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Module III: Air Pollution Monitoring & Control

Pollution Sources: Stationary & Mobile emission Sources, Monitoring & Control of air
pollutants using high volume sampler, cyclone separators, wet scrubbers, electrostatic
precipitators, etc. automobile emission control.

Sources of pollutants:
Stationary Emission Source
Point sources: Large, stationary sources of emissions that have specific locations and release
pollutants in quantities above an emission threshold are known as.
Area sources: facilities whose individual emissions do not qualify them as point sources
Major source: has the potential to emit, pollutants over a major source threshold
Minor source: emits less pollutant than the major source threshold.
Emission point: smokestacks, storage tanks, equipment leaks, process wastewater
handling/treatment area, loading and unloading facilities
Process vent: Distillation columns and oxidation vents.
[Discuss about what are the gases emitted by these sources]
Mobile sources:
Transportation
Mobile sources include both on road vehicles and off road equipments
Highway Vehicles: Gasoline and diesel powered automobiles, buses and trucks.
Marine Vessels: Commercial, military and recreational.
Aircraft and Railroads
Paved and Unpaved Roads
Off-Road Equipment: Gasoline and diesel powered lawn and garden equipment, industrial and
recreational engines
[Discuss about what are the gases emitted by these sources]
Natural Sources:
Volcanos, plant metabolism, lightning, soil microbes, soil, rock etc.
[ note: A brief discussion should be needed about the pollutants which are emitted by coal
fired plants, industry (oil , gas, coal), metal ore smelting, power plants, petroleum
refineries, transportations.]
Automobile emission control:
The main pollutants in automobile emission are CO, NOx, and hydrocarbon (HC) along with
some particulates. When one of the pollutants in internal combustion engines is subjected to
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control measure, the amount of the others affected at the same time. In four stroke internal
combustion engine the most important factor is the air to fuel ratio.
[note: The students are already familiar with four stoke engine and how it works in the
first semester engineering chemistry, we are giving a brief, the main components of the
four stoke engine, not in detail. But we should show them the diagram of the four strokes.]
The conventional Otto cycle engine: Four stroke internal combustion engines contains-
I. Intake stroke: The descending piston draws in a mixture of fuel and air through
the open intake valve.
II. Compression stroke: the raising of piston compresses the air/fuel mixture in the
cylinder against the now closed intake and exhaust valve. As the piston approaches
the top of the compression stroke, the spark plug fires, igniting the mixture.
III. Power stroke: in the power stroke, the burning mixture expands and forces the
piston down which turns crankshaft and delivers power to drive the train.
IV. Exhaust stroke: in exhaust stroke, the exhaust valve opens and the raising piston
forces the combustion products out of the cylinder through the exhaust system and
into the air. [ this is the exhaust system, which need to be control to minimise the
emission of the pollutants]
In diesel engine operates with a similar cycle, but they compress fuel more during
the compression stroke which makes the cylinder so hot that they ignite of their own
accord without needing a spark plug.
[Diagram of the four strokes of internal combustion engines should be here]
[Note: Before going to the exhaust control system to minimise the emission of pollutants
from automobiles, we need to discuss about air/fuel ratio in the intake stroke of the
internal combustion engine]
Air to fuel ratio and lean/rich fuel:
The single most important factor in determining emissions from a four stroke internal
combustion engine is the ratio of air to fuel in the mixtures as it enters the cylinder during the
intake stroke.
To analyse that mixture ration and its impact on emission, let us begin with the stoichiometry
of the gasoline combustion. Modern gasolines are blend of various hydrocarbons, an average
formulation can be represented as C7H13.
For complete combustion in oxygen,
C7H13 + 10.25 O2 7CO2 + 6.5 H2O
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In air N2 is present, 3.76 mol of N2 accompanying in every mole of oxygen. Thus 10.25 x 3.76
= 38.54 moles of N2 can be placed each side of the reaction which will give-
C7H13 + 10.25 O2 + 38.54 N2 7CO2 + 6.5 H2O + 38.54 N2

Where any oxidation of N2 to nitrogen oxides has been neglected.

Stoichiometric Air to fuel ratio:
1 mol of C7H13 = 97 g
10.25 mol of O2 = 328 g
38.54 mol of N2 = 1079 g
Considering air to be made up only oxygen and nitrogen, the air fuel ratio needed for complete
oxidation of gasoline is = air/ fuel =14.5
Stoichiometric ratio of gasoline is 14.5
Air fuel ratio >14.5 – Lean fuel
Air fuel ratio <14.5 – Rich fuel
If the actual air/fuel mixture has less air than what the stoichiometric ratio, indicates is
necessary for complete combustion, the mixture is said to be rich fuel.
If more air is provided than what is necessary, the mixture is then said to be lean.
[Note: a brief discussion about the pollutants emitted by motor vehicles indicating the
role of lean and rich fuel mixture.]
[Effect of air/fuel ration on emission, power and fuel economy should be discussed by
describing a figure of the relation among air/fuel ration, emissions, power and fuel economy]
Exhaust system control:
During the exhaust stroke of an internal combustion engine, combustion gases are pushed
through the manifold and out the tailpipe. It is the exhaust system that most of the control of
automobiles emission now occurs.
Commonly used system for the treatment of exhaust gases are-
(i) Thermal reactor
(ii) Exhaust gas recirculation system
(iii) Catalytic converter
[A brief discussion about thermal reactor and exhaust gas recirculation system for the
control of automobile emission should be discussed in the class.]
Earlier two way catalytic converter are used to control the HC and CO pollutant, but as NOx
has also immense effect on the atmosphere, a three way catalytic converter needed where one
can control all the three important pollutants.
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Three way catalytic converter: A three way catalytic converter is able to oxidise
hydrocarbons and CO to H2O and CO2 while reducing NOx to N2 all in the same bed of
catalyst. It is very effective in controlling emissions near stoichiometric conditions where the
engine performance and efficiency are greatest.
Finely divided Pt used as a catalyst (Pd and Rh can also be used) which reduces NOx to N2
(NH3) and oxidise HC and CO to CO2 and H2O.
Pl free gasoline is used as Pb poisoned the Pt catalyst and thereby reduces the catalytic activity
of the catalyst.

Octane number and Knocking:

[Discussion about octane number and knocking (Octane rating, enhancer of octane
rating, and factors of knocking) should be in brief as it is already discussed in engineering
chemistry, in first semester]

Particulates
Volcanic eruptions, wind and dust storms, salt spray etc. are natural sources of particulate
constituents of the atmosphere. Burning of coal, oil, wood, gaseous fuels; Industrial processes;
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Smelting and mining operations; fly-ash emissions from power plants, burning of coal refuse
and agricultural refuse are man-made activities which release considerable tonnage of
particulate matter in atmosphere. Particulate matter has large surface areas hence they provide
excellent sites for absorption of various organic and inorganic species. They also scatter right
and reduce visibility. The typical particulate air pol1utants their sources and effects are summa-
rized below in;
Particulate Sources Effects
Dust Asbestos and cement Causes respiratory and
factories allergic diseases
Smoke In complete oxidation of Causes skin diseases
fuels in automobiles
Lead dust
lead batteries and
Causes lead poisoning
automobile exhausts

Particulate matter can be removed from industrial gaseous effluents with the help of following
devices; cyclone collectors, electrostatic precipitators, wet scrubbers and settling chambers .

Control of particulate matter:

The control techinques of particulate matters depends on the particle size, concentration,
corrosivity, toxicity, volumetric flow collection efficiency, allowable pressure drops and cost.
For relatively large particles cyclone collector/ separator is used whereas for small particulates
baghouse filter or electrostatic precipitators are used.
Cyclone separator:
The general principle of inertia separation is that the particulate-laden gas is forced to change
direction. As gas changes direction, the inertia of the particles causes them to continue in the
original direction and be separated from the gas stream. The walls of the cyclone narrow toward
the bottom of the unit, allowing the particles to be collected in a hopper. The cleaner air leaves
the cyclone through the top of the chamber, flowing upward in a spiral vortex, formed within
a downward moving spiral. Cyclones are efficient in removing large particles but are not as
efficient with smaller particles. For this reason, they are used with other particulate control
devices.
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Electrostatic precipitators:
An ESP is a particle control device that uses electrical forces to move the particles out of the
flowing gas stream and onto collector plates. The ESP places electrical charges on the particles,
causing them to be attracted to oppositely charged metal plates located in the precipitator. The
particles are removed from the plates by "rapping" and collected in a hopper located below the
unit. The removal efficiencies for ESPs are highly variable; however, for very small particles
alone, the removal efficiency is about 99 percent. Electrostatic precipitators are not only used
in utility applications but also other industries (for other exhaust gas particles) such as cement
(dust), pulp & paper (salt cake & lime dust), petrochemicals (sulfuric acid mist), and steel (dust
& fumes).

Baghouse filter:
Fabric filters, or baghouses, remove dust from a gas stream by passing the stream through a
porous fabric. The fabric filter is efficient at removing fine particles and can exceed efficiencies
of 99 percent in most applications. The selection of the fiber material and fabric construction
is important to baghouse performance. The fiber material from which the fabric is made must
have adequate strength characteristics at the maximum gas temperature expected and adequate
chemical compatibility with both the gas and the collected dust. One disadvantage of the fabric
filter is that high-temperature gases often have to be cooled before contacting the filter medium.
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Wet scrubbers:
It is used to control and remove flue gases as precipitators. Finely pulverised limestone is mixed
with water to create slurry that is sprayed into the flue gases. The flue gas, SO 2 is absorbed by
the slurry producing a CaSO3 or CaSO4 precipitate. The precipitator is removed from the
scrubbers as sludge.
CaCO3 + SO2 + H2O CaSO3. 2H2O + CO2
Sometime, lime is also used instead of limestone in the slurry.
CaO + SO2 + H2O CaSO3.2H2O
CaCO3 + H2O CaSO4
Lime is more expensive than limestone and SO 2 removal efficiency upto 95%

High volume samplers:

High volume sampler is used for the collection of atmospheric particulate material. Filtration
is the most common technique for sampling particulate matter. Although there are varieties of
filter material used for the filtration, in high volume sampler glass fibres is used which
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effieciency is upto 99% of particles with 0.8 micron diameter. High volume of air samples are
used to pump large volume of air upto 2000 cubic meter at a rate of about 1.7 cubic metere /
min. Depending upon the particle size, one should use very small glass fibre for the efficient
collection.

Analaysis of gaseous pollutants:

The common techniques for the analysis of gaseous pollutants are in the table below:

Nitrogen Oxide
Chemiluminescence Analyzer:
Nitric oxide (NO) is measured by the gas-phase chemiluminescent reaction between nitric
oxide and ozone. This technique is also used to determine nitrogen dioxide (NO2) by
catalytically reducing NO2 in the sample air to a quantitative amount of NO. Sample air is
drawn through a capillary into a chamber held at 25 in. Hg vacuum. Ozone produced by
electrical discharge in oxygen is also introduced into the chamber. The luminescence resulting
from the reaction between NO and ozone is detected by a temperature-stabilized
photomultiplier tube and wavelength filter. An automatic valving system periodically diverts
the sample air through a heated activated-carbon catalyst bed to convert NO2 to NO before it
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enters the reaction chamber. The sample measured from the converter is called NOx. Since it
contains the original NO plus NO produced from the NO 2 conversion, the differences between
the sequential NOx and NO readings are reported as NOx. Primary dynamic calibrations are
performed with gas-phase titration using ozone and nitric oxide standards and with NO 2
permeation tubes.
Carbon Monoxide
Infrared (IR) Analyzer:
This method utilizes dual beam photometers with detection accomplished by means of parallel
absorption chambers or cells that are separated by a movable diaphragm. The IR energy passes
into each chamber—one containing the sample with CO, the other containing the reference gas.
The reference gas heats up more than the ambient air sample with CO since CO absorbs more
of the IR energy. This results in higher temperature and, hence, the volume–pressure in the
reference chamber that is transmitted to the separating diaphragm designed to provide an
electrical output to measure the CO concentration. However, it is necessary to remove water
vapor interference as the humidity in ambient air absorbed
by IR energy can introduce a significant error in CO readings. In one instrument (the EPA
reference method), the interference due to water vapor is eliminated by first passing one portion
of the ambient air sample through a catalytic converter where CO is converted to CO2 prior to
entry into the reference chamber. The other half of the air sample containing CO passes directly
into the sample chamber. This procedure cancels out the effect of moisture since both gas
streams are identical except for the presence of CO.37 Carbon monoxide is also measured by
gas-phase correlation.
Ozone
Chemiluminescence Analyzer:
Ozone is measured by the gas-phase chemiluminescence technique, which utilizes the reaction
between ethylene and ozone (O3). Sample air is drawn into a mixing chamber at a flow rate of
1 L /min where it is mixed with ethylene gas and introduced at a flow rate of 25 cc/min. The
luminescence resulting from the reaction of the ethylene with ambient ozone in the air supply
is detected by a temperature-stabilized photomultiplier tube. This signal is then amplified and
monitored by telemetry and on-site recorders. These ozone instruments contain provision for
weekly zero and span checks. Primary dynamic calibrations are periodically performed that
require standardization against a known, artificially generated ozone atmosphere. Ozone is also
measured by UV light instrumentation.
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Sulfur dioxide:
West Gaeke Spectrophotometric method:
The modified West-Gaeke spectrophotometric method remains the standard method for the
monitoring 0.0005-5 ppm SO2 in ambient air. SO2 is collected in a scrubbing solution
containing HgCl42- (HgCl2 + KCl), the collection efficiency being around 95%. The solution is
allowed to react with HCHO and then with para-rosaniline hydrochloride which form a red-
violet dye. The absorbance of the product red-violet dye is measured at 548 nm.
The major interference from NO2 ( > 2 ppm) when present is eliminated by the addition of
sulfamic acid H2NSO3H. This reagent acts as a reducing agent converting NO 2 to N2.

Alternative fuels: A brief discussion necessary of the following fuels including advantage and
disadvantage of each fuel. [For reference, please go through G. M. Masters]

Cleaner gasoline: Motor vehicle hydrocarbon emission are not only the results of inefficient
combustion, but also caused by vaporisation of the fuel itself. To help control of these
evaporative emissions, automobiles are equipped with vapour recovery system. Gasoline can
be formulated to help reduce tailpipe emission of CO and HC by adding oxygenates that
encourage complete combustion, e.g. Ethanol, MTBE. To enhance octane rating replacing
TEL, BTX is also used.
A number of alternative gasoline are being investigated as possible fuels for the future. These
includes ethanol, methanol, CNG, Hydrogen, electricity etc. The motivation for developing
vehicles capable of running on these fuels is a combination of the potential to reduce air
pollution and to reduce our demand for petroleum nd the negative environment, non-renewable
resource depletion and the security issues associated with its use.
[A brief introduction the following fuels is necessary]
Ethanol:
Methanol:
Biodiesel:
Compressed natural gases:

Electric drive vehicles:

Fuel cell vehicles:

Clean air act and their amendments: (Preventing and reducing air pollution)
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The US congress passed clear air act in 1955, 1970, 1977 and 1990 providing federal air
pollution regulation to deal with the air pollution problems.
[Here we have to discuss the aim of the clean air act and their amendments to attain the goal.]
Environmental protection agency was established by the amendments in 1970. EPA was
required to establish national ambient air quality standards (NAAQS), New source
performance standards (NSPS).
NAAQS now exists for six criteria pollutants CO, Pb, NO 2, ground level O3, SO2 and two
categories of particulate matters. The clean air act requires that the list of six criteria pollutants
be reviewed periodically and that standards according to the latest scientific information.
The clean air act amendments 1990: The clean air act amendments of 1990 broaded its scope
to include the control of pollutants that effect global problem- stratospheric ozone depletion.
Principal changes in the act included the following-
i. Creation of new acid rain program
ii. New requirements for nonattainment areas
iii. Tightened automobile emission standards and new fuel requirements
iv. New toxic air pollutant control
v. Phase out schedule for ozone depleting substances
[Discuss about the acid rain program and ozone depleting substances.]