Biomass and Bioenergy 31 (2007) 222242

Characterization of bio-oils in chemical families

M. Garcia-Perez
a
, A. Chaala
c
, H. Pakdel
a
, D. Kretschmer
b
, C. Roy
a,d,
a
Chemical Engineering Department, Universite Laval, Quebec, Canada
b
Mechanical Engineering Department, Universite Laval, Quebec, Canada
c
SEREX, Amqui, Quebec, Canada
d
Pyrovac International, 1560 Avenue du Parc-Beauvoir, Sillery/ Quebec, Canada G1T 2M4
Received 16 May 2005; received in revised form 6 February 2006; accepted 28 February 2006
Available online 12 December 2006
Abstract
This paper describes an analytical approach to determine the chemical composition of bio-oils in terms of macro-chemical families.
Bio-oils from the vacuum pyrolysis of softwood bark and hardwood were rst fractionated using solvent extraction. Fractions obtained
were then characterized using GC-MS, thermogravimetric techniques (TG) and Gel Permeation Chromatography (GPC).
Thermogravimetric and molar mass distribution curves of each fraction were interpreted in terms of macro-families applying curve-
tting procedures. The composition of the different macro-fractions obtained was in agreement using both methods. The proposed
procedure enables a thorough description of bio-oil composition as a mixture of water, monolignols, polar compounds with moderate
volatility, sugars, extractive-derived compounds, heavy polar and non-polar compounds, MeOHtoluene insolubles and volatile organic
compounds.
r 2006 Elsevier Ltd. All rights reserved.
Keywords: Bio-oil; Composition; Pyrolysis; GC-MS; TG; GPC
1. Introduction
The need for clean sources of energy is receiving
an increasing attention since the middle of the 20th
century. The rst oil shock in 19731974 and the recent
environmental concerns changed for ever the inter-
national oil markets and the energy policies of most
industrialized nations [1]. The conversion of biomass into
char, bio-oils and gaseous products using pyrolysis
technologies is one of the most promising alternatives
under study today to convert biomass into useful products
and energy.
The chemical composition of bio-oils is very complex.
Bio-oils are mainly composed of water, organics and a
small amount of ash. According to Meir [2], these materials
can be globally represented as: around 20 mass% water,
around 40 mass% GC-detectable compounds, around
15 mass% non-volatile HPLC detectable compounds and
around 15 mass% high molar mass non-detectable com-
pounds. A complete analysis of bio-oils requires the
combined use of more than one analytical technique. A
precise description of bio-oil composition has not yet been
achieved. The accuracy of some of these analytical
techniques has been highlighted in Round Robin tests [3]
conducted by different laboratories.
Fractionation strategies reported in the literature [49]
use differences in polarity and/or acidity as a driving force
to achieve the separation of fractions. One important
question that remains unanswered is whether the fractions
obtained using these separation approaches are group
chemicals with the same composition and independent of
the bio-oil investigated. When this is the case, the
separation scheme proposed may be good enough to fully
characterize and compare bio-oils. If the chemical compo-
sition of the separated fractions changes depending on the
initial oil sample or pyrolysis process, then additional
chemical information is needed for each fraction involved
ARTICLE IN PRESS
www.elsevier.com/locate/biombioe
0961-9534/$ - see front matter r 2006 Elsevier Ltd. All rights reserved.
doi:10.1016/j.biombioe.2006.02.006

Corresponding author. Pyrovac International, 1560 Avenue du Parc-

Beauvoir, Sillery/Que bec, Canada G1T 2M4. Tel.: +1 418 580 2632;
fax: +1 418 889 8723.
E-mail address: chroy@videotron.ca (C. Roy).
in order to have a description allowing a meaningful
comparison between bio-oils.
Sipila et al. [6] noted that bio-oil compounds which
form chemical families tent to be grouped in rela-
tively narrow ranges of retention times on GC-MS
chromatograms. Sheu et al. [10] reported that the
separation of fractions by molecular sizes also leads to a
relatively neat separation of fractions with pronounced
differences in their chemical structure. In fact each of the
separated fractions was assigned to a certain chemical
family.
The grouping of bio-oil compounds in chemical families
is very useful and necessary because these materials
can be treated as a mixture of few groups instead of
hundred of compounds [9,1114]. This kind of des-
cription can be useful in the modelling bio-oils evaporation
and combustion [15] as well as in the development
of bio-oil up-grading strategies. A promising alternative
to describe the composition of bio-oils could be the use of
continuous thermodynamics which represents the
mixture composition as a probability density function
rather than in terms of discrete components [15].
Chemical families characterized by a few distri-
bution parameters (molar mass distribution or boiling
points) could provide a rather realistic description of bio-
oils behavior.
Thermogravimetry seems to be a promising techni-
que to study bio-oil fuel properties since the mass
losses measured by this method depend on the volatility
(or molar mass) of the fractions investigated. This
technique has been used to compare the evaporation
and cracking behavior of different bio-oils and their
fractions [11,16].
Gel Permeation Chromatography (GPC) can also be
used to characterize bio-oils in chemical families.
Tetrahydrofuran (THF) has been extensively used as
eluent and polystyrene as standard in most of bio-oil
GPC analyses reported in the literature [7,10,1723].
The use of THF to characterize the molar mass distri-
bution of bio-oils presents however some limitations.
For example, high molar mass compounds and some
poly-sugars are partially or totally insoluble in
THF. Dimethyl-formamide (DMF) on the other hand is
reported to be one of the most effective organic solvent to
dissolve lignins [2426] over a wide range of molar masses.
DMF is also effective for sugars and polar heavy
compounds.
The purpose of this paper is to develop a characteriza-
tion approach to determine bio-oil chemical composition in
term of macro-chemical families using solvent extraction
and then analyzing the fractions obtained using TG, GC-
MS and GPC.
ARTICLE IN PRESS
Nomenclature
A

ngstrom (10
10
m)
A pre-exponential factor (min
1
)
E activation energy (kJ mol
1
)
m mass (g)
n reaction order (adimensional)
R gas constant (8.314) (J mol
1
K)
R
s
nal residue (adimensional)
T temperature (K)
T
b
boiling point (K)
T
o
temperature corresponding to 1 mass% of dry
material mass loss (K)
T
Pi
peak temperature corresponding to a maximum
mass loss (K)
X
N
maximum volatile fraction (adimensional)
y
jo
initial mass fraction of component j (adimen-
sional)
z
jo
mass fraction of volatile materials from com-
ponent j (adimensional)
Greek letters
a
j
degree of conversion (adimensional)
da/dt instantaneous reaction rate (min
1
)
da
j
/dt instantaneous rate for component j (min
1
)
Acronyms
ASTM American Society for Testing and Materials
DTG differential thermogravimetry
DMF N,N Dimethylformamide
GC gas chromatography
GC-MS gas chromatographymass spectroscopy
GPC gel permeation chromatography
HP Hewlett-Packard
HPLC high performance liquid chromatography
HWRF hardwood rich in bres
M molar mass
MSD mass selective detector
M
n
number average molecular mass
MeOH methanol
M
w
mass average molecular mass
MWD molecular weight distribution
NBS National Bureau of Standards
PL pyrolytic lignin
SWBR softwood bark residues
T-EtOH TolueneEthanol
TG thermogravimetry
TGA thermogravimetric analysis
THF tetrahydrofuran
Sufx
j used to indicate compound j
M. Garcia-Perez et al. / Biomass and Bioenergy 31 ( 2007) 222242 223
2. Experimental section
2.1. Materials
2.1.1. Production of Bio-oils
Bio-oils were produced, by vacuum pyrolysis, from two
wood industry residues provided by Energex, Lac Me gan-
tic, Que bec. The detailed characterization of used feed-
stocks and pyrolysis conditions are described elsewhere
[27]. The rst feedstock called Softwood Bark Residue
(SWBR) was mainly composed of bark from softwood
species. The second feedstock, called Hardwood Rich in
Fibres (HWRF), was composed of bres from hardwood
species. The product yields obtained are presented in Table
1. The bio-oils readily separated into two layers during
storage at 60 1C. The phase oating on the top was called
upper layer. The phase at the bottom was called
bottom layer. More information about the physico-
chemical properties of these oils can be found elsewhere
[27].
2.1.2. Bio-oil fractionation
Primarily, water content of the bio-oils was determined
by Karl Fisher titration (ASTM D-1744). The method used
for bio-oil chemical fractionation is presented in Fig. 1.
Seven grams of bio-oil were rst extracted using 200 mL of
toluene. This operation was performed in order to separate
some of the wood-extractive derived compounds that
interfere with heavy compounds precipitating. Waxy
materials remaining in suspension in the toluene-soluble
fraction were separated using a Whatman N1 42 lter (this
type of lter was used in all ltrations). The toluene-
insoluble fraction was solubilized in 200 mL of MeOH and
ltrated in order to remove the char, non-polar waxy
materials and other very heavy oligomeric compounds. The
solvents were eliminated from the ltrates in a rotary-
evaporator and the dry residue was weighted. This residue
was solubilized again in MeOH (5 mL of MeOH per 1 g of
residue). A 10 g of the MeOHoil mixture was added to
300 mL ice-cooled distilled water drop wise under agita-
tion. The water-insoluble fraction was removed by ltra-
tion. The solid residue was washed with distilled water
during 1 h then was further extracted with dichloromethane
until the ltrate was colourless. The solid remaining in the
lter was dried at 105 1C over night. The water-soluble
fraction was further extracted with 300 mL of diethylether
in a separation funnel. Diethyl-ether-soluble and CH
2
Cl
2
-
soluble fractions were evaporated in a rotary-evaporator at
40 1C. Low molar mass compounds were also removed
during the solvent removal. These losses were reported as
volatile compounds.
2.1.3. Thermogravimetric analysis
A SSC-5200 TG-DTG (220) microbalance from Seiko
was used for the thermogravimetric tests. This equipment
uses a horizontal differential balance mechanism. The
samples are heated from room temperature to 575 1C,
under a nitrogen ow of 150 mLmin
1
at 10 1Cmin
1
.
Samples of 4 mg were used.
2.1.4. GC-MS
The separation was made on a 30 m0.25 mm i.d. fused
silica capillary column HP-5MS using a 5890 Gas
Chromatograph Hewlett-Packard. The GC oven tempera-
ture was held at 50 1C for 2 min then programmed to
ARTICLE IN PRESS
Table 1
Product yields of vacuum pyrolysis of SWBR and HWRF (mass%,
feedstock anhydrous basis) in different pyrolysis reactors
Fraction SWBR
a
HWRF
b
Pyrolysis oil 25.0 (13.0% water) 26.4 (13.0% water)
Aqueous phase 20.0 27.5
Gas 27.4 19.9
Charcoal 27.6 26.2
Total 100 100
a
Pilot plant 15 kg h
1
.
b
15 L batch laboratory reactor.
Fig. 1. Fractionation scheme for bio-oil chemical characterization.
M. Garcia-Perez et al. / Biomass and Bioenergy 31 ( 2007) 222242 224
290 1C at 5 1Cmin
1
. The injector temperature was 290 1C
with split mode. A 1 mLmin
1
of helium was used as the
carrier gas. The end of the column was directly introduced
into the ion source of the Hewlett-Packard model 5970
series mass selective detector (MSD) operated with electron
impact ionization mode. The data acquisition system used
was G1034 C Chemstation software with a NBS library.
2.1.5. Gpc
The molar mass distribution (MWD) was determined
using a Waters 510 pump with 410 refractive index
detector. The tests were performed using two solvents:
DMF and THF.
The tests with DMF and THF tests were carried out at
ow rate of 1 and 0.8 mLmin
1
, respectively. Bio-oil
samples were dissolved in both solvents at a concentration
of 0.2% by mass and ltrated on a 2 mm lter before being
injected into the GPC columns. The injection volume was
20 mL. All the data were analysed using the software
Millennium 3.05. The reference cell in the detector was
maintained at 30 1C.
Four columns in series were used in these tests using
DMF. The columns used were Shodex type from Waters:
(1) KD-803, exclusion range (ER): 10
3
7 10
4
g mol
1
,
pore diameter 100 A

, (2) AD 802.5/S, ER: 200-

2 10
4
g mol
1
, pore diameter 80 A

, (3) KD-802, ER:

100-5 10
3
g mol
1
pore diameter 60 A

and (4) AD 802/S,

ER: 100-5 10
3
g mol
1
, pore diameter 60 A

. These col-
umns were packed with porous styrene-divinylbenzene co-
polymer gels. The DMF solution contained 0.4 g of
tetrachloroacetic acid (TCAA) and 0.44 g of LiBr per litre
of solution. These compounds were added to minimize the
association effect between molecules.
The tests using THF were performed in a system with
three columns in series. The columns used were: (1)
Styragel
s
HR4E, 7.8 300 mm, ER: 50-1 10
5
g mol
1
,
pore diameter 10
4
A

; (2) Phenogel 5 m N1 00H-0444-KO,

ER: 10
3
7.5 10
4
g mol
1
, pore diameter 10
3
A

(3) Styr-
agel
s
HR1, 7.8 300 mm, ER: 100-5 10
3
g mol
1
, pore
diameter 100 A

. The Styragel columns were packed with

rigid 10 mm divinylbenzene particles.
GPC calibration was made with monodisperse polystyr-
ene, polyethylene glycol and with other organic compounds
typically found in bio-oils (see Fig. 2). The calibration
curve obtained with THF is relatively independent of
compound polarity. However, when using DMF the
calibration curve showed an important dependency on
the polarity of the calibration standard used. Since the
column used is a copolymer of styrene and di-vinyl
benzene, the afnity of non-polar compounds for the
packing material should increase as solvent polarity
increases. The observed dependency is almost certainly an
adsorption effect [25]. The low molar mass non-polar
compounds were much more strongly adsorbed due to a
large surface of the column which is available for small
molecules. These experimental results indicate that poly-
styrene standards cannot be used for calibration in GPC
analysis when using DMF as eluent in styrene-divinylben-
zene co-polymer gels columns. Instead polyethylene glycol
should be used.
2.1.6. Elemental analysis
The concentration of C, H and N was determined with a
LECO CHN-600 apparatus. The amount of oxygen was
determined by difference.
3. Results and discussion
3.1. Bio-oil fractionation
Table 2 presents the composition of HWRF and SWBR
bio-oils by liquidliquid extraction following the sequence
shown in Fig. 1. The results obtained for all the fractions
correspond very well with the range of values previously
reported for other oils using the same separation approach
[6,17]. The upper layer from SWBR is mainly composed of
compounds soluble in toluene (79.0 mass%). This fraction
has been attributed to the wood extractives-derived
compounds [2830]. The water-insoluble fraction was
separated into two sub-fractions (Fractions 5 and 6, Fig. 1)
depending on their solubility in CH
2
Cl
2
. The CH
2
Cl
2
-
soluble sub-fraction (Fraction 6, Fig. 1) is an important
portion of SWBR bottom layer with 12.5 mass% and
HWRF bottom layer with 13.7 mass%. This fraction is rich
in low molar mass pyrolytic lignin [6]. The CH
2
Cl
2
-
insoluble sub-fraction (Fraction 5, Fig. 1) has been referred
to as the high molar mass pyrolytic lignin by Sipila
et al. [6].
The presence of MeOH during bio-oil precipitation in
water does not seem to drastically affect the yields of
pyrolytic lignin. The total water-insoluble fraction
(Fraction 1+ Fraction 2+Fraction 5+Fraction 6,
Fig. 1) is 28.9 mass% of the SWBR bottom layer. This
value is 1 mass% less than that found (29.6 mass%) during
the direct precipitation of SWBR bottom layer in water.
The small difference observed is attributed to experimental
error.
3.2. Thermogravimetric and GC-MS analyses
DTG curves and GC-MS chromatograms for the
fractions obtained from SWBR upper and bottom layer
and for the HWRF bottom layer are presented in Figs. 37.
The mass losses for all the fractions investigated are
assumed to be the sum of their components released upon
evaporation and thermal degradation. Curve tting is
based on the hypothesis that macro-families do not interact
during evaporation and thermal degradation. This hypoth-
esis may not be completely realistic but can be considered
as a rst approximation to study bio-oil composition. DTG
curves are tted using the equations that describe the
thermal degradation kinetics of different macro-chemical
families. The equations generally used in the literature
[3133] to describe the thermal decomposition of individual
ARTICLE IN PRESS
M. Garcia-Perez et al. / Biomass and Bioenergy 31 ( 2007) 222242 225
families are the following:
da
dt

X
N
j1
z
jo
da
j
dt
, (1)
da
j
dt
A
j
exp
E
j
R T

1 a
j

nj
, (2)
X
N
i1
z
jo
1, (3)
z
jo

m
jo
m
j1

m
o
m
1

, (4)
where da
j
=dt is the instantaneous reaction or vaporization
rate; a
j
, the parameter dened as a
j
m
jo
m
j
=
m
jo
m
j1
; z
jo
, the mass fraction of volatile materials
ARTICLE IN PRESS
Table 2
Fractionation of Bio-oils using different solvents (mass% on bio-oils as
received basis)
Fraction SWBR (Run: H-67) HWRF
(Run: G
823830)
Upper layer Bottom
layer
Bottom
layer
Water 3.50 14.60 13.00
Toluene solubles 78.95 1.29 7.76
MeOH insolubles 0.99 2.09 0.36
Water solubles: 6.04 41.26 46.85
Diethylether soluble 0.74 7.94 4.78
Diethylether insoluble 5.30 33.32 42.07
Water insolubles 8.65 25.51 20.86
CH
2
Cl
2
soluble 6.47 12.54 13.70
CH
2
Cl
2
insoluble 2.18 12.97 7.16
Volatile loss (by difference) 1.87 15.25 11.17
0
1
2
3
4
5
6
20 25 30 35 40 45 50 55
Retention Time (min)
L
o
g

M
w
Polystyrene
Polyethylene
Glycol
5
8
7
6
9
1
2
3
4
16
15
14
13
12
11
10
DMF
0
1
2
3
4
5
6
7
15 20 25 30 35 40
Retention time (min)
L
o
g

M
w
Polystyrene
Polyethylene
Glycol
THF
5
7
6
11 10
12
1
4 9
Fig. 2. Calibration curve of retention time vs. molar mass. (1) Dibenzo-anthracene, (2) Benzene, (3) Phenantrene, (4) Anthracene, (5) Ergocalciferol, (6)
Abietic acid, (7) Cholesterol, (8) Tannic acid, (9) Naphtalene, (10) Phenol, (11) Pyrogallol, (12) 2,6 Dimethoxyphenol, (13) Flavon, (14) Warfarin, (15)
Cellobiose, (16) Lactose.
M. Garcia-Perez et al. / Biomass and Bioenergy 31 ( 2007) 222242 226
from component j; A
j
, the pre-exponential factor corre-
sponding to component j thermal degradation; E
j
, the
activation energy corresponding to component j thermal
degradation; n, the reaction order; m, the mass of solid
residue.
E
j
, A
j
, n
j
and the values of z
jo
used to t the DTG curves
are calculated following a least-square regression analysis.
The number of macro-families adjusted depends upon
the shape of the DTG curves. Eqs. (1)(4) describe thermal
degradation of oligomeric and polymeric materials. These
equations could also be used to describe evaporation.
Fitted parameters (E
j
, A
j
, n
j
) however, do not have physical
meaning. The values of z
jo
have the same meaning as in the
case of thermal degradation reactions: mass fraction of
volatile from the sub-fraction j.
The GC-MS chromatograms corresponding to each
fraction (Figs. 37) are very useful for the identication
of the chemical species that are associated with each DTG
peak. Table 3 shows the peak temperature (T
max
), the range
of average molecular mass and the boiling points of
assigned volatile compounds per peak.
Bio-oil fractions can be represented as a mixture of eight
macro-families (Figs. 37). These macro-families are
designated as: AVolatile non-polar compounds, B
Volatile polar compounds, CMonolignols, DPolar
compounds with moderate volatility, ESugars,
FExtractive-derived compounds, GHeavy non-polar
compounds, and HHeavy polar compounds. A number
of compounds assigned to each of these chemical families
were identied in the GC-MS chromatograms.
(a) Volatile non-polar compounds: The peak corresponding
to this macro-family includes compounds insoluble in
water that evaporate between 60 and 220 1C (DTG
peak between 116 and 153 1C, Figs. 3 and 6). The main
compounds identied by the GC-MS and assigned to
this chemical family were ethylbenzene and p-Xylene.
(b) Volatile polar compounds: This macro-family is com-
posed of species soluble in water that evaporate
between 50 and 220 1C (DTG peak between 120 and
130 1C, Figs. 4 and 5). The weakly attached volatile
polar compounds in the waterCH
2
Cl
2
-insoluble frac-
tions are removed at higher temperatures (DTG peak
176192 1C, Fig. 7). The main compounds identied by
GC-MS and assigned to this group were: 2(5H)-
furanone, 2-hydroxycyclopent-2-en-1-one, 3-methyl-1,
ARTICLE IN PRESS
A
b
u
n
d
a
n
c
e
5.00 10.00 15.00 20.00 25.00 30.00
Time-->
A
b
u
n
d
a
n
c
e
A
b
u
n
d
a
n
c
e
0.00
1.00
2.00
3.00
4.00
5.00
6.00
7.00
8.00
9.00
10.00
0 100 200 300 400 500 600 700 800
Temperature (C)
D
T
G

(
m
a
s
s

%

/
m
i
n
)
.
.
.
0.00
1.00
2.00
3.00
4.00
5.00
6.00
7.00
8.00
9.00
10.00
0 100 200 300 400 500 600 700 800
Temperature (C)
D
T
G

(
m
a
s
s

%

/
m
i
n
)
.
.
.
0.00
1.00
2.00
3.00
4.00
5.00
6.00
7.00
8.00
9.00
10.00
0 100 200 300 400 500 600 700 800
Temperature (C)
D
T
G

(
m
a
s
s

%

/
m
i
n
)
.
.
.
SWBR upper layer
G
C
F
G
A
C
HWRF bottom layer
F
G A
C
A
SWBR bottom layer
F
A
A
A
C
C
C
F
F
F
a
b
c
Fig. 3. DTG and GC/MS corresponding to the toluene soluble fractions (A: volatile non-polar, C: monolignols, F: extractives, G: Heavy non-polar
compounds).
M. Garcia-Perez et al. / Biomass and Bioenergy 31 ( 2007) 222242 227
2-cyclopentadione, tetrahydro-2-furanmethanol, Cy-
clopropyl carbinol, Cyclopentanol (see Tables 3 and 4).
(c) Monolignols: The monolignols are associated with
species that evaporate between 100 and 300 1C with a
peak between 170 and 215 1C (Figs. 3 and 6). The
monolignols weakly linked to the waterCH
2
Cl
2
-
insoluble fractions are removed at high temperatures
(peaks around 260 1C, Fig. 6). Molar mass and boiling
point of species found in the GC-MS chromatograms
are presented in Tables 3 and 4. The compounds
associated to this group were mainly alkylated and
methoxylated phenols and benzenediol (Compounds: 6,
8, 11, 13, 14, 16, 17, 21, 22, 2326, 2830, 32, 33, 38, 44,
47 and 49).
(d) Polar compounds with moderate volatility: These com-
pounds are observed in the water-soluble fractions and
cannot be considered a unique chemical family.
However, they share relatively high polarities and
similar volatility. The maximum evaporation rate
determined in the DTG curves was found between
178 and 198 1C (Figs. 4 and 5). The compounds
identied by GC-MS were mainly monolignols (com-
pounds: 17, 22, 24, 28, 29, 31, 32, 35, 44, 48, 49). The
5-methyl-2-furaldehyde (compound 19) was also iden-
tied. Other compounds derived from cellulose and
hemicellulose must also form part of this group
however, the GC column used and MS detector did
not provide any information about their identity.
(e) Sugars: The peaks assigned to the sugars were observed
between 235 and 300 1C (Figs. 4 and 5). These peaks
included the evaporation of some monosugars and the
cracking of poly-sugars. Only levoglucosane
(M
w
162 g mol
1
, T
b
285 1C) was detected in GC-
MS chromatograms (Fig. 3). The GC-MS chromato-
gram from the ether-soluble fraction does not show the
presence of any sugar (Fig. 5). One can conclude that
the poly-sugars that are soluble in diethylether do not
contain important amounts of levoglucosane. How-
ever, the presence of sugars in this fraction has been
reported earlier [6].
(f) Extractive-derived compounds: T
max
for this macro-
family is located between 255 and 296 1C (Fig. 2). The
main compounds assigned to this family were fatty and
resin acids, parafns and phenanthrenes. The boiling
ARTICLE IN PRESS
0.00
1.00
2.00
3.00
4.00
5.00
6.00
7.00
0 100 200 300 400 500 600 700 800
Temperature (C)
D
T
G
(
m
a
s
s

%

/
m
i
n
)
.
.
.
SWBR upper layer
A
b
u
n
d
a
n
c
e
A
b
u
n
d
a
n
c
e
6.00 8.00 10.00 12.00 14.00 16.00 18.00
Time-->
A
b
u
n
d
a
n
c
e
E
B
D
H
SWBR Bottom layer
H
E
D
B
HWRF Bottom layer
H
E
D
B
0.00
1.00
2.00
3.00
4.00
5.00
6.00
7.00
0 100 200 300 400 500 600 700 800
Temperature (C)
D
T
G
(
m
a
s
s

%

/
m
i
n
)
.
.
.
0.00
1.00
2.00
3.00
4.00
5.00
6.00
7.00
0 100 200 300 400 500 600 700
Temperature (C)
D
T
G
(
m
a
s
s

%

/
m
i
n
)
.
.
.
a
b
c
Fig. 4. DTG and GC/MS corresponding to the water soluble/ether insoluble fractions (B: volatile polar, D: polar compounds with moderate volatility, H:
Heavy polar compounds).
M. Garcia-Perez et al. / Biomass and Bioenergy 31 ( 2007) 222242 228
points and molar mass distribution of compounds
forming this family can be found in Tables 3 and 4.
(Compounds: 50, 53, 54, 5558, 6062, 64, 6668,
72, 73).
(g) Heavy non-polar compounds: The heavy non-polar
compounds cannot be identied by GC-MS due to
their low volatility. The molar mass distribution of this
fraction was determined using GPC techniques. Max-
imum decomposition temperature is observed at
350 1C (Figs. 3, 6 and 7).
(h) Heavy polar compounds: The peaks associated with this
group are observed between 340 and 365 1C (Figs. 4
and 5). The position of these peaks is very similar to
that of the peaks observed in TG curves of lignin. To
our knowledge this is the rst time that the existence of
heavy polar compounds with a thermal behaviour
similar to lignin is reported in bio-oils.
Quantication of chemical macro-families: Table 5
summarizes the experimental values of z
jo
for each
macro-family of each fraction. The actual mass fraction
of each macro-family (y
jo
) is computed using
y
jo

z
jo
X
1
X
j1
, (5)
where y
jo
is the initial mass fraction of macro-family j; z
jo
,
the mass fraction of volatile material for macro-family j;
X
jN
, the maximum conversion of macro-family j; X
1
, the
maximum volatile fraction, m
o
m
1
=m
o
(global conver-
sion of bio-oil fractions).
The value of maximum volatile yield per fraction (X
N
)
can be obtained from the values of solid residues (% R
s
)
reported in Table 3 X
1
1 %R
s
=100. If the chemical
families do not interact, then the nal conversion, X
1
, can
be expressed as
X
1

X
N
j0
y
jo
X
j1
. (6)
In order to use Eqs. (5) and (6) it is necessary to know
the maximum volatile yield (X
jN
) (or the solid residue)
ARTICLE IN PRESS
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b
u
n
d
a
n
c
e
6.00 8.00 10.00 12.00 14.00 16.00 18.00
Time-->
0.00
1.00
2.00
3.00
4.00
5.00
6.00
7.00
8.00
9.00
0 100 200 300 400 500 600 700 800
Temperature (C)
D
T
G

(
m
a
s
s

%
/
m
i
n
)

.
SWBR upper layer
H
E
B
D
0.00
1.00
2.00
3.00
4.00
5.00
6.00
7.00
8.00
9.00
0 100 200 300 400 500 600 700 800
Temperature (C)
D
T
G

(
m
a
s
s

%

/
m
i
n
)

.
SWBR bottom layer
H
E
D
B
0.00
1.00
2.00
3.00
4.00
5.00
6.00
7.00
8.00
9.00
0 100 200 300 400 500 600 700
Temperature (C)
D
T
G

(
m
a
s
s

%

/
m
i
n
)
.
.
.
HWRF bottom layer
H
E
D
B
c
a
b
Fig. 5. DTG and GC/MS corresponding to the water-ether soluble fractions. (B: volatile polar, D: Polar compounds with moderate volatility, E: Sugars,
H: Heavy polar compounds).
M. Garcia-Perez et al. / Biomass and Bioenergy 31 ( 2007) 222242 229
corresponding to each of the eight macro-families pre-
viously identied. As a rst approach, only heavy polar
and non-polar fractions are considered sources of char
formation. Thus, the values of X
jN
of heavy sub-fractions
are calculated using the value of solid residue for each
fraction X
N
(see Table 3). The estimation of X
jN
for the
heavy fractions is performed using the values of X
N
, z
jo
(z
jo
values are presented in Table 5) and Eq. (5), knowing that
P
N
j0
y
jo
1.
The values of X
jN
were estimated using a least-square
method programmed in the Solver routine (Microsoft
Excel). The estimated values are presented in Table 5. With
the simplications made, the quality of correlation can be
considered as satisfying. The heavy polar and non-polar
fraction showed similar tendencies to form char
(X
jN
0.5357 for the non-polar heavy compounds and
X
jN
0.5684 for the polar heavy compounds).
Fig. 8 presents the correlation between experimental and
calculated values of X
N
for the analysed fractions when
heavy fractions are considered as the main source of solid
residue. The estimated values of X
jN
are used to calculate
the mass fraction corresponding to each macro-family (y
jo
)
(see Table 6). The bio-oil composition is calculated
multiplying y
jo
by the amount of each fraction in the bio-
oil (Table 2). Bio-oil chemical composition obtained by TG
is presented in Table 7.
3.3. GPC
Molar mass distribution (MWD) curves obtained using
DMF for each bio-oil fraction are presented in Figs. 9 and
10. GPC curves obtained with this solvent exhibit reason-
ably clean separations. The molar mass distribution curves
obtained with THF do not exhibit the same level of
separation due to the differences in the columns used. The
columns used for the DMF separation have smaller pore
diameter (100, 80, 60 and 60 A

) than the ones used with

THF (10
4
, 10
3
and 100 A

). Clean separations are necessary

to reduce the uncertainties during the tting of macro-
families in MWD curves. That is why the discussion in this
section will be mostly limited to resolve MWD curves
obtained with DMF.
The MWD curves obtained using DMF were resolved
using Gaussian distributions. As a result of this method the
mass fraction, average molar mass and a parameter
representing the level of dispersion of each macro-family
were obtained. The tted Gaussian distribution peaks
ARTICLE IN PRESS
A
b
u
n
d
a
n
c
e
A
b
u
n
d
a
n
c
e
A
b
u
n
d
a
n
c
e
5.00 30.00 25.00 20.00 15.00 10.00
Time-->
C
C
C
F
F
F
A
A
A
0.00
1.00
2.00
3.00
4.00
5.00
0 100 200 300 400 500 600 700 800
Temperature (C)
0 100 200 300 400 500 600 700 800
Temperature (C)
0 100 200 300 400 500 600 700
Temperature (C)
D
T
G

(
m
a
s
s

%

/
m
i
n
)
.
.
.
0.00
1.00
2.00
3.00
4.00
5.00
D
T
G

(
m
a
s
s

%

/
m
i
n
)
.
.
.
0.00
1.00
2.00
3.00
4.00
5.00
D
T
G

(
m
a
s
s

%

/
m
i
n
)
.
.
.
SWBR upper layer
A
F
G
C
SWBR bottom layer
G
F
C
A
HWRF bottom layer
F
G
C
A
a
b c
Fig. 6. DTG and GC/MS corresponding to the water insoluble/CH
2
Cl
2
soluble fractions. (A: volatile non polar, C: monolignols, F: extractives, G: Heavy
non-polar compounds).
M. Garcia-Perez et al. / Biomass and Bioenergy 31 ( 2007) 222242 230
corresponded to the same eight macro-families previously
identied by TG and GC-MS analyses.
The main differences between the shape of DTG and
molar mass distribution curves were found in the toluene-
soluble fraction of the SWBR upper layer and the water-
insoluble/ CH
2
Cl
2
-soluble fraction contained in the SWBR
bottom layer. It is not surprising that these two fractions
were the ones that contain the higher amount of non-polar
extractives-derived compounds. Compounds with low
polarity are likely to be adsorbed in the GPC columns
increasing their retention times (see Fig. 2). Consequently
they are expected to appear in a position corresponding to
compounds with considerable lower molar mass. The
Gaussian distribution initial tting for these fractions was
corrected adding two new curves (F
2
see Fig. 9) represent-
ing the adsorbed compounds. The calibration curve
obtained for the polystyrene (see Fig. 2) can be used to
approximately estimate the actual molar mass of these
adsorbed species. According to our estimates, the average
molar mass of these compounds must be between 300 and
800 g mol
1
.
Average molar mass and mass fractions estimated for
each macro-family are presented in Table 8. Fig. 11
presents the relationship between the values of mass
fraction (y
jo
) obtained by TG and the ones obtained by
GPC for the different macro-families. The linear relation-
ship indicates a good agreement between the results
obtained by these two methods.
The values of M
w
determined by GPC also agree
reasonably well with those from GC-MS. The small
differences observed between the molar masses determined
by GPC and those estimated by GC-MS analysis can be
attributed to the difference in the molecular structure of
bio-oils molecules and the standard used for calibration, to
the effect of solvent on the solute hydrodynamic volume, to
the proximity of the low molar mass compounds to the
total permeation limits of the column and to solute
intermolecular interactions.
Most poly-sugars are not volatile enough to be detected
by GC-MS. Only a few mono-sugars (chiey levoglucosane
M
w
162 g mol
1
) can be detected by this technique. The
average molar mass estimated by GPC gave values between
390 and 486 g mol
1
(poly-sugars having between 2 and 4
sugar units). Heavy compounds soluble in water but
insoluble in diethylether exhibited higher molar mass
(630772 g mol
1
) than the heavy compounds soluble in
diethylether (561576 g mol
1
).
The heavy non-polar compounds insoluble in water but
soluble in CH
2
Cl
2
and those soluble in toluene have similar
molar masses (between 538 and 1000 g mol
1
). One
ARTICLE IN PRESS
A
b
u
n
d
a
n
c
e
Time-->
B
C
B
C
6.00 8.00 18.00 16.00 14.00 12.00 10.00
B
C
SWBR bottom layer
G
C
B
0.00
0.50
1.00
1.50
2.00
2.50
0 100 200 300 400 500 600 700 800
Temperature (C)
0 100 200 300 400 500 600 700 800
Temperature (C)
0 100 200 300 400 500 600 700 800
Temperature (C)
D
T
G

(
m
a
s
s

%

/
m
i
n
)

.
0.00
0.50
1.00
1.50
2.00
2.50
D
T
G

(
m
a
s
s

%

/
m
i
n
)

.
0.00
0.50
1.00
1.50
2.00
2.50
D
T
G

(
m
a
s
s

%

/
m
i
n
)

.
SWBR upper layer
G
C
B
HWRF bottom layer
G
C
B
b c
a
Fig. 7. DTG and GC/MS corresponding to the waterCH
2
Cl
2
insoluble fractions. (B: volatile polar, C: mono-lignols, G: Heavy non-polar compounds).
M. Garcia-Perez et al. / Biomass and Bioenergy 31 ( 2007) 222242 231
exception is the G
2
fraction identied in the toluene-soluble
fraction and in the SWBR upper layer which corresponded
to rather heavy molecules (around 1927 g mol
1
). The
existence of this macro-family could not be conrmed in
the tests performed using THF. This apparent disagree-
ment might be explained if the macro-family G
2
was not
ARTICLE IN PRESS
Table 3
DTG results for the different bio-oils fractions (heating rate at 10 1Cmin
1
)
Fraction assigned to each peak SWBR (H-67) HWRF (G
823830)
Bottom layer Upper layer Bottom
layer
Peak temperature (1C)
Toluene-soluble fraction
Volatile non-polar compounds 116 122 136
106oM
w
o112 g mol
1
(GC/MS), 136oT
b
o162 1C
Mono-lignols 174 170 187
94oM
w
o154 g mol
1
(GC/MS), 182oT
b
o262 1C
Extractives derived 288 255 274
256oM
w
o414 g mol
1
(GC/MS), 267oT
b
o450 1C
Heavy non-polar compounds 387 387 310
652oM
w
o1927 g mol
1
(GPC)
Solid residue ( % Rs) 5.8 3.0 6.9
Water soluble di-ethyl-ether insoluble
Volatile polar compounds 120 128 127
86oM
w
o112 g mol
1
(GC/MS), 123oT
b
o187 1C
Polar compounds with moderate
volatility
178 191 187
110oM
w
o210 g mol
1
(GC/MS), 245oT
b
o277 1C
Sugars 238 255 247
416oM
w
o486 g mol
1
(GPC)
Heavy polar compounds 343 364 351
630oM
w
o772 g mol
1
(GPC)
Solid residue ( % R
s
) 20.2 13.8 10.4
waterdi-ethylether soluble
Volatile polar compounds 130 126 130
86oM
w
o112 g mol
1
(GC/MS), 123oT
b
o187 1C
Polar compounds with moderate
volatility
198 183 192
110oM
w
o210 g mol
1
(GC/MS), 245oT
b
o277 1C
Sugars 300 290 284
390oM
w
o398 g mol
1
(GPC)
Heavy polar compounds 345 340 319
561oM
w
o575 g mol
1
(GPC)
Solid residue ( % Rs) 6.98 11.5 3.58
Water insolubleCH
2
Cl
2
soluble
Non-polar volatile compounds 153 125 120
100oM
w
g mol
1
(GC/MS), ?oT
b
o ?
Monolignols 214 212 213
110oM
w
o182 g mol
1
(GC/MS), 235oT
b
o266 1C
Extractives derived compounds 281 282 296
256oM
w
o414 g mol
1
(GC/MS), 267oT
b
o450 1C
Heavy non-polar compounds 353 349 344
707oM
w
o891 g mol
1
(GPC)
Solid residue ( % R
s
) 17 20.7 18.2
WaterCH
2
CL
2
insoluble materials
Volatile polar compounds 176 192 176
72oM
w
o112 g mol
1
(GC/MS), 123oT
b
o173 1C
Monolignols 259 261 259
124oM
w
o150 g mol
1
(GC/MS), 241oT
b
o258 1C
Heavy non-polar compounds 350 349 349
1198oM
w
o1251 g mol
1
(GPC)
Solid residue ( % R
s
) 39.5 43.1 39.5
Oils
Solid residue ( % R
s
) 22.4 8.1 12.3
M. Garcia-Perez et al. / Biomass and Bioenergy 31 ( 2007) 222242 232
ARTICLE IN PRESS
Table 4
Chemical compounds identied by GC/MS in bio-oils fractions
Sl.
no
Tentative compound name T
b
(1C) M
w
Ethyl ether
soluble
Water soluble Pyrolytic lignin CH
2
Cl
2
soluble
Toluene soluble
1 Ethylbenzene 136 106 SWBR (u,b) HWRF (b)
2 p-Xylene 138 106 SWBR (u,b) HWRF (b)
3 1-(2-furanyl) ethanone 173 118 SWBR (u,b)
HWRF (b)
4 2(5H)-furanone 87 84 SWBR (b) HWRF (b)
5 2-Hydroxycyclopent-2-en-1-one 98 HWRF (b)
6 Phenol 182 94 SWBR (u,b)
HWRF (b)
SWBR (u,b) HWRF (b)
7 3-methyl-1,2-cyclopentadione 162 112 SWBR (u,b)
HWRF (b)
SWBR (u,b)
HWRF (b)
SWBR (u,b) HWRF (b)
8 2-methylphenol 205 108 SWBR (u,b)
HWRF (b)
SWBR (u,b) HWRF (b)
9 tetrahydro-2-furanmethanol 178 102 HWRF (b)
10 4-methylphenol 201 108 SWBR (u,b)
HWRF (b)
SWBR (u)
HWRF (b)
SWBR (u,b) HWRF (b)
11 2-methoxyphenol 205 124 SWBR (u,b)
HWRF (b)
SWBR (u,b) HWRF (b)
12 cyclopropyl carbinol 123 72 HWRF (b) SWBR (u)
HWRF (b)
13 3,4-dimethylphenol 211 122 SWBR (u,b)
HWRF (b)
SWBR (u,b) HWRF (b)
14 2-ethylphenol 205 122 SWBR (u,b)
HWRF (b)
SWBR (u,b) HWRF (b)
15 cyclopentanol 140 86 SWBR (u,b)
HWRF (b)
16 2-methoxy-4-methyl phenol 221 138 SWBR (u,b)
HWRF (b)
SWBR (u,b) HWRF (b)
17 1,2-Benzenediol 245 110 SWBR (u,b)
HWRF (b)
SWBR (u,b)
HWRF (b)
SWBR (u)
HWRF (b)
SWBR (u,b) HWRF (b)
18 1,4,3,6-Dianhydro-a-D-
glucopyranose
144 SWBR (u,b)
HWRF (b)
19 5-methyl-2-furaldehyde 187 110 SWBR (u,b)
HWRF (b)
20 3-methyl-1,2-benzenediol 241 124 SWBR (b) HWRF (b)
21 4-ethyl-2-methoxyphenol 235 152 HWRF (b) SWBR (u,b) HWRF (b)
22 3-methyl-1,2-benzenediol 241 124 SWBR (u,b)
HWRF (b)
SWBR (u,b)
HWRF (b)
SWBR (u,b) SWBR (u,b) HWRF (b)
23 4-ethyl-2-methoxyphenol 235 152 SWBR (u,b)
HWRF (b)
24 4-methyl-1,2-benzenediol 264 124 SWBR (u,b)
HWRF (b)
SWBR (u,b) SWBR (u)
25 3,4-diethylphenol 150 SWBR (u,b)
HWRF (b)
SWBR (b)
HWRF (b)
26 2,6-dimethoxyphenol 262 154 HWRF (b) HWRF (b) SWBR (u,b)
HWRF (b)
HWRF (b)
27 Eugenol 253 164
28 2,5-dimehtyl-1,2-benzenediol 277 138 SWBR (u,b)
HWRF (b)
SWBR (u,b) SWBR (u) SWBR (u,b)
29 Vanillin 265 152 SWBR (u,b) SWBR (u,b) SWBR (b)
30 2-methoxy-4-(1-propenyl)-
phenol
266 164 SWBR (u,b) SWBR (u,b)
HWRF (b)
SWBR (b)
31 1,2,3-trimethoxybenzene 235 168 HWRF (b) SWBR (u,b)
HWRF (b)
HWRF (b)
32 2-methoxy-4-(1-propenyl)
phenol
266 164 SWBR (u,b)
HWRF (b)
SWBR (u,b)
HWRF (b)
SWBR (u,b) HWRF (b)
33 2-propyl-1,2-benzenediol, 270 152 SWBR (u,b)
34 Urea 146 SWBR (u,b)
HWRF (b)
35 1-(4-hydroxy-3-
methoxyphenyl)-ethanone
295 166 SWBR (u,b)
HWRF (b)
SWBR (u,b) HWRF (b)
36 1,6-Anhydro-b-D-
glucopyranose (levoglucosane)
285 162 SWBR (u,b)
HWRF (b)
37 Hydroquinone 285 182 HWRF (b) SWBR (u,b)
HWRF (b)
HWRF (b)
38 2,2-dimethylbiphenyl 256 182 HWRF (b)
M. Garcia-Perez et al. / Biomass and Bioenergy 31 ( 2007) 222242 233
soluble in THF. WaterCH
2
Cl
2
insoluble fractions contain
the heaviest molecules (between 1475 and 1967 g mol
1
).
This result is in agreement with the literature [7].
Heavy compounds can be classied into three classes
depending on their molar mass and their solubility. The low
molar mass ranging between 561 and 1000g mol
1
is
ARTICLE IN PRESS
Table 4 (continued )
Sl.
no
Tentative compound name T
b
(1C) M
w
Ethyl ether
soluble
Water soluble Pyrolytic lignin CH
2
Cl
2
soluble
Toluene soluble
39 6,7-dihydro-3,6-dimethyl-4-
Benzofuranone,
180 SWBR (u,b)
HWRF (b)
SWBR (b)
40 Propylhexanoate 187 158 SWBR (u,b)
HWRF (b)
41 3,4-dimethoxybenzaldehyde 258 166 HWRF (b) HWRF (b)
42 1-Hexadecene 284 168 HWRF (b)
43 1-methyl-7-(1-methylethyl)
naphthalene
184 SWBR (u) HWRF (b)
44 2,6-dimethoxy-4-(2-propenyl)
phenol
194 HWRF (b) SWBR (u,b)
HWRF (b)
SWBR (u) HWRF (b)
45 4-hydroxy-3,5-dimethoxy
benzenoic acid
198 SWBR (u,b)
HWRF (b)
SWBR (u,b)
HWRF (b)
HWRF (b) SWBR (b)
46 4-hydroxy-3,5-dimethoxy
benzaldehyde
182 SWBR (u,b)
HWRF (b)
HWRF (b)
47 2,6-dimethoxy-4-(2-propenyl)
phenol
194 SWBR (u)
HWRF (b)
HWRF (b) HWRF (b)
48 1,2-dimethoxy-4-(2-propenyl)
benzene
255 178 SWBR (u,b)
HWRF (b)
HWRF (b) SWBR (u,b)
49 2-pentanone 1-(2,4,6-
trihydroxyphenyl)-
210 SWBR (u,b)
HWRF (b)
SWBR (u,b)
HWRF (b)
HWRF (b) SWBR (u) HWRF (b)
50 Hexadecanoic acid 267 256 SWBR (u,b)
HWRF (b)
SWBR (u,b) HWRF (b)
51 1-Eicosene 310 210 SWBR (u) HWRF (b)
52 2-Allyl-3-ethoxy-4-methoxy-
phenol
208 HWRF (b)
53 Heptadecanoic acid 270 SWBR (u,b)
54 3,6-dimethylphenthrene 206 SWBR (u,b)
HWRF (b)
SWBR (u)
55 9,12-Octadecadienoic acid
(Oleoic acid)
360 282 SWBR (u,b)
HWRF (b)
SWBR (u)
56 1-Eicosanol 357 298 SWBR (u,b)
57 Docosane 368 238 HWRF (b) SWBR (u)
58 3,4,5,6-tetramethyl phenanthene 234 SWBR (u,b) SWBR (u,b)
59 Tricosane 380 240 HWRF (b)
60 1-tetracosene 390 266 SWBR (u,b)
HWRF (b)
SWBR (u,b)
61 1, 2,3,4,4a, 9,10, 10a- octahydro-
1,4a-dimethyl-1-7-(1-
methylethyl) [1R
(1.alpha.4a.beta, 10a. Alpha)],
1-phenanthrenecarboxylic acid
314 SWBR (u,b) SWBR (u,b)
62 Pentacosane 402 352 HWRF (b) SWBR (u,b)
63 2,4-Bis(dimethylbenzyl) phenol 330 HWRF (b)
64 Hexacosane 412 366 HWRF (b) SWBR (u,b) HWRF (b)
65 9H-xanthen-9-one, 1,3-
dihydroxy-6-methoxy-8-methyl-
272 SWBR (u,b)
HWRF (b)
66 Heptacosane 422 380 SWBR (u,b)
HWRF (b)
SWBR (u,b)
67 Octacosane 431 282 HWRF (b) SWBR (u,b) HWRF (b)
68 Eicosane, 9 octyl 394 HWRF (b) SWBR (u,b) HWRF (b)
69 6H-Benzofuro[3,2-c]
benzopyran
344 SWBR (u)
HWRF (b)
70 Triacontane 450 342 HWRF (b)
71 Bikaverin 382 SWBR (u)
72 Ergosterol 396 SWBR (u,b) SWBR (b)
73 Benzene, 1,1
0
,1
00
,1
0 00
-(1,2-
ethenediylidene)tetrakis-
332 HWRF (b)
74 b-sitosterol 414 SWBR (u,b)
HWRF (b)
u, Upper layer; b, Bottom layer.
M. Garcia-Perez et al. / Biomass and Bioenergy 31 ( 2007) 222242 234
normally soluble in water, in toluene or in CH
2
Cl
2
,
depending on their polarity. The fraction insoluble in water
and CH
2
Cl
2
corresponds to the high molar mass com-
pounds (10002000g mol
1
). A fraction with M
w
ranging
between 2000 and 10,000g mol
1
was also identied and the
results will be published in a forthcoming paper [34]. These
heavy compounds are generally insoluble in MeOH and are
formed at very advanced stages of ageing.
ARTICLE IN PRESS
Table 5
Values of z
jo
for the different fractions analysed
Sub- Fraction SWBR (H-67) (z
jo
) HWRF (G 823830) (z
jo
) X
jN (estimated)
Bottom layer Upper layer Bottom layer
Toluen-soluble fraction
Volatile non-polar 0.06 0.06 0.18 1
Monolignols 0.72 0.17 0.50 1
Extractive derived compounds 0.16 0.68 0.25 1
Heavy non-polar compounds 0.05 0.09 0.07 0.54
Water-soluble, diethyl-ether insoluble
Volatile polar 0.13 0.12 0.12 1
Polar compounds with moderate volatility 0.39 0.53 0.51 1
Sugars 0.28 0.18 0.17 1
Heavy polar compounds 0.20 0.17 0.20 0.57
Waterdiethyl-ether soluble
Volatile polar 0.10 0.13 0.12 1
Polar compounds with moderate volatility 0.63 0.58 0.57 1
Sugars 0.13 0.15 0.17 1
Heavy polar compounds 0.14 0.14 0.14 0.57
Water insolubleCH
2
Cl
2
soluble
Non-polar volatile 0.09 0.09 0.10 1
Monolignols 0.18 0.25 0.21 1
Extractive derived compounds 0.45 0.38 0.37 1
Heavy non-polar compounds 0.27 0.27 0.32 0.54
WaterCH
2
Cl
2
insoluble materials
Volatile polar compounds (associated) 0.17 0.13 0.13 1
Mono-lignols (associated) 0.08 0.08 0.15 1
Heavy non-polar compounds (very condensed structures) 0.77 0.78 0.72 0.54
0.5
0.55
0.6
0.65
0.7
0.75
0.8
0.85
0.9
0.95
1
0.5 0.55 0.6 0.65 0.7 0.75 0.8 0.85 0.9 0.95 1
X

measured
X

c
a
l
c
u
l
a
t
e
d
Water-CH
2
Cl
2
insoluble
Toluene soluble
Water insoluble-
CH
2
Cl
2
soluble
Water soluble-diethyl-
ether insoluble
Water -diethyl-
ether soluble
Fig. 8. Relationship between X
N
measured and X
N
calculated. Considering that the Solid Residue is Mainly Formed from the Oligomeric Fractions. (X
N
(non-polar) 0.5357; X
N
(polar) 0.5686).
M. Garcia-Perez et al. / Biomass and Bioenergy 31 ( 2007) 222242 235
ARTICLE IN PRESS
Table 6
Values of y
jo
(mass fraction) for the different analysed fractions
Sub-fraction SWBR (H-67) (y
jo
) HWRF (G 823830)
(y
jo
)
Bottom layer Upper layer Bottom layer
Toluene soluble fraction
Volatile non-polar 0.06 0.06 0.17
Monolignols 0.70 0.15 0.47
Extractive derived 0.15 0.63 0.24
Heavy non-polar compounds 0.09 0.15 0.12
Water-soluble, diethyl-ether insoluble
Volatile polar 0.11 0.10 0.11
Polar compounds with moderate volatility 0.33 0.47 0.45
Sugars 0.24 0.16 0.15
Heavy polar compounds 0.31 0.26 0.30
Water-diethyl-ether soluble
Volatile polar 0.09 0.12 0.11
Polar compounds with moderate volatility 0.57 0.52 0.51
Sugars 0.12 0.13 0.15
Heavy polar compounds 0.22 0.22 0.22
Water insolubleCH
2
Cl
2
soluble
Non-polar volatile 0.08 0.07 0.08
Mono-lignols 0.15 0.21 0.16
Extractive derived compounds 0.37 0.31 0.29
Heavy non-polar compounds 0.41 0.41 0.46
WaterCH
2
Cl
2
insoluble materials
Volatile polar 0.09 0.08 0.08
Mono-lignols (associated) 0.05 0.05 0.09
Heavy non-polar compounds 0.86 0.87 0.83
Table 7
Mass% of bio-oils chemical families (heating rate at 10 1Cmin
1
)
Fraction SWBR (y
jo
) HWRF (y
jo
)
Bottom layer Upper layer Bottom
Water 14.6 3.5 13.0
Highly volatile organic compounds ( T
b
p150 1C)
Volatile polar compounds 5.6 0.8 5.5
Volatile non-polar compounds 1.0 5.1 2.4
Determined as losses (unidentied) 15.3 1.9 11.2
Total 21.9 7.8 19.2
Compounds of relatively low volatility ( 150 1CpT
b
p450 1C)
Mono-lignols 3.4 13.7 6.6
Polar compounds with moderate volatility 15.7 2.9 21.2
Sugars 9.0 1.0 6.8
Extractive derived compounds 4.8 52.1 5.8
Total 32.8 69.6 40.4
Heavy compounds
Heavy polar compounds 12.2 1.6 13.8
Heavy non-polar compounds 16.4 16.5 13.2
Total 28.6 18.1 27.0
MeOH-insoluble 2.1 1.0 0.4
Total 100 100 100
M. Garcia-Perez et al. / Biomass and Bioenergy 31 ( 2007) 222242 236
3.4. Elemental analysis
Table 9 presents the elemental analysis of bio-oil derived
fractions. As expected, the content of carbon for the water
insoluble fractions was higher than that for the water-
soluble fractions. The considerably higher content of
carbon in the toluene-soluble fraction from the
SWBR upper layer is due a large amount of extractives
found in this fraction. The carbon content in water-
insoluble fractions decreased in the following order:
SWBR upper layer4SWBR bottom layer4HWRF bot-
tom layer. This result indicates that some reactive low
ARTICLE IN PRESS
A
C
F
G
SWBR bottom layer
Toluene
soluble
0
0.2
0.4
0.6
0.8
1
1.2
1.4
1.6
1.8
10 100 1000 10000
Log (M) [g/mol]
d
m
a
s
s

/

d

(
l
o
g

M
)
0
0.2
0.4
0.6
0.8
1.2
1
1.4
1.6
1.8
10 100 1000 10000
Log (M) [g/mol]
d
m
a
s
s

/

d

(
l
o
g

M
)
0
0.2
0.4
0.6
0.8
1
1.2
1.4
1.6
1.8
10 100 1000 10000
Log (M) [g/mol]
d
m
a
s
s

/

d

(
l
o
g

M
)
0
0.2
0.4
0.6
0.8
1
1.2
1.4
1.6
1.8
10 100 1000 10000
Log (M) [g/mol]
d
m
a
s
s

/

d

(
l
o
g

M
)
0
0.2
0.4
0.6
0.8
1
1.2
1.4
1.6
1.8
10 100 1000 10000
Log (M) [g/mol]
d
m
a
s
s

/

d

(
l
o
g

M
)
0
0.2
0.4
0.6
0.8
1
1.2
1.4
1.6
1.8
10 100 1000 10000
Log (M) [g/mol]
d
m
a
s
s

/

d

(
l
o
g

M
)
A
C
F1
F2
G1
G2
SWBR upper layer
Toluene
soluble
Toluene
soluble
HWRF bottom layer
F
A
G
C
CH
2
Cl
2
soluble
A
C
F
G
SWBR upper layer
SWBR bottom layer
CH
2
Cl
2

soluble
F1
F2
A
C
G
G
F
C
A
HWRF bottom layer
CH
2
Cl
2
soluble
Fig. 9. Molar mass distribution in the toluene and CH
2
Cl
2
-soluble fractions. (A: Volatile non-polar compounds, C: Mono-lignols, F: Extractives derived
compounds, G: Heavy non-polar compounds).
M. Garcia-Perez et al. / Biomass and Bioenergy 31 ( 2007) 222242 237
polar compounds (perhaps extractives-derived compounds)
form part of the structure of heavy compounds in
SWBR-derived oils. In the water-soluble fractions the
same tendency is also observed but to a lower extent,
indicating perhaps that the integration of extractives-
derived compounds in heavy polar compounds is less
important.
3.5. Comparison between the composition determined by the
proposed method and that reported in the literature for other
oils
It is difcult to compare results obtained by the
proposed method with the data determined using conven-
tional analytical techniques. The conventional methods
ARTICLE IN PRESS
B
D
E
H
SWBR bottom layer
Water
soluble
0
0.2
0.4
0.6
0.8
1
1.2
1.4
1.6
1.8
10 100 1000 10000
Log (M) [g/mol]
d
m
a
s
s

/

d

(
l
o
g

M
)
0
0.2
0.4
0.6
0.8
1.2
1
1.4
1.6
1.8
10 100 1000 10000
Log (M) [g/mol]
d
m
a
s
s

/

d

(
l
o
g

M
)
0
0.2
0.4
0.6
0.8
1
1.2
1.4
1.6
1.8
10 100 1000 10000
Log (M) [g/mol]
d
m
a
s
s

/

d

(
l
o
g

M
)
0
0.2
0.4
0.6
0.8
1
1.2
1.4
1.6
1.8
10 100 1000 10000
Log (M) [g/mol]
d
m
a
s
s

/

d

(
l
o
g

M
)
0
0.2
0.4
0.6
0.8
1
1.2
1.4
1.6
1.8
10 100 1000 10000
Log (M) [g/mol]
d
m
a
s
s

/

d

(
l
o
g

M
)
0
0.2
0.4
0.6
0.8
1
1.2
1.4
1.6
1.8
10 100 1000 10000
Log (M) [g/mol]
d
m
a
s
s

/

d

(
l
o
g

M
)
B
E
H
D
SWBR upper layer
Water
soluble
Water
soluble
HWRF bottom layer
H
B
E
D
Ethylether
soluble
Ethylether
soluble
Ethylether
soluble
B
D
E
H
SWBR upper layer
SWBR bottom layer
E
B
D
H
H E
D
B
HWRF bottom layer
Fig. 10. Molar mass distribution of water-ether soluble fractions. (B: Volatile polar compounds, D: Polar compounds with moderate polarity, E: Sugars,
H: Heavy polar compounds).
M. Garcia-Perez et al. / Biomass and Bioenergy 31 ( 2007) 222242 238
used to determine the chemical composition of bio-oils
suffer from the lack of reproducibility and certainly
because they rather focus on individual species [3].
The comparison with the bio-oils composition reported
in the literature is helpful to support the present
nding.
Bio-oils volatile polar compounds are mainly formed of
organic compounds having 15 atoms of carbon with
boiling points up to around 150 1C. This macro-family
includes: carboxylic acids, alcohols, ketones, aldehydes,
furans, cyclopentanones, cyclopentenes and butanones [12].
Adding the lower and upper limits reported in the literature
[12], it can be concluded that these compounds do
represent between 9.5 and 41.8 mass% of bio-oils. The
volatile non-polar compounds are mainly formed of alkenes
and aromatics [35].
Branca et al. [36] analysed the bottom layer of a bio-oil
produced from the vacuum pyrolysis of SWBR. After
adding all identied compounds with boiling point lower
than 177 1C, the total content in volatile organic com-
pounds was found to be 16.6 mass% of the SWBR bottom
layer. This value is probably underestimated due to the
limitations to identify and quantify all the compounds by
GC-MS. Radlein [30] has reported that the total organic
compounds with less than 4 atoms of carbon can represent
between 20 and 35 mass% of oils. The content determined
by TG for SWBR bottom layer was of 22 mass%. This
result is well in the range of values reported in the literature
[12,30,36].
The monolignols in bio-oils are formed of phenols and
benzenediols, guaiacols and syringols [12]. Monolignols
contents between 6 and 15 mass% have been reported
earlier [30]. The proposed method does not allow
determination of the total content of monolignols in bio-
oils, because the monolignols soluble in water evaporate
over the same range of temperatures as other polar
compounds poorly identied by GC-MS.
The amount of polar compounds with moderate volatility
(boiling point up to 280 1C) determined by the proposed
method was 15.7 mass% for SWBR bottom layer,
21.2 mass% for HWRF and 2.9 for the SWBR upper
layer. Pakdel et al. [37] reported that the oxygenated cyclic
compounds with moderate polarity represent between 10
and 25 mass% on a whole bio-oil basis.
The monolignols and other polar compounds with
moderate volatility have similar boiling points and repre-
sented around 19.1 mass% of SWBR bottom layer. Branca
et al. [36] analysed a similar oil using GC-MS. It was
estimated that compounds with boiling point between 180
and 280 1C accounted for 5.8 mass% of SWBR bottom
layer. The important difference between the amount
estimated by TG and the one estimated using GC-MS is
clear evidence that there is a signicant part of this fraction
that is still poorly known.
ARTICLE IN PRESS
Table 8
Values of y
jo
b
and M
w
for the different fractions analysed obtained by GPC
Sub-fraction SWBR (H-67) HWRF (G 823-830)
Bottom layer Upper layer Bottom layer
Toluene-soluble fraction (y
jo
b
, M
w
g mol
1
)
Volatile non-polar compounds (0,092; 44) (0,070; 50) (0,160; 56)
Mono-lignols (0,645; 100) (0,155; 107) (0,466; 109)
Extractives-derived (0,150; 416) (0,303; 531) (0,2367; 389)
(0,283; 107
a
)
Heavy non-polar compounds (0,122; 652) (0,088; 1000) (0,134; 653)
(0,081; 1927)
Water-soluble, diethyl-ether insoluble (y
jo
b
, M
w
g mol
1
)
Volatile polar compounds (0,113; 126) (0,060; 79) (0,110; 98)
Polar compounds with moderate volatility (0,292; 281) (0,432; 173) (0,363; 219)
Sugars (0,186; 416) (0,134; 422) (0,202; 486)
Heavy polar compounds (0,408; 630) (0,325; 632) (0,332; 772)
Waterdiethyl-ether soluble (y
jo
b
, M
w
g mol
1
)
Volatile polar compounds (0,104; 61) (0,137; 63) (0,101; 59)
Polar compounds with moderate volatility (0,516; 122) (0,448; 115) (0,516; 125)
Sugars (0,167; 390) (0,130; 398) (0,160; 399)
Heavy polar compounds (0,224; 561) (0,283; 575) (0,250; 576)
Water insolubleCH
2
CL
2
soluble (y
jo
b
, M
w
g mol
1
)
Non-polar volatile compounds (0,076; 71) (0,056; 50) (0,067; 71)
Mono-lignols (0,149; 151) (0,112; 112) (0,155; 151)
Extractives-derived (0,151; 397) (0,387; 467) (0,328; 446)
(0,239; 84
a
)
Heavy non-polar compounds (0,382; 538) (0,444; 891) (0,455; 851)
a
Values affected by the adsorption of non-polar compounds on the column.
b
y
jo
, mass fraction.
M. Garcia-Perez et al. / Biomass and Bioenergy 31 ( 2007) 222242 239
The sugars present in bio-oils are mainly polysacchar-
ides. The monosaccharides represent a relatively small
portion between 1 and 5 mass% on bio-oil basis [31,36].
The content of total mono and poly sugars can reach
values as high as 10 mass% of bio-oils [3,37]. Total sugar
content determined by the proposed method was in
between 6.8 and 9.0 mass% for bottom layers which is
very close to the expected value.
The SWBR upper layer matrix contains 52.1 mass% of
extractive-derived compounds. The amount of extractives
in bottom layers is relatively low, with 4.8 and 5.8 mass%
for SWBR and HWRF, respectively. These results are
quite close to the values reported by Pakdel et al. [37] for
the total non-polar hydrocarbons in other bio-oils (be-
tween 510 mass%).
So far, the study of heavy compounds from bio-oils has
been limited to fractions insoluble in water. The heavy
polar compounds accounted for 12.2 and 13.8 mass% of
bottom layers and for only 1.6 mass% in the SWBR upper
layer. It has been previously reported in the literature [3]
that the bio-oil non-volatile compounds (only detectable by
HPLC) soluble in water represent around 15 mass% on
bio-oil basis. Our result is not far from this reference value.
Bottom layers contain almost the same amount of heavy
polar and non-polar compounds.
4. Conclusions
A characterization approach is proposed enabling a fast
overall chemical characterization of bio-oils. The technique
uses a well-known fractionation scheme in combination
with TG, GPC and GC-MS techniques. The fractions
obtained by solvent extraction were clearly mixtures. Bio-
oils were described as mixtures of eight macro-families.
Thermogravimetry and GPC were used to quantify the
different macro-families. The compounds forming the
ARTICLE IN PRESS
Table 9
Elemental composition of bio-oil fractions (mass %)
Fraction SWBR (H-67) (mass%) HWRF (G 823-830) (mass %)
Upper layer Bottom layer Bottom layer
C H N O
a
C H N O
a
C H N O
a
Toluene soluble 77.68 9.10 0.15 13.07 69.96 7.41 0.17 22.46 67.69 7.37 0.07 24.87
Water insoluble
CH
2
Cl
2
soluble 72.76 7.15 0.44 19.65 71.66 7.29 0.22 20.83 67.44 6.69 0.20 25.67
CH
2
Cl
2
insoluble 70.69 5.95 1.23 22.13 67.05 5.54 1.28 26.13 64.06 5.70 0.67 29.57
Water soluble
diethyl ether soluble 67.59 7.16 0.22 25.03 65.85 6.72 0.17 27.26 64.09 6.66 0.06 29.19
diethy ether insoluble 53.02 7.12 0.57 39.29 49.94 6.86 0.56 42.64 50.65 6.84 0.23 42.28
Me-OH insoluble 75.65 8.77 0.63 14.95 64.33 5.41 1.56 28.7 74.56 8.75 0.64 16.05
a
By difference.
0
0.1
0.1
0.2
0.2
0.3
0.3
0.4
0.4
0.5
0.5
0.6
0.6
0.7
0.7 0.8 0
y
jo
values obtained by TG
y
j
o

v
a
l
u
e
s

o
b
t
a
i
n
e
d

b
y

G
P
C
Fig. 11. Relationship between the values of mass fraction (y
jo
) for the different macro-families obtained from the TG and the GPC analyses.
Waterdietheyl ether soluble fraction, Water solublediethyl ether insoluble fraction, Water insolubleCH
2
Cl
2
soluble fraction, Toluene-soluble fraction.
M. Garcia-Perez et al. / Biomass and Bioenergy 31 ( 2007) 222242 240
volatile macro-families were identiedby GC-MS. The
shape of GC-MS chromatograms in general matches the
shapes observed for the corresponding DTG and GPC
curves. The use of GPC columns with small pore diameters
is necessary to obtain relatively clean separation of bio-oil
macro-families. The eluent must be chosen taking into
account its solvating power and its potential to induce
adsorption phenomena of non-polar compounds. Water-
soluble fractions and water-insoluble/CH
2
Cl
2
-insoluble
fractions should be analysed with DMF. In this case the
calibration must be performed using polyethylene glycol. It
is recommended to use THF for the analysis of toluene-
soluble and water-insoluble/CH
2
Cl
2
-soluble fractions. The
calibration in these cases can be carried out using
polystyrene standards. The use of DMF for these systems
may induce important adsorption of non-polar com-
pounds.
Acknowledgements
The authors are very grateful to Mrs. Joanne Lagace
who has performed some of the tests reported in this paper.
La Fondation de lUniversite Laval provided a scholarship
to the rst author. Thanks are due to the Natural Science
and Engineering Research Council of Canada (NSERC)
and CANMET for nancing this project.
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