2.

Origin and Sources of Air Pollution

The most important anthropogenic source groups of air pollution are industrial furnaces and
industrial processes, traffic, small scale businesses and domestic furnaces as well as special
sources such as confinement systems, sprays cans, CFC refrigerators etc.

A major proportion of the pollutants caused in these different areas have their origin in
combustion processes, either in industrial and domestic furnaces or in traffic from combustion
engines and aircraft engines.

2.1 Emission of Pollutants caused by combustion Processes

When burning fuels for generating heat or power, a wide variety of air polluting substances
can be created. Combustion plays a role in the energy needs of most societies. The US
Transportation system relies almost entirely on combustion. About 85 % of energy used in the
US came from combustion. These are in the iron, steel, aluminium and other metal refining
industries as well as ground vehicles and aircrafts depend heavily on combustion. The major
downside of combustion is environmental due to unburbed or partially burned hydrocarbons,
nitrogen oxides, carbon monoxide, sulphur oxides, particulate matter (soot, fly ash, metal
fumes, various aerosols) and greenhouse gases particularly CO2. Type and amount of the air
pollutants emitted depend on the type of combustion process, on the fuel used and on the
processing of combustion. For the area of furnaces the influencing factors and the possible
emissions of air pollutants with their interdependence are shown in the diagramme.

2.2 Products of complete and incomplete Combustion

The fossil fuels gas, petrol, fuel oils and coal consist of hydrocarbon compounds with varying
C/H ratios.

During complete combustion the carbon in the fuel reacts with oxygen to become carbon
dioxide, the hydrogen to become water according to the following gross reaction equation

CnHm + (n + m/4)O2 nCO2 +(m/2) H2O

Depending on the type of combustion process and fuel used, technical processes need a
certain amount of excess oxygen or air for complete combustion. Lack of air causes
incomplete combustion with higher pollutant emissions.

Excess of air during combustion processes is defined as follows:

= actual amount of air A / stoichiometrically required amount of air Amin

The minimum amount of air can be determined by applying the combustion equations. The
same is true for the theoretical amount of exhaust gas Vmin. As the actual amount of air can
in practice only be determined with difficulty, excess air is determined alternatively from the
remaining oxygen content O2 in the exhaust gases or from the carbon dioxide content CO2,
complete combustion, is, however, a precondition for this:
= (1 + Vmin / Lmin)( O2/ 21 O2)

If pure carbon is burned completely, only CO2 results. In this case the exhaust gas volume
Vmin is equal to the air Volume. However if water is vapour is also formed, the Vmin is no

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longer equal to Amin. Where fuels with a high C/H ratio are concerned Vmin = Amin. In this
case the following applies:

= 21/(21 - O2)

During complete combustion the maximum possible reduction of CO2 is effected exclusively
via the dilution of the exhaust gases with excess air. Thus, the CO2 content can also be used to
determine excess air. For this, however, the maximum possible CO2 content CO2max must be
known. During stoichiometrical combustion of pure carbon n molecules O2 become n
molecules CO2; thus the CO2max content amounts to 20,93 % of volume.

In fuels consisting of hydrocarbons the CO2 will be lower depending on the hydrogen, for
light fuel oils e.g., it amounts to 15,4 % of volume.

The following equations are then valid for determining the excess air from the CO2 content
of the exhaust gases:
= (1 + Vmin/Lmin).(( CO2max CO2)/CO2)

or estimated with the simplified assumption Vmin = Amin

= CO2max/CO2

Excess air is important factor for the low pollution conduct of combustion processes. Lack of
air causes incomplete combustion. Apart from this factor, the following causes can impair the
completeness of the combustion

Inadequate mixing of fuel and combustion air (local lack of air)

Insufficient pulverizing of solid fuels or atomizing of liquid fuels
Sudden cooling of the flame gases through combustion chamber walls
Residence time at high temperatures too short
Flames burning in lifted condition, escaping of intermediate products from under the
flame base.

During incomplete combustion products of incomplete combustion (PIC) can be formed and
reach the environment in the form of emissions. These are carbon monoxide, hydrocarbons
(CnHm) , oxidizing hydrocarbons and others such as odorous substances and soot.

2.3 Exhaust Gases from Motorised Vehicles Influences on their formation

Most of the automobiles in street traffic are driven by combustion engines Otto or Diesel
engines. In these engines an intermittent, unstationary combustion takes place in the
combustion chambers; with every other piston stroke the sucked in air / fuel mixture ignites,
expand due to the released oxidation heat and drives the piston downward. The rising piston
subsequently presses the exhaust gas out of the cylinder.
One of the main problems is caused by the fact that that automobile engines are not operated
with a constant load and a constant number of revolutions. It is hardly possible to achieve
minimal exhaust gas emissions with a maximum exploitation of fuel at every point of engine
operation.

Carbon Monoxide

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CO is the intermediate product in the combustion process of carbon to CO2. CO oxidation
requires a so-called ignition temperature of at least 990 K, and for a complete burn-up a
certain residence time. Using oil furnaces as an example, the dependency of CO emission on
air or oxygen excess during combustion is shown in the attached diagram. As can be seen,
there is a dramatic increase of the exhaust gases CO content when there is not enough air.
How high the minimum air has to be so that combustion is as complete as possible depends
on the combustion temperature, on the residence time and on how well mixed the fuel-air
mixture is.
The dependency of CO emission on temperature is shown in the diagram. Using a stove with
an oil evaporation burner as an example, there is a clear CO emission increase in the lower
temperature range.

Hydrocarbons

If hydrocarbons are not totally oxidized during combustion, a variety of substances can appear
in the exhaust gas, e.g. alcohols, aldehydes or organic acids. Hydrocarbons can be oxidized
via the following more or less stable oxidation states which are also possible emission
components.
CH4 CH3OH HCHO HCOOH CO CO2, H2O
Methane methanol formaldehyde formic acid

If there is lack of air, thermal decomposition (pyrolysis) can set in. This decomposition
process either takes place via the reaction of a partial oxidation leading to the formation of
new hydrocarbons, particularly aromatic hydrocarbons e.g. benzene, toluene and polycyclic
aromatic hydrocarbons, some of which are cancerogenic.

Soot

If fuels are heated in the absence of oxygen, thermal decomposition processes ensue. In these
processes the H is split off and soot can be the resulting final product. It consists of elemtary
carbon, and in part, of hydrocarbons. Soot formation is favoured by lack of fuel and air and by
high temperatures in this phase. The burning conditions and the fuel used play a role in its
formation.

Sulphur compounds

More than 80 % of anthropogenic SO2 emissions ( 70 80 million tons per year worldwide)
The emissions of sulphur oxides are directly related to the sulphur content of the fuel. Heavy
fuel oil has between 0,3 to over %. Lighter products contain <0,3 % They are formed during
combustion of fuels containing sulphur compounds. These found their way via the amino
acids which are the fundamental components of the plant protein.

Oxides of Nitrogen

These are formed during combustion at high temperatures. Primarily NO is formed, whereas
the more poisonous nitrogen dioxide is formed only after the combustion when there is
adequate oxygen content in the exhaust gas and finally in the atmosphere. The highest NOx

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emissions occur in furnaces with high temperatures, in the smelting chamber and cyclone
furnaces.

Particles

When furnace chimneys or automobile exhaust pipes emit smoke, then this is visible due to
the particles or droplets suspended in the exhaust gases. The fine particles, in combination
with the carrier gas- exhaust gas or air also called aerosol, are of particular significance as:
They have a small mass and large surface; this is why gases are visible even in small
particle mass concentrations; the layer of smog over large cities also stem from the
fine particles or drops which do not sediment
They are respirable, they can have a toxic effect in the respiratory system itself or they
can transport toxic substances into the lungs due to their absorptive properties
Their formation depends on the type of fuel, type of fuel preparation and on the conditions of
combustions.

In developing countries, though, with less industrialization and motorization, the technical
processes applied have not been optimized yet, so that their specific emissions are frequently
higher. Combustion processes of, e.g., motor vehicles, thus often emit more products of
incomplete combustion (CO, hydrocarbons, soot) than the same processes in the industrial
states of north America, Europe and Japan. As an example, the diagramme below shows the
specific emissions (per capita) of an African country as compared to that of Germany. Total
emissions of the typically consumption-related compounds CO2, SO2 and NOx are much
lower in the developing countries than in the industrial ones.