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 - rst 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 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
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-re technology supplies >50% of US electricity production
http://www.iea.org/statist/keyworld2002/key2002/keystats.htm
Global Total Primary Energy Supply Outlook
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Geographical Distribution of Coal Reserves
http://www.eia.doe.gov/emeu/iea/table82.html
By country:
Country
Total Recoverable
Coal (x10
6
tons)
United States
Russia
China
India
Australia
Germany
South Africa
Ukraine
Kazakhstan
Poland
273,656
173,074
126,215
93,031
90,489
72,753
54,586
37,647
37,479
24,427
By region:
Region
Total Recoverable
Coal (x10
6
tons)
Asia & Oceania
Eastern Europe
North America
Western Europe
Africa
Central &
South America
Middle East
322,394
290,183
282,444
101,343
61,032
23,977
1,885
! The geopolitics of coal is very different from the geopolitics of petroleum
! Coal mining is labor-intensive and dangerous work
~2.1x10
7
BTU/short ton (2000 lbs);1 BTU = 1.055x10
3
J
Hence 2.1x10
22
J
Consume 1x10
20
J/yr; so 200 yrs of coal reserves
% World Oil/Coal Reserves By Region:
C./S. America
Asia & Oceania
Middle East
57
North America
W. Europe
Eastern Europe
Africa
26
18
2
8
6 6
9
27
7
30
3
Source: EIA, International Energy Outlook, 2002
Oil
Coal
http://www.ket.org/Trips/Coal/AGSMM/agsmmwhere.html
US Distribution of Coal Resources
State Coal Resources
(x 10
6
tons)
Montana
Illinois
Wyoming
West Virginia
Kentucky
Pennsylvania
Ohio
Colorado
Texas
Indiana
Other
120
78
68
37
30
29
19
17
13
10
51
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
lignin source (ie
tree brances/twigs)
10 m
Remnants of
cellular structure
of source material
! Coal deposits are formed from plant material that died and was deposited in a
swampy environment - low in O
2
! 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 rst step in coal formation is accumulation of organic debris in a peat swamp.
In most environments, such as the forest oor, 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 uctuations.
In this model the land surface remains stationary and sea level rises and falls.
Geologic Time Scales
The majority of earths 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 ourished 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
Type
Origin
Resinite
Sporinite
Bituminite
Alginite
Vitrinite
Fusinite
Sclerotinite
Plant resins
Spores, pollens
Degraded algae
Algae
Woody tissues
Carbonized woody tissues
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
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.
kJ/g
12.5
16.6
22.8
27.7
35.8
Oil:43.6
Gas: 51.6
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 difcult to solve
unlike petroleum, coal cannot be separated into its components easily
Heat coal to 100 C, loses weight from H
2
O evaporation
Heat coal to higher temperatures, organic constituents begin breaking down, release
low FW hydrocarbon gasses
Organic matter remaining can be combusted, products are H
2
O and CO
2
a small amount of inorganic ash is left behind
Instrumental analysis:
X-ray crystallography - composed of clusters of benzene rings, but this is difcult
because coal is not highly crystalline
NMR - as C/H ratio increases, aromaticity increases
Chemical Composition of Coal
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/
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
specic for some coal scientists
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
Graphite is perfect coal
Chemistry of Coal
COAL Coke Oven
Coke
Ash
Condensation
and Separation
Gasses
Tar
Distillation
and Separation
Heavy Oils
Wash oils
OH
OH
OH
OH
CH
4
H
2
+ CO
Fischer-Tropsch
Process
Synthetic
Gasoline
Light Oils
Creosote,
Pitch
Coal Gas
Coal carbonization: coal is heated at moderate temperature, thermal
decomposition of the organic material releases small amounts of ammable
gas
C
m
H
n
CH
4
+ (m-n)/4 C
Carbonization carried out at ~400 C, products are H
2
and CH
4
Important historically because this was the rst large source of CH
4
which was
used for lighting in the early 20th century
Not a useful process anymore because of the large known reserves of CH
4
C + 2 H
2
= CH
4
+ 74.9 kJ
But hydrogasication requires high temps, 800 C
Also is inefcient because is exothermic and driven to left at high T
Coal Gas
Coal gasication: conversion of coal into methane:
More efcient route to methane:
CO + 3 H
2
= CH
4
+ H
2
O + 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)H
2
= C
n
H
2n+2
+ n H
2
O
Or can even make methanol:
CO + 2 H
2
= CH
3
OH
But, where do the CO and H
2
come from?
Coal Gas
Steam reforming:
C + H
2
O = CO + H
2
- 131.4 kJ (1)
Produces equal amounts of CO and H
2
If need extra H
2
, run water-gas shift reaction:
CO + H
2
O = CO
2
+ H
2
+ 41.4 kJ (2)
This makes the needed CO and H
2
So overall, use two equiv. of (1), add to (2) and methanation to get:
2 C + 2 H
2
O = 2 CO + 2 H
2
- 262.8 kJ
CO + H
2
O = CO
2
+ H
2
+ 41.4 kJ
CO + 3 H
2
= CH
4
+ H
2
O + 206.3 kJ
2 C + 2 H
2
O = CH
4
+ CO
2
- 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 liquidication: Product of coal gasication (CO and H
2
mixture, also called
synthetic gas or syngas) is reacted to form larger FW hydrocarbons
Fischer-Tropsch Process: react CO and H
2
at ~400-500 C and ~100-150 atm over
Fe or Co catalysts
products vary depending on reaction conditions
CO + H
2 Fischer-Tropsch
Reactor
OH
O
O
OH
alkanes
alkenes
alcohols
ketones
carboxylic acids
Indirect liquidication can produce synthetic
gasolines (and was an important source of gas
for oil-poor Germany and Japan during
WWII), but it is not yet economically viable.
Production and Use of Coke
Gasication 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, avoring agents, and perfumes
Integrated Gasification Combined Cycle (IGCC)
--High efciency (~60%)
--Already near zero emission, could be made zero emission
--Products are electricity, H
2
(sold as fuel), and CO
2
(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
800-300
800
= 62.5%
= 43.7%
800-450
800
450-300
450
= 33.3%
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/mi
2
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 y 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 FeS
2
(pyrite), organic suldes (R-S-R), and sulfates (SO
4
2-
)
About 15% of S is left behind in ash, the rest is emitted as SO
2
and SO
3
(SO
x
)
Major environmental pollutant
SO
2
deposits on surfaces (ie buildings, skin)
SO
3
forms SO
4
2-
, which dissolves in H
2
O and is washed from the air as acid rain
S Emission Reduction Strategies:
Out of sight, out of mind: Early solutions emitted the SO
x
out of very tall stacks to disperse
it, carry it away from the point of origin, make it someone elses 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 CaSO
4

sludge
Environmental Issues
Nitrogen
N
2
in air reacts with O
2
at high temperatures to form NO, NO
2
, NO
3
(NO
x
)
NO
x
contributes to smog formation
Coal combustion emissions account for only ~5% of NO
x
formation, and there is
currently no commercial process that removes NO
x
from vapor streams