3.2. Thermal Behaviour of an Iron Ore Briquette and a Coal Briquette
The mass loss curves of different sizes of EX show similar profiles (
Figure 3a), indicating that the mass loss of these three particle sizes of iron ores changes slowly with increasing temperature due to moisture release and mineral decomposition. Additionally, larger particle size of EX exhibits a higher mass loss, which may be because the larger particles contain a higher moisture content. The maximum mass losses of EX1, EX2, and EX3 are 4.11%, 2.11%, and 2.50%, respectively.
The pyrolysis curve of JM can be divided into three stages, which is similar to previous work [
42]. From the mass loss curve of coal in
Figure 3b, an initial mass loss of 2–3% is observed near 150 °C which is mainly because of the removal of the moisture content of the coal. Above 390 °C, the obvious mass loss indicates that the pyrolysis of coal has started. The period from 390 °C to 570 °C is the active decomposition stage of caking coal, which produces a large number of free radicals through depolymerization and decomposition reactions [
43,
44]. Therefore, a significant mass loss occurred. The gradual mass loss up to 1100 °C can be explained by the removal of the residual volatile matter in coal [
45].
3.3. Effect on the Mass Loss of the Coal-Iron Ore Briquettes
To quantitatively analyse the effect of different particle sizes of iron ore in the coal-iron briquettes during coking, the theoretical mass loss of the briquettes was calculated based on the mean mass loss of iron ore and coal during separate pyrolysis processes. The calculated data was obtained as represented in the following equation:
where
,
, and
are the theoretical mass loss of the coal-iron ore briquettes, the mass of the iron ore briquettes, and the mass loss of the coal briquette, respectively, under an Ar atmosphere.
The interaction index
was applied to evaluate the effect of iron ore in the coal-iron briquettes during the coking process at different temperatures. The interaction index
was calculated from the following equation:
where
is the mass loss of coal-iron ore briquettes at temperature
T and
is the theoretical mass loss of coal-iron ore briquettes at temperature
T. The interaction indexes
are analysed as shown in
Figure 4. A higher
value indicates a stronger synergistic effect of the iron ore and coal during coking. The interaction indexes
of JE1 and JE2 are almost the same before 850 °C and then increase quickly. Notably,
of JE3 decreases dramatically at approximately 400 °C and then increases with temperature. This behaviour may be caused by a strong depolymerization and decomposition reaction. In this period, large quantities of volatile matter (CO, CH
4 and CO
2) are generated and discharged. However, iron ore, which exists between coal particles, hinders the movement channel of the volatile matter and prolongs its discharge and then weakens the synergistic effect. All the
values of the coal-iron ore briquettes experience significant increases at around 850 °C due to the reduction of iron ore, according to Equations (6)–(11). Considerable H
2 gas is generated during the later stage of coking and promotes the reduction of iron ore. Therefore, the synergistic effect of iron ore and coal mainly occurs in the later reaction stage of coking and is much stronger than that in the primary stage. In addition, the promotion effect of the particle size of EX iron ore on the coal reaction during the later stage from high to low is 0.5–1.00 mm, 0.25–0.50 mm, and <0.074 mm, which indicates that the smaller particles of iron ore are more easily reduced during coking.
3.4. Effect on the Pyrolysis Characteristics of the Coal-Iron Ore Briquettes
The TG and DTG curves are shown in
Figure 5 for the briquettes. Compared with JM, the conversion curves of JE1, JE2, and JE3 gradually move into the high-temperature region. From the DTG curves, the acute decomposition reaction region of coal is reduced due to iron ore addition. Furthermore, the reaction intervals of JE1, JE2, and JE3 sequentially decrease. In the range of 400–600 °C, the conversion rate of JM is higher than that of JE1, JE2, and JE3. However, the deviations between the coal briquette and coal-iron ore briquettes are closing with an increase in the temperature. The conversion rate of JE3 begins to exceed the other briquettes at the later reaction stage (approximately 800 °C) and shows a strong synergistic effect, which is consistent with the discussion in
Section 3.3.
According to
Figure 5, some characteristic temperatures [
42] of pyrolysis can be analysed and are presented in
Table 4. The start temperature of briquette pyrolysis
T0 is defined as the temperature at
= 0.05;
Tp is temperature at the maximum conversion rate and the final temperature
Tf is at
= 0.85.
T0 and
Tf indicate the difficulty of the progress of the briquette pyrolysis reaction [
46,
47,
48].
Tp is related to the coal structure. Normally, the coals that consist of the same structure have the same
Tp.
Table 4 shows that the different particle sizes of iron ore have little effect on the
T0 and
Tp of the briquettes during coking. However, the addition of iron ore in the coal briquette results in
Tf increasing by approximately 36–67 °C. The temperature region of intense pyrolysis directly determines the properties of coke, because the generation of metaplast will not be completed in an arrow temperature range [
29,
48]. From
Figure 5, the acute decomposition reaction region of JM is broader than that of JE1, JE2, and JE3.
There is a significant increase in both the conversion and conversion rate at approximately 350 °C for all briquettes. This finding is because the mass loss before 350 °C is caused by the removal of adsorbed water, adsorbed gases, and carboxyl groups, which agrees with previous research [
49]. Therefore, according to the analysis of TG and DTG curves, briquette pyrolysis can be divided into three reaction stages from 350 °C to 1100 °C [
29].
3.5. Effect on the Kinetics of the Coal-Iron Ore Briquettes
The nomenclature report for symbols in the following equations can be seen in
Table 5.
The mass loss rate of the briquettes during coking is a function of the reaction time and temperature and can be presented as:
where
is the weight loss rate, s
−1;
is the rate constant, which is a function of temperature;
is the differential form of the reaction mechanism function;
is the reaction time, s; and
is the reaction conversion.
The rate constant
is calculated by the Arrhenius equation:
where
A is the pre-exponential factor;
E is the activation energy, kJ/mol; and
R is the standard molar gas constant, kJ mol
−1 K
−1.
During a non-isothermal process, the heating rate
β is constant:
The following formula can be obtained from Equations (13) and (14):
Equation (15) can be integrated to give:
Equations (17) and (18) can be obtained by the approximate calculation:
The following formula can be obtained from Equations (17) and (18):
The expression In(
AR/
βE) in Equation (19) is essentially constant. A straight line may be obtained if the left-hand side of Equation (19) is plotted versus 1/
T. From the slope, −
E/
R, the activation energy
E can be determined. The intercept of the curve represents the value of pre-exponential factor
A. The mechanism function can also be confirmed by the best fit between the theoretical curve and the experimental curve. The mechanism functions that are commonly used in solid-phase reactions are listed in
Table 6 [
50,
51,
52,
53,
54].
The weighted apparent activation energy [
55] is used to evaluate the reactivity of the briquettes and can expressed as Equation (20):
where
E1–
En is the apparent activation during the different stages and
f1–
fn is the percentage of the weight loss in the different stages. The weighted apparent activation of all the briquettes can be calculated using this method.
The fitting lines for the pyrolysis reaction of the JM briquette and kinetic parameters are shown in
Figure 6 and
Table 7, respectively. R
2 is the correlation coefficient. The larger the R
2 is, the better the correlation of the mechanism function is. The best fitting for both the first and second reaction stage is the F2 model, which indicates that the reaction is suitable for the chemical reaction (
n = 2) model, whereas the best fitting for the third reaction stage is the D4 model. The model fitting results show that the early stage of the pyrolysis process is mainly controlled by a chemical reaction and the later stage is mainly controlled by diffusion. The activation energy of the first stage is the highest, mainly because of the decomposition of the polymer compound during 350–550 °C.
The optimal mechanism function for all the coal-iron ore briquettes can be confirmed by the same analytical method above, as shown in
Figure 7. The kinetic parameters are presented in
Table 8. The three different kinds of coal-iron ore briquettes show the same reaction mechanism control according to the fitting results. The reaction mechanism control for all stages of JE1, JE2, and JE3 is diffusion control. The difference is that the diffusion control of the first and third stages are represented by the D2 model, whereas the second stage is fitted by the D3 model. Compared with the coal briquette, the reaction mechanism of coal-iron ore briquettes has obviously changed. The results indicate that after adding iron ore into the coal briquette, the iron ore particles will obstruct the gas diffusion and change the reaction mechanism from reaction control to diffusion control.
Comparing the activation energies of different samples, as shown in
Table 8, at the first and third stages, all the activation energies for the coal-iron ore briquettes are larger than those of the coal briquette. These findings can be explained by two aspects. During the first reaction stage, the iron ore particles in the coal briquettes hinder gas diffusion, which results in an increase in the activation energies and a change in the reaction mechanism. During the third reaction stage, the increasing activation energies are due to the reaction of iron ore, which needs more energy. Furthermore, the activation energies during the first and third stages of JE1, JE2, and JE3 gradually increase. This increase implies that the smaller size of iron ore particles have a greater effect on the pyrolysis reaction of coal briquettes.
According to Equation (20), the weighed apparent activation energies of different briquettes can be obtained, as shown in
Figure 8. The weighted activation energy of the coal-iron ore briquettes are approximately 38–55 kJ/mol, which are all larger than that of the JM briquette (35.523 kJ/mol). Previous studies [
56,
57] have shown that for the same coal, even though external factors (heating rate, gas atmosphere, etc.) change the activation energy at all stages of coal pyrolysis, the total activation energy required for pyrolysis remains constant. However, in this study, the addition of iron ore into the coal briquette not only changed the reaction activation energy of each stage, however it also changed the total activation energy. With a decrease in iron ore particles, the weighted apparent activation energy increases gradually.
3.6. Mechanismofthe Synergistic Effect betweenIron Ore and Coal during Coking
The whole pyrolysis reaction consists of several complex reactions, therefore, the synergistic effect between iron ore and coal was analysed particularly on two main stages, namely, the primary pyrolysis stage and secondary pyrolysis. The conceptual diagram of the synergistic effect between iron ore and coal during coking is illustrated in
Figure 9. The iron ore particles are evenly distributed around the coal particles, as shown in
Figure 9a. The decomposition and depolymerization reactions mainly occur during the primary stage of pyrolysis. A large number of volatile compounds including the reduction gases CO and H
2 are produced and discharged during this stage. The addition of iron ore particles reduces the thermal conductivity of the coal-iron ore briquette. A higher ambient temperature is required for pyrolysis to occur. Additionally, iron ore, which exists between coal particles, hinders the movement channel of the volatile matter and prolongs its discharge path. Therefore, the pyrolysis reaction is weakened by iron ore, and the smaller the iron ore particles are, the stronger the weakening effect is. The reduction of iron ore particles begins in the latter part of the primary pyrolysis stage. In
Figure 9d, the reaction conforms to the unreacted core shrinkage model [
37,
58], which comes out along the surface of the iron ore particles during reduction. The reduction reaction occurs much more easily in smaller iron ore particles. The iron ore was completely reduced during secondary pyrolysis, which was proved by XRD analysis, as shown in
Figure 10. The results show that even relatively large iron ore particle can be reduced completely during coking.