Bioresource Technology 177 (2015) 328–336

Contents lists available at ScienceDirect

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

Combustion behavior of different kinds of torrefied biomass and their

blends with lignite
Asli Toptas, Yeliz Yildirim, Gozde Duman, Jale Yanik ⇑
Faculty of Science, Department of Chemistry, Ege University, 35100 Bornova, Izmir, Turkey

h i g h l i g h t s

 Torrefaction process improved the reactivity of char combustion step of biomasses.

 No interaction between lignite and torrefied biomass at initial step of co-combustion.
 Poultry litters can be used as a solid fuel by mixture with lignocellulosic biomass.

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

Article history: In this study, the combustion behavior of different kinds of torrefied biomass (lignocellulosic and animal
Received 8 October 2014 wastes) and their blends with lignite was investigated via non-isothermal thermogravimetric method
Received in revised form 14 November 2014 under air atmosphere. For comparison, combustion characteristics of raw biomasses were also deter-
Accepted 15 November 2014
mined. Torrefaction process improved the reactivity of char combustion step of biomasses. Characteristic
Available online 3 December 2014
combustion parameters for blends showed non-additivity behavior. It was found that the mixture of torr-
efied biomasses and lignite at a ratio of 1:1 had a lower ignition and burnout temperature than the coal-
Keywords:
only sample. Although no interactions were observed between the lignite and torrefied biomass at initial
Co-combustion
Biochar
step of combustion, a certain degree of interaction between the components occurred at char combustion
Poultry litters step. Kinetic parameters of combustion were calculated by using the Coats Redfern model. Overall, this
Biomass study showed that poultry litters can be used as a substitute fuel in coal/biomass co-firing systems by
Kinetic blending with lignocellulosic biomass.
Ó 2014 Elsevier Ltd. All rights reserved.

1. Introduction addition, co-combustion is a very effective way to dispose of waste

Turkey’s domestic resource potential is 15.4 billion tons of coal
and of this total 14.1 billion tons is lignite. And in energy consump-
tion, coal has a share of 31.3% of energy consumption (http://
www.enerji.gov.tr/). However, by 2023, government wants domes-
tic resources to make up the main share rather than imported nat-
ural gas. Because of this, coal is now referred to as the energy
source of the future in Turkey. But it is well known that combus-
tion of brown coal causes significant greenhouse gas emissions.
On the other hand, co-combustion of biomass with coal provides
the reducing net CO2 emissions from coal-based power plants
besides it provides the most efficient and inexpensive uses of
biomass. Because of the high content of volatiles and low sulfur
in biomass, the combustion of biomass with coal also provides in
reduction of NOx and SO2 emissions (Munir et al., 2010a,b). In
⇑ Corresponding author. Tel./fax: +90 232 3888264.
E-mail address: jale.yanik@ege.edu.tr (J. Yanik).
materials. Much work on co-combustion of coal with various ligno-
cellulosic biomasses has been reported in literature, such as cotton
stalk (Munir et al., 2010b), forest residues, olive kernel, and wood
(Kastanaki and Vamvuka, 2006), fir wood (Tasß and Yürüm, 2012),
wastes from palm oil production (Idris et al., 2012), olive tree prun-
ing (Vamvuka et al., 2014), pine sawdust and oat straw (Kubacki
et al., 2012). There are technical challenges in co-combustion of
biomass with coal in existing coalfired power plants. The most
common challenges include: (1) poor grindability resulting in
higher grinding energy requirements, (2) low energy density caus-
ing flame instabilities in the combustion chambers, (3) low bio-
mass flowability and fluidization properties leading to difficulties
in feeding biomass into combustors (Sarvaramini et al., 2014). All
these downsides cause the difficulty of utilization of biomass. In
order to eliminate these downsides, the quality of biomass can
be improved by a pre-treatment process, such as torrefaction.
Torrefaction is a slow pyrolysis process carried out at low temper-
atures, within a temperature range of 200–300 °C. Torrefaction

http://dx.doi.org/10.1016/j.biortech.2014.11.072
0960-8524/Ó 2014 Elsevier Ltd. All rights reserved.
 A. Toptas et al. / Bioresource Technology 177 (2015) 328–336
produces charry material which has lower moisture content and
higher calorific value compared to the raw biomass. The low
moisture increases the storage duration of the torrefied product.
Furthermore, torrefaction greatly enhance the grindability of the
treated biomass. It should be also noted torrefaction may led to
release of a significant amount of chlorine in biomass as HCl. As
known, biomass may have a high content of chlorine which is very
undesirable in power plant fuels. It leads to formation alkali chlo-
rides leading to corrosion during combustion. The studies related
to pyrolysis of different types of biomass showed that between
20% and 60% of the chlorine was released at moderate temperature
pyrolysis (Björkman and Strömberg, 1997; Jensen et al., 2001) as
HCl.
It is clear that the use of torrefied biomass instead of raw bio-
mass may be a preferred option in co-combustion with coal. The
combustion behavior of blends of torrefied biomass and coal has
not been studied so much (Sarkar et al., 2014a,b; Li et al., 2012;
Goldfarb and Liu, 2013; Kastanaki and Vamvuka, 2006; Park
et al., 2012; Farrow et al., 2013). More recently, Sarkar et al.
reported that the use of rice husk char and sawdust char with lig-
nite provides synergistic effect in burning performance (Sarkar
et al., 2014a,b). They observed the lowering of activation energy
and improvement of reactivity in major combustion zone for the
co-combustion of blends an Indian coal with saw dust and rice
husk. A case-study boiler showed that boiler can be operated with
the blends containing high ratio of torrefied biomass without
decreasing of energy efficiency and fluctuation of boiler load (Li
et al., 2012). In the study on the oxidation kinetics of coal–torrefied
biomass blends, it was observed that the activation energy for the
initiation of thermal decomposition decreased sharply as the per-
cent of torrefied biomass increased (Goldfarb and Liu, 2013). Park
et al. (2012) reported that burnout time for the coal–torrefied bio-
mass blend increased and ignition temperature decreased as the
torrefied biomass ratio was increased.
Turkey is one of the biggest grape and olive producer countries
in the world. So, huge amount of pruning residues (stem) from
olive tree and vine may become an important energy resource in
Turkey. Corncob also is the widely planted in Turkey.
These wastes are disposed as burning on the field. Besides these
plants, poultry production is an important and diverse component
of Turkey agriculture as world agriculture. Today, most of the pro-
duction of poultry is carried out by a large number of farmers. The
intensification and concentration of poultry operations pose major
pollution problems at regional and global scales. The waste pro-
duced by farmer raises serious concerns about treatment and dis-
posal. Traditionally, farmers have managed manure by spreading
it on fields. But the intensive poultry production is resulted in more
manure than agriculture can use. Poultry manure is produced dur-
ing the normal operation of hatcheries, broiler production and egg
laying production. There is a difference in the set-up of layer and
broiler operations which leads to a difference in the type of litter
produced. The manure from chicken broiler (broiler litter) is a mix
of poultry excreta, spilled feed, feathers, and bedding materials
(straw, sawdust, etc.), while the other (laying hens litter) contains
only poultry excreta. Laying hens litter is relatively dry as it falls
through layer cages into a concrete storage area. A growing legal
restrictions for poultry manure are inducing the search for appropri-
ate methods of disposal. The previous study dealing with co-firing of
broiler litter and coal in a circulating fluidized bed combustor (CFBC)
showed that co-firing in an existing CFBC boiler firing coal is a good
way to utilize litter (Jia and Anthony, 2011). Co-combustion of all
these wastes with lignite is an effective alternative to decrease both
the dependence on oil and environmental pollution.
Thermal gravimetric analysis (TGA) is effective way to analyze
combustion behavior of different kinds of fuels. In this study, we
used thermogravimetric analysis to investigate the combustion
329
characteristics of both raw- and torrefied-biomasses and their
blends with coal. Different types of biomass were investigated.
The main objective of this paper is the study of agricultural and
animal wastes as potential substitute fuels for co-combustion with
coal. To the best of our knowledge, there has been no study on the
combustion and co-combustion behavior of torrefied-biomasses
used in this study.
2. Methods
2.1. Materials
The solid fuels used in this study included a Turkish lignite
(from the Soma basin), vine pruning (VP) and olive tree pruning
(OP), corn stalk (CS), poultry litters (broiler litter – BL and laying
hens litter – LL). Poultry litters were kindly provided by CP Group,
Izmir, Turkey. Agricultural wastes were collected from the agricul-
tural fields of Izmir, Turkey.
Prior to experiments, the coal and biomasses were previously
dried at room temperature and ground to <2 mm, then in a drying
oven at 105 °C overnight. Dry samples were further ground to
<250 lm, and then they were stored in sealed containers until
use. The characteristics of biomasses and lignite are given in
Table 1.
2.2. Characterization of materials
Proximate analysis of samples was made according to standard
analysis methods; thus ASTM D3174-04 for ash analysis and ASTM
D3175-89 for volatile matter. The gross calorific values of samples
was determined using an IKA C-2000 basic model calorimeter
according to ASTM D240-02. The elemental analysis was carried
out by a LECO CHNS 932 elemental analyzer according to ASTMD
5291-96. The ash content was analyzed by Atomic Absorption
Spectrometry (A.A.S.) following acid digestion. Component analysis
(extractives, lignin, hemicellulose, and cellulose) was carried out
according to TAPPI standards.
2.3. Torrefaction
Torrefaction experiments were carried out in a stainless steel
1 L vertical reactor which was a fixed bed design at 300 °C with a
reaction time of 30 min. In a typical run, 50 g of biomass was
placed into the reactor and then the system was heated to 300 °C
under N2 atmosphere at a heating rate of 5 °C min1, and held at
this temperature for 30 min. After then, reactor was cooled down
under nitrogen gas stream. The amount of resulting char product
(torrefied biomass) were determined by weighting and then were
ground to <250 lm and stored in sealed containers until further
analysis. For torrefaction, the temperature of 300 °C was selected,
taking into account the mass yield and energy yield which is
defined as fuel value of solid product (biochar) as a fraction of fuel
value of raw biomass. The mass yield and energy yield of the torr-
efied-biomass are defined as follows:
Mass yield; % ¼ ðmass of biochar=mass of biomassÞ  100 ð1Þ
Energy yield ¼ mass yield of biochar
 
energy content of the biochar
 ð2Þ
energy content of the biomass
2.4. Thermogravimetric analysis
Combustion characteristics of biomasses and their blends with
lignite were determined by a thermo gravimetric analyser (Perkin
330 A. Toptas et al. / Bioresource Technology 177 (2015) 328–336

Table 1
Properties of raw biomasses and lignite.

Corn stalk Olive tree pruning Vine pruning Egg laying litter Broiler litter Lignite
Proximate analysis (wt.%, dry basis)
Ash 6.3 3.3 4.3 22.5 8.2 11.5
Volatile matters 32.2 71.6 70.9 61.2 68.3 49.9
Fixed carbon 61.4 25.1 24.8 16.3 23.5 38.6
FC/VM 1.9 0.4 0.3 0.3 0.3
HHVb, MJ kg1 18.12 17.83 16.86 12.09 14.42 25.1
Ultimate analysis (wt.%, dry basis)
C 29.59 43.47 40.86 32.64 35.7 –
H 3.92 5.78 5.27 4.28 5.27 –
N 1.29 1.29 1.03 5.85 9.61 –
S 0.23 0.18 0.47 0.22 0.24 1.11
H/C 1.59 1.59 1.55 1.57 1.77 –
Ash analysis (wt.%, dry basis)
Na2O 5.53 2.09 4.41 2.55 5.11 0.76
K2O 30.33 22.48 25.69 6.69 26.53 1.41
CaO 16.44 59.78 53.25 81.86 39.52 2.48
MgO 11.14 6.94 6.46 4.55 6.22 1.73
SiO2 31.16 5.59 6.32 2.92 18.73 53.71
Al2O3 2.56 0.86 1.48 0.16 1.09 24.08
Fe2O3 1.33 0.59 0.67 0.36 0.78 4.17
TiO2 0.01 0.01 0.01 0.01 0.01 0.05
MnO 0.10 0.10 0.12 0.10 0.11 0.01
Component analysis, (wt.%, dry basis)
Hemicellulose 6.3 7.1 5.1
Cellulose 52.0 52.4 63.1
Lignin 34. 5 26.7 25.4
Extractives 1. 6 11.0 2.4

Elmer Diamond TG/DTA) under air atmosphere. The flow rate of air Therefore, we utilized different g(x) models to calculate the activa-
was kept at 100 ml min1. The sample with a mass of 30 mg, tion energy and lnA by using the Coats Redfern model (Gil et al.,
approximately, was heated from room temperature up to 900 °C 2010; Zhou et al., 2006). The reaction rate can be expressed as
with a heating rate of 20 °C min1. Weight loss and its rate were follows:
continuously recorded during the process. Each sample was ana-
dx
lysed at twice. In case of co-combustion experiments, the coal/torr- ¼ kf ðxÞ ð3Þ
efied biomass blends were prepared by physical mixing in the dt
proportion 50:50 and then were ground to <250 lm in order to  
E
provide homogeneity of blend. k ¼ A exp  ð4Þ
The combustion parameters, such as ignition temperature (IT),
RT
burnout temperature (BT) and combustion reactivity were calcu- where x is the mass loss, E is the apparent activation energy
lated from TG/DTG curve according to literature (Xiang-guo et al., (kJ/mol), A is a pre-exponential factor (s1), R is the constant for
2006; Park and Jang, 2012). Burnout temperature is the tempera- gas (8.314 J/mol K) and T is the temperature (K). f(x) represents
ture at which the rate of weight loss become smaller than the hypothetical model of the reaction mechanism.
1 wt.%/min. The ignition temperature was determined based on For a constant heating rate (b = dT/dt, °C/min), Eqs. (3) and (4)
the temperature at which the DTG had its peak value and the cor- can be rewritten and integrated as:
responding slope to the intersection with respect to the TG profile. Z Z  
x T
The combustion reactivity of sample is considered directly propor- dx A E
gðxÞ ¼ ¼ exp  dT ð5Þ
tional to the maximum rate of mass loss, whereas it is inversely 0 f ðxÞ b T0 RT
proportional to the corresponding peak temperature. The use of
both two properties in a parameter provides an average of fuel The g(x) is the integral function of conversion and x is defined as,
reactivity. In this study, mean reactivity, Rm, was calculated based x ¼ ðm0  mt Þ=ðm0  mf Þ ð6Þ
on the literature (Park and Jang, 2012). Thus; a parameter
100  (dm/dt)max was calculated for each peak. Rm values in the where m0 is the initial mass of the sample, mt the mass of the sam-
Tables 3 and 4 represent an average reactivity. ple at time t and mf the final mass of the sample.
Repeatability of the experimental results was within a range Eq. (5) is integrated by using the Coats–Redfern method and
of ± 4 °C. becomes:
    
gðxÞ AR 2RT E
2.5. Kinetic studies ln ¼ ln 1  ð7Þ
T2 bE E RT
The chemical kinetics of biomass combustion gives information Since the expression ln[AR/bE(1  2RT/E)] in Eq. (7) is essen-
for the design and optimization of combustion systems. Combus- tially constant, plotting of ln[g(x)/T2] versus 1/T should give a
tion kinetic was analyzed with an integral method using dynamic straight line if combustion is assumed as a first order reaction
analysis of the non-isothermal TG data. Although, in most of liter- (Zhou et al., 2006). From the slope, E/R, the activation energy E
ature combustion reactions are considered as first order reaction to can be determined, and the pre-exponential factor A can also be
simplify the kinetic calculations, the combustion is a more com- calculated by taking the temperature at which mt = (m0 + mf)/2 as
plex process, including solid–gas phase and gas phase reactions. the intercept term of Eq. (7).
 A. Toptas et al. / Bioresource Technology 177 (2015) 328–336
3. Results and discussion
3.1. Characterization of materials
As seen from Table 1, agricultural and animal wastes signifi-
cantly differ from each other. Egg laying litter (LL) has highest
ash content and high nitrogen because it is pure poultry excreta.
The broiler litter (BL) is a mixture of poultry litter and bed materi-
als, straw, sawdust, etc. Therefore it has different properties in
comparison to LL. Although, BL is similar to agricultural wastes
in terms of proximate analysis, its’ nitrogen content is highest
due to the accumulation of poultry excreta (generally, a poultry
house is ground level every 47–49 days). In utilization of biomass
in the energy sector, ash composition is a critical parameter. Many
biomass fuels lead to slagging and fouling in the boiler. Due to the
higher concentration of basic components in the ashes of bio-
masses used in this study, it is expected that their fouling tendency
and slagging index are high. But taking into account the lower ash
content of biomasses, the slagging/fouling tendency of blends can
be acceptable limits in co-combustion. Sarkar et al. (2014a)
observed no sign of particle agglomeration after burning of the
blend containing 50% biomass char in a drop tube furnace. Due
to the low sulfur contents in biomasses, SOx emissions are
expected to be in the range of emission limits. But, the high nitro-
gen content for animal wastes suggests a possibility increase in
NOx emission during co-combustion.
When wastes were torrefied, the carbon content was increased,
while decreases were observed in oxygen content (Table 2). It is to
be noted that torrefaction led to a decrease in nitrogen content in
case of broiler litter, whereas it led to little changing in nitrogen
content for other biomasses. The major N components are proteins
in lignocellulosic wastes, whereas they are mainly urea in animal
wastes. The partitioning of nitrogen between the volatiles and char
during torrefaction is not clear because it depends on composition
of biomass as well as type of nitrogen precursor (Darvell et al.,
2012). Hence, it is difficult to discuss the effect of type of nitrogen
precursor on the nitrogen transformation during torrefaction. After
torrefaction, the mass of biomass decreased due to the partly dev-
olatilization, but the energy content of the biomass is mainly pre-
served in the solid product, resulting that the energy density of the
torrefied biomass was higher than the raw biomass. The yields of
torrefied biomass were in the range of 53.2–74.3% depending on
the type of biomass. For lignocellulosic wastes, the difference
may be attributed to the catalytic effect of inorganic matter, cata-
lyzing the pyrolysis reactions leading to the formation of more bio-
char (Xu and Sheng, 2012). Although the yields of biochar derived
from animal wastes were high, as from agricultural wastes, but
these were certainly due to their high ash content.
As seen by other researchers (Sarkar et al., 2014a,b; Li et al.,
2012), torrefaction increased the C content and reduced volatiles
content. The energy content of torrefied biomasses was similar or
close to that of lignite. Only, torrefied laying hen litter has lower
energy content than lignite because of high ash content and carbon
Table 2
The mass and energy yields of torrefied biomasses and their properties.
Energy yield (%) Yield, (wt.%) Proximate analysis (wt.% (dry basis))
Ash
CS 75.7 53.6 10.6
OP 84.3 67.5 4.1
VP 91.8 59.0 6.8
LL 90.3 74.3 24.7
BL 86.3 53.2 12.8
a
Volatile matter.
b
Fixed carbon.
331
content. For all torrefied biomasses, the energy yield was higher
than the mass yield. It is noted that the fuel ratio of torrefied bio-
masses (FC/VM) is <2.5, which shows that the satisfactory combus-
tion performance can be obtained from lignite–torrefied biomass
blends in pulverized fuel firing systems (Sarkar et al., 2014a).
3.2. Combustion behavior of individual biomasses
The behavior of biomasses and torrefied biomasses in air atmo-
sphere with 20 °C/min heating rate was studied in the first series of
experiments. Comparing the TGA curves for all the tested bio-
masses different character becomes evident. In case of agricultural
wastes, two main stages were distinguished during the combus-
tion process. Similar results for other lignocellulosic biomasses,
such as olive tree pruning and cardoon (Vamvuka et al., 2014),
palm empty fruit bunches (Parshetti et al., 2013), sawdust
(Sarkar et al., 2014b), pine sawdust and oat straw (Kubacki et al.,
2012), date palm wastes (Sait et al., 2012), have been reported in
literature. The first stage extended from 190 to 376 °C which was
attributed to oxidation and removal of volatile matters leading to
char formation. The second stage extended from 401 to 551 °C
which was due to oxidation of char remaining after the volatiles
were removed from the samples. The weight loss below 150 °C cor-
responds to a loss of moisture and the very light volatile materials.
From the DTG curves of the raw biomass samples (Fig. 1), it is evi-
dent that the rate of burning of corn stalk is significantly lower
than other biomasses. And also the char combustion stage of corn
stalk shifted to higher temperatures. Interestingly, the combustion
of corn stalk produced around 65% residual mass, whereas the res-
idue amount was maximum 30% for other biomasses. However, it
contains 5.7% ash. This difference showed the presence of
unburned carbon in combustion residue. This makes it unattractive
for combustion. We also studied the thermal behavior of corncob
in nitrogen atmosphere; weight loss was only around 40%. Biomass
combustion is complex processes due to differences in the chemi-
cal composition of components in the biomass material. The differ-
ent combustion behavior between biomasses is due to the
heterogeneous nature of the oxidation reactions and the different
properties biomasses, such as the morphological structure, the
content of inorganic matter, and the elemental composition
(Branca and Di Blasi, 2010).
As expected, the combustion characteristics of animal wastes
were different from that of agricultural wastes. For broiler litter,
although two peaks were observed, the volatile release and com-
bustion begins earlier (i.e. at lower temperature), the nitrogen
compounds are preferential to decompose and release at very
low temperatures, but the char combustion stage shifted to higher
temperatures. For the laying hens litter, the combustion process
apparently took place at four stages due to multi component
decomposition and different reactivity of chemical components.
This is also in line with the findings of Florin et al. (2009). It can
be speculated that in the first and second stage, volatilization
and oxidation of lighter and higher molecular weight compounds,
Ultimate analysis (wt.% (dry basis))
VMa FCb FC/VM C H N S H/C
44.6 44.8 1.1 54.79 4.63 1.38 0.55 1.01
54.3 41.6 0.8 55.19 5.52 1.59 0.39 1.19
45.8 47.4 1.2 57.00 4.14 2.09 0.38 0.87
49.1 26.2 0.6 36.56 2.59 6.40 0.48 0.84
44.3 43.1 1.1 53.57 3.69 5.41 0.19 0.82
332 A. Toptas et al. / Bioresource Technology 177 (2015) 328–336
Corn stalk
Fig. 1. TGA–DTG profiles of biomasses- and torrefied biomasses in air.
respectively, occurred and third stage was char oxidation stage.
After third combustion step (>600 °C), decomposition of inorgan-
ics, CaCO3, took place.
In contrast to biomasses, the combustion DTG profile of lignite
showed one board peak (250–669 °C) which was attributed to the
simultaneous combustion of volatile matter and char. Similar
results for different coals have been reported in literature (Tasß
and Yürüm, 2012; Idris et al., 2012). For torrefied lignocellulosic
biomass, only one main DTG peak with a shoulder between 246
and 500 °C was observed, as in the previous studies (Xu and
Sheng, 2012; Bridgeman et al., 2008). This is attributed to low vol-
atile matter and high fixed carbon. The devolatilization peaks were
not apparent because hemicellulose and most cellulose had
already decomposed during torrefaction. However, two peaks
(around 355–360 °C and 470–480 °C) in combustion DTG profile
of the commercial torrefied biomass were observed by Goldfarb
and Liu (2013). They suggested that first peak related to full devol-
atilization of hemicellulosic components. Similarly, the DTG curves
of the torrefied eucalyptus showed a double peak in a study relat-
ing to investigation of torrefaction on the reactivity of woody bio-
mass (Arias et al., 2008). These different results may be due to the
differences in torrefaction condition, such as temperature and hold
time, as well as in biomass nature. In contrast to raw CS, torrefied-
CS showed similar combustion behavior with torrefied-OP and -VP.
It is clearly understood that char oxidation took place easily and
faster as the fixed carbon and homogeneity increased in fuel. The
development porous and highly disordered carbon structure in tor-
refaction may lead to high reactivity (Sahu et al., 2010). The higher
DTG peaks relating to oxidation of char in torrefied biomasses
(except VP) than that in raw biomass shows that torrefaction
improved the reactivity of char. Similar results were reported by
Li et al. (2012).
The combustion characteristic parameters are given in Table 3.
It is noted that, in the case of LL, the weight loss above 600 °C for
burn out determination was not considered, because it reflects
the decomposition of calcium carbonates. Since the ignition
 A. Toptas et al. / Bioresource Technology 177 (2015) 328–336 333

temperature depends on early release of volatiles (Razuan et al., 100

2010), as expected, the ignition temperature and Tmax of torrefied Lignite
90 blend 1
biomasses is higher than that of raw biomasses. On the other hand, 80
blend 2
blend 3
torrefaction had little impact on the burn out temperatures of bio- TGA
70
masses. It agrees with the results obtained in a study on rice husks

Weight loss, wt.%

and woody biomass (Park and Jang, 2012). According to the data in 60

Table 3, it is difficult to draw a generalized conclusion representing 50

the effect of the torrefaction on the combustion reactivity of sam- 40
ple. It is interesting to note that the reactivity of torrefied CS was
30
more than that of raw CS whereas reactivity of other torrefied bio-
20
mass was almost similar to that of raw materials. Overall, all bio-
mass samples (except torrefied-LL) had higher combustion 10

reactivity than lignite. 0

0 100 200 300 400 500 600 700 800 900
Temperature, oC
3.3. Combustion behavior of blends
7
Lignite
Today, the direct co-combustion plants are operated generally 6
blend 1
DTG blend 2
with a blend containing maximum 10% biomass (Basu et al., blend 3
2011). However, a study relating to the modeling of torrefaction 5

dm/dt, wt.%/min
based co-firing system showed that torrefaction is able to provide
a technical option for high substitution ratios of biomass in the 4

co-firing system (Li et al., 2012). In this study, because of the

3
promising chemical and physical properties, torrefied biomass
samples were chosen for co-combustion experiments. The TGA/ 2
DTA thermograms in Fig. 2 and Table 4 show the difference
between the combustion properties of both lignite and blends. 1

Blend 1 consisted of lignite and torrefied-animal biomasses

0
(1:0.5:0.5; lignite:LL:BL), Blend 2 consisted of lignite and torr- 0 100 200 300 400 500 600 700 800 900
efied-lignocellulosic biomasses (1:0.3:0.3:0.3; lignite:OP:CS:VP) Temperature, oC
and Blend 3 consisted of lignite and torrefied all biomasses
(1:0.2:0.2:0.2:0.2:0.2; lignite:OP:CS:VP:LL:BL). Characteristic com- Fig. 2. TGA–DTG profiles of blends.

bustion parameters in the TGA for blends showed non-additivity

behavior. Combustion profiles of blends (Fig. 2) were similar to
those of the torrefied biomasses. In case of Blend 2 and Blend 3,
the peak temperatures (Tmax) and burnout temperatures (BT) were Table 4
similar to those of the torrefied lignocellulosic biomass samples. Combustion characteristics of lignite and blends.
However, in case of Blend 1, Tmax and BT was lower than those of Lignite Blend 1 Blend 2 Blend 3
the components in blend. Ignition temperatures of blends are very IT (°C) 359 320 305 307
close to that of torrefied biomass, which shows that in the initial BT (°C) 644 539 499 517
phase of combustion there was practically no interaction between Tmax (°C) 484 439 400 432
the blend components. Rm 1.3 0.8 1.3 1.1
To see the interaction between lignite and torrefied biomasses,
the theoretical DTG curves were calculated using below equation
(Eq. (8)).The theoretical curves represent the sum of the curves torrefied-agricultural and -animal wastes improved the burnout
for individual components in the blend. performance of lignite. The lower the burnout temperature means
the less the time for fuels to burn out, minimizing unburnt carbon
ðdm=dtÞsum ¼ yðdm=dtÞ þ x1 ðdm=dtÞ þ :::::::::::xn ðdm=dtÞ ð8Þ
loss.
where, y – mass fraction of lignite in the blend, x – mass fraction of It is possible to speculate on possible reasons for the difference
each torrefied biomass in the blend, (dm/dt) – weight loss rate between experimental and calculated datas. Torrefied biomasses
(%/min). begin to first and heat released plays a preheating role in the vol-
The experimental and calculated DTG curves of blends are given atilization and combustion of coal (Fumin et al., 2010). In addition,
in Fig. 3. A comparatively important difference can be seen that inorganics in biomass may catalyze the combustion of coal. On the
may be related to a certain degree of interaction between the other hand, interactions occurred between the components of
components. It is clear that the burnout temperature of the blends caused little lowering of reactivity (antisynergistic effect).
experimental DTG curves decreased, which indicates that both The negative interactive interactions have been also reported by

Table 3
Combustion characteristics of raw- and torrefied-biomasses.

OP VP CS LL BL
Raw Char Raw Char Raw Char Raw Char Raw Char
IT (°C) 228 317 250 302 262 303 256 310 226 345
BT (°C) 493 497 476 503 517 503 556 566 551 548
Tmax (°C) 313 417 307 407 302 413 306 498 282 493
Rm 3.03 3.16 3.67 3.18 1.08 3.10 1.42 1.04 1.76 1.89
334 A. Toptas et al. / Bioresource Technology 177 (2015) 328–336

9 model functions used for the kinetic study of solid-state reac-

8 tions (Parshetti et al., 2013). The function g(x) provides to esti-
Blend 1 experimental
mate the reaction mechanisms during combustion (Park et al.,
7 calculated
2012). The form of g(x) which gave a straight line with the high-
dm/dt, wt% /min

6
est correlation coefficient was considered the function of the
5 model that best represents the kinetic mass loss for each sepa-
4 rate reaction.
Table 5 shows the values of E and A obtained from the plots of
3
ln[g(x)/T2] against 1/T that gave the highest correlation coefficient
2
values for all samples. As seen from Table 5, most of the reaction
1 stages follow diffusion mechanisms which means rate determin-
0 ing step is diffusion reaction. However, the combustion reaction
0 100 200 300 400 500 600 700 800 900 mechanism for the third stage combustion of LL and for the sec-
Temperature, oC ond stage combustion of CS were fitted the chemical reaction
9 model.
The activation energies for the first stage and the second stage
8
Blend 2 experimental for all samples differed from each other. Since combustion of raw
7 calculated biomass involves two or three independent reactions while a sin-
6 gle reaction describes combustion of torrefied biomasses, it is dif-
dm/dt, wt% /min

5
ficult to draw a generalized conclusion explaining to the effect of
the torrefaction on the combustion reactivity of sample. On the
4
other hand, the fact that high amount of residue from corn stalk
3 combustion (Section 3.1) can be explained by kinetic parameters.
2 Because of high activation energy (167.74 kJ mol1) in oxidation
step of corn stalk combustion, the temperature and duration of
1
combustion might not be sufficient to complete combustion of
0 corn stalk. In addition this, the combustion reaction mechanism
0 100 200 300 400 500 600 700 800 900
Temperature, oC of corn stalk was fitted to third order reaction model, in which
chemical reaction limits overall reaction to complete total com-
8
bustion. It is worth noting that combustion model of torrefied
Blend 3 experimental
7
calculated corn stalk fitted to diffusion limited model. Because of this, acti-
6
vation energy for torrefied corn stalk was much lower than raw
corn stalk.
dm/dt, wt% /min

5 The activation energy of blends was higher than that of lig-

4 nite. Therefore, it can be expected that the combustion reaction
3
2 thermograms, we can conclude that the calculated activation
1
0 type. For example, although the value of mean reactivity for lig-
0 100 200 300 400 500 600 700
Temperature, oC
Fig. 3. DTG curves of experimental and calculated blends.
Sarkar et al. (2014a) for lignite–torrefied rice husk combination.
But, many researcher also reported the synergistic effects
(Goldfarb and Liu, 2013; Kastanaki and Vamvuka, 2006; Farrow
et al., 2013; Sarkar et al., 2014b) for coal–torrefied biomass combi-
nation. Since the interactive effects varied with the characteristics
of the components in blend, such as heterogeneity, nature and dis-
tribution of reacting species etc. (Sahu et al., 2010), the synergies in
co-combustion process is difficult to predict.
3.4. Kinetic parameters
Kinetic parameters in combustion were calculated for the
temperature ranges as given in Table 5. According to the DTG
curves (Figs. 1 and 2), a single reaction could be used to describe
lignite, torrefied lignocellulosic biomasses and blend samples,
whereas two or three independent reactions are appeared for
raw biomasses and torrefied litters. The kinetic parameters were
determined assuming separate reactions for particular stages of
combustion. The term of g(x) in Eq. (5) is utilized for the basic
is decelerated at the time of co-combustion. By comparison of
results obtained kinetic study with the results obtained DTA
energies are not always consistent with the trends of combus-
tion properties of biomasses and blends, depending on biomass
800 900
nite is similar to that of Blend 2, Ea for lignite is lower than Ea
for Blend 2. But in case of Blend 1 and 3, higher activation
energy comparing to that of lignite results lower mean reactiv-
ity. In order to modeling the co-combustion of coal with bio-
masses, it is necessary to expose to the required combustion
parameters after studying both the combustion characteristics
and combustion kinetic.
Activation energies calculated for the torrefied lignocellulosic
biomass and blends were in the range of 45.34–75.51 kJ mol1,
which are lower than activation energies calculated for different
kinds of biomass, chars and blends in literature.
The activation energies of the combustion of sawdust char and
the rice straw char were calculated as 137.50 kJ mol1 and
110.61 kJ mol1, respectively (Wang et al., 2012). In case of their
blend with coal char, the activation energy of the blend lied
between that of the biomass char and that of coal char. With
increasing of the biomass ratio in blend, activation energy of blend
decreased. In a previous study related to co-combustion of coal/
pine sawdust blend (Gil et al., 2010), first stage was fitted first
order reaction model while further stage was fitted diffusion reac-
tion. In their study, the calculated lowest Ea values were
102.0 kJ mol1 for first stage and 195.5 kJ mol1 for second stage.
In another study, the Ea values of co-combustion of lignite/wood
blend were found as 141.0–147.5 kJ mol1 (Vhathvarothai et al.,
2014).
 A. Toptas et al. / Bioresource Technology 177 (2015) 328–336 335

Table 5
Kinetic parameters of all samples.

Sample Temp. range (°C) Weight loss (wt.%) Reaction mechanism Ea (kJ mol1) lnA (min1) R2
a
Broiler litter Raw 171–366 30.35 D1 44.82 ± 1.8 5.46 0.96
426–566 23.27 D1 20.77 ± 0.9 0.54 0.96
Torrefied 241–391 16.50 D1 31.04 ± 1.5 1.26 0.95
391–571 50.61 D1 46.97 ± 1.4 4.30 0.97
Laying hens litter Raw 206–361 26.53 D1 44.25 ± 2.6 4.91 0.94
361–471 21.83 D3b 39.85 ± 0.4 2.23 0.99
471–576 12.54 O3d 80.62 ± 2.4 13.83 0.97
Torrefied 236–446 19.02 D1 58.58 ± 3.5 5.64 0.94
446–596 26.24 D1 48.47 ± 1.0 4.01 0.98
Corn stalk Raw 196–376 28.91 D1 48.47 ± 2.4 6.56 0.95
446–556 6.73 O3 167.74 ± 5.0 41.14 0.97
Torrefied 211–521 84.63 D4c 75.51 ± 1.5 8.17 0.98
Olive tree pruning Raw 167–377 51.40 D1 46.23 ± 1.4 6.04 0.97
377–512 26.69 D3 48.24 ± 1.4 4.71 0.97
Torrefied 237–517 85.03 D1 58.85 ± 0.6 7.20 0.99
Vine pruning Raw 181–381 56.88 D1 60.89 ± 3.6 6.37 0.94
381–501 22.42 D3 45.12 ± 2.3 4.37 0.95
Torrefied 181–521 79.42 D3 51.70 ± 1.6 5.51 0.97
Blend 1 218–553 66.60 D1 49.02 ± 1.0 4.99 0.98
Blend 2 209–529 76.53 D1 48.18 ± 1.6 5.35 0.97
Blend 3 201–561 72.35 D1 45.34 ± 1.8 4.56 0.96
Lignite 271–686 76.55 D1 38.31 ± 1.9 2.32 0.95
a
D1: one way transport–diffusion limited reaction.
b
D3: three way transport–diffusion limited reaction.
c
D4: Ginstling–Brounshtein equation–diffusion limited reaction.
d
O3: third order reaction–chemical reaction.

4. Conclusion
The combustion properties of different kind biomasses for co-
firing were examined. Torrefaction of agricultural and animal bio-
masses modified their combustion behavior. Characteristic com-
bustion parameters for blends showed non-additivity behavior.
Ignition temperatures of blends were very close to that of biomass,
showing that in the initial phase of combustion there was practi-
cally no interaction between the blend components. The addition
of biomasses improved the burnout performance of lignite. With
respect to reactivity, poultry litters decreased the reactivity of lig-
nite. But the reactivity of blend containing lignocellulosic bio-
masses was found similar to that of lignite.
Acknowledgements
The financial support from TUBITAK under contract 114M001 is
gratefully acknowledged. The authors would like to acknowledge
the contribution of the COST Action TD1107 (Biochar as option
for sustainable resource management).
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