144 Ind. Eng. Chem. Res.

2001, 40, 144-151

Ammonia Pyrolysis and Oxidation in the Claus Furnace

W. D. Monnery, K. A. Hawboldt, A. E. Pollock, and W. Y. Svrcek*
Department of Chemical and Petroleum Engineering, The University of Calgary,
Calgary, Alberta T2N 1N4, Canada

The modified Claus process is commonly used in oil refining and gas processing to recover sulfur
and destroy contaminants formed in upstream processing. In oil refining, in addition to the
typical modified Claus plant feed of H2S and CO2, NH3 is also often present. NH3 is a process
contaminant and must be destroyed in the front-end furnace of the modified Claus plant,
otherwise, it poses a risk of poisoning the catalyst beds and plugging off downstream equipment
because of the formation of ammonium salts. In this paper, the pyrolysis and oxidation of NH3
was studied under Claus furnace temperatures and residence times. Experimental data was
taken, and new reaction rate expressions were developed for NH3 pyrolysis and oxidation.
The derived rate expressions are outlined as follows: the NH3 pyrolysis rate expression r ) A
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exp(-Ea/RT)PNH31.25, where A is 0.004 21 mol s-1 atm-1.25 cm-3 and Ea is 16.5 kcal mol-1, and
the NH3 oxidation rate expression r ) A exp(-Ea/RT)PNH3PO20.75, where A is 4430 mol s-1 atm-1.75
cm-3 and Ea is 40.0 kcal mol-1. The rate expression for NH3 pyrolysis matched experimental
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data within 13% and matched well with published data. The rate expression for NH3 oxidation
matched experimental data within 10%.

Introduction
The modified Claus sulfur recovery process is the
most common process used to remove sulfur from acid
gas streams occurring in oil and gas processes. This
process is comprised of a high-temperature furnace
followed by catalytic reactor(s). The reactions occurring
in the furnace are numerous, and several authors have
attempted to delineate the important ones (Clark et al.,
1997). As part of our ongoing study, we have previously
published kinetic data and reaction rate expressions for
H2S cracking/reassociation (Hawboldt et al., 1999a) and
the Claus reactions (Hawboldt et al., 1999b).
The reaction furnace has three functions: the conver-
sion of one-third of the H2S to SO2 for downstream
catalytic processing, the destruction of any contami-
nants which may foul downstream equipment, and the
production of elemental sulfur, which can account for
up to 70% of the inlet sulfur for a “straight-through-
type plant”. The types of contaminants in the sour gas
stream depend on the source of the feed gas. For
instance, in oil refinery operations, NH3 is formed as a
byproduct of denitrogenation operations, such as hydro-
cracking and hydrotreating. Subsequent sour water
stripping results in a sour gas feed stream containing
NH3, which is then directed to the sulfur recovery
facility for destruction.
The desired NH3 destruction reactions in the furnace
are the complete pyrolysis and/or oxidation of NH3
2NH3 T N2 + 3H2 (1)
3
2NH3 + O2 T N2 + 3H2O (2)
2 Literature Review
5
2NH3 + O2 f 2NO + 3H2O (3)
2
Incomplete pyrolysis or combustion of NH3 in the
furnace results in NH3 and NO carryover into the
catalyst beds. Ammonia can form ammonium salts,
which can plug or foul the catalyst beds, other equip-
ment, or piping. Although the formation of SO3 occurs
in the catalyst bed regardless of the presence of NO,
the presence of NO in the beds acts as a catalyst for
the conversion of SO2 to SO3, which in turn causes
catalyst sulfation (Garside and Phillips, 1962). Of the
primary causes of catalyst activity loss, catalyst sulf-
ation is regarded as the most significant (Grancher,
1978). It is therefore critical to convert as much of the
NH3 to N2, H2, and H2O as possible.
One of the obstacles to designing and operating the
furnace properly, i.e., determining optimal residence
times and temperatures, is the absence of kinetic rate
expressions for the key reactions (Monnery et al., 1993).
For ammonia destruction, an empirical rule of thumb
that is generally agreed with in industry is that tem-
peratures greater than 1200-1250 °C are required.
However, there appears to be some debate as to how
much residence time is required and how ammonia
oxidation competes for oxygen versus hydrocarbon and
H2S oxidation (Johnson and Rempe, 1997; Goar, 1994).
As such, ammonia pyrolysis and oxidation kinetic data
are badly needed. In this paper, we will present new
experimental data and new kinetic rate expressions for
the NH3 pyrolysis and NH3 oxidation reactions at Claus
front-end furnace (FEF) conditions and residence times.

Under excess oxygen conditions and incomplete mixing, NH3 Pyrolysis. Davidson et al. (1990) performed a
series of high-temperature pyrolysis experiments at a
the following reaction may also occur (Clark et al., 1997):
temperature range of 2000-3200 K, a pressure range
of 0.8-1.1 atm, and an NH3 concentration range of 0.1-
* To whom correspondence should be addressed. 1.0%. Under these conditions, NH3 is completely con-
10.1021/ie990764r CCC: $20.00 © 2001 American Chemical Society
Published on Web 12/01/2000

Figure 1. Apparatus schematic.
sumed within a 1 ms residence time. A detailed reaction
mechanism was proposed, consisting of 21 free-radical
reactions. These experiments were performed behind
reflected shock waves. The severity of the temperatures
and the mechanism of the experiment (shock tube)
prevent direct comparison with data generated in our
experiments. However, these studies do give an indica-
tion of trends and therefore the significance of inter-
mediate species (NH2, NH, N2H2, etc.).
Clark et al. (1998) conducted a study on NH3 pyrolysis
at FEF conditions to determine the effects of other
chemical species occurring at furnace temperatures,
pressures, and residence times. In general, both H2S
and H2O were found to inhibit NH3 pyrolysis, whereas
SO2 enhances NH3 pyrolysis. Their results also showed
oxidation being much more rapid than pyrolysis.
NH3 Oxidation. Published studies have indicated
that the oxidation of NH3 is a much more rapid process
than pyrolysis (Clark et al., 1998; Lindstedt and Selim,
1994; Miller et al., 1983; Fujii et al., 1981). In the Fujii
et al. (1981) study, the reaction was investigated at
temperatures between 810 and 2100 K, pressures from
1.1 to 8.4 atm, NH3 concentrations from 0.5 to 75%, and
O2 concentrations from 0.5 to 90%, with the balance of
the gas being argon.
Miller et al. (1983) used a reaction model consisting
of 98 reactions to determine the reaction mechanism for
NH3 oxidation. The model predictions were compared
with experimental data generated by MacLean and
Wagner (1967). The developed kinetic model predictions
were in good agreement for the lean to moderately rich
gases. However, for the rich flames, the agreement was
poor, possibly indicating inadequate modeling of am-
monia pyrolysis. The model and experimental results
also showed very low concentrations (approximately
0.001 mole fraction) of NO in the post-flame gases.
In 1994, Lindstedt and Selim proposed a reaction
mechanism consisting of five steps based on experimen-
tal data generated by MacLean and Wagner (1967) and
Vandooren (1992). Both Lindstedt and Selim (1994) and
Miller et al. (1983) based their reaction mechanisms on
flame studies, and therefore temperatures were not
stated.
Other studies on NH3 oxidation have focused on the
reduction of NO by NH3 in NH3-NO-O2 systems. Lyon
and Benn (1978) were the first to conduct a kinetic study
of the reduction of NO by NH3 in the presence of O2 at
temperatures between 872 and 980 °C and pressures
between 1.07 and 2.14 atm. Provided O2 was present
in large excess compared to NO, NH3 addition was
Ind. Eng. Chem. Res., Vol. 40, No. 1, 2001 145
effective in reducing NO at all temperatures and pres-
sures of the study. However, when the NH3 concentra-
tion was comparable to O2, the reduction of NO was
inhibited. Miller and Bowman (1989) came to the same
conclusions and, in addition, found that the process
occurs in the narrow temperature range of 1100-1400
K in the absence of other additives. They also found that
the presence of H2O had a slight inhibiting effect on NO
reduction. Dou et al. (1992) proposed a simple kinetic
model that predicts the rate of NO and NH3 conversion
in the NO-NH3-O2 system. Major conclusions from the
Dou et al. (1992) study indicate that NH3 conversion
increases with temperature, whereas NO conversion
increases with temperature until approximately 1200
K, after which conversion decreases. Furthermore, NO
conversion rapidly levels off within 50 ms, indicating
that longer residence times will not affect NO conver-
sion. In their experiments, O2 was in large excess.
Clark et al. (1998) performed oxidation studies on
NH3 at residence times between 0.34 and 0.55 s and
inlet concentrations of NH3 and O2 of 4 and 3%,
respectively. The study found that between 700 and
1100 °C conversion of NH3 is below 10%, whereas at
temperatures greater than 1100 °C, the conversion
increases to between 60 and 100%.
New Experimental Data Generation
Experimental Apparatus. The experimental ap-
paratus, in Figure 1, consists of pressurized gas cylin-
ders delivering reactants through a controlled flow
system to a flow reactor housed in a high-temperature
furnace, a quench system, and a gas chromatograph for
analyzing reactants and products. The apparatus was
designed by Fookes (1996) specifically for the kinetic
study of the gas-phase reactions occurring in the Claus
FEF.
Reactant gases are dropped from cylinder pressures
to the reactor pressure across the regulators. Subse-
quently, flow rates are controlled by Linde FM4660
mass flow controllers (MFC) connected to a main
console. MFCs were calibrated prior to experimental
work; however, to ensure flow rates were accurately
known, an Alexander Wright wet test meter was also
used. Ultimately, flows were consistent to within 1.0%.
Temperatures were measured with thermocouples, also
accurate to within 1.0%.
Quartz flow reactors were used in these experiments
to avoid possible metal or ceramic catalytic effects. Each
reactor is 5.0 mm in diameter, and three different
146 Ind. Eng. Chem. Res., Vol. 40, No. 1, 2001
lengths were used to provide residence times from about
0.5 s to about 2.0 s, at temperatures between 800 and
1300 °C, typical of Claus front-end reaction furnace
conditions. The reactors have a preheat length, followed
by a mixing chamber, and then an isothermal hot zone.
The reactors are coiled for two reasons: to have
sufficient length to attain the desired range of residence
times in a compact arrangement and to create secondary
flow, which reduces axial diffusion or Poiseuille flow,
thereby enhancing plug flow (Nauman, 1977; Truesdell
and Alder, 1970). The reactor was designed to satisfy
the conditions Cutler et al. (1988) set out for the design
of a plug-flow reactor. Cutler et al. (1988) showed that,
even in laminar flow, the error in deriving kinetic data
from assuming plug flow is typically a few percent, up
to a maximum of 11%, providing certain dimensional
and heat- and mass-transfer criteria are met. Indeed,
Cutler et al. (1988) showed that in attaining kinetic data
there is more error incurred because of systematic error,
such as thermocouple precision. Furthermore, to verify
that the reactor operated in plug flow, a computational
fluid dynamic (CFD) model of the reactor was developed
by British Oxygen Corp.. The results of this simulation
showed that the flow regime closely approximates plug
flow (Hawboldt, 1998). Last, we verified the apparatus
by comparing experimental results to accepted model
results of ethane pyrolysis and matching these to within
5% (Hawboldt et al., 1999b). On the basis of the Cutler
criteria, ethane pyrolysis results, and the results of the
CFD simulation, the reactor was considered to operate
in plug flow with negligible error.
Product gases from the quartz reactors were quenched
rapidly against water in a double pipe exchanger,
typically down to less than 100 °C within 5-10 ms. This
was shown to provide an accurate sample of reactor
products (Hawboldt et al., 1999a). Finally, before prod-
uct gases went to the gas chromatograph, they passed
through a separator and filter to remove solid sulfur.
A key characteristic of this reactor system is that it
operates nearly isothermally, which simplifies data
analysis because temperature variations within the
reacting system do not have to be corrected for. Isother-
mality was ensured with a rapid preheat zone and by
conduction of experiments under dilute conditions. By
keeping reactant concentrations lower than 5%, the
effect of any temperature changes due to the heat of
reaction are minimized, if not eliminated (Hawboldt,
1998). Figure 2 shows the experimental temperature
profile for the 3.05 m reactor as a plot of the deviation
from the furnace setpoint temperature as a function of
length. This figure clearly shows that the temperature
rises rapidly to within 30 °C of the setpoint within the
first 25 cm of length, after which the deviation falls
rapidly, being within 1.2% at 1.0 m.
Experimental Conditions. Pyrolysis. Our experi-
mental conditions were at much lower temperatures
than those of the Davidson et al. (1990) study. Thirty-
seven pyrolysis experiments were performed using
temperatures between 850 and 1200 °C, NH3 concentra-
tions from 0.5 to 2.0%, and residence time ranges from
50 to 800 ms (Hawboldt, 1998). Helium was the gas
chromatograph (GC) carrier gas for the majority of the
experiments; however, to measure the produced N2 and
H2 and close the material balance, the carrier gas was
switched to argon.
Oxidation. Twenty-one NH3 oxidation experiments
were performed. Temperatures were varied between 850
Figure 2. Experimental measurements of the deviation of the
temperature of the reactor from set point temperature along the
reactor length at a flow rate of 8 SLPM.
and 1200 °C, residence times ranged from 30 to 700 ms,
inlet concentrations of NH3 varied between 0.3 and
2.5%, and O2/NH3 ratios varied from 0.85 to 2.55
(Hawboldt, 1998). Argon was used as the dilution gas
for this set of experiments. GC measurements of NH3
were made for all experiments, and to check the mate-
rial balance in selected experiments, N2 concentrations
were also measured. For stoichiometric mixtures of NH3
and N2, the agreement between NH3 consumed and N2
produced was within 10% (Hawboldt, 1998). This excel-
lent material balance closure was also found for experi-
ments with O2/NH3 feed ratios greater than the stoichi-
ometric 0.75. Although some NO may be formed and
the GC cannot separate NO from N2, the results of
equilibrium calculations by both ourselves and Miller
et al. (1983) show that the concentration of NO formed
comprises a maximum of 0.001 mol % of the product.
As such, the excellent material balance that was ob-
served was valid for all experiments.
New Experimental Results
Pyrolysis. Figures 3 and 4 present the conversion of
NH3 with temperature and residence time for the
ammonia pyrolysis experiments. As the figures show,
between 850 and 1050 °C, the conversion of NH3 was
below 25%. At 1150 °C and residence times below 300
ms, conversions are less than 20%; however, at longer
residence times, conversions increase to 55%. At 1200
°C, conversions increased substantially and varied from
27 to 83%. Material balances were verified by comparing
NH3 conversion measurements with N2 and H2 compo-
sition measurements. These measurements agreed to
within 10%, indicating a good material balance. Clark
et al. (1998) showed similar results, in that at residence
times from 0.6 to 1.0 s conversions varied from 10% at
900 °C to 75% at 1200 °C.
Oxidation. Figures 5 and 6 show NH3 conversions
as a function of residence time and temperature for the
oxidation experiments. In general, when compared to
pyrolysis, conversion of NH3 via oxidation is faster and

Figure 3. Experimental and predicted conversion of NH3 in
pyrolysis experiments as a function of temperature and residence
time.
Figure 4. Experimental and predicted conversion of NH3 in
pyrolysis experiments as a function of temperature and residence
time.
occurs to a greater extent for the same temperature. For
example, at 850 °C, conversion by pyrolysis never
exceeds 20%, whereas at the same temperature, conver-
sion by oxidation is observed at nearly double this value.
Direct comparison with the data generated by Lyon
and Benn (1978) is difficult because their experiments
were performed using a large excess of O2. When
compared to the Clark et al. (1998) data, our NH3
conversions were significantly greater at lower temper-
atures. Clark et al. (1998) predict conversions of 4-10%
at residence times from 0.34 to 0.55 s in the temperature
range from 700 to 1100 °C, whereas our conversions in
this same range were 2-60%. The formation of NO in
these experiments could not be substantiated because
of the difficulty in analyzing for this component; how-
ever, equilibrium calculations suggest negligible quanti-
ties to be present.
Modeling Methodology
The determination of the new rate expression was
accomplished by developing a mathematical model that
Ind. Eng. Chem. Res., Vol. 40, No. 1, 2001 147
Figure 5. Experimental and predicted conversion of NH3 in
oxidation experiments as a function of temperature and residence
time.
Figure 6. Experimental and predicted conversion of NH3 in
oxidation experiments as a function of temperature and residence
time.
simulated the reactor. This reactor model contained the
proposed kinetic expressions for the reactions, and the
parameters of the kinetic model were regressed using
our experimental data. Details of the modeling and
regression procedure are provided in Hawboldt (1998).
Reactor Model. The reactor simulation numerically
modeled the experimental apparatus from the inlet
through to the quench, solving a set of differential
equations to determine the reactor product distribution.
The key assumptions in the development of the model
are plug flow in the reactor, steady-state operation, and
ideal gas behavior. The validity of the plug-flow as-
sumption was previously discussed. Because the ap-
paratus operates at high temperatures and close to
atmospheric pressure, the assumption of ideal gas
behavior is also valid, given compressibility factors
greater than 0.99.
The set of differential equations is comprised of the
plug-flow reactor design (eq 4), the reaction rate equa-
tion (eq 5) in terms of reacting species partial pressures,
and an equation for the reactor pressure drop. The
148 Ind. Eng. Chem. Res., Vol. 40, No. 1, 2001

Arrhenius law (eq 6) represents the specific rate con-

stant.

dF/dV ) rj (4)

r ) kΠjPjm (5)

k ) Ae-Ea/RT (6)
In addition, an equation of the reactor axial temperature
profile was included, which was established using
experimental data obtained from a temperature calibra-
tion reactor (Hawboldt, 1998). Pure component viscosity
was calculated using Chung’s method, and the mixing
rules of Wilke were used for the prediction of gas
mixture viscosity (Reid et al., 1987). The set of algebraic
and differential equations that describe the physical
system were solved using an adaptive step-size Runge-
Kutta method taken from Press et al. (1992).
Optimization Method. Simulated annealing, de-
tailed in Bohachevsky et al. (1986), was used to mini-
mize the objective function:

OF ) ∑|xp,i - xm,i| (7) Figure 7. Arrhenius plot for NH3 pyrolysis.

where xp,i is the predicted exiting gas conversion and

xm,i is the experimental (measured) gas conversion. The
optimization method uses the reactor model to calculate
the exiting reactor conversions, which are compared to
the experimental conversions. The temperature, pres-
sure, and residence time were set at the beginning of
each experiment, and the independent parameters used
to minimize the objective function were the Arrhenius
constant (A) and activation energy (Ea).
Pyrolysis Modeling Results. Reaction Order.
Previous studies indicated that NH3 conversions under
pyrolysis conditions are small; however, equilibrium
calculations show 100% conversion of NH3 to N2 and
H2, indicating that the pyrolysis of ammonia (eq 1) is
not equilibrium limited at Claus FEF temperatures
(Hawboldt, 1998). Hence, the following rate equation is
proposed for FEF conditions:

r ) kPNH3m (8)

The order and initial estimates of A and Ea were made

prior to parameter optimization. The reaction order (m)
was determined by performing experiments where the
temperature and residence time were kept constant
while the inlet concentration of NH3 was varied from
0.5 to 2.0%. By plotting inlet versus exit NH3 concentra-
tions, we calculated the value of m to be 1.25. This value
was verified using the parameter optimization program.
On the basis of the derived form of the rate equation,
an Arrhenius plot for NH3 pyrolysis is shown in Figure
7. The slope of the line is -11.0, yielding an Ea of 21.0
kcal mol-1, which was used as an initial estimate for
the optimization.
Parameter Optimization Results. In the optimiza-
tion, parameters A, Ea, and m were optimized to match
NH3 conversions. The resulting rate equation is shown
below as eq 9:
r ) Ae-Ea/RTPNH31.25 (9)
where A is 0.004 21 mol cm-3 s-1 atm-1.25 and Ea is 16.5
kcal mol-1. Figures 3 and 4 show the comparison
Figure 8. Clark et al. (1998) NH3 conversions compared to model
predictions. The Clark et al. data is based on a residence time (J)
range of 0.6-1.0 s.
between the model predictions and experimental data.
The average absolute error (AAE) between the model
and data is 13%.
Data generated by Clark et al. (1998) was also
compared to model predictions, and the results are
shown in Figure 8. The experimental conditions of the
Clark et al. (1998) data were an inlet NH3 concentration
of 14.5% and a residence time range of 0.6-1.0 s. The
proposed kinetic model was run at 0.6 and 1.0 s and, as
shown in Figure 8, the data falls between these two
simulations, further verifying our model.
Ammonia Oxidation Modeling. Reaction Order.
Equations 2 and 3 show the two primary oxidation
pathways for NH3. In this study, the focus has been on
eq 2, and consequently, the experiments were run at

Figure 9. Natural logarithm of the regressed rate constant versus
inverse temperature for the NH3 oxidation reaction.
conditions where eq 3 was minimized. The proposed
form of the rate equation is as in eq 10:
r ) kPNH3mPO2n
Because direct measurement of O2 is difficult with our
apparatus, the reaction orders m and n were determined
by the method of excess reactants. That is, to determine
m, the O2 was kept in excess of the stoichiometric value
(0.75 O2/NH3). Although this ratio exceeds the quantity
of O2 required to form NO, as stated previously,
negligible amounts of NO are formed. In determining
the reaction order with respect to NH3, we varied the
NH3 levels from 0.44 to 1.35% at a temperature of 1050
°C and a residence time of 70 ms. The reaction order of
NH3 was then calculated by plotting the inlet concen-
tration against the outlet concentration.
For the reaction order with respect to O2, n, the NH3
was kept constant at 1.37% and the O2 increased from
2.6 to 4.4% at a residence time of 720 ms and 950 °C.
The order with respect to O2 was calculated via eq 11:
( )
NH3,exit
log ln ) n log O2 + constant
NH3,inlet
The calculated values of m and n were 0.98 and 0.72,
respectively. These values were set to 1.0 and 0.75 in
the oxidation kinetic rate expression.
Parameter Optimization Results. Previous studies
(Fujii et al., 1981; Clark et al., 1998) have suggested
that the temperature dependence of the rate constant
changes at approximately 1050-1100 °C, indicating
that the Arrhenius constant and activation energy must
also change. To verify this result, individual rate
constants were regressed at each temperature and
plotted as shown in Figure 9. The linear relationship
between ln(k) and inverse temperature indicates that
there is no significant change in the temperature
dependence of the rate constant between 850 °C and
1200 °C, a result that is in disagreement with previous
work by Fuji et al. (1981). It is worthwhile to note that
in the regression of the rate constants for the oxidation
reaction, kinetic expressions for both ammonia pyrolysis
and oxidation were included in the simulation, because
Ind. Eng. Chem. Res., Vol. 40, No. 1, 2001 149
Figure 10. Comparison of model predictions with Clark et al.
(1998) data for NH3 oxidation (residence time ) 0.34-0.55s).
this more accurately describes the chemistry of the
system. As such, the apparent change in the tempera-
(10) ture dependence is due to the combined effect of pyroly-
sis and oxidation. Given the above conclusion that the
temperature dependence of the rate constant follows the
Arrhenius law, the form of the rate equation is as shown
in eq 12:
r ) kPNH3PO20.75 (12)
Figures 5 and 6 compare the model predictions to the
experimental data for the complete range of tempera-
tures. The AAE for the data set was 10%, indicating an
excellent agreement between the predicted and experi-
mental values.
The model was compared with the data generated by
Fujii et al. (1981). In this study, the residence time
required to consume 5% of NH3 was calculated as a
function of temperature. According to the study, for a
temperature range of 909-1250 K, the residence time
to reach 5% was between 10 and 20 ms. Given their ex-
(11) perimental conditions as inputs, our model predicts the
same range of residence times, suggesting a good fit.
Our oxidation data are compared to the data of Clark
et al. (1998) in Figure 10. It is immediately apparent
that our measured conversions are much higher than
those of Clark et al. (1998). Our data follow an NH3
cracking trend until 800 °C, after which oxidation
becomes significant. Note that our cracking results are
very similar to those of Clark et al. (1998). According
to Clark (personal communication, 2000), their oxidation
conversion data are much lower than even cracking
until oxidation becomes significant at 1100 °C, because
of the inhibition effect of substantial amounts of water
present. As such, it can be concluded that we did not
experience the inhibition effect. It must be noted that,
although the experimental feed concentrations and
temperature were similar, the apparatus of Clark et al.
(1998) is considerably different than ours with a ceramic
reactor and a much slower quench. Thus, the reason
for the large difference in conversions could be at-
tributed to the formation of larger amounts of water
prior to oxidation in their apparatus. However, this
150 Ind. Eng. Chem. Res., Vol. 40, No. 1, 2001
needs to be investigated in future work, because it is
beyond the scope of this paper.
Conclusions
In this paper, NH3 pyrolysis and oxidation were
studied at Claus FEF temperatures, pressures, and
residence times. New experimental data were generated
in order to develop global kinetic rate expressions for
the pyrolysis and oxidation of NH3 at FEF conditions.
At conditions similar to those in a Claus FEF,
ammonia oxidation can be much more significant than
pyrolysis at temperatures of less than 1150 °C. In fact,
conversion of NH3 through oxidation varied between 1
and 50% for temperatures between 850 and 950 °C and
50-700 ms, whereas pyrolysis conversions at these
conditions never exceeded 20%. The increase in NH3
conversion due to oxidation is even more significant at
temperatures between 1050 and 1200 °C, where the
conversion varied from 25 to 90% at the same residence
times.
For ammonia pyrolysis, the newly developed rate
expression is
r ) Ae-Ea/RTPNH31.25
where A is 0.004 21 mol cm-3 s-1 atm-1.25 and Ea is 16.5
kcal mol-1. The AAE between the model and the data
was 13%. The model was also used to simulate experi-
ments performed by Clark et al. (1998), and the model
predictions agreed well with their data.
For ammonia oxidation, the following rate equation
was developed:
r ) kPNH3PO20.75
where A and Ea were 4430 mol cm-3 s-1 atm-1.75 and
40.0 kcal mol-1, respectively. Model predictions and
experimental data showed good agreement with an AAE
of 10%.
Although oxygen competition needs to be addressed
in a more definitive manner to fully judge industrial
recommendations for ammonia destruction, simulations
based on our new rate expressions give preliminary
indications of what minimum temperatures and resi-
dence times are necessary to obtain 60 ppm of ammonia
in the furnace effluent, as typically desired for ammonia
destruction in the Claus FEF. Specifically, temperatures
need to be greater than 1200 °C with residence times
greater than 1.0 s or greater than 1250 °C with
residence times greater than 0.5 s.
In industry, it is generally accepted that the furnace
should be designed with residence times greater than
0.8 s, and flame temperatures of 1300 °C or higher are
desired. As such, guidelines for actual conditions are
somewhat more conservative to account for the incom-
plete mixing and oxygen competition that occur in Claus
plant FEFs. In addition, calculated results based on the
new rate expressions clearly show that ammonia py-
rolysis accounts for significant destruction.
Finally, it should be noted that there appears to be
an inhibition of ammonia pyrolysis when significant
amounts of water are present and under certain experi-
mental conditions. This phenomenon requires further
study to delineate its occurrence.
Acknowledgment
The authors thank the following supporters of this
work: Shell Canada, British Oxygen Corp., Stork-
Comprimo, HEC Technologies, and NSERC. In particu-
lar, the authors thank the Gas Research Institute for
their continued support of this research project. In
addition, we thank Alberta Sulfur Research for their
cooperation and contributions to our continuing studies.
List of Symbols
A ) Arrhenius constant
D ) diameter (cm)
Ea ) activation energy (kcal mol-1)
k ) reaction rate constant
K ) equilibrium constant
m and n ) reaction order
OF ) objective function
P ) pressure (atm)
R ) gas constant (kcal mol-1 K-1)
r ) reaction rate (mol m-3 s-1)
T ) temperature (°C or K)
t ) time (s)
V ) elemental reactor volume (cm3)
xm,I ) experimental fractional conversion
xp,I ) predicted fractional conversion
z ) axial position (m)
Greek Symbols
τ ) residence time (s)
Subscripts
l ) species
j ) species
Acronyms
AAE ) average absolute error
SLPM ) standard liters per minute
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Received for review October 22, 1999
Revised manuscript received September 27, 2000
Accepted September 27, 2000
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