Fuel 212 (2018) 626–637

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Fuel
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Full Length Article

Air- and oxygen-blown characterization of coal and biomass by MARK

thermogravimetric analysis
⁎
Mauro Mureddu , Federica Dessì, Alessandro Orsini, Francesca Ferrara, Alberto Pettinau
Sotacarbo S.p.A. – Grande Miniera di Serbariu, 09013 Carbonia, Italy

G RA P H I C A L AB S T R A C T

A R T I C L E I N F O A B S T R A C T

Keywords: This paper reports on the results of air-blown combustion and oxy-combustion kinetic characterization (com-
Thermogravimetric analysis (TGA) paring two different isoconversional methods: Flynn-Wall-Ozawa and Kissinger-Akahira-Sunose) of different
Combustion kinds of coal (from Italy, South Africa and Hungary) and biomass (pine and eucalyptus chips) by thermo-
Oxy-combustion gravimetric analysis (TGA) and differential scanning calorimeter (DSC) together with the assessment of different
Coal
characteristic combustion parameters. It can be observed that the burning rate of fuels can be improved by the
Biomass
oxy-combustion process, shortening the burning time (a mean reduction of the burnout time of 14% and 22%
can be observed for coal and biomass samples, respectively). Moreover, biomass shows better ignition perfor-
mance than coal and enhances combustibility indexes (S and Hf), especially in oxy-combustion conditions. For
example, the S index, which reflects combustion properties, increases by an order of magnitude for biomass
combustion and oxy-combustion with respect to coal values, thus indicating a higher combustion activity for
biomass; an opposite trend can be observed for the Hf index, which describes the rate and intensity of the process
and is lower for biomass than for coal, thus indicating better performance for wood chips combustion. Kinetic
analysis shows that the activation energy Ea varies with conversion values, reflecting the kinetic complexity in
both the processes. Moreover, with the same range of heating rates (10 ≤ β ≤ 50 °C/min) and for the overall
range of conversion (0.1 ≤ α ≤ 0.9), both of the models used fit the experimental data in combustion regime,
whereas the increase of the oxygen concentration makes the results reliable for coal samples and more sensitive
to weight loss for biomass samples.

⁎
Corresponding author.
E-mail address: mauro.mureddu@sotacarbo.it (M. Mureddu).

http://dx.doi.org/10.1016/j.fuel.2017.10.005
Received 3 April 2017; Received in revised form 14 September 2017; Accepted 3 October 2017
Available online 15 October 2017
0016-2361/ © 2017 Elsevier Ltd. All rights reserved.
M. Mureddu et al.
Nomenclature
Acronyms
CCUS carbon capture, utilization and storage
DSC differential scanning calorimetry
DTG derivative thermogravimetry
FWO Flynn-Wall-Ozawa model
HHV higher heating value
KAS Kissinger-Akahira-Sunose model
TG thermogravimetry
TGA thermogravimetric analysis
Symbols
Df Burnout index (wt.%/min4)
Di ignition index (wt.%/min3)
DTGmax maximum combustion rate (wt.%/min)
DTGmean mean combustion rate (wt.%/min)
Ea activation energy (kJ mol−1)
Hf combustion index (°C)
k(T) reaction rate (function of the kinetic model expression)
A pre-exponential factor (function of the kinetic model
1. Introduction
The utilization of fossil fuels (coal, oil and natural gas) has led an
outstanding era of prosperity and advancement for human develop-
ment. Nevertheless, carbon dioxide concentration in the atmosphere
has consequently risen from about 280 ppm (by volume) before the
industrial revolution to about 400 ppm in 2016 [1]. A further increase
up to about 570 ppm could be expected by the end of this century [2].
The increase in CO2 emissions can contribute to global warming and
climate changes due to the enhanced greenhouse effect. The in-
creasing attention towards climate changes and the recent strategic
policies to stabilize and reduce CO2 emissions has spurred the devel-
opment of technologies for the use of renewable energy sources. In
particular, the European Commission has agreed to reduce their
carbon emission by 20% by 2020, by 40% by 2030 and by 80–95% by
2050, with reference to 1990 levels [3]. This is also promoting re-
search in the field of carbon capture, utilization and storage (CCUS)
technologies, whereby CO2 is captured from industrial flue gas and
reused (for example for the production of liquid fuels) or permanently
stored in geological formations, such as depleted oil and gas fields or
saline aquifers [4].
After fossil fuels, biomass is the most important source of energy,
which can supply about 14% of the world’s energy consumption [5,6].
Among renewable sources, biomass can be considered almost carbon-
neutral and presents the lowest risk and capital required to be used in
energy generation [7]. Moreover, whereas power generation from sun
and wind cannot be programmed, biomass can be used instead of fossil
fuels for base-load power generation.
In this context, Sotacarbo is engaged in several theoretical and ex-
perimental studies on the potential use of coal and/or biomass for
distributed power generation. The aim is the development of CO2-free
power generation technologies for small-scale commercial applications,
including the feeding of smart grids in integration with other renewable
energy sources. Several experimental campaigns have been carried out
in a pilot fixed-bed up-draft gasifier [8,9] and a new bubbling fluidized-
bed gasifier is currently under construction in the Sotacarbo Research
Centre in Carbonia (Sardinia, Italy) [10].
The fine optimization of both the previously mentioned gasification
technologies requires, among other issues, an extensive knowledge of
the thermochemical processes occurring in the gasifier (i.e.
627
Fuel 212 (2018) 626–637
expression)
mf residual mass of samples (mg)
mi initial mass of samples (mg)
mα actual mass of samples (mg)
R gas constant (J/(mol ∗K))
R2 correlation coefficient (non-dimensional)
S combustion index (wt.%/(min2 ∗°C3))
T temperature (K)
Tf burnout temperature (°C)
tf burnout time (min)
Ti ignition temperature (°C)
ti ignition time (min)
Tp maximum peak temperature (°C)
tp maximum peak time (min)
α conversion degree (non-dimensional)
β heating rate (°C/min)
Δt1/2 time range of DTG/DTGmax = 0.5 (min)
t time (s)
f(α) kinetic model (function of the kinetic model expression)
g(α) integral form of kinetic model (function of the kinetic
model expression)
devolatilization, pyrolysis, gasification and combustion reactions). In
particular, it is well known that the knowledge of thermal decomposi-
tion of coal and biomass is essential to assess the performance of car-
bonization, combustion and gasification processes [11]. Non-isothermal
thermogravimetric analysis (TGA) is the most simple, the least ex-
pensive and the most effective technique to observe both the pyrolysis
and combustion profiles of a fuel [12]. Fuel samples are typically he-
ated up to 800–1000 °C in a predefined atmosphere and sample weight
losses are measured continuously. Pyrolysis behaviour is typically as-
sessed by performing the analysis in an inert (nitrogen or argon) at-
mosphere, whereas combustion profiles are determined by feeding the
thermogravimetric analyser with an oxidant gas (air or oxygen). De-
tailed combustion features of the fuels, in terms of characteristics
combustion parameters, can also be evaluated, including the ignition,
peak and burnout temperatures and combustion rate [13]. This in-
formation is of great importance to enhance the knowledge of this
process and to estimate its efficiency; it can be successfully used to
establish the optimum process conditions.
Several studies have been recently published on combustion per-
formance assessment of different kinds of fuel (coal, biomass, waste,
etc.) by thermogravimetric analysis. Table 1 shows a brief summary of
the most interesting ones.
As shown in Table 1, many investigations have been conducted and
published on combustion (and sometimes co-combustion) of biomass
and coal under air atmosphere. Several studies consider oxy-combus-
tion by operating TGA in a O2/CO2 atmosphere [14,17], where CO2
shifts the equilibrium of several reactions, with a significant impact on
the process. But it can be noticed that there is a real shortage of pub-
lished data on oxy-combustion assessment [19,33].
So far, to the best of the present authors’ knowledge, only a few
papers dealing with the use of oxygen at high concentration in oxy-
combustion have been published. The study of oxy-combustion of coal
and microalgae in O2/N2 or O2/CO2 atmosphere at an oxygen con-
centration of 70–80% by volume is reported by Chen et al. (2013 and
2015) [25,34], respectively. Only for one of these mentioned works has
the kinetic study with different models been performed. Only Liu et al.
(2016) [19] assess the combustion performance indexes up to an
oxygen concentration of 100%.
In this light, a detailed investigation on the oxygen-enriched beha-
viour of coal and biomass, including both the evaluation of the
M. Mureddu et al. Fuel 212 (2018) 626–637

Table 1
Brief review of several previous studies on combustion characterization by TGA.

Source Fuel Max. Temp. (°C) Heating rate (°C/min) Atmosphere (% by volume)

Shan et al. 2017 [14] Pine and rice husk 800 Variable 21–100% (O2/CO2)
L.-González et al. 2017 [15] Solid animal waste 1000 10, 20, 30 Var. (O2/CO2-Ar)
Zhou et al. 2016 [16] Chinese bit. coal, corn, sawdust 1000 15, 60 Air
Niu et al. 2016 [17] Dried sewage sludge 1000 20, 40, 60, 80 21–40% O2 (+ CO2)
Wang et al. 2016 [18] Waste biomass and coal 627 2.5, 5, 10, 20 Air
Liu et al. 2016 [19] Corncob, hardwood, bitum. coal 800 40 21–100% O2 (+N2)
Liu et al. 2015 [20] Herbaceous biomass, bit. coal 800 10–90 Air
F.-Lopez et al. 2015 [21] Canadian solid animal waste 900 10 21% O2, 79% Ar
Lin et al. 2015 [22] Paper sludge and oil palm waste 1000 20 21% O2, 79% N2
Magdziarz, Werle 2014 [23] Polish coal and sewage sludge 800 10 20% O2, 80% N2
Parshetti et al. 2014 [24] Indonesian coal and palm residue 900 20 30% O2, 90% N2
Chen et al. 2013 [25] Chlorella vulgaris microalgae 800 10, 20, 40 Var. (O2/N2-CO2)
Cheng et al. 2012 [26] Cellulose, hemicellulose, lignin 600–800 5 Air
Idris et al. 2012 [27] Malaysian oil palm 1100 10, 20, 40, 60 Air
Lai et al. 2011 [28] Chinese municipal solid waste 1000 10, 20, 40 Variable (O2/N2)
Skreiberg et al. 2011 [29] Wood and waste wood 900 5, 10, 100 21% O2, 79% Ar
Selçuk and Yuzbasi 2011 [30] Turkish lignite 950 40 Air
Yuzbasi and Selçuk 2011 [7] Turkish lignite and olive residue 950 40 Air
Marinov et al. 2010 [31] Biodesulphurized coals 800 10 Air
Biswas et al. 2006 [32] Two Indian coals 750 10 Air

combustion performance indexes and the kinetic study, seems worthy
of being undertaken.
This work presents the main results of a non-isothermal TGA char-
acterization of different kinds of coal and biomass, carried out to define
the kinetic process during combustion (with both air and oxygen) to
support the pilot-scale gasification tests. The analysis integrates the
results of a preliminary assessment on the pyrolysis process [35,36].
The experimental scheme adopted for this study can be summarized
as following: (i) characterization of fuels (proximate, ultimate and ca-
lorimetric analyses), (ii) preparation of samples, (iii) non-isothermal
TGA for the assessment of the key process parameters, (iv) kinetic
analysis (carried out with different methods to compare the results).
2. Experimental
2.1. Materials and sample preparation
Different kinds of fuel, selected as the most representative among
those tested in the Sotacarbo experimental units [9,35–37], have been
characterized: (i) a high ash South African bituminous coal; (ii) a high
sulphur sub-bituminous coal from the Sulcis coal mine (south-west
Sardinia, Italy); (iii) a high sulphur brown coal from Miskolc basin
(northern Hungary); (iv) stone pine (Pinus pinea) wood chips and (v)
eucalyptus (Eucalyptus regnans) wood chips, both from Sardinian for-
ests.
A sample (about 200 g) of each fuel is crashed in a cross beater mill
(Retsch SK100) and sieved in order to obtain a particle size lower than
125 μm. It is dried in an oven with a constant temperature of
105 ± 2 °C for at least 24 h and then stored in a desiccator to prevent
As shown in Table 2, coal typically has higher heating value than
biomass (except for the Hungarian coal, characterized by a very high
ash content). This is mainly due to its higher carbon content. Amongst
biomass, stone pine has a higher heating value than eucalyptus.
It is interesting to underline the higher volatile content of Sulcis and
Hungarian coal with respect to South African coal; this parameter has a
strong impact on the combustion and oxy-combustion performance and
influences coal reactivity. In particular, it is difficult to ignite fuel due
to the absence of inherent oxygen and low volatile matter content.
Finally, the very high sulphur content in both Hungarian and Sulcis coal
can be observed.
2.2. Methods
Simultaneous thermogravimetry (TG) and differential scanning ca-
lorimetry (DSC) analyses have been carried out under dynamic condi-
tions, as a function of time and temperature, in a Mettler Toledo TGA/
DSC 3+ thermogravimetric analyser, by heating samples from ambient
temperature to 1000 °C. In order to avoid heat and mass transfer lim-
itations, a small amount of the sample (8–10 mg) has been loaded into a
70 µl aluminium oxide crucible. All the experiments have been per-
formed under non-isothermal conditions at atmospheric pressure, under
air or pure oxygen atmosphere (both provided in bottles with controlled
Table 2
Primary fuel characterization (dry basis).
(i) (ii) (iii) (iv) (v)
S. African Sulcis Hungarian Stone pine Eucalyptus

moisture absorption from the atmosphere [38,39]. The choice to op- Proximate analysis (% by weight)
erate the experimental tests with dry samples comes from an experi- Fixed carbon 77.51 42.55 24.00 23.23 20.38
mental evaluation described in previous works [35,36]. Volatiles 14.38 43.27 32.57 73.74 72.41
Table 2 shows proximate, ultimate and calorimetric analyses (the Ash 8.11 14.18 43.43 3.03 7.21
latter to determine higher heating value, HHV) of the considered fuels; Ultimate analysis (% by weight)
the analyses have been carried out in the Sotacarbo laboratories ac- Total carbon 85.88 63.22 35.80 50.88 48.30
Hydrogen 2.84 4.43 2.86 6.71 5.90
cording to the international standards. In particular, proximate analysis
Nitrogen 1.50 1.59 0.70 0.50 0.12
has been performed by a LECO TGA-701 thermogravimetric analyser Sulphur 0.56 7.14 4.88 0.08 0.00
(based on the ASTM D 5142-04 “Moisture Volatile Ash” standard); ul- Oxygen 1
1.11 9.44 12.33 38.80 38.47
timate analysis has been carried out on a LECO Truspec CHN/S analyzer Ash 8.11 14.18 43.43 3.03 7.21
(based on ASTM D 5373-02 for carbon, hydrogen and nitrogen, and Calorimetric analysis (MJ/kg)
ASTM D 4239-05 for sulphur); finally, higher heating values have been Higher heating value 31.77 25.31 13.69 19.64 17.57
measured by a LECO AC-500 calorimeter according to the ISO
1
1928:1995 standard. Note: By difference.

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M. Mureddu et al. Fuel 212 (2018) 626–637

concentrations) with a flow rate of 100 ml/min and using 70 ml/min
nitrogen as purge gas. All the samples have been heated from 25 °C to
105 °C at which they have been held for 10 min to ensure a complete
removal of moisture, and then further heated up to 1000 °C at different
heating rates of 10, 20, 30, 40 and 50 °C/min and held at this tem-
perature for 10 min to complete the process.
Blank experiments have been carried out to obtain the baselines,
used to subtract the buoyancy effect, calibrating the experiments with
samples [22,28]. All the samples have been analysed under exactly the
same conditions [23] and the experiments have been replicated three
times to decrease the error of the experimental results and to determine
their reproducibility [40].
2.3. TG and DSC: key parameters
curve tangentially before the thermal effect and re-joins the curve in the
same way after the effect. A spline baseline type obtained using a
flexible ruler to manually interpolate between two points (known as
Bezier curve) has been used for all the samples; this bow-shaped or S-
shaped baseline is based on the left and right tangents. DSC profiles for
all the fuels have been recorded under the same operating conditions
and simultaneously to TG curves.
2.4. Kinetic models: FWO and KAS
The results of thermogravimetric analysis at different heating rates
can be used to calculate the kinetic parameters. The general kinetic
description of solid-state reaction, constituted by a single process, is
based on the following assumptions.

The obtained TG and DTG (derivative thermogravimetric) curves i) The reaction rate, defined as the change in conversion per unit of
have been used to evaluate the combustion and oxy-combustion para- time, is a function of the conversion degree (α):
meters that reflect the thermal behaviour [41] such as ignition tem-
dα
perature (Ti), burnout temperature (Tf) and maximum peak tempera- = k (T ) f (α )
dt (5)
ture (Tp). In particular, Ti represents the temperature at which the
sample starts to burn and is determined by the TG-DTG tangent method where t is the time, k(T) the constant rate and f(α) is the kinetic model.
[13,17,42]; it indicates how easily a specific fuel ignites. Tf represents The conversion α is defined as follows:
the point at which fuel oxidation is completed; it can be defined as the
temperature at which the combustion rate decreases to 1 wt.%/min at (mi−mα )
α=
the end of the combustion process [43]. Tp represents the temperature (mi−mf ) (6)
corresponding to the peak of the DTG profile [44]. The characteristic
where mi is the initial mass of sample, mα the actual sample mass and mf
temperatures have been correlated with different combustibility in-
the residual mass after the process.
dexes such as the ignition index (Di), the burnout index (Df), and the so-
called “combustion indexes” (S and Hf).
ii) The temperature depends on the constant reaction rate, k(T), de-
In particular, Di is defined as:
scribed by the Arrhenius equation:
DTGmax
Di = −Ea
t p ti (1) k (T ) = A exp RT (7)

where DTGmax is the maximum combustion rates, tp is the corre- where Ea is the activation energy, T the absolute temperature, R the gas
sponding time of DTGmax, ti is the ignition time. The larger Di value, the constant and A the pre-exponential factor.
more volatile compounds are separated from fuel, so combustion occurs
easily in the early stage. Df is defined as: iii) Substituting k(T) defined in Eq. (7) into Eq. (5) results that:
DTGmax dα −Ea
Df = = A exp RT f (α )
Δt1/2 tp t f (2) dt (8)

where Δt1/2 is the time range of DTG/DTGmax = 0.5 and tf is the burnout
time. iv) For the experiments performed under non-isothermal conditions, it
The S index reflects the ignition, combustion and burnout properties is possible to introduce the heating rate β = dT/dt obtaining the
of a fuel [45]: follow equation:

DTGmax DTGmean dα A −Ea

S=
Ti2 Tf (3)
where DTGmean represents the mean combustion rate, Ti the ignition
temperature and Tf the burnout temperature. The larger the value of S
index, the higher combustion activity is.
Hf describes the rate and the intensity of the combustion process:
Δt1/2 ⎞
Hf = Tpln ⎛ ⎜ ⎟
⎝ DTG mean ⎠ (4)
where Tp is the corresponding temperature of DTGmax and ΔT1/2 is the
temperature range of DTG/DTGmax = 0.5 [46]. The smaller the value of
Hf index, the better combustion properties are [47,48].
DSC analysis has been used in order to measure the heat flow during
combustion and oxy-combustion processes, allowing to detect en-
dothermic and exothermic reactions in the fuels and determining
temperatures that characterize the peaks or other effects. The in-
tegrated area, calculated using the Mettler Toledo STARe software, is
that between the DSC curve and a baseline. The choice of the right
baseline is crucial for the evaluation of the reaction. The interpolated
= ⎜⎛ ⎟⎞ exp RT f (α )
dT β
⎝ ⎠ (9)
The non-isothermal kinetic study of the combustion process is very
complex due to the presence of several components and consecutive or
parallel reactions. It is possible to classify the kinetic methods in model-
fitting or model-free mode, and the latter allows to determine the ac-
tivation energies independently on the particular mechanism that
govern the transformation. Most of the model-free methods are iso-
conversional, allowing the assessment of a given parameter as a func-
tion of conversion. In this work, both isoconversional Flynn-Wall-
Ozawa (FWO) and Kissinger-Akahira-Sunose (KAS) methods have been
used to calculate the activation energy for combustion and oxy-com-
bustion of coal and biomass samples. The FWO model is a linear in-
tegral method based on Doyle’s approximation [49] which allows ac-
tivation energy to be obtained from the plot of natural logarithm of
heating rates (lnβ) versus (T)−1. The latter represents the linear relation
of a given value of conversion at different heating rates [50,51]:
Ea AEa ⎞
lnβ = −1.052 −5.331 + ln ⎜⎛ ⎟

baseline for the determination of reaction enthalpy leaves the DSC

RT ⎝ Rg (α ) ⎠ (10)

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M. Mureddu et al. Fuel 212 (2018) 626–637

α
1
g (α ) = ∫ f (α )
dα
0 (11)

where the integral form of kinetic model g(α) is constant at a given

value of conversion and Ea is the activation energy as a function of α.
The activation energy Ea can be calculated from the slope of the straight
line (−1.052 Ea/R).
The KAS model is a linear integral method based on Coats-Redfern
approximation [52] and described by the following equation [53,54]:

β AR ⎞ Ea
ln⎛ 2 ⎞ = ln⎛⎜ ⎟−

⎝T ⎠ ⎝ Ea g (α ) ⎠ RT (12)

where the activation energy can be calculated from the slope of the
straight line (−Ea/R) obtained from the plot of ln(β/T2) versus (T)−1.

3. Results and discussion

The thermogravimetric experimental results for the considered fuels

are represented and compared by using thermogravimetric (TG) pro-
files, differential thermogravimetric (derivative of the TG profile, DTG)
curves and differential scanning calorimeter (DSC) profiles. DTG peaks
correspond to the inflection points of the TG profiles and represent the
maximum weight loss rates.

3.1. Thermal and calorimetric analyses

The burning features obtained from thermal analysis technique have

been used to effectively compare the reactivity and combustibility of
solid fuels. Combustion and oxy-combustion profiles for the considered
fuels are shown in Figs. 1–3, which show the weight loss curve, deriva-
Fig. 2. DTG profiles in combustion (a) and oxy-combustion (b) modes at β = 20 °C/min.
tive thermogravimetric evolution profiles and differential scanning ca-
lorimeter profiles, respectively, all obtained at a heating rate of 20 °C/

Fig. 1. TG profiles in combustion (a) and oxy-combustion (b) modes at β = 20 °C/min. Fig. 3. DSC profiles in combustion (a) and oxy-combustion (b) modes at β = 20 °C/min.

630
M. Mureddu et al.
min (chosen as reference temperature by several authors, as can be seen
in Table 1). In general, in the DTG curves, the peak’s height can be
considered directly proportional to the reactivity, whereas the tempera-
ture corresponding to the peak is inversely proportional to it [55].
According to the general TGA results, it can be observed that it is
possible to divide the combustion process into two stages (which can be
classified on the basis of weight and heat changes): (i) combustion
stage, with the oxidation and volatile matter release, which is an exo-
thermic process, and oxidation of the carbon residue; (ii) burnout stage.
Both TG and DTG profiles mainly display different trends. During the
combustion stage, all the curves show a main peak (Fig.2a) that in-
dicates the temperature corresponding to the maximum reaction rate.
The whole of the above TG results indicates that the overall weight
loss is significantly higher for biomass (weight loss of pine > weight
loss of eucalyptus) with respect to coal (weight loss of Sulcis > weight
loss of South African > weight loss of Hungarian). Furthermore, it
seems that oxygen concentration (air or pure oxygen) does not sig-
nificantly influence the overall mass loss of each fuel, thus indicating
that, in all the considered cases, the combustion is almost complete. On
the contrary, it is worth noting that the high oxygen concentration
shifts TG and DTG curves to the low temperature area (see Fig. 1b and
Fig. 2b), indicating the advance in combustion and complete combus-
tion at lower temperatures.
From the DTG point of view (Fig. 2), the differences between coal
and biomass are clear. Due to a high content of cellulose, hemicellulose
and lignin with a low degree of order, the temperature at which weight
loss begins is lower for biomass than for coal. The peaks in coal com-
bustion and oxy-combustion profiles are wide (there is not a clear peak
temperature), in contrast to biomass profiles; in particular, under
higher oxygen concentration (Fig. 2b), the maximum value of DTG
curves increases and a shorter time is required to reach that value. This
is due to the devolatilization of coal, which progresses more slowly
compared to biomass and partially overlaps with char oxidation. A
different trend can be noticed for South African coal, especially in the
combustion process (Fig. 2a): due to its low reactivity, the corre-
sponding DTG curve does not present a marked peak and only at a high
heating rate (40 and 50 °C/min) is it possible to observe a shoulder at a
high temperature, superimposed to the main peak.
Biomass samples (pine and eucalyptus) present marked peaks,
proportional to fuel reactivity, even if a shoulder, or a nearly separated
peak (located at higher temperatures), can be observed, overlapping to
the main peak [56]. The first significant peak at 330–340 °C for the two
biomass samples may be associated with the degradation of hemi-
cellulose and cellulose, while the second peak (or shoulder, depending
on the heating rate) may be attributed to the degradation of lignin [29].
Although lignin degradation occurs in the wide temperature range,
dechotomizing it from hemicellulose and cellulose decomposition is
difficult (as can be seen in Fig. 2). The peak complexity at a higher
heating rate can be observed due to a relatively high content of hemi-
cellulose degradation at lower temperatures than cellulose. The de-
composition energy of the volatile matter from biomass is relatively
weaker than the char reaction, and this phenomenon accounts for the
high reactivity.
Fig.3 shows the experimental thermograms for all the samples. The
combustion and oxy-combustion behaviour of coal and biomass seems
to be slightly different. As in the TG and DTG profiles, the combustion
DSC curves (Fig.3a) present two distinct phenomena in all the fuels,
whereas in oxy-combustion DSC profiles (Fig.3b) it is possible to reveal
only one clear peak in both biomass samples and partially overlapped
peaks in coal samples. Ideally, DSC curves obtained from a chemical
reaction show just one single smooth peak. In practice, the shape of the
peak is often distorted by overlapping reactions or decomposition re-
actions occurring at different temperatures (depending on the solid
fuels, generally included between 350 and 750 °C). As expected, all the
main peaks are exothermic; the first region is due to the combustion of
light volatile matters and the second region represents the combustion
631
Fuel 212 (2018) 626–637
of fixed carbon. The exothermic peaks shift to lower temperatures and
narrow with the increasing of the oxygen content. The limits of the two
peaks for coal samples become more obvious in oxy-combustion regime
than that in a combustion one, because the higher oxygen concentration
enhances the burning rate of volatile compound; on the contrary, bio-
mass samples show only one clear peak in an oxy-combustion regime
due to the high oxygen amount.
Figs. 4 and 5 show DTG and DSC profiles obtained at different
heating rates (β = 10, 20, 30, 40 and 50 °C/min) in both combustion
and oxy-combustion modes for one coal (Sulcis) and one biomass
(pine), selected as the most representative ones. For both the samples,
during air-blown combustion (Fig. 4a and c) the main peak shifts
slightly towards a higher temperature with the increase of β due to heat
transfer limitation [57], and the combustion temperature range be-
comes wider, showing that an increase of β tends to postpone the
thermal decomposition process. As shown in Fig. 4, with an increasing
heating rate, DTG profiles shift to higher temperatures, and the rate of
weight loss increases since the heat transfer is not as effective as it was
for lower heating rates. This is indicative that the decomposition pro-
cess is slower with the increasing of β. The maximum combustion rate
of samples increases when the heating rate is increased, as heightening
of mass transfer results from the enhancement of heat transfer. This can
be reasonably attributed to the fact that the heating of solid particles
occurs more gradually at lower heating rates, thus leading to an im-
proved and more effective heat transfer to the inner portions and
among the particles. It has also been found that burnout temperature
increases when the heating rate is increased; this is confirmed by the
greater temperature gradient through the inside and outside the par-
ticle, which does not promote the release of volatile matter. The DSC
curves in a combustion atmosphere (Fig. 5) follow the same behaviour
of the DTG profiles, showing a band that shifts toward higher tem-
peratures and becomes wider with the increase of the heating rate,
especially for Sulcis coal (Fig. 5a). In addition, with the increase of the
heating rate, temperature rises very quickly involving an overlapping of
the decomposition peaks, since the individual reaction does not have
enough time to be completed; this phenomenon is mainly visible on a
biomass sample (Fig. 5c). On the other hand, an oxy-combustion at-
mosphere results in a narrower temperature range and the increasing of
the heating rate has the same effect as for the combustion regime.
Nevertheless, with the increase of the oxygen concentration, the exo-
thermic peak results at lower temperatures (between 200 °C and 400 °C
for biomass and coal samples, respectively, for the highest heating
rates) showing that an increase of oxygen concentration tends to hasten
the thermal decomposition process (Fig. 5b and d). From the DTG curve
(Fig. 4b and d) it is possible to observe that both samples do not present
relevant differences in terms of maximum temperature of the main
decomposition peak with the increase of the heating rate. The same
curves for all the other considered fuels have been reported as Sup-
plementary Material.
Table 3 reports the heat released during the combustion and oxy-
combustion processes of all the considered fuels, based on the area
under the peaks of the DSC curve. Enthalpy values are in the range
8.3–22.5 kJ/g for the combustion process, and 8.4–23.2 kJ/g for the
oxy-combustion process, pointing out a poor variation of the enthalpy
of reaction. These findings confirm that coal samples are more energetic
compared to biomass samples and that the oxygen concentration has
only a slight effect on the enthalpy of reaction.
The combustion and oxy-combustion characteristic parameters for
all the fuels at heating rate of 30 °C/min are reported in Tables 4 and 5,
respectively.
As shown in Table 4, the peak temperatures (Tp) of coal samples are
in the range of 527–668 °C, higher than those of biomass (337–345 °C);
this indicates that the maximum reaction rate of biomass occurs at
lower temperatures than for coal. The ignition temperatures (Ti) follow
the same trend, showing the higher value for South African coal, in-
dicating the low reactivity of this fuel.
M. Mureddu et al. Fuel 212 (2018) 626–637

Fig. 4. DTG profiles in combustion for Sulcis coal (a) and stone pine biomass (c), and oxy-combustion for Sulcis coal (b) and stone pine biomass (d) at different heating rates.

The ignition behaviour can be assessed by the ignition index (Di); as
reported in Table 4, Sulcis and South African coal present an expected
trend: the higher ignition index corresponds to the lower ignition
temperature. A different behaviour has been observed for the Hun-
garian coal, implying that the ignition index may not be only factor to
be concerned, related to the ignition temperature. The possible reasons
are the effect of ash content on ignition performance because high ash
content can affect oxygen diffusion and heat transfer. As reported in
Table 2, ash content for the Hungarian coal is much higher than that of
Sulcis coal, resulting in the greater resistance of oxygen diffusion and

Fig. 5. DSC profiles in combustion for Sulcis coal (a) and stone pine biomass (c), and oxy-combustion for Sulcis coal (b) and stone pine biomass (d) at different heating rates.

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M. Mureddu et al. Fuel 212 (2018) 626–637

Table 3 if compared with coal, biomass presents a higher oxygen content and a
Enthalpy of reaction values during the combustion and oxy-combustion processes. lower amount of carbon. In the literature, it is reported that the hy-
drogen and oxygen indexes (H/C and O/C ratios, respectively) in fuels
Coal Biomass
result in different bonding energies, as described by a van Krevelen-
Sulcis S. African Hungarian Stone pine Eucalyptus type diagram, because the bond energy of carbon–oxygen is lower than
that of carbon–carbon bonds [58]. These component characteristics can
Combustion
induce faster ignition, as shown in Table 4. Furthermore, the enhanced
Entalphy of
reaction (kJ/g) reactivity of the volatile matter with the enriched oxygen of biomass
10 °C/min 13.4 18.6 15.8 8.3 14.1 results in higher mass weight loss with respect to temperature, if
20 °C/min 12.9 19.2 15.7 11.7 13.7 compared with coals. These results are consistent with previously de-
30 °C/min 13.5 21.4 13.6 11.8 11.3 scribed findings [59]. A possible reason could be the effect of ash
40 °C/min 14.5 22.5 14.9 15.9 10.8
50 °C/min 16.4 22.5 15.3 16.3 10.5
content on ignition performance since high ash amounts can affect
oxygen diffusion and heat transfer [60]. The connection with the ig-
Oxy-combustion
nition and burnout temperatures may be highlighted; it can be ex-
Entalphy of
reaction (kJ/g) plained by the burnout process, which is affected by the ignition pro-
10 °C/min 23.2 19.4 18.0 8.7 12.6 cess. Regarding the burnout temperature, the low values for biomass
20 °C/min 17.3 19.9 18.9 8.4 12.3 samples are a clear indication of a reduced presence of unburnt com-
30 °C/min 17.1 19.2 12.4 11.2 13.4 pounds; on the contrary, high burnout temperature values are an in-
40 °C/min 16.8 18.6 15.4 10.1 13.1
50 °C/min 17.3 17.6 16.8 10.9 9.1
dication of the difficulty in burning of coal samples, thus requiring
longer residence times and higher temperatures for completing con-
version. As reported in Table 4, the values of S index for biomass are
the higher temperature gradient between the inside and outside of the greater than that for coal, indicating a better combustion performance
particle. This implies a lower temperature than that of the Sulcis coal of the former. This behaviour follows the results of ignition index. Fi-
even if the ignition index of the Hungarian sample is lower (Di = 7.4) nally, the trend of Hf index is in accordance to the ignition and burnout
than that of the Sulcis one (Di = 8.5). Same behaviour has been ob- indexes (Di, Df), showing smaller values for biomass samples, thus
served for biomass samples, although the ignition temperatures are confirming their better combustion properties. In contrast, the high Hf
lower than those of the coal samples. Also in this case, eucalyptus value for South African coal is, again, a clear indication of the poor
samples present a higher ash content compared to that of the stone pine reactivity of the fuel.
samples which is reflected in the lower ignition temperature. Moreover, Table 5 summarizes the same parameters referred to the oxy-

Table 4
Main combustion parameters.

Coal Biomass

Sulcis S. African Hungarian Stone pine Eucalyptus

Ignition temperature Ti (°C) 371.2 560.1 328.4 299.2 295.5

Peak temperature Tp (°C) 527.3 668.3 529.3 345.0 337.5
Burnout temperature Tf (°C) 768.5 904.7 635.7 526.5 527.7
Ignition time ti (min) 27.0 33.3 25.6 24.6 24.5
Peak time tp (min) 32.2 36.9 32.3 26.1 25.9
Burnout time tf (min) 40.4 44.8 35.9 32.2 32.3
DTGmax (%/min) 7.4 8.6 6.1 25.6 22.9
DTGmean (%/min) 1.4 1.3 1.0 1.6 1.5
ΔT1/2 (°C) 351.0 301.5 263.5 57.1 63.2
Di (wt.% /min3 *10−3) 8.5 7.0 7.4 40.0 36.1
Df (wt.% /min−4 *10−5) 1.6 1.7 2.0 53.5 43.4
S (wt.% /(min−2 *°C−3)*10−8) 9.7 4.1 9.1 84.9 73.7
Hf (°C *103) 2.0 2.4 2.0 0.3 0.3

Table 5
Main oxy-combustion parameters.

Coal Biomass

Sulcis S. African Hungarian Stone pine Eucalyptus

Ignition temperature Ti (°C) 395.4 489.0 347.3 297.0 290.2

Peak temperature Tp (°C) 434.7 574.5 364.6 308.2 302.1
Burnout temperature Tf (°C) 622.0 648.6 514.4 350.5 348.8
Ignition time ti (min) 27.7 30.8 26.1 24.4 24.2
Peak time tp (min) 28.8 33.3 26.5 24.6 24.4
Burnout time tf (min) 35.5 36.3 31.8 25.3 25.3
DTGmax (%/min) 36.1 20.3 33.8 154.1 127.4
DTGmean (%/min) 1.4 1.3 1.1 1.6 1.5
ΔT1/2 (°C) 214.2 110.0 13.3 21.8 22.9
Di (wt.% /min3 *10−3) 45.2 19.8 44.5 256.5 215.6
Df (wt.% /min−4 *10−5) 16.5 15.2 273.9 1131.9 903.4
S (wt.% /(min−2 *°C−3)*10−8) 53.2 17.5 52.7 782.5 634.1
Hf (°C *103) 0.77 1.0 0.31 0.60 0.52

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M. Mureddu et al. Fuel 212 (2018) 626–637

combustion process. It can be observed that the values of Ti slightly

change for the two biomass samples, thus indicating that the initial
volatile evolution is not (or weakly) affected by the oxygen con-
centration. On the other hand, there is a fluctuating behaviour for coal
samples; Sulcis and Hungarian coals show the same change pattern,
which are different from the South African one. This can be related to
the volatile content of the samples, which affects the amount of oxygen
functional groups [61]. The effect of oxygen concentration is more re-
markable on peak and burnout temperatures, showing an outstanding
decrease passing from a combustion to an oxy-combustion process.
Comparing the results shown in Tables 4 and 5, it can be observed that
the combustibility indexes for the oxy-combustion process are higher
than those referred to the combustion one; this indicates that a higher
oxygen concentration can improve the combustion performance of both
coal and biomass samples. This evolution is more significant on biomass
compared to coal. To summarize, oxy-combustion atmospheres exhibit
the best ignition performance and best combustion activity with a
higher ignition index and higher combustion index, in comparison with
a combustion regime. As can be seen from the comparison between
Tables 4 and 5, the values of the combustibility indexes (Di, Df, S) in-
crease with the increase of the amount of oxygen, which indicates that
enriched-oxygen atmospheres can improve the combustion perfor-
mance, irrespective of the considered fuels (coal or biomass). The result
of the comprehensive index (Hf) is also in agreement with the results of
the ignition index and the burnout index.

3.2. Kinetic analysis

As mentioned, kinetic analysis has been performed by using both

the FWO and KAS methods. For example, Figs. 6 and 7 show, for Sulcis
coal, the plots for activation energy calculation at various conversions Fig. 7. Activation energy calculation in combustion (a) and oxy-combustion (b) modes by
by both the methods, respectively. KAS method for Sulcis coal.

According to different studies [15,25], all the conversion ranges

(0.1 ≤ α ≤ 0.9) and heating rates (β = 10, 20, 30, 40 and 50 °C/min)
have been used to investigate better the effect of the different oxygen
concentrations on the kinetic parameters for all the considered fuels,
determining the variation of activation energy with the conversion.
According to these models, when α is constant, the values of lnβ and ln
(β/T2) versus T−1, obtained at different β values, have been correlated
by a straight line, whose slope is associated with the activation energy.
As shown in Tables 6–10, it can be observed that the correlation coef-
ficient (R2) of most curves are within the range of 0.9–0.99, and most of
the activation energy values calculated with the two methods are in
good accordance.
The analysis shows that the activation energy varies with conver-
sion values, reflecting the kinetic complexity in combustion and oxy-
combustion regimes.
The activation energy values in combustion regime, as a function of
conversion degree (α) are reported in Fig. 8a. It is possible to observe a
different behaviour between coal and biomass samples in both pro-
cesses. Coal samples show a clear asymptotic trend with a reduction of
the Ea with the increasing of the conversion degree, whereas the trends
for biomass samples show a maximum at α = 0.4, followed by a pro-
gressive reduction of Ea down to α = 0.9.
The unexpected result about the higher activation energy in both of
the biomass samples can be reasonably attributed to the energy re-
quired for the beginning of hemicellulose and cellulose degradation
[27]. These findings further support the idea that no simple correlation
exists between the activation energy and volatile matter of biomass. For
all coal and biomass samples, the significant decreasing of the activa-
tion energy could be associated with an intense burning of volatile
matter.
Fig. 6. Activation energy calculation in combustion (a) and oxy-combustion (b) modes by The values of activation energy in oxy-combustion regime, as a
FWO method for Sulcis coal.
function of conversion, are presented in Fig. 8b. As far as the coal is

634
M. Mureddu et al. Fuel 212 (2018) 626–637

Table 6 Table 9
Activation energy (Ea) and correlation coefficient (R2) at different conversion degree (α) Activation energy (Eα) and correlation coefficient (R2) at different conversion degree (α)
for Sulcis coal. for stone pine chips.

Sulcis Coal α FWO method KAS method Stone pine chips α FWO method KAS method

Ea (kJ mol−1) R2 Ea (kJ mol−1) R2 Ea (kJ mol−1) R2 Ea (kJ mol−1) R2

Combustion 0.1 253.7 0.993 256.9 0.992 Combustion 0.1 160.4 0.999 159.6 0.998
0.2 173.1 0.997 170.4 0.997 0.2 180.2 0.997 179.6 0.997
0.3 129.6 0.999 124.7 0.998 0.3 188.1 0.996 187.9 0.996
0.4 103.5 0.998 96.4 0.998 0.4 192.0 0.992 192.1 0.991
0.5 81.4 0.993 72.3 0.989 0.5 179.4 0.995 178.0 0.994
0.6 65.6 0.989 52.2 0.982 0.6 168.3 0.995 158.1 0.994
0.7 54.5 0.986 41.1 0.971 0.7 128.0 0.982 117.8 0.978
0.8 48.2 0.982 22.2 0.958 0.8 102.0 0.953 90.9 0.941
0.9 42.7 0.976 27.7 0.937 0.9 62.4 0.902 50.4 0.855

Oxy-combustion 0.1 – – – – Oxy-combustion 0.1 161.2 0.999 160.5 0.999

0.2 209.8 0.897 209.9 0.887 0.2 205.5 0.992 207.0 0.991
0.3 194.2 0.927 192.8 0.919 0.3 373.8 0.907 383.3 0.903
0.4 207.9 0.899 206.9 0.889
0.5 190.9 0.868 188.7 0.853
0.6 145.8 0.898 140.5 0.881
0.7 120.1 0.877 113.7 0.852 concerned, a different trend in the Ea versus α plot is clearly visible. A
0.8 122.9 0.915 116.2 0.896 significant variation of the activation energy with conversion indicates
0.9 152.9 0.934 147.3 0.922 a kinetically complex process. In the literature, the commonly reported
feature for this behaviour [15,62] is the dependence of Ea with the
conversion rate in dynamic experiments due to the change in the oxi-
Table 7 dation mechanism. In this light, the dependence of Ea on α can be se-
Activation energy (Ea) and correlation coefficient (R2) at different conversion degree (α) parated into two distinct regions with similar Ea values. For Sulcis coal,
for South African coal.
the first region, in which iso-conversional Ea can be considered to be
South African Coal α FWO method KAS method stable, corresponds to 0.2 < α < 0.5; the second region, in which a
different variation of Ea has been observed, is defined by
Ea (kJ mol−1) R2 Ea (kJ mol−1) R2 0.5 < α < 0.9. These two regions fit well with the two main stages of
the oxidation process discussed above; the low conversion range is as-
Combustion 0.1 124.8 0.996 177.2 0.995
0.2 97.2 0.994 88.1 0.992 sociated with the devolatilization stage, whereas the high conversion
0.3 81.4 0.989 69.8 0.984 range corresponds to the oxidation of the sample. South African coal
0.4 67.2 0.979 54.9 0.962 shows a similar behaviour with a higher value of Ea in the first region
0.5 55.3 0.968 42.4 0.934 0.1 < α < 0.3, followed by a second region, wider than Sulcis coal,
0.6 47.4 0.962 31.6 0.907
0.7 41.9 0.961 25.3 0.887
between 0.4 < α < 0.9, where the activation energy is constant.
0.8 39.5 0.971 23.0 0.901 Based on the findings of the obtained results, the higher activation
0.9 40.3 0.980 22.9 0.933 energy characterizes the low conversion area, corresponding to the
Oxy-combustion 0.1 170.7 0.980 166.3 0.977 devolatilization stage; this can be ascribed to the change in the oxy-
0.2 185.7 0.995 182.9 0.994 combustion mechanism from chemical kinetic control (rate limiting) to
0.3 146.2 0.997 140.5 0.997 diffusion-chemical kinetic control (fast step) [15,62]. Hungarian coal
0.4 129.1 0.993 122.2 0.927
shows a fluctuating behaviour, probably associated with different oxi-
0.5 115.4 0.995 108.1 0.994
0.6 105.9 0.992 97.3 0.990
dation mechanisms. The oxy-combustion behaviour of biomass has only
0.7 99.6 0.990 90.6 0.986 been assessed with conversion values up to 0.3; as later explained, this
0.8 98.8 0.987 85.6 0.982 is due to the loss of linearity of the straight line of the activation energy
0.9 97.2 0.984 87.3 0.978 calculation, so that the alpha values up to 0.9 would not have re-
presented a clear indication on the behaviour of the biomass sample in

Table 8 Table 10
Activation energy (Ea) and correlation coefficient (R2) at different conversion degree (α) Activation energy (Ea) and correlation coefficient (R2) at different conversion degree (α)
for Hungarian coal. for eucalyptus chips.

Hungarian Coal α FWO method KAS method Eycalyptus chips α FWO method KAS method

−1 −1 −1
Ea (kJ mol ) R 2
Ea (kJ mol ) R2
Ea (kJ mol ) R2
Ea (kJ mol−1) R2

Combustion 0.1 137.5 0.867 135.5 0.852 Combustion 0.1 160.4 0.999 159.8 0.999
0.2 150.2 0.987 148.0 0.984 0.2 176.2 0.999 175.4 0.999
0.3 177.8 0.994 112.2 0.992 0.3 199.9 0.998 200.4 0.997
0.4 97.2 0.992 89.8 0.989 0.4 201.5 0.996 201.2 0.995
0.5 83.8 0.985 75.7 0.979 0.5 178.6 0.996 177.9 0.995
0.6 76.7 0.974 64.8 0.963 0.6 153.3 0.973 143.1 0.972
0.7 70.3 0.966 57.7 0.950 0.7 120.9 0.951 109.9 0.941
0.8 62.4 0.952 49.0 0.923 0.8 90.9 0.929 79.0 0.907
0.9 56.9 0.939 42.68 0.896 0.9 72.3 0.903 60.0 0.864

Oxy-combustion 0.1 118.6 0.954 116.4 0.947 Oxy-combustion 0.1 158.1 0.997 163.8 0.996
0.2 165.2 0.988 163.8 0.987 0.2 173.1 0.997 213.7 0.987
0.3 173.1 0.985 171.3 0.983 0.3 429.1 0.988 442.3 0.714

635
M. Mureddu et al.
Fig. 8. Activation energy behaviour in combustion (a) and oxy-combustion (b) modes by
KAS method.
an oxy-combustion atmosphere. The oxy-combustion trend seems not to
be subject to significant differences if compared to the combustion
process, except for the steeper trend between 0.1 and 0.3. Both the
biomass samples show a maximum in terms of activation energy around
α = 0.35. It is evident that the maximum values of activation energy for
both pine and eucalyptus samples are strongly dependent on oxygen
concentration and Ea values have doubled passing from combustion to
oxy-combustion conditions. This can be reasonably clarified with the
increase of oxygen concentration. According to Chen et al. (2011) [63]
and Fang et al. (2006) [64], the increase in oxygen concentration in-
volves an increase of heat released by semi-coke during the oxidation
process and, as a consequence, an increase of the surface temperature of
semi-coke itself.
It can be observed that the correlation coefficient (R2) of the straight
lines in combustion regime presents high values (0.90 < R2 < 0.99)
for both the FWO and KAS models; this means that all the points are
well fitted and the methods provide reliable values of activation energy.
However, for the oxy-combustion process, activation energy presents a
linear correlation with good R2 values only in a narrow range of con-
version (between α = 0.1 and 0.4). The assumption for this finding can
be ascribed to the violent exothermic reaction due to high oxygen
concentration, where, for α > 0.4, it is not possible to appreciate the
linear variation of the weight loss as a function of the heating rate.
Based on the findings of the kinetic study, it should be concluded that
both methods (FWO and KAS) match the experimental data under all
the conversion ranges in combustion regime, but they are not so ef-
fective, especially for biomass samples, when a high oxygen con-
centration is taken into consideration.
4. Conclusions
Kinetic study and assessment of the combustion performance in-
dexes have been qualitatively and quantitatively carried out by
636
Fuel 212 (2018) 626–637
thermogravimetric analysis on two different kinds of solid fuels (coal
and biomass) in combustion and oxy-combustion conditions.
TG results indicate that the overall weight loss is significantly higher
for biomass (in particular for eucalyptus chips) than for coal (mainly for
Sulcis type), but it is not significantly influenced by oxygen con-
centration. The peaks in coal combustion and oxy-combustion DTG
profiles are wide (except for South African coal), whereas marked peaks
can be noticed for biomass.
Oxy-combustion process can improve the burning rate of the con-
sidered fuels, shortening the burning time (25–36 min) with respect to
air-blown combustion (32–49 min). Most of the transformations occur
in a relatively narrow range of temperatures (around 300–670 °C, with
respect to 300–900 °C for air-blown combustion).
The S index (which reflects ignition, combustion and burnout
properties of a fuel) is significantly higher for biomass (mean values of
79.3 and 708.3 wt.%/(min2 ∗°C3) for combustion and oxy-combustion,
respectively) than for coal (7.6 and 41.1 wt.%/(min2 ∗°C3)), indicating
that wood chips present better combustion performance and enhanced
combustion properties, especially in oxy-combustion conditions.
The application of FWO and KAS methods to perform the kinetic
study to the combustion and oxy-combustion processes shows that,
under the same range of heating rate (10 ≤ β ≤ 50 °C/min) and for the
overall range of conversion (0.1 ≤ α ≤ 0.9), both the models comply
with the experimental data in combustion regime for all the considered
fuels; on the other hand, with the increase of the oxygen concentration
(oxy-combustion regime), both the models result reliable for the coal
samples and more sensitive to the weight loss for the biomass samples.
Acknowledgements
This work has been carried out within the “Centre of Excellence on
Clean Energy” research project (D82I13000250001) led by Sotacarbo
and funded by the Regional Government of Sardinia.
Appendix A. Supplementary data
Supplementary data associated with this article can be found, in the
online version, at http://dx.doi.org/10.1016/j.fuel.2017.10.005.
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