Fly Ash

nous coal) occurs in the form of minerals of various types and sizes that are closely
associated with the organic matter (included minerals) or they occur excluded from
the organic matter (excluded minerals). Organically-bound inorganic elements such
as Na, K, Ca, and Mg, which are distributed within the coal macerals and are gener-
ally the more volatile species, are commonly found in lower rank coals such as lig-
nites and subbituminous coals. The modes of occurrence of minerals and other
inorganic constituents in coal are illustrated in Figure 3.2 [modified from 11].
During the combustion process, these constituents undergo chemical and physi-
cal transformations to form ash. The mechanisms of ash formation have been stud-
ied extensively and include fusion, agglomeration, shedding, fragmentation,
vaporization, and condensation [12!14]. These stages are not sequential and are
influenced by the combustion conditions and the coal characteristics. Examples of

Composition and Mineralogy of Coal two simplified mechanisms for producing fly ash (which must then be captured by
control technologies discussed in this chapter) are provided in Figures 3.3 [modified
from 14] and 3.4 [modified from 15], which, respectively, depict mechanisms for
• Organic Material pulverized coal and fluidized-bed combustion, the two primary combustion technol-
ogies for power production.
• Heterogenous material composed of
different quantities of organic
components termed as macerals
• Inorganic Material
• Accumulation of the minerals from the
nearby area due to weathering and
erosion of associated minerals during
streamflow or flooding events during the
coalification process.
• Mineral matter in coal commonly
includes:
• Alumino-silicate clays
• Silicates Figure 3.2 Modes of occurrence for minerals and other inorganic constituents in coal.
• Carbonates
• Disulfides as major components
Coal Ash
• Coal Combustion Residuals (CCRs)
• Fly Ash
• Bottom Ash
• Boiler Slag
• FGD Material
Disposal
• Coal ash is disposed of or used in different ways depending on:
• Type of by-product
• Processes at the plant
• Regulations the power plant has to follow
• Some power plants may dispose of it in surface impoundments or in
landfills.
• Coal ash may also be recycled into products like concrete or
wallboard.
 Particulate formation and control technologies

Compositional ranges of inorganic species of coal fly as

Table 3.2
and heavy fuel oil fly ash from combustion systems (ppm)
Element Coal fly ash Heavy fuel oil fly asha
Major/Minor elements

Coal Fly Ash Aluminum (Al)

Calcium (Ca)
Iron (Fe)
70,000!280,000
9,500!360,000
34,000!235,000 4,300
Silicon (Si) 150,000!605,000

• Finely divided particles of ash entrained

Magnesium (Mg) 3,900!66,000
Potassium (K) 6,200!21,000
Sodium (Na) 1,100!26,000
in flue gas. Particles may contain Sulfur (S)
Titanium (Ti)
1,300!390,000
3,500!27,000
585!126,000

unburned fuel. Trace elements

Antimony (Sb) BDLb!16
• Generally, 60%-88% of fly ash is Arsenic (As)
Barium (Ba)
22!260
380!5,100
26

produced from the coal-fired thermal Beryllium (Be)

Boron (B)
2!26
120!1,000

power station. Cadmium (Cd)

Chromium (Cr)
BDL!4
27!300
0.8
7
Copper (Cu) 62!220 87!287
Lead (Pb) 11!230 57!342
Manganese (Mn) 91!700 125
Mercury (Hg) 0.01!0.51 0.42
Molybdenum (Mo) 4.8!60 85!720
Nickel (Ni) 47!230 90!13,800
Selenium (Se) 1.8!18 3.8
Strontium (Sr) 270!3,100
Thallium (Tl) BDL!45
Uranium (U) BDL!19
Vanadium (V) BDL!360 6,700!61,000
Zinc (Zn) 63!680 72.5
a

Compositional
Below detection level. ranges of inorganic species
In some cases, no values available or single values available.
b

of coal fly ash (ppm)

3.2.3 Natural gas and liquefied petroleum gas fly ash formatio
Particulate matter emissions from natural gas and liquefied petroleum gas (LP
are typically low. Particulate matter in natural gas combustion is usually lar
molecular weight hydrocarbons that are not fully combusted. Particulate ma
emissions from LPG result from soot, aerosols formed by condensable emitted s
cies, or boiler scale dislodged during combustion.
Mechanisms of Coal Fly Ash Formation
• Fusion
• Agglomeration
• Shedding
• Fragmentation
• Vaporization
• Condensation
Mechanism – Pulverized Coal Combustion
150 Fossil Fuel Emissions Control Technologies

Figure 3.3 Formation of particles in pulverized coal combustion.

 Figure 3.3 Formation of particles in pulverized coal combustion.

Mechanism – Circulating
Fluidized Bed Combustion

Figure 3.4 Formation of fly ash during circulating fluidized-bed combustion of coal.
 Partitioning of the trace elements in the bottom ash, ash collected in the air
pollution control device, and fly ash and gaseous constituents emitted into the
atmosphere depends on many factors including the volatility of the elements,
temperature profiles across the system, pollution control devices, and operating
conditions [18,19]. Numerous studies have shown that trace elements can be clas-
sified into three broad categories based on their partitioning during coal combus-
tion. A summary of these studies is presented by Clarke and Sloss [19].
Figure 3.5 illustrates the classification scheme for selected elements (modified

Classification Scheme for Selected Trace Elements

after [16] and [19]).

Figure 3.5 Classification scheme for selected trace elements relative to their volatility and
partitioning in power plants.
Mineralogical Composition of Fly Ash
• Inorganic material: consists of amorphous matter, such as a variety of
glassy particles and crystalline matter like grains and crystals and a
collection of a variety of minerals.
• Organic material: comprises char such as coked and semicoked
particles and organic matter.
• Fluid material: consists liquid (moisture), gas-liquid inclusions, and
liquid in association with both organic and inorganic matter.
Mineralogical Composition of Fly Ash
• The phases and minerals in fly ash can be grouped into four types
depending upon the percentage present.
• Forming (> 10%)
• Major (lies in between 1 – 10%)
• Minor (lies in between 0.1 – 1%)
• Accessory (Less than 0.1%)
Elemental Composition of Fly Ash
• The elemental composition of fly ash has a natural origin, which can
be categorized into primary (original) or secondary and tertiary
(newly formed) phases and minerals.
• Primary or original constituents—constitutes those phases or coal minerals
that do not undergo phase change during combustion of coal such as
carbonates, oxides, phosphates, some stable silicates, sulfates, and some
other minerals with relatively high melting temperatures or high
decomposition;
• Secondary constituents—char, glass, sulfides, oxides, various silicates formed
via phase transformations during combustion of coal;
• Tertiary constituents—during storage and transport of fly ash, new phases or
minerals such as amorphous material, hydroxides, Al and Fe, dolomite,
calcite, Fe sulfate, gypsum, brucite, portlandite are formed, termed as tertiary
constituents.
Classification of Fly Ash
• The taxonomy of this classification system is based on the seven basic
groups/units depending upon the chemical composition, formed by
the intersection of three-end members depicted in a triangular graph,
namely:
• Sialic (SiO2 + Al2O3 + TiO2)
• Calcic (CaO + MgO + Na2O + K2O)
• Ferric (Fe2O3 + MnO + SO3 + P2O5)
Classification of Fly Ash
• According to ASTM C618, fly ash is classified globally into two
chemical types, namely:
• Class F Fly Ash
• Low Calcium
• Produced from high rank coals (Bituminous and anthracite)
• Pozzolanic in nature but requires cementing agent
• Class C Fly Ash
• High Calcium
• Produced from low rank coals (Lignite and subbituminous)
• Pozzolanic and cementitious in nature
Characteristics of Coal Fly Ash
• Morphology
• Fineness
• Specific Surface Area
• Specific gravity
• Unburnt carbon and loss on ignition
Applications
• Construction Industry
• Ceramic Industry
• Catalysis
• Soil Amelioration
• Environmental Protection
• Depth Separation
• Zeolite Synthesis
• Recovery of Valuable Metals
• Utilization in Polymer Matrix Composites