Coal

“Big Musky”
 Fossil Fuels: Coal

Outline:
Brief history of coal
Origin and geographical distribution
Chemical composition of coal
Chemistry of coal use
--gas, liquid, coke, tar
Environmental impact of coal combustion
References:
On Reserve
Coal: The Energy Source of the Past and Future, Harold H. Schobert
An Introduction to Coal Technology, N. Berkowitz
On the web
http://chemistry.anl.gov/carbon/coal-tutorial/
http://www.eia.doe.gov/emeu/iea/contents.html
 Coal in History

Coal Timeline:
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
early 1600’s - Great Britain runs out of wood, switches to coal,
beginning of the industrial revolution
1800’s - 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

The rise of western industry was tied to coal,

until the discovery of petroleum
 Global Coal Use
--25% of US primary energy consumption is coal
--Coal-fire technology supplies >50% of US electricity production

Global Total Primary Energy Supply Outlook

Million tons of oil equivalent (Mtoe)

Energy usage (x 1020 J)

6.0

5.0

4.0

3.0

2.0

1.0

http://www.iea.org/statist/keyworld2002/key2002/keystats.htm
 Geographical Distribution of Coal Reserves
By country: By region:
Country Total Recoverable Region Total Recoverable
Coal (x106 tons) Coal (x106 tons)

United States 273,656 Asia & Oceania 322,394

Russia 173,074 Eastern Europe 290,183
China 126,215 North America 282,444
India 93,031 Western Europe 101,343
Australia 90,489 Africa 61,032
Germany 72,753 Central & 23,977
South Africa 54,586 South America
Ukraine 37,647 Middle East 1,885
Kazakhstan 37,479
Poland 24,427 ~2.1x107 BTU/short ton (2000 lbs);1 BTU = 1.055x103 J
Hence 2.1x1022 J
Consume 1x1020 J/yr; so 200 yrs of coal reserves

 The geopolitics of coal is very different from the geopolitics of petroleum

 Coal mining is labor-intensive and dangerous work

http://www.eia.doe.gov/emeu/iea/table82.html
 % World Oil/Coal Reserves By Region:

North America
27
57
7
26
18
Eastern Europe
W. Europe 30
9

3
Asia & Oceania
8 Middle East
2
C./S. America 6 6
Africa
Coal

Oil
Source: EIA, International Energy Outlook, 2002
 US Distribution of Coal Resources

State Coal Resources

(x 106 tons)
Montana 120
Illinois 78
Wyoming 68
West Virginia 37
Kentucky 30
Pennsylvania 29
Ohio 19
Colorado 17
Texas 13
Indiana 10
Other 51

http://www.ket.org/Trips/Coal/AGSMM/agsmmwhere.html
 Formation of Coal
The origin and formation of coal is better understood than the origin of
petroleum, largely because it has 3-dimensional structure that can be traced to
the original organic material that formed it

Marks left by Remnants of

lignin source (ie cellular structure
tree brances/twigs) of source material

10 µm

 Coal deposits are formed from plant material that died and was deposited in a
swampy environment - low in O2
 Anaerobic bacteria convert the organic material until environment becomes too
acidic and the bacterial die - decomposition stops when the plants have been converted
to peat
 Peat becomes buried at bottom of swamp
 Peat is transformed at high pressure and low temperature (< 200 ˚C) over ~300
million years to coal
http://chemistry.anl.gov/carbon/coal-tutorial/
 Peat Swamp

The first step in coal formation is accumulation of organic debris in a peat swamp.
In most environments, such as the forest floor, plant material decays as fast as it is
produced, so it does not accumulate. However, in a peat swamp, stagnant water
that does not contain oxygen inhibits the decay of organic material allowing it to
accumulate and form peat. Burying the peat with sediment further inhibits the decay of peat.
 Delta Deposits

The coal deposits in the Appalachian Basin are associated with delta deposits.
This outcrop from NE Kentucky shows alternating layers of sandstone, siltstone,
shale and coal which are characteristic of deltas.
Glacial Eustatic Sea Level Fluctuations

Another model for cyclothems is glacial eustatic sea level fluctuations.

In this model the land surface remains stationary and sea level rises and falls.
Geologic Time Scales

The majority of earth’s history is

represented by the Precambrian,
which consist of unfossiliferous rocks
that were deposited before there was
abundant life on earth.

The remainder of geologic time is

divided into the Paleozoic, Mesozoic
and Cenozoic Eras which represent
ancient life, middle life and recent
life, respectively.

The last three eras are further divided

into the Periods of the Geologic Time
Scale.
 Age of Coal Deposits

Majority of the coal deposits are Pennsylvanian (P) in age; no coal deposits that are older than the
Devonian (D). Land plants had not fully evolved prior to Devonian therefore coal deposits which are the
remains of plants could not have formed. The Pennsylvanian Period which corresponds to the majority of
coal deposits including the Appalachian Basin was a time when plant life flourished in North America. It is
also a time in geologic history when major continental glaciers occurred in the southern continents. The
coal deposits in the western states, such as Wyoming, are younger than those in the Appalachian Basin and
are mostly Jurassic (J), Cretaceous (C) and Tertiary (T) in age.
Changes After Burial

Burial of peat by overlying sediments results

in an increase in the temperature and
pressure. One change that happens is
compaction.

It is estimated that it takes 20 feet of peat to

form a one foot coal bed.

In addition to compaction there is a loss of

moisture and volatiles. Much of the water
that is lost was trapped in pore spaces and is
expelled during compaction. Some of the
water, plus the volatiles (gases) are released
due to chemical changes in the peat.
Peat vs Coal
 Continuous Mining

Coal is cut from face and loaded into

a truck/rail car that brings it to the surface
Roam and Pillar Mining
Longwall Mining
Surface Mining
 Formation of Coal
The different organic constituents that form coal can be distinguished in the coal material
-- called macerals
Maceral Origin
Type
Resinite Plant resins
Sporinite Spores, pollens
Bituminite Degraded algae
Alginite Algae
Vitrinite Woody tissues
Fusinite Carbonized woody tissues
Sclerotinite Fungal hyphae

Study of macerals is necessary

because different starting
materials will give different
C/H ratios in the coal product,
which is important in coal use
 Energy Value of Coal Ranks
Oil:43.6
Gas: 51.6
kJ/g
12.5
16.6
22.8
27.7
35.8

The higher the coal rank the higher the temperature and pressure of coal formation.
The higher coal ranks have a higher percent carbon and less water.
As moisture and volatiles are driven off during coal maturation, carbon is left behind.
The increased carbon content increases the heat content (Btu/lb) of the coal.
 US Coal Reserves

The majority of U.S. coal is bituminous.

The highest rank coal anthracite only makes up 2 percent of coal reserves.
This coal is too valuable to be burned as a fuel and is used mainly for coking steel.
 Chemical Composition of Coal
Observations:
Chemical composition of coal was very difficult to solve
unlike petroleum, coal cannot be separated into its components easily

Heat coal to 100 ˚C, loses weight from H2O evaporation

Heat coal to higher temperatures, organic constituents begin breaking down, release
low FW hydrocarbon gasses

Organic matter remaining can be combusted, products are H2O and CO2
a small amount of inorganic ash is left behind

Instrumental analysis:
X-ray crystallography - composed of clusters of benzene rings, but this is difficult
because coal is not highly crystalline

NMR - as C/H ratio increases, aromaticity increases

 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
Model of coal, although even this is too
specific for some coal scientists

Graphite is “perfect” 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
(synthetic fuels) or combusted to capture
the heat.
http://chemistry.anl.gov/carbon/coal-tutorial/
 Chemistry of Coal CH4

Gasses
Condensation
COAL Coke Oven
and Separation H2 + CO

Tar Fischer-Tropsch
Ash Coke Process

Distillation
and Separation
Synthetic
OH Gasoline
OH
Wash oils Heavy Oils
OH
Light Oils
OH

Creosote,
Pitch
 Coal Gas
Coal carbonization: coal is heated at moderate temperature, thermal
decomposition of the organic material releases small amounts of flammable
gas
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
 Coal Gas

Coal gasification: conversion of coal into methane:

C + 2 H2 = CH4 + 74.9 kJ
But “hydrogasification” requires high temps, 800 C
Also is inefficient because 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 C with Ni catalyst
• Or if wanted, can produce liquids by Fischer-Tropsch chemistry:
n CO + (2n+1)H2 = CnH2n+2 + n H2O
• Or can even make methanol:
CO + 2 H2 = CH3OH
• But, where do the CO and H2 come from?
 Coal Gas
Steam reforming:
C + H2O = CO + H2 - 131.4 kJ (1)
Produces equal amounts of CO and H2

If need extra H2, run “water-gas shift” reaction:

CO + H2O = CO2 + H2 + 41.4 kJ (2)
This makes 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 C, endothermic one at 900 C
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
 Coal Liquidification
Indirect liquidification: Product of coal gasification (CO and H2 mixture, also called
synthetic gas or syngas) is reacted to form larger FW hydrocarbons

Fischer-Tropsch Process: react CO and H2 at ~400-500 ˚C and ~100-150 atm over

Fe or Co catalysts
products vary depending on reaction conditions

alkanes
CO + H2 Fischer-Tropsch alkenes
Reactor
OH

alcohols

Indirect liquidification can produce synthetic O

gasolines (and was an important source of gas ketones

for oil-poor Germany and Japan during
WWII), but it is not yet economically viable. OH carboxylic acids

O
 Production and Use of Coke
Gasification breaks apart hydrocarbons - products 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
 Production and Use of Tar
Coal carbonization also produces a small amount of sticky, black liquid - called tar
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
 Integrated Gasification Combined Cycle (IGCC)

--High efficiency (~60%)

--Already near zero emission, could be made zero emission
--Products are electricity, H2 (sold as fuel), and CO2 (which can be sequestered)
--IGCC plants currently producing 1500 MW electricity; 2200 MW more online soon
Figure from Julio Friedmann, U. of Maryland
Integrated Gasification Combined Cycle (IGCC)
Combine gas turbine generators with steam turbine generators powered by
steam from the waste heat of the gas turbine generator

450-300
800-300 = 62.5% 450
800
= 33.3%

800-450
800
= 43.7%

43.7+33.3=
77.0%
Mass Balance During Coal Combustion

Numbers in Joules
 Environmental Issues
Smoke
Smoke is particulate matter containing either uncombusted coke or coal tars, or ash
Particulate matter eventually falls to the ground or is inhaled
Pittsburgh, 1911 - 1031 tons/mi2 of soot deposited (highest in the world)
death rate from pneumonia highest in the world
Uncombusted coke can be eliminated by a well-designed furnace
Ash (called fly ash) must be removed from the emission vapors in the furnace
Electrostatic Precipitators: Smoke passes between two electrode plates,
charged ash particals are attracted to the plates where they are collected
Cyclone Collectors: Furnace gas sent into a vortex, heavy ash particles are
centrifuged down to collectors
Collected ash is used as raw material
Currently ash is used in concrete
In the future it may become an important source of Al, Ga, and Ge
 Environmental Issues
Sulfur
Coal is < 3% S, has no effect on the combustion of coal and coke
Sources of S are FeS2 (pyrite), organic sulfides (R-S-R’), and sulfates (SO42-)
About 15% of S is left behind in ash, the rest is emitted as SO2 and SO3 (SOx)
Major environmental pollutant
SO2 deposits on surfaces (ie buildings, skin)
SO3 forms SO42-, which dissolves in H2O and is washed from the air as acid rain

S Emission Reduction Strategies:

Out of sight, out of mind: Early solutions emitted the SOx out of very tall stacks to disperse
it, carry it away from the point of origin, make it someone else’s problem
Burn less S: Use coals with lower S content (most coal in the US is ~ 2.5% S)
Clean coal before combusting (this is expensive)
Scrubbing: Vapor emission is run over an aqueous limestone (Ca) slurry, forms CaSO4
sludge
 Environmental Issues
Nitrogen
N2 in air reacts with O2 at high temperatures to form NO, NO2, NO3 (NOx)
NOx contributes to smog formation
Coal combustion emissions account for only ~5% of NOx formation, and there is
currently no commercial process that removes NOx from vapor streams