Physical and chemical properties

of coal and its products

Lecture no.L-02-1
Dr hab. in. Marek ciko
Prof. nadzw.

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Chemical properties of coal

Coal comes in four main types or ranks:
lignite or brown coal, bituminous coal or
black coal, anthracite and graphite. Each
type of coal has a certain set of physical
parameters which are mostly controlled by
moisture, volatile content (in terms of
aliphatic or aromatic hydrocarbons) and
carbon content.
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Proximate analysis
The objective of coal proximate analysis is to determine the
amount of fixed carbon (FC), volatile matters (VM), moisture,
and ash within the coal sample.
The variables are measured in weight percent (wt. %) and are
calculated in several different bases. AR (as-received) basis is the
most widely used basis in industrial applications. AR basis puts all
variables into consideration and uses the total weight as the basis of
measurement.
AD (air-dried) basis neglect the presence of moistures other than
inherent moisture while DB (dry-basis) leaves out all moistures,
including surface moisture, inherent moisture, and other moistures.
DAF (dry, ash free) basis neglect all moisture and ash constituent in
coal while DMMF (dry, mineral-matter-free) basis leaves out the
presence of moisture and mineral matters in coal, for example:
quartz, pyrite, calcite, etc. Mineral matter is not directly measured
but may be obtained by one of a number of empirical formula based
on the ultimate and proximate analysis.
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Moisture

Moisture is an important property of coal, as all coals are mined wet.

Groundwater and other extraneous moisture is known as adventitious
moisture and is readily evaporated. Moisture held within the coal itself is
known as inherent moisture and is analysed quantitatively. Moisture may
occur in four possible forms within coal:
Surface moisture: water held on the surface of coal particles or macerals
Hydroscopic moisture: water held by capillary action within the microfractures of
the coal
Decomposition moisture: water held within the coal's decomposed organic
compounds
Mineral moisture: water which comprises part of the crystal structure of hydrous
silicates such as clays

Total moisture is analysed by loss of mass between an untreated sample

and the sample once analysed. This is achieved by any of the following
methods;
Heating the coal with toluene
Drying in a minimum free-space oven at within a nitrogen atmosphere
Drying in air at 100 to 105 C (212 to 221 F) and relative loss of mass
determined
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Source: http://en.wikipedia.org/wiki/Coal_assay#Chemical_properties_of_coal

Volatile matter
Volatile matter in coal refers to the components of coal,
except for moisture, which are liberated at high
temperature in the absence of air. This is usually a
mixture of short and long chain hydrocarbons, aromatic
hydrocarbons and some sulfur. The volatile matter of
coal is determined under rigidly controlled standards. In
Australian and British laboratories this involves heating
the coal sample to 900 5 C (1650 10 F) for 7
minutes in a cylindrical silica crucible in a muffle furnace.
American Standard procedures involve heating to 950
25 C (1740 45 F) in a vertical platinum crucible.

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Ash
Ash content of coal is the non-combustible
residue left after coal is burnt. It represents
the bulk mineral matter after carbon,
oxygen, sulfur and water (including from
clays) has been driven off during
combustion. Analysis is fairly
straightforward, with the coal thoroughly
burnt and the ash material expressed as a
percentage of the original weight.
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Detailed ash analysis

An analysis of coal ash may also be carried out
to determine not only the content of coal ash,
but also to determine the levels at which
trace elements occur in ash. These data are
useful for environmental impact modeling.
Beside composition of coal ash, ash fusion point
is also one significant parameter in ash analysis.
The optimum operating temperature of coal
processing will depend on the gas temperature
and also the ash fusion point. Melting of the
ashes may cause them to stick to the walls of
the reactor and result in a build-up.
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Fixed carbon

The fixed carbon content of the coal is the

carbon found in the material which is left after
volatile materials are driven off. This differs
from the ultimate carbon content of the coal
because some carbon is lost in hydrocarbons
with the volatiles. Fixed carbon is used as an
estimate of the amount of coke that will be
yielded from a sample of coal. Fixed carbon is
determined by removing the mass of volatiles
determined by the volatility test, above, from
the original mass of the coal sample.
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Conversion of the data basis

Proximate Analysis

unit

(ar)

(ad)

(db)

(daf)

Moisture

(wt. %)

3.3

2.7

Ash

(wt. %)

22.1

22.2

22.8

Volatile Matter

(wt. %)

27.3

27.5

28.3

36.6

Fixed Carbon

(wt. %)

47.3

47.6

48.9

63.4

Gross Calorific Value

(MJ/kg) 24.73 24.88 25.57 33.13

(ar) as received
(ad) air dried
(db) dry basis
(daf) dry ash free
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Ultimate analysis
Ultimate analysis is the determination of
the percentage composition in terms of
carbon, hydrogen, sulfur, nitrogen, and
ash, and the calculation of the oxygen
content the difference.

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Conversion of the data basis

Ultimate Analysis

unit

(ar) (ad) (db) (daf)

Carbon (C)

(wt. %) 61.1 61.5 63.2 81.9

Hydrogen (H)

(wt. %) 3.00 3.02 3.10 4.02

Nitrogen (N)

(wt. %) 1.35 1.36 1.40 1.81

Total Sulfur (S)

(wt. %)

0.4

0.39 0.39

Oxygen (O)

(wt. %)

8.8

8.8

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9.1

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Conversion table
Desired
Basis >
As Received
Given Basis

Air Dried

100-Mad
100-Mar

As Received
100-Mar
Air Dried
100-Mad
Dry
Dry, ash
free

100-Mar
100

100-Mad
100

100(Mar+Aar)
100

100(Mad+Aad)
100

Dry

Dry, ash
free

Dry, mineral
matter free

100
100Mar

100
100(Mar+Aar)

100
100Mad

100
100
100100(Mad+Aad) (Mad+MMad)
100
100-Ad

100Ad
100

Dry,
100100100mineral (Mar+MMar) (Mad+MMad) MMd 100-MMd
100-Ad
matter free 100
100
100

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100
100(Mar+MMar)

100
100-MMd
100-Ad
100-MMd

Definition of Variables
M = moisture (%)
A = ash (%)
MM = mineral matter (%)

Definition of Subscripts
ar = as received basis
ad = air dried basis
d = dry basis

Specific Energy Conversions

For conversions between units:
1 Btu/lb = 0.002326 MJ/kg
1 kcal/kg = 0.0041868 MJ/kg
1 Metric Ton (tonne) = 1.10231
short tons

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Chemical constitution of coal

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Atomic composition of different fossil fuels

(kmol at. in 100 kg of org. substance)
9
8

Number of atoms

7
6

No.

Type of fuel

1
2
3
4
5
6
7

Peat
Lignite
Flame coal, type 31
Gas coal, type 33
Ortho-coking coal, type 35
Semi-coking coal, type 37
Anthracite

Hydrogen

Oxygen

Carbon

5
4
3
2
1
0
1

4
Type of fuel

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Atomic ratio of (C/O)at, (C/H)at, (H/O)at in different

fossil fuels
70
C/O

C/H*10

H/O

60

Stosunki atomowe

50

The critical change

is observed in oxygen
content

40

30

20

10

0
1

Typ paliwa

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Atomic structure of coal

On the average in a bituminous coal hydrogen content
equals to ca. 5% w/w daf., and carbon content ca. 84%.
It means, that statistically every 7 atoms of carbon
meets 5 atoms of hydrogen.
The next substantial element is oxygen, that can be
found in a coal at the average concentration 10% w/w. It
means that for every 7 atoms of carbon acounts for only
0.5 atoms of oxygen, however what will be shown its
content substantially effects the coal properties.
The remaining elements like sulfur - S and nitrogen - N
can be found in coal on the average in amount of 0.5 i
1% and due to its concentration does not influence the
coal gross properties very much.
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Atomic composition of different fossil fuels

(kmol at. in 100 kg of org. substance)
9
8

Number of atoms

7
6

No.

Type of fuel

1
2
3
4
5
6
7

Peat
Lignite
Flame coal, type 31
Gas coal, type 33
Ortho-coking coal, type 35
Semi-coking coal, type 37
Anthracite

Hydrogen

Oxygen

Carbon

5
4
3
2
1
0
1

4
Type of fuel

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Atomic ratio of (C/O)at, (C/H)at, (H/O)at in different

fossil fuels
70
C/O

C/H*10

H/O

60

Stosunki atomowe

50

The critical change

is observed in oxygen
content

40

30

20

10

0
1

Typ paliwa

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Atomic structure of coal

On the average in a bituminous coal hydrogen content
equals to ca. 5% w/w daf., and carbon content ca. 84%.
It means, that statistically every 7 atoms of carbon
meets 5 atoms of hydrogen.
The next substantial element is oxygen, that can be
found in a coal at the average concentration 10% w/w. It
means that for every 7 atoms of carbon acounts for only
0.5 atoms of oxygen, however what will be shown its
content substantially effects the coal properties.
The remaining elements like sulfur - S and nitrogen - N
can be found in coal on the average in amount of 0.5 i
1% and due to its concentration does not influence the
coal gross properties very much.
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High heating value vs. carbon

content in a fuel (daf)
40000

35000

Ciepo spalania [kJ/kg]

30000

25000

20000

15000

10000

5000

0
60

65

70

75

80

85

90

95

100

105

Zawarto pierwiastka C [%]

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Coal heating - devolatilization

Heating rate, K/min

Source: Journal of Analytical and Applied Pyrolysis
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5859 (2001) 685701

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Content, % mas.
Moisture

Ash

Volatile

Carbon

Hydrogen

Nitrogen

Sulphur

Oxygen

Wa

Aa

Va

Ca

Ha

Na

Sc a

Oda

2,5

16,8

30,2

69,57

3,93

1,17

0,17

5,86

0,6

Gas composition, kmol/kmol

0,4

Yield of products, kg/kg

Biuminous coal
- Wieczorek -

0,3

0,2

0,5

0,4

0,3

0,2

0,1
0,1

0
500

700

900
Temperature, K

H2
CH4
C2H6
V

CO
CO2
H2O
Tar

1100

1300

0
500

700

900

1100

1300

Temperature, K

Enthalpy
of formation
H o, kJ/kg
Q daf, MJ/kg
f
s
34,7
-463,2
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Heating value

Activation
energy
E, kJ/kmol
11181,2

Frequency
index
ln (k8 )
-5,97 22

Coke
Coke is the solid carbonaceous material
derived from destructive distillation of lowash, low-sulfur bituminous coal. Cokes
from coal are grey, hard, and porous.
Coke is used as a fuel and as a reducing
agent in smelting iron ore in a blast
furnace. It is there to reduce the iron oxide
(haematite) in order to collect iron.
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Coal tar
Coal tar is a brown or black liquid of extremely
high viscosity, which smells of naphthalene and
aromatic hydrocarbons.
Coal tar is among the by-products when coal is
carbonized to make coke or gasified to make
coal gas.
Coal tars are complex and variable mixtures of
phenols, polycyclic aromatic hydrocarbons
(PAHs), and heterocyclic compounds, about 200
substances in all.
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Coke gas
Coal gas (also town gas and illumination gas) is a
flammable gaseous fuel made by the destructive
distillation of coal containing a variety of calorific gases
including hydrogen, carbon monoxide, methane and
volatile hydrocarbons together with small quantities of
non-calorific gases such as carbon dioxide and nitrogen.
It was the primary source of gaseous fuel both the
United States and Great Britain until the widespread
adoption of natural gas during the 1940s and 1950s. It
was used for lighting, cooking and heating and was often
supplied to households via a municipally-owned piped
distribution system.
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