IJEP 31 (11) : 933-939 (2011)

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A Study on Leachability of Trace Elements from Coal Flyash in Different Medium

R. K. Singh, N. C. Gupta and B. K. Guha GGS Indraprastha University, School of Environment Management, New Delhi- 1100075 India uses coal as a major fuel for power generation and fly ash is a byproduct generated from thermal power plant. Hydraulic ash transport systems are used in most coal fired power plants, which leads to serious water pollution contamination due to leaching of trace elements. The leaching behavior of trace contaminants from coal ash in different medium is critical to environmental risk assessment. Batch shake extraction tests have been performed on the fly ash collected from the hopper of the electrostatic precipitator (ESP) of Indraprastha Power Station, Delhi to study the leaching characteristics of Fe, Cr, Cu, Pb, Cd and Ni. Leaching solution includes Extraction fluid (pH~4.93 0.05), Aqueous Solution (pH~7) and Buffer solution (pH~10-11). The liquid/solid (L/S) ratio was about 20:1 in all leaching tests. Four leaching time intervals were selected, ranging from one week to four week. From the experiments it was observed that Cr has a relatively higher leachability in aqueous and buffer solution, whereas in extraction solution, Ni has a relatively higher leachability. Further with the increase of leaching time, the leachability of Cr in aqueous solution increases. In buffer solution the leachability of Cr increases first and then decreases with increase in leaching time. With the increase of leaching time, the leachability of Ni in extraction fluid increases.

KEYWORD Fly ash, Leaching, Leaching medium, Trace elements, Shake test. INTRODUCTION The term `coal` is believed to have originated from the Sanskrit world `kaal`, meaning black. In ancient time, coal was known as burning rock and was believed to possesses supernova power (Sharan et al. 1994). Coal is a major source of energy in India, and its utilization is supposed to increase in future to meet increasing demand of electrical energy production. With increasing coal combustion fly ash becomes a serious environmental concern due to leaching of many trace metals. India ranked third in the world with 7 percent coal reserves of the total world reserves. Coal production increased from 30 million tones to over 427 million tones in 2010. India uses coal as a major fuel input for power generation. About 59.2 percent of total electricity production is based

on coal in the country. There are 72 coal based thermal power plants are operational in India. Presently, about 110 million tones of coal-ash is generated annually in India from these 72 thermal power plants. By the year 2012 this is predicted to increase to 170 million tons per annum. In Delhi alone the production of fly ash is nearly 1.5 million tonnes per annum by the three thermal power stations. The usual methods of ash disposal employed are (i) dumping in a disposal area, (ii) placement and compaction in a controlled fill and (iii) slurring with water followed by pumping into a lagoon or impoundment. The Indraprastha Power Station (IPS) with 28 37 N latitude and 77 15 W longitude is located on the western bank of the River Yamuna in Delhi. IPS has a capacity of 285MW, (Clarke et al,1997) and burns about 1.46 million tonnes per annum of bituminous coal with 35.9% ash content, from collieries in Bihar and West Bengal, producing about 0.5 million tones of
0 / 0 /

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EXTRACTION VESSEL Sample (Fly ash + Extraction Fluid)

MOTOR 1005 rpm

Figure 1. Extractor ash annually (Holding, 1992; Walia and Mehra, 1998). This ash comprises about 400000 tonne of PFA and 100000 T of BFA. The particulate material is removed using ESPs, with the PFA sluiced using 14 400m of River Yamuna water daily in a slurry to settling and decanting lagoons of 2 km extent (Walia and Mehra, 1998). Presently some part of fly ash is supplied to cement manufacturers and brick manufacturers and remaining are dumped in ash ponds. These ashes are not processed in anyway prior to dumping. Fly ash from Indraprastha Power Station is being dumped openly for the last several years in the form of wet slurry to the pond, where the leaching of trace metal contaminate both surface and ground water. In India, at present, the major portion of fly ash produced goes for disposal in ash ponds and landfills and only a small fraction of it is utilized and the utilization rate (13%) is far below the global utilization rate at (25%). Fly ash is the mineral matter in coal that has been thermally altered as it cycles through the combustion process. Ash may contain As, B , Be, Ca, Cd, Cr, Fe, Hg, Mg, Mo, Na, Ni, Pb, Ra, Se, Th, U, V, Zn etc. either on the surfaces of ash particles or in the aluminosilicate matrix phase or in both, as a consequence
2 3

of volatilization and condensation during combustion (Henry and Knapp 1980; Hansen et al,. 1984; Smith 1987). The leaching of coal fly ash during disposal is of great concern for possible contamination, especially for the aquatic environment when ash is in direct contact with water. Therefore, it is important to predict the leaching behavior of residues to prevent the environmental effects. The toxic elements leached from fly ash can contaminate soil, ground water as well as surface water. Human beings, livestock and other animals can be poisoned through water and food chain because the heavy metals can be transformed into heavy metal compounds by biological accumulation. Therefore, the study of the leaching behavior of heavy metals on coal fly ash is paramount for environmental risk assessment. Generally, leaching experiments in the laboratory mainly use the batch leaching and column leaching methods. A suitable batch leaching condition can help us quickly obtain the kinetic parameters of leaching tests. Batch extraction method is the most economical and fast method to examine the leaching characteristics of traces metals. Metal recovery is sometimes considered as the effective method to reduce leaching of heavy

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Figure 2. Leachability of Iron in different eaching solution

Figure 5. Leachability of Cadmium in different l leaching solution

Figure 3. Leachability of Copper in different leaching solution

Figure 6. Leachability of Chromium in different leaching solution

Figure 4. Leachability of Lead in different leaching solution

metals. But, it is difficult for wide application because of higher cost input. Study area This paper aims to elucidate the leaching characteristics of heavy metals in fly ash from Indraprastha Power Station in different leaching medium through long-time batch leaching tests. Four different shaking periods were used and the long-

Figure-7. Leachability of Nickel in different leaching solution

est period is four week. The considered heavy metal involves Fe, Cr, Cu, Pb, Cd and Ni.

MATERIAL AND METHOD Leaching is a method to remove soluble components from a solid matrix. A survey of the literature identified over 100 leaching methods (Hesbach

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and Lamey 2001). Leaching can be described by a very simple equation: material (leachee) + leachant leachate. It can be assumed that the material to be leached is known, although its physical and chemical/mineralogical properties can affect the final result. The purpose or what you expect to find in the leachate will determine the selection of a leachant and also the conditions of the test. The main method of disposal of fly ash in the IP Station is slurry form. The resultant slurry is transferred to an ash disposal pond. For the purpose of study freshly generated fly ash was collected (5 kg) from the hopper of electrostatic precipitator of Indraprastha Power Station, Delhi. In this power house bituminous coal is being used for power generation. The average concentration of various metals in Indian fly ash is given in Table 1. Table 1: Trace elements in fly ash from different states in India in mg/kg (Dutta et al. (2009); Sushil et al. (2006) Trace elements As Pb Cr Zn Cu V Zr Ba Sc Y Co Ni Mn West
2 1 2

Visually IPS fly ash was light grey in color and irregular in shape. Fly ash sample was dried at 105 C for 48 hours. For the leaching experiment batch leaching method is employed, in which a fix quantity of fly ash sample was placed in given volume of leachant solution for a set period of time. Most of these methods require some type of agitation to insure constant contact between the sample and the leachant. At the end of the leaching period, the liquid was removed, filtered and analyzed. This test method is intended as rapid means for obtaining an extract & solid waste. The shake test was performed as per the American Society of Testing Materials (ASTM) method using a agitation device designed to rotate about a central axis at the rate of 100 rpm (as shown in figure-1) with an L/S ratio of 20:1, using 10 gm dried fly ash in 200ml of extraction solutions over varying periods of leaching. In the study three extraction solutions have been selected; i.e. (i) Extraction fluid (pH~4.93 0.05), (ii) Aqueous Solution (pH~7) and (iii) Buffer soluO

Delhi 56 103 124 18 18 63 62

Orissa 83.63 145.75 69 83.36 16. 88 56.50 338.91

tion (pH~10-11). Each medium was tested, using a glass bottle of 500ml capacity. After agitation for 168 hours, 336hours, 504 hours and 672 hours, the samples were allowed to settle for five minutes, and then they are filtered through a 0.45m filter paper for analysis. For the analysis of trace metals the filtrates were acidified (pH< 2) with HNO3 and preserved at 4 C to prevent any additional reaction. The elements like Fe, Cr, Cu, Pb, Cd and Ni were analyzed by Atomic Absorption Spectrophotometer (Perkin Elmers, Model No. A Analyst 700). RESULTS AND DISCUSSION Of the various trace elements present in fly ash only Fe, Cr, Cu, Pb, Cd and Ni were analyzed in extraction fluid, aqueous solution and buffer soluO

Bengal 490 9.5 20 290 20 30 30 550 10 10

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tion leachates. Considerable variation was found in the heavy metal concentration in all leachant from same thermal power plant and for same leaching period. Figure-2 shows the relationship between leachability of Iron and leaching time in different leachant. The leaching of iron in fly ash with buffer solution rises significantly with time. The leachability of Fe fluctuates over time with extraction fluid and aqueous solution. The leachability does not reach stability in the leaching process in extraction fluid and aqueous solution. The leachability of Fe is slightly higher when the fly ash is mixed with the extraction solution. The highest leachability approaches 0.085 mg/l in aqueous solution, 0.141 mg/l in buffer solution and 0.303 in extraction fluid. Fe is easy to enrich in the surface of the fly ash particles. The relationship of leachability of Fe with three leachants is LExtration > LBuffer > LAqueous. Figure-3. exhiibits the relationship between leachability of Copper and leaching time in different leachant medium. The leaching of copper in fly ash with aqueous solution increase significantly with time. The leachability of Cu fluctuates over time with buffer solution and extraction fluid. The leachability does not reach stability in the leaching process in buffer solution and extraction fluid. It is seen that leachability of Cu is higher when the fly ash is mixed with the extraction solution. The highest leachability approaches 0.021 mg/l in aqueous solution, 0.031 mg/l in buffer solution and 0.104 in extraction fluid. The relationship of leachability of Cu with three leachants is LExtration > LBuffer > LAqueous. Figure-4 shows the relationship between leachability of Lead in different leachant and leaching time. The leachability of Pb fluctuates over time. The leachability does not reach stability in the leaching process in any of the leachant medium. The leach-

ability of Pb is slightly higher when the fly ash is mixed with the buffer solution. The highest leachability approaches 0.058 mg/l in aqueous solution, 0.059 mg/l in buffer solution and 0.051 in extraction fluid. Pb is easy to enrich in the surface of the fly ash particles. The leaching characteristics of Pb is closely associated with minerals characteristics of dissolving. Pb3(CO3)2(OH)2, PbSO4 and PbCO3 were considered to be the major mineral that will affect the leachability of Pb. The compounds of Pb have low solubility. These factors may lead to the low leachability of Pb in the experiment. Figure-5 shows the relationship between leachability of cadmium in different leachant and leaching time. The leachability of Cd in all three leachants is not stable and has no significant difference in leaching in different solution. The leachability does not reach stability in the leaching process in any of the leachant. The leachability of Cd is slightly higher when the fly ash is mixed with the extraction solution. The highest leachability approaches 0.064 mg/l in aqueous solution, 0.059 mg/l in buffer solution and 0.183 in extraction fluid. Some studies indicate that Cd is rich in the surface of fly ash particles so it is easy to leach out in fly ash. On the other hand, Cd can combine with Zinc Oxide and Fe Oxides (e.g. FeS2 or ZnS) in the coal. These sulphides can form spinel which is insoluble (as ZnFe2O4) in coal combustion process. Partial Cd could be included in these minerals, which leads to leaching incompletely. Figure-6 shows the relationship between leachability of Chromium in different leachant and leaching time. Whether the fly ash leaching with aqueous solution, buffer solution or extraction fluid, the leachability of Cr rises significantly with the time. The leachability is on higher side with the extraction fluid solution as compared to aqueous and

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buffer solution. The relationship of leachability of Cr with three leachants is LExtration > LBuffer > LAqueous. 50-90% of chromium is enriched in the organic matter in coal, and 10-50% exist in clay minerals and only a small amount of chromium occurs in sulphides, Cr is likely to concentrate on the particle surface through the combustion process. The dissolution of main minerals will affect the leaching characteristics of Cr, especially the element absorbed on the surface of the particle. In addition, Cr can exist in Al and Fe oxides and is possible to concentrate in illite clay. Cr can also be enriched in other minerals by the effect of conversion of organic material in the coal. Figure-7 shows the relationship between leachability of Nickel in different leachant and leaching time. Whether the fly ash leaching with aqueous solution, buffer solution or extraction fluid, the leachability of Ni increases substantially with time. The leachability is on higher side with the extraction fluid medium than aqueous and buffer solution.

The relationship of leachability of Cr with three leachants is LExtration > LBuffer > LAqueous. CONCLUSION Coal fly ash is disposed off in ash pond with higher environmental risk. The result of shake test, with pre-leached fly ash showed that the release of elements into different leachant continues over a period of time. Leaching of fly ash in different leachant have different amount of metallic elements. The pH value of leachates obtained during leaching process appears to be related to the alkalinity of the original ashes. The leachability of trace element in fly ash is affected by time of leaching. The leachability of Fe, Cu, Cr and Ni shows the trend as LExtration > LBuffer > LAqueous. The leachability of Pb and Cd fluctuates over time. It was observed that leachability does not reach stability in the leaching process in any of the leachant. The leachability of Pb is slightly higher when the fly ash is mixed with the buffer solution and the leachability of Cd is also on higher side when the fly ash is mixed with the extraction solution.

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Sharan, A., Sharma, A. and P. Govind (1994). Impact of coal mining on social ecology- A tentative note. In: Dhar, B. B. and Saxena, N. C. (eds.), Socio-economic Impact of Environment. Akashi Publishing House. New Delhi. pp. 46-65. Smith IM (1987). Trace elements from coal combustion: emissions, chap 2, Source of trace elements, IEACR/01 IEA Coal Research, London. Sushil, S. and S. V. Batra (2006). Analysis of fly ash heavy metal content and disposal in three AUTHOR 1 *. Mr. R. K. Singh, University School of Environment Management, GGS Indraprastha University, Sector-16C, Dwarka, New Delhi-110075, India. 2. Dr. N. C. Gupta, Associate Professor, University School of Environment Management, GGS Indraprastha University, Sector-16C, Dwarka, New Delhi-110075, India. 3. Prof. B. K. Guha, Department of Chemical Engineering, IIT Delhi, Hauz Khas, New Delhi110016, India.

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