Вы находитесь на странице: 1из 16

energies

Article
Study on the Low-Temperature Oxidation Law in the
Co-Mining Face of Coal and Oil Shale in a Goaf—A
Case Study in the Liangjia Coal Mine, China
Gang Wang 1,2,3, *, Yue Wang 2 , Lulu Sun 2 , Xiang Song 2 , Qiqi Liu 2 , Hao Xu 2 and Wenzhou Du 2
1 Mine Disaster Prevention and Control-Ministry of State Key Laboratory Breeding Base,
Shandong University of Science and Technology, Qingdao 266590, China
2 College of Mining and Safety Engineering, Shandong University of Science and Technology,
Qingdao 266590, China; sdkdwangyue@163.com (Y.W.); sunsdust@126.com (L.S.);
15764250761@163.com (X.S.); 15764227280@139.com (Q.L.); 15764250244@163.com (H.X.);
duwenzhou-01@163.com (W.D.)
3 Hebei State Key Laboratory of Mine Disaster Prevention, North China Institute of Science and Technology,
Beijing 101601, China
* Correspondence: Gang.Wang@sdust.edu.cn; Tel.: +86-0532-80698100

Received: 18 November 2017; Accepted: 9 January 2018; Published: 11 January 2018

Abstract: The low-temperature oxidation law of coal and rock mass is the basis to study spontaneous
combustion in goafs. In this paper, the low-temperature oxidation laws of coal, oil shale, and mixtures
of coal and oil shale were studied by using laboratory programmed heating experiments combined
with a field beam tube monitoring system. The results from the programmed heating experiments
showed that the heat released from oil shale was less than that from coal. Coal had a lower carbon
monoxide (CO)-producing temperature than oil shale, and the mixture showed obvious inhibiting
effects on CO production with an average CO concentration of about 38% of that for coal. Index gases
were selected in different stages to determine the critical turning point temperature for each stage.
The field beam tube monitoring system showed that the temperature field of the 1105 co-mining face
of coal and oil shale in the goaf of the Liangjia Coal Mine presented a ladder-like distribution, and
CO concentration was the highest for coal and lower for the mixture of coal and oil shale, indicating
that the mixture of coal with oil shale had an inhibiting effect on CO production, consistent with the
results from the programmed heating experiments.

Keywords: coal and oil shale; low-temperature oxidation; programmed heating; goaf; beam tube
monitoring system

1. Introduction
Mine fires are among the most dangerous disasters that affect a safe production in mines.
After mining the working face, the empty space of the mined coal is defined as goaf, where residual
coal is continuously oxidized in the goaf, with flammable gas released and temperature increased,
which can potentially lead to fire in the goaf. According to studies, more than 60% of mine fires in
China are caused by the spontaneous combustion of residual coal in goafs [1,2]. The prevention of fire
in goafs is of great significance for a safe production in mines. Oil shale is a fine-grained sedimentary
rock containing large quantities of organic matter capable of yielding oil upon retorting, with an oil
content of 3.5–30%. When heated above 500 ◦ C in an oxygen-poor environment, it can yield shale
oil, which has a significant role in mitigating the pressure of oil crisis as an alternative to oil energy
in some industrial production [3]. Oil shale is commonly associated with coal, and both coal and oil
shale can be slowly oxidized in goafs resulting in a temperature increase and flammable gases release.
Therefore, the risk of spontaneous combustion exists at the co-mining face of coal and oil shale in

Energies 2018, 11, 174; doi:10.3390/en11010174 www.mdpi.com/journal/energies


Energies 2018, 11, 174 2 of 16

goafs [4]. Meanwhile, when coal and oil shale are mixed, their oxidation behaviors will be mutually
affected by their physical and chemical properties and will thus change, becoming different from those
of coal or oil shale alone. Therefore, the study of the oxidation law in the co-mining face of coal and oil
shale is of great significance to guiding a safe production in coal and oil shale mines.
There is a long history of coal utilization, and the oxidation characteristics of coal have been
studied for a long time, while oil shale research started to develop later. Regarding the oxidation
characteristics of oil shale, scholars have mainly paid attention to the gas and temperature during the
pyrolysis process [5]. Jiang et al. studied the influence of hydrothermal pretreatment on the distribution
of pyrolysis product and oil characteristics [6]. Mohammad Al-Harahsheh et al. investigated the effects
of the mineral content in oil shale on pyrolysis [7]. Miao et al. measured the volatile components
of Daqing oil shale using a thermogravimetric analysis, examined the impact of the temperature
rise rate and of the final temperature of pyrolysis characteristic of the oil shale, and found that final
temperature of pyrolysis was the most important factor influencing the volatile content: the higher the
final temperature of pyrolysis, the higher the volatile content [8]. A. Mumtaz Tugluhan divided the
oxidation reaction into three stages based on the variation law of CO, oxygen, and carbon dioxide (CO2 )
of Turkey oil shale under the air flow rate of 1.5 L/min: namely, low temperature stage, transition stage,
and high temperature stage [9]. Li et al. studied the thermodynamic properties and gas compositions
of bituminous coal and lignite during the co-heating of oil shale using the TG-FTIR coupling technique
(Nicolet™ iS™ 10 FT-IR, Thermo Fisher Scientific, Shanghai, China) and found that the thermodynamic
properties of oil shale were similar to those of bituminous coal at the stage of devolatilization [10].
Furthermore, they analyzed the influence of the oil shale ratio on the volatile components of samples
throughout the experiments.
For the exploration of the oxidation characteristics of residual coal in goafs, field experiments
and laboratory experiments are mainly adopted. Programmed heating is an experimental method in
which the ambient temperature is controlled through constant heat transfer to increase it at a constant
rate under specific initial temperature conditions. With the advantages of its good experiment process
continuity as well as its simple and quick operation, it has been widely used in the spontaneous
combustion of coal, including index gas tests [11,12] and cross-point temperature tests [13,14]. Qin et al.
studied the oxygen consumption rate of pulverized coal in different particle sizes using a self-developed
CSC-B2 programmed heating system (China University of Mining and Technology (Beijing), Beijing,
China) based on the oxygen concentration at the inlet and outlet of the vessel, and obtained an
empirical formula of oxygen consumption [15]. Kucuk et al. investigated the effects of different coal
particle sizes, coal water content, and air humidity on the spontaneous combustion of coal using
a programmed temperature-raising device [16]. Tan et al. analyzed the characteristics of the gases
derived from the spontaneous combustion of coal samples of varying degrees of metamorphism at
different temperature stages, using a programmed heating device, and studied the corresponding
relation between the index gas and the characteristic temperature range [17]. In a real goaf, as the
temperature rises, gas sequestration in coals changes, while coal’s adsorption ability, gas permeability,
and gas sorption affect gas release by coal oxidation [18,19]. The change of gas production in a goaf will
also affect the adsorption and desorption of the coal matrix, resulting in the expansion and contraction
of the coal skeleton and in changes in coal’s internal permeability [20,21], thereby changing coal’s
oxidation characteristics. The fracture characteristics and geometrical characteristics of the field also
affect the oxidation of coal [22]. Because the existing simulation and theoretical derivation are not
enough to directly indicate the oxidation state of coal in a goaf, the simplest method is to directly
observe the temperature and gas variation in a goaf. In field experiments, the method of laying a beam
tube monitoring system is one of the most commonly used means to monitor the oxidation of coal and
rock mass in goafs. The data of temperature, CO, oxygen, and other gases in a goaf obtained by the
beam tube monitoring system can be used for the determination of coal and rock mass oxidation and
the division of three zones [23–25].
Energies 2018, 11, 174 3 of 16

The scholars mentioned above studied the pyrolysis and the oxidation temperature rise properties
of oil shale and coal. However, when there is a co-mining face of coal and oil shale, the interaction
between coal and oil shale causes considerable changes in heat liberation and gas concentration. As for
the results of the direct interaction between coal and oil shale, scholars have not carried out in-depth
research. Therefore, the research described in this paper aims mainly to (1) determine the changes of
temperature and gas concentration of coal, oil shale, and mixtures of coal and oil shale; (2) measure
the temperature and gas composition in goafs on the field using a beam tube monitoring system
and (3) eventually obtain the spontaneous combustion rules of coal and oil shale in goafs related to
low-temperature oxidation. Our laboratory results and on-site monitoring data provide technical
support for fire prevention and extinguishment in the co-mining face of coal and oil shale in goafs.

2. Experiment Device and Process

2.1. Preparation of the Experimenalt Samples


The oil shale and coal wall just exposed at the 1105 co-mining face of coal and oil shale in the
Liangjia Mine was selected. A total of six fresh samples were collected at the upper, middle, and lower
heights, sealed on-site in sealing bags, and sent to the laboratory. When preparing the samples, the
surface oxide layers were first striped, a certain amount of samples were quickly crushed to prevent
exposure to the air at room temperature, sieved out with a particle size of 0.18–0.38 mm, sealed in
sealing bags, placed in a closed container covered with desiccant (we made sure that the desiccant was
not in contact with the samples), dried for 5 h, and stored at room temperature.

2.2. Programmed Heating Experiment Device and Process


The experiment device was composed of three parts: (a) laboratory gas source, (b) programmable
oven, and (c) gas chromatograph, as shown in Figure 1. The laboratory gas source was the QPT-300G
Nitrogen Hydrogen Air Generator from Shanghai Lingxi Instrument Co. Ltd. (Shanghai, China),
in which the air output part consisted of an oil-free compressor and a stainless steel gas tank, and used
a secondary regulator and a three-stage filtration technology to achieve gas stability, high precision
output, as well as perfect automatic drainage protection measures. The air output pressure was
maintained at 0.4 MPa with an adjustable range of 0–0.5 MPa. The output nitrogen and hydrogen
had a purity of >99.999%. During the experiments, the gas chromatograph was first calibrated with
a standard gas, and air was introduced to conduct the experiment. The programmable oven was
a ZRJ-2000 coal spontaneous tendency detector from Beijing Sida Hengtong Technology Co. Ltd.
(Beijing, China). It was supplied with a heater of 1200 W, whose heating power was controlled
by a computer program, and a built-in fan of 1400 r/min to ensure a uniform air temperature in
the furnace. The temperature control precision was ±0.1 ◦ C. The sample tank was a cylindrical
container made of brass material and had an inner diameter of 43 mm, an outer diameter of 48 mm,
an inner height of 100 mm, and an outer height of 105 mm. The actual sample height was about
70 mm. The bottom and top of the sample tank were provided with a gas inlet and outlet, respectively.
The small hole in the center of the sample tank was used to install the temperature sensor contact.
The top of the contact was located at the geometric center of the sample tank. The sample tank was
made of a polytetrafluoroethylene sealing material, which can withstand high temperatures above
350 ◦ C. Inside, the sample tank was equipped with a precision platinum resistance temperature sensor
to monitor the sample temperature and the oven temperature. The gases were analyzed using a
GC9790 Gas Chromatograph manufactured by Fuli instruments Co. Ltd. (Taizhou, China), which
can detect a gas concentration in the range of 8–399 ◦ C, meeting the requirements of this experiment.
Gas concentrations calculated by the gas chromatograph are usually infinite non-cyclic fractions; two
digits after the decimal point were retained as the significant figures.
Energies 2018, 11, 174 4 of 16

Energies 2018, 11, 174 4 of 16

Figure1.1.Programmed
Figure Programmed heating
heating system.
system.

The programmed heating experiments were conducted for coal, oil shale, and mixed coal and
The programmed heating experiments were conducted for coal, oil shale, and mixed coal and
oil shale with a coal to oil shale ratio of 1:0.22 (that is the ratio of coal to oil shale in the goaf in the
oil shale with a coal to oil shale ratio of 1:0.22 (that is the ratio of coal to oil shale in the goaf in the
field experiments) to study the variations of the behaviors of temperature and gas concentration
field experiments) to study the variations of the behaviors of temperature and gas concentration
during programmed heating. In the experiment, 40 g of each sample was placed into the sample tank
during programmed heating. In the experiment, 40 g of each sample was placed into the sample
and covered with a layer of asbestos to filter the air flow and prevent clogging of the gas line. A
tank and covered
previous with a layer
study showed that theof asbestos
reaction rateto filter
rises the
by anairorder
flow of and prevent clogging
magnitude for every of10 the gas in
°C rise line.
A previous study showed that the reaction rate rises by an order of magnitude for every 10 ◦ C rise in
temperature [26]. Consequently, within the allowable temperature range, the same heating rate for
temperature [26].
different sets Consequently,
of experiments within
must the allowable
be strictly guaranteed. temperature
In agreement range,
withthe same heating
relevant literature, rate
thefor
different
heatingsets
rateoffor
experiments mustwas
this experiment be strictly
set at 0.5guaranteed.
°C/min, and Inthe
agreement with relevant
gas composition literature, the
and concentration
heating rate for this experiment was set at 0.5 ◦ C/min, and the gas composition and concentration
were analyzed every 20 min, with the air supply rate set at 50 mL/min [15,17]. The gas flowed into
were
theanalyzed every 20 min,
gas chromatograph, andwith the air
the data supply
were outputratetoset at 50 mL/min
a computer [15,17]. The gas
to be automatically flowed into the
saved.
gas chromatograph, and the data were output to a computer to be automatically saved.
2.3. Analysis of the Experimental Results
2.3. Analysis of the Experimental Results
Based on the experimental results, as shown in Tables 1 and 2, the relationships between
Based on and
temperature the time,
experimental
as well asresults,
betweenasgas shown in Tables
concentration and1 temperature
and 2, the relationships between
were mainly selected
for analysis.
temperature In time,
and field practice,
as well asthe index ofgas
between theconcentration
gas concentration ratio is usually
and temperature wereselected
mainlyforselected
analysisfor
to eliminate
analysis. thepractice,
In field influencetheofindex
the airofflow
the gasrateconcentration
on concentration ratio[27]. Similar selected
is usually to previous research to
for analysis
results, the relationships temperature–time, CO–temperature, CO/CO –temperature,
eliminate the influence of the air flow rate on concentration [27]. Similar to previous research results,
2 C 2H 4/C2H6– the
temperaturetemperature–time,
relationships and C3H8/C2H6–temperature were selected
CO–temperature, CO/CO for 2analysis in this paper
–temperature, C2 H4 [28,29].
/C2 H6 –temperature
and C3 H8 /C2 H6 –temperature were selected for analysis in this paper [28,29].
Table 1. Programmed heating experimental results (CO, CO/CO2).
Table 1. Programmed heating
CO/ppm experimental results (CO, CO/CO
CO/CO22 ).
Temperature/°C
Coal Oil Shale Mixture Coal Oil Shale Mixture
30.00 5.42 CO/ppm 0.00 0.00 0.02 - CO/CO2 -
Temperature/◦ C
40.00 Coal 6.38 Oil Shale 0.00 1.48
Mixture 0.02
Coal - Shale 0.01Mixture
Oil
30.00 50.00 5.42 24.84 0.00 0.00 8.46
0.00 0.06
0.02 - - 0.04 -
40.00 60.00 6.38 52.85 0.0024.06 14.58
1.48 0.09
0.02 0.05 - 0.05 0.01
50.00 70.00 24.84 95.58 0.0042.37 28.86
8.46 0.10
0.06 0.05 - 0.06 0.04
60.00 80.00 52.85 165.22 24.0664.22 45.09
14.58 0.11
0.09 0.070.05 0.08 0.05
70.00 90.00 95.58 223.05 42.37 107.47 28.86
48.54 0.10
0.11 0.090.05 0.08 0.06
80.00 100.00 165.22 309.53 64.22 189.43 45.09
74.16 0.11
0.11 0.130.07 0.11 0.08
90.00 110.00 223.05 408.72 107.47 315.58 48.54
121.09 0.11
0.12 0.170.09 0.14 0.08
100.00 120.00 309.53 432.16 189.43 579.15 74.16
206.00 0.11
0.15 0.200.13 0.17 0.11
110.00 408.72 315.58 121.09 0.12 0.17 0.14
130.00 1215.16 1120.26 486.89 0.17 0.24 0.27
120.00 432.16 579.15 206.00 0.15 0.20 0.17
130.00 140.00 1215.162560.37 1120.262006.52 486.89
1006.25 0.20
0.17 0.260.24 0.24 0.27
140.00 150.00 2560.376530.46 2006.524866.66 1006.25
1910.92 0.26
0.20 0.280.26 0.27 0.24
150.00 160.00 6530.469150.12 8193.66
4866.66 2611.71
1910.92 0.29
0.26 0.310.28 0.27 0.27
160.00 170.00 9150.129956.08 8193.66
14,095.58 2611.71
3620.90 0.29
0.29 0.310.31 0.30 0.27
170.00 180.00 9956.08 14,095.58
11,161.43 14,765.70 3620.90
4570.72 0.29
0.30 0.310.31 0.31 0.30
180.00 190.00 11,161.43 14,765.70
12,505.99 15,730.71 4570.72
5277.36 0.30
0.30 0.310.31 0.33 0.31
190.00 200.00 12,505.99 15,730.71
13,644.21 16,557.66 5277.36
5636.88 0.30
0.31 0.300.31 0.34 0.33
200.00 13,644.21 16,557.66 5636.88 0.31 0.30 0.34
Energies 2018, 11, 174 5 of 16

Table 2. Programmed heating experiment results (C2 H4 /C2 H6 , C3 H8 /C2 H6 ).


Energies 2018, 11, 174 5 of 16
C H4 /C2 H6 C3 H8 /C2 H6
Temperature/ ◦ C 2. Programmed 2heating
Table experiment results (C2H4/C2H6, C3H8/C2H6).
Coal Oil Shale Mixture Coal Oil Shale Mixture
C2H4/C2H6 C3H8/C2H6
110.00
Temperature/°C- 0.00 - - 0.00 -
120.00 0.00 Coal Oil
0.85Shale Mixture
0.00 Coal
0.00 Oil Shale
0.00 Mixture0.00
130.00 110.00 0.51 - 0.00
0.82 0.30- -
0.00 0.000.66 - 0.00
140.00 120.00 0.56 0.00 0.67 0.85 0.00
0.25 0.00
1.01 0.000.77 0.00 0.40
150.00 130.00 0.35 0.51 0.50 0.82 0.30
0.35 0.00
0.68 0.660.67 0.00 0.52
160.00 140.00 0.27 0.56 0.36 0.67 0.28
0.25 0.65
1.01 0.770.70 0.40 0.41
170.00 150.00 0.26 0.35 0.29 0.50 0.32
0.35 0.70
0.68 0.670.73 0.52 0.56
180.00 160.00 0.24 0.27 0.18 0.36 0.31
0.28 0.65
0.65 0.70 0.59 0.41 0.62
190.00 0.24 0.31 0.31 0.63 0.74 0.62
170.00 0.26 0.29 0.32 0.70 0.73 0.56
200.00 0.22 0.30 0.31 0.63 0.75 0.62
180.00 0.24 0.18 0.31 0.65 0.59 0.62
190.00 0.24 0.31 0.31 0.63 0.74 0.62
2.3.1. Temperature 200.00 0.22 0.30 0.31 0.63 0.75 0.62

As shown in Figure 2, the sample temperature changed with time in the programmed heating
2.3.1. Subsection
experiment. The temperature of the programmable oven increased linearly with time (the slope was
As shown in heating
the set programmed Figure 2,rate
the sample
of 0.5 ◦temperature
C/min). Atchanged withstage
the initial time between
in the programmed
0–180 min, heating
the three
experiment. The temperature of the programmable oven increased linearly with ◦ time (the slope was
samples were at the slow oxidation stage with a temperature rise rate of <0.5 C/min. The heating rate
the set programmed heating rate of 0.5 °C/min). At the initial stage between 0–180 min, the three
was the greatest for coal, followed by the mixture, and was the smallest for oil shale. However, the
samples were at the slow oxidation stage with a temperature rise rate of <0.5 °C/min. The heating rate
difference
was thein greatest
heatingfor rate between
coal, followed coal
by and the mixture
the mixture, and was wasthevery subtle,
smallest forand theirHowever,
oil shale. rates of increase
the
were difference
basically the same, indicating that at the initial stage of mixture
in heating rate between coal and the mixture was very subtle, and their ratesoxidation, the heat release was
of increase
mainly from coal and barely from oilthatshale. ◦ C, the
were basically the same, indicating at theWhen the ambient
initial stage of mixture temperature
oxidation, theexceeded
heat release70was
temperature rise rate
mainly from coal ofandoilbarely
shalefrom
decreased first.
oil shale. WhenAfterthe100 min, the
ambient temperature
temperature rise rate
exceeded fellthe
70 °C, for all
three temperature
samples, and rise
oilrate of oil
shale hadshale
thedecreased first. After 100
lowest temperature risemin,
ratethe
andtemperature rise rate fell
the least oxidation for release.
heat all
With three samples,
oxidation rateand oil shale had
increasing, thethe lowest
curve of temperature
the temperature rise rate and thefor
change least
oiloxidation heat release.
shale became steeper at
With oxidation rate increasing, the curve of the temperature change for
180 min, and heat was released from 180 min to 270 min. By contrast, the temperature change curvesoil shale became steeper at
180 min, and heat was released from 180 min to 270 min. By contrast, the temperature change curves
of coal and mixture samples became steeper at 220 min, lagging behind that of oil shale, and heat was
of coal and mixture samples became steeper at 220 min, lagging behind that of oil shale, and heat was
released from 220 min to 300 min, with less heat released than from oil shale.
released from 220 min to 300 min, with less heat released than from oil shale.

250 60

200 40
Temperature in ℃

150 20
20 40 60 80

100
Tank
Coal
50 Oil shale
Mixture

0
0 50 100 150 200 250 300 350 400
Time in min

Figure 2. Relationship between temperature and time in the programmed heating experiment.
Figure 2. Relationship between temperature and time in the programmed heating experiment.
The temperature at which the sample becomes hotter than the oven is referred to as the cross-
The
pointtemperature
temperatureat[30].
which theexceeding
After sample becomes hotter temperature,
the cross-point than the oventhe is sample
referredtemperature
to as the cross-point
rises
rapidly to reach the ignition point, and the coal oxidation in the goaf could become difficult
temperature [30]. After exceeding the cross-point temperature, the sample temperature rises rapidly to control.
The the
to reach cross-point
ignitiontemperature
point, and of each sample
the coal could be calculated
oxidation in the goaffrom the curve,
could and difficult
become was 123.3 to°C control.
for
oil shale, 136.4 °C for the mixture of coal and oil shale, and 137.7 °C for coal. At the
The cross-point temperature of each sample could be calculated from the curve, and was 123.3 ◦ C later stage of the
for oil shale, 136.4 ◦ C for the mixture of coal and oil shale, and 137.7 ◦ C for coal. At the later stage
Energies 2018, 11, 174 6 of 16

of the experiment, the temperature rise trends of the three samples were consistent with the slowed
temperature rise rate, and were basically maintained at 0.5 ◦ C/min. After 180 min, oil shale showed a
significantly greater temperature rise than coal or mixture, and the highest final heat release.
Energies 2018, 11, 174 6 of 16
In summary, the temperature rise curve of the three samples after oxidation showed the following
experiment,
characteristics. the initial
At the temperature rise trends
oxidation stage,ofthethetemperature
three samplesofwere consistent
the three with increased
samples the slowed slowly
with an increase rate smaller than the set value of the programmed heating rate, andshowed
temperature rise rate, and were basically maintained at 0.5 °C/min. After 180 min, oil shale heat release
a significantly greater temperature rise than coal or mixture, and the highest final heat release.
decreased in the order from coal, to mixture of coal and oil shale, and to oil shale. With the increase
In summary, the temperature rise curve of the three samples after oxidation showed the
of the ambient temperature, according to both the turning point of the temperature rise rate and the
following characteristics. At the initial oxidation stage, the temperature of the three samples increased
cross-point temperature,
slowly with an increase the temperature increased
rate smaller than in theoforder
the set value from oil shale,
the programmed to mixture
heating rate, and of coal and
heat
oil shale,release
to coal. At the in
decreased end
theof the from
order low temperature
coal, to mixtureoxidation
of coal andstage, theand
oil shale, heatto release
oil shale.was
Withthethehighest
increase
for oil shale, of the ambient
followed by coaltemperature,
and finally according to both the
the mixture, turning point
indicating that,ofabove 100 ◦ C, the
the temperature rise mixture
rate of
and the cross-point temperature, the temperature
coal and oil shale had slight inhibiting effects on heat release. increased in the order from oil shale, to mixture of
coal and oil shale, to coal. At the end of the low temperature oxidation stage, the heat release was the
highest
2.3.2. Gas for oil shale, followed by coal and finally the mixture, indicating that, above 100 °C, the
Products
mixture of coal and oil shale had slight inhibiting effects on heat release.
Figure 3 shows the curve of the relationship between CO concentration and temperature. At 30 ◦ C,
2.3.2. Gasof
a small amount Products
CO was detected in coal, and, at 40 ◦ C, CO came from the mixture of coal and oil
◦ C, CO
shale. At 60 Figure 3 shows the curve
was also of the in
detected relationship
oil shalebetween
samples, CObut
concentration
the initialandCOtemperature. At 30 of the
concentrations
°C, a small amount of CO was detected in coal, and, at 40 °C, CO came from
three samples were less than 30.00 ppm, with a low growth rate. After 70 C, the concentration ◦ the mixture of coal andgrowth
oil shale. At 60 °C, CO was also detected in oil shale samples, but the initial CO concentrations of the
rate of CO produced from coal and oil shale increased with the temperature, and the concentration
three samples were less than 30.00 ppm,◦with a low growth rate. After 70 °C, the concentration growth
of CO began to increase slowly. At 120 C, the oxidation of coal and oil shale increased, thus the
rate of CO produced from coal and oil shale increased with the temperature, and the concentration
CO concentration
of CO begancurve rose slowly.
to increase steeply,Atand COthe
120 °C, concentration
oxidation of coalincreased dramatically,
and oil shale >10,000.00
increased, thus the CO ppm.
When the coal sample was heated to 160 ◦ C and the oil shale sample to 170
concentration curve rose steeply, and CO concentration increased dramatically, >10,000.00 ppm. ◦ C, CO concentration
showed When
a slowedthe coal sample trend
increase was heated
with tothe160increase
°C and theof oil
theshale sample to 170
temperature, but°C,still
COremained
concentration
at a high
level. CO concentration from oil shale grew more rapidly, resulting in the highest COatconcentration.
showed a slowed increase trend with the increase of the temperature, but still remained a high
level. CO concentration from oil shale grew more rapidly, resulting in the highest CO concentration.
The concentration increase rate of CO from the mixture of coal and oil shale rose to 120 ◦ C and
The concentration increase rate of CO from the mixture of coal and oil shale rose to 120 °C and
◦ C, which was obviously lower than that from coal and oil shale.
decreased to <6000.00
decreased ppmppm
to <6000.00 at 200
at 200 °C, which was obviously lower than that from coal and oil shale.

18,000
Coal ② ③
Oil shale
Mixture
15,000
CO concentration stage
30
① stable stage of coal
CO concentration in ppm

12,000
CO concentration in ppm

① stable stage of oil shale


20 ②
① stable stage of mixture
9,000 ② rapid growth stage of coal
10
② rapid growth stage of oil shale

6,000 ② rapid growth stage of mixture
0
③ slow growth stage of coal
30 40 50 60 ③ slow growth stage of oil shale
3,000 Temperature in ℃
③ slow growth stage of mixture
①①①
0 ② ③

0 20 40 60 80 100 120 140 160 180 200


Temperature in ℃

Figure 3. Relationship between CO concentration and temperature.


Figure 3. Relationship between CO concentration and temperature.
In conclusion, the CO concentration curve showed the following characteristics in the
programmedthe
In conclusion, heating experiment. The
CO concentration curves
curve of the three
showed samples can
the following be divided intointhree
characteristics stages,
the programmed
namely, stable stage, rapid growth stage, and slow growth stage, as shown
heating experiment. The curves of the three samples can be divided into three stages, namely, in Table 3. At the stable stable
stage, the temperature interval of the three samples was the same, and the amount of CO
stage, rapid growth stage, and slow growth stage, as shown in Table 3. At the stable stage, the
concentration was small. CO was first produced from coal, and its concentration was slightly higher
temperature interval
than that ofshale.
from oil the three samples
The three samples was the then
entered same,theand
rapidthe amount
growth stageof COsame
at the concentration
time, and was
small. CO wasamount
a large first produced from coal,
of CO was produced and its
rapidly. Theconcentration
oxidation rate ofwas
coal,slightly
oil shale, higher thansamples
and mixture that from oil
shale. Thefellthree
at 160samples entered
°C, 170 °C, and 190then the rapid growth
°C, respectively, enteringstage at the
the slow same
growth time,
stage. and a large
In contrast amount of
with coal
CO was produced rapidly. The oxidation rate of coal, oil shale, and mixture samples fell at 160 ◦ C,
170 ◦ C, and 190 ◦ C, respectively, entering the slow growth stage. In contrast with coal and oil shale, the
Energies 2018, 11, 174 7 of 16

oxidation rate of the mixture fell at 190 ◦ C, and the CO production rate decreased from 70.67 ppm to
35.95 ppm. Therefore, we believe that 190 ◦ C was the temperature point at which the mixture entered
the slow growth stage. At the slow growth stage, the CO production rate of the mixture tended to be
stabilized, while that of coal and oil shale samples continued to increase. At the rapid growth stage
and the slow oxidation stage, the ratio of the average CO production of the mixture sample to the
coal sample was 38%, and that of the mixture sample to the oil shale sample was 36%, indicating that
Energies 2018, 11, 174
mixing oil shale and coal could inhibit the CO production rate and decrease the total7 ofCO 16
amount
during oxidation.
and oil shale, the oxidation rate of the mixture fell at 190 °C, and the CO production rate decreased
from 70.67 ppm to 35.95 ppm. Therefore, we believe that 190 °C was the temperature point at which
Table
the mixture entered Three
the3.slow sample
growth stages
stage. with
At the respect
slow growthtostage,
CO concentration.
the CO production rate of the
mixture tended to be stabilized, while that of coal and oil shale samples continued to increase. At the
rapid growth
Index stage and the
Sample slowStage/
Stable ◦ C stage,
oxidation Rapid theGrowth
ratio ofStage/ ◦C
the average CO production
Slow ◦C
of the
Growth Stage/
mixture sample to the coal sample was 38%, and that of the mixture sample to the oil shale sample
Coal 30–120 120–160 160–200
was 36%, indicating that mixing oil shale and coal could inhibit the CO production rate and decrease
COtotal COOil
the amount
shale during oxidation.
30–120 120–170 170–200
Mixture 30–120 120–190 190–200
Table 3. Three sample stages with respect to CO concentration.

Index Rapid Growth Stage/°C Slow Growth Stage/°C


Sample Stable Stage/°C
2.3.3. Ratio Indexes for Different
Coal
Samples
30–120 120–160 160–200
CO Oil shale 30–120 120–170 170–200
Figure 4 shows the relationship between the CO/CO2 ratio and the box temperature. The CO/CO2
Mixture 30–120 120–190 190–200
ratio for different samples increased continuously with the temperature. At 30 ◦ C, the ratio could
be obtained
2.3.3.already for both
Ratio Indexes coal and
for Different mixture samples, but not for oil shale. After 60 ◦ C, CO was
Samples
produced from oil shale,
Figure 4 showsand the ratio of
the relationship CO/CO
between could2 ratio
the 2CO/CO be obtained.
and the boxBased on theThe
temperature. trend
CO/CO of 2CO/CO2 ,
the curvesratio for different samples increased continuously with the temperature. At 30 °C, the ratio could be ◦ C and
of the three samples could be divided into three stages, as shown in Table 4. At 30–40
◦ obtained
60–100 C, all samples alreadywerefor both coalslow
at the and mixture
growthsamples, but notatfor
stage, while ◦ C and
oil shale.
40–60 After100–160
60 °C, CO ◦ C,wasall samples
produced from oil shale, and the ratio of CO/CO2 could be obtained. Based on the trend of CO/CO ,
were at the rapid growth stage. The slow stage of oil shale and mixture terminated at 80 ◦ C 2and 90 ◦ C,
the curves of the three samples could be divided into three stages, as shown in Table 4. At 30–40 °C
respectively. At this
and 60–100 °C,stage, the ratio
all samples were of CO/CO
at the 2 was stage,
slow growth the highest
while at for coal,
40–60 followed
°C and 100–160by °C,theall mixture,
and the lowest
samples for wereoilat shale.
the rapidAfter
growthentering
stage. The the rapid
slow stagegrowth stage,
of oil shale the CO/CO
and mixture terminated2 ratio
at 80for°C oil shale
and mixture
and 90increased rapidlyAtand
°C, respectively. this was
stage,the
thehighest for oil2 shale,
ratio of CO/CO was thefollowed,
highest for in turn,
coal, by the
followed by mixture
the and

mixture, and the lowest for oil shale. After entering the rapid growth
coal. At 130 C, the CO/CO2 ratio of the mixture was 0.2674323. This anomalous surge in CO/CO2 stage, the CO/CO 2 ratio for oil

shale and mixture increased rapidly and was the highest for oil shale, followed, in turn, by the
was caused by a dramatically low CO2 production due to an insufficient reaction of a large amount of
mixture and coal. At 130 °C, the CO/CO2 ratio of the mixture was 0.2674323. This anomalous surge
CO produced
in CO/CO from the mixture with oxygen. After that, the CO/CO2 curve of
2 was caused by a dramatically low CO2 production due to an insufficient
the coal
reaction and oil shale
of a large
samples entered
amount ofthe COstable
produced stage,
fromwhile that of
the mixture withthe mixture
oxygen. Aftersample
that, thewas still
CO/CO at the
2 curve of rapid
the coalgrowth
and stage.
After theoil shale samples
mixture enteredover
was heated 190 ◦stage,
the stable C, thewhile
CO/COthat of
2
the
curvemixture
entered sample
the was still
stable at the
stage. rapid
When all the
growth stage. After the mixture was heated over 190 °C, the CO/CO2 curve entered the stable stage.
three samples were at the stable stage, the CO/CO2 ratio stabilized at 0.3 for coal and oil shale, and at
When all the three samples were at the stable stage, the CO/CO2 ratio stabilized at 0.3 for coal and oil
0.35 for the mixture.
shale, and at 0.35 for the mixture.

Coal ② ③③
0.35
Oil shale
0.30 Mixture
CO/CO2 ratio
0.25
① slow growth stage of coal
① slow growth stage of oil shale
0.20
CO/CO2 ratio

① slow growth stage of mixture


② rapid growth stage of coal
0.15 ① ② rapid growth stage of oil shale
② rapid growth stage of mixture
0.10
③ stable stage of coal
③ stable stage of oil shale
0.05
③ stable stage of mixture
① ②
0.00 ③
① ②
20 40 60 80 100 120 140 160 180 200 220
Temperature in ℃
Figure 4. Relationship between the CO/CO2 ratio and temperature for the experimental samples.
Figure 4. Relationship between the CO/CO2 ratio and temperature for the experimental samples.
Energies 2018, 11, 174 8 of 16

Table 4. Three sample stages divided with respect to the CO/CO2 ratio.
Energies 2018, 11, 174 8 of 16
Index Sample Slow Growth Stage/◦ C Rapid Growth Stage/◦ C Stable Stage/◦ C
Table 4. Three sample stages divided with respect to the CO/CO2 ratio.
30–40 40–60
Coal 160–200
Index 60–100Stage/°C Rapid Growth
Sample Slow Growth 100–160
Stage/°C Stable Stage/°C
CO/CO2
Oil shale 30–40
60–80 40–60
80–160 160–200
Coal 160–200
60–100 100–160
CO/CO2 Mixture 30–90 90–190 190–200
Oil shale 60–80 80–160 160–200
Mixture 30–90 90–190 190–200
Figure 5 shows the relationship curve between C2 H4 /C2 H6 and temperature for the experimental
samples. Figure
The 5curve
shows the relationship
could curve between
be mainly divided C2Hstages,
into three 4/C2H6 and temperature
as shown in Tablefor 5.
theThe
experimental
C2 H4 /C2 H6
samples.
ratio of the The
three curve couldfirst
samples be mainly
showed divided
a rapidinto three stage.
growth stages, At
as this
shown in Table
time, the coal5. The C2H4reached
sample /C2H6
ratio
◦ of the three samples first showed
◦ a rapid growth stage. At this
◦ time,
140 C, the oil shale reached 120 C, and the mixture reached 150 C. The C2 H4 /C2 H6 ratio was the the coal sample reached
140 °C,
highest forthe
oiloil shalefollowed
shale, reached by 120coal
°C, and
and then
the mixture reached
the mixture. 150 that,
After °C. Thethe CC22HH4/C 2H6 ratio was the
4 /C2 H6 ratio for coal
highest for oil shale, followed by coal and then the mixture. After that, the
and oil shale began to decrease rapidly, entering into the decline stage. When coal reached 160 C, C 2H4/C2H6 ratio for coal◦

oiland
shaleoil reached
shale began 180to◦ C,
decrease
and the rapidly, entering
mixture reachedinto150
the◦decline stage. When
C, the curves for thecoal reached
three 160 °C,
samples oil
entered
shale reached 180 °C, and the mixture reached 150 °C, the curves for the three samples entered into
into the stable stage. The curve was stabilized at 0.3 for oil shale and the mixture, and at 0.22 for
the stable stage. The curve was stabilized at 0.3 for oil shale and the mixture, and at 0.22 for coal.
coal. According to the experiment, C2 H4 and C2 H6 are all gases produced by oxidation. The index
According to the experiment, C2H4 and C2H6 are all gases produced by oxidation. The index of
of C2 H4 /C2 H6 was defined as the ratio of the C2 H4 content to the C2 H6 content. This index was not
C2H4/C2H6 was defined as the ratio of the C2H4 content to the C2H6 content. This index was not
available for the original coal seams. Using this index, the influence of the air volume and other
available for the original coal seams. Using this index, the influence of the air volume and other
factors
factorscould
couldbebeeliminated.
eliminated.The Thecurves
curves of the three
of the threesamples
samplescouldcouldbebeclearly
clearly divided
divided into
into three
three stages.
stages.
Therefore,
Therefore, the C2H4/C2H6 ratio could be used as an index to determine the temperature variations of of
the C 2 H 4 /C 2 H 6 ratio could be used as an index to determine the temperature variations
coal and
coal andoiloil
shale.
shale.

1.4
Coal
1.2
Oil shale
Mixture
1.0 ① ②
C2H4/C2H6 ratio stage
C2H4/C2H6 ratio

0.8
① rapid growth stage of coal
① rapid growth stage of oil shale
0.6 ① ③
① rapid growth stage of mixture
② descent stage of coal
0.4 ② descent stage of oil shale
③ stable stage of coal
0.2 ③ stable stage of oil shale
② ③ stable stage of mixture

0.0 ① ② ③

100 120 140 160 180 200


Temperature in ℃
Figure 5. Relationship between the C2H4/C2H6 ratio and temperature for the experimental samples.
Figure 5. Relationship between the C2 H4 /C2 H6 ratio and temperature for the experimental samples.

Table 5. Three sample stages divided according to the C2H4/C2H6 andC3H8/C2H6 ratios.
Table 5. Three sample stages divided according to the C2 H4 /C2 H6 and C3 H8 /C2 H6 ratios.
Index Sample Rapid Growth Stage/°C Decline Stage/°C Stable Stage/°C
Index Sample Rapid Growth Stage/◦ C Decline Stage/◦ C Stable Stage/◦ C
Coal 120–140 140–160 160–200
Coal 120–140 140–160 160–200
C2H4/C2H6 Oil shale 110–120 120–180 180–200
C2 H4 /C2 H6 Oil shale 110–120 120–180 180–200
Mixture
Mixture 120–150
120–150 -- 150–200
150–200
Coal
Coal 120–140
120–140 140–150
140–150 150–200
150–200
C3 H8 /C2 H6 Oil shale 120–140 140–150 150–200
C3H8/C2H6 Oil shale 120–140 140–150 150–200
Mixture 120–150 160–160 160–200
Mixture 120–150 160–160 160–200
Energies 2018, 11, 174 9 of 16

Energies 2018, 11, 174 9 of 16

Figure
Figure
6 shows the variation of the C3 H8 /C2 H6 ratio with temperature for the three samples.
Energies 2018,611,
shows
174 the variation of the C3H8/C2H6 ratio with temperature for the three samples. 9The of 16
The CC33HH8/C/C H
8 2H26 ratio
6 ratio of the
of the three
three samples
samples firstfirst presented
presented a rapid
a rapid growthgrowth and tended
and then then tended to be stable.
to be stable.
Before ◦ C, the ratios for the three samples were all at the rapid growth stage. At 140–150 ◦ C, the
140Figure
Before 140 °C,6 shows
the ratios thefor
variation
the three of the C3H8/C
samples 2H6 all
were ratio
at with temperature
the rapid for theAt
growth stage. three samples.
140–150 The
°C, the
ratiosCof3H8coal
ratios /C
of2H and
6 ratio
coal andoilofoil
shale
the were
three
shale ininthe
samples
were descent
thefirst stage.aHowever,
presented
descent stage. However,
rapid growth there
there waswas
and then atended
significant
a significant to lag period
lagbeperiod
stable.
Before
(150–160
(150–160 ◦ C)
140for°C,
°C) for
thethe
the ratios for
mixture
mixture atthe
atthe three
the samples
descent
descent were
stage.
stage. Atall
At at stage,
this
this the rapid
stage, thegrowth
the CC3H stage.
/C82/C HAt
H6 2ratio 140–150
of °C,
theofoilthe theshale
shale
38H 6 ratio oil
and the mixture of coal and oil shale decreased similarly, but much less than that of coal. After 150 ◦ C,
ratios
and the of coal
mixture and
of oil
coal shale
and were
oil shalein the descent
decreased stage.
similarly,However,
but much there
less was
than a significant
that of coal. lag
After period
150
(150–160
°C,
the ratio the °C)of
of ratio
coal for
coal
tended the mixture
tended
to to beat stabilized
the descent
be stabilized at stage.
at 0.62, 0.62, At to
thisthat
similar
similar tostage,
that thethe
of
of the C3mixture.
H8/C2HAccording
mixture. 6 ratio of theto
According oilTable
to shale5, the
Table
5,and
the the mixture
turning point ofvalues
coal and oil different
of the shale decreased
stages cansimilarly, but much
be obtained. less than
Therefore, that to
similar of the
coal.
C2After
H4/C2H 150
turning point values of the different stages can be obtained. Therefore, similar to the C2 H4 /C2 H66 ratio,
°C, the
ratio, theratio
C3Hof 8/Ccoal tended
2H6 ratio to bealso
could stabilized
be usedatas0.62, similartotodetermine
an index that of thethe mixture.
oxidationAccording to Table
of coal and oil
the C3 H8 /C2 H6 ratio could also be used as an index to determine the oxidation of coal and oil shale.
5, the turning point values of the different stages can be obtained. Therefore, similar to the C2H4/C2H6
shale.
ratio, the C3H8/C2H6 ratio could also be used as an index to determine the oxidation of coal and oil
shale. ① ②② ③③③
1.0
Coal
① ②② ③③③
Oil shale
1.0
0.8 Mixture
Coal
Oil shale
0.8 C3H8/C2Mixture
H6 ratio
H /C2H6 ratio

0.6
① rapid growth stage of coal
C3growth
① rapid H8/C2H stageratio
of oil shale
3 8 ratio

6
0.6
0.4 ① rapid growth stage of mixture
① rapid growth stage of coal
② descent stage of coal
6

① rapid growth stage of oil shale


C3H8/CC2H

② descent stage of oil shale


0.4 ① rapid growth stage of mixture
0.2 ② descent stage of mixture
② descent stage of coal
③ stable stage of coal
② descent stage of oil shale
③ stable stage of oil shale
0.2 ② descent stage of mixture
0.0 ① ③ stable stage of mixture
① ② ③ stable stage of coal
③ stable stage of oil shale
0.0 120 ①140 160 180 200 ③ stable stage of mixture
① ②
Temperature in ℃
120 140 160 180 200
Figure 6. Relationship between the C3H8/C2H6 ratio and temperature for the experimental samples.
Temperature
Figure 6. Relationship between the C3 H8 /C2 H6in ℃ and temperature for the experimental samples.
ratio
3. FieldFigure
Experiment
6. Relationship between the C3H8/C2H6 ratio and temperature for the experimental samples.
3. Field Experiment
3.1. Introduction
3. Field of the Field
Experiment
3.1. Introduction of the Field
The Liangjia Coal Mine is located in Longkou City of Shandong Province in China, as shown in
3.1. Introduction of the Field
Figure 7. The 1105
The Liangjia Coalworking
Mine is face was designed
located in Longkoufor mining theShandong
City of seam of Coal1 Oil shale2.
Province The working
in China, as shown in
seam
Figure The aLiangjia
7. had
The 1105 Coal
thickness of Mine
working faceiswas
4.04~4.23 located in an
Longkou
m, designed
with average City of Shandong
of 4.15
for mining m. The
the seam Province
upper
of layer,in
Coal1 China,
Coal1,
Oil as ashown
had
shale2. in
simple
The working
Figure 7.
structure, The 1105
without working
or, face
occasionally, was designed
with a layer for
of mining
gangue.the seam
This of
layer Coal1
had a Oil shale2.
thickness
seam had a thickness of 4.04~4.23 m, with an average of 4.15 m. The upper layer, Coal1, had a simple The working
0.66~0.81 m,
seamanhad
with a thickness
average of 0.74ofm.4.04~4.23 m, with anOil
The middle average ofUpper2,
4.15 m. had
The aupper layer,ofCoal1, had m.a simple
structure, without or, occasionally, with alayer,
layer ofshale2
gangue. This layer thickness
had 2.15~2.30
a thickness 0.66~0.81 with
m, with
structure,
an average without
of 2.24 m.or,The
occasionally,
lower layer,with
Oil2a Upper1,
layer of had
gangue. This layer
a thickness had a thickness
of 1.10~1.30 m. with 0.66~0.81
an average m,
an average of 0.74 m. The middle layer, Oil shale2 Upper2, had a thickness of 2.15~2.30 m. with an
ofwith
1.17an
m.average of 0.74 m. The middle layer, Oil shale2 Upper2, had a thickness of 2.15~2.30 m. with
average of 2.24 of
an average m.2.24
The m.lower layer,
The lower Oil2Oil2
layer, Upper1,
Upper1, had
hadaathickness of1.10~1.30
thickness of 1.10~1.30 m.m. with
with an average
an average
of 1.17 m.
of 1.17 m.

Figure 7. Location of the Liangjia Coal Mine.

Figure 7. Location of the Liangjia Coal Mine.


Figure 7. Location of the Liangjia Coal Mine.
Energies 2018, 11, 174 10 of 16
Energies 2018, 11, 174 10 of 16

The roof
roofofofthethe
11051105
working face contains
working oil-containing
face contains mudstones,
oil-containing which belong
mudstones, to mudstones
which belong to
with noncombustible, evenly distributed gray matter, and 13.28 m thick siltstones.
mudstones with noncombustible, evenly distributed gray matter, and 13.28 m thick siltstones. The 1105 working
The
face
1105isworking
a 1406.4 face
m long
is amonoclinic structure
1406.4 m long in the mining
monoclinic direction
structure in thewith an average
mining directionhorizontal
with an distance
average
of 184.6 m,distance
horizontal average of of 9◦m,
dip184.6 . Itaverage
strikes NEdip and
of 9°.tends to SE.NE
It strikes The whole
and tendsworking facewhole
to SE. The is a co-mining
working
face of coal and oil shale. Because of the limitations of the mining angle and the geological
is a co-mining face of coal and oil shale. Because of the limitations of the mining angle and the structure,
residual
geological oilstructure,
shale was left in oil
residual theshale
goaf was
at the
leftintake
in theend
goafofatthe
the co-mining
intake end working face, whereas
of the co-mining working in
the
face,middle
whereas of the
in working
the middle face,
ofthe
theamount
working of residual
face, thecoal of coal1
amount increasescoal
of residual progressively from the
of coal1 increases
intake end to the
progressively return
from the end,
intakeand,
endthus, there
to the is a large
return end, amount of residual
and, thus, there is coal at the
a large returnofend
amount of the
residual
working
coal at theface.
return end of the working face.

3.2. Field Experiment


3.2. Field Experiment
The
The method
method ofof burying
burying aa beam
beam tube
tube monitoring
monitoring system
system inin the
the experimental
experimental field
field was
was adopted.
adopted.
In
In brief, after the temperature sensor and the beam tube were placed at the five measuring points of
brief, after the temperature sensor and the beam tube were placed at the five measuring points of
the
the working
working face,
face, as
as the
the working
working face
face advanced,
advanced, the
the temperature
temperature sensor
sensor and
and the
the beam
beam tubetube would
would
gradually
gradually bebe buried in the
buried in the goaf. The protection
goaf. The protection of
of the
the outer
outer steel
steel pipe
pipe ensured
ensured thethe normal
normal use use of
of the
the
beam tube and that the temperature measuring tube collected data at the airway. The
beam tube and that the temperature measuring tube collected data at the airway. The air sample was air sample was
extracted
extracted through
throughthetheextraction pipes
extraction and sent
pipes andtosent
the gas
to chromatograph for analysis.for
the gas chromatograph The temperature
analysis. The
variation in the goaf was measured by the buried temperature sensors. Figure 8 shows
temperature variation in the goaf was measured by the buried temperature sensors. Figure 8 shows the layout of
the measuring points for the 1105 working face.
the layout of the measuring points for the 1105 working face.

Figure
Figure 8.
8. Schematic
Schematic diagram
diagram of
of the
the 1105
1105 working
working face measuring points.
face measuring points.

According to the specific field conditions, five measuring points were equidistantly spaced from
According to the specific field conditions, five measuring points were equidistantly spaced from
the air intake end to the return end. Among them, three were arranged in the central part and the
the air intake end to the return end. Among them, three were arranged in the central part and the
other two were arranged at the inlet and outlet of the airway, respectively. The locations of the five
other two were arranged at the inlet and outlet of the airway, respectively. The locations of the five
measuring points were as follows: #1 measuring point was set at the junction of the intake airway
measuring points were as follows: #1 measuring point was set at the junction of the intake airway and
and the working face to monitor oil shale; #2, #3, #4 measuring points were located in the middle of
the working face to monitor oil shale; #2, #3, #4 measuring points were located in the middle of the
the goaf to measure the mixture of coal and oil shale; #5 measuring point was set at the junction of
goaf to measure the mixture of coal and oil shale; #5 measuring point was set at the junction of the
the return airway of the working face to monitor coal.
return airway of the working face to monitor coal.
3.3. Analysis of the Experimental Data
3.3. Analysis of the Experimental Data
Because the temperature measurement wire and beam tube of the #3 measuring point were
Because the temperature measurement wire and beam tube of the #3 measuring point were
damaged during the transfer of the hydraulic support, data from #1, #2, #4, and #5 measuring points
damaged during the transfer of the hydraulic support, data from #1, #2, #4, and #5 measuring points
were collected and analyzed. The curve, as shown in Figure 9, was made according to the available
were collected and analyzed. The curve, as shown in Figure 9, was made according to the available
experimental data. When the measuring points were 95.2 m from the working face, the temperature
experimental data. When the measuring points were 95.2 m from the working face, the temperature
values at these measuring points in the goaf showed a significant decline process and the gases
values at these measuring points in the goaf showed a significant decline process and the gases tended
tended to be stable. In this paper, the low-temperature oxidation law of coal and oil shale was studied
to determine the variation of the behaviors of high temperature zones and gas concentration in the
goaf. Therefore, data collection was stopped after 95.2 m.
Energies 2018, 11, 174 11 of 16

to be stable. In this paper, the low-temperature oxidation law of coal and oil shale was studied to
determine
Energies 2018,the variation of the behaviors of high temperature zones and gas concentration in the
11, 174 11goaf.
of 16
Energies 2018, 11, 174 11 of 16
Therefore, data collection was stopped after 95.2 m.
The overview of the temperature distribution in the goaf is shown in Table 6. Figure 10 displays
The overview of the temperature distribution in the goaf is shown in Table 6. Figure 10 displays
the measured temperature results across the working face in aa three-dimensional
three-dimensional color-coded
color-coded surface
the measured temperature results across the working face in a three-dimensional color-coded surface
plot of temperature through time and distance from from the
the working
working face.
face.
plot of temperature through time and distance from the working face.
Table
Table 6. Overview of the temperature distribution in the goaf.
Table 6. Overview of the temperature distribution in the goaf.
Measuring Initial Highest Amplitude of Temp Distance of Highest Temp Location
Measuring Initial
Measuring Initial Highest
Highest Amplitude of
Amplitude of Temp
Distance of Highest
Distance Temp Location
of Highest Temp Location
Point Point Temp (°C)(◦ C) Temp
Temp Temp(°C)
(◦ C) TempRise
Rise ((°C)
◦ C) from from the Working
the Working Face (m)Face (m)
Point Temp (°C) Temp (°C) Rise (°C) from the Working Face (m)
1# 21.6 29.4 7.8 80.8
1# 1# 21.6 21.6 29.4
29.4 7.87.8 80.8 80.8
2# 2# 25 25 35.2
35.2 10.2
10.2 77.2 77.2
2# 25 35.2 10.2 77.2
4# 4# 25.125.1 34.1
34.1 9 9 73.6 73.6
4# 5# 25.126.4 34.1
37.8 11.4 9 77.2 73.6
5# 26.4 37.8 11.4 77.2
5# 26.4 37.8 11.4 77.2

40
40 1# measuring point
38 1# measuring point
2# measuring point
38 2# measuring point
4# measuring point
36 4# measuring point
36 5# measuring point
34 5# measuring point
34
Temperatureinin℃℃

32
32
30
Temperature

30
28
28
26
26
24
24
22
22
20
20 0 10 20 30 40 50 60 70 80 90 100
0 10 20 30 40 50 60 70 80 90 100
Distance from the working face in m
Distance from the working face in m
Figure
Figure 9.
9. Temperature
Temperature curve
curve for
for #1,
#1, #2,
#2, #4,
#4, #5
#5 measuring
measuring points.
points.
Figure 9. Temperature curve for #1, #2, #4, #5 measuring points.

Figure 10. Cloud picture of the actual temperatures in the goaf.


Figure
Figure 10.
10. Cloud
Cloud picture
picture of
of the
the actual
actual temperatures in the goaf.

In the initial measurement, the starting temperature was the highest at the #5 measuring point
In the initial measurement, the starting temperature was the highest at the #5 measuring point
for coal and the lowest at the #1 measuring point for oil shale. This may be due to the fact that the air
for coal and the lowest at the #1 measuring point for oil shale. This may be due to the fact that the air
flowing through the work surface brought the heat from the coal seam into the return airway,
flowing through the work surface brought the heat from the coal seam into the return airway,
increasing the temperature at the #5 measuring point. However, with the advancement of the
increasing the temperature at the #5 measuring point. However, with the advancement of the
working face, the effects of the temperature of the fresh airflow and the initial temperature of coal
working face, the effects of the temperature of the fresh airflow and the initial temperature of coal
and rock mass on the temperature of the goaf gradually decreased. Thus, the temperature rise in the
and rock mass on the temperature of the goaf gradually decreased. Thus, the temperature rise in the
goaf can be regarded as the heat released by the oxidation of coal and rock mass. In order to study
goaf can be regarded as the heat released by the oxidation of coal and rock mass. In order to study
Energies 2018, 11, 174 12 of 16

In the initial measurement, the starting temperature was the highest at the #5 measuring point
for coal and the lowest at the #1 measuring point for oil shale. This may be due to the fact that the
air flowing through the work surface brought the heat from the coal seam into the return airway,
increasing the temperature at the #5 measuring point. However, with the advancement of the working
face, the effects of the temperature of the fresh airflow and the initial temperature of coal and rock
mass on the temperature of the goaf gradually decreased. Thus, the temperature rise in the goaf can be
regarded as the heat released by the oxidation of coal and rock mass. In order to study the oxidation
heat release behaviors of coal, oil shale, and their mixture, the amplitude of the temperature rise at
each measuring point was analyzed to determine the amount of heat release. In the range of 31 m from
the working face, the porosity was high since the collapse material in the goaf was not compacted,
and air leakage took away part of the heat, so that an effective heat storage environment could not
be formed, resulting in a slow temperature rise for various measuring points in the goaf. When the
distance from the working face exceeded 31 m, the temperature increased rapidly, and the amplitude
of the temperature rise at the #5 measuring point for coal was the largest, with the temperature rise
rate higher than that at the measuring points for mixture and oil shale. The measuring point for oil
shale had the smallest temperature rising rate with minimal heat release. The heat release from the
mixture was between those from coal and oil shale. The temperatures at the mixture measuring points
#2 and #4 were basically the same before 45 m. After 45 m, the #2 temperature measuring point near
oil shale slightly exceeded the #4 measuring point near coal. Our analysis suggested that oil shale
may slightly promote the cooling of coal and played a catalyst role. During the measurement, the coal
measuring point had the highest amount of heat release and the highest temperature point of 37.8 ◦ C
in the goaf. The high-temperature area was 77–80 m away from the working face in the whole goaf.
The temperature was the highest for the residual coal points, followed by the mixture points of coal
and oil shale, and the lowest for the oil shale points. Therefore, the temperature in the goaf gradually
increased from the end of the oil shale to the coal sample and showed a ladder-like distribution.
Figure 11 shows the relationship of CO concentration to the distance. For the first detection,
CO was already detected at the measuring points for coal and the mixture, but not for oil shale.
With the advance of the working face, CO concentration increased rapidly for coal and the mixture,
reaching the peak values of: 36.00 ppm at #2 measuring point which was 64.6 m away from the working
face; 44.00 ppm at #4 measuring point which was 73.6 m away from the working face; 80.00 ppm
at #5 measuring point, which was 70.6 m away from the working face. The higher the amount of
the remaining coal, the higher the CO peaks. CO was basically not detected for oil shale with only
occasional CO fluctuations. Considering the finding from the programmed heating experiment that no
CO was produced from oil shale by oxidation below 40 ◦ C, it is speculated that CO came from other
locations to the oil shale measuring points because of the airflow in the goaf. For the mixture sample
in the goaf, when the distance was >65 m, CO concentration was obviously higher at the #4 measuring
point than at the #2 measuring point. This was probably due to the fact that the #4 measuring point
was closer to the coal and contained a larger proportion of coal in the mixture, therefore producing
more CO. A high concentration of CO was mainly detected in the area from 61.6 m to 80.8 m from
the working face in the goaf. For the peak values, CO concentration was the highest at the measuring
points for coal and the lowest at the measuring points for the mixture.
sample in the goaf, when the distance was >65 m, CO concentration was obviously higher at the #4
measuring point than at the #2 measuring point. This was probably due to the fact that the #4
measuring point was closer to the coal and contained a larger proportion of coal in the mixture,
therefore producing more CO. A high concentration of CO was mainly detected in the area from 61.6
m to 80.8
Energies m from
2018, 11, 174the working face in the goaf. For the peak values, CO concentration was the highest
13 of 16
at the measuring points for coal and the lowest at the measuring points for the mixture.

120
1# measuring point
2# measuring point
100 4# measuring point
5# measuring point

CO concentratioon in ppm
80

60

40

20

0 20 40 60 80 100
distance from working face in m

Figure
Figure 11.
11. CO
CO concentration
concentration for#1,
for#1, #2,
#2, #4,
#4,#5
#5measuring
measuringpoints.
points.

4. Discussion
In this paper, the 1105 co-mining face of coal and oil shale at the Liangjia Coal Mine in Shandong
Province of China was chosen as the object to study, and the low-temperature oxidation laws of
coal and oil shale were obtained by comparing the results from the laboratory programmed heating
experiments and the actual field measurements.
When the selected coal and oil shale samples were at the initial low-temperature oxidation stage
in the programmed heating experiment, the three tested samples were all at a slow oxidation stage,
with the temperature rise rate lower than that set in the programmed heating experiment, and their
temperatures were lower than the oven temperature. The amount of heat released from oil shale was
less than that from coal at the initial oxidation stage. Since different coal mines have different ambient
thermal states, ventilation, mining time, and coal and oil shale properties, as well as rubbles with
different porosity and permeability in the goaf, we chose the co-mining face of coal and oil shale at
the Liangjia Coal Mine as the research object. Through the field beam tube monitoring system in the
goaf, it was found that the temperature at various measuring points never exceeded 38 ◦ C, which
corresponds to the low-temperature oxidation in the programmed heating experiment. Among the five
measuring points, the temperature was the lowest at the #1 measuring point and the highest at the #5
measuring point. This was because coal content was the lowest at the #1 measuring point, higher at the
#2 and #4 measuring points, and the highest at the #5 measuring point. The initial temperatures from
field monitoring are consistent with those from the programmed heating experiment. According to the
programmed heating experiment, it was found that, when the ambient temperature exceeded 85 ◦ C,
the acceleration of the temperature rise rate increased and the cross-point temperature was reached for
oil shale, followed by the mixture and then coal, and the final temperature was the highest for oil shale,
followed by coal, and the lowest for the mixture, indicating that at the end of the low-temperature
oxidation, if cooling measures were not taken timely for the goaf of the co-mining face of coal and oil
shale, the temperature of oil shale would rapidly increase and reach the highest temperature, easily
leading to goaf fires. The fire risk is the second highest for coal and the lowest for mixed coal and oil
shale because there is a slight mutual suppression effect on heat liberation in mixed coal and oil shale.
According to the programmed heating experiment, it was found that there were three stages for
both gas concentrations and their ratios. For CO, the slow growth phase of the three samples was
the same. However, the coal sample had a lower initial CO producing temperature than the oil shale
sample, and produced the highest amount of CO. The oil shale had the highest initial CO producing
temperature. The concentration of CO produced by the mixture of coal and oil shale was the lowest,
Energies 2018, 11, 174 14 of 16

with an average of 38% of that produced by coal, because of the suppression effect of the mixture on
CO production. These results combined with those obtained from the field beam tube monitoring
system, indicated that the residual coal was the main component at the #5 measuring point, and thus,
at this point, CO was produced first, and its concentration increased rapidly and was the highest in
the goaf. Oil shale was the main component at the #1 measuring point, and at this point CO was not
produced because the temperature did not reach the CO production temperature point. There was a
slight CO fluctuation due to the airflow distribution in the goaf. Mixed coal and oil shale were the
main components at #2 and #4 measuring points. At these points, the average CO concentration was
only 46% of that at the measuring points for coal because of the mutual inhibiting effect of coal and oil
shale on CO production.
Based on the concentration ratio of various gases, several critical temperature points could be
determined. As shown in Tables 3–5, a rapid increase of the CO/CO2 ratio indicated that the oxidation
temperature for oil shale, mixture, and coal had reached 80 ◦ C, 90 ◦ C, 40 ◦ C or 100 ◦ C, respectively.
When the temperature exceeded 110 ◦ C, the C2 H4 /C2 H6 ratio for oil shale presented a rapid growth
and, at 120 ◦ C, it showed a decline trend. When the C3 H8 /C2 H6 ratio increased rapidly, coal, oil shale,
and mixture had reached 120 ◦ C. At 140 ◦ C, the ratios of C3 H8 /C2 H6 of coal and oil shale declined at
the same time. The small fluctuation of the C3 H8 /C2 H6 curve suggested that coal and oil shale had
both reached 150 ◦ C. When, above 160 ◦ C, the CO/CO2 ratio of coal changed from rapid growth to
slow growth, at the same time the C2 H4 /C2 H6 curve had been almost stable, and the C3 H8 /C2 H6
ratio of the mixture tended to be stable. The CO curve and the CO/CO2 curve for oil shale changed
from rapid growth to slow growth at 160 ◦ C and 170 ◦ C, respectively. At 180 ◦ C, the C2 H4 /C2 H6
curve slowed the decline trend, entering the stable stage. After the mixture of coal and oil shale
reached 190 ◦ C, the growth rate of the CO/CO2 ratio decreased, with a transition from fast growth to
slow growth.

5. Conclusions
The programmed heating experiment showed that when coal was at the initial stage of
low-temperature oxidation, the amount of heat release was mostly from coal, followed by the mixture
of coal and oil shale, and then by oil shale. The field experiment showed that the temperature field in
the goaf of a co-mining face of coal and oil shale had, generally, a ladder-like distribution, and that the
temperature was the highest for the residual coal followed by the mixture, and the lowest for oil shale.
If there was a continuous thermal storage environment in the goaf, heat release was mainly from oil
shale; and at high ambient temperature, heat release was basically the same for the mixture and coal.
According to the programmed heating experiment, if no measures were taken, there would be high
temperature points at the location of oil shale.
The CO concentration in the goaf at the time of co-mining of coal and oil shale was analyzed.
CO was first produced at the place of residual coal in the goaf with the highest concentration, and
oil shale had a high CO generation temperature. When coal was mixed with oil shale, CO was first
produced from the coal in the mixture. However, mixing coal and oil shale eventually inhibited CO
production from both. Actually, the field measurements showed that the average CO concentration at
the measuring points for the mixture of coal and oil shale was 46% of that for coal. This inhibition of
CO production was more significant beyond the point of initiation of rapid heating and CO generation,
when control becomes difficult.
The gas compositions during low-temperature oxidation of coal, oil shale, and mixture were
analyzed based on the programmed heating experiment. The curves of the indexes, namely, CO,
CO/CO2 , C2 H4 /C2 H6 and C3 H8 /C2 H6 , were analyzed and divided into different stages, and the
turning points of each index were determined. According to those turning points, the oxidation stages
of coal and oil shale were established.
Energies 2018, 11, 174 15 of 16

In this study, we only investigated the face of the Liangjia Coal Mine in China. In goafs with
different geological conditions and different coal-to-oil shale stoichiometry, the characteristics of the
oxidation and the interaction mechanisms between coal and oil shale need to be further explored.

Acknowledgments: The work presented in this paper was supported by the National Key Research and
Development Program of China (Project No. 2017YFC0805201), the National Natural Science Foundation of China
(Project No. 51674158), the Taishan Scholar Talent Team Support Plan for Advantaged & Unique Discipline Areas,
the Source Innovation Program (Applied Research Special-Youth Special) of Qingdao (Project No. 17-1-1-38-jch),
the Open Fund of Hebei State Key Laboratory of Mine Disaster Prevention (Project No.KJZH2017K10), and the
Shandong University of Science and Technology Research Fund (Project No. 2015JQJH105). In addition, thanks
are due to related people at the Liangjia coal mine in China. It is because of their support, that the work described
in this paper could be successfully completed.
Author Contributions: Gang Wang and Yue Wang conducted the main work and wrote the paper; Lulu Sun
took part in laboratory experiments and designed the field tests; Xiang Song and Qiqi Liu carried out laboratory
experiments; Hao Xu and Wenzhou Du finished the field experiment and the related data analysis. They all
provided insightful suggestions and revised the paper.
Conflicts of Interest: The authors declare no conflict of interest. The founding sponsors had no role in the design
of the study; in the collection, analyses, or interpretation of the data; in the writing of the manuscript, and in the
decision to publish the results.

References
1. Liang, Y.-T.; Luo, H. Current situation and development trend for coal mine fire prevention & extinguishing
techniques in China. J. China Coal Soc. 2008, 33, 126–130.
2. Song, J.; Littke, R.; Weniger, P.; Ostertag-Henning, C.; Nelskamp, S. Shale oil potential and thermal maturity
of the lower toarcian posidonia shale in NW Europe. Int. J. Coal Geol. 2015, 150, 127–153. [CrossRef]
3. Aboulkas, A.; El Harfi, K. Study of the kinetics and mechanisms of thermal decomposition of Moroccan
Tarfaya oil shale and its kerogen. Oil Shale 2008, 25, 426–443. [CrossRef]
4. Dyni, J.R. Geology and resources of some world oil-shale deposits. Oil Shale 2003, 20, 193–253.
5. Wang, Q.; Sun, B.; Liu, H.; Bai, J.; Xiao, G. Analysis of mineral behavior during pyrolysis of oil shale. J. Fuel
Chem. Technol. 2013, 41, 163–168.
6. Jiang, H.; Deng, S.; Chen, J.; Zhang, M.; Li, S.; Shao, Y.; Yang, J.; Li, J. Effect of hydrothermal pretreatment
on product distribution and characteristics of oil produced by the pyrolysis of Huadian oil shale.
Energy Conver. Manag. 2017, 143, 505–512. [CrossRef]
7. Al-Harahsheh, M.; Al-Ayed, O.; Robinson, J.; Kingman, S.; Al-Harahsheh, A.; Tarawneh, K.; Saeid, A.;
Barranco, R. Effect of demineralization and heating rate on the pyrolysis kinetics of Jordanian oil shales.
Fuel Process. Technol. 2011, 92, 1805–1811. [CrossRef]
8. Miao, Z.; Wu, G.; Li, P.; Meng, X.; Zheng, Z. Investigation into co-pyrolysis characteristics of oil shale and
coal. Int. J. Mining Sci. Technol. 2012, 22, 245–249. [CrossRef]
9. Tuğluhan, A.M.; Mehmetoğlu, M.T.; Bağcı, S. Oxidation kinetics of a Turkish oil shale. Fuel Process. Technol.
1991, 29, 231–240. [CrossRef]
10. Li, S.; Ma, X.; Liu, G.; Guo, M. A TG–FTIR investigation to the co-pyrolysis of oil shale with coal. J. Anal.
Appl. Pyrolysis 2016, 120, 540–548. [CrossRef]
11. Lu, P.; Liao, G.; Sun, J.; Li, P. Experimental research on index gas of the coal spontaneous at low-temperature
stage. J. Loss Prev. Process. Ind. 2004, 17, 243–247. [CrossRef]
12. Zhang, X.-H.; Wen, H.; Deng, J.; Zhang, X.-C.; Tien, J.C. Forecast of coal spontaneous combustion with
artificial neural network model based on testing and monitoring gas indices. J. Coal Sci. Eng. 2011, 17,
336–339. [CrossRef]
13. Ogunsola, O.I.; Mikula, R.J. A study of spontaneous combustion characteristics of Nigerian coals. Fuel 1991,
70, 258–261. [CrossRef]
14. Chen, X.; Chong, L. Several important issues related to the crossing-point temperature (CPT) method for
measuring self-ignition kinetics of combustible solids. Process. Saf. Environ. Prot. 1998, 76, 90–93. [CrossRef]
15. Qin, Y.; Liu, W.; Yang, C.; Fan, Z.; Wang, L.; Jia, G. Experimental study on oxygen consumption rate of
residual coal in goaf. Saf. Sci. 2012, 50, 787–791. [CrossRef]
339.
13. Ogunsola, O.I.; Mikula, R.J. A study of spontaneous combustion characteristics of Nigerian coals. Fuel 1991,
70, 258–261.
14. Chen, X.; Chong, L. Several important issues related to the crossing-point temperature (CPT) method for
measuring self-ignition kinetics of combustible solids. Process. Saf. Environ. Prot. 1998, 76, 90–93.
Energies 2018, 11, 174 16 of 16
15. Qin, Y.; Liu, W.; Yang, C.; Fan, Z.; Wang, L.; Jia, G. Experimental study on oxygen consumption rate of
residual coal in goaf. Saf. Sci. 2012, 50, 787–791.
16. Küçük,
16. Küçük, A.; A.; Kadıo
Kadıoğlu, Y.; Gülabo
ğlu, Y.; Gülaboğlu, M. A
ğlu, M. A study
study ofof spontaneous
spontaneous combustion
combustion characteristics
characteristics ofof aa Turkish
Turkish
lignite: Particle
lignite: Particle size,
size, moisture
moisture of of coal,
coal, humidity
humidity of of air.
air. Combust.
Combust. Flame
Flame 2003,
2003, 133,
133, 255–261.
255–261. [CrossRef]
17. Tan,
17. Tan, B.;
B.; Li,
Li, H.;
H.; Gao,
Gao, P.;
P.; Li,
Li, K.
K. Temperature-programmed
Temperature-programmedexperimental experimentalstudy study onon stage
stage characteristics
characteristics ofof coal
coal
spontaneous combustion disaster gas indicators. Zhongguo Anquan Kexue
spontaneous combustion disaster gas indicators. Zhongguo Anquan Kexue Xuebao 2013, 23, 51–57. Xuebao 2013, 23, 51–57.
18. Perera,
18. Perera, M.S.A.;
M.S.A.; Ranjith,
Ranjith, P.G.;
P.G.; Choi,
Choi, S.K.;
S.K.; Bouazza,
Bouazza, A.; A.; Kodikara,
Kodikara, J.;J.; Airey,
Airey, D.D. AA review
review ofof coal
coal properties
properties
pertinent to
pertinent to carbon
carbon dioxide
dioxide sequestration
sequestration in coal seams:
in coal seams: With
With special
special reference
reference to to Victorian
Victorian brown
brown coals.
coals.
Environ. Earth Sci. 2011,
Environ. 2011, 64, 223–235.
223–235. [CrossRef]
19. Masoudian,
19. Masoudian, M.S.; M.S.;Airey,
Airey, D.W.;
D.W.; El-Zein,
El-Zein, A. Mechanical
A. Mechanical and behaviours
and flow flow behaviours
and theirandinteractions
their interactions
in coalbed in
coalbed geosequestration of CO . Geomech. Geoengin. 2013,
geosequestration of CO2 . Geomech. Geoengin. 2013, 8, 229–243. [CrossRef]
2 8, 229–243.
20. Connell,
20. Connell, L.D.;
L.D.;Detournay,
Detournay, C. Coupled
C. Coupled flowflow and geomechanical
and geomechanical processes
processes during during
enhanced enhanced
coal seamcoal seam
methane
methane through
recovery recoveryCO through
2 CO 2 sequestration.
sequestration. Int. J. Int.
Coal J.
Geol. Coal Geol.
2009, 77, 2009,
222–233.77, 222–233.
[CrossRef]
21. Wold,
21. Wold, M.B.;
M.B.; Connell,
Connell, L.D.;
L.D.; Choi,
Choi, S.K.
S.K. The
The role
role of
of spatial
spatial variability
variability inin coal
coal seam
seam parameters
parameters on on gas outburst
outburst
behaviour during coal coal mining.
mining. Int. J. Coal Geol. 2008, 75, 1–14. [CrossRef]
22. Masoudian,
22. Masoudian, M.S.;M.S.;Airey,
Airey,D.W.;
D.W.; El-Zein,
El-Zein, A.A.TheThe
rolerole of coal
of coal seamseam properties
properties on coupled
on coupled processes
processes duringduring
CO2
CO2 sequestration:
sequestration: A parametric
A parametric study. study. Greenh.
Greenh. GasesGases Sci. Technol.
Sci. Technol. 2016,2016, 6, 492–518.
6, 492–518. [CrossRef]
23. Xie, Z.;
23. Z.; Cai,
Cai,J.;J.;Zhang,
Zhang,Y.Y. Division
Division of of spontaneous
spontaneous combustion
combustion “three-zone”
“three-zone” in goaf
in goaf of fully
of fully mechanized
mechanized coal
coal face with big dip and hard roof. Procedia Eng. 2012,
face with big dip and hard roof. Procedia Eng. 2012, 43, 82–87. [CrossRef] 43, 82–87.
24. Rong-kun, P.;
24. P.; Chang,
Chang, L.; L.; Ke,
Ke, Y.;
Y.; Ming-gao,
Ming-gao, Y. Y.Distribution
Distribution regularity
regularity andand numerical
numerical simulation
simulation study
study onon
spontaneous combustion “three zones” under the ventilation type of ventilation type of Ч ++ J.
the coal spontaneous
Procedia Eng.
Procedia Eng. 2011, 26, 704–711.
704–711. [CrossRef]
25.
25. Pan, R.; Cheng, Y.; Yu,
Y.; Yu, M.;M.; Lu,
Lu, C.;
C.; Yang,
Yang, K.
K. New
New technological
technological partition
partition for
for “three
“three zones”
zones” spontaneous
spontaneous coalcoal
combustion in goaf. Int. J. Min. Sci. Technol. Technol. 2013, 23, 489–493. [CrossRef]
26. Wang,
26. Wang, H.;H.; Dlugogorski,
Dlugogorski, B.Z.; Kennedy,
Kennedy, E.M. E.M. Coal
Coal oxidation
oxidation atat low
low temperatures:
temperatures: Oxygen consumption,
oxidation products,
oxidation products,reaction
reactionmechanism
mechanismand and kinetic
kinetic modelling.
modelling. Prog.
Prog. Energy
Energy Combust.
Combust. Sci.Sci. 2003,
2003, 29, 487–
29, 487–513.
513.
[CrossRef]
27. Cliff, D.; Brady, D.; Watkinson, M. Spontaneous Combustion in Australian Coal Mines; Simtars: Redbank,
Australia, 2015.
28. Jun, D.; Jingyu, Z.; Yanni, Z.; Ruilin, G. Study on coal spontaneous combustion characteristic temperature of
growth rate analysis. Procedia Eng. 2014, 84, 796–805. [CrossRef]
29. Su, H.; Zhou, F.; Li, J.; Qi, H. Effects of oxygen supply on low-temperature oxidation of coal: A case study of
Jurassic coal in Yima, China. Fuel 2017, 202, 446–454. [CrossRef]
30. Xuyao, Q.; Wang, D.; Milke, J.A.; Zhong, X. Crossing point temperature of coal. Min. Sci. Technol. 2011, 21,
255–260. [CrossRef]

© 2018 by the authors. Licensee MDPI, Basel, Switzerland. This article is an open access
article distributed under the terms and conditions of the Creative Commons Attribution
(CC BY) license (http://creativecommons.org/licenses/by/4.0/).

Вам также может понравиться