Originally appeared in: CHEMICAL ENGINEERING
TRIMMING NOx FROM FURNACES
Ashutosh Garg,
Furnace Improvements
Each passing year seems to bring about
increasingly stringent pollutant-emission
laws governing combustion equipment. In
the future, one can expect even-stricter
emissions limits to be imposed on the
chemical process industries (CPI).
As regulations tighten, the necessity to
consider environmental concerns in the
operation of furnaces is also mounting. Of
the various environmental laws now
affecting the CPI, laws covering nitrogen
oxides (NOx) are among the most
sweeping.
For example, in the U.S., the South
Coast Air Quality Management District, or
SCAQMD, which covers the Los Angeles
basin, already has one of the strictest
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November 1992 Issue, pgs 122-128. Reprinted with publisher’s permission.
standards. Under SCAQMD’s standard,
furnaces with capacities of less than 40
Emissions-control
million Btu/h must release less than 40 technologies need
ppm of NOx by September 1991. For
furnaces larger than 40 million Btu/h, the not limit a fired
limit is less than 25 ppm by December
1995 (NOx emissions from 36 % of the heater’s perform-
units greater than 40 million Btu/h must be
cut down to 25 ppm by September, 1992). ance
Finding the means for limiting NOx
from fired heaters has become a major
thrust of many sectors in the CPI. The
utility industry – the first industrial sector
in the U.S. to be affected by NO x controls
FIGURE 1. CPI furnaces, available in
– has been the spawning ground for many
of the new technologies now being used to box or cylindrical designs, can be fitted
stem NOx from CPI furnaces. Other with a number of coil configurations.
1

sectors that have also been strongly
affected by NOx standards are petroleum
refining and petrochemicals.
The stricter NOx limits means that it is
increasingly important to understand both
the capabilities of these new emission-
control technologies, and how they affect a
fired heater’s overall performance,
reliability and operating flexibility. This is
especially significant when retrofitting
combustion equipment with new emission
controls.
The NO x Dilemma
Vertical heaters used in the CPI fall
broadly into two categories: cylindrical
and box heaters. In both types, the tubes
are laid out on the walls of the radiant
section.
In cylindrical heaters, the tubes are
installed vertically, while in box heaters,
the tubes are arranged horizontally. In both
designs, the burners are installed on the
floor, and fire vertically upwards.
Most of the burners employ a natural-
draft design, in which the stack provides
the draft for drawing air into the furnace
for combustion. Newer units are equipped
with forced-draft firing systems and air
preheaters to improve fuel efficiency. The
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convection section consists of bare and
extended-surface tubes to recover heat
from the flue gases before they exit from
the stack. Figure 1 shows the typical heater
types used in the CPI.
The pollutants generated by burning
fuel fall into three primary categories:
carbon monoxide, unburned hydrocarbons,
and partially oxidized organic materials
and soot that result from incomplete
combustion; sulfur oxides and ash directly
attributable to fuel composition; and
nitrogen oxides formed at firebox
temperatures by the reaction of the oxygen
and nitrogen present in the air and fuel.
Incomplete combustion products can
usually be held to tolerable minimums by
the proper operation of modern burner
equipment, while sulfur oxide and ash
emissions can be cut by using the right
fuel. However, nitrogen oxide
concentrations are primarily functions of
fuel composition, burner design and
firebox temperature, and so have to be
controlled by choosing the right operating
conditions.
There are several ways that NOx is
formed in a furnace. Thermal fixation of
atmospheric nitrogen and oxygen in the
combustion air produces “thermal NOx”
2
Trimming NOx from Furnaces
while the conversion of chemically bound
nitrogen in the fuel produces “fuel NOx”.
For natural-gas and light-distillate-oil
firing, nearly all NOx emissions result
from thermal fixation. With residual fuel
oil, the contribution from fuel-bound
nitrogen can be significant and, in certain
cases, predominant. This is because the
nitrogen content in residual fuel oil can be
as high as 0.3% N2, and conversion to
NOx may be 50-60%.
The formation rate of thermal NOx is
dependent on the reaction temperature, the
local stoichiometry, and the residence
time. The fuel-NOx formation mechanism
is more complex, depending upon fuel
pyrolysis and subsequent reaction between
many intermediate nitrogenous species and
the oxidant species.
The rates for formation of both
thermal NOx and fuel NO x are kinetically
or aerodynamically limited, with the
amount of NOx formed being much less
than the equilibrium value. The rate of
formation of NOx is dominated by
combustion conditions and can be
suppressed by modifying the combustion
process. Both thermal and fuel NOx are
promoted by rapid mixing of oxygen with
the fuel. Thermal NOx is greatly increased

FIGURE 2. Actual
measurements (in
ppm) of nitrogen
oxides in fluegases
can be converted
to the more com-
mon way of repre-
senting emissions,
in lb NOx (as NO2)/
million Btu of
gross heat re-
leased
by long residence time at high
temperature.
Emission limits are usually specified
in terms of pounds of NOx per million
Btu of gross heat released, or pounds per
hour. NOx concentrations, however, are
measured in terms of ppm (volume)
basis. Since operating conditions vary
among various furnaces, the NOx
measurements are converted to standard
conditions at 3% oxygen.
By calculating the dry combustion
production per million Btu and the heat
release rate, R, it is possible to convert
from ppm to lb/million Btu or lb/h. NOx
emission calculations are made on the
basis of NO2 (molecular weight of 46),
although NO2 is only 10-15% of the total
NOx.
ppm vol. (at 3% O2) = ppm vol.
measured x (21-3)/21 - % O2)
where, % O2 = vol. % O2, dry basis
NOx, in lb/million Btu = (ppm NOx) x
(DSCF/ million Btu) x 46/ (1,000,000 x
379.3)
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Trimming NOx from Furnaces
Modifying combustion conditions to
inhibit the mechanisms for formation of
NOx
Lowering NO x generated during
combustion by either catalytic or non-
catalytic reduction.
The NOx-control processes discussed
below utilize one or a combination of the
above techniques.
Flue gas recirculation (FGR) extracts a
portion of the flue gas from the stack and
returns it to the furnace along with
combustion air (Figure 3). This lowers
the peak flame temperature, and cuts
thermal-NOx formation. The addition of
fluegas also reduces the oxygen available
to react with the nitrogen. A comparison
of the two heat duties for a furnace with
and without – flue gas recirculation is
shown in the table.
Increasing the recirculation rate
generally corresponds to a decrease in
thermal NOx, but flame instability and a
decrease in the net thermal output limits
the recirculation rate. Recirculation rates
for gas-fired units are limited to about
15% to 25%, resulting in maximum
thermal-NOx reductions on the order of
50%. It is useful where low nitrogen
fuels, such as natural gas, are used.
Recirculating flue gas temperature should
For quick NOx level estimations, the not be more than 600oF.
following DSCF – dry volume of flue-gas Flue gas recirculation has been
in standard cubic feet/ million Btu at 3% mostly applied to forced-draft burners.
O2 concentration – values are Installation requires additional duct work,
recommended: a flue gas recirculation fan, a flow control
damper, special burners and combustion
Natural Gas 10,127 control instrumentation (such as
Propane 10,127 continuous oxygen and carbon monoxide
Butane 10,127 analyzers in the stack). If the heat content
Fuel Oil 10,684 of the fuel is highly variable, a flame
safeguard system is required to monitor
Post Combustion NOx Treatment the flames continuously. The technique is
The concentration of NOx in combustion suitable for heaters with a few burners,
flue gases can be cut by: such as vertical, cylindrical heaters.
Flue gas recirculation
does not affect the overall
efficiency of fired heaters
if the temperature of
fluegas leaving the
convection zone is the
same as that of the flue gas
being recirculated.
However, the split of
radiant heat and
convection heat duty will
change, since the
TABLE. Fluegas recirculation changes the split recirculating flue gas acts
of convection -and radiant - heat duties. as a diluent, reducing the
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 Trimming NOx from Furnaces

uptake of heat in the radiant section and deactivation. However, this can be reduces NOx to N2 and H2O. Ammonia is
increasing it in the convection section. avoided if care is taken during the design injected into the upper part of combustion
stage. For example, if SO 2 is present in chamber or into a thermally favorable
Selective catalytic reduction (SCR) the flue gas, then a minimum temperature location downstream. The various
involves injecting ammonia into the flue of 608oF is recommended for SCR reactions are:
gas upstream of a catalyst bed. The operation. A catalyst’s life depends on its
chemical reaction involved is: type, the application and other factors, 6NO + 4NH 3 5N2 + 6H2O
with numbers of three to six years being
O2 + 4NO + 4NH3 4N2 + 6H2O reported in oil and gas applications.
SCR systems have the highest 6NO2 + 8NH 3 7N2 + 12H2O
NOx and NH3 combine on the catalyst’s installation costs and requires the greatest
surface, forming an ammonium salt amount of space of all NOx-control
intermediate that subsequently methods. They can be easily retrofitted in Recently, a urea-based regent is
decomposes to produce elemental fired heaters with air-preheating systems, increasingly being used in place of NH3
nitrogen and water. The catalyst lowers since all this involves is re-rating of the because it is safer and easier to handle.
the activation energy of the NOx fan and re-routing the duct to the air Urea decomposes into NH3 and carbon
decomposition reaction, thereby enabling preheater via an SCR unit. The left dioxide inside the firebox.
use of this technology at lower flue gas portion of Figure 3 shows a typical SCR The flue gas temperature is critical to
temperatures. The optimum temperature unit retrofitted in a furnace with an air the successful reduction of NOx. For
range for SCR is 600oF to 700oF. preheating system. convectional combustion, the optimal
SCR removes 70 to 90% of the NOx, range for NH3 injection is 1600o to
using between 0.9 to 1.0 mole NH3 for Selective noncatalytic reduction (SNCR) 1,750oF; for urea, 1,000o to 1,900oF. As
every mole of NOx; this leaves behind 5 is a post combustion-control method that the temperature increases, the NH3 reacts
to 10 ppm of unreacted NH3. The major
components of an SCR system are a Figure 3: Popular post-combustion methods of removing NOx
catalyst bed reactor, an ammonia injection include selective catalytic reduction (left part of figure) and
grid, and an ammonia storage unit. fluegas recirculation.
Ammonia can be injected in anhydrous
form or as an aqueous solution. Typically
a residence time of 0.5 to 1.0s allows for
adequate mixing of the ammonia and NOx
before the catalyst bed.
Several factors in addition to
operating temperature influence SCR
performance. These include the catalyst
composition and configuration, sulfur and
metals content of the fuel, and the design
of the ammonia-injection system.
Catalysts are commercially
available in a wide variety of materials.
These include such metals (such as
titanium, vanadium and platinum),
zeolites and ceramics. Catalyst shapes
include honeycomb plates, parallel-ridged
plates, rings and pellets.
Each combination presents
advantages and disadvantages in terms of
allowable operating temperatures, catalyst
fouling and pressure drop. Typical gas
velocities over the catalyst are around
20ft/s, and the pressure drop is 3-4 in.
(water column.)
The early applications of SCR had
been prone to a number of problems.
These include: catalyst plugging by fine-
particle dust; catalyst poisoning by SO 2;
conversion of SO 2 to SO 3; formation of
ammonium bisulfate; and the deposition
of ammonium bisulfate on the catalyst at
temperatures below 518oF.
All these factors lead to catalyst

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 Trimming NOx from Furnaces

While SCR and SNCR maintain control

over NOx after is has been formed in
the combustion reaction, modifications
of the combustion equipment or the
burners can also significantly reduce
NOx formation. There are a number of
advantages in using such modified
burners, the major ones being
simplicity and low cost. At the same
time, since burners form the heart of a
furnace. The process of implementing
new ones should always be tried
cautiously.

Staged air burner systems divide the

incoming combustion air into primary
and secondary paths: All of the fuel is
injected into the throat of the burner
and is combined with the primary air,
which floss through the venturi and
burns (Figure 4).
In this fuel-rich zone, the fuel
partially burns and the nitrogen is
Figure 4: Two ways of modifying the fuel air stoichiometry during com- converted into reducing agents.
bustion is to use a staged fuel burner (left) or a staged air burner. These nitrogenous compounds are
subsequently oxidized to elemental
more with oxygen than with NO, forming to be used along with a second NOx- nitrogen, thereby minimizing the
more NOx. At flue gas temperatures reduction technique. generation of fuel NOx.
below the optimal range, the rate of Also, the peak flame temperature is
reaction declines, resulting in reduced Redesigning The Equipment lowered in the fuel-rich primary
NOx control and greater amounts of combustion zone, since the generated heat
unreacted NH3 slipping into the dissipates rapidly. Recirculation of
effluent. combustion products within the burner
The NOx reduction achieved is of further cuts the flame temperature and
the order of 50-60%, with the NH3 slip oxygen concentration, reducing NOx (in
in the 20 to 30 ppm range. The this case the thermal NOx even more. In
technique is effective in the presence of the secondary-combustion zone,
carbon monoxide, and with oxygen additional air is injected through
contents of up to 1% (calling for very refractory ports to complete combustion
close control of excess air). and optimize the flame profiles.
The disadvantages of SNCR are Staged air burners are simple and
similar to those of SCR: Ammonium inexpensive, and NOx reductions as high
salts, namely ammonium sulfate and as 20 to 35% have been demonstrated.
bisulfate, may form if excess NH3 The main disadvantage of the burners is
reacts with sulfuric acid, form a prior the long flames, which need to be
reaction between SO 3 and water. controlled. Further, staged-air burners
Ammonium bisulfate can contribute to have proven to be quite successful in
fouling and corrosion in low formed-draft applications, and have even
temperature heat-recovery equipment. been used with flue gas-recirculation
Ammonium chloride can also be systems.
formed, which is undesirable since it
causes visible plumes. High levels of Staged fuel burners inject a portion of the
NH3 slip, up to 50 to 100 ppm, can fuel gas into the combustion air, and the
occur if the NH3-to-NOx ratio is not resulting combustion is very lean (i.e. air
optimized. Overall, the method has not rich). This lean combustion reduces
become widely popular with process thermal NOx. The remainder of the fuel
fired heaters since it cannot meet gas is injected into a secondary
NOx-reduction requirements by Figure 5. NOx levels can be cut very low combustion zone through secondary
levels by combining staged fuel burners with
itself, and needs nozzles (Figure 4).
internal fluegas recirculation

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The combustion products and inert
gases from the primary zone reduce the
peak temperatures and oxygen
concentration in the secondary zone,
further the inhibiting NOx formation.
Some of the NOx formed in the first stage
combustion zone is reduced by the
hydrogen and carbon monoxide that is
formed in staged combustion.
Staged fuel burners can reduce NOx
emissions by as much as 50-60%. This
type of burner can operate with a small
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Trimming NOx from Furnaces
used to reduce NOx to very low levels. In
this design, the fuel gas’s pressure or
external agents, such as medium-pressure
steam or compressed air, are used to
induce flue gas recirculation within the
burner.
Low excess-air burners works on the
principle that low levels of excess air
suppress NO x formation. Typically, excess
air levels are maintained at 5%. The
burners are often of a forced-draft design,
and employ a self-recirculating technique
to produce a multi-stage combustion
effect. A NOx level of 0.06 to 0.08 lb/
million Btu is typically encountered.
Generally, it has been found that reducing
excess air from 30% to 10% cuts NOx
emissions by 30%.
References
Air Pollution Engineering Manual, AP-
42, U.S. Environmental Protection
Agency.
NOx Control In fired heaters, Martin,
R.R. and W.M. John Zink Co.
Cleaning Up NOx Emissions, McInnes,
R., and M.B. Van Wormer, Chem.
Eng., Sept 1990
Reduce Heater NOx In the Burners,
Seabold, J.G., Hydrocarbon Process,
Nov. 1982.
The author
flame length, and at lower excess-air levels
than can staged air burners. The flames in
staged fuel burners are about one and a Ashutosh Garg is Manager of Thermal
half times longer than those in standard Engineering at Kinetics Technology
burners. Staged fuel burners have been International Corp. He has more than 18
found more effective in reducing NOx in years of experience in process design,
gas-fired heaters and, so, the majority of sales and troubleshooting of all
the applications are gas fired. combustion systems. He graduated in
chemical engineering in 1974 from Indian
Ultra Low NOx Burners, a combination of Institute of Technology, Kanpur. He is
staged fuel burning and internal flue gas registered professional engineer in
circulation (Figure 5), have recently been California, and a member of AIChE.
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