Bioresource Technology 102 (2011) 2062–2067

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Bioresource Technology
journal homepage: www.elsevier.com/locate/biortech

Kinetics of sequential reaction of hydrolysis and sugar degradation of rice husk

in ethanol production: Effect of catalyst concentration
Megawati a,⇑, Wahyudi B. Sediawan b, Hary Sulistyo b, Muslikhin Hidayat b
a
Chemical Engineering, Faculty of Engineering, Semarang State University Bldg. E1, Sekaran, Gunungpati, Semarang 50229, Indonesia
b
Chemical Engineering, Faculty of Engineering, Gadjah Mada University, Jl. Grafika 2, Yogyakarta 55281, Indonesia

a r t i c l e i n f o a b s t r a c t

Article history: This study focuses on kinetics of rice husk hydrolysis using sulfuric acid catalyst to produce sugars. The
Received 10 June 2010 experiments were conducted at various catalyst concentrations. It turned out that during hydrolysis, deg-
Received in revised form 17 September radation of sugars was encountered. The kinetics was expressed with both homogeneous and heteroge-
2010
neous models. At catalyst concentration of higher than 0.44 N, heterogeneous model works better than
Accepted 20 September 2010
Available online 27 September 2010
homogeneous model, while at the lower, both models work well. In the heterogeneous model, it is
observed that the mass transfer of sulfuric acid in the particles and the hydrolysis reaction control the
rate of hydrolysis. The mass transfer can be described by Fick’s law with the effective diffusivity of
Keywords:
Ethanol
1.4  1011 cm2/s, while the hydrolysis and sugar degradation rate constants follow Arrhenius equations.
Heterogeneous model In addition, it was experimentally observed that the sugars produced can be converted to ethanol by fer-
Homogeneous model mentation using yeast.
Hydrolysis Ó 2010 Elsevier Ltd. All rights reserved.
Rice husk

1. Introduction The bioethanol produced from lignocellulosic biomass such as

Indonesia as an agricultural country has about 60,000 rice mills
with rice husk production of 15 million tons per year. Rice husk
predominantly contains hemicellulose (approx. 29.3%) and cellu-
lose (approx. 34.4%). It can be hydrolyzed into sugars at approxi-
mately 0.426 g of sugars per 1 g of dry rice husk. With further
process the sugars can be fermented into ethanol at about 0.21 g
of ethanol per 1 g of dry rice husk (Demirbas, 2005). Therefore rice
husk is showing its potential as raw material to produce bioetha-
nol. This is also supported by Abbas and Ansumali (2010) who re-
ported that rice husk was to be a very promising biomass for
conversion into bioethanol and estimated to benefit in the Asian
and Southeast Asian regions.
Important steps in the production of ethanol from lignocellu-
losic biomass are hydrolysis to convert hemicellulose and cellulose
into sugars, fermentation of sugars to produce ethanol, and ethanol
purification (Hahn-Hagerdal et al., 2006). According to Badger
(2002) there are two types of hydrolysis, i.e. enzyme and chemical
hydrolysis. Chemical hydrolysis was selected because it is rela-
tively lower on cost and having faster process (Palmqvist and
Hagerdal, 2000).
⇑ Corresponding author. Tel.: +62 274 902171; fax: +62 274 902170.
E-mail address: megawatie@yahoo.com ( Megawati).
woody substrate (Gupta et al., 2009), Lantana camara (Kuhad
et al., 2010), corncob residue (Liu et al., 2010), wheat and barley
straw (Persson et al., 2009), winter rye, oilseed rape and faba bean
(Petersson et al., 2007), rice straw (Karimi et al., 2006), rice hull
(Saha et al., 2005), corn cob (Zhang et al., 2010; Latif and Rajoka,
2001) has not been demonstrated at industrial level. In the present
work, we want to achieve ethanol concentration at industrial level
(±5% v/v) and consequently sugar concentrations are higher than
100 g/l (sugar yields higher than 33.33%). As reported in several
previous references, hydrolysis of lignocellulosic biomass with
higher catalyst concentration produces higher sugar yield
(Taherzadeh and Karimi, 2007; Demirbas, 2005; Herrera et al.,
2004; Lee et al., 2000; Kim et al., 2000) and subsequently higher
ethanol yield. On the other hand, in studying dilute-acid hydroly-
sis, previous researchers used catalyst concentration of 0.5% wt
to 5% wt. Dilute-acid hydrolysis of rice straw with 0.5% sulfuric
acid concentration in batch reactor achieved yields of glucose
and xylose at as much as 44.6 and 84.7 g/kg, respectively, as well
as the total sugar yield of 12.93% (Karimi et al., 2006). Acid hydro-
lysis (5% sulfuric acid, 140 °C for 30 min) of L. camara produced
144.29 mg/g sugars or sugars yield of ±14.43% (Kuhad et al.,
2010). Total sugars (148.87 mg/g or sugar yield of 14.89%) resulted
when dilute sulfuric acid hydrolysis (5% sulfuric acid, 140 °C) of
Prosopis juliflora wood was carried for 30 min (Gupta et al.,
2009). Furthermore, we have conducted hydrolysis of rice husk
with 0.5% sulfuric acid concentration in batch reactor and obtained

0960-8524/$ - see front matter Ó 2010 Elsevier Ltd. All rights reserved.
doi:10.1016/j.biortech.2010.09.084
 Megawati et al. / Bioresource Technology 102 (2011) 2062–2067
sugar yield of 12.72% (Megawati et al., 2010). Above references can
be used as consideration related to amount of catalyst concentra-
tion required for the hydrolysis to succeed. For this study we opted
to conduct the hydrolysis at acid concentrations higher than 6% to
obtain higher sugar concentration. Additionally, experiments were
conducted with various catalyst concentrations (10–15%) to study
its effect on kinetic of hydrolysis.
Accurate kinetic models of lignocellulose hydrolysis by dilute
acid are important for designing and optimizing processes for rice
husk conversion to bioethanol. Study of kinetic of hydrolysis of lig-
nocellulosic biomass can be approached with pseudo-homoge-
neous model, as in Canettieri et al. (2007), Herrera et al. (2004),
Xiang et al. (2004), Mosier et al. (2002), Kim et al. (2000), and Tor-
get et al. (2000). Joksimovic and Markovic (2007) reported that
hydrolysis of lignocellulosic biomass with dilute-acids is a heteroge-
neous reaction. However it can be treated as a pseudo-homogeneous
reaction when particles size is <840 lm. Kim et al. (2000) studied
the kinetics of cellulose hydrolysis using batch and shrinking-bed
reactors. The result showed that the hydrolysis time of glucan is
about three times lower with shrinking-bed reactor compared to
the one with batch reactor. Cause of this difference is not yet fully
understood and further research is necessary to investigate details
of the reaction mechanism of these heterogeneous catalytic reac-
tions (Taherzadeh and Karimi, 2007). Furthermore, Kim and Lee
(2002) studied diffusion of sulfuric acid within lignocellulosic bio-
mass particles. Diffusivity of sulfuric acid is dependent on the nat-
ure of the lignocellulosic materials (Taherzadeh and Karimi, 2007).
Therefore, in this study homogeneous and heterogeneous model is
selected to generate accurate kinetics of dilute-acid hydrolysis of
rice husk.
The lignocellulosic biomass is a complex mixture of carbohy-
drate polymers known as cellulose and hemicellulose, lignin and
smaller amount of other compounds known as extractives. To ana-
lyze total of carbohydrate polymers, rice husk is completely hydro-
lyzed using HCl followed by Fehling method (Taherzadeh and
Karimi, 2007). Since Fehling solution is standardized by a solution
of glucose monohydrate, therefore carbohydrate polymers are re-
garded as glucose monohydrate.
At certain condition, hydrolysis reaction can produce another
kind of sugars as effect of sugar degradation caused by high tem-
perature. Sugar degradation occurrence can be detected using
chemical analysis and mass balance equation approach. In mass
balance equation approach if sugar degradation does not occur
then single reaction is suitable to express hydrolysis reaction
mechanism. The sugars mass balance of single reaction can be
written as follows:
dC D
¼ khyd C m
B; ð1Þ
dt
and the hydrolysis reaction mechanism can be formulated by
khyd
B þ H2 O ! D; ð2Þ
However, if the sugar degradation occurs during the process then
the series reaction is more suitable to express this mechanism.
The sugars mass balance of series reaction can be expressed as
follows:
dC D
¼ khyd C m n
B  kdeg C D ; ð3Þ
dt
and the hydrolysis reaction mechanism can be formulated by
khyd kdeg
B þ H2 O ! D ! U; ð4Þ
where B = polysaccharide (in term of glucose equivalent),
D = monosaccharide (sugars), U = by-products.
2063
The effect of sugar degradation does not only lower the yield of
fermentable sugars from biomass but also form degradation prod-
ucts like hydroxymethyl furfural (HMF), levulinic acid and formic
acid, which is inhibitory in fermentation using yeast (Karimi
et al., 2006). Variation of catalyst concentration of hydrolysis af-
fects the sum of inhibitor compound of hydrolyzates. This study
conducted the hydrolysis to convert rice husk to sugars and fer-
mentation of sugars to produce ethanol using Saccharomyces
cerevisiae. Fermentation was conducted to verify if sugars formed
could be converted into ethanol with a high yield. Furthermore,
ethanol production from hydrolyzates with difference sum of
inhibitor compound by fermentation is analyzed. Afterward, result
of fermentation will be compared with result from previous
researchers, e.g. Latif and Rajoka (2001); Govindaswamy and Vane
(2010), Kuhad et al. (2010); Gupta et al. (2009).
2. Methods
2.1. Raw Material
Rice husk was collected from local rice mill, sun-dried and
ground to a particle size lower than +1 lm (20 mesh screener). La-
ter it was oven-dried at 85 °C until the weight is constant. One
sample of rice husk was analyzed following standard method
(Datta, 1981) to know its main composition. In order to detect
amount of carbohydrate polymers in term of glucose equivalent,
another sample of rice husk was completely hydrolyzed with 73%
HCl at 100 °C for 4 h followed by analyzing using Fehling method.
2.2. Dilute-acid Hydrolysis
The hydrolysis of rice husk was conducted in an autoclave with
volume of approximately 2 l. The autoclave is equipped with an
electric heater and a temperature controller. It is continuously sha-
ken during operation. Initially, 1 l of various sulfuric acid solution
(0.37, 0.40, 0.44, 0.48, 0.51, and 0.55 N) and 300 g of rice husk were
put in the autoclave, and then the autoclave was perfectly closed.
The heater was turned on as well as the temperature controller.
As result, temperature increased and when it reached 140 °C the
time was recorded as zero and a sample (7 cm3) was taken through
sample outlet pipe. When temperature reached 180 °C, it was kept
constant at that level. During the process, at every 5 min interval,
temperature was recorded and sample was taken. The sugars con-
centrations in the samples were analyzed by Fehling method.
2.3. Fermentation using Baker’s yeast
Prior to fermentation, hydrolyzate was detoxified to neutralize
pH and eliminate inhibitor compounds. Initially, all hydrolyzates
were pH-adjusted to 5.5 with a slurry of 1 N of Ca(OH)2. Then
hydrolyzates were added by 16.65 g alum and 2.497 g activated
carbon per 1 l hydrolyzate. After detoxification, the liquid fraction
of hydrolyzates was separated by filtration. The filtrate fermenta-
tions were prepared using 150 ml of liquid fraction and supple-
menting minerals such as 0.15 g Urea ((NH2)2CO) and 0.045 g
N–P–K Fertilizer. Medium was then sterilized in Autoclave with
temperature of 100 °C for 4 h and cooled down for 24 h. After that,
the medium was fermented with 1.1% w/v Baker’s yeast for
5  24 h. The ethanol concentration was analyzed by GC (gas chro-
matography) method.
2.4. Analytical methods
The sugar concentrations in both completely hydrolyzed and
samples were analyzed using Fehling method. The concentration
2064 Megawati et al. / Bioresource Technology 102 (2011) 2062–2067

of Fehling solution standardized by glucose monohydrate solution
was 0.025 N. Ethanol resulted from fermentation was analyzed
using Gas Chromatography (GC) using a Porapak P-Shimadzu sys-
tem equipped with a D-4617 column and Thermal Conductivity
Detector (TDC) at 80 mA current. Helium at 60 kPa was used as
the carrier gas. The ethanol standards were prepared using com-
mercial grade ethanol (Merck, Darmstadt, Germany).
The experiment provides data of temperatures (T) and sugars
concentrations (CD) at various times (t) for six runs with catalyst
concentrations of 0.37, 0.40, 0.44, 0.48, 0.51, and 0.55 N respec-
tively. Since the hydrolysis is conducted in non-isothermal opera-
tion, therefore the temperature data during the process is required.
Based on the temperature data, the empirical equation of temper-
ature as function of time can be expressed by

3. Results and discussion T ¼ 140 þ 8:395t 0:6781 ð10Þ

3.1. Main composition of rice husk Above equation applies to all catalyst concentration variants. Sugar
concentrations in the hydrolyzates were shown in Figs. 1–3.
Result of rice husk composition analysis using standard method
is written in Table 1. 0.26 310
The primary stoichiometric equations for sugar conversion of
290

Sugars concentration, CD (mole/L)

rice husk composition (Table 1) are as follows:
0.24
Hemiselulosa: pentosan to pentose: 270
nC5 H8 O4 þ H2 O ! nC5 H10 O5 ; CD
0.22 250
1g 1:136 g ð5Þ
230

T ( C)
69:1896 g 78:5994 g
0.2

o
Celulosa: hexosan to hexose 210

nC6 H10 O5 þ H2 O ! nC6 H12 O6 ; 0.18 T 190

1g 1:111 g ð6Þ
170
66:5141 g 71:6713 g 0.16
150
Rice husk contains 133.7007 g of pentosan and hexosan and above
calculation shows that hydrolizate contains 150.2712 g of pentose 0.14 130
and hexose (148.743 g glucose). 0 5 10 15 20 25 30 35
From completely hydrolyzed rice husk, polysaccharide contents Time (min)
are equivalent to 0.71 mol/l (127.8 g/l) glucose. The sum of glucose
from complete hydrolysis matches to stoichiometric analysis. Fig. 1. Effect of catalyst concentration on hydrolysis kinetics. Hydrolysis was
conducted at non-isothermal condition and various catalyst concentrations. The
experiment provides data of temperatures (open symbols) and sugars concentra-
3.2. Effect of catalyst concentration on kinetics tions (closed symbols) at various times for catalyst concentrations of 0.37
(triangular) and 0.40 N (dot). The empirical equation of temperature as function
3.2.1. Homogeneous kinetic model of time (————) can represent the temperature recorded during the process.
Hydrolysis kinetics was expressed with homogeneous ( ) and heterogeneous
Mass balance equation of series reaction (Eq. (3)) is more suit-
() models to verify mass balance of sugars.
able to express the hydrolysis of dilute acid of rice husk compared
to single reaction (Eq. (1)). Therefore it is obvious that sugar degra-
dation has occurred. Subsequently, the hydrolysis reaction mecha- 0.3 310
nism can be formulated by Eq. (4). To solve the series reaction, we
need the mass balance equation of polysaccharide: 0.28 290
Sugars concentration, CD (mole/L)

dC B 270
¼ khyd C m
B; ð7Þ 0.26
dt
CD 250
The reaction rate constants, khyd and kdeg, are influenced by temper- 0.24
ature. They can be expressed by the Arrhenius’s equations, as in 230
T ( C)

  0.22
o

Ehyd
khyd ¼ Ahyd exp ; ð8Þ 210
RT 0.2
T 190
and
  0.18
Edeg 170
kdeg ¼ Adeg exp : ð9Þ
RT 0.16 150

0.14 130
0 5 10 15 20 25 30 35
Table 1 Time (min)
Chemical composition of the rice husk used in this study.

Constituents Composition (% of dry weight) Fig. 2. Effect of catalyst concentration on hydrolysis kinetics. Hydrolysis was
conducted at non-isothermal condition and various catalyst concentrations. The
Run 1 Run 2 Average experiment provides data of temperatures (open symbols) and sugars concentra-
Water ±11.9506 ±11.5860 ±11.7683 tions (closed symbols) at various times for catalyst concentrations of 0.44
Hemicellulose ±22.1118 ±24.0145 ±23.0632 (triangular) and 0.48 N (dot). The empirical equation of temperature as function
Cellulose ±20.5330 ±22.4763 ±21.5047 of time (————) can represent the temperature recorded during the process.
Lignin ±14.4621 ±14.7785 ±14.6253 Hydrolysis kinetics was expressed with homogeneous ( ) and heterogeneous
() models to verify mass balance of sugars.
 Megawati et al. / Bioresource Technology 102 (2011) 2062–2067 2065

0.34 310 Table 3

The frequency factor and activation energy at sugar degradation (homogeneous
0.32 290 model).
Sugars concentration, CD (mole/L)

0.3 Catalyst Frequency factor, Adeg (l/ Activation energy, Edeg

CD 270 concentration (N) (mole.min)) (J/mole)
0.28 0.37 ±295,044 ±67,514
250
0.40 ±295,600 ±62,455
0.26 0.44 ±295,383 ±61,441
230

T ( C)
0.48 ±295,439 ±60,080
0.24

o
0.51 ±295,296 ±59,807
210
0.22 0.55 ±295,557 ±59,066

0.2
T 190

0.18 170 Similarly with hydrolysis, the higher catalyst concentration,

0.16
0.14
0 5 10 15 20 25 30 35
Time (min)
Fig. 3. Effect of catalyst concentration on hydrolysis kinetics. Hydrolysis was
conducted at non-isothermal condition and various catalyst concentrations. The
experiment provides data of temperatures (open symbols) and sugars concentra-
tions (closed symbols) at various times for catalyst concentrations of 0.51
(triangular) and 0.55 N (dot). The empirical equation of temperature as function
of time (————) can represent the temperature recorded during the process.
Hydrolysis kinetics was expressed with homogeneous ( ) and heterogeneous
() models to verify mass balance of sugars.
Empirical Eq. (10) and sugars concentration data were then ap-
plied to curve-fitting method to evaluate the values of Ahyd, Ehyd,
Adeg, and Edeg. For a set of values of m, n, Ahyd, Ehyd, Adeg, and Edeg,
the values of CD can be calculated based on Eqs. ((3), (7)–(10)).
Since Eqs. (3) and (7) are differential equations, Runge–Kutta
method is chosen to solve them numerically. The chosen values
were the ones giving the minimum values of the Sum of Squares
of Error (SSE) for run data. The SSE was defined as
X 2
SSE ¼ ðC D calc  CD data Þ : ð11Þ
Obtained values of Ahyd, Ehyd, Adeg, and Edeg then listed in Tables
2 and 3. In this case, the value of m (order of reaction for hydroly-
sis) was chosen to be 1 and the value of n (order of reaction for su-
gar degradation) was 2.
For hydrolysis, catalyst concentration influences activation en-
ergy as can be seen in Table 2. When catalyst concentrations in-
crease from 0.37 N to 0.55 N; the activation energy values
decrease from ±61,776 to ±57,052 J/mole. However, frequency fac-
tor values are relatively constant at ±69,688 1/min. Subsequently
hydrolysis reaction speeds up due to decreasing of activation en-
ergy. This result is in line with other experiment on effect of hydro-
chloric acid concentration on hydrolysis of sorghum straw. The
increase of catalyst concentration from 2% to 4% improves the
hydrolysis reaction (Herrera et al., 2004). Table 3 shows both fre-
quency factor (Adeg) and activation energy (Edeg) for sugar
degradation.
activation energy is lower. When catalyst concentrations increase
150
from 0.37 to 0.55 N, the values of activation energy decrease from
130 ±67,514 to ±59,066 J/mole, but the values of frequency factor are
relatively constant (±295,387 l/(mole.min)). The activation energy
of sugar degradation is relatively higher compared to hydrolysis.
At catalyst concentration of 0.37 N, activation energy is ±61,776
and ±67,514 J/mole, for hydrolysis and sugar degradation, respec-
tively. This is an indication that sugar degradation is more sensitive
to temperature compared to hydrolysis.
The frequency factor in Tables 2 and 3 can be applied at certain
catalyst concentration. Generally, frequency factor is independent
from catalyst concentration, therefore frequency factor values are
taken as fixed number, i.e. average of the values in Tables 2 and
3. The average values were Ar1 of ±69,788 1/min and Ar2 of
±295,387 l/(mole.min). Furthermore, the activation energy values
were recalculated with the new values of the frequency factors
and the result is listed in Table 4. The values of calculation of CD
are plotted in Figs. 1–3.
3.2.2. Heterogeneous kinetic model
In heterogeneous model, the rate of disappearance of lignocel-
lulose is not homogeneous in solid particle. The mass transfer of
H2O in the solid particle is faster than mass transfer of H2SO4,
therefore the mass transfer of H2SO4 controls hydrolysis mecha-
nism. The mass transfer of H2SO4 in the solid particle can be devel-
oped using Ficks’ law (Bird et al., 2002), as in
dC H2 SO4
NH2 SO4 ¼ De : ð12Þ
dr
Concentration gradient of H2SO4 in solid particle that was assumed
as sphere is formulated as follows
@ 2 CH2 SO4 2 @C H2 SO4 1 @C H2 SO4
þ ¼ : ð13Þ
@r r r @r De @t
Eq. (11) is discretised at the interior point i as symbol of position
and j as symbol of time. Solving numerically using Backward Finite
Difference Approximation Method gives
2 2
AM:C H2 SO4 ði;jþ1Þ ¼ ð1  ÞC H2 SO4 ði1;jÞ  ð2   AMÞC H2 SO4 ði;jÞ
i i
þ C H2 SO4 ðiþ1;jÞ ; ð14Þ

Table 2 Table 4
The frequency factor and activation energy at hydrolysis (homogeneous model). The activation energy at hydrolysis and sugar degradation (homogeneous model).

Catalyst Frequency factor, Ahyd Activation energy, Ehyd (J/ Catalyst Activation energy, Activation energy, SSE.104
concentration (N) (1/min) mole) concentration (N) Ehyd (J/mole) Edeg (J/mole)

0.37 ±69,518 ±61,776 0.37 ±61,356 ±64,087 ±0.1162

0.40 ±69,683 ±60,880 0.40 ±60,773 ±61,876 ±0.9643
0.44 ±69,786 ±59,684 0.44 ±59,575 ±60,897 ±1.7842
0.48 ±69,816 ±58,673 0.48 ±58,990 ±60,599 ±2.5722
0.51 ±69,945 ±57,930 0.51 ±58,148 ±60,095 ±5.9667
0.55 ±69,979 ±57,052 0.55 ±57,794 ±59,916 ±8.5918
2066 Megawati et al. / Bioresource Technology 102 (2011) 2062–2067

where: ues of De, Ahyd, Ehyd, Adeg, and Edeg, the values of CD can be calculated
2
based on Eqs. ((10), (14), (16), (17), (19)–(22)). The chosen values of
ðDrÞ De, Ahyd, Ehyd, Adeg, and Edeg were the ones giving the minimum val-
AM ¼ ð15Þ
ðDtÞDe ues of the Sum of Squares of Error (SSE) for run data. The SSE was
Eq. (13) is used to calculate H2SO4 concentration in solid particle defined as Eq. (11).
from i = 1 to N2. However at i = 0, H2SO4 concentration can be for- The obtained values of De, Ahyd, and Adeg are 1.4  1011 cm2/s,
mulated as follows 2  1012 and 1.4  1013 1/min, respectively. The obtained values of
Ehyd and Edeg are listed in Table 5. The values of CD are calculated by
AM:C H2 SO4 ð0;jþ1Þ ¼ ð6  AMÞC H2 SO4 ð0;jÞ þ 6C H2 SO4 ð1;jÞ : ð16Þ using those values of De, Ahyd, Ehyd, Adeg, and Edeg are shown in
Figs. 1–3.
H2SO4 concentration in solid particle surface, C H2 SO4 ðN;jÞ , is assumed
Both homogeneous and heterogeneous model can describe
equal to H2SO4 in liquid (Cf), thus at i = N1, H2SO4 concentration
mechanism of dilute-acid hydrolysis of rice husk (Figs. 1–3). For
can be arranged from equation (14) with substitution of
more accurate result, considering SSE values, heterogeneous model
C H2 SO4 ðN;jÞ ¼ C f :
  is more suitable for this case compared to homogeneous model,
2 especially for catalyst concentration higher than 0.44 N. Conse-
AM:C H2 SO4 ðN1;jþ1Þ ¼ 1  C H2 SO4 ðN2;jÞ
N1 quently, the mass transfer of sulfuric acid within the solid particle
  is considered very important. Therefore, the penetration of sulfuric
2
 2  AM C H2 SO4 ðN1;jÞ þ C f : ð17Þ acid within the biomass particle, as well as dispersion in the reac-
N1
tor, can significantly affect the overall reaction.
The selected reaction order of lignocellulose was 1, consequently The values of kinetic parameters obtained were in good agree-
the mass balance equation of lignocellulose in a batch reactor is de- ment with the ones from other investigators. Canettieri et al.
fined as (2007) reported that hydrolysis of Eucalyptus grandis follows a
pseudo first order homogeneous reaction with activation energy
@C lig
khyd C lig C H2 SO4 ¼ ; ð18Þ of 101.3 kJ/mole. Sulfuric acid hydrolysis of corn fiber as co-product
@t
of corn wet-milling by Mosier et al. (2002) resulted in activation
and it can be solved using Backward Finite Difference Approxima- energy of 110.5 ± 29.6 kJ/mole. For sugars degradation, the activa-
tion Method: tion energy can be compared with kinetics study of glucose decom-
position during dilute-acid hydrolysis (0.1 wt.%) of lignocellulosic
C ligði;jþ1Þ ¼ C ligði;jÞ  ðDtÞðkhyd ÞC ligði;jÞ C H2 SO4 ði;jÞ ; ð19Þ
biomass by Xiang et al. (2004). They estimated activation energy
The reaction rate constant of hydrolysis, khyd, is influenced by tem- of glucose decomposition of 139 kJ/mol. Kinetics study of sequen-
peratures. The constant can be expressed by the Arrhenius’s equa- tial reaction of hydrolysis and sugar degradation of hardwood
tion, as in Eq. (8). Theoretically, the effect of catalyst hemicellulose in a percolation reactor revealed activation energy
concentration of hydrolysis reaction can be detected clearly with of approximately 27,100 cal/mol (113.5 kJ/mol) and 30,700 cal/
evaluation the Arrhenius’ parameter. Reaction conversion of ligno- mol (128.5 kJ/mol) for hydrolysis and sugar degradation, respec-
cellulose (x) is given by tively (Kim et al., 2000).
R Z
4
pR3 ðC lig Þ0  4p 0R C lig :r2 dr 3 R
x¼3 ¼1 3 C lig :r2 dr; ð20Þ
4
3
pR3 ðC lig Þ0 R ðC lig Þ0 0 3.3. Sugar yields of hydrolysis

The mass balance equation of sugar at any time t is formulated as Sugars yields from hydrolysis as well as ethanol yields from fer-
follows: mentation were listed in Table 6. It can be observed that higher
Z t catalyst concentration will increase sugars concentration. Sugar
mlig :x
CD ¼  kdeg C D dt; ð21Þ yield resulted from this research was approximately 57.06/300 g
180:v 0
raw materials (19.2667% of raw materials). It was achieved at final
where kdeg is reaction rate constant of sugar degradation. The con- temperature of 220 °C and catalyst concentration of 0.55 N (15%).
stant can be expressed by the Arrhenius’s equation, as in Eq. (9). Kuhad et al. (2010) carried out acid hydrolysis of L. camara (5% v/
Similarly with homogeneous model, the empirical equation of tem- v acid, 120 °C for 30 min) and produced 144.29 mg/g total sugars
perature as function of time is arranged with Eq. (10).The initial (14.43% of sugar yield). A study on concentrated acid conversion
condition on C H2 SO4 and Clig are: of pine sawdust to sugars conducted by Miller and Hester (2007)
results in optimum condition at acid concentration of 30% and
t ¼ 0; C H2 SO4 ¼ 0; C lig ¼ C lig0 : ð22Þ
temperature of 130 °C, with the sugars yield was about 50%. This
Empirical Eq. (10) and sugars concentration data were then applied comparison suggests that higher yield of sugar can be obtained
to verify the kinetics model as well as to evaluate the values of De, by higher concentration of acid.
Ahyd, Ehyd, Adeg, and Edeg using curve-fitting method. For a set of val-

Table 6
Table 5 Ethanol concentration.
The activation energy at hydrolysis and sugar degradation (heterogeneous model).
Catalyst Sugars Ethanol Sugars Ethanol yield
Catalyst Activation energy, Activation energy, SSE.104 concentration concentration concentration yield (% theoritically)
concentration (N) Ehyd (J/mole) Edeg (J/mole) (N) (g/l) (% v/v) (% rice husk)
0.37 ±113,154 ±137,181 ±0.3477 0.37 ±43.91 ±1.89 ±14.64 ±88.11
0.40 ±112,572 ±129,615 ±0.9901 0.40 ±43.92 ±2.07 ±14.64 ±96.50
0.44 ±112,239 ±129,283 ±1.8534 0.44 ±48.60 ±2.25 ±16.20 ±92.59
0.48 ±111,906 ±122,715 ±1.8450 0.48 ±51.48 ±2.39 ±17.16 ±93.03
0.51 ±111,241 ±122,050 ±4.1549 0.51 ±54.54 ±2.43 ±18.18 ±92.50
0.55 ±110,576 ±121,384 ±5.8168 0.55 ±57.06 ±2.63 ±19.02 ±92.18
 Megawati et al. / Bioresource Technology 102 (2011) 2062–2067
3.4. Ethanol yields of fermentation
The maximum ethanol concentration is 2.63% v/v indicating
92.18% ethanol yield. The result of ethanol yield of this study is
in agreement with previous report on fermentation of lignocellu-
losic hydrolyzates using yeast. Latif and Rajoka (2001) conducted
SSF of corn cobs to produce ethanol with yield of 0.42 g/g (2.1%
v/v and 82.20% ethanol yield) using S. cerevisiae. Fermentation of
glucose-xylose mixtures of lignocellulosic biomass using S. cerevi-
siae by Govindaswamy and Vane (2010) produced ethanol yield of
0.49 g/g (2.45% v/v and 95.89% ethanol yield). Ethanol yield ob-
tained from L. camara hydrolyzate (34.75 ± 1.54 g/l sugars) using
yeast (Kuhad et al., 2010) was 17.7 ± 0.96 g/l (±1.87% v/v and
±93.93% ethanol yield).
4. Conclusion
Effect of catalyst concentration on both homogeneous and het-
erogeneous kinetic models is clearly described. Especially, for cat-
alyst concentration of higher than 0.44 N, heterogeneous model
works better than homogeneous model. The mass transfer of sulfu-
ric acid can be represented by Fick’s law with effective diffusivity is
1.4  1011 cm2/s. The kinetic constant follows Arrhenius equation
with frequency factors for hydrolysis and sugar degradation of
2  1012 and 1.4  1013 1/min, respectively. Catalyst concentration
influences activation energy. When catalyst concentrations in-
crease from 0.37 to 0.55 N; the activation energy values decrease
from ±61,776 to ±57,052 J/mole.
Acknowledgements
The financial support provided by the Doctorate Research Foun-
dation of Ministry of National Academic, Government of Indonesia
is gratefully acknowledged.
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