Assoc. Prof. Ts. Dr.

Wan Nor Roslam

Wan Isahak
[email protected]
Department of Chemical and Process
Engineering, FKAB, UKM.

AIR POLLUTION
 Air Pollution

Data collected by NASA from year 1850 to year 2000 2

 Air Pollution
• Pollution
– Kinds of Pollution
– Sources
– Transport
• Effects of Air Pollution
• Air Pollution Control

3
 Source of Air Pollution

• Natural sources of air pollution

Some of the natural sources of air pollution are organic compounds from
vegetation, ground dust, salt spray from oceans, hydrogen sulfides from
natural sources, cosmic dust etc. During catastrophes large amount
of gases and ash from volcanic eruptions, gases and smoke from forest,
grass, and swamp fires blacken the skies and increase the background
pollution levels for years even at points distant from the original
source. Radon, fog and mist, and ozone are the most common natural air
pollutants.
• Man-made air pollution
Man-made air pollution sources can be divided into three different groups, as
(1) point sources, (2) area sources, and (3) line sources. Industries, power
plants, oil refineries etc. with their tall stacks are a major
source of air pollution and are considered to point sources. Residential
areas, apartments, office buildings, hospitals, and schools are also major
contributors of air pollution. These are area sources of air pollution.
Highways are considered to be line sources of air pollution. Some man-
made air pollution sources are motor vehicles, industrial facilities, power
plants, space heating, refuse disposal, and transportation services.

4
 Air Pollutants

Sources of pollution
All air contains natural contaminants such as : pollen, fungi spores, salt
spray,and smoke and dust particles from forest and volcanic eruptions.
Air contain also carbon monoxide from breakdown of methane (CH4),
hydrocarbons in the form of terpenes from pine trees; and hydrogen
sulfide (H2S) and methane from anaerobic decomposition of organic
matter.
The most anthropogenic five pollutants are listed in the following table:
National air pollution emission , by pollutants , 1940 to 1980.
Total Sulfur Nitrogen hydrocarbons Carbon
suspended dioxide oxide monoxide
particulates
1940 21.9 17.4 6.5 13.9 74.7
1970 17.6 27.9 18.5 27.1 110.9
1980 7.8 23.7 20.7 21.8 85.4
Unit: In million tones per year.
5
 Primary and Secondary Pollutants

• Air pollutants occur either as

gases or particulate matter
• Primary air pollutants: emitted directly into the
air
• Secondary pollutants: reactions between
primary pollutants and atmospheric
compounds

6
Sources of pollution

7
 Air Pollutant
Pollutant Source
Sulfur Dioxide Burning Coal & Oil
Nitrogen Oxide Burning fuel: transportation power station and other
burning
Carbon Monoxide Combustion process in low oxygen, burning wood
coal, oil
Carbon Dioxide Volcanic activity, hot spring, combustion process,
transportation, power plant
Volatile organic compound Evaporation from source, cleaning, furniture polish,
fabric softening, fuel stations, Automobiles, solvent,
vegetation, bacteria,
Particulate matter Fine particle from natural erosion, from human
activities, such as burning fuel
Ammonia Use as fertilizer, agriculture process, farm animal

Lead Naturally occurring, lead smelting, paint , plumbing

Persistent Organic Pollutant Industrial process, Incineration

Ozone Chemical reaction during sunlight 8
 Major Air Pollutants: Problems
• Sulfur dioxide - acid rain, health damage,
visibility reduction
• Nitrogen oxides - acid rain, eutrophication (stimulate
excessive plant growth) or excess water in the body),
growth of weedy species
• Carbon monoxide - inhibited respiration
• Lead and mercury - neurological damage
• Chlorofluorocarbons - ozone depletion
• Particulate matter - lung damage, cancer
• Volatile organic compounds – (isoprenes,
terpenes, methane, benzene,
chloroform, etc) oxidized to CO,
CO2 in the atmosphere; carcinogens?

9
 Source of Air Pollution In Malaysia
• natural sources of air pollution such as eruption of volcanoes, biological decay and lightning-
caused forest fire. Naturally, the Earth already has its own air pollution loading
• Industrial and development activities: Malaysia’s economic growth is mainly based on its
manufacturing (especially electronics), chemical and rubber industries. But higher production
rates also lead to higher emissions of organic and inorganic gases.
• the chemical industry releases emissions that contain many nitrogen and sulphur compounds
while refineries discharge sulphur dioxide and hydrocarbons. The metal working industry is
partially responsible for the emissions of sulphur dioxide and large amounts of toxic dust.
Human activities have resulted in harmful substances and polluting emissions being released
into the air.
• Motor vehicles: cars, trucks, and railways. Movement of people and goods requires energy
which relies mostly on the burning of fossil fuels, thus causing emissions and noise with
adverse local effects.
The air quality of the different transport modes depends on the kind of energy, engine
technology and the amount of energy consumed. Within the transport sector motorized road
traffic is the main emission source while public transport is environmentally friendlier than
passenger car
• Power Generation: Most of the energy is produced in conventional power plants burning fossil
fuels like natural gas, oil or coal. The effectiveness of these power plants is about 35 to 40 per
cent with the remaining chemical energy converted into heat.
At the moment, Malaysia produces 86% of its electricity in conventional power plants and 14%
in hydroelectric power plants. 10
11
12
 Air Pollution

Is the presence of undesirable material in air, in a quantities large

enough to produce harmful effects. The undesirable materials may
damage human health, vegetation, human property, or the global
environment as well as create aesthetic insults in the form of brow
or haze air or unpleasant smells. Many of these harmful materials
enter the atmosphere from sources currently beyond human control
such as volcanic eruption and pollution from natural source. This by
itself dose not pose severe enough to danger life and property.
Human activity are to be blame for pollution problems that problems
threaten to make portions of the earth’s atmosphere an inhospitable
environment.

There are five materials classified as a main pollutants:

Sulfur oxides, nitrogen oxides, carbon monoxide,
hydrocarbons, and particulate.
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 Air Pollutant
SULFUR COMPOUNDS
• Sulfur is relatively inert and harmless to human.
• Sulfur oxides are widely recognized as air pollutants.
Oxidation and reduction of sulfur is presented in the following
pattern :

H2S S SO2 SO3 H2SO4

Hydrogen Sulfur Sulfur dioxide Sulfur trioxide Sulfuric acid
Sulfide

• Exists as SO2, H2S and SO4 particles

• Also as a little of mercaptane (R–SH) and dimethyl sulfide,
(CH3)2S.
• SO2 is discharged by mainly human activity through combustion
• Emission rate of SO2 = 64.9x 106 t yr-1

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 Air Pollutant
Source of SULFUR COMPOUNDS
All fuels used by humans (coal, oil, natural gas, wood) are
contain some sulfur.
Wood has less than 0.1%; coals have 0.5% to 3%;
During burning , all sulfur will be oxidized to sulfur dioxide

S + O2 SO2

Source Emission rate %

( x106 t yr-1 )
Coal combustion 45.4 70
Oil combustion 5.5 8.4
Smelting and 13.6 21
oil refining
Transportation 0.4 0.6
Total 64.6
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 Sulfur Dioxide
• It is invisible and has a nasty, sharp smell. It reacts
easily with other substances to form harmful
compounds, such as sulfuric acid, sulfurous acid
and sulfate particles.
• About 99% of the sulfur dioxide in air comes from
human sources. The main source of sulfur dioxide
in the air is industrial activity that processes
materials that contain sulfur, eg the generation of
electricity from coal, oil or gas that contains sulfur.
Some mineral ores also contain sulfur, and sulfur
dioxide is released when they are processed. In
addition, industrial activities that burn fossil fuels
containing sulfur can be important sources of
sulfur dioxide.
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 Air Pollutant
Sulfur dioxides (SOx)
The oxides of sulfur (Sox) are the most widespread and the
most intensely studied of all anthropogenic air pollutants.
They are 6 different gaseous compounds:
Sulfur monoxide SO, sulfur dioxide (SO2), sulfur trioxide
(SO3), sulfur tetroxide (SO4), sulfur sesquioxide (S2O3) ,
and sulfur hepoxide ( S2O7) .
Example:
Sulfur dioxide : Is a colorless, nonflammable gas, with
suffocating odor.
3
• Taste threshold = 784 μg/m (0.3 ppm)
• Odor threshold = 1306 μg/m3 (0.5 ppm)
• Highly soluble in water (11.3 g/100ml at 20oC)
• It is estimated remains airborne an average of 2 to 4 days,
during which time it may transported as far as 1000 km
• Problem of SO2 is an international
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 Air Pollutant
Hydrogen Sulfide (H2S)
Hydrogen Sulfide (H2S) is a colorless gas that smells like
rotten eggs (from the sulfur). Often referred to as "sewer
gas," hydrogen sulfide is highly poisonous. Usually, the
poisoning caused by hydrogen sulfide is though inhalation
and has a toxicity similar to cyanide. It is found in
petroleum and natural gas and is sometimes present in
ground water. Natural gas can contain up to 28%
hydrogen sulfide gas and may be considered an air
pollutant when found near a natural gas production area or
refinery.
• H2S emitted by sulfate reduction in swamps, mud and
aerobic water pools by sulfate reduction bacteria
• Total production rate of sulfur by microorganisms is
106 x 106 t/yr-1 18
 Air Pollutant
Low Levels of H2S
The odor or hydrogen sulfide gas can be perceived at levels as
low as 10 ppb (parts per billion). At levels of 50-100 ppm (parts
per million), it may cause the human sense of smell to fail. Low
levels can cause eye irritation, dizziness, coughing, and
headache.
High levels of H2S
At high exposures (usually greater than 300 ppm), H2S has the
amazing effect of causing the nose to stop perceiving its smell
after a few inhalations, which may lead to the inhalation of a
toxic or fatal dose (which can occur at 600 ppm). At high levels,
hydrogen sulfide gas may paralyze the lungs, meaning that the
victim may then be unable to escape from the toxic gas without
assistance.
Deaths are not uncommon when people enter poorly ventilated
spaces such as deep wells, underground tanks or sewer
systems. Since H2S gas is heavier than air, its concentration is
highest near the bottom of enclosed spaces.
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 Air Pollutant
H 2S
Hydrogen sulfide produced from natural gas and
from petroleum refineries is converted to sulfur
element as a solid powder. About 25% of all
sulfur is obtained from natural gas and crude oil
by conversion of 1/3 of the H2S to SO2 and then
followed by the reaction between H2S and SO2:

2 H2S(g) + 3 O2 (g) 2 SO2 (g) + 2 H2O(g)

16 H2S(g) + 8 SO2 (g) 3 S8 (g) + 16 H2O(g)

• The reaction H2S → SO2 is not known

• Some claim reaction with ozone
H2S + O3 → SO2 + H2O
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 Air pollutant
Oxidation of H2S in the atmosphere
• Oxidation H2S in solution (cloud) is quite
slow
H2S + O → OH + HS
• Which is followed by the formation of SO2,
SO3 and acid sulfuric acid vapour.
H2S + OH → H2O + HS
HS + O2 → OH + SO

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 Air pollutant

Oxidation of SO2

• Photochemical oxidation of SO2

SO2 + h → SO2*
SO2 + 2O2 → SO3 + O3
SO3 + H 2O → H2SO4

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 Air pollutant

Oxidation of SO2

• NO2 could also influence the reaction by

producing free O atoms after being irradiated
by the sun and the O is used in the following
equation :

SO2 + O + M → SO3 + M

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 Air pollutant

Oxidation of SO2
Sulfur transformation scheme:
several hours several days/hours
O h
H2S + O2 → SO2 + O → SO3 + H2O
O3 O2
O3
Olefin 
XSO4  X + H2SO4
(Commonly NH3)

24
 Air pollutant
Effect of SO2 on humans
Concentration Exposure Effect
ppm time
0 –0.6 No detectable response
0.15 – 0.25 1 – 4 day Cardiorespiratory response
1.0 – 2.0 3 – 10 min Cardiorespiratory response
in healthy subject
1.0 – 5.0 Detectable responses,
tightness in chest
5.0 1h Choking and increased lung
resistance to air flow
10.0 1h Severe distress, some
noesebleeding
Grater than 20 Digestive tract affected, also
eye irritation
400 – 500 Dangerous for short period of
time 25
 Air pollutant
SO2 and NO2 Concentration at Petaling Jaya

26
 Air pollutant
SO2 and NO2 Concentration at Tanah Rata

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Air pollutant

28
Air pollutant

29
 Nitrogen Compounds in
atmosphere
The most important forms of reactive nitrogen in the air are nitrogen monoxide
(NO) and nitrogen dioxide (NO2)
Nitrogen oxides are formed in the atmosphere mainly from the breakdown of
nitrogen gas (N2).
A few bacteria have developed special mechanisms to do nitrogen oxidation
producing NO2.
Vehicle engines operate at high enough temperatures and nitrogen oxides are
emitted in the exhaust fumes. Catalytic converters fitted to cars decrease the
production of these harmful compounds. Nitrogen oxides can also be formed
when biomass is burnt and during lightning.
Nitrogen oxides can also be formed when biomass is burnt and during lightning.
Ammonia is emitted from both solid and liquid livestock waste and can also
induce nitrous oxide production in soils by deposition after its initial release.
Plumes of ammonia can often be detected arising from intensive livestock
rearing facilities, such as poultry and pig farms.

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 Nitrogen Oxides
The role of nitrogen oxides in some of the most important
processes in atmospheric chemistry.

31
 Names of nitrogen
compounds:
Formula Systematic Name Common Name

NO nitrogen monoxide nitric oxide

N 2O dinitrogen monoxide nitrous oxide

NO2 nitrogen dioxide nitrogen peroxide

N 2O5 dinitrogen pentoxide nitric anhydride

N 2O3 dinitrogen trioxide nitrous anhydride

HNO3 - nitric acid

NH3 - ammonia
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 Importance of nitrogen oxides

Nitrogen oxides are very important in the formation and loss of tropospheric ozone. They are
involved in catalytic cycles and continuously react and reform. Nitrogen dioxide (NO2) is
broken down by sunlight to form nitrogen monoxide (NO). This NO then re-reacts to form
more NO2. Ozone and unstable oxygen compounds known as peroxy-radicals can also be
involved in this cycle.
BUT, the emission far too much of these nitrogen oxides during combustion processes,
particularly from vehicles.
Other important nitrogen gases in the atmosphere include:

Nitrous oxide (N2O) which is formed during microbiological degradation processes. It is an

important greenhouse gas but does not react in the troposphere. In the stratosphere it
destroys ozone.
Ammonia (NH3) is the most important basic gas in the atmosphere. It comes mainly from
agriculture, both from the storage of animal wastes and from fertilizer use. It reacts in the
atmosphere with acid species like nitric acid to form aerosol particles.
Livestock are the largest source of atmospheric ammonia emission, with areas of extensive
animal rearing giving 'hot spots' of ammonia production as described above. Fertilizer
application and agricultural chemical use are also significant sources of atmospheric
ammonia.
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 Primary Pollutant NO
Nitric oxide (NO) is an odourless, colourless gas which is produced during high
temperature burning of fuel in, for example, cars and other road vehicles, heaters and
cookers. Once it is mixed with air it quickly combines with oxygen, forming nitrogen
dioxide (NO2).
Most nitrogen dioxide in the atmosphere is formed from the oxidation of nitric oxide (NO)
in this way, although some is release directly from source. It is a reddish brown,
nonflammable, gas with a detectable smell. In significant concentrations it is highly
toxic, causing serious lung damage with a delayed effect. Other health effects of
exposure to nitrogen dioxide include shortness of breath and chest pains. Nitrogen
dioxide is a strong oxidizing agent that reacts in the air to form corrosive nitric acid, as
well as toxic organic nitrates. It also plays a major role in the atmospheric reactions
that produce ground-level ozone or smog.
Since nitrogen dioxide is a traffic-related pollutant, emissions are generally highest in
urban rather than rural areas.
Annual mean concentrations of nitrogen dioxide in urban areas are generally in the range
10-45 ppb, and lower in rural areas. Levels vary significantly throughout the day, with
peaks generally occurring twice daily as a consequence of rush hour traffic.
Concentrations can be as high as 200 ppb.

34
 Nitrogen oxides - at the centre of
atmospheric chemistry
Nitrogen oxides are at the centre of atmospheric chemistry. Most
chemical compounds which are oxidised and removed from
the air or are transformed into other chemical species come
into touch directly or indirectly with NO or NO2.

35
 Air pollutant
NITROGEN COMPOUNDS

• Exist as N2 , NH3 , N2O , NO , NO2 and as NH4+

and NO3-
• Species NO3 , N2O3 , N2O4 & N2O5 are unstable
and decompose to become NO and NO2.
N2O3 → NO + NO2
N2O5 → N2O3 + O2
N2O4 → 2 NO2

36
 Air pollutant
NITROGEN COMPOUNDS

• NO3 decomposes by photolysis

NO3 + h → NO2 + O
NO3 + h → NO + O2
NO3 + NO → 2 NO2
• N2 could be converted to very reactive
nitrogen through lightning and bacterial
action
37
 Air pollutant
NITROGEN COMPOUNDS

• N2O produced by de-nitrification bacteria

NO3- + 2H2 + H+ → ½ N2O + 2½H2O
• Removal of N2O
N2O + O → N2 + O2
N2O + O → 2NO
N2O + h → N2 + O
(  < 337 nm )

38
 Air pollutant
NITROGEN COMPOUNDS

• Ammonia (NH3) concentration in tropical areas 6 ppm

(4.6 mg m-3 STP)
• NH3 produced by decay of nitrogenous organic
material including urea
• Production rate ~ 100 x 106 tone yr-1
• 3 % is produced by man.
• Most of the NH3 is washed out by rain (wet
deposition) ~ 85 x 106 t yr-1

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 Air pollutant
NITROGEN COMPOUNDS

• NO is produced by combustion at high temperature

• NO, NO2 and hydrocarbon form photochemical smog
• By the effect of Sun light , then:

NO2 + h → NO + [O] ( = 380

nm)
[O] + O2 + M → O3 + M
O3 + NO → NO2 + O2

40
 Air pollutant
NITROGEN COMPOUNDS

• Equilibrium partial pressure of NO in incinerator

Partial Pressure of NO
(equilibrium)
(10-6 atm) PNO
104

103

102

10

10-1

10-2

10-3
Temperature
10-4
500 1000 1500 2000 2500 (K)

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 Air pollutant

NITROGEN COMPOUNDS

• The equilibrium ozone concentration is given by

 k1CNO CNO2
CO3 = 2

k2CNO CNO

The nitric oxide reaction also produces peroxinitrates

such as the very toxic peroxiacetylnitrate (PAN)

42
 Air pollutant
NITROGEN COMPOUNDS
Are the necessary ingredient compounds for the production
photochemical smog
Sunlight
Hydrocarbon + NOx Smog

There are many reactions producing NOx:

O3 + NO O2 + NO2
. .
HO2 + NO HO + NO2
. .
RO2 + NO RO + NO2
43
 Interactions between NO and
Production of HNO
NO 23

Early in the morning, commuter traffic releases NO and hydrocarbons. At the

same time, NO2 may decrease through because the sunlight can break it down
to NO and O. The O is then free to react with O2 to form O3. Shortly thereafter,
oxidized hydrocarbons react with NO to increase NO2 by midmorning. This
reaction causes NO to decrease and O3 to build up, producing a midday peak
in O3 and minimum in NO 44
 Removal of Nitrogen Oxides

• Nitrogen oxides are formed at two stages during combustion:

• The reaction of oxygen with nitrogen compounds in the fuel - this is termed Fuel NOX;
• The reaction of nitrogen with oxygen in the combustion air - this is termed Thermal NOX;
The relative contribution of fuel and thermal NOX depends on the type of fuel being used and the
operating conditions. A reduction in the atmospheric emissions of NOX produced by fossil
fuel combustion processes can be achieved at one of two stages:
❖ Preventing the production and release of nitrogen oxides during combustion;
❖ Removal of nitrogen oxides after combustion.

Unlike sulphur, it is not possible to reduce the nitrogen content of the fuel by physical cleaning
as it is combined within the organic matter of the fuel, and at present there are no
commercially available methods to reduce organic nitrogen. Fuel switching is also not
effective as this will only reduce the fuel NOX contribution and not the thermal NOX.

45
 Nitrogen Oxide Removal During Combustion
• Low NOX burners ensure that initial fuel combustion occurs within fuel rich conditions, that is with low oxygen concentrations, such that
any gaseous nitrogen produced is reduced to N2. Once initial combustion has taken place, further air is added to the combustion
chamber to ensure complete combustion of the fuel. This greatly reduces the opportunities for NOX production. Advanced low NOX
burners can reduce NOX concentration by up to 30%. Low NOX burners can be installed on either new or existing combustion plants, and
as such have been retrofitted to a number of power stations. They have also been incorporated into the design of many of the new gas-
fired power stations that are under construction or operational.

• Staged Combustion
• The combustion modifications required for staged combustion involves introducing air and fuel at different levels within the furnace. In
general a furnace contains a number of burners with similar fuel / air ratios. Staged combustion involves altering the fuel / air ratios of
individual burners whilst maintaining an overall ratio. For example, by allowing less air into the hottest part of the flame at the bottom of
the furnace, less thermal NOX is formed. Further air admitted to the coolest part of the flame at the top of the furnace allows complete
combustion of the fuel, whilst maintaining an overall ratio of fuel / air.

• Fluidised Bed Combustion (FBC)

• Fluidised bed combustion involves the combustion of coal in a bed of inert material, commonly sand, with air being blown up from
beneath the bed at high velocities. As velocity increases individual particles are forced upwards and become suspended in the air
stream. The bed in this state behaves like a liquid and can be described as fluidised. Tubes containing water are immersed in the bed to
absorb the generated heat (this water is converted to steam which is used to drive the steam turbine and thus produces electricity). The
fluidised movement within the combustion chamber results in a greater heat transfer efficiency to the water filled tubes, and therefore
operating temperatures are lower than in a conventional system. The low operational temperatures in the region of 750 - 950°C prevent
the formation of thermal NOX. Furthermore, the FBC system can achieve in the region of 80 - 90% SO2 removal. This system can also
burn coals of low or variable quality which are relatively cheap, with combustion and emission control carried out in a single unit.
46
Consequently, the flue gases do not have to be removed from the boiler for treatment. The FBC system can not easily be fitted to existing
plant and therefore will only be suitable for new generation plant.
 Nitrogen Oxide Removal After Combustion
• Emissions of NOX generated during the combustion process can be reduced, as with SO2, by treating the flue gases. There are a number of
systems available, and a brief description of the following systems will be given.

• Selective Catalytic Reduction (SCR)

• Selective Non-Catalytic Reduction (SNCR)

• Activated Carbon Process

Selective Catalytic Reduction (SCR)

• Within the SCR, ammonia is injected into the flue gas. The nitrogen oxides present in the flue gases react with the ammonia and are
converted to nitrogen and water. This reaction takes place in the presence of the catalyst, which is usually vanadium or tungsten oxide. The
catalysis allows the reaction to take place at low temperatures between 300 - 400°C. This process is suitable for fitting to existing plant and
new build applications, and can achieve a NOX reduction of up to 80 - 90%, with minimal waste production. The main disadvantages with
this system are the high costs involved; the cost of the catalyst can amount to between 40 - 60% of operating costs, and it is necessary to
replace the catalyst every 2 - 3 years. This system being used extensively in Japan.

Selective Non-Catalytic Reduction (SNCR)

• Denitrification of the flue gas is achieved by a reaction with ammonia as with the SCR, however, within this system there is no catalyst. As
no catalyst is used higher operational temperatures are required, between 930 - 1030°C to ensure that a reaction between the ammonia
and nitrogen oxides occurs. This process is also suitable for fitting to existing plant and new build applications, and can achieve a NOX
reduction of up to 50 - 60%, again with minimal waste production. This system is far cheaper than the SCR, but maintaining the correct
operational temperatures to ensure an adequate reduction of NOX is a drawback of this system. Consequently, the NOX reducing
capabilities of the SNCR are less than the SCR. This system is also being used extensively in Japan.

Activated Carbon Process

• The Activated Carbon (coke or char) Process reduces NO2 produced during combustion to NO via a reaction with carbon at about 80°C.
47
Ammonia can then be added to reduce the NO to N2 and water. NOX removal can be in the region of 40 - 60%.
Incinerator with two stage scraping system

48
 Carbon Dioxide

• Is CO2 considered as an air pollutant:

There are some reason given for not classifying CO2 as
a pollutant is based upon the fact that it is a natural
component of the atmosphere and needed by plants in
order to carry out photosynthesis. In fact that carbon
dioxide is a necessary component of the atmosphere.
But When one substance is present in excess and as a
result threatens the wellbeing of an ecosystem, it
becomes toxic, and could be considered to be a
pollutant, despite the fact that it is required in small
quantities.

49
 Carbon Cycle
• Some scientists have suggested that when the earth was new (about 4.5 billion years ago), CO2
may have made up as much as 80% of the earth's atmosphere. About 2 billion years ago, the
concentration of CO2 was likely 20 or 30%. Human life and even most life could not have
survived in such an atmosphere. With the evolution of photosynthesizing plants, the
concentration of CO2 dropped and the percentage of oxygen in the atmosphere increased.

• Photosynthesis:
CO2 +H2O + energy from sun O2 + sugar

• Both plants and animals undergo respiration in which

Sugar + O2 CO2 +H2O + energy

In addition, when plants and animals die, the dead organisms decay and give off CO2.
• the present amount of carbon dioxide taken out of the atmosphere every year by plants is almost
perfectly balanced by amount of carbon dioxide put back into the atmosphere by respiration and
decay. The carbon dioxide produced in this manner is part of a cycle in which new carbon does
not enter the system, but rather it keeps changing in form. They might be contained in sugars,
proteins, starches, cellulose and the list goes on and on. As living organisms undergo respiration
(the metabolism of sugars to produce energy for basic metabolic needs), or as organisms die and
decompose, the carbon compounds are broken down and add CO2 to the atmosphere. The CO2
is used by plants in the photosynthesis reaction, and the cycle keeps going.
50
 Unbalanced Cycle: Deforestation

• When trees die and decompose, CO2 is released. This is part of the normal
carbon cycle.
• When trees are cut down and used for fuel, the CO2 is also released. The rate at
which CO2 is released as a result of using trees for fuel is increased.
• When trees are used for building construction, furniture, etc, the carbon is not
released rapidly into the environment. One would suspect then that harvesting
trees for this purpose would result in less CO2 release into the atmosphere for
any given period. That might be correct, except that the tropical forests are
being depleted, and with a reduction in vegetation, there is a reduction in
photosynthesis. As a result, the carbon cycle is interrupted and the CO2 is not
being converted into sugars and oxygen. CO2 .

51
 Unbalanced Cycle
• Fossil Fuels
A third source of carbon dioxide comes from stored CO2.
The carbon found in fossil fuels was laid down over
millions of years. Because the organisms did not decay
completely, the carbon was never released into the
atmosphere as CO2. Instead, it was stored up in the
earth. Once fossil fuel has been recovered, processed
and burned, the CO2, which would normally have been
released over tens of millions of years, is suddenly all
released within a period of a few hundred years, thus
increasing the amount of CO2 in the environment.

52
 Effect of Carbon Dioxide
• Global Warming
Some scientists have suggested that ocean warming
is resulting in increased CO2 and not the other way
around. This is based on the idea that there is a lot of
CO2 trapped in the oceans, and as the temperature
rises, the CO2 is released, since the solubility of gases
is inversely proportional to temperature. Oceans have
long been considered to be a sink for atmospheric
carbon. If it is releasing CO2 as a result of warming
temperatures, the CO2 should be decreasing in the
oceans.

53
 Carbon Increasing source

• It is important to determine the source of the increase in

CO2 from 280 to 380 parts per million by volume between
1800 and 2005.
• Isotopes of carbon may hold a key to determining the source
of the increased carbon in the atmosphere . The studies are
based on the ratio of the three different carbon isotopes in
atmospheric CO2. Carbon has three possible isotopes: C-12,
C-13 and C-14. C-12, which has 6 neutrons, is by far the most
prevalent carbon isotope and is a stable isotope. Carbon 13 is
also a stable isotope, but plants prefer Carbon 12 and
therefore photosynthetic CO2 (fossil fuel or wood fuels) is
much lower in C-13 than CO2 that comes from other sources
(e.g.: animal respiration) Carbon-14 is radioactive. Studies of
carbon isotopes in CO2 has resulted in the following findings :

54
 Carbon Increasing source

• There has been a decline in the 14C/12C ratio in CO2 that parallels the
increase in CO2. In 1950 a scientist named Suess discovered that fossils do
not contain 14C because they are much older than 10 half lives of 14C.
• There has been a parallel decline in 13C/12C ratio of atmospheric CO2. This
has been linked to the fact that fossil fuels, forests and soil carbon come from
photosynthetic carbon which is low in 13C. If the increased CO2 was due to
warming of the oceans, there should not be a reduction in the ratios of C-13
and C-14 to C-12.
• There are other clues that suggest the source of increased CO2 is not related
to the warming of the ocean and subsequent release of CO2 from the ocean.
• There has been a decline in the oxygen concentration of the atmosphere. If
ocean warming was responsible for the CO2 increase, It has been also
observed an increase in atmospheric O2, because O2 is also released as the
water is warmed.
• The ocean is a sink for atmospheric carbon, and the carbon content of the
oceans has increased by 118±19 PgC in the last 200 years. If the atmospheric
CO2 was the result of oceans releasing CO2 to the atmosphere, the CO2 in the
ocean should not be rising as a result of ocean warming.

55
 Carbon Increasing source

• There is still some resistance to the theory that the increase in CO2
results from the burning of fossil fuel, and that the increase in CO2 is
responsible for global warming. There is little pressure on the US power
plants to reduce CO2 emissions; so here it's still "Burning of fossil fuel is
good for the environment" and "the world is flat." The power plants
faced with reducing their CO2 emissions significantly by 2008 and even
more between 2008 and 2012 as required by the Kyoto Protocol, have
embarked upon a unique way to reduce the CO2 emitted into the
atmosphere.
• The technique known as carbon capture and storage (CCS) involves
siphoning off and burying the CO2 underground. While the CO2 is not
"gone," it is contained. For now they have to report it as "released CO2,"
but USA is working out plans to give industries credit for carbon
capturing and storing in the second phase, from 2008-12, of the
European carbon trading scheme. It will be interesting to see the effect
of keeping the CO2 from being emitted into the atmosphere. Of course,
the next step would be to find a way to treat the stored CO2 or find a
use for it.
56
 Carbon Dioxide
• Present concentration ~ >400 ppm
• Rate of rise in concentration =2 ppm yr-1
• CO2 absorbs infrared radiation and causes global warming
• Therefore CO2 is a ‘green house’ gas
• It was predicted that there will be a net increase of 0.5 C in global
mean temperature by the beginning of the millenium due to
continuous CO2 increasing in the atmosphere

57
 Carbon Dioxide

Carbon dioxide (CO2)

• The most abundant source is from human activity
because the C12/C14 ratio increases with time
• CO2 concentration in influenced by :
▪ Reduction of CO2 level in surface water
▪ Increase in tree oxidation (deforestation, fire)
▪ Increase in photosynthesis in trees

58
 Carbon Dioxide removal

• Absorption: Amine treating units are the well

proven for CO2 removal.
• Membrane unit acceptance continues to grow.
• Molecular Gate system for CO2 removal is a new
option for gas treating. Molecular adsorbents are
a new type of molecular sieve that can adsorb
and remove CO2 (as well as N2) from
contaminated natural gas.

59
 Carbon dioxide capture

• Is a form of carbon capture. It removes carbon dioxide from ambient air by carbon
dioxide scrubbing. It is a different approach to removing CO2 from the stack
emissions of large point sources, such as fossil fuel fired power stations. It is
regarded as greenhouse gas remediation, which is a branch of geoengineering.
Some commentators regard air capture as a form of carbon capture and storage, but
CCS is usually used to describe capture at source rather than capture from ambient
air.
• Air capture is not generally seen as an attractive alternative to capture at large, point
source emitters (such as power plants), as it is likely to be more efficient and cheaper
to capture and store carbon dioxide from more concentrated streams. There are,
however, some advantages of air capture as it removes the need for CO2 piping to
transport the gas to underground storage sites, and allows the use of renewable
energy and optimal storage sites. In addition, the cost of air capture, unlike capture
at power plants, likely benefits from not having to remove all, or even most, of the
CO2 it processes.
• It is particularly effective at dealing with small point sources such as domestic
heating systems and vehicle exhausts, where piping of exhaust gases is impractical.

60
 CO2 Ambient air removal: Proposed
methods
➢ Artificial trees
• A notable example of an atmospheric scrubbing process are the artificial trees. This
concept imagines huge numbers of artificial trees around the world to remove ambient
CO2.
• The chemistry used is a variant of that described below, as it is based on sodium
hydroxide. However, in a more recent design proposed, the process can be carried out at
only 40 °C by using a polymer-based ion exchange resin, which takes advantage of
changes in humidity to prompt the release of captured CO2, instead of using a kiln. This
massively reduces the energy required to operate the process.
➢ Scrubbing towers
A tower, 4 feet wide and 20 feet tall, with a fan at the bottom that sucks air in, which comes
out again at the top. In the process, about half the CO2 is removed from the air. This device
uses the chemical process described in detail below. The reagents are regenerated in a
separate facility. The main costs of a the full plant will be the cost to build it, and the energy
input to regenerate the chemicals and produce a pure stream of CO2.
➢ Quicklime process
Quicklime will absorb CO2 from atmospheric air mixed with steam at 400 °C, (forming
calcium carbonate) and release it at 1000 °C. This process,, can be performed using
renewable energy from thermal concentrated solar power
61
 Example of CO2 Scrubbing Chemistry

• First, CO2 is absorbed by an alkaline NaOH solution to produce dissolved sodium

carbonate. The absorption reaction is a gas liquid reaction, strongly exothermic, (below)
2NaOH(aq) + CO2(g) → Na2CO3(aq) + H2O(l) ΔH° = -109.4 kJ/mol
• The carbonate ion is removed from the solution by reaction with calcium hydroxide
(Ca(OH)2), which results in the precipitation of calcite (CaCO3). The causticization reaction
is a mildly exothermic, aqueous reaction that occurs in an emulsion of calcium hydroxide
(below)
Na2CO3(aq) + Ca(OH)2(s) →-> 2NaOH(aq) + CaCO3(s) ΔH° = -5.3 kJ/mol
• Causticization is performed ubiquitously in the pulp and paper industry and readily
transfers 94% of the carbonate ions from the sodium to the calcium cation Subsequently,
the calcium carbonate precipitate is filtered from solution and thermally decomposed to
produce gaseous CO2. The calcination reaction is the only endothermic reaction in the
process and is shown (below).
CaCO3(s) → CaO(s) + CO2(g) ΔH° = + 179.2 kJ/mol
• The thermal decomposition of calcite is performed in a lime kiln fired with oxygen in order
to avoid an additional gas separation step. Hydration of the lime (CaO) completes the
cycle. Lime hydration is an exothermic reaction that can be performed with water or steam.
Using water, it is a liquid/solid reaction as shown (below).
CaO(s) + H2O(l) → Ca(OH)2(s) ΔH° = -64.5 kJ/mol 62
 Industrial CO2 Removal by membrane
Gas treating membrane systems provide a safe and efficient option for water vapor and carbon
dioxide removal from natural gas, especially in remote locations. Membrane systems are
extremely adaptable to various gas volumes, CO2 concentrations, and/or product-gas
specifications. A spiral wound cellulose acetate membrane unit offers the greatest efficiency per
Mcf of product removed compared to any other competing CO2 removal system.
Carbon dioxide membranes operate on the principle of selective permeation. Each gas component
has a specific permeation rate. The rate of permeation is determined by the rate which a
component dissolves into the membrane surface and the rate at which it diffuses through the
membrane.
The components with higher permeation rates (such as CO2, H2, and H2S) will permeate faster
through the membrane module than components with lower permeation rates (such as N2,
methane, ethane and heavier hydrocarbons). For example, carbon dioxide is a "fast," more
permeable, gas than methane. When a stream consisting of these two gases contacts the
membrane, the carbon dioxide will permeate through the fiber at a faster rate than the methane.
Thus, the feed stream is separated into a methane-rich (residual) stream on the exterior of the
membrane fiber and a carbon dioxide-rich (permeate) stream on the interior of the membrane
fiber.

63
 Carbon Compounds

Carbon monoxide (CO)

• Mostly produced by human activity ~ 70 %
• Produced from partial combustion of fossil fuel
especially in motorized vehicles
• Background level ~ 0.1 ppm
• In urban areas ~ 10 ppm

64
 Carbon Compounds

Carbon monoxide (CO)

• CO is produced if ratio of fuel to O2 is too high or the
temperature is too low that slows down oxidation
• CO could easily combine with hemoglobin in blood 200 times
faster than O2 and could cause death by asphyxia
• CO reaction in the atmosphere
CO + [OH] → CO2 + [H]
• The hydrogen produced may participate in other chain
reactions

65
 Global Carbon Monoxide (Air Pollution)
Measurements
• Carbon monoxide is a gaseous byproduct from the burning of fossil fuels,
in industry and automobiles, as well as burning of forests and grasslands.
The image below was taken in the April 30, 2000, that levels of carbon
monoxide are much higher in the Northern Hemisphere, where human
population and human industry is much greater than in the Southern
Hemisphere
• The image represent levels of carbon monoxide in the lower atmosphere,
ranging from about 390 parts per billion (dark brown pixels), to 220 parts
per billion (red pixels), to 50 parts per billion (blue pixels).

2010 2015
66
 Toxicity of Carbon Monoxide
• Carbon monoxide is a toxic gas, but, being colorless, odorless, tasteless, and
non-irritating, it is very difficult for people to detect. Carbon monoxide is a
product of incomplete combustion of organic matter with insufficient oxygen
supply to enable complete oxidation to carbon dioxide (CO2) and is often
produced in domestic or industrial settings by motor vehicles and other
gasoline-powered tools, heaters, and cooking equipment. Exposures at 100
ppm or greater can be dangerous to human health.
• Symptoms of mild acute poisoning include headaches, dizziness, and flu-like
effects; larger exposures can lead to significant toxicity of the central nervous
system and heart, and even death. Following acute poisoning, long-term sleep
disorders often occur. Carbon monoxide can also have severe effects on the
fetus of a pregnant woman. Chronic exposure to low levels of carbon monoxide
can lead to depression, confusion, and memory loss.
• Carbon monoxide mainly causes adverse effects in humans by combining with
hemoglobin to form carboxyhemoglobin (HbCO) in the blood. This prevents
oxygen binding to hemoglobin, reducing the oxygen-carrying capacity of the
blood, leading to hypoxia. Additionally, myoglobin (monomeric heme protein
found mainly in muscle tissue where it serves as an intracellular
storage site for oxygen) and mitochondrial cytochrome oxidase are thought
to be adversely affected. Carboxyhemoglobin can revert to hemoglobin, but the
recovery takes time because the HbCO complex is fairly stable.
67
 Air pollutant

Carbon Compounds
Other hydrocarbon and organic gases
Methane
• The most abundant hydrocarbon gas in the
atmosphere ~ 1 - 2 ppm
• Difficult to react in the atmosphere except at
concentrations above its lower flammability limit and
in the presence of an ignition source
• Also a ‘green house’ gas
• Produced mainly by decay of fallen trees in swampy
areas & gas pockets below ground

68
 Air pollutant

Carbon Compounds
Other hydrocarbon and organic gases
Terpene
• Including -pinene, mircene dan limonene
• Monocyclic and dicyclic organic compounds
consisting of combinations of isoprene
CH2=C-CH=CH2
|
CH3

69
 Air pollutant

Aerosols
• Aerosol is a gas containing suspended solid and/or
liquid particles
• Particle settling velocity is very low
• Inertial effect on particle motion could be neglected
because the ratio of inertial forces/ viscous forces is
small
• Brownian motion due to thermal agitation of gas
molecules is significant
• Ratio of particle surface area/volume is large

70
 Air pollutant
Aerosols
• Particle settling velocity is given by

2  p gr
2

vs =
9 f
where r = particle radius, p = particle density,
f = gas viscosity and g = gravitational constant
Inertia force/viscous force given by particle Reynolds number < 1.0

 f vs d
Re =
f
Settling velocity of 10m radius particle<30cm yr-1 Settling
71
velocity of 30m radius particle<10 cm yr-1
 Air pollutant

Sources of Aerosol
• Dispersed material, r > 0.1 m
– Sea salts, bubble breakage
– soil / metal - dust cloud/ dust storm
• Chemical reaction and vapour condensation
– r < 0.1 m
• Photochemical reaction - smog

72
 Air pollutant
r (m)

10-3 10-2 10-1 1.0 10 102

Particle Aitken large giant

Fields particle particle particle

Air
electricity small large
ion ion
Atmospheric
optics smog particle
Cloud
physics Active condensation nucleus
Air
Chemistry Particle that contains
the most aerosol mass

73
 Air pollutant

Thermal coagulation of aerosol

• The result of Brownian motion is coagulation. Number of
coagulated particles per unit volume, N is given by :
dN dN
= 8 DrN 2  N2
dt dt
D = particle diffusion coefficient
kT  AL 
D=  1 + 
6 r  r 

k = Boltzmann constant (1.3807 x 10-23 J K-1 molecule1)

A =Stoke-Cunningham correction
L = molecular mean free path
74
 Air pollutant

Aerosol Classification
• Aitken particle r < 0.1 m
• Large particle 0.1 < r < 1.0 m
• Giant particle r > 1.0 m
• Aitken particle is very small and diffusion effects are
significant, therefore thermal coagulation is fast
• For giant particle, diffusion effects could be neglected
and its behaviour is governed by settling due to gravity

75
 Air pollutant

Aerosol Classification

Radius Settling Brownian Residence Removal

(m) velocity diffusion time process
(cm s-1) coefficient, D
(cm2 s-1)
0.001 - 10-2 ~ 1 hour Coagulation
0.01 4 x 10-7 10-4 ~ 1 week Coagulation
0.1 0.00015 2 x 10-6 - Nucletaion
1.0 0.025 10-7 ~ 1 month Settling
10.0 2.5 - ½ day Settling
100.0 150 - 10 minute Settling

76
Plume Rise
 Air pollutant

Chemical Composition of Troposphere Aerosol

Component Total (g Nm-3)

Organic 79 - 178
Sulfate 24 - 43
Nitrate 4 - 13
Sea salts 5 - 26
Cement dust 3 - 9
Transport dust 6 - 12
Ammonia 0 - 10
Ar 10 - 16

78
 Air pollutant

Daily profile of aerosol concentration

I II III
Formation Formation & Condensation &
of new coagulation coagulation
particles
V – Total particle volume
Particle
Concentration
A – Total particle area

N – Number of particles

79
Time
 Air pollutant

Aerosol (r < 20m) formation rate

Natural Sources 106 t yr-1

Soil and rocks 100 – 500
Forest fire 3 - 150
Sea salts 300
From gas:
Sulfate from H2S 130 - 200
Ammonium salts from NH3 80 - 270
Nitrates from. NOx 30 - 38
Hydrocarbon from. plants 75 - 750
Total 773 - 2 200
80
 Air pollutant

Aerosol (r < 20m) formation rate

Human Sources 106 t/yr-1

Particles (direct discharge) 10 - 90
From gas :
Sulfate from SO2 130 - 200
Nitrates from NOx 30 - 35
Hydrocarbon 15 - 90
Total 185 - 415

Grand total 958 - 2 615

81
 Air pollutant

104

103

102 Particle size distribution

Probability 10
Density 1.0
f(r)
10-1

10-2

10-3

10-4

10-5

10-6
Radius, r (m)
10-3 10-2 10-1 1.0 10 822
10 103
 Air pollutant

Particle size distribution

• Particle size distribution based on number is given

by

1 dN
N dr
= f (r )  f (r )dr = 1
Particle size distribution based on volume is given by

 F (r )dr = 1
1 dV
= F (r )
V dr

83
 Air pollutant

Particle size distribution

• Particle size distribution based on volume is constant
per log radius
4 3 dN dN
r = constant  r −4
3 d ln r dr

Particle size distribution function could be written as

= C2 r ( )
dN dN −  +1
f ( ln r ) = = C1r −  2 3
d ln r dr

84
 Volatile Organics VOCs
• VOCs are a volatile materials emitted to atmosphere from
several sources. VOCs include a variety of chemicals, some
of which may have short- and long-term adverse health
effects. Concentrations of many VOCs are consistently
higher indoors (up to ten times higher) than outdoors.
• VOCs are emitted by a wide array of products numbering in
the thousands. Examples include: paints and lacquers, paint
strippers, cleaning supplies, pesticides, building materials
and furnishings, office equipment such as copiers and
printers, correction fluids and carbonless copy paper,
graphics and craft materials including glues and adhesives,
permanent markers, and photographic solutions.
• The major VOC source are the fuel and fuel handling such as
fuel station, storage, solvent usage transportation , storing
and application.

85