AGRICULTURAL AND ZEOLITIC APPLICATION OF FLYASH : AGRICULTURAL AND ZEOLITIC APPLICATION OF FLYASH Guided By
Dr. K Balakrishna
Dept. of Civil Engineering, Presented By,
M Tech Environmental Engg Manipal Institute of Technology, Manipal Contents: : Contents: Introduction
Classification of flyash
Importance of proposed research investigation
Problems due to flyash
Use of Flyash
In Agriculture(crop cultivation)
As zeolite (Types, Synthesis and application )
Reference INTRODUCTION : INTRODUCTION In an industrial context, flyash usually refers to ash produced during combustion of coal [1.1].
The Ministry of Power, Govt. of India estimates 1800 million tons of coal is being used every year.
600 million tones of flyash will be generated by 2031-2032.
Generally one acre land is needed per M.W. of power production. [1.3].
About 40000 hectares of land is required for the construction of ash ponds [1,1.3]. Slide 4: Characteristics
Physical characteristics [3.1,1] Chemical characteristics [3.1,1] Table 1: Normal range of flyash produced from different coals  Slide 5: Figure 1: SEM images of the flyash morphology. (a) Typical view of the flyash particles with a predominantly spherical morphology. (b) Smaller particles attached to the surface of a larger particle serving as a substrate. (c) Hollow and empty spheres (cenospheres). (d) Hollow sphere containing smaller spheres (plerosphere) Slide 6: Classification
Flyashes are classified as [1.1,3]
class C (high CaO content >20%,subbituminous coal or lignite)
class F (low CaO < 20% content, bituminous coal)
Based on pH flyash can
Slightly alkaline (6.5-7.5),
Moderately alkaline (7.5-8.5),
Highly alkaline (>8.5).
According to ASTM standards, bituminous and subbituminous coal in India produces class F ash, and lignite produces class C ash with a high degree of self-hardening capacity [1.1].
In India, fly ash is generally highly alkaline due to low sulfur content of coal and presence of hydroxides and carbonates of calcium and magnesium. IMPORTANCE OF PROPOSED RESEARCH INVESTIGATION : : IMPORTANCE OF PROPOSED RESEARCH INVESTIGATION : Flyash problems [6,7,8]
Leaching-Ground water contamination,
Diseases like silicosis, fibrosis, bronchitis and pneumonitis.
Flyash Mission (Fly Ash Utilization Programme)
Department of Science and Technology, Government of India during 1994 has started Fly Ash Mission (FAM).
The coal requirement and generation of fly ash during the year 2031-32 would be around 1800 million tonne and 600 million tonne respectively .
Flyash Management Slide 8: UTILIZATION OF FLYASH Figure 2: Relationships between different flyash utilization strategies  Slide 9: Agricultural Application Soil texture :
Application of high rates of flyash can change the surface texture of soils, usually by increasing the silt content .
Bulk density :
Soil flyash (50%) mixture has lower bulk density.
Improves porosity, workability, root penetration and moisture-retention capacity of the clay soil .
Water Holding Capacity :
Under rainfed agriculture, Sandy soil.
The coarser size fractions of flyashes have higher water-holding capacity than the finer ones . Slide 10: Soil pH:
Most of the flyash produced in India is alkaline in nature.
Neutralization of acidic soils .
Flyash at the rate 30 g/2.5 kg soil increased soil pH from 5.02 in the control to 6.62 and up to 7.49 at a rate 90 g/2.5 kg soil .
Detoxification of Cd, Al, Mn .
Unweathered flyash particularly to sandy soil greatly inhibited the microbial respiration, enzymatic activity and soil N cycling processes like nitrification and N mineralization .
These adverse effects were partly due to the presence of excessive levels of soluble salts and trace elements in unweathered flyash. Slide 11: Plant Nutrient:
Lime in flyash readily reacts with acidic components in soil leading to release of nutrients such as S, B and Mo in the form and amount favourable to crop plants.
The high concentration of elements like K, Na, Zn, Ca, Mg and Fe in flyash increases yield of agricultural crops .
Flyash + Cow dung 
Sewage sludge composting .
Vermicomposting (Lampito mauritii). Slide 12: Table 2 Elemental composition of flyash, coal and soil Slide 13: Crop growth and yield: Arivazhgan et al.  revealed that the application of fly ash at the rate of 50Mt/ha increases the yield of
Rice (4920-5625 kg/ha)
Red gram (12.70-20.10q/ha),
Sugar cane (25500-41400kg/h)
Vegetable crops brinjal (10-20%),
Flyash and brick kiln dust were beneficial to the plant at lower levels i.e. 20% and 30% respectively . Slide 14: Table 3: Field crops and vegetables grown with flyash at various project sites  Slide 15: Figure 3: The pot plant trial results of K and Na zeolite. For each sets of photo the pots were arranged (from left to right) as) % (control pot), 1%, 2% and 5%.  Slide 16: Saving of chemical fertilizers :
Flyash based herbal pesticide (40kg/hectare) 
SLASH (25:10:60): Class F flyash can, if suitably augmented with quicklime, be used to pasteurise a toxic waste like sewage sludge.
Suitable for soil ameliorant.
Early growth of corn . Slide 17: Uptake of Heavy metals and toxic elements by plant:
The magnitude of heavy metal adsorption by plants depends upon heavy metal content in flyash, rate of addition of flyash to soil, the soil type and its pH, the plant species etc.
RRL, Bhopal observed that the uptake of heavy and trace metals by some vegetable is quite low and remains within the normal range .
Central Fuel Research Institute, Dhanbad
Toxic elements in Indian flyash are with relatively less concentration. Slide 18: Radio nuclides:
Bhaba Atomic Research Centre, Bombay .
Central Fuel Research Institute, Dhanbad .
Ground water contamination threat:
Relative mass leached is generally low.
At Central Fuel Research Institute (CFRI), Dhanbad it was also observed that flyash has no significant polluting effect on ground water . Slide 19: Zeolite: Zeolites are crystalline aluminium–silicates, with group I or II elements as counter ions. Their structure is made up of a framework of [SiO4]-4 and [AlO4]-5 tetrahedra linked to each other at the corners by sharing their oxygen (Figure. 4) [3, 24].
The tetrahedra make up a three-dimensional network, with lots of voids and open spaces. The substitution of Si (IV) by Al (III) in the tetrahedral accounts for a negative charge of the structure (Figure 3) which may give rise to high cation exchange capacity when the open spaces allow the access of cations. Figure 4: Idealized structure framework of tetrahedral with Si/Al substitution  Zeolite Synthesis : Zeolite Synthesis The synthesis of zeolites from flyash is classified into 
Direct (< 1200C)
Non-direct synthesis (> 1200C). Figure 5: Reaction mechanism for the batch hydrothermal conversion of flyash to zeolite  Table 6: Chemical sources and their function in zeolite synthesis. Slide 21: Figure 6: Process flow diagram for a zeolite synthesis plant employing flyash  Factors influencing zeolitization: : Factors influencing zeolitization: Flyash characteristics
Presence of Impurity
Grounded Flyash Figure 5: Scanning electron micrographs of a)Flyash B)Synthesized zeolite C)18X zeolite  Factors influencing zeolitization [cont] : Factors influencing zeolitization [cont] Fusion Temperature (823K)
Acids and bases (Si/Al)
Hydro thermal time
Aging Time (crystal growth)
Charge molecules and templates (Na or K)
Solvents (18ml/gm) Table 5 :Different types of zeolites  Application : Application Water Vapor Adsorption 
Sulphur dioxide removal - 38mg/gm :: SO2/zeolite , Fludized Bed
Heavy metal removal [33,34]- FAZ-A 500mg/l, Pb, Cd Cu
Water/Wastewater treatment [30,31,42]- Phousphorus, Chlorophenol
Immobilization of microorganism 
Ammonium Removal [26, 30, 31]
Cost Ammonium Removal : Ammonium Removal Class F (Zhang et al.)
Ammonium uptake capacities was 23.8 mg/g.
Contact time, pH, initial ammonium concentration, adsorbent dosage, presence of other cations and anions.
The effect of cations followed the order K+>Ca2+>Na+>Mg2+, while the effect of anions followed the order CO32->Cl−>SO42−. Table-6:Comparative behavior of flyash and zeolite  Conclusion: : Conclusion: This review aimed to act as a stepping-stone to reveal the potential of flyash for agricultural and zeolitic applications. More analysis of long-term economic and environmental impacts, possibly through employing life cycle assessments (LCAs) is needed.
The limitations of flyash application in agriculture and forestry include
Heterogeneity of flyash;
Contamination during flyash transport
Awareness of advantages of flyash uses among
The development of suitable mathematical models is needed for judicious combination of
selectivity of plant species. Conclusion (cont): : Conclusion (cont): More research is required in the zeolitic application of flyash.
Synthesis of zeolite
There is a scarcity of information on the environmental impact of fly ash as an ingredient in the preparation of materials.
More analysis of long-term economic and environmental impacts, possibly through employing life cycle assessments (LCAs) is needed.
The outdoors stability
The affordable price,
The local availability
Environmental non-toxicity Reference : Reference A.K. Chatterjee, Indian flyashes- their characteristics and potential for mechano-chemical activation for enhanced usability, Journals of Materials in Civil Engineering 23(6) (2011) 783-788.
S. Sushil, V.S. Batra, Analysis of fly ash heavy metal content and disposal in three thermal power plants in India, Journal of Fuel (2006) 2676-2679.
M. Ahmaruzzaman, A review on the utilization of fly ash Progress in Energy and Combustion Science 36 (2010) 327–363.
R&D and technology development-application in fly ash area, Department of science & technology fly ash unit, Govt of India 1-12.
A.K. Rai, B. Paul, G. Singh, Assessment of physico chemical properties of fly ash from tisco power plant, jamadoba, jhariacoalfields, jharkhand,india, Journal of advanced laboratory research in biology 1(1) (2010) 1-9.
R. Meij and H. te Winkel, Health aspects of coal fly ash International Ash Utilization Symposium, Center for Applied Energy Research, University of Kentucky (2001) 1-7.
S Sushil, V. S. Batra, Analysis of fly ash heavy metal content and disposal in three thermal power plants in India, j.fuel (2006) 2676-2679.
B.Lokeshappa , A. K. Dikshit, Disposal and management of flyash International Conference on Life Science and Technology 3 (2011) 11-14.
M. Basu, M. Pande, P.B.S. Bhadoria, S.C. Mahapatra, Potential fly-ash utilization in agriculture-a global review, Progress in Natural Science 19 (2009) 1173–1186.
L.C. Ram, R.E. Masto, S. Singh, R.C. Tripathi, S.K. Jha, N.K. Srivastava, A.K. Sinha, V.A. Selvi, A. Sinha, An appraisal of coal fly ash soil amendment, 1-12.
K. Arivazhakan, M. Ravichandran, Effect of fly ash on agricultural crops. World of Coal Ash Conference (2011) 1-12.
S.K.Sharma, K.Naveen, Effect of fly ash incorporation on soil properties and productivity of crops. Journal of Scientific and Industrial Research 65 (2006) 383-390.
L.C. Ram, R.E. Masto, Smriti Singh, R.C. Tripathi, S.K. Jha, N.K. Srivastava, A.K. Sinha, V.A. Selvi, A. Sinha, An appraisal of coal fly ash soil amendment, 1-12.
C.D. Tsadilas, V. Samaras, P. Kazai, and J. Sgouras, Fly ash and sewage sludge application on an acid soil and their Influence on Some Soil Properties and Wheat Biomass Production. 12th ISCO Conference, Beijing (2002) 118-123.
M. Saxena, A. Chauhan and P. Asokan, Flyash vemicompost from non-friendly organic wastes, Pollution research, 17 (1) (1998) 5-11.
S. Singh, B.K. Tiwary, A. Sinha, Performance of agricultual crops in flyash amended soil World of Coal Ash Conference (2011) 1-21.
M.W. Aktar, Fly ash use in agriculture: a perspective Pesticide Residue Laboratory, Department of Agricultural Chemicals.
K. Reynolds, R. Kruger, The manufacture and evaluation of an artificial soil (slash) prepared from fly ash and sewage sludge International Ash Utilization Symposium, Center for Applied Energy Research, University of Kentucky (2001) 1-18.
K.Reynolds, R.Kruger, Crop responses to slash (mixture of sewage sludge, lime and fly ash) as influenced by soil texture, acidity and fertility. Center for Applied Energy Research, University of Kentucky (2001).
M. Eisenbud, H.C. Petro, Radioactivity in the atmospheric effluents of power palnts that use fossil fuel. Science 144(288) (1964) 33-38.
A. Georgakopoulos, A. filippidis ,A. kassoli-fournaraki ,Leachability of major and trace elements of leachability of major and trace elements of northern Greece. Energy Sources 24 (2002) 103–113. Slide 29: C.A. Palmer, R.B. Finkelman, M.R. Krasnow. C.F. Eble, US. Geological Survey, National Center Moratory leaching behaviour of environmentally sensitive Fly ash and bottom ash samples.
S. Sarojini, S. Ananthakrishnasamy, G. Manimegala, M. Prakash and G. Gunasekaran Effect of lignite fly ash on the growth and reproduction of earthworm. E-Journal of Chemistry 6(2) (2009) 511-517.
R. Rizvi, A.A. Khan, Response of Eggplant (Solanum melongena L.) to fly ash and brick, Biology and Medicine 1 (2) (2009) 20-24.
F. Canpolat, K. Yılmaz, M.M. Köse, M. Sümer, M.A. Yurdusev, A discussion of the paper, Use of zeolite, coal bottom ash and fly ash as replacement materials in cement production, Journal of Cement and concrete research 35 (2005) 1020-1021.
F. Canpolat, A reply to the discussion by H. Un of the paper “Use of zeolite, coal bottom ash and fly ash as replacement materials in cement production, Journal of Cement and concrete research 35 (2005) 1022-1023.
C.S. Poona, U.L. Lama, S.C. Koua, Z.S. Lin, A study on the hydration rate of natural zeolite blended cement pastes, Construction and Building Materials 13 (1999) 427-432.
D. Karamanis, E. Vardoulakis, Application of zeolitic materials prepared from fly ash to water vapor adsorption for solar cooling Department of Environmental & Natural Resources Management, University of Ioannina, Greece.
M. Zhang, H.Zhang, D. Xu, L.Han, D.xiao Niu, L. Zhang, W.Wu , B.Tian, Ammonium removal from aqueous solution by zeolites synthesized from low-calcium and high-calcium fly ashes, Desalination 277 (2011) 46–53.
M.L. Zhang, H.Y. Zhang, D. Xu, L. Han, D.X. Niu, B.H. Tian, J. Zhang, L.Y. Zhang, W.S. Wu, Removal of ammonium from aqueous solutions using zeolite synthesized from fly ash by a fusion method, Desalination 271 (2011) 111–121.
M. Zhang, H.Zhang, D.Xu, L.Han, D.xiao Niu, L. Zhang, W.Wu, B.Tian, Ammonium removal from aqueous solution by zeolites synthesized from low-calcium and high-calcium fly ashes ,Desalination 277 (2011) 46-53.
T. T. Suchecki, T. Wałek, M. Banasik, Fly Ash Zeolites as Sulfur Dioxide Adsorbents Polish Journal of Environmental Studies 13(6) (2004) 723-727.
M.G. Lee, Conversion of Coal Fly Ash into Zeolite and Heavy Metal Removal, Korean ournal of Chemical Engineering 17(3) (2000) 325-331.
N. Moreno, X. Querol, Immobilization of Heavy Metals in Polluted Soils by the Addition of Zeolitic Material Synthesized from Coal Fly Ash, International Ash Utilization Symposium, Center for Applied Energy Research, University of Kentucky (2001) 1-8.
J. C. T. Endres, L. S. Ferret, The Removal of Fe, Zn, Cu, and Pb from Wastewaters Using Chabazite Zeolites Produced from Southern Brazilian Coal Ashes International Ash Utilization Symposium, Centre for Applied Energy Research, University of Kentucky (2001) 1-7.
S. S. Rayalu, A. K. Bansiwal, S. U. Meshram, N.Labhsetwar, and S. Devotta, Fly ash based zeolite analogues-versatile materials for energy, Catalysis Surveys from Asia 10(2) (2006) 74-89.
X. Querol, J.C.Umana, Synthesis of zeolite from fly ash, International Ash Utilization Symposium, Center for Applied Energy Research, University of Kentucky (2001) 1-8.
K. Ojha, N.C. Pradhan, A.N. Samanta, Zeolite from fly ash synthesis and characterization, Bull. Mater. Science 27(6) (2004) 555–564.
C. Belviso, F. Cavalcante, Zeolite Synthesised from Fused Coal Fly Ash at Low Temperature Using Seawater for Crystallization, Coal Combustion and Gasification Products 1(2009) 8-13. Slide 30: P. Solanki, V. Gupta and R. Kulshrestha, Synthesis of Zeolite from Fly Ash and Removal of Heavy Metal Ions from Newly Synthesized Zeolite, E Journal of Chemistry 7(4) (2010) 1200-1205.
X .Querol, R. Juan, Synthesis of high ion exchange zeolites from fly ash,Geologica Acta 5(1) (2007) 49-57.
N. Moreno, X .Querol, Synthesis of zeolite from fly ash, International Journal of coal geology (2002) 413-423.
L.S. Ferret, I.D. Fernades, Zeolification of ashes obtained from the combustion of Sourthern’s Brazil Canadiota Coal, International Ash Utilization Symposium, Centre for Applied Energy Research (1999) 1-6.
O. Font, N .Moreno, Differential Behaviour of Combustion and Gasification Fly Ash from Puertollano Power Plants (Spain) for Zeolite Synthesis and Silica Extraction, World of Coal Ash (2005).
H.W. Nugteren, X. Querol, Determination of the Available Si and Al from Coal Fly Ashes under Alkaline Conditions with the Aim of Synthesizing Zeolite Products, International Ash Utilization Symposium, Center for Applied Energy Research, University of Kentucky (2001) 1-8.
C. Rongsayamanont, Modification of Synthetic Zeolite Pellets from Lignite Fly Ash A -The Pelletization, World of Coal Ash (2007) 7-12.
C. Rongsayamanont, Modification of Synthetic Zeolite Pellets from Lignite Fly Ash B -Treatability Study, World of Coal Ash (2007) 7-10.
C.D. Woolard, K. Petrus and M. van der Horst, The use of a modified fly ash as an adsorbent for lead, Water SA 26(4) (2000)531-537.
E.Otal, N.Moreno, Application of Zeolitized Coal Fly Ashes to the Depuration of Liquid Wastes, International Ash Utilization Symposium, Centre for Applied Energy Research, University of Kentucky (2003) 1-14.
X. Querol, N. Moreno, Fly Ash Zeolitization Products Applied to Waste Water and Flue Gas Decontamination, International Ash Utilization Symposium, Center for Applied Energy Research, University of Kentucky (2001) 1-8.
N. Koukouzas, C.Vasilatos, Characterization of CFB-Coal Fly Ash Zeolitic Materials and Their Potential Use in Wastewater Treatment, World of coal ash conference (2009) 1-12.
H.Fanzuri, D. Pritchard, Manufacture of Low grade Zeolite from fly ash for fertilizer application, Centre for Fuels and Energy, Curtin University of Technology (2008) 1-136.
X.Querol, N.Moreno, Synthesis of zeolite from coal fly ash, International Jornal of Coal Geology (2002) 413-423. Websites:
www.bangalorebio.com Slide 31: Thank you