COMBUSTION

By: Michael Biarnes

In collaboration with:
Bill Freed and Jason Esteves

E Instruments Group LLC- www.einstrumentsgroup.com

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 Combustion
What is Combustion?
Combustion takes place when fuel, most commonly a fossil fuel, reacts with the oxygen in air
to produce heat. The heat created by the burning of a fossil fuel is used in the operation of
equipment such as boilers, furnaces, kilns, and engines. Along with heat, CO2 (carbon
dioxide) and H20 (water) are created as byproducts of the exothermic reaction.

CH4 + 2O2 CO2 + 2H2O + Heat

C + O2 CO2 + Heat
2H2 + O2 2H2O + Heat
By monitoring and regulating some of the gases in the stack or exhaust, it is easy to improve
combustion efficiency, which conserves fuel and lowers expenses. Combustion efficiency is
the calculation of how effectively the combustion process runs. To achieve the highest levels
of combustion efficiency, complete combustion should take place. Complete combustion
occurs when all of the energy in the fuel being burned is extracted and none of the Carbon
and Hydrogen compounds are left unburned. Complete combustion will occur when the proper
amounts of fuel and air (fuel/air ratio) are mixed for the correct amount of time under the
appropriate conditions of turbulence and temperature.

Although theoretically stoichiometric combustion provides the perfect fuel to air ratio, which
thus lowers losses and extracts all of the energy from the fuel; in reality, stoichiometric
combustion is unattainable due to many varying factors. Heat losses are inevitable thus
making 100% efficiency impossible.

In practice, in order to achieve complete combustion, it is necessary to increase the amounts

of air to the combustion process to ensure the burning of all of the fuel. The amount of air that
must be added to make certain all energy is retrieved is known as excess air.

In most combustion processes, some additional chemicals are formed during the combustion
reactions. Some of the products created such as CO (carbon monoxide), NO (nitric oxide),
NO2 (nitrogen dioxide), SO2 (sulfur dioxide), soot, and ash should be minimized and accurately
measured. The EPA has set specific standards and regulations for emissions of some of
these products, as they are harmful to the environment.

Combustion analysis is a vital step to properly operate and control any combustion process in
order to obtain the highest combustion efficiency with the lowest emissions of pollutants.

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Objective of Combustion
The objective of combustion is to retrieve energy from the burning of fuels in the most efficient
way possible. To maximize combustion efficiency, it is necessary to burn all fuel material with
the least amount of losses. The more efficiently fuels are burned and energy is gathered, the
cheaper the combustion process becomes.

Complete Combustion – Complete combustion occurs when 100% of

the energy in the fuel is extracted. It is important to strive for complete combustion to preserve
fuel and improve the cost efficiency of the combustion process. There must be enough air in
the combustion chamber for complete combustion to occur. The addition of excess air greatly
lowers the formation of CO (carbon monoxide) by allowing CO to react with O2. The less CO
remaining in the flue gas, the closer to complete combustion the reaction becomes. This is
because the toxic gas carbon monoxide (CO) still contains a very significant amount of energy
that should be completely burned.

Stoichiometric Combustion – Stoichiometric combustion is the

theoretical point at which the fuel to air ratio is ideal so that there is complete combustion with
perfect efficiency. Although stoichiometric combustion is not possible, it is striven for in all
combustion processes to maximize profits.

Oil Flame Gas Flame

Fuel - Air Ratio – The fuel-air ratio is the proportion of fuel to air during
combustion. The optimal ratio (the stoichiometric ratio) occurs when all of the fuel and all of
the oxygen in the reaction chamber balance each other out perfectly. Rich burning is when
there is more fuel than air in the combustion chamber while lean burning occurs when there is
more air than fuel in the combustion chamber.

Fuels – There are many fuels currently used in combustion processes throughout the
world, the most common are: Coal, Oils (#2, # 4, and # 6), Diesel Oil, Gasoline, Natural Gas,
Propane, Coke Oven Gas, and Wood. Each fuel has different chemical characteristics
including, a unique C/H2 ratio, and calorific value, among others. The amount of combustion
air required to completely burn a specific fuel will depend on those characteristics especially
the C/H2 ratio. The higher the carbon in the fuel the more air is required to achieve complete
combustion. When monitoring the efficiency of a combustion process, it is important to know
the fuel being burned since this information will help not only determine a boiler’s optimal
working conditions but also maximize the boiler’s efficiency.

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 Effect of burning different fuels
- Coal – There are many varieties of coal being used in combustion processes around the
world; the most widely used are anthracite, bituminous, sub-bituminous, and lignite. When
burning coal a considerable amount of carbon dioxide is generated given the extremely high
levels of carbon in coal; since carbon requires more oxygen to burn, more combustion air is
needed to burn coal that other fossil fuels.

In addition to the carbon dioxide emissions, coal burning creates some other pollutants
including NOx, sulfur dioxide (SO2), sulfur trioxide (SO3), and particle emissions. Sulfur
dioxide chemically combines with water vapor in the air to produce a weak form of sulfuric
acid, one of the main causes of acid rain.

- Oil –Oil fuels are mostly a mixture of very heavy hydrocarbons, which have higher levels
of hydrogen than those found in coal. At the same time, oil contains less carbon than coal and
therefore requires less combustion air to achieve complete combustion. Therefore, burning oil
releases less carbon dioxide than burning coal, but more carbon dioxide than burning natural
gas. Most of the pollutants produced when burning coal are also a byproduct of burning oil.

- Natural Gas – Natural gas requires much less air in combustion because of its
relatively low amounts of carbon and high amounts of hydrogen. The burning of natural gas is
cleaner than the burning of oil and coal. When gas is burned with insufficient combustion air
some volatile hydrocarbons can be created, which could become a safety hazard; care should
be taken to avoid dangerous conditions.

The burning of natural gas produces less greenhouse gases, which are believed to be one of
the main sources for global warming. In equivalent amounts, burning natural gas produces
about 30% less carbon dioxide than burning oil and 45% less carbon dioxide than burning
coal.

In addition to the carbon dioxide emissions, gas burning creates NOx emissions, while the
emissions of sulfur dioxide (SO2) and Particles are negligible.

- Other Fuels – Other fuels including wood, diesel, gasoline, propane, butane, bio fuels
such as ethanol, etc. have there own combustion properties that will affect the combustion
efficiency and emissions of the process.

Biomass Dust Burner

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Air Flow
Maintain appropriate airflow during combustion is fundamental to ensure safe and complete
combustion. The total airflow includes combustion air, infiltration air, and dilution air.

• Combustion Air – Combustion air is the air that is used to actually burn the fuel.
Without combustion air, which is normally forced into the furnace, combustion is
impossible.
• Infiltration Air – Infiltration air is the outdoor air that is not deliberately in the boiler.
Sources of infiltration air maybe cracks or leaks.
• Dilution Air – Dilution air is the air that combines with the flue gases and lowers the
concentration of the emissions. There are two types of dilution air, natural and induced
(artificially created).

Time, Temperature and Turbulence

The combustion process is extremely dependent on time, temperature, and turbulence. Time
is important to combustion because if a fuel is not given a sufficient amount of time to burn, a
significant amount of energy will be left in the fuel. Too much time to burn on the other hand
will produce very long flames, which can be a function of bad mixing. The correct balance of
time and mixing will achieve complete combustion, minimize flame impingement (boiler
maintenance hazard), and improve combustion safety. In addition, a properly controlled
combustion process strives to provide the highest combustion efficiency while maintaining low
emissions of harmful gases.

Excess Air – In order to ensure complete combustion, combustion chambers are

fired with excess air. Excess air increases the
amount of oxygen and nitrogen entering the flame
increasing the probability that oxygen will find and
react with the fuel. The addition of excess air also
increases turbulence, which increases mixing in
the combustion chamber. Increased mixing of the
air and fuel will further improve combustion
efficiency by giving these components a better
chance to react. As more excess air enters the
combustion chamber, more of the fuel is burned
until it finally reaches complete combustion.
Greater amounts of excess air create lower
amounts of CO but also cause more heat losses.
Because the levels of both CO and heat losses
affect the combustion efficiency, it is important to
control and monitor excess air and the CO levels
to ensure the highest combustion efficiency
possible.

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- Calculating Excess Air
As discussed earlier, under stoichiometric (theoretical) conditions, the amount of oxygen in the
air used for combustion is completely depleted in the combustion process. Therefore, by
measuring the amount of oxygen in the exhaust gases leaving the stack we should be able to
calculate the percentage of excess air being supplied to the process.

The following formula is normally used to calculate the excess air:

%O2 measured
% Excess Air = x 100
20.9-%O2 measured

Typical Excess Air Values

Fuel Type of Furnace Excess Air
%
Pulverized Partially Water Cooled 15-40%
Coal Furnace
Coal Spreader stoker 30-60%
Coal Underfeed Stoker 20-50%
Fuel Oil Oil Burners, register type 5-10%
Fuel Oil Multifuel burners & flat-flame 10-20%
Natural Gas Register type Burners 5-10%

What is Draft?
The pressure of the gases in the stack must be carefully controlled to insure that all the gases
of combustion are removed from the combustion zone at the correct rate. This draft pressure
can be positive or negative depending of the boiler design; natural draft, balance draft, and
forced draft boilers are the most commonly used in the industry.

Monitoring draft is important not only to increase combustion efficiency, but also to maintain
safe conditions. Low draft pressures create build-ups of highly toxic gases such as carbon
monoxide and highly explosive gases. These build ups may take place in the combustion
chamber or may even be ventilated indoors creating the risk of injury and death. Conversely,
extremely high draft pressures can cause unwanted turbulences in the system preventing
complete combustion. Unwanted high draft pressures tend to damage the combustion
chamber and heat exchanger material by causing flame impingement.

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What is a Boiler?
A boiler is an enclosed vessel in which water is heated and circulated, either as hot water,
steam, or superheated steam for the purpose of heating, powering, and/or producing
electricity. The furnace of the boiler is where the fuel and air are introduced to combust; fuel/
air mixtures are normally introduced into the furnace by using burners, where the flames are
formed. The resulting hot gases travel through a series of heat exchangers, where heat is
transferred to the water flowing though them. The combustion gases are finally released to the
atmosphere via the stack of exhaust section of the boiler.

Different Boiler Types

• Utility Boilers

• Industrial Boilers

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 • Commercial Boilers

• Condensing Boilers
A condensing boiler preserves energy by using heat exchangers designed to remove
additional energy from the gases of combustion before leaving the stack. The flue gases
produced from condensing boilers are at a much lower temperatures than those of non
condensing boilers to the extent that the water vapor in the flue gases condenses, thus
releasing their latent heat and increasing efficiency of the boiler. Condensing boilers have
efficiencies of 95% or greater as compared to the normal 70%-80% for non-condensing
boilers.

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 Total Efficiency Concept
Total Efficiency Concept is an innovative method to maximize the overall performance of a
combustion process by measuring and controlling the different parameters corresponding to
the four most important areas of process operation, which are Combustion Efficiency,
Maintenance Efficiency, Safety, and Environmental Efficiency. By balancing all of the
requirements set forth in each of these areas, it is possible to operate under conditions that
allow for the most cost efficient and safe working environment, while still complying with the
environmental regulations applicable to the combustion process.

- Combustion Efficiency – It is important to strive for perfect combustion

efficiency, but many times perfect combustion efficiency is impractical due to the requirements
of maintenance efficiency, safety, environmental efficiency, and fuel efficiency.

- Maintenance Efficiency – Although a brand new burner or boiler may run

extremely efficiently with little or no problems, as time goes on, the same boiler slowly begins
to lower its efficiency. This is because as a boiler or burner gets older it becomes dirtier and
deteriorates. This affects the combustion process greatly and can seriously affect emissions
and safety. In most cases, as a burner wears down, more excess air will be needed to ensure
proper combustion and reduce CO emissions. To ensure that efficiency is maintained when a
boiler ages, it is important to closely monitor the amount of O2 needed to produce proper
combustion and CO emissions.

- Safety – Safety is a major concern when dealing with any form of combustion. The toxic
emissions that are released along with the risk of possible explosions can cause great harm.
Older parts that are used in the combustion process can create more dangerous conditions.
To ensure complete safety it is essential to monitor levels of CO and CxHy (hydrocarbons). It
is also necessary to check the amounts of oxygen needed to ensure low levels of CO and
hydrocarbons. CO is a toxic gas that can be lethal in higher concentrations. Hydrocarbons
contain unburned fuel, which can cause explosions and consequently, great injury.

- Environmental Efficiency – Toxic compounds such as sulfur dioxide, carbon

monoxide, nitrogen oxides, and particles are undesirable emissions that are frequently results
of the combustion of fossil fuels. These compounds cause smog, acid rain, and respiratory
problems. In effort to reduce these
pollutants federal and state laws Total Efficiency Concept
have been established under the
guidelines of the Clean Air Act and
the EPA (Environmental Protection
Agency). Combustion analysis aids SAFETY
in monitoring these toxic gases and
meeting the regulations set forth by Maintenance Efficiency
Combustion Efficiency
the government and EPA.
Environmental Efficiency

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 Combustion Efficiency
Heat Losses
It is vital to keep heat losses to a minimum so that efficiency is maximized and more energy is
conserved. Heat losses are inevitable, especially through the stack, but great amounts of heat
losses may be prevented with the proper measurement and control procedures.
Total heat losses are normally tallied by adding the stack losses, the skin/shell losses, and the
losses due to the un-burned fuel in ash collection hoppers.
Stack losses will combine the sensible heat losses or dry gas losses and the latent heat
losses. Sensible heat losses relate to the heat used to heat the combustion gases exiting the
stack; the higher the volume and temperature of the flue gases the larger the dry gas heat
losses. Latent heat losses are due to the water vapor in the flue gases (a large amount of
energy is used as water evaporates).
Skin/shell losses, which are the losses due to radiation from the boiler walls can be minimized
with proper insulation and in general are relatively small.

Concentration in Flue Gas

Efficiency

Highest
Efficiency
Operating
CO Region

Oxygen
Hydrocarbons

0 1 2 3 4 5 6
Flue Gas Oxygen (%)
Excess Fuel Excess Air

In coal and wood fired boilers, ash is normally a by-product of combustion that is collected in
hoppers or ash collection areas; it is imperative that the amount of carbon left in those ashes
is reduced to extremely small amounts given the resulting heat losses and the negative effects
that carbon has in disposing of those ashes.

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Measuring Combustion Efficiency
Although combustion efficiency can not be measured directly, it can be calculated by
identifying all of the losses that occur during combustion. It is important to consider all factors
including sensible heat losses, unburned gases, radiation, and unburned particles. In most
instances, the values of the skin losses and latent heat losses are not taken into account. The
following equation can be used to calculate combustion efficiency:

Total Heat losses

%Efficiency = 100% - x 100
Fuel heating value

Typical combustion process efficiencies:

Home fireplace: 10 - 40 %
Space heater: 50 - 80 %
Residential gas furnace with low efficiency atmospheric burner: 70 - 80 %
Oil burner heating system: 70 - 85 %
Gas powered boiler: 75 - 85 %
High efficiency gas or oil condensing furnace: 85 - 95 %

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 Emissions
Nitrogen Oxides: What is NOx?
Nitrogen Oxides (mainly NO and NO2), or NOx, is the generic term for a group of
highly reactive gases, which contain nitrogen and oxygen in various amounts and
chemical configurations. Most of the nitrogen oxides are colorless and odorless.
However, one very common pollutant, nitrogen dioxide (NO2) along with other
particles in the air can often be seen as a reddish-brown layer of smog over many
cities or heavily populated areas.

How is NOx Created?

Nitrogen oxides form when fuels are burned at high temperatures, as in a combustion
process. The primary sources of NOx are motor vehicles, electric utilities, and other
industrial, commercial, and residential sources like home boilers that burn fuels.

Causes for Concern about NOx

When NOx reacts with the oxygen in the air, the result is ground-level ozone. Ground-
level ozone has very negative effects on the Man-made sources of NOx
respiratory system, such as causing lung cancer, and on
agricultural production. NOx also reacts to form nitrate
particles, and acid aerosols, which all cause respiratory
problems. Nitric acid, formed when NOx reacts with water,
can cause acid rain and the deterioration of the quality of
water. Acidic gases along with airborne particles cause
visibility impairment and lower air quality.

Types of NOx
There are generally three primary sources of NOx: thermal NOx, fuel NOx, and prompt
NOx. Although all of these are formed through combustion processes, they all differ
slightly.

- Thermal NOx – Thermal NOx is formed at very high temperatures, usually

above 2200° F, and is a result of the oxidation of the diatomic nitrogen found in
combustion air. Thermal NOx is the most produced form of NOx created during
combustion. It is a function of the temperature and the residence time of the nitrogen
at that temperature; the higher the temperature of the flame the higher the formation of
thermal NOx.

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- Fuel NOx – Fuel NOx is formed when the nitrogen in fuels combines with the
excess oxygen in the air. Fuel NOx is a major problem in the burning of oil and coal as
it can make up as much as 50% of total emissions when combusting oil and as much
as 80% of total emissions when combusting coal.

- Prompt NOx – Prompt NOx is formed in the earliest stage of combustion.

Prompt NOx is made by the reaction of atmospheric nitrogen with radicals in the air.
The levels of prompt NOx are generally very low, so it is usually only of interest for the
most exacting emission targets.

NOx Reduction – NOx reduction is important in lowering the levels of NOx

being released into the atmosphere during combustion. When a form of NOx reduction
is used, it is important to have accurate measurements of not only NO but also NO2
because the ratio of NO to NO2 is changed. The traditional NO2 amounts as a percent
of total NOX (10% or 1.1 factor) cannot be used when NOx reducing methods are
used since it will lead to very significant errors in the calculations. When NOx
reduction methods are used, the values for NO2 can be greater than 50% of the total
NOx. It is important to measure True NOx (NO + NO2) when using NOx reducing
methods to maintain the integrity of the measurements.

NOx Reduction Methods

- Staged Combustion – In this NOx reducing method, only a portion of the
fuel is burned in the main chamber. All of the fuel is eventually burned, producing the
same amount of energy, but this method greatly reduces the temperature in the main
chamber. As temperatures decreased, the amount of thermal NOx is reduced.

- Catalytic Converters – These devices are utilized to lower the toxicity of the
emissions of many combustion processes
such as stationary engines, boilers,
heaters and internal combustion engines.
Catalytic converters break down nitrogen
oxides into separate nitrogen and oxygen
particles. Some catalytic converters are
also used to reduce the high CO levels
produced when reducing NOx, as low CO
levels are important to ensuring complete
combustion.

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- Flue Gas Recirculation – Flue Gas Recirculation, FGR, is a method of
NOx reduction that lowers the temperature of the flame, and therefore reduces
thermal NOx. A portion of the exhaust gas is re-circulated into the combustion
process, cooling the area. This process may be either external or induced, depending
on the method used to move the exhaust gas. Flue Gas Recirculation may also
minimize CO levels while reducing NOx levels.

- Reducing O2 levels – By reducing the amount of O2 that is available to react

with the nitrogen, NOx is reduced. This is achieved through the use of oxygen trim
controls. To minimize the O2 levels, a combustion analyzer is used to adjust the fuel
and air mixture. This method can reduce the level of NOx produced by up to 10%, but
it may increase the emissions of Carbon Monoxide (CO) very significantly. This
method is widely used in many processes such as in rich burn engines.

- Low NOx Burners – By changing the shape and formation of the flame by
using plates to control
airflow, a more elongated
flame is created in the
burner. The temperature is
decreased due to the
extended flame and
surface area, and the
lower temperature reduces
the amount of thermal
NOx. CO levels may be
elevated when using low
NOx burners. It is
important to monitor CO
and True NOx levels to better control Low NOx burners.

- Low Nitrogen Fuel Oil – The use of low nitrogen oils, which can contain up
to 15-20 times less fuel bound nitrogen than standard No. 2 oil, can greatly reduce
NOx emissions as fuel bound nitrogen can contribute anywhere between 20-50% of
total NOx levels.

- Water/Steam Injection – Water or steam injection reduces the amount of

NOx produced by lowering the temperature of the flame during combustion. The lower
temperature allows for the decrease of thermal NOx. This method can result in an
increase of 3-10% boiler efficiency losses and excess amounts of condensation may
form. Some advanced designs of steam injection technology do not have significant
impact on boiler efficiency.

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- SCR (Selective Catalytic Reduction) – SCR is a process where a
reductant, most often ammonia, is added to the flue. The reductant then reacts with
the NOx in the emissions and forms H20 and N2 (ambient nitrogen). This process may
take place at anywhere between 500ºF and 1200ºF depending on the catalyst used.
SCR may reduce NOx emissions by up to 90%. SCRs are mainly used in large
industrial and utility boilers.

- SNCR (Selective non-catalytic Reduction) – SNCR is a process

that involves a reductant, usually urea, being added to the top of the furnace and
going through a very long reaction at approximately 1400-1600 ºF. This method is
more difficult to apply to boilers due to the specific temperature needs, but it can
reduce NOx emissions by 70%.

Measuring NOx – The traditional way to find the value of NOx is to take a
sample of the gases exiting the stack and measure the level of NO. It is then
necessary to multiply this value by 1.1 to account for the additional NO2, as NOx is the
amount of NO added to the amount of NO2. This method of measurement is
acceptable depending upon the process for EPA reporting, but it is not the most
accurate way to measure the quantity as the ratio of NO to NO2 may vary. Measuring
both NO and NO2 (True NOx) is a much more accurate way to determine NOx than
measuring NO only.

O Reference
2 – The O2 reference is a standard that has been set to help
monitor NOx emissions. This standard calculates NOx emissions based on a set
oxygen level, to standardize the monitoring and reporting of total amounts of NOx
emitted. The O2 reference is effective in removing any attempts of diluting emissions,
which can make NOx levels appear lower than they actually are.

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Low NOx – Low NOx is typically defined as any value of NOx that is under 500
ppm. The most common values are between 9 and 300 ppm. It is most imperative to
measure True NOx (NO+NO2) when dealing with these low values to reduce the error
since a few ppm error accounts for a significant amount of the Total NOx.

True NOx – True NOx is a method of measuring the value of NOx emissions
without using any factors or presumptions. The concentrations of NO and NO2 are
measured separately with high accuracy sensors and the values are then added
together to find the True “Total” NOx value. It is especially important to measure True
NOx when dealing with low NOx emissions to reduce error.

True NOx vs. NOx

True NOx NOx
NO + NO2 (Measured) = NOx NO + NO2 (Calculated) =NOx

Measuring True NOx – There are specific instruments that quantify the
level of NO and NO2 in a sample. Before being able to measure NOx, it is important to
locate a sample that is representative of the emissions being released into the
atmosphere. Therefore, it is important to take the sample from the right location and to
be sure that there are no gas leaks.

Problems With Measuring NO2 – It is very important that when

taking NO2 measurements all precautions are taken to ensure that the integrity of the
data is kept. This can be achieved by making sure that condensation does not build
up, as NO2 is very water-soluble. If there is condensation, as much as 50% of the NO2
can dissolve out of the gas phase into the condensate, affecting the readings greatly.

Best Method for Measuring NO2

Given the solubility of the NO2 gas, it is imperative that the integrity of the gas sample
is maintained and all the water is eliminated under
a controlled environment minimizing any contact
with the sample gas; this can be achieved by
using a sampling system that includes the
following components:

- Heated Probe
- Heated Sample Line
- Chiller

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- Heated Probe – A heated probe allows for flue gas sampling without
condensation, which maximizes the accuracy of the measurement. With the heated
probe, the combustion gases cannot dissolve into the condensate. Therefore, the
sample remains representative of the emissions in the stack.

- Heated Sample Line – A heated sample line is used to keep the gas sample
above to dew point to prevent the absorption of gases into the water phase. This
provides conditions for more accurate measurements as gases are not lost into the
condensate.

- Chiller - An internal chiller dries the flue gas to avoid dilution of NO2 and SO2 into
the condensate. This allows for a sample that is most representative of the emissions
being released, as none of the gases are lost into the water phase.

Carbon Monoxide – Carbon monoxide, CO, is a highly toxic gas that can
form during incomplete combustion. CO is colorless, odorless, and extremely harmful
to the respiratory system. Overexposure to carbon monoxide
can cause headache, dizziness, and sometimes death. It is
of the greatest importance to measure CO emissions to
maintain safety. During combustion most of the carbon
burned reacts to form carbon dioxide, however some of the
carbon stays in the intermediary stage as carbon monoxide.
Excess levels of CO can be created due to incomplete
combustion, poor burner design, bad firing conditions, or a
leaky furnace. Motor vehicles, industries, and incomplete
combustion are the primary producers of manmade CO. Man-made Sources of CO

As discussed earlier,
some of the NOx
reduction methods used
in boilers bring with them
an increase of CO
emissions that may be
regulated by the federal,
state, and/or local
environmental regulatory
agencies.

This graph shows a

traditional correlation
between the NOx and
CO emissions at different
relative combustion
temperatures.
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Emissions of Sulfur Compounds
Sulfur Dioxide – Sulfur dioxide, SO , makes up about 95% of all of the
2
sulfur oxides that is released during combustion. Sources of Sulfur Dioxide
SO2 is a main cause of acid rain when it reacts with water
vapor. The EPA regulates the emissions of sulfur dioxide
through its Acid Rain Program. Most sulfur dioxide is
produced through the production of electricity and through
industrial processes.

Sulfur Trioxide – Sulfur trioxide, SO , is not 3

abundant in combustion but is problematic as it is a source
of corrosion in the cold areas of boilers. In most processes,
measuring SO3 emissions is not required, but SO3 should be eliminated to avoid
deterioration of parts.

Hydrogen Sulfide – Hydrogen Sulfide, H S, is a colorless, flammable,

2
and toxic gas that can form in combustion. Certain gases, such as natural gas, can
contain up to 28% of H2S. H2S can be formed through many processes such as
hydrodesulphurization.

Sulfur Oxide Reduction

- Low Sulfur Fuel – Low sulfur fuel reduces the initial amount of sulfur in the
system, therefore lowering the amount of SO2 being released into the atmosphere.

- Fuel Desulfurization – Fuel desulfurization involves removing some of the

sulfur from the fuel before it is burned. Fuel desulfurization is mainly used when coal is
the fuel being utilized.

- Flue Gas Desulfurization Systems – Flue gas desulfurization, FGD,

involves the use of scrubbers that chemically react with the SO2 to form other
compounds. There are two methods, regenerable FGD and non-regenerable FGD that
vary in how much and what kind of waste is produced. This method is very effective
and can reduce sulfur oxide emissions by up to 90%.

Best Method to Measuring SO2 - Given the solubility of the

SO2 gas, it is imperative that the integrity of the gas sample is maintained and all the
water is eliminated under a controlled environment minimizing any contact with the
sample gas; this can be achieved by using a similar sampling system as the one
discussed to measuring NO2, which should include a Heated Probe, Heated Sample
Line, and Chiller.
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Carbon Dioxide
Carbon Dioxide, CO2, is always a byproduct of combustion. The level of carbon
dioxide released is dependent upon the type of fuel used and
the combustion process. Although naturally produced through
respiration and other organic processes, carbon dioxide is a
green house gas and thus advances global warming. The
primary sources of manmade carbon dioxide are motor
vehicles, industries, and electric utilities.

Man-made Sources of CO2

Calculating vs. Measuring CO2
Calculating CO2 (Actual) is a function of the stoichiometric maximum amount of CO2
(Maximum) that can be released by a given fuel and the O2 concentration, as shown in
the following equation:

(20.9 - %O2 measured)

% CO2 (Actual) = CO2 (maximum) x
20.9

Most combustion processes use fuels, or a combination of different fuels, that have
variable amounts of carbon, making the calculation of the CO2 max extremely difficult.
With the CO2 max constantly changing, it is impossible to accurately calculate CO2
based on the oxygen levels in the flue gases. In those situations, monitoring the CO2
levels is imperative.

Measuring CO2 is normally achieved by using non-dispersive infrared (NDIR)

technology.

Mass Emissions and Gas Velocity

Mass emissions are a calculation of the total amounts of gases being released during
the combustion process. Instead of finding concentrations of gases in ppm (parts per
million volume), mass emissions indicate the total amount of emissions being released
in units such as LB/H (pounds per hour) or tons per year. Mass emissions can be
found by knowing the concentration of the gases being released, the amount of fuel
that is burned, and the mass of the fuel. To know the mass of the fuel however, it is
necessary to know the exact chemical formula for the fuel. Another way to calculate
mass emissions is based on the velocity of the gases being sent out of the stack, the
cross sectional area of the stack, and the concentration of the gases being sent out of
the stack.

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What is Combustion Analysis?
During combustion analysis, the quantities and concentrations of gases are measured
precisely in order to maintain the safest and most efficient conditions possible. The first step in
combustion analysis is the measurement of gas temperature, flue gas concentrations, as well
as draft pressures and soot levels. These measurements are made by inserting a probe into
the exhaust flue and taking a sample. A carefully positioned thermocouple measures the
highest exhaust gas temperature. The draft pressure is calculated by finding the difference in
pressure between the inside and the outside of the exhaust flue. The concentrations of the
undesired combustion gases can be measured using different kinds of methods such as the
electrochemical and non-dispersive infrared sensors.

O2 and CO2 Depending on Excess Air

Gas Analyzers- Gas Analyzers are the ideal tool to monitor gas emissions
and therefore maintain the best Total Efficiency, which, as we discussed, is a balance
between the combustion efficiency, environmental efficiency, and a safe working
environment. In addition, Combustion Analyzers/Gas Analyzers can help identify
maintenance problems as the boilers deteriorate with time.

Many gas analyzers measure and calculate a wide array of parameters including:

Combustion Efficiency Oxygen CO2 Flue Gas Temperature

Ambient Temperature Draft CO Excess Air
True NOx (NO+NO2) SO2 H2S Hydrocarbons (CxHy)
Gas Velocity Mass Emissions

Analyzers with greater resolution and accuracy help to meet the standards set by the
EPA.

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Using Gas Analyzers
How to Take Gas Samples- The first step in taking a gas sample
is to make a small hole in the flue pipe that is sized to fit the probe closely, so air leaks
are minimized. To get the most accurate measurement, the gas-sampling probe must
be placed prior to any draft damper or diverter, so that the gases are not diluted, and
as close to the equipment breach as possible so the gases have not cooled in the flue.
If there is a stack economizer or similar device, the measurement should be taken just
downstream of the installed device. It is important to note that in order to have the
most accurate, representative measurements, there should be no gas leaks.

Making Temperature Measurements-

In order to make temperature measurements, the
thermocouple probe is placed at the point of highest
exhaust gas temperature at the base of the flue and
toward the center for small ducts. If the stack gas
temperature is underestimated, the operating efficiency
will be overstated.

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Taking O2 Measurements - After calibrating the instrument used to
measure O2 levels, it is necessary to put the analyzer where the emissions are
released, usually the stack. Start the combustion process and look for stability in the
oxygen readings for anywhere between one to three minutes.

Soot/Smoke/Particulate Measurements-
Soot is most commonly measured during equipment tune-up and maintenance by
extracting a sample of the exhaust gases using a manual
sampling pump or a special soot probe. The sample is taken
from the same location as the stack temperature
measurements. These measurements may be made with smoke
pumps or with probes that have filters.

Keeping Records- Documenting your measurements is fundamental to

insure short and long term understanding of your combustion
process. As the boiler changes with time, it is important to
compare today’s measurements to past data to identify
components in the combustion system that justify replacing to
maximize the combustion efficiency of the process.

Gas analyzers with built-in printers and/or data logging

capabilities provide for the best methods of data storing and
record keeping.

Summary- Every combustion process has its own independent identity and
behavior. Extrapolating results from one boiler to another will not provide for the best
operating results. For that reason, it is important to measure the many parameters discussed
in this paper, in order to set and operate the combustion process at the point where the best
balance between the Combustion Efficiency, Maintenance Efficiency, Safety, and
Environmental Efficiency is reached. At that point, you will have a boiler operating at its best
Total Efficiency.

SAFETY
Maintenance Efficiency
Combustion Efficiency
Environmental Efficiency

Total Efficiency Concept 22