Bioresource Technology 46 (1993) 233-240
ON THE BEHAVIOUR OF LIGNIN A N D HEMICELLULOSES
DURING THE ACETOSOLV PROCESSING OF WOOD
J.C. Paraj6, J.L. A l o n s o & D. V~izquez
Department of Chemical Engineering, University of Vigo (Campus Orense), Las Lagunas, 32004 Orense, Spain
(Received 10 February 1993; revised version received 6 april 1993)
Abstract
Eucalyptus globulus wood samples were submitted to
fractionation with 95% acetic-acid solutions catalysed by
small quantities of HCI. Experiments were performed at
the normal boiling temperature using a liquor/wood
ratio equal to lO g/g. The effects of treatment time (0-180
min) and catalyst concentration (0-0"2%) on pulp yield,
sofid residue composition and cooking liquor composi-
tion were determined. Pulp yields in the range
51.5-90"6% were obtained. Extensive delignification of
wood was achieved under a variety of operational condi-
tions, leading to sofid residues with less than 4% lignin.
The lignin removal was modelled kinetically as the con-
tribution of two parallel, first-order reactions. Pulps con-
taining over 90% polysaccharides and
glucan/polysaccharide ratios higher than 0"95 were
obtained under selected conditions. Pentoses and
furfural were identified as hemicellulose hydrolysis
products. The kinetics of hemicellulose saccharification
was modelled assuming two sequential, first-order,
irreversible reactions. The maximum pentose recovery
accounted for 37% of the potential amount. Under the
conditions leading to optimum pentose recoveries, good
delignification was achieved. Furfural concentrations up
to 4"3 g/l were obtained under the severest experimental
conditions studied.
Keywords: Acetic acid pulping, organosolvent delignifi-
cation, acetosolv processing, hemicellulose hydrolysis.
INTRODUCTION
The processing of lignocellulosic materials by
organosolvents provides an interesting alternative to
conventional chemical processes. A variety of organo-
solvents (including alcohols, ketones, amines, glycols,
esters, peroxides and acids) has been used to perform
the fractionation of biomass into its main constituents.
Organosolv-based processes allow the selective
separation and recovery of cellulose, hemicelluloses
Bioresource Technology 0960-8524/93/S06.00 © 1993
Elsevier Science Publishers Ltd, England. Printed in Great
Britain
233
and lignin (untouched or as degradation products; see
Davis et al., 1986; Young & Davis, 1986; Johansson et
al., 1987; Kin, 1990; Shukry et al., 1992; V~izquez et
al., 1992), which can be convened by chemical or bio-
technological means into a variety of chemicals.
Acetic-acid media (with or without catalyst addition)
have been employed for the fractionation of several
lignocellulosics, including hardwoods, softwoods and
bagasse (Davis et al., 1986; Nimz & Casten, 1986;
Young & Davis, 1986; Kin, 1990; Shukry et al., 1992;
V~izquez et al., 1992). In the presence of small amounts
of strong mineral acids (which act as catalysts), exten-
sive and selective delignification of raw materials can
be achieved by acetic acid solutions under mild experi-
mental conditions. During the fractionation treatments,
the hemicellulose fraction is hydrolysed, whereas cellu-
lose remains as a solid residue.
In an earlier work (V~quez et al., 1992), the authors
studied the delignification of Eucalyptus globulus by
HCl-catalysed acetic-acid solutions. The effects of
acetic-acid concentration, catalyst concentration and
reaction time on the pulp yield and solid residue com-
position were assessed using empirical models. Under
selected experimental conditions, eucalypt wood was
extensively delignified and the hemicelluloses were
selectively hydrolysed at pulp yields in the vicinity of
50%.
Further studies demonstrated the possibility of
improving the above results (including both delignifica-
tion extent and pulp yield) using shorter reaction times
than those previously studied. Additionally, the influ-
ence of the operational conditions on the type and
amount of hemicellulose hydrolysis products was
included in this study, in order to provide an evaluation
of the catalysed acetic-acid process as treatment for
biomass fractionation.
This work deals on the optimization of the catalysed
acetic-acid processing of Eucalyptus globulus wood.
The main objective was to provide further information
on the potentiality of acetic-acid-based processes for
performing an extensive and selective separation of the
main biomass constituents, leading to fractions which
could be used as chemical intermediates. Delignifica-
tion and hemicellulose hydrolysis were accomplished
in a single step. Obtaining marketable products (xylose
234 J.C Paraj6, J.L. Alonso, D. V6zquez
or furfural) from hemicelluloses was considered.
Experiments were performed at the normal boiling
temperature using a liquor/wood ratio of 10 g/g. Since
high acetic acid concentration favours the overall pro-
cess (V~quez et al., 1992), 95% acetic acid solutions
were chosen as delignification media. The operational
variables considered were reaction time (in the range
0-180 min) and catalyst concentration (in the range
0-0"2% HC1). Pulp yield, solid residue composition
and hemicellulose hydrolysis products (glucose,
pentoses and furfural) were considered as experimental
variables.
METHODS
Raw material
Eucalyptus globulus wood samples were collected in a
local pulp mill (ENCE, Pontevedra), milled and
screened to select the fraction of particles with a size
between 0"25 and 1 mm. The wood particles were air-
dried, homogenised in a single lot to avoid differences
in composition, and stored.
Analysis of wood
Aliquots from the homogenised wood lot were sub-
mitted to moisture determination and to quantitative
acid hydrolysis with 72% sulphuric acid following
standard methods (Browning, 1967; Vfizquez et al.,
1987). The solid residue after hydrolysis was con-
sidered as Klason lignin. The monosaccharides con-
tained in hydrolysates were determined by
spectrophotometric or HPLC methods (see below).
Processing of wood samples
Wood chips and acetic-acid-water solutions were
placed in Erlenmeyer flasks and heated to the normal
boiling temperature. Then, concentrated HC1 solutions
were added to the desired concentration and the flasks
were maintained under reflux at atmospheric pressure.
The liquor/wood ratio used in experiments was 10 g/g.
It was assumed that both prehydrolysis and delignifica-
tion started when the catalyst was added. The moisture
content of wood (10%) was considered as water in the
material balances. At the end of delignification, the
solid residue was recovered by filtration, washed with
acetone, air-dried and submitted to quantitative
saccharification. The pulping liquors were mixed with
water (1:10) to precipitate the lignin fraction, and the
solid residues were removed by centrifugation.
Aliquots from supernatants were filtered through 0.45
/~m membranes and analysed by HPLC.
HPLC analysis of monosaccharides and furfural
Samples from quantitative acid hydrolyses or from
pulping liquors were analysed for glucose, pentoses
(xylose and arabinose) and furfural using a Waters
HPLC with refractive-index detector. The operational
conditions were: columns Shodex SH1011 (two);
mobile phase, H2SO 4 0"015 m; column temperature,
90°C; flow rate, 1 ml/min.
Fitting of data
The experimental data were fitted to theoretical
models by non-linear regression using commercial
software (TableCurve from Jandel Scientific, Corta
Madera, CA, USA).
RESULTS AND DISCUSSION
Raw material composition
The wood lot used for experimentation contained
23-3% Klason lignin and 62' 3% polysaccharides. The
glucan fraction of polysaccharides accounted for the
42.3 wt % of wood. These values are in agreement with
previously reported results (Paraj6 et al., 1992;
Vfizquez et al., 1992).
The hemicellulose fraction of eucalypt wood is
mainly composed of xylose, followed by glucose and
arabinose. The HPLC columns used for analysis
separate glucose and arabinose as individual peaks,
whereas galactose, mannose and xylose are eluted in a
single peak. Since the relative proportion of mannose
and galactose polymers in hemicelluloses is quite low
(David et al., 1988) and the xylose/arabinose ratio is
high (within the range 10-15 g/g in all the experiments
performed), the authors have preferred to report all the
non-glucose, hemicellulosic sugars as pentoses; but it
must be taken into account that at least 90% of these
pentoses were xylose.
Operational conditions used in fractionation
experiments
In an earlier work (Vfizquez et al., 1992), the authors
studied the delignification of Eucalyptus globulus wood
by HCl-catalysed acetic acid solutions. Empirical
models were developed to assess the effects of acetic
acid concentration (within the range 75-95%), HCI
concentration (0-0"2%) and reaction time (5-6 h) on
both pulp yield and solid residue composition. All the
experiments were carried out at the normal boiling
point of solutions using liquor/wood ratio of 10 g/g.
T h e experimental variables depended mainly on the
catalyst concentration used, whereas high acetic acid
concentrations improved the reaction selectivity. The
experimental variables were not significantly affected
by the reaction time in the range considered. Using
0.15% HC1 and 95% acetic-acid solutions, the models
predicted solid residues with 6"6% lignin, 87.4% poly-
saccharide and 0-928 glucan/polysaccharide ratio at
45% pulp yield.
Additional studies demonstrated that several factors
involved in the fractionation process could be
improved by using shorter reaction times, including
pulp yields, degree of delignification and recovery of
valuable hemicellulose hydrolysis products.
This paper reports on the additional work per-
formed to provide further insight on the chemical pro-
cessing of eucalypt wood using HCl-catalysed acetic
acid solutions. Experiments were performed using the
same temperature and liquor/wood ratio previously

studied (V~quez et aL, 1992). In order to improve the
selectivity of fractionation, delignification media con-
taining 95% acetic acid were used in all the cases con-
sidered. The operational variables studied were
catalyst concentration (in the range 0-0.2% HCI) and
reaction time (0-180 min). Pulp yield, solid residue
composition and cooking liquor composition were
measured. Figure 1 summarises the whole processing
of samples, including both fractionation and analysis
stages.
Pulp yield
The weight loss of wood during fractionation is
mainly caused by the combined effect of extractives
removal, delignification and carbohydrate hydrolysis.
Table 1 shows the experimental conditions assayed and
the results obtained. Pulp yields in the range
90-6-51" 5% were obtained in the various experiments.
Even in the experiments performed under the severest
operational conditions studied (120-180 min reaction
time, 0" 15-0.20% catalyst concentration), good pulp
yields (within the range 51 "5-53.9%) were obtained.
The kinetics of weight loss followed general trends
similar to reported results (Young & Davis, 1986;
Davis et aL, 1986). The variation pattern of data listed
in Table 1 suggests two sequential stages with different
rates, the first being faster than the second. In experi-
ments performed with catalyst concentrations higher
than 0" 10%, the weight loss observed after 60 min of
Wood s a m p l e s
Acetic acid/ ~D
H20/HCI ELIGNIFICATIO
~ Suspension
Solid residue ~ FILTRATIONI
Acetone ~ WASHING
I ~
r Solid r e s i d u e
~i~quotAIR DRYING~----~ tl2so~
1 Aliquot 2~
(To m o i s t u r e
and yield
]SACCHARI
[
FICATI/~-~]
ON
determination ) (lignin)
Solid I
residue~
[OVENDRYING]
K l a s o n Iignin
Fig. 1. Scheme of the experimental work performed.
A cetosolv processing of wood 235
reaction time accounted for over 86% of the values
determined for samples treated for 180 min.
For a given reaction time, an increase in catalyst con-
centration caused a decrease in pulp yield. This behav-
iour is in agreement with the data obatined for
delignification and carbohydrate hydrolysis (see
below). Significant decreases in pulp yield were
observed when the catalyst concentration was
increased. In experiments lasting 180 min, an increase
in HCI concentration from 0"05 to 0-10% caused a
marked decrease in yield (from 62.3 to 55.4%, see
experiments 6 and 12 of Table 1 ); but when the catalyst
concentration was increased from 0"15 to 0-20%,
minor variations in pulp yield were observed (from
52.4 to 51"5%, see experiments 18 and 24 of Table 1).
This fact suggests that under the experimental condi-
tions assayed, a practical limit for yield in the vicinity of
50% exists.
In comparison with reported results, lower yields
(48-48" 5%) were obtained for eucalypt wood in treat-
ments with HCl-catalysed acetic acid lasting 5-6 h
(V~izquez et aL, 1992). The acetic-acid pulping of
woods from other tree species (such as beech, aspen or
spruce) gave yields in good agreement with the values
found in this work (Davis et aL, 1986; Young & Davis,
1986; Kin, 1990).
Lignincontentanddelignificationkinetics
Table 1 lists the lignin content of solid residues
obtained under the conditions studied. It can be noted
Liquors
Washing liquors ILIGNIN PRECIPITATION ]4 Water
Suspension
I CENTR|FUGATION I
Liquors
Solid residue Supernatant
(to m o n o s a e c h a r i d e
~' and furfural d e t e r m i n a t i o n )
~
NEUTRALIZATION Ba(OH) 2
J liquot 1
~r ,
(To m o n o s n c c h a r i d e d e t e r m i n a t i o n )
r~_.~ Aliquot 2 (To glucose determination)
236 J.C. Paraj6, J.L. Alonso, D. V6zquez

Table 1. Operational conditions studied and experimental results obtained for yield and pulp composition

Experiment Operational variables Experimental variables

HCI (%) Time (min) Yield (%) Lignin (%) Polysaccharide (%) GPR"

1 0.05 15 90"6 18"3 67.2 0.758

2 0.05 30 81.7 16.1 74'1 0.794
3 0-05 60 73"2 15"5 74"8 0.820
4 0.05 90 69-1 13"0 80-0 0.874
5 0.05 120 62.7 8"3 83"2 0.888
6 0.05 180 62.3 6"8 82-1 0.881
7 0-10 15 86'5 17"7 69"2 0"800
8 0.10 30 66"8 13-3 79'3 0"801
9 0.10 60 61.1 9"6 84"8 0.859
10 0.10 90 56.8 8"2 88.0 0-892
11 0.10 120 55.8 6.1 91.1 0"910
12 0-10 180 55-4 5.0 89"0 0"901
13 0.15 15 73.5 13-7 73"6 0.836
14 0.15 30 63"3 10.7 85"6 0"896
15 0.15 60 57.8 6"2 86.6 0.906
16 0-15 90 55"1 5"6 89.7 0.948
17 0.15 120 53-9 3.7 91.3 0-951
18 0.15 180 52.4 3'9 90"7 0"926
19 0.20 15 72"5 13"6 73.8 0"842
20 0.20 30 62.2 8"8 84.9 0"888
21 0.20 60 56.2 4.4 90.2 0-917
22 0-20 90 54.9 3-1 89.1 0"948
23 0.20 120 53.4 3"3 90-8 0"964
24 0.20 180 51"5 3'5 89.4 0"911
"GPR, Glucan/polysaccharide ratio.

that extensive delignification can be achieved under a
variety of experimental conditions. The lowest lignin
content obtained (3" 1 wt % of solid, experiment 22) is
less than 50% of the minimum lignin content reported
in our previous work using longer reaction times
(V~izquez et al., 1992). This fact is thought to be caused
by lignin repolymerization reactions. In fact, the
analysis of data corresponding to experiments 17, 18,
22, 23 and 24 suggests that repolymerisation occurred
even under the mild conditions considered in this
work. Extensive repolymerisation has been reported in
acid-catalysed delignification of beechwood (Kin,
1990).
The kinetic pattern of delignification is closely
related to that of weight loss previously discussed. An
initial, fast stage (bulk delignification) is followed by a
slower residual delignification stage. Similar behaviour
has been reported for both Kraft- and organosolv-
processing of wood (Cho & Sarkanen, 1985; Tirtowi-
djojo et al., 1988). An interpretation of the
experimental results can be provided by a kinetic
model assuming the presence in wood of two lignin
fractions, a fast-reacting fraction (L f) and slow-reacting
fraction (Ls), which are depolymerised at different
rates to give soluble lignin-fragments (L0); whereas the
depolymerised lignin L 0 can undergo repolymerisation
reactions to give insoluble, repolymerised lignin (Lr).
Since the repolymerisation effects have a limited
importance under the experimental conditions studied,
the data of Table 1 can be correlated according to the
following scheme:
Lf
Ld
Z
Ls
Assuming first-order kinetics for both reactions, it can
be shown that:
P R L = y L C =a'e-k~'+ (1 - a)e -k~'
LCo
where PRL is the percentage of residual lignin in wood,
Y is the pulp yield; LC and LCo are the lignin contents
of treated and untreated wood, respectively; a is the
fraction of fast-reacting lignin (defined as L f/[L f + L s]);
t is the reaction time, and kf and k s are first-order
kinetic coefficients for the fast- and slow-reacting lignin
fractions.
Table 2 lists the values of kf, k s and a obtained by
nonlinear regression of a PRL/time series of data
corresponding to a given HCI concentration, as well as
the values obtained for the statistical parameters ra and
F measuring the correlation and significance of models.
Figure 2 allows a comparison between experimental
results of PRL (calculated from the data listed in Table
1) and the model predictions for the various catalyst
concentration used. The close agreement between
 Acetosolv processing of wood 237

/
Table 2. Regression and statistical parameters obtained in
the modelling of wood delignification qgO
tu
>.
HCl a kf ks r2 F
concentration (min- ]) (min- 1) ~, 80.
(%) rl

70
0"05 0'244 0"120 0"008 0"988 166
...'"
0"10 0"765 0"043 0"004 0"995 410
0"15 0"756 0"080 0"007 0"997 746 60
ii~ ' A " . . J l , , r•.
0"20 0"908 0"065 0"001 0"999 2527
50
0 2 4 6 8 10 12 14 16 18 20

L I G N I N C O N T E N T (%)

Fig. 3. Interrelationship between pulp yield and operational

_z 80
Z
L~
_J
~ 60
-'1
a importance on the polysaccharide content. Samples
uJ
r~ 40
ZI..- 20 O 0-10-0"20% HCI and 120 min reaction time. When
uJ ,
0 :
w i
0 20 40 60 80 100 120
TIME (min)
Fig. 2. Experimental and predicted dependence of the
percent of residual lignin in wood samples (PRL) on the
operational variables studied (A ,0"05% HCI; o, 0.10% HCI;
s, 0.15% HC1; , , 0.20% HCI)
experimental and predicted data confirms the reliabil-
ity of the above equation in describing the whole
delignification process.
Figure 3 shows the interrelationship between pulp
yields and lignin contents of samples ~treated under the
conditions listed in Table 1. Experiments performed
using 0-05% catalyst show a different behaviour to
those carried out with 0" 10-0"20% catalyst. Pulps with
6"8% residual lignin can be obtained at 62-3% pulp
yield using low HCI concentrations (see experiment 6),
whereas a similar lignin content was obtained at shorter
reaction times in trials performed with 0-10% catalyst,
but with decreased pulp yield (55.8% in experiment
11).
Polysaccharide and glucan content
The polysaccharide content of solid residues from
the fractionation process depended on two factors:
delignification (which caused an enrichment of treated
samples in polysaccharides) and carbohydrate-
hydrolysis reactions (mainly hemicellulose hydrolysis)
which led to pulps with improved cellulose contents.
The data listed in Table 1 show that for a given
reaction time significant changes in polysaccharide
content were obtained when the catalyst concentration
was increased from 0-05 to 0" 1%. Further increases in
catalyst concentration caused effects of decreasing
variables (A, 0.05% HC1; o, 0'10% HCI; n, 0-15% HCI; Y,
0.20% HCI)
with polysaccharide contents in the vicinity of 91%
were obtained in experiments performed with
the reaction time was increased from 120 to 180 min,
small decreases in the polysaccharide content were
140 160 180 observed. The lower polysaccharide content reported
for delignification treatments lasting 5-6 h (87-5-84" 5)
can be explained in part by lignin repolymerisation
reactions.
The glucan/polysaccharide ratio (GPR) of solid
residues provides information about the behaviour of
hemicelluloses during the chemical processing of
wood. The value of GPR determined for untreated
wood (0-675) increased to values in the range
0"758-0"964 for delignified solid residues. Both the
kinetics and the extent of hemicellulose hydrolysis
increased when higher catalyst concentrations were
used (see Table 1). The GPR values increased steadily
with time in the range 0-120 min for all the catalyst
concentrations assayed. Reaction times higher than
120 min resulted in decreased values of GPR. This
behaviour, which is difficult to explain from a theoreti-
cal viewpoint, could be related to reversion reactions of
sugars and/or experimental errors. In fact, glucan
recoveries after fractionation slightly higher than 100%
can be calculated from the experimental results.
Reported results on the acetic treatment of wood are in
good agreement with the values of GPR determined in
this work (Kin, 1990; V~izquez et al., 1992).
Hemiceilulose hydrolysis
The recovery of hemicellulose reaction products as
valuable chemicals (such as sugars or furfural) is an
important factor affecting the economic feasibility of
biomass fractionation processes. The HPLC analysis of
pulping liquors (after precipitation of the lignin fraction
by water addition) provided useful information on the
type and amount of marketable compounds generated
from hemicelluloses.
Xylose was the main product of hemicellulose
hydrolysis. Other sugars (arabinose and glucose) were
238 J.C. Paraj6, J.L. Alonso, D. V~zquez

also identified in chromatograms, but their relative model (Saeman, 1945):

concentrations were low. Since the resolution of xylose Pentosan ~ Pentoses ~ Decomposition products
and arabinose was poor owing to the large proportion
of xylose, both compounds were integrated as a single The equation giving the dependence of the pentose
peak, and the whole amount determined is referred to concentration (Cp) with time derived from the above
as 'pentoses'. The glucose concentrations determined reactions assuming first-order kinetics, is:
in the various experiments performed (0-0.63 g/l)
were not significant for the objectives of this study.
In experiments performed under strong operational
Cp=CpP'k~kl " ( e - k l / - - e

conditions, significant amounts of furfural (produced

by pentose decomposition) were observed. Furfural has
been previously reported to be a byproduct of the
acetolysis of beechwood (Kin, 1990). The pattern of
hemicellulose degradation (pentosan hydrolysis to
sugars, followed by sugar decomposition) is the same
as that reported for the acid-catalysed hydrolysis of
hemiceiluloses in aqueous media (Conner, 1984;
Ranganathan et al., 1985; Maloney et al., 1986; Naka-
gawa et al., 1986; Kim & Lee, 1987), but the reaction
rate of the reaction was quite different in of the present
authors' case.
Table 3 includes the experimental values of pentose
concentration determined under the conditions
assayed. In all the series of data, the pentose concentra-
tion reach a maximum. Both the maximum pentose
concentration and the time necessary to achieve this
maximum depended on the catalyst concentration
used. Since this behaviour was in qualitative agreement
with the kinetic pattern described above, the data were
fitted according to the well known Saeman's kinetic
where Cpp is the potential pentose concentration corre-
sponding to theoretical conversion of pentosan into
sugars, calculated from material balances; and k~ and
k 2 are the first-order coefficients for pentosan hydroly-
sis and pentose degradation, respectively.
Table 4 lists the kinetic coefficients obtained by
regression as well as the r 2 and F statistical parameters.
Figure 4 shows the agreement between experimental
and calculated data of pentose concentration. The
maximum pentose concentration (Cpmax)can be calcu-
lated using the equation:
kll(k2/k2-kl)
Cpmax=Cpp'~k22)
The values of Cpmaxcalculated from the data listed in
Table 4 varied in a narrow range (7"3 - 7"5 g/l), corre-
sponding to 3 6 . 5 - 37.5% of the potential concentra-
tion (?pp.

Table 4. Kinetic coefficients and statistical parameters

obtained in the modelling of hemiceilulose hydrolysis
Table 3. Pentose concentration (Cp) determined in pulping
liquors HCI k1 k2 R2 F
concentration (min- t) (min- l)
Experiment Cp
(g/litre) 0-05 0.0050 0-0051 0-976 200
0-10 0.0130 0"0132 0"945 86
1 1"74 0"15 0.0201 0-0202 0"929 65
2 1"81 0"20 0.220 0-0210 0.976 206
3 4"32
4 5"88
5 7"11
6 6-94
A
7 1"83
8 6"10 d~
9 7-11 Z 6-
10 7"22 _o
11 6-62
12 4"23 z
LtJ 4-
0
13 5"79 Z
C,
14 6"02
15 6"75
16 5"78
17 4-74
18 2"20
19 4"79 0 ~

0
i

20
i

40
i

60 80
i ,

100
i , i

120
, i

140
• i

160 180
20 7"32 TIME (rnin)
21 6"72
22 5-33 Fig. 4. Experimental and predicted dependence of the
23 4"38 pentose concentration in pulping fiquors (C_) on temperature
"
24 2"10 and catalyst concentrataon ( • ,0"05 0YoHCI,• Pe, 0"10 0YoHCI,• m,
0.15% HCI; T, 0"20% HCI)
 A cetosoIv processing of wood 239

Under the experimental conditions which led to It can be observed that the whole amount obtained by
maximum pentose concentration, samples with addition of the pentose concentration in liquid phase to
80-88% delignification can be obtained (see Fig. 2). the potential pentose concentration corresponding to
This compatibility of conditions for hemicellulose the pentosan remaining in solid phase and the concen-
hydrolysis and delignification reactions is a favourable tration of pentoses necessary to give the furfural con-
feature of the studied process. centration observed assuming theoretical yield, is far
Furfural was the main product of pentose degrada- below the value of the potential pentose concentration
tion. Figure 5 shows the dependence of the furfural Cpp in all the experiments performed (see Table 5).
concentration on the operational variables considered. This finding can be caused by several factors such as
formation of water-soluble xylose oligomers, genera-
tion of reversion products from sugars in solution (in
5 the same way as found for carbohydrate hydrolysis in
--I
aqueous media, see Mok et al., 1992), formation of
z
0
4 condensation products from furfural, and generation of
acetic-acid soluble, water-insoluble xylose polymers
rr
I--
z
3 which are associated with the phenolic fraction and
uJ
:z
which coprecipitate with lignin after water addition
0 2 (see Fig. 1 ).
el-

n-"
ACKNOWLEDGEMENT
o
20 40 60 80 100 120 140 160 180 The authors are grateful to 'Xunta de Galicia' for the
TIME (rain) financial support of this work (Proj. X U G A 3 8 3 0 2
Fig. 5. Influence of temperature and catalyst concentration A91).
on the furfural concentration (& ,0-05% HCI; o, 0" 10% HCI;
", 0" 15% HCI; I1', 0"20% HC1)
REFERENCES

Table 5. Pentosan and pentosan reaction products deter- Browning, B.L. (1967). Methods of Wood Chemistry. John
mined in experiments (results expressed as percent of the Wiley, New York.
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measurements in the Kraft process. Paperi ja Puu, 67,
Experiment Treatment liquors Solid Total 121-4.
residue Conner, A.H. (1984). Kinetic modeling of hardwood pre-
Pentoses Furfural a Pentosan ~ hydrolysis. Part I. Xylan removal by water prehydrolysis.
Wood Fiber Sci., 16, 268-277.
1 8.7 0 73"6 82"3 David, C., Fornassier, R., Lejong, W. & Vanlautem, N.
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