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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
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 2
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- 5
-24.0
THE CANADIAN JOURNAL OF CHEMICAL ENGINEERING, VOLUME 70. OCTOBER. 1992 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 to zero. The lines in these figures are the results calculated
mmmm. T=1235 K Lines: based on the present kinetic model which is to be shown.
It is seen that both the NO reduction rate and NH, con-
1.oo
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
0.75 increases with temperature. At very high temperatures no
NH3 breakthrough is observed.
6 A series of curves, or temperature windows. of NO reduc-
0.50 tion by NH3 with excess O2 were observed in the prcscnt
2z
study as shown in Figure 4 in which each curve is only a
function of temperature, holding the residence time and the
0.25 initial molar concentrations of the reactants constant, while
their initial volume fractions for each curve vary with tem-
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 than volume fractions.
t, s Similar temperature windows were also demonstrated in
Figure 3 - Variation of NH, conversion with residence time other investigations (Muzio et al., 1977; Lucas and Brown.
Inlet (mol/m3):NO, 5.15 x 10-j; NH,, 8.45 x O,, 0.405. 1982; Duo et al., 1989). As mentioned earlier, however. in
those previous experiments the total mass flow rates of gas
N,, were adjusted) with temperature, corresponding to 507 mixtures and the volume fractions of the reactant species were
ppmv NO, 830 ppmv NH, and 4.1% (vol.) O2 at 1235 K. held constant. Consequently, both molar concentrations of
The residence times in the experiments varied between 0.039 reactants and residence times were changed when the tem-
and 0.227 s at each temperature. This procedure is different perature varied. This means that each temperature window
from that employed by previous studies (Muzio et al., 1977; in those illustrations was a function of temperature, residence
Lucas and Brown, 1982; Duo et al., 1989) in which the mass time and initial molar concentrations of the reactants.
flow rates of all the components (including inerts like N2) With the present experimental procedure the comparison
of the reaction gas mixtures were kept constant while of experimental results under different conditions is
changing temperatures. facilitated.
It is seen from Figure 4 that the optimum temperatures
Results are decreased and the maximum degrees of NO reduction
are increased as residence time is prolonged. Comparison
The fraction of NO remaining after reaction, y l of Figure 3 and Figure 4 may lead to a conclusion that a
(= [NO] / [NO J ;), and the fraction of NH, breakthrough, longer residence time shifts both the optimum reduction tem-
y2 ( = [NH3] I [NH,] ;), as a function of residence time are perature of NO and the complete conversion temperature of
shown in Figure 2 and Figure 3, respectively. At lower tem- NH3 downwards to the same extent.
peratures, the degree of NO reduction, 1 - y I , and the Figure 4 also demonstrates that the variation of residence
degree of NH3 conversion, 1 - y2, increase with residence time results in a significant change of the degree of NO reduc-
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 reduction curves at shorter residence times tend to join those
[NO] remains at a constant value and [NH3] approaches at longer residence times. At sufficiently high temperatures
The estimation of the parameters in the differential equa- To verify the kinetic model, a more extensive investiga-
tions was performed by adjusting parameters utilizing the tion has been carried out to compare the model with the
Simplex method of optimization. Detailed descriptions of the experimental results other than those based on which the
procedure are presented in Duo (1990). parameters were estimated. Three examples are presented
The values of k,,., and k, were estimated at 5 different tem- in the following.
peratures between 1140 and 1335 K, at atmospheric pres-
sure and about 4% (vol.) 0 2 . The fitting results are A TEMPERATURE WINDOW
satisfactory, as shown in Figure 2 for NO and in Figure 3
for NH,. The plots for Ink,, and Ink, versus 1/T approxi- The observed temperature window of NO reduction and
mately obey a linear relation, as shown in Figure 5 , indicating 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
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 (“H3jf - “ H ~ ] ) / K= (“01, - “OI)/K
the presence of additives, depending on both the species and
concentrations of additives. For no additive addition, E l , + ~ ~ ( ( [ N O ] , - K ) / ( [ N O-] K)) . . . . . . . . . . (12)
and E l , equal zero. With additives present, E l , and El[,
were estimated via a two-parameter optimization to fit the Although the kinetic model, Equations (3), (4) and ( 5 ) ,
experimental data. The estimated values of E l , and EZafor was not based on elementary reactions and hence essentially
alkane addition are shown in Table 2, and the fitting results empirical, the integrated expression of the model, Equa-
for CH4 at 21 1 ppmv and for C2H6 at 105 ppmv are illus- tion (12), has the same form as that derived by Fenimore
trated in Figure 8(a,b). (1980) based on a simple mechanism consisting of 6 elemen
It is seen from Table 2 that the activation energies lowered tary reactions. The parameter K was defined by Fenimore
by the addition of C2Hhand C4Hla at a constant carbon con- (1980) and Lyon and Benn (1978) as the steady state con-
tent are approximately the same but substantially greater than 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 Dean, A. M., J. E. Hardy and R. K. Lyon. “Kinetics and
engineering calculations. Complex nitrogen chemistry Mechanism of NH3 Oxidation”, Nineteenth Symposium {lnt.)
involved in the process and the influence of additives on on Combustion, The Combustion Institute, Pittsburgh. PA ( 1982).
nitrogen chemistry have been explained in details (Dean et pp. 97-105.
al., 1982; Miller and Bowman, 1989; Duo et al., 1990a). DUO,W., “Kinetic Studies of the Reactions Involved in Selective
It should be noticed that [ 0 2 1 involved in the present study Non-Catalytic Reduction of Nitric Oxide“, Ph.D. thesis, Tech-
nical University of Denmark, Lyngby, Denmark (1990).
was about 50 times higher than [ NH3] and about 200 times Duo, W., K. Dam-Johansen and K. astergaard, “The Influence
higher than the concentrations of the alkanes and the reduc- of Additives on Selective Non-Catalytic Reduction of Nitric Oxide
tion of NO by NH, must be selective in the both absence with Ammonia”, paper Presented at ACHEMASIA ‘89. Beijing,
and presence of additives. China, Oct. 11-17 (1989).
The following conclusions may be drawn from the present Duo, W., K. Dam-Johansen and K. gstergaard, “Widening the
study: Temperature Range of the Thermal DeNOx Process. An
The kinetics of the reactions occurring in the SNR process Experimental Investigation”, Twenty-Third Symposium (Int.)
can be described by a simple model assuming first order oxi- on Combustion, The Combustion Institute, Pitisburg. PA ( I W a ) ,
dation of NH3 to NO and second order reduction of NO to pp. 297-303.
Duo, W., K. Dam-Johansen and K . $stergaard. ”Kinetic Model-
NZ.The two rate constants in the model were estimated and ling of the SNR Process”, paper presented at the Second Nordic
expressed in the Arrhenius form. Conference on “NOx-SOX Reduction in Combustion of Solid
The experimentally observed curves of NO reduction and Fuels”, Lyngby, Denmark, Nov. 12-13 (1990b).
NH3 conversion, and effect of /3 on the rate of N O reduc- Fenimore, C . P., “Destruction of NO by NH, in Lean Burnt
tion can be quantitatively predicted by the model; the Gas”, Combust. Flame 37, 245-250 (1980).
influences of combustible additives can be simulated using Jflal, M., C. Nielsen, T. Hulgaard and K. Dam-Johansen, “Pilot-
reduced activation energies in the rate constants; the model Scale Experiments with Ammonia and Urea as Reductanth in
can also give a reasonably good prediction of the results Selective Non-Catalytic Reduction of Nitric Oxide”. Twenty-
obtained in pilot experiments. Third Symposium (Int.) on Combustion, The Combustion Insti-
tute, Pittsburgh, PA (1990), pp. 237-243.
Kimball-Linne, M. A. and R. K. Hanson. “Combustion-Driven
Acknowledgements Flow Reactor Studies of Thermal DeNOx Reaction Kinetics”.
Combust. Flame 64,337-351 (1986).
The authors gratefully acknowledge financial support from the Leckner, B., M. Karlsson, K. Dam-Johansen, C. Weinell. P. Kil-
Energy Ministry of Denmark and valuable discussions with pinen and M. Hupa, “Influence of Additives on Selective Non-
colleagues in the Department. The authors would also like to thank catalytic Reduction of NO with NH, in Circulating Fluidized
Aalborg Ciserv International for providing the pilot plant Bed Boilers”, Ind. Eng. Chem. Res., 30. 2396-2404. 1991.
experimental data. Lucas, D., and N. J. Brown, “Characterization of the Selective
Reduction of NO by NH,“, Combust. Flanie 47. 219-234
Nomenclature (1982).
Lyon, R. K., “The NH,-NO-0, Reaction”, Int. J. Cheni. Kin.
A, = pre-exponential factor of rate constant k,>,,, s 8, 315-318 (1976).
A2 = pre-exponential factor of rate constant k,, m3/mol . s Lyon, R. K., “Kinetics and Mechanism of Thermal DeNOx: A
El, E, = activation energies of rate constants k,,, and k,., Review”, Prepr. Pap. - Am. Chem. SOC.,Div. Fuel Chem. 32.
kJ/mol 433-443 (1987).
E,,, = activation energies lowered by additives, kJ/mol Lyon, R. K. and D. Benn, “Kinetics of the NO-NH\-02 Reac-
k ,r = rate constant related to the oxidation of NH, to NO, s tion”, Seventeenth Symposium (Int.) on Combustion. The Com-
kr
= rate constant related to the reduction of NO, m3/mol . s bustion Institute, Pittsburgh, PA (1978), pp. 601-610.
r, = rate of reaction: formation rate of species X, Miller, J. A. and C. T. Bowman, “Mechanism and Modeling of
mol/m3 . s Nitrogen Chemistry in Combustion”, Prog. Energy Combust.
R = gas constant, 8.314 x 10-? kJ/mol . K Sci. 15, 287-338 (1989).
f = reaction time, s Miller, J . A , , M. C. Branch and R. J. Kee, “ A Chemical Kinetic
T = temperature, K Model for the Selective Reduction of Nitric Oxide by Ammonia”.
[XI = concentration of any species X , mol/m’ Combust. Flame 43, 81-98 (1981).
Yi = [NO]/[NO], Miller, 1. A., M. D. Smooke, R. M. Green and R. J. Kee, “Kinetic
?’> [NH,I/ “H,l I Modeling the Oxidation of Ammonia in Flames”. Combust. Sci.
Technol. 34, 149-176 (1983).
Greek letters Muzio, L. J., J. K. Arand and D. P. Teixeira, “Gas Phase Deconi-
position of Nitric Oxide in Combustion Products”, Sixteenth
P = initial molar ratio of NH3 to NO, [NH,] , / [NO]{ Symposium (Int.) on Combustion, The Combustion Institute.
K = “steady state” concentration of NO, k,,.r/ k r , mol/m. Pittsburgh, PA (l977), pp. 199-208.
7 = gas residence time, s Rosenberg, H. S . , L. M. Curran, A. V . Slack, J. Ando and J . H.
Oxley, “Post Combustion Methods for Control of NOx Emis-
Subscripts sions”, Prog. Energy Combust. Sci. 6, 287-302 (1980).
I = initial
References
Branch, M. C., R. J. Kee, and J. A. Miller, “A Theoretical Inves- Manuscript received January 22, 199 1; revi\ed manuscript
tigation of Mixing Effects in the Selective Reduction of Nitric received November 26. 1991; accepted for publication March 25.
Oxide by Ammonia”, Combust. Sci. Technol. 29, 147-165 1992.
(1982).
I020 THE CANADlAN JOURNAL OF CHEMICAL ENGINEERING. VOLUMI-. 70, OCTOBER. 1992