LECTURE 5

CLEAN COAL CONVERSION

TECHNOLOGIES

1
The objectives of this lecture are
 To introduce the impact of coal usage on the environment and its
associated pollutants
 To look at technologies used to mitigate the negative effects of burning
coal

2
A CULTURAL NOTE

 Surgical masks are used in parts

of Asia
 If you are sick and don’t want to
spread germs
 If you have allergies
 If you want to make a fashion
statement
 To avoid breathing
smog/pollutants (especially
Beijing)
 Recently COVID 19

3
COAL IMPACTS ON SOCIETY

Coal is a Good Thing! Coal is a Bad Thing 

 Coal is a relatively  Coal is blamed for much
inexpensive, secure, local of our air pollution
energy source
 Coal is blamed for high
 Coal supplies more than
levels of greenhouse
40% of electricity
gases
generated globally
 Coal provides our modern
smart phone, cloud
computing lifestyle

4
 WHY IS COAL STILL USED?
 Cheapest for power stations relative to the amount of heat it generates
when burnt

http://www.economist.com/business/displaystory.cfm?story_id=101454
92
HOW MANY PEOPLE DO YOU THINK DIE IN
COAL MINES EACH YEAR?
 A: Thousands
 B: Hundreds
 C: Dozens
 D: a Few
 E: Nobody

6
EXTRACTION – WORKER FATALITIES

 Coal deaths – from a peak of thousands to a few dozen per year

Coal Mining Fatalities in USA

3,500

3,000

2,500

2,000

Fatalities
1,500

1,000

500

0
1905

1917

1974

1986
1902

1908
1911
1914

1920
1923
1926
1929
1932
1935
1938
1941
1944
1947
1950
1953
1956
1959
1962
1965
1968
1971

1977
1980
1983

1989
1992
1995
1998
2001
2004
2007
2010
Year

7
EXTRACTION

 Coal fatalities – from a peak of thousands to a few

dozen per year
 Globally, China and Ukraine lag in making mining safer
 From 2000-2008, an average of 5,404 fatalities per
year in China
 Since 1990, an average of 317 fatalities per year in
Ukraine

8
WATER CONTAMINATION DURING MINING

Mining operations can negatively impact water supplies, often

with long-lasting effects.
It involves contamination of nearby rivers, lakes, and aquifers by
what comes out of a coal mine—usually highly acidic water
containing heavy metals like arsenic, copper, and lead – a
process known as acid mine drainage.

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ACID MINE DRAINAGE

 Historically, mined areas were abandoned once the

coal was removed
 Water draining from abandoned mines is a large
source of water pollution – high acidity and heavy
metal content
 Now mine operators must post a bond to ensure
cleanup
 An ‘externalized’ cost borne by society in general is
now ‘internalized’ - borne by the mining company

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POLLUTANTS

• Carbon Monoxide (CO)

• Particulate Matter (PM10, PM2.5)
• Sulfur Dioxide (SO2)
• Nitrogen Oxides (NOx)
• Unburned Hydrocarbons (VOC’s)
• Carbon Dioxide (CO2)
• Acid Rain
• Smog and ground level ozone

11
HOW DOES PARTICULATE MATTER FORM?

 Due to impurities (e.g.sand) in coal, which do not burn

 Finely powdered coal produces finely powdered ash
 Diesel engines can produce fine particles of unburned
carbon – black smoke or soot

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EFFECTS OF PARTICULATE MATTER

 Particles can
 damage human and animal health
 retard plant growth
 reduce visibility
 damage soil, buildings, and other materials

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PARTICLE CHARACTERISTICS

Small particles can stay in the atmosphere for

a long time. Very small particles can become
“stuck” in the lungs and smaller particles can
enter the blood stream. This is bad as often
the small particles have carcinogenic
compounds on their surface.
 PM10 – particles smaller than 10 micrometers in size
 PM 2.5 Particles smaller than 2.5 micrometers in
size

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PARTICULATE MATTER - HUMAN HEALTH

 Particles > 2µm do not penetrate beyond nasal cavity

or trachia – removed by coughing and sneezing
 Particles < 0.1µm tend not to settle
 Particles > 0.1µm and < 2.0µm penetrate deep into
the lungs and settle in bronchial branches or alveolar
sacs

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PARTICULATE MATTER - HUMAN HEALTH

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PARTICULATE MATTER - HUMAN HEALTH

 SO2, As, Se, Cd (toxic) are adsorbed on these

particles.
 Lead, Asbestos, Manganese, Beryllium, Arsenic,
Copper and Zinc are some of the other particulates.

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PARTICULATE MATTER-VISIBILITY

Particulates decrease visibility by scattering

and absorbing some of the light emitted or
reflected by objects, reducing the contrast.
Scattering of light by particles is a strong
function of particle size.
Most effective scatterers are particles about
the same size as the wave length of visible
light (0.1 -1.0µm)

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 ELECTROSTATIC PRECIPITATORS (PARTICLE
EMISSIONS)
 Creates an electrical field that removes unwanted charged particles (99%
effective)
 The unit is normally comprised of a series of parallel, vertical metallic plates
(collecting electrodes or CEs) forming ducts or lanes through which the flue
gas passes. Centered between the CEs are discharge electrodes (DEs) which
provide the particle charging and electric field

http://news.bbc.co.uk/1/hi/sci/tech/4468076.stm
SULFUR

 Sulfur is present in
 Coal 0.5 – 5 wt%
 Diesel 0.05 wt%
 Gasoline approximately 330 ppm
 Fuel oil 0.1-2.5%

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SO2 FORMATION
All coals contain sulfur. Some of this sulfur, known as organic sulfur, is
intimately associated with the coal matrix.

The rest of the sulfur, in the form of pyrites or sulfates, is associated with the
mineral matter.

Upon combustion, most of the sulfur is converted to SO2, with a small amount
being further oxidized to sulfur trioxide (SO3).

S(Coal) + O2 = SO2
SO2 + ½O2 = SO3

Because, in the absence of a catalyst, the formation of SO3 is slow, over 98%
of the combusted sulfur is in the form of SO2.

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SULFUR SOLUTIONS

 One way is to wash the sulfur out of the coal before it

is burned.
 Another is to wash the sulfur out of the smoke before
it goes up to the smokestacks. Scrubbers remove
sulfur from the smoke by spraying a mixture of water
and powdered limestone into the flue gases. The
mixture traps the sulfur before it can escape into the
air above.

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COAL WASHING
 Grinding coal into pieces and passing it through gravity filtration
 One technique: Putting coal into a barrel with a liquid with a specific
density where the coal floats and the impurities sink

http://news.bbc.co.uk/1/hi/sci/tech/4468076.stm
The efficiency of conventional coal cleaning techniques in removing sulfur is
variable.

Only inorganic sulfur can be removed by conventional methods and the

degree of removal is influenced greatly by mineral type and coal particle size
- the larger the particle, the lower the potential for sulfur removal.

Physical cleaning can remove from coal 30-50% of the pyretic sulfur (which
is not organically bound into the coal), or 10-30% of the total sulfur content.

Advanced physical cleaning methods include flotation, agglomeration and

flocculation, and dry cleaning.

Works carried out to date indicate that these techniques could yield 80-90%
removal of inorganic sulfur.

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To remove sulfur that is organically bound in coal requires chemical or biological coal
cleaning.

Reports suggest that it is possible to remove up to 90% of either pyretic or organic

sulfur from coal using an oxidation agent at high temperature and pressure, and
micro-organisms (the use of bacteria to eat the sulfur in coal).

These processes are still in development.

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SO2 SCRUBBING

 Coal cleaning is insufficient

 Wet Flue Gas Desulfurization (FGD) is dominant technology –
“scrubs” SO2 out of flue gas
Absorption
SO2 + H2O → H2SO3
Neutralization
CaCO3 + H2SO3 → CaSO3 + CO2 + H2O
Oxidation
CaSO3 + ½ O2 → CaSO4
Crystallization
CaSO4 + 2H2O → CaSO4∙2H2O
SO2 SCRUBBING – FGD DIAGRAM
 WET SCRUBBERS

 When the emissions reach the flue of

the furnace, limestone and water are
sprayed
 The SO2 reacts with the calcium
carbonate (limestone) to form gypsum
(calcium sulfate)
 The gypsum is collected and used for
construction
 95% effective

http://news.bbc.co.uk/1/hi/sci/tech/4468076.stm
Advantages and Disadvantages of Wet Scrubbers:

Advantages:
 Relatively small space requirements
 Can collect gases as well as particulates
 Can handle high-temperature, high-humidity gas streams
 Particulate matter cannot escape from hoppers or during transport.
 Various dry dusts are flammable. Using water eliminates the possibility of explosions.
 High collection efficiencies on fine particulates
 Handle gas streams containing flammable or explosive materials.
 Wet scrubbers can neutralize corrosive gases.

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Wet Scrubbers:
Disdvantages:
 Possible creation of water-disposal problem and the product collected is wet.
 Moist exhaust gas precludes use of most additional controls
 Pressure-drop and power requirements are possibly high and Solids buildup at the wet-
dry interface might be a problem
 Relatively high maintenance costs and Must be protected from freezing
 Low exit gas temperature reduces exhaust plume dispersion

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 Dry scrubber :
A dry Scrubbing system does not saturate the flue gas stream that is being treated
with moisture. In some cases no moisture is added; while in others only the
amount of moisture that can be evaporated in the flue gas without condensing is
added.
Dry scrubbers generally do not have wastewater handling/disposal requirements.
Dry scrubbing systems are used to remove acid gases(such as SO2 and HCl)
primarily from combustion sources

Advantages and Disadvantages of Dry Scrubbers

Advantages:
No wet sludge is produced.
Relatively small space requirements
Can collect acid gases at high efficiencies
Can handle high-temperature gas streams
Dry exhaust allows addition of fabric filter to control particulate

Disadvantages
Acid gas control efficiency not as high as with wet scrubber

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LIFAC Sorbent Injection Desulphurization

Process Description
The abbreviation LIFAC refers to the process which involves Limestone Injected
into the Furnace with Activation of untreated Calcium oxide.

LIFAC technology is designed to remove sulfur dioxide (SO2) produced in a coal-

fired utility boiler, using a limestone sorbent at a calcium/sulfur molar ratio of 2.0 -
2.5.

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THE FIGURE BELOW IS SCHEMATIC FLOW OF THE
LIFAC PROCESS.

A unique feature of this technology is humidification of the flue gas in a

separate activation reactor, which increases SO2 removal.

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An electrostatic precipitator downstream from the point of injection captures the
reaction products, along with the fly ash entrained in the flue gas.

Pulverized limestone is pneumatically blown into the upper part of the boiler
furnace near the superheater where it absorbs some of the SO2 in the boiler flue
gas.

The limestone is calcined into calcium oxide and is available for capture of additional
SO2 downstream in the activation, or humidification, reactor.

In the vertical chamber, water sprays initiate a series of chemical reactions leading to
SO2 capture.

After leaving the chamber, the sorbent is easily separated from the flue gas along
with the fly ash in the electrostatic precipitator.

34
The sorbent material from the reactor and electrostatic precipitator are recirculated
back through the reactor for increased efficiency.

The waste is dry, making it easier to handle than the wet scrubber sludge produced
by conventional wet limestone scrubber systems.

The technology enables power plants with space limitations to use high-sulfur coals
by providing an injection process that removes 75 - 85% of the SO2 from flue gas and
produces a dry solid waste product suitable for disposal in a landfill.

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SO2 Removal

Finely pulverized limestone (CaCO3) is injected into the furnace at a point where
temperatures range from 1000 - 1100°C, which results in decomposition to lime
(CaO), which is more reactive:

CaCO3 = CaO + CO2

About 25% of the SO2 in the flue gas reacts with the lime to form calcium sulfite
(CaSO3) and calcium sulfate (CaSO4):

SO2 + CaO = CaSO3

SO2 + CaO + ½ O2 = CaSO4

As a result of the SO2 oxidizing, the flue gas also contains a small amount of sulfur
trioxide (SO3), essentially all of which reacts with lime, yielding additional CaSO4:

SO3 + CaO = CaSO4

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The flue gas, containing the remaining 75% of the SO2 plus unreacted lime, exits the boiler and
passes through the furnace air preheater, after which the mixture enters the LIFAC activation
reactor.
This reactor is an elongated vertical duct equipped with spray nozzles at the top. A water
spray humidifies the gas, converting the lime to hydrated lime, Ca(OH)2:

CaO + H2O = Ca(OH)2

Further SO2 removal occurs through reaction with hydrated lime, yielding additional CaSO3:

SO2 + Ca(OH)2 = CaSO3 + H2O

The flue gas leaving the activation reactor enters the existing electrostatic precipitator, where
the spent sorbent and fly ash are removed.
A portion of the solids is recycled to the activation reactor and the remainder is sent to a
landfill for disposal.

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Environmental and Economic Performances

The SO2 removal efficiency can reach at least 70% for coal with sulfur ranging from
low to middle, depending on the calcium/sulfur molar ratio.

Other emissions, including particulates in the stack gas and solids in the water
effluent are low enough to comply to local environmental requirements.

The ash by-product does not require additional treatment before being disposed of
in a landfill.

The main advantage of LIFAC is its low capital cost, which makes it a retrofit option
for moderate sulfur removal where regulations permit.

However, the overall cost is relatively higher than traditional flue gas desulfurization.

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NITROGEN OXIDES
 NO and NO2 are collectively called NOx
 NO is colorless but is photochemically converted to
NO2 which is one of the major components of smog.
 NO2 causes a reddish brown plume.
 NO2 contributes to the formation of aldehydes and
ketones
 O2 +NO2 +uv light ---> NO + O3

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US sources of NOx
NOx characteristics

NO – Nitric oxide
• Colorless and odorless gas
• Insoluble in water
• Toxic

NO2 – Nitrogen dioxide

• Usually a dimer compound (N2O4) at low 0C
• Distinct reddish-brown color
• Moderately soluble in aqueous liquids
• Toxic
• Contributes to brown haze that occurs with smog
 NOx Formation

• Formed at elevated temperatures during combustion of fuel in the

presence of air.

• Approximately 90 to 95% of the nitrogen oxides generated in

combustion processes are in the form of nitric oxide (NO).

• Once in the atmosphere, the NO reacts in a variety of

photochemical and thermal reactions to form NO2.
NOx formation

Most of the NOx formed during the combustion process is the result of
three oxidation mechanisms:
(1) Thermal NOx reaction of nitrogen and oxygen in the combustion air
(2) Prompt NOx the relatively fast reactions between the hydrocarbon
radicals (CHx eg. CH, CH2,CH3 with atmospheric nitrogen and oxygen
to form HCN then NO)
(3) Fuel NOx reaction of nitrogen that is chemically bound in the coal. As nitrogen
containing fuel burns (devolatilization stage), hydrogen cyanide, (HCN),
ammonia (NH3), N,CN, NH radicals are released as intermediate radicals which
further react with O, OH, H to form NO in post-flame zone

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Thermal NOx generally represents about 25% of the
total and fuel NOx about 75%.

“Also, minor amounts of NOx are formed through

complex interaction of molecular nitrogen with
hydrocarbons in an early phase of the flame front..…”

The quantity of NOx formed depends primarily on the

"three t’s:" temperature, time, and turbulence.
These, along with the nitrogen content of the coal and
the quantity of excess air used for combustion,
determine NOx levels in the flue gas.

Combustion modifications delay the mixing of fuel and

air, thereby reducing temperature and initial turbulence,
which minimize NOx formation.

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 NOx CONTROL TECHNOLOGIES

See also:
http://www.netl.doe.gov/technologies/coalpower/ewr/nox/control.html
 Control Techniques

1. Modify combustion to suppress NOx formation

• Low (Less) excess air operation

• Off-stoichiometric combustion
• Flue gas recirculation
• Natural gas reburning

2. Reduce NOx to molecular nitrogen through controls (also

known as flue gas treatment)

• Selective Non-Catalytic Reduction (SNCR)

• Selective Catalytic Reduction (SCR)
• Dry Sorption
STRATEGIES FOR COMBUSTION MODIFICATION

 Reduce peak temperatures

of the flame zone
 Reduce gas residence time
in the flame zone
 Combustion Modifications
Low (Less) excess air operation LEA
Boilers may be operated at higher than necessary excess air conditions for the
following reasons:

• The presence of extra air supports complete combustion at all normal firing
rates and conditions, even when air/fuel mixing is relatively poor thus
minimizing the creation of carbon monoxide, soot and other unburned
hydrocarbons.

• Higher excess air levels provide an operational safety margin that prevents
inadvertent operation at fuel-rich conditions reducing the formation of
combustible vapor mixtures and the possibility of a firebox explosion

49
 Combustion Modifications
Low (Less) excess air operation LEA: Involves a reduction in
the total quantity of air used in the combustion process. By using less
oxygen, the amount of NOx produced is not as great. (due to lower flame
temperature at high excess air levels and lower oxygen at low excess air
levels)
 Combustion Modifications

Off-stoichiometric (staged) combustion: involves mixing of fuel and air

in a way to reduce peak gas temperatures and peak oxygen
concentrations. Staged combustion techniques can reduce NOx
emissions by 20–50%.

❑ Low NOx burners: Keeps temperatures down and dissipates heat

quickly

❑ Overfire air (OFA): Keeps mixture fuel rich and completes

combustion process using air injection nozzles

❑ Burners out of service (BOOS): Operates alternate burners in

combustion zone as fuel rich, air rich, and air only
LOW NOx BURNERS (LNB)

A LNB provides a stable flame that has several different zones.

The division of combustion air reduces the oxygen concentration in the primary burner
combustion zone, lowering the amount of NOx formed and increasing the amount of
NOx reducing agents. Secondary and tertiary air complete the combustion downstream of
the primary zone, lowering the peak temperature and reducing thermal NOx formation.
OVER FIRE AIR (OFA)
The stage combustion is achieved by firing all the burners fuel-rich in the primary
combustion zone and admitting the remaining air over the top of the flame zone

When primary
combustion uses a
fuel-rich mixture,
use of OFA
completes the
combustion.
Because the
mixture is always
off-stoichiometric
when combustion
is occurring, the
temperature
is held down.
BURNERS OUT OF SERVICE (BOOS)
Multiple-burner equipment can have part of an array of burners with some “burners out of
service” (not feeding fuel, but supplying air or flue gas). This allows the burners around them to
supply fuel and air to air or flue gas flowing from the BOOS. The result is combustion by stages
with temperature always lower than when all burners are in service. Thus, thermal NOx is
lower. The degree to which NOx generation is reduced depends upon the spatial relationship of
the BOOS to the other burners
Combustion Modifications
Flue gas recirculation:
• Involves the return of cooled combustion gases
to the burner area of the boiler.
• Recirculation of cooled flue gas reduces
temperature by diluting the oxygen content of
combustion air and by causing heat to be
diluted in a greater mass of flue gas.
• Heat in the flue gas can be recovered by a heat
exchanger.
• Reduced temperatures produce less NOx.
• The process requires a recirculation fan and
duct system.
 Combustion Modifications
Fuel reburning (fuel staging): Involves the operation
of the main burners in a boiler at very low excess air (fuel rich
conditions). A series of overfire air ports are used in this upper
region to provide all of the air needed for complete combustion.
 Add-On Controls (Flue Gas
Treatment )

Selective non-catalytic reduction systems (SNCR)

Involves the injection of ammonia (NH3) or urea into the hot gas zone
where reactions leading to reduction of nitrogen oxides can occur. The
reactions are completed within the boiler, and no waste products are
generated. There is a risk of ammonia (NH3) being emitted into the
atmosphere if temperatures are too low, however. SNCR systems are
capable of reducing nitrogen oxides from 20 to 60%.
 Add-On Controls (Flue Gas
Treatment )
Selective Noncatalytic Reduction (SNCR) Reactions:

4 NH 3 + 4 NO + O2 → 4 N 2 + 6 H 2O

4 NH 3 + 5O2 → 4 NO + 6 H 2O
~ 1000 oC
In SNCR ammonia or urea is injected within a boiler or in ducts in a region where
temperature is between 900C and 1100C. This technology is based on temperature
ionizing the ammonia or urea instead of using a catalyst.
The temperature “window“ –is important because outside of it either more
ammonia “slips” through or more NOx is generated than is being chemically
reduced. The temperature “window” is different for urea and ammonia.
 Add-on Controls (Flue gas
treatment )
Selective catalytic reduction (SCR)
Involves using beds containing ammonia or urea to
reduce nitrogen oxides to molecular nitrogen and water.
Two or three catalysts (usually titanium and vanadium)
are arranged in honeycomb shapes in the beds so air
can flow through. NOx reduction efficiencies ranging
from 75 to 90% are possible when the amount of
catalyst is sufficient, the catalyst is in good condition,
the ammonia reagent flow is sufficient, and the
ammonia is adequately distributed across the gas
stream.
 Add-On Controls (Flue Gas
Treatment )

Selective Catalytic Reduction (SCR) Reactions

4 NO + 4 NH 3 + O2 ⎯TiO
⎯2⎯ ⎯⎯⎯⎯⎯ ⎯→ 4 N 2 + 6 H 2O
or V2 O 5 supported catalyst

2 NO2 + 4 NH 3 + O2 ⎯TiO
⎯2⎯ ⎯⎯⎯⎯⎯ ⎯→ 3N 2 + 6 H 2O
or V2 O 5 supported catalyst

Temperature ~ 300 - 400 oC

The ammonia (NH3) is injected into the hot flue gas through an injection grid,
the flue gas with the ammonia passes across the catalyst surface, and the
NOx reactions occur within the micropores of the catalyst. Nitrogen oxides
are present in flue gas in the form of both NO and NO2 with NO being the
greater; however, NO2 is preferentially reduced in this process.
Add-On Controls (Flue Gas Treatment )
Emerging Technologies:

A variety of advanced post-combustion NOx control

systems are at various stages of development and
demonstration. Many of these are combined NOx and
SO2 control systems. While the SNCR and SCR
systems discussed earlier basically feature dry
reduction of NOx by ammonia or urea, advanced
systems under development offer a variety of options,
for example wet (aqueous) or dry absorption by solids,
absorption plus oxidation by a liquid, and absorption
plus reduction by a liquid.

63
 Add-On Controls (Flue Gas Treatment )

Dry Sorption

 Shell Flue Gas Treating System (~ 400 oC)

 Alkali Metal and Alkali Earth Metal based sorbents

CuO + 0.5O2 + SO2 → CuSO4

4 NO + 4 NH 3 + O2 ⎯⎯ ⎯ ⎯ ⎯ ⎯ ⎯→ 4 N 2 + 6 H 2O
CuO or CuSO 4 as catalysts

CuSO4 + 2 H 2 → Cu + SO2 + 2 H 2O
Cu + 0.5O2 → CuO
 Insight question

Would wet scrubbers be a good control

technique for NOx emissions?
 Answer

Wet scrubbers would not be a good control

technique for NOx emissions.
Clean Coal Technologies

It is actually a vague term that does not describe any one process (eg it can include
removal of SOx/NOx or capture and storage of CO2)
Clean coal technologies are being developed to remove or reduce pollutant
emissions to the atmosphere.

They seek to reduce the environmental effects by using multiple technologies to

clean coal and contain its emissions.

They constitute several generations of technological advances that have led to more
efficient combustion of coal with reduced emissions.

According to statistics, power plants being built today emit 90 percent less
pollutants than the plants they replace from the 1970s while use of coal has tripled.

67
 “CLEAN” COAL TECHNOLOGIES

Examples of several different technologies that are deployed today and continue
to be improved upon include:

 Coal washing
 Wet scrubbers
 Low NOx burners
 Electrostatic precipitators
 Advanced pulverised fuel (PF) combustion (e.g.super critical boilers)
 Carbon Capture and Storage (CCS)
 Oxyfuel combustion
 Gasification and Integrated gasification combined cycle (IGCC)
 Fluidized bed combustion
 Fuel Cells and hydrogen plants
 Magnetohydrodynamic (the study of the magnetic properties and
behaviour of electrically conducting fluids.)
CARBON DIOXIDE CAPTURE AND
STORAGE (CCS)

69
WHAT IS IT?

 CCS is a method used to capture CO2 that is produced via the combustion of
fossil fuels and then store it away from the atmosphere for a long time for the
mitigation of global warming.
 Certain governments are setting mandatory caps on CO2 emissions, causing
companies to develop and test methods to mitigate their carbon footprint.
 One possible way to accomplish this is by Carbon dioxide Capture and Storage.
 The focus of CCS is on power generation and industry sectors, mainly because
they emit such a large volume of carbon dioxide that the capture and storage
there will be the most beneficial.

70
CARBON SEQUESTRATION: WHAT IT IS

 Stores CO2 removed from the atmosphere or captured from emissions and
stores it in another form somewhere else (a ‘carbon sink’)
 Occurs naturally: oceans and plants are already absorbing much of what
we emit
 We can speed the process along or deposit CO2 in sinks that it wouldn’t
have entered before
 Possible sinks: plants and soils, carbonate minerals, geologic formations,
ocean

71
WHERE IS THE CO2 COMING FROM?

Industry and power sectors account for an overwhelming % of the

global CO2 emissions.
Carbon dioxide emissions are projected to increase until at least year
2050.
Coal is the major energy source for industrial processes and emits a
lot of CO2.
A coal fire power plant is an ideal spot for CCS because of the large
amount of CO2 it emits and the fact it is stationary.

72
HOW IS THE CO2 CAPTURED

The most researched/developed ways to capture CO2 are by pre-

combustion capture, post-combustion capture, and oxy-fuel combustion
capture.

73
74
POST-COMBUSTION CAPTURE SYSTEMS
 This refers to the capture of CO2 from exhaust gases of combustion
processes.
The flue gas from the combustion is cooled and then fed into an
absorber where it comes into contact with the solvent (mono ethanol
amine -MEA).
The solvent-- typically an amine solution-- binds with the CO2.
The carbon dioxide/amine solvent solution passes through a heat
exchanger into a hot stripper.
The heat drives off relatively pure CO2 which is ready for
compression and storage
POST-COMBUSTION CAPTURE SYSTEMS

Source: http://www.claverton-energy.com/download/137/

76
 ABSORPTION / STRIPPING

Clean gas CO2

Flue gas

ABS STRP
40°C H 120°C
X

ENERGY

Recirculating
(amine) solvent 77
ABSORPTION / STRIPPING
PROCESS DETAILS
Absorption of CO2 by MEA at 40°C
MEA recovery by desorption at 120°C
Reboiler provides heat to desorber in the form of steam from the
boiler, reducing plant output and efficiency
Optimize loading, operating temperature, minimize solvent losses

78
CHALLENGES
POST-COMBUSTION CAPTURE SYSTEMS
Percentage of carbon dioxide removed in this process is between
80% and 95%, making it very efficient.
High recovery rate comes from tall absorption columns and expensive
amine solvents, making it a pricy process.
Contaminants in the combusted flue gas such as NOx and SOx take
up absorption capacity, form solids in the solution, and create
unwanted waste.
Corrosion of equipment by the solvent
Degradation of the solvent
Energy use

79
CARBON SEQUESTRATION
Ways that carbon can be stored (sequestered):
In plants and soil “terrestrial sequestration” (“carbon sinks”)
Underground “geological sequestration” -These forms include
gaseous storage in various deep geological formations
(including saline formations, exhausted gas fields unmineable
coal seams)
Deep in ocean “ocean sequestration”-liquid storage in the
ocean
As a solid material (still in development) reaction of CO2
with metal oxides to produce stable carbonates

80
TERRESTRIAL CARBON SEQUESTRATION

81
 TERRESTRIAL CARBON SEQUESTRATION
The process through which CO2 from the atmosphere is absorbed naturally
through photosynthesis & stored as carbon in biomass & soils.
When trees are cut down and burned or allowed to rot, their stored carbon
is released into the air as carbon dioxide.
Tropical deforestation is responsible for about 15% of world’s annual CO2
emissions, though offset by uptake of atmospheric CO2 by forests and
agriculture
Ways to reduce greenhouse gases:
 avoiding emissions by maintaining existing carbon storage in trees and soils
 increasing carbon storage by tree planting or conversion from conventional to conservation tillage
practices on agricultural lands

82
TERRESTRIAL CARBON SEQUESTRATION (CONTINUED)

Carbon seq. rates differ based on the species of tree, type of soil,
regional climate, topography & management practice
Carbon accumulation eventually reaches saturation point where
additional sequestration is no longer possible (eg. when trees reach
maturity)
After saturation, the trees or agricultural practices still need to be
sustained to maintain the accumulated carbon and prevent
subsequent losses of carbon back to the atmosphere

83
GEOLOGICAL SEQUESTRATION

Midwest Geological Sequestration

Consortium (Illinois) 84
GEOLOGICAL SEQUESTRATION

Also known as geo-storage, this method involves injecting carbon

dioxide directly into underground geological formations. Oil fields, gas
fields, saline formations, unminable coal seams, and saline-filled basalt
formations have been suggested as storage sites.
Here, various physical (e.g., highly impermeable caprock) and
geochemical trapping mechanisms would prevent the CO2 from
escaping to the surface. CO2 is sometimes injected into declining oil
fields to increase oil recovery (enhanced oil recovery). This option is
attractive because the storage costs are offset by the sale of
additional oil that is recovered. Disadvantages of old oil fields are
their geographic distribution and their limited capacity.
 GEOLOGICAL SEQUESTRATION

Storing of CO2 underground in

rock formations able to retain
large amounts of CO2 over a long
time period
 Held in small pore spaces (have
held oil and nat. gas for millions of
years)

Layers shown: Coal, brine aquifer, gas bearing

sandstone, gas bearing shale

86
After capture, compress (>70 atms → liquid) transmit
and store (>700m):

87
88
……STORAGE

 Unminable coal seams can be used to store CO2 because CO2 adsorbs to the
surface of coal. However, the technical feasibility depends on the permeability of
the coal bed. In the process of adsorption the coal releases previously absorbed
methane, and the methane can be recovered (Enhanced Coal Bed Methane
recovery). The sale of the methane can be used to offset the cost of the CO2
storage.

89
….. STORAGE
 Saline formations contain highly mineralized brines, and have so far been
considered of no benefit to humans. Saline aquifers have been used for storage
of chemical waste in a few cases.
 The main advantage of saline aquifers is their large potential storage volume and
their common occurrence. This will reduce the distances over which CO2 has to
be transported.
 The major disadvantage of saline aquifers is that relatively little is known about
them, compared to oil fields. To keep the cost of storage acceptable the
geophysical exploration may be limited, resulting in larger uncertainty about the
aquifer structure.
 Unlike storage in oil fields or coal beds no side product will offset the storage
cost. Leakage of CO2 back into the atmosphere may be a problem in saline
aquifer storage. However, current research shows that several trapping
mechanisms immobilize the CO2 underground, reducing the risk of leakage.

90
….. STORAGE

For well-selected, designed and managed geological storage sites, IPCC

estimates that CO2 could be trapped for millions of years, and the
sites are likely to retain over 99% of the injected CO2 over 1,000
years.

91
OCEAN SEQUESTRATION

92
….. STORAGE

Two main concepts exist. The 'dissolution' type injects CO2 by ship or
pipeline into the water column at depths of 1000 m or more, and
the CO2 subsequently dissolves. The 'lake' type deposits CO2 directly
onto the sea floor at depths greater than 3000 m, where CO2 is
denser than water and is expected to form a 'lake' that would delay
dissolution of CO2 into the environment.

93
DISSOLUTION AND LAKE TYPE STORAGES

94
OCEAN SEQUESTRATION

 Direct injection into the deep ocean involves the capture, separation, transport,
and injection of CO2 from land or tankers
 1/3 of CO2 emitted a year already enters the ocean
 Ocean has 50 times more carbon than the atmosphere
 Eventually equilibrium between the ocean and the atmosphere will be reached
with or without human intervention and 80% of the carbon is expected to
remain in the ocean. The same equilibrium will be reached whether the carbon is
injected into the atmosphere or the ocean.

95
'A FAMILY OF SOLUTIONS'
 Critics of carbon sequestration argue that the technology will divert attention
from research on long-term clean energy options, such as renewable power.
Worse, they fear it will prolong fossil fuel use, if fossil fuels from some stationary
sources can be used more cleanly.
 Continual emphasis on the need to adopt other technologies in addition to
carbon sequestration needed
 Geological sequestration be one of a family of solutions for addressing the
greenhouse gas issue.
 Energy efficiency and renewable energy are already feasible today and also can
define the long-term energy picture.
 Carbon dioxide sequestration is only a bridge technology.

96
Oxy-fuel combustion capture.

97
BACKGROUND
 In most conventional combustion processes, air is used as the source of oxygen
 Nitrogen is not necessary for combustion and causes problems by reacting with
oxygen at combustion temperature
 A high concentration of nitrogen in the flue gas can make CO2 capture
unattractive
 The use of pure oxygen in the combustion process instead of air ‘eliminates’ the
presence of nitrogen in the flue gas
 With the current push for CO2 sequestration to ease global warming, it is
imperative to develop cost-effective processes that enable CO2 capture

98
BACKGROUND
 Combustion with pure oxygen results in high temperatures and lower fuel
consumption since the N2 component of air is not heated
 Historically the primary use has been in cutting and welding metals
 In 1982 oxy-fuel combustion was proposed to produce CO2 for Enhanced Oil
Recovery (before climate change became a global concern)
 Recycling of hot flue gas has also been suggested to reduce furnace size and
NOx emissions for metal heating furnaces
 Lately, interest has been paid to oxy-fuel combustion as a means to reduce
pollutant emission control cost and create a CO2 gas stream that can easily be
compressed and sequestered

99
The oxygen required is separated from air prior to combustion (in the
air separation unit ASU) and the fuel is combusted in oxygen diluted
with recycled flue-gas rather than by air.
This oxygen-rich, nitrogen-free atmosphere results in final flue-gases
consisting mainly of CO2 and H2O (water), so producing a more
concentrated CO2 stream for easier purification.

100
The CO2-rich gas from oxy-fuel processes contains various impurities.
The impurities are removed through various air quality control systems
The CO2/H20 mixture is then cooled to condense the water vapor and
remove the CO2.
Flue gas cleaning used for CO2 capture from oxy-fuel combustion must
handle high concentrations of impurities, compared with air-firing cases,
although the total amount of impurities is not larger

101
PROCESS VARIATIONS

 Is the plant to be retrofitted or purpose-built?

 What is the optimum O2 proportion in the oxidant gas?
 What is the desired proportion of CO2 in the flue gas?
 To what extent will the flue gas be cleaned of NOx, SOx, and Hg?
 Will CO2 be fully/partially sequestered?

102
OXY-FUEL COMBUSTION FLOW SHEET

 Oxygen at greater than 95% purity and recycled flue gas are used for fuel
combustion, producing a gas that is mainly CO2 and water
 Recycled flue gas is also used to control the flame temperature and replace the
volume of the missing nitrogen needed to carry heat through the boiler (gas
volume reconstitution for proper convective heat transfer to all boiler areas) and
also to carry the fuel into the boiler

103
 DIFFERENCES FROM REPLACING N2
 To have a similar adiabatic flame temperature, oxygen must have a concentration of
about 30% (not 21% since the adiabatic temperature is suppressed-specific heat of CO2
is higher than N2)
 For an oxygen concentration of 30%, ~60% of the flue gases are recycled
 Because of high concentrations of carbon dioxide and water, the furnace gas has a
higher emissivity
 Flue gas volume after recycling is 80% smaller than conventional combustion (less heat
lost in the flue gas), and its density is increased (molecular weight of CO2 is 44
compared to 28 for N2)
 Size of flue gas treatment equipment can be reduced by ~75%
 3-5% excess of oxygen is required (20% excess air in coal air-firing to ensure complete
combustion)

104
DIFFERENCES
 Nox production is greatly reduced
 Species present in flue gases (impurities) are in higher concentrations after oxy-fuel combustion
making separation easier
 Most of the flue gases are condensable, making compression separation possible
 Heat of condensation can be captured and reused rather than lost with the flue gas
 Power must be provided for flue gas compression and air separation (about 15% of power
produced)
 Oxy-fuel combustion with CO2 sequestration involves oxygen separation, flue gas recycling, CO2
compression, and transport and storage
 A number of modifications to conventional pf coal technology must occur
 Running more processes leads to a reduction in availability
 The use of carbon sequestration increases capital and operating costs

105
 OXY-FIRED PF POWER PLANT

 O2 is separated from air and mixed with the recycle stream from the boiler
 Fuel is fired into this mixed stream, and a portion of the flue gases is recycled
 Water vapor in the flue gas is condensed to form a stream of supercritical CO2 of high purity,
70% by mass CO2 as compared to 17% with air-fired combustion
 CO2 can then be cooled and compressed for transportation and storage

106
ADVANTAGES
 Low NOx emission, thanks both to the use of oxygen for combustion which
eliminates nitrogen from air and to the NOx re-burning mechanism with flue gas
recycling.
 More interestingly, recent research has shown that integrated emissions control of
SOx, NOx, and mercury (Hg) may be possible as part of the oxy-fuel flue gas
CO2 capture process.
 Oxy-fuel combustion is also being mentioned as an excellent option for
retrofitting the existing fleet of modern pulverized coal-fired power plants for
CO2 reduction.

107
ADVANTAGES/DISADVANTAGES

 Industry is familiar with this type of  Reduced efficiency

technology  Not demonstrated at commercial-
 Viable for near-zero emissions scale – might be unforeseen
 Can be retrofitted to existing plant technical difficulties
 Can be implemented in new plant or  SOx removal might be required
put into new plant design for later  Oxygen separation plant needed
retrofit
 Low NOx emissions

108
DESIGN AND OPERATIONAL ISSUES

 Concentration of tri-atomic flue gas molecules is much higher in oxy-fuel

combustion - changes the emissivity
 CO2 and H2O also have higher thermal capacities than nitrogen, which leads to
a higher heat transfer in the convective section of the boiler
 Several studies have shown problems with flame stability and ignition
 Effects of flue gas recycling on trace elements emissions and fly ash size
distribution have not been experimentally determined

109
Pre-combustion capture.

110
PRE-COMBUSTION CAPTURE
Pre-combustion clean coal technologies mainly refer to coal cleaning
or beneficiation before combustion. The purpose is to remove
impurities and improve coal’s heat content, which affects generating
efficiency.
The fossil fuel is oxidized to produce a “syngas” composed of CO and
H2.
The CO is then shifted in a converter, producing CO2 and more H2.
 CO2 is then separated from the hydrogen before combustion takes
place.
Most common form of separation is by solvent absorption process
(amines).

111
PRODUCING THE SYNGAS - GASIFICATION

Coal is reacted with steam in the gasifier to produce the gaseous fuel,
mainly H2 and CO.
The exothermic reactions between coal and oxygen to produce CO and CO2
provide enough energy to drive the reaction between steam and coal.
 The reaction of coal, oxygen, steam result in a mixture of CO,CO2 and H2
being produced
The ratio of H2 to CO can be increased by adding steam to this mixture,
to take advantage of a reaction known as the shift reaction

112
 Reactions are complex, given by Sha as:

Coal → Char(C) + volatile matter(VM) Pyrolysis (1)

VM + H 2 → CH 4 -ΔH Hydrocracking (2)

VM + H 2O → CO + H 2 +ΔH Gasification (3)

C + 2H 2 → CH 4 -ΔH Hydro-gasification (4)

C + H 2O → CO + H 2 +ΔH Gasification (5)

Gasification (6)
C + CO2 → 2CO +ΔH
Shift conversion (7)
CO + H 2O → CO2 + H 2 +ΔH
C + O2 → CO 2 -ΔH Combustion (8)
The properties of the product species depends on the coal type, gasifying agents
and process operation conditions such as temperature, heating rate, pressure,
time and particle size 113
GASIFICATION
• The coal is fed into a high-temperature pressurized container (Gasifier)
along with steam and a limited amount of oxygen to produce a gas.
• Gasifiers convert carbonaceous feedstock into gaseous products at high
temperature and elevated pressure in the presence of oxygen and
steam.
• Partial oxidation of the feedstock provides the heat.
• At operating conditions, chemical reactions occur that produce synthesis
gas or "syngas," a mixture of predominantly CO and H2.
• The gas is cooled and undesirable components, such as carbon dioxide
and sulfur are removed.

114
115
INTEGRATED GASIFICATION COMBINED CYCLE (IGCC)

Integrated Gasification Combined Cycle (IGCC) is emerging as one of

the best available technologies to utilize fossil fuels (coal or oil).
It can meet emission limits not achievable by other conventional or
advanced competing technologies.
It also drastically cuts SO2 emissions.
It is a combination of: coal gasification (to create clean burning gas
(syngas) AND ‘combined cycle’ –an efficient method of producing
electricity

116
HOW DOES IGCC WORK?

The gasification portion produces a clean coal gas (syngas)

The syngas goes through a gas clean up process where pollutants
such as NOx, SOx, Hg are removed.
The gas clean up may include carbon capture for CO2 removal
The syngas (mainly H2) is used to power a gas turbine that spins a
generator

117
 CO2 PRE-COMBUSTION CAPTURE FOR IGCC

Hydrogen to
gas turbine

Coal plus Gasification and Acid gas CO2 to

Shift
oxygen solids removal removal system storage

Steam Hydrogen sulphide

to sulphur recovery

118
 INTEGRATED GASIFICATION COMBINED CYCLE (IGCC)

Gasification is essentially partial oxidation under pressure

119
HOW DOES IGCC WORK? CNTD
Heat is recovered from the hot gases at the exit of the gas turbine
and used to produce steam in a HRSG (Heat Recovery Steam
Generator)
The temp of the gas entering the HRSG is usually around 500°C
while the exit temp to the stack will be around 200°C
The steam is then used to drive a steam turbine to generate
electricity
◼ IGCC plants have obtained 60% efficiency (compared to about 41%
from conventional coal plants).

120
IGCC + CARBON CAPTURE AND STORAGE

121
 IGCC + CCS + POLY GENERATION
(2n+1)H2+nCO→CnH (2n+2) +nH20

122
One must also remember that gasified coal is not only
very clean, but is a far more versatile fuel than regular coal.
123
Integrated Gasification Combined Cycle
(IGCC):

Source: US Dept. of Energy/National Energy

Technology Labs (NETL) 124
INTEGRATION BETWEEN AIR SEPARATION AND GAS TURBINE
 An important area of IGCC technology improvement is the optimization of
the design and integration among the various components.
 Integration means recovery of the waste energy available, improvement of
the efficiency and, where possible, reduction of the investment cost.
 There are potential benefits of integrating two major components of the
IGCC: the gas turbine and the air separation plant.
 There are several possible degrees of integration between the air separation
plant and the gas turbine.
 In the case of total integration, 100% of the air required by the air
separation is supplied by bleeding some of the air from the discharge of the
gas turbine compressor as required by the air separation plant (high
pressure type).
 Oxygen is recompressed and used in gasification, while nitrogen is
recompressed and reinjected in the syngas to replenish the mass deficit
caused by the air bleeding.

125
DIFFERENTIATORS THAT FAVOR IGCC OVER OTHER TECHNOLOGIES
➢ Pre-combustion clean-up of fuel prior to power generation
➢ Accept inferior and varying quality of coals
Environmental Technology => Greatest potential for future
✓ proven lowest NOx, SOx, particulate matter and lower hazardous air
pollutants,
✓ proven mercury and carbon dioxide removal,
✓ lower particulates emissions
✓ proven polygeneration flexibility
✓ power, hydrogen, steam, chemicals, zero-sulfur diesel
➢ Practical opportunity to retrofit carbon capture equipment.

126
 MERCURY EMISSIONS
 IGCC can effectively remove mercury from the
environment.
 Carbon beds have demonstrated 99.9% mercury
removal from syngas (post “gas-clean-up”).
 Carbon beds are less expensive and produce
vastly smaller volumes of solid waste than
activated carbon injection at PC plant.
 Many toxic industrial compounds are safely
disposed of through the use of high-temperature
combustion. However mercury is not "destroyed"
when coal containing mercury impurities
is burned. This is because, when the mercury in
the carbon ( coal Hg) is burned it turns into a
gas which is released into the atmosphere.
 The mercury is converted into a far more toxic
Mercury removal tanks using a single packed bed of sulfur
form when it enters the food chain. impregnanted carbon. Photo credit: Eastman Chemical

127
 BARRIERS TO IGCC COMMERCIAL DEPLOYMENT
• Currently higher capital and operating costs
• Standard designs and guarantee packages not yet fully developed
• Reluctance by customers to be early ‘adopters’ and assume technology application
risk
• Traditional PC can meet current environmental standards
• IGCC financing costs higher than PC – perceived risk profile
• Lack of familiarity with IGCC in the power industry (it is a ‘chemical plant’ and not
a ‘combustion boiler’)

128
BARRIERS TO IGCC COMMERCIAL DEPLOYMENT

• Few units in operation

• Environmental benefits threaten existing coal power fleet
• Lingering availability/reliability concerns
• Questions about feasibility and cost using low-rank coals,
particularly lignite
• IGCC is an emerging industry, vs. established boiler industry

129
BUT…?

Increased efficiency will help, not hurt, the coal industry

IGCC is much more expensive, but the benefits will eventually
outweigh costs.
Regulations are becoming more and more stringent, making it
harder for PC plants to comply
Real interest in coal gasification to SNG, zero sulfur diesel,
ammonia and other chemicals will in turn assist IGCC development

130
Fluidized Bed Combustion(FBC)
Fluidized beds burn fuel in an air-suspended mass (or bed) of particles.
By controlling bed temperature and using reagents such as limestone as
bed material, emissions of nitrogen oxides (NOx) and sulfur dioxide (SO2)
can be controlled.
The fluidizing process induces an upward flow of a gas through a stacked
height of solid particles. At high enough gas velocities, the gas/solids mass
exhibits liquid-like properties, thus the term fluidized bed.
Additional benefits of fluidized-bed combustion include wide fuel flexibility
and the ability to combust fuels such as biomass or waste fuels, which are
difficult to burn in conventional systems because of their low heating value,
low volatile matter, high moisture content or other challenging
characteristics.

131
FLUIDIZED BED COMBUSTION

Key Reaction:
CaO (lime) + 1/2O2 +SO2 = CaSO4 (calcium sulfate)

Limestone = CaCO3

FBC reduces NOx by lowering temperature of burning

Air distributor ducts and bubble caps

Circulating fluidized Bed Combustion

A further increase in air flow causes the particles to blow out of the bed and the
container. If the solids are caught, separated from the air, and returned to the bed,
they will circulate around a loop, defined as a circulating fluidized bed
 Circulating Fluidized Bed Combustion (CFBC) technology has selectively been applied
for firing high sulfur refinery residues, lignite, etc.
CFBC Technology is superior to PC Power Plant Technology:
 Lower NOx formation and
 The ability to capture SO2 with limestone injection in the furnace.

133
 Circulating fluidized Bed Combustion
 Good combustion efficiencies comparable to PC Power Plants.

 The heat transfer coefficient of the CFB furnace is nearly double that of PC which
makes the furnace compact.

 Fuel Flexibility: The CFB can handle a wide range of fuels such as inferior coal,
washery rejects, lignite, anthracite, petroleum coke and agricultural waste with lower
heating.

134
 Circulating Fluidised Bed Boiler
Steam to Super Heater

Cyclone

Back-Pass
Coal Feed
Furnace
Hopper ESP

External
Heat-Exchanger
Ash Cooler
HP Air

135
CFBC VS OTHER CLEAN COAL TECHNOLOGIES

ITEM CFBC PF+FGD/SCR IGCC

Cycle Eff. % 34.8 36.7 41-42

Relative Capital
1.0 1.03-1.19 1.15-1.42
Cost/kW

Relative O&M
1.0 1.49 0.8-0.98
Cost/kW

At present pulverized fuel firing with FGD are less costly than prevailing
IGCC technology. However, firing in CFB Boiler is still more economical
when using high sulfur lignite and low-grade coals and rejects.
Renovation & Modernization (R&M) and Life Extension (LE) of old
power plants is a cost-effective option as compared to adding up
green field plant capacities.
Growing environmental regulations would force many utilities to go
for revamping these polluting old power plants using environmentally
benign technology such as CFBC.
Sustainable Power Development calls for adoption of Clean Coal
Technologies like Supercritical cycles, IGCC and FBC technologies

137