Fuel 310 (2022) 122268

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Fuel
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Full Length Article

Study on the inhibition effect of citric acid on coal spontaneous combustion

Peiyu Liu a, b, Zenghua Li a, b, *, Xiaoyan Zhang a, b, Jinhu Li c, Guodong Miao a, b, Shaodong Cao a, b,
Song Li b, d
a
Key Laboratory of Gas and Fire Control for Coal Mines (China University of Mining and Technology), Ministry of Education, Xuzhou 221116, China
b
School of Safety Engineering, China University of Mining and Technology, Xuzhou 221116, China
c
College of Safety and Engineering, Anhui University of Science and Technology, Huainan 232001, China
d
Jiangsu Key Laboratory of Fire Safety in Urban Underground Space (China University of Mining and Technology), Xuzhou 221116, China

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

Keywords: Transition metals ions in coal can accelerate the coal spontaneous combustion by reducing the activation energy
Citric acid of the coal-oxygen reaction during coal oxidation. The catalytic action of metal ions may be decreased by adding
Coal spontaneous combustion metal chelators to coal. In this article, an environment-friendly metal chelating agent, citric acid, was proposed
Inhibitor
as an inhibitor of coal spontaneous combustion. Experiments were carried out to investigate the inhibitory effect
Functional groups
of citric acid on coal spontaneous combustion. The results showed that the generation of CO, CO2 and the
consumption of O2 in the oxidation of inhibited coal samples were much lower than those of raw coal. Compared
to raw coal, the crossing point temperature of inhibited samples increased by 9–12 ◦ C, and the advent time of the
crossing point temperature was delayed by 30 to 40 min. In addition, the temperature of the characteristic points
of the experimental coal samples after inhibition was higher than that of raw coal. The reaction enthalpy of
inhibited coal samples was smaller than raw coal when experimental samples entered the rapid combustion
stage. Through Fourier Transform infrared spectroscopy (FTIR) experiments, it was found that the amount of
-CH3 and -CH2- groups in coal samples increased after inhibition, but the amount of -COOH and C=O groups
decreased. Scanning electron microscope (SEM) analysis showed that the surface of the coal sample became
smoother and the pore size decreased after citric acid treatment. In conclusion, citric acid has a good inhibitory
effect on different types of coal.

1. Introduction
There are many kinds of accidents in daily coal mining. Mining fire is
one of the main types of accidents, which seriously affect the safety
production in coal mines [1–3]. With the continuous growth of coal
mining mechanization, fully mechanized cave mining is being applied in
more coal mines. However, this method can create problems such as
residual coal in goaf and air leakage. Therefore, preventing coal spon­
taneous combustion is extremely important [4,5].
Coal spontaneous combustion is a very complex physical and
chemical process [6,7]. This process can be affected by several variables
[8–11]. The metal ions in coal have varying degrees of influence on coal
spontaneous combustion. The spontaneous combustion tendency of coal
increases with increasing Fe2+/3+ content [12]. However, NaCl and
MgCl2 can inhibit the coal spontaneous combustion because of the
inhibiting effect of Na+ and Mg2+ on combustion [13]. Some scholars
have found that the content of metal ions is a significant factor affecting
the tendency of coal to spontaneously combust and have carried out
thorough research on this topic. Jiang [14] added different metal ions to
Shenfu coal, analyzed the oxidation products by infrared spectroscopy
experiments, and found that La3+, Co2+, and Ni2+ have sound catalytic
oxidation effects on coal. Wang [15] proposed that the inert reaction of
active groups with O2 in coal was caused by ligands and coordination
chemical bonds between Ca2+ and them, such as O2, phosphorus, and
sulfur. Tang [16], through infrared spectroscopy experiments and
research on the effects of different manganese salts on coal spontaneous
combustion, showed that manganese ions can enhance the spontaneous
breakdown of coal alkoxy groups. Moreover, he also pointed out the
possible catalytic mechanism in which manganese ions promote the
oxidation and decomposition reactions. The above studies show that
different metal ions have different effects. The coal spontaneous com­
bustion can be promoted by transition metal ions (Co2+, Ni2+, etc.), but
metal ions in halogen salts (Ca2+, Mg2+, etc.) can inhibit this process.
Halogen salt is often used as a kind of inhibitor to control and prevent

* Corresponding author at: School of Safety Engineering, China University of Mining and Technology, Xuzhou 221116, China.
E-mail address: lzh6512@126.com (Z. Li).

https://doi.org/10.1016/j.fuel.2021.122268
Received 22 June 2021; Received in revised form 27 September 2021; Accepted 8 October 2021
Available online 21 October 2021
0016-2361/© 2021 Elsevier Ltd. All rights reserved.
P. Liu et al. Fuel 310 (2022) 122268

coal spontaneous combustion, achieving certain results in production
and application. Although many scholars have studied the influence of
metal ions on coal spontaneous combustion, there are few studies on
how to control the promotion of some metal ions on coal spontaneous
combustion. If the catalytic effect of transition metal ions can be
decreased, inhibiting the coal spontaneous combustion can be achieved.
At the same time, in the research on the inhibitory effect, application
and mechanism of inhibitors on the spontaneous combustion oxidation
process of coal, the research on the mechanism of chemical inhibitors to
inhibit coal oxidation is relatively limited.
Citric acid is an essential organic acid and an excellent natural
environment-friendly metal chelator [17–19]. This organic acid has an
excellent chelating ability for a variety of metal ions. It can chelate most
divalent and trivalent metal ions to form a stable metal chelate, making
transition metal ions lose their reactivity. Because of this characteristic,
metal chelating agents are widely used to remove heavy metals in soil
and extract heavy metals from plant waste liquid [20–22]. In the realm
of health, citric acid is an essential intermediate product in the tricar­
boxylic acid cycle [23,24]; in food processing, citric acid is often applied
as a food additive acidifier and flavoring [25–28]. However, the appli­
cation of citric acid is restricted in the mining industry, and it is mainly
applied to reduce the content of heavy metal elements in coal ash [29].
The inhibitory effect of citric acid, therefore, remains to be studied.
Accordingly, this paper proposes to use the environment-friendly
metal chelating agent citric acid as an inhibitor. Changes in the gas
composition, mass, heat release, functional groups and surface
morphology of coal samples before and after inhibitor treatment were
studied through experiments such as temperature-programmed experi­
ments, thermogravimetry, FTIR spectroscopy and SEM. The study of this
content can not only further reveal the mechanism of coal spontaneous
combustion but also provide a new reference for the production of new
and efficient inhibitors.
were determined using a Germany Bruker S8 Tiger device to describe the
contents of metal transition elements in coal. First, the experimental coal
samples were ashed in the muffle furnace. Then the burned bottom ash
samples were ground and crushed to under 74 μm, after which boric acid
was used as a binder to make 6 cm3 flakes for testing and analysis.
Table 2 shows the composition and content of transition metal elements.
2.2. Temperature-programmed experiment
In this paper, temperature-programmed experiments were used to
research the oxidation gas products and the temperature of the crossing
point in raw coal and inhibited samples. 40 g of the processed coal
sample was placed into the temperature-programmed oven sample tank
for these experiments. After checking the airtightness of the gas channel,
the experiment was operated at an airflow of 30 mL/min and a heating
rate of 0.5 ◦ C/min. While increasing the temperature from 30 ◦ C to
170 ◦ C, a 20 mL syringe was used to withdraw a gas sample from the end
of the rubber tube every 10 ◦ C and inject the obtained gas to the gas
chromatograph. Each sampling temperature was maintained constant
for 20 min. The gas composition and concentration data at the outlet
were recorded and processed, and the changes in coal temperature and
oven temperature were recorded.
The temperature-programmed experimental device primarily con­
sisted of a gas supply system, a temperature-programmed heating de­
vice, and a gas chromatograph (see Fig. 1). A QPT-300G
nitrogen–hydrogen-air integrated machine was used as the air supply
system, and the programmed heating device was a 2000 briquette
spontaneous combustion heating oven. The meteorological chromatog­
raphy system was a three-channel FULI9790-type chromatography in­
strument; when the gas concentration was within the 0.5% error range,
the gas outlet peak area could be measured, and the concentrations of
CO, CO2, O2 and other gases could be analyzed accordingly.

2. Experimental 2.3. TG-DTA thermal analysis

2.1. Coal samples
Three kinds of coal samples with different levels of metamorphism
were selected, namely Chi Feng coal sample from the Inner Mongolia
Autonomous Region, Da Fosi and Da Liuta coal samples from Shaanxi
Province. Proximate analysis of the industrial composition of the coal
samples was carried out based on China’s National Standard GB/T 212
[30]. The industrial composition analysis of the three experimental
samples is displayed in Table 1. First, the appropriate coal samples were
gathered and vacuum sealed. Next, the samples were taken to the lab­
oratory to remove the oxide layer on the surface and collect the central
part. Finally, the experimental samples were crushed in a nitrogen at­
mosphere and then screened with a selected particle size range of
0.180–0.250 mm. After the preparation was complete, a raw coal group
and an inhibited coal sample group were established for each coal type
to conduct a comparative verification experiment. The inhibited coal
sample group consisted of 40 g raw coal with 10 g water and 2 g citric
acid, and the raw coal group is 40 g raw coal with only 10 g water. Each
group of coal samples was stirred evenly and soaked for 48 h. Finally, the
experimental coal samples were kept for vacuum drying for 10 h at
40 ◦ C.
The content and composition of chemical elements in the samples
A thermal analysis experiment is an effective means to study and test
the oxidation of coal [31–33]. This paper used the method of synchro­
nous thermal analysis. The coal samples were placed in a German
NETZSCH-STA409C thermal analyzer for experiments. Dry air was used
to provide an oxidizing environment with a flow rate of 50 mL/min. The
heating rate was 5 ◦ C/min, and the temperature was increased from
room temperature to 500 ◦ C. The experimental data were collected
every 0.01 min.
2.4. FTIR experiments
Infrared spectroscopy experiments were used to study the changes of
functional groups of coal samples before and after citric acid inhibition
and analyzed the inhibitory effect of it on coal spontaneous combustion
to better explain the micro-inhibition process of inhibitors on coal
spontaneous combustion. The raw coal samples and the samples
inhibited by citric acid were ground to below 0.075 mm and then dried
Table 2
Data table content in experimental samples of transition metal elements.
Element Z Content(ppm)
CF DFS DLT

Table 1 Sc 21 8.1 7.3 12.1

Ti 22 159.2 117.0 312.1
Industrial analysis of three kinds of experimental samples.
Mn 25 185.9 83.7 258.2
Coal samples Industrial analysis Metamorphic degree Fe 26 4383.2 885.6 9256.6
Co 27 11.3 9.3 22.4
Mad/% Aad/% Vad/% FCad/%
Ni 28 21.2 11.8 10.5
CF Coal 8.31 22.14 27.48 42.07 Sub-bituminous Cu 29 7.6 17.2 8.2
DFS coal 6.32 7.75 29.66 56.27 Bituminous Zn 30 16.5 26.8 11.1
DLT Coal 7.39 4.92 32.72 54.97 Long flame Zr 40 65.2 134.0 24.1

2
P. Liu et al.
Fig. 1. Schematic diagram of the temperature-programmed experimental device.
for 24 h at 40 ◦ C in a vacuum drying chamber. The dried coal samples
were placed in the program control box for constant temperature
oxidation, and the temperature was set at 30 ◦ C, 50 ◦ C, 70 ◦ C, 100 ◦ C,
120 ◦ C, 150 ◦ C, and 170 ◦ C. Experimental samples were oxidized for 30
min in a dry air atmosphere of 25 mL/min. Then, the samples were
cooled and placed in sealed tubes for later use. The experiment used an
FTIR-650 Fourier transform infrared spectrometer, and the spectrum
experiment used the KBr tablet method to prepare experimental sam­
ples. A precision electronic scale was used to weigh out 1 mg of raw coal
sample and 1 g of dried KBr analysis reagent and ground them in the
sample mill for about 10 min to mix them thoroughly. From this, a mixed
sample of 200 mg was weighed and evenly spread in a 13 mm diameter
mold and pressed at 17 MPa for 1 min into uniform slices for testing. The
sample was scanned 32 times, and the experimental wave number range
is 400 ~ 4000 cm− 1. Before each experiment, a blank background was
collected. The spectral baseline was corrected, and the data obtained
from the experiment were smoothed.
2.5. SEM experiments
In this paper, the TESCAN VEGA COMPACT scanning electron mi­
croscope was used to study the surface morphology of coal particles
before and after citric acid treatment. Before the experiment, the coal
samples (0.180 ~ 0.250 mm) before and after the citric acid treatment
were placed in test tubes, and absolute ethanol was added, and then the
KQ-600KDE ultrasonic instrument was used for ultrasonic dispersion.
After the ultrasonic dispersion was completed, a dropper was used to
drop the sample-ethanol suspension on a clean glass slide. After air-
drying, conductive tape was used to adhere the samples and they were
sprayed gold. And then the samples were placed in the instrument.
3. Analyses of results
3.1. Results of the temperature-programmed experiment
3.1.1. Gas changes before and after inhibition
Gas concentration and O2 consumption can usually be an effective
evaluation index for the inhibition effect [34,35]. Fig. 2 shows the CO,
CO2 production, and outlet O2 concentrations at each reaction stage
(30 ◦ C-170 ◦ C) before and after the three experimental samples were
inhibited by citric acid. The coal samples exhibit a low oxidation level in
3
Fuel 310 (2022) 122268
the first stage (30 ◦ C-50 ◦ C) and do not emit CO. However, as the tem­
perature of coal samples increases progressively, and the concentrations
of CO and CO2 show an increasing trend in the samples before and after
citric acid treatment. Comparing the whole process, the concentrations
of CO and CO2 in raw coal and inhibited samples have similar overall
trends. However, the CO concentration and CO2 concentration in raw
coal are significantly higher than those of inhibited samples, which
shows that citric acid has a certain inhibitory function on the release of
CO and CO2. Starting at 70 ◦ C, the CO2 release from samples treated with
citric acid treatment is much smaller than that from raw coal, and
starting from 85 ◦ C, the CO concentration of samples after citric acid
treatment is much smaller than it. In addition, the inhibiting effect is
particularly obvious after 100 ◦ C. The comparison curve of the three coal
samples shows that the concentration of CO from temperatures of
30–80 ◦ C is relatively low, and the increase is not large, while the
concentrations of CO and CO2 increase steadily during the process from
100 to 150 ◦ C. In addition, the CO and CO2 concentrations of samples
after citric acid treatment are lower than those from raw coal during the
entire process. The above phenomena show that citric acid has a more
significant inhibition effect at 100–150 ◦ C. Furthermore, comparing the
CO2 change curves, the result shows that the inhibition effect of the CF
coal sample is more obvious than that of the other two coal samples.
Fig. 2 shows a substantial rise in O2 consumption from 70 to 150 ◦ C
for each experimental sample. The O2 concentrations for the inhibited
samples are higher than raw coal, indicating that less O2 is consumed for
the inhibited samples. However, with increasing temperature, the coal-
oxygen reaction speed accelerates, and the O2 concentration of experi­
mental samples begins to decrease when the coal samples enter the rapid
oxidation stage, the O2 concentration drops rapidly at approximately
80 ◦ C. At this time, the O2 consumption for the inhibited CF and DLT
samples changes significantly compared with that of the raw coal sam­
ples, but the inhibited DFS coal sample changes slowly. This result shows
that citric acid can inhibit different coal samples to varying degrees.
3.1.2. Crossing point analysis of the change in temperature
With the heat transfer from the oven temperature and interaction of
heating of coal samples through exothermic oxidation produced by O2,
the temperature of the coal increases. The temperature at which the coal
sample has the same temperature as the oven is known as the crossing
point temperature [36–38]. The crossing point temperature indirectly
indicates the critical temperature at which the coal spontaneous
P. Liu et al. Fuel 310 (2022) 122268

Fig. 2. Concentrations of outlet gases before and after treatment with citric acid.

combustion can occur; a lower crossing point temperature indicates a
stronger tendency for coal to spontaneously combust [39].
As shown in Fig. 3, the CF raw coal sample reaches the crossing point
temperature of 150 ◦ C at 240 min, and the inhibited sample reaches
crossing point temperature of 162 ◦ C at 270 min. This result implies that
the crossing point temperature increases by 12 ◦ C with a delay of 30 min
for the inhibited sample of CF coal. DFS raw coal achieves a crossing
point temperature of 153 ◦ C at 245 min, while the inhibited sample
reaches a crossing point temperature of 164 ◦ C at 270 min. This result
implies that the temperature of the crossing point increases by 11 ◦ C

Fig. 3. Schematic diagram of the temperature change at the crossing point before and after citric acid treatment.

4
P. Liu et al.
with a delay of 25 min. DLT raw coal reaches a crossing point temper­
ature of 143 ◦ C at 225 min, and the inhibited sample reaches a crossing
point temperature of 152 ◦ C at 265 min. This result implies that the
temperature of the crossing point increases by 9 ◦ C with a delay of 40
min. This study reveals that compared to the value of raw coal, the
crossing point temperatures of samples after inhibition have increased,
and the time necessary to reach the crossing point temperature has also
delayed, indicating that citric acid has an efficient inhibitory effect on
coal spontaneous combustion.
3.2. TG-DTA experimental results
The Tof DFS coal uses different temperatures because DFS coal has a
lower tendency to spontaneous combustion. The other two coal samples
can enter the burnout stage at approximately 500 ◦ C, while the DFS coal
sample can enter the burnout stage at approximately 600 ◦ C.
3.2.1. Analysis of the TG curves of coal samples
It is shown in Fig. 4 that the thermogravimetric curves of experi­
mental samples before and after citric acid treatment produce similar
trends with the increase in temperature, the mass of experimental
samples shows a tendency of alternating changes.
Using the CF coal sample as an example, the process of heating coal
samples from room temperature to 285 ◦ C is divided into two stages. The
first stage ranges from 30 ◦ C to 150 ◦ C, during which the mass of the CF
sample decreases with increasing temperature. This effect is primarily
due to the evaporation of water in the sample as the temperature rises,
the desorption of primal adsorbed gases (CH4, CO2, etc.) in fissures, and
the release of organic gases produced in low-temperature oxidation. The
TG curve reaches the initial valley at 150 ◦ C, after which the O2 ab­
sorption capacity of the sample increases, the weight of the CF sample
gradually increases, and the TG curve shows a slight rise. At 285 ◦ C, the
mass of the sample reaches the maximum value before pyrolysis. After
285 ◦ C, the CF sample begins to enter the pyrolysis period. During this
period, the aromatic ring structures in the sample are cracked, produc­
ing a large amount of volatiles and heat. The mass of the sample de­
creases rapidly and reaches the ignition point at approximately 350 ◦ C.
Beyond 350 ◦ C, the sample continues to burn, and the rate of the sam­
ple’s weight loss rate rapidly accelerates. At approximately 380 ◦ C,
when the coal-oxygen composite reaction is the most vigorous, the
maximum point of the weight loss rate in the entire reaction process
occurs. When the temperature reaches the burnout temperature of
410 ◦ C, the TG curve tends to flatten, indicating that most of the sub­
stance in the CF sample has been exhausted and that the coal-oxygen
reaction has basically stopped. Comparing the raw coal and inhibited
CF samples, it is found that the mass of the inhibited sample is greater
than that of the raw coal sample under the same temperature conditions,
and its mass has been declining. There is no phenomenon of O2 ab­
sorption or weight gain, and the ignition temperature of the inhibited
Fig. 4. TG curve of raw coal and inhibited samples.
5
Fuel 310 (2022) 122268
sample is 60 ◦ C higher than that of raw coal. The ignition temperatures
of the DLT- and DFS-inhibited samples are 20 ◦ C and 10 ◦ C greater than
those of their associated raw coal counterparts, respectively.
3.2.2. Analysis of the DTA curves of coal samples
As shown in Fig. 5, over the course of the entire heating process, each
coal sample exhibits a reaction process that first absorbs heat and then
releases it. The heat change curve of the inhibited samples is found to be
roughly the same as that of raw coal. As is shown in the figures, the heat
release of the three samples after being inhibited is less than that of raw
coal. Additionally, the temperature points corresponding to the
maximum heat release rate have different degrees of increase than their
raw coal counterparts; the temperature point of the inhibited CF sample
has the most significant increase, followed by the DLT sample, and then
the DFS sample. The heat release of the DLT coal sample decreased the
most, followed by the CF coal sample, and the DFS coal sample had the
smallest change. This result shows that citric acid has varying degrees of
inhibiting effect on coal spontaneous combustion.
3.3. Analysis of the experimental infrared spectroscopy results
To better explain the microscopic inhibition process for spontaneous
coal combustion, FTIR experiments were used to study changes in coal
functional groups before and after citric acid treatment.
Peakfit software was applied to fit the original infrared spectrum of
the experimental samples and divide the peaks. Fourier deconvolution
and Gaussian function methods were used to smooth and separate the
overlapping and interfering spectral peaks to study the functional
groups in the coal samples more accurately. According to previous
studies [40,41], 1500–1850 cm− 1 and 2800–3000 cm− 1 are the two
parts of the wavenumber range. This paper finds accurate positions of
absorption peaks and shoulder peaks corresponding to the original
spectrum through peak and valley positions of the second derivative and
then performed peak fitting processing to analyze the changes and
trends of each functional group quantitatively. Fig. 6 shows the peak
fitting diagram of coal samples after segmentation.
Among the peaks shown, 2955 cm− 1 is the asymmetric vibration of
the methyl group, and 2922 cm− 1 is the asymmetric vibration of the
methylene group; 1710 cm− 1 is the peak assigned to the carboxyl group,
and 1648 cm− 1 is the peak assigned to the carbonyl group. Fig. 7 illus­
trates variations in the percentage of the main functioning groups in raw
coal and inhibited samples as the temperature increases.
As is shown in Fig. 7, as the temperature increases, the quantity of
–CH3 and –CH2- groups in the experimental samples before and after
inhibition gradually decreases and the decrease rate of each coal sample
is faster during the 70 ◦ C − 100 ◦ C process. This result shows that a large
amount of –CH3 and –CH2- participate in the oxidation reaction as the
coal-oxygen recombination reaction proceeds. Compared with the raw
coal, the peak area percentages of –CH3 and –CH2- of the three kinds of
P. Liu et al.
Fig. 5. DTA curve of raw coal and inhibited samples.
Fig. 6. Peak fitting diagram of coal samples after segmentation.
inhibited coal samples decrease slightly with the oxidation rising, and
the trend slows down. This finding shows that the inhibitor reduces the
consumption rate of aliphatic hydrocarbons in the reaction process of
coal, and to a certain extent, the coal spontaneous combustion process is
inhibited.
It can be found that at 30 ◦ C, the amount of –COOH groups in the
experimental samples after citric acid treatment is higher than that
found in raw coal. This may be because the added citric acid molecules
originally contained –COOH groups. As the temperature rises, the
change in –COOH abundance in inhibited coal samples shows a gently
increasing trend compared to the raw coal samples. When the temper­
ature reaches 100 ◦ C, the increase rate of –COOH of the inhibited coal
samples becomes slower. This is mainly because the original –COOH in
the coal starts to participate in the oxidation reaction during the heating
process, consuming the –COOH produced by the reaction of aliphatic
hydrocarbons and oxygen, and at the same time, the original –COOH in
the citric acid is also broken and decomposed. The C = O peak area
percentage in the raw coal samples shows an overall increasing trend
during the oxidation heating process. At 30 ◦ C, the content of C = O
groups in the experimental samples after citric acid treatment is higher
than that in the raw coal samples. Similar to –COOH, this result may be
due to the added citric acid molecules originally containing C = O
groups. With increasing temperature, the abundance of C = O groups in
the raw coal and inhibited coal samples continues to increase. However,
the increase in C = O abundance in the inhibited experimental samples is
smaller than that in the raw coal samples. The curve for the samples
treated with citric acid tends to flatten when the reaction reaches
150 ◦ C. This may be due to the decomposition of citric acid, which does
not participate in the chelation reaction, and the destruction of a large
amount of C = O bonds. Thus, the addition of inhibitors decreases the
6
Fuel 310 (2022) 122268
reaction rate of aliphatic hydrocarbons and O2 and inhibits the gener­
ation of oxygen-containing functional groups.
3.4. Analysis of the SEM experimental results
The micro-morphology of the coal particle surface before and after
the citric acid treatment is shown in Fig. 8. It can be seen from the figures
that the surface of the coal particles of raw coal is attached with abun­
dant mineral particles and many pores. After citric acid treatment, the
surface mineral particles of coal particles are reduced, the surface
structure became smoother, and the pore size is significantly reduced.
This may be due to the reaction of citric acid with mineral particles on
the surface of the coal. And citric acid enters the micropores and small
pores of the coal and reacted with the metal ions in the coal to produce
complexes, resulting in a decrease of the pore size. The decrease of the
pore size prevents the coal from contacting more oxygen, and indirectly
hinders the coal-oxygen recombination reaction, which has an inhibit­
ing effect.
3.5. Oxidation kinetic parameter calculation
To further study the kinetic parameters of the oxidation of coal at low
temperature, especially focus on the activation energy [42,43], the
Arrhenius formula was used to calculate the apparent activation energy
of the experimental samples [44]. Fig. 9 shows the experimental device.
Coal + O2 →mCO + gCO2 + other products
After adding citric acid to the coal, a temperature-programmed
experiment was used to measure the changes in the amount of
consumed O2 and the consumption rate of O2 with the temperature of
P. Liu et al. Fuel 310 (2022) 122268

Fig. 7. The area of main functional groups in coal varying with temperature.

the experimental samples. Using these values, the activation energy of rO2 represents the consumption rate of O2, m3/(m3/s); Vg represents the
the experimental sample was calculated through the Arrhenius formula. airflow rate, m3/s; dCO2 represents the decrease in O2 concentration
With reference to other research [45,46], the following formulas can be after airflow through the dx-thickness coal sample in the tank, %; and x
derived. represents the height of the coal sample in the tank, m.
The consumption rate of O2 is calculated by: Substituting Eq. (1) into Eq. (2) and adding the integral:
rO2 = k0 CO2 exp(− Ea/RT) (1) ∫L ∫ Co
Sk0 exp(− Ea /RT) O2 1
dx = d(− CO2 ) (3)
Vg C O2
where k0 represents the former factor, s− 1; CO2 represents the concen­
0 i
CO
2

tration of O2 in the gas mixture, %; Ea represents the apparent energy of

where L represents the height of the model compound in the tank, m; CiO2
activation, J/mol; R represents the constant of gas, 8.314 J/(mol ⋅K);
and T represents the temperature of coal, K. and CoO2 are the concentrations of O2 in the inlet and outlet airflows in
For these heating experiments, assuming the direction of air flow is the tank, respectively, %.
along the central axis of the coal sample tank, and taking a volume Eq. (3) is then integrated to obtain Eq. (4):
element of thickness dx along any axis, the equation of the consumption Sk0 L Ea Co
rate of O2 is: exp(− ) = − ln( Oi 2 ) (4)
Vg RT CO2
Sdx⋅rO2 = Vg ⋅d(− CO2 ) (2)
The natural logarithm can be taken on both sides of Eq. (4) to obtain:
2
whereSrepresents the cross-sectional area of the coal sample tank, m ;

7
P. Liu et al. Fuel 310 (2022) 122268

Fig. 8. SEM images of raw coal and inhibited samples.

8
P. Liu et al. Fuel 310 (2022) 122268

Fig. 8. (continued).

each experimental sample using fitted curve parameters. From the re­
sults in the table, the apparent activation energies of the inhibited
samples are higher than those of the raw coal samples. The apparent
activation energy for the CF sample rises by 8.11 kJ⋅mol− 1 after citric
acid treatment, compared with the CF raw coal sample, and the apparent
activation energies of DLT and DFS inhibited samples increase by 4.66
kJ⋅mol− 1 and 5.20 kJ⋅mol− 1 respectively. These data demonstrate that
the inhibitor can increase the coal-oxygen reaction activation energy
and that the coal spontaneous combustion can thus be inhibited.

4. Discussion

As a complex solid combustible organic rock, coal contains not only

main elements such as oxygen, hydrogen, carbon, sulfur, and nitrogen
but also a wide variety of other elements. Studies have shown that some
alkali metal compounds and transition metal elements have an obvious
catalytic effect in the gasification reaction of coal, coke, and other
Fig. 9. Schematic diagram of the coal sample tank.
carbonaceous materials. The presence of metal ions, even in small
amounts, may have a major catalytic effect on chemical reactions,
thereby promoting the coal spontaneous combustion [47].
( ( )) ( ) The vacant d orbitals of the transition metal ions in the coal are able
COo 2 SLk0 Ea
ln − ln i
= In − (5) to accept pairs of conjugated bonds and electrons and then become
CO2 Vg RT
empty again [48]. The carboxyl groups in coal are catalyzed and
From Eq. (5), by drawing a linear relationship diagram for decompose into active free radicals, catalytic methyl groups, oxidized
Co hydroxyl groups, and the activation process of the C–H bond can all be
ln(− ln(COi 2 )) ∼ T1, the slope of the straight line can be used to obtain the catalyzed by transition metal ions. Many types of research have revealed
O2

energy of apparent activation of each tested coal sample, and the pre- that the reaction process of metal ions in coal catalyzing the oxidation of
exponential factor k0 can be obtained from the intercept of the line. organic matter is [49]:
Fig. 10 shows the kinetic curve fitting diagrams for the raw coal and (1) C–H bond is activated [50];
inhibited samples. Table 3 displays the apparent activation energy for

9
P. Liu et al. Fuel 310 (2022) 122268

Fig. 10. Kinetic fitting curve of coal samples before and after citric acid treatment.

Table 3
Calculated results of the apparent activation energy.
1
Coal samples Apparent activation energy/kJ⋅mol−

Coal Coal + Citric Acid

CF 42.9 51.01
DFS 44.7 49.90
DLT 64.8 69.46

where [M] refers to metal ions. These metal ions are oxidatively
added to the C–H bond to produce transition metal hydride in­
termediates, thereby changing the reaction path. The metal hydride
intermediate bonds are unstable and easily break to produce active free
radicals, which activate the C–H bond.
(2) Methyl and hydroxyl groups are oxidized [51];
where M refers to metal ions. Carboxyl groups undergo Fenton-like
reactions under the catalysis of metal ions to produce active free
radicals.
Citric acid appears colorless translucent crystals, white particles, or
white crystalline powder. Its chemical name is 3-hydroxy-3-carboxy-
pentanedioic acid, and its molecular formula is C6H8O7. The structural
formula of citric acid is:

where X and R represent groups including H, Cl, NO2, etc. This re­
action can oxidize the hydroxyl group to aldehyde under certain con­
ditions, oxidize the methyl group to a carboxyl group and increase the
activity of the functional group.
(3) Carboxyl groups are cleaved [52]；
One citric acid molecule contains three carboxyl groups and one
alcohol hydroxyl group. Alcohol hydroxyl groups can be substituted
with halogen atoms. The three carboxyl groups can form coordination
bonds with metal ions, coordination reaction can occur, and complexes
with ring structures can be generated.
The process of reacting citric acid reacting with metal ions (denoted
by X) to form a metal chelate is shown below:

10
P. Liu et al.
After metal ions in the coal combine with citric acid, the chelate is
formed through coordination bonds. The d orbital in the transition metal
ion loses the ability to transfer electrons due to the strong coordination
between the ligand and the transition metal ion, thereby increasing the
activation energy and preventing functional groups in the coal from
being activated, which makes the coal oxidation process more difficult
to initiate. It can be concluded by analogy that a metal chelator chelates
with transition metal ions through coordination bonds. This process
weakens the transition metal ion catalysis and increases the activation
energy, thus inhibiting coal spontaneous combustion.
The inhibitory ability of citric acid and other commercial inhibitors
is worth comparing. Deng [53] analyzed the inhibitory effects of three
commercial inhibitors (NH4)2HPO4, Na3PO4 and self-prepared Zn/Mg/
Al-CO3-LDHs. It was found that (NH4)2HPO4 and self-prepared Zn/Mg/
Al-CO3-LDHs can effectively inhibit the coal spontaneous combustion,
but the inhibition ability of Na3PO4 was poor and even promoted the
coal spontaneous combustion. It is difficult to compare citric acid with
them due to the limitation of experimental conditions. However, ac­
cording to the prices of the four inhibitors provided by an authoritative
website [54], a comparative analysis of their economic value can be
carried out. Self-prepared Zn/Mg/Al-CO3-LDHs is expensive and will not
be analyzed here. The citric acid per 100 g is 12.5% lower than
(NH4)2HPO4 and 31.1% lower than Na3PO4. The price of citric acid is
low, and it has a good inhibitory effect on different coal samples. As a
low-cost and environment-friendly inhibitor, citric acid has broad
research and application prospects.
5. Conclusion
The inhibitory effect of citric acid was studied using a number of
experiments, from which the following conclusions were drawn:
1) The concentrations of generated CO and CO2 and consumed O2 from
the coal samples after citric acid treatment decreased compared to
those from the raw coal samples, and the crossing point temperatures
increased.
2) The characteristic point temperatures of the inhibited samples were
higher than those of the raw coal samples, while the rate of weight
loss at the same temperature was smaller.
3) The amounts of –CH3 and –CH2- groups in inhibited coal samples
increased, while the amounts of –COOH and C = O groups decreased
and the pore size of the coal surface decreased after citric acid
treatment.
4) Citric acid coordinates and combines with transition metal ions to
weaken their catalytic activity and increase the activation energy,
thereby having an inhibitory effect on the coal spontaneous
combustion.
CRediT authorship contribution statement
Peiyu Liu: Writing – original draft, Formal analysis, Investigation.
Zenghua Li: Supervision, Conceptualization. Xiaoyan Zhang:
11
Fuel 310 (2022) 122268
Validation. Jinhu Li: Methodology. Guodong Miao: Conceptualization.
Shaodong Cao: Data curation. Song Li: Writing – review & editing.
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.
Acknowledgments
This research was supported by the National Natural Science Foun­
dation of China (No. 52074275) and is gratefully acknowledged. The
support provided to Jinhu Li from National Postdoctoral Program for
Innovative Talents (No. BX2021001), and this support is also gratefully
acknowledged.
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