Kinetics of the Gas-Phase Reaction Between Nitric Oxide.

Ammonia and Oxygen

W. DUO', K . DAM-JOHANSEN' and K. fiSTERGAARD
Department of Chemical Engineering, Technical University of Denmark, Building 229, 2800 Lyngby, Denmark
For the purpose of developing a simple and quantitativedescription of the rate of reactions occurring in the Thermal
DeNOx process, the kinetics of the homogeneous reaction between NO and NH, with excess of O2 has been studied
in an isothermal plug flow reactor.
Temperature windows of NO reduction were observed with the optimum temperature decreasing with increasing resi-
dence time. The degree of reduction of NO increases with residence time at lower temperatures but is sensitive to resi-
dence time only at very short residence times at higher temperatures. The degree of conversion of N H I increases with
both temperature and residence time.
A simple model has been proposed to describe the reaction rates:
NO = k,,, "41 - k,- "H,I "01

~ N H ,= -k,,, "H31 - k,. "H,I "01

The two rate constants in the model were estimated based on the experimental data obtained in the present plug flow
reactor at about 4% (vol.) oxygen:
k,,, = (2.21 5 0.33) x 10'' exp (-(38160 +_ 1 7 0 ) / T ] ,I/s

k,. = (2.45 F 0.49) x exp { -(29400 k 2 5 0 ) i T ) . mT/mol . s

It is verified that the kinetic model can give a satisfactory prediction of the experimental results under different conditions.

Afin de mettre au point un modele de description simple et quantitatif de la vitesse des reactions survenant dans le
processus thermique DeNOx, on a ktudit la rkaction homogkne entre NO et NH, avec exces de 0: dans un rkacteur
a Ccoulement piston isotherme.
Les gammes de temperatures pour la rkduction du NO ont i t 6 observees, et on a constate que la temperature optiniale
diminuait avec I'augmentation du temps de sejour. Le degre de reduction du NO augmente avec le temps de sejour
aux tem$ratures infkrieures mais cette sensibilitk s'observe seulernent h des temps de sejour trks courts et des temphtures
klevees. Le degre de conversion du NH, augmente a la fois avec la tenipkrature et le temps de se.jour.
On propose un modkle simple pour decrire les vitesses de reaction:
rNO = k,,, "H,I - k,. "H,I "01

rNH, = -k,,, "Hjl - k,- "H3I

"01
Les deux constantes de vitesse du modkle ont i t 6 estimees B partir des donntes experimentalesobtenues avec le rkacteur
icoulement piston utilisi ici B environ 4% (volume) d'oxygkne:
k,>, = (2.21 0,33) x 10'' exp { -(38160 170)/Tj, 11s

k, = (2,45 _+ 0.49) X 10" exp -(29400 k 250)/T], m'/mol .s

On a pu dklnontrer que le modkle cinetique peut predire de manikre satisfaisante les resultats expkrimentaux dan:,
di ffkrentes conditions.

Keywords: gas-phase reaction, nitric oxide, ammonia, kinetic model.

quantities of ammonia (NH3) to the combustion products.

T he emissions of nitrogen oxides (NOx) from stationary
combustion installations such as utility boilers are
important sources of air pollution and need to be controlled.
The conventional control techniques entail combustion
modifications to limit the formation of NOx. An alternative,
and more effective recipe for a low emission of NOx espe-
cially for a coal-fired system, is flue gas treatment to remove
NOx already formed. For a practical combustion system
which operates with excess oxygen (02) selective reduction
of NOx is desired. Thus, the Selective Catalytic Reduction
(SCR) of NOx and Selective Non-Catalytic Reduction (SNR)
of NOx have received much attention.
Lyon (1976) discovered that the SNR reaction could occur
in the presence of excess O2 by the addition of small
'Current address: Department of Cheniical and Process Engineering.
U;ivcrsity of Surrey, Guildford. Surrey GU2 5XH. UK.
-To whom correspondence should be addressed.
This process could rapidly and efficiently reduce nitric oxide
(NO) to nitrogen (N2) and water (H20) around 1250 K.
Since then a number of investigations have been published
in this field, including experimental observations with
different flow reactors and mathematical niodelling (Muzio.
et al., 1977; Lyon and Benn, 1978; Lucas and Brown. 1982;
Dean et al., 1982; Kimball-Linne and Hanson. 1986; Miller
and Bowman, 1989).
Simple kinetic models were proposed based on the overall
reaction (Lyon and Benn, 1978; Fenimore, 1980), while
complex models were based on detailed elementary reactions
(Kimball-Linne and Hanson, 1986; Dean et al., 1982; Miller
et al., 1981; Branch et al., 1982).
A kinetic model based on elementary reactions is theoret-
ically more tenable. In principle, a mechanism should incor-
porate all elementary reactions possibly occurring in the
+
system. For the system NH3 + NO 02.reaction schemes

I014 THE CANADIAN JOURNAL OF CHEMICAL ENGINEERING. VOLUME 70. OCTOBER. 1992
published are complex. For example, the models of Miller
et al. ( 1983) and Miller and Bowman (1989) contained 98
and 73 chain radical reactions, respectively. It has been
difficult to use those models since the rate constants of many
reactions incorporated are not available.
The simplification of a mechanism is often done through
sensitivity analysis by selecting the most significant reactions
(Dean et al., 1982; Branch et al., 1982; Kimball-Linne and
Hanson, 1986). The simplified mechanisms are different
from each other in how many reactions and which reactions
are selected. Unfortunately, the reactions with unknown rate
constants were found to be significant and the modelling
results were sensitive to their values.
In the model of Miller et al. (1981) the values of the
unknown rate constants were estimated on purely theoret-
ical grounds. However, that is only a qualitative and explana-
tory model (Miller et al., 1981; Lyon, 1987; Duo et al.,
1990b). The model of Dean et al. (1982) has been demon-
strated to be more predictive (Duo et al., 1990b), although
it is a semi-empirical model in which the rate constants of
reactions that are uncertain and sensitive were adjusted to
fit the experimental data.
A kinetic model based on the overall reactions is mainly
empirical but perhaps more useful for quantitative predic-
tions, since it is simpler and easier to be combined with flow
and transportation models. Based on the experimental results
for [ NH3]; > > [NO] !, Lyon and Benn (1978) found that
the rate of NO reduction was related to [NO] in first order
and to [NH3] in half order. However, the values of
P ( = [ NH3] ; / [NO] ;) they used were much higher than
those practically required by the SNR process. Furthermore,
that study only covered the lower part of the temperature
range of interest for the SNR process.
Fenimore (1980) observed a critical concentration of NO,
[NO] (..He proposed that the ratio of [NO] to [OH] was
equal to the ratio of oxidation rate to reduction rate. An
integral form of the kinetics of the reactions was deduced
by assuming the above ratio was 10 k 5 and was indepen-
dent of reaction time. Although that relation covered a wide
temperature range it did not clearly demonstrate any tem-
perature dependency of [NO] <, nor of [NO] / [OH I .
In the present study, the kinetics of the homogeneous reac-
tion between NO and NH3 in the presence of excess 0 2 is
investigated in an isothermal plug flow reactor over the tem-
perature range of interest for the SNR process. The main
purpose of the study is to develop a simple, quantitative
description of the rate of the reaction.
Experimental
The experimental equipment and procedures have been
described previously (Duo, 1990; Duo et al., 1989), and only
a brief description will be given here. Reaction gas mixtures
were compounded using pure (N2, 02)and mixture
(NO/N2, NH3/N2) cylinder gases. N2, as diluent, and 0 2
were mixed before they were introduced into the reactor
through the main stream inlet (2 in Figure la). NH3 and NO
were separately injected through the in,jectors(3 in Figure la)
on the top of the reactor.
The design of the quartz flow reactor is shown in
Figure la. Reactions proceed in the reactor tube (1) of inside
diameter 0.51 cm and length 13.5 cm. The inside diameter
of the outlet tube (5) is 0.19 cm. Outside the reactor tube
which is located at the centerline of the overall vessel is
annular space (4) for preheating the mixture of N2 + 0 2 .
THE CANADIAN JOURNAL OF CHEMICAL ENGINEERING, VOLUME 70. OCTOBER. 1992
2
5
-24.0
a: Reactor design b Temperature profile
Figure I - Reactor design and temperature profile along the reactor
a: Reactor design. I . flow reactor (tube); 2 . main stream inlet: 3.
four injectors; 4. preheating zone; 5. outlet (tube) for reacted gases:
6. cooling zone; 7 . small extension (nozzle); 8. thermocouple: 9.
neck of the vessel; 10. cooling gas inlet; I I . preheating zone: b:
Temperature profile.
The upper end of the reactor tube is open and serves as inlet
for the preheated gas mixture. Above the reactor tube there
are four injectors (3) which are joined together just above
the open end of the reactor tube to form a small extension
(7) inserted into the mouth of the reactor tube. The end of
the extension is closed but on its side wall there are several
small holes. In this design the gas streams from the preheating
zone and the injectors, respectively. meet at the entrance to
the reactor tube in crossflow with high velocities due to the
narrowed gas paths. It is expected that strong turbulence
should occur in the region and complete mixing be obtained.
The vessel was housed in a three zone controlled electri-
cally heated oven. A uniform temperature profile (within
5°C) in the reaction zone was attained, as typically shown
in Figure 1b. The ordinate axis in Figure 1 is common to
a and b.
NO and O2 were measured on line by Hartmann & Braun
gas analyzers, Radas 1G utilizing the UV resonance absorp-
tion principle and Magnos 3 utilizing the paramagnetic nature
of O2 respectively (accuracy +_2%).A batch chemical
method was used to determine NH3 concentration. Samples
were collected by bubbling the gas mixture to be analyzed
through distilled water and the measurement was performed
with a Tecator flow injection analyzer (FIAstar 5020). the
accuracy of which is +2%. The analysis is based on the reac-
tions NH; + +
OH- = NH3(g) H 2 0 and NHI + HI =
NH: +
I - occurring, respectively, in two streams of
aqueous solutions separated by a gas (NH,) permeable
membrane. A colour shift is measured photometrically.
Measured NH:, concentrations were normally about 5 O/c
lower than calculated based on the concentration of NH3 in
the gas cylinder.
Experiments were carried out at different temperatures in
the range between 1140 and 1335 K at the constant initial
concentrations of 5.16 X mol/ni3 of NO.
8.45 x lo-' mol/m' of NH3 and 0.405 mob? of 0:. The
volume fractions vary (as mass flow rates of the dilucnt gas.
101s
 * * * * * t=0.039 s
s ..=.. t=0.102 s
tz0.151
0 0 ~ 0 0
AAAA ty0.227
s
S

0.80
1.oo

0.75 0.60

0 6
0.50 0.40
0 0
z z

0.25
0.20

0.00
0.00 0.05 0.10 0.15 0.20 0.25 0.30
1100 1150 1200 1250 1300 1350 1400
t, s T. K
Figure 2 - Variation of NO reduction with residence time Figure 4 - Variation of NO reduction with temperature
Inlet (mol/m3):NO, 5.15 x lo-,; NH,, 8.45 x O,, 0.405. Inlet (mol/m3):NO, 5.15 X lo-'; NH,. 8.45 X 10 j; 0,. 0.405.

* * * * * T=1142 K Symbols:
OOOOO T=1190 K experimental
mmmm. T=1235 K Lines:
1.oo
0.75
6 A series of curves, or temperature windows. of NO reduc-
0.50
2z
0.25
0.00
- peratures. This is of significance since kinetics of a reaction
I- I I I I I i m l l l I IisInormally expressed in terms of molar concentrations rather
0.00 0.05 0.10 0.15 0.20 0.25 0.30
t, s
Figure 3 - Variation of NH, conversion with residence time
Inlet (mol/m3):NO, 5.15 x 10-j; NH,, 8.45 x O,, 0.405.
N,, were adjusted) with temperature, corresponding to 507
ppmv NO, 830 ppmv NH, and 4.1% (vol.) O2 at 1235 K.
The residence times in the experiments varied between 0.039
and 0.227 s at each temperature. This procedure is different
from that employed by previous studies (Muzio et al., 1977;
Lucas and Brown, 1982; Duo et al., 1989) in which the mass
flow rates of all the components (including inerts like N2)
of the reaction gas mixtures were kept constant while
changing temperatures.
Results
The fraction of NO remaining after reaction, y l
(= [NO] / [NO J ;), and the fraction of NH, breakthrough,
y2 ( = [NH3] I [NH,] ;), as a function of residence time are
shown in Figure 2 and Figure 3, respectively. At lower tem-
peratures, the degree of NO reduction, 1 - y I , and the
degree of NH3 conversion, 1 - y2, increase with residence
time, whereas at high temperatures they are sensitive to resi- tion only up to the optimum temperature above which the
dence time only at very short residence times beyond which
[NO] remains at a constant value and [NH3] approaches
to zero. The lines in these figures are the results calculated
based on the present kinetic model which is to be shown.
It is seen that both the NO reduction rate and NH, con-
version rate are markedly dependent on temperature. At
lower temperatures a heavy NH3 breakthrough occurs even
for a residence time as long as 0.23 s. NH3 conversion rate
increases with temperature. At very high temperatures no
NH3 breakthrough is observed.
tion by NH3 with excess O2 were observed in the prcscnt
study as shown in Figure 4 in which each curve is only a
function of temperature, holding the residence time and the
initial molar concentrations of the reactants constant, while
their initial volume fractions for each curve vary with tem-
than volume fractions.
Similar temperature windows were also demonstrated in
other investigations (Muzio et al., 1977; Lucas and Brown.
1982; Duo et al., 1989). As mentioned earlier, however. in
those previous experiments the total mass flow rates of gas
mixtures and the volume fractions of the reactant species were
held constant. Consequently, both molar concentrations of
reactants and residence times were changed when the tem-
perature varied. This means that each temperature window
in those illustrations was a function of temperature, residence
time and initial molar concentrations of the reactants.
With the present experimental procedure the comparison
of experimental results under different conditions is
facilitated.
It is seen from Figure 4 that the optimum temperatures
are decreased and the maximum degrees of NO reduction
are increased as residence time is prolonged. Comparison
of Figure 3 and Figure 4 may lead to a conclusion that a
longer residence time shifts both the optimum reduction tem-
perature of NO and the complete conversion temperature of
NH3 downwards to the same extent.
Figure 4 also demonstrates that the variation of residence
time results in a significant change of the degree of NO reduc-
reduction curves at shorter residence times tend to join those
at longer residence times. At sufficiently high temperatures

1016 THE CANADIAN JOURNAL OF CHEMICAL ENGINEERING. V O L U M E 70. OCTOBE3l. I902

all the curves are merged into one line which may be consi-
dered as the asymptote of NO reduction for the value of 6 * * * * * Estimated, k,,, s-'
Arrhenius correlation, k,,
used.
OCOOO Estimated, k,, m3 mol-' s - '
.._._
Arrhenius correlation, k,
The kinetic model 5.0

As generally accepted by many investigators (Lyon and

Benn, 1978; Rosenberg et al., 1980), the overall reactions
occurring in the SNR process may be described as two com- 3.0 4 \ 111.0
petitive (for NH3) or successive (for NO) reactions:

+ NO + 114 0 2 - N2 + 3/2 H20 . . . . . . . (1)

1 ,I
NHJ

NH3 + 5/40 2 -..NO + 3/2 H20 . . . . . . . . . . . . . (2) I , , , , , ,,, , - , y > : , , , ,, , ,

-1.0 0.
7.0
Referring to the above reactions, a power law model is used
7.0 7.5 8.0 5 9.0 9.5
to describe the reaction kinetics. It is assumed that the reverse 10'xl/T, K-
of reactions (1) and (2) is negligible in the temperature range
concerned. Oxygen is present in the system in great excess Figure 5 - Dependencies of k,,, and k, on temperature
and its concentration must be constant during the process of
reaction. As a first approximation, further assume first order that the Arrhenius law may be used to describe the tempera-
oxidation of NH3 to NO and second order reduction of NO ture dependencies of the reaction rate coefficients, i.e.
to N2 which as shown in Figure 2 and Figure 3 gives a good
data fit. Thus, a simple kinetic model describing the rates k, = Al . exp ( - E l IRT) lis . . . . . . . . . . . . . . . . (6)
of the gas phase reactions is obtained.
k, = A2 . exp ( - E 2 / R n m3/moI . s . . . . . . . . . . (7)
TNO = k, [NH3] - k, [NH3] [NO] . . . . . . . . . . . (3) The values of parameters A , , A2. E , and Ez may be obtained
from the data in Figure 5. Alternatively, the four parameters
may also be estimated directly by incorporating the
experimental data obtained at different temperatures into the
where k,, and k, may be dependent on temperature, the O2 same objective function of optimization. This was carried
concentration and the total pressure. In an isothermal plug out primarily by inserting Equations (6) and ( 7 ) into Equa-
flow system tions (3) and (4).
The estimation of parameters using the above two proce-
dures, i.e. two-parameter optimization and four-parameter
optimization, resulted in similar values of the two rate
constants:
with the following initial conditions
k, = (2.21 i 0.33) x 1014
[NO] = [NOIi, [NH,] = [NH3Ii at t = 0
exp [ -(317.3 k 1.4)/RT), I/s . . . . . . . . . . . . . (8)
The parameters k , and k, were estimated, using the least-
square method, based on the present experiment data shown k, = (2.45 _+ 0.49) X lOI4
in Figures 2 and 3. Considering that the experiments were
performed in an isothermal plug flow reactor (the reactions exp ( -(244.4 k 2.1)/RT), m'/mol .s . . . . . . (9)
should cause practically no thermal or hydrodynamic changes
to the reaction system due to the very low concentrations where the activation energies are measured in kJ/mol and the
of the reactants) and that heterogeneous reaction on quartz gas constant in kJlmo1 . K. Equations (8) and (9) are shown
surface was negligible due to the high temperatures and short by the straight lines in Figure 5. The maximum errors were
residence times applied (Dean et al., 1982; DUO,1990), the estimated by taking account of the experimental errors and
present data should be applicable. the deviations of the data in Figure 5 from the straight lines.

Estimation of the rate constants Prediction of experimental results

The estimation of the parameters in the differential equa-
tions was performed by adjusting parameters utilizing the
Simplex method of optimization. Detailed descriptions of the
procedure are presented in Duo (1990).
The values of k,,., and k, were estimated at 5 different tem-
peratures between 1140 and 1335 K, at atmospheric pres-
sure and about 4% (vol.) 0 2 . The fitting results are
satisfactory, as shown in Figure 2 for NO and in Figure 3
for NH,. The plots for Ink,, and Ink, versus 1/T approxi-
mately obey a linear relation, as shown in Figure 5 , indicating
To verify the kinetic model, a more extensive investiga-
tion has been carried out to compare the model with the
experimental results other than those based on which the
parameters were estimated. Three examples are presented
in the following.
A TEMPERATURE WINDOW
The observed temperature window of NO reduction and
the curve of NH3 conversion (Duo et al., 1990a) could be

THE CANADIAN JOURNAL OF CHEMICAL ENGINEERING, VOLUME 70, OCTOBER. 1992 1017
 1.00 ,
1
4j
0 a. I **. Experimental
Predicted
0.75
I

\-
\

I
0.75
0-
z \

2 0.50 0
,? 0.50
z
0
z
0.25
0.25
a
0.00 1 1 I , , , I , , , \ I , , , , , , 1 )
* a
1000 1100 1200 1300 1400 0.00 ~
T, K 0 1 2 3 4 5
NHJNO,
Figure 7 - Effect of [ NH,] , / [NO], on NO reduction
Inlet: 507 ppmv NO, 4% (vol.) O,, varying N H 3 concentrations
1 A b.
T = 1213 K: 7 = 0.077 s.
0.75 4 \t
TABLEI
Comparison of the Model With Pilot Plant Experiments
(Temperature at NH1 Injector: 1223 K )
“01, dT1dt “01 1 “01, “HI1 1 “HI],
0.25
i-
-
A\
A
ppmv 0 Kls 7. s exp. model exp. model

- A
A
390 1.22 -227 0.088 0.372 0.408
0.22 0.356 0.349
0.038
0.01
0.160
0.049
0.00 I I I 1 I l l I 1 I I I 1 1 - 1 1 - 1 I

440 1.30 -248 0.32 0.216 0.283 0.01 0.04

Figure 6 - a. Temperature window of NO reduction
b. Curve of NH, conversion
Inlet: 507 ppmv NO, 832 ppmv NH,, 4% (vol.) 0,; 7 = 93.3/Ts
Symbols: experimental; Lines: predicted.
predicted by the model. Variations of 7 , [NO] and [ NH3]
with temperature were considered. The comparisons of the
predictions with the experimental results are shown in
Figure 6(a,b).
EFFECTOF [ NH3] ; / [NO] ; ON NO
The observation that degree of NO reduction increases with
increasing the [NH3]; / [NO] ; molar ratio (Duo et al.,
1989) was quantitatively predicted by the simple kinetic
model with a good agreement, as shown in Figure 7.
PILOT PLANT EXPERIMENTS
SNR experiments were carried out in a pilot plant at NEFO
power plant, Aalborg, Denmark (Jadal et al., 1990). The
pilot plant is a stainless steel tube of inside diameter 0.3 m
and length 15 m, which is built as an integrated part of a
coal-fired boiler of 135 MWe. A flue gas stream of about
0,083-0.194 kg/s was passed through the pilot reactor with
a constant temperature gradient of 20 K/m. One set of the
pilot plant experimental data are listed in Table I (by courtesy
of Aalborg Ciserv International). In the prediction, the
non-uniform temperature profile in the pilot reactor was
considered by coupling Equations (3), (4) and (5) with
Equation (lo),
520 1.23 -165 0.36 0.283 0.260 0.003 0.01
where values of Constant are shown in Table 1 . Table 1
demonstrates that the present model gives a satisfactory
prediction of the NO reductions and a reasonably good
prediction of NH3 conversions.
The overestimations of NH3 breakthrough may be
explained by the pilot experimental conditions being different
from the conditions of laboratory experiments using synthetic
gases. For example, H20 vapour, combustion ash. unburnt
REDUCTION fragments of fuel, CO, CO?, byproduct gases. etc. must be
present in the flue gas through the pilot reactor. In addition,
the pilot reactor was assumed as a plug flow reactor in the
present predictions and the radial temperature profile in it
was not considered.
Simulation of the effect of additives
The observation that combustible additives shift both NO
reduction temperature and NH3 conversion temperature
downwards to the same extent indicates that the presence of
additives leads to the ignition of the reaction mixture at a
lower temperature (Duo et al., 1989; 1990a). That is. the
addition of additives can lower the activation energies of the
SNR reactions. The analysis of bond strengths of NH3 and
additives supports the hypothesis (Duo, 1990; Duo et al.,
1989). Based on this idea, the expressions of rate constants
are modified as follows:
= A , -exp [ - ( E l - E , , , ) / R T ] , 11s . . . . . . (6a)

dTldt = Constant K l s . . . . . . . . . . . . . . . . . . . ... (10) k, = A2 . exp [ -(E2 - E2(,)I R T ] , ni’imol .s . (74

1018 THE CANADIAN JOURNAL OF CHEMICAL ENGINEERING. VOLUME 70. OCTOBER. I W

 000.0 Experimental, 21 1 ppm CH,
Predicted, 211 ppm CH,
00000 Experimental, 105 p p m CZHB
Predicted, 105 ppm CzHe

1.oo 0

0.75 4 0

\\
0 a.

i
0-
z
\ 0.50
0
z
0.25
0 100 200 300
CPHBI ppm
0.00
Figure 9 - Concentration dependencies of E,,, and E?,,.
950 1050 1150 1250 1350
T. K
those by the addition of CH4 at the same carbon content.
1.00 ,
i
I The results are in accordance with the differences of the
b. C-H bond strengths in alkanes (Duo et al., 1990a). For the
same additive, an increased concentration causes greater
values of E l , and Ell,, as shown for CIH6 in Figure 9.
Attempts have been made to model the SNR experimental
z results obtained in a 12 MW coal-fired circulating fluidized
z bed boiler (Leckner et al., 1990) using the present model.
\ 0.50
32
z NH3 or NH3 together with additives was injected before or
after the cyclone of the boiler. The preliminary results have
0.25 demonstrated that the predictions are in quantitative agree-
ment with the experimental results in the absence of addi-
tives and in qualitative agreement with those in the presence
of additives.
950 1050 1150 1250 1350
T, K Discussions and conclusions

Figure 8 - Effect of additives The relationship between [ NH3] and [NO] during the
a. on NO reduction; b. on NH, conversion reactions in plug flow reactors may be explicitly expressed
Inlet: 507 ppmv NO, 832 ppmv NH,, 4% (vol.) 0,; T = 93.3/T s in an integral form of the kinetic model. Combine Equations
Additive: 21 1 ppmv CH, or 105 ppmv C,H,. (3) and (4) with Equation (5).For the period of reaction time
considered within which [ NH31 > 0, dividing Equation (4)
TABLE2 by Equation (3) eliminates t from the resultant equation,
Activation Energies Lowered by Alkane Additives
(El = 317.3 W/mol, E2 = 244.4 kJ/mol)
d “H31 “01
Concentration El,, E2U
Additive PPmv kJ/mol W/mol
CH, 21 1 9.47 5.37 = 1 + 2k,,, / ( k r [NO] - k(,,) . . . . . . . . . . . . . ( 1 I)
C?H, 105 21.6 14.I
C,H, 21 1 30.0 18.6 let K = k , ik,, the solution to Equation ( 1 1) under the ini-
C4H 10 53 20.8 13.9 tial conditions, [NH,] = [ NH31 I when [ N O ] = [ N O ] I
is obtained:

where E l , and Eltr are activation energies lowered due to
the presence of additives, depending on both the species and
concentrations of additives. For no additive addition, E l ,
and E l , equal zero. With additives present, E l , and El[,
were estimated via a two-parameter optimization to fit the
experimental data. The estimated values of E l , and EZafor
alkane addition are shown in Table 2, and the fitting results
for CH4 at 21 1 ppmv and for C2H6 at 105 ppmv are illus-
trated in Figure 8(a,b).
It is seen from Table 2 that the activation energies lowered
by the addition of C2Hhand C4Hla at a constant carbon con-
tent are approximately the same but substantially greater than
(“H3jf - “ H ~ ] ) / K= (“01, - “OI)/K
+ ~ ~ ( ( [ N O ] , - K ) / ( [ N O-] K)) . . . . . . . . . . (12)
Although the kinetic model, Equations (3), (4) and ( 5 ) ,
was not based on elementary reactions and hence essentially
empirical, the integrated expression of the model, Equa-
tion (12), has the same form as that derived by Fenimore
(1980) based on a simple mechanism consisting of 6 elemen
tary reactions. The parameter K was defined by Fenimore
(1980) and Lyon and Benn (1978) as the steady state con-
centration of NO, which increases with temperature.

THE CANADlAN JOURNAL OF CHEMICAL ENGINEERING, VOLUME 70, OCTOBER, 1992 1019
 The present kinetic model may only be used for
engineering calculations. Complex nitrogen chemistry
involved in the process and the influence of additives on
nitrogen chemistry have been explained in details (Dean et
al., 1982; Miller and Bowman, 1989; Duo et al., 1990a).
It should be noticed that [ 0 2 1 involved in the present study
was about 50 times higher than [ NH3] and about 200 times
higher than the concentrations of the alkanes and the reduc-
tion of NO by NH, must be selective in the both absence
and presence of additives.
The following conclusions may be drawn from the present
study:
The kinetics of the reactions occurring in the SNR process
can be described by a simple model assuming first order oxi-
dation of NH3 to NO and second order reduction of NO to
NZ.The two rate constants in the model were estimated and
expressed in the Arrhenius form.
The experimentally observed curves of NO reduction and
NH3 conversion, and effect of /3 on the rate of N O reduc-
tion can be quantitatively predicted by the model; the
influences of combustible additives can be simulated using
reduced activation energies in the rate constants; the model
can also give a reasonably good prediction of the results
obtained in pilot experiments.
Acknowledgements
The authors gratefully acknowledge financial support from the
Energy Ministry of Denmark and valuable discussions with
colleagues in the Department. The authors would also like to thank
Aalborg Ciserv International for providing the pilot plant
experimental data.
Nomenclature
A, = pre-exponential factor of rate constant k,>,,, s
A2 = pre-exponential factor of rate constant k,, m3/mol . s
El, E, = activation energies of rate constants k,,, and k,.,
kJ/mol
E,,, = activation energies lowered by additives, kJ/mol
k ,r = rate constant related to the oxidation of NH, to NO, s
kr
= rate constant related to the reduction of NO, m3/mol . s
r, = rate of reaction: formation rate of species X,
mol/m3 . s
R = gas constant, 8.314 x 10-? kJ/mol . K
f = reaction time, s
T = temperature, K
[XI = concentration of any species X , mol/m’
Yi = [NO]/[NO],
?’> [NH,I/ “H,l I
Greek letters
P = initial molar ratio of NH3 to NO, [NH,] , / [NO]{
K = “steady state” concentration of NO, k,,.r/ k r , mol/m.
7 = gas residence time, s
Subscripts
I = initial
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