Manual M0001 rev01 03/00

AN INTRODUCTION TO COMBUSTION
CHAPTER 1
A DEFINITION OF COMBUSTION
Combustion is the process of oxidation of molecules of combustible combustion of carbon is accompanied by the formation of carbon
substances that occurs readily at high temperatures with the release monoxide, a very toxic gas:
of energy. It is accompanied by that phenomenon which is called
2C + O2 = 2CO + heat
"flame" and by the generation of "heat energy".
The combination of carbon with oxygen forms carbon dioxide, a non In this phase the amount of heat released during the process is less
toxic gas. This process liberates heat and is described as follows: than the amount of heat which would be released during a complete
combustion. However the incomplete combustion or reducing com-
C + O2 = CO2 + heat
bustion is sometimes necessary for some special heat industrial
Similarly, hydrogen combines with oxygen and form water vapour processes. However, such conditions must be avoided as far as possi-
(steam) liberating heat. The equation is: ble, in all other circumstances.
Viceversa if we add excess oxygen to the mixture, the mixture is said
2H2 + O2 = 2H2O + heat
to be "fuel lean" or just "lean" and the combustion is said to be oxi-
It is important to observe that the fuel-air ratio is specific and fixed. dizing. The flame in this case is blue and very short.
As a matter of fact the amount of oxygen and fuel in the mixture As we will explain better later in this chapter, air, which is made up of
are in perfect or "stoichiometric" proportions when such substances oxygen and nitrogen, is the oxidizer which is usually used.
allow for complete oxidation of the fuel without any residual of oxy- If we add "excess air", that is a more than stoichiometric quantity of
gen. oxygen, all the nitrogen and part of the oxygen which do not react
With excess fuel or oxygen deficiency there would be a rich mixture with the fuel do not take part in the oxidation process.
and a reducing flame which is long, yellowish and smoky. Such com- Obviously they absorb a certain quantity of the heat released during
bustion is also called "incomplete combination", since even though combustion, hence the final heat energy is distributed to a greater
some particles are completely oxidized, the remaining ones do not volume of gas and the heat level is lower (lower flame temperature).
get sufficient oxygen to react completely. The partial or incomplete

COMMERCIAL GASEOUS FUELS

These gases are characterized by variables which depend on the features of some of the most widespread gases.
quantity of each chemical substance. Here are some fundamental

LOWER HEATING VALUE FLAME PROPAGATION RATE

(TYPE OF) GAS MAIN COMPOUNDS (LHV: kCal/m³) DENSITY (m/s)
Town gas CO + H2 4.000 ÷ 4.500 0,56 3
Mixed gas CO + H2 + CH4 or other 4.500 ÷ 6.000 0,60 1,5
Natural gas CH4 8.500 0,64 0,6
Mixture of propane and air C3 H8 + air 6.000 1,20 0,7
Propane C3 H8 22.000 1,52 0,7
Butane C4 H10 28.000 2,00 0,7
Mixture of propane and butane C3 H8 + C4 H10 26.000 1,75 0,7

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 Manual M0001 rev01 03/00

STOICHIOMETRIC GAS COMBUSTION

For simplicity, we assume throughout this section, that natural gas In the chemistry of combustion nitrogen molecules are inert hence do
only contains methane (CH4). Now the combustion of methane occurs not enter the reaction, yet they absorb some of the heat.
as follows: In short, to burn a m3 of natural gas completely, 10 m3 of air are
necessary.
CH4 + 2O2 = CO2 + 2H2O + heat
that is The combustion of propane, on the other hand, is defined by the fol-
methane + oxygen = carbon dioxide + water vapour + heat lowing equation:
C3H8 + 5O2 + 20N2 = 3CO2 + 4H2O + 20N2 + heat
As both the reactants and products of the reaction are in a gaseous
phase, we can say that a m3 of methane (natural gas) needs two m3 This confirms that one m3 of propane needs 25 m3 of air to complete
of oxygen to complete combustion. It will moreover produce a m3 of its combustion.
carbon dioxide and two m3 of water vapour. From the reactions of propane and methane mentioned above, we
The combination of pure oxygen and methane is only used in partic- can deduct that to release 8,500 kCal of heat using 1 m3 of natural
ular industrial applications, that is when high flame temperatures are gas (whose lower heating value is equal to 8,500 kCal/m3) 10 m3 of
needed, such as in blowpipes. However most industrial combustion air are necessary. Whereas to release 21,000 kCal, using 1 m3 of
applications make use of air, not just pure oxygen, as a comburent. propane, 25 m3 of air are necessary.
For simplicity, we assume that the simplified composition of air is Given these equations, it is clear that both methane and propane fol-
20% O2 and 80% N2. Now as 10 m3 of air per m3 of methane are low the same law by which 1.18 Normal volume of combustion air is
necessary, we will have: necessary to liberate 1,000 kCal. To a certain extent we can say that
all commercial combustible gases follow this law. We may even say
that to some extent it is valid not only for gaseous fuels but also for
10 AIR = 2O2 + 8N2 liquid and solid ones.
Therefore the chemical reaction of methane with air is:
CH4 + 2O2 + 8N2 = CO2 + 2H2O + 8N2 + heat

QUANTITY OF AIR REQUIRED FOR INDUSTRIAL COMBUSTION

The heat output of burner systems, in particular industrial ones, combustion at some fixed heat potential is known, that system will
depends on the quantity of combustion air they manage to mix with be able to work with no matter what commercial gaseous fuel to pro-
gas. Hence the maximum gas capacity in a combustion system is duce the same quantity of heat in perfect combustion conditions. The
determined by the maximum quantity of air the system can process. only change to make when shifting from one fuel to another for
Catalogues of burners usually reports the power rating in kCal/h equal heat capacities concerns the amount of gas, bearing in mind
(thousands of calories/hour). At the designing stage and at the the calorific capacity of each gas per m3.
moment of choosing which burner or mixer to buy, not only the For instance, a system having some heat output of 10,000 kCal/h
power rating and gas capacity but also and particularly the quantity needs 118 Nm3 of air in order to attain perfect combustion. A lower
of primary and secondary air must be taken into account as well as quantity of air would result in a reducing combustion.
the capacity of the system to process such quantities. If the capacity of fuel was increased in order to deliver 120,000
As the quantity of air necessary for combustion amounts to 1.18 Nm3 kCal/h (which is easy to do by increasing the nozzle diameter of the
per 1,000 kCal produced, no matter what gas is used, all industrial burner) we would have imperfect combustion if we didn't increase
combustion systems complying with this principle, may be considered the amount of air in the mixture proportionally. The only way to
as "universal" if they are capable of working with any type of always obtain perfect combustion conditions, when an increase in the
gaseous fuels. heat rating is desired, is to increase the gas and air capacity at the
In other words, once the quantity of air necessary to obtain good same time.

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 Manual M0001 rev01 03/00

PRIMARY AIR
Most gas-burner appliances premix some air with fuel gas before it For instance, if a natural-gas burner operates with 80% primary air
burns. This primary air is less than the stoichiometric air required for it means that it is capable of mixing 8 m3 of air per m3 of natural gas
complete combustion. The remaining air which is mixed with gas before combustion starts. The remaining air, 2 m3 of air per m3 of
before ignition is called "primary air". The air mixed after ignition is natural gas, will be added after ignition and is referred to as "sec-
called "secondary air". The quantity of primary air in the mixture is ondary air".
usually expressed as a percentage of the total theoretical air Many features relating to flames, depend on the amount of primary
required for combustion; the term referring to all this process is "aer- air a combustion system can process. The less the primary air, the
ation". softer and longer the flame.

THE MECHANISM OF COMBUSTION

The chemical equations relating to natural gas mentioned above in 650° C and over the free carbon and hydrogen atoms start looking
this chapter quantify the air and natural gas necessary for theoreti- for oxygen: combustion has just started. The chemical reaction of
cal combustion as well as the amount of the final products of such oxidation of the hydrogen and carbon atoms results in the physical
combustion. However these equations do not explain the physical phenomenon called flame and heat. The latter is often used in ther-
and chemical aspects of combustion. mal processes.
Concerning the nature of the gaseous state, it is known that the mol- Combustion occus generally by reaction chains. For instance, at 650
ecules of a gas are in rapid motion, or "thermally agitated" and col- °C, a high-energy collision breaks up a molecule into atoms or "free
lide frequently with each other. The higher the temperature the radicals"; such a molecular fragment reacts with a molecule of fuel
faster the motion of the molecules; viceversa the lower the tempera- gas, which thereby becomes capable of reacting with an oxygen mol-
ture the slower the motion. ecule; in the latter process, an atom or free radical is again released,
In a perfect mixture of oxygen and natural gas (methane) there are thus continuing the chain. Chains are broken when two atoms com-
always 2 oxygen molecules per methane molecule. Methane contains bine to form a stable bond. The speed at which this chain reaction
4 hydrogen atoms that are linked by one chemical bond to the car- takes place determines the "flame propagation rate" of a mixture.
bon atom. The oxygen molecules contain 2 oxygen atoms linked one The amount of heat liberated during the combustion of a mixture of
to the other by two bonds. pure oxygen and natural gas is sufficient to increase the flame tem-
perature to some 2,850 °C.
H O O O H H As we have already said, in industrial combustion applications, apart
H C H + C + O O + heat from very particular circumstances, oxygen is taken from the air of
H O
H H the atmosphere.
O O

FM001I01
During the combustion reaction, the nitrogen in the air absorbs a cer-
tain quantity of the heat which has been released. This phenomenon
In order to start combustion, it is necessary that the hydrogen atoms obviously results in a slowed-down chain reaction, hence the transfer
split from the carbon atoms and that oxygen breaks the bonds which of heat from one molecule to the other is slowed-down and the flame
link them together so that they are free to react with carbon and propagation rate is also slowed-down. Nitrogen acts as a diluent of
hydrogen. the combustion reaction.
The splitting of the hydrogen, carbon and oxygen atoms is the result The maximum theoretical temperature which can be obtained in the
of the collision of the molecules with each other. At ordinary temper- flame produced by methane combustion with air amounts to some
atures the collision is so weak that atoms are not able to break the 1,930 °C; in reality the maximum temperature which can be
bonds. reached in a methane-air industrial oven is about 1,800 °C. The heat
At high temperatures, collisions involving high energy become more radiated by the flame as well as other losses prevent the tempera-
frequent, and at 650 °C this lead to breakup and chemical combina- ture from reaching the maximum theoretical temperature.
tion of the colliding molecules. Higher combustion temperatures may be reached by mixing oxygen
Methane oxidation is impossible below 650 °C, on the other hand at to combustion air. This results in proportionally reduced quantities of

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 Manual M0001 rev01 03/00

nitrogen in the reaction and therefore in a weaker diluting effect. ture of the molecules to the ignition point. For instance, by preheat-
Higher temperatures may also be obtained by preheating combus- ing a mixture of air and natural gas to 260°C, an increase in the
tion air or air and fuel gas at the same time so as to save a certain flame temperature of some 100 °C may be obtained.
amount of calorific energy which is necessary to raise the tempera-

INCOMPLETE COMBUSTION - FLAMELOSS

Scientific research on the mechanisms of combustion have shown reach the ignition temperature, combustion either stops altogether or
that the chemical process of combustion go through intermediate stops in those areas where it touches the cooling medium. This would
products before producing the final products of maximum oxidation, take place even if the fuel and comburent were in a stoichiometric
which are carbon dioxide and water vapour. The main intermediate proportion.
products of combustion being carbon monoxide and aldehydes. In practice the hazard of incomplete combustion or flameloss only
During the chain reaction, started by the colliding molecules, allow- exists in low-temperature industrial applications, as for instance in
ing for the oxidation of atoms with the subsequent heat release, combustion systems working with recirculation air as the latter may
these intermediate products are formed. The latter are readily trans- act as a cooling medium. Long flames, which are not protected and
formed through oxidation as they get in contact with oxygen in car- hence subject to important cold air current may be disturbed by the
bon dioxide and water vapour molecules. current particularly on the outer surface. Though in the inner part of
Once started, the combustion reaction must go on at a temperature the flame, combustion pursues at a temperature ranging from 1,000
higher than the minimum ignition temperature. If at any moment, in to 1,700 °C, it may happen that the mixture licking the outer cold
the flame mass, the burning mixture is cooled down to a level lower air, blows-by though still unburned.
than the minimum ignition temperature, combustion stops and the Incomplete combustion due to a cooling medium may stop the reac-
flame extinguishes. tion of the fuel with the comburent at the intermediate stages. In
When plunging any cooling or refrigerating medium in the mixture these conditions it is easy, for some particularly sensitive people to
during combustion, this medium absorbs heat and subtracts it to the smell pungent aldehydes.
combustion process. If the cooling medium absorbs enough heat to Should this happen it is advisable to check the system, look for the
avoid the molecules of the compounds in the reaction in contact to causes and readily solve the problem.

FLAME PROPAGATION RATE

Mixtures operating with 100% primary air, that is needing no addi- needs some time to mix with fuel gas.
tional air to complete combustion, even before reaching the point The flame propagation rate is proportional to the quantity of pre-
where combustion starts, have the maximum flame propagation rate mixed air.
therefore for equal gas capacity they produce the shortest flames. In some particular circumstances the flame propagation rate incrases
Rich mixtures, which on the contrary need some secondary air to with an increase in the speed of air-gas mixing.
complete combustion, will produce longer flames as secondary air

NOTE: Based on the company’s policy aimed at a continuous improvement on product quality, ESA-PYRONICS reserves the right to
bring changes to the technical characteristics of this device without previous notice. Our catalog updated to the latest version is
available on our web site www.esapyronics.com and it is possible to download modified documents
WARNING: When operating, this combustion system can be dangerous and cause harm to persons or damage to equipment. Every
burner must be provided with a protection device that monitors the combustion. The installation, adjustment and maintenance 4/4
operations should only be performed by trained and qualified personnel.