3190 Ind. Eng. Chem. Res.

2003, 42, 3190-3202

KINETICS, CATALYSIS, AND REACTION ENGINEERING

GC/MS Characterization of Liquids Generated from

Low-Temperature Pyrolysis of Wood
Carmen Branca, Paola Giudicianni, and Colomba Di Blasi*
Dipartimento di Ingegneria Chimica, Universitá degli Studi di Napoli “Federico II”P.le V. Tecchio,
80125 Napoli, Italy

Conventional pyrolysis of beech wood has been carried out for heating temperatures in the range
600-900 K, reproducing conditions of interest in countercurrent fixed-bed gasification. The yields
of liquids (water and tars) increase with the heating temperature from about 40 to 55% of dry
wood mass, confirming results previously obtained with a laboratory-scale gasifier. Apart from
qualitative identification of ∼90 species, GC/MS techniques have been applied to quantify 40-
43% of tars (40 species, with major contributions from acetic acid, hydroxypropanone, hydroxy-
acetaldehyde, levoglucosan, formic acid, syringol, and 2-furaldehyde). Decomposition of holo-
cellulose leads to the formation of furan derivatives and carbohydrates, with a temperature-
dominated selectivity toward hydroxyacetaldehyde against levoglucosan. Syringols and guaiacols,
originating from primary degradation of lignin, present a maximum for heating temperatures
of about 750-800 K whereas, owing to secondary degradation, phenols continuously increase.
A comparison is also provided with fast pyrolysis liquids obtained from four commercial plants.

Introduction gasifiers, appear to be less reactive than the larger

Fixed-bed gasification technologies1-3 are based on
two configurations, the concurrent (downdraft) and the
countercurrent (updraft) modes. Downdraft gasification
technology is reliable only for relatively dry, coarse, low-
ash feedstocks and, because of scaling difficulties, for
capacities up to 500 kWe. On the contrary, in principle,
there is no scaling limitation for updraft gasifiers, which
also present a higher feedstock flexibility (moisture
contents up to 50 against 30%), lower emissions after
burning, simple automation (unmanned operation for
about 96-98%), lower maintenance costs, and very high
thermal efficiency.1-5
The main drawback of the updraft gasification tech-
nology lies in the very high yields of condensates,1-3,6
which should be separated from the gas and disposed
of. For this reason, it is generally considered not suited
for electricity production. However, two important
industrial applications of updraft gasification for elec-
tricity production are under optimization in Europe,
using catalytic tar cracking (Wellman Process Engi-
neering Limited7) or a combination of in situ tar oxida-
tion and liquid collection, through an electrostatic pre-
cipitator, and utilization (Babcock & Wilcox Volund).8
It is also suggested9 that it might be easier to remove
updraftsthan downdraftsgasification tars from the gas
stream. Indeed, these compounds present different
chemical structure and different cracking/oxidation
characteristics in dependence of the different reaction
conditions where they originated. More precisely, con-
densed aromatics (heavy tars), produced under high
thermal severity to favor cracking as in the downdraft
* To whom correspondence should be addressed. Tel.:39-081-
7682232. Fax: 39-081-2391800. E-mail: diblasi@unina.it.
10.1021/ie030066d CCC: $25.00 © 2003 American Chemical Society
Published on Web 06/11/2003
amounts of light tars produced under low-temperature
and slow-heating rate (conventional) pyrolysis, such as
in the case of updraft gasification.
A quantitative chemical characterization is needed to
evaluate the reactivity of tars derived from updraft
gasification of wood, in view of their destruction or
exploitation of of the related energetic content. However,
the literature on this issue is very scarce apart from
the qualitative analysis provided by Evans and Mil-
ne.10,11 From a chemical point of view, they included
oxygenated compounds, such as furan derivatives, car-
boxylic acids, alcohols, dihydroxyphenols, and dimethoxy-
phenols. Thus, they are qualitatively similar to fast
pyrolysis liquids, whose chemicophysical characteriza-
tion has received significant attention10-29 given their
strategic importance as substitute fuel oil or for chemi-
cal production.30-33
The majority of the fast pyrolysis studies10,11,16,18,22,23,29
examine the chemical composition only for optimal con-
ditions (maximum liquid yield), and the temperature de-
pendence of only a few species is reported.12-15,17,19,21,24,27
The number of species identified is of the order of 300,23
but only a few of them are listed by all the authors23
(formic, acetic and propanoic acids, levoglucosan, glu-
cose, xylose, methylcyclopentenone, methanol, phenol,
2-furaldehyde). The round-robin testing recently pub-
lished29 also evidences very large quantitative differ-
ences between different laboratories. On the other hand,
studies on cellulose and other model compounds34-42
have clarified the role played by temperature and
inorganics on the relative yields of two major liquid
components, that is, levoglucosan and hydroxyacetal-
dehyde. Significant insight has also been gained on the
evolution of phenolics during vacuum pyrolysis of
wood.43,44

This study applies gas chromatographic/mass spec-
trometry (GC/MS) techniques for the chemical charac-
terization of wood pyrolysis liquids. The aim of the study
is to determine the yields of a significant number (40)
of compounds on dependence of the reaction tempera-
ture and heating rate, in the view of formulating
detailed reaction schems and developing chemical reac-
tors. More specifically, the effects of the first parameter
(range 600-900 K) are investigated for conventional
pyrolysis. Given the moderate heating rates of the
process, the results are useful for the optimization of
updraft gasification plants and the exploitation of the
liquids produced. The effects of heating rate on the
liquid composition are also investigated by comparing
conventional and fast pyrolysis samples. Again this
information can be useful for the selection of the most
appropriate configuration and operating conditions of
chemical reactors on dependence of the desired composi-
tion and yields of the products. The fulfillment of these
objectives represents a significant advancement with
respect to the current state of the art because, as pointed
out above, the majority of studies on pyrolysis liquids
are only qualitative whereas quantification is limited
to a few species for the optimal conditions of fast
pyrolysis (reaction temperatures of ∼800 K correspond-
ing to maximum yields of liquid products).
Experimental Section
The liquids being characterized are derived from
beech wood by means of laboratory-scale tests using a
fixed-bed pyrolyzer and an updraft gasifier (conven-
tional pyrolysis). Fast pyrolysis liquids, obtained from
wood mixtures by four different commercial systems, are
also examined. The experimental conditions established
in the different tests and the technique of chemical
analysis are given below.
Conventional Pyrolysis. The characteristics of the
pyrolysis reactor (6.3-cm internal diameter and 45-cm
length) have already been described,45 so only the chief
information is provided here. Nitrogen, fed through a
jacket (internal diameter 8.9 cm) at the reactor top, is
heated by an electrical furnace and distributed by a per-
forated steel plate, which also supports the bed. Tem-
perature profiles along the reactor axis are measured
by seven thermocouples (chromel-alumel type, 500-
µm diameter), with their tips exiting from a protective
steel tube, at chosen distances from the flow distributor.
The lower reactor zone (∼15 cm) is isothermal at a
temperature determined by a proper set point of the
furnace (PID controller), but gradients in the upper part
are high. Thus, vapor condensation is avoided and the
activity of secondary reactions is limited.
Beech wood particles present the same characteristics
as in the updraft gasification tests already discussed.6
They are cut in parallelepipeds 5 mm thick (90%, the
largest dimension comprised in the range 5-20 mm)
and predried (at least 6 h at 376 K), resulting in bed
densities of 350 kg/m3. Then they (∼180 g) are placed
in the feeder, and after nitrogen flushing, when the
desired reactor temperature is achieved, the feeding
valve is opened, so that they are dropped inside the hot
reactor (in ∼30 s). Based on the reactor diameter and
the bulk density, the initial length of the packed bed is
estimated to be ∼15 cm. Hence, the particles are
positioned within the isothermal reactor zone. The range
of temperatures along the isothermal region, indicated
in the following as reactor (or heating) temperature, Tr,
is varied between 600 and 900 K, reproducing the
Ind. Eng. Chem. Res., Vol. 42, No. 14, 2003 3191
conditions of the pyrolysis zone in continuous updraft
gasification.6 In all cases, the nitrogen fed at ambient
temperature is 2 × 103 cm3/min, resulting in nominal
residence times of vapors along the isothermal reactor
zone of 14 s.
Nitrogen and volatile pyrolysis products pass through
a condensation train consisting of two water-cooled
condensers (with a catch pot, where the liquids are
collected for chemical characterization), a wet scrubber,
two cotton wool traps, and a silica gel bed (all connected
in series). Gas sampling and analysis are carried out
at selected times during the duration of the tests (15-
18 samples). Steady global mass balances over the
system allow the exit volumetric flow rate and mass of
each gaseous species to be determined.46
Details about the gasification system and results for
beech wood have been already presented,6 so that only
the chief information on the process is listed here. The
laboratory-scale updraft gasifier is a cylindrical steel
shaft 63 cm high above the grate and 10 cm around
(internal diameter). Biomass is continuously fed at the
top (feed rates 1.6-2.3 kg/h) and air at the bottom. For
a steady-state operation, biomass moves across a region
of increasing temperature and solid consumption. In the
first region, close to the feed, preheating and drying of
the biomass take place, as a consequence of convective
heat transfer from the hot stream. This is followed by
the pyrolysis zone, where the volatile content of the
biomass is made available, the char gasification zone,
with the production of carbon monoxide and hydrogen,
and the char combustion zone. This supplies heat for
the other endothermic processes stratified along the
reactor axis.
The gas stream enters two condensers (20 tubes with
1.4-cm-i.d. and a total exchange surface of 4500 cm2 for
each unit), where steam and tars are condensed and
collected at the bottom for chemical analysis. The gas
is further purged through a closed water tank and a
packed-bed filter.
Tests were executed6 for air-to-fuel ratios (kg/kg) in
the range 1.27-1.05 with composition of the gas repro-
ducing that established at industrial scale (29-30% CO,
5.5-7% CO2, 7% H2, 2% CH4, and small amounts of C2
hydrocarbons, apart from nitrogen, with gas heating
values of 5.35-5.5 MJ/N‚m3). Temperature profiles
indicate that pyrolysis takes place over a wide portion
of the bed with slow heating rates (0.5-1.5 K/s) and
maximum temperatures, Tmax, in the range 725-852 K.
The total condensate (tars plus water) yields, evaluated
by weighing (before and after the tests) the water and
ash filters and collecting the liquids at the exit of the
condensers, are in the range 34-53% (by weight of dry
wood), again corresponding to those reported for indus-
trial-scale updraft wood gasification.47 Liquids collected
for the optimal gasification conditions, with R ) 1.11
and 1.05 and maximum pyrolysis temperatures of 831
and 852 K (total liquid yields of 43 and 53% of dry wood,
respectively), are examined here.
Fast Pyrolysis. The fast pyrolysis liquids have been
provided by the network PyNe.48 They were obtained
by four commercial systems (used in the following to
indicate the sample) and are the same already used in
the round-robin testing carried out by 12 European
laboratories.29 They were produced in a rotating cone
reactor at 773 K (BTG) and a bubbling fluid-bed reactor
at 733 K (Dynamotive) from softwood mixtures, in a
transported bed reactor (Ensyn) from hardwood mix-
tures, and in a vacuum pyrolysis reactor at 783 K
3192 Ind. Eng. Chem. Res., Vol. 42, No. 14, 2003

(Pyrovac) from softwood barks. Other details can be

found in ref 29.
GC/MS Analysis. The pyrolysis liquids are stored at
a temperature of 277 K with no light exposure. Before
analysis, filtration is made with 0.45-µm microfilters
(Millex-Gx). Chemical analysis is performed by GC/MS
(Fison GC 8000/MD 800 system) with a quadrupole
detector and a DB-1701 capillary column (60 m × 0.25
mm i.d., 0.25-mm film thickness). Helium (99.9999%)
is used as carrier gas with a constant flow of 1.0 mL/
min. The oven temperature is programmed from 318 (4
min) to 508 K at a heating rate of 3 K/min and held at
508 K for 13 min. The injector (Fison SSL 71) and the
GC/MS interface are kept at a constant temperature of
523 and 508 K, respectively. A sample volume of 1 mL
(4.5% of pyrolysis liquid in acetone) is injected.
The MS is operated in electron ionization mode, and
a m/z range from 30 to 300 is scanned. Standard mass
spectra with 70-eV ionization energy are recorded. Qual-
itative analysis uses the total ion chromatograms (TICs)
obtained from a full-scan acquisition method, using a
voltage applied to the photomultiplier detector of 350
V (cycle time of 0.1 s). The identification of the peaks is
based on computer matching of the mass spectra with
the NIST library or on the retention times of known
species injected in the chromatographic column.
For quantitative analysis, selected ion recording chro-
matograms, obtained by monitoring only three masses
corresponding to the three major fragments of each
compound, are employed in order to decrease the
duration of each scan (cycle time of 0.02 s), so improving
peak definition. The voltage applied to the photomul-
tiplier detector is again 350 V, except for the quantifica-
tion of acetic acid, hydroxypropanone, and hydroxyac-
etaldehyde. In this case, to avoid detector overload,
which would cause deformation of peaks and spectra,
the applied voltage is lowered to 280 V. Forty com-
pounds are quantified by the internal standard method,
using fluoranthene as internal standard.22 For each of
the quantified compounds, calibration lines are prepared
by injection of at least four standard solutions. The
concentrations range is determined by successive ap-
proximations, until it becomes relatively narrow and
comprises the quantified value. Injections of the liquid
samples are made at least in triplicate, showing devia-
tions between 0.01 and 5% of the quantified values
(averaged values are provided in the following).
Water Content. The water content of the pyrolysis
liquid is determined by means of Karl-Fisher titration
(Crison Compact tritator) according to the standard test
method ASTM E203-96.
Results
The dependence of the product yields (gas, char,
liquids) and gas and liquid composition of the conven-
tional pyrolysis tests on the external temperature is
discussed first. Then the composition of liquids obtained
from updraft gasification and fast pyrolysis is examined.
Conventional Pyrolysis and Updraft Gasifica-
tion. As anticipated, the conventional pyrolysis tests
have been executed for reactor temperatures in the
range 600-900 K. As feeding takes only a few seconds,
it can be assumed that the packed bed of particles is
suddenly exposed to high temperature, in this way
simulating the conditions of continuous updraft gasifi-
cation for different air-to-fuel ratios.6
Examples of the temperature dynamics along the
reactor axis and gas concentration at the exit are shown
Figure 1. (A) Temperature dynamics, measured along the axis
of the fixed-bed reactor at several distances, z, from the flow
distributor for reactor temperatures, Tr, of 600 and 900 K. (B)
Dynamics of gaseous species release, measured at the exit of the
fixed-bed reactor for reactor temperatures, Tr, of 600 and 900 K.
in panels A and B of Figure 1, respectively, for Tr )
600 K and Tr ) 900 K. The process dynamics show the
same qualitative trends, independently of the heating
conditions. Owing to the addition of a cold feed, a sudden
decrease of the temperature appears (minima of about
465 and 685 K for the two cases under examination).
The delays in the gas release (with respect to the feeding
time assumed as t ) 0) are, however, relatively short,
possibly as a consequence of high spatial gradients
across the packed bed. On the other hand, the temper-
ature registered can be considered an average value
between gas and solid (that is, the particle surface for
distances less than 15 cm above the perforated plate)
or volatiles (higher distances). Shrinkage of the bed may
also play an important role in this issue.
Gas and vapor release takes place under tempera-
tures slowly increasing toward the initial bed value, and
especially for the higher temperatures, pyrolysis is
completed well before steady-state conditions are again
established. Hence, even for the lowest temperature,
pyrolysis occurs under dynamic conditions with average
reaction temperatures increasing with the reactor tem-
perature. The actual temperature and heating rate of
the particles during degradation are difficult to deter-
mine. However, it is worth noting that accurate mea-
surements49,50 and numerical simulation51 show that
pyrolysis temperatures are barely above 725 K, and
even for the conditions of fast pyrolysis, the maximum
heating rates at the particle center do not exceed 80-
20 K/s. A rough evaluation for the tests under study,
made with reference to the time needed to reach 90%
of the reactor temperature, gives figures below 1 K/s,
which compare well with those obtained for updraft
gasification.6 In contrast with fast pyrolysis processes,
heating rates slower by at least 1 or 2 orders of
magnitude achieved in this case are typical of the so-
called conventional pyrolysis.

Figure 2. Product yields, expressed as percent of the initial dry
wood mass (wt), as functions of the reactor temperature (conven-
tional pyrolysis tests).
The duration of the process can be associated with
gas evolution and, as expected, is dramatically affected
by the reactor temperature. Indeed, it varies from about
60 (Tr ) 600 K) to 20 min (Tr ) 900 K).
The yields of char, total liquids, water, and gas
reported, on the basis of the initial dry wood mass (w),
as functions of the reactor temperature in Figure 2 show
that mass closure is very good (95.5-99%) (the water
yield is determined for the liquid collected after con-
densation, which corresponds to 84-88% of the total
liquid). The temperature dependence is in agreement
with previous studies conducted for thick particles52,53
and, from the qualitative point of view, also for small
particles undergoing fluid-bed pyrolysis (for instance,
see refs 12-15, 21, and 24). The yields of total liquid
Figure 3. Total ion chromatogram registered for the conventional pyrolysis liquid (Tr ) 800 K). IS indicates the internal standard peak.
The peak assignment corresponds to the retention time of some species listed in Table 1.
Ind. Eng. Chem. Res., Vol. 42, No. 14, 2003 3193
vary from about 40 to 55% of dry wood, again reproduc-
ing the figures obtained for the updraft gasification
tests.6
As widely discussed in the literature,35,54,55 the ther-
mal analysis of wood reflects the sum of the thermal
response of its three main components (cellulose, hemi-
cellulose, lignin), which degrade over relatively narrow
and overlapping ranges of temperature. In accordance
with the reaction mechanism of cellulose pyrolysis
usually indicated as Broido-Shafizadeh54 and the analy-
sis of fast pyrolysis of cellulose carried out by means of
fluidized-bed reactors,39,40 initially a competition occurs
between the low-temperature charring reactions (forma-
tion of char, steam, carbon monoxide, and carbon
dioxide) and a high-temperature depolymerization pro-
cess followed by the formation of volatile species. The
reactions (and products) of hemicellulose pyrolysis are
qualitatively similar35 to those of cellulose, though
quantitative differences are significant (higher yields of
char). Due to the complex structure, highly cross-linked,
the mechanism for the thermal degradation of lignin is
not well understood. It is postulated that depolymeri-
zation is associated with significant homolysis of the
backbone and cleavage of ether and C-C bonds56,57
again accompanied by a competition between charring
and devolatilization reactions. The selectivity for the
latter is favored by temperature,58 though the yields of
char always remain high.
In accordance with these findings, the results of
Figure 2 show that, by increasing the reactor temper-
ature, the final char yield decreases with a correspond-
ing increase in the liquid and gas yields. For Tr values
of 800-900 K, the liquid yields are leveled around the
Table 1. Pyrolysis Liquid Compounds Identified by GC/MS with Retention Times Reported in Figure 3a
ID RT ID RT
3194

no. compound formula MW origin (min) ref no. compound formula MW origin (min) ref
1 furan (i) C4H4O 68 6.938 C 10, 23, 41 45 guaiacol (i) C 7H 8O 2 124 36.286 L-G 10, 22, 23,
27, 29, 62
2 methyl acetate C3H6O2 74 7.317 C 10, 27 46 3-ethylciclopenten-2- C7H10O 110 36.686 C 27
en-1-one
3 2-propen-1-ol C3H6O 58 8.924 C 27 47 o-cresol (i) C 7H 8O 108 37.658 L-H 10, 22, 23, 27,
29, 41, 62
4 ethyl acetate (i) C4H8O2 88 9.101 C 48 2-cyclopenten-1-one, C7H10O2 126 38.142 C
3-ethyl-2-hydroxy
5 2-butanone C4H8O 72 9.334 C 10, 23, 27, 41 49 2,6-dimethylphenol (i) C8H10O 122 38.369 L-H 23
6 propionic acid C4H8O2 88 9.567 C 50 p-cresol (i) C 7H 8O 108 39.337 L-H 10, 22, 23, 27,
methyl ester 29, 41, 62
7 3-pentanone C5H10O 86 9.784 C 27 51 m-cresol (i) C 7H 8O 108 39.412 L-H 10, 22, 23,
29, 41, 62
8 benzene (i) C6H6 78 10.069 C 41 52 3-methyl guaiacol C8H10O 122 39.510 L-G
9 hydroxyacetaldehyde (i) C2H4O2 60 10.801 C 10, 22, 23, 27, 53 4-methyl guaiacol (i) C8H10O 122 41.237 L-G 10, 22, 23,
29, 40, 41 27, 29, 62
10 isobutanol (i) C4H4O 68 10.823 C 54 2-ethylphenol C8H10O 122 41.426 L-H 10, 23, 27
11 formic acid (i) CH2O2 46 11.534 C 10, 22, 23, 27, 55 2,5 + 2,4-dimethylphenol C8H10O 122 41.549 L-H 22, 23, 27, 62
29, 40, 41
12 3-buten-2-one, 3-methyl C5H8O 84 11.667 C 41 56 2,4,6-trimethylphenol C9H10O 134 42.552 L-H
13 acetic acid (i) C2H4O2 60 12.351 C 10, 22, 23, 27, 57 3-ethylphenol C8H10O 122 43.590 L-H 10
29, 40, 41
Ind. Eng. Chem. Res., Vol. 42, No. 14, 2003

14 2-pentanone (i) C5H10O 86 12.527 C 58 3-ethyl guaiacol C9H10O2 152 43.590 L-G 62
15 2,3-pentanedione C5H8O2 100 13.051 C 10, 23, 27, 41 59 3,4-dimethyphenol (i) C8H10O 122 44.623 L-H
16 hydroxypropanone (i) C3H6O2 74 14.084 C 10, 22, 23, 27, 60 4-ethyl guaiacol C9H12O2 152 45.104 L-G 22, 23, 27,
29, 40 29, 62
17 propionic acid (i) C3H8O 60 17.268 C 10, 23, 27, 29 61 1,4-3,6-dianhydro- C 6H 8O 4 144 46.553 C 41
R-D-glucopyranose
18 acrylic acid C3H4O2 72 18.820 C 10, 27, 29 62 3-methoxy catechol C 7H 8O 3 140 47.469 L-G
19 cyclopentanone C5H8O 84 18.953 C 10, 27, 23 63 2-methoxy-4-vinyl- C9H10O2 151 47.671 L-G 10, 22, 27, 62
phenol
20 1-hydroxy-2-butanone C4H8O2 88 19.218 C 10, 22, 27, 64 3-methoxyphenol (i) C 7H 8O 2 124 48.036 L-G
29, 41
21 hydroxy propanal C3H6O2 74 19.335 C 10, 22, 41 65 eugenol (i) C10H10O2 162 48.645 L-H 10, 22, 23,
29, 62
22 furantetrahydro-2,5- C6H12O3 132 20.570 C 22 66 2-methoxy-4-propyl- C10H14O2 166 48.762 L-G 22, 23, 27
dimethoxy (cis) (i) phenol
23 butanedial C7H14O 114 21.668 C 22 67 5-hydroxymethyl-2- C 6H 6O 3 126 49.237 C 22, 27, 29, 41
furaldehyde
24 styrene C8H8 104 21.785 P 68 catechol C 6H 6O 2 110 49.603 L-H 10, 23, 27,
41, 29, 62
25 furantetrahydro-2,5- C6H12O3 132 22.421 C 22 69 syringol (i) C8H10O2 138 49.938 L-S 10, 22, 23,
dimethoxy (trans) (i) 29, 62
26 2-furaldehyde (i) C5H4O2 96 22.635 C 10, 22, 23, 27, 70 1,2,3-trimethoxy-5- C10H14O3 182 50.020 L-S
29, 41 methylbenzene
27 cyclohesanone (i) C6H10O 98 24.735 C 71 isoeugenol (cis) (i) C10H12O2 164 51.012 L-G 10, 22, 23,
27, 29, 62
28 R-angelicalactone (i) C5H6O2 98 24.787 C 10, 22, 27 72 3-methyl catechol (i) C 7H 8O 2 124 51.215 L-H 27, 62
29 furfuryl alcohol (i) C5H5O2 97 24.971 C 10, 22, 23, 27 73 4-methyl catechol (i) C 7H 8O 2 124 52.885 L-H 27, 62
30 acetoxyacetone (i) C5H8O3 116 25.385 C 10, 22, 27 74 isoeugenol (trans) (i) C10H12O2 164 53.238 L-G 10, 22, 23,
27, 29, 62
31 2-methyl-2-cyclo- C6H8O 96 25.636 C 10, 27, 41 75 4-methyl syringol (i) C9H12O3 168 53.738 L-S 10, 22, 23, 29
pentenone (i)
32 2-acetylfuran (i) C6H6O2 110 26.522 C 22, 41 76 vanillin (i) C 8H 8O 3 152 54.196 L-G 10, 22, 23,
27, 29, 62
33 benzaldehyde C7H7O 107 28.565 C 41 77 hydroquinone (i) C 6H 6O 2 110 54.196 L-H 10, 23
34 2,5-hexanedione C6H10O2 114 29.169 C - 78 acetoguaiacone C9H10O3 166 57.388 L-G 10, 22, 62
 Ind. Eng. Chem. Res., Vol. 42, No. 14, 2003 3195

a Abbreviations: i, identification by injection of standard samples; M , molecular weight; RT, retention time; C, carbohydrate; L-H, hydroxyphenyl lignin; L-G, guaiacyl lignin; L-S, syringyl
10, 22, 23, 27, 29, 40, 62
ref

10, 22, 23, 62

22, 29, 62

10, 22, 23

10, 22, 23

10, 22, 62
62
(min)
RT

L-G
L-S

L-S

L-S

L-S

L-S
L-S
C

Figure 4. Yields of major carbohydrates, minor carbohydrates,

58.485
59.422
59.655

61.589

63.005

63.739

64.866

67.233
68.806
origin

furans, guiacols, syringols, and phenols (definitions in Table 2),

expressed as percent of the initial dry wood mass (wt), as functions
of the reactor temperature (conventional pyrolysis tests).
122
180
194

194

162

194

182

196
210
MW

C10H12O3
C11H14O3

C11H14O3

C11H14O3

C10H12O4
C11H14O4
C6H10O5
formula

C9H10O4
C7H6O2
4-hydroxybenzaldehyde
4-acetone guaiacol (i)

4-propenyl syringol

4-propenyl syringol

syringaldehyde (i)

acetosyringone (i)
compound

syringol acetone
levoglucosan (i)
4-allyl syringol

(trans) (i)
(cis) (i)

Figure 5. Yields of major carbohydrates, expressed as percent

of the initial dry wood mass (wt), as functions of the reactor
temperature (conventional pyrolysis tests).
no.
ID

79
80
81

82

83

84

85

86
87

maximum whereas the yields of chars are still decreas-

ing, indicating an enhancement of both primary wood
devolatilization and secondary decomposition of primary
10, 22, 23, 27,
10, 23, 27, 41

vapor-phase products. As already reported in previous

10, 22, 27,

29, 41, 62
ref

studies,12-15,17-19,21,46,52,53 gas consists mainly of carbon

10, 27

29, 41

dioxide (contributions up to 13 wt %), carbon monoxide

23

22

22

27
22

(8 wt %), and methane (1.5 wt %) with lower amounts

of hydrogen and C2 hydrocarbons.
Chemical characterization of the liquid is made again
L-H/C

w
(min)
RT

C
C
C

C
C

in relation to the samples collected at the conclusion of

the condensation process, corresponding to 84-88% of
the total liquid yields. An example of the TICs (Tr )
30.056
30.185
30.469

30.875

31.636

32.290

33.803

33.836
34.719
35.291
origin

800 K) is shown in Figure 3 and the compounds

identified are listed in Table 1. These are the same as
reported for fast pyrolysis liquids10-24,26-29 and include
carboxylic acids, alcohols, aldehydes, ketones, sugars.
110
130
110

112

120
MW

96

88

98

98

94

and phenolic compounds. Following the mild severity

of the thermal treatment undergone by wood, the liquid
C6H5OH

components can be classified as “primary vapors”.2,9

C6H10O3
formula
C6H6O2

C7H10O

C4H8O2

C5H6O2

C6H8O2

C5H6O2
C6H8O

C8H8O

Pyrolysis products are qualitatively similar35 to both

cellulose and hemicellulose (more precisely, for xylan,
the main constituent of hardwood hemicellulose), which
are indicated as carbohydrates (C). The hydroxypheno-
5-methyl-2-furaldehyde (i)

2,3-dimethylcyclopenten-

5-methyl-5H-furan-2-one

3-methyl-5H-furan-2-one

lics (L-H), guaiacols (L-G), and syringols (S-L) are

2-acetyloxy-1-butanone

1-cyclopenten-3-one-2-

derived from the lignin building blocks.57

(5H)-furan-2-one (i)
compound

hydroxy-1-methyl

Forty compounds of the pyrolysis liquids have been

3-methyl-2-cyclo-
Table 1. (Continued)

quantified. They have been grouped as major carbohy-

acetophenone
pentenone (i)

drates, minor carbohydrates, furans, guialcols, syrin-

2-en-1-one

phenol (i)

gols, and phenols, as summarized in Table 2 (apart from

benzene, polyaromatic hydrocarbons, which are present
only in ppm,18,19 have not been examined). Figure 4
provides the trends for the lumped component classes,
lignin.

whereas the details are given in Figures 5-10 (yields

no.
ID

35
36
37

38

39

40

41

42
43
44

always expressed as percent of the dry wood mass). All

3196 Ind. Eng. Chem. Res., Vol. 42, No. 14, 2003

Table 2. Lumped Classes of Pyrolysis Liquid Compounds, Quantified by GC/MS and the Internal Standard Method
major carbohydrates minor carbohydrates furans
hydroxyacetaldehyde 3-ethyl-2-hydroxy-2-cyclopentenone 2-acetylfuran
hydroxypropanone acetoxyacetone 5-methyl-2-furaldehyde
acetic acid propionic acid 2-furaldehyde
levoglucosan 3-methyl-2-cyclopentenone furantetrahydro-2,5-dimethoxy cis
2-methyl-2-cyclopentenone furantetrahydro-2,5-dimethoxy trans
1-hydroxy-2-butanone furfuryl alcohol
formic acid 2(5H)-furanone

phenols guaiacols syringols

phenol guaiacol syringol
o-cresol 4-acetoneguaiacol syringaldehyde
p-cresol 4-ethylguaiacol acetosyringone
m-cresol 4-methylguaiacol 4-methylsyringol
2-methyl-4-propylphenol isoeugenol cis
3,4-dimethylphenol isoeugenol trans
2,5+2,4-dimethylphenol eugenol
2-ethylphenol vanillin
hydroquinone

Figure 6. Yields of minor carbohydrates, expressed as percent Figure 8. Yields of guaiacols, expressed as percent of the initial
of the initial dry wood mass (wt), as functions of the reactor dry wood mass (wt), as functions of the reactor temperature
temperature (conventional pyrolysis tests). (conventional pyrolysis tests).

Figure 7. Yields of furans, expressed as percent of the initial Figure 9. Yields of syringols, expressed as percent of the initial
dry wood mass (wt), as functions of the reactor temperature dry wood mass (wt), as functions of the reactor temperature
(conventional pyrolysis tests). (conventional pyrolysis tests).

the lumped product classes present an initial increase
with temperature, reflecting the primary degradation
of wood components, that is, holocellulose (cellulose and
hemicellulose) and lignin. Secondary reactions in the
vapor phase also take place, as indicated by the maxi-
mums shown by furans, guaiacols, and syringols. The
most abundant species are acetic acid (4.8-5.5%),
hydroxypropanone (1.1-1.6%), hydroxyacetaldehyde
(0.7-2.3%), levoglucosan (0.2-0.8%), formic acid (0.4-
0.6%), syringol (0.3-0.4%), and 2-furaldehyde (0.3-
0.35%).
The 40 chemical compounds quantified by GC/MS and
water correspond to 62-65% of the total liquid (or, with
reference to dry liquid (tars), to 40-43%, with a
contribution from major carbohydrates of 25-30%).
According to the methods for chemical characterization
developed for fast pyrolysis liquids,59 the amount of
liquid not quantified by GC/MS is presumably consti-
tuted of nonvolatile compounds (∼15% of the total liquid
in the case of fast pyrolysis), to be characterized by high-
performance liquid chromatography, and pyrolytic lig-
nin (∼25% of the total liquid again for fast pyrolysis),
to be determined by water extraction.
In accordance with previous literature,35-37,44 the
increase in the yields of furans and their derivatives
observed at low temperatures can be attributed mainly
to hemicellulose decomposition. Together with these
compounds, other species are formed44 such as low
molecular weight carboxylic acids, ketones, carbon
monoxide, carbon dioxide, and steam. It can be observed
that, for some species (i.e., acetoxyacetone, 3-ethyl-2-
hydroxy-2-cyclopentenone, furfuryl alcohol, and 5-meth-
 Ind. Eng. Chem. Res., Vol. 42, No. 14, 2003 3197

volatile formation from primary degradation reactions.

Then, as the temperature is increased, a weak thermal
stability and secondary vapor-phase degradation may
cause a decrease in the amounts of these products (i.e.,
furfuryl alcohol and 5-methyl-2-furaldehyde).
The continuous increase in the yields of hydroxyac-
etaldehyde and levoglucosan with temperature confirm
that both are products of primary decomposition of
depolymerized holocellulose (secondary decomposition
does not appear to prevail for the mild thermal condi-
tions examined). In fact, a competition has been postu-
lated between ring fragmentation to yield hydroxyace-
taldehyde38 and depolymerization by transglycosylation
Figure 10. Yields of phenols, expressed as percent of the initial
to yield levoglucosan.35-37 Higher temperatures are
dry wood mass (wt), as functions of the reactor temperature
(conventional pyrolysis tests). confirmed to favor the hydroxyacetaldehyde-forming
pathway38-40 a feature that, in kinetic analysis, would
yl-2-furaldehyde), a maximum at low temperatures is appear as a higher activation energy of the correspond-
attained, attributable to an increase in the rate of ing global reaction. The selectivity between the two
Table 3. Yields of Liquid Compounds, Expressed as Percent of the Initial Dry Wood Mass (wt), for Conventional
Pyrolysis (for Two Reactor Temperatures, Tr) and Updraft Gasification (for Two Air-to-Fuel Ratios, R, and Maximum
Pyrolysis Temperatures, Tmax)
gasification
conventional pyrolysis R ) 1.11 kg/kg R ) 1.05 kg/kg
Tr ) 800 K Tr ) 900 K Tmax ) 831 K Tmax ) 842 K
compound (wt % mf) (wt % mf) (wt % mf) (wt % mf)
water 21.00 22.26 21.44 24.91
hydroxyacetaldehyde 1.831 2.291 1.112 2.024
acetic acid 5.307 5.521 4.774 6.544
hydroxypropanone 1.531 1.547 1.056 1.470
levoglucosan 0.660 0.776 0.430 0.644
total major carbohydrates 9.329 10.135 7.373 10.683
propionic acid 0.220 0.234 0.218 0.213
1-hydroxy-2-butanone 0.222 0.187 0.267 0.229
formic acid 0.667 0.594 0.535 0.718
2-methyl-2-cyclopentenone 0.069 0.068 0.039 0.037
3-methyl-2-cyclopentenone 0.114 0.097 0.080 0.069
3-ethyl-2-hydroxy-2-cyclo- 0.053 0.046 0.035 0.038
penten-1-one
acetoxyacetone 0.154 0.154 0.087 0.088
total minor carbohydrates 1.498 1.379 1.263 1.391
2-furaldehyde 0.363 0.327 0.214 0.240
furfuryl alcohol 0.064 0.049 0.027 0.031
furantetrahydro-2,5-dimethoxy 0.130 0.073 0.047 0.050
(cis + trans)
2-acetylfuran 0.025 0.022 0.019 0.019
5-methyl-2-furaldehyde 0.068 0.066 0.042 0.040
(5H)-furan-2-one 0.262 0.234 0.205 0.235
total furans 0.913 0.772 0.554 0.615
phenol 0.053 0.095 0.078 0.076
cresol (m + o + p) 0.063 0.116 0.071 0.069
2-ethylphenol 0.002 0.006 0.001 0.001
2,5+2,4-dimethylphenol 0.025 0.047 0.020 0.019
3,4-dimethylphenol 0.004 0.006 0.005 0.005
hydroquinone 0.154 0.134 0.082 0.096
2-methyl-4-propylphenol 0.012 0.005 0.007 0.006
total phenols 0.313 0.409 0.263 0.271
guaiacol 0.201 0.102 0.174 0.166
4-methylguaiacol 0.237 0.101 0.205 0.203
eugenol 0.086 0.044 0.054 0.058
4-ethylguaiacol 0.122 0.042 0.103 0.100
isoeugenolo (cis + trans) 0.426 0.258 0.226 0.233
vanillin 0.101 0.103 0.056 0.067
4-acetoneguaiacol 0.046 0.030 0.043 0.050
total guaiacols 1.219 0.680 0.861 0.876
syringol 0.739 0.365 0.685 0.737
4-methylsyringol 0.226 0.127 0.202 0.212
syringaldehyde 0.286 0.175 0.145 0.206
acetosyringone 0.079 0.053 0.052 0.071
total syringols 1.330 0.721 1.084 1.227
benzene 0.0012 0.001 0.001 0.001
total 35.601 36.356 32.835 39.973
3198 Ind. Eng. Chem. Res., Vol. 42, No. 14, 2003

Table 4. Yields of Liquid Compounds, Expressed as Percent of the Total Liquid Mass, for Conventional Pyrolysis (for
One Reactor Temperature, Tr) and Fast Pyrolysis (Samples Are Indicated by the Name of Producer and the Water
Content is Derived from Ref 29)
conventional
pyrolysis fast pyrolysis
Tr ) 800 K BTG Dynamotive Ensyn Pyrovac
compound (% liquid) (% liquid) (% liquid) (% liquid) (% liquid)
water 38.100 30.400 21.100 20.300 15.700
hydroxyacetaldehyde 3.322 6.645 5.645 3.690 2.535
acetic acid 9.631 3.180 2.458 4.733 2.247
hydroxypropanone 2.778 2.815 3.905 1.630 1.095
levoglucosan 1.197 2.960 4.480 3.705 3.715
total major carbohydrates 16.928 15.600 16.488 13.758 9.592
propionic acid 0.398 0.280 0.325 0.655 0.295
1-hydroxy-2-butanone 0.376 0.070 0.205 0.090 0.100
formic acid 0.666 0.190 0.128 0.122 0.069
2-methyl-2-cyclopentenone 0.124 0.060 0.165 0.140 0.525
3-methyl-2-cyclopentenone 0.207 0.105 0.160 0.225 0.205
3-ethyl-2-hydroxy-2-cyclo- 0.096 0.037 0.045 0.039 0.090
penten-1-one
acetoxyacetone 0.279 0.145 0.215 0.215 0.110
total minor carbohydrates 2.147 0.887 1.243 1.486 1.394
2-furaldehyde 0.660 0.350 0.530 0.530 0.300
furfuryl alcohol 0.117 0.074 0.080 0.080 0.085
furantetrahydro-2,5- 0.236 0.037 0.060 0.005 0.000
dimethoxy (cis + trans)
2-acetylfuran 0.045 0.025 0.030 0.045 0.030
5-methyl-2-furaldehyde 0.123 0.055 0.145 0.075 0.120
(5H)-furan-2-one 0.476 0.535 0.615 0.500 0.510
total furans 1.656 1.076 1.460 1.235 1.045
phenol 0.096 0.075 0.095 0.225 0.315
cresol (m + o + p) 0.108 0.095 0.110 0.170 0.360
2-ethylphenol 0.004 0.002 0.004 0.009 0.021
2,5- + 2,4-dimethylphenol 0.045 0.020 0.050 0.065 0.220
3,4-dimethylphenol 0.008 0.000 0.010 0.010 0.020
hydroquinone 0.280 0.170 0.300 0.325 0.470
2-methyl-4-propylphenol 0.022 0.022 0.085 0.010 0.031
total phenols 0.563 0.384 0.655 0.813 1.437
guaiacol 0.364 0.355 0.530 0.210 0.325
4-methyl guaiacol 0.431 0.650 1.225 0.230 0.405
eugenol 0.157 0.415 0.710 1.795 0.240
4-ethyl guaiacol 0.222 0.120 0.365 0.075 0.125
isoeugenolo (cis + trans) 0.772 1.412 2.798 0.492 1.175
vanillin 0.183 0.815 0.290 0.080 0.245
4-acetoneguaiacol 0.083 0.095 0.140 0.065 0.110
total guaiacols 2.213 3.862 6.058 2.947 2.625
syringol 1.341 0.160 0.140 0.605 0.210
4-methyl syringol 0.411 0.130 0.120 0.220 0.150
syringaldehyde 0.520 0.040 0.000 1.155 0.065
acetosyringone 0.143 0.010 0.000 0.205 0.015
total syringols 2.414 0.340 0.260 2.185 0.440
benzene 0.0021 0 0 0.008 0

reaction paths has also been reported to be highly
dominated by salts and metal ions35-36,60 and thus by
feed pretreatments (hot water or acid washing), which
reduce the ash content. More specifically, the large
increase in the levoglucosan yield following these pre-
treatments is associated with a corresponding decrease
in the yield of hydroxyacetaldehyde. These two major
reaction pathways are preceded and accompanied by
dehydration and elimination reactions35,36,39,40 leading
to formation of other components quantitatively impor-
tant, such as the above-mentioned furans, acetic and
formic acids, and hydroxypropanone.
Syringols, guaiacols, and phenols originate from lignin
degradation.44,56,57,61-63 The total yield attains a maxi-
mum of ∼2.9% (of dry wood) for Tr ) 800 K with major
contributions from syringol, syringaldehyde, and isoeu-
genol. However, guaiacols and syringols are intermedi-
ate species, given their decline at high temperature. On
the contrary, phenols continuously increase, indicating
that they are also formed from secondary degradation.44
It is worth pointing out that other species, such as acetic
acid and permanent gases,35,63 are also formed from the
degradation of lignin components.
The TICs registered for the liquid collected from the
updraft gasification tests for the two conditions listed
above (Tmax of 831 and 842 K) are qualitatively similar
to those obtained from the conventional pyrolysis tests.
The compound yields are listed in Table 3 together with
those obtained for conventional pyrolysis and compa-
rable maximum temperatures (Tr ) 800-900 K). It can
be seen that the figures are roughly the same, so that
the findings obtained for conventional pyrolysis can be
 Ind. Eng. Chem. Res., Vol. 42, No. 14, 2003 3199

Table 5. Yields of Liquid Compounds, Expressed as Percent of the Total Liquid Mass, for Fast Pyrolysis (Samples Are
Indicated by the Name of the Producer) As Determined in This Study and the Round Robin Testing of Ref 29
BTG Dynamotive Ensyn Pyrovac
(wt %) (wt %) (wt %) (wt %)
this round this round this round this round
compound study robin study robin study robin study robin
hydroxyacetaldehyde 6.645 6.89-11.1 5.645 3.32-7.7 3.690 1.81-3.34 2.535 1.09-3.2
acetic acid 3.171 3.23-8.98 2.458 2.7-7.84 4.733 3.9-11.2 2.247 2.05-5.26
hydroxypropanone 2.815 3.28-7.3 3.905 2.07-7.82 1.630 1.48-3.65 1.095 0.84-3.17
propionic acid 0.280 0.21-0.64 0.325 0.17-0.63 0.655 0.26-0.31 0.295 0.19-0.35
1-hydroxy-2-butanone 0.070 0.27 0.205 0.31 0.090 0.17 0.100 0.17
furantetrahydro-2,5- 0.030 0.050 0.000 0.000
dimethoxy (cis)
furantetrahydro-2,5- 0.010 0.20-0.54 0.010 0.20-0.81 0.005 0.16-0.65 0.000 0.15-0.47
dimethoxy (trans)
2-furaldehyde 0.350 0.530 0.530 0.300
furfuryl alcohol 0.074 0.080 0.080 0.085
acetoxyacetone 0.145 0.215 0.215 0.110
2-methyl-2-cyclo- 0.060 0.165 0.140 0.525
pentenone
2-acetylfuran 0.025 0.030 0.045 0.030
5-methyl-2-furaldehyde 0.055 0.145 0.075 0.120
3-methyl-2-cyclo- 0.105 0.160 0.225 0.205
pentenone
(5H)-furan-2-one 0.535 0.54 0.615 0.6 0.500 0.32 0.510 0.53
3-ethyl-2-hydroxy-2- 0.037 0.045 0.039 0.090
cyclopenten-1-one
4-hydroxybenzaldehyde 0.011 0.010 0.015 0.033
levoglucosan 2.960 3.31-5.5 4.480 3.98-7.5 3.705 2.9-4.41 3.715 3.06-8.4
formic acid 0.190 0.9-13.55 0.126 0.29-9.35 0.122 0.52-11.32 0.069 0.48-8.26
phenol 0.075 0.04-0.15 0.095 0.07-0.10 0.225 0.10-0.26 0.315 0.16-0.44
cresol (m + o + p) 0.095 0.04-0.2 0.110 0.04-0.2 0.170 0.13-0.32 0.360 0.49-0.75
2-ethylphenol 0.002 0.004 0.009 0.021
2,5+2,4-dimethylphenol 0.020 0.050 0.065 0.220
3,4-dimethylphenol 0.000 0.010 0.010 0.020
2-methyl-4-propylphenol 0.022 0.085 0.010 0.031
hydroquinone 0.170 0.300 0.325 0.470
eugenol 0.415 0.03-0.21 0.710 0.06-0.29 1.795 0-0.07 0.240 0.02-0.12
guaiacol 0.355 0.11-0.51 0.530 0.16-0.54 0.210 0.05-0.18 0.325 0.17-0.37
4-methyl guaiacol 0.650 0.48-0.59 1.225 0.8-0.83 0.230 0.13-0.18 0.405 0.36-0.61
4-ethyl guaiacol 0.120 0.11-0.12 0.365 0.24 0.075 0.05-0.08 0.125 0.14-0.15
isoeugenol (cis + trans) 1.412 0.34-0.36 2.798 0.54-0.79 0.492 0.05-0.07 1.175 0.07-0.5
vanillin 0.815 0.16-0.33 0.290 0.23-0.34 0.080 0.07-0.32 0.245 0.17-0.19
4-acetone guaiacol 0.095 0.140 0.065 0.110
syringol 0.160 0.09 0.140 0.13 0.605 0-1.81 0.210 0-0.58
4-methyl syringol 0.130 0.120 0.220 0.150
syringaldehyde 0.040 0.000 1.155 0.065
acetosyringone 0.010 0.000 0.205 0.015
total 22.154 20.23-50.98 26.171 15.91-46.02 22.439 12.10-38.59 16.567 10.14-33.52

extended to pyrolysis liquids generated from updraft
gasification.
Fast Pyrolysis. The TICs registered for the fast
pyrolysis liquids are also qualitatively similar to those
obtained from conventional pyrolysis tests. A quantita-
tive comparison is provided through Table 4 (conven-
tional pyrolysis results for Tr ) 800 K, a temperature
close to those of the fast pyrolysis tests, are included).
In this case, the yields are expressed as percent of the
total liquid, given that the exact amounts of product
classes (liquid, char, gas) produced for the fast pyrolysis
tests were not available. Though the different conver-
sion technology (vacuum versus atmospheric) may be
an important issue, it is believed that feedstock char-
acteristics and method of liquid collection are the main
causes for the very large differences shown by the
Pyrovac sample with respect to the other fast pyrolysis
liquids. The entire amount of liquid collected was
provided by BTG and Dynamotive and presumably by
Ensyn, whose collection method also included water
scrubbing. For the Pyrovac technology, apart from the
use of bark (versus wood), the liquid was collected into
two fractions: a low-volatility organic fraction, which
was provided for the analyses, and the water- and
volatile-rich fraction. In this case, much lower amounts
of major carbohydrates (hydroxyacetaldehyde, acetic
acid, hydroxypropanone) and furans (in particular,
2-furaldehyde) are produced. On the contrary, the yields
of phenolics are roughly 2-4 times higher.
Some differences between the fast pyrolysis liquids
derived from wood can be explained by the different
nature of the lignin components. In fact, the yields of
lignin-derived products are known to be dependent on
the wood category.62 Softwood lignins typically degrade
to guaiacyl products, whereas hardwood lignin typically
gives rise to both guaiacyl and syringyl products. Hence,
in accordance with the different lignin structures, the
yields of guiacols are higher for the softwood liquids
(BTG and Dynamotive samples), whereas the hardwood
liquids (Ensyn sample) show much higher contents of
syringols. Also, it can be noted that the lignin-derived
products are higher for the Dynamotive and Ensyn
liquids (7 and 6%, respectively, versus 4.6% of the BTG
3200 Ind. Eng. Chem. Res., Vol. 42, No. 14, 2003
sample), in accordance with the higher percent of C in
the elemental composition.29
As shown by the data listed in Table 5, the quantifi-
cations determined here for the fast pyrolysis liquids
are comprised in the range of values given by Oasmaa
and Meier in ref 29. On the other hand, these authors
pointed out that the differences between the results of
the different laboratories are high, so that they suggest
a calibration of the gas and liquid chromatographic
systems with (common) standard solutions. As stated
above, to improve the accuracy of the quantification, in
this study, calibration curves have been constructed
with the use of at least four standard solutions. Fur-
thermore, in some cases, it has been necessary to recon-
struct the calibration curves by adequate selection of
the standard values. Indeed, extrapolations outside the
calibration range resulted in significant over- or under-
estimations of the concentrations to be determined.
In addition to thermal conditions (heating rate and
temperature) and feedstock properties, the different
scale of the process, also in relation to the collection
systems, between conventional and fast pyrolysis (labo-
ratory versus commercial plants) introduces a further
difference. So the comparison should be considered only
as preliminary. With reference to the wood-derived
liquids, conventional pyrolysis produces lower yields of
levoglucosan and hydroxyacetaldehyde (up to factors of
4 and 2, respectively). On the contrary, the yields of
acetic acid, formic acid, and 2-furadehyde are higher (up
to factors of 4, 5.5, and 2, respectively). Furthermore,
the water content is also higher. It can be postulated
that the slower heating rates, which result in lower
reaction temperatures, may enhance dehydration and
elimination reactions with respect to transglycosylation.
Furthermore, as already observed for cellulose pyroly-
sis,35,36 low yields of hydroxyacetaldehyde are associated
with high yields of char (these are ∼20-25% for
conventional pyrolysis versus ∼10% for fast pyrolysis,
percentages referred to dry wood). The distribution and
yields of lignin-derived products do not appear to be
significantly affected by the heating conditions, while
the importance of the wood category is confirmed with
a close similarity between the results obtained for
hardwoods (conventional pyrolysis and Ensyn liquids).
Conclusions
The first part of this study investigates the depen-
dence on the heating temperature of the composition,
determined by means of GC/MS, of liquids derived from
wood pyrolysis. The experimental tests have been
executed under conditions reproducing those of the
pyrolysis section in updraft gasifiers, by feeding wood
particles to a preheated reactor (temperatures in the
range 600-900 K).
Identification of liquid components confirms previous
findings. That is, liquids obtained from updraft gasifica-
tion (conventional pyrolysis) and fast pyrolysis are
qualitatively the same. Indeed, for both cases, the
pyrolysis temperatures are relatively low (∼725-850 K
in the pyrolysis zone of an updraft gasifier and ∼800 K
in fluid-bed fast pyrolysis), though the heating rates
may be significantly different.
Quantification, carried out for 40 compounds of the
pyrolysis liquid and corresponding to 40-43% of the
organic fraction (tars), indicates that the thermal analy-
sis of wood reflects the sum of the thermal response of
holocellulose and lignin, with the former leading to the
formation of furans and carbohydrates and the latter
to phenolics. The high number of liquid compounds
quantified represents a significant advancement with
respect the current state of the art, for improving both
reactor development/optimization and formulation of
detailed reaction mechanisms.
Furan derivatives first attain a maximum at very low
heating temperatures (∼650 K), as a consequence of
primary degradation, and then slightly decrease, plau-
sibly due to secondary, vapor-phase reactions (the most
abundant product is 2-furaldehyde, which attains yields
up to ∼0.35% of dry wood). Major contributions to
carbohydrates are given by acetic acid, hydroxypro-
panone, hydroxyacetaldehyde, levoglucosan, and formic
acid (maxima of 5.5, 1.6, 2.3, 0.8, and 0.6% of dry wood,
respectively). The mild thermal conditions examined do
no affect significantly the yields of acetic acid, formic
acid, and hydroxypropanone, whereas both hydroxyac-
etaldehyde and levoglucosan continuously increase with
temperature, supporting a common origin from primary
decomposition reactions. In this way, the existence of
two main routes already postulated in the fast pyrolysis
of cellulose is also confirmed for slow heating rates. The
first (transglycosylation) leads to levoglucosan forma-
tion, the second (fragmentation and partial recombina-
tion) gives hydroxyacetaldehyde, hydroxypropanone,
acetic acid, and other minor species.
Syringols, guaiacols, and phenols, originating from
lignin degradation, attain a maximum of ∼2.9% of dry
wood with major contributions from syringol, syringal-
dehyde, and isoeugenol. Decomposition of guaiacols and
syringols already becomes important for heating tem-
peratures of ∼800 K, whereas phenols continuously
increase.
In the second part of the study, the influence of the
heating rate on the yields of 40 compounds of the
pyrolysis liquids, not reported by previous literature,
has also been investigated. Heating rates of conven-
tional pyrolysis are at least 1 or 2 orders of magnitude
slower than those typically achieved in fast pyrolysis.
Results obtained for conventional pyrolysis (laboratory
scale) and fast pyrolysis (four commercial-scale plants)
indicate that faster heating rates enhance the formation
of levoglucosan and hydroxyacetaldehyde with a dimi-
nution in the yields of carboxylic acids.
Acknowledgment
The experimental tests were carried out in the
framework of a R&D project partially funded by the
European Commission. The kindness of the producers
of the fast pyrolysis liquids (BTG in The Netherlands
and Dynamotive, Ensyn, and Pyrovac in Canada), who
made samples available through the European network
PyNe, is greatly appreciated. C.D.B. also thanks the
PyNe group, in particular Stefan Czernik, Tony Bridg-
water, Dietrich Meier, Anja Oasmaa, Jan Piskorz, and
Wolter Prins, for many useful discussions during the
years on the subject of this paper.
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Received for review January 23, 2003
Revised manuscript received April 21, 2003
Accepted May 1, 2003
IE030066D