Thermal NOx Formation

The formation of thermal NOx is determined by a set of highly temperature-dependent chemical re- actions
known as the extended Zeldovich mechanism. The principal reactions governing the formation of thermal NOx
from molecular nitrogen are as follows:
(9.5)
(9.6)

A third reaction has been shown to contribute to the formation of thermal NOx, particularly at near-
stoichiometric conditions and in fuel-rich mixtures:
(9.7)

Thermal NOx Reaction Rates

The rate constants for these reactions have been measured in numerous experimental stud-
ies [65] (p. 1026), [180] (p. 1033), [435] (p. 1048), and the data obtained from these studies have been critically
evaluated by Baulch et al. [45] (p. 1025) and Hanson and Salimian [224] (p. 1035). The expressions for the rate
coefficients for Equation 9.5 (p. 343) – Equation 9.7 (p. 343) used in the NOx model are
given below. These were selected based on the evaluation of Hanson and Salimian [224] (p. 1035).

= =

= =
= =

In the above expressions, , , and are the rate constants for the forward reactions Equa-
tion 9.5 (p. 343) – Equation 9.7 (p. 343), respectively, and , , and are the corresponding reverse rate
3
constants. All of these rate constants have units of m /mol-s.

The net rate of formation of NO via the reactions in Equation 9.5 (p. 343) – Equation 9.7 (p. 343) is given by

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 (9.8)

where all concentrations have units of mol/m3.

To calculate the formation rates of NO and N, the concentrations of O, H, and OH are required.

The Quasi-Steady Assumption for [N]

The rate of formation of NOx is significant only at high temperatures (greater than 1800 K) because fixation
of nitrogen requires the breaking of the strong N2 triple bond (providing dissociation energy
of 941 kJ/mol). This effect is represented by the high activation energy of reaction Equation 9.5 (p. 343), which
makes it the rate-limiting step of the extended Zeldovich mechanism. However, the activation energy for
oxidation of atoms is small. When there is sufficient oxygen, as in a fuel-lean flame,
the rate of consumption of free nitrogen atoms becomes equal to the rate of its formation, and therefore a
quasi-steady state can be established. This assumption is valid for most combustion cases, except in extremely
fuel-rich combustion conditions. Hence the NO formation rate becomes

(9.9)

Thermal NOx Temperature Sensitivity

From Equation 9.9 (p. 344) it is clear that the rate of formation of NO will increase with increasing oxygen
concentration. It also appears that thermal NO formation should be highly dependent on temperature but
independent of fuel type. In fact, based on the limiting rate described by , the thermal NOx production
rate doubles for every 90 K temperature increase beyond 2200 K.

Decoupled Thermal NOx Calculations

To solve Equation 9.9 (p. 344), the concentration of O atoms and the free radical OH will be required, in
addition to the concentration of stable species (that is, O2, N2). Following the suggestion by Zeldovich, the
thermal NOx formation mechanism can be decoupled from the main combustion
process by assuming equilibrium values of temperature, stable species, O atoms, and OH radicals.
However, radical concentrations (O atoms in particular) are observed to be more abundant than their
equilibrium levels. The effect of partial equilibrium O atoms on NOx formation rate has been
investigated [430] (p. 1047) during laminar methane-air combustion. The results of these investigations indicate
that the level of NOx emission can be under-predicted by as much as 28% in the flame
zone, when assuming equilibrium O-atom concentrations.

Approaches for Determining O Radical Concentration

There has been little detailed study of radicals concentration in industrial turbulent flames, but
work [146] (p. 1031) has demonstrated the existence of this phenomenon in turbulent diffusion flames. Presently, there is
no definitive conclusion as to the effect of partial equilibrium on NOx formation

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rates in turbulent flames. Peters and Donnerhack [500] (p. 1052) suggest that partial equilibrium radicals can
account for no more than a 25% increase in thermal NOx and that fluid dynamics has
the dominant effect on the NOx formation rate. Bilger and Beck [57] (p. 1026) suggest that in turbulent diffusion
flames, the effect of O atom overshoot on the NOx formation rate is very important.

To overcome this possible inaccuracy, one approach would be to couple the extended Zeldovich mechanism
with a detailed hydrocarbon combustion mechanism involving many reactions, species, and steps. This
approach has been used previously for research purposes [425] (p. 1047). However, high computational cost of
such approaches limits their use in turbulent reacting flows.

To determine the O radical concentration, Ansys Fluent provides the equilibrium, partial equilibrium, and the
predicted concentration approaches described below.

Method 1: Equilibrium Approach

The kinetics of the thermal NOx formation rate is much slower than the main hydrocarbon oxid- ation
rate, and so most of the thermal NOx is formed after completion of combustion. Therefore, the thermal
NOx formation process can often be decoupled from the main combustion reaction mechanism and the
NOx formation rate can be calculated by assuming equilibration of the combustion reactions. Using this
approach, the calculation of the thermal NOx formation rate is considerably simplified. The assumption of
equilibrium can be justified by a reduction in the im- portance of radical overshoots at higher flame
temperature [145] (p. 1031). According to Westen- berg [683] (p. 1062), the equilibrium O-atom
concentration can be obtained from the expression
(9.10)

With included, this expression becomes

(9.11)

where is in Kelvin.

Method 2: Partial Equilibrium Approach

An improvement to method 1 can be made by accounting for third-body reactions in the O2
dissociation-recombination process:
(9.12)

Equation 9.11 (p. 345) is then replaced by the following expression [672] (p. 1061):
(9.13)

which generally leads to a higher partial O-atom concentration.

Method 3: Predicted O Approach

When the O-atom concentration is well predicted using an advanced chemistry model (such as the
flamelet submodel of the non-premixed model), [O] can be taken simply from the local O- species mass
fraction.

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Approaches for Determining OH Radical Concentration
Ansys Fluent uses one of three approaches to determine the OH radical concentration: the exclusion of OH
from the thermal NOx calculation, the partial equilibrium, and the use of the predicted OH concentration.

Method 1: Exclusion of OH Approach

In this approach, the third reaction in the extended Zeldovich mechanism (Equation 9.7 (p. 343)) is
assumed to be negligible through the following observation:

This assumption is justified for lean fuel conditions and is a reasonable assumption for most cases.

Method 2: Partial Equilibrium Approach

In this approach, the concentration of OH in the third reaction in the extended Zeldovich mech- anism
(Equation 9.7 (p. 343)) is given by [46] (p. 1025), [682] (p. 1062):
(9.14)

Method 3: Predicted OH Approach

As in the predicted O approach, when the OH radical concentration is well predicted using an advanced
chemistry model such as the flamelet model, [OH] can be taken directly from the local OH species mass
fraction.

Summary
To summarize, the thermal NOx formation rate is predicted by Equation 9.9 (p. 344). The O-atom concentration
needed in Equation 9.9 (p. 344) is computed using Equation 9.11 (p. 345) for the equilibrium assumption,
using Equation 9.13 (p. 345) for a partial equilibrium assumption, or using the local O-species mass fraction.
You will make the choice during problem setup. In terms of the
transport equation for NO (Equation 9.1 (p. 342)), the NO source term due to thermal NOx mechanisms is

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where is the molecular weight of NO (kg/mol), and is computed from Equa- tion 9.9 (p. 344).

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Release 2023 R1 - © ANSYS, Inc.All rights reserved.- Contains proprietary and confidential
information of ANSYS, Inc. and its subsidiaries and affiliates. 34