Assessment of spontaneous heating susceptibility of coal ...

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H. B. SAHU D. C. PANIGRAHI and N. M. MISHRA Assessment of spontaneous heating susceptibility of coal seams by differential scanning calorimetry - The paper presents the method offinding out the spontaneous heating susceptibility of coal samples by using differential scanning calorimetry (DSC). 30 coal samples collectedfrom 7 different Indian coalfields have been studied by this method and the onset temperature for all the samples have been determined. In addition, the crossing point temperature (CPT) of all the samples have been determined and a comparative study between onset temperature and CPT has also been presented. Introduction C oal mine fires have been a great concern both for the industry and researchers in this field. It causes accidents resulting in loss of lives, property and in some cases severe environmental pollution. One of the important contributing factors for these fires is the spontaneous heating of coal. The spontaneous heating susceptibilityof different coals varies over a wide range and it is important to assess their degree of proneness for taking preventive measures against the occurrence of fires. In the past, a number of researchers have attempted to assess the spontaneous heating tendency of coal by carrying out differentexperiments in the laboratory and different countries of the worldfollow different methods for this purpose. These are crossing point temperature (CPT) in India, Russian U- index in Russia, Olpinski index in Poland, adiabatic calorimetry in USA. etc. Some of the other methods attempted by different researchers are peroxy complex analysis (Yohe and Harman, 1941; Jones and Townend, 1949), differential thermal analysis (Banerjee and Chakravarty,1967; Gouws and Wade, 1989a), wet oxidation method (Singh et aI., 1985; Tarafdar and Guha, 1989; Panigrahi et a\., 1996), modified CPT index (Feng et a\., 1973; Mahadevan and Ramlu, 1985; Gouws and Wade, 1989b),self heating temperature (Smith and Lazara, 1987; Mironet a\., 1990)etc. It has also been observed by different researchersthat some of these methods are time consuming, Mr. H. B. Sahu, Sr. Lecturer, Department of Mining Engineering, National Institute of Technology, Rourkela 769 008, Prof. D. C. Panigrahi, Department of Mining Engineering, Indian School of Mines Dhanbad 826 004 and Dr. N. M. Mishra, Asst!. Professor, Department of Applied Chemistry, Indian School of Mines, Dhanbad 826 004 JOURNAL OF MINES, METALS & FUELS tedious and do not give reproducible results. Keeping this in view, the authors have carried out an extensive study for determining the spontaneous heating tendency of a large number of coal samples collected from different Indian coalfields by using differential scanning calorimetry (DSC). In addition, the crossing point temperatures of these samples have also been determined to have a comparative analysis between these two methods. Differential scanning calorimetry Differential scanning calorimetry (DSC) is a technique in which the difference in energy inputs into a substance and a reference material is measured as a function of temperature while the substance and reference materials are subjected to a controlled temperature program. In this technique the ordinate value of an output curve at any given temperature is directly proportional to the differential heat fiow between a sample and reference material and in which the area under the measured curve is directly proportional to the total differential calorific input. By this technique, coal samples can be studied under experimental conditions that simulate spontaneous heating process of materials (Mahajan et a\., 1976). DSC provides both qualitative and quantitative information about material transition during the spontaneous heating process. For some of these transitions, DSC can provide not only the temperature at which the transition (reaction) occurs and how much heat is evolved, but can also provide valuable information about the rate (kinetics) of reaction. Furthermore, with the advent of easy-to-use computer based data analysis programs, the ability to obtain such kinetic information has become more practical. EXPERIMENTAL SET UP In the present investigation a DSC-7 differential scanning calorimeter manufactured by Perkin-Elmer, Germany was used. The coQ.1pleteexperimental set up comprises the differential scanning calorimeter, a thermal analysis controller, purge gas supply arrangement, a computer with softwares and a graphic plotter. The photographic view of the experimental set up is presented in Fig. 1. 117

Transcript of Assessment of spontaneous heating susceptibility of coal ...

H. B. SAHUD. C. PANIGRAHI

andN. M. MISHRA

Assessment of spontaneous heatingsusceptibility of coal seams by differentialscanning calorimetry-The paper presents the method offinding out the spontaneousheating susceptibility of coal samples by using differentialscanning calorimetry (DSC). 30 coal samples collectedfrom

7 different Indian coalfields have been studied by this methodand the onset temperature for all the samples have beendetermined. In addition, the crossing point temperature(CPT) of all the samples have been determined and a

comparative study between onset temperature and CPT hasalso been presented.

Introduction

Coal mine fires have been a great concern both for theindustry and researchers in this field. It causesaccidents resulting in loss of lives, property and in

some cases severe environmental pollution. One of theimportant contributing factors for these fires is thespontaneous heating of coal. The spontaneous heatingsusceptibilityof different coals varies over a wide range andit is important to assess their degree of proneness for takingpreventivemeasures against the occurrence of fires. In thepast, a number of researchers have attempted to assess thespontaneous heating tendency of coal by carrying outdifferentexperiments in the laboratory and different countriesof theworldfollow different methods for this purpose. Theseare crossing point temperature (CPT) in India, Russian U-index in Russia, Olpinski index in Poland, adiabaticcalorimetry in USA. etc. Some of the other methodsattempted by different researchers are peroxy complexanalysis (Yohe and Harman, 1941; Jones and Townend,1949), differential thermal analysis (Banerjee andChakravarty,1967; Gouws and Wade, 1989a), wet oxidationmethod (Singh et aI., 1985; Tarafdar and Guha, 1989;Panigrahiet a\., 1996), modified CPT index (Feng et a\.,1973; Mahadevan and Ramlu, 1985; Gouws and Wade,1989b),self heating temperature (Smith and Lazara, 1987;Mironet a\., 1990)etc. It has also been observed by differentresearchersthat some of these methods are time consuming,

Mr. H. B. Sahu, Sr. Lecturer, Department of Mining Engineering, NationalInstitute of Technology, Rourkela 769 008, Prof. D. C. Panigrahi,Department of Mining Engineering, Indian School of Mines Dhanbad 826004 and Dr. N. M. Mishra, Asst!. Professor, Department of AppliedChemistry, Indian School of Mines, Dhanbad 826 004

JOURNAL OF MINES, METALS & FUELS

tedious and do not give reproducible results. Keeping this inview, the authors have carried out an extensive study fordetermining the spontaneous heating tendency of a largenumber of coal samples collected from different Indiancoalfields by using differential scanning calorimetry (DSC).In addition, the crossing point temperatures of these sampleshave also been determined to have a comparative analysisbetween these two methods.

Differential scanning calorimetry

Differential scanning calorimetry (DSC) is a technique inwhich the difference in energy inputs into a substance and areference material is measured as a function of temperaturewhile the substance and reference materials are subjected toa controlled temperature program. In this technique theordinate value of an output curve at any given temperature isdirectly proportional to the differential heat fiow between asample and reference material and in which the area underthe measured curve is directly proportional to the totaldifferential calorific input. By this technique, coal samplescan be studied under experimental conditions that simulatespontaneous heating process of materials (Mahajan et a\.,1976).

DSC provides both qualitative and quantitativeinformation about material transition during the spontaneousheating process. For some of these transitions, DSC canprovide not only the temperature at which the transition(reaction) occurs and how much heat is evolved, but can alsoprovide valuable information about the rate (kinetics) ofreaction. Furthermore, with the advent of easy-to-usecomputer based data analysis programs, the ability to obtainsuch kinetic information has become more practical.

EXPERIMENTAL SET UP

In the present investigation a DSC-7 differential scanningcalorimeter manufactured by Perkin-Elmer, Germany wasused. The coQ.1pleteexperimental set up comprises thedifferential scanning calorimeter, a thermal analysiscontroller, purge gas supply arrangement, a computer withsoftwares and a graphic plotter. The photographic view ofthe experimental set up is presented in Fig. 1.

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Published in Journal of Mines, Metals and Fuels, 2004
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I.2.

Differential scanning calorimeterThermal analysis controller

3.4.

Personal computerGraphics plotter

Fig.l Photographic view showing experimental setup of differential scanning calorimeter

Differential scanning calorimeter

The Perkin-Elmer DSC-7 differential scanningcalorimeter is of power compensated type. It is based on"thermal null balance" principle in which energy absorbed orevolved by the sample is compensated by adding orsubtracting an equivalent amount of electrical energy to aheater located in the sample holder throughout the controlledtemperature program. Platinum resistance heaters andthermometers are used in the DSC-7 calorimeter toaccomplish the temperature and energy measurements in thisdesign. Any energy difference in the independent supplies tothe sample and the reference is then recorded against theprogram temperature. Thermal events in the sample thusappear as deviations from the DSC baseline, in eitherendothermic or exothermic direction, depending uponwhether more or less energy has to be supplied to the samplerelative to the reference material. In DSC therefore,endothermic responses are usually represented as beingpositive, i.e. above the baseline, corresponding to anincreased transfer of heat to the samples compared to thereference.

Swing awayenclosure cover

Purge gas exit

Latch

Knurled adjustingthumb nut

Guard ring insert

Platinum-iridium

sample furnace

DSC7 cell/sample holder

The important part of the DSC7 differential scanningcalorimeter is the DSC cell (Fig. 2). It is composed of low-mass platinum-iridium sample cells (furnaces) embedded ina large aluminium heat sink. A swing-away lid with a rubbera-ring seal is used to seal the furnaces from the externalatmosphere during an analysis. The left furnace is used forencapsulated sample materials, while the right furnace is usedfor reference materials. For example, the right furnace istypically an empty sample pan and lid or sample container ofthe type used in the sample cell.Thermal analysis controller

The controller is TAC7/DX type and is an intelligentmicroprocessor controller that links the PC to the thermalanalysis module. The high-speed microprocessor controls a11functions and the built in diagnostics continuously monitorand analyse all system functions.

Purge gas supply arrangement

Purge gas is supplied from a cylinder equipped withsuitable regulators. For oxidation or degradation studies, air

or oxygen is recommended. Therecommended now rates of the purge gas are20 to 30cc per minute.

Personal computer with softwares

All the operations of the DSC-7calorimeter are controlJed from the personalcomputer through software. The softwareperforms all the controls, calibration, datadisplay, standard calculations, curvecomparison and calculations etc.

Graphics plotter

It is a high resolution alpha numeric X-Y printer/plotter with graphics arrangementand has the provision of multiple penoperation for generating multicolour plots.

Platinum-iridium referencefurnace with ventedplatinum lid in place

Aluminiumheat sink

Fig.2 Schematic of the DSC-7 sample holder and sample holder enclosure cover

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Coal samples collected for the study

Coal samples were collected from different Indian coalfieldscovering both fiery and non-fiery coal. seams of differentranks spreading over 7 different mining companies. Thename of the coal seam, mine and the subsidiary from wherethe coal samples were col1ected are presented in Table I.Some of the coal samples col1ected like Jhingurda seam(sample no. 30), Samla seam (sample no. 24), Chirimiri-IIIseam (sample no. 28) and Burra Dhemo seam (sample no.25), Kampti-lVB seam (sample no.29) are well known for

110 300

TellPeralure I'C!

Fig.3(c) DSC thermogram for sample no.24

200 WO 500

their high susceptibility; whereas seam-O of Bastacola

colliery (sample no. 21) is considered the least susceptible tospontaneous heating.

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TABLE I: CPT AND ONSETTEMPERATUREOF COAL SAMPLES..

--lSample Coal Colliery CPT Onsetseam ("C) temperature. --....... ,--- I

TlI("C)

I Seam - IX Hingula 149 249.37

2 Seam - VII Lingaraj 149 235.21"i 250

3 Seam - V Lingraj 146 240.76 ill:

4 Seam - IV Lingaraj 148 240.02 !5 Seam - III Ananta 147 234.30 !6 Seam-III Bharatpur 148 236.39 I7 Seam -II Ananta 155 225.40

8 Seam - II Bharatpur 150 233.22

Seam-II Jagannath 148 236.960

9 no 210 310 UO 51010 Seam-II Lingaraj 147 229.17 Tllllptl'alurl I'ci

\1 Seam - I Deulbera 144 229.89 Fig.3(a) DSC thermogram for sample no.7

12 Seam- I Nandira 144 226.66

13 Lajkura - IV Orient-3 150 240.79 500

14 Lajkura- III Orient-3 151 242.75

15 Lajkura - II Orient-2 142 233.89

16 Lajkura - I Orient-3 150 237.77

\17 Rampur- IV Hingir-Rampur 148 245.63

18 Rampur- B Hirakhand Bundia 141 245.84 -;;;19 Rampur - A Hirakhand Bundia 143 248.90 250

20 Ib Belpahar 154 245.75 Ii \21 Seam-0 Bastaco1a 180 286.02 I

\'"

\22 Mahuda bottom Murlidih 155 235.20 ji23 Laikdih West Victoria 160 259.46

24 Samia Samla 152 230.91

25 Burro Dhemo Methani 150 217.61 0

26 Dakra Dakra Bukbuka 144 225.94 90 190 290 390 ,gO

27 Hatidhari Saunda 152.5 216.28Temperalure('CI

28 Seam -1II Chirimiri 155 224.14Fig.3(b) DSC thermogram for sample no.21

29 Seam- IVB Kampti 150 222.06 5030 Jhingurda Jhingurda 138 235.32

Sample nos. 1-20 : Mahanadi Coalfields Ltd.Samplenos. 21-23: Bharat Coking Coals Ltd.Samplenos. 24-25: Eastern Coalfields Ltd.Samplenos. 26-27: Central Coalfields Ltd.

3Sampleno. 28: South Eastern Coalfields Ltd.Sampleno. 29: Western Coalfields Ltd. J 25

Sampleno. 30: Northern Coalfields Ltd. I

500

'"

~ 250!..,g

1

90 190 390 .90290

Temperature t'CI

Fig.3(d) DSC thermogram for sample no.30

Experimental procedure adopted for DSC study

The cover and the silver lid were removed from the DSCcell. The instrument was calibrated using standard zinc andindium samples. About 10 mg coal sample of -212 m wastaken in the perforated aluminium sample pans and weighedaccurately using a Mettler AE-240 single pan electronicbalance (0.01mg sensitivity). After placing cover on the panit was crimped using a crimper press. The crimped containerwith the sample was put on the sample furnace while thereference furnace was kept empty. The DSC thermogram wasnow obtained up to 550°C at a heating rate of 30°C perminute with oxygen as purge gas at a rate of 20cc per minute.

The above procedure was followed to obtain the DSCthermograms for all the 30 coal samples. Four representativethermograms for sample nos. 7, 21, 24 and 30 are presentedin Fig. 3(a), (b), (c) and (cD.(Figs. 3 (a), (b), (c), (d).)

Determination qf crossing point temperatureof coal samples

The crossing point temperature (CPT) of the coal sampleswere determined following the procedure and experiment~lset up described by Panigrahi et al.(l999). Glycerine bathwas used as the heating medium. The rate of rise oftemperature was maintained at 1°C per minute and air wassupplied at 80cc per minute. The CPT of all the coal samplesare presented in Table 1.

Analysis of results from DSC thermograms

The DSC thermograms represent the various reactionsoccurring during coal oxidation. It is difficult to isolate anindividual reaction and pinpoint the exact temperature ofinitiation of a particular reaction. However, the firstderivative of the thermograms may give an idea about theinitiation of different reactions. One such plot of the firstderivative of a thermogram is presented in Fig. 4. It can be

120

80

,. .

ii,I

.1' .I

i

'I]II1\

,,Il_-

VI 50~'"~..~ .0J!

20

,-' _.:::d~iV~V~ ~./-._-.-.--.

m ~ ~ ~ mTelllperature I'CI

Fig.4 The first derivative of DSC thermogram for sample no.?

50 ----

1J~i-25~~

Onset temperature

Ir.J \\:\ :

200 lZ30."'. 300

TeMperature I'CI

Fig.S Determination of onset temperature for sample no.24

100 500.00

observed from all the thermograms that initially theendothermic reaction dominates followed by the exothermicreactions. The temperature of initiation of the exothermicreaction can be considered as an indicator of spontaneousheating susceptibility of coal samples, which is known as theonset temperature. The lower is this temperature, higher isthe spontaneous heating susceptibility.

Determination of characteristics/onset temperature forsample no. 24 is presented in Fig. 5 for ready reference. Theprocedure of determination of onset temperature orcharacteristics temperature (To) of exothermic reaction is asgiven below.

. A tangent is drawn at the inflexion point of the pre-transition.

. A second tangent is drawn at the greatest slope of thefirst exothermic reaction.

. The intersection of the two tangents gives thecharacteristics or onset temperature.

In DSC-7 calorimeter the onset temperature is determined

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by selecting the point (temperature) at which the tangents areto be drawn. The onset temperature is read out (displayed)directly from the intersection of the tangents.

The onset temperature of all the 30 coal samples aredetermined following the above procedure and the results arealso presented in Table 1.

Conclusion

It may be observed from Table 1 that seams like Samia(sample no. 24), Chirimiri-lII (sample no. 28), Burra Dhemo(sample no. 25) and Kampti-1VB (sample no. 29) areshowing higher values of CPT indicating that the coals areless susceptible, whereas in actual field condition they arehighly susceptible. The onset temperature (To) of DSCthermo grams are lower for the aforementioned samplesindicating that these coal samples are highly susceptible tospontaneous heating. This reveals that differential scanningcalorimetry predicts the spontaneous heating susceptibilitymore accurately than crossing point temperature for the coalsamples studied in this investigation.

It has also been observed in the past that it is not alwayspossible to maintain the same experimental standard, viz.packing density etc., while determining the CPT of coalsamples and therefore, the results are not reproducible.Whereasit is possible to fix the standard parameters for thedetermination of onset temperature, To by DSC and theresults have been found to be highly reproducible.

It takes approximately 3 hours to determine the CPT of acoal sample and failure of power supply for a few minutesduring experiments, especially when the temperatureapproachesthe crossing point, gives erroneous value of CPTand the whole experiment has to be repeated. The onsettemperature, To from DSC thermograms can be obtainedwithin25 minutes and thus much of the time and energy canbe saved.

The acceptability of a method for determiningspontaneous heating characteristics of coal mainly dependsupon how closely it predicts the spontaneous heatingbehaviourin the field conditions. Considering this, it may beconcluded that the onset temperature obtained fromdifferentialscanninq calorimetry may be a better method thancrossingpoint temperature.

References

I. Banerjee, S. C. and Chakravarty, R. N. (1967): "Use ofD.T.A.in the study of spontaneous combustion of coal",Journal of Mines, Metals and Fuels, January, pp.1 -5.

2. Feng, K. K., Chakravarty, R. N. and Cochrane, T. S.(1973): "Spontaneous combustion - a coal mining

JOURNAL OF MINES, METALS & FUELS

hazard", CIM Bulletin, October, pp. 75-84.

3. Gouws, M. 1. and Wade, L. (1989a): "The self-heatingliability of coal: Prediction based on simple indices",Mining Science and Technology, Vo1.9,pp. 75-8D.

4 .Gouws, M. 1. and Wade, L. (1989b): "The self-heatingliability of coal: Prediction based on composite indices",Mining Science and Technology, Vo1.9,pp.81-85.

5. Jones, R. E. and Townend, D. T. A. (1949): "Oxidationof coal", Journal of Society of Chemical Industries, Vol.68, p. 197.

6. Mahadevan, V. and Ramiu, M. A. (1985): "Fire riskrating of coal mines due to spontaneous heating",Journal of Mines, Metals and Fuels, August, pp. 357-362.

7. Mahajan, O. P., Tomita, A. and Walker, P. L. (1976):"Differential scanning calorimetry studies on coal. I.Pyrolysis in an inert atmosphere", Fuel, Vol. 55,January, pp. 63-69.

8. Miron, Y. Smith, A. C. and LaaITa, C. P. (1990): "Sealed flask test for evaluating the self heatinatendencies of coals", USBM RI 9330.

9. Panigrahi, D. c., Udaybhanu, G. and Ojha, A. (1996):"A comparative study of wet oxidation method andcrossing point temperature method for determining thesusceptibility of Indian coals to spontaneous heating",Proceedings of Seminar on Prevention and Control ofMine and Industrial Fires - Trends and Challenges,Calcutta, India, Dec., pp.10l-1O7.

10. Panigrahi, D. c., Saxena, V. K. and Udaybhanu, G.(1999): Research project report on "Development ofhandy method of coal categorisation and prediction ofspontaneous fire risk in mines", Deptt. of Mining Engg.,ISM, Dhanbad, VoU, December, p. 61-64.

11. Singh, R. N., Demirbilek, S. and Azis, A. I. (1985): "Anapproach to safe design of mine workings against a riskof spontaneous combustion", Proceedings of 2] 5tInternational Conference on Safety in Mines researchInstitute, Sydney, 21-25 October.

12. Smith, A. C. and Lazara, C. P. (1987): "Spontaneouscombustion studies of U.S. coals" USBMRI-9079, pp.]-28.

13. Tarafdar, M. N. andJJuha, D. (1989): "Application ofwet oxidation processes for the assessment of thespontaneous heating of coal", Fuel, Vol. 68, March,pp.315-317.

14. Yohe, G. R. and Harman, C. A. (1941): "Oxidisingpowerof Illinois coal", Journal of American ChemicalSociety, Vo. 63, p. 555.

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