oven at 105 C, and then the NaOH- and Na2CO3-loaded APL sample were obtained.
Black liquor solids (BLSs) were prepared by totally drying black
liquor in an air dry oven at 105 C. Afterward, it was ground and
sieved to less than 200 lm in particle size for the runs performed
in this work.
2.2. Experimental methods
The elemental analysis of the samples was performed at an elemental analyzer (Perkin-II CNHS/O2400 Elmer) and an inductively
coupled plasma atomic emission spectrometer (Vario-I elementar
Germany). The proximate analysis was carried out using a thermo-gravimetric analyzer [1]. Gross caloric values of the samples
were determined by an automatic bomb calorimeter. The results
of ultimate and proximate analysis of the samples are shown in
Table 1. From Table 1, the marked difference of constituents
between APL and other samples were the contents of ash and Na.
Fundamental tests were carried out on a Jupiter Thermo Gravimetric Analyzer STA 449 F3, coupled with a thermo electron corporation Fourier Transformation Infrared Spectrometer TENSOR 27 by
using a pipe. The experiments were done on TGA at a heating rate
of 20 C/min within the temperature range from 50 to 1000 C.
High purity nitrogen was used as carrier gas with a ow rate of
20 mL/min, and carbon dioxide was used as gasifying agent with
a ow rate of 40 mL/min throughout the pyrolysis and gasication
process. The sample weight was required to be less than 10 mg.
The volatile released from pyrolysis and gasication would be
swept into a Fourier Transform Infrared Spectrometer gas cell
quickly by pure nitrogen. Moreover, the FTIR gas cell and the pipe
were already preheated to 150 C before each experiment. The
spectrum scope was located in the range 4000667 cm1 and the
resolution factor was set at 4 cm1.
3. Results and discussion
3.1. Determine the time ranges of pyrolysis and gasication reaction
Identication of pyrolysis and gasication reactions was mainly
based on the DTG curve and the rst order derivative of DTG curve

24

D.-l. Guo et al. / Applied Energy 95 (2012) 2230

Table 1
Utimate and proximate analysis of the materials.
Materials

APL
BLS
10%
10%
60%
60%
a

Proximate analysis (dry basis) (wt%)

NaOH-loaded APL
Na2CO3-loaded APL
NaOH-loaded APL
Na2CO3-loaded APL

Ultimate analysis (wt%)

Ash

Volatiles

5.95
42.47
21.93
21.80
40.25
40.37

78.83
50.14
72.48
72.65
52.45
52.46

56.01
32.46
40.47
40.58
34.58
34.63

8.54
6.41
4.31
4.32
3.21
3.30

35.34
60.99
55.15
55.03
62.17
62.03

T'1

QHHV (MJ/kg)

8.11  104
0.72  104
0.72  104
6.12  104
6.12  104

22.87
11.32
18.77
18.83
12.35
12.46

N
0.08
0.14
0.07
0.07
0.04
0.04

DTG (%/s)

pyrolysis and gasication. As shown in Fig. 1b, the appreciable difference between catalyzed and un-catalyzed pyrolysis was the
number of the pyrolysis stage. There were three DTG peaks during
BLS pyrolysis process, however, only one DTG peaks can be found
during APL pyrolysis. It indicated that BLS pyrolysis underwent
three different weight losses, whereas APL pyrolysis underwent
only one weight loss. The pyrolysis and gasication reaction regions
of APL, BLS and other samples are shown in Table 2. From Table 2,
adding 10% NaOH and Na2CO3 to pure APL, the start temperature
of gasication decreased from 818 C to 642 and 643 C, respectively, especially this value decreased to 617 and 616 C as adding
60% NaOH and Na2CO3 to APL. This phenomenon may be indicated
that the start temperature of gasication reaction was decided by
the adding quantities of NaOH and Na2CO3.

T'2

-0.05
-0.10

D(DTG)

0.0004
0.0000
-0.0004
0

500

1000

1500

2000

2500

3000

3500

4000

3.2. TG and DTG analysis

Time (s)
Fig. 1a. Determine the time-limit of each stage during APL pyrolysis and gasication.

T1

0.00

DTG (%/s)

Na (ppm)

Oxygen content was determined by difference.

0.00

T2

T4

T3

-0.03
-0.06
0.0002

D (DTG)

0.0000

-0.0002
0

500

1000

1500

2000

2500

3000

3500

4000

Time (s)
Fig. 1b. Determine the time-limit of each stage during BLS pyrolysis and
gasication.

(D(DTG)). As shown in Fig. 1a, as soon as the APL pyrolysis reaction

occurred, the DTG curve varied from zero to y direction along
y-axis, reached the maximum, and then moved from the maximum
value to zero. In mathematics, the D(DTG) value contained three
zero values in above process. The rst and the third zero values of
D(DTG) corresponded to the start and end of the APL pyrolysis reaction. The second zero value of D(DTG) due to the maximum value of
DTG. As shown in Fig. 1a, the temperature range of APL pyrolysis
was marked as T 01 , and the temperature range of APL gasication
was marked as T 02 .
For NaOH and Na2CO3 catalytic reactions, the same method was
adopted to distinguish between the pyrolysis stage and the gasication stage. Fig. 1b presented the time-limit of each stage during BLS

The TG and DTG curves of APL pyrolysis and CO2-gasication

with NaOH and Na2CO3 additives are shown in Figs. 2 and 3. For
comparison, the TG and DTG curves of pure APL and BLS are also
presented in Figs. 2 and 3.
As shown in Figs. 2 and 3, pure APL pyrolysis and CO2-gasication
was characterized by two weight loss stages between 112 and
1000 C (Table 2). The rst stage between 112 and 688 C was
responsible for the pyrolysis of APL, accounting for 54.79% weight
loss with a maximum mass loss rate at 382 C (Table 3). The second
stage from 818 to 1000 C was the main gasication stage, accounting for a weight loss of 30.32% with a maximum rate of thermal degradation at 1000 C. However, BLS, 10% NaOH and 10% Na2CO3
catalyzed pyrolysis and gasication exhibited four distinct weight
loss stages: the rst weight loss process was due to the release of
water with the maximum mass loss rate at 135, 165 and 157 C,
respectively (Table 3). The second and third stages could be ascribed
to the catalyzed pyrolysis processes. The fourth stage occurred at
higher temperatures (9001000 C) was the main CO2 gasication
stage. For 60% NaOH-loaded and 60% Na2CO3-loaded APL, the pyrolysis and gasication process was characterized by three weight loss
stages. From Table 2, it could be found that the end temperatures of
this two samples pyrolysis (616 and 615 C) were lower than the end
temperatures of 10% NaOH and 10% Na2CO3 catalyzed pyrolysis (641
and 642 C). The main reason was quite likely the higher ash content
of 60% NaOH-loaded and 60% Na2CO3-loaded APL. In this paper, in
order to eliminate the effect of additives content on the weight
fraction of volatile matter in raw sample, dm/dt was replaced by
1/(m0  mf) (dm/dt) to compare the reactivity among different
samples. For clear description, a summary of pyrolysis and CO2
gasication parameters are given in Table 3.
Table 3 shows that the absolute value of dm=dt01 =m0  mf
was higher than the absolute value of (dm/dti,i = 1,2,3)/(m0  mf),
however, the absolute value of dm=dt 02 =m0  mf was lower than
the absolute value of (dm/dt4)/(m0  mf). It meant that pure APL had
the highest pyrolysis reactivity but had the lowest gasication reactivity. Meanwhile, according to the value of T 02 max was higher than

25

D.-l. Guo et al. / Applied Energy 95 (2012) 2230

Table 2
The reaction regions of pyrolysis and gasication.
Experiments

Pyrolysis
T 01

APL
10%
10%
60%
60%
BLS

Gasication

(C)

112688

NaOH-loaded APL
Na2CO3-loaded APL
NaOH-loaded APL
Na2CO3-loaded APL

T1 (C)

T2 (C)

T3 (C)

T 02 (C)

T4 (C)

103214
94201
92211
96211
94191

215435
202460
212616
212615
192414

435641
461642

415612

8181000

6421000
6431000
6171000
6161000
6131000

Heating Curve

100

1000

800

60

APL
BLS

600

10% NaOH + APL

60% NaOH + APL
60% Na2CO3 +APL

40

400

20

200

Temperature (

Mass (%)

10% Na2CO3 +APL

80

0
0

1000

2000

3000

4000

5000

gasication reactivity increased with increasing the amounts of

NaOH and Na2CO3. The absence of (dm/dt3)/(m0  mf) during 60%
NaOH and 60% Na2CO3 additives pyrolysis presumably due to the
increased amount of additives; the reduced T4max was mainly
attributed to the catalysis of NaOH and Na2CO3 [19,30]. For BLS,
containing quantity of NaOH and Na2CO3 were between 10% and
60%, the absolute value of (dm/dt4)/(m0  mf) and T4max also
accorded with above tendency. In summary, we proposed that, by
increasing the total NaOH and Na2CO3 additives in gasication reactions, the temperature of the maximum mass loss rate may be decreased due to an increase in the number of the catalytic surface
groups [18]. Also, increased NaOH and Na2CO3 additives amount
in the system may result in enhanced gasication reactivity of alkali
lignin.

6000

Time (s)

3.3. Analysis the composition of the volatile products

Fig. 2. Inuence of NaOH and Na2CO3 additives on TG curves of lignin samples and
BLS.

the value of T4max, It can be speculated that the presence of NaOH

and Na2CO3 moved the max mass loss rate to lower temperature
side in the gasication stage. As shown in Table 3, the loading quantities of NaOH and Na2CO3 also had a signicant effect on (dm/dt4)/
(m0  mf) and T4max. An important observation of this study was
that the absolute value of (dm/dt4)/(m0  mf) and T4max both
decreased with increasing amount of NaOH and Na2CO3 additives
(Table 3). In the case of pure APL gasication, the absolute value
of dm=dt 01 =m0  mf was 2.74E4; when 10% NaOH- and 10%
Na2CO3- loaded APL gasication, the absolute values of the former
was 8.37E4, the latter was 1.03E3; while in the case of that with
60% NaOH and 60% Na2CO3 additives, these values increased to
1.51E3 and 1.42E3, respectively. It indicated that the catalyzed

The evolved volatiles from TGA were real-timely swept into the
gas cell. Then the information of absorbance at various wave numbers and times could be obtained by the 3D infrared spectrum.
When a time was xed, the absorbance information at various
wave numbers could be obtained to analyze the composition of
the gas. When a wave number was xed, the absorbance information at various times could be obtained to analyze a given composition as a function of time. According to the concentration of a
volatile component was in proportion to its absorbance [31], the
variation of absorption intensity in the whole process can reect
the tendency of product yields of the gas species.
Typical 3D infrared spectra from pyrolysis and gasication of
60% Na2CO3-loaded APL is presented in Fig. 4. As shown in Fig. 4,
it could be observed that water, methane, hydrocarbons, alcohols,
phenols, aldehydes, and ketones (C@O) were released out as vola-

(a)

(b)
0.00

DTG (%/s)

DTG (%/s)

0.00

-0.05

-0.05

60% Na2CO3 + APL

10% Na2CO3 + APL

-0.10

-0.10

10% NaOH + APL

APL
BLS
0

1000

2000

3000

Time (s)

4000

5000

6000

60% NaOH + APL

APL
BLS
0

1000

2000

3000

Time (s)

Fig. 3. Inuence of NaOH and Na2CO3 additives on TG curves of lignin samples and BLS.

4000

5000

6000

26

D.-l. Guo et al. / Applied Energy 95 (2012) 2230

Table 3
Characteristic parameters of pyrolysis and gasication.
Un-catalytic

APL

Catalytic

10% NaOH
loaded APL

10% Na2CO3
loaded APL

60% NaOH
loaded APL

60% Na2CO3
loaded APL

BLS

dm=dt01 =m0  mf

1.28E3

(dm/dt1)/(m0  mf)
(dm/dt2)/(m0  mf)
(dm/dt3)/(m0  mf)

1.10E4
8.60E4
1.28E3

8.36E5
9.63E4
9.25E4

2.58E4
8.65E4

2.39E4
7.35E4

2.58E4
8.70E4
5.48E4

dm=dt02 =m0  mf

2.78E4

(dm/dt4)/(m0  mf)

8.37E4

1.03E3

1.51E3

1.42E3

1.08E3

T 01 max

382 C

T1max
T2max
T3max

165 C
350 C
492 C

157 C
341 C
522 C

115 C
365 C

115 C
354 C

135 C
308 C
464 C

(C)

T 02 max (C)

1000 C

T4max

935 C

909 C

797 C

828 C

908 C

Dm01 (%)

54.79

Dm1 (%)
Dm2 (%)
Dm3 (%)

2.48
24.00
26.16

2.77
27.05
12.10

3.43
31.00

4.32
32.21

3.45
21.73
9.82

Dm02 (%)

24.16

Dm4 (%)

32.95

38.78

24.27

25.74

28.66

Table 4
The main products of pyrolysis and gasication by 3D infrared spectra.

Fig. 4. Typical 3D infrared spectra from 60% Na2CO3-loaded APL pyrolysis and
gasication.

tiles between 500 s and 2000 s [3138]. The release of these products mainly occurred at low temperatures, corresponding to the
main pyrolysis temperature zone in the TG curve (Fig. 2). However,
after 2000 s, carbon monoxide was the main gas product evolving
from BLS, NaOH and Na2CO3 catalyzed gasication. The typical
functional groups and the IR signal with the possible compounds
are listed in Table 4.
3.4. Inuence of NaOH and Na2CO3 additives on the species of volatile
products
Based on the maximum mass loss rate of DTG curves, three levels of temperature were selected to compare the IR spectra of pure
APL pyrolysis with those of NaOH and Na2CO3 catalyzed pyrolysis
and gasication (Fig. 5). For example, the spectra of volatiles released at 135, 308, and 908 C for BLS are shown in Fig. 5(a1),
(a2), and (a3), respectively.
As shown in Fig. 5(a1)(f1), a conclusion could be drawn that
the weight loss in the initial pyrolysis stage was mainly caused
by the release of H2O. For pure APL pyrolysis, the generation of
H2O was not conspicuous (Fig. 5(a1)), while this was obvious for
BLS, NaOH and Na2CO3 catalyzed pyrolysis (Fig. 5(b1)(f1)). From
Table 3, the weight losses of BLS, 10% NaOH- and Na2CO3-loaded
APL, 60% NaOH- and Na2CO3-loaded APL in the initial pyrolysis
were 3.45%, 2.48%, 2.77%, 3.43%, 4.32%, respectively. According to
previous researches [32,39], the generated H2O at low temperature
is released out by the cracked of aliphatic hydroxyl groups in the
lateral chains. This elucidated that the presence of NaOH and

Wavenumber
(cm1)

Functional
group

Vibration

Evolution
Product

References

35593964
12751775
20582131
21502212
3024
28503200
27753115
13001400
14951525

OAH
HAOAH
CAO
CAO
AOCH3
CAH
CAH
OAH

Stretching
Bending
Stretching
Stretching

H2O

[23,24]

CO

[25,26]

CH4

[24,29,37]

Hydrocarbons
Phenols

[14,24,29]
[24,28,29]

9601131
35593964
11451211

CAO
OAH
CAC

Stretching
Stretching
Stretching

Alcohols

[24,37]

Aldehydes and
ketones

[14,29]

17001740

C@O

Stretching

Stretching
Stretching
Stretching
Skeleton

Na2CO3 stimulated the aliphatic hydroxyl groups to convert to

H2O. With temperature increasing, pyrolysis reaction proceeded
into the main pyrolysis stage, and then more gaseous products
were released out. As shown in Fig. 5(a2)(f2), the absorption band
of H2O was still present. Besides H2O, the evolution of alcohols,
phenols, aldehydes, ketones, and hydrocarbons were also responsible for the weight loss in this stage. The absorption bands of these
volatiles for pure APL, BLS, and NaOH- and Na2CO3-loaded APL appeared to be at the same wave numbers, while some diversities of
the absorbance existed. Therefore, it was reasonable to postulate
that the catalytic effects of NaOH and Na2CO3 additives on the
pyrolysis products mainly varied in amounts but not in species.
Meanwhile, as shown in Tables 2 and 3, the temperature range
(T2) and the weight loss (Dm2) in the main pyrolysis stage increased with increasing the NaOH and Na2CO3 amount. Specically, it could be seen that the characteristic absorbance intensity
of alcohols at 10401180 cm1 apparently increased with 10%
NaOH and 10% Na2CO3 catalyzed pyrolysis. This observation further demonstrated the above analysis that the released H2O was
indeed affected by NaOH and Na2CO3 additives during the initial
pyrolysis stage. Moreover, the characteristic absorbance intensity
of aldehydes and ketones rst increased and then decreased with
the increasing Na2CO3 additive amount, while this was decreased
with the increasing NaOH additive amount. In contrast, the characteristic absorbance intensity of phenols decreased with NaOH catalyzed pyrolysis, while it was increased with and Na2CO3 catalyzed
pyrolysis. In summary, NaOH-loaded and Na2CO3-loaded APL have

27

D.-l. Guo et al. / Applied Energy 95 (2012) 2230

0.02

(a1)

0.02 (b1)
0.01

(a) - APL

0.00
0.04
0.02

3000

2500 2000

1500

1000

(a2)

0.00
0.10

(b) - BLS

0.00
3500

3500

3000

2500 2000

1500

Absorbance

Absorbance

0.01

1000

0.04

0.05

3000

2500 2000

1500

1000

3000

2500 2000

1500

1000

3000

2500 2000

1500

1000

0.02
0.00
0.10

(a3)

3500

(b2)

3500

b3)

0.05

0.00

0.00
3500

0.02 (c1)

3000

2500 2000

1500

1000

3500

0.02 (d1)

(c) - 10% Na2CO3 loaded APL

(d) - 60 %Na2CO3 loaded APL

0.01

0.01

3500

3000

2500 2000

1500

1000

(c2)
0.02
0.00
0.10

3500

3000

2500 2000

1500

Absorbance

Absorbance

0.00
0.00
0.04

1000

(e1)

0.01

3000

2500 2000

1500

1500

1000

3000

2500 2000

1500

1000

3000

2500 2000

1500

1000

0.00

1000

3500

(d3)

3500

0.02

(e) - 10% NaOH loaded APL

(f1)

(f) - 10% NaOH loaded APL

0.01

0.00

0.00
3500

3000

2500 2000

1500

1000

(e2)

0.02
0.00
3500

3000

2500 2000

1500

1000

(e3)

0.05

Absorbance

Absorbance

2500 2000

0.00
3500

0.10

3000

0.05

0.00

0.04

3500

(d2)

0.02

0.10

(c3)

0.05

0.02

0.04

0.04

3500

3000

2500 2000

1500

1000

3000

2500 2000

1500

1000

3000

2500 2000

1500

1000

(f2)

0.02
0.00
0.10

3500

(f3)

0.05

0.00

0.00
3500

3000

2500 2000

1500

1000

Wavenumbers (cm-1)

3500

Wavenumbers (cm-1)

Fig. 5. FTIR spectra of volatile products at the maximum weight loss rate from lignin samples and BLS.

the same change trend on the quantity of alcohols, but different

change trend on the quantity of phenols, aldehydes, and ketones.
Fig. 5(a3)(f3) compared the IR spectra at the maximum mass
loss in the gasication stage. It could be seen that CO was the main
gas released in this stage. Unlike pure APL gasication, which only
limited CO was detected, the absorbance intensity of CO was largely enhanced in BLS, NaOH and Na2CO3 catalyzed gasication.
The results were also deduced from the regular weight loss in
the gasication. As shown in Table 3, the value of Dm02 (%) was
24.16%, for 10% NaOH- and Na2CO3-loaded APL, BLS, 60% NaOHand Na2CO3-loaded APL, the values of Dm4 were 32.95%, 38.78%,
28.66%, 24.27%, 25.74%%, respectively. It appeared clearly that
NaOH and Na2CO3 increased the weight loss in the gasication
stage. To sum up the above arguments, NaOH and Na2CO3 favored
the generation of CO in the gasication stage. On the contrary,
Fig. 5(a2)(f2) showed that all the samples appeared very weak
absorption intensity at 22601990 cm1, this meant that the pres-

ence of NaOH and Na2CO3 had an insignicant catalytic effect on

the formation of CO in the pyrolysis stage.
3.5. Inuence of NaOH and Na2CO3 additives on the evolution patterns
of volatile products during the pyrolysis stage
Fig. 6 presented the evolution proles of the volatile products,
which were constructed by selected the characteristic absorption
bands and followed the intensity with time. The sample mass of
APL for each run had been accurately controlled at 10 mg, thus
the effect of NaOH and Na2CO3 additives on the evolution of the
volatile products could be compared by the absorption intensity
of the IR spectra [40,41].
According to the literatures [37,42], alcohols are mainly released
with cracking of the aromatic methoxyl groups and cinnamyl alcohol-type propanoid side chains. For pure APL pyrolysis, alcohols release started at 1197 s (397 C), reached a max at 1361 s (454 C)

28

D.-l. Guo et al. / Applied Energy 95 (2012) 2230

0.025

0.015

(a) Alcohols

(b) Phenols

Absorbance

Absorbance

0.020

0.015

0.010

0.010

0.005

0.005

0.000

0.000
1000

1500

1000

2000
0.08

(c) Hydrocarbons

1500

2000

(d) Aldehydes & Ketones

0.03

Absorbance

Absorbance

0.06
0.02

0.01

0.04

0.02
0.00
0.00
1000

1500

2000

2500

Time (s)

1000

1500

2000

Time (s)

Fig. 6. Volatile evolution proles during pyrolysis stage (h: pure APL; }: BLS; : with 10% NaOH; : with 60% NaOH; : with 10% Na2CO3; : with 60% Na2CO3).

and then decreased dramatically till 1512 s (504 C) followed by a

slow continuous decreased (Fig. 6a). However, in the case of BLS,
NaOH and Na2CO3 catalyzed pyrolysis, the evolution patterns of
alcohols were apparently different. Alcohols release begun at
1525 s (508 C), reached a max at 1701 s (567 C) and nished at
1840 s (613 C). These results implied that the addition of NaOH
and Na2CO3 pushed back the time of alcohols release.
As a result of the cleavage of the ether bonds between the lignin
building units, followed by cracking and reforming of the alkyl side
chains of these units [37], phenols were released from APL pyrolysis over a time range between 1121 s (374 C) and 1487 s (496 C)
(Fig. 6b). However, in the presence of 10% NaOH and 10% Na2CO3,
the generation time of phenols was postponed for about 370 s
(123 C); in the case of 60% NaOH and 60% Na2CO3, the delayed
time was approximate 619 s (206 C) (Fig. 6b). Therefore, we may
be concluded that the release time of phenols was delayed with
increasing NaOH and Na2CO3 additive amount. A possible reason
could be that phenols generated by the secondary reaction between sodium phenolate and the volatile need to higher reaction
temperature. With regard to hydrocarbons, it is produced mainly
from the cracking of the methoxy group (AOCH3A) and the methylene group (ACH2A) [32,37]. From Fig. 6c, for pure APL pyrolysis,
hydrocarbons were released in a single peak between 1134 s
(378 C) and 1676 s (559 C). In the presence of NaOH or Na2CO3,
the formation of hydrocarbons showed a double peak, the rst
peak between 1537 s (512 C) and 1846 s (615 C), was from the
decomposition of methyl functional groups and the second higher
temperature peak from 2000 s (667 C) to 2420 s (807 C), might be
attributed to the secondary pyrolysis of the volatile. As shown in
Fig. 6d, the absorbance intensity of aldehydes and ketones were

both reduced during NaOH and Na2CO3 catalyzed pyrolysis. In

addition, the increasing amount of NaOH and Na2CO3 additives
seemed to have no further effect on the absorbance intensity of
aldehydes and ketones. It is well known that aldehydes and ketones are probably attributable to the CbACc cleavage in the alkyl
side chains with ACH2OH or ACOOH groups in c position
[37,43]. It might be reasonable to speculate that the aliphatic
ACH2ONa and ACOONa groups were difcultly removed by alkyl
CAC fragmentation of phenyl-propane side chains, yielding aldehydes and ketones.
3.6. Inuence of NaOH and Na2CO3 additives on the evolution patterns
of volatile products during the gasication stage
Unlike NaOH and Na2CO3 catalyzed pyrolysis reaction, The CO
evolution in gasication stage was obviously affected by the additives. As shown in Figs. 5b and 7, a small quantity of CO was generated from pure APL, BLS, NaOH- and Na2CO3-loaded APL pyrolysis.
The reason could be that NaOH and Na2CO3 additives had little effect
on the cracking of ether bridges which is the main source of CO at the
lower temperature range below 667 C (2000 s) [37,43]. However, in
the gasication stage, the absorbance intensity of CO was totally increased under all NaOH and Na2CO3 catalyzed gasication conditions. From Fig. 7, for 60% NaOH-loaded APL gasication, the
evolution range of CO was from 2199 s (733 C) to 2755 s (918 C);
when 10% NaOH was added to APL, CO was released from 2367 s
(789 C) to 2934 s (978 C). Similarly, for 60% Na2CO3-loaded APL,
CO formation was from 2251 s (750 C) to 3240 s (1000 C); when
10% Na2CO3-loaded APL gasication, CO generation was from
2338 s (779 C) to 3070 s (1000 C). For BLS, in the presence of NaOH

D.-l. Guo et al. / Applied Energy 95 (2012) 2230

was relatively concentrated and intensively increased from 754

to 920 C. Several investigated volatile species, including water,
carbon monoxide, methane, hydrocarbons, alcohols, phenols, aldehydes, and ketones, were identied from 3D FTIR spectra. The FTIR
analysis revealed that the effect of NaOH and Na2CO3 additives on
the pyrolysis products mainly varied in amounts but not in species.
Specically, the weight loss in the initial pyrolysis stage was
mainly caused by the release of H2O. The evolution of alcohols,
phenols, aldehydes, ketones, and hydrocarbons were responsible
for the mass loss in the main pyrolysis stage, and CO was the main
gas released in the gasication stage. Moreover, The addition of
NaOH and Na2CO3 pushed back the releasing time of alcohols
and phenols.

Absorbance

0.08

0.06

0.04

0.02

0.00
1500

29

2000

2500

3000

3500

Acknowledgements

Time (s)
Fig. 7. The evolution proles of CO from the gasication stage (h: pure APL; }: BLS;
: with 10% NaOH; : with 60% NaOH; : with 10% Na2CO3; : with 60% Na2CO3).

and Na2CO3, The generation of CO was concentrated and increased

from 2262 s (754 C) to 2760 s (920 C). These observations were
consistent with the mechanisms proposed by Sams and Shadman
[44] for the gasication of organic carbon catalytic with Na2CO3 by
carbon dioxide (Eqs. (1)(5)).

Na2 CO3 s Cs ! ACOONa ACONa

ACOONa Cs ! ACONa COg

ACONa Cs ! ACNa COg

ACNa CO2 g ! ACONa COg

ACONa CO2 g ! ACOONa COg

Eqs. (2) and (3) are conceived as the reduction of the catalytic sites
by the organic carbon. Eqs. (4) and (5) are identied as the oxidation
of the NaAC catalytic sites by CO2. The gasication reactions for BLS
by Na2CO3 were best described by the combination of Eqs. (2) and
(5) as follows:

ACOONa Cs ! ACONa COg

ACONa CO2 g ! ACOONa COg

Cs CO2 g ! COs

According to Connolly [18] who pointed out that the reaction

rate of ACONa with CO2 is far faster than that of ACOONa with organic carbon, so the Eq. (2) will be the rate determining step of the
gasication of BLS. For APL, without the presence of NaOH or
Na2CO3, The gasication reactions should only be represented as
Eq. (6), which is highly endothermic and will not proceed until signicantly high temperatures are reached [44]. Therefore, the presence of NaOH and Na2CO3 has a signicant effect on CO formation
between 754 and 920 C during alkali lignin gasication.
4. Conclusions
The effects of NaOH and Na2CO3 additives on the thermogravimetric characteristics and the evolutions patterns of volatile products during alkali lignin pyrolysis and gasication were studied by
using TG-FTIR analysis. In the pyrolysis stage, the maximum mass
loss rate decreased with increasing amounts of NaOH and Na2CO3
additives. In the gasication stage, NaOH and Na2CO3 moved the
max mass loss rate to lower temperature side. The CO evolution
in gasication stage was obviously affected by NaOH and Na2CO3.
For pure APL gasication, a small quantity of CO was generated;
for NaOH and Na2CO3 catalyzed gasication, the evolution of CO

This work was supported by the National Natural Science

Foundation of China (NSFC, No. 21176095 and No. 51176195),
the National High Technology Research and Development Program
of China (863 Program, 2012AA101806) and the Major Research
Projects of Guangdong Province, China (No. 2011A090200006).

References
[1] Sricharoenchaikul V. Assessment of black liquor gasication in supercritical
water. Bioresour Technol 2009;100:63843.
[2] Cardoso M, Oliveira KD, Costa G, Passos ML. Chemical process simulation for
minimizing energy consumption in pulp mills. Appl Energy 2009;86:4551.
[3] Naqvi M, Yan J, Dahlquist E. Black liquor gasication integrated in pulp and
paper mills: a critical review. Bioresour Technol 2010;101:800115.
[4] Snchez J, Gea G, Gonzalo A, Bilbao R, Arauzo J. Kinetic study of the thermal
degradation of alkaline straw black liquor in nitrogen atmosphere. Chem Eng J
2004;104:16.
[5] Pettersson K, Harvey S. CO2 emission balances for different black liquor
gasication biorenery concepts for production of electricity or secondgeneration liquid biofuels. Energy 2010;35:11016.
[6] Eriksson H, Harvey S. Black liquor gasicationconsequences for both industry
and society. Energy 2004;29:581612.
[7] Naqvi M, Yan J, Frling M. Bio-renery system of DME or CH4 production from
black liquor gasication in pulp mills. Bioresour Technol 2010;101:93744.
[8] Lou R, Wu SB. Products properties from fast pyrolysis of enzymatic/mild
acidolysis lignin. Appl Energy 2011;88:31622.
[9] He J, Zhang W. Techno-economic evaluation of thermo-chemical biomass-toethanol. Appl Energy 2011;88:122432.
[10] Andersson E, Harvey S. Comparison of pulp-mill-integrated hydrogen
production from gasied black liquor with stand-alone production from
gasied biomass. Energy 2007;32:399405.
[11] Demirbas A. Pyrolysis and steam gasication processes of black liquor. Energy
Convers Manage 2002;43:87784.
[12] Carlsson P, Wiinikka H, Marklund M, Grnberg C, Pettersson E, Lidman M, et al.
Experimental investigation of an industrial scale black liquor gasier. 1. The
effect of reactor operation parameters on product gas composition. Fuel
2010;89:402534.
[13] Whitty K, Kullberg M, Sorvari V, Backman R, Hupa M. Inuence of pressure on
pyrolysis of black liquor: 2. Char yields and component release. Bioresour
Technol 2008;99:6719.
[14] Whitty K, Backman R, Hupa M. Inuence of pressure on pyrolysis of black
liquor: 1. Swelling. Bioresour Technol 2008;99:66370.
[15] Purtolas R, Gea G, Murillo MB, Arauzo J. Pyrolysis of black liquors from
alkaline pulping of straw. Inuence of a preoxidation stage on the char
characteristics. J Anal Appl Pyrol 2001;5859:95566.
[16] Zhan X, Zhou ZJ, Wang F. Catalytic effect of black liquor on the gasication
reactivity of petroleum coke. Appl Energy 2010;87:17105.
[17] Kumar V. Pyrolysis and gasication of lignin and effect of alkali addition. PhD
thesis, Georgia Institute of Technology, US; 2009.
[18] Connolly TS. CO2 pyrolysis and gasication of kraft black liquor char. PhD
thesis, The University of Maine; 2006.
[19] Guo DL, Wu SB, Lou R, Yin XL, Yang Q. Effect of organic bound Na groups on
pyrolysis and CO2-gasication of alkali lignin. BioResources 2011;6:414557.
[20] Quyn DM, Wu H, Bhattacharya SP, Li CZ. Volatilisation and catalytic effects of
alkali and alkaline earth metallic species during the pyrolysis and gasication
of Victorian brown coal. Part II. Effects of chemical form and valence. Fuel
2002;81:1518.
[21] Yang H, Yan R, Chen H, Lee DH, Zheng C. Characteristics of hemicellulose,
cellulose and lignin pyrolysis. Fuel 2007;86:17818.
[22] Raveendran K, Ganesh A, Khilar KC. Pyrolysis characteristics of biomass and
biomass components. Fuel 1996;75:98798.

30

D.-l. Guo et al. / Applied Energy 95 (2012) 2230

[23] Teng H, Wei YC. Thermogravimetric studies on the kinetics of rice hull
pyrolysis and the inuence of water treatment. Ind Eng Chem Res
1998;37:380611.
[24] Jensen A, Johansen K, Wjtowicz MA, Serio MA. TG-FTIR study of the inuence
of potassium chloride on wheat straw pyrolysis. Energy Fuels
1998;12:92938.
[25] Sun RC, Tomkinson J, Bolton J. Effects of precipitation pH on the physicochemical properties of the lignins isolated from the black liquor of oil
palm empty fruit bunch bre pulping. Polym Degrad Stabil 1999;63:
195200.
[26] Luo CD, Chen ZT, Chen. Preliminary studies on the mechanism of lignin
precipitation during acidication of kraft wheat straw black liquor. Trans Chin
Pulp Pap 1990;5:3342.
[27] Lawther JM, Sun RC, Banks W. Rapid isolation and structural characterization
of alkali-soluble lignins during alkaline treatment and atmospheric rening of
wheat straw. Ind Crop Prod 1996;5:97105.
[28] Quyn DM, Wu H, Li C-Z. Volatilisation and catalytic effects of alkali and
alkaline earth metallic species during the pyrolysis and gasication of
Victorian brown coal. Part I. Volatilisation of Na and Cl from a set of NaClloaded samples. Fuel 2002;81:1439.
[29] Ohtsuka Y, Zhiheng W, Furimsky E. Effect of alkali and alkaline earth metals on
nitrogen release during temperature programmed pyrolysis of coal. Fuel
1997;76:13617.
[30] Lv D, Xu M, Liu X, Zhan Z, Li Z, Yao H. Effect of cellulose, lignin, alkali and
alkaline earth metallic species on biomass pyrolysis and gasication. Fuel
Process Technol 2010;91:9039.
[31] Tao L, Zhao GB, Qian J, Qin Yk. TG-FTIR characterization of pyrolysis of waste
mixtures of paint and tar slag. J Hazard Mater 2010;175:75461.

[32] Liu Q, Wang S, Zheng Y, Luo Z, Cen K. Mechanism study of wood lignin
pyrolysis by using TG-FTIR analysis. J Anal Appl Pyrol 2008;82:1707.
[33] Bassilakis R, Carangelo RM, Wjtowicz MA. TG-FTIR analysis of biomass
pyrolysis. Fuel 2001;80:176586.
[34] Zhu HM, Yan JH, Jiang XG, Lai YE, Cen KF. Study on pyrolysis of typical medical
waste materials by using TG-FTIR analysis. J Hazard Mater 2008;153:6706.
[35] Lee SB, Fasina O. TG-FTIR analysis of switchgrass pyrolysis. J Anal Appl Pyrol
2009;86:3943.
[36] Jiang X, Li C, Wang T, Liu B, Chi Y, Yan J. TG-FTIR study of pyrolysis products
evolving from dyestuff production waste. J Anal Appl Pyrol 2009;84:1037.
[37] Lv GJ, Wu SB, Lou R, Yang Q. Analytical pyrolysis characteristics of enzymatic/
mild acidolysis lignin. Cellul Chem Technol 2010;44:33542.
[38] Caballero JA, Font R, Marcilla A. Study of the primary pyrolysis of Kraft lignin at
high heating rates: yields and kinetics. J Anal Appl Pyrol 1996;36:15978.
[39] Madarasz J, Varga PP, Pokol G. Evolved gas analyses (TG/DTA-MS and TG-FTIR)
on dehydration and pyrolysis of magnesium nitrate hexahydrate in air and
nitrogen. J Anal Appl Pyrol 2007;79:4758.
[40] Nowakowski DJ, Jones JM, Brydson R, Ross AB. Potassium catalysis in the
pyrolysis behaviour of short rotation willow coppice. Fuel 2007;86:2389402.
[41] Han L, Wang Q, Ma Q, Yu C, Luo Z, Cen K. Inuence of CaO additives on wheatstraw pyrolysis as determined by TG-FTIR analysis. J Anal Appl Pyrol
2010;88:199206.
[42] Caballero J, Conesa J, Font R, Marcilla A. Pyrolysis kinetics of almond shells and
olive stones considering their organic fractions. J Anal Appl Pyrol
1997;42:15975.
[43] Wang S, Wang K, Liu Q, Gu Y, Luo Z, Cen K, et al. Comparison of the pyrolysis
behavior of lignins from different tree species. Biotechnol Adv 2009;27:5627.
[44] Sams D, Shadman F. Mechanism of potassium-catalyzed carbon/CO2 reaction.
AICHE J 1986;32:11327.