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Fuel 86 (2007) 23892402

www.fuelrst.com

Potassium catalysis in the pyrolysis behaviour


of short rotation willow coppice
Daniel J. Nowakowski a, Jenny M. Jones
a

a,*

, Rik M.D. Brydson b, Andrew B. Ross

Energy and Resources Research Institute, School of Process, Environmental and Materials Engineering (SPEME), University of Leeds, Leeds LS2 9JT, UK
b
Institute for Materials Research, SPEME, University of Leeds, Leeds LS2 9JT, UK
Received 9 July 2006; received in revised form 18 January 2007; accepted 23 January 2007
Available online 27 February 2007

Abstract
Short rotation willow coppice (SRC) and a synthetic biomass, a mixture of the basic biomass components (cellulose, hemicellulose
and lignin), have been investigated for the inuence of potassium on their pyrolysis behaviours. The willow sample was pre-treated
to remove salts and metals by hydrochloric acid, and this demineralised sample was impregnated with potassium. The same type of
pre-treatment was applied to components of the synthetic biomass. Characterisation was performed using thermogravimetric analysis
with measurement of products by means of Fourier transform infrared spectroscopy (TGAFTIR) and pyrolysisgas chromatographymass spectrometry (PYGCMS). A comparison of product distributions and kinetics are reported. While the general features
of decomposition of SRC are described well by an additive behaviour of the individual components, there are some dierences in the
magnitude of the inuence of potassium, and on the products produced. For both SRC and the synthetic biomass, TGA traces indicate
catalytic promotion of both of the two-stages of biomass decomposition, and potassium can lower the average apparent rst-order activation energy for pyrolysis by up to 50 kJ/mol. For both SRC and synthetic biomass the yields and distribution of pyrolysis products
have been inuenced by the presence of the catalyst. Potassium catalysed pyrolysis increases the char yields markedly and this is more
pronounced for synthetic biomass than SRC. Gas evolution proles during pyrolysis show the same general features for both SRC and
synthetic biomass. Relative methane yields increase during the char formation stage of pyrolysis of the potassium doped samples. The
evolution proles of acetic acid and formaldehyde change, and these products are seen in lower relative amounts for both the demineralised samples. A greater variation in pyrolysis products is observed from the treated SRC samples compared to the dierent synthetic
biomass samples. Furthermore, substituted phenols from lignin pyrolysis are more dominant in the pyrolysis proles of the synthetic
biomass than of the SRC, implying that the extracted lignins used in the synthetic biomass yield a greater fraction of monomeric type
species than the lignocellulosic cell wall material of SRC. For both types of samples, PYGSMS analyses show that potassium has a
signicant inuence on cellulose decomposition markers, not just on the formation of levoglucosan, but also other species from the noncatalysed mechanism, such as 3,4-dihydroxy-3-cyclobutene-1,2-dione.
 2007 Elsevier Ltd. All rights reserved.
Keywords: Biomass; Pyrolysis; Catalysis; Potassium; Mechanism

1. Introduction
Biomass is well recognised as a potential renewable
source of energy and is considered to be the obvious candidate for contributing to carbon dioxide reduction in the

Corresponding author. Tel.: +44 113 343 27 44; fax: +44 113 244 0572.
E-mail address: j.m.jones@leeds.ac.uk (J.M. Jones).

0016-2361/$ - see front matter  2007 Elsevier Ltd. All rights reserved.
doi:10.1016/j.fuel.2007.01.026

short-term, since it can be co-combusted with coal in existing facilities, and in longer term in dedicated systems. The
main alternatives for utilisation of biomass are pyrolysis,
gasication and combustion. Much of the energy consumed for electricity production, 97% in the case of the
UK [1], comes from non-renewable sources. The present
use of carbon-based non-renewable energy is unsustainable, among other things because of the eect of the resultant carbon dioxide (CO2) emissions on the global climate.

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D.J. Nowakowski et al. / Fuel 86 (2007) 23892402

Biomass already contributes approximately 5% of the EU


energy supply and 65% of the total renewable energy production [2]. In the long term, the biomass contribution in
EU energy supply may increase up to 20%, depending on
the policies adopted by the EU in relation to agriculture,
sustainability, secure energy supply and Kyoto obligations.
The pyrolysis process of biomass is highly complex and
depends on several factors such as composition of lignocellulosic material, heating rate, content of inorganic material,
etc. From a chemical point of view, biomass can be
regarded as a mixture of cellulose, hemicellulose, lignin
and inorganic components (minerals). For instance, the
average content of the basic biomass components in energy
crops is as follow: cellulose 50%, lignin 30%, hemicellulose 20% [3]. The main elemental constituents of biomass
minerals are Si, K, Ca and Mg with smaller amount S, P,
Fe, Al and Mn [4]. At low heating rates (<100 K/min)
many biomass materials decompose in well discernible
stages of: (i) moisture evaluation, (ii) hemicellulose decomposition, (iii) lignin and cellulose decomposition [4].
The metals species in biomass are important in conversion processes because of their impact on slagging, fouling
and other ash related problems. Transformation and
release of potassium has been studied during the pyrolysis
processes of biomass [510]. These experiments revealed
that the potassium evolves during decomposition of the
organic matrix at 473673 K from the original binding sites
and may re-deposit as discrete particles (mainly KCl) or
dispersed in the organic char matrix. Further evaporation
of potassium to the gas phase occurs at approximately
973 K, and evaporation of deposited KCl particles contributes to this.
Alkali metals also play a crucial role in thermal degradation of biomass. Some authors have considered the catalytic role of potassium in char formation and pyrolysis
product distribution [1114]. A catalytic eect due to presence of potassium in the biomass samples (willow SRC,
wheat straw) was observed during combustion experiments
in a DTA [15] and methane-air ame [16,17]. Potassium
catalyses both volatile combustion and char burn-out reactions, at least under low temperature combustion.
Potassium is a key plant nutrient and present in varying
amounts depending upon the type of biomass, its growing
conditions and time of harvest. Of all the metals present in
biomass, it is potassium that has the greatest inuence on
its thermal conversion properties, catalysing both the pyrolysis and the combustion/gasication stage. This inuence
is still not completely understood for lignocellulosic material, although there have been some excellent mechanistic
studies in catalysed cellulose pyrolysis [12,18]. It has been
proposed for cellulose that the catalysed decomposition
reaction proceeds via an ionic mechanism rather then a
radical process [12,18]. The particularly potent catalytic
properties of potassium have still not been explained fully
and this is the topic of on-going work by our group. Furthermore it is not clear if the other cell-wall components
in biomass are catalysed to the same extent, and whether

they can be considered to behave independently in catalytic


thermal conversion.
A preliminary comparative study of catalysis by potassium on the pyrolysis processes of short rotation willow
coppice samples and a mixture of the basic biomass components (cellulose, hemicellulose and lignin) has been carried out in this laboratory [19]. These results suggested
that the general features of pyrolysis can be described in
terms of additive behaviour of its components at least
in a qualitative way providing that the eect of catalytic
metals is taken into account. The present work extends this
previous study. It compares the inuence of potassium on
the pyrolysis behaviour of SRC to that of a synthetic biomass, a mixture of the basic biomass components (cellulose, hemicellulose and lignin) and examines in some
detail the pyrolysis product distribution and components.
2. Experimental
2.1. Materials
The biomass sample of short rotation willow coppice
was obtained from Rural Generation Ltd. (Londonderry,
Northern Ireland). The sample was ground and sieved.
The fraction 0.150.18 mm was used for demineralisation,
impregnation and analyses. Analytical properties for willow SRC sample are given in Table 1. Moisture content
and metal analyses for all willow samples are given in Table
2. Cellulose, lignin organosolv and xylan from oat pellets
(as hemicellulose) were purchased from Sigma Aldrich
Company Ltd. A synthetic mixture of the basic biomass
components: cellulose (50 wt.%), lignin alkali (15 wt.%),
lignin organosolv (15 wt.%) and xylan (20 wt.%) was used
for analyses. Demineralisation and impregnation of the
single components were also carried out to generate samples for comparison. These samples are referred to as synthetic biomass in the text. Mass losses of samples subjected
to demineralisation were calculated. The following results
were obtained: willow 4.0%, cellulose 9.9%, lignin
organosolv 7.3%, lignin alkali 15.4%.
2.2. Sample preparation
Demineralisation. Hydrochloric acid treatment of the
biomass sample was performed by heating of 10 g of sample in 50 cm3 of 2.0 M HCl for 6 h at 333 K. After 48 h the
sample, left in the HCl solution, was again heated at 333 K
Table 1
Analysis of raw willow, as received
Analyses

wt.%

Volatile matter
Fixed carbon
Ash
Moisture

69.83
17.53
5.20
7.44

Caloric value MJ/kg

18.68

D.J. Nowakowski et al. / Fuel 86 (2007) 23892402

2391

Table 2
Metal analyses for willow samples; as received, after drying at 333 K
Sample

Moisture
(wt.%)

Al
(mg/kg)

Ca
(mg/kg)

Cd
(mg/kg)

Co
(mg/kg)

Cr
(mg/kg)

Cu
(mg/kg)

Fe
(mg/kg)

K
(mg/kg)

Mg
(mg/kg)

Mn
(mg/kg)

Willow raw
Willow HCl
treated
Willow
K-impregnated

5.89
3.75

50
42

11 020
119

6.35
<0.005

<0.009
<0.009

2.50
<0.007

38.1
<0.045

137
7.6

3770
<107

1350
5.3

181
<0.009

19

<0.005

<0.009

<0.007

0.9

17 000

6.5

<0.009

4.80

0.1

for 6 h. The sample was then ltered, then washed using deionised water until the ltrate was Cl free (checked by
0.1 M silver nitrate solution). Then sample was oven dried
at 333 K to constant weight. After demineralisation samples were analysed for minerals presence using energy dispersive X-ray (EDX) analysis. EDX results show that
demineralisation with HCl is very ecient, resulting in
complete removal of minerals [20].
Impregnation. Three grams of sample, analysed before
impregnation for moisture content, was impregnated
by potassium (as potassium acetate) to yield a 1 wt.%
K-impregnated sample. After addition of potassium acetate
the sample was moistened by 1 cm3 of de-ionised water,
mixed and then oven dried at 333 K to constant weight.

6.8

3. Results and discussion


3.1. TGA pyrolysis
Dierential thermogravimetric (DTG) results comparing the inuence of potassium on the pyrolysis of the willow SRC and synthetic biomass mixture are shown in
Fig. 1a and b, respectively.
In Fig. 1a it is seen that the raw willow sample has two
main unresolved peaks. It is reported [21,22] that the basic
0

-5

2.3. Thermogravimetric analysis (TGA)


DTG, %/min.

Pyrolysis tests were performed using a TGA analyser


(Station Redcroft Simultaneous Analyser STA-780 Series).
A typical sample mass of 10 mg was heated at 25 K/min in
a purge of nitrogen with the nal temperature of 1173 K,
and then the sample was held at 1173 K for 15 min.

506
-10

-15

586

Willow raw
Willow HCl treated
Willow K-impregnated

647
-20

2.4. FTIR analysis

653
-25
500

Evolution of gases and light volatile organic compounds


were measured using the TGA analyser connected via
heated transfer line to a Nicolet Magma-IR 560 Spectrometer. Spectra of the gas mixture were measured every 30 s at
4 cm 1 resolution. The one-minute delay between the TGA
and FTIR gas cell has been taken into account in the presentation of the results.

PYGCMS tests were performed on each sample using


a CDS 1000 pyrolyser coupled to a Hewlett-Packard GCMSD gas chromatograph. The column was a RTX 1701
(14% cyanopropylphenyl, 86% dimethylpolysiloxane;
60 m, 0.25 mm id., 0.25 lm df). The gas chromatograph
oven was held at 313 K for 2 min and then programmed
at 4 K/min to 523 K, held for 30 min. Approximately
1.5 mg of sample was placed in 20 mm quartz tube in
between quartz wool. The sample was pyrolysed at a set
point temperature of 873 K at a ramp rate of 20 K/ms with
the nal dwell time of 20 s.

700

800

900

Temperature, K

-5

533

DTG, %/min.

2.5. Analytical pyrolysis tests

600

588

-10

595

-15

606

Mixture raw
Mixture HCl treated
Mixture K-impregnated

-20

647 662
-25
500

600

700

800

900

Temperature, K

Fig. 1. DTG proles for (a) willow SRC and (b) synthetic biomass
samples.

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D.J. Nowakowski et al. / Fuel 86 (2007) 23892402

biomass components, hemicellulose, cellulose and lignin,


decompose thermochemically in the following temperature
ranges: 423623 K, 548623 K and 523773 K, respectively. The rst step of thermal degradation is attributed
to the decomposition of hemicellulose and the initial stage
of degradation of cellulose (Fig. 1a, peak between 503 K
and 623 K, with the peak temperature at 606 K), while
the second step is attributed to the degradation of lignin
and the nal degradation of cellulose (Fig. 1a, peak
between 623 K and 703 K, with the peak temperature at
647 K). Upon acid treatment to remove metals from the
SRC the rst peak becomes much weaker indicating some
change in the hemicellulose content. Also, the second main
peak shifts to slightly higher temperature, which shows that
some catalytic species have been removed by acid washing.
Table 2 shows that all metals decrease in concentration
during this treatment. Upon addition of potassium, a
strong catalytic eect on the degradation is observed, and
two clearly resolved peaks are present with peak maxima
at 506 K and 586 K.
Fig. 1b compares the results for pyrolysis of the synthetic biomass samples. It is clear that the general features
of willow SRC thermal decomposition can be described by
additive decomposition of the main biomass cell-wall components. DTG analysis reveals that the thermal degradation also occurs in two steps. The rst step, both for raw
and HCl treated synthetic biomass, occurs at 573623 K
and the second one at 623698 K. The rst step of thermal
degradation (raw and HCl treated mixture samples,
Fig. 1b) is attributed to the decomposition of hemicellulose
and the initial stage of degradation of cellulose, while the
second step is attributed to the degradation of lignin and
the nal degradation of cellulose.
The catalytic inuence on the degradation is greater for
the willow than for synthetic biomass. The cellulose decomposition peak shifts from 647 K to 606 K for the synthetic
biomass, and from 647 K to 587 K for the willow sample.
The yields for TGA pyrolysis of willow samples and
synthetic biomass mixtures are given in Table 3. In both
cases HCl treatment decreases the char yield, presumably
because inorganic constituents that promote char formation are no longer present. This eect is more noticeable
for SRC since this has a higher original metal content than
the synthetic biomass. The presence of potassium has a crucial inuence on the char formation stage increasing the
char yield, and this is more signicant in the synthetic bioTable 3
Pyrolysis yields for pyrolysis of willow and synthetic biomass samples
Sample

Pyrolysis yields (%)

Table 4
Activation energies for pyrolysis of willow and synthetic biomass samples
Sample
Willow
Willow
Willow
Willow

raw
HCl treated
K-impregnated [A]
K-impregnated [B]

Mixture
Mixture
Mixture
Mixture
Mixture

raw [A]
raw [B]
HCl treated
K-impregnated [A]
K-impregnated [B]

Ea (kJ/mol)

ln A (s 1)

k623 (s 1)

89.0
178.4
131.7
132.7

13.03
29.80
28.56
24.22

1.58 10
9.56 10
22.90
2.48 10

121.5
194.8
174.2
113.2
147.9

21.01
32.45
29.05
21.88
26.41

8.60 10
5.56 10
1.02 10
1.03
1.17 10

3
2

mass. So, while the potassium is more eective in catalysing


pyrolysis in the SRC, as seen by a larger decrease in the
peak maximum temperature in the DTA plot (Fig. 1), it
is more eective in increasing the char yield from pyrolysis
of the synthetic biomass (Table 3). Work on individual
components in the synthetic biomass should help to elucidate the reason for this, and this work is in progress.
For all pyrolysed samples the relationship: da/dt =
k(1 a), where a = fractional conversion, was used to
derive the apparent rst-order (n = 1) kinetic parameters
from the dierential thermogravimetric analyses (DTG proles in Fig. 1a and b) and these are listed in Table 4. To
enable comparison of relative rates, Table 4 also includes
the pyrolysis rate (k) calculated at 623 K. The respective
Arrhenius plots for the willow and synthetic mixture samples are shown in Fig. 2a and b, respectively. The DTG curve
for K-impregnated willow sample shows two resolved peaks
(see Fig. 1a) with the peak maximum temperatures 506 K
and 586 K. Hence two Arrhenius plots exist for this sample,
[A] for the lower temperature, and [B] for the higher temperature weight loss region. The same situation occurs in case of
raw and K-impregnated synthetic biomass mixture samples
(resolved peaks on the DTG curves with the peak maximum
temperatures 595 K and 662 K for the raw sample, and
533 K and 606 K for the K-impregnated sample see Fig. 1b).
The kinetic data shows the inuence of potassium in the
pyrolysis of synthetic mixture and willow SRC samples.
These values represent the average apparent rst-order
activation energies for pyrolysis of hemicellulose, cellulose
and lignin as the basic biomass components. The presence
of potassium provides a mechanistic route with lower activation energy, while the uncatalysed route (with no potassium HCl treated) has higher activation energy. The
inuence on the product evolution is described in the following sections.
3.2. TGAFTIR pyrolysis products evolution patterns

Volatiles

Char

Willow raw
Willow HCl treated
Willow K-impregnated

87.7
93.3
80.2

12.3
6.7
19.8

Mixture raw
Mixture HCl treated
Mixture K-impregnated

81.7
83.1
68.7

18.3
16.9
31.3

The main volatile components such as carbon monoxide, carbon dioxide, methane, acetic acid, formaldehyde
and acetone have been identied by FTIR. The typical
spectral output from the TGAFTIR analysis is shown in
Fig. 3 for the potassium impregnated sample and is known
as a waterfall spectrum. The gas evolution proles shown

D.J. Nowakowski et al. / Fuel 86 (2007) 23892402

in Fig. 4 were constructed from the waterfall spectra by


selecting a key characteristic IR absorbance for the specie
of interest and following the intensity with time (temperature). Some interference is possible for the aldehydes and
furfural. The proles have been normalised to the sample
weight (intensity per mg of sample), so the comparisons
for the eect of pre-treatment can be made on the relative
amount of the evolved gas product.
The species evolution proles were found to have
remarkably similar features for pyrolysis of both the synthetic biomass and the willow samples. For raw and HCl
treated samples all species show coincident evolution proles and peak maxima, although intensities (amount
evolved per mg) are generally lower for the HCl treated
samples. It can be clearly noticed that the evolution rate
of volatile products and in some cases the yields of species
(formaldehyde, acetic acid, acetone) have been inuenced
by potassium. The presence of potassium shifts evolution
proles of each component (except methane) to lower temperatures. The biggest shift (approximately 150 K) is in
case of carbon monoxide, carbon dioxide and formaldehyde. For other cases the shift is approximately 75 K.
The evolution pattern of acetic acid and formaldehyde
appears as a wide peak and occurs in the whole temperature range of pyrolysis. Acetic acid is formed mostly from
hemicellulose and formaldehyde form cellulose [23]. The
products from potassium acetate decomposition would
appear above 800 K and so the evolution proles in Figs.
3 and 4 are from the decomposition of the lignocellulose.
Acetic acid and formaldehyde arise from ring opening
and cracking, reactions that are known to be favoured in
the presence of alkali metals [12,18], and the lower relative
amounts produced from both the HCl treated samples is
consistent with this.
The behaviour of methane evolution is interesting. At
least two temperature ranges for methane evolution are
apparent, and the dierent treatments aect the relative

-2

-3

-4

[A]

[B]

ln k

-5

-6

-7

-8

-9
0.0014

Willow raw
Willow HCl treated
Willow K-impregnated
0.0016

0.0018

0.0020

0.0022

-1

1/T [K ]
Mixture raw
Mixture HCl treated
Mixture K-impregnated

-2

-3

ln k

-4

-5

[A]
[B]
[A]

-6
[B]
-7

-8
0.0014

0.0016

0.0018

0.0020

-1

1/T [K ]

Fig. 2. Arrhenius plots for the pyrolysis of (a) willow SRC and
(b) synthetic biomass samples.

CH3COCH3

CO2

HCHO
CH3CHO

0.14

Absorbance

CO2

H2O

0.10

CH3OH
HCOOH
CH3COOH

CO

CH4

0.12

2393

CO

0.08
0.06

750
625

0.04
500
375

0.02

3500

3000

2500

2000

1500

1000

500

125

(C

ra

pe

250
0.00

e
ur

em

Wavenumbers (cm-1)

Fig. 3. Waterfall spectrum showing volatile components from the TGA-FTIR pyrolysis of potassium impregnated willow SRC sample.

2394

D.J. Nowakowski et al. / Fuel 86 (2007) 23892402


-3

1.4x10

Carbon monoxide

-3

Willow raw
Willow HCl treated
Willow K-impregnated

1.4x10

-3

Mixture raw
Mixture HCl treated
Mixture K-impregnated

-3

1.2x10

-3

Intensity/mg of sample

Intensity/mg of sample

1.2x10

Carbon monoxide

-3

1.0x10

-4

8.0x10

-4

6.0x10

-4

4.0x10

1.0x10

-4

8.0x10

-4

6.0x10

-4

4.0x10

-4

2.0x10

-4

2.0x10

0.0

0.0
-4

-2.0x10

400

500

600

700

800

900

1000

400

1100

500

600

700

800

900

1000

1100

Temperature, K

Temperature, K
-2

1.4x10

Carbon dioxide

-2

1.2x10

Willow raw
Willow HCl treated
Willow K-impregnated

-2

1.0x10

Carbon dioxide

Mixture raw
Mixture HCl treated
Mixture K-impregnated

-2

1.2x10

Intensity/mg of sample

Intensity/mg of sample

-2

1.0x10
-3

8.0x10

-3

6.0x10

-3

4.0x10

-3

2.0x10

-3

8.0x10

-3

6.0x10

-3

4.0x10

-3

2.0x10

0.0

0.0
-3

-3

-2.0x10

-2.0x10

400

500

600

700

800

900

1000

400

1100

500

600

700

800

900

1000

1100

900

1000

1100

Temperature, K

Temperature, K

-3

1.6x10

Methane

-3

1.4x10

Willow raw
Willow HCl treated
Willow K-impregnated

-3

Mixture raw
Mixture HCl treated
Mixture K-impregnated

-3

1.5x10

Intensity/mg of sample

Intensity/mg of sample

1.2x10

Methane

-3

1.8x10

-3

1.0x10

-4

8.0x10

-4

6.0x10

-4

4.0x10

-3

1.2x10

-4

9.0x10

-4

6.0x10

-4

-4

3.0x10

2.0x10

0.0

0.0

-4

-2.0x10

400

500

600

700

800

900

1000

1100

Temperature, K

400

500

600

700

800

Temperature, K

Fig. 4. Species evolution proles during the TGAFTIR pyrolysis of willow SRC and synthetic biomass sample (mixture).

yields of production over these temperature ranges. This


product arises from cracking of primary and secondary

decomposition species but also from char production,


and it is likely that the higher temperature peak is associ-

D.J. Nowakowski et al. / Fuel 86 (2007) 23892402

2395

-4

7.0x10

Acetic acid
0.0016

Willow raw
Willow HCl treated
Willow K-impregnated

-4

6.0x10

-4

Mixture raw
Mixture HCl treated
Mixture K-impregnated

0.0012

Intensity/mg of sample

Intensity/mg of sample

5.0x10

Acetic acid

0.0014

-4

4.0x10

-4

3.0x10

-4

2.0x10

-4

0.0010
0.0008
0.0006
0.0004

1.0x10

0.0002

0.0

0.0000

-4

-0.0002

-1.0x10

400

500

600

700

800

900

1000

1100

400

500

600

Formaldehyde

-3

1.0x10

-4

900

1000

1100

-4

6.0x10

-4

4.0x10

Mixture raw
Mixture HCl treated
Mixture K-impregnated

-4

6.0x10

Intensity/mg of sample

Intensity/mg of sample

800

Formaldehyde

-4

7.0x10

Willow raw
Willow HCl treated
Willow K-impregnated

8.0x10

700

Temperature, K

Temperature, K

-4

5.0x10

-4

4.0x10

-4

3.0x10

-4

2.0x10

-4

2.0x10

-4

1.0x10

0.0

0.0

-4

-1.0x10
400

500

600

700

800

900

1000

1100

400

500

600

700

800

900

1000

1100

Temperature, K

Temperature, K
-3

1.0x10

Acetone
-4

Willow raw
Willow HCl treated
Willow K-impregnated

6.0x10

-4

-4

4.0x10

-4

3.0x10

-4

2.0x10

Mixture raw
Mixture HCl treated
Mixture K-impregnated

-4

8.0x10

Intensity/mg of sample

Intensity/mg of sample

5.0x10

Acetone

-4

6.0x10

-4

4.0x10

-4

2.0x10

-4

1.0x10

0.0

0.0
-4

-1.0x10

400

500

600

700

800

900

1000

400

1100

Temperature, K

500

600

700

800

900

1000

1100

Temperature, K

Fig. 4 (continued)

ated with the latter. Thus, the increase in relative methane


yield (and relative CO yield at temperatures >873 K) in the

presence of potassium is linked to the increased char yields


observed and reported in Table 3.

2396

D.J. Nowakowski et al. / Fuel 86 (2007) 23892402


3500000

3000000

Abundance

2500000
2000000
44
17

1500000

37

33
21-24
7-13

___

500000

20

18
15
16 19

42

28

26

__ 14

41

31

25

3 56

_______

1000000

36

__

27

29
30

39
32 34 38
40
35

45
47
48
46 49
50

43
43a

0
10

20

40

30
Time, min.

50

60

Fig. 5. PyrolysisGCMS chromatogram for raw willow sample. The main peaks are assigned from mass spectral detection as follows: (1) acetic acid; (2)
2-methyl-1-propanol; (3) 1-hydroxy-2-propanone; (4) 3-butenoic acid, ethyl ester; (5) propanal; (6) furfural; (7) 5-methyl-2(3H)-furanone; (8) 2,5-dihydro3,4-dimethyl furan; (9) acetic acid, ethyl ester; (10) 2-ethyl-butanal; (11) methyl-cyclohexane; (12) 2H-pyran-2-one; (13) 2-cyclohexen-1-one; (14)
2-hydroxy-2-cyclopenten-1-one; (15) 5-methyl-2-furancarboxaldehyde; (16) 2H-furanone; (17) 3,4-dihydroxy-3-cyclobutene-1,2-one; (18) cycloheptanone;
(19) phenol; (20) 2-methoxy-phenol; (21) 4-methyl-phenol; (22) 4-ethyl-2-hydroxycyclopenten-2-en-1-one; (23) carbonic acid, ethyl 2-propenyl ester; (24)
2- or/and 3-methylphenol; (25) 2-methoxy-4-methylphenol; (26) cyclopropyl carbinol; (27) 4-ethyl-2-methoxyphenol; (28) 2-octenoic acid; (29) (Z)-2butene-1,4-dione; (30) 2-methyl-4-pentenoic acid; (31) 2-methoxy-4-vinylphenol; (32) 2-methoxy-4-(1-propenyl)-phenol; (33) 2,6-dimethoxy-phenol; (34)
(E)-3-methoxy-5-(1-propenyl)-phenol; (35) 3,6-dimethoxy-phenol; (36) 2-methoxy-4-(1-propenyl)-phenol; (37) 4-methoxy-3-(methoxymethyl)-phenol; (38)
vanillin; (39) 1-(2,6-dihydroxy-4-methoxyphenyl)-ethanone; (40) 1-(4-hydroxy-3-methoxyphenyl)-ethanone; (41) 4-formylphenoxy acetic acid; (42)
4-hydroxy-3-methoxy-benzoacetic acid; (43, 43a) 2,6-dimethoxy-4-(2-propenyl)-phenol; (44) levoglucosan; (45) 4-hydroxy-3,5-dimethoxy benzaldehyde;
(46) 1-(4-hydroxy-3,5-dimethoxyphenyl)-ethanone; (47) 1-(2,4,6-trihydroxy-3-methylphenyl)-1-butanone; (48) desaspidinol; (49) aspidinol; (50) 1-(2,6dihydroxy-4-methoxyphenyl)-ethanone.
45

1800000
1600000

35,36

24

1000000

38

32
26-31

800000

20
7-13

400000

200000

25
18
19

15

14

_______

600000

__

16

_______

Abundance

34

17

1200000

____________________

1400000

39

___ 33
22 23
21

43 44

48

41
46

37

49

44 a
40
42

47

50

0
10

20

30
Time, min.

40

50

60

Fig. 6. PyrolysisGCMS chromatogram for HCl treated willow sample. The main peaks are assigned from mass spectral detection as follows: (1)
methoxyethanone; (2) propanonic acid; (3) carbonic acid, diethyl ester; (4) 2,3-dihydro-4-methyl-furan; (5) propanal; (6) furfural; (7) 5-methyl-2(3H)furanone (8) 2-furanmethanol; (9) acetic acid, ethyl ester; (10) pentane; (11) 1-(2-furanyl)-ethanone; (12) furan; (13) 2H-pyran-2-one; (14) 2-hydroxy-2cyclopenten-1-one; (15) hydroquinone; (16) 2(5H)-furanone; (17) 3,4-dihydroxy-3-cyclobutene-1,2-dione; (18) cycloheptanone; (19) phenol; (20)
2-methoxy-phenol; (21) 4-methyl-phenol; (22) 2-methyl-1,3-cyclohexanedione; (23) 2- or/and 3-methylphenol; (24) 2-methoxy-4-methyl-phenol; (25)
3,5-dihydroxy-2-methyl-4H-pyran and/or 5-hydroxy-2-(hydroxymethyl)-4H-pyran-4-one; (26) 4-ethyl-2-methoxyphenol; (27) 2-hydroxy-5-methoxybenzaldehyde; (28) 1,4-dimethoxy-2-methyl-benzene; (29) 2,5-dihydrofuran; (30) 1-hydroxy-2-butanone; (31) 4-methyl-2-hexene (cis and trans); (32)
2-methoxy-4-vinylphenol; (33) 2-methoxy-3-(2-propenyl)-phenol; (34) 2,6-dimethoxy-phenol; (35) 1,2-epoxy-3-propyl acetate; (36) 3,6-dimethoxy-phenol;
(37) (E)-2-methoxy-5-(1propenyl)-phenol; (38) 2-methoxy-4-(1-propenyl)-phenol; (39) 4-methoxy-3-(methoxyphenyl)-phenol; (40) vanillin; (41) 1-(2,6dihydroxy-4-methoxy-phenyl)-ethanone; (42) 1-(4-hydroxy-3-methoxyphenyl)-ethanone; (43) 4-hydroxy-3-methoxy-benzoacetic acid; (44, 44a)
2,6-dimethoxy-4-(2-propenyl)-phenol; (45) levoglucosan; (46) 4-hydroxy-3,5-dimethoxy-benzaldehyde; (47) 1-(2,6-dihydroxy-4-methoxyphenyl)-ethanone;
(48) 1-(4-hydroxy-3,5-dimethoxyphenyl)-ethanone; (49) desaspidinol; (50) aspidinol.

D.J. Nowakowski et al. / Fuel 86 (2007) 23892402

2397

6000000
1

5500000
5000000
4500000

Abundance

4000000
3500000
3000000

31

2500000
18-22
17
13-15
2

______

1500000

23-25

16

1000000
500000

12
6 8
7
11
5
9 10

4
3

______
_________

2000000

35
38

29
34
32 33

__ _

27
26 28 30

36
37

40
39

0
10

20

40

30
Time, min.

50

60

Fig. 7. PyrolysisGCMS chromatogram for potassium impregnated willow sample. The main peaks are assigned from mass spectral detection as follows:
(1) acetic acid; (2) 2-methyl-1-propanol; (3) 2-hydroxy-propanonic acid; (4) propanonic acid, anhydride or/and carbonic acid, diethyl ester; (5) propanal;
(6) furfural; (7) 2-furanmethanol; (8) acetic acid, ethyl ester; (9) 1-hydroxy-2-propanone; (10) 2-hydroxy-2-cyclopenten-1-one; (11) 3-methyl-2cyclopenten-1-one; (12) butyrolacetone; (13) 2,3-dimethyl-2-cyclopenten; (14) 32-hydroxy-3-methyl-2-cyclopenten-1-one; (15) 2-hydroxy-3,5-didimethylcyclopenten-2-en-1-one; (16) phenol; (17) mequinol or/and 2-methoxy-phenol; (18) 3-methyl-phenol; (19) 3-methyl-2-butenal; (20) 2,6-dimethyl-phenol;
(21) acetic acid, phenyl ester; (22) 2- or/and 3- or/and 4-methyl-phenol; (23) 2-methoxy-4-methyl-phenol; (24) cyclopropyl carbinol; (25) 2,3- or/and 3,5or/and 2,4- or/and 2,5-domethyl-phenol; (26) 2,3,5- or/and 2,4,6-trimethyl-phenol; (27) 4-ethyl-2-methoxy-phenol; (28) 2-ethyl-4-methyl-phenol; (29)
2-methoxy-4-vinylphenol; (30) eugenol or/and 2-methoxy-3-(2-propenyl)-phenol; (31) 2,6-dimethoxy-phenol; (32) 2-methoxy-4-(1-propenyl)-phenol or/
and 3-allyl-6-methoxy-phenol; (33) 4-methoxy-3-(methoxymethyl)-phenol; (34) 1-2,6-dihydroxy-4-methoxyphenyl-ethanone; (35) 1-(2,5-dimethoxyphenyl)-ethanone; (36) 4-hydroxy-3-methoxy-benzeneacetic acid; (37, 37a) 2,6-dimethoxy-4-(2-propenyl)-phenol; (38) levoglucosan; (39) 4-hydroxy-3,5dimethoxy-benzaldehyde; (40) desaspidinol.

3500000
3000000

Abundance

2500000
2000000

15
24,25

______

22

500000

13
5
7
11 14
6 8 9 12
10

26

21

__

23

38,39

__________
_______
___

27

16-20

1000000

__________

1500000

33-36

28-32

__

37

__

41
42

40

44
43

0
10

20

30
Time, min.

40

50

60

Fig. 8. PyrolysisGCMS chromatogram for raw synthetic biomass sample. The main peaks are assigned from mass spectral detection as follows: (1)
acetic acid; (2) acetic acid, 2-propenyl ester; (3) 1-hydroxy-2-propanone; (4) propanal; (5) 3(2H)-pyridazinone; (6) cycloheptane; (7) 1-methylenencyclopropenyl)-ethanone; (8) 2-butanone; (9) 3-furanmethanol; (10) 2H-pyran-2-one; (11) butyrolacetone; (12) 2(5H)-furanone; (13) 2-hydroxy-3-methyl-2cyclopenten-1-one; (14) phenol; (15) 2-methoxy phenol; (16) 2-methyl phenol; (17) 2-hexyn-1-ol; (18) 2,3-dimethyl phenol; (19) propanal; (20) 2-methyl
phenol; (21) 2-methoxy-4-methyl; (22) 2,4-dimethyl phenol; (23) 4-ethyl-2-methoxy phenol; (24) (Z)-2-butene-4-diol; (25) 3,3-dimethyl-1-pentene; (26)
2-methoxy-4-vinyl-phenol; (27) 2,6-dimethoxy-phenol; (28) 2-methoxy-4-(1-propenyl)-phenol; (29) 4-hydroxy-3-methoxy benzoic acid; (30) vanillin; (31)
hydroquinone; (32) 4-hydroxy benzaldehyde; (33) 3-methoxy-phenol; (34) 1-(2,6-dihydroxy-4-methoxyphenyl)-ethanone; (35) 2-methoxy-1,4-benzenediol;
(36) 1-(4-hydroxy-3-methoxyphenyl)-ethanone; (37) 1-(3,4-domethoxyphenyl)-ethanone; (38) 4-hydroxy-3-methoxy-benzeneacetic acid; (39) 1-(4-methylphenyl)-ethanone; (40) levoglucosan; (41) 2,6-dimethoxy-4-(2-propenyl)-phenol; (42) 4-hydroxy-3,5-dimethoxy-benzaldehyde; (43) 1-(4-hydroxy-4,5dimethoxyphenyl)-ethanone; (44) 1-(2,4,6-trihydoxy-3-methylphenyl)-1-butanone.

2398

D.J. Nowakowski et al. / Fuel 86 (2007) 23892402


6500000
6000000
5500000
5000000

4000000
3500000

27,28

3000000
18-22

2000000

1 2

17
9-14

_____

1500000

16
15

1000000
3

500000

67 8

_________

2500000

__

___

26

23

_____________
_______

Abundance

4500000

32

30

24

25 29

31

34
33

35 38
36
37 39

40
41
42

43

0
10

20

40

30
Time, min.

50

60

Fig. 9. PyrolysisGCMS chromatogram for HCl treated biomass mixture sample. The main peaks are assigned from mass spectral detection as follows:
(1) acetic acid; (2) acetic acid, 2-propenyl ester; (3) formic acid, ethyl ester; (4) pentenyl, hydroperoxide; (5) 2H-pyran-2-one; (6) isobutane; (7) 2-butanone;
(8) 3-furanmethanol; (9) 5-methyl-2-furancarboxaldehyde; (10) (Z)-2-butene-1,4-diol; (11) 1-ethyl-cyclopentene; (12) butyrolacetone; (13) cyclopentanone;
(14) 3,4-dimethyl-3-cyclobutene-1,2-dione; (15) 2-hydroxy-3-methyl-2-cyclopenten-1-one; (16) phenol; (17) 2-methoxy-phenol; (18) 3-methyl-phenol; (19)
2-hexyn1-ol; (20) 2-methyl-1,3-cyclohexanedione; (21) propanal; (22) 2-methyl-phenol; (23) 2-methoxy-4-methyl-phenol; (24) 2,4-dimethyl-phenol; (25)
4-ethyl-2-methoxy-phenol; (26) 2,5-dihydro-furan; (27) (Z)-2-butene-1,4-diol; (28) 3-methoxy-1-propanone; (29) 4-methyl-2-hexene (cis and trans); (30)
2-methoxy-4-vinylphenol; (31) 2-methoxy-4-(1-propenyl)-phenol; (32) 2,6-dimethoxy-phenol; (33) 2-methoxy-4-(1-propenyl)-phenol/strong/; (34)
4-hydroxy-3-methoxy-benzoic acid; (35) vanillin; (36) 4-hydroxy-3-methoxy-benzoacetic acid; (37) 1-(4-hydroxy-3-methoxyphenyl)-ethanone; (38)
1-(3,4-dimethoxyphenyl)-ethanone; (39) 1-(4-hydroxy-3-methoxyphenyl)-2-propanone; (40) levoglucosan; (41) 4-hydroxy-3,5-dimethoxy-benzaldehyde;
(42) 1-(4-hydroxy-4,5-dimethoxyphenyl)-ethanone; (43) 1-(2,4,6-trihydoxy-3-methylphenyl)-1-butanone.

5500000
5000000
4500000

3500000
18-22

3000000
2500000

13-16

2
12

1000000
500000

23-25

17

2000000
1500000

_________
______________
_________

Abundance

4000000

__

7
9
6 8
3

11

__ _26 28

31

30

27 29

10

32 33
34

35

36
39
40
37
38

41

0
10

20

30
Time, min.

40

50

60

Fig. 10. PyrolysisGCMS chromatogram for potassium impregnated synthetic biomass sample. The main peaks are assigned from mass spectral
detection as follows: (1) acetic acid; (2) acetic acid, 2-propenyl ester or/and 1-hydroxy-2-propanone; (3) 1-methoxy-2-propanone; (4) 2-propen-1-ol; (5)
2-octenoic acid; (6) 2-methyl-butanal; (7) 2-cyclopenten-1-one; (8) 2-furanmethanol; (9) 2-methyl-2-cyclopenten-1-one; (10) 3-furanmethanol; (11)
3-methyl-2-cyclopenten-1-one; (12) butyrolacetone; (13) 2,3-dimethyl-2-cyclopenten-1-one; (14) 2-hydroxy-3-methyl-2-cyclopenten-1-one; (15) 2-hydroxy3,5-dimethylcyclopenten-2-en-1-one; (16) phenol; (17) 2-methoxy-phenol; (18) 2-methyl-phenol; (19) 3-methyl-2-hydroxy-2-cyclopenten-1-one; (20)
4,6-dimethyl-2H-pyran-2-one; (21) 2-ethyl-2-methyl-1,3-cyclopentanedione; (22) 4-methyl-phenol; (23) 2-methoxy-4-methyl-phenol; (24) cyclopropyl
carbinol; (25) 2,4-dimethyl-phenol; (26) 3,4,5-trimethyl-phenol; (27) 2,5-dimethyl-phenol; (28) 4-ethyl-2-methyl-phenol; (29) 2,4,6- or/and 2,3,5-trimethylphenol; (30) 2-methoxy-4-vinylphenol; (31) 3,4-dimethoxy-phenol; (32) 2-methoxy-4-(1-propenyl)-phenol; (33) 4-methoxy-3-(methoxymethyl)-phenol; (34)
vanillin; (35) 1-(2,6-dihydroxy-4-methoxyphenyl)-ethanone; (36) 4-methyl-2,5-diethoxybenzaldehyde; (37) 1-(4-hydroxy-3-methoxyphenyl)-2-propanone;
(38) 2,5-dimethoxy-4-ethylbenzaldehyde; (39) levoglucosan; (40) 4-hydroxy-3,5-dimethoxy-benzaldehyde; (41) 1-(2,4,6-trihydoxy-3-methylphenyl)-1butanone.

D.J. Nowakowski et al. / Fuel 86 (2007) 23892402

3.3. PYGCMS tests


Pyrolysisgas chromatographymass spectrometry (PY
GCMS) analysis has been introduced to study the generation of heavier hydrocarbons produced during pyrolysis
of willow SRC and the synthetic biomass mixture samples.
The results are given in Figs. 57 for the raw, HCl treated

2399

and potassium impregnated willow samples and for synthetic mixture in Figs. 810, respectively. The main peaks
were assigned from mass spectral detection and from the
literature [2426] and are given under the each gure.
One product, namely squaric acid, 3,4-dihydroxy-3-cyclobutene-1,2-dione, has not been identied previously in the
literature.

Table 5
Key markers assignment for PYGCMS of willow and synthetic biomass samples
Name of compound, chemical formula

Structure, chemical
formula

Phenol, C6H6O
Furfural, C5H4O2

Molecular
weight

m/z

Cellulose and
lignin

94.11

94.04 (100.0%), 95.05 (6.6%)

Cellulose

96.08

96.02 (100.0%), 97.02 (5.4%)

Cellulose

98.10

98.04 (100.0%), 99.04 (5.6%)

Cellulose

98.10

98.04 (100.0%), 99.04 (5.6%)

OH

Cellulose

114.06

114.00 (100.0%), 115.00 (4.5%)

Guaiacol lignin

124.14

124.05 (100.0%), 125.06 (7.7%)

Guaiacol lignin

150.17

150.07 (100.0%), 151.07 (9.9%)

Guaiacol lignin

152.10

152.05 (100.0%), 153.05 (8.9%)

Syringol lignin

154.16

154.06 (100.0%), 155.07 (8.9%)

Cellulose

162.05

162.05 (100.0%), 163.06 (6.8%),


164.06 (1.2%)

Guaiacol lignin

164.20

164.08 (100.0%), 165.09 (11.0%)

Guaiacol lignin

168.19

168.08 (100.0%), 169.08 (10.0%)

Lignin

182.17

182.06 (100.0%), 183.06 (10.0%),


184.06 (1.2%)

Syringol lignin

182.17

182.06 (100.0%), 183.06 (10.0%),


184.06 (1.2%)

Syringol lignin

194.23

194.09 (100.0%), 195.10 (12.2%),


196.10 (1.3%)

Lignin

210.23

210.09 (100.0%), 211.09 (12.0%)

OH

Type of key
marker

O
HO

2-Hydroxy-2-cyclopenten-1-one, C5H6O2
3-Furanmethanol, C5H6O2

HO

3,4-Dihydroxy-3-cyclobutene-1,2-dione,
C4H2O4

O
OH
OH

2-Methoxy-phenol, C7H8O2

O
OH

2-Methoxy-4-vinylphenol, C9H10O2
O
HO

Vanillin, C8H8O3

2,6-Dimethoxyphenol, C8H10O3

O
OH

HO

O
O

1,6-Anhydro-b-D-glucopyranose
(levoglucosan), C6H10O5

HO

OH

OH

2-Methoxy-4-(1-propenyl)-phenol, C10H12O2
O
O

4-Methoxy-3-(methoxymethyl)-phenol,
C9H12O3

OH

OH

4-Hydroxy-3-methoxy benzoacetic acid,


C9H10O4

O
HO
O

4-Hydroxy-3,5-dimethoxy benzaldehyde,
C9H10O4

O
OH

O
O
O

2,6-Dimethoxy-4-(2-propenyl)-phenol,
C11H14O3

HO
O
HO

1-(2,4,6-Trihydroxy-3-methylphenyl)-butan-1one, C11H14O4

OH

OH

2400

D.J. Nowakowski et al. / Fuel 86 (2007) 23892402

components such as acetic acid, formic acid, glyoxal,


hydroxyacetaldehyde and acetol [23].
Selected cellulose and lignin (Guaiacol and Syringol) key
markers were identied for the most abundant thermal degradation compounds from pyrolysis of willow SRC and synthetic biomass, and these are listed in Table 5, together with
the main charged species, fragments and relative abundance
determined by the NIST98 library. The key markers for
cellulose [24,25] are: phenol, furfural, 2-hydroxy-2-cyclopenten-2-one, 3-furanmethanol, 3,4-dihydroxy-3-cyclobutene1,2-dione and levoglucosan. The key markers for Guaiacol
(G) and Syringol (S) lignin [23,25] are: phenol (G,S), 2-methoxyphenol (G), 2-methoxy-4-vinylphenol (G), vanillin (G),
2,6-dimethoxyphenol (S), 2-methoxy-4-(1-propenyl)-phenol
(G), 4-methoxy-3-(methoxymethyl)-phenol (G), 4-hydroxy3-methoxy benzoacetic acid (unknown), 4-hydroxy-3,
5-dimethoxy benzaldehyde (S), 2,6-dimethoxy-4-(2-propenyl)-phenol (S) and 1-(2,4,6-trihydroxy-methylphenyl)-1butanone (unknown). Peak area percentages from the
chromatograms in Figs. 510 were re-calculated excluding
potassium acetate decomposition products and normalised
per mg of volatile products. In this way peak areas for key
decomposition products from PYGCMS proles could
be compared for willow and synthetic biomass pyrolysis
and these comparisons are given in Figs. 11 and 12,
respectively.

There are some similarities between the proles for the


SRC and the synthetic biomass. Peaks are identied for
low molecular weight components (acetic acid, acetic acid
propenyl ester, propanol, n-alkanes), alkyl-, methoxyand ethoxy phenols, cyclic compounds (cyclopropyl carbinol, cyclobutanol), furfural as well as levoglucosan and
sugar derivatives originating from the lignocellulosic material. Acetic acid was identied in each sample, but in the
case of the synthetic biomass samples, well-resolved peaks
can be observed for acetic acid and it derivatives (hydroxyacetic acid, acetic acid 2-propenyl ester). These compounds
elute between 7 and 9 min. Levoglucosan (1,6-anhydrobeta-D-glucopyranose) elutes in 44 min and is observed in
all raw and HCl treated samples.
In general, the PYGCMS proles of the K-impregnated fuels are simpler and have a higher yield of lighter
species. In the case of the potassium impregnated synthetic
biomass sample, the levoglucosan abundance is very low,
while in the case of the potassium impregnated willow sample the yield of this compound has been decreased signicantly. This supports previous work [19] on the inuence
of potassium on the pyrolysis process of cellulose and on
the formation of levoglucosan. Inorganic cations can act
as catalysts for complete decomposition of glucosidic units
by an heterolytic mechanism and favour its direct depolymerisation and fragmentation to low molecular weight

Furfural

Willow raw
Willow HCl treated
Willow K-impregnated

2-hydroxy-2-cyclopenten-1-one

3,4-dihydroxy-3-cyclobutene-1,2-dione

Phenol

2-methoxyphenol

2-methoxy-4-vinylphenol

2,6-dimethoxyphenol

2-methoxy-4-(1-propenyl)-phenol

4-methoxy-3-(methoxymethyl)-phenol

4-hydroxy-3-methoxy-benzoacetic acid

2,6-dimethoxy-4-(2-propenyl)-phenol

Levoglucosan
0

Area, %

Fig. 11. Peak areas for key markers from PYGCMS analysis for willow samples (raw, HCl treated and potassium impregnated). (Peak areas have been
normalised per mg of volatile products.)

D.J. Nowakowski et al. / Fuel 86 (2007) 23892402

2401

3-furanmethanol

Phenol

2-methoxyphenol

2-methoxy-4-vinylphenol

2,6-dimethoxyphenol

2-methoxy-4-(1-propenyl)-phenol

Vanillin

Levoglucosan
Mixture raw
4-hydroxy-3,5-dimethoxy benzaldehyde

Mixture HCl treated


Mixture K-impregnated

1-(2,4,6-trihydroxy-methylphenyl)-1butanone
0.0

1.0

2.0

3.0

4.0

5.0

Area, %

Fig. 12. Peak areas for key markers from PYGCMS analysis for synthetic biomass, a mixture of the basic biomass components (raw, HCl treated and
potassium impregnated). (Peak areas have been normalised per mg of volatile products.)

Firstly, by comparison of Figs. 11 and 12, it is clear that


the substituted phenols from lignin pyrolysis are more
dominant in the pyrolysis proles of the synthetic biomass
than of the SRC. This implies that the extracted lignins
used in the synthetic biomass yield a greater fraction of
monomeric type species than the lignocellulosic cell wall
material of SRC. Also apparent from Figs. 11 and 12 is
that a greater variation in pyrolysis products from dierently treated samples is observed for SRC compared to
synthetic biomass. Comparing raw and demineralised samples, we see that the inherent metals in SRC, and their
removal by demineralisation, have a large impact on the
pyrolysis products. The metal content of the synthetic biomass is low and hence demineralisation has a much less
pronounced eect on its degradation products.
In both cases, in the K-impregnated samples, there is a
signicant inuence on the formation of volatile products.
The presence of metals, particularly potassium, promotes
the generation of phenol and phenol derivatives (2-methoxy-phenol, 2,6-dimethoxy-phenol) and reduces the formation of levoglucosan, a major product from the pyrolysis of
cellulose. It is worth noticing that 3,4-dihydroxy-3-cyclobutene-1,2-dione was observed in high abundance in raw
and HCl treated samples, while this compound has not
been identied in the presence of potassium. The same
behaviour was observed during pyrolysis of pure cellulose
and levoglucosan [27].

4. Conclusions
A willow SRC biomass sample and a synthetic biomass,
a mixture of the basic biomass components were subjected
to two types of pretreatment: HCl demineralisation and
impregnation of the demineralised sample by potassium
(as potassium acetate).
Pyrolysis tests revealed additive properties of the mixture of the basic biomass constituents, in that the features
of the DTG pyrolysis proles were directly comparable
to those of the willow samples. The yields of pyrolysis
products were inuenced by the presence of the catalyst.
Potassium catalysed pyrolysis resulted in increased char
yields (from 6.7% for HCl treated willow sample to
19.8% for K-impregnated willow sample and from 16.9%
to 31.3% for synthetic biomass sample). Furthermore,
potassium lowered the average apparent rst-order activation energy for pyrolysis by up to 50 kJ/mol, and the catalysis was greater in SRC than in the synthetic biomass.
DTG analysis of the potassium impregnated sample
revealed that its thermal degradation occurs in two steps,
and the main pyrolysis DTG peak temperature shifted
67 K for the willow sample and 41 K for the synthetic biomass. A similar shift to lower temperature was observed in
gas evolution proles for all species, except methane. Relative methane yields increased during the char formation
stage of pyrolysis of the potassium doped samples. The

2402

D.J. Nowakowski et al. / Fuel 86 (2007) 23892402

evolution proles of acetic acid and formaldehyde change,


and these products are seen in lower relative amounts for
both the demineralised samples.
A greater variation in pyrolysis products was observed
from the treated SRC samples compared to the dierent
synthetic biomass samples. Furthermore, substituted phenols from lignin pyrolysis are more dominant in the pyrolysis proles of the synthetic biomass than of the SRC,
implying that the extracted lignins used in the synthetic
biomass yield a greater fraction of monomeric type species
than the lignocellulosic cell wall material of SRC. Levoglucosan was identied with very low abundance in the
pyrolysis of the K-impregnated synthetic biomass and
was decreased signicantly in the willow sample, compared
to the analogous demineralised sample. This is consistent
with a catalytic mechanism involving heterolytic ring opening and cracking reactions to favour the formation of low
molecular weight components and char over levoglucosan.
Squaric acid, 3,4-dihydroxy-3-cyclobutene-1,2-dione, was
also identied as a degradation product from samples with
no added potassium and is proposed as an alternative
product in the pyrolysis mechanism of the untreated fuels.
Acknowledgements
J.M.J. is an Engineering and Physical Sciences Research
Council (EPSRC, United Kingdom) Advanced Research
Fellow and the authors are grateful to the EPSRC for
nancial support under Contract Numbers GR/S49018
and GR/S49025. The authors wish to thank the Supergen
Consortium in Biomass, Biofuels and Energy Crops
(http://www.supergen-bioenergy.net) for providing the willow SRC sample and some analytical data. Appreciation is
also given to Mr. Peter Thompson for his assistance.
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