Originalarbeiten Originals

Holz als Roh- und Werkstoff 57 (1999) 191202 Springer-Verlag 1999

Hydrothermal processing of lignocellulosic materials

G. Garrote, H. Domnguez, J. C. Parajo

Hydrothermal processing of lignocellulosic materials

(wood or agricultural residues) causes a variety of effects
including extractive removal, hemicellulose hydrolysis and
alteration of the properties of both cellulose and lignin.
This article reviews the chemical composition of raw materials potentially useful for hydrothermal processing as
well as the results reported on the kinetics of hemicellulose
hydrolysis by water treatments. The fundamentals of the
mathematical modelling of hemicellulose degradation reactions by pseudohomogeneous kinetics and by severity
factors are reviewed. Additional information on the effects
caused by hydrothermal treatments on lignin and cellulose
is also provided.

Hydrothermischer Aufschlu von Lignocellulosen

Der hydrothermische Aufschlu von Lignocellulosen

(Holz und Agrarruckstande) hat mehrere Nebeneffekte wie
Auslosen von Extraktstoffen, Hydrolyse der Hemicellulosen und Veranderung von Eigenschaften der Cellulose und
bersicht uber verdes Lignins. Diese Arbeit gibt eine U
schiedener Rohstoffe, die fur den hydrothermischen Aufschlu in Frage kommen sowie uber Ergebnisse zur
Kinetik der Hydrolyse von Hemicellulosen durch die
Heiwasserbehandlung. Die Grundlagen der mathematischen Simulation des Polysaccharidabbaus als pseudohomogene Kinetik und mit gewichteten Einufaktoren
werden dargestellt. Zusatzlich enthalt dieser Beitrag Informationen uber die Auswirkung der hydrothermischen
Behandlung auf Ligin und Cellulose.

1
Introduction
The chemical utilization of lignocellulosic materials (LCM)
requires the separation of their main polymeric components (hemicelluloses, cellulose and lignin). In the largescale pulping processes (sulfate or sulte technologies),
lignin is degraded by sulfur-containing chemicals, and the
hemicellulose degradation products are wasted or utilized
for power generation, an utilization with low added-value.
A modication of the Kraft process includes a prehydrolysis step allowing the separation of hemicelluloses
G. Garrote, H. Domnguez, J. C. Parajo (&)
Department of Chemical Engineering,
University of Vigo (Campus Orense),
Faculty of Science, Las Lagunas.
32004 Orense, Spain
E-mail: jcparajo@uvigo.es

(Schultz et al., 1984; Overend & Chornet, 1989; Kubikova

et al., 1996); but the utilization of lignin degradation
products for chemical purposes is hindered by their sulfur
content.
Water treatments provide an interesting alternative for
the chemical utilization of lignocellulose owing to the
following reasons: i) no chemicals different from water are
necessary, the whole process being environment-friendly;
ii) hemicelluloses can be converted into hemicellulosic
sugars at good yields with low byproduct generation
(Lamptey et al., 1985), leading to solutions of sugar oligomers and/or sugars that can be utilized for a variety of
practical purposes (Modler, 1994; Saska & Ozer, 1995;
Aoyama et al., 1995; Aoyama, 1996; Lopez-Alegret, 1996);
iii) in comparison with acid prehydrolysis, no problems
derived from equipment corrosion are expected owing to
the mild pH of the reaction media; iv) stages of sludge
handling and acid recycling are avoided, resulting in a
simplied process structure; v) the physico-chemical alteration provoked by treatments on lignin and cellulose
facilitates the further separation and processing of these
fractions (see below); vi) when operating with steam at
temperatures about 200 C, the reaction media can be
suddenly ``exploded'' to atmospheric pressure (``steam
explosion'') in order to disrupt the solid residues, causing
a favourable structural desaggregation of their structures
(Schultz et al., 1984a; Rubio et al., 1994); vii) economic
estimates (Schaffeld, 1994b; Kubikova et al., 1996) showed
advantages for water treatments over alternative technologies.
The studies on the processing of LCM by water or steam
have been referred to in literature as autohydrolysis (Lora
& Wayman, 1978; Conner, 1984; Carrasco, 1989; Tortosa
et al., 1995), hydrothermolysis (Bonn et al., 1983;
Hormeyer et al., 1988; Kubikova et al., 1996), aqueous
liquefaction or extraction (Heitz et al., 1986; Saska & Ozer,
1995), aquasolv (Kubikova et al., 1996), water
prehydrolysis (Conner, 1984), hydrothermal pretreatment
or treatment (Overend & Chornet, 1987; Schaffeld, 1994b;
Kubikova et al., 1996) and steam pretreatment or steam
extraction (Puls & Dietrichs, 1981; Ramos et al., 1992). All
these studies are based on the same kind of reactions and
are referred to as ``hydrothermal treatments'' in this work.

2
Fundamentals of the hydrothermal processing
of lignocellulose
At temperatures in the range of 150230 C, LCM undergoes hydrolysis reactions in the presence of the hydronium

191

192

ions generated by water autoionization, which act as catalysts. The heterocyclic ether bonds of hemicelluloses are
the most susceptible ones to this type of reaction, leading
to both generation of oligosaccharides and splitting of the
acetyl groups from the hemicellulosic fraction of the raw
materials. In further reaction stages, the hydronium ions
generated from acetic acid autoionization also act as catalysts in the degradation of polysaccharides. Under the
operational conditions usually employed in hydrothermal
treatments, the formation of hydronium ions from acetic
acid is more important than from water (Heitz et al., 1986;
Carrasco, 1989), the role of water autoionization being
limited to the initial reaction stages. Uronic acids can also
contribute to the generation of hydronium ions, but their
effects are not well established (Conner, 1984).
Depending on the operational conditions used in experiments, polysaccharides (mainly hemicelluloses) are
depolymerized to oligomers and monomers, and the correspondent sugars (pentoses and hexoses) can be dehydrated to furfural and hydroxymethylfurfural, respectively.
Other fractions of LCM different from hemicelluloses can
also react in the presence of water: for example, cellulose
and lignin can be partially depolymerized by similar hydrolysis reactions (see below). Additional condensation
reactions involving furfural, lignin and/or reaction intermediates have been reported (Lora & Wayman, 1978;
Dekker & Wallis, 1983; Muzzy et al., 1983; Aoyama et al.,
1995), and Carrasco et al. (1987) found that CO2 was
generated from uronic acids by decomposition of the
carbonyl groups.

3
Composition of raw materials
Hardwoods are more favourable than softwoods as raw
materials for hydrothermal processing, owing to their
higher contents in acetyl groups that provide increased
catalyst concentrations in the reaction media. Because of
this, the water treatments of hardwoods have been considered by a number of authors (Lora & Wayman, 1978;
Bonn et al., 1983; Muzzy et al., 1983; Biermann et al., 1984;
Conner, 1984; Schultz et al., 1984a; Wallis & Wearne, 1985;
Conner & Lorentz, 1986; Carrasco et al., 1987; Hormeyer
et al., 1988; Abatzoglou et al., 1990; Bouchard et al., 1991;
Heitz et al., 1991; Ramos et al., 1992; N'Diaye et al., 1996),
whereas little information exists on the application of this
technology to softwoods (Kokta et al., 1992; Martnez et al.,
1997a).
Some lignocellulosic agricultural residues have been
employed as raw materials for hydrothermal treatments
(Bonn et al., 1983; Dekker & Wallis, 1983; Tewari et al.,
1987; Szczodrack, 1988; Ropars et al., 1992; Aoyama et al.,
1995; Saska & Ozer; 1995; Tortosa et al., 1995; Kubikova
et al., 1996) owing to their favourable contents on both
acetyl groups and hemicelluloses. For comparative purposes, Table 1 lists the composition of selected woods and
agricultural residues.
Table 2 shows the distribution of monomeric sugars in
hemicelluloses of representative MLC. Since xylose is the
main hemicellulosic sugar of the most interesting raw materials, some studies considered directly the hydrolysis of
xylan (the hemicellulose fraction built from xylose units).

4
Operational conditions used in hydrothermal treatments
The studies dealing with the hydrothermal processing of
MLC have considered a wide variety of operational conditions. Table 3 summarizes representative literature data
on the ranges explored for the most inuential operational
variables.
Hydrothermal treatments intending a selective hemicellulose hydrolysis are usually carried out at temperatures
within the range of 150230 C. This variation range is
xed by both the little extent of hydrolytic reactions observed below 100 C (Abatzoglou et al., 1992; Tortosa
et al., 1995) and the fact that cellulose degradation reactions became important above 210220 C (Heitz et al.,
1986; Rubio et al., 1994). In the same way, Biermann et al.
(1984) reported that cellulose was signicantly affected at
270 C, whereas Bonn et al. (1983) employed hydrothermal
treatments at 260270 C for cellulose saccharication.
The charge of solids, measured by the liquor/solid ratio
(LSR), is also an important operational parameter. LSR in
the range of 140 g/g have been explored, the most usual
values being in the vicinity of 10 g/g (see Table 3). Moderate variations of LSR cause little effects on the hydrothermal processing of LCM (Lamptey et al., 1985; Aoyama,
1996).
The duration of treatments reported in literature varied
in a wide range, from some seconds in high-temperature
experiments (Biermann et al., 1984; Capek-Menard et al.,
1987; Barnet et al., 1989) up to several hours for milder
conditions (Conner, 1984; Saska & Ozer, 1995). In hydrothermal assays carried out at high temperatures, the
heating time can be comparatively long in comparison
with the duration of the isothermal reaction, leading to a
substantial hemicelullose conversion during heating
(Carrasco & Roy, 1992). Table 4 lists data on the reaction
times and heating rates utilized in reported studies. Little
comparative effects have been observed during the cooling
periods, in which temperature can be decreased at rates as
high as 30 C/min (Martnez et al., 1995, 1997a).
5
Industrial processes based on hydrothermal treatments
The Masonite process was the rst one to be based on the
``steam explosion'' phylosophy cited above (Rijkens, 1984;
Schultz et al., 1984a). Wood chips are contacted in batch
reactors during 110 min with saturated steam at pressures up to 90 atm and released to atmospheric pressure
through a valve. Owing to the sudden decompression and
expansion, wood is de-structured and bers are depolymerized. The bers in the solid residue are covered by a
layer of lignin, being unable for pulp production but useful
for making berboards.
The Stake II is a modication of the Masonite process
allowing a continuous operation. The operational procedure (Rabanni, 1989; Heitz et al., 1991; Ballerini et al.,
1994; Rubio et al., 1994) is based on the utilization of an
extruder that allows the utilization of thick suspensions.
The characteristics of solid residues are similar to the ones
from the Masonite process.
The Rapid Steam Hydrolysis/Continuous Extraction
(RASH) process also utilizes the steam explosion, but the

Table 1. Cellulose, hemicellulose and lignin contents (as weight percent of dry biomass) of representative lignocellulosic materials
(LCM)
Tabelle 1. Gehalt an Cellulose, Hemicellulose und Lignin (in Gewichtsprozent der Trockenmasse) von einigen typischen
Lignocellulosen (LCM)
Raw material

Cellulose

Hemic.

Lignin

References

a) Hardwoods
White birch
Poplar/aspen
Red maple
Hybrid poplar
Eucalyptus viminalis
Eucalyptus globulus

41.0
50.853.3
44.1
41.7
41.7
42.354.0

36.2
26.228.7
29.2
20.2
14.1
1636.6

18.9
15.516.3
24.0
29.3
31.0
17.923.3

46
48
40.4
38.9

19
23
35.9
23.8

24
17
24.1
21.5

Holtzapple, 1993a
Holtzapple, 1993a; Schaffeld 1994a
Holtzapple, 1993a
Torget & Hsu, 1994
Ramos et al., 1992
Parajo et al., 1993a; Pereira, 1988;
Schaffeld, 1994a; Vazquez et al.,
1991
Fan et al., 1987
Fan et al., 1987
Schaffeld, 1994a
Conner, 1984

b) Softwoods
Pinus banksiana
Pinus banksiana
Pinus pinaster
Pinus radiata
Fir
White r
Red r

41.6
41
42.9
4250
43.9
44
43

25.6
13
17.6
2427
26.5
11
12

28.6
27
30.2
20
28.4
27
27

Holtzapple, 1993a
Fan et al., 1987
Parajo et al., 1993b
Schaffeld, 1994a
Schaffeld, 1994a
Fan et al., 1987
Fan et al., 1987

c) Agricultural residues
Corn cobs

33.741.2

31.936

6.115.9

Sugar cane bagasse

Wheat straw

4041.3
32.950

2737.5
2435.5

1020
8.917.3

Rice straw

36.247

1924.5

9.924

Corn stalks

3539.6

16.835

718.4

Barley straw

33.837.5

21.924.7

13.814.5

Rye straw
Oat straw
Flax
Soya stalks
Sunower stalks

37.6
39.4
34.9
34.5
38.142.1

30.5
27.1
23.6
24.8
19.529.6

19.0
17.5
22.3
19.8
11.013.4

Vine shoots

35.638.3

20.635.0

22.823.4

Cotton stalks

38.442.6

20.934.4

21.45

Sunowers seed hulls

Thistle

24.1
31.1

28.6
12.2

29.4
22.1

Ropars et al., 1992; Schaffeld,

1994a
Playne, 1984; Schaffeld, 1994a
Blanch and Wilke, 1983; Bjerre
and al., 1996; Carrasco et al.,
1994; Fan et al., 1987; Jimenez
and Lopez, 1993; Ranganathan
et al., 1985; Schaffeld, 1994a
Blanch and Wilke, 1983; Fan
et al., 1987; Patel and Bhatt, 1992
Barrier 1985; Blanch andWilke,
1983; Lamptey et al., 1985
Blanch and Wilke, 1983; Fan et al.,
1987
Fan et al., 1987
Fan et al., 1987
Fan et al., 1987
Fan et al., 1987
Jimenez et al., 1996; Jimenez and
Lopez, 1993
Jimenez et al., 1996; Jimenez and
Lopez, 1993
Jimenez and Lopez, 1993; Jimenez
et al., 1996
Dekker and Wallis, 1983
Jimenez and Lopez, 1993

Populus deltoides
Populus tremoloides
Oak
Red oak

soluble reaction products are continuosly drained from the

reactor for minimizing the degradation reactions (Biermann et al., 1984; Schultz et al., 1984a). The usual operational conditions are temperatures in the range of 160
260 C and reaction times about 1 min.
The Iotech process also utilizes a batch reactor with
steam explosion, but the solid residue is treated with organic solvents in a further step for removing up to 90% of
the initial lignin (Rijkens, 1984; Marchessault et al., 1983).

The Siropulper is similar to the Iotech process, but an

inert, non condensable gas is also introduced in the digestor in order to increase the total pressure up to about
70 atm at mild temperatures (Wallis & Wearne, 1985;
Schaffeld, 1994b). The solid residues are susceptible to
bleaching and lignin can be extracted with organosolvents
or alkaline solutions.
The wet oxidation process is similar to the Siropulper,
but the extra pressure is reached with air or oxygen

193

Table 2. Distribution of hemicellulosic sugars of selected lignocellulosic materials (data shown as weight percent of dry samples)
Tabelle 2. Zuckerverteilung in Hemicellulose ausgewahlter Lignocellulosen (in Gewichtsprozent der Trockenmasse)

194

Raw material

Mannose

Galactose

Xylose

Arabinose

Hemicel.
sugars

References

a) Softwoods
Balsam Fir
Fir
Pinus banksiana

12.4
9.8
9.410.6

1
1.2
1.42.2

4.8
7.2
7.17.4

0.5
0.9
1.91.8

18.7
19.1
20.520.8

Pinus radiata
Pinus resinosa

9.5
10.7

3.3
2.0

6.2
7.9

2.1
2.0

21.1
22.6

Pinus taeda

10.5

2.4

6.5

1.5

20.9

White spruce

11.6

1.2

6.8

1.6

21.2

Holtzapple, 1993b
Schaffeld, 1994a
Holtzapple, 1993b;
Eberhardt & Young,
1996
Schaffeld, 1994a
Eberhardt & Young,
1996
Eberhardt & Young,
1996
Holtzapple, 1993b

0.71.2

1.32.5

12.021.5

0.81.8

15.327.0

Hybrid poplar

2.83.0

1.0

14.815.6

0.51.2

19.120.8

Oak
Poplar

2.4
2.22.3

2.1
0.00.8

21.7
16.017.3

1.6
0.42.0

27.8
19.521.5

Red Maple
Timothy Hay
White birch

3.5
0.9
1.5

0.6
1.5
0.6

17.3
13.8
24.6

0.5
2.6
0.5

21.9
18.8
27.2

c) Agricultural residues
Bamboo grass
Barley straw
Corn cobs
Corn stalks

0.4
1.26
0.0
00.25

1.71
0.0
0.750.8

21.6
15.00
29.1
13.0021.1

2.9
4.00
2.8
2.803.7

24.9
21.97
31.9
16.8026.7

Rice husk
Rice straw
Sorghum straw
Sugar cane bagasse
Wheat straw

2.7
1.6
0.8
0
00.72

0.1
0.4
0.2
0.7216

12.3
13.0
15.0
21.5
16.918.5

2.6
4.0
3.0
2.7
2.11.6

17.7
19.0
19.0
24.2
20.821.88

b) Hardwoods
Eucalyptus

(Schultz et al., 1984; Schaffeld, 1994b). Oxygen participates

in the degradation reactions, enhancing the generation of
organic acids and allowing operation at comparatively
reduced temperatures. The fast reaction rates and heat
generation by reaction make the temperature control of
the reactor critical.
Table 5 summarizes the operational conditions used in
the above industrial processes.

6
Modelling of hemicellulose degradation
Hydrothermal treatments are suitable for hemicellulose
solubilization. Under selected conditions, hemicelluloses
can be almost quantitavely removed from some LCM
(Carrasco et al., 1994). The experimental results summarized in Table 6 demonstrate the ability of this technology
for removing a substantial part of hemicelluloses from a
variety of raw materials. The same Table includes data on
the recovery of reaction products (measured as sugars or
as the overall amount of sugars and oligomers) and on the
furfural concentrations reached in the reaction media.

David et al., 1988;

Schaffeld, 1994a
Torget & Hsu, 1994;
Ucar, 1990
Schaffeld, 1994a
Holtzapple, 1993b;
Ucar, 1990
Holtzapple, 1993b
Horwath et al., 1983
Holtzapple, 1993b
Aoyama et al., 1995
Blanch & Wilke, 1983
Ropars et al., 1992
Blanch & Wilke, 1983;
Tortosa et al., 1995;
Schaffeld, 1994a
Blanch & Wilke, 1983
Blanch & Wilke, 1983
Blanch & Wilke, 1983
Schaffeld, 1994a
Blanch & Wilke, 1983;
Schaffeld, 1994a

Substantial hemicellulose removal was achieved with

reduced furfural concentrations in most of the cases.
Hemicellulose recovery degrees lie in the range of 6582%
of the initial ones (Conner & Lorentz, 1986; Bouchard et al.,
1991; Heitz et al., 1991).
The mathematical interpretation of data of hemicellulose hydrolysis by hydrothermolysis has been carried out
using two different approaches: pseudohomogeneous kinetic models and severity parameters. Both methods are
described in the following paragraphs.

6.1
Pseudohomogeneous kinetic models
Mathemathical models based on pseudo-rst order kinetics have been successfully employed for modelling the acid
prehydrolysis of LCM, as kind of processes closely related
to the hydrothermal ones: in fact, both cases are based on
hydronium-catalysed reactions of polysaccharide heterocyclic ethers, and the interpretation of data has been carried out by closely related methods in hydrothermal
(Conner, 1984; Conner & Lorentz, 1986; Carrasco et al.,

Table 3. Operational conditions used in hydrothermal treatments of lignocellulosic materials

Tabelle 3. Prozebedingungen beim hydrothermischen Aufschlu von Lignocellulosen
Raw material

Temp.
(C)

Time
(min)

Particle size

Liquor/solid
ratio (g/g)

References

a) Woods
Eucalyptus
Poplar
Poplar
Populus tremoloides
Populus deltoides
Populus deltoides
Pine (Pinus silvestris)
Pine (Pinus pinaster)
Mixed hardwoods
(oak and gum)
Oak
Mixed hardwoods
Aspen

230
230
215225
180230
220245
180235
210
190
160280

2
4
37
0.74
0.421.47
2
4
8
1

4 mm
4 mm
1 mm
20 mm
2040 mesh

4 mm
4 mm
6 mm

10
10

7.110

10
10

Carrasco et al., 1994

Carrasco et al., 1994
Muzzy et al., 1983
Heitz et al., 1991
Capek-Menard et al., 1987
Bouchard et al., 1991
Carrasco et al., 1994
Carrasco et al., 1994
Biermann et al., 1984

230
200230
187240

4
2.082.23
0.55

4 mm
0.5 mm
2 mm

10
20

Carrasco et al., 1994

Abatzoglou et al., 1990
Kuznetsov et al., 1996

b) Agricultural residues
Corncobs
Corn stover
Sunower seed hulls
Sugar cane bagasse
Wheat straw
Vine shoots
Thistle biomass
Sweet sorghum bagasse
Almond shells
Corn stalk
Sugar cane bagasse
Wheat straw
Bamboo grass
Wheat straw
Almond shells

180223a
120190
200
185208c
190
190
210
230
180200
190230
150170
120
169.6206.2
205230
180240

35
15120b
5
2029d
8
8
2
0.5
168
1020

15300
10
2
1225

35200 mesh
1 mm

4 mm
4 mm
4 mm
4 mm
60 mesh
0.5 mm
0.8 mm
60 mesh
0.5 mm

60 mesh

210

4
10
10
10
10
3
25
510
38

14.3

Ropars et al., 1992

Lamptey et al., 1985
Dekker et Wallis, 1983
Fontana et al., 1995
Carrasco et al., 1994
Carrasco et al., 1994
Carrasco et al., 1994
Carrasco et al., 1994
Martnez et al., 1995
Tortosa et al., 1995
Saska & Ozer, 1995
Lawther et al., 1996
Aoyama, 1996
Montane et al., 1997
Montane et al., 1994b

Temperature calculated from R0 values

Holding time
c
Maximum temperature
d
Non-isothermal operation
b

Table 4. Data on the heating

conditions used for hydrothermal treatments
Tabelle 4. Heizphasen wahrend der hydrothermischen
Behandlung

Heating rate
(C/min)

Preheating
time (min)

Reaction
time (min)

Final temperature
(C)

References

23

59.7
8.810.3

5.010.3

7
0.67
2.23.5
1012

1
2029

1530
0.67
5
4157

5
1
5
15120
2
10
2029a
168
344

0.57
15300
15
144

200
105
200
120190
135
169.6206.2
185208b
180
200
150170
220
120
185215
180200

Dekker & Wallis, 1983

Biermann et al., 1984
Playne, 1984
Lamptey et al., 1985
Carrasco et al., 1987
Aoyama, 1996
Fontana et al., 1995
Martnez et al., 1995
Martnez et al., 1995
Saska & Ozer, 1995
San Martn et al., 1995
Lawther et al., 1996
Angles et al., 1997
Martnez et al., 1997

a
b

Non-isothermal operation
Maximum temperature

1989) and prehydrolysis stages (Grant et al., 1977; Melhberg & Tsao, 1979; Horwart et al., 1983; Bhandari et al.,
1984; Harris et al., 1984; Maloney et al., 1985; Ranganathan
et al., 1985; Brennan et al., 1986; Maloney et al., 1986;

Nakagawa et al., 1986; Kim & Lee, 1987; Abatzoglou et al.,

1990; Carrasco, 1991; Riera et al., 1991; Parajo et al., 1993c,
1994, 1995a and b). Since the same fundamentals are
applicable to both prehydrolysis and hydrothermal

195

Table 5. Industrial processes

based on hydrothermal technologies
Tabelle 5. Industriell eingesetzte Prozesse mit hydrothermischer Behandlung

196

Table 6. Effect of hydrothermal treatments on hemicelluloses

Tabelle 6. Auswirkungen hydrothermischer Behandlungen

Process

Operational conditions

Residue
yield
(%)

References

Rijkens, 1984; Schultz

et al., 1984a; Carrasco
et al., 1992
Heitz et al., 1991
Biermann et al.,1984;
Schultz et al., 1984a
Marchessault et al.,
1983; Rijkens, 1984
Wallis & Wearne, 1985;
Schaffeld, 1994b
Rijkens, 1984; Schultz
et al., 1984a

T (C)

t (min)

Masonite

190300

110

7580

Stake II
R.A.S.H.

220
160280

2
1

Iotech

250

0.5

Siropulper

200

220

6676

Wet oxidation

148200

30

Raw material

Hemicellulose
removal
(%)

Hemicellulose
recovery
(%)

Furfurala

References

Bamboo grass
Corn stalks
Corn stover
Hardwoods
Hardwoods
P. deltoides
P. tremoloides

98
95
87.3
96
98
90
92.5

55

79.6
60
19
65
19

32
3.2

3.0

Aoyama et al., 1995

Tortosa et al., 1995
Lamtley et al., 1985
Biermann et al., 1984
Abatzoglou et al., 1990
Bouchard et al., 1991
Heitz et al., 1991

Data expressed as percent of equivalent in initial hemicelluloses

treatments, the general modelling exposed in this section

is valid for both treatments and no distinction is made
between references dealing with these two technologies.
A rigourous kinetic study of the polysaccharide hydrolysis by the catalytic action of hydronium ions is a
difcult problem involving at least the following sequential
steps (Fengel & Wegener, 1984): i) diffusion of the catalyst
in the polysaccharide heterogeneous matrix; ii) protonation of the heterocyclic ether; iii) breaking of the ether
bond with generation of a carbonium ion and a new
polymer, oligomer or monomer (depending on the position of the broken bond on the polymer chain); iv) regeneration of the hydronium ion by hydrolysis of water,
with the generation of a saccharide having a polymerization degree dependent on the position of the broken bond;
v) diffusion of the reaction products through the solid
matrix and in the liquid phase.
Other aspects affecting the hydrolysis of polysaccharides of LCM include (Lora & Wayman, 1978; Conner,
1984; Maloney et al., 1985; Abatzoglou et al., 1990; Carrasco & Roy, 1992): i) interferences caused by other
components present in wood, such as tannins, ashes and
starch; ii) simultaneous reaction of other fractions present
in the raw material, as lignin; iii) presence of non-sugar
compounds in hemicelluloses, including acetyl groups and
uronic acids; iv) limitations in the accessibility of hydronium ions to ether bonds caused by the presence of lignin
and by the structure of cell walls; v) variations in specic
surface, available surface area and substrate accessibility
during reaction; vi) time-dependence of the effective
concentration of hydronium ions.

In order to reduce the problem of the kinetic modelling

to a practical limit, the following simplications are
commonly accepted: i) the polysaccharide hydrolysis and
related reactions are assumed to follow irreversible,
pseudohomogeneous, rst-order kinetics as it was proposed by Saeman (1945) for wood processing with dilute,
aqueous solutions of sulfuric acid; ii) the apparent kinetic
coefcients are calculated from experimental data, and
their temperature dependence is assumed to follow the
Arrhenius equation; iii) hemicellulose hydrolysis is considered to be independent from other reactions (involving
cellulose and lignin) occurring in the medium; iv) the
effects derived from the time dependence of parameters
such as particle size and acidity are neglected.
The simplied models based on these assumptions do
not describe the elementary reaction steps and cannot be
used to predict reaction rates, but are useful for interpreting the experimental results obtained under a wide
variety of operational conditions and provide all the information necessary for comparative studies and design
purposes (Maloney et al., 1986). Figure 1a shows a general
idea on the mechanisms governing the hydronium-catalized hydrolysis of xylan, the major hemicellulose component of the most interesting lignocellulosic materials. This
reaction framework provides a generalized interpretation
of models reported in literature (Root et al., 1959; Mehlberg & Tsao, 1979; Conner & Lorentz, 1986; Carrasco,
1991). Depending on the severity of the operational conditions and on the raw material utilized, simplied reaction schemes (omitting some of the reaction stages of
Fig. 1a) can be utilized for data interpretation. Conner &

Fig. 1ac. Pseudohomogeneous, rst-order mechanisms proposed for the hydronium-catalysed hydrolysis of xylan:
a) Generalised mechanism based on the ideas of Root et al.
(1959), Melhberg and Tsao (1979), and Conner and Lorentz
(1986); b) Simplied model for mild operational conditions;
c) Model for mild operational conditions with fast oligomer
decomposition (Parajo et al., 1993c)
Bild 1ac. Peudehomogene Kinetik erster Ordnung fur die
THF-katalysierte Auslosung von Xylan: a) Allgemeiner Mechanismus nach Vorschlagen von Root et al. (1959), Melhberg und
Tsao (1979) und Conner und Lorentz (1986); b) vereinfachtes
Modell fur milde Bedingungen; c) vereinfachtes Modell fur
milde Bedingungen und schnellem Abbau der Oligomere (Parajo et al. 1993c)

Lorentz (1986) proposed a time-dependent kinetic coefcient for oligomer decomposition based on the reasonable
idea that the compounds obtained from oligomer hydrolysis in the rst reaction stages were predominantly other
oligomers with lower molecular weight, whereas the major
compound obtained in the last reaction stages was
the monomeric sugar. Under mild operational conditions, the general reaction scheme can be simplied, since:
i) the recondensation reactions are negiglible (Heitz et al.,
1991; Allen et al., 1996); ii) low furfural concentrations are
reached in the reaction media (Lamptey et al., 1985;
Abatzoglou et al., 1990; Bouchard et al., 1991; Heitz et al.,
1991; Saska & Ozer, 1995; Allen et al., 1996); iii) little xylose decompositon occurs, and iv) the experimental results
can be successfully modelled considering k2 constant with
time in isothermal operation. These assumptions lead to
the mechanism shown in Fig. 1b. The mathematical
interpretation of the hydrolysis models shown in Fig. 1a
and b involves the time dependence of oligomers, which

are difcult to quantify (Ranganathan et al., 1985). In some

cases, the step of oligomer generation has been neglected
(Ranganathan et al., 1985; Abatzoglou et al., 1990),
whereas other authors report their data as soluble xylan
hydrolysis compounds (including xylose and xylose oligomers) (Conner & Lorentz, 1986; Kim & Lee, 1987; Carrasco & Roy, 1992). These ideas lead to the model of
Fig. 1c (Parajo et al., 1993c).
As can be seen from Fig. 1a, two xylan fractions (with
different susceptibility towards hydrolysis) can exist in the
raw material (Conner, 1984; Carrasco & Roy, 1992), although single-fraction models have been used successfully
in related experiments (Carrasco et al., 1987). The existence of two fractions was rst proposed for cellulose
hydrolysis, based on the structural differences between
amorphous and crystalline cellulose. For hemicellulose
hydrolysis, this structural difference does not exist, and
the two-fractions hypothesis has to be justied on the basis
of other factors, such as the inuence of transport limitation, differences in physicochemical nature of the polymer and/or dependence of the available reaction surface
on the reaction time (Conner, 1984; Maloney et al., 1985;
Carrasco & Roy, 1992). Some kinetic studies have been
carried out with pure components instead of lignocellulosic materials, but the validity of this kind of results could
be limited owing to the participation of other fractions of
the raw material (for example, such as lignin) (Lora &
Wayman, 1978).
For comparative purposes, Fig. 2 shows the time course
of xylan removal calculated from the set of kinetic coefcients reported by Conner (1984) for hydrothermal treatments of hardwoods (considering two xylan fractions).

6.2
Severity Factors
The severity factors utilized in the study of the hydrothermal processing of lignocellulose provide an easy way
for comparing results among experiments carried out

Fig. 2. Time course of xylan degradation for several raw materials calculated from the results reported by Conner (1984)
Bild 2. Verlauf des Xylanabbaus in einigen Rohstoffen berechnet
aus Daten von Conner et al. (1984)

197

under different conditions of temperature and time. The

``severity factor'' R0 utilized for describing the effects
caused on substrates is closely related to other parameters
used for similar purposes in the oil industry (Abatzoglou
et al., 1992) or in pulping processes (Chum et al., 1990;
Montane et al., 1994a; Martnez et al., 1997b).
The ``severity factor'' R0 is dened by the equation
(Overend & Chornet, 1987):

that assumes a rst-order dependence between the percent

of xylan remaining in the solid phase (PX) and R0 involving a parameter K independent from the severity of
the reaction. Figure 3 shows the dependence of the percent
of solubilized xylan on the log (R0) calculated for selected
raw materials from Eq. (2) and literature data.

dPX
K
PX
dR0

rechnet aus Daten von Overend und Chornet (1989), Bouchard

et al. (1991), Heitz et al. (1991), und Tortosa et al. (1995)

7
Effects on cellulose
eq. 1 The data of Table 7 show that little cellulose degradation
occurs in treatments of woods at temperatures below
where t is the reaction time in minutes and T is temper- 230 C. A different behaviour, characterized by an inature in C. Since R0 depends on temperature and time, it creased susceptibility towards cellulose hydrolysis, has
can be used to measure the combined effect of both
variables in a given treatment (Overend & Chornet, 1989).
The results are usually presented as a function of log (R0),
the optimum conditions corresponding to a narrow range
of log (R0). Further studies resulted in a generalization of
the severity factor to include the effects derived from the
presence of catalysts (Chum et al., 1990; Abatzoglou et al.,
1992; Montane et al., 1994a) and its application to other
processes such as prehydrolysis or organosolv delignication (Montane et al., 1994a).
The severity factor has been used for modelling several
individual stages of the chemical processing of LCM, including the solubilization of the raw material (Bouchard
et al., 1991; Heitz et al., 1991; Abatzoglou et al., 1992), the
behaviour of hemicelluloses during reaction (Overend &
Chornet, 1989; Bouchard et al., 1991; Heitz et al., 1991;
Saska & Ozer, 1995; Tortosa et al., 1995) and the lignin
removal (Bouchard et al., 1991; Heitz et al., 1994; Montane
Fig. 3. Dependence of the percent of xylan removal with log R0
et al., 1994a). The mathematical interpretation of xylan
removal in terms of R0 (Overend & Chornet, 1989; Bou- (R0 = severity factor) for selected raw materials calculated from
chard et al., 1991; Heitz et al., 1991; Abatzoglou et al., 1992; the data of Overend and Chornet (1989), Bouchard et al. ( 1991),
and Tortosa et al. (1995)
Tortosa et al., 1995) is based on the following differential Heitz et al. (1991),
Bild 3. Abhangigkeit dert Xylanauslosung (in Prozent) von log
equation:
R (gewichteter Einufaktor) fur ausgewahlte Rohstoffe, be

198


T 100
R0 t
exp
14:75

Table 7. Effects of hydrothermal treatments on cellulose

Tabelle 7. Einu hydrothermischer Behandlung auf
Cellulose

eq. 2
Raw material

Temp.
C

Solubilized
cellulose (%)

References

a) Hardwoods
Eucalyptus
Mixed hardwoods
Mixed hardwoods
Pinus pinaster
Pinus silvestris
Poplar
Populus tremuloides

230
275
230
190
210
230
230

8
20

Carrasco et al., 1994

Biermann et al., 1984
Abatzoglou et al., 1990
Carrasco et al., 1994
Carrasco et al., 1994
Carrasco et al., 1994
Heitz et al., 1991

b) Agricultural residues
Bamboo grass
Corn stalks
Corn stover
Sugarcane bagasse
Sugarcane bagasse
Sunower seed hulls
Sweet shorgum bagasse
Thistle
Vine shoots
Wheat straw

206.2
230
190
185
170
200
230
210
190
190

Cellulose degradation <5%

a
a

12
15
a

52
29
a
a
a

5
27
16
20

Aoyama et al., 1995

Tortosa et al., 1995
Lapmtey et al., 1985
Fontana et al., 1995
Saska & Ozer, 1995
Dekker & Wallis, 1983
Carrasco et al., 1994
Carrasco et al., 1994
Carrasco et al., 1994
Carrasco et al., 1994

been determined for agricultural residues. For these raw

materials, up to 50% cellulose hydrolysis has been reported for experiments performed at temperatures within
the usual range in hydrothermal treatments.
The structural modication caused during hydrothermolysis causes an increased reactivity of solid residues,
particularly in substrates subjected of steam explosion.
The favourable effects induced by hydrothermal treatments include: i) increased available surface area, caused
by delignication, hemicellulose degradation and higher
pore volume (Grouss et al., 1986; Grethlein & Converse,
1991); ii) changes in microstructure, including loss of
crystallinity, debration and defribilation (Marchessault
et al., 1983; Schultz et al., 1983; Capek-Menard et al., 1987;
Boocok & Kosiak, 1988; Barnet et al., 1989; Kallavus &
Gravitis, 1995). Owing to these factors, hydrothermal
pretreatments can also be conceived as a pretreatment of
the raw materials for improving their behaviour as substrates for the enzymatic hydrolysis of cellulose (Dekker &
Wallis, 1983; Biermann et al., 1984; Schultz et al., 1984a;
Schultz et al., 1984b; Grouss et al., 1986; Capek-Menard
et al., 1987; Szczodrak, 1988; Biermann & McGinnis, 1990).
The reaction mechanism of the hydrothermal degradation of cellulose is essentially the same as described above
for hemicelluloses. However, the physicochemical characteristics of cellulose (linear conguration, high polymerization degree and crystalline structure) make
hydrolization more difcult than hemicelluloses does.

8
Effects on lignin
In aqueous media, lignin can undergo both degradation
and repolymerization reactions. The fraction of solubilized
lingnin depends on the operational conditions (Shimizu
et al., 1989) and on the raw material (Wallis & Wearne,
1985). The lignin solubilization involves both the breaking
of lignin-carbohydrate bonds and lignin depolymerization
reactions. Syringil units have been reported as the lignin
fragments most susceptible to hydrothermal degradation
(Shimizu et al., 1989). For a given temperature, the fraction
of solubilized lignin increases with the reaction time to
reach a maximum value, and then decreases (Lora &
Wayman, 1978; Dekker & Wallis, 1983; Heitz et al., 1991;
Montane et al., 1994a; Aoyama et al., 1995; Tortosa et al.,
1995). A two-step mechanism has been proposed for lignin
reaction (Lora & Wayman, 1978): in a rst, fast stage,
lignin fragments with low molecular weight and high reactivity are solubilized by breaking lignin-carbohydrate
bonds (Burstcher et al., 1987); and in a subsequent, slower
stage, lignin repolymerization occurs in the presence of the
organic acids released by hydrothermal treatments to yield
insoluble condensation products. This idea was completed
by other authors (Dekker & Wallis, 1983; Schultz et al.,
1983; Heitz et al., 1991; Montane et al., 1994a; Aoyama
et al., 1995; Tortosa et al., 1995) suggesting that sugar and/
or sugar degradation products (such as furfural) also react
with lignin. The generation of insoluble lignin by condensation (also called ``pseudolignin'') results in increased
Klason lignin (acid-insoluble lignin) content in solid residues from treatments (Heitz et al., 1991; Montane et al.,
1994a; Aoyama et al., 1995).

Under harsh operational conditions, up to 60% lignin

can be depolymerized during hydrothermal treatments
(Biermann et al., 1984), but a signicant fraction of cellulose (up to 20%) can be degraded. Under milder conditions, Saska & Ozer (1994) reached 39.4% lignin removal
from sugarcane bagasse with less than 2% cellulose degradation.
The lignin contained in the solid residues from autohydrolysis has lower molecular weight than the original
one (Biermann et al., 1984), but no structural differences
between them have been reported (Heitz et al., 1991).
As a result of hydrothermal treatments, solid residues
show improved susceptibility towards delignication with
alkaline solutions or organic solvents. Table 8 lists some
representative works on this eld. NaOH allowed almost
quantitative lignin removal of solid residues from hydrothermal treatments (Lora & Wayman, 1978; Biermann
et al., 1984; Heitz et al., 1991), but signicant amounts of
cellulose (up to 50% of the initial one) were also solubilized. Organic solvents allowed a selective solubilization of
lignin from lignocellulose subjected to hydrothermal
processing: for example, Lora & Wayman (1978) reported
90% lignin removal with dioxane, and Biermann et al.
(1984) reached 84% lignin removal using acetone, in both
cases delignication being performed with a remarkable
selectivity towards cellulose degradation. As a modication of this operational procedure, Shimizu et al. (1989)
proposed a sequential extraction with organic solvents for
obtaining lignin fractions with different properties. As a
summary, Table 9 shows the operational conditions used
for delignication of solid residues from hydrothermal
treatments.

9
Conclusions
Hydrothermal processes are environment-friendly technologies that can be conceived as a rst step for the
chemical utilization of lignocellulose. The low operational
costs derived from both consumption of chemicals and
corrosion as well as the compositional and structural
modications provoked in substrates are important

Table 8. Solvents for lignin extraction

Tabelle 8. Losemittel fur die Extraktion von Lignin
Solvent

References

Acetic acid
Acetone
Dioxane

Lawther et al., 1996

Biermann et al., 1984
Lora & Wayman, 1978; Barnet et al.,
1989; Excofer et al., 1989; Shimizu
et al., 1989
Marchessault et al., 1983
Marchessault et al., 1983; Wallis &
Wearne, 1985
Barnet et al., 1989
Barnet et al., 1989
Lora & Wayman, 1978; Biermann et al.,
1984; Wallis & Wearne, 1985;
Shimizu et al., 1989; Heitz et al., 1994
Marchessault et al., 1983

DMSO and ethanol

Ethanol
Ether
Ethyl acetate
NaOH
Tetrahydrofuran

199

Table 9. Solvents assayed for lignin extraction from solid residues of hydrothermal treatments
Tabelle 9. Losemittel fur die Extraktion von Lignin aus festen Ruckstanden des hydrothermischen Aufschluses
Raw material

200

Hydrothermal
treatment

Lignin extraction

t (min)

T (C)

Solvent conc.

t (min)

T (C)

MLRa (%)

Hardwoods

270

Acetone 100%

84

Biermann et al., 1984

Aspen wood
Hardwoods
Aspen wood

425
220
17

195215
180230
205

Dioxane 90%
Dioxane 90%
NaOH 1%

240

180

89.5

98.8

Lora & Wayman, 1978

Shimizu et al., 1989
Lora & Wayman, 1978

Hardwoods
Populus
tremuloides

1
24

275
220230

NaOH 2%
NaOH 2%

60
30

Room
temperature

Normal
boiling point
100
100

94
90

Biermann et al., 1984

Heitz et al., 1991

References

Maximum lignin removal achieved in experiments

advantages of these technologies. The effects caused by

hydrothermal treatments include hemicellulose depolymerisation (to yield sugar oligomers, hemicellulosic sugars
and degradation products), cellulose alteration (mainly in
relation with its physicochemical features) and chemical
alteration of lignin (that facilitates further delignication
steps with organosolvents and/or alkaline solutions). The
kinetic modelling of hemicellulose depolymerisation has
been carried out by pseudouhomogeneous, rst-order
models and by methods involving severity factors. Based
on the data reported in literature, both types of models are
useful to interpret the dynamics of treatments for selected
raw materials, allowing an optimization based on technical
criteria. Cellulose degradation during hydrothermal
treatments is important only when operating under harsh
operational conditions, whereas the solid residues produced show enhanced susceptibility towards delignication. All the above aspects have been reviewed on the basis
of the available information.

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