quantifying spontaneous combustion inhibition of reactive coals

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1 Water Technologies & Solutions technical paper 14th United States/North American Mine Ventilation Symposium, 2012 Calizaya & Nelson 2012, University of Utah, Dept. of Mining Engineering quantifying spontaneous combustion inhibition of reactive coals B. Beamish The University of Queensland, Brisbane, Queensland, Australia P. McLellan, U. Turunc & M. Raab SUEZ Water Technologies & Solutions Rowan Beamish The University of Queensland, Brisbane, Queensland, Australia ABSTRACT: A moist coal adiabatic oven test has been used to quantify the effect of applying a known inhibiting agent to alter the self-heating rate of highly reactive coals. The inhibitor significantly reduces the coal selfheating rate and extends the time taken to reach thermal runaway by a factor of approximately 3, for the dosage rate applied to the coals. A distilled water placebo test on the most reactive coal using the same application amount increased the initial self-heating rate, but the time taken to reach thermal runaway remained unchanged. These results are in agreement with practical experience and have major implications for the mining, handling and transportation of reactive coals. 1 Introduction Spontaneous combustion (sponcom) continues to pose a significant hazard to the mining, storage and handling of coal. All underground coal mines need to assess the risk of a spontaneous combustion event occurring. In New South Wales leading industry practice is the development and implementation of a Spontaneous Combustion Management Plan (SCMP) that complies with the Spontaneous Combustion Management Guideline MDG1006 (Industry and Investment NSW, 2011a). A supplementary document (MDG1006 Technical Reference) accompanies the guideline (Industry and Investment NSW, 2011b). Operationally, mines mainly mitigate the sponcom hazard using a Trigger Action Response Plan (TARP) system and there are some mines who adopt a proactive goaf inertisation strategy (for example San Juan Mine in New Mexico (Bessinger et al, 2005)). Another mitigation strategy is to apply inhibitors to the coal to delay the onset of spontaneous combustion. Smith, Miron and Lazzara, (1988) studied the effects of a range of inhibitors on coal spontaneous combustion, with varying degrees of success. The index parameter used to quantify the effectiveness of each inhibitor was the minimum self-heating temperature (SHT) of the coal as defined by earlier work of Smith and Lazzara (1987). However, there has been no subsequent publication of any practical application of their findings. Panigrahi et al (2005) presented the results of laboratory inhibition Find a contact near you by visiting and clicking on Contact Us. *Trademark of SUEZ; may be registered in one or more countries SUEZ. All rights reserved. Aug-12

2 studies on a range of Indian coals. The index parameter used to quantify the effectiveness of each inhibitor was the crossing point temperature (CPT) of the coal as defined by Banerjee et al (1972). This index parameter is obtained when the coal has reached a high temperature and does not provide any time perspective of the inhibition delay in reaching thermal runaway. Beamish and Beamish (2010) proposed a new moist coal adiabatic oven test that can be used to benchmark laboratory performance against actual site performance of a range of coals from Australia and overseas that cover the rank spectrum from sub-bituminous to high volatile bituminous. The test is known as the Moist Adiabatic Benchmark (MAB) test. Since introducing this test to the coal industry a number of additional benchmark coals have been added to the database that extend the rank range from lignite to low volatile bituminous. This new test method is extremely accurate and definitive for assessing the spontaneous combustion propensity of coal in a range of environmental situations, particularly during periods of high Relative Humidity (Beamish and Beamish, 2011, 2012). As the MAB test measures the time taken to reach thermal runaway, it provides an ideal method for quantifying the effectiveness of applying spontaneous combustion inhibiting agents to coal. This paper presents preliminary results of a series of tests using an inhibiting agent supplied by SUEZ Water Technologies & Solutions that has been applied to two reactive coals. 2 Adiabatic Oven Testing 2.1 Coal Samples Spontaneous combustion (sponcom) continues to pose a significant hazard to the mining, storage and handling of coal. All underground coal mines need to assess the risk of a spontaneous combustion event occurring. In New South Wales leading industry practice is the development and implementation of a Spontaneous Combustion Management Plan (SCMP) that complies with the Spontaneous Combustion Management Guideline MDG1006 (Industry and Investment NSW, 2011a). A supplementary document (MDG1006 Technical Reference) accompanies the guideline (Industry and Investment NSW, 2011b). Operationally, mines mainly mitigate the sponcom hazard using a Trigger Action Response Plan (TARP) system and there are some mines who adopt a proactive goaf inertisation strategy (for example San Juan Mine in New Mexico (Bessinger et al, 2005)). Another mitigation strategy is to apply inhibitors to the coal to delay the onset of spontaneous combustion. Smith, Miron and Lazzara, (1988) studied the effects of a range of inhibitors on coal spontaneous combustion, with varying degrees of success. The index parameter used to quantify the effectiveness of each inhibitor was the minimum self-heating temperature (SHT) of the coal as defined by earlier work of Smith and Lazzara (1987). However, there has been no subsequent publication of any practical application of their findings. Panigrahi et al (2005) presented the results of laboratory inhibition studies on a range of Indian coals. The index parameter used to quantify the effectiveness of each inhibitor was the crossing point temperature (CPT) of the coal as defined by Banerjee et al (1972). This index parameter is obtained when the coal has reached a high temperature and does not provide any time perspective of the inhibition delay in reaching thermal runaway. Beamish and Beamish (2010) proposed a new moist coal adiabatic oven test that can be used to benchmark laboratory performance against actual site performance of a range of coals from Australia and overseas that cover the rank spectrum from subbituminous to high volatile bituminous. The test is known as the Moist Adiabatic Benchmark (MAB) test. Since introducing this test to the coal industry a number of additional benchmark coals have been added to the database that extend the rank range from lignite to low volatile bituminous. This new test method is extremely accurate and definitive for assessing the spontaneous combustion propensity of coal in a range of environmental situations, particularly during periods of high Relative Humidity (Beamish and Beamish, 2011, 2012). As the MAB test measures the time taken to reach thermal runaway, it provides an ideal method for quantifying the effectiveness of applying spontaneous combustion inhibiting agents to coal. This paper Page 2

3 presents preliminary results of a series of tests using an inhibiting agent supplied by SUEZ Water Technologies & Solutions that has been applied to two reactive coals. Table 1. Coal quality data for benchmark and reactive coals used for inhibition studies. Sample R70 ( C/h) Benchmark coals VM (%, dmmf) CV (Btu/lb, mmmf ) ASTM rank Ash (%, db) Kideco subc 1.8 Spring Creek Reactive coals hvbb 1.2 PRB subb 6.8 GB hvcb Self-heating Test Procedures The R70 testing procedure essentially involves drying a 150 g sample of <212 mm crushed coal at 110 C under nitrogen for approximately 16 hours. Whilst still under nitrogen, the coal is cooled to 40 C before being transferred to an adiabatic oven. Once the coal temperature has equilibrated at 40 C under a nitrogen flow in the adiabatic oven, oxygen is passed through the sample at 50 ml/min. A data logger records the temperature rise due to the selfheating of the coal. The time taken for the coal temperature to reach 70 C is used to calculate the average self-heating rate for the rise in temperature due to adiabatic oxidation. This is known as the R70 index, which is in units of C/h and is a good indicator of the intrinsic coal reactivity towards oxygen. The major changes from the normal R70 method for MAB testing are, testing the coal with its as-received moisture content from the ambient mine start temperature, an increased sample size of approximately 200 g and a decreased oxygen flow rate of 10 ml/min. Increasing the sample size to 200 g provides a greater mass of coal to react that is still manageable without modifying the reaction vessel. Decreasing the oxygen flow rate to 10 ml/min reduces any cooling effect experienced by the coal from moisture evaporation as it self-heats. Effectively, these changes optimise the worst case scenario of developing a heating from as-mined coal. 2.3 Inhibiting Agent The inhibiting agent used for laboratory testing, is currently used to treat large quantities of Powder River Basin coal. Normal treatment rates range from lb/t of coal (approximately g/t), depending on the characteristics of the coal, climatic factors and the duration of inhibition effectiveness required. Dosage requirements for solids treatment are known to be proportional to particle size, so increased (surface area equivalent) dose rates were used for test purposes, to compensate for the < 212 μm crushed coal samples used in the laboratory testing. Adequate mixing is critical for effective treatment, as with all chemical applications, to ensure a uniform distribution of the inhibiting agent throughout the coal. In site applications, moisture addition can be minimised and mixing enhanced, by using specialty foam to distribute the inhibitor during a material handling process. Additional moisture is required under laboratory conditions, to effectively wet the < 212 mm coal and uniformly distribute the active chemical. 3 Adiabatic Testing Results and Interpretation 3.1 Coal Reactivity The relative reactivity of each of the coals is indicated by the R70 self-heating rate (Table 1). When interpreting R70 values it is important to realise that the value is not only rank dependent (Beamish, 2005; Beamish and Arisoy, 2008), it is also affected by coal type (Beamish and Clarkson, 2006; Beamish and Arisoy, 2008) and mineral matter constituents (Beamish and Blazak, 2005; Beamish and Arisoy, 2008; Beamish and Sainsbury, 2008). All four samples have relatively low ash contents and their coal type is predominantly vitrinite-rich. Therefore, the relative reactivity of each coal is principally consistent with the rank of each coal. The low rank sub-bituminous coals have a very high reactivity compared to the high volatile bituminous coals. An R70 self-heating rate test was also conducted on the Powder River Basin coal after applying the inhibiting agent at a surface area compensated dose rate, equivalent to 100 g/t for -20 mm coal to determine the effect of the inhibitor on the coal Page 3

4 reactivity. The R70 value was reduced by 23.6% to ºC/h. Hence, the inhibitor has been able to reduce the availability of reactive sites for coal oxidation to take place. However, as the R70 test is performed on a dry basis, this test only provides a partial measure of the effectiveness of the inhibitor, as a proportion of it would have been removed from the sample during the drying process. Hence, the true effectiveness of the inhibitor can only be measured by testing the coal in its treated state, which is readily achieved using the new MAB test. 3.2 Effectiveness of Inhibitor on Powder River Basin Coal For the purpose of this study, two coals with vastly differing intrinsic spontaneous combustion reactivities have been used for benchmarking. These are: Kideco a sub-bituminous coal from Indonesia with an R70 of ºC/h and an as-received moisture content of 24.0 %; and Spring Creek a high volatile B bituminous coal from New Zealand with an R70 of 5.87 ºC/h and an as-received moisture content of 11.7 %. The site experience with each of these coals indicates that heating events will develop in loosely piled coal in approximately days for the Kideco coal and days for Spring Creek coal. The initial conditions for each of the moist adiabatic benchmark tests on Powder River Basin coal are shown in Table 2. Dry oxygen was used as the reactant in all of the tests. The first test to be conducted was on the raw coal with its as-received moisture content of 24.3%. The initial self-heating rate is consistent with the coal reactivity where the high moisture content suppresses the self-heating for some time, before accelerated heating takes place (Figure 1). Table 2. Moist adiabatic benchmark test conditions for Powder River Basin Coal. Sample Initial temperature ( C) Moisture content (%) Coal state PRB1M As-received coal PRB2M PRB3M Inhibitor, 10 g/t (surface area equivalent) Moisture placebo, equivalent to water coming in with inhibitor PRB4M PRB5M Inhibitor, 100 g/t (surface area equivalent), using lower aliquot Inhibitor, 100g/t (surface area equivalent), using higher aliquot From the site experience of the two benchmark coals, the time taken for spontaneous combustion issues in a loose stockpile of raw Powder River Basin coal would be in the order of 13 to 20 days. Actual site experience with this coal indicates that heating events at the mine can take place in 15 days. Hence, the MAB test provides an acceptable match with site experience for this coal and the Powder River Basin coal now provides a benchmark in its own right for comparing the effectiveness of spontaneous combustion inhibiting agents. Figure 1. Moist adiabatic benchmark test results with relative scale comparing projected minimum days to thermal runaway for loosely piled coal found in coal roof falls and uncompacted stockpiles. The first inhibition test (PRB2M) was conducted on treated Powder River Basin coal using a 10 g/t dosage rate (surface area compensated) as shown in Table 2. The self- heating curve (PRB2M, Figure 2) shows a different behaviour to the raw coal, and the initial self-heating is slower. There is a more pronounced decrease in self- heating rate at approximately 90 C and this corresponded to significant moisture expulsion from the outlet tube that was not observed in the raw coal test. There is a noticeable delay in the time taken to reach thermal runaway. To rule out that this is simply a response to the additional moisture content a distilled water placebo test was conducted using the same volume application to the raw coal as shown in Table 2. This test (PRB3M, Figure 2) shows that the initial selfheating rate is accelerated by the presence of the Page 4

5 loose surface moisture, somewhat akin to a rain event situation as has been observed in practice. This is primarily due to the extra heat generated from the moisture adsorption by the coal (heat of wetting effect). However, the time taken to reach thermal runaway is effectively the same as the raw coal. A significant amount of moisture was expelled in this test, which counterbalanced the faster initial selfheating rate. The result obtained is similar to field trial experience found with Kideco coal, when moisture was added to the loose stockpile. reactivity, but the test does not show the complete retardation of the self-heating. Figure 3. Moist adiabatic benchmark test results for inhibitor application at 100 g/t (surface area equivalent dose rate). Figure 2. Moist adiabatic benchmark test results for inhibitor application at 10 g/t (equivalent dose rate) and moisture placebo application. The next test (PRB4M) used an increased dosage rate surface area compensated to be equivalent to 100 g/t for - 20 mm coal, by applying a more concentrated dose of the inhibitor at the same mixing ratio (Table 2), since it was clear that the inhibitor was having some effect in delaying thermal runaway. The selfheating curve (PRB4M, Figure 3) shows the effectiveness of the inhibitor at reducing the initial self-heating rate as it reaches a maximum of 43.9 C after 13 hours and actually loses heat over the next 10 hours before the self-heating begins to accelerate again at a much more reduced rate compared to the raw coal and the lower dosage rate test. The test also shows a small moisture liberation shoulder between 90 and 105 C. Less moisture was also expelled in this test. The time taken to reach thermal runaway is substantially prolonged (approximately 2.5 times the raw coal) and therefore according to the coal site performance scale in Figure 3 the time taken for spontaneous combustion issues in a loose stockpile of treated Powder River Basin coal would be in the order of 34 to 51 days. This result is consistent with actual site experience using the inhibitor. An R70 self-heating rate test at the same dosage rate also confirmed the inhibitor substantially lowered the coal A further test (PRB5M) was conducted using the same inhibitor dosage (equivalent to 100 g/t), but applied at a greater fluid mixing ratio as shown in Table 2. The self- heating curve (Figure 4) again shows the effectiveness of the inhibitor at reducing the initial self-heating rate, although the presence of higher moisture content appears to reduce the initial effectiveness compared to the same dosage with less moisture present. The time taken to reach thermal runaway is again significantly delayed using this application dosage rate (30 to 45 days based on site performance), but it would appear that the concentrated application of the inhibitor is more effective at delaying thermal runaway. Figure 4. Moist adiabatic benchmark test results for inhibitor application at 100 g/t (surface area equivalent dose rate) using a lower concentration and greater mixing amount. 3.3 Effectiveness of Inhibitor on Galilee Basin Coal Page 5

6 The initial conditions for each of the moist adiabatic benchmark tests on Galilee Basin coal are shown in Table 3. The first test to be conducted was on the raw coal with its as-received moisture content of 14.1%. The coal does not reach thermal runaway after 90 hours on test (GB1M, Figure 5). This is despite the R70 of the coal being substantially higher than the Spring Creek coal. However, when moist oxygen is used as the reactant (GB2M, Figure 5) the coal reaches thermal runaway in a similar timeframe to the Powder River Basin coal. Table 3. Moist adiabatic benchmark test conditions for Galilee Basin Coal. Sample Initial temperature ( C) Moisture content (%) GB1M GB2M GB3M Coal state As-received coal, dry oxygen As-received coal, moist oxygen Inhibitor, 100 g/t (surface area equivalent) The moist oxygen condition is similar to that experienced in Queensland s coalfields during the wet season, and many spontaneous combustion incidents in stockpiles have been observed during this climatic period. These results for the Galilee Basin coal are also consistent with earlier research by the US Bureau of Mines (Smith and Lazzara, 1987), who proposed that the presence of moisture has a synergistic effect on coal self-heating. This would appear to be demonstrated by both the moisture placebo tests on the Powder River Basin coal and the moist oxygen test on Galilee Basin coal. Figure 5. Moist adiabatic benchmark test results for Galilee Basin coal compared with Powder River Basin coal. A test was conducted on treated Galilee Basin coal (GB3M) again using a 100g/t (surface area equivalent) dosage of SUEZ s inhibitor with a test moisture of 16.6%. The self-heating curve GB3M, (Figure 5) shows the effectiveness of the inhibitor at reducing the initial self- heating rate as there is an approximate threefold increase in the time taken to reach a given temperature in the low ambient temperature region. At the point of thermal runaway however, the time delay is approximately double. This may be due to poor coverage of the coal when applying the inhibitor solution or it may be a feature of this particular coal (rank related). Nevertheless it is clear from this testing that the inhibitor works equally as well for both Powder River Basin coal and Galilee Basin coal. 4 Conclusions The mitigation of coal spontaneous combustion using inhibiting agents has not been documented in any detail in recent years. An opportunity now exists to apply a more definitive test to quantify the effectiveness of applying inhibiting agents to coal to delay the onset of thermal runaway. The newly developed Moist Adiabatic Benchmark (MAB) test has been used to assess the performance of a known inhibiting agent on the self- heating behaviour of Powder River Basin coal. The laboratory results are able to accurately simulate the site performance of the inhibiting agent on this coal. The same inhibiting agent has been applied to Galilee Basin coal and MAB testing clearly demonstrates the inhibiting effectiveness of the product. Field trials are needed to confirm that the MAB test results for this coal are again replicated. 5 Acknowledgements The authors would like to thank the Coal Industry for their continued support of spontaneous combustion benchmarking, along with SUEZ and UniQuest Pty Limited for granting permission to publish this paper. 6 References Page 6

7 Banerjee, S C, Nandy D K, Banerjee, D D and Chakravorty, R N, Classification of coal with respect to their susceptibility to spontaneous combustion, Trans. Min. Geol. & Met. Inst. of India, 59(2): Beamish, B B, Comparison of the R70 selfheating rate of New Zealand and Australian coals to Suggate rank parameter, International Journal of Coal Geology, 64(1-2): Beamish, B B and Arisoy, A, Effect of intrinsic coal properties on self-heating rates, in Proceedings of the 12th US/North American Mine Ventilation Symposium, pp (The Society of Mining, Metallurgy and Exploration Inc., Littleton, USA). Beamish, B and Beamish R, Testing and sampling requirements for input to spontaneous combustion risk assessment, in Proceedings of Australian Mine Ventilation Conference (The Australasian Institute of Mining and Metallurgy: Melbourne). Beamish, B and Beamish, R, Experience with using a moist coal adiabatic oven testing method for spontaneous combustion assessment, in Proceedings 11th Coal Operators Conference, (ed: N Aziz), pp (University of Wollongong and The Australasian Institute of Mining and Metallurgy). Beamish, B and Beamish, R, Benchmarking moist coal adiabatic oven testing, in Proceedings 10th Coal Operator s Conference (ed: N Aziz), pp (University of Wollongong and The Australasian Institute of Mining and Metallurgy). Beamish, B B and Blazak, D G, Relationship between ash content and R70 self-heating rate of Callide coal, International Journal of Coal Geology, 64(1-2): Beamish, B B and Clarkson, F, Self-heating rates of Sydney Basin coals The emerging picture, in Proceedings of the 36th Sydney Basin Symposium, pp 1-8 (University of Wollongong). Beamish, B B and Sainsbury, W., Development of a site specific self-heating rate prediction equation for a high volatile bituminous coal, in Proceedings 8th Coal Operator s Conference (ed: N Aziz), pp , (University of Wollongong and The Australasian Institute of Mining and Metallurgy). Bessinger, S L, Abrahamse, J F, Bahe, K A, McKluskey, G E and Palm, T A, Nitrogen inertization at San Juan Coal Company s longwall operation, in Proceedings 2005 SME Annual Meeting, pp (The Society of Mining, Metallurgy and Exploration Inc: Littleton). Industry and Investment NSW, 2011a. MDG 1006 Spontaneous combustion management guideline, Mine Safety Operations Branch. Industry and Investment NSW, 2011b. Technical reference for spontaneous combustion management guideline, Mine Safety Operations Branch Page 7

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