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Composition, Trace Element Contents and Major Ash Constituents of Thar Coal, Pakistan
M. Afzal Farooq Choudry Department of Environmental Science, FUUAST, Karachi, Pakistan E-mail: drafzalfarooq@yahoo.com Yasmin Nurgis Environmental Research Center, Bahria University, Karachi, Pakistan E-mail: ercbu@bimcs.edu.pk Mughal Sharif Environmental Research Center, Bahria University, Karachi, Pakistan E-mail: ercbu@bimcs.edu.pk Amjad Ali Mahmood Geological Survey of Pakistan, Karachi, Pakistan Haq Nawaz Abbasi Department of Environmental Science, FUUAST, Karachi, Pakistan E-mail: hn.abbasi@yahoo.com Abstract Thar coalfield is a part of the Thar Desert of Pakistan. Pakistan has coal reserves of 185 billion tons, of this Thar coal reserves account for 175 billion tons spread over a single geographically contained area of 9100 sq km in the south eastern part of the Sindh. It is bounded in the north, east and south by India, in the west by the irrigated Indus river flood plain. The terrain is sandy and rough with sand dunes forming the topography. Various physio-chemical parameters including chemical composition of coal ashes, distribution of trace elements in them, were analyzed to understand the coal prospects and its share in the domestic energy production. In addition a preliminary study have also undertaken on the factors that effect the chemical composition of coal ashes. The apparent rank is high volatile Lignite B coal. Arithmetic mean values for proximate analysis of coals (as received basis; n=54) show these coals to be 6.83% Ash, 29.55% volatile matter, 19.2% fixed carbon and 44.3% moisture and have a heat of combustion of 6094 BTU/lb. Average values for ultimate analysis of the coal show these coals to be 4.96% hydrogen, 51.18% carbon, 0.31% nitrogen, 2.45% sulphur and 14.88% oxygen. The geometric mean values of these, as viewed from the analysis of coal ash samples collected from the Thar coal field region, it can be seen that coal ashes from region studied are composed of organic matter and the major chemicals are SiO2, Al2O3, Fe2O3 and CaO as well as minor amounts of SO3,P2O5, Na2O, K2O and TiO2. During the combustions of coal, its trace elements will be redistributed and most of them are enriched in coal ashes.The mineralogy of Sindh coal samples suggests that these coals have quartz and Kaolinite as the dominant phase and minor amount of calcite, Illite and Muuscovite. The dominant minerals of Thar coals are
Composition, Trace Element Contents and Major Ash Constituents of Thar Coal, Pakistan quartz. Quartz also tends to occur in the form of comparatively large particles of free mineral matter, whereas much of the pyrite is dispersed in the coal substances and clay sediments. Keywords: Coal, Thar, Bara, Trace Elements, Ash
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1. Introduction
Energy has become an important prerequisite for the economic development of a country. On one hand it is used for the industrial and agricultural purposes and on other hand it is required for domestic use of the citizens. Pakistan is presently facing an acute power shortage, with a rapidly growing population and economy, and relying heavily on thermal power generation. About half of the thermal power generation is based on imported oil or on natural gas. Oil is very expensive and rising unpredictable to unprecedented height. Where as reserves of natural gas are limited. Pakistan is presently facing a demand and supply gap of electricity approximately 5000MW and may increase in the coming years. Out of total generation capacity of 17664MW, coal fired power generation is presently only 50MW. Whereas Pakistan has total coal reserves of 185 billion tons of these Thar coal reserves account for 175 billion tons spread over a single geographical contained area of 9100 sq km in Thar desert in South-Eastern corner of the province of Sindh, Pakistan. Coal is projected as a primary source for power generation through its combustion and could even surpass oil and natural gas in use, especially when the real costs of energy are compared to the costs of using indigenous coal resources of Pakistan. In this scenario coal presents itself as the foremost solution to country energy crises. In the process of combustion organic and inorganic materials in it will undergo a complex variation part of them will become volatiles, together with coal smoke, enter into atmosphere in the form of solid particles and the rest will be retained in ash and slag. Coal ashes are the residues of organic and inorganic substances in coal left after coal combustion ( Abernethy et al; 1969).The concentration of trace elements are much higher than those of bottom ash ( Swaine, 1975) coal combustion not only produce heat and energy but significantly harm the environment and human health ( Hepplaston et al; 1984; Borm, 1994; Vanhee et al, 1995; Borm and Driscoll, 1996; Driscoll et al; 1996, 1997; Paul, 1997; Frinkelman et al; 1999). Under leaching action the ashes will find their way into underground water, causing underground water pollution (Mareal Pires et al; 2000; Liuguijian, 2000 a). Therefore, coal combustion and ash slag formation will lead to obvious redistribution of elements on the earth surface. Coal quality is now generally recognized as being an impact, often significant, on coal combustion especially in many areas of power plant operation. The parameters of rank, mineral matter content (ash content) sulfur and moisture contents are regarded as determining factors in combustibility as it relates to both heating value and ease of reaction. Therefore this study is undertaken the geochemical characteristics, chemical composition and element composition of Thar coal .In addition this study is a brief effort to stimulate the already growing interest in the possibilities of raising the coal prospects and its share in the domestic energy production. Coal ashes analysis will provide the scientific basis for their comprehensive utilization and for reducing environmental pollution.
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M. Afzal Farooq Choudry, Yasmin Nurgis, Mughal Sharif, Amjad Ali Mahmood and Haq Nawaz Abbasi
platform slope. Shelf platform and carbonate deposits ranging in age from Triassic to recent overlie the basement slope (Kazmi and Jan, 1995). The Thar coalfield is located between latitudes 24o15'N and 25o 45'N and longitudes 69o45'E and in the south-eastern part of Sindh. The Thar desert lies in the south-eastern part of Pakistan on the stable western margin of the Indian plate (Kazmi and Jan, 1995).
3. Geology of Thar
The Thar coalfield is covered by dunes with an average depth varying from 14-93 meters and is located on the Indus platform in the eastern part of the desert. This structural platform is underlain by relatively shallow granitic basement. This granite complex dips down abruptly beneath the western part of the Thar Desert and is highly faulted (Fasset and Durrani, 1994). An unconformity at the base of underlying sedimentary sequence east ward to the point where the Paleocene/Eocene rocks rest directly on the basement granite is present. The maceral components indicate less maturity of coal formed herbaceous plants in warm climate with rapid rise and fall in water level and environment of raised bogs (Fasset and Durrani, 1994). The quality of coal is liginite B, Clay stone forms the roof as well as floor of coal benches (Jaleel et. al., 2002). Thar coals are Paleocene to Eocene in age and may be deposited in raised bog environment (Jaleel et. al., 2002). The geological studies shows that coal bearing strata of palocene-Eocene sediments unconformabaly overlie the pre-cambrian basement igneous rocks exposed al-Nagar Parkar ( Fasset and Durrani, 1994) and this is only out crop bed rock in the region. At the depth of 110 to 277 meters the basement rock is generally granite and granodiorite. The granite is of white, pinkish grey to very light grey in colour and coarse grained having feldspar to highly altered Kaolinite (Jaffery, 1994). The Paleocene-Ecocene coal bearing horizons of clay stone, carbonaceous clay stone, sand stone and silt stone with inter-laminated coal beds. Sand stone is very fine to coarse grained and consists of ferro magnesium mineral grains. The metabasalts are medium to coarse grained volcanic and plutonic rocks that have metamorphosed to epidote amphibolites and contain acidic dykes of rhyolite to quartz trachyte composition (Jan et al., 1997). The coal bearing horizon of the Paleocene-Eocene sediments above the basement complex is designated as Bara formation is highly altered Kaolinite (Jaffery, 1994). The granite is white, pinkish grey. The stratigraphic sequence in the Thar coal test holes is generally the same (Table 1)
Composition, Trace Element Contents and Major Ash Constituents of Thar Coal, Pakistan
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7. Correlation Analyses
Correlation analysis is applied to the multivariate data set to investigate the degree of similarities and probable interrelations among the chemical and physical parameters (Nurken, 1997). Correlation coefficient between the variables for proximate and ultimate (as determined, as received) were calculated and listed in Table 9-12. Statistical analysis for the determination of correlation coefficient has been calculated. An overall view of the correlation mean results reveals that the numbers of parameters are not correlating with each other and which are correlated indicated by bold faces in the Table 9-12, suggesting that they are dependent on each other.
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M. Afzal Farooq Choudry, Yasmin Nurgis, Mughal Sharif, Amjad Ali Mahmood and Haq Nawaz Abbasi
The values obtained in proximate analyses (as determined and as received) suggesting that those variables which are correlating are similar in both types of analysis, indicating that energy values are dependent on volatile matter whereas the ash contents depend on % of sulfur in coal. The strong correlation existing between carbon: hydrogen and ash: sulfur in ultimate analyses (as determined and as received), pointing out that these variables are dependent on each other.
Table 1: Stratigraphic Sequence in the Thar Coal Field (Jaleel et al.,1999)
Age Recent Sub recent Thickness 14 to 93m 11 to 209m Lithology Sand, silt, clay Sandstone, siltstone, claystone, mottled Claystone, shale, coal, sandstone, carbonaceous claystone Granite, Gabbro and Diorite,
Formation Dune sand UN CONFORMITY Alluvial deposit UN CONFORMITY Bara formation, Ranikot group UN CONFORMITY Nagar Parkar Granite (Basement complex)
0 to 185m
Pre-cambrian
Table 2:
No 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22
SiO2 57.78 10.50 51.95 15.75 4.60 6.33 41.75 15.20 55.76 54.61 51.05 12.06 20.40 23.04 13.78 31.40 47.28 25.46 20.08 1.32 5.94 31.22
Table 3:
Coal Quality Moisture (AR) Ash (AR) Volatile Matter (AR) Fixed Carbon (AR) Sulphur (AR) Heating Value (Btu/Lb.) As Received Dry
Composition, Trace Element Contents and Major Ash Constituents of Thar Coal, Pakistan
Table 4:
Variable Moisture Ash% Volatile Fixed Ca Sulphur% Energy V
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Table 5:
Variable Moisture Ash% Volatile Fixed Ca Sulphur% Energy V
Table 6:
Variable Carbon Hydrogen Nitrogen Sulfur Ash Moisture Oxygen
Table 7:
Variable Carbon Hydrogen Nitrogen Sulfur Ash Moisture Oxygen
Table 8:
S No 1. 2. 3. 4.
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M. Afzal Farooq Choudry, Yasmin Nurgis, Mughal Sharif, Amjad Ali Mahmood and Haq Nawaz Abbasi
Correlation of proximate analysis as determinant
Moisture % -0.695 -0.255 0.269 -0.432 -0.058 Ash % -0.351 -0.666 0.589 -0.581 Volatile % Fixed Ca % Sulfur %
Table 9:
-0.237 0.416
-0.351
-0.096 0.268
-0.114
-0.693 -0.190
-0.034
-0.575 -0.310
-0.297
Composition, Trace Element Contents and Major Ash Constituents of Thar Coal, Pakistan
Figure 2: Showing the % of different variables of Thar coal (as-determent).
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H y d ro g e n As h
N i tro g e n M o istu re
C a rb o n Su l fu r O xy g en
H y d ro g en A sh
N i tro g e n M o i s tu re
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M. Afzal Farooq Choudry, Yasmin Nurgis, Mughal Sharif, Amjad Ali Mahmood and Haq Nawaz Abbasi
Figure 4: Flow Chart showing sequence of Sample Preparation and Chemical Analysis
Raw Coal as Received (about 2.5 kg, broken to 3 cm) About 100 gm of coal split out for standard coal analysis crushed to 60 mesh Air dried (D-2013, D-3302)
Crushed to 8 mesh
Sample pulverized to 60 mesh Ultimate and Proximate Analysis following ASTM (100 150 gm)
Proximate Analysis D 3172 to D 3175 % moisture D 3302 Volatile Matter Fixed carbon & Ash
Coal Ash
ICP- AES Acid Digest Na2O Calorific value D-1989 Sinter SiO2 K2O Al2O3 Fe2O3 CaO TiO2 MgO P2O5
Figure 5: Histogram showing the comparative proximate analysis of four blocks as-received (Thar coal).
III
IV
Composition, Trace Element Contents and Major Ash Constituents of Thar Coal, Pakistan
Figure 6: Histogram showing the comparative heating values of four blocks as received (Thar coal).
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6400 Heating Value (BTU/lb) 6200 6000 5800 5600 5400 1 I 2 II Block 3 III 4 IV
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M. Afzal Farooq Choudry, Yasmin Nurgis, Mughal Sharif, Amjad Ali Mahmood and Haq Nawaz Abbasi Kazmi A.H. and M.Q. Jan, 1997, Geology and Tectonics of Pakistan, Graphic Publishers, Pakistan, pp. 545. Lawrence L. B. and Joseph R.H. Chemical analysis of middle and upper Pennsylavanin coals from southeastern Kansas. Liu G., 2000. Experiment on coal leaching and study of the separation of trace elements Acta Geological Sinica 74 (2), pp. 386-390. Marcal P., Haidi F. and Elba C. T., 1997. Geochemical distribution of trace elements in coal: modeling and environmental aspects, Fuel 76 (14-15), pp. 1425-1437. Miesch, A.T., 1967. Methods of computation for estimating geochemical abundances U.S. Geological Survey, Professional Paper 574-B, pp. 15. Paul J. A. B., 1997. Toxicity and occupational health hazards of coal fly ash (CFA): A review of data and comparison to coal mine dust, Ann. Occup. Hyg. 41 (6), pp. 659-676. Robert B. F., Harvey E. B. and Baoshan Z., 1999. Health impacts of domestic coal use in China, Proc. Natl. Acad. Sci. USA l (96), pp. 3427-3431. Swaine, D.J., 1975. Trace elements in coal. In: Tugatinov A.I., (Ed.) Recent contribution to geochemistry and analysis. Halsted Press, New York, pp. 539-550. Vanhee, D., Gosset, P., Boitelle, A., Wallaert, B. and Tonnel, A. B., 1995. Cytokines and cytokine network in silicosis and coal workers, pneumoconiosis, European Respiration Journal 8, pp. 834-842.