Waste Processing

and Management
FMO543
By
Dr. Vishnu Teja Mantripragada
Assistant Professor
Dept. of Fuel Minerals & Metallurgical Engineering
IIT (ISM) Dhanbad.
Email: vishnuteja@iitism.ac.in
Module-2
 Contents
Utilization of Solid Wastes (CCR, Slags, Slimes, Tailings, Red mud, Mining waste, etc.)
• Building Materials

• Fertilizers

• PVC Products

• Paints & Pigments

• Raw Materials for Cement Manufacturing

• Brick Making

• Coatings

• Filtration & Purification, etc.

FMO 543: Waste Processing and Management 3

 Construction Materials
Traditional Construction Materials
• Concrete, Bricks, tiles, blocks, cement, mortar, etc.
• Produced from natural resources
• Continuous exploitation and depletion of natural resources
• Toxic substances are released into the environment during their manufacturing
• Contamination of air, water, soil, biosystems, human health, living standards, etc.
• Cost of construction materials is increasing by the day
• High demand
• Scarcity of raw materials
• High energy costs
• Environment friendly policies, etc.
• Alternative constituents/ingredients for construction materials are needed for
• Conservation of natural resources
• Energy savings
• Sustainable & environment friendly construction materials

FMO 543: Waste Processing and Management 4

 Solid Wastes as Construction Materials

• Solid wastes generated increasing every year, due to

• Population growth
• Technological innovations
• Increased urbanization
• Rising standard of living

• Fly ash, BF slag, red mud, etc., are successfully being used
as alternate construction materials.
• Recycling of non-hazardous components from hazardous
wastes is a challenge that is being tackled.
• Their utilization potential as an alternate construction material
is being explored.

• There is a great scope for setting up secondary industries

• For recycling
• For using solid wastes as construction materials.

Source: Safiuddin et al., Int. J. Phy. Sci., 2010

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Cement Manufacturing
Inclined rotary kiln
• 1 – 2 RPM, to inclination
• 2 – 3 m Dia, 90 – 120 m length
• Fuel burnt at the bottom; Material
charged at the top
• Drying (400oC)  Calcination (1000oC) 
Clinkering (>1500oC)
Conventional Raw Materials:
• Limestone, Clay, Sand
Alternate Raw Materials:
• Fly ash, Slag, Mill scale, Seashells, etc.
Cement Manufacturing Process:
• Dry Process
• Crushing  Grinding  Mixing
• Wet Process
• Crushing  Washing  Mixing
(Slurry)  Grinding

FMO 543: Waste Processing and Management 6

 Manufacturing of cement
• Clinker: Calcium aluminates and calcium silicates fused together
• Hard particles of 5 – 10 mm size.
2𝐶𝑎𝑂 + 𝑆𝑖𝑂 = 𝐶𝑎 𝑆𝑖𝑂 (𝐷𝑖𝑐𝑎𝑙𝑐𝑖𝑢𝑚 𝑆𝑖𝑙𝑖𝑐𝑎𝑡𝑒 𝐶 𝑆 )
3𝐶𝑎𝑂 + 𝑆𝑖𝑂 = 𝐶𝑎 𝑆𝑖𝑂 (𝑇𝑟𝑖𝑐𝑎𝑙𝑐𝑖𝑢𝑚 𝑆𝑖𝑙𝑖𝑐𝑎𝑡𝑒 𝐶 𝑆 )
2𝐶𝑎𝑂 + 𝐴𝑙 𝑂 = 𝐶𝑎 𝐴𝑙 𝑂 (𝐷𝑖𝑐𝑎𝑙𝑐𝑖𝑢𝑚 𝐴𝑙𝑢𝑚𝑖𝑛𝑎𝑡𝑒 𝐶 𝐴 )
3𝐶𝑎𝑂 + 𝐴𝑙 𝑂 = 𝐶𝑎 𝐴𝑙 𝑂 𝑇𝑟𝑖𝑐𝑎𝑙𝑐𝑖𝑢𝑚 𝐴𝑙𝑢𝑚𝑖𝑛𝑎𝑡𝑒 𝐶 𝐴
4𝐶𝑎𝑂 + 𝐴𝑙 𝑂 + 𝐹𝑒 𝑂 = 𝐶𝑎 𝐴𝑙 𝐹𝑒 𝑂 (𝑇𝑒𝑡𝑟𝑎𝑐𝑎𝑙𝑐𝑖𝑢𝑚 𝐴𝑙𝑢𝑚𝑖𝑛𝑜𝑓𝑒𝑟𝑟𝑖𝑡𝑒 𝐶 𝐴𝐹 )

• Clinker mixed with gypsum (2% – 5%) and finely grinded to form cement.
• Gypsum acts as a retarding agent and prevents early settling and hardening
• Cement composition: 50% C3S, 25% C2S, 10% CxA, 10% C4AF, 2 – 5% Gypsum

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 Concrete
Concrete = Filler + Binder + Admixture (optional)
Filler:
• Fine or coarse aggregate (Sand, crushed stone, etc.) that is held together by binder
• Chemically inert, hard, strong.
• Used to minimize the amount of cement; 70 – 80 % of concrete volume
Binder: Cement and water mix Source: matse.Illinois.edu

• Concrete needs moisture to hydrate & cure. Hydrolysis Dormancy

• Hydration reaction: Compounds in cement form Period
chemical bonds with water to become hydrates Hydration Slow
Hydration
• Exothermic Initial
Setting Hydration
• Hydrate formation hardens concrete  Curing
• Less water ⇒ Not fully reacted ⇒ Concrete dries
and doesn’t get stronger

FMO 543: Waste Processing and Management 8

 Concrete
• Calcium silicate hydrate crystals are formed first.
• Acts as seeds on which further CSH can form and grow
• As the crystals grow thick, it becomes more difficult for water to reach unhydrated CS
• Rate of reaction controlled by diffusion
2𝐶 𝑆 + 6𝐻 = 𝐶 𝑆 𝐻 + 3𝐶𝐻
2𝐶 𝑆 + 4𝐻 = 𝐶 𝑆 𝐻 + 𝐶𝐻
• Pores are formed in the concrete
(a) Hydration not started. Empty spaces are filled with
water (blue) around the grains (yellow)
(b) Hydration begins (pink)
(c) Hydration continues, empty spaces filled with water
and calcium hydroxide solution
(d) Nearly hardened cement paste
• More heat released during the hydration of C3S than C2S
• In general, the rates of hydration are as follows Source: matse.Illinois.edu

3 3 4 2

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 Concrete
Admixture:
• Substances added to concrete other than the key ingredients

Source: matse.Illinois.edu

FMO 543: Waste Processing and Management 10

 Coal Combustion Technologies
Pulverized Coal Combustion Fluidized Bed Combustion
• Conventional technology, 80% of coal-based power generation • Newer technology, Clean coal combustion technology
• Finer coal sizes (< 75 microns)
• Relatively coarser coal
Source: Computational Flow Physics Laboratory, Oregon University.

• 1300 – 1700oC combustion temperature

• Short residence time • 850 – 950 oC combustion temperature
• Volatiles entrapped inside molten ash particles • Non-porous bottom ash
• Ash of porous nature
• Molten ash exposed to relatively lower temperatures
• Molten ash exposed to higher temperatures

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 Fly Ash
Composition: Uses:
• Aluminosilicates, ferric/ferrous oxides
• Spherical particles, Amorphous • Cost effective substitute for Portland cement due to its
• 60 – 80 % composition pozzolanic properties
• Clay particles (Silica, Alumina, Magnesia, etc.) • Improves the strength of concrete
• Irregular shaped, Amorphous
• Small, spherical particles makes concrete workable
• Quartz
• Unburnt fuel (Carbon) • Raw material component for making bricks
• Improved compressive strength (80-100 kg/cm2)
Characteristics:
• Resistant to frost attack under certain conditions
• 0.5 – 300 microns size. • Reduces the firing energy
• Pozzolanic material • Lower permeability ⇒ Lower efflorescence
• Siliceous and aluminous material • Up to 20% lower water absorptivity
• No cementitious value in itself
• More dimensional stability than a red brick
• Cementitious in the presence of calcium hydroxide and
moisture, at ordinary temperatures. • Less wastage during transit
• Lime addition during melting increases the pozzolanic • Lower thermal conductivity (about 20%)
reactivity
• Grinding of ash increases the pozzolanic reactivity
Source: Handbook of Environment and Waste Management, Univ. of California.

FMO 543: Waste Processing and Management 12

 Bottom Ash
• Composition:
• Quartz, Aluminum silicates, alumina, hematite, C, etc.
• Particle Size:
• 10 microns – 1 mm
• Uses:
• Partial replacement for sand in construction
• Similar coefficient of curvature
• More internal friction than sand due to interlocking.
• More porosity than sand ⇒ More permeability,
degradation with time.
• Raw material for concrete and bricks
• Adsorbent for removal of toxic gases and dyes
• Filter for separating solid contaminants in water
• Manufacturing of Al based composite materials for better
strength & hardness
• Using liquid & powder metallurgy techniques.
• Recovery:
• About 90% of alumina can be recovered by acid leaching Original and ground coal bottom ash
• 50 – 60 % C can be recovered by floatation Source: Effects of ground bottom ash on properties of concrete, Mangi et al., 2019

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 Bottom Ash Utilization
Area Separation construction product Others
Wear resistant
Route C Al2O3 Concrete Bricks Adsorbent
particles
1. Sinter 1. Liquid
Methods

Floatation

Cement and 1. Cold bonded Removal

2. Acid metallurgy
Sand aggregate of toxic
leaching 2. Powder
substitute 2. Fired aggregates dye & gas
metallurgy
1. Geo-polymerization by
Results

alkali solution
1. 20% cement 1. 100% Dyes
replaced 2. Bricks with 15%
53% C, removal Al- based
90% Al2O3 bottom ash for
recovery composite with
recovery strengthening
1. 50% sand 2. CO2 better properties
3. Fired aggregates with
replaced removal
clay binder (800-
1100°C)
Source: Cheriaf et al, 1999; Targan et al, 2002; Jaturapitakkul and Cheerarof, 2003; Chindraprasirt et al, 2009; Sthonsaowaphak et al, 2009 Topku et al, 2014 ; Geetha and Rammurty, 2010, 2011; Chen et al, 2012

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 Coal Ashes Fly ash & Bottom ash mixtures Properties

Chemical Composition of Fly ash & Bottom Ash

Constituents Fly Ash (% wt) Bottom Ash (% wt)
SiO2 68 68
Al2O3 24 25
Fe2O3 + Fe3O4 2.18 2.18
MDD: Maximum Dry Density
TiO2 2.64 1.45
OMC: Optimal Moisture Content
CaO 1.49 1.66
MgO 0.06 0.02

Dry density
Fly ash & Bottom ash mixtures size analysis

% Water content

Source: Geotechnical properties of fly ash and bottom ash mixtures in different proportions, Kumar et al., 2014

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 Limitations of Ash in Concrete
• Ash admixtures lengthen the setting time
• Curing time: Time taken from pouring of concrete to till it hardens & gains strength
• Continues to gain strength for weeks after initial setting period
• Increased curing time desirable in hot weather, where setting is faster
• Undesirable in other times, delays construction speed
• Low temperatures lengthen setting time & cause low strength gain
• Use of fly ash in winter months banned in some regions
• Reduced air entrainment increases frost attack susceptibility
• Porosity reduced due to pozzolanic nature of ash.
• Can also reduce with low water-cement ratios, applying hydrophobic coatings, etc.
• Reduced porosity makes it more susceptible to frost attack or freeze-thaw cycles.
• Color variability
• Visual inconsistencies, dark streaks from carbon particles
• Inconsistent product quality
• Ash obtained from different sources has different composition & properties
• Not all of it is suitable for construction

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 Iron ore Slimes
• Major waste generated during Iron ore beneficiation.
• Iron ore contains alumina (about 7%) among other impurities in Gangue.
• Higher alumina, alumina/silica ratio detrimental to blast furnace chemistry
• Must be removed/reduced from ore
• During Ironmaking in blast furnace, a 1% increase in alumina
• Increases coke rate by 2.2%
• Increases basic fluxes consumption by 30 kg/T of hot metal.
• Alumina and content in iron ore is reduced by washing with water
• Red colored slurry; Iron slime
• 10% – 25% wt. of iron ore lost in iron slimes. (about 18 MT per year in India)
• 50% – 60% iron, 2% Alumina in the concentrate
Source: (Sengupta and Prasad, 1990), (Pradip,1995), (Singh and Singh, 1997).

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Material Characterization
Iron Slime SEM Image of Iron slime

Gangue

FBC bottom ash SEM Image of FBC bottom ash

Metal
phase

Source: Mandal and Sinha, 2014 J. Inst. Engg,A, 95(4)

Electron-Matter Interactions Scanning Electron Microscope (SEM)

PCC bottom ash SEM Image of PCC bottom ash

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 Physiochemical properties of iron slime & bottom ash
X-Ray Diffraction (XRD) peaks for phase identification
Physical Chemical

Proximate Ultimate
Surface area(m2/kg)
Bulk density(kg/m3)

(%) (%)
Specific gravity

Sample
pH

Fe2O3
Al2O3

Na2O

MnO
MgO

P2O5

TiO2
SiO2

CaO

K2O
Ash

SO3
VM

FC

Iron slime 3.39 2320 2200 7.63 7.1 92.9 - 31.4 24.1 42.1 0.1 - - 1.5 0.02 0.05 0.02 0.25

FBC BA 2.72 1230 1280 10.00 1.5 95.5 3.00 67.3 25.7 3.7 0.3 0.5 - 0.8 0.09 0.19 0.03 0.28

PCC BA 2.25 612 1650 9.42 1.1 94.7 4.20 70.0 22.1 2.5 0.8 1.2 - 0.6 0.10 0.16 0.03 0.34

Source: Mandal and Sinha, 2014 J. Inst. Engg,A, 95(4)

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Iron Slime Utilization
Area Beneficiation (~90% work) Conversion into Ceramic products

Pyro /
Routes Mechanical Hydro- metallurgy Pyro + Hydro- Firing Curing
metallurgy

1. Shaking Table 1. Roasting

1. Bio- leaching 1. Clay + flux
Method/ 2. Cyclone 2. Magnetic Lime + Sand +
2. Solvent extraction 2. Clay + Ash + Sludge
Materials 3. Spiral Separation Gypsum
3. Flocculation 3. Clay + Ash
4. Floatation 3. Leaching

1. Ceramic tiles
Pellet grade concentrate having up to 67% Fe (T) achieved from 30-40% 2. Light weight Temperature
Results
ceramic
Fe (T) resistant bricks
3. Construction bricks

Source: Roy et al, 2007, Srivastava et al, 2001, Prakash and Sridharan, 2009; Das et al, 2000; Liu et al, 2010; Chen et al, 2011; Zhao et al, 2012

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 Some Other Solid Wastes
Composition: gold mine tailings vs. red mud

Composition: copper mine tailings vs. soil Composition of various compounds in silver tailings

Source: Adajar et al., Int. J. Geomate, 2018 Source: Celep et al., Proc. XV Int. Min. Proc. Symp. & Exhib., 2016
Source: Kim et al., Geosystem Eng. , 2012

FMO 543: Waste Processing and Management 21

 Fertilizers
• Fertilizer: Substances containing the chemical elements that support the growth and
productivity of plants.
• Compost: Decomposed organic matter (leaves, kitchen scraps, etc.)
• Manure: Animal waste mixed with soil
• Synthetic: inorganic & organic mixtures
• Nutrition for plants: Primary: N, P, K Secondary: Ca, Mg, S Micro: Fe, Zn, Mn, Cu, etc.
• Nitrogen fertilizers: Ammonium nitrate (AN), Calcium ammonium nitrate (CAN), urea ammonium
nitrate (UAN), etc.
• Phosphorous fertilizers: Single superphosphate (SSP), di-ammonium phosphate (DSP),
monoammonium phosphate (MAP), etc.
• Potassium fertilizers: Potassium chloride (KCl), Potassium sulphate (K2SO4), Potassium nitrate (KN),
etc.
• Ca, Mg, S fertilizers: In combination with primary nutrients.
• S usually added to N fertilizers
• Kieserite is a Magnesium sulphate fertilizer
• Calcium nitrate, calcium sulphate (gypsum), limestone, etc., are Ca sources.

FMO 543: Waste Processing and Management 22

 Fly Ash in Soil
• When fly ash is mixed, it affects the soil texture.
• Lower bulk density
• Greater water holding capacity
• Reduced permeability
• Enhanced microporosity
• Enhanced electrical conductivity
• Indirect measure of salinity of soil
• Should be in the optimum range suitable for plant growth
• Enhanced cation exchange capacity
• Holds on to essential nutrients
• Buffer against soil acidification (due to hydroxide and carbonate salts in fly ash)
• Enhanced soil nutrition (source of K, Ca, Mg, Fe, Zn, B Mo, S, etc.)
• Fly ash is also used in composting to raise the pH and kill pathogens.
• Also, the lime in fly ash adsorbs any heavy metals and reduces their availability
• Reduced use of chemical fertilizers
• Many insect species are susceptible to fly ash dusting  Pesticide
FMO 543: Waste Processing and Management 23
 Fly ash in soil
• Fly ash dumping in soil is hazardous as negatively affects the human & ecology health.
• Can be used as a fertilizer, if used in measured & determined quantity.
• Fly ash contains radioactive compounds & heavy metals
• Safe, if applied in optimum quantity.
• Could possibly be hazardous in the long term.
• Unsafe, if used excessively, in bulk.
• Fly ash benefits on soil were studied in short term, i.e., for a few crop cycles
• Long term impacts on the soil, plant health, crop quality, etc., are unknown.
• Soil & fly ash quality & composition to be continuously/regularly monitored.
• Necessary action must be taken based on the collected data

FMO 543: Waste Processing and Management 24