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Quantifying NOx for Industrial Combustion Processes

a

C.E. Baukal & P.B. Eleazer

Air Products and Chemicals, Inc. , Allentown , Pennsylvania

Published online: 27 Dec 2011.

To cite this article: C.E. Baukal & P.B. Eleazer (1998) Quantifying NOx for Industrial Combustion Processes, Journal of the Air
& Waste Management Association, 48:1, 52-58, DOI: 10.1080/10473289.1998.10463664
To link to this article: http://dx.doi.org/10.1080/10473289.1998.10463664

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Baukal and Eleazer

TECHNICAL
PAPER

ISSN 1047-3289 J. Air & Waste Manage. Assoc. 48:52-58

Copyright 1997 Air & Waste Management Association

Quantifying NOX for Industrial Combustion Processes

Downloaded by [139.195.49.224] at 00:55 09 February 2015

C.E. Baukal and P.B. Eleazer

Air Products and Chemicals, Inc., Allentown, Pennsylvania

ABSTRACT
The objectives of this paper are to (1) identify the problems with many of the units that are used to report
and regulate NOX, (2) show how to properly correct
NOX measurements for oxygen-enhanced combustion,
and (3) recommend a preferred type of NO X unit. The
current variety of NO X units make comparisons difficult and can cause considerable confusion. NOX may
be measured on a wet or dry basis, but it is commonly
reported on a dry basis. The reported NOX may differ
from the actual measurements, which may be converted to a specific O2 basis level. Nearly all of the measured NOX from industrial combustion systems is in
the form of NO, which is converted to NO2 in the atmosphere. However, when given on a mass basis, the
measured NO is commonly reported as NO2 for regulatory purposes, but may be reported as NO, NO2, or
simply NOX in technical papers. Some existing regulations may penalize combustion technologies with
higher efficiencies and lower flue gas volumes, such
as oxygen-enhanced combustion. Confusion may occur when applying some of the conventional NOX
units to oxygen-enhanced processes. A better unit is
the mass of NOX generated per unit of production,
which also incorporates the overall process efficiency
into the emissions. That unit does not penalize more
efficient processes that may generate more NOX on a
volume basis, but less NOX on a production basis.

IMPLICATIONS
This paper recommends changing the units of measurement used to report and regulate NO X emissions. The
plethora of units that are used (e.g., ppm, lb/106 Btu) makes
it difficult to compare NOX among industries and technologies. Some existing NOX regulations penalize technologies with higher thermal efficiencies that generate less NOX
but seem to produce more NOX when reported in an inappropriate type of unit. A more appropriate unit is based on
the mass of NO X generated per unit of industrial production (e.g., lb NOX /ton glass). This type of unit encourages
technologies that increase production efficiency, which
reduces NOX by reducing fuel consumption.

52 Journal of the Air & Waste Management Association

INTRODUCTION
There is a wide range of industrial heating and melting
processes that generate NOX (nitric oxide, NO, and nitrogen dioxide, NO2) emissions. These processes include, for
example, copper and lead smelting, steel and aluminum
production, and glass and mineral wool manufacturing.
The fuel of choice in the United States for these processes
is natural gas, which typically contains a small amount
of molecular N2 and no organically bound N2.1 Therefore,
prompt and thermal NOX are the important mechanisms,
while fuel NOX is not a concern.
There are at two types of problems with the units
that are commonly used to report and regulate NOX in
those industrial combustion processes. The first concerns
the variety of units that have been used, which makes
comparisons difficult. The second concerns how to make
the proper corrections to a given unit, when oxygen or
oxygen-enriched air is used as the oxidizer. One purpose
of this paper is to alert both the end users and the regulatory agencies to the potential for confusion. Another purpose is to suggest more uniform and consistent units for
reporting NOX.
Most combustion processes use air as the oxidizer. Air
contains approximately 21% O2 and 79% N2 by volume. It
has been recognized that replacing air with pure oxygen
can significantly increase the performance of a combustion system.2 For example, pure oxygen has been used as
the oxidizer to enhance the performance of metal melting,3 glass making,4 and waste incineration.5 There are also
benefits to enriching air with oxygen, so that the O2 concentration is higher than 21%. Some of the common benefits of using oxygen-enhanced combustion include higher
productivity and thermal efficiency with lower exhaust gas
volume and pollutant emissions. 2 Quantifying those emissions will be considered here. It should be noted that NOX
is the pollutant of specific interest in this paper; however,
the discussion would apply to other pollutants emitted from
combustion processes, such as CO.
NOx UNITS
One source of confusion regarding NOX is the lack of a consistent unit of measurement for industrial heating processes,
which makes it difficult to compare measurements and
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Baukal and Eleazer

regulations. This confusion can be illustrated by studying
the proceedings of a recent combustion conference. Thirteen different units were used in the various papers that
were presented. These included uncorrected ppm,6 ppm
at 0% O2,7 ppm at 3% O2,8 ppm at 6% O2,9 ppm at 7%
O2,10 ppm at 11% O2,11 ppm at 15% O2,12 g/kg CH4,13 mass
NOX /mass dry fuel (where the fuels tested included humus, rice straw, waste paper, wood and a wood blend),14
lb/ton glass,15 lb/MMBtu (106 Btu),16 lb/hr,17 and mg/Nm3
at 3% O2.18 In most cases, it was not stated, but it was
assumed that ppm was by volume and not by mass,
since this is the normal convention. It was assumed that
the volume NOX measurements were on a dry basis. It
also was not stated, but assumed, that total NOX, not just
NO, was reported. In some of the papers, multiple units
were used. For example, Wang et al. used both ppm at 3%
O2 and ppm at 6% O2.9
METHODS OF REPORTING NOX
There are many factors to consider when comparing NOX
measurements that may be converted to a variety of units.
The various methods of reporting NOX are discussed next.
Dry Versus Wet Basis
Most gas analyzers commonly used in continuous emissions monitoring (CEM) systems measure the volume
concentration of a particular gas. The most common NOX
unit is ppmv or parts per million by volume. Depending on the sampling technique, the measurement may be
on either a dry or a wet basis. For a dry basis measurement, the water is removed from the sample prior to
analysis. For a wet basis analysis, none of the water is
removed from the sample. Therefore, measurements

Figure 1. Adiabatic equilibrium NO (on both a dry and wet basis) vs.
oxidizer composition, for a stoichiometric CH4 flame.
Volume 48 January 1998

should be reported as either ppmvd for a dry basis, or

as ppmvw for a wet basis. Unfortunately, it is usually
left to the reader to assume that ppm actually means
ppmvd. For example, in an air-CH4fuel system, 100
ppmvd is equivalent to 83 ppmvw, when both are corrected to 3% O2. For other oxidizer compositions, there
may be an even larger difference between the dry and
wet bases. Figure 1 shows that there is a substantial difference between those bases for intermediate oxidizer compositions that occur in oxygen-enhanced combustion
processes. Note that when the fuel is pure CH4 and the
oxidizer is pure O2, no NOX would be generated since all
the N2 has been removed from the combustion process
(assuming that there is no air leakage into the system).
Oxygen Correction
NOX measurements are commonly normalized to a specific
O2 concentration. This is done so that measurements from
different combustion systems can be compared against one
regulation. For example, from 40 CFR 60.55a,19 the NOX
standard for municipal waste combustors is 180 ppmvd corrected to 7% O2. Another example, from 40 CFR 60.332,19
is the NOX standard for stationary gas turbines. Depending
on the fuel, the limit is written as NOX by volume on a dry
basis, corrected to 15% O2. The method for converting NOX
measurements to a standard basis is given by:20

20.95 O2
BASIS
ppm CORR = ppm MEAS
20.95 O 2

MEAS

(1)

where ppmMEAS = measured pollutant concentration in flue

gases (ppmvd), ppmCORR = pollutant concentration corrected
to a standard O2 basis (ppmvd), O2MEAS = measured O2 concentration in flue gases (vol. %, dry basis), and O2BASIS = standard O2 basis (vol. %, dry basis). In this formula, it has been
assumed that standard air contains 20.95% O2 by volume
and that the oxidizer is air. Figure 2 shows how a NOX measurement of 100 ppmvd at 2% O2 can vary when corrected
to various O2 standard bases.
For air-fuel systems, NOX values may then be directly
compared to each other if they are converted to the same
basis. It is assumed that any excess O2 in the exhaust gases
comes from air. However, eq 1 is not applicable for oxygenenhanced combustion systems. This may lead to confusion
when comparing NOX data and is discussed later.
Volume Versus Mass Basis
In some industries, it is common to report NOX on the
basis of mass-per-unit firing rate. The firing rate is calculated from the higher heating value (HHV) of the fuel. It is
referred to here as the gross firing rate. For example, the
NOX regulations for steam generators (40 CFR 60.4419) are
given as lb/106 Btu, or pounds of NOX per million Btu of
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Baukal and Eleazer

Figure 2. Corrected NOx (ppmv) vs. O2 basis (%) for a raw NOx
measurement of 100 ppm at 2% O2, for an air-fuel system.

fuel input. This type of unit makes it easier to compare the

NOX for different types of processes, especially across industries. For example, NOX from a municipal waste combustor,
where the standard basis is 7% O2, must be converted in order
to compare it to the NOX from a gas turbine, where the standard basis is 15% O2. A mass unit like lb NOx/106 Btu does not
require conversion to a standard basis. Figure 3 shows the conversion between ppmvd NO2 at 3% O2 and lb/106 Btu for air/
fuel combustion systems.
One potential complication for this type of unit is
the difference between U.S. and English weights. One U.S.
pound is equivalent to 1.215 British pounds. Another
potential complication is the basis used for the heating
unit Btu. It could be based on the higher heating value
(HHV) or the lower heating value (LHV) of the fuel.
Measured Versus Reported
According to 40 CFR 60,19 nitrogen oxides consist of all
oxides of nitrogen except nitrous oxide (N2O). According
to the EPA,21 approximately 95% of the NOX formed during industrial combustion processes is nitric oxide (NO).
The balance is mostly nitrogen dioxide (NO2). In the atmosphere, NO reacts with ozone to form NO2. Many regulations are written on an NO2 basis, where it is assumed that
the measured NO exiting the combustion process is all converted to NO2. Therefore, the reported value is actually
higher than the measured value due to the higher molecular weight of NO2. For example, 0.100 lb NO/10 6 Btu
would be converted to 0.153 lb NO2/106 Btu. This can be
a source of confusion because some of the NOX data in
the literature may actually refer to NO or NO measurements that have not been converted to NO2, depending
on what is meant by NOX. For example, the data may be
54 Journal of the Air & Waste Management Association

Figure 3. NO2 (lb/106MM Btu) vs. NO2 (ppmvd at 3% O2), where the
oxidizer is air and the fuel is CH4.

given as lb NOx/106 Btu without specifying whether NOX

refers to NO or NO2. To avoid this potential source of confusion, NOX should be more clearly given as lb NO/106 Btu,
or as lb NO2/106 Btu.
Net Versus Gross Energy Input
Some technologies may be penalized if NOX is reported
in mass units, based on the gross fuel input. For example, it is well established that preheating the combustion air using a heat recuperation system increases
the overall thermal efficiency of a heating process.22
However, air preheat also increases NOX on a volume
basis.23 What is more important, though, is how the
NOX is affected on a production basis. For example, if
the thermal efficiency using preheated air is increased
by 20% while the NOX is increased by only 10%, the
preheating system overall produces less NOX per unit
of production than the system without preheat. However, this lower NOX would neither be reflected on a
ppmv basis, nor on a lb/106 Btu-gross basis. A fictitious example is given below. Assume that the base
combustion process produces 1.0 lb NOx/106 Btu and
that it takes 1,000 Btu to process a given unit of material. Also assume that the modified combustion process using air preheat makes 10% more NOX (1.1 lb
NOx/106 Btu) but uses 20% less energy (800 Btu).
Base Case:

1. 0 lbNOx
1000 Btu
0. 00100 lb NOx

=
106 Btu unit of production unit of production

Preheat 1. 1lbNOx
800 Btu
0. 00088 lb NOx

=
Air case: 106 Btu unit of production unit of production

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Baukal and Eleazer

The above example shows that the preheat air case
produces more NO X based on a gross fuel basis (lb NOx/
106 Btu) but actually emits 12% less NOX into the environment (lb NOX /unit of production) because of the
increased fuel efficiency. If the NOX regulation was 1.0
lb NOx/106 Btu, the preheat air case would fail to meet
that regulation, even though it would actually emit
less NOX into the atmosphere. Simple efforts to increase
the fuel efficiency of a combustion process (e.g., minimizing air leakage into a furnace) could produce more
NOX (e.g., due to higher gas temperatures caused by
less air dilution) per unit of fuel but may actually produce less net NOX, due to the increased fuel efficiency.
A preferred unit would be the mass of NOX generated per net unit of energy that goes into the process
(e.g., lb NOX /10 6 Btu-net). That type of unit would
incorporate the efficiency of the process. That unit is
more commonly applied as the mass of NO X generated per unit of production, since the net energy into
the process is directly related to the production rate.
An example of this type of unit is the regulation for
nitric acid plants in 40 CFR 60.72,19 where the NOX
limit is 1.5 kg NOX (expressed as NO 2) per metric ton
of 100% nitric acid. Another example is the regulation in the South Coast Air Quality Management District in southern California for glass manufacturers,
which is in lb NO X per ton of glass produced. 24
A NOX unit based on production has other ramifications. It is affected by the rest of the process. For
example, consider the interruptions in a production
operation. Two assumptions will be made in this example. The first is that the interruption is not caused
by the combustion system. The second is that the combustion system remains on during the interruption,
which is assumed to be of a relatively short duration.
Possible causes for the interruption might be a shortage of feed material, failure of the material handling
system, or failure of some other equipment in the production process. In this scenario, NOX based on a unit
of production would increase as a result of downtime.
The combustion system would still be emitting NOX
at the same rate, even though nothing is being processed during the interruption. On the other hand, a
production system with very little downtime but highNOX burners could actually produce less NOX than a
poorly run production system with low-NOX burners.
Therefore, a NO X unit based on production gives incentive to have both low-NOX burners and a well-run
production system. A NOX unit like lb/10 6 Btu-gross
does not incorporate the efficiency of the heating process or the efficiency of the production process.
Bluestein notes that there are potential drawbacks
to a NOX unit based on production.25 By including the
Volume 48 January 1998

process efficiency in the emissions, it is difficult to

compare NOX values between different industries. It
also makes it difficult to compare NO X reduction technologies used in the same process, but at different locations. One location may be poorly run, while another may be very efficient. Differences in NOX may
be attributable to either the combustion system, or to
the production process, or to both. This type of NOX
unit may also increase the number of regulations, since
each would have to be specifically written for a particular process. This could be very complicated for industries where the material being processed varies
widely. Consider a municipal waste incinerator processing trash. One day the trash may be very dry, so
the processing rates would be higher. Another day the
trash may be very wet, so the processing rates would
be lower. For that type of a process, it may not make
sense to normalize NOX regulations to a production
basis, or the measurements may have to be averaged
over a longer period of time to average out the daily
variations in the material feed composition.
NOX IN OXYGEN-ENHANCED COMBUSTION
Another major source of confusion regarding units of
measurement pertains to converting NOX measurements
for an oxygen-enhanced combustion process. One problem with current regulations that are written on a volume
basis is how to correct the measurements for oxidizers other
than air. The correction in eq 1 assumes that any excess O2
comes from air. This may or may not be the case with oxygen-enhanced combustion. If the excess O2 measured in
the flue gases came from an oxygen-enriched oxidizer, then
eq 1 should be modified as follows:

O2
O2 BASIS

ppm CORR = ppm MEAS OXID

O2

OXID O2 MEAS

(2)

where ppmMEAS = measured pollutant concentration in flue

gases (ppmvd), ppmCORR = pollutant concentration corrected to a standard O2 basis (ppmvd), O2OXID = O2 concentration in the oxidizer (vol. %), O2MEAS = measured O2 concentration in the flue gases (vol. %, dry basis), and O2BASIS
= standard O2 basis (vol. %, dry basis).
Air leakage into an oxygen-enhanced combustion
process further complicates this conversion. For example, if the oxidizer supplied to the burners is pure
O2 and there is significant air infiltration into the process, then the effective oxidizer is a combination of the
O2 to the burners and the infiltrated air. In that case, the
O2 concentration in the oxidizer (O2OXID) would have to be
calculated based on the flue gas volume flow rate or on the
amount of N2 in the flue gases.
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Baukal and Eleazer

Figure 4. Flue gas volume (at standard temperature and pressure

conditions) per unit volume of CH4, and available heat (assuming a
2000 F exhaust gas temperature) vs. oxidizer composition, for a
stoichiometric CH4 flame.

From Figure 4, it may be seen that the exhaust volume

per unit of fuel input is dramatically reduced as the O2 concentration in the oxidizer increases. It may also be seen
that the available heat increases as well. Available heat is
defined as the gross heating value of the fuel less the energy carried out of the process by the hot exhaust gases.
Reducing the flue gas volume and increasing the thermal
efficiency are two common reasons for using oxygen-enhanced combustion.2 Both result from the removal of N2
from the oxidizer and both have a dramatic impact on the
relevance of some of the NOX units.
Volume Versus Mass Basis
Because the flue gas volume may be reduced by >90% when
replacing air with pure oxygen, comparing air/fuel NOX to
O2/fuel NOX on a ppmv basis is not appropriate. For example, 200 ppmvd NOX from an O2/fuel system is actually
less NOX by mass than 100 ppmvd NOX from an air/fuel
system because of the vast differences in flue gas volumes.
Figure 5 shows a comparison of NOX in ppmvd corrected
to 0% O2 for systems using air and pure O2. The ppmvd of
NOX using O2 as the oxidizer is equivalent to 8.52 times the
ppmvd of NOX using air as the oxidizer, when the fuel is
CH4. This is strictly due to the change in the volume of the
dry products of combustion as a function of the oxidizer.
As can be seen, care must be exercised when comparing
NOX on a volume basis for systems using different oxidizers. Hence, if it is assumed that air/fuel and O2/fuel systems
have equal efficiencies (which they usually do not), it makes
more sense to compare the NOX on a mass basis. Figure 6
shows NOX in both mass and volume units, as a function
of the oxidizer composition.
56 Journal of the Air & Waste Management Association

Figure 5. NOx (ppmvd at 0% O2) comparison when the oxidizer is air,

and pure O2 when the fuel is CH4.

Net Versus Gross Basis

As shown in Figure 4, O2/CH4fuel systems are often significantly more efficient than air-CH4fuel systems. Less
fuel is required for a given unit of production. Therefore, a better NOX unit would be the mass of NO X generated per unit mass of production.
This concept can be illustrated with a unit like lb/
6
10 Btu-net. This unit is derived by combining the NOX/
106 Btu-gross curve in Figure 6 and the available heat
curve in Figure 4. It is assumed that the base case is
air/CH 4fuel combustion. Then, as the O 2 concentration in the oxidizer increases, the thermal efficiency
increases. The gross and net Btu curves are shown in
Figure 7. The net Btu curve is similar to a production
basis since production rates are directly proportional
to the amount of energy that goes into the product. It
is assumed that the heat losses from the system and
the heat transfer to the product would not vary significantly using different oxidizers. This figure shows
that it can be very deceiving to compare NOX based
only on the gross firing rate when the oxidizer compositions are different. Therefore, the recommended
unit is the mass of NOX per unit of production since
the system efficiency is also included.
CONCLUSIONS
This paper discussed the wide variety of methods that
are used for quantifying NOX. For a number of reasons,
reporting NOX on a volume basis has many drawbacks.
A better unit for NOX is on a mass basis normalized to
the gross firing rate. This unit can be further improved
by normalizing the NOX to a unit production basis.
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Baukal and Eleazer

Figure 6. Adiabatic equilibrium NO (in lb/106 Btu and ppmvd) vs.

oxidizer composition when the fuel is CH4.

Currently, regulations exist in all three types of units.

A further complication arises when the oxidizer is not
air, as is the case in oxygen-enhanced combustion. For
that case, the best unit for comparison is the mass of
NOX normalized to the mass of material processed. That
unit takes into account the reduction in flue gas volume and the increase in the thermal efficiency that
occurs when using oxygen-enhanced combustion.
However, even that unit has some concerns. More regulations may be required because of the specific nature
of that unit, which includes the material processing
rate. Also, that type of NOX unit makes it more difficult to directly compare emissions across a range of
industries and even across different processes within a
given industry.
Regarding the NAAQS, the concern is the total mass
of pollutant emissions entering the atmosphere. Existing
regulations written for ppmv of NOX can also be written
in terms of the proposed unit (mass of NOX/unit of production) with no change in the actual mass of pollutants
emitted to the atmosphere. A potential benefit of the proposed NOX unit is that the manufacturer would, in effect,
be penalized for generating NOX during times of reduced
thermal efficiencies. For example, if there is an interruption in production but the combustion system is still on,
then NO is still being emitted into the atmosphere. There
would be no regulatory penalty for a ppmv NOX unit since
the same amount of pollution would be emitted to the
atmosphere. However, the average amount of NOX produced per unit of production would increase since NOX
would be generated with little or no production. For that
type of regulatory unit, the manufacturer would then have
incentive to fix production problems more quickly, do
preventative maintenance, and install improved technolVolume 48 January 1998

Figure 7. Adiabatic equilibrium NO (in lb/106 Btu on both a gross and

a net basis) vs. oxidizer composition, for a stoichiometric CH4 flame,
assuming a 2000 F flue gas temperature.

ogy to maintain or increase throughput rates for a given

unit of thermal heat input. The manufacturer would also
have incentive to turn off the combustion system during
prolonged production outages, to avoid increasing the
NOX emissions per unit of production.
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1.
2.
3.
4.
5.
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About the Authors

Dr. Baukal is a combustion research engineer and Mr. Eleazer
is the manager of the Combustion Center-of-Excellence, both
in the Global Applications Development department of Air
Products and Chemicals, Inc., 7201 Hamilton Blvd., Allentown, PA 18195. Correspondence may be directed to Dr.
Baukal (e-mail: baukalce@apci.com).

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22. IHEA. Combustion Technology Manual, Fourth ed.; Industrial Heating
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23. Control Techniques for Nitrogen Oxide Emissions from Stationary Sources,
Revised Second Edition; U.S. Environmental Protection Agency, Research Triangle Park, NC, 1983; EPA-450/3-83-002.

58 Journal of the Air & Waste Management Association

Volume 48 January 1998