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LECTURE4:

COAL & CHEMICALS FROM COAL

CHEMICAL TECHNOLOGY (CH-206)

Dr. Vimal Kumar
Department of Chemical Engineering

INTRODUCTION COAL
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Coal is the largest source of energy all over the world.

Coal can serve a potential source of

synthetic

fuel,
a source of power production,
coke production, and
Fine chemicals which are now being derived from petroleum
and natural gas.

Some of the alternate feed stocks for chemical

industries from coal are
coal

gasification,
coal to synthesis gas,
coal to oil through FT synthesis,
coal to methanol,
coal to plastic

COAL ORIGIN
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Coal is carbonaceous solid black or brownish black

sedimentary rock matter
It is made from the accumulation of partially
decomposed vegetation.

Biological

changes and subsequent effects of temperature

and pressure altered these deposits to coal.

Coal is composed of chiefly carbon and other elements

like hydrogen, sulphur, oxygen, nitrogen, moisture
and non-combustible inorganic matter containing,
silica, iron, calcium, magnesium, mercury etc.
The coal composition, sulphur content, mercury
content and calorific value of the coal vary widely from
one coal reserve to another coal reserve.

COAL TIMELINE
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200 BC - first published record of coal used for heating

(Greece)
300 AD - Coal adopted as heat source in China
900 AD - Coal mining begun in western Europe
1285 AD - Coal burning begins to pollute London
1600s - Great Britain runs out of wood, switches to
coal, beginning of the industrial revolution
1800s - US becomes leading producer of coal
1945 - coal is leading energy source in US
1950 - USSR becomes leading producer of coal, coal
provides 60% of world energy sources
2000 - coal provides 30% of world energy sources as
dependence on petroleum grows

GEOGRAPHICAL DISTRIBUTION OF
COAL RESERVES
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http://www.eia.gov/countries/reports.cfm

WORLD OIL/COAL RESERVES BY

REGION (%)
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COAL PRODUCTION AND

CONSUMPTION
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The global coal production in 2011 was 7 billion

tones.
China accounted for approximately half of the
production and consumption.
Total coal production in India during 2009-10
was 532.29 million tones.
Lignite production in India in 2009-10 was 23.95
million tones

COAL RESOURCES:
BASED OF DEGREE OF
ASSURANCE
Coal reserve

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Proved

reserve are those resources which has been

reliably estimated and can be recovered economically.
Indicated reserves is the coal resource which is
based on combination of direct measurement and
reasonable geological assumptions.
Inferred coal resource is based on the assumed
continuity of coal beds.

Depth range determines the economy of

extraction and a cope of exploration.
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COAL RESOURCES IN INDIA

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COAL DEMAND PROJECTION (million tones)

DISTRIBUTION OF COAL RESOURCES (MILLION TONES)

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COAL RESOURCES IN SEDIMENTARY

ROCKS (MILLION TONES)
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COAL LETTERS OF ASSURANCE

(LOA)
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COAL BED METHANE (CBM)

Petroleum and Natural gas].

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Coal bed methane is an environmentally friendly

clean fuel similar to natural gas.
Preliminary activities related to exploration of CBM
in India started in early 1990s
Till 1997 the Ministry of Coal had allotted some coal
bearing areas for CBM exploration.
In India 33 CBM contracts were signed for
explorations of CBM gas.
In July 1997, Ministry of Petroleum and Natural gas
was made administrative ministry.
CBM gas production is about 2 lakhs cubic meter
per day [Annual Report 2011- 12 Govt. of India Ministry of

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TYPES OF COAL
Coal are classified into various grades based on the
Composition

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calorific

value
Degree of coalification that has occurred during its formation.

Coal may be also classified as

hard

or soft coal,
low sulphur or high sulphur coal.

Coal may be also classified in rock types based on

petrological components known as maceral:
clarain,
durain,
fusain

vitrain

and

[http://www.britannica.com/EBchecked/topic/1703417/coalclassifi
cation].

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CLASSIFICATION OF DIFFERENT TYPE OF COAL

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TYPICAL COAL CHARACTERISTICS

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CHEMICAL COMPOSITION OF COAL

Conclusion: Coal is a 3D cross-linked polymer of aromatic rings and
alkane linkers with a small amount of inorganic contaminants
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Model of coal
Inorganic constituents are from
original plant material, plus minerals
leached into the coal from
surrounding sediments
Na, Ca, Mg, K salts,
Al, Si, Fe, S oxides
Coal also contains trace amounts of
Ga and Ge, both of which are
important for the modern electronics
industry

Unlike petroleum, coal cannot be

separated into individual
products. It must be reformed
into smaller FW useful material
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(synthetic fuels) or combusted to
capture the heat.

CHEMISTR
Y OF COAL
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COAL GAS
Coal carbonization: coal is heated at moderate
temperature, thermal decomposition of the
organic material releases small amounts of
flammable gas

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CmHn CH4 + (m-n)/4 C

Carbonization carried out at ~400 C, products are H2 and CH4
Important historically because this was the first large source of CH4 which
was used for lighting in the early 20th century
Not a useful process anymore because of the large known reserves of CH4

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COAL GAS

Coal gasification: conversion of coal into methane:

But hydrogasification requires high temps, 800 0C

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C + 2 H2 CH4 + 74.9 kJ
Also is inefficient because it is exothermic and driven to left at high T

More efficient route to methane:

CO + 3 H2 CH4 + H2O + 206.3 kJ

Reaction is more exothermic but operates at 400 0C with Ni catalyst

Process can produce liquids by Fischer-Tropsch chemistry:

n CO + (2n+1)H2 CnH2n+2 + nH2O

Production of methanol:
CO + 2 H2 = CH3OH

What is the feedstock for CO and H2?

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COAL GAS

Steam reforming:

C + H2O CO + H2 - 131.4 kJ

(1)

If extra H2 is needed, perform water-gas shift reaction:

CO + H2O CO2 + H2 + 41.4 kJ

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Produces equal amounts of CO and H2

(2)

This fulfil the needed CO and H2

So overall, use two equiv. of (1), add to (2) and methanation to get:
2 C + 2 H2O = 2 CO + 2 H2 - 262.8 kJ
CO + H2O = CO2 + H2 + 41.4 kJ
CO + 3 H2 = CH4 + H2O + 206.3 kJ
2 C + 2 H2O = CH4 + CO2 - 15.1 kJ

Hence in theory can convert coal to methane with energy of only 15.1 kJ
But exothermic reaction goes at 400 0C, endothermic one at 900 0C
Need to supply heat to endothermic one, to do so burn more coal
Requires 262.8 kJ/mole of methane, about 32% of energy content of methane
Hence upper limit is 68%, lower in practice due to other losses

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COAL LIQUIDIFICATION
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Indirect liquidification: Product of coal gasification (CO and H 2 mixture, also called
synthetic gas or syngas) is reacted to form larger FW hydrocarbons

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PRODUCTION AND USE OF COKE

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Gasification breaks apart hydrocarbonsproducts are volatile gases and

carbonized coal
Carbonized coal is called coke - can be burned at high temperatures up to
1100 C
If coal carbonization is carried out at high temperature:
Coke is used in blast furnaces in the steel industry
Although coke can support high combustion temperatures, some unburned
coke is carried out of the furnace as small particulate matter called smoke
Smoke is a major contributor to air pollution
If coal carbonization is carried out at low temperature:
Coke burned at temperatures lower than 750 C combusts completely (no
smoke)
This is commonly used for small-scale industries that cannot afford the
scrubbers used to clean smoke

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PRODUCTION AND USE OF TAR

Coal carbonization also produces a small amount

of sticky, black liquidcalled tar

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Tar contains low FW aromatic compounds

distilled

to produce benzene, toluene, xylenes, and

their corresponding alcohols, which are important
petrochemical feedstocks

Secondary products that can be made from tars

are synthetic dyes, antibiotics and anesthetics,
flavoring agents, and perfumes

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COKING OF COAL
Beehive oven

Byproduct oven (or coke oven plant)

BEEHIVE OVEN
Beehive coke ovens were called that because they
were built in a beehive-like hemispherical shape,
and then covered with earth.

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http://patheoldminer.rootsweb.ancestry.com/coke2.html

BY-PRODUCT COKE OVEN

PROCEDURE

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The carefully blended coal charge is heated on both

side so that heat travels towards the center and thus
produces shorter and more solid pieces of coke (no
air is introduced, to avoid burning of coal).

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BY-PRODUCT COKE OVEN PROCEDURE

(KOPPER-BECKER UNDERJET LOW-DIFFERENTIAL

COMBINATION COKE OVEN WITH WASTE GAS RECIRCULATION )

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COKING COALS:

COAL ANALYSIS BEFORE CHARGING INTO THE COKE

OVEN
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The average temperature in the center of the coal

is 980 0C.
The flue gas temperature is 1290 0C.
The temperature varies with

the

condition of operations
The coking time
The width of the oven, and
The type of coal, its moisture contents and its
fineness of division.

The typical coking time is ~17 h.

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BY-PRODUCT COKE OVEN

PROCEDURE
Process is divided into following sequences:
1.
2.
3.
4.
5.
6.
7.
8.
9.
10.

Coal is transferred, crushed and screened,

Coal is charged to hot empty oven,
Coal is chemically transformed to coke and volatiles by
pyrolysis,
Hot coke is pushed out of the oven, quenched and
transported,
Condensable product of distillation are liquefied and
collected in the hydraulic main,
Foul gas is cooled, and tar extracted
Ammonia is removed from gas as ammonium sulfate
Gas is cooled and subjected to benzene and toluene removal
by absorption in straw oil,
Hydrogen sulfide is removed,
Purified gas is metered and transferred to consumers.

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COAL TAR CONTINUOUS

DISTILLATION
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CONTINUOUS TAR DISTILLATION

PRODUCTS
Product

Boiling point (oC)

Side stream 1

Light oil

Side stream 2

Carbolic oil

170205

Side stream 3

Naphthalene oil

205204

Side stream 4

Creosote or wash oil

240280

Residue 5

The residue or anthracene

280340

Pitch 6

Residuum or pitch

340400

to 170

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Streams

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RECOVERY OF COAL CHEMICALS

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BY-PRODUCT COKE OVEN

PROCEDURE
AN AMMONIA STILL
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BY-PRODUCT COKE OVEN

PROCEDURE
The following materials are required in order to
produce:

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Gas

0.280.35 Mm3 of 20.5 MJ/m3,

Coke
700 kg, 38 L tar;
Ammonium sulfate
11.4 kg
Light oil
7.6 15.2 L

Bituminous coal

1t

Steam

200 600 kg

Sulfuric acid (60o Be)

12.5 kg

Electricity

25 MJ

Lime

0.75 1 kg

Direct labor 0.8 1.3 work-h

Water

4150 8000 L

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APPROXIMATE YIELDS PER METRIC

TON OF COAL CARBONIZED
Low temperature

kg

kg

Furnace coke

715

Coke breeze

46.5

Semicoke (12% volatiles)

720

Tar

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75

Ammonium sulfate

10

Light oil (removed from

gas by oil scrubbing)

10

1750

125

Gas

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High Temperature

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VARIATION OF GAS FROM LOW AND HIGH

TEMPERATURE COAL CARBONIZATION
Coking temperature, Coking temperature,
500 OC,

1000 OC,

CO2

9.0

2.5

CnHm

8.0

3.5

CO

5.5

8.0

H2

10.0

50.0

CH4 and homologs

65.0

34.0

N2

2.5

2.0

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Gas

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CONTINUE

ACKNOWLEDGEMENT
Slides are developed from the following references:
Austin

G. T., "Shreves Chemical Process Industries",

Fifth edition, Tata McGraw Hill, NY.
Kent J.A., "Riegel's Handbook of Industrial
Chemistry, CBS Publishers.
Gopala Rao M. & Marshall Sittig, "Drydens Outlines of
Chemical Technology for the 21st Century", Affiliated
East West Press, New Delhi.
Mall I. D., "Petrochemical Process Technology",
Macmillan India Ltd., New Delhi.
NPTEL (online)

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