Environmental Protection

Controlling
NOx Emissions
Part 1

N
Mike Bradford and Rajiv Grover,
Jacobs Engineering Group Inc.
Pieter Paul, itrogen oxides, or NOx, are a combination of nitrogen oxide,
Jacobs Consultancy Nederland B. V. NO, and nitrogen dioxide, NO2. As part of the Clean Air Act
Amendments of 1990 (CAAA), the Environmental Protection
Agency (EPA) and state agencies have promulgated regulations
NOx emission requiring stricter control of NOx emissions from stationary point sources.
Compliance planning requires serious homework.
standards are The emission control requirements of the existing, as well as future, regula-
becoming very tight, tions require an understanding of NOx-emitting sources, pollution prevention
opportunities, emissions reduction technologies, costs of controls, and impacts
especially in the on existing operations and plant safety. This article, Part 1 of a two-part series,
Houston area and first presents some general information about NOx control, then discusses NOx
reduction through process changes and/or energy efficiency improvements,
in Southern California. and by using the latest generations of burners. Part 2, which is scheduled to
appear in the next issue, will cover post-combustion NOx reduction using se-
Among the technologies lective catalytic reduction (SCR), selective noncatalytic reduction (SNCR) and
available to meet catalytic oxidation/scrubbing.
When evaluating these technologies, remember that in many cases
these standards are retrofitting the NOx controls has positive side benefits. In many instances, the
process modifications installation of NOx controls will result in better energy efficiency and in lower
maintenance requirements. This article also discusses areas where the side
and energy efficiency benefits should be considered.
improvements, as Summary of de-NOx technology
well as advanced burner Table 1 lists various technologies available for NOx reduction. It lists the
approximate reduction that can be achieved by each technology and the ap-
designs and flue gas proximate NOx concentration that can be achieved firing natural gas. Table 2
recirculation. lists the most likely NOx control options for areas like Houston and Southern
California that have tight NOx control requirements. The following sections
discuss the main technologies in more detail.

42 www.cepmagazine.org March 2002 CEP

 Table 1. NOx reduction technologies.

Technology Approximate Approximate Approximate

Reduction, % Emissions, Emissions,
lb/MMBtu ppmv @ 3% O2

Process modifications Standard Burners Base Case 0.14 120

Plants can make various process modi- Process Modifications Up to 100% N/A N/A
fications and/or energy efficiency im-
Low-NOx Burners (LNB) 60% 0.06 48
provements to reduce NOx emissions. Ultra-Low-NOx Burners 80% 0.03 24
Some of the standard NOx reduction tech- (ULNB), First Generation*
nologies also have the side benefit of im- ULNB, Current Guarantee 89% 0.015 13
proving energy efficiency. Level
ULNB, Currently Being 95% 0.007† 6
Boilers can be replaced with a cogenera- Developed
tion system. This option has a number of
Flue Gas Recirculation 55%‡ 0.025 22§
advantages. The boilers can be replaced (FGR)
with a more-efficient system that generates Water or Steam Injection 50% to 60% 0.06 20
power as well as steam. It is less expensive at Gas Turbines
to install emission controls on one big unit
Selective Noncatalytic 40% 0.033§ to 0.085 27§ to 70
than on a number of smaller units. And, Reduction (SNCR)
technologies such as an SCR can be used Catalytic Scrubbing 70%# 0.017§ # to 0.044 14§ # to 36
that can achieve greater NOx reductions Selective Catalytic 90% to 97% 0.006§ to 0.015 2.5§ to 12
compared with using burners alone. Reduction (SCR)
Inefficient heaters can be replaced with Notes:
more-efficient heaters. In most cases this will * Can potentially fit in opening for existing burner, avoiding shutdown.
not be an economical approach. However, if † Levels achieved during "shop tests." At the time this article was written, these NO levels had
x
a heater is a candidate for replacement, the not yet been demonstrated in fired heaters in the field; 0.012 lb/MMBtu has been demonstrated
in boilers with FGR and firing natural gas.
extra benefit of NOx reduction may sway the ‡ On boilers; little data available on fired heaters.
economics in favor of replacement. § Level that can be achieved assuming LNBs are installed in combination with the technology listed.
A heater can be provided with a new con- # The injection of ozone upstream of the scrubber can reportedly achieve a 95% NO reduction,
x
vection section or the existing convection but low operating temperatures are required.
section can be upgraded. These modifica-
tions can be used to preheat the process fluid, thus improving tion has been prompted by the new regulations proposed for
the heater’s efficiency and decreasing the firing rate. The the Houston area.
lower firing rate results in less NOx generation, plus the reduc- If new burner technology meets the proposed require-
tion in fuel costs could pay for the modification. Note that ments, it will be the most economical NOx reduction alterna-
modifications to the convection section are often required to tive. If the new burners can fit in the existing hole, the instal-
provide the proper temperature for installation of an SCR. lation cost may be very low, and it may be possible to install
However, an increase in energy efficiency may be a side bene- the burner without a plant turn-around. Installing new burners
fit of installing an SCR. may have a number of additional advantages: it does not in-
Better heater controls can be installed to allow tighter con- crease, and could even decrease, operating costs; the new
trol of the excess air. Tighter controls could also be used to burners may be able to better match the capacity of the
reduce the oxygen concentration in the flue gas. A reduction heater; and if the existing burners are old, this may be an op-
in the oxygen concentration in the flue gas from 6% to 2% portunity to reduce maintenance costs.
reduces the firing rate by only a few percent. But this still has However, new burners alone may not be able to meet the
two advantages. The lower firing rate marginally decreases most stringent requirements for large fired heaters. Additional
the NOx generation and less NOx is generated if the oxygen disadvantages of burner replacements include: the latest gen-
concentration is low. In general, a decrease in oxygen con- eration of ULNB has not been fully tested; ULNBs tend to
centration from 6% to 2% reduces the NOx generation by ap- have smaller-diameter fuel tips and thus plugging is more of
proximately 30% (Figure 1). Combining the above two bene- a concern; for large units, the plugging of leaks in the heaters
fits results in a NOx reduction of a little over 30%, just from will be critical; upgrades to the control system will probably
improving the control of excess air. be required; and significant modifications may be required to
Sealing the heater can also reduce the oxygen concen- fit the larger burners into the firebox.
tration in the firebox, improve heater efficiency and im-
prove safety. Similar to the upgrade in controls, this can be Impacts on standard burner NOx generation
an additional advantage from the installation of ultra-low- NOx forms in fired heaters in three ways: “thermal NOx,”
NOx burners (ULNB). “fuel NOx,” and “prompt NOx. ” Thermal NOx forms because
of local hot spots in the flame. Fuel NOx results from the
Standard, low-NOx and ultra-low-NOx burners burning of fuels containing organic nitrogen, some of which
Burners have been undergoing rapid development due to is oxidized into NOx. The latter type of NOx formation tends
pressures to reduce NOx formation. The latest stage of evolu- to be negligible with natural gas and fuel gas firing. Prompt

CEP March 2002 www.cepmagazine.org 43

 Environmental Protection

Table 2. Likely NOx control options.

Unit Options

All • Replace boilers with cogeneration systems.

• Replace inefficient heaters with new, more-efficient heaters
or with a hot-oil system.
• Provide new or upgrade existing convection sections to
improve energy efficiency.
• Upgrade heater controls to reduce excess air requirements.
• Seal heaters to minimize heat losses.
Fired Heaters • First or second generation ULNBs.
< 40 MMBtu/h • Possible dilution of fuel gas with steam or flue gas
recirculation, for systems with high firebox temperatures or
air preheat.
Fired Heater • Latest generation of ULNB or SCR.
40–100 MMBtu/h • ULNBs will require firebox sealing and may require the
installation of tighter controls.
• SCR may not be economical for some cases, if the area is
congested or if tie-ins are expensive.
units were retrofitted with LNBs for NOx reduc-
tion. LNBs by themselves will not achieve the
Houston area standards, but the installation of
LNBs or better burners may be required in con-
junction with other technologies such as SCR. If
an existing unit is currently equipped with LNBs,
NOx levels below 0.01 lb/MMBtu can be achieved
by installing an SCR.
Characteristics of LNBs include long flame
lengths and large-diameter burners. These charac-
teristics could preclude the installation of new
burners. ULNBs also tend to have a large diame-
ter, but have shorter flame lengths and may be eas-
ier to retrofit.

Fired Heaters • Latest generation of ULNBs or SCR. Ultra-low-NOx burners

> 100 MMBtu/h • Downfired reformers will require SCRs.
• ULNBs will require firebox sealing and will require the
installation of tighter controls.
Boilers • ULNBs with FGR.
• Larger units may also require SCR.
Gas Turbines • Repowering: the use of gas turbine exhaust as combustion
air for boilers and furnaces.
• Cogeneration: installation of a heat recovery unit.
• Combined cycle operation.
• SCR combined with some other technology such as water
or steam injection or dry low-NOx burners.
Incinerators • LNBs with or without FGR, waste-heat recovery, SCR,
SNCR or catalytic oxidation.
NOx forms because of the transformation of N2 into NO at
the edge of the zone of rich hydrocarbon flames.
Standard burners typically result in NOx formation in the
0.12 to 0.14 lb/MMBtu (100 to 120 ppmv) range. A number
of factors influence this number.
Figure 1 shows the relationship between oxygen concen-
tration and NOx generation. The lower the excess air (% O2),
the lower the NOx.
Figure 2 shows the relationship between firebox tempera-
ture and NOx generation. High firebox temperatures result in
higher NOx formation.
The effect of air preheat on NOx formation is illustrated in
Figure 3. Air preheat increases efficiency and can increase
heater capacity. But, the air preheat comes with a NOx gener-
ation penalty — the higher the preheat temperature, the high-
er the flame temperature, so more thermal NOx is formed.
This applies to standard burners and LNBs. While not fully
tested, recent data indicate that air preheat has a much lower
impact on the NOx from ULNBs.
Fuel gas containing hydrogen tends to burn hotter and
thus tends to produce more NOx than the firing of natural gas.
LNBs use staged fuel to reduce NOx. By con-
trast, ULNBs reduce NOx by inducing the internal
circulation of fuel gas within the heater.
There currently are at least three generations of
ULNBs. The first generation may meet the Houston
and California requirements for small heaters. The
advantage of these units is that it may be possible to
retrofit them into the openings for existing burners
without a shutdown. A second generation of ULNBs
provides lower NOx emissions than the first genera-
tion. In addition, some of the burners currently under
development may be able to meet the requirements
for large fired heaters in the Houston area.
A typical application for ULNBs is in a verti-
cal cylindrical fired heater, which has burners mounted in the
floor firing upward. Figure 4 is a view of one of the latest ver-
sions of ULNBs, viewed from inside the heater.
Most ULNBs use internal flue-gas recirculation to dilute
and cool the flame. These burners require tight oxygen con-
trol, so air leaks into the heater must be minimized and tight
controls are required.
In addition, vendor guarantees will be based on the fire-
box temperature — the lower the temperature, the better —
and will be based on the type of fuel used. Some vendors like
high-hydrogen fuel gases, because it is easier for the fuel to
internally entrain and recirculate fuel gas. However, some
vendors do not like fuel gas because hydrogen burns hot and
because NOx emissions will be higher burning fuel oil.
Advanced control systems may be required to ensure the
performance of the burners. Control modifications that may
be required include: the installation of a continuous emission
monitoring system (CEMS), the use of oxygen analyzers
near the bridgewall and/or in the floor of the heater, automat-
ic controls on stack dampers, and automatic modulation of
the burner inlet registers.

Low-NOx burners Flue gas recirculation

Many existing units are equipped with LNBs. This has Flue gas recirculation has been used extensively on boilers
been a standard for new fired heaters, plus a number of older to reduce NOx. Recirculating the flue gas reduces the oxygen

44 www.cepmagazine.org March 2002 CEP

 0.8 0.4
Combustion Air Preheat 10% Excess Air
0.7 Temperature
1,000 ˚F

NOx Emissions, lb/MM Btu

0.3
NOx Formation, lb/MM Btu

0.6
Oil-Fired Conventional Burner
0.5 800 ˚F
0.2
0.4

0.3 650 ˚F
0.1
0.2 Gas-Fired Conventional Burner

0.1
0.0
0 100 200 300 400 500 600
0.0
0 1 2 3 4 5 6 7 8 9
Combustion Air Preheat Temperature, ˚F
Oxygen Content of Flue Gas, % O2
■ Figure 3. Impact of air preheat on NOx generation.
■ Figure 1. Oxygen content in stack gas vs. NOx formation.

1.6

Excess Air = Constant

1.5
Relative Thermal NOx Emissions

1.4

1.3

1.2

1.1
1.0
0.9
1,300 1,400 1,500
Firebox Temperature, ˚F
■ Figure 2. Impact of firebox temperature on NOx generation.
concentration and thus reduces flame temperatures. Reported
flame temperatures are 3,500°F with no recirculation, and
2,900°F at 20% FGR. Figure 5 shows the NOx reduction that
can be achieved with and without preheat in a boiler.
Because of the much higher volumetric heat release, the
combustion zone within a boiler tends to be inherently hotter.
This causes NOx concentrations tend to be significantly high-
er than in a typical process heater. To achieve very low NOx
in a boiler, FGR is required.
The installation of FGR requires a motive force to recycle
the flue gas. This has typically been accomplished using a re-
circulation fan, but if there is already a forced-draft (FD) fan
installed, some recirculation can be educted in the discharge or
■ Figure 4. ULNB inside a fired heater. Photo courtesy of Callidus Technologies.
the suction of the FD fan. The installation also requires some
method of introducing the recirculated air into the burners. For
1,600 1,700 1,800 1,900 FD systems, the air can be added to the existing plenum. For
natural-draft (ND) systems, the burners can be modified.
FGR can be economical in fired heaters with air preheat sys-
tems if induced-draft (ID) and FD fans are already available, so
new fans are not required, and if the existing air preheat system
increases the NOx levels. FGR can also be economical in sys-
tems using an SCR, because the SCR will already be providing
an ID fan that can be used to recirculate the gas.
Only a small number of fired heaters are equipped with
FGR. This is partially because fired heaters tend to have
lower firebox temperatures, so there is less need for FGR. In
addition, many fired heaters do not have FD fans, and it can
be more expensive to install FGR in natural-draft heaters.
Some users are also concerned that tube leaks in process
heaters can recycle hydrocarbons back to the firebox and can
potentially cause a fire or explosion. However, there are no
known cases of fired heaters exploding because of FGR, so
this fear may not be justified.
Historically, recirculation rates in the 15% to 20% range

CEP March 2002 www.cepmagazine.org 45

Environmental Protection
100
80 500˚F Preheat
NOx Reduction, %
No Preheat
60
40
20
0 conversion of fired heaters to FD, although in theory, air could
0 5 10 15 20 25 30
Flu Gas Recirculation, %
■ Figure 5. NOx reduction vs. recirculation rate.
have been used, with NOx reductions in the 40% to 55%
range. Recirculation of 40% is the maximum stochiometri-
cally possible. The latest regulations have been forcing recir-
culation close to 40%, for NOx reductions as high as 70%,
but these systems require very tight control systems to main-
tain flame stability.
FGR has several advantages. It reduces both thermal NOx
and prompt NOx by reducing the flame temperatures. It is
Further Reading
Bradford, M., and R. Grover, “Comprehensive Review of NOx Reduc-
tion Technologies,” presented at the AIChE 2001 Spring National
Meeting, Houston, TX, (Apr. 22–26, 2001).
Bradford, M., and R. Grover, “Just Say NOx — A Review of Nitrogen
Oxide Reduction Technologies for Chemical, Petrochemical, and
Refining Industries,” Environmental Protection, II (12), pp. 31–33,
49 (Dec. 2000).
Cetinkaya, B., et al., “Control Flue Gas Emissions,” Hydrocarbon Pro-
cessing, 79 (7), pp. 55–62 (July 2000).
Grover, R., and M. Bradford, “NOx Abatement — A Comprehensive
Review,” presented at the Eighth Annual South Texas Environmental
Conference 2000, Corpus Christi, TX (Oct. 2000).
Hamilton, D. M., et al., “A Novel Approach to the Removal of Nitro-
gen Oxides (NOx) From Waste Incinerator Flue Gas Streams Using
the Shell DeNOx System,” presented at the International Incinera-
tion Conference, Savannah, GA, sponsored by the Univ. of Maryland
(May 6–10, 1996).
Holland, C. D., “Special Report — A Summary of NOx Reduction Tech-
nologies,” The Texas Institute for Advancement of Chemical Technol-
ogy, Texas A&M Univ., College Station, TX, Special Report 1 (2000).
Lovblad, R., et al., “NOx Reduction from a Recovery Boiler by Injection of
an Enhanced Urea Solution (NOxOUT® Process),” Presented at TAPPI
Environmental Conference, San Antonio, TX, (Apr. 7–10, 1991).
Paul, P., and O. Maaskant, “Catalytic NOx Emission Reduction at a
Cogeneration Plant in the Food Industry,” presented at NOXCONF
— NOx and N2O Emission Control Conferene, organized by
ADEME (Agency for Environment and Energy Management), Paris,
France (Mar. 2001).
Topsoe, Nan-Yu, “Catalysis for NOx Abatement,” in “Proceedings of
CATTECH — Catalyst Technology,” Baltzar Science Publishers, pp.
125–133 (Dec. 1997).
U.S. Environmental Protection Agency, “Alternative Control Tech-
niques Document — NOx Emissions from Process Heaters (Re-
vised),” Publication No. EPA-453/R-93-034, EPA, (Sept. 1993).
46 www.cepmagazine.org March 2002 CEP
less expensive than SCR on boilers. It can be used in combi-
nation with ULNBs to achieve very low NOx concentrations
in boilers. And it can be used to recirculate flue gas into the
fuel gas to reduce the heat of combustion of the fuel and thus
reduce flame temperatures.
The disadvantages of FGR include: It could require the
35 be recycled to the inlet plenums. It has a higher investment
cost than the installation of ULNBs alone. For fired heaters, it
may not work in combination with ULNBs that depend on in-
ternal flue gas recirculation. It may be necessary to increase
the capacity of the FD fan and to install a new recycle fan.
And the higher power consumption increases electrical costs.
Relative costs of alternative technologies
The technologies in Table 1 are listed in approximate
order of cost. The following additional comments should be
noted. All of the technologies except for SCRs have relatively
low investment requirements — for example, the installation
of ULNBs in existing fired heaters is in the $100,000 to $1
million per heater range. There is essentially no operating
cost increase to install new burners, including ULNBs, and
there is even a potential energy savings. FGR, SNCR, catalyt-
ic scrubbing and SCRs have significant operating costs; cat-
alytic scrubbing tends to have the highest operating cost.
SCRs have a high investment cost ($1 million to $4 million
per fired unit). CEP
MIKE BRADFORD is the environmental manager for Jacobs Engineering Group,
Inc. (5995 Rogerdale Rd., Houston, TX 77072; Phone: (832) 351-7085;
E-mail: mike.l.bradford@jacobs.com). He has over 35 years of experience in
process engineering, especially the design of environmental control
systems. He has over 30 papers and publications on environmental topics,
including over ten papers on NOx control. He has a BS in chemical
engineering from Ohio Univ. and an MS in chemical engineering from
Northwestern Univ. He is a member of AIChE.
RAJIV GROVER is the environmental section manager for Jacobs Engineering
Group, Inc. (5995 Rogerdale Rd., Houston, TX 77072; Phone: (832) 351-
7088; E-mail: rajiv.grover@jacobs.com). He has over 18 years of experience
in environmental compliance and environmental process engineering. He
has over ten papers and publications on environmental topics, including
several on NOx regulations. He has a BTech in chemical engineering from
the Indian Institute of Technology, New Delhi, and an MS in chemical
engineering from the Univ. of Pittsburgh. He is a member of the Air and
Waste Management Association and the Water Environment Federation.
PIETER PAUL is the environmental principal engineer at Jacobs Consultancy
Nederland B.V. (Plesmanlaan 100, 2332 CB Leiden; Phone: +31-71-582-7382;
Fax: +31-71-582-7050; E-mail: pieter.paul@jacobs.com). He has over 23 years
of experience in process engineering, especially in the design of
environmental control systems. Presently, he works in the Safety, Health &
Environment (SHE) Dept. of Jacobs Consultancy. He joined the company (the
former Comprimo) in 1982, and his areas of specialization include wastewater
treatment, waste and flue gas treatment, and biotechnological processes. He
has extensive experience in the design and troubleshooting of de-NOx
installations and works as a consultant and engineer in off-gas, flue gas and
wastewater treatment projects. He has published numerous articles on these
subjects. He has an MSc in biochemical engineering from Delft Technical Univ.
He is a member of the Royal Netherlands Chemical Society, the Netherlands
Biotechnological Society, and the Netherlands Society for Water Management.