3.1. Fuel Properties
The ultimate analysis and the proximate analysis results of the samples used in this study are shown in
Table 2. The ultimate analysis results of the fuels in their “ar” basis show that sewage sludge was 28.4 wt.% carbon, 5.29 wt.% hydrogen, and 25.58 wt.% oxygen. Compared to Australian coal (73.1 wt.% carbon) and shiitake (40.49 wt.% carbon), sewage sludge has the lowest carbon content. The oxygen content of Australian black coal and shiitake is 5.27 wt.% and 29.03 wt.%, respectively. The results also show that the nitrogen content, 4.65 wt.%, and the sulfur content, 2.66 wt.%, are the highest for sewage sludge. Consequently, the combustion of sludge should receive attention with respect to some pollution and corrosion issues.
From the proximate analysis results of the samples, the sun-dried sewage sludge (DSS) was 8.07 wt.% moisture, 48.9 wt.% volatile matter, 39.61 wt.% ash, and 3.42 wt.% fixed carbon. However, drying the sludge and estimating its proximate analysis on an ash-free basis yields 91.5 wt.% and 8.5 wt.% for volatile matter and fixed carbon content, respectively. Shiitake and Australian black coal’s volatile matter content on an as-received basis is 69.05 wt.% and 30.77 wt.%, respectively. The fixed carbon content of the shiitake substrate and Australian black coal is 4.15 wt.% and 50.09 wt.%, respectively. The amount of volatiles strongly influences the thermal decomposition and combustion behavior of solid fuels, while the amount of fixed carbon influences the char oxidation process. Australian black coal has the lowest moisture and ash content of the samples; with sewage sludge ash content, 39.61 wt.%, being the highest because of its high inorganic content.
The measured heating value of the individual fuels are also shown in
Table 2. Sewage sludge, with a heating value of 11.37 MJ·kg
−1, has the lowest HHV of the studied fuels. Such low HHV is perhaps due to the fact that sewage sludge has high inorganic matter and low carbon content. However, taken on an ash-free basis, its HHV increased to 21.67 MJ·kg
−1, similar to that of shiitake, 21.66 MJ·kg
−1. The HHV of Australian black coal is 26.1 MJ·kg
−1. The heating value of the sewage sludge and the shiitake is almost 80% of that of Australian black coal.
3.2. Thermogravimetric Analysis
The combustion profile of sewage sludge is shown in
Figure 3. Sludge oxidation occurred in three stages. A dehydration stage, where moisture in the fuel is released, and a combustion stage that can be divided into main and final oxidation stages. The main oxidation stage is referred to as stage 1 in this study, and has a temperature range of 192.60 to 370.78 °C. It might be attributed to the reaction of air with the volatiles and some reactive structures in the sludge. During this stage, the volatiles released did not burn intensely, as shown by the heat flow curve. The maximum oxidation rate in this stage occurs at 286.61 °C. The weight loss during stage 1 is about 24.89 wt.%. The final oxidation stage, stage 2, started at about 370.78 °C, and showed a total weight loss of 25.86 wt.% at 800 °C. It might be attributed to the reaction of air with the heavier components or more complex structures and char oxidation. The maximum oxidation rate occurs at 481.55 °C. Stage 2 is associated with intense heat release, as shown by the DSC curve. Comparing the weight loss rates of the two stages, it is found that the burning rate (−4.80 wt.%·min
−1) of stage 1 was faster than that of stage 2 (−3.93 wt.%·min
−1), which is due to the high porosity [
4] and high surface area [
29] of the sludge.
The TGA results of Australian black coal are shown in
Figure 4, and display a typical combustion profile of sub-bituminous coal with one-stage thermal decomposition, as shown by the DTG curve. The peak (−6.33 wt.%·min
−1) of the burning rate was at 580.73 °C and corresponded to intense heat release, as shown by the DSC curve. This stage is referred to as stage 2 in this study, and it is the result of the devolatilization process as well as char oxidation of the coal. The total weight loss of the oxidation stage at 800 °C is approximately 80.24 wt.%.
Shiitake oxidation occurred in two stages, as shown in
Figure 5. Stage 1 showed one peak between 200 and 407 °C with a maximum value of −14.86 wt.%·min
−1 at 317.54 °C. This peak can be attributed to the release and oxidation of the holocellulose (hemicellulose + cellulose) and a small amount of the lignin in the substrate, showing a total weight loss of about 51.77 wt.%. Further decomposition of the lignin and char oxidation occurred in the final oxidation stage, which showed a burning rate peak, at 439.13 °C, of −6.48 wt.%·min
−1. The total weight observed in the final oxidation stages at 800 °C is 27.89 wt.%. At higher temperatures (620–720 °C), a small weight loss can be observed. As this was not associated with any significant heat release, it is not considered as a stage itself and therefore is included in stage 2. It might be related to an intrinsic characteristic of the substrate, which is beyond the scope of this study.
3.3. Synergistic Effect Analysis
The prediction of the TG curves in
Figure 6 and
Figure 7 for the blends using Equations (1) and (2) revealed that they are non-additive and therefore might show some synergistic effects. A comparison of the weight loss from the experimental TGA curves for various BBRs to that calculated from the linear additive rule is shown in
Figure 8 for the sludge-coal blends. The figure shows the various trends of
Wexp and
Wcal for the different blends for
β = 20 °C·min
−1. For the BBR = 25% blend, the residual values of the experimental curve were lower than those of the calculated curve between 600 and 800 °C. This suggests that a positive synergistic effect may exist between coal and sludge for this blend in this temperature range. A similar tendency can be seen in
Figure 9 for all sludge-shiitake blends at higher temperatures. In contrast, the residual values of the experimental curve for BBR = 50% and 75% were greater than the calculated values, implying negative synergy.
Plots of the deviation between the experimental and calculated curves are shown in
Figure 8 and
Figure 9. Those two figures clearly show that synergistic effects exist in the blends to a certain extent. For the BBR blends, positive synergy occurred during char oxidation. The catalytic effects of the sludge char might promote reactions at high temperature. However, at low temperature, the large quantity of released volatiles from the sludge may hinder the release of volatiles from the coal, which explains the negative synergistic effect. For the SSR blends, the addition of shiitake to the blends promoted reactions in the blend at both high and low temperatures. For all the blends, negative or low synergistic effects existed for temperatures between 300 and 500 °C. The values of the root mean square (RMS) of Δ
W were all between 1.06 and 1.57 for the blends, higher than those used to measure synergistic effects and reported in previous studies [
23,
30], indicating that there were synergistic effects in the blends.
3.4. Combustion Characteristics Parameters
The combustion characteristics for the sludge-coal blends are shown in
Table 3. Sludge high porosity and high surface area can explain why its devolatilization started at a lower temperature compared to the other fuels, and this led to a decrease in the ignition temperature with sludge addition to the blends in stage 1. Increasing sludge content in the blends resulted in an increase in burnout temperature in stage 1. Sewage sludge having higher devolatilization rate than Australian coal can explain why both the maximum and mean burning rates increased for the blends in the main oxidation stage (stage 1) with increasing sludge ratio, which also explained the increase in the values calculated for both the flammability index and the combustion characteristics index. The highest values for
C and
S in stage 1 for the blend were observed for BBR = 75% (
C1 = 5.72 × 10
−5 and
S1 = 3.91 × 10
−7, respectively). Sludge, having less material in the final decomposition stage (stage 2), showed the lowest maximum and mean burning rate values, and thus had the lowest values for both indexes. Positive synergistic effects in the blends decreased their burnout temperature. Although
Tb2 decreased with sludge addition to the blends, the flammability index and combustion characteristics index values decreased due to the decrease of the maximum and mean burning rates. The lowest values for both indexes in stage 2 were observed for BBR = 75%, and they are
C2 = 2.15 × 10
−5 and
S2 = 1.01 × 10
−7, respectively. On the other hand, sludge addition to the blends resulted in an increase in the ignition temperature, up to BBR = 50%, which then decreased with further sludge addition in stage 2.
The combustion characteristics for the sludge-shiitake blends are also shown in
Table 3. As shown, the ignition and burnout temperatures of the blends both increased with shiitake addition in stage 1. The results also show that the flammability index and combustion characteristics index of the shiitake substrate have the highest values among SSRs for the main oxidation stage, namely,
C1 = 19.30 × 10
−5 and
S1 = 33.56 × 10
−7, respectively. The Shiitake high devolatilization rate may explain why both the maximum and mean burning rates of the blends in the main decomposition stage were higher for the blends with lower sludge ratio. As a result, both the flammability index and the combustion characteristics index in stage 1 decreased with increasing sludge ratio in the blends.
C and
S values increased from
C1 = 9.12 × 10
−5 and
S1 = 10.39 × 10
−7 for SSR = 25% to
C1 = 14.61 × 10
−5 and
S1 = 19.42 × 10
−7 for SSR = 75%. In the final oxidation stage (stage 2), the flammability index and the combustion characteristics index values of shitake are
C2 = 3.56 × 10
−5 and
S2 = 0.96 × 10
−7, respectively. A 25 wt.% addition of shiitake to the blend (SSR = 75%) increased both indexes of pure sludge, resulting from increases in the values of the maximum and mean burning rates of the blend. The values of
C and
S both decreased for SSR = 50%, with further shiitake addition, due to the synergistic effects between shiitake and sludge at higher temperatures. The highest value for the flammability index of the blends,
C2 = 2.29 × 10
−5, was found for SSR = 25%. The highest values for the combustion characteristics index,
S2 = 0.66 × 10
−7, was found for SSR = 75%.
3.5. Kinetic Parameters Analysis
According to the fitting results of linear regression using various kinetic mechanism equations, reaction orders of 1.2 and 1.5 were found to be the best model functions for stage 1 and stage 2, respectively; with corresponding correlation coefficients ranging from 0.950 to 0.994. The results of the calculated activation energy and frequency factor are shown in
Table 4. As shown, the calculated
E and
A for stage 1 of sewage sludge are 80.42 kJ·mol
−1 and 6.18 × 10
12 s
−1, respectively. Those for shiitake are 97.07 kJ·mol
−1 and 1.46 × 10
14 s
−1, respectively. This shows that more energy is needed for the combustion of the volatiles in the shiitake substrate during stage 1. The kinetic parameters of the blends are non-additive, and therefore their values could not be predicted. BBR = 25% could be divided into two oxidation stages, and the calculated activation energy and frequency factor for stage 1 are 85.68 kJ·mol
−1 and 2.80 × 10
12·s
−1, respectively. The addition of 50 wt.% sludge resulted in a decrease of both parameters due to the catalytic effect of sludge addition to the blend. Further sludge addition to the blend resulted in increases in both the activation energy and the frequency factor. This might be due to the occurrence of secondary reactions in the main oxidation stage. The activation energy and the pre-exponential factor are
E1 = 80.90 kJ·mol
−1 and
A1 = 3.83 × 10
12 s
−1, respectively, for BBR = 75%. For the sludge-shiitake blends, increases in both the activation energy and the frequency factor were observed in stage 1 with shiitake addition to the blends, except when 50 wt.% shiitake was added to the sludge, as shown in
Table 4.
A comparison of the activation energy values of the individual fuels in the final oxidation stage shows that Australian black coal has the highest value for
E (105.74 kJ·mol
−1), as expected. The values for sludge and shiitake are 64.89 and 62.93 kJ·mol
−1, respectively. The catalytic effect of sludge addition to the blends was also noticed in the final oxidation stage. The activation energy and the pre-exponential factor both decreased with sludge addition, except for BBR = 75%, due to the occurrence of secondary reactions. The inorganic materials in the sludge catalytically promoted char formation and tar-cracking reactions in the sludge-coal blends, and the lignin in the substrate produced the same effect to the sludge-shiitake blends, which is shown by a decrease in the calculated E values for the sludge-shiitake blends. A previous study found that the presence of alkaline salts in biomass may lower the apparent activation energy of thermal reactions and promote the formation of char [
36]. However, the opposite effect was observed with further addition of sludge and shiitake to the sludge-coal and sludge-shitake blends, respectively, due to further reactions between the heavier and complex compounds in the fuels.
3.6. Fourier Transform Infrared Spectroscopy
Figure 10 shows the CH
4 emission profiles for the sludge, the Australian black coal and their blends. The curve for sewage sludge shows two peaks, one at 280 °C and the other one at 474 °C, corresponding to two burning regions involving volatiles and fixed carbon. The release of CH
4 during the final decomposition stage was much lower than that in the main decomposition stage. The release of CH
4 in stage 1 is due to the primary pyrolysis of the volatiles and the cellulose in the sludge. A significant amount of the cellulose is converted into tar during the primary pyrolysis, and then some residual parts of the tar are converted into gases during the secondary reaction, which explains the occurrence of the second peak. The Australian coal, having low amount of volatile and one thermal decomposition stage, has one main peak around 471 °C. Adding sludge to the blends increased the amount of CH
4 released in the main decomposition stage, but decreased that of stage 2. The peaks for 25 wt.% sludge appeared to be the lowest. This was confirmed by taking the integral area under the curves and evaluating the gas yield using Equation (13). The results are shown in
Table 5. They reveal that BBR = 25% yielded the lowest amount of CH
4.
Figure 10 also shows the CH
4 emission profiles for the sludge-shiitake blends. Shiitake, having higher volatile and fixed carbon content than that of sludge, released a higher amount of CH
4 in both the main and final decomposition stages compared to that released by sludge. Adding shiitake to the blends reduced both peaks to approximately the same absorbance range, with SSR = 50% having the lowest peak for both stages. As shown in
Table 5, adding sludge to the blends increased the amount of CH
4 emitted, and SSR = 25% showed the lowest methane emission.
The CO emission profiles for the individual fuels and their blends are shown in
Figure 11. Only one absorption peak was observed for coal and the sludge-coal blends. In contrast, all profiles of the sludge-shiitake blends showed two peaks, in the temperature ranges of 275–400 °C and 425–575 °C, respectively. The first CO peak for sludge was observed at about 341 °C and the second one was observed at about 495 °C. The CO generation of stage 1 and stage 2 was attributed to the decomposition of the volatiles and decarbonylation reaction, respectively. Adding sludge to the blends reduced the absorption value of their peak, which is consistent with the results in
Table 5. BBR = 75% yielded the lowest value (0.078). However, adding shiitake to the sludge-shiitake blends increased the CO emission in stage 1, which was compensated with a reduction in CO in stage 2. Overall, CO emission of the blends decreased with shiitake addition to the blends, with SSR = 25% having the lowest gas yield value (0.049).
Figure 12 shows the CO
2 emission profiles of the respective fuels and their blends. All profiles displayed only one peak. The peak of the sludge-coal blends occurred at higher temperature, 425–700 °C, compared to that of the sludge-shiitake blends, which was observed between 300–600 °C. As shown in
Figure 12, sludge addition to the blends decreased the amount of CO
2 emitted. BBR = 75% showed the lowest value of the yielded CO
2 of the blends, as shown in
Table 5. In contrast, an addition of 25 wt.% shiitake to sludge led to an increase of about 30% for CO
2 emissions, as shown in
Table 5. However, CO
2 emission decreased with further shiitake addition to the blends.
NO
x formation during fuel combustion arises from three possible routes, thermal-NO
x, prompt-NO
x and fuel-NO
x [
35]. Generally, thermal-NOx is generated from thermal oxidation of nitrogen at high temperature (>1500 °C). Although its emission increases with increasing oxygen concentration and combustion temperature, its role is negligible at temperatures below 1500 °C, as is the case in this study. The formation of prompt-NO
x is more complex, involving CH radical intermediates that react with the nitrogen in air to form HCN, which further reacts to generate NO. The fuel-NO
x formation mechanism is even more complicated. It is formed from the nitrogen content in the fuel via two routes: (1) by homogeneous reactions of the nitrogenous compounds of the volatiles and (2) via heterogeneous reactions of the nitrogen components bound to the char. For the experiments conditions in this study, most of the NO
x came from fuel-NO
x.
Figure 13 shows the NO
x emission profiles of the individual fuels and their blends, showing one peak between 250 °C and 375 °C, which indicates significant NO emission produced by the volatile-N oxidation, for all the blends. Sewage sludge, having the highest nitrogen content yielded the highest NO
x of the fuels. The yielded values of NO
x emission in
Table 5 are all lower than that of pure coal, with NO
x emissions of BBR = 25% being the lowest. A similar observation was made for the yielded NO
x values for the sludge-shiitake blends in
Table 5, with a decrease in NO
x emissions found with increasing shiitake ratio. The oxides in the char/ash play an active role in NO
x reduction. Lower oxygen concentration in the oxidizer was beneficial for reducing NO
x. As the volatiles in the blends increased, their combustion consumed the oxygen near the char particles, and therefore decreased the oxygen concentration around the char.
Figure 14 shows the SO
2 emission profiles for the individual fuels and their blends. As shown, all curves have smooth peaks, except the shiitake one. SO
2 generation was closely related to the sulfur content in the fuels, as shown by the results of
Table 5. Sewage sludge, having the highest sludge content, showed the highest values of yielded SO
2. An addition of 25 wt.% sludge to the sludge-coal blends reduced the amount of yielded SO
2. An increase of SO
2 emission was observed with sludge further addition. The alkali and alkaline earth metal oxides in the sludge might act as a desulfurizing catalyst for such blends. However, further sludge addition of sludge increased the amount of yielded SO
2. For the sludge-shiitake blends, increasing the shiitake ratio decreased SO
2 emissions.
In summary, BBR = 25% showed the lowest CH4, NOx and SO2 emissions. The values of emitted CO and CO2 decreased with addition of sludge to the blends. NOx and SO2 emissions both decreased with shiitake addition to the sludge-shiitake blends. An addition of 25 wt.% shiitake to the sludge increased the amount of CH4, CO and CO2. However, further shiitake addition decreased their respective yields.
3.7. Single-Pellet Combustion
The combustion process of a pure sludge pellet and the way used to demarcate some of the parameters are shown in
Figure 15 for ambient temperatures of 700 °C. They show the volatiles, from the pellet, burning in the gas phase after the pellet fell into the hot environment before extinguishing. Then, char oxidation occurs homogeneously until burnout. The results of the studied parameters for the blends, i.e., ignition delay time (
tid), volatile combustion duration (
tf), and total combustion time (
ttot) for the single-pellet combustion experiments at 600 °C, 700 °C and 800 °C are shown in
Table 6 and
Table 7. The weight loss history and its first derivative for pure sewage sludge pellet at 700 °C are presented in
Figure 16 for illustration. Different temperatures have similar trends. An abrupt change in the pellet weight could be noticed during the devolatilization and volatiles combustion stage, whereas char combustion occurred at an almost constant weight loss rate until burnout.
At 600 °C, the pure sludge pellets (BBR = 100%) took on average 26.27 s to ignite. No gas-phase ignition occurred for pure coal pellets and sludge-coal blends pellets with BBR = 25–75%. This might be because the volatiles released from Australian coal and the blends have an auto-ignition temperature that is higher than 600 °C. As shown from the FTIR experiments, the hydrocarbons released from the devolatilization process of the blends with BBR= 25–75% (peaks at 225–425 and 425–550 °C) turned into CO at higher temperature (peak between 550–650 °C), which then oxidized. Methane and carbon monoxide auto-ignition temperature was reported to be higher than 600 °C [
37,
38]. However, in contrast to the sludge-coal pellets, all the sludge-shiitake pellets ignited at 600 °C. This is consistent with the FTIR results, which shows that the hydrocarbons released from the devolatilization process of the blends with SSR= 25–75% (peaks at 200–400 and 400–500 °C) turned into CO at lower temperature (peaks between 250–475 and 475–575 °C) than those in sludge-coal blends, which then oxidized.
All the BBR pellets ignited in the gas phase at 700 °C. It took on average 7.60 s for the pellets made of sewage sludge to ignite, and pure coal pellets ignited after 9.04 s. Sludge pellets, having more volatiles content, took less time to ignite compared to pure coal ones; as predicted by Equation (15). The ignition delay time decreased for BBR = 25% and 50%. The addition of sludge to the blends increased their volatiles content, resulting in a decrease of their ignition delay time. The slight increase in ignition delay time, might be due to the endothermic evaporation of moisture delayed volatiles evolution. Adding more sludge to the blend might increase the required drying time. A similar trend was observed at 800 °C. Higher volatile content of shiitake explains why pellets made of pure shiitake took the lowest amount of time to ignite, as shown in
Table 7. Adding shiitake to the blends decreased their ignition delay time.
The combustion of volatiles, tf, is an important step in the combustion process of solid fuels, as the maximum weight loss takes place in this stage. Although the sludge volatile content is higher than that of coal, the pure coal pellet flame lasted longer than that of pure sludge pellets. A majority of the volatiles in the sludge pellet vaporized before homogeneous gas phase combustion took place. Adding 25 wt.% sludge to the blend increased the volatile combustion duration from 75.94 to 83.89 s at 700 °C, which is due to the increased volatiles content of the blend. A decrease in the volatile combustion duration was observed for blends with sludge content greater than or equal to 50 wt.%. Pellets with a higher sludge ratio have more volatiles and, in theory, should have a longer volatile combustion duration. However, conducting TGA experiments of sewage sludge under pyrolysis conditions shows that volatiles in sludge escape at a higher rate in sludge than in coal. Therefore, the volatile combustion duration reduced for BBR = 50–75% pellets. Moreover, the pure sludge pellet volatile flame lasted 69.03 s on average, the shortest time. On average, volatile combustion took about 13.36% of the total combustion time for the pure sludge pellets; for pure coal pellet, volatile combustion took about 4.71% of the total combustion time at 700 and 800 °C. Single-pellet combustion experiments conducted at 800 °C showed similar patterns to those observed at 700 °C. For the sludge-shiitake blends, tf increased with shiitake addition to the blends. On average, volatile combustion took about 14.10% of the total combustion time for the pure shiitake pellets, 13.29% for the pure sludge pellets, and 4.65% for the pure coal pellets.
The total combustion (
ttot) time for various BBR pellets is also shown in
Table 6. As expected, the total combustion time of the coal pellet was much greater than that of the sludge pellet. Since coal has more fixed carbon content than does sewage sludge, its char oxidation takes longer than that of sludge at the same ambient temperature, which explains why pure coal pellets had the longest total combustion time. A linear decrease in the total combustion time was observed with the addition of sludge to the blends, with the pure sludge pellets having the shortest total combustion time. Char formed from sludge is more reactive than that of coal and possesses more pores and thus takes less time to burnout. This explains why the addition of sewage sludge to the blends significantly decreased their total combustion time for all ambient temperatures. As shown in
Table 7, the char of the shiitake pellets, having more fixed carbon, took more time to burnout than that of the sludge pellet. A linear increase in the total combustion time was observed with shiitake addition to the blend, due to the increase in fixed carbon content in the blends. Shiitake addition to the sludge can help with the issues related to ash, such as de-ashing, ash transport, storage, and disposal. Shiitake addition to the sludge may also minimize fouling, as the blend deposited ash might retain the low-melting-point salts in sludge.
Sewage sludge, having higher inorganic content than coal, left on average more residues after the pellet combustion experiments. About 41.50% of the initial weight of the sludge pellet was left on the stainless mesh platform. The pure coal pellets left, on average, a residual weight of about 18.48%. As shown in
Table 6, ash formed in the single-pellet combustion experiments increased with the addition of sewage sludge to the blends. Experiments conducted at higher temperatures showed that a high temperature in the combustor enhanced the volatilization of some of the ash-forming heavy metals resulting in lower residues. However, it should be mentioned that such a decrease in bottom ash might cause an increase in the amount of fly ash carried with the flue gas. Shiitake addition to the sludge can help with the issues related to ash, such as de-ashing, ash transport, storage, and disposal. Shiitake addition to the sludge may also minimize fouling, as the blend deposited ash might retain the low-melting-point salts in sludge. The results in
Table 7 show that shiitake addition to the blends decreased the amount of ash formed in the single-pellet combustion experiments.
The heating values of the blended fuels were measured, and the results are shown in the last column in
Table 6 and
Table 7 for reference. As shown, adding sludge to the blends decreased their HHV, with the HHV for BBR = 25% and 75% being 22.48 and 15.17 MJ·kg
−1, respectively. Adding shiitake to the sludge also had a positive effect on the heating values of the blended fuels. As the heating value of the blended fuels increased with shiitake addition. The heating values for SSR = 75% and 25% being 12.69 and 15.20 MJ·kg
−1, respectively.