Fuel Processing Technology 91 (2010) 942950

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Fuel Processing Technology

j o u r n a l h o m e p a g e : w w w. e l s ev i e r. c o m / l o c a t e / f u p r o c

Pyrolysis of pine wood in a slowly heating xed-bed reactor: Potassium carbonate

versus calcium hydroxide as a catalyst
Zhenya Wang 1, Fu Wang, Jianqin Cao, Jie Wang
Department of Chemical Engineering for Energy, East China University of Science and Technology, No. 130 Meilong Road, Shanghai 200237, PR China

a r t i c l e

i n f o

Article history:
Received 13 April 2009
Received in revised form 17 September 2009
Accepted 27 September 2009
Keywords:
Pine wood
Catalytic pyrolysis
K2CO3
Ca(OH)2

a b s t r a c t
Catalytic pyrolysis of pine wood was carried out in a xed-bed reactor heated slowly from room temperature to
700 C under a stream of purging argon to examine the effects of the physically mixed K2CO3 or Ca(OH)2 on the
pyrolysis behaviors. K2CO3 demonstrated a stronger catalysis for decomposition of hemicellulose, cellulose and
lignin constituents, leading to the reduced yield of liquid product in conjunction with the increased yields of
gaseous and char products because of the promoted secondary reactions of liquid product. With the addition of
17.7 wt.% of K2CO3, none of saccharides, aldehydes and alcohols was formed and the formation of acids, furans
and guaiacols was substantially reduced, whereas the yields of alkanes and phenols were increased. Potassium
led to an increase in the cumulative yields of H2, CO2 and CO at 700 C. Ca(OH)2 somewhat promoted the
decomposition of cellulose and lignin constituents, and the effect of Ca(OH)2 on the yields of liquid and char
was opposite to that of K2CO3. With the addition of 22.2 wt.% Ca(OH)2, some groups of liquid product such as
acids and aldehydes disappeared completely and the yields of saccharides, furans and guaiacols were
somewhat reduced, while the yield of alcohols was remarkably increased in contrast to the result of K2CO3. The
addition of Ca(OH)2 did not signicantly change the total yield of gaseous product at 700 C but enhanced the
yield of H2.
2009 Elsevier B.V. All rights reserved.

1. Introduction
It is well known that alkali and alkaline earth metals have catalytic
effects on the pyrolysis of biomass. Since the alkali and alkaline earth
metals, especially some of them including potassium, sodium, calcium
and magnesium, are indigenous to a variety of biomass relatively in
abundance, attentions have early been paid to their catalytic effects
from viewpoints of chemistry and application. Recently, interests have
been expanded to produce bio-oils and heat-intensive gases via biomass pyrolysis [14]. Catalytic biomass pyrolysis offers a potential
route to modify or upgrade the compositions and qualities of the biooil and/or gaseous product.
Intentional addition of various potassium compounds such as KCl,
CH3COOK, K2CO3 and KOH have been examined with respect to their
impacts on the behavior of biomass pyrolysis. Previous studies showed
that the impregnation of 2 wt.% KCl to wheat straw [5] and 1 wt.%
CH3COOK to willow [6] lowered the temperature of decomposition by
35 C and 65 C, respectively. Jensen et al. [5] and Nowakowski et al. [6]
observed that the potassium impregnated by a solution enhanced the
yields of gaseous product in the slow pyrolysis of wheat straw and
Corresponding author. Tel./fax: +86 21 64252853.
E-mail address: jwang2006@ecust.edu.cn (J. Wang).
1
Present address: State Nuclear Power Plant Service Company, No. 169 Tianlin Road,
Shanghai 200233, PR China.
0378-3820/$ see front matter 2009 Elsevier B.V. All rights reserved.
doi:10.1016/j.fuproc.2009.09.015

short rotation willow coppice, with an increase in the yields of char.

Raveendran et al. [7] reported that more char was produced in the
pyrolysis of ten biomass samples including bagasse, coconut coir,
coconut shell, corn cob, corn stalks, cotton gin waste, millet husk, rice
straw, subabul wood and wheat straw when KCl or K2CO3 was impregnated to these demineralized biomass samples, but the results
were opposite for coir pith, groundnut shell and rice husk. Raveendran
et al. [7] claimed that the cation of alkali metal rather than the anion
plays a dominant role in the catalytic pyrolysis of biomass.
Potassium leads to changes not only in the yields of gaseous, liquid
and char products, but also in their compositions, especially in the
liquid composition. There have been a few studies that are focused on
the liquid components derived from the potassium-catalyzed pyrolysis with different biomass species and pyrolysis conditions [6,810].
It is well evident that potassium is strongly favorable for the formation of low molecular weight compounds in biomass pyrolysis at the
expense of a reduced amount of levoglucosan. In a recent investigation, Blasi et al. have quantied in detail the compositions of the biooils produced from the rapid pyrolysis of r wood impregnated with
0.17.7 wt.% KOH [8].
Calcium cation has a weaker ionic strength than potassium cation,
and it is generally expectable that calcium has a less catalytic activity
on the biomass pyrolysis than potassium. De Groot et al. [11] reported
that calcium ion only slightly affected the yield of char and it retarded
the decomposition of cotton wood. However, Kleen and Gellerstedt

Z. Wang et al. / Fuel Processing Technology 91 (2010) 942950

[12] found that during pyrolysis of pulps, more polysaccharide

was converted to anhydrosugar by loading a small quantity of ionexchanged calcium into the pulps (0.1 wt.%). Shimada et al. [9]
investigated the catalytic actions of alkali metal chlorides (NaCl and
KCl) and alkali earth metal chlorides (MgCl2 and CaCl2) towards the
low-temperature pyrolysis of cellulose (b400 C), and they observed
that alkali earth metals signicantly lowered the pyrolysis temperature, while alkali metals had little inuence. They observed that
each catalyst accelerated the cracking of levoglucosan to form low
molecular weight products such as furfural, acetic acid, and hydroxyl
acetone, but the yields of methanol and 5-hydroxymethyl furfural
decreased in the presence of each catalyst. Such catalytic effects on the
liquid products appear to be very complex, and it is worthwhile doing
more studies.
In this study, we have performed the slow pyrolysis of pine wood
using K2CO3 or Ca(OH)2 as a catalyst. We focus on a comparison of the
catalytic features between them. In terms of the information that most
previous studies use the impregnation method for loading catalyst
to biomass sample, we employ a straightforward physical method for
blending catalyst with biomass sample. Attempts have been made to
examine the catalytic effects on the compositions of both gaseous and
liquid products.
2. Experimental
2.1. Sample and catalysts
The biomass sample used in this study was the wood sawdust of
Chinese white pine which grows widely in the southwest and middle
regions of China. The raw sawdust sample was supplied by a local
wood processing factory, and it was ground and sieved to less than
1 mm. The sample was dried at 105 C prior to use. The proximate and
ultimate analysis showed that the dried pine wood had 0.37% ash,
47.4% C, 6.1% H and 0.1% N.
Potassium carbonate and calcium hydroxide used in this study were
of Chemical Reagent Grade, and both reagents were purchased from
Shanghai Lingfeng Chemical Co. Ltd. The reagent was thoroughly mixed
with the wood sample in an agate mortar for about 15 min, but the
sample was not strongly forced. The mixtures with different catalyst
loadings were used for pyrolysis to examine the effect of catalyst.
2.2. Biomass pyrolysis

943

ultrasonically stirred to prepare the liquid sample for analysis. Gas

chromatograph mass spectrometry (GCMS, PerkinElmer clams 500)
equipped with a HP-5 capillary column was used for identifying the
compounds in the liquid sample. Quantitative determination was implemented for seven typical products including hydroxyl propanone,
furan methanol, phenol, methyl-phenol, guaiacol, 2,4-dimethylphenol, D-allose, using a gas chromatograph (Agilent 6820) equipped
with a ame ionization detector (FID) and HP-5 capillary column.
The commercial reagents of analytic grade were used to prepare the
standard solutions for calibration, and the concentrations of these
compounds in the standard solutions were 8.1 mg/g hydroxyl propanone, 4.4 mg/g furan methanol, 0.5 mg/g phenol, 0.5 mg/g methylphenol, 7.7 mg/g guaiacol, 0.7 mg/g 2,4-dimethyl-phenol, 0.7 mg/g
D-allose. The concentrations of other main compounds in the liquid
were semi-quantitatively estimated, based on their relative peak areas
determined by GCMS to the peak area of a structurally closer compound which was one of the seven quantied compounds.
The gaseous product was collected using gas bags after the condensation at a temperature interval of 50 C. The major compositions
(H2, CO, CH4 and CO2) of the gaseous product were measured by a
gas chromatograph (Agilent 6820) equipped with a thermal conduct
detector (TCD) and a packed column (Unibeads C 80/100).
Elemental analysis (C, H, and N) was carried out on an Elementar
Vario EL III analyzer. X-ray diffraction analysis (XRD) was accomplished on a Rigaku D/max 2550VB/PC diffractometer. Scanning electron microscopy (SEM) was implemented on a modeled JEOL JSM6360LV scanning electron microscope.
3. Results and discussion
3.1. Yields of gaseous, liquid and char products
Fig. 1 shows the inuences of K2CO3 and Ca(OH)2 loadings on the
total yields of gaseous, liquid and char products at a nal pyrolysis
temperature of 700 C. The catalyst loading is dened as the weight
percents of catalyst in the mixture. The variations of yield are statistically calculated from the duplicate or triplicate runs. In the case of
only one run nished, no variations are shown in the gure. The data
of gas yield are obtained by a difference between the amount of the
fed sample and the amounts of liquid and char products. The yields of
gas were also measured directly by quantication of the four major
gases (H2, CO, CO2 and CH4). For all runs, the mass closures of gas,
liquid and char yields were 9498%.

Pyrolysis experiment was carried out in a xed-bed reactor under

atmospheric pressure. The apparatus was mainly made of a vertical
stainless steel tubular reactor, a heated off-gas line, and two series of
ice-cooled trappers. The detailed set-up diagram was depicted elsewhere [13]. In each pyrolysis run, a 2.2 g wood sample or its mixture
with catalyst was heated in a purging stream of argon at a heating rate
of 10 C/min from room temperature to 700 C, held for 5 min, and
then cooled to room temperature by turning off the power. The ow
rate of argon was 300 mL/min. The average residence time of the
tar vapor purged through the heated sample zone was about 2.7 s. The
tar vapor was condensed in the ice-cooled trappers, and the yield of
liquid product including aqueous and tarry products was obtained by
weighing the trappers. The yield of char was obtained by weighing the
sample and the solid residue before and after pyrolysis. The weight of
the catalyst added to the wood sample was subtracted in calculation
of the yield of char. In the case of using Ca(OH)2 as a catalyst, the yield
of liquid product was subtracted by the fraction of water due to the
dehydration of Ca(OH)2.
2.3. Characterizations
In determining the components of liquid oil, the trappers and
the connecting tubes were carefully washed using acetone and then

Fig. 1. Effects of K2CO3 and Ca(OH)2 loading on the yields of char, liquid and gaseous
products derived from the pine wood pyrolysis (10 C/min from room temperature to
700 C).

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Z. Wang et al. / Fuel Processing Technology 91 (2010) 942950

Table 1
Effect of nal temperature on the yields (wt.% dry biomass) of pyrolysis products in the
absence and presence of catalysts.
Temperature
C

No catalyst

17.7 wt.% K2CO3

22.2 wt.% Ca(OH)2

Char

Liquid

Gas

Char

Liquid

Gas

Char

Liquida

Gas

300
350
400
700

64.9
34.9
27.8
19.6

25.8
50.6
54.0
57.0

9.3
14.5
18.2
23.4

57.2
39.1
28.2
22.9

29.1
47.5
48.7
49.2

13.6
13.4
23.2
28.0

46.2
32.1
16.3

40.8
53.3
60.0

11.6
12.9
23.7

The data are subtracted by the water yield from the dehydration of Ca(OH)2.

The addition of K2CO3 led to an increase in the yields of gas and

char against a decrease in the liquid yield. This trend of change
became increasingly pronounced with increasing catalyst loadings
to 17.7 wt.%. Jensen et al. [5] observed a similar trend in the slow
pyrolysis of wheat straw by impregnation of potassium chloride. It
was clear that the physically added K2CO3 played a similar catalytic
role in the biomass pyrolysis. Potassium appeared to strongly catalyze
the secondary reactions of primary liquid products, leading to a
reduction in the yield of liquid in conjunction with an increase in the
yields of gas and char. Table 1 shows the yields of gas, liquid and char

Fig. 2. SEM images of the char samples obtained from the pyrolysis of pine wood at 700 C in the absence and presence of catalysts. (a) pine wood; (b) pine wood mixed with
17.7 wt.% K2CO3; (c) pine wood mixed with 22.2 wt.% Ca(OH)2.

Z. Wang et al. / Fuel Processing Technology 91 (2010) 942950

945

Fig. 3. XRD patterns of the original wood sample and its chars obtained from the pyrolysis at different temperatures in the absence and presence of catalyst. Identied compounds:
, KHCO3; , Ca(OH)2; , CaCO3. PK-17: pine wood mixed with 17.7 wt.% K2CO3; PK-22: pine wood mixed with 22.2 wt.% Ca(OH)2.

obtained at different pyrolysis temperature with and without addition

of catalyst. Potassium started to display its catalysis for the decomposition of liquid product at a temperature as low as 350 C.
In contrast, the addition of Ca(OH)2 somewhat raised the yield
of liquid with a decrease in the yield of char at 700 C. This is not
always the case, depending on the pyrolysis temperature. As shown
in Table 1, the addition of Ca(OH)2 appeared to suppress the decom-

position of wood to form liquid product at 350 C. It should be kept in

mind that the conversion of Ca(OH)2 to CaCO3 released water, this
part of water is excluded from the yield of liquid by estimating the Ca
(OH)2 conversions from the XRD peak intensities of Ca(OH)2 for the
original and heat-treated samples.
Incidentally, it was visually seen that the liquid product produced
by the non-catalytic pyrolysis of wood at a nal temperature of 700 C

Fig. 4. Release of gases during the pine wood pyrolysis with different K2CO3 loadings. : No catalyst; : 5.0 wt.% K2CO3 loading; : 9.9 wt.% K2CO3 loading; --:
17.7 wt.% K2CO3 loading.

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Z. Wang et al. / Fuel Processing Technology 91 (2010) 942950

Fig. 5. Cumulative amounts of gases evolved from the pyrolysis of pine wood with different K2CO3 loadings. : No catalyst; : 5.0 wt.% K2CO3 loading; : 9.9 wt.% K2CO3
loading; --: 17.7 wt.% K2CO3 loading.

was a heavily brown color, and in sharp contrast, the corresponding

products obtained with addition of either K2CO3 or Ca(OH)2 were a
light yellow color.
3.2. Characterization of char products
Fig. 2 shows the SEM images of the chars produced from the
pyrolysis at a nal temperature of 700 C in the absence and presence
of catalyst. It could be seen that the char produced without catalyst

consisted of many large particles (Fig. 2a), whereas the corresponding

chars produced with addition of both catalysts consisted of a large
number of small grains (Fig. 2b and c), indicating the effect of catalyst
on the particle disintegration. The char produced without catalyst
signicantly traced the morphological structure of wood, with many
round open cavities that might be caused by the release of the volatile
matter [14,15]. Such round cavities were not observed on the chars
produced with the addition of catalyst, because the catalyst disintegrated the char particles. The SEM images of the chars obtained with

Fig. 6. Release of gases during the pyrolysis of pine wood with different Ca(OH)2 loadings. : No catalyst; : 6.9 wt.% Ca(OH)2 loading; : 10.3 wt.% Ca(OH)2 loading;
--: 22.2 wt.% Ca(OH)2 loading.

Z. Wang et al. / Fuel Processing Technology 91 (2010) 942950

K2CO3 and Ca(OH)2 exhibited that the latter char remained some
larger grains with a clear wood structure.
Fig. 3 shows the XRD analysis of the solid residues obtained at
different temperatures without catalyst and with both catalysts. In
the case of non-catalytic pyrolysis, the crystalline structure of cellulose in wood remained unimpaired at 350 C and destructed at 400 C,
whereas in the presence of K2CO3, the crystalline structure disappeared completely at 350 C, indicating that K2CO3 facilitated the
destruction of cellulose. The peaks of cellulose in the residue obtained
at 350 C with Ca(OH)2 became substantially weaker than those in the
non-heated mixture but remained some peak traces. This indicated
that Ca(OH)2 facilitated the structural damage of cellulose, but its
effect was relatively small, compared to the effect of K2CO3. A salient
difference between two catalysts was that the latter catalyst did not
form more liquid products at 350 C (Table 1), although it catalyzed
the destruction of cellulose. Some carboxylic groups in the hemicellulose may be neutralized by calcium hydroxide, forming more thermally stable calcium-replaced carboxylic groups.
3.3. Gas compositions
Figs. 4 and 5 show the gas release rate and cumulative amount
of gas in the course of pine wood pyrolysis with different K2CO3
loadings. The release of H2, CO2 and CO was remarkably promoted by
K2CO3. The starting or peak evolution temperatures of these gases
were shifted to a lower temperature in the presence of potassium. The
cumulative yields of H2, CO2 and CO at 700 C increased by a factor
of 3.5, 2.4 and 1.3, respectively, as 9.9 wt.% of K2CO3 was added. The
release rate of CH4 with temperature exhibited a narrow pattern in
the presence of catalyst, compared to that in the absence of catalyst.
Potassium appeared to lessen the cumulative yield of CH4 at a higher
temperature, differing from the results of the other three gases. It
is indicated from Figs. 4 and 5 that below 400 C, potassium facilitated
the decarboxylation and decarbonylation, and above 400 C, it facilitated the dehydrogenation. It can be seen from Table 1 that the
catalyzed cracking of the tarry materials contributed to the decarboxylation, decarbonylation and dehydrogenation reactions.

947

In the case of adding K2CO3, some CO was released at temperatures

around 650 C. This is likely to be due to the reaction between K2CO3
and char:
K2 CO3 2C2K 3CO

Morterra et al. [16] observed a similar result in the carbonization of

cellulose with the addition of K2CO3. However, this part of CO only
amounted to 4% of the total yield of CO, an increase in the total yield of
CO was primarily ascribed to the catalyzed decarbonylation of wood.
It should be noted that if the amount of CO released after 650 C was
fully attributed to the decomposition of K2CO3 according to reaction
(1), only 37% of K2CO3 was decomposed.
Figs. 6 and 7 show the inuence of the Ca(OH)2 loadings on the
gas release rate and cumulative amount of gas. Ca(OH)2 exerted a
relatively small inuence on pyrolysis gases evolution, compared to
K2CO3. The release patterns of CO, CO2 and CH4 with Ca(OH)2 were
not so much different from those without Ca(OH)2. The cumulative
amounts of CO and CO2 at a temperature lower than 650 C with Ca
(OH)2 were lower than those without Ca(OH)2. A reduction in the
release rate of CO2 was discernable at temperatures between 275 C
and 325 C with higher Ca(OH)2 loadings. This is probably because
part of Ca(OH)2 reacted with CO2, resulting in the xation of gaseous
CO2:
CO2 CaOH2 CaCO3 H2 O

This reaction could be evident from Fig. 3, in which CaCO3 was

assigned to be present in the residues obtained after the pyrolysis of
the wood/Ca(OH)2 mixture at 350 and 400 C, in contrast to no peaks
of CaCO3 in the not-heated mixture.
Compared to the non-catalytic pyrolysis, both CO and CO2 was appreciably released at temperatures higher than 650 C with the addition of Ca(OH)2 (Fig. 6). This is probably due to the decomposition
of CaCO3 via the following reaction:
2CaCO3 C2CaO CO2 2CO

Fig. 7. Cumulative amounts of gases evolved from the pyrolysis of pine wood with different Ca(OH)2 loadings. : No catalyst; : 6.9 wt.% Ca(OH)2 loading; : 10.3 wt.%
Ca(OH)2 loading; --: 22.2 wt.% Ca(OH)2 loading.

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Z. Wang et al. / Fuel Processing Technology 91 (2010) 942950

Ohtsuka and Tomita found that calcium is apt to disperse on char,

and on the carbon surface, CaCO3 started to decompose at a lower
temperature of about 700 C [17]. Because of the re-decomposition of CaCO3, the cumulative yields of CO and CO2 at 700 C with
the addition of Ca(OH)2 became close to or slightly larger than those
without catalyst. The cumulative yield of CH4 with the addition of
Ca(OH)2 was lower than that without catalyst at all temperatures
above 400 C.
The evolution of H2 was greatly increased by adding Ca(OH)2, and
the cumulative yield of H2 at 700 C with 22.2 wt.% of Ca(OH)2 was
twice as much as that without catalyst. In the case of adding Ca(OH)2,
a marked peak of H2 evolution was observed in a lower temperature
range of 275425 C, and this corresponded to the sank curves of CO

Table 2
GCMS analysis of liquid compounds from pyrolysis and catalytic pyrolysis of pine
wood from room temperature to 700 C (mg/g dry biomass).
No.

Compounds

Pine

PC-22

PK-17

1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48

2-butanone
acetic acid
1-hydroxy-2-propanone
1-acetyloxy-2-butanone
1,2-ethanediol monoacetate
1-hexanol
2-methyl-1-pentene
methoxy-cyclobutane
2-oxo-propanoic acid methyl ester
2,5-dimethyl-furan
2-cyclopenten-1-one
1,5-dimethyl-1H-imidazole
3-methyl-cyclopenten-1-one
2-furan methanol
2,4-dimethyl-furan
acetamido acetaldehyde
5-methyl-2-furancarboxaldehyde
2-methyl-2-cyclopenten-1-one
2-hydroxy-2-cyclopenten-1-one
phenol
2-methyl-3-heptene
2,3-dimethyl-2-cyclopenten-1-one
2,3,4-trimethyl-2-cyclopenten-1-one
4-methyl-phenol
guaiacol
cyclopropyl carbinol
1-methylethylidene-cyclohexane
1,7,7-trimethyl-bicyclo[2.2.1]heptane
2,4-dimethyl-phenol
4-methyl guaiacol
1,4:3,6-dianhydro--D-glucopyranose
3,4-anhydro-D-galactosan
2,3-anhydro-D-mannosan
3,4-dimethoxy toluene
2,3-anhydro-D-galactosan
4-ethyl guaiacol
4-vinyl guaiacol
3-(2-propenyl) guaiacol
2-ethyl-5-propylphenol
4-propyl guaiacol
5-(1-propenyl) guaiacol
4-(1-propenyl) guaiacol
methyl-2,6-anhydro--D-altroside
1,6-anhydro--D-talopyranose
1-(3-hydroxy-4-methoxy phenyl)-ethanone
D-allose
4-(ethoxymethyl) guaiacol
4-(1,5-dimethyl-3-oxohexyl)-1cyclohexene-1-carboxylic acid
6-amino-2,4-dimethyl-phenol
2,3,9-trimethoxy-dibenz[D,F]cycloheptanone
2-(triphenyl methoxy)-ethanol
3-ethyl-4-hydroxy-benzeneamine

0.0
5.4
15.0
0.0
3.0
0.0
0.0
0.8
4.2
2.9
0.0
0.0
0.0
5.4
0.4
1.1
2.5
0.0
2.5
1.7
0.0
0.0
0.0
1.2
3.5
4.2
0.0
0.0
0.0
8.6
0.6
0.6
0.9
0.2
0.1
1.6
2.6
0.5
0.0
0.3
1.8
2.3
1.7
0.4
0.5
3.8
1.0
1.6

0.0
0.0
17.1
0.0
6.6
8.1
0.0
2.3
0.0
0.0
0.0
1.9
0.0
4.2
0.0
0.0
0.0
1.3
5.0
2.0
1.1
0.0
0.0
1.6
2.9
0.0
0.0
0.0
0.0
6.8
0.0
0.0
0.8
0.0
0.0
1.8
2.0
0.0
0.0
0.4
0.4
2.3
0.6
0.0
0.2
3.8
0.0
0.0

9.6
0.0
9.0
0.7
0.0
0.0
1.4
0.0
0.0
0.0
0.5
0.0
0.3
0.8
0.0
0.0
0.0
0.4
0.0
2.1
0.0
0.7
0.3
2.7
4.7
0.0
0.4
0.3
0.6
2.5
0.0
0.0
0.0
0.0
0.0
1.8
1.2
0.0
0.2
0.3
0.0
0.9
0.0
0.0
0.0
0.0
0.0
0.1

0.1
0.3
0.1
0.1

0.0
0.0
0.0
0.0

0.0
0.0
0.0
0.0

49
50
51
52

PC-22: pine wood mixed with 22.2 wt.% Ca(OH)2; PK-17: pine wood mixed with
17.7 wt.% K2CO3.

and CO2 evolution in this temperature range, probably because Ca

(OH)2 inuences the gas water shift reaction:
CO H2 OH2 CO2

Water is formed by the signicant dehydration occurring in this

temperature range [13]. The adsorption of CO2 to Ca(OH)2 via reaction (2) is favorable for moving the reaction towards the right side,
resulting in the formation of H2. In addition to the inuence of Ca
(OH)2 on the formation of H2 via the gas water shift reaction, calcium
appeared to directly facilitate the decomposition of wood to form
H2, in the light of an observation that more H2 was released at temperatures between 500 C and 600 C. In this temperature range,
the gas water shift reaction might not be signicant because little
difference in the release rate of CO occurred with and without Ca
(OH)2.
3.4. Liquid compositions
Table 2 lists 52 compounds in the liquid products derived from the
non-catalytic and catalytic pyrolysis of pine wood, in order of their
retention times through the capillary column in the GCMS analysis.
The liquid products generated whether adding catalyst or not consist mostly of oxygenated compounds, with some non-oxygenated
aliphatics formed in the presence of either catalyst. The liquid compounds can be grouped as cyclopentenones (e.g., cyclopentenone,
hydroxy-cyclopentenone), furans (e.g., dimethyl-furan, furan methanol), saccharides (e.g., D-allose, anhydro-D-mannosan, anhydro-Dgalactosan), ketones (e.g., butanone, hydroxyl propanone), aldehydes
(e.g., acetamido acetaldehyde, methyl furancarboxaldehyde), alkanes
(e.g., methyl pentene), acids (e.g., acetic acid), alcohols (e.g., 1-hexanol,
1,2-ethanediol monoacetate), guaiacols (e.g., guaiacol, methyl guaiacol, vinyl guaiacol) and phenols (e.g., phenol and methyl-phenol). It
should be mentioned that the sum amounts of the compounds quantied were 83.5, 41.5, and 73.2 mg/g dry biomass, respectively, for
the original biomass, the biomass/K2CO3 mixture and the biomass/Ca
(OH)2 mixture, much smaller than the corresponding yields of liquid
product (Fig. 1). This is because a large fraction of water and heavy tar
could not be determined by GCMS. We examined the liquid product
obtained without catalyst by the evaporation of the sample at 105 C
for 6 h, the liquid yield decreased from 57.6% to 34.1% (dry biomass
basis). The vaporized fraction were water and some light hydrocarbons, and the residual fraction (34.1%) was mainly the heavy tarry
materials, with some light hydrocarbons.

Fig. 8. Yields of different groups of liquid product obtained in the non-catalytic and
catalytic pyrolysis of pine wood.
: no catalyst;
: 22.2 wt.% Ca(OH)2 loading;
:
17.7 wt.% K2CO3 loading.

Z. Wang et al. / Fuel Processing Technology 91 (2010) 942950

949

Fig. 9. A speculated reaction pathway of Ca-attacked decomposition of cellulose to hexanol.

To more clearly illustrate the effects of K2CO3 and Ca(OH)2 on

the distributions of liquid product, the yields of the different groups
of liquid product are presented in Fig. 8. Saccharides, that are well
known to be a primary product produced by de-polymerization of
hemicellulose and cellulose [13], entirely disappeared in the case of
adding K2CO3. Nowakowski et al. [10] reported that the impregnation
of 1 wt.% potassium to levoglucosan promoted its fragmentation to
low molecular weight compounds (acids, aldehydes, acetol, etc.). In
our case, however, the yields of acids and aldehydes were found to
decrease considerably with the addition of K2CO3, probably because
the addition of a large proportion of the catalyst promoted the further decomposition of acids and aldehydes. This was consistent with
the evolution of more gaseous products with the addition of K2CO3
(Fig. 5). The yield of furans, that are mainly degraded from cellulose [8,13], became very low in the case of adding K2CO3, implying the
strongly catalyzed decomposition of cellulose to more stable compounds or gaseous products rather than to furans as in the noncatalytic pyrolysis. Guaiacols, which are characteristic of the degradation of lignin constituent in wood, decreased by half in their yield
with the addition of K2CO3. This mainly came from a decrease in the
yield of 4-methyl guaiacol (Table 2). While the yield of guaiacols decreased, the yield of phenols increased with the addition of K2CO3,
implying the catalyzed demethoxylation of the lignin units. This is
in agreement with the observation by Nowakowski et al. [6] that
potassium facilitated the secondary decomposition of guaiacols. In the
secondary reactions, however, part of guaiacols is subjected to crosslinking and re-polymerization to form a char deposit [18], and K2CO3
is likely to promote this reaction, resulting in an increase in the yields
of char (Fig. 1).
The addition of Ca(OH)2 reduced the yields of saccharides, furans
and guaiacols. Compared to K2CO3, however, Ca(OH)2 had a relatively
small effect. The formation of these compounds was still signicant.
Acids completely diminished with the addition of Ca(OH)2, whereas some trace of acids was observed with the addition of K2CO3. The
completely suppressed formation of acids might be due to the neutralization of carboxylic groups in hemicellulose by Ca(OH)2; this
neutralization was responsible for the suppressed formation of liquid
product at 350 C, as shown in Table 1. The yield of ketones was somewhat increased in line with the disappearance of aldehydes with the
addition of either catalyst. Some alkanes were not formed in the noncatalytic pyrolysis but formed in the presence of either catalyst. It
was interesting to see that the yields of alcohols were signicantly
increased in the presence of Ca(OH)2, and a main product was hexanol.
We speculate a formation pathway from cellulose to hexanol catalyzed
by calcium cation, as shown in Fig. 9.
4. Summary
(1) The physically mixed K2CO3 or Ca(OH)2 was found to inuence
a few aspects of the slow pyrolysis of pine wood. Either additive
catalyzed the decomposition of cellulose and lignin constituents
and the disintegrated the char particles; however, potassium
showed a stronger effect than calcium. K2CO3 promoted the

decomposition of hemicellulose and cellulose even at a low

temperature of 350 C, whereas Ca(OH)2 appeared to delay the
decomposition of hemicellulose at this low temperature by the
neutralization with carboxylic groups in hemicellulose.
(2) K2CO3 reduced the yield of liquid product in conjunction with
an increase in the yields of gas and char, indicating its stronger
catalytic effect on the secondary reaction of the liquid product.
In contrast, calcium did not demonstrate such a pronounced
catalysis for decomposing the liquid product to gases, and the
yield of liquid product was slightly increased at 700 C, with a
marginal decrease in the yield of char.
(3) Both additives signicantly altered the compositions of liquid
product. The liquid compounds obtained in the non-catalytic
pyrolysis mainly embraced furans, saccharides, ketones, aldehydes, acids, alcohols, guaiacols and phenols. With the addition
of K2CO3, none of saccharides, aldehydes and alcohols was
formed, and a substantial reduction in the yield was observed
for acids, furans and guaiacols; the yields of alkanes and phenols
were increased. With the addition of Ca(OH)2, the yields of
furans and saccharides were somewhat reduced, and none of
aldehyde and acids was formed; the yield of alcohols was remarkably increased.
(4) K2CO3 resulted in a shift of the release of gases (H2, CO, CO2) to
a lower temperature, while Ca(OH)2 had no such an effect. The
former additive signicantly increased the cumulative yields
of H2, CO and CO2, whereas the latter only led to a marked
increase in the cumulative yield of H2. The increased yields of
these gases were mainly ascribed to the promoted decomposition of biomass, and partly to the adsorption and decomposition reactions of the catalyst occurring during the pyrolysis.
Acknowledgements
This research is sponsored mainly by Shanghai Pujiang Program
(Project no.: 07pj14028), and partly by the Program for Changjiang
Scholars and Innovative Research Team in University in China
(IRT0620) and the National 863 Research Project (2006AA05Z116).
The authors thank students Dan Lu and Xin Rong for doing part of
experiment.
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