Fuel 330 (2022) 125556

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Fuel
journal homepage: www.elsevier.com/locate/fuel

Full Length Article

Investigation on thermal conversion, kinetics and thermodynamics of coal

gasification filter cake ash in oxygen fuel combustion
Zhichao Chen *, Jiawei Li, Xuyang Zhang, Yanyu Qiao, Zhenhua Yuan, Zhengqi Li
School of Energy Science and Engineering, Harbin Institute of Technology, 92, West Dazhi Street, Harbin 150001, PR China

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

Keywords: Coal gasification fine ash (CGFA) has the characteristics of high carbon content, fine-grained, and large annual
CGFA output, causing environmental pollution and energy wastage. Oxygen fuel combustion is an effective way to
Solid waste solve the CGFA problem. In this paper, the effects of thermal conversion, kinetics and thermodynamics during the
Oxygen fuel combustion
oxygen-fuel combustion of CGFA are analysed. The results show that the combustion of CGFA in an oxygen-fuel
Thermokinetics
atmosphere significantly improves its burn-up performance and combustion stability, but the improvement in
ignition performance is not significant. an increase in oxygen concentration of more than 30% in an O2/Ar at­
mosphere also improves the activation energy to some extent, but the improvement in combustion performance
is not significant. The average activation energy of CGFA under 30% O2/70% Ar condition is 104.25 kJ/mol, and
its combustion performance is comparable to that of bituminous coal blended gasification ash at 70%. A kinetic
model was developed to describe the oxygen-fuel combustion process of FCA, which can be efficiently and
cleanly burned under oxygen-fuel conditions and consumed on a largescale.

1. Introduction
In view of the current proven energy reserves and the level of tech­
nology available for energy development and utilisation, one of the two
pillars that can be relied upon in the era of ’energy transition’ is coal.
Coal gasification is at the heart of the coal chemical industry and the
industrial technology for the clean use of coal to produce syngas. The
coal gasification process still inevitably produces a solid waste, coal
gasification filter cake ash (CGFA). As the world’s petroleum resources
continue to decrease, coal chemical industry has a broad prospect[1].
The number of coal chemical enterprises has increased, and the coal
chemical industry has developed rapidly, the emission of CGFA will also
increase, with its annual production exceeding 33 million tonnes[2,3].
Due to factors such as treatment technology as well as cost, The main
consumption method of CGFA is to bury and put it in a certain area,
which will pollute the surrounding environment, and also leading to
energy wastage, affecting the sustainability of the coal chemical in­
dustry and the region [3-7].
CGFA contains a large amount of inorganic minerals (silicon and
aluminium), which can available as a basic material for architecture and
ceramics with high value-added, but at the same time contains 20%-60%
porous ungassed carbon residue, which can lead to reduced strength as a
material for construction [8–10]with loose and porous carbon residue,
and cannot handle large quantities, so it is necessary to realize large-
scale processing of CGFA to promote the efficient use of energy and
the high-quality development of circular economy. The current methods
of CGFA decarbonisation mainly include: physical methods (flotation,
re-election and electric separation) [11–16] and combustion methods.
Flotation method separates micro-fine particles with small mass, low
kinetic energy and weak inertia with low efficiency and high cost of
chemical agents, which cannot achieve the large-scale elimination of
coal gasification ash; electric separation method for carbon and ash with
low degree of monomer dissociation, ash and carbon are linked to each
other, which cannot be achieved by electric separation method and is
difficult to industrialize; re-election method has a clean and pollution-
free process, but the separation efficiency of fine particles is low [7];
the above physical methods cannot achieve the large-scale elimination
of coal gasification ash. Combustion is the most direct method to achieve
large-scale removal of unburned carbon from coal gasification fines.
CGFA contains very low volatile matter and 40–80% ash [2,7], and its
relatively low reactivity (high ignition temperature, high combustion
temperature and high activation energy) under air atmosphere limits its
direct use as a primary fuel in industrial production [2].
As CGFA combustion during industrial production also releases large

* Corresponding author.
E-mail address: chenzc@hit.edu.cn (Z. Chen).

https://doi.org/10.1016/j.fuel.2022.125556
Received 30 June 2022; Received in revised form 29 July 2022; Accepted 5 August 2022
Available online 17 August 2022
0016-2361/© 2022 Elsevier Ltd. All rights reserved.
Z. Chen et al.
Fig. 1. The gasification process and sample collection.
amounts of CO2, carbon capture and storage technologies for flue gases
must be developed. Oxygen-fuel combustion technology is currently
considered to have great prospects for capturing carbon dioxide emis­
sions from power plants [3]. Conventional combustion atmospheres
have a low CO2 concentration (around 15%), which makes it more
difficult to separate CO2 from the exhaust gas and thus increases oper­
ating costs [4]. Oxygen-fuel combustion results in lower ignition and
burn-up temperatures of the fuel, higher combustion temperatures and
higher CO2 concentrations in the flue gas, and makes CO2 capture and
separation very easy. Therefore, the direct combustion of CGFA as a
primary fuel in an oxygen-fuel atmosphere overcomes the difficulties of
CGFA ignition and combustion, and enables CGFA to be converted into
low-carbon secondary ash, which is an effective new way to achieve
carbon reduction and resource recycling in industrial applications. In
order to better understand the mechanism of CGFA oxygen-fuel com­
bustion and to develop CGFA oxygen-fuel combustion equipment for
large-scale CGFA consumption, research on thermal conversion, ki­
netics, and thermodynamics during oxyfuel combustion of CGFA is
highly desirable.
In recent years, Much research has been done on oxy-combustion of
coal and solid waste.[8–10]. Selcuk et al. [8] studied the combustion
behaviour of Turkish lignite under 21%O2, 30%O2 oxygen-fuel condi­
tions using a non-isothermal thermogravimetric method (TGA) com­
bined with Fourier transform infrared (FTIR) spectroscopy, where the
combustion rate increased and shorter burned time as the oxygen con­
centration increased. Yao et a. l[9] used thermogravimetric analysis to
study the combustion characteristics and kinetic behaviour of semi-coke
under 21%O2, 30%O2, 40%O2 oxygen-fuel atmosphere, although
increasing the oxygen concentration (21% to 40%) increased the acti­
vation energy but improved the ignition and burning behaviour. Zhang
[10] used thermogravimetric analysis to study the combustion charac­
teristics of coal gangue under 21%O2, 40%O2, 60%O2, the increase of
oxygen concentration can significantly improve the ignition and
burnout behavior of coal gangue. Sun, Hu and Wu [11,18–20] investi­
gated the combustion characteristics and kinetic behaviour of solid
waste gangue and sludge at 21%O2, 30%O2, 40%O2 and 50%O2, and the
results showed that although the increase of oxygen concentration in­
creases the activation energy of sludge and coal gangue, it also
2
Fuel 330 (2022) 125556
significantly improves the ignition and burnout behavior of sludge,
which is consistent with Yao et al. [9]. Murphy et al. [21] conducted a
kinetic study on the combustion of pulverised coal in 6%-36%O2 at­
mosphere and showed that the activation energy decreased and the
combustion performance improved with increasing O2 concentration.
Although the kinetics of the oxygen-fuel combustion process of solid
fuels varies, an oxygen-fuel atmosphere improves the combustion per­
formance of the fuel. It is inferred that the combustion performance of
CGFA can be improved under oxygen-fuel conditions and that the energy
utilised in the combustion process also reduces the environmental
threat. Furthermore, little attention has been paid to the thermal
transformation, kinetics, and thermodynamics of CGFA during com­
bustion under oxygen-fuel conditions. A better understanding of the
thermal transformation, kinetics and thermodynamics of the combus­
tion process under oxygen-fuel conditions is essential to promote and
realise the resourceful and environmentally friendly use of CGFA.
In this paper, the filter cake ash (FCA) from an 40,000 Nm3/h CFB
gasifier,which is used to study the thermal transformation, apparent
kinetics and thermodynamics of the combustion of FCA in an oxygen-
rich atmosphere through thermogravimetric experiments, to reveal the
combustion mechanism during the combustion of FCA in an oxygen-rich
atmosphere, and to establish a kinetic model to provide basic data for
the resource utilization of FCA.
2. Materials and methods
2.1. Sample preparation
The samples for this study were taken from FCA from the gasification
field, CFB in China. The gas production of the gasifier is 40,000 Nm3/h,
the gasification temperature is about 980 ℃, the coal feeding amount is
22.3 t/h, the coal temperature into the gasifier is 80 ℃, and the gasifying
agent flow is 6.59 kg/s. Fig. 1 shows the processing engineering of filter
cake ash (FCA). As the FCA sample is in fine powder form with a particle
size of approximately 40 μm, the basic properties of the ash sample are
directly investigated.
The proximate analysis and ultimate analysis of FCA were performed
according to Chinese standards. For details, please refer to reference [1].
Z. Chen et al. Fuel 330 (2022) 125556

Table 1
Proximate and Ultimate analysis.
Sample Proximate analysis (%) Low calorific value Ultimate analysis (%)

Mad Vad Aad FCad Qnet,ar(MJ/kg) Cad Had Oad Nad Sad

FCA 1.57 8.29 50.32 39.82 14.558 43.40 0.78 2.83 0.40 0.72

The proximate analysis and ultimate analysis are shown in Table 1. experiment was performed under each group of experimental conditions
to obtain the baseline required for the experiment. Each experiment was
2.2. Experiment repeated twice and the error was found to be within 2% after repeated
experiments.
Thermogravimetric analysis and TG (Thermogravimetry)/DSC (Dif­
ferential Scanning Calorimetry) experiments were performed with a 2.3. Kinetic analysis
thermogravimetric analyzer (NETZSCH-STA449F) in air/oxygen-fuel
atmosphere (20%O2/80%Ar, 30%O2/70%Ar, 70%O2/30%Ar, 20%O2/ TG experiments can be used to calculate experimental related pa­
80%CO2, 30%O2/70%CO2). The test sample with a mass of about 6 mg rameters and the formula is shown as follows:
was placed in a crucible made of alumina, and the furnace temperature dα
gradually increased to 1000 ◦ C under three heating rates of 100 ml/min = k(T)⋅f (α) (1)
dt
and 10, 20 and 30 K/min. conduct experiment. At the same time, a blank

Fig. 2. O2/Ar and O2/CO2 combustion profiles of FCA at 20 K/min heating rate for samples (a) TG, (b) DTG, (c) DSC, (d) DDSC.

3
Z. Chen et al. Fuel 330 (2022) 125556

Fig. 3. Combustion curves of FCA at O2/Ar and O2/CO2 oxygen concentrations (a) TG, (b) DTG, (c) DSC, (d) DDSC.

The parameters in the formula can be found in reference[1] and k

ΔS = (ΔH − ΔG)/Tp (8)
(T), α can be expressed as:
Eα In the formula, KB and h are constants, see the literature [1] for
k(T) = Aexp(− ) (2) details；.
RT
FWO, DAEM, Starink and Friedman methods are commonly used in
α=
m0 − mt
(3) the study of solid fuel combustion kinetics. The formula of the above
m0 − m∞ method is (9)-(12), the E is given by their slopes of the straight line in
The parameters in the formula can be found in reference [1], β = dT/ equations (9)-(12):
dt and Eq. (1) can be transformed into Eq. (4): Friedman:
dα E
dα A −
= e (ERTα )
⋅f (α) (4) ln(β ) = ln[Af (α) ] − (9)
dt β dT RT
Fwo:
A, ΔG, ΔS and ΔH can be obtained according to the model-free
method calculation formulas (5)–(8) for the estimation of E: AE E
lgβ = lg( ) − 2.315 − 0.4567 (10)
( )/ Rg(α) RT
E
A = β⋅E⋅exp( ) (RTp2 ) (5)
RTp Daem:

β AR E
ΔH = Eα − RT (6) ln( 2 ) = ln( ) + 0.6575 − (11)
T E RT
KB T p Starink:
ΔG = Eα + RTp ln( ) (7)
hA

4
Z. Chen et al. Fuel 330 (2022) 125556

Fig. 4. Four model-free methods for estimating E values for different values of α.

5
Z. Chen et al.
Fig. 4. (continued).
( )
β E
ln = Cs − 1.0008 (12)
T 1.92 RT
For Tp and g(α) in the formula, see Reference [1].
The Malek method was used to determine the FCA oxygen-rich
combustion reaction model. Malek calculates the combustion reaction
model can be divided into y(α) and Z(α), and this study uses the y(α)-α
principal diagram method to derive the reaction model [22,23].
The experimental data obtained through the experiment is drawn
into a curve and the curve obtained by the formula through the software
is compared and analyzed, so as to obtain the optimal value of the ki­
netic model. If at a certain moment or interval, the two curves obtained
completely coincide, the optimal dynamic model function in this time
period or moment can be described by the corresponding G(α) of the
theoretical overall planning.
The reliability of the fit of the theoretical curve to the experimental
curve is assessed using the mean square error (MSE), which is expressed
6
Fuel 330 (2022) 125556
as follows:
1∑n
( )2
MSE = ythero − yexp (13)
n 1
In the equation, n is the number of equally spaced conversion rate
values. A smaller MSE value indicates a high reliability of the derived
reaction model [22]. If the MSE value between the theoretical model
curve and the experimental curve is greater than 5, it indicates that the
reaction model is poorly matched undesirably.
The other four parameters in the model-free approach can be ob­
tained by obtaining an estimate of E calculated by references [25].
2.4. Combustion characteristics parameters
The following eight indicators are used to evaluate combustion
performance. For details, please refer to Reference[24,25].
Z. Chen et al. Fuel 330 (2022) 125556

Results and Discussion. Table 2

Combustion characteristics of FCA in O2/Ar and O2/CO2 at different rates of
2.5. FCA air/oxygen-rich combustion characteristics at 20 K/min temperature.
ATM β Ti Tp Tb -Rp tb Re
Fig. 2 shows the combustion curves of FCA at different oxygen 20O2/80Ar 10 448.73 495.68 532.28 5.12 50.28 48.07
concentrations. Fig. 2(a and b) shows that the increase in oxygen con­ 20 450.92 537.22 579.72 7.79 27.53 45.28
centration of FCA in both O2/Ar and O2/CO2 atmospheres leads to a 30 466.47 578.95 612.89 9.82 19.45 49.55
gradual shift of the TG curve towards the low temperature, and the DTG
curve also shifts towards the low temperature region, with the DTG 30O2/70Ar 10 430.02 480.24 524.03 5.49 49.46 47.30
curve becoming narrower and sharper at higher oxygen concentrations, 20 445.64 517.74 538.80 9.83 25.46 48.29
and the maximum weight loss rate also increasing. The content of water 30 460.11 554.17 590.22 9.96 18.69 48.19

and volatile matter in FCA is less (about 9.86%), and in the range of
environment to 400 ℃, this stage is mainly the precipitation and 70O2/30Ar 10 432.97 458.02 479.41 5.36 44.98 50.76
20 436.45 465.85 492.25 14.86 23.13 49.16
decomposition of volatile matter and functional groups, the increase of
30 444.24 469.54 513.84 20.37 16.12 48.96
O2 concentration, the TG and DTG curve of FCA changes very little,
which also indicates that the increase of O2 concentration does not have
20O2/80CO2 10 451.38 512.88 877.38 5.06 47.49 47.48
a significant effect on the initial combustion of FCA. In the range of
20 469.26 555.76 928.76 5.94 25.93 47.26
400–600 ◦ C, the TG and DTG curves in the O2/Ar and O2/CO2 atmo­ 30 482.99 579.99 967.49 6.43 18.06 49.50
spheres show significant changes. With increasing oxygen concentra­
tion, the TG and DTG curves gradually shift towards lower temperatures, 30O2/70CO2 10 439.75 485.75 763.75 6.19 51.07 50.36
and the higher the O2 concentration the narrower and sharper the DTG 20 445.85 522.35 870.85 8.47 41.72 48.90
curve is, and DTG also increases. This part is the violent combustion of 30 456.91 542.91 941.41 9.17 30.20 49.78
the remaining residual carbon in FCA, which strengthens the combus­ β: heating rate in K/min; Ti, Tp and Tb: ignition, peak and burned-out temper­
tion performance in high temperature areas of FCA. At the same oxygen ature in K, respectively; − Rp: maximum mass loss rate in %/min; tb: burnout
concentration, the maximum weight loss rate in O2/Ar atmosphere is time in min; Re: residual percentage of sample at the end of the thermal
higher than in O2/CO2, mainly because the specific pressure heat ca­ experiment in %.
pacity and density of CO2 is higher than that of Ar, and the release of CO2
during the combustion of O2/CO2 makes the heat absorption capacity trends of the DSC and DTG curves are similar, with the exothermic peak
stronger and more heat is emitted. Fig. 2(c)(d) shows the DSC and DDSC of FCA shifting to higher temperatures as the heating rate increases in an
curves for FCA, with increasing oxygen concentration causing the DSC oxygen-rich concentration atmosphere, and a wider temperature range
and DDSC curves to gradually shift towards lower temperatures, with is observed. The shift of the DSC and DDSC peaks to higher temperatures
the DSC curve becoming narrower and sharper at higher oxygen con­ again indicates that between the inner and outer particles There is a
centrations. In the 400–600 ◦ C range, the exothermic peak of the DSC hysteresis effect that impede the release of heat. In the 400–600 ◦ C stage,
curve is the main reaction phase and the zero point of DDSC is also the volatilization in the main FCA is analyzed and accompanied by the
shifted to the left. The higher the O2 concentration, the faster the O2 combustion of fixed carbon, resulting in the obvious exotherm of the
diffusion rate and the larger the exothermic peak, the larger the DSC peak of the FCA in this interval. As the temperature rise increases
maximum exothermic peak and the lower the corresponding tempera­ from 10 K/min to 20 K/min, 30 K/min, the peak DSC exotherm in­
ture. 600–1000 ◦ C range, the TG, DTG and DSC curves are flatter and the creases. The DDSC curves are similar for 20% and 30%O2 concentra­
main combustion reaction is completed at this stage. tions, but when the heating rate increases to 20℃/min, the 30%O2 peak
Combustion characteristics of FCAs with different heating rates at exotherm is significantly higher than 20%, which means that the change
different oxygen concentrations. in oxygen concentration and the change in heating rate have a double
Fig. 3 (a)(b) shows the combustion behaviour under different oxygen effect on the release heat. The DDSC curve is obtained by a derivation of
concentrations in O2/Ar atmosphere. As the temperature rises from 10 DSC, which reflects the relationship between the rate of change of DSC
K/min to 20 K/min or 30 K/min, the TG and DTG curves of FCA shift to and also shows the relationship between heat flow rate and temperature.
the right, resulting in thermal hysteresis. The reason is the temperature At low ramp rates, the temperature of the FCA rises slowly and the
difference between the inside and outside of the particles. In the process sample is heated for a longer period of time in a given temperature
of the reaction, the heat and mass transfer of the particles is hindered, range, allowing more than enough time for the fixed carbon to decom­
and thermal hysteresis occurs, and the overall reaction moves to the pose completely and release more heat. On the other hand, the time
right. When the oxygen concentration is 70%, the thermal hysteresis required to reach a specific temperature is shortened at higher heating
phenomenon is significantly weaker than other oxygen concentrations. rates, resulting in a temperature gradient between the surface temper­
This is probably because when the oxygen concentration is high, the ature of the particles and their internal temperature, which hinders the
diffusion rate of oxygen accelerates and FCA has well-developed pores, release of heat flow between the inner and outer particles. Fig. 4(e and f)
oxygen reacts rapidly with the inside and outside of the FCA particles, shows the combustion behaviour under different oxygen concentrations
The temperature difference between the inside and outside of the par­ in O2/CO2 atmosphere. The TG and DTG curves of O2/CO2 and O2/Ar
ticle is reduced, and the obstruction phenomenon inside and outside the are basically the same, but the TG and DTG curves of O2/CO2 lag behind
particle is weakened during the reaction process, making the thermal those of O2/Ar. The maximum DTG of O2/CO2 is smaller than that of O2/
hysteresis weaker than other oxygen concentrations. As the temperature Ar for the same O2 concentration and heating rate.
rise increases from 10 K/min to 20 K/min, 30 K/min, The graph of the Combustion characteristics parameters, kinetic and thermodynamic
DTG curve of the FCA is presented as a single peak, and the weight loss analysis.
peak becomes wider and higher. Especially at 70% oxygen concentra­
tion, the increase in temperature rise rate leads to a significantly higher 2.5.1. Combustion characteristics parameters
peak increase in DTG than other oxygen concentrations. Due to the low Table 2 shows the combustion characteristics of FCA in O2/Ar and
volatile fraction content of FCA, there was no change in ignition mode O2/CO2 at different rates of temperature rise. With increasing oxygen
and volatile fraction combustion was not evident throughout the com­ concentration, the ignition temperature (Ti), peak temperature (Tp),
bustion process. Fig. 4(c and d) shows the trends of the DSC and DDSC burnout temperature (Tb) and burnout time all decrease, due to the high
curves for different oxygen concentrations in an O2/Ar atmosphere.The

7
Z. Chen et al.
Fig. 5. Four kinetic methods for calculating E for combustion in different atmospheres.
diffusion rate and reactivity of high O2 concentration which in turn
improves the ignition and burnout of FCA [26]. However, with the in­
crease of oxygen concentration, the decrease of Ti is significantly smaller
than that of Tb, which also shows that the effect of increasing oxygen
concentration on the ignition performance of FCA is less than that of
burnout performance. The increase in heating rate leads to a thermal
hysteresis phenomenon which further causes an increase in both Ti and
Tb.But, at the same O2 concentration, Ti and Tb are higher in O2/CO2
than in O2/Ar. The O2/CO2 atmosphere delays the decomposition of
residual carbon in FCA, the O2/Ar atmosphere leads to improved FCA
ignition and burn-up properties, and the O2/CO2 atmosphere inhibits
the combustion of FCA. In conclusion, whether in O2/Ar or O2/CO2, the
increase of oxygen concentration promotes the ignition and burnout
performance. In practice, the behavior in O2/CO2 atmosphere is more
important. The combustion performance of 30%O2/70%CO2 is slightly
higher than that of 20%O2/80%Ar, which indicates that in the actual
process, after CO2 replaces Ar, the decrease of FCA combustion perfor­
mance can make up through increasing oxygen concentration. If O2/CO2
achieves the combustion performance of 20%O2/80%Ar, it needs to
8
Fuel 330 (2022) 125556
increase the oxygen concentration to about 30% to promote the com­
bustion reactivity.
2.5.2. Kinetic analysis
The experimental images derived from formulas (9)-(12) are shown
in Fig. 4. Fig. 5 shows the values of E and the R2 of the fit for the above
four methods at different values of α. The value of E depends mainly on
the energy potential required for the combustion reaction of the fuel. A
strong linear relationship is shown in Fig. 4, giving R2 values greater
than 0.9 obtained by the isoconversion method, resulting in accurate E
values. 5(a)(b)(c)(d)(e) shows the variation of activation energy be­
tween the two points with a value of 0.1–0.90 and 0.1. After comparison,
the FWO method has the highest activation energy value and the best fit.
The activation energy varies with α, reflecting the kinetic complexity of
the samples under different oxygen concentrations. The activation en­
ergy curves of FCA under O2/Ar and O2/CO2 conditions have roughly
the same trend. In the O2/Ar atmosphere, E was lower at the beginning
of the FCA reaction at oxygen concentrations of 20% and 30%, mainly
due to the decomposition of some volatile fractions. As the conversion
Z. Chen et al.
Fig. 6. (a) Theoretical and experimental curves of the reaction model of FCA in 20% O2/80% Ar, 30% O2/70% Ar, 70% O2/30% Ar, 30% O2/70% CO2 and 20% O2/
80% CO2 atmospheres at different rates of temperature rise.
rate increases, E peaks at a conversion rate of 0.2, which is also the stage
with the greatest change in TG and DTG. More energy is required in this
stage to maintain the combustion and decomposition of the fixed carbon
of FCA, hence the larger activation energy E values in this stage. The
activation energy is minimised when the conversion rate increases to
0.6, this is the intense combustion phase and finally the E rises as the
remaining residue tends towards the end of the reaction. At 70% oxygen
concentration, FCA has the highest E value at a conversion rate of 0.4
and the lowest E value at a conversion rate of 0.7. This differs from other
oxygen concentrations, mainly because the combustion process changes
considerably when the oxygen concentration exceeds 30%. The increase
in oxygen concentration causes an increase in the reaction rate at the
particle surface and a rapid increase in temperature, resulting in a
change in the coke lattice. In the O2/CO2 atmosphere, the initial E of the
FCA reaction is higher at 20% and 30% oxygen concentrations, mainly
because the higher CO2 volume fraction hinders the diffusion of O2 to
the particle surface and requires higher energy for the initial reaction to
occur. The reaction rate is accelerated, the energy required is reduced
and the E value is lowered.
As can be seen from Fig. 5(f), in both O2/Ar and O2/CO2 atmo­
spheres, the average activation energy of the FCA reaction decreases as
the concentration of O2 increases from 20% to 30%. In contrast, in the
O2/Ar atmosphere, the average activation energy of the FCA reaction
increases when the concentration of oxygen exceeds 30% [19,27-34]. It
is possible that the ratio of activated molecules, diffusion limitations and
inorganic impurities decrease during the combustion of FCA, which in
turn affects the E value [27]. Similar results have been reported by
9
Fuel 330 (2022) 125556
several researchers in studies related to fuel combustion under oxygen-
fuel conditions [28]. As O2 concentration increases it increases the heat
generated during combustion of the remaining porous coke of FCA,
which in turn increases the surface temperature of the coke[29]. As the
final surface temperature of the coke increases further, it also enlarges
the structural grain size of the coke and increases the amount of ash
remaining [29]. The increased oxygen concentration allows combustion
reactions to occur at lower temperatures, which in turn slows down the
surface reaction rate and kinetically controlled regions and weak
diffusion effects occur [30–32]. As a result, the E value of FCA increases
with increasing oxygen concentration. the average activation energy
(FWO method) of 30%O2/70%Ar FCA is 104.25 kJ/mol and the average
activation energy of co-combustion of bituminous coal with 70%
blending of gasification dry ash is 108.47 kJ/mol [35], which indicates
that the combustion of FCA in 30%O2/70%Ar oxygen-fuel atmosphere.
This indicates that the performance of FCA combustion under 30%O2/
70%Ar oxygen-fuel atmosphere achieves the performance of bituminous
coal blended with 70% gasified ash, and that oxygen fuel combustion
greatly improves the combustion characteristics of FCA, which can
further reduce coal consumption and improve its combustion perfor­
mance. In addition, under the same oxygen concentration O2/CO2 at­
mosphere, the activation energy of FCA is lower than that of biomass,
municipal sludge, aluminum electrolysis waste cathode carbon and
other solid wastes [19,27-29,34]. This also shows that it is feasible to
reuse coal-based solid waste as reburning fuel under oxygen enriched
conditions, which provides a basis for the recycling and large-scale
consumption of solid waste.Overall, the reaction activation energy
Z. Chen et al. Fuel 330 (2022) 125556

Table 3 2.5.3. Reaction model

Mean Square Error (MSE) and correlation coefficient R2 of the response model. Forty-one standard curves for the reaction models were derived from
10 K/min 20 K/min 30 K/min the standard reaction functions. The experimental reaction model curves
2 2 for different conditions were obtained by substituting the experimental
MSE R MSE R MSE R2
data at different α into the equations. The theoretical and experimental
20O2/ 0.013866 0.9891 0.021801 0.9816 0.019253 0.9911 reaction model curves at different conversions were compared to obtain
80Ar
30O2/ 0.008200 0.9835 0.010864 0.9803 0.017075 0.9844
the most probable reaction mechanism. Fig. 6(a) shows the standard
70Ar curve of the reaction model, while Fig. 6(b–d) show the experimental
70O2/ 0.005628 0.9869 0.008491 0.9694 0.016536 0.9591 curves of the reaction model for 20%O2/80%Ar, 30%O2/70%Ar and
30Ar 70%O2/30%Ar atmospheres at 10, 20 and 30 K/min temperature rise
20O2/80 0.024594 0.8995 0.012125 0.9445 0.004436 0.9647
rates.
CO2
30O2/70 0.037114 0.8980 0.009706 0.9724 0.009492 0.9705 Fig. 6(b–d) shows that the matching between the theoretical and
CO2 experimental curves is low in the range of conversion rate α = 0.1–0.3
and high in the range of conversion rate α = 0.3–0.9, mainly because the
reaction substances and combustion reactions are more complex and
value E is higher for the O2/CO2 atmosphere than for O2/Ar, and the O2/ unstable at the early stage of the reaction, and a single chemical reaction
CO2 atmosphere is not conducive to FCA combustion. Increasing the mechanism model does not describe the reaction process. The MSE of
oxygen concentration improves the combustion characteristics of FCA to the theoretical and experimental curves were both less than 0.0371
some extent. However, increasing the oxygen concentration by more (Table 3), indicating that the FCA combustion reaction model was
than 30% also increases the activation energy to a certain extent. This selected with some accuracy [22]. Therefore, the reaction models for
also indicates the need for a comprehensive analysis of FCA oxygen-fuel FCA Oxygen-fuel combustion (OFC) at different heating rates are: F1-4,
combustion performance, kinetics and feasibility in order to select the F5-9, G1-4, P2, D7.
right oxygen concentration for the design and optimisation of oxygen-
fuel combustion systems. 2.5.4. Thermodynamic analysis
Fig. 7 Estimated thermodynamic parameters of A, ΔH, ΔS, and ΔG
according to the FWO method. the trend of the curve for A is similar to

Fig. 7. Thermodynamic parameters A (S-1), ΔH (kJ/mol), ΔG (kJ/mol), ΔS (J/mol) of FCA during combustion in different oxygen atmospheres.

10
Z. Chen et al.
that of E. The A values for FCA in 70%O2/30%Ar and O2/CO2 atmo­
spheres are much higher than for the other atmospheres, and the A
values range from 1010 to 1014, indicating that the transfer of material
in complex reactions during combustion may be more restricted than at
the beginning of the reaction [33]. FCA requires more reaction energy
for combustion and decomposition of fixed carbon in 70%O2/30%Ar
and O2/CO2 atmospheres. The ΔH value of FCA represents the endo­
thermic and exothermic reactions of the reaction, and the curve gener­
ated by the ΔH value is similar to the activation energy E. The ΔH curves
at different temperature rises basically overlap, and Different tempera­
ture rises have no effect on the ΔH curve. When the highest point ap­
pears in the ΔH curve, the temperature corresponding to the
corresponding conversion rate is the same as the temperature at the
minimum value of DTG. This shows that the endothermic trend of the
reaction system increases before complete combustion of FCA in an
oxygen-fuel atmosphere, and decreases during complete combustion.
When the value of α is between 0.8 and 0.9, the ΔH curve increases
again, which also reflects After the high temperature inorganic minerals
absorb heat and decompose. The decrease in ΔH indicates that the re­
action system requires less heat energy, with the lowest average ΔH for
the decomposition of 30%O2/70%Ar atmosphere, which indicates that
the heat demand is lowest throughout the reaction in the 30%O2/70%Ar
atmosphere. ΔG values reflect the increase in total energy of the reaction
system. the overall ΔG values are higher for the combustion of FCA in
the 30%O2/70%Ar atmosphere. In the early stages of the reaction, FCA
has a higher ΔG value. During oxygen-fuel combustion, FCA requires
more energy to sustain combustion in an O2/CO2 atmosphere than in an
O2/Ar atmosphere. The ΔS curves for FCA in O2/Ar and O2/CO2 are
basically the same, as the conversion rate increases, the system reac­
tivity increases, FCA in O2/CO2 is less reactive than in O2/Ar, and the
system reactivity in O2/CO2 is less than inO2/Ar.
3. Conclusion
In O2/Ar and O2/CO2 atmospheres, With the increase of O2 con­
centration, the combustion fixation performance and combustion sta­
bility of FCA are improved, with limited improvement in the ignition
performance of FCA, which can substantially improve its burnout per­
formance. In O2/Ar atmosphere, the thermal hysteresis is significantly
weaker at 70%O2 concentration than other O2 concentrations. The
higher the O2 concentration, the narrower the combustion reaction
temperature range of FCA, which has a well-developed pore structure,
and the well-developed pore structure provides favourable conditions
for high concentrations of oxygen to diffuse through the pores of FCA.
The average activation energy of FCA under 30% O2/70% Ar fuel con­
ditions is 104.25 kJ/mol, which is comparable to the combustion per­
formance of bituminous coal blended with 70% gasification ash. The
kinetic models for oxygen-fuel combustion at different oxygen concen­
trations varied and mainly followed the Random nucleation model.
Compared with ΔS, ΔG, and ΔH, the chemical properties of CGFA are
unstable with the increase of O2 concentration, and the reaction can be
maintained with less energy. Compared to O2/Ar, the O2/CO2 atmo­
sphere inhibits the combustion performance of FCA. Combustion under
oxygen-enhanced conditions is expected to achieve large-scale CGFA
consumption and is more conducive to generating secondary ash with
low carbon content as a raw material for building materials.
Declaration of Competing Interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
Data availability
Data will be made available on request.
11
Fuel 330 (2022) 125556
Acknowledgement
This work is supported by the National Key Research and Develop­
ment Program of China (Grant No. 2017YFB0602001).
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