Documente Academic
Documente Profesional
Documente Cultură
PII: S03601285(97)000221
a
Chemical Engineering Department, Brigham Young University, Provo, UT 84602, U.S.A.
Advanced Combustion Engineering Research Center, Brigham Young University, Provo, UT 84602, U.S.A.
Nomenclature
1. Introduction
2. Technologies
3. Measurements
4. Mechanisms and Rates
5. Predictive Methods
6. Reburning Model Applications
6.1. Reaction Parameters
6.2. Particle Size
6.3. Reburn Gas Composition
6.4. Injection Velocity
6.5. Comparisons with Data
7. Summary
Acknowledgments
References
NOMENCLATURE
385
386
386
389
392
394
398
399
400
400
403
405
405
405
405
Gas temperature
Time
Xi
Concentration of species i
Equivalence ratio
d mm
fi
ABBCE
ki
ACERC
B&W
ri
Rate of reaction i
CAA
CARS
CCT
CFD
CHEMKIN
385
386
L. D. Smoot et al.
EER
GRI
HiPPS
LDA
LNB
Low NO x burner
MCRD
MSW
MWe
Megawatt, electric
MWt
Megawatt, thermal
NYSEG
PCGC-3
PETC
ppm
REI
SCR
SNCR
(1)
(2)
2. TECHNOLOGIES
387
Fig. 1. Effect of CH 4 flowrate on NO x concentration with primary flame at 10% excess air, for a small laboratory-scale burner
without tertiary air addition16.
388
L. D. Smoot et al.
Fig. 3. Results of NO x reduction of three GRI-sponsored, fullscale, long-term projects for evaluation of gas reburning in coalfired power plants24.
Boiler
Reburn fuel
% NO reduction
Comments
B&W
Coal
2030%
3652%, w/bitum
5362%, w/sub-bitum
Complete
EER
Natural gas
1525%
Natural gas
2233%
Natural gas
520%
NO x 67%
SO 2 5280%
NO x 6066%
SO 2 3263%
NO x . 30% LNB
6073% LNB/RB
EER
EER
389
[(Na)HOH] M (Na) OH H M
(8)
3. MEASUREMENTS
(3)
NH2 NO N2 H2 O
(4)
(5)
H O2 OH O
(6)
O H2 O OH OH
(7)
390
L. D. Smoot et al.
Table 3. Wisconsin Power & Light sponsored project to demonstrate that pulverized coal is an effective reburning fuel for cyclone
boiler (from PETC23)
Load (MWe)
Baseline NO x
(ppm @ 3% O 2)
Reburn NO x
(ppm @ 3% O 2)
Percent reduction
Bituminous coal
110
82
60
3738
609
531
506
600
290
265
325
400
52.4
50.1
35.8
33.3
Sub-bituminous coal
110
82
60
560
480
464
250
230
220
55.4
52.1
52.6
minor differences in the measured NO profiles, regardless of the nitrogen content in different reburning fuels.
On the basis of investigations into the reduction
efficiency of different reburning fuels, Kicherer et al.43
concluded that a high NO x reduction level can be
achieved under the following conditions: high volatile
matter of reburning fuel, long residence time, optimized
mixing conditions, and very fine grinding if solid
reburning fuels are used. He indicated that the homogeneous reduction mechanisms are more effective than
the heterogeneous processes. However, Chen and Ma44
observed, as shown in Fig. 6, that lignite as a reburning
fuel has a higher efficiency for NO x reduction than CH 4
or other coals in their small-scale laboratory reactor.
They noted that heterogeneous reactions contributed to
higher levels of NO x reduction than homogeneous
reactions under certain conditions. Moyeda et al.45 also
confirmed experimentally that the low-rank coals generally performed in an equivalent manner to natural gas,
while high-rank coals were generally less effective as
reburning fuels. They found that increasing the reburning
zone residence time improved the NO x reductions
achieved with all of the coals, but not for natural gas.
Payne et al.46 believe that fuel volatility influences the
391
Fig. 6. Comparison of coal, char and methane as reburning fuels simulated for a lab-scale reactor44.
392
L. D. Smoot et al.
used to drive the turbines, and use is made of state-ofthe-art ash management technologies. Bench-scale
experimentation has been conducted to determine the
role of reburning to lower NO x levels in the coal-fired
laboratory flame, in conjunction with other low-NO x
technologies51.
A new 29 kW, refractory-lined, pulverized coal
combustion research facility was fabricated with a
16 cm diameter and a 7.3 m length, with composite
refractory walls to minimize heat losses. The burner was
mounted on the top left side of the U-shaped furnace.
The long, vertical path below the burner allowed long,
axial flames. This facility has been used extensively to
evaluate technologies to achieve NO x emissions below
0.06 lb/MM Btu using several alternative combinations
of optimized SNCR with stage, gas-stabilized axial coal
flames and reburning. Results show an almost 90% NO x
reduction from the current standards51. This work has
also explored the important parameters in the nearburner region, using a natural gas-stabilized burner. The
final step in this study was to determine the lowest levels
of NO that could be obtained from the optimized use of a
gas-stabilized, pulverized coal flame in conjunction with
air staging, natural gas reburning and SNCR. Figure 8
summarizes the results of a wide spectrum of tests
conducted to evaluate various combinations of these
schemes in an integrated mode. These data indicate that
the desired range of emissions can be achieved,
depending on which of the various combinations of
techniques are used51.
A hardwood and softwood have also been evaluated as
reburning fuels in the U-shaped furnace52. Results
showed that a reduction of 5060% NO was obtained
with approximately 10% wood heat input. There is a net
reduction in CO 2 and SO 2 since wood is a regenerable
biofuel and contains no sulfur. These results suggest that
wood is as effective as natural gas or coal as a reburning
fuel.
Measurements of the reburning process are important
to gain a fundamental understanding of this process, and
for validation of predictive techniques for NO reactions
like that described previously. Tree53 and colleagues are
working to provide detailed in situ measurements for a
laboratory-scale, coal-fired, control-profile reactor
(CPR) utilizing reburning and advanced reburning
Wendt42 has recently published a review of mechanisms governing the formation and destruction of NO x.
NO reduction through the reburning-NO mechanism
usually includes the interactions of HCN and NO
species, as described in the elementary reaction steps
of reburning noted by Wendt et al.16. Under fuel-rich
conditions, the formation of HCN relies strongly on the
concentration of hydrocarbon species,
CHi NO HCN
(9)
(10)
NCO H NH CO
(11)
NH H N H2
(12)
N NO N2 O
(13)
(14)
(15)
HCN O, OH N2
(16)
20
(17)
(18)
393
(19)
394
L. D. Smoot et al.
(21)
73
k22
XHC XNO
XHC XNO
(24)
5. PREDICTIVE METHODS
(26)
395
Fig. 10. Comparison between measured and predicted nitrogenous species for three laboratory-scale gas reburning experiments,
using the model developed by Mereb and Wendt8.
d[HCN]
[HCN]( f3 f4 ) [CH4 ] [NO] f2
dt
(27)
[N2 ] f5 [NH3 ] f6
d[N2 ]
[NO][NH3 ] f7 [CH4 ][N2 ] f5
dt
(28)
d[NH3 ]
d[NO] d[HCN]
d[N2 ]
2
dt
dt
dt
dt
(29)
(30)
396
L. D. Smoot et al.
(31)
(32)
(33)
397
Fig. 14. Arrhenius plots of the reaction constants for NO reduction for three char types (from Guo and Hecker98), where NDL
is North Dakota Beulah Zap lignite char, NDW is NDL washed
with HCl, and NCa is NDW reloaded with calcium oxide.
398
L. D. Smoot et al.
Table 4. Input conditions for two cases with gas reburning laboratory furnace, coal-fired8
Variables
Case 1
Case 2
1.1
0.9
1.06
1.1
0.88
Primary stream
Temperature (K)
Air flow rate (kg s 1)
Type of coal
Est. mass mean particle size (mm)
Mass coal/mass air
590
5.5 3 10 4
Utah bituminous
80
0.494
590
5.5 3 10 4
Utah bituminous
80
0.691
Secondary stream
Temperature (K)
Air flow rate (kg s 1)
590
2.079 3 10 3
590
3.2079 3 10 3
Reburning stream
Temperature (K)
CH 4 flow rate (kg s 1)
N 2 flow rate (kg s 1)
Mass CH 4 /(coal CH 4)
Injection location (m)
300
3.088 3 10 5
0.00
0.125
0.533
300
4.88 3 10 5
2.216 3 10 4
0.114
0.533
Tertiary stream
Temperature (K)
Air flow rate (kg s 1)
Injection location (m)
590
4.673 3 10 4
0.99
950 a
1400 a
No measured wall temperatures were available. Value adjusted to match temperature profile data.
399
Fig. 15. Effect of activation energy (E) on predicted NO concentrations for Case 1.
Fig. 16. Effect of pre-exponential factor (A) on predicted NO concentrations for Case 1.
400
L. D. Smoot et al.
Fig. 17. Effect of activation energy (E) on predicted NO concentrations for Case 2.
Table 5. Selected particle size distributions for model simulations
P1
P2
P3
P4
P5
Size (mm)
Mass fraction
Size (mm)
Mass fraction
Size (mm)
Mass fraction
Size (mm)
Mass fraction
Size (mm)
Mass fraction
1.7
0.0024
11.8
0.1
25.0
0.15
51.4
0.479
80.0
0.0024
6.5
0.0126
35.3
0.3
55.0
0.3
73.5
0.169
80.0
0.0126
40.0
0.51
75.0
0.3
89.0
0.3
86.4
0.094
80.0
0.51
105.0
0.366
132.0
0.2
120.0
0.2
122.5
0.194
80.0
0.366
195.0
0.109
195.0
0.1
185.0
0.05
175.1
0.064
80.0
0.109
d mm 80.2
80.2
80.2
80.1
80.0
401
Fig. 19. (a) Effect of particle distributions on gas temperature for Case 1. (b) Effect of particle distributions on NO profiles for Case 1.
402
L. D. Smoot et al.
Fig. 21. Effect of changes in the CH 4 mass percentage in the reburning fuel on predicted NO concentrations for Case 2.
Fig. 22. Effect of changes in the reburning injection velocity on predicted NO concentrations for Case 1.
403
Fig. 23. (a) Comparison of measured and predicted gas temperatures as a function of axial location in the reactor for Case 1. (b)
Comparison of measured and predicted CO 2 and O 2 concentrations as a function of axial location for Case 1. (c) Comparison of
measured and predicted average NO concentrations as a function of axial location for Case 1.
404
L. D. Smoot et al.
Fig. 24. (a) Comparison of measured and predicted temperatures as a function of axial location in the reactor for Case 2. (b)
Comparison of measured and predicted CO 2 and O 2 concentrations as a function of axial location for Case 2. (c) Comparison of
measured and predicted average NO concentrations as a function of axial location for Case 2.
405
REFERENCES
7. SUMMARY
406
L. D. Smoot et al.
23.
24.
25.
26.
27.
28.
29.
30.
31.
32.
33.
34.
35.
36.
37.
38.
39.
40.
41.
42.
43.
44.
45.
46.
47.
48.
49.
50.
51.
52.
53.
54.
407
408
73.
74.
75.
76.
77.
78.
79.
80.
81.
82.
83.
84.
85.
86.
87.
88.
L. D. Smoot et al.
combustion. PhD dissertation, Chemical Engineering
Department, Brigham Young University, Provo, UT (1994).
Chen, W., Smoot, L. D., Fletcher, T. H. and Boardman, R.
D., Part 1. A computational method for determining global
fuel-NO rate expressions. Energy & Fuels, 1996, 10,
10361045.
Chen, W., Smoot, L. D., Hill, S. C. and Fletcher, T. H., A
global rate expression for nitric oxide reburning. Part 2.
Energy & Fuels, 1996, 10, 10461052.
Zabarnick, S., A comparison of CH 4/NO/O 2 and CH 4/
N 2O flames by LIF diagnostics and chemical kinetic
modeling. Combust. Sci. Tech., 1992, 83, 115134.
Kee, R. J., Rupley, F. M. and Miller, J. A. ChemkinII: A
FORTRAN chemical kinetics package for the analysis of
gas-phase chemical kinetics. SANDIA Report, SAND898009.UC-401, Livermore, CA (1991).
De Soete, G. C., "Nitric oxides" formation and decomposition in the combustion of hydrocarbon flames (La
formation et la decomposition doxyde nitrique dans les
produits de combustion de flammes dhydrocarbures).
Rev. Pet. Inst. Fr., 1972, XXVII, 372.
De Soete, G. C., Mechanisms of nitric oxides from
ammonia and amines in hydrocarbon flames (Le
mechanisme de formation doxyde azotique a partir
dammoniac et damines dans les flammes dhydrocarbures). Rev. Pet. Inst. Fr., 1973, XXVIII, 171.
De Soete, G. C., Overall reaction rates of NO and N 2
formation from fuel nitrogen, in Fifteenth Symposium
(International) on Combustion. The Combustion Institute,
Pittsburgh, PA, pp. 10931102 (1975).
Glarborg, P., Miller, J. A. and Kee, R. J., Kinetic modeling
and sensitivity analysis of nitrogen oxide. Combust.
Flame, 1986, 65, 177202.
Glarborg, P., Lilleheie, N. I., Byggstyl, S., Magnussen, B.
F., Kilpinen, P. and Hupa, M., A reduced mechanism for
nitrogen chemistry in methane combustion, in TwentyFourth Symposium (International) on Combustion. The
Combustion Institute, Pittsburgh, PA, pp. 889898
(1992).
Peters, N., Reduced mechanisms, in Reduced Kinetic
Mechanisms and Asymptotic Approximations for
MethaneAir Flames, ed. M. D. Smooke. SpringerVerlag, Berlin, Chapter 3, pp. 4867 (1991).
Payne, R. and Moyeda, D. K., Scale up and modelling of
gas reburning. Combustion modeling, scaling and air
toxins. ASME Fact, 1994, 18, 115122.
Ballester, J., Fueyo, N. and Dopazo, C., Natural gas
reburning in coal-fired boilers: experiments and computations, in ProceedingsInternational Gas Reburn
Technology Workshop, ed. W. Bartok, Malmo, Sweden,
February 79, pp. D187218 (1995).
Rasmussen, N. B. K., Modelling of flow and combustion
in a MSW incineration plant, in ProceedingsInternational Gas Reburn Technology Workshop, ed. W.
Bartok, Malmo, Sweden, February 79, pp. D175185
(1995).
Tyson, T., Gas reburning design process considerations, in
ProceedingsInternational Gas Reburn Technology
Workshop, ed. W. Bartok, Malmo, Sweden, February 7
9, pp. D121138, D173 (1995).
Freklach, M., in Numerical Approaches to Combustion
Modeling, ed. E. S. Oran and J. P. Boris. AIAA, New
York, Chapter 5 (1991).
Fiveland, W., Personal communication. Babcock and
Wilcox, Alliance, OH (1996).