Standard On Explosion Prevention Systems

NFPA 69-2014 Edition
Standard on Explosion Prevention Systems

TIA Log No.: 1212
Reference: Annex B.8 (new)
Comment Closing Date: February 19, 2016
Submitter: Martin Clouthier, Clouthier Risk Engineering, and Laurence Britton, AIChE Fellow
and Process Safety Consultant
1. Add a new Annex B.8 to read as follows:
B.8 Limiting Oxygen Concentration for Fuel Mixtures. The limiting oxidant concentration
(LOC) for a fuel mixture can be estimated based on the relationship that the LOC is
approximately equal to the LFL multiplied by the stoichiometric oxygen ratio, S. The
approximation LOC = LFL x S is usually conservative because it assumes the LOC occurs at the
LFL concentration of the fuel.
Two types of calculations can be performed to estimate the LOC for fuel mixtures. First, if only
LFL data are available, the LOC of the mixture can be calculated from the mixture LFL. Second,
if LOC data are available for the mixture components, a calculation can be performed for the
LOC of the mixture. When performing the second type of calculation manually, as opposed to
using a spreadsheet, it is better to do it in parts to avoid errors.
The LOC estimation method is not applicable for diluents other than nitrogen because the diluent
must have a very similar heat capacity to the oxygen and nitrogen components present at the
LFL.
Similar to the considerations with regard to methane enrichment of vent collection headers in
7.7.3, the LOC estimation method is not recommended for mixtures containing components with
a UFL greater than 75 mol% in air. Such gases typically have UFLs in oxygen greater than 90
mol%, and in some cases the “upper LOC” value might be less than the “lower LOC” value
(Kuchta, 1985) [1]. Furthermore, this method is not recommended for mixtures containing a
decomposable gas or a gas that might be decomposable at elevated temperature and pressure.
B.8.1 Method 1 – Estimating Mixture LOC from Known Component LFLs. This method
starts with known component LFLs (either determined by experiment or by using a reliable
method) and uses Le Chatelier’s rule to estimate the LFL for the mixture. The stoichiometric
oxygen ratio for the mixture is calculated. The results of both calculations are used to estimate
the LOC for the mixture.
Step 1: Calculate LFL of mixture using Le Chatelier’s rule:
Equation B.8.1(a)
where xi is the mole fraction of component i having LFL = Li (mol%) in mixture.

Step 2: Calculate stoichiometric oxygen Si needed for each mixture component i.
Let CcHhOoNnXx = some arbitrary gas (where X represents Cl or other halogen). Equating
coefficients in the stoichiometric combustion equation gives the following:
Equation B.8.1(b)
Then S = moles of oxygen are needed for stoichiometric combustion; hence
Equation B.8.1(c)
Step 3: Calculate stoichiometric oxygen Smix. The mathematical expression for this calculation is
the following:
Equation B.8.1(d)
Step 4: Calculate the limiting oxygen concentration of the mixture LOCmix. Assume the LOC is
equal to the minimum concentration of oxygen needed to completely combust the LFL
concentration of fuel:
LOCmix = LFLmix x Smix B.8.1(e)
Example 1
Calculate LFL for a mixture containing 0.20 mole methane, 0.40 mole methanol, 0.30 mole
methylamine, and 0.10 mole methyl chloride. Using “reported” LFL data from Britton and Frurip
[2], as shown in Table 1:
Hence
Following Steps 1 through 3, calculate LOCmix:
LOCmix = LFLmix x Smix = 5.59 x 1.825 = 10.2 mol% O2
B.8.2 Method 2 – Estimating Mixture LOC from Known Component LOCs. This approach
was presented by Zlochower and Green [3] and starts with known component LOC data and then
assumes the LOC is equal to the stoichiometric ratio S times a derived fuel concentration (or
pseudo LFL) at limiting oxidant concentration, L*i . The fuel mixture flammable limit is implicit
in the solution, which results in a weighted average of the LOCs of the components. The pseudo
LFL at the LOC is
B.8.2(a)
where LOCi is the LOC for component i. The mixture LOC is the product of the derived mixture
fuel concentration and the mixture molar average stoichiometric ratio.
B.8.2(b)
The derived mixture fuel concentration from Le Chatelier’s rule is as follows:
B.8.2(c)
The LOC of the mixture is as follows:
B.8.2(d)
Example 2
Consider a fuel mixture consisting of methane, ethylene, carbon monoxide, and methanol, with
the mole fractions and component LOCs in nitrogen [3, 4] as summarized in Table 3.
The stoichiometric ratios for each component and the intermediate values from Equation
(B.8.2d) are summarized in Table 4.
The LOC of the mixture is calculated using Equation (B.8.2d) is as follows:

B.8.3 References for B.8.
[1] J. M. Kuchta, Bulletin 680, U.S. Bureau of Mines, Pittsburgh, PA, 1985.
[2] L. G. Britton and D. J. Frurip, “Further Uses of the Heat of Oxidation in Chemical Hazard
Assessment,” Process Saf. Prog. 22 (2003), no. 1, 1–19.
[3] I. A. Zlochower and G. M. Green, “The Limiting Oxygen Concentration and Flammability Limits of
Gases and Gas Mixtures,” J. Loss Prev. Process Ind. 22 (2009), no. 4, 499–505.
[4] H. F. Coward and G. W. Jones, “Limits of Flammability of Gases and Vapors,” Technical Report 503,
U.S. Bureau of Mines, 1952.
Substantiation: This second TIA provides users with a simple method for estimating the LOCs
of single gases and gas mixtures based on the equation LOC = LFL x S, where LFL is the lower
flammable limit and S the molar stoichiometric ratio of oxygen to fuel.
Furthermore, NFPA 69 does not offer any guidance for users on estimating the LOC for
mixtures. The consequence of not providing such guidance is that users are forced to assume the
LOC for the lowest mixture component, which means more inert gas will be required than
necessary.
Emergency Nature: Justification for the emergency nature of the proposed TIAs is based on
Section 5.3, Item (f) of the “Regulations Governing the Development of NFPA Standards:”
(f) The proposed TIA intends to correct a circumstance in which the revised document
has resulted in an adverse impact on a product or method that was inadvertently overlooked in
the total revision process, or was without adequate technical (safety) justification for the action.
Furthermore, this proposed TIA would provide users a method to determine the LOC of
mixtures.
We therefore propose two Tentative Interim Amendments (TIAs). This second TIA describes a
technique for estimating LOC values from LFL values, plus worked examples showing how to
estimate LOCs of gas mixtures starting either from measured LOC or LFL values. The detailed
TIA is presented here.
This TIA Provides new annex material which offers guidance and example calculations on how
to estimate the LOC for a fuel or a fuel mixture using established methods. The method is only
applicable for nitrogen diluent and is not presently recommended for mixtures containing any
component with a UFL greater than 75 mol% in air.
The LOC estimation method in this TIA is not applicable for diluents other than nitrogen
because the diluent must have a very similar heat capacity to the oxygen and nitrogen
components present at the LFL. The approximation represented by LOC = LFL x S assumes that
the heat capacity stays approximately constant as diluent gas is added to the mixture of fuel and
oxidant that defines the LFL.
The LOC estimation method in this TIA is not presently recommended for mixtures containing
components with a UFL greater than 75 mol% in air. Such gases typically have UFLs in oxygen
greater than 90 mol% and in some cases the “upper LOC” value might be less than the “lower
LOC” value. This problem might be academic owing to various practical limits on the
composition of the gas mixture. Another possible factor is the presence either of decomposable
gases or gases with high reported UFLs that might become decomposable at elevated
temperatures and pressures. NFPA 69 previously considered this issue with respect to the
methane enrichment of vent collection headers and decided that, in the absence of specific data,
it would be prudent to limit general use of the method to gases whose UFL in air is no larger than
that of hydrogen (75 mol%).
Anyone may submit a comment by the closing date indicated above. To submit a comment, please
identify the number of the TIA and forward to the Secretary, Standards Council, 1 Batterymarch Park,
Quincy, MA 02169‐7471.

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NFPA 69-2014 Edition

Standard on Explosion Prevention Systems

1. Add a new Annex B.8 to read as follows:

Step 1: Calculate LFL of mixture using Le Chatelier’s rule:

where xi is the mole fraction of component i having LFL = Li (mol%) in mixture.

Then S = moles of oxygen are needed for stoichiometric combustion; hence

LOCmix = LFLmix x Smix B.8.1(e)

Following Steps 1 through 3, calculate LOCmix:

LOCmix = LFLmix x Smix = 5.59 x 1.825 = 10.2 mol% O2

The derived mixture fuel concentration from Le Chatelier’s rule is as follows:

The LOC of the mixture is as follows:

The LOC of the mixture is calculated using Equation (B.8.2d) is as follows:

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