Research Article

Energy Exploration & Exploitation

2019, Vol. 37(4) 1286–1305
Physicochemical ! The Author(s) 2019
DOI: 10.1177/0144598719834766
characterization of Thar journals.sagepub.com/home/eea

coal and torrefied corn cob

Sumaira Kanwal1,2 , Shahid Munir1,

Nawaz Chaudhry3 and Hafiza Sana1

Abstract
In this study, the corn cob was torrefied at five different temperatures (200, 225, 250, 275 and
300
C) for four different residence times (15, 30, 45 and 60 min). The physical and chemical
properties such as proximate and ultimate analysis, true density, grindability and hydrophobicity
of Thar coal along with raw and torrefied corn cob were investigated. To examine the changes in
the functional groups of torrefied corn cob, more information was taken from spectrometric
studies, by using Fourier transform infrared spectroscopy (FTIR). It was found that there is no
significant improvement in the physical and chemical characteristics of torrefied corn cob at low
torrefaction temperatures of 200 and 225
C, although as the torrefaction temperature and
residence time increased, a significant improvement was found in the physical and chemical
characteristics of the torrefied corn cob. At the maximum torrefaction temperature (300
C)
and longer residence time (60 min), the physical and chemical characteristics of the torrefied
biomass were found to be equivalent to Thar coal. The FTIR studies showed that due to
torrefaction, the R-OH groups decrease and C¼O groups were increased within the fuel. Due
to this change, the tendency of corn cob to absorb water decreases and the biomass becomes
more hydrophobic in nature. Thus, torrefaction is an effective way to improve the characteristics
of corn cob to such an extent that it could be comparable to Thar coal, which is a lignite coal.
Previously, different researchers proposed that energy intensification and mass loss of biomass
are proportional to the heating temperatures of 200–300
C. All were tinged with uncertainty, as
the temperature range is too wide and does not specify a precise effect of different torrefaction
temperature towards particular biomass. While the present study gives a point by point com-
prehensive information, utilizing single biomass (Corn cob), underneath the maximum feasible
temperature levels from 200
C to 300
C (for example 200, 225, 250, 275 and 300
C) and

1
Centre for Coal Technology, University of the Punjab, Lahore, Pakistan
2
College of Earth & Environmental Sciences, University of the Punjab, Lahore, Pakistan
3
Department of Environmental Science and Policy, Faculty of Basic Sciences, Lahore School of Economics, Lahore, Pakistan
Corresponding author:
Sumaira Kanwal, Center for Coal Technology, University of the Punjab, Quaid-e-Azam Campus, Lahore 54000, Pakistan.
Email: sumaira.cct@pu.edu.pk

Creative Commons CC BY: This article is distributed under the terms of the Creative Commons Attribution
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distribution of the work without further permission provided the original work is attributed as specified on the SAGE and
Open Access pages (https://us.sagepub.com/en-us/nam/open-access-at-sage).
Kanwal et al. 1287

residence time (15, 30, 45, and 60 minutes). This comprehensive data may facilitate better opti-
mization of the torrefaction conditions.

Keywords
Thermal treatment, fuel characterization, energy retained, grindability, hydrophobicity

Introduction
Pakistan has 185 billion tons of Thar lignite coal. On the other side, Pakistan is an agricul-
tural country rich in agricultural residues. The annual production of corn cob is 600 million
metric tons. There are some challenges associated with the biomass. Biomass absorbs
moisture easily, which leads to degradation upon long storage and results in a low heating
value fuel. This characteristic, coupled with low energy density, makes it more expensive for
transportation (McKendry, 2002). Furthermore, biomass is fibrous in nature and tenacious
to grind to desired particle sizes which require high energy input. Prior to grinding,
the biomass requires drying, as moisture is an important factor during milling (Arias
et al., 2008).
The chemical and physical properties of a biomass can be upgraded by carrying out
torrefaction, a developing process, which is believed to become a leading technology
(Bergman and Kiel, 2005). It is a mild pyrolysis pre-treatment, which involves a moderate
temperature of about 200–300
C in the absence of oxygen. Several studies have been con-
ducted using different temperatures within the range of 200–300
C and at residence times
from 30 to 60 min (Mani et al., 2004). Characterization of solid torrefied biomasses such as
standard fuel analysis, mass retained and energy retained is vastly under research at present.
A few studies extended the reaction time from 3 to 5 h. In general, all results have shown
that the more severe the torrefaction conditions, the easier is the grinding of the biomass and
the greater the amount of energy that can be saved during this process. However, with the
elevated torefaction temperature, mass loss of the solid torrefied product also goes on and
there should be a balanced between temperature and other torrefaction conditions to retain
high energy in solid torefied fractions. Therefore, choosing an optimum operating condition
is crucial, as different types of biomass give different outcomes (Ibrahim et al., 2013). This
thermal pre-treatment produces a more hydrophobic and grindable solid product compared
to the raw material as reported in few previous studies where significant improvement of
their grindability properties was observed (Arias et al., 2008; Chen et al., 2011). The present
study focuses on the investigation of the physicochemical composition of the solid torrefied
biomass (corn cob) along with Thar coal. A range of characterization methods were used,
including proximate and ultimate analyses, hydrophobicity, grindability and true density.
Fourier transform infrared spectroscopy (FTIR) was used to study the changes in the chem-
ical structure of torrefied biomass. Moreover, another objective of this study was to inves-
tigate the effect of torrefaction on the physical characteristics of the corn cob at different
temperatures and at different residence times. Previously, different researchers proposed
that energy intensification and mass loss of biomass are proportional to the heating temper-
atures of 200–300
C. All are tinged with uncertainty, as the temperature range is too wide
and does not specify a precise effect of different torrefaction temperatures towards a
1288 Energy Exploration & Exploitation 37(4)

particular biomass (Teh and Jamari, 2016). The present study gives a detailed baseline data,
employing a single biomass fraction (Corn cob), under the maximum possible temperature
ranges from 200
C to 300
C (i.e. 200, 225, 250, 275 and 300
C) and residence times (15, 30,
45, 60 min). These comprehensive data may facilitate better optimization of the torrefaction
conditions. Furthermore, torrefaction improves the characteristics of corn cob to such an
extent that it becomes comparable to Thar coal, which is lignite coal. Corn cob was torrefied
at different temperatures, i.e. 200, 225, 250, 275 and 300
C.

Experimental methodology
Sample collection
The samples used in this study are corn cob and Thar coal. The corn cob was collected
from an agricultural field of Okara (southern Punjab), Pakistan, cultivated during
February–March season and handpicked in May–June. Thar coal was taken from block
III of coal deposit in Sindh Province. The corn cob measuring 3 mm was taken for the study.

Pre-treatment analyses
Proximate analysis of coal was performed according to the ASTM standard D-3172-07a,
whereas the proximate analysis of raw corn cob was performed according to the ASTM
standards: E-871 for total moisture, E-872 for volatile matter, E-1755 for ash content and
D-3172 for fixed carbon content. Ultimate analysis of raw coal and corn cob was carried out
using an elemental analyzer Flash 2000 CHONS according to ASTM D-5291. The heating
value was measured in a Digital Bomb Calorimeter (LECO AC500) according to ASTM
D-5865. Subsequently, the true density was measured in a PMI Helium Pycnometer as
per DIN-66137–215. All the analyses were repeated thrice and their mean values are
reported here. The results of raw corn cob and coal are listed in Table 1.

Table 1. Proximate and ultimate analysis of Thar coal and raw corn cob (dried basis).

Sr. no. Percent composition Thar coal Corn cob

1 Volatile matter (%) 43.17  0.5 81.22  0.6

2 Ash (%) 10.8  0.8 3.23  0.4
3 Fixed carbon (%) by difference 45.96  1.3 15.55  1
4 True density (g/cc) 1.64  0.001 1.03  0.001
5 C (%) 60.9  0.02 41.26  0.02
6 H (%) 4.5  0.02 5.96  0.02
7 N (%) 0.5  0.02 0.45  0.02
8 S (%) 1.01  0.02 0.62  0.02
9 O (%) by difference 33.09  0.08 51.71  0.08
10 HHV (MJ/kg) 24.6  0.5 15.99  0.5
HHV: higher heating value.
Kanwal et al. 1289

Figure 1. Lab. scale torrefaction setup.

Torrefaction
Prior to the main torrefaction experiments, corn cob was dried at 105
C for 24 h to elim-
inate the free water. Torrefaction was carried out in a lab scale tube furnace (Figure 1).
A dried corn cob sample of about 10 g was used per batch. A constant flow of nitrogen at a
flow rate of 3 ml/min was supplied to the tube furnace to ensure an inert atmosphere and to
avoid any combustion of biomass in the tube, whereas the heating rate was fixed at 50
C/
min for all the runs. In the inner stainless tube, a fine mesh was inserted and fixed to prevent
any transference of un-torrefied particles with flow of nitrogen towards flue gasses.
Therefore, complete torrefaction was ensured and internal diffusion of solid particles was
restricted. The corn cob was torrefied at five different temperatures (200, 225, 250, 275 and
300
C) and at four different residence times (15, 30, 45 and 60 min).
After the desired temperature and residence time, the sample was taken out of the furnace
and desiccated. Each test was repeated three times under the same conditions to ensure repro-
ducibility of results. The resultant torrefied product was desiccated, weighed and the mass
yield, was calculated as percentage of the original dry mass sample, by using equation (1)
mt
Mass Yield ¼  100 (1)
mr

Where mt is the mass of the torrefied product and mr is the dry mass of the raw biomass
(both on a dry basis).
From measured calorific values and mass yield, energy yield, was determined, by using
equation (2)  
HHV t
Energy Yield ¼ Mass Yield  (2)
HHV r

where HHVt is the higher heating value of the torrefied biomass and HHVr is the higher
heating value of the raw biomass both on dry basis.

Post-torrefaction analyses
Proximate and ultimate analysis of the torrified fractions of corn cob was performed as
referred in the ‘Pre-treatment analyses’ section. All the analyses on torrefied samples were
not repeated three to four times, but results are reported after obtaining constant weights as
1290 Energy Exploration & Exploitation 37(4)

per their respective ASTM standards. All the figures and tables show the results after
achieving constant weights. Moreover, some additional tests were performed to investigate
the physicochemical nature of corn cob, which are as follows.

Composition analysis. The contents of hemicellulose, cellulose and lignin in biomass were
determined by the analytical methods, following their respective Tappi standards (Di
Blasi et al., 1999).

Estimation of extractives.
• 1 g of dried biomass sample with 60 ml acetone was placed in a round bottommed flask at
90
C for 2 h.
• After that the sample was dried at 105
C until a constant weight was obtained.
• The weight difference before and after the extraction is the amount of the extractives.
The formula of extractives was calculated by

Weight of sample taken  Weight of dired residue

Extractives ð%Þ ¼  100
Weight of the sample taken

Estimation of hemicellulose.
• 1 g of extractive free biomass with 10 ml of 0.5 mol/l of sodium hydroxide solution was
mixed and held at 80
C for 3.5 h.
• After that the sample was washed with distilled water until the solution attained neutrality.
• Then it was dried to a constant weight.
• Weight difference before and after drying was hemicellulose content.
• The formula of hemicellulose was calculated by

Weight of the sample taken  Weight of dired residue

Hemicellulose ð%Þ ¼  100
Weight of the sample taken

Lignin estimation.
• 30 ml of concentrated sulfuric acid was added in an extractive free dried biomass.
• The sample was held overnight for 24 h and boiled at 100
C for 1 h.
• Decantation of boiled samples was done.
• After that the mixture was filtered and the residue was titrated with 10% barium chloride
solution until the sulfate ion in the filtrate was unexposed.
• Clear filtrate was dried in a heating oven at 100
C till constant weight was achieved.
• This weight difference was recorded as the lignin content.
The formula of lignin is as follows

Weight of the sample taken  Weight of dired residue

Lignin ð%Þ ¼  100
Weight of the sample taken

Cellulose estimation. Cellulose was estimated by summing up the percentages of extrac-

tives, hemicellulose and lignin.
The formula of cellulose was calculated by

Cellulose ð%Þ ¼ 100  ðextractives þ hemicellulose þ ligninÞ

Kanwal et al. 1291

Grindability test. The grindability of raw and torrefied corn cob was evaluated and compared
by using a modified version of the Hardgrove Grindability Index (HGI) previously used by
Bridgeman et al. (2014). In this modified method, the same fixed volume (50 cm3) for
each coal and biomass sample was used instead of a fixed weight. The HGI machine
was calibrated with coals of known HGI values (39, 57, 87 and 100) as described in
Bridgeman et al. (2014).

Calibration of HGI Machine.

• About 1000 g of a standard reference coal with known HGI is ground using a crushing
mill and sieved the entire amount (1000 g) of air-dried 4.75-mm (No. 4) sieve size sample,
for 2 min in the mechanical sieving machine.
• The sample is then sieved using 1.18 mm and 600 mm size sieves.
• About 50 cm3 of each sample is then measured out and weighed using a measuring cyl-
inder with an accuracy of  0.1 cm3 and a balance accurate to  0.01g.
• The 50 cm3 sample is then distributed evenly in the grinding bowl, which contains the
balls and ground for 2 min at 165 rpm.
• The sample is then removed from the grinding bowl and separated using a 75 mm sieve
and a sieve shaker (5min). The two separate fractions are weighed to the nearest 0.01 g. if
there is a loss of sample greater than 0.5 g the test is aborted and repeated.
• The mass in grams passing through the 75 mm sieve is calculated using

m ¼ mv  m 1

where mv ¼ mass of 50 cm3 sample

m1 ¼ mass of sample collected on 75 mm sieve

• The process is repeated three more times and an average value from the four
results calculated.
• The process is repeated for the three other coals. (for this study four coals of HGI values
of 39, 57, 87 and 100 were used.)
• The results are used to plot a calibration curve for the mill of HGI versus m.

The particle size distribution profiles for the raw and torrefied biomass in comparison to
Thar coal were also determined, using the method described in Ibrahim et al. (2013).
The samples were ground and sieved using a series of 1.18 mm and 600 mm sieves.
About 50 cm3 volume of the sample collected on the 600 mm sieve was taken to a mill for
further grinding. The obtained ground sample was then sieved using a series of sieves of
mesh sizes 600, 335, 212, 150, 75 and 53 mm. The sample mass retained on each sieve was
calculated and documented as a percentage of the original sample mass.

Hydrophobicity. Hydrophobicity of raw and torrefied biomass was determined by immersion

test. About 0.5 g of corn cob sample having particle size <1 mm was taken and immersed in
deionized water at room temperature in a sintered glass filter for 2 h, followed by air drying
for 1 h, before the estimation of its moisture content.
1292 Energy Exploration & Exploitation 37(4)

FTIR analysis. Carry-630 FTIR Agilent Tech. Spectrometer was used to carry out the spec-
troscopic studies of raw and torrefied corn cob samples and the changes in the functional
groups of the corn cob were reported by using this instrument. For all the raw and torrefied
samples, fixed weight was taken.

Thermogravimetric analysis. Combustion characteristics of raw corncob, Thar coal and torre-
fied corn cob (at 300
C and 60 min) were determined by a thermogravimetric analyzer (TGA
LECO 701) under air atmosphere. The flow rate of air was kept at 3.5 l/min. The sample
with a mass of about 0.5 g was heated from 25 to 950
C with a heating rate of 20
C/min.

Results and discussion

Chemical characterization of torrefied biomass
Proximate analyses. The effect of torrefaction conditions (different temperatures and residence
times) on the proximate analysis of corn cob in comparison to non-torrefied sample is pre-
sented in Figure 2. It can be seen from the presented results that with an increase in torre-
faction temperatures from 200 to 300
C, the volatile matter gradually decreased. The volatile
matter content changed little at 200 and 225
C, while at 250, 275 and 300
C, a significant
reduction was observed. The presented data indicate that an increase in the torrefaction
temperatures and residence times leads to a decrease in the volatile matter content and an
increase in fixed carbon content (Ohliger et al., 2013; Sadaka and Negi, 2009; Wannapeera
et al., 2011). It was found that at severe torrefaction conditions (300
C and 60 min), the
proximate constituents of corn cob become equal to Thar coal. The % of VM and fixed
carbon in corn cob were 44.55% and 48.51%, respectively, at 300
C and 60 min that is almost
equal to the values of Thar coal that were 43.17% and 48.51%, respectively.
As the torrefaction temperature and residence time increases, ash content also increases
(Figure 2). It could be due to a loss of mass of organic matter content in the form of volatile
matter released during torrefaction. This could result in retention of ash in the solid prod-
ucts leading to an increase in ash content in torrefied corn cob (Chen et al., 2014;
Phanphanich and Mani, 2011).

Ultimate analyses. An increasing trend in the carbon content was found with an increase in
torrefaction temperature and residence time (Table 2). A maximum carbon content of
55.27% was recorded at 300
C and 60 min, which is almost equal to carbon content in
Thar coal. The oxygen content of the torrefied corn cob was found to be significantly
reduced. This could be due to different reactions during torrefaction involved in the forma-
tion and release of CO, CO2 and water vapors (Park et al., 2013; Poudel and Oh, 2014).
A decrease in hydrogen content at low torrefaction temperatures (200 to 225
C) was found
to be almost negligible. It was found that with an increase in torrefaction temperature and
residence time, the hydrogen content decreases. A maximum reduction of 3.77% was found
at maximum torrefaction temperature and residence time (300
C and 60 min). This could be
due to the fact that some of the hydrocarbons such as C2H6 and CH4 are released only at
higher temperatures (Arias et al., 2008; Chen et al., 2014). The torrefaction can release some
of the volatile organic sulfur as per the findings of Ren et al. (2017a, 2017b). In the current
study, the torrefaction process also significantly reduces the sulfur content of the torrefied
biomass but has a negligible impact on the nitrogen content (Yoo and Choi, 2016).
Kanwal et al. 1293

Figure 2. Effect of residence time and temperature on percent composition of torrefied corn cob.

However, it could be observed from Tables 1 and 2 that at severe torrefaction condition, the
CHNSO contents of torrefied corn cob almost become similar to Thar coal.

Heating values. It was found that with an increase in the torrefaction temperature and res-
idence times, the heating value also increases. A maximum increase was observed at 300
C
and at 60 min residence time, i.e. 25.45 MJ/kg which is almost equal to heating value found
in Thar coal, i.e. 24.6 MJ/kg. An increase in heating value could be due to decrease in
1294 Energy Exploration & Exploitation 37(4)

Table 2. Effect of temperature and residence time on Elemental composition and HHV (MJ/kg) of torrefied
corn cob (dried basis).

Temperature Time HHV

Sr. no. Sample ID (
C) (min) C (%) H (%) N (%) S (%) O (%)a (MJ/kg)

1 Corn cob 41.26 5.96 0.45 0.62 51.78 15.99

Torrified 200 15 41.86 5.90 0.45 0.59 51.483 16.22
corn 30 42.3 5.89 0.45 0.58 51.06 16.41
cob 45 42.9 5.85 0.46 0.58 50.45 16.76
60 43.276 5.8 0.47 0.56 50.216 17.35
225 15 44.65 5.75 0.45 0.58 48.876 18.007
30 45.31 5.73 0.47 0.56 48.26 18.41
45 45.90 5.71 0.47 0.57 47.656 18.45
60 46.52 5.65 0.48 0.54 47.166 19.15
250 15 46.71 5.62 0.46 0.52 47.019 19.67
30 48.3 5.54 0.48 0.50 45.475 20.59
45 49.02 5.43 0.48 0.49 45.02 21.32
60 50.82 5.33 0.50 0.42 43.154 24.66
275 15 48.78 5.2 0.47 0.49 45.311 20.96
30 49.8 4.90 0.49 0.43 44.673 22.39
45 50.01 4.75 0.49 0.40 44.633 24.08
60 52.75 4.66 0.51 0.38 42.037 24.79
300 15 49.14 5.01 0.49 0.40 45.12 23.28
30 50.02 4.62 0.50 0.38 44.69 23.79
45 52.78 4.4 0.50 0.35 42.171 24.50
60 55.27 3.77 0.51 0.34 40.416 25.45
HHV: higher heating value.
a
O is calculated by difference.

moisture content and increase in C/O ratio that resulted due to torrefaction (Chen et al.,
2014; Meng et al., 2012).

Composition analysis. The effect of torrefaction temperature and residence time on the chem-
ical composition of corn cob is shown in Table 3. During torrefaction, hemicellulose decom-
posed rapidly, as it is the more reactive constituent of biomass (Lipinsky et al., 2002; Prins
et al., 2006). The decomposition of hemicellulose starts at low temperature, and at mild
torrefaction temperature of 250
C, the hemicellulose was found to be 14.5%, and at 275
C,
it was found to be 10.9% at a residence time of 60 min. At severe torrefaction temperature of
300
C and 60 min residence time, the hemicellulose could have decomposed rapidly and the
value dropped to 6.5%. The cellulose content slightly decomposed between the temperatures
of 200 to 250
C. It is evident that cellulose partially decomposed at 275
C, and at 300
C, a
rapid decomposition was recorded (Table 3). It could be due to the fact that cellulose is
formed from glucose polymer with no branches that make it thermally stable, and thus it
was decomposed at high temperature (Chen et al., 2011; Yang et al., 2007). A remarkable
degradation of hemicellulose followed by a moderate decomposition of cellulose increased
the lignin content to a large extent (Chen et al., 2011). These findings are in accordance with
the findings of Chen et al. (2011, 2014), Phanphanich and Mani (2011), Zheng et al. (2012).
It could be observed from Table 3 that after severe torrefaction conditions (300
C and
Kanwal et al. 1295

Table 3. Effect of temperature and residence time on fiber composition of torrefied corn cob (dried basis).

True
Temperature Time Cellulose Hemicellulose Lignin Extractives density
Sr. no. Sample ID (
C) (min) (%)a (%) (%) (%) (g/cm3)

1 Corn cob 48.4 25.5 10.4 9.24 1.03

Torrified 200 15 48.3 24.9 10.8 8.5 1.07
corn 30 48.1 24.01 13.01 7.8 1.21
cob 45 48.5 22.8 13.9 7.4 1.33
60 47.4 22.6 14.9 7.2 1.43
225 15 47.7 22.9 13.1 8.4 1.37
30 46.9 21.4 15.6 8.0 1.43
45 46.8 19.9 17.8 7.5 1.48
60 44.9 19.5 20.4 7.1 1.52
250 15 44.7 19.5 21.6 6.4 1.40
30 44.1 18.2 23.7 5.9 1.48
45 42.9 16.9 25.9 5.8 1.50
60 40.3 14.5 31.1 5.6 1.55
275 15 38.8 17.9 28.9 5.8 1.45
30 35.2 15.5 35.8 4.3 1.49
45 31.7 14.4 40.4 3.4 1.52
60 28.8 10.9 46.7 2.8 1.56
300 15 30.4 16.4 39.2 3.9 1.50
30 24.8 12.8 48.3 3.0 1.53
45 20.5 10.3 55.5 2.5 1.57
60 13.9 6.5 65.4 2.1 1.60
a
Cellulose was calculated by difference.

60 min), the true density of corn cob was recorded as 1.60 g/cm3 which is almost equal to the
true density of Thar coal that was 1.64 g/cm3.

Physical characterization of torrefied fuel

Effect of torrefaction on mass yield and energy yield. The resultant mass yield and energy yield of
torrefied corn cob under different torrefaction conditions are shown in Figure 3. Figure 3
shows that at lower temperatures, i.e. 200 and 225
C there was no significant effect on mass
and energy yield, whereas the temperature and residence time changed mass and energy yield.
A decrease in mass yield under severe torrefaction conditions could be due to loss of moisture
and volatile organic matter content in torrefied corn cob (Ciolkosz and Wallace, 2011). A loss
of water took place in two different steps. Firstly during the drying of corn cob prior to
torrefaction and secondly due to the dehydration reactions of organic matter of biomass
during torrefaction (Poudel and Oh, 2014). A reduction in mass yield could also be due to
the decomposition of cellulose and hemicelluloses at severe torrefaction conditions (Wang
et al., 2012). A reduction in mass yield at temperatures 200 and 225
C was found to be
negligible. A significant reduction in mass yield, i.e. 69.08 and 62.4% was found at 250 and
275
C at 45 and 60 min residence times, respectively. A maximum reduction in mass yield was
found at 300
C, i.e. 63.09%, 60.88%, 57.09% and 54.76% at 15, 30, 45 and 60 min residence
times, respectively, as shown in Figure 3. A decrease in mass yield at higher torrefaction
1296 Energy Exploration & Exploitation 37(4)

Figure 3. Effect of temperature and residence time on energy and mass retained (%) after torrefaction of
corn cob.

temperatures could be linked with the thermal decomposition of biomass. The energy
yield can be calculated from the mass yield, as described by Bridgeman et al. (2008). The
energy yield increases at 200 and 225
C. As the temperature and residence time increased,
the energy yield also decreased and it dropped from 93.03% at 200
C to 88.38% at 300
C
(Figure 3).

Grindability. The particle size distribution of the raw corn cob, Thar coal sample and its
torrefied corn cob fractions at different temperatures (200, 225, 250, 275, 300
C) after
milling are shown in Figure 4. It was found that as the torrefaction temperature and
residence time increased, the grinding of torrefied sample became easier. The grindability
behavior of torrefied samples is improved enough and it becomes comparable to coal.
After torrefaction, the particle size of biomass was found to be reduced. This could be
Kanwal et al. 1297

Figure 4. Effect of temperature and residence time on grindability of torrefied corn cob.

due to the decomposition of cellulose and hemicelluloses in corn cob. The reduced particle
size of corn cob can improve the grindability of corn cob leading to better energy consump-
tion during its grinding. Thus, the energy consuming torrefaction process become energy
saving owing to the easy grinding of torrefied solids which thereby, reduces its grinding cost
(Chen et al., 2014; Batidzirai et al., 2013).
At particle size distribution of raw corn cob, it was observed that most of the fraction was
retained on the coarsest sieve (i.e. 600 mm). A very small quantity (i.e. 4.5%) of biomass was
found to be retained on rest of the sieves (i.e. 355, 212, 150, 75, 53 mm). It could be due to the
fibrous nature that prohibits its complete sieving.
At lowest temperature (200
C with 30 min), the results were same like raw corn cob and
no appreciable effect was noticed. On the contrary, after increasing the residence time up to
60 min, a small proportion of mass was retained on all the sieves but still have reasonable
quantity on 600 mm (91%). It can be due to the low temperature treatment (i.e. 200
C)
which could not favor the reduction in particle size efficiently.
Ultimately, a noticeable impact of torrefaction temperature with respect to particle size
distribution was observed (Figure 4). A major portion was split onto other finer sieves that
showed a remarkable reduction in particle size after torrefaction at higher temperatures. A
small figure of 0.25% (at 200
C with 30 min) was changed into 2.1% at finest sieve (i.e. 53
mm) with 300
C and 60 min residence time.
It was observed that at highest temperature and residence time (i.e. 300
C and 60 min),
only 40% mass was retained on 600 mm, whereas remaining 60% mass was distributed to all
other finer sieves. Similar trend was encountered in size reduction of Thar coal which may
support the comparable grinding cost of both fuels.
1298 Energy Exploration & Exploitation 37(4)

Hydrophobicity. Figure 5 shows that as the torrefaction temperature and residence time
increased, the tendency of torrefied corn cob to absorb moisture was found to be reduced
(Felfli et al., 2005; Ferro et al., 2004). At the severe torrefaction condition (300
C, 60 min),
the biomass became more hydrophobic. This could be due to the degradation of hemicel-
lulose that has the large capacity to absorb water (Acharjee et al., 2011). The raw corn cob
had the tendency to absorb 15.76% water. At increasing torrefaction temperature and res-
idence time of 300
C and 60 min, the biomass becomes hydrophobic. It absorbed only 0.1%
of moisture. This investigation is in agreement with the Pim Chuai et al. (2010).

Figure 5. Effect of temperature and residence time on moisture uptake (%) of torrefied corn cob.
Kanwal et al. 1299

Spectroscopic studies
FTIR analysis
To investigate changes in the chemical structure of the torrefied corn cob, Fourier transform
infrared spectroscopy was used, and the FTIR spectrum is shown in Table 4. The results are
given in Figures 6 to 9. It can be observed from Figure 6 that at lower temperatures (i.e. 200 and
250
C), no visible peak was found at 3500–3000 cm1, which could be due to the loss of O–H
group. Figures 7 and 8 demonstrate a decrease in the intensity of the O–H band around 3500–
3000 cm1 at 275 and 300
C torrefaction temperature. It is evident from Figure 8 at 300
C and
30 min, the intensity of OH group at 3500–3000 cm1 decreases which could be due to increase
in torrefaction temperature and the functional groups shifted towards lower wavenumber, a
sharp peak has been observed at 1000 cm1. Similar trend can be observed in Figure 9.

Table 4. FTIR spectra of corn cob and coal.

Wavenumber (cm1 ) Functional groups Intensity

3000–3500 O-H stretching m

3400–3200 H-bonded m
2900–2800 Aldehyde w
2250–2100 CC m-w
1790–1700 C¼O stretching (acids, aldehydes, ketones) s
1680–1600 C¼C stretching (alkenes) s
1300–1000 C-O (Alcohols, ethers, esters, carboxylic acids, anhydrides) s
1050 S¼O s
w: weak; m: medium; m-w: medium to strong; s: strong.

Figure 6. FTIR spectra of raw and torrefied corn Cob at 200
C and 250
C (at 30 min).
1300 Energy Exploration & Exploitation 37(4)

Figure 7. FTIR spectra of raw and torrefied corn cob at 200
C and 225
C (at 60 min).

Figure 8. FTIR spectra of raw and torrefied corn cob at 275
C and 300
C (at 30 min).

In raw corn cob, the vibrations could be due to the carboxylic acid in hemicellulose.
Previous work suggests that during torrefaction, degradation of hemicellulose could be
linked with the reduction of carboxylic acid and new products were found at lower wave-
numbers (Shang et al., 2012). The loss of O–H group explains the improved hydrophobicity
of the torrefied corn cob, and similar decrease in intensity of the OH vibrations had been
reported previously for torrefied bamboo (Rousset et al., 2011).
It is evident from Figure 10 that Thar coal shows spectrum similar to corn cob torrefied
at 300
C and 60 min. Coal is hydrophobic in nature and no distinct peak is observed at
3000–3500 cm1. A sharp peak is found at 2900–2800 cm1 and most of the functional
groups are present at lower wavenumbers.
Kanwal et al. 1301

Figure 9. FTIR spectra of raw and torrefied corn cob at 250
C, 275
C and 300
C (at 60 min).

Figure 10. FTIR spectra of Thar coal.

Combustion behavior of biomass and coal

The combustion behavior of raw corn cob, torrefied corn cob at (300
C and 60 min) and
Thar coal in air atmosphere with 20
C/min heating rate was studied. The combustion
characteristics such as ignition temperature (Ti), peak temperature (Tp) and burnout tem-
perature (Tb) were calculated from TG/DTG curve according to literature.
Table 5 shows that torrefaction is able to increase char ignition temperatures (Ti). The
ignition temperature (Ti) increased from 140
C to 170
C. This could be due to decrease in
volatile matter during torrefaction. These slightly higher ignition temperatures may partially
reduce the risk of self-ignition of the chars providing safer storage.
1302 Energy Exploration & Exploitation 37(4)

Torrefaction reduced the rate of combustion of pyrolytic products and shifted the peak
and burnout temperatures to higher temperatures. The peak temperature (Tp) increased
from 290
C to 380
C (Table 5). Although a very slight increase was observed in the burnout
temperature of raw and torrefied corn cob, it is very closer to burnout temperature of Thar
coal. Increasing the temperature of torrefaction resulted in lower reactivity (Valix et al.,
2017). However, it is evident from Figure 11 that reactivity of torrefied corn cob is almost
similar to Thar coal.

Table 5. Combustion characteristics of raw, torrefied corn cob and Thar coal.

Ignition Peak Burnout

Heating Rate temperature temperature temperature


Sample ID C/min Ti (
C) TP (
C) Tb (
C)

Raw corn corb 20 140 290 946

Torrefied corn corb 170 380 949
(300
C and 60 min)
Thar coal 280 460 950

(a) 100
Raw Corn Cob
80 Torrefied Corn Cob
Mass Loss %

Thar Coal
60

40

20

0
0 100 200 300 400 500 600 700 800 900 1000
Temperaure 0C
(b) 8

6
Raw Corn Cob
dm/dt,wt %/min

5
Torrefied Corn
4 Cob
3

0
0 100 200 300 400 500 600 700 800 900 1000
Temperature 0C

Figure 11. TGA (a), DTG (b) profiles of raw, torrefied corn cob and Thar Coal.
Kanwal et al. 1303

Conclusions
1. The results of corn cob torrefaction indicate that after torrefaction the corn cob has the
properties similar to lignite coal. The % of VM and fixed carbon in torrefied corn cob at
severe torrefaction conditions (300
C and 60 min) were 44.55% and 48.51%, respectively,
that is almost equal to the values of Thar coal that were 43.17% and 45.96%,
respectively.
2. Similar trend has been observed in case of % of C, H, N, HHV (MJ/kg) and true density.
Particularly, the HHV and true density of torrefied corn cob at severe torrefaction con-
dition are almost equal to Thar coal.
3. The particle size of torrefied corn cob had a tendency to decrease, as it becomes brittle
and fragile after torrefaction.
4. At mild torrefaction temperature, no significant improvement was observed, but at 275
C
and 300
C, the characteristics of corn cob such as hydrophobicity, grindability and
heating value improved with little loss of energy retained.
5. The results of FTIR indicate that at severe torrefaction conditions the functional groups
shifted towards lower wavenumber and due to loss of hydroxyl group biomass became
more hydrophobic.
6. As a result of torrefaction, the combustion profile of torrefied corn cob at severe torre-
faction conditions (300
C and 60 min) becomes similar to Thar coal.

Declaration of conflicting interests

The author(s) declared no potential conflicts of interest with respect to the research, authorship, and/or
publication of this article.

Funding
The author(s) received no financial support for the research, authorship, and/or publication of
this article.

ORCID iD
Sumaira Kanwal http://orcid.org/0000-0002-4825-7505

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