Biomass and Bioenergy 23 (2002) 367 380

The acid hydrolysis of sugarcane bagasse hemicellulose to

produce xylose, arabinose, glucose and other products
B.P. Lavaracka , G.J. Gri(nb; , D. Rodmanc
b School

a Sugar Research Institute, Mackay, Qld 4740, Australia

of Engineering, James Cook University, Townsville, Qld 4811, Australia
c CSR Ltd., Pioneer Mill, Ayr, Qld 4807, Australia

Received 10 December 2001; received in revised form 17 May 2002; accepted 22 May 2002

Abstract
Experimental trials of the dilute acid hydrolysis of bagasse hemicellulose to produce xylose, arabinose, glucose, acid-soluble
lignin (ASL) and furfural were conducted using a temperature-controlled digester. The reaction conditions varied were;

temperature (80200 C), mass ratio of solid to liquid (1:5 1:20), type of bagasse material (i.e. bagasse or bagacillo),
concentration of acid (0.25 8 wt% of liquid), type of acid (hydrochloric or sulphuric) and reaction time (10 2000 min).
Kinetic modelling of the global rates of formation of products was performed. The most accurate kinetic model of the global
reaction for the decomposition of xylan was a simple series hydrolysis of xylan to xylose followed by xylose decomposition.
Similar schemes were used to model the production of arabinose, glucose and furfural from the hemicellulose. The production
of ASL was modelled by a 9rst-order decomposition of lignin to ASL followed by a reversible decomposition of ASL.
Yields of up to 220 mg xylose=g solid were achieved, i.e. about 80% of the theoretical xylose available from the bagasse.
The bagasse particle size was found to negligibly a<ect the rate of hydrolysis. Hydrochloric acid was found to be less active
for the degradation of xylose compared to sulphuric acid. ? 2002 Elsevier Science Ltd. All rights reserved.
Keywords: Bagasse; Hemicellulose; Acid hydrolysis; Xylose; Arabinose; Glucose; Lignin; Acid-soluble lignin; Furfural

1. Introduction
Sugarcane bagasse constitutes the 9brous residue of
sugar cane after undergoing conventional milling. An
absolute minimum of about 50% of this 9bre is needed
to generate heat and power to run the sugar milling
process [1] and the remainder can be stockpiled. The

Corresponding author. Tel.: +61-7-47814435; fax: +61-747751184.

E-mail address: gregory.gri(n@jcu.edu.au (G.J. Gri(n).

stockpiled bagasse is of low economic value and constitutes an environmental problem to sugar mills and
surrounding districts, especially if stockpiled for extended periods, due to the risk of spontaneous combustion occurring within the pile [2]. As a means of
minimising this hazard, many mills have highly inef9cient furnaces that burn large portions of the excess
bagasse. It has been estimated that bagasse consumption within sugar mill boilers could be reduced by up
to 36% by ceasing such practices and adopting more
energy e(cient modes of operation [3,4]. If a suitable
use could be found for the excess bagasse there is,

0961-9534/02/$ - see front matter ? 2002 Elsevier Science Ltd. All rights reserved.
PII: S 0 9 6 1 - 9 5 3 4 ( 0 2 ) 0 0 0 6 6 - 1

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B.P. Lavarack et al. / Biomass and Bioenergy 23 (2002) 367 380

potentially, 2 million tonnes p.a. of bagasse feedstock

available in Australia alone [5].
As bagasse 9bre is constituted, mainly, of lignocellulosic material, considerable research e<ort has been
extended on investigating acid catalysed hydrolysis
to cleave the intrachain linkages in hemicellulose and
cellulose chains contained in bagasse to produce commercial quantities of xylose, glucose and other sugars.
With sustained hydrolysis the sugars may be degraded
to such decomposition products as furfural, hydroxymethylfurfural and furan resins. Furfural may also
be a desirable product, however, the process also results in the degradation of bagasse lignin to the soluble form, acid-soluble lignin (ASL), an impurity that
would need to be removed from the more desirable
monosaccharide or furfural products.
Prior research on the hydrolysis of bagasse and
similar materials has concentrated on the use of low
concentration mineral acids [6 13]. In this paper research is presented on the hydrolysis of bagasse by
using dilute sulphuric acid or hydrochloric acid at elevated temperature and pressure so as to break down
the constituent hemicellulose. In this technique, the elevated temperatures softens the lignin protective layer
around the hemicellulose 9bres and allows the acid to
hydrolyse the hemicellulose to form polysaccharides
and monosaccharides of, mainly, xylose and arabinose
[6]. The conditions are not as severe as to produce
signi9cant amounts of cellulose decomposition products. This research presents data on the yield of the
products xylose, arabinose, glucose, furfural and ASL
under varying reaction conditions. Kinetic modelling
of the global rates of formation of products, based on
earlier researchers models of acid hydrolysis using
mineral acids, is presented. The reaction conditions

tested were temperature (80 200 C), ratio of bagasse

mass to water mass (1:5 1:20), type of bagasse material (i.e. bagasse or bagacillo), concentration of acid
(0.25 8 wt% of liquid), type of acid (sulphuric or hydrochloric) and reaction time (10 2000 min).
2. Methods
2.1. Characterisation of materials tested
Two bagasse fractions were used in the study: (1)
mill run bagasse and (2) bagacillo. All feed samples

were taken from Victoria Mill, located near Ingham

on the North Queensland Coast. The terms mill run
bagasse and bagasse are interchangeable and refer
to samples of sugar cane 9bre collected from the last
tandem roller in the milling train. Bagacillo constitutes
the 9ner size fraction of bagasse that is used as a 9lter
aid in the re9ning process of the raw sugar factory.
Its composition tends to be higher in parenchyma and
broken cells and it is separated from the bagasse by
a cross Qow of air blown through a stream of falling
bagasse.
The hemicellulose in bagasse is composed of a xylan polymer backbone onto which other groups are
bondedmainly glucuronic acid and arabinose [14].
The standard TAPPI method (method T 223 cm-84)
[15] was applied to determine the pentosan (i.e. combined polysaccharides of xylose monomers and arabinose) content of each of the bagasse fractions (see
Table 1). The repeatability within a laboratory was reported in the method as 6.6% and the analytical error
was calculated using this 9gure. Bagacillo and bagasse
had, as expected, similar pentosan contents. The pentosan contents of the various bagasse fractions studied in this work fell within the range 192323 mg g1
that have been reported for bagasse [16].
Previous research has indicated a wide range in the
relative amounts of xylose (or its polymer xylan),
bound arabinose and bound glucuronic acid found in
hemicellulose. The data on the mole ratio of arabinose
to xylose and xylose to glucuronic acid range between
0.019 0.247 and 7.4 100, respectively [8,12,14,17
20]. The method by which the xylan=xylose, bound
arabinose and bound glucuronic content of hemicellulose was determined is presented in the Results
section.
During acid hydrolysis of bagasse some portion
of the lignin content (the Klason lignin) is hydrolysed to form ASL [21]. The Klason lignin content
of the bagasse was measured by the standard TAPPI
method (method T222 om-88) [15,22] as 222:5 mg g1
bagasse. This was in the upper range of 143226
quoted by others [8,9,16,20,2326].
2.2. Hydrolysis experiments
Bagasse samples were frozen to inhibit the growth
of bacteria and fungi commonly found in bagasse piles
that can degrade the available hemicellulose. Prior to

B.P. Lavarack et al. / Biomass and Bioenergy 23 (2002) 367 380

369

Table 1
Chemical content of dried bagasse fractions

Bagasse
fraction

Pentosan content
(mg g1 material) (dry basis)

Maximum potential pentose

yield (mg g1 material)

Ratio of arabinose=xylose

Bagacillo
Bagasse

277 18
268 18

315 20
305 20

0:11 0:01
0:11 0:01

0.68
0.58

hydrolysis, the bagasse would be dried at 105 C for

16 h and then stored in a desiccator so as to ensure
low residual moisture content. Three di<erent hydrolysis apparatus were used depending on the duration
and temperature of hydrolysis. For short trials (i.e. hydrolysis lasting less than 1 h) at temperatures greater

than 100 C a sample of bagasse (0.750 1:000 g) was

placed in a 86 ml TeQon reaction vial. The desired
volume of dilute acid (5 15 ml) was pipetted into the
vial and the vial then sealed. The TeQon reaction vial
was mounted in a Milestone MLS 1200 microwave
oven. The vial contained a temperature sensor connected to the microwave control unit to ensure rapid
heating and accurate temperature control. The heating
time to the desired temperature was 23 min. At the
end of the reaction time period the sample was cooled
promptly using a water-cooled bath. The product was
9ltered and washed with hot water until the 9ltrate
volume had reached 50 ml.
Hydrolysis tests longer than 1 h and at temperatures

greater than 100 C were performed using reactor vials

manufactured from 316 stainless steel that were inserted into a high temperature silicone oil bath. Each
reaction vial was of 170 ml volume, threaded at the
open end and sealed by fastening on a threaded top.
Each top was made of stainless steel and had a PTFE
seal. A K-type thermocouple was inserted into one of
the reactor vials to provide a reference temperature.
The bagasse sample was weighed to an accuracy of
0:001 g into a 20 ml beaker and transferred into the
vial via a funnel and the correct volume of liquid was
pipetted in. The reaction vial was sealed and placed
in oil. The temperature inside the vial was measured
to ensure the accuracy of the oil bath temperature setting. The temperature of the reaction mixture typi
cally reached within 2 C of the set temperature within
10 min. The vial was withdrawn from the oil bath
at the due time and placed in a water bath at ambient temperature for 10 min. The bagasse residue was

9ltered and washed with hot water and the 9ltrate

made up to volume in a 50 ml volumetric Qask.
Inspection of the reactor vials after the completion of each run showed no indication of corrosion of
the inside surface or contamination of the hydrolysate
with corrosion products that may have inQuenced the
catalytic activity of the acid solution.
Hydrolysis tests conducted at temperatures less than

100 C were performed in sealed 1 litre glass reagent

bottles placed in a temperature-controlled water bath.
Samples of hydrolysate were taken at regular intervals
and 9ltered.
Samples of the 9ltrate were analysed for xylose,
arabinose, glucose and furfural by high-pressure liquid chromatography (HPLC) using the analysis conditions listed in Table 2. The ASL was determined
using a method developed by Maekawa et al. [27].
The absorbance of the hydrolysate was measured at
205 nm with 10 mm quartz cuvettes with reference
to 3% sulphuric acid as zero absorbance. The hydrolysate sample was diluted with 3% sulphuric acid
solution to give an absorbance in the range 0.2 0.7.
The absorbances were measured on a spectrophotometer (Unicam 8625 UV=VIS). The 3% acid solution
was prepared from laboratory distilled water and 98%
sulphuric acid, (Univar) AR grade.
3. Kinetic models
3.1. Xylose formation
A variety of models for hemicellulose acid hydrolysis in batch reactors are postulated in the literature
[6]. The simplest model for xylan hydrolysis involves a series of irreversible reactions from solid
xylan to aqueous xylose and then onto decomposition
products (Scheme 1). This scheme has often been
considered de9cient, as the decomposition of xylan

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B.P. Lavarack et al. / Biomass and Bioenergy 23 (2002) 367 380

Table 2
HPLC analytical conditions

Column
Packing
Mobile phase
Flow rate
Pre-column 1
Pre-column 2
Temperature
Injection volume
Run time
Detector

xylan(s)

k1

k2
xylose(aq)

Xylose, arabinose and glucose

Furfural

300 6:5 mm
Interaction CHO-620
0:05 mol=dm3 Na2 Ca(EDTA)
0:5 ml=min
Keystone Scienti9c, Inc. C-18
guard column, 11 6 mm
Interaction CHO-620 guard
column, 23 6 mm

90 C
20 l
22 min
GBC 1240 RI detector

23 6 mm (Guard column)
Interaction GC-coregel 87H
0:05 mol=dm3 sulphuric acid
0:5 ml=min

40 C
20 l
5 min
GBC 1240 RI detector

xylaneasy-to-hydrolyse (s)
k 1,e

decomposition products

k2

xylose(aq)

Scheme 1.

furfural

k 1,h

to xylose cannot be considered a single-step process

[28]. Rather, the xylan chain is 9rst decomposed to
xylo-oligosaccharides, then the decomposition proceeds to yield xylose monomer [29]. The xylose
decomposes further to furfural and then onto furan
resins and other products. For the purpose of practical calculation, the decomposition of xylan has often
been modelled as the sum of two parallel 9rst-order
reactions, namely a fast hydrolysis reaction and a
slow hydrolysis reaction (Scheme 2).
Consequently, the xylan has been categorised into
an easy-to-hydrolyse fraction and a hard-to-hydrolyse
fraction [6,30,31]. It must be noted that these fractions have been de9ned for convenience of rate calculations and, in previous work, has not been linked
to any physical or chemical characteristics of the raw
material.
Scheme 2 has been further re9ned to take account
of the possibility of multiple decomposition products
xylaneasy-to-hydrolyse (s)
k 1,e

xylanhard-to-hydrolyse (s)

k3

decomposition products
Scheme 3.

that may form from xylose [32,33]. Consequently a

di<erent mechanism (Scheme 3) has been proposed
[6]. In this scheme, furfural is the major decomposition product with known activation energy for the
decomposition process (140:5 kJ mol1 [34]).
In all schemes, the reaction rate has been assumed
to be 9rst order with respect to the reactants in each
reaction step. Under conditions of isothermal reaction,
the concentration of xylose present in the aqueous solution for Schemes 13 are, respectively:



k1
L
s
Cx = Cx0
(ek1 t ek2 t );
(1)
k2 k1

k2

xylose(aq)
k 1,h
xylanhard-to-hydrolyse (s)
Scheme 2.

decomposition products

B.P. Lavarack et al. / Biomass and Bioenergy 23 (2002) 367 380

k1
bound arabinose(s)

371

k2
arabinose(aq) decomposition products
Scheme 4.

k1
k2
bound glucuronic acid(s) glucose(aq) decomposition products
Scheme 5.

k1; e
(ek1; e t ek2 t )
k2 k1; e




(1 )k1; h
(ek1; h t ek2 t ) ;
(2)
+
k2 k1; h




k1; e
L
s
(ek1; e t e(k2 +k3 )t )
Cx = Cx0
(k2 + k3 ) k1; e




(1)k1; h
(ek1; h t e(k2 +k3 )t ) ;
(3)
+
(k2 + k3 )k1; h

s
CxL = Cx0

where CxL is the concentration of xylose in liquid

s
(g g1 solid), Cxo
the equivalent xylose concentration
if all xylan were converted to xylose (g g1 solid),
n
ki = Cacid
Ai eEi =RT a pseudo reaction rate constant

for reaction step i (s1 );

(4)

where Ai is the pre-exponential constant for reaction

i (s1 ), Cacid is the sulphuric or hydrochloric acid
concentration (wt% of liquid), Ei the activation energy for reaction i (J mol1 ), n the order of reaction w.r.t. acid concentration, T the temperature (K),
t the reaction time (s),  the fraction of xylan that is
easy-to-hydrolyse,  the ratio of solid bagasse material to liquid (g g1 ).
In analysing the xylose yields from the experimental
trials, these three equations were 9t to the experimental
data to determine which scheme best agreed with the
experimental data. The unknown adjusted parameters
were the activation energies, pre-exponential factors
and exponent, n.
3.2. Arabinose, glucose and furfural formation
Kinetic models of the formation of arabinose and
glucose by hemicellulose hydrolysis have not been

k1
k2
pentosans(s) furfural(aq) decomposition products
Scheme 6.

reported in the literature. It was decided to test a model

of the formation of these product using the simplest
modelconsecutive 9rst-order reactions, Schemes 4
and 5. As with Scheme 1, the reactions were assumed
to be 9rst order with respect to the reactants.
Furfural is one of the decomposition products from
the hydrolysis of arabinose and xylose. Previous researchers data have indicated that the rate of xylose
degradation is much slower than that leading to the
formation of furfural [30,31,35]. Hence, Scheme 6 was
adopted for the model. As with the xylose kinetic models, in these schemes the reaction rate was assumed
to be 9rst order with respect to the reactants in each
reaction step. Hence, under conditions of isothermal
reaction, the concentration of arabinose, glucose or
furfural present in the aqueous solution had the same
form as Eq. (1):



k1
L
s
Cj = Cj0
(ek1 t ek2 t );
(5)
k2 k1
where CjL is the concentration of component j (arabinose, glucose or furfural) in liquid (g g1 bagasse),
s
Cj0
the equivalent concentration of component j if
all bound arabinose, bound glucuronic acid or pentosans, were converted to arabinose, glucose and furfural, respectively (g g1 bagasse), other terms are as
de9ned earlier.
3.3. ASL formation
Three kinetic models for the solubilisation of lignin
are presented in the literature. Sidiras and Koukios
[36] found that the hydrolysis mechanism for solubilisation of wheat lignin with ethanol is di<usion
controlled. This model was not considered as

372

B.P. Lavarack et al. / Biomass and Bioenergy 23 (2002) 367 380

k1
k2
lignin(s) ASL(aq) decomposition products
Scheme 7.

experimental results indicated that bagasse particle

size was not a controlling factor in the hydrolysis
process (see experimental results).
Two models were presented by Vazquez et al. [37].
The simpler, Scheme 7, is a consecutive 9rst-order
reaction mechanism that is similar to that proposed
for the production of xylose, glucose and arabinose in
this study. This yields a kinetic equation of the same
form as Eq. (5).
The second mechanism given by Vazquez et al. suggests that the formation of the decomposition products
is a reversible reaction, Scheme 8. In this scheme, the
concentration of ASL is given by
LASL
k1 k3
=
exp(k1 t)
Lo
k3 + k2 k1


k1 k3
k3
+

k2 + k 3
k3 + k2 k1
exp ((k2 + k3 )t) +

k3
;
k2 + k 3

(6)

where LASL is the concentration of ASL (g g1 solid),

Lo the original concentration of lignin in bagasse
(g g1 solid), and other terms are as de9ned earlier.
4. Results and discussion
4.1. Determination of the easy-to-hydrolyse,
hard-to-hydrolyse and total arabinose=xylose
fractions
As noted in the previous section, the modelling of
the xylose formation by hemicellulose hydrolysis has
often required the determination of the easy-to hydrolyse and hard-to-hydrolyse fraction of the xylan. To

lignin(s)

determine these fractions, and the total amount of xylose present in the bagasse, samples were hydrolysed

with 4 wt% sulphuric acid at 90 C in 1 l reagent bot

tles placed in a water bath at 90 C. Samples of hydrolysate were taken at regular intervals and analysed
for xylose. Under these mild conditions, degradation
of the xylose and arabinose is minimised over the hydrolysis period.
Fig. 1 shows a typical plot of the aqueous xylose and arabinose concentration versus time. Fig. 2
s
shows a plot of the natural log of (1 CxL =Cx0
)
versus time. It can be seen that the concentration
of xylose increases relatively rapidly over the 9rst
300 600 min and follows a trajectory that would be
expected for a 9rst-order reaction. This period has
been interpreted as representing the hydrolysis of the
easy-to-hydrolyse fraction of the xylan. The hydrolysis then proceeded at a slower but measurable rate.
This period has been interpreted as representing the
hydrolysis of the hard-to-hydrolyse fraction of the
xylan. The fraction of easy-to-hydrolyse material ()
was determined by extrapolating the data points, for
times greater than 400 min, back to time=0. From this
analysis the value of  was determined (see Table 1).
These results indicated a slight variation in the xylan
degradation rates existed between the bagasse and
bagacillo, with bagacillo undergoing more rapid xylan degradation, i.e. containing a higher proportion of
easy-to-hydrolyse xylan. A possible explanation for
this could be the smaller mean size of the bagasse
particles, indicating intra-particle resistance to mass
transfer may be a<ecting the overall rate.
The production of arabinose was found to be more
rapid over the 9rst hour but, after this initial period, the
ratio of arabinose to xylose in the hydrolysate reached
a constant value of between 0.107 and 0.118. This was
well within the range reported by other researchers. It
was assumed that this ratio reQected the ratio of bound
arabinose to xylan in the bagasse hemicellulose. There
was little di<erence between the ratio for bagasse
and bagacillo. Thus, using the potential pentose
k2

ASL(aq)

decomposition products
k3

Scheme 8.

Aqueous concentration of xylose or arabinose (mg/g solid)

B.P. Lavarack et al. / Biomass and Bioenergy 23 (2002) 367 380

373

250

200

Bagasse - xylose
Bagacillo - xylose
Bagasse - arabinose
Bagacillo - arabinose

150

100

H2SO4 concentration = 4%
= 0.05
Temperature = 90oC

50

0
0

200

400

600

800

1000

1200

1400

1600

1800

2000

1600

1800

2000

time (min)
Figure 1. Hydrolysis of bagasse=bagacillo.

e0

1 - (CLx / Csx0 )

Easy-to-hydrolyse

Hard-to-hydrolyse

e1

Bagasse
Bagacillo

H2SO4 concentration = 4%
= 0.05
Temperature = 90 C

e2
0

200

400

600

800

1000

1200

1400

time (min)
Figure 2. Determination of easy-to-hydrolyse xylan fraction in bagasse material.

yield from the hemicellulose pentosan content, the

amount of arabinose in the bagasse and bagacillo was
calculated as 30 and 33 mg g1 solid, respectively,
with a potential maximum xylose yield of 274 and
282 mg g1 solid.

4.2. Xylose kinetics results

A total of 350 separate hydrolysis experiments were
conducted using the conditions described in the Introduction. A MarquardtLevenberg curve-9tting routine

374

B.P. Lavarack et al. / Biomass and Bioenergy 23 (2002) 367 380

available in Sigmaplot version 2.01 was used to 9t

Eqs. (1) (3) to the experimental data using the
activation energies, pre-exponential constants and
exponent, n, as adjustable parameters. The predicted
results from the curve-9tting routine were compared
with the experimental results and analysed to determine the standard error and regression coe(cient
by anova. Table 3 shows the predicted parameters,
regression coe(cients and standard error for each
scheme using the data collected for hydrolysis using
sulphuric acid. The table clearly shows the predicted
xylose yields for the three di<erent models give very
similar levels of accuracy, the variation between the
predictions of the di<erent models were found to be
small. In fact, applying the easy-to-hydrolyse and
hard-to-hydrolyse concept in Scheme 2 gave the
worst model 9t to the experimental data. It appears
that the hard-to-hydrolyse component of the xylan
was so inert to hydrolysis that little of that component
was converted in the experimental trials undertaken.
Scheme 3 gave better predictions than Scheme 2 and
nearly matched Scheme 1. Therefore, any further
discussion has been restricted to the simplest model,
Scheme 1. Using this scheme, the activation energy for
xylan hydrolysis to xylose determined for all bagasse
materials (82.8107:2 kJ mol1 ) were in the same
range as has been reported for a range of lignocellulosic materials (53142 kJ mol1 ) [8,13,28,38,39].
Fig. 3 shows typical results for the predicted and
experimental data for bagasse hydrolysis to produce
xylose as a function of time. There is some scatter in
the experimental data that is ascribed to the variation
in bagasse properties between tests and analytical error. The plots show a clear increase in xylose concentration as the xylan degrades, reaching a maximum,
then decreasing when the xylose degradation rates be
come signi9cant. At the higher temperature (200 C),
the rates of reaction are increased and the maximum
xylose concentration is reached after less time. Similarly, at higher acid concentration the rates of hydrolysis are increased with consequent rapid degradation
of xylose. In all tests conducted the maximum xylose
yield was only 220 mg g1 solid, some 80% of the
theoretical xylose contained in the hemicellulose.
Fig. 4 compares the xylose yields obtained from the
di<erent bagasse materials. These data showed there
was little evidence to suggest that di<usion through
the bagasse 9bres a<ected the rate of reaction as the

9ner material (bagacillo) showed no measurable difference in yield over the coarser bagasse material.
Table 4 shows the predicted parameters, regression
coe(cients and standard error for Scheme 1 using
the data collected for xylose yield with hydrochloric
acid. As results using sulphuric acid had indicated
that particle size was not a strong inQuence on the
degradation rates, only bagacillo was tested using hydrochloric acid. Fig. 5 shows a typical set of hydrolysis results with the experimental data (data points)
and 9tted model (solid and dashed lines). Included in
the 9gure are the predicted results using the kinetic
parameters derived from the sulphuric acid trials. To
compare the results of the two acids, an equivalent sulphuric acid concentration was calculated by multiplying the hydrochloric acid concentration by 98=35.5 and
using this concentration in the sulphuric acid model.
As the pH of all hydrolysis solutions was well below
1.9 (the approximate pKa of the bisulphate ion) it was
assumed the sulphuric acid acted as a monoprotic acid.
It can be seen that the rate of xylose production for
the 9rst 100 min is very similar for both models, indicating that the type of acid used does not inQuence the
degradation of the bagasse. However, after this 9rst
100 min, the sulphuric acid model shows a much more
rapid degradation of the xylose and lower maximum
yield. Comparison between the xylose kinetic parameters derived for bagasse hydrolysis using sulphuric
acid (Scheme 1, Bagasse, Table 3) and hydrochloric
acid (Xylose, Table 4) show the main di<erence lies
with the pre-exponential function for xylose degradation. This is an order of magnitude lower when HCl
is used as the catalyst. This indicates that the type of
acid used does inQuence xylose degradation kinetics.
Fig. 5 also shows the a<ect of changing the solid
to liquid ratio, . As expected, decreasing the solid
to liquid ratio reduced the rate at which the xylose
decomposed as the xylose produced is more dilute
within the hydrolysate.
4.3. Arabinose, glucose and furfural kinetics
results
Fig. 6 shows a typical set of data for the yield of
arabinose, glucose and furfural from the hydrolysis of
bagasse. The kinetic models of these data are shown
as lines. To determine the amount of glucuronic acid
in the bagasse, experiments were conducted under

B.P. Lavarack et al. / Biomass and Bioenergy 23 (2002) 367 380

375

Table 3
Kinetic model results for xylose yield using sulphuric acid

Scheme 1
Feed

Bagasse

s1

Bagacillo

106

A1 ;
E1 , kJ mol1
A1; e , s1
E1; e , kJ mol1
A1; h , s1
E1; h , kJ mol1
A2 , s1
E2 , kJ mol1
A3 , s1
E3 , kJ mol1
n
Correlation coe(cient, R
Std error in xylose yield, mg g1

21:6
82.8

2:66 1012
118.9

0.82
0.88
32.5

250

Scheme 2
109

30:3
105.9

2:66 1012
117.6

0.97
0.96
22.6

Scheme 3

Bagasse

Bagacillo

Bagasse

Bagacillo

97:6 106
88.1
1:46 106
73.5
0:294 1012
111.2

0.79
0.88
32.5

1346:0 106
98.6
11:9 106
76.5
0:353 1012
113.8

0.27
0.83
44.2

28:5 106
83.8
28:5 106
83.8
4:72 109
140.5
87:0 1010
115.0
0.81
0.88
32.5

46370 106
107.2
46370 106
107.2
4:72 109
140.5
70:6 1010
113.0
0.97
0.96
23.2

= 0.05

Xylose yield (mg/g bagasse)

200

150

100
Model

Exp.

T = 120oC, Cacid=1wt%
T = 160oC, Cacid=1wt%
T = 120oC, Cacid=4wt%

50

0
0

50

100

150

200

250

300

Time (min)
Figure 3. E<ect of hydrolysis temperature and sulphuric acid concentration on xylose yield.

conditions of low severity (i.e. T = 120 C and Cacid =

0:51:0 wt% H2 SO4 ) and the glucose to xylose
ratio calculated. It was found that after 300 min of
hydrolysis the glucose to xylose mass ratio in the hy-

drolysate reached a steady state value of 0:15 0:01.

This ratio was used to determine the theoretical
amount of glucose that could be extracted from the
bagasse hemicellulose (42 3 and 41 3 mg g1

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B.P. Lavarack et al. / Biomass and Bioenergy 23 (2002) 367 380

250

= 0.05 T = 120oC

Xylose yield (mg/g solid)

200

150

100
Model

Exp.

bagasse

Cacid = 1 wt%

bagacillo

50

bagasse

Cacid = 0.25 wt%

bagacillo
0
0

50

100

150

200

250

300

350

Time (min)
Figure 4. E<ect of bagasse material on xylose yield.
Table 4
Kinetic model results for xylose, arabinose, glucose and furfural yield using hydrochloric acid

A1 ; s1
E1 ; kJ mol1
A2 ; s1
E2 ; kJ mol1
n
Correlation coe(cient, R
Std error in yield, mg g1

Xylose

Arabinose

Glucose

Furfural

2:30 106
74.5
6:81 1011
114.8
0.93
0.79
32.5

0.604
21.3
4:41 1013
135.1
0.63
0.81
5.5

18:0 109
105.0
6:65 1011
117.6
1.24
0.77
7.3

87:2 1015
165.6
1:28 1014
131.1
1.87
0.87
7.4

solid for bagacillo and bagasse, respectively). As

with the xylose production, there was no appreciable di<erence between the production rates between
bagasse and bagacillo and hydrochloric acid was
found to provide a greater rate of production. The
model parameters for hydrochloric and sulphuric acid
are shown in Tables 4 and 5 respectively. Unlike

xylose, under severe conditions (i.e. T 160 C)

complete recovery of the bound arabinose and glucose was possible. Furfural yields, however, were

very low with only about 15% ( 40 mg g1

solid) of the theoretical maximum yield being
produced.
4.4. ASL kinetics results
Fig. 7 shows a typical set of experimental results for
the ASL concentration in the hydrolysate versus time
and the model predictions for Schemes 7 and 8. It can
be seen that the model predictions of Scheme 8 9t the

B.P. Lavarack et al. / Biomass and Bioenergy 23 (2002) 367 380

250

Cacid = 3.0 wt% HCl

T = 90oC

= 0.05

Xylose yield (mg/g solid)

200

150
= 0.2

100

= 0.2
H2SO4 Model Prediction

50

0
0

200 400 600 800 1000 1200 1400 1600 1800 2000
Time (min)

Figure 5. Comparison of sulphuric acid and hydrochloric acid models.

20
Arabinose, glucose, furfural yield (mg/g bagasse)

Cacid = 0.25 wt% H2SO4

18

= 0.05

T = 120oC
Arabinose

16
14
12
10
8
6

Glucose

4
Furfural

2
0
0

50

100

150

200

250

300

Time (min)
Figure 6. Yields of arabinose, glucose and furfural from acid hydrolysis.

377

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B.P. Lavarack et al. / Biomass and Bioenergy 23 (2002) 367 380

Table 5
Kinetic model results for arabinose, glucose and furfural yield using sulphuric acid

Arabinose
Feed

Glucose

Bagasse

s1

Bagacillo

106

A1 ,
E1 , kJ mol1
A2 , s1
E2 , kJ mol1
n
Correlation coe(cient, R
Std error in yield, mg g1

Bagasse

106

17:1
84.1
1:51 108
87.9
0.49
0.733
5.7

Furfural
Bagacillo

109

375:0
90.3
2:12 107
79.2
0.82
0.542
8.2

18:0
107.3
2:66 1012
125.5
1.010
0.8751
4.6

20

109

18:0
107.4
2:66 1012
128.7
0.7747
0.9298
4.8

Bagasse
108

1:0
103.1
4:12 104
60.3
0.7217
0.8804
5.7

Bagacillo
3:25 1013
145.6
1:85 108
85.7
0.8425
0.9714
3.3

Scheme 7 Model

18
Scheme 8 Model

16
- experimental data points

ASL (mg/g solid)

14
12

= 0.05
T = 120oC

10

Cacid = 1.0 wt% H2SO4

8
6
4
2
0
0

50

100

150

200

250

300

350

Time (min)
Figure 7. Yields of ASL from acid hydrolysis.

data more closely and indeed, analysis of the models

agreement with the experimental results showed the
Scheme 8 had a standard error 25% less than that of
Scheme 7. Table 6 shows the model parameters for
Scheme 8. The yield of ASL was, at most, 47 mg g1
solid representing only about 20% of the lignin present
in the solid. As indicated in Fig. 7, ASL concentrations
reached a steady state value within about 30 min and
this 9nal steady state may indicate that a large propor-

tion of lignin was insoluble in the acid solution rather

than reQect a equilibrium condition as suggested by
Scheme 8 (Table 6).
5. Conclusions
Three kinetic models of xylose production by
the dilute acid hydrolysis of bagasse have been

B.P. Lavarack et al. / Biomass and Bioenergy 23 (2002) 367 380

379

Table 6
Kinetic model results for ASL yield

H2 SO4
Feed
s1

A1 ,
E1 , kJ mol1
A2 , s1
E2 , kJ mol1
A3 , s1
E3 , kJ mol1
n
Correlation coe(cient, R
Std error in yield, mg g1

HCl

Bagasse
106

2:16
85.2
1:23 109
95.7
4:54 104
64.4
0.390
0.90
4.7

tested. Scheme 1 gave the most accurate model. The

predicted value of activation energy for the xylan
degradation in the bagasse materials was of the same
order as previously reported for other lignocellulosic
materials. The two types of bagasse material tested
(mill-run bagasse and bagacillo) produced similar
amounts of xylose product when subjected to the
same reaction conditions suggesting the reaction was
kinetically controlled. Hydrochloric acid was found
to be a less active catalyst for the degradation of
xylose compared to sulphuric acid. Yields of xylose
were up to 80% of the maximum possible.
A simple consecutive series reaction scheme was
used to model the production of arabinose, glucose
and furfural. ASL formation was modelled with a
consecutive 9rst-order model containing an equilibrium reaction.
Acknowledgements
The Australian Research Council and CSR Sugar
Mills supported this work.
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