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Article history: Water vapor desorption isotherm studies were performed on lignite at the temperature 30, 40 and 50 °C
Received 25 June 2015 to investigate the behavior of water on coal. For a description of desorption process, a Guggenheim–An
Received in revised form 6 December 2015 derson–de-Boer (GAB) model provided a good fit. At the monolayer region, the overlapping isotherms
Accepted 24 December 2015
at different temperatures could not provide valid data to calculate the isosteric heat by applying the
Available online 31 December 2015
Clausius–Clapeyron equation, and hence the isosteric heat was only determined at the moisture content
from 0.125 to 0.280 mg/mg dry coal. Then, the Brunner–Emmet–Teller (BET) theory was applied to cal-
Keywords:
culate the isosteric heat at the moisture content below 0.125 mg/mg dry coal. Net isosteric heat of des-
Lignite
Desorption
orption determined from the isotherms increases from 1.88 kJ/mol in the capillary water to 8.17 kJ/mol at
Isotherm the monolayer region. This increase is most likely that the forces from coal surface act on all types of
BET water in raw lignite, and as the moisture content decreases, the forces are becoming stronger. Besides,
Isosteric with the effect of the interaction among adsorbed water molecules and the bonding force between water
Heat molecules and active sites, at the monolayer region, a maximum energy peak appears on the curve of
isosteric heat.
Ó 2015 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.fuel.2015.12.054
0016-2361/Ó 2015 Elsevier Ltd. All rights reserved.
102 K. Wan et al. / Fuel 171 (2016) 101–107
The differential heat of sorption can be estimated through two (P/P0) [2]. To eliminate the possible effect of irreversible changes
different methods. The most common method is the application and maintain the sample as close as possible to the original
of Clausius–Clapeyron equation to the sorption isotherms at differ- as-mined coal, approximately 100 mg of fresh sample without
ent temperatures [1,6–8]. Although not always true the assump- vacuum degassing was directly used for each measurement. The
tion that isosteric heat of sorption is invariant with temperature relative humidity was increased/decreased to a fixed value, and
has often been accepted, it provides a rapid computational proce- water uptake versus time was recorded under isothermal condi-
dure. The second method estimates the heat of sorption by means tions until equilibrium, which was assumed to be established when
of calorimetric techniques [9,10]. In some cases, depending on the there was no weight change of more than 1 lg over a period of
high precision calorimetric measurement, the method could gener- 5 min. This process was repeated at 96%, 90%, 80%, 70%, 60%, 50%,
ate a series of experimental data which is more accurate. However, 40%, 30%, 20%, 15%, 11%, 8%, 6%, 4%, 2% and 0% relative humidity.
for the lignite with high volatile matter content, directly determin- Measurements were performed at temperatures of 30, 40 and
ing the heat of sorption by calorimetric measurement cannot avoid 50 °C, respectively. The experiments were repeated three times
the large error caused by rupture of weak chemical bonds in the in order to verify the results.
temperature programmed desorption. According to Allardice and
Evans [11], due to the effects of the thermal decomposition of func- 2.3. Methods
tional groups in the coal, the amount of water which could be des-
orbed after prolonged evacuation to a constant weight increased 2.3.1. Water desorption isotherm models
with increasing temperature. Furthermore, Chen [12] calculated This paper reported on the application of eight models to fit the
the thermal properties by equations that were derived directly isotherms of water vapor desorption on lignite, and the models
from isotherm model equations by the Clausius–Clapeyron ther- were also recommended for other similar porous media such as
modynamic theory, and he summarized that the isosteric heat, foods and woods. The corresponding equations included two or
expressed as a function of temperature and moisture content, three parameters except modified Halsey model involved four
showed good agreements with the values calculated by the above parameters as in Table 2. These parameters were identified by
two methods. Nevertheless, semi-empirical or empirical model of non-linear least square regression analysis. The optimal fitting
sorption is applied to formula transformation, and this method model was chosen according to the minimum residual sum of
may be not always accurate. Therefore, the Clausius–Clapeyron squares (RSS), the minimum mean relative deviation (MRD), and
theory would be better suitable for lignite. the maximum degrees of freedom adjusted correlation coefficient
However, we must stress that the lignite from Inner Mongolia of square (Adj. R2) that Adj. R2 > 0.98 was considered here to be a rea-
China has particular sorption nature, dramatically different from sonable fitting [6].
the typical brown coal or lignite such as famous Victorian brown X
n
coal, and particular properties of sorption also make the Clau- RSS ¼ ^ i Þ2
ðyi y
sius–Clapeyron equation being not always applicable in full mois- i¼1
ture content range to calculate the isosteric heat of sorption.
The aim of this study is (1) to measure desorption of water on RSSðn 1Þ
Adj: R2 ¼ 1
Inner Mongolia lignite and to describe the process with an appro- SSTðv Þ
priate desorption isotherm model, (2) to determine the isosteric
heat of desorption in new ways and (3) to analysis coal–water X
n
SST ¼ i Þ2
ðyi y
interactions during desorption process.
i¼1
N
2. Materials and methods 100 X ^
yi yi
MRD ¼
N i¼1 yi
2.1. Sample characterization
where yi was the experimental data, y ^i was the fitted values, SST
Shengli (SL) raw lignite from Inner Mongolia of China was used i was the mean of experimental
was the total sum of squares, and y
for the present study. All samples were ground to obtain a grain data.
size below 0.15 mm and then sealed in a plastic bag to protect
against moisture loss. The basic qualitative parameters of the sam- 2.3.2. Brunner–Emmet–Teller (BET) theory
ple are presented in Table 1. An important characteristic of the BET equation was that it pro-
vided a simple method to estimate the heat of sorption and the
2.2. Dynamic vapor sorption (DVS) analyzer monolayer value of coverage, both parameters were important in
thermodynamic calculation. The classical BET equation [20] was
Water desorption measurements were conducted using Aqua- given by:
dyne DVS supplied by Quantachrome Ins, USA. It was a very useful
m0 Cx
means of determining accurate sorption isotherms at different M¼ ð1Þ
ð1 xÞð1 x þ CxÞ
temperatures and using a range of pre-set relative humidity values
Table 1
Proximate and ultimate analysis of the sample.
Moisture (wet basis, %) Proximate analysis (wt.% dba) Ultimate analysis (wt.% dafb)
Ash yield Volatile mater Fixed carbon C H S N Oc
28.68 22.28 32.41 45.32 65.71 4.92 2.42 1.26 25.69
a
Db: dry basis.
b
Daf: dry ash free basis.
c
By difference.
K. Wan et al. / Fuel 171 (2016) 101–107 103
Table 2
Mathematical models for fitting the desorption isotherms of SL lignite.
Table 3
Predicted parameters of the fitted models to the experimental data for the water desorption isotherm of coal at 30, 40 and 50 °C.
Table 4
The values of the constants C and m0 of BET equation at different temperatures.
Temperature R2 Fitting m0 C E1 EL
(°C) range (mg/mg) (kJ/mol)
30 0.999 0.04–0.4 0.083 6.873 4.858
40 0.999 0.04–0.4 0.077 8.042 5.428
50 0.999 0.04–0.4 0.074 8.159 5.640
given in Table 4 against T, and the Adj. R2 is 93%. Iglesias and Chirife
[25] also reported similar linear relation. According to Eq. (6), the
correlation coefficient for monolayer capacity with temperature is
calculated as 0.00045, and the magnitude is approximates to zero.
Hence, the value of m0 can be expected to be independent of the
temperature within the range from 30 °C to 50 °C, and it can be
expressed by Eq. (7),
@ ln m0
¼0 ð7Þ
Fig. 4. Desorption isosteric curves of SL lignite. @T
ðC 1Þx2 þ 1
d ln x ¼ d ln C þ d ln m0 ð8Þ
ð1 xÞð1 x þ CxÞ
therefore,
½ðC 1Þx2 þ 1 @ ln x @ ln C @ ln m0
¼ þ ð9Þ
ð1 xÞð1 x þ CxÞ @T @T @T
The assumption that E1 EL is invariant with temperature is
acceptable [17]. Thus, the differentiating Eq. (2) is given by
@ ln C 1
¼ 2 ðE1 EL Þ ð10Þ
@T RT
Substituting Eqs. (4), (7) and (10) into (9), we obtained the expres-
sion of isosteric heat which is given by
C Shrinkage
C
Lignite Lignite
3.3.3. Sorption behavior derived from isosteric heat of desorption [31,32], and the increase had been explained that the sorption of
The isosteric heat of desorption on SL lignite is presented in water on the dry matrix leaded to swelling of the material, which
Fig. 5 as function of the moisture content of coal. The net isosteric resulted in the exposure of sorption sites of higher binding ener-
heat is given as a positive quantity, which illustrates that the gies not previously available. Nevertheless, there is few report on
endothermic character of desorption and that the energy of bind- this increase found for desorption process. Only Maskan and
ing between the sorption sites and the water molecules is higher Göğüsß [32] found that the isosteric heat of desorption of mulberry
than the energy holding the molecules of pure water in the liquid appeared similar phenomenon, and the swelling explanation of the
phase. According to the trend of curve, the isosteric heat is approx- material was hardly convincing in the case of desorption. In gen-
imately equal to the heat of vaporization of pure water at the mois- eral, the pore surface of coal is roughness and the adsorbed water
ture content down to 0.40 mg/mg dry coal, although we can’t get molecules are not uniform distribution on the surface. Hence, there
the exact experimental data. The heat in this moisture region also may be interaction between adsorbed water molecules, when the
illustrates that the water being desorbed is not bound to the coal in moisture coverage of coal surface is high. During desorption at
any way, but is merely the water from the spaces between coal the monolayer region, the binding force of the water molecules
particles [1]. In the region between 0.28 and 0.23 mg/mg dry coal, on the coal surface is strengthened by attractive forces between
the isosteric heat of desorption increases from 1.30 to 1.88 kJ/mol, the water molecules [22]. More specifically, the energy required
as the moisture content decreases. The phenomenon can be attrib- to remove the water molecule a in Fig. 5 from the coal surface will
uted to the desorption of water from the capillaries or pores within be larger than for the molecule b. In the process of desorption, the
the coal particles, and thus the water in this region is classified as water molecules are dispersed gradually from all over of the rolling
capillary water. Below moisture contents of 0.23 mg/mg dry coal, coal surface to sparseness, and the attractive forces between water
the isosteric heat increases steeply from 1.88 kJ/mol to about molecules will gradually vanish, which results in the decrease of
7.59 kJ/mol at 0.077 mg/mg dry coal. The abrupt change can be net isosteric heat of desorption at lower moisture contents.
attributed to the desorption of multilayer and monolayer water Furthermore, in monolayer region, the shrinkage and collapse of
that is progressively more strongly bound to the coal surface with pores during desorption results in the formation of smaller diameter
the moisture content decreasing. There is a clear-cut boundary pores, and the monolayer water c in the pores may be gathered and
between the multilayer and monolayer water shown in Table 4 transformed into multilayer water, as shown in Fig. 6. Hence, the
to be 0.077 mg/mg dry coal, but the transition in the isosteric heat corresponding isosteric heat will be weakened.
data from capillary to multilayer is indistinct. In the monolayer
region, the water is tightly bound to the coal surface, correspond-
ing with high interaction energy. It can be concluded that, for the 4. Conclusion
whole process of desorption, the forces from coal surface act on
all types water in raw lignite, and as the moisture content (1) Water desorption isotherms for SL lignite have the
decreases, the forces are becoming stronger. In addition, the inte- sigmoidal-shaped profile according to the BET classification.
gral of net isosteric heat provides the extra theoretical minimum Temperature effects are observed for the coal at the multi-
amount of energy required to remove a given amount of water layer and capillary region, but the effects are negligible at
from coal. According to the integral value at different moisture monolayer region.
regions in Fig. 5, it will consume extra energy of 27.0 J/g dry coal (2) The GAB model is shown to be suitable for describing the
and 29.3 J/g dry coal, which does not include the latent heat of desorption isotherms of water on SL lignite with maximum
vaporization of pure liquid water, to take out the multilayer mois- value of Adj. R2 and minimum value of RSS and MRD.
ture (in the range of 0.077–0.23 mg/mg dry coal) and monolayer (3) The isosteric heat of desorption is given as a positive quan-
moisture (in the range of 0.02–0.077 mg/mg dry coal) from the tity, illustrating the endothermic character of desorption.
coal, respectively. Finally, according to the study results, a sketch At the region of moisture content above 0.077 mg/mg dry
of desorption process is also shown in Fig. 5. coal, the net isosteric heat increases with decreasing of
With moisture content increasing, the net isosteric heat (in moisture content. At the region below 0.077 mg/mg dry coal,
Fig. 5) shows an increase at very low moisture content, and the with the effect of the interaction among adsorbed water
maximum net isosteric heat (qnst = 8.17 kJ/mol) is achieved at molecules and the bonding force between water molecules
0.054 mg/mg dry coal. An initial increase of the net isosteric heat and active sites, the net isosteric heat curve appears a max-
of sorption was found in the adsorption process of other materials imum energy peak.
K. Wan et al. / Fuel 171 (2016) 101–107 107
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