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Advanced Coal Science

Coal – How It Is Formed
Coal is made from Peat that has been compressed and then subjected to high temperature ( +
100° Celcius) for a few million years to drive off moisture, methane and carbon dioxide
bearing molecules.  This process causes the peat to progress through brown coal, lignite, sub-
bituminous coal and then to bituminous coal (the category most of Australia’s coal currently
mined belongs to) and finally anthracite.  Through this process, the carbon content of the coal
increases as does the energy content of the coal.  Commensurate with this process is a
reduction in the moisture content and oxygen content of the coal.
The process by which peat accumulates is complex but in general it:
• requires a source of vegetal material (plant material in the form of trees, branches, leaves,
spores and resins),
• requires a preserving medium (normally water) where microbial activity is restricted.
• requires a sinking floor or rising water table for the duration of the peat formation
• requires a long period of time where quiescent condition predominate

Where Does Coal Form?

Coal, as with most organic sediments, tends to accumulate in structures known as basins. 
These structures are normally controlled by a series of faults that provide the constant sinking
of the floor of peat swamps.  These basins may be several thousand kilometres long and
several hundred kilometres wide and are normally associated with “Plate Tectonics” at the
time of formation.  These basins are often associated with the accumulation of many
thousands of metres of sediment and are found behind zones of subduction where ocean floor
sinks beneath crustal rocks depiceted below.

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Schematic Diagram of Coal Basin Setting

This type of peat-forming environment is responsible for the Sydney-Bowen Basin

that hosts the majority of Australia’s bituminous coal.  Most of the major coalfields
around the world have been developed as a result of similar types of tectonic
environment.
 
Coal Types
Although all coal can be described by the basic constituents of moisture, volatile
matter, fixed carbon, ash and sulphur, a microscopic evaluation of coal reveals the
plant type and depositional environment that the coal was formed from.  The
components in coal that can be recognised by microscope are described very
simply by coal specialists as macerals and are divided into 4 groups shown below.
 
Coal Maceral Groups

Maceral
Description Additional Information
Type
This material is formed from woody
The vitreous part of coal material This maceral group has the
Vitrinite that is normally lowest ash content and is responsible for
represented as bands. the coking properties for coals that meet
the coking coal criteria.
Derived from resin bodies,
Produce large quantities of volatile
Liptinite waxy cuticles and spores
matter.
from plants.
This maceral group comprises charcoal
As the name suggests this
and products of fungal breakdown of
group is inert (to the coking
Inertinite woody tissue. It contains low volatile
process) and does not
matter and is responsible for the sooty
soften or swell on heating
effect of coal.
Mineral Comprises the non-organic This material makes up most of the ash of

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 a coal, where mineral matter comprises
component of coal such as
mostly clay the ash is very refractory,
Matter clay, quartz, and minerals
when is comprises mostly carbonate
introduced later.
minerals the ash melts readily
 
Examples of the various macerals groups are shown below where banding of coal from the
Gunnedah area is clearly visible with dull inertinite at the top, a mixture of vitrinite and liptinite
in the middle and pure vitrinite at the bottom of the picture.
 
Gunnedah Coal Showing Three Maceral groups

Source Organic Petrology G Taylor, M Teichmuller, A Davis & C Diessel et al. 1998

Coal Rank Progression

Coal is a sedimentary deposit (laid down in water) that comprises preserved plant
material from ages past.  Over time a great thickness of plant material
accumulates that is broken down into peat.  This represents a storehouse of
organic matter produced via photosynthesis by plants using the sun’s energy.  In
this form even the peat is a source of preserved solar energy.
Peat contains a lot of water and subsequent burial of the peat results in the water

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 being squeezed out.  This process normally extinguishes bacterial activity and as
temperatures rise with increasing depth of burial, the coalification processes begin
to transform the peat to brown coal, then lignite, sub-bituminous coal, bituminous
coal and finally to anthracite.
This coalification process is accompanied by a decrease in moisture, a decrease
in volatile matter and increase in carbon and an increase in calorific value and a
commensurate decrease in oxygen until the end of the bituminous rank shown in
the table below.

Changes in Coal Properties as Rank Increases

Volatile Carbon Oxygen

  Moisture Calorific Value
Matter Content Content
As
Coalification Stage Dry Ash Free  Dry Ash Free Asrecieved Dry Ash Free
Recieved
Peat ~75% 69 - 63% <60% 3,500 kcal/kg >23%
4,000 - 4,200
Lignite 35 - 55% 63 - 53% 65 - 70% 23%
kcal/kg
4,200 - 4,600
Sub-bituminous C 30 - 38% 53 - 50% 70 - 72%  20%
kcal/kg
4,600 - 5,000
Sub-bituminous B 25 - 30% 50 - 46% 72 - 74% 18%
kcal/kg
5,000 - 5,500
Sub-bituminous A 18 - 25% 46 - 42% 74 - 76% 16%
kcal/kg
High Volatile Bituminous C 12 - 18% 46 - 42% 76 - 78% 5,500 5,900 kcal/kg 12%
5,900 - 6,300
High Volatile Bituminous B 10 -12% 42 - 38% 78 - 80% 10%
kcal/kg
6,300 - 7,000 8%
High Volatile Bituminous A 8 - 10% 38 - 31% 80 - 82%
kcal/kg
Medium Volatile 7,000 - 8,000
8 - 10% 31 - 22% 82 - 86% 4%
Bituminous kcal/kg
8,000 - 8,600
Low Volatile 8 - 10% 22 - 14% 86 - 90% 3%
kcal/kg
Semi-Anthracite 8 - 10% 14 - 8% 90% 7,800 8,000 kcal/kg 3.5%
7,600 - 7,800
Anthracite 7 - 9% 8 -3% 92% 4.5%
kcal/kg
Meta-Anthracite 7 - 9% 8 - 3% >92% 7,600 kcal/kg 5%
 
 

Coal Formation

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 Plant material normally accumulates in peat swamps that are low lying areas
shielded from the incursion of sediment bearing streams by vegetative barriers.  A
peat swamp normally accumulates 7 – 20 metres of peat to produce 1 metre of
bituminous coal and the rate of peat accumulation is extremely slow, measured in
mm per year.  The peat comprises fallen trees, leaves, branches, spores and
pollen that can accumulate at rates varying from 1 mm/year in reed swamps to 4 –
5 mm year in tropical forest swamps.  The formation of a coal seam therefore
requires very stable conditions for long periods of time – about 2,500 - 6,000 years
per metre of coal.

To prevent the peat swamp drying out it is necessary for either the water table to
rise at the same rate as peat accumulates or for the stratum that the peat swamp
rests upon to subside below the water table at the rate of peat accumulation.
The peat continues to accumulate until it is either drowned by a rising water table
or it is covered by sediments from fluvial channels. Drowning normally results in
the peat being covered by mud where as an approaching stream channel will
normally be associated with sandstones and other coarse sediments deposited on the top
of the peat as a result of flooding activity.

While accumulating in the peat swamp, the plant material is broken down to peat
by bacterial, actinomycal and fungal activity while the peat has access to the air
and anaerobic bacteria once the peat swamp has been buried. This process is
controlled by temperature and the degree of acidity.  Highly acid peat swamps do
not promote bacterial activity while more alkaline peat swamps promote bacterial
activity.  This process is called peatification.

Effects of Climate

Peat accumulation requires that the rate of inflow of plant material into the swamp
is greater than the rate of decay of the plant material.  Cellulose decomposing
bacteria are the most active at temperatures in the range of 35 – 40 °C.   Peat
accumulated under such conditions is normally degraded and partially

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 homogenised forming coal that is devoid of the characteristic banding found in
cool climate coals such as those formed in Gondwana Land during the Permian
Period.

Permian coal seams from Australia, South Africa, Madagascar, India and
Antarctica were all deposited during cold conditions.  As a consequence peat
accumulated normally at a faster rate than subsidence and the peat swamps were
exposed to the atmosphere for long periods of time. As a consequence fungal
activity and fires converted much of the woody material near the top of the seam to
either charcoal or material from which the soft cell lumens had been consumed by fungi
leaving behind the lignin rich precursors of inertinite.

Worldwide the major coalfields reflect a diversity of climatic environments under

which they formed and as time has progressed they also represent a greater
diversity of plant life. (Table 13).

 
Coal Forming Periods

Age Coal Basins Climate / Dominant Plant Types

Warm climate, moist,tropical/sub-tropical.
Kuzbass (Russia) Donets (Ukraine), Kazakhstan Coal made from Lycopods
Carboniferous coalfields, Saar-Lorraine coalfields, UK/French (Lepidodendron and sigolaria),
(360 – 290 my BP) coalfields, Appalachain coalfields, Cape Gymnosperms (Cordaites) and
Bretton/Newfoundland coalfields Cycadophytes.
 
Climate considered to be cold with warm
East Coast Australia, South Africa, India,
Permian (290 – 251 wet summers and freezing winters. Main
Madagascar, South America, Antarctica.
MY BP) plants Gymnosperms (Glossopteris and
Zimbabwe, China
Gangangopteris)
Triassic (251 – 205 Cool climate warmer than Permian with
 Callide and Tarong Australia
MY BP) similar plants
Appearance of flowering plants such as
Jurassic (205 -  Gunnedah, Walloon, Milmerran basins Australia, Angiosperms, but gyymnosperms and
141 My BP) Yakutia and Pechora Basins Russia cycads remain the major peat forming
plant
Cretaceous (141 – Canadian, Wyoming, Colorado, Spitzbergen, Cool Climate to warm, Angiosperms
65 MY BP) New Zealand, Venezuela predominate
Tertiary Indonesia (Eocene & Miocene), New Zealand Canada Warm – Angiosperms
(65 – 1.78 MY BP) (Paleocene, Eocene, Miocene, Oligicene), predominate.

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 Australia (Eocene, Oligocene Miocene), China,
Germany, Japan, USA,
 
USAGE OF COAL

As discussed previously the volatile matter and fixed carbon of the coal contain energy
and this can be harnessed for the purposes of raising steam for electricity generation
and general boiler use or for the calcining of limestone in the manufacturing of cement. 
The sale of coal for thermal purposes constitutes the major use of coal, but there are
other uses for coal that are broadly termed metallurgical where the coal is used in some
way to reduce metallic oxides to metals.

 Metallurgical coals

Metallurgical coals generally fall into two categories:

Coking coals and non-coking coals.  The coking coals are used to make coke, a
hard porous substance that comprises about 90% carbon with the balance being
ash (non-combustible material), volatile matter and other impurities such as
sulphur and phosphorus.  The non coking coals are those coals used in other
processes that are used in the reduction of metallic oxides to metals.

Coking coals are those coals that soften, swell and then solidify as they are
heated through the temperature range 350°C to 550°C.  By definition these coals
all have a low ash content (1 – 10%), have low permeability as determined by
inherent moisture, moderate vitrinite content (to provide volatile matter) and
volatile matter in the range 18 – 45%

The reflectance of the maceral vitrinite is also used as a measure of a coal’s

suitability for coking.  Reflectance measures the amount of light that is reflected
from a polished piece of vitrinite and for coking coals it is in the range 0.6%
through 1.8% (range of bituminous coals).  The coals with the lowest reflectance

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have the lowest rank and highest volatile matter.  Reflectance measures the
degree of graphite crystallite order within the coal.  These are a precursor to the
degree of graphitisation that is achieved when the coal is coked.

Low rank coals have few aromatic ring structures and none of these are aligned.  
As the rank of the coal increases the number and alignment of these ring
(graphitic structures) increases.  These increase through the condensation of
alpiphatic compounds and the loss of methane and carboxyl groups until graphite
has been produced.  Aliphatic compounds are long chain hydrocarbons that break
and condense as rank increases releasing methane and soluble metallic carboxyl
groups.

Lower rank coking coals have a lot of oxygen containing groups that link the
aromatic ring structures and on rapid heating (as in a coke oven) these oxygen
linkages cleave only at elevated temperatures where maximum volatile matter
release occurs and consequently the plastic properties are short lived.  As the
rank increases the oxygen content of the vitrinite component of the coal decreases
and the temperatures required to create a plastic mass are reduced, as a
consequence the plastic range increases.  Once coals reach the top end (low
volatile matter) of the bituminous rank, the coals have very low oxygen content
and also low volatile matter content, and consequently the plastic range begins to
decrease again until no plasticity occurs at about 16% volatile matter.

The type of carbon produced in the resultant coke is a function of the rank of the
precursor coal. Coals with more ordered graphitic structures produce cokes with
highly ordered and unreactive carbon (mosaic).  Mosaic is the term used to define
the graphitic structure observed in cokes.  The larger the domain of each of the
mosaic units the higher the rank (lower oxygen content) of the precursor vitrinite.  
Crude oil has a low oxygen content and the coke produced after cracking out all
the liquid and gaseous products produces a very unreactive form of carbon.

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Increase and Alignment of Graphitic Ring Structures as Rank Increases

Mosaics from three coal seams located in the northern Bowen Basin are shown
below with rank increasing from Q Seam (Upper Goonyella equivalent) 0.8% Rv
max through E Seam (Middle Goonyella equivalent) to 1.3% Rv max in the Blake
seam at the base of the Collinsville Coal Measures.  The size of the mosaic
domains increases with increasing rank.

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Figure 6: Q Seam - Moranbah Coal Measures Rv Max 0.8%, note fine "Equant"Mosaic fining toward inertinite.  Field of view 66 microns

The mosaic shown in Figure 6 is typical of a soft coking coal and contrasts with
the mosaic from a seam with 1.0% reflectance (Figure 7).

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Figure 7: Large Flame Mosaic from the E Seam (Moranbah Coal Measures) Rv max 1.0%, Field of View 165 microns – Note large gas vesicles

Figure 7 shows the effects of higher rank and lower oxygen content on the
morphology of the coke mosaic – note the presence of large gas vesicles.  This
mosaic is more ordered and thus less susceptible to attack by carbon dioxide in a
blast furnace.

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Figure 8:Ropey Mosaic Derived from Blake seam Coal with 1.3% Rv max - note small gas vesicles- Field of view 165 microns

The structure and size of the graphitic crystallites is not the only factor impacting
on the reactivity of the coke, the composition of the ash of the coal that made the
coke is also of prime importance to the manufacturers of blast furnace coke. 
Alkali and alkali Earth metals are known to catalyse the reactions in the blast
furnace that lead to premature oxidation of the coke.

Blast furnace operators prefer coke to remain inert until it reaches the base of the
blast furnace where temperatures are high enough to melt iron (1,538°C).  Prior to
this temperature any coke that reduces carbon dioxide to carbon monoxide is
effectively lost to the system.  Two factors influence the propensity of a coke to
react with carbon dioxide before 1,538°C, the size (and thus reactivity) of the
mosaic and the presence of catalysts that promote the carbon solution reaction at
lower temperatures.  The two important reactions in a blast furnace are simply
expressed below:

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Equation 1: Carbon Solution Reaction

 C (coke) + CO2 (gas)   →    2 CO

Since carbon monoxide is the reductant for Iron ore, Equation 1 must occur if the ore is to be

reduced.  The reduction reaction is simply represented in Equation 2.

 
Equation 2: Reduction of Iron Ore

 FeO + CO  →   Fe (liquid) + CO2 (gas)

 
The main function of coke in a blast furnace is to provide an open structure to
allow the reacted gases to move up the blast furnace. When the coke reacts
prematurely with the carbon dioxide in the blast furnace atmosphere, the coke
becomes weakened and finally crushes reducing the permeability and thus
productivity of the blast furnace.

The secondary functions of coke are to provide both heat and carbon dioxide to
drive the reduction reactions that produce the iron at the bottom of the furnace.
Since coke is a very expensive commodity (up to US$400/tonne), blast furnace
operators prefer to use it for creating permeability in the blast furnace and they
use pulverised coal injection (PCI) at the base of the blast furnace to provide both
heat and a source of carbon dioxide.  Enhancement of the carbon dioxide
generation is attained by use of low volatile matter coals for PCI which
coincidentally have very high specific energy values and are able to provide
conditions hot enough to allow the unreactive coke to react with CO 2 at the base
of the blast furnace.

Manufacturers of blast furnace coke use a combination of coals to make up the

coke oven blend and in addition to this they also use various techniques to
maximise the coke strength and reduce reactivity of the coke.  Coking coals within
the rank range 1.15 – 1.4% reflectance are considered prime coking coals if the
ash content is < 9.5% and sulphur approximates 0.6%.  Coal such as this is the

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 most expensive and coke manufacturers try and reduce costs by using coals
classed as soft coking (make a weaker coke) and semi-soft coking (are weakly
coking) coals.  Soft coking coals by definition tend to have a high volatile matter
content and produce a weak and frothy coke.  To overcome these short comings
coke manufacturers add inert material in the form of coke breeze or petroleum
coke to reduce the overall volatile matter of the blend. The coke oven blend is
stamp charged to remove air between coal particles to allow for better bonding. 
Finally the coal charged is dried to ensure faster heating rates (that promote
plasticity in the coal mass) and to prevent dissolution of the coke through the
water shift reaction.

Where coke manufacture is undertaken as part of an integrated steel mill, the

production of coke oven gas for use in the rolling mills and for generation of
electricity becomes an important consideration when choosing coals to use in a
coke oven blend.  Steel mills that have smaller blast furnaces are able to use
coals with a lower coke strength after reactivity (CSR) and as a consequence
have a wider range of cheaper coals to choose from.

 
Non-Blast Furnace Route for Metals Production
 
Iron

In India, South Africa, Korea, China and New Zealand, hot iron metal is produced
from routes other than the blast furnace route through the employment of direct
reduction rotary kilns. This system uses similar chemical reactions but does not
require the coal to be converted to coke.  Low ash coal that is reactive is charred
in a multi hearth kiln to remove volatile matter before it is mixed with iron ore
(normally magnetite) and allowed to react in a counter-current kiln where carbon
from the char reacts with carbon dioxide to form the reducing gas carbon
monoxide which reduces the iron ore fines.  This process does not require the
melting of the iron, but produces a sponge iron instead. The sponge iron is melted
in an electric furnace where it is converted to steel.  Typically the process requires

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 highly reactive (lower rank) coals that have low ash, low sulphur and low
phosphorus contents.

Other metallic oxides such as lead are reduced using foundry type cokes (large
lumps of coke) as the reductant in a process similar to a blast furnace.  The
requirements of the coke are less stringent and operating temperatures lower than
iron blast furnaces.

Silicon

Silicon metal is a major component in electronics (photovoltaics), as the basis for

the production of silicones and as a hardening agent for aluminium. It is produced
by removing the oxygen content from quartz (SiO2) and is a very endothermic
process requiring a large amount of energy.  Very pure coal is added to sized pure
quartz and large amount of electricity produced from a carbon anode are used to
produce a submerged arc that provides heat at 2,000 °C. The coal is required as a
source of reactive carbon to remove oxygen from the quartz in Equation 3:

 
Equation 3: Quartz to Silicon Metal Reaction

 SiO2 + C (from coal)   2,000°C →  Si (metal) + CO2

The requirements for the coal are very stringent as it is the primary source of any
contaminants.  Typically chemical grade silicon must have the following minimum
qualities:

Silicon  98.5%
Iron    0.5%
Calcium   0.07%
Aluminium   0.2%

Aluminium Grade Silicon must have the following

Silicon  98.5%
Iron    0.35%
Calcium   0.07%

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 As a consequence the coal used must have very low quantities of iron, calcium
and aluminium which are normally achieved through use of coal with <1% ash. To
achieve the requisite reactivity the coal normally has 28 – 40% volatile matter.

Other uses for coal

Activated carbon

Carbon has a positive charge and when coal has been charred and then steam
activated it develops a very large surface area that can be used to attract
negatively charged anions such as chlorine to purify water or act as a substrate
onto which gaseous or liquid hydrocarbons can be attached such as dry-cleaning
vapours and petrol vapours that can be collected in activated carbon filters to
prevent them entering the atmosphere.  Activated carbon is also used to take
molasses out of sugar syrup to produce white sugar.

Anthracite Uses

Anthracite is very high rank coal in which there is virtually no volatile matter and
consequently has a high percentage of carbon.  Very high rank anthracites (meta-
anthracite) which have volatile matter of <3% are used extensively in the reduction
of silica to silicon metal and in the production of ferro-silicon.  Anthracites are also
used extensively for water treatment both as a filtration medium and as a
scavenger for unwanted chemicals in the water.

Meta-anthracites are also used in the manufacture of carbon anodes and

cathodes as it has good electrical conductivity and good abrasion resistance.
Anthracites are also used extensively as a smokeless fuel.

Thermal coals

All metallurgical coals can be used as thermal coals, but competing pressures
from other consumers of more specialised coals results in only the cheapest coals

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being used for thermal purposes.  The greatest use of thermal coal is in the
generation of electricity via the pulverised fuel method.
Although this market sector is the repository of most of the coal mined in New
South Wales and Indonesia the requirements on a power-station by power-station
basis are often quite exacting and governed by the equipment at the power
station.  Factors that affect coal fired power stations are:

 Free moisture in the coal – this affects handling of the coal

 Total moisture of the coal – this impacts on the drying capacity of the grinding
circuit
 Hardness of the coal – this affects the mill and power requirements to reduce
the coal to 70% passing 75 microns
 Ash fusion characteristics – normally the higher the temperature at which the
ash fuses (melts) the better as ash deposits that form on the steam tubes act
as insulators and reduce the efficiency of the transfer of heat energy from the
burning of coal into steam energy
 Volatile Matter – this is the most readily combustible part of the coal and high
volatile matter coals readily evolve large amounts of gas and tar leaving
behind particles of char that are oxidised.  Low volatile matter coals require
special furnaces to achieve good char burnout
 Sulphur content of the coal is converted on combustion to sulphur dioxide
which is a pollutant gas.  Some dust removal systems work best with some
sulphur in the coal.
 Ash contents should generally be lower than 30% and this level is dependent
on the economics of transport the coal from the mine to the power plant.  Ash
is a dilutent and requires transportation while contributing nothing to the
process of generating electricity.  Following combustion, ash collected from
baghouses or electrostatic precipitators must be disposed of. Coal ash with
high silica and alumina content produces fly ash that can be used as an
additive to concrete.  Fly ash addition can increase the density of concrete,

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 reduce shrinkage and reduce heat during the setting process. The use of fly
ash reduces the quantity of cement required to attain a certain concrete
strength
 Specific energy of coal – the specific energy of a coal is that amount of
energy contained in the organic matter less the dilution caused by mineral
matter (ash) and moisture.  Clearly the higher the energy content of the coal
the better it is from the economics of running a power station, less coal is
required to be transported to the power station site, less coal requires
grinding and as a consequence there is less ash to be disposed of. Energy
content of the coal is measured in 4 different ways:
o Dry basis (db)– an American method that uses dry basis energy
and treats the effect of moisture separately
o Air-dried basis (adb) – a British based system that uses the energy
of a coal that has been air-dried and so retains the inherent
moisture of the coal.
o As received basis (ar) – The energy contained in coal as it is
delivered to a power station, this includes all the moisture and ash.
o Net as-received basis (nar) – This basis determines the amount of
usable energy a coal contains and is the as-received energy less
the amount of energy required to vaporise the moisture in the coal
and moisture formed from the combustion of the hydrogen in the
coal.

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