1-2 Hydrocarbons Ignition and Flammability

TECHNICAL SAFETY ENGINEERING (TSE)
FOUNDATION 101
1.2 HYDROCARBON (HC)

IGNITION AND
FLAMMABILITY
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LEARNING OBJECTIVES
At the end of this module, you will be able to:

Describe basic flammability properties.
Define parameters for hydrocarbon gases, vapours and liquids.
Recall hydrocarbon fluid classification according to National Fire
Protection Association (NFPA) 30 and/or IP15.
Analyse, develop and apply flammability diagrams.
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CONTENTS
Definitions and parameters

Flammable atmospheres
Flammability diagrams
Summary

1.0
DEFINITIONS AND PARAMETERS
DEFINITIONS AND PARAMETERS
Flammability Limits:
 Lower Flammability Limit (LFL): Just sufficient flammable material present in
the air to be flammable
 Upper Flammability Limit (UFL): The maximum amount of flammable
material present in the air to be flammable
In safety engineering, we also use Lower and Upper Explosive Limits (LEL and
LFL) interchangeably with LFL and UFL. Flammability and explosive limits are
quantitatively different. (In an explosive mixture, the fuel oxidiser mixture is
closer to stoichiometric proportion.) However, vapour clouds are turbulent,
with varying fuel or oxidiser proportions. As a result, the difference is
immaterial in safety engineering.
Maximum Safe Oxygen Concentration (MSOC): The oxygen concentration in
a flammable mixture below which combustion is not possible. MSOC is also
known as Limiting Oxygen Concentration (LOC) or Minimum Oxygen
Concentration (MOC).

DEFINITIONS AND PARAMETERS (CONT.)
Auto-Ignition Temperature (AIT):

The temperature at which there
is sufficient energy in the
environment to allow the self-
ignition of a flammable fluid in
the air
Minimum Ignition Energy (MIE):
The minimum spark energy
required to ignite an optimum
concentration of flammable
material using a capacitative
spark under ideal conditions
The auto-ignition temperatures of

hydrocarbons at atmospheric pressure

Flash Point (FP): The temperature of a liquid at which sufficient vapour is

generated in the air that can be ignited by an open ignition source (flame,
spark)
 Low Flash Product: Hydrocarbon with FP < 38°C (100°F)
 High Flash Product: Hydrocarbon with FP > 38°C (100°F)
For safe handling and operation, hydrocarbon fluids are typically classified
according to their FPs. Within Shell, the following two main systems are used
(although local regulations may require other or additional classification).
 The NFPA in North America
 The Institute of Petroleum 15 (IP15) outside North America
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Month2014
2010 7
Fluid or FP IP15 or NFPA 30 IP15 NFPA 30
LPG 0
FP < 21°C or 23°C (73°F) I IA or IB*
21°C or 23°C (73°F) < FP < 38°C (100°F) II IC
38°C (100°F) < FP < 55°C or 60°C (140°F) II II
55°C or 60°C (140°F) < FP < 100°C or 93°C (200°F) III IIIA
FP > 100°C or 93°C (200°F) NC IIIB

2.0
FLAMMABLE ATMOSPHERES
Flammability Limits
Ignitibility
Liquid Flammability
Typical Flammability Data
FLAMMABLE ATMOSPHERES
Flammable atmospheres are formed when flammable materials mix with air
or oxygen.
Flammable materials include gases, vapours (gases in contact with their
liquids), suspended droplets (that is, mists or sprays), or suspended dusts and
powders.
The susceptibility of an atmosphere to ignitions can be characterised by its
flammability and ignitability.
 Flammability specifies whether or not the atmosphere can burn.
 Ignitability specifies how readily the atmosphere is ignited.
The upper (rich) and lower (lean) flammability limits define the range of
concentrations of a gas or vapour in the air that can be ignited and sustain
combustion. Any composition outside of these limits cannot be ignited.

FLAMMABILITY LIMITS
For flammable gases or vapours, UFL and LFL are normally expressed as
percentages by volume* of the flammable component in the gas mixture.
For hydrocarbon gases and vapours, the flammable range is typically from
0.7%v to 10%v, although it is wider than this for light hydrocarbons such as
ethane, ethylene and particularly acetylene. Hydrogen has an especially wide
flammable range of 4%v to 75%v.
When more than one type of flammable material is present in the
atmosphere, it may be flammable even when each component is present in a
concentration below its LFL. This occurs with hybrid mixtures of dust and
flammable vapour.
*For dusts or droplet suspensions, flammability limits are expressed as the

mass of flammable material per unit volume.

IGNITIBILITY
The ignitability of a flammable atmosphere is related to MIE.

Each fuel (air mixture) has a different MIE.
A flammable mixture that is close to either the upper or lower limits
may require a higher amount of energy than the MIE to ignite.
A fuel (air mixture) can ignite without the introduction of an ignition
source.

IGNITIBILITY (CONT.)
The minimum auto-ignition temperature is the lowest temperature at

which fuel vapours spontaneously ignite.
Hydrocarbons that have been heated can ignite if they are exposed to
air.
Ignitability limits of flammability for methane or air

mixtures at atmospheric pressure at 25ºC.
LIQUID FLAMMABILITY
Liquids give off vapours at a rate that increases with temperature (as per the
vapour pressure curve). The ability to give off vapours and the rate at which
this occurs defines the volatility of the liquid.
Except for a few reactive or unstable substances, liquids do not ignite. The
vapours given off from the surface of the liquids ignite.
FP: The FP of a liquid is defined as the lowest temperature at which that liquid
gives off vapours at a sufficient rate to support a momentary flame across its
surface. The FP temperature corresponds with the LFL concentration.
 At temperatures below the FP (= LFL temperature), the saturated vapour is
too dilute (too lean) to be flammable. At temperatures above the UFL
temperature, it is too concentrated (over-rich).
 Liquids with low vapour pressures typically have high FPs. High vapour
pressure liquids typically have low FPs.

LIQUID FLAMMABILITY (CONT.)
This typical diagram is Vapour Pressure/Concentration in Air

in particularly relevant
to storage systems, P/%
LIQUID
vapor pressure
curve VAPOUR
loading and transport
and SorU and SorD UEL
conditions.
At FP temperature, the FLAMMABLE
concentration in the
air reaches LEL. LEL
Further heating leads

to a higher flashpoint T T uel AIT
concentration in the T lel Temperature
air (UEL) and the Fluid P-T diagram (vapour pressure curve)
atmosphere becomes
too rich.

The FP is an empirical measurement rather than a fundamental physical

parameter. It should only be used as an approximate reference because the
liquid may behave differently in the field than in laboratory tests designed to
determine FPs.
Explosive atmospheres can exist at temperatures below the FP. Therefore, it is
assumed that a flammable atmosphere exists when the temperature of the liquid
is 5–15°C (59°F) below the specified FP. For instance, kerosene has a FP of
about 38°C (100°F), but its flammable range could start as low as 23°C (38–
15).
A very fine mist from a hydrocarbon liquid may act as a pure gaseous
substance, also called an aerosol. These aerosols may form an explosive
mixture at temperatures that are far below the liquid’s FP. The droplets in the
mist have to vapourise, but because of the small volume of the drops, the energy
required to do this is lowered significantly. Therefore, operations such as splash
filling that tend to form sprays should be avoided.
Above the UFL, a saturated vapour is over-rich (that is, non-flammable).

However, under certain (operating) conditions, an unsaturated vapour may
be in the flammable range.
 It can take a long time to establish saturation (possibly several days in a
large storage tank).
 In the absence of mixing, the vapour concentration may decrease with
distance from the liquid surface so that, far from the liquid, the vapour is
not saturated.
 The vapour concentration may be reduced by mixing with air. This occurs at
openings such as vents or hatches or during emptying.
For these reasons, it is often necessary to assume that an atmosphere could be
flammable even when the saturated vapour-air mixture is over-rich.

TYPICAL FLAMMABILITY DATA
Component FP C LEL % UEL % AIT0C MSOC %

Hydrogen Gas 4 75 572 5
Gas
Methane 5.3 15 515 12
(-222)
Propane -104 2.2 9.5 493 11.5
Butane -60 1.9 8.5 462 12
Ethylene Gas 3.1 32 450 10
Toluene 4.4 1.4 6.7 480 9.5
Benzene -11 1.4 7.1 498 11.4
EO -20 3 100 429 -
Gasoline <-20 1.4 7.6 ~250 12
Kerosene 38 0.7 5 ~250 10
Diesel 65 0.6 6 260 -
Crude -20 1.3 6 282 -
3.0
FLAMMABILITY DIAGRAMS
Flammability Diagrams
Reading and Understanding Flammability Diagrams
Effect of Temperature and Pressure
Flammability Envelopes for Gas Mixtures
Application of a Ternary Diagram (Example)
Conclusion
Other Relevant Hydrocarbon Considerations
FLAMMABILITY DIAGRAMS
Flammability is conveniently represented on triangular Ternary diagrams. These

diagrams show the regimes of flammability in mixtures of combustibles, oxidant (air
or O2) and an inert gas (typically N2 or CO2).
Each corner represents a pure

Hydrocarbon
Hydrocarbon in Air line

component.
All points in the triangle
represent O2, N2 and HC UEL or
Non-Flammable
composition. UFL (in O2)
Outside the colored range, the

mixtures are not flammable. SC Flammable UEL or
UFL (in Air)
SC stands for Stoichiometric LEL or

Combustion point. LFL (in
O2) LEL or MSOC
MSOC is also known as LOC or LFL (in
Air)
MOC. Oxygen 80% N2/20% O2 Nitrogen
Typical Flammability Diagram: O2, N2 and HC Mixtures

READING FLAMMABILITY DIAGRAMS

UNDERSTANDING FLAMMABILITY DIAGRAMS
In most cases, the flammability envelope can be approximated by drawing

straight lines between three key mixing points.
1. The upper limit in air or oxygen
2. The lower limit
3. The nose
The nose usually corresponds to the minimum oxygen level at which the
mixture will burn (MSOC). Conversely, the nose can be viewed as
corresponding to the minimum amount of inert gas that must be added to
make the mixture non-flammable.
As triangular diagrams are not commonplace, the easiest way to understand
them is to briefly go through three basic steps in their construction, which we
will do through the next three slides.
Note: The following three slides are taken from Wikipedia.
http://en.wikipedia.org/wiki/Flammability_diagram.
UNDERSTANDING FLAMMABILITY DIAGRAMS: STEP 1
The following Ternary diagram shows all possible mixtures of

methane, oxygen and nitrogen.
Air is a mixture of about 21 vol%

oxygen, and 79 vol% inerts CH4
(nitrogen).
Any mixture of methane and air will
therefore lie on the straight line
between pure methane and pure
air. This is shown as the blue air-
line.
The upper (UEL =15 vol%) and
lower flammability limits (LEL = 5.3
O2 N2
vol%) of methane in air are located
on this line, as shown.

The stoichiometric combustion of methane is CH4 + 2O2 -> CO2 + 2H2O.

The stoichiometric concentration of methane in oxygen is therefore 1 or
(1+2), which is 33%.
CH4
 Any stoichiometric mixture of
methane and oxygen will lie on the
straight line between pure nitrogen
and 0% methane and 33% methane
and 67% oxygen. This is shown as
the red stoichiometric line in the
diagram. This line represents the
optimal concentrations for
combustion to occur.
 The upper and lower flammability
O2 N2
limits of methane in oxygen are
located on the methane axis, as
shown.
The envelope passes through the upper and lower flammability limits of
methane in oxygen and in air, as shown in the diagram below.
The nose of the envelope defines the

MSOC, also known as LOC. This is CH4
an experimentally determined
value.
The actual envelope defining the
flammability zone can only be
determined based on experiments.
However, drawing straight lines
provides a good approximation.
O2 N2

EFFECT OF TEMPERATURE AND PRESSURE
Temperature influences flammability Pressure influences flammability limits.

limits. A higher temperature results in The LFL decreases slightly when pressure
lower LFL and higher UFL, leading to an increases. However, the UFL can increase
expansion of the flammability envelope. substantially as pressure increases.
Hydrocarbon
Hydrocarbon
Flammable Flammable
LEL or
LFL (in
O2)
Oxygen Nitrogen Oxygen Nitrogen
Effect of Temperature Increase Effect of Pressure Increase

FLAMMABILITY ENVELOPES FOR GAS MIXTURES
For combustible mixtures, the UFL or LFL in air (or O2) and the Nose point on the
Ternary diagram can be estimated from individual component data based on Le
Chatelier's Law.
In Le Chatelier’s Law,
L = the upper or lower flammability limit (volume percent basis) in the mixture
L1, L2, .. Ln = the individual component limits
p1, p2, .. pn = the percent of each individual component in the mixture (free from air and inerts/diluents)
APPLICATION OF A TERNARY DIAGRAM (EXAMPLE)
Scenario:
An operator contacts you on a Friday afternoon. The flare
gas in the flare system contains 8 vol% O2. He asks if this
could result in a process safety risk. No emergency
procedure is available.
You know that:

Flare gas could be flammable in combination with
oxygen as it primarily contains hydrocarbons and
hydrogen. Also below ignition sources are present:
The following ignition sources are present in the air.
 Pyrophoric FeS in the flare system (H2S in flare gas)
 Flare stack tip pilot burners
What would you do? Reflect on this situation before moving on to the next slide.
(CONT.)
You can:
Try to eliminate the oxygen source first.
However, the root cause is found to be a
leak in the refinery vacuum system, which
routes the uncondensables (including air
ingress) to the flare system. No alternative
routing is available. Leak repair will take
at least 24 hours.
The next step is to determine if a
flammable mixture is present in the flare
system. For that purpose, a Ternary
diagram could be very helpful. However,
you do not have one available for the
flare gas mixture, and you do not know
the average flare.
We learnt earlier about the Nose, which defines the MSOC. Can you use that
information to manage this situation?

(CONT.)
You can find the following typical MSOC data (also called the LOC) from a
quick literature search.
Hydrogen: 5 vol%
Hydrocarbons: 11 vol% to12 vol%
[3] Perry 8.ed:23-9

(CONT.)
Based on these numbers, you can assume that a flammable mixture could
exist in the flare system if enough hydrogen is present in the flare gas. The
presence of hydrogen in the flare gas can result in deflagration and/or
explosion when ignited. This is, therefore, an unsafe situation.
You can calculate the MSOC of the flare gas mixture using the equation
based on Le Chatelier's Law. However, to do this, you need the current flare
gas composition. Sampling, including composition analysis, takes at least
three hours, and in the meantime, the oxygen concentration has increased to
15%.
The vacuum system has connections to the nitrogen and the natural gas grid.
Is there something you can do with one or both of these connections?

(CONT.)
The result of the addition of N2 (or
another inert gas) or natural gas
can be shown by using a Ternary
diagram.
Here, it is assumed that the flare
gas composition is 40% CH4 and
60% N2, which is indicated as point
‘A’ in the diagram.
Due to air ingress, the ultimate flare
gas composition could reach air
composition (21% O2 and 79% N2),
which is indicated as point ‘air’ in
the diagram.

(CONT.)
The flare gas composition is,
therefore, presented by point ‘B’,
which is located inside the flammable
region (on a straight line between ‘A’
and ‘air’).
By adding N2, the ultimate flare gas
concentration could result in the ‘N2’
point in the diagram.
However, most importantly, point B
begins to move out of the flammable
region.
The same concept applies to the
addition of natural gas. The point
‘HC’ correspondents with 100% CH4
(natural gas) in the diagram.

CONCLUSION
Be aware of and use flammability diagrams, including terms like

MSOC, UEL and LEL.
Add either inert gas or hydrocarbons to effectively move a gas or
oxygen mixture outside the flammable region.
Determine the MSOC based on the average flare composition.
Ensure that a procedure listing operator actions is available. For
example, add an inert gas or hydrocarbons when the oxygen
concentration increases above (a certain percentage of) the MSOC, in
case the root cause cannot be eliminated on short notice.

OTHER RELEVANT HYDROCARBON CONSIDERATIONS
Specialised hydrocarbon fluids such as ‘frac’ fluids or ‘lean oils’ used

in processing facilities readily absorb other hydrocarbons. Their
properties will, therefore, change dramatically when they come in
contact with other hydrocarbons, such as formation fluids. As a result,
the potential hazards associated with these fluids may be altered
significantly. Any fluid being re-used must be tested to confirm that its
properties are appropriate for the intended use.
Chemical and hydrocarbon-based liquids typically used by the oil and
gas industry have the potential for creating explosive mixtures,
including:
 Chemicals used for well servicing and stimulations.
 Solvents and cleaning agents.
 Specially formulated hydraulic fluids and lubricants.
4.0
SUMMARY
SUMMARY
Flammability limits refer to:

 LFL or LEL: Sufficient flammable material present in the air, for the air to be
flammable (explosive).
 UFL or UEL: The maximum amount of flammable material present in the air
for the air to be flammable (explosive).
AIT is the temperature at which there is sufficient energy in the environment to
allow a flammable fluid in the air to self-ignite.
MIE is the minimum spark energy required to ignite an optimum concentration
of flammable material using a capacitative spark under ideal conditions.
MSOC refers to the oxygen concentration in a flammable mixture below
which combustion is not possible. MSOC is also known as LOC or MOC.
FP is the temperature of a liquid at which sufficient vapour is generated in the
air that can be ignited by an open ignition source (flame, spark).

SUMMARY (CONT.)
Flammable atmospheres are formed when flammable materials mix with air
or oxygen.
 Flammability specifies whether or not the atmosphere can burn.
 Ignitability specifies how readily the atmosphere is ignited.
With the exception of a few reactive or unstable substances, liquids do not
themselves ignite. The vapours given off from the surface of liquids cause the
ignition.
The concentration of a vapour depends upon the temperature of the liquid
with which it is in contact.
It is often necessary to assume that an the atmosphere could be flammable
even when the saturated vapour-air mixture is over-rich.
A very fine mist from a hydrocarbon liquid may act as a pure gaseous
substance, also called an aerosol. These aerosols may form an explosive
mixture at temperatures that are far below the liquid’s FP.
SUMMARY (CONT.)
Flammability is conveniently represented as triangular Ternary diagrams.

These diagrams show the regimes of flammability in mixtures of combustibles,
oxidant (air or O2) and an inert gas (typically N2 or CO2).
Specialised hydrocarbon fluids such as ‘frac’ fluids or ‘lean oils’ used in
processing facilities readily absorb other hydrocarbons.
Chemicals and hydrocarbon-based liquids typically used by the oil and gas
industry have the potential for creating explosive mixtures.

1-2 Hydrocarbons Ignition and Flammability

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TECHNICAL SAFETY ENGINEERING (TSE)

1.2 HYDROCARBON (HC)

Use this area for sub-brand logo, business or

Copyright of Shell Projects & Technology RESTRICTED October

At the end of this module, you will be able to:

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Definitions and parameters

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Auto-Ignition Temperature (AIT):

The auto-ignition temperatures of

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Flash Point (FP): The temperature of a liquid at which sufficient vapour is

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Fluid or FP IP15 or NFPA 30 IP15 NFPA 30

FP < 21°C or 23°C (73°F) I IA or IB*

21°C or 23°C (73°F) < FP < 38°C (100°F) II IC

38°C (100°F) < FP < 55°C or 60°C (140°F) II II

FP > 100°C or 93°C (200°F) NC IIIB

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*For dusts or droplet suspensions, flammability limits are expressed as the

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The ignitability of a flammable atmosphere is related to MIE.

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The minimum auto-ignition temperature is the lowest temperature at

Ignitability limits of flammability for methane or air

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This typical diagram is Vapour Pressure/Concentration in Air

Further heating leads

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The FP is an empirical measurement rather than a fundamental physical

Above the UFL, a saturated vapour is over-rich (that is, non-flammable).

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Component FP C LEL % UEL % AIT0C MSOC %

Flammability is conveniently represented on triangular Ternary diagrams. These

Each corner represents a pure

Hydrocarbon in Air line

Outside the colored range, the

SC stands for Stoichiometric LEL or

Typical Flammability Diagram: O2, N2 and HC Mixtures

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In most cases, the flammability envelope can be approximated by drawing

The following Ternary diagram shows all possible mixtures of

Air is a mixture of about 21 vol%

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The stoichiometric combustion of methane is CH4 + 2O2 -> CO2 + 2H2O.

The nose of the envelope defines the

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Temperature influences flammability Pressure influences flammability limits.

Oxygen Nitrogen Oxygen Nitrogen

Effect of Temperature Increase Effect of Pressure Increase

You know that:

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[3] Perry 8.ed:23-9

Is there something you can do with one or both of these connections?

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Be aware of and use flammability diagrams, including terms like

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Specialised hydrocarbon fluids such as ‘frac’ fluids or ‘lean oils’ used

Flammability limits refer to: