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a r t i c l e
i n f o
Article history:
Received 31 August 2011
Received in revised form 7 December 2011
Accepted 8 December 2011
Available online 14 December 2011
Keywords:
Biomass
Poplar sawdust
Effective moisture diffusivity
Drying kinetics
Thermogravimetric analysis
a b s t r a c t
The current study presents a thermogravimetric method to determine the effective moisture diffusivity
and drying kinetics of biomass. Drying experiments on poplar sawdust were performed at four temperatures (60, 70, 80, and 90 C) by a thermogravimetric analyzer (TGA). The major assumption in experimentally determining effective diffusivity by Ficks diffusion equation is that drying is mass transfer
limited and temperature remains isothermal during drying. The results indicated that TGA could well
achieve these determining conditions. The drying process of sawdust mostly took place in the falling rate
period. MidilliKucuk model showed the best t for all experimental data. The effective diffusivity values
changed from 9.38 1010 m2/s to 1.38 109 m2/s within the given temperature range, and the activation energy was calculated to be 12.3 kJ/mol.
2011 Elsevier Ltd. All rights reserved.
1. Introduction
Biomass utilization is gaining increasing attention as a potential
source of renewable energy (Sims et al., 2010). Thermochemical
conversions (pyrolysis, gasication, and combustion) are the major
biomass utilization techniques for gas, liquid, and char production.
Unfortunately, biomass materials often contain considerable
amount of water (Chen et al., 2009). The presence of water has
many negative effects on the performance of biomass and the
development of conversion technology (Cai and Chen, 2008).
Therefore, drying pretreatment of materials is essential to improve
the efciency of biomass utilization.
Drying is one of the most common methods used to improve
raw biomass (Fagerns et al., 2010). Ficks second law of diffusion
has been widely used to describe the drying process for most biological materials (Doymaz, 2010). Effective moisture diffusivity
(Deff) is the key drying parameter that represents the conductive
term of all moisture transfer mechanisms (Srikiatden and Roberts,
2006). This parameter is usually determined from experimental
drying curves. The activation energy is another important drying
parameter that represents the energy level of water molecules
for moisture diffusion and evaporation. The temperature dependence of the effective moisture diffusivity can be represented by
an Arrhenius relationship. Thus, the activation energy can be determined from the slope of the Arrhenius plot, ln(Deff) vs. 1/T (Shi
452
Alzamora et al. found that only 10% of the total moisture remains
when the sample temperature is within 5 C of the dry-bulb
temperature (Alzamora et al., 1979). A similar behavior was also
observed by Rovedo et al. (1995). The temperature of the potato
samples in their study did not reach the drying temperature until
95% of the potatoes moisture was removed.
Therefore, without a specic isothermal condition established,
there is evident difculty in determining effective diffusivity and
activation energy. However, the application of the thermogravimetric method in the drying process may prevent this problem. Thermogravimetric analysis, which rapidly measures a materials weight
loss over a wide temperature range or over a long period at a specic
temperature, has proven to be one of the best techniques for the
experimental research and kinetic analysis of biomass (Damartzis
et al., 2011). The application of thermogravimetric analyzer (TGA)
for biomass drying has many advantages, such as the immediate
heating of biomass to the set temperature, online recording of the
drying process, and minimal material requirement (Gardelle et al.,
2011). Most importantly, TGA could effectively restrict the temperature gradients between inside and outside the biomass particles.
Moreover, drying kinetics plays an importance role in the design
of a dryer. Some researchers have applied TGA to the mathematical
modeling of mass transfer, which is a very useful tool in investigating the intrinsic kinetics of a drying process (Madhava et al., 2001;
Cai and Liu, 2007). Thus, with the immediate establishment of
isothermal conditions and precise temperature control, as well as
online sample weight measurements, the thermogravimetric method is probably suitable for isothermal drying studies. However, no
reports have been found regarding the use of thermogravimetric
method to investigate moisture diffusivity mechanism and to determine the drying kinetics of biomass.
The objectives of the current work are to present the thermogravimetric method for calculation of Deff and activation energy
of poplar sawdust, and to determine a mathematical model that
suitably describes the drying characteristics.
2. Methods
2.1. Raw material
The biomass material used in the present study was poplar sawdust, which was selected from a local furniture factory. The particles chosen for the drying experiments were 0.1250.3 mm in size.
The initial moisture content of poplar sawdust was determined by
means of AOAC method No. 934.06 (AOAC, 1990). Sawdust at high
temperatures (>200 C) undergoes pyrolysis reactions with signicantly morphological changes in color and volume. Whereas, in the
drying temperature range (<150 C), these changes are negligible.
MR
M Me
M0 Me
where M is the moisture content at any time, M0 is the initial moisture content, and Me is the equilibrium moisture content of the
sample. Me values were obtained from the drying curves and were
set to be equal to moisture content, at which sample weight became
constant with drying time. The drying curves were tted with ve
common mathematical models listed in Table 1, namely, Page,
Newton, MidilliKucuk, Logarithmic, HendersonPabis (Midilli
et al., 2002; Midilli and Kucuk, 2003).
2.4. Statistical evaluation of drying data
The model parameters determined using non-linear regression
analysis. The goodness of t of the tested mathematical models
to the experimental data was evaluated from the coefcient of
determination (R2) and the chi-square (v2) between the predicted
and experimental values. The higher R2 values and the lower v2
values, the better is the goodness of t (Miranda et al., 2010). v2
can be calculated as follows:
v2
PN
MRexp;i 2
Nn
i1 MRpre;i
@MR
rDeff rMR
@t
MR
1
8 X
p2
n0
1
2n 12
exp
2n 12 p2 Deff t
!
4
4L2
where n is a positive integer, t is the drying time (s) and L is the half
thickness of the sample (m).
When sample shrinkage is negligible, initial moisture distribution is uniform, and constant moisture diffusivity is assumed, Eq.
(4) is suitable for determining Deff. This equation could be further
simplied into Eq. (5) by taking the rst term of a series solution
as follows (Vega-Glvez et al., 2010):
Table 1
Five commonly used models for isothermal drying.
No.
Model
Equation
Parameters
1
2
3
4
5
Page
Newton
MidilliKucuk
Logarithmic
HendersonPabis
MR = exp(ktn)
MR = exp(kt)
MR = a exp(ktn) + bt
MR = a + b exp(kt)
MR = a exp(kt)
k,
k
a,
a,
a,
n
k, n, b
k, b
k
lnMR ln
p2 Deff
4L2
453
5
k0
p2 Deff
4L2
Deff D0 exp
Ea
RT 273:15
7
Fig. 2. Drying curves of poplar sawdust at different drying temperatures.
2
454
surface, the drying rate was then dominated by the moisture diffusion from the inside to the surface of sawdust. Therefore, the drying rate started to decrease and the falling rate period begun,
similar to the drying characteristics of many agricultural products
(Kaya and Aydin, 2009). With less water in the sawdust, the drying
rate gradually decreased to zero. The time needed for the two drying periods depended on the energy supplied. In the present study,
the time for the rising rate period was signicantly shorter than
that for the falling rate period. Most of the water was removed in
the falling rate period, which made drying a time-consuming
process.
Thus, most of the drying process clearly took place during the
falling rate period, and internal diffusion was the dominant physical mechanism governing moisture transfer in the samples. Other
researchers have reported similar results (Shi et al., 2008).
3.3. Calculation of effective diffusivity and activation energy
Fig. 4. Correlation between Deff and drying temperatures.
The drying data obtained by TGA were tted using the ve drying models listed in Table 1. The best model describing the drying
kinetics of sawdust was chosen as the one with the highest R2 and
the least v2. Table 2 lists the statistical analysis results for the
Table 2
Statistical results obtained from all drying models.
Model
Temperature (C)
MidilliKucuk
60
70
80
90
Page
Model parameters
R2
v2
1.03
1.04
1.04
1.00
1.40 106
2.38 105
2.74 105
2.23 105
1.63 103
3.44 103
4.90 103
4.32 103
1.28
1.21
1.18
1.29
0.9992
0.9984
0.9972
0.9962
7.62 105
1.27 104
1.89 104
2.15 104
60
70
80
90
1.09 103
2.54 103
3.75 103
4.45 103
1.35
1.26
1.23
1.28
0.9985
0.9970
0.9956
0.9955
1.33 104
2.31 104
2.97 104
2.52 104
Newton
60
70
80
90
6.53 103
9.01 103
1.08 102
1.48 102
0.9733
0.9841
0.9866
0.9847
2.43 103
1.23 103
9.13 104
8.53 104
Logarithmic
60
70
80
90
6.32 102
1.05 102
2.12 104
5.21 105
6.35 103
9.79 103
1.20 102
1.64 102
0.9962
0.9960
0.9953
0.9920
3.45 104
3.11 104
3.21 104
4.46 104
HendersonPabis
60
70
80
90
1.15
1.13
1.12
1.11
7.47 103
1.01 102
1.21 102
1.64 102
0.9917
0.9956
0.9953
0.9920
7.61 104
3.40 104
3.21 104
4.46 104
1.18
1.13
1.12
1.11
455
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