Journal of Chemical Technology and Biotechnology J Chem Technol Biotechnol 74:1101±1109 (1999)

Mild autohydrolysis: an environmentally

friendly technology for xylooligosaccharide
production from wood
Gil Garrote, Herminia Domı́nguez and Juan Carlos Parajó*
Department of Chemical Engineering, University of Vigo (Campus Ourense), Edificio Politécnico, As Lagoas, 32004 Ourense, Spain

Abstract: Eucalyptus globulus wood samples were subjected to hydrothermal treatments under mild
operational conditions (145±190° C, liquor to solid ratio 6±10 g gÿ1, reaction times up to 7.5 h). Residual
xylan, xylooligosaccharides, other sugars, furfural, glucan and lignin contents were determined.
Negligible effects were caused by hydrothermal treatments on both cellulose and lignin. Kinetic models
were developed which describe the hydrolysis of hemicelluloses. Xylan degradation, xylooligosacchar-
ide and xylose generation, and xylose dehydration to furfural were accurately described by models
based on pseudohomogeneous, ®rst-order kinetics with Arrhenius-type temperature dependence.
These models are useful for a technical evaluation of this environmentally friendly technology.
# 1999 Society of Chemical Industry

Keywords: autohydrolysis; Eucalyptus globulus; hydrothermal treatments; xylan; xylooligosaccharides; wood

1 INTRODUCTION both water- and steam-based processes. Other bene®ts

Current technologies for the chemical utilization of
wood use a `destructive strategy' to obtain a single,
highly pure, component (cellulose). Other fractions
are either wasted or used for power generation that
gives low added-value and contributes to atmospheric
carbon dioxide pollution. The `biomass re®ning'
philosophy1 provides an alternative approach for
utilization of lignocellulosic materials (LCM). LCM
can be `fractionated' into their main components by
sequential treatments to give separate streams that
may be used for different product applications, so
maximizing the bene®ts of a renewable and complex
resource of increasing importance.
The main problem in `biomass re®ning' is that the
major constituents of LCM (cellulose, hemicelluloses
and lignin) cannot be simultaneously isolated as
polymers and several processes involve the degrada-
tion of at least one of the polymers. One approach is
initially to treat the LCM with a hemicellulose-
degrading step such as prehydrolysis or autohydroly-
sis, leaving both cellulose and lignin as essentially
undegraded polymers. Autohydrolysis uses water and
LCM as the only reagents. Hydronium ions from both
water and in situ-generated compounds (eg acetic,
uronic and phenolic acids) catalyse the hemicellulose
depolymerization. Hydrothermal (or autohydrolysis)
technology covers a range of treatments, including
of autohydrolysis are that corrosion problems are
limited, no sludges are generated, capital and opera-
tional costs are low,2 and cellulose is not signi®cantly
degraded under normal operating conditions.
Autohydrolysis has a wide range of applications,3
including: (i) fractionation or pulping processes, in
which there is removal of hemicelluloses with selectiv-
ity towards cellulose degradation and splitting the a
and b aryl ether bonds of lignin,4,5 (ii) de®bration for
®breboard production, in processes using high
pressure steam, and (iii) as a pretreatment for the
enzymatic hydrolysis of cellulose.6,7
This study focused on the degradation kinetics of
Eucalyptus globulus wood hemicellulose, in order to
assess which operational conditions produce the
maximum concentration of sugar oligomers. Since
xylan is the main component of Eucalyptus globulus
wood hemicelluloses, xylooligomers and xylose are the
main products obtained in hydrothermal treatments of
this raw material. Sugar-degradation products (such as
furfural or hydroxymethylfurfural) and acetic acid
(generated from acetyl groups) can also appear in the
reaction media.
Xylooligomers are currently used as novel sweet-
eners in food additives.8,9 Health applications of
indigestible oligosaccharides have been recently re-
ported in this ®eld: for example, Imaizumi et al 10

* Correspondence to: Juan Carlos Parajó, Department of Chemical Engineering, University of Vigo (Campus Ourense), Edificio Politécnico,
As Lagoas, 32004 Ourense, Spain
E-mail: jcparajo@uvigo.es
Contract/grant sponsor: Xunta de Galicia; contract/grant number: XUGA 38303A98
(Received 14 January 1999; revised version received 5 July 1999; accepted 12 July 1999)

# 1999 Society of Chemical Industry. J Chem Technol Biotechnol 0268±2575/99/$17.50 1101

G Garrote, H DomõÂnguez, J C ParajoÂ
found that a xylooligosaccharide-based diet reduced
the blood concentrations of sugars and lipids on
diabetic rats, and Toyoda et al 11 reported that xylo-
oligosaccharides improved calcium absorption by rats.
The phagocytic activity of neutrophils in mice was
enhanced by either oral or intraperitoneal administra-
tion of xylooligosaccharides,8 and increased resistance
of mice towards infection by Clostridium dif®cile caused
by xylo- and fructo-oligosaccharides was reported by
May et al.12 Improvements in the gastrointestinal
health of rats caused by a xylooligosaccharide-contain-
ing diet have been reported by Campbell et al.13 In
relation to human health, xylooligosaccharides selec-
tively enhance the growth of bi®dobacteria, thus
promoting a favourable intestinal environment.14,15
In order to explore the possibility of obtaining
xylooligosaccharides in high yield from Eucalyptus
wood, a series of hydrothermal treatments was carried
out. The main operational variables governing the
autohydrolysis process (temperature, reaction time
and liquor/solid ratio) were varied in the ranges 145±
190 °C, 0±7.5 h and 6±10 g gÿ1, respectively. In order
to assess the viability of an integrated process for wood
utilization, the composition of both solid residues and
liquors was determined in each assay. The experi-
mental data regarding both xylan and xylan-derived
products were ®tted to a kinetic model based on
consecutive, pseudohomogeneous, ®rst-order reac-
tions. This model allowed a satisfactory interpretation
of the time courses of xylan, xylan-degradation
products (xylooligosaccharides and xylose) and a
pentose-dehydration product (furfural).
2 MATERIALS AND METHODS
2.1 Raw material
Eucalyptus globulus wood samples from a local pulp
factory were milled to pass a 8 mm screen, since in
preliminary studies no diffusional limitations were
observed for this particle size. Samples were air-dried,
homogenized in a single lot to avoid differences in
compositions among aliquots, and stored.
2.2 Analysis of wood
Aliquots from the homogenized wood lot were sub-
jected to moisture determination (drying at 105 °C to
constant weight) and to quantitative acid hydrolysis
following standard methods.16 The solid residue after
hydrolysis was recovered by ®ltration (number 3
porosity glass ®lter) and considered as Klason lignin.
The monosaccharides and acetic acid contained in the
hydrolysates were determined by HPLC, as reported
elsewhere.17
2.3 Hydrothermal processing of wood samples
Wood chips and water were mixed in the desired
proportions and treated in a 600 cm3 stainless steel
reactor (Parr Instruments Company, Moline, Illinois,
USA) with PID temperature control. The moisture
content of wood was considered as water in the
1102
material balances. The reaction media were heated to
the desired temperature (15±20 min). Since a portion
of the substrate may have reacted during the period of
heating, only data corresponding to the isothermal
part of the reaction were used for kinetic modelling.
Time zero was considered to be the beginning of the
isothermal stage.
2.4 Analysis of solid residues and liquors from
hydrothermal treatments
After treatment, solid residues were recovered by
®ltration, washed with water and air-dried. The
samples subjected to analysis were previously milled
to a particle size <0.5 mm in order to ensure
quantitative polysaccharide hydrolysis. Milled solid
residues from treatments were assayed for cellulose,
hemicellulose and lignin using the same methods as for
raw wood analysis. A sample of the liquors was ®ltered
through 0.45 mm membranes and used for direct
HPLC determination of monosaccharides, furfural,
hydroxymethylfurfural and acetic acid. A second
sample of liquors (20 cm3) was subjected to quantita-
tive posthydrolysis (with 4 weight percent H2SO4 at
121 °C for 60 min) before HPLC analysis. The
increase in monosaccharide concentration caused by
posthydrolysis provided a measure of the oligomer
concentration.18
2.5 Fitting of data
The experimental data were ®tted to the proposed
kinetic models by minimization of the sum of squares
using commercial software with a built-in optimization
routine based on the Newton's method.
3 RESULTS AND DISCUSION
3.1 Operational conditions and definition of
variables
The operational variables considered in this work were
temperature (T, °C), reaction time (t, h) and liquor to
solid ratio (LSR, kg liquor kgÿ1 oven-dry wood). The
variation ranges explored for T and LSR were 145±
190 °C and 6±10 g liquor kgÿ1 oven-dry wood (see
headings of Tables 1±6). The maximum reaction times
were selected to allow a complete observation of the
time course of xylooligosaccharide concentration. The
effects caused by using different liquor/solid ratios
were explored at a single temperature because of the
limited in¯uence of this variable (see below). The
dependent variables selected and their nomenclature
are as follows:
(a) Variable utilized to measure the degree of solid
phase recovery:
(a.1) SY = solid residue yield, g solid recovered
after treatments per 100 g untreated wood,
oven dry basis (odb)
(b) Variables used to measure the composition of
raw and treated wood samples:
J Chem Technol Biotechnol 74:1101±1109 (1999)

(b.1) %Gn = glucan content of treated samples,
g glucan per 100 g treated wood, odb
(b.2) %Xn = xylan content of treated samples, g
xylan per 100 g treated wood, odb
(b.3) %Arn = araban content of treated samples,
g araban per 100 g treated wood, odb
(b.4) %Acl = acetyl content of treated samples, g
acetyl per 100 g treated wood, odb
(b.5) %Lg = lignin content of treated samples, g
lignin per 100 g treated wood, odb
(c) Variables used to measure the composition of
liquors:
(c.1) XoC = xylooligomer concentration, g xylo-
oligomers kgÿ1 liquor (xylooligomers ex-
pressed as xylose equivalent)
(c.2) XyC = xylose concentration, g xylose kgÿ1
liquor
(c.3) GlC = glucose concentration, g glucose
kgÿ1 liquor
(c.4) FuC = furfural concentration, g furfural
kgÿ1 liquor
(c.5) ArC = arabinose concentration, g arabi-
nose kgÿ1 liquor
(c.6) HmC = hydroxymethylfurfural concentra-
tion, g hydroxymethylfurfural kgÿ1 liquor
(c.7) AcC = acetic acic concentration, g acetic
acid kgÿ1 liquor
(d) Variables de®ned for calculation purposes:
(d.1) PRXn = percent of xylan remaining in
solid phase after treatments (calculated
with respect to the xylan contained in raw
wood)
(d.2) PRGn = percent of glucan remaining in
solid phase after treatments (calculated
with respect to the glucan contained in raw
wood)
(d.3) PRLg = percent of lignin remaining in solid
phase after treatments (calculated with
respect to the lignin contained in raw
wood)
The composition of the raw material (expressed in
terms of the variables de®ned in sections b.1 to b.5
with superscriptsRM), was: %GnRM = 46.3; %XnRM =
16.6; %ArnRM = 0.54; %Acl RM = 3.56; %LgRM = 22.9.
According to the above de®nitions, variables d.1 to
d.3 can be calculated as:
%Xn
SY
PRXn ˆ …1†
%XnRM
%Gn
SY
PRGn ˆ …2†
%GnRM
%Lg
SY
PRLg ˆ …3†
%Lg RM
The concentrations of xylooligomers, xylose and
furfural can be also expressed in terms of `equivalent
percents of the initial xylan' using the following
J Chem Technol Biotechnol 74:1101±1109 (1999)
Xylooligosaccharide production from wood
expressions:
 
SY
XoC
LSR ‡ 1 ÿ
10
100 132
OEP ˆ
…4†
%XnRM 150
 
SY
XyC
LSR ‡ 1 ÿ
10
100 132
XEP ˆ
…5†
%XnRM 150
 
SY
FuC
LSR ‡ 1 ÿ
10
100 132
FEP ˆ
…6†
%XnRM 96
where: OEP = equivalent oligomer percent (calculated
with respect to the xylan contained in raw wood);
XEP = equivalent xylose percent (calculated with
respect to the xylan contained in raw wood); FEP =
equivalent furfural percent (calculated with respect to
the xylan contained in raw wood); whereas the terms
(132/150) and (132/96) are the stoichiometric factors
giving the conversion of xylose or furfural into xylan,
respectively.
From the de®nition of PRXn (percent of xylan
remaining in solid phase after treatments), it can be
seen that this variable can be directly used for
measuring the time course of xylose polymers remain-
ing in solid phase on the same basis as variables OEP,
XEP and FEP.
3.2 Results obtained in hydrothermal treatments
Tables 1±6 show the experimental data of the variables
de®ned in items a.1 to c.7 corresponding to the various
assays performed.
Qualitative analysis of the experimental results listed
in Tables 1±6 shows that the highest proportion of the
initial xylan recovered as soluble saccharides (includ-
ing xylose and xylooligomers) varied from 71.5% (in
experiment 1) up to 80.1% (in experiment 6)
(calculated as the sum of OEP and XEP, de®ned in
eqns (4) and (5) respectively). The proportion of xylan
recovered as soluble saccharides was slightly increased
with increased temperature, but the in¯uence of the
liquor/solid ratio was negligible (see data of experi-
ments 3, 4 and 5 obtained after to 0.6±1 h). This
®nding is in agreement with literature data.8,10
The proportions of xylan recovered as xylose and
xylooligomers were close to the data reported for the
autohydrolysis of southern red oak,19 Populus del-
toides20 and Populus tremuloides.3
The kinetics of degradation of araban in solid
residues (%Arn) was characterized by an initial fast-
degradation phase with a subsequent slower one.
Correspondingly, the arabinose concentration in
liquors (ArC ) increased signi®cantly in the initial
stages of the reaction to reach plateau concentrations
in the range 0.5±0.6 g dmÿ3.
As expected, the data concerning the amount of
glucan in solid residues (%Gn), showed that little
cellulose degradation was caused by hydrothermal
treatments. Considering the percent of glucan recov-
1103
G Garrote, H DomõÂnguez, J C ParajoÂ

Table 1. Experimental results of the operational variables a.1 to c.7 obtained in experiment 1, carried out at 145 °C with 8 kg water kgÿ1
oven-dried wood (see text for definition and units)

Time (h)

Variable 0 0.5 1 1.5 2 2.5 3.03 4 5 6 7.5

SY 98.8 96.4 92.5 87.3 84.2 80.3 78.3 76.9 75.4 73.3 74.0
%Gn 47.0 47.6 50.0 52.8 55.6 56.8 59.3 60.5 60.8 62.3 63.1
%Xn 16.4 15.4 13.8 11.7 10.4 8.74 7.97 7.17 6.22 5.94 5.39
%Arn 0.31 0.13 0.09 <0.01 0.05 <0.01 <0.01 <0.01 <0.01 <0.01 <0.01
%Acl 6.59 3.56 2.82 2.45 1.94 1.50 1.96 1.19 1.02 1.10 0.86
%Lg 22.2 23.2 22.9 24.3 25.0 28.2 26.3 27.3 27.6 28.5 nd
XoC 0.183 1.43 4.23 7.40 10.2 12.4 12.3 12.7 11.9 9.33 7.35
XyC 0.078 0.292 0.466 0.797 1.11 1.71 2.44 3.57 5.76 6.99 9.20
ArC 0.032 0.180 0.288 0.373 0.450 0.522 0.534 0.552 0.574 0.558 0.553
GlC 0.048 0.098 0.185 0.193 0.214 0.260 0.290 0.327 0.395 0.426 0.490
FuC 0.038 0.027 0.047 0.055 0.085 0.100 0.180 0.165 0.371 0.500 0.769
HmC <0.005 <0.005 <0.005 <0.005 <0.005 0.019 nd nd 0.036 0.050 0.062
AcC 0.080 0.211 0.268 0.518 0.693 1.02 1.17 1.50 2.13 2.51 3.03
nd: not determined.

Table 2. Experimental results of the operational variables a.1 to c.7 obtained in experiment 2, carried out at 160°C with 8 kg
water kgÿ1 oven-dried wood (see text for definition and units)

Time (h)

Variable 0 0.125 0.25 0.5 0.75 1 1.5 2.02 2.5 3

SY 97.7 95.3 91.8 84.6 78.1 78.3 74.4 74.9 72.8 72.5
%Gn 47.3 48.7 51.2 54.4 58.0 59.3 61.9 61.0 64.2 65.4
%Xn 16.7 15.0 14.2 12.2 8.41 7.28 5.96 5.07 5.01 4.72
%Arn 0.39 0.34 0.50 0.08 <0.01 0.21 0.06 0.07 <0.01 <0.01
%Acl 3.67 3.69 3.79 2.40 1.49 1.53 1.02 0.87 0.71 0.50
%Lg 22.4 23.3 23.2 26.0 26.9 27.7 30.4 31.2 30.6 30.5
XoC 0.326 1.24 3.56 8.91 12.73 13.38 12.47 10.72 8.62 6.74
XyC 0.025 0.196 0.352 0.858 1.52 2.63 5.04 7.31 8.66 10.0
ArC 0.064 0.165 0.281 0.445 0.470 0.559 0.618 0.636 0.597 0.599
GlC 0.018 0.085 0.122 0.215 0.204 0.373 0.439 0.501 0.542 0.583
FuC 0.000 0.000 0.021 0.024 0.104 0.194 0.312 0.522 0.770 1.10
HmC nd nd nd nd nd nd nd nd nd nd
AcC 0.108 0.087 0.224 0.433 0.617 0.977 1.53 2.16 2.52 3.01
nd: not determined.

Table 3. Experimental results of the operational variables a.1 to c.7 obtained in experiment 3, carried out at 175 °C with
6 kg water kgÿ1 oven-dried wood (see text for definition and units)

Time (min)

Variable 0 2.5 5.17 7.5 13 18.2 25 35 45 60

SY 99.2 96.6 92.1 88.3 81.7 79.1 77.1 75.7 75.3 74.6
%Gn 48.7 50.0 51.6 54.3 58.5 60.8 61.3 62.1 63.1 63.5
%Xn 16.4 15.8 13.5 11.8 8.68 7.37 5.78 5.27 4.98 4.05
%Arn nd nd nd nd nd nd nd nd nd nd
%Acl 4.28 3.36 3.37 2.98 2.52 1.73 1.14 1.46 1.27 0.79
%Lg 21.0 23.6 23.2 25.2 27.0 27.3 28.8 30.6 30.1 30.2
XoC 1.05 3.34 8.22 12.1 16.9 19.0 18.1 16.5 13.7 10.1
XyC 0.152 0.320 0.565 0.988 1.91 2.92 4.63 7.04 10.1 12.3
ArC 0.133 0.244 0.400 0.490 0.656 0.756 0.701 0.823 0.865 0.818
GlC 0.108 0.142 0.209 0.248 0.335 0.405 0.405 0.616 0.787 0.930
FuC 0.001 0.007 0.027 0.078 0.110 0.157 0.295 0.553 1.00 1.35
HmC <0.005 <0.005 0.005 0.015 0.017 0.021 0.043 0.058 0.100 0.151
AcC 0.086 0.150 0.268 0.404 0.623 0.936 1.38 1.90 2.80 3.65
nd: not determined.

1104 J Chem Technol Biotechnol 74:1101±1109 (1999)

 Xylooligosaccharide production from wood

Table 4. Experimental results of the operational variables a.1 to c.7 obtained in experiment 4, carried out at 175°C
with 8 kg water kgÿ1 oven-dried wood (see text for definition and units)

Time (min)

Variable 0 2.5 5 7.5 13 18.2 25 35 45.5 60

SY 98.7 94.8 89.9 85.7 80.3 77.8 75.7 74.3 73.7 72.6
%Gn 47.0 48.6 51.1 54.8 57.7 59.7 62.4 64.7 62.9 63.8
%Xn 16.5 15.3 13.7 11.8 8.79 6.78 6.01 5.19 4.64 3.99
%Arn nd nd nd nd nd nd nd nd nd nd
%Acl 3.66 3.19 3.19 2.36 2.27 1.73 1.05 0.91 0.91 0.73
%Lg 22.8 23.2 24.1 24.7 27.0 27.9 27.9 28.2 29.5 30.0
XoC 0.797 3.05 6.04 9.49 13.6 15.0 14.6 12.8 11.1 7.76
XyC 0.144 0.287 0.379 0.637 1.39 2.19 3.61 5.51 7.36 8.89
ArC 0.114 0.223 0.262 0.354 0.509 0.553 0.616 0.609 0.628 0.605
GlC 0.078 0.136 0.150 0.221 0.262 0.301 0.392 0.469 0.566 0.697
FuC 0.011 0.011 0.014 0.032 0.083 0.131 0.287 0.428 0.667 1.05
HmC <0.005 <0.005 0.005 0.007 0.012 0.024 0.028 0.045 0.074 0.101
AcC 0.108 0.153 0.184 0.259 0.474 0.708 1.05 1.50 2.04 2.57
nd: not determined.

Table 5. Experimental results of the operational variables a.1 to c.7 obtained in experiment 5, carried out at 175°C with
10 kg water kgÿ1 oven-dried wood (see text for definition and units)

Time (min)

Variable 0 2.5 5.08 7.5 13 18.2 25 35 45 60

SY 98.2 94.7 90.9 87.1 79.5 77.0 76.7 75.1 73.7 72.7
%Gn 47.3 48.4 50.9 53.4 57.3 59.5 59.9 60.0 62.6 62.8
%Xn 16.4 15.5 13.8 11.4 8.25 6.46 6.57 5.89 4.50 4.04
%Arn 0.34 0.29 0.19 0.19 0.12 0.11 0.10 0.09 <0.01 <0.01
%Acl 3.40 2.99 2.80 2.32 1.56 1.62 1.05 1.28 0.79 0.73
%Lg 22.8 22.5 23.6 24.4 26.4 27.0 27.4 27.9 28.1 29.1
XoC 0.651 2.10 4.95 8.03 10.6 11.9 11.5 10.5 8.65 6.74
XyC 0.101 0.183 0.346 0.536 1.03 1.83 2.70 4.33 5.77 7.59
ArC 0.094 0.154 0.226 0.291 0.380 0.461 0.483 0.518 0.527 0.530
GlC 0.063 0.099 0.141 0.164 0.197 0.262 0.298 0.412 0.466 0.564
FuC 0.002 0.004 0.008 0.026 0.055 0.104 0.215 0.306 0.538 0.843
HmC <0.005 <0.005 <0.005 0.007 0.008 0.011 0.023 0.037 0.061 0.093
AcC 0.060 0.091 0.155 0.231 0.365 0.555 0.794 1.11 1.56 2.22

Table 6. Experimental results of the operational variables a.1 to c.7 obtained in experiment 6, carried out at 190°C with
8 kg water kgÿ1 oven-dried wood (see text for definition and units)

Time (min)

Variable 0 1 2 4 6 9 12 16 20 24

SY 91.1 83.7 80.3 77.0 76.0 74.2 73.0 72.1 70.7 71.3
%Gn 50.9 54.6 57.6 58.8 60.9 62.2 62.0 64.3 66.4 66.6
%Xn 13.8 11.1 9.21 6.85 5.57 4.41 3.94 3.60 2.96 2.98
%Arn 0.11 0.10 <0.01 0.05 0.05 <0.01 <0.01 0.05 0.07 <0.01
%Acl 2.76 2.43 1.91 1.35 0.95 0.73 0.66 0.59 0.69 0.6
%Lg 24.3 23.3 24.6 27.0 27.3 28.8 28.7 28.8 28.5 30.4
XoC 4.26 8.91 12.5 15.0 15.8 14.1 13.8 11.4 9.07 7.16
XyC 0.429 0.669 0.968 1.82 2.69 4.02 5.08 7.22 8.27 8.84
ArC 0.228 0.360 0.460 0.555 0.590 0.608 0.625 0.659 0.675 0.615
GlC 0.120 0.248 0.258 0.311 0.351 0.423 0.498 0.654 0.691 0.742
FuC 0.022 0.047 0.057 0.134 0.211 0.399 0.477 0.776 1.02 1.34
HmC <0.005 0.008 nd 0.018 0.025 nd 0.050 0.081 nd nd
AcC 0.197 0.230 0.298 0.486 0.744 0.981 1.29 1.85 2.23 2.61
nd: not determined.

J Chem Technol Biotechnol 74:1101±1109 (1999) 1105

G Garrote, H DomõÂnguez, J C ParajoÂ
ery (PRGn) in the experiments of Tables 1±6 as a
single variable independent from the operational
conditions, a monovariate statistical analysis showed
a mean value of 100.4%, with 95% con®dence limits
of 97.1 and 103.7%.
Furfural and hydroxymethylfurfural are sugar-
dehydration products that inhibit fermentation.
Generally, the concentrations of both compounds
(measured by the variables FuC and HmC) increased
with time and with temperature and were signi®cantly
affected by the liquor/solid ratio; but only reached
values that affected fermentation after prolonged
reaction times. For example, HmC reached 0.151 g
dmÿ3 at the end of experiment 3 (having the lower
liquor/solid ratio), but HmC in the same experiment
was only 0.021 g dmÿ3 when the oligomer concen-
tration was maximal. Similarly, FuC was maximal
(1.35 g dmÿ3) at the end of experiment 4, but the
corresponding value at the time of maximum oligomer
concentration was 0.157 g dmÿ3.
The acetyl group content of solid residues from
treatments (measured by variable %Acl) followed
similar kinetic trends to those observed for xylan. In
the liquor samples withdrawn from the reaction media
at the beginning of the isothermal stage of reactions,
the acetic acid concentrations (measured by variable
AcC) varied from 0.06 g dmÿ3 in experiment 5 (carried
out with the lowest solid concentration) up to 0.197 g
dmÿ3 in experiment 6 (performed under the severest
conditions assayed). The values of AcC increased
steadily with the reaction times to achieve maximum
values (2.2±3.7 g dmÿ3) dependent on the operational
conditions. Acetic acid concentration signi®cantly
increased after the secondary hydrolysis of xylo-
oligomers, with acetyl groups of the oligomers
accounting for 48±66% of the acetyl groups contained
in raw wood. After secondary hydrolysis, 72±83% of
the acetyl groups contained in the raw material
(measured by variable %Acl RM) were recovered as
acetic acid.
The behaviour of the lignin fraction of wood can be
easily assessed by the proportion of lignin remaining in
the solid phase after treatment (PRLg). PRLg varied
from 96.7% (at the lowest liquor/solid ratio) to 90.7%
(at the highest temperature assayed). Consequently,
deligni®cation was seen not to be an important effect
of hydrothermal treatments, even if there was a partial
depolymerization of this fraction under harsh condi-
tions.
3.3 Kinetics of xylan degradation
The published mathematical interpretations of LCM
processing present two different approachs: (i) studies
based on the severity factor3,20,21 and (ii) studies based
on pseudohomogeneous kinetic models. In this study,
problem of heterogenous catalysis, involving sequen-
tial steps of catalyst diffusion in the porous substrate,
chemical reaction and product diffusion.22 The
heterogeneous nature of substrates, the accessibility
of ether bonds and the time-dependence of the
concentration of hydronium ions during reaction are
also factors that might in¯uence the overall reaction.
Because of these multiple factors, both autohydrolysis
and prehydrolysis reactions have been modelled on the
basis of sequential reaction steps with pseudo-®rst
order kinetics and Arrhenius-type temperature depen-
dence. This approach provides all the information
necessary for comparative studies and design purposes
even if it is not useful for predicting reaction rates.23
Several authors19,24,25 have reported studies on
hydronium-catalysed xylan degradation (both auto-
hydrolysis and prehydrolysis reactions) based on the
degradation of xylan or xylan fractions to oligomers,
generation of xylose from oligomers and degradation
of xylose to furfural with further generation of
degradation products. The main drawback of this
approach is that oligomers generated in the early
reaction stages, with comparatively high polymeriza-
tion degrees (DP), are progressively degraded, mainly
to oligomers with lower DP; whereas in the late
reaction stages, the xylooligomers with low DP are
more likely to be hydrolysed to xylose. Conner and
Lorenz19 proposed a time-dependent kinetic coef®-
cient to account for the different probabilities of
obtaining xylose by xylooligomer hydrolysis. An
alternative approach was used here: DP reduction by
xylooligosaccharide hydrolysis was simpli®ed to a
mechanism involving two sequential stages of DP
reduction. It was assumed that: (i) Eucalyptus xylan
(Xn) is made up of two fractions, one being unreactive
under the operational conditions and the other
yielding xylooligosaccharides; (ii) the hydrolysable
proportion of xylan (XnS) is related to the total xylan
of wood (Xn) by the `susceptible fraction' measured by
the parameter a(0 < a < 1), (iii) the hydrolysable xylan
fraction is ®rst degraded to high-DP xylooligomers
(XOH); (iv) in a sequential step, the high-DP
xylooligomers are hydrolysed to low-DP xylooligomers
(XOL) and these are converted into xylose (X),
yielding furfural (F) on dehydration. This mechanism
is summarized by:
k1 k2 k3 k4
XnS ÿÿÿÿ! XOH ÿÿÿÿ! XOL ÿÿÿÿ! X ÿÿÿÿ! F
where k1 to k4 are pseudohomogeneous, ®rst-order,
kinetic coef®cients.
By integration of the kinetic model derived from the
above mechanism in terms of the selected variables, it
can be inferred that:
the second approach was preferred owing to its PRXn ˆ PRXn0
‰…1 ÿ  † ‡ 
exp…ÿk1
t †Š …7†
superior ability for interpretating the effects of auto-
hydrolysis in hemicelluloses. OEP ˆ …C1 ‡ C3 †
exp…ÿk2
t †
A rigorous kinetic study of polysaccharide hydrolysis
‡ …C2 ‡ C4 †
exp…ÿk1
t † ‡ C5
exp…ÿk3
t † …8†
by hydronium ion-catalysed reactions is a complex

1106 J Chem Technol Biotechnol 74:1101±1109 (1999)

 Xylooligosaccharide production from wood

 
k3
C3 k3
C4 k3
C5
XEP ˆ XEP 0 ÿ ÿ ÿ
k4 ÿ k2 k4 ÿ k1 k4 ÿ k3

k3
C3
 exp…ÿk4
t † ‡
exp…ÿk2
t †
k4 ÿ k2

k3
C4 k3
C5
‡
exp…ÿk1
t † ‡
exp…ÿk4
t † …9†
k4 ÿ k1 k4 ÿ k3

FEP ˆ PRXnRM ÿ PRXn ÿ OEP ÿ XEP

…10†

where the superscript 0 corresponds to the concentra-

tion of species at the beginning of the isothermal
reaction stage, and the integration constants can be
calculated by the equations:

PRXn0
k1
C1 ˆ OEP 0 ÿ …11†
k2 ÿ k1


PRXn0
k1
C2 ˆ …12†
k2 ÿ k1

C1
k2
C3 ˆ …13†
k3 ÿ k2

C2
k2
C4 ˆ …14†
k3 ÿ k1

C5 ˆ ÿC3 ÿ C4 …15†

The parameter b corresponds to the soluble fraction

of unreacted substrate at t = 0, which is related to the Figure 1. Experimental and calculated time courses of residual xylan and
`susceptible fraction' a by the equation: xylan degradation products (measured by variables PRXn, OEP, XEP and
FEP defined in text). Operational conditions corresponding to:
PRXnRM (a) experiment 1 of Table 1 (145 °C, 8 g liquor gÿ1 solid); (b) experiment 4 of
 ˆ 1 ÿ …1 ÿ †
…16† Table 4 (175°C, 8 g liquor gÿ1 solid); (c) experiment 6 of Table 6 (190 °C, 8 g
PRXn0 liquor gÿ1 solid). &, PRXn exp; ——, PRXn calc; ~, OEP exp; – – – –,
Since the experimental data did not allow a OEP calc; *, XEP exp; - - - - -, XEP calc; ^, FEP exp; -

-
, FEP calc.

distinction between high- and low-DP, the values of

the kinetic coef®cients k2 and k3 were calculated by
minimization of the sum of the deviation squares
between the variable OEP (de®ned as a function of the
overall oligosaccharide concentration) and the experi-
mental values. The optimization algorithm was per-
formed on the basis of the ideas already reported.26
Table 7 shows the values determined for the
regression parameters, and Fig 1 presents data
corresponding to representative experiments, which
demonstrate the utility of the models to interpret
quantitatively data for degradation of xylan. The
proportions of xylan recovered as xylooligosacharides
were similar to those reported by Conner and
Lorenz,19 where 51% of xylan was converted to
xylooligomers at 171±185 °C and 66±69.3% within

Regression parameters (kinetic

coef®cients in hÿ1, a dimensionless) R 2 for variables

Experiment k1 k2 k3 k4 a PRXn OEP XEP FEP

1 0.405 0.369 0.369 0.048 0.833 0.968 0.914 0.995 0.965

2 1.42 0.695 1.61 0.164 0.832 0.974 0.927 0.993 0.924
3 5.01 1.43 7.25 0.460 0.829 0.987 0.969 0.995 0.951
4 5.23 1.33 7.29 0.468 0.834 0.990 0.977 0.997 0.959
Table 7. Values of kinetic coefficients, 5 5.32 1.27 8.30 0.426 0.826 0.981 0.960 0.995 0.969
parameter a and R2 (see text for definition
6 24.7 2.78 29.9 1.10 0.842 0.989 0.973 0.991 0.977
and units)

J Chem Technol Biotechnol 74:1101±1109 (1999) 1107

G Garrote, H DomõÂnguez, J C ParajoÂ

Figure 2. Arrhenius plots showing the temperature dependence of the

kinetic parameters k1–k4. &, ln(k1); ~, ln(k2); *, ln(k3); ^, ln(k4).

the range 201±237 °C. Aoyama and Colleagues27,28

reported 197.4 °C as the optimum temperature for
xylose, xylobiose and xylooligosaccharide recovery
from bamboo grass by steaming, with 55% xylan
recovered as soluble saccharides.

3.4 Generalization of the kinetic model

The data in Table 7 can be used to establish the tem-
perature dependence of the kinetic coef®cients k1±k4
using Arrhenius-type equations (see Fig 2 and Table
8(a)). Since the values of the `susceptible fraction' a
varied in a narrow range, a further regression analysis
was performed with the data from experiments 1, 2, 4
and 6 (which were performed at the same liquor/solid
ratio). In this case, the regression analysis was carried
out assuming that a single value of a should describe
the entire set of experiments, independently from the Figure 3. Experimental time courses of residual xylan and xylan
reaction temperature. Furthermore, the kinetic coef®- degradation products under the conditions of experiments 2, 4 and 6 of
cients k1±k4 were expressed in terms of preexponential Tables 2, 4 and 6 (measured by variables PRXn, OEP, XEP and FEP
factors and activation energies, according to the defined in text) and results calculated from the generalized kinetic
parameters shown in Table 8. &, PRXn exp; ——, PRXn calc; ~, OEP
Arrhenius equation. Table 8(b) shows the results of exp; – – – –, OEP calc; *, XEP exp; - - - - -, XEP calc; ^, FEP exp;
the best-®t parameters obtained with this procedure. It -

-
, FEP calc.
can be noted that the value determined for a (0.843)
was close to the average value of the results listed in
Table 7 for this parameter. Based on these results, the
Table 8. Results obtained when fitting the kinetic parameters to the validity of the models can be con®rmed by comparing
Arrhenius equation (k 0i, preexponential factors; Ea i, activation the experimental and calculated time courses of
energies) autohydrolysis (see Fig 3).
(a) Results obtained for the data listed in Table 7

Kinetic coef®cient ln (k0i) (k0i in hÿ1) Eai (kJ molÿ1) 4 CONCLUSIONS

k1 41.0 146 Hydrothermal treatments of Eucalyptus wood had little
k2 19.7 71.9 effect on either cellulose (which was almost quantita-
k3 44.3 158 tively retained in solid phase), or lignin. The main
k4 29.2 112 effects of hydrothermolysis were deacetylation and
polysaccharide (araban and xylan) hydrolysis. Xylose
(b) Results obtained from a generalized Arrhenius equation with and xylooligosaccharides were the major reaction
a = 0.843 products, but sugar-degradation compounds (furfural
Kinetic coef®cient ln (k0i) (k0i in hÿ1) Eai (kJ mol ÿ1) and hydroxymethylfurfural) also appeared in the
reaction media. A kinetic model based on four
k1 39.3 140 consecutive, pseudohomogeneous, ®rst-order reac-
k2 22.1 81.5 tions closely reproduce the experimental results. The
k3 44.1 156 temperature dependence of the kinetic coef®cients was
k4 25.6 98.3
well described by Arrhenius-type equations.

1108 J Chem Technol Biotechnol 74:1101±1109 (1999)


ACKNOWLEDGEMENTS
The authors are grateful to `Xunta de Galicia' for the
®nancial support of this work (Project XUGA
38303A98).
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