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Copyright © 1985 by ASME

The Prediction of Thermal NO x in Gas Turbines

J. ODGERS & D. KRETSCHMER
Departement de genie mecanigue
Universite Laval
Quebec, QC, Canada G1K 7P4

ABSTRACT interwoven into complex chemical models describing

the entire combustion process. Some typical (simple)
Two correlations enabling predictions of models are given in Table I and Fig.1 [1 to 10]*. The
thermal NO x are considered. The first correlation first eight correlations depend solely upon changes
is a purely empirical one, and its uses and in inlet parameters, and because of this they exhibit
limitations are defined. Providing that "base" data certain deficiencies. As proposed, they cannot take
are available the correlation is found to be into account-
generally very satisfactory. The second correlation (a) the effects of using different liquid fuels
has a more theoretical background and when tested (b) the effects of using water injection
with the limited amount of data available, it (unless this may be represented as a reduction
promises to be even more useful than the first one. of inlet temperature)
(c) the use of (say) low calorific gaseous
INTRODUCTION fuels, especially if inert gases form part of
the fuel.
The mixed oxides of nitrogen, which are formed
during and after the combustion of fuels in gas 100
turbines, cause continuous concern because of their g/kg fuel
role in air pollution. A great deal of work, both
practical and theoretical, has been aimed at their
eradication. From this work has stemmed a large EI1•10x
number of models ranging from simple empirical ones
to very large complex models involving both kinetics
and aerodynamics. Nearly all of the models predict 10
well for the environment from which they were
derived, a few give reasonable extrapolations, and
still others have a wider range of application
providing that a baseline test is available to
calibrate the model
In the combustion laboratories at Universite
Laval, a very simple model was first used to pre-
dict the NO x concentrations within gas turbine
combustors. As time went by, this has been replaced
with another empirical model which is somewhat
more versatile. The use and limits of this model
will form a major part of this paper. Another
section of the paper will be devoted to the descrip- 0,1
tion of a new and more promising correlation which
18 20 22 24 26
has a better theoretical basis, and which may be of 100 K
a wider application than the present one.
Fig.1 Effect of Theoretical Maximum Temperature Upon
NOx Formation [9]
EXISTING CORRELATIONS
The scatter band includes gas turbine combustors
with and without water/steam injection and fully
It is impossible to cite all the existing
premixed stirred reactors
correlations, but most of those used with gas
turbines are of an empirical nature, or are * Figures in [] denote references.

Presented at the 1985 Beijing International Gas Turbine Symposium and Exposition
Beijing, People's Republic of China - September 1-7, 1985

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 TABLE I
Formula Reference 1)9 (1 - e-BT)
EINOR = k eC/T
1,5 -0,5 .1
EI = A p T m (f/a) exp(T /253) [1] (1) where the term C represents some kind of
4 3 3
NOx activation energy, n is the effective reaction
1 48 pressure exponent, T is the effective flame
0,29 .-0,1
(f/a) ' exp(T /251) [2] (2) temperature, and B is the time constant for the
EI NO = A P4 m 3
x effective time for NO x formation. Considerations of
the information available when the original
,5 1
EI = A p m (f/a) exp(T /248) [3] (3) correlation was proposed suggested that Eqn. (11)
NO 4 3
x could be expressed as -

EI
NO
= A 4'5 (f/a) exp(T /200) [4] (4) EI NOR = 29 , e -21670/T ,0,66
1-3
( 1e-250 0) (12)
x 3

6 ,25 . -1 -1 Since Eqn.(12) was first derived, considerably more

EI = A p T m (1+f/a) [5] (5)
NO 4 3 data have become available. Predictions for some of
x these data are given below to justify the equation
1,5 -0,5 .-1 2 5 and to enable a better estimate of its accuracy, and
EI = A p T m (f/a) ' exp(T /144) [6] (6)
4 3 3 its limitations, to be established.
NOx
1 ,5 1 . 1 2 5 Verification of the time constant.
EI = A p T m (f/a) ' exp(T /288) [7] (7)
NO 4 3 3 In an experimental study of the effect of
x premixed flames on NO x formation, Roffe et al.[11]
0,5 — 0,22 1,4 investigated the effect of residence time, as well as
EI = A p m (f/a) exp(T /250) [8] (8)
NO 4 3 pressure and inlet temperature effects. Some of the
x data are suspect (e.g. there are cited values of NO x
AT which are higher at short residence times than those
lg EI NG = A IT, + 1 - B [9] (9) at long ones), and it was necessary to eliminate such
-31 + 1,084 w
points. The remaining values were grouped into test
-21670/T 0,66 -250T series each of which yielded a variation of NO x
EI = A e p (1 e [10] (10)
NOx 3 over a range of times from 1 to 3 ms at time
intervals of 0,5 ms. If the value of B (250 sii i )
was correct, then the actual measured values of NO x
emission index divided by the value of (1 - exp(-250
Examination of Eqns. (1) to (8) shows the wide
T)) should give a constant value ( i.e. the value for
variations obtained for the pressure and inlet
T==.). Table II summarizes the results of these
temperature exponents. This might represent some
investigations, and bearing in mind the experimental
design feature(s) of the particular combustor(s) accuracy, the standard deviation value of 12,1 % is
from which any given correlation was derived.
considered to be quite a satisfactory confirmation of
In an attempt to obtain something of more the original time constant.
general application, Kretschmer et al. [9] took
advantage of the following assumptions in order to
TABLE II
produce Eqn.9 -
(a) Temperature predominates in the formation of NO R .
SUMMARY OF RESULTS OF TIME CONSTANT INVESTIGATION
(b) The effect of water (liquid or vapour) is solely
to reduce the flame temperature.
Total number of experimental points 59
(c) For diffusion flames the relevant temperature is
that corresponding to the maximum equilibrium 5 - 20 atm
Range of pressures
temperature possible corresponding to the inlet
conditions.
Range of inlet temperatures 600 - 1000 K
(d) For premixed gases the relevant temperature is
the dissociated flame temperature corresponding to
Range of residence times 1 - 3 as
the equivalence ratio and the inlet conditions.
The results are expressed in Fig.1. The curve
Range of EI Noat
x T 0,59 - 35,1 g/kg
has been used to determine the degree of premixing by
comparing the'measured NO x with (a) that predicted
for a premixed flame corresponding to the air/fuel Range of EI Noactual
x 0,19 - 16,1 g/kg
ratio in the primary zone and (b) the corresponding
diffusion flame. Figure 1 appears to serve well for Range of flame temperatures 1825 - 2375 K
hydrocarbon fuels within the limits of the indicated
scatter band, but it has been shown to exhibit Standard deviation of EINOx 0,121
significant errors with non-hydrocarbons and low
calorific fuels. Verification of the pressure exponent.
The variation of the pressure exponents
THE PRESENT LAVAL CORRELATION obtained by previous workers has already been
commented upon (Table I). The original value of 0,66
From observation of published literature, such assumed for Eqn.(12) was somewhat "guesstimated" by
as that discussed above, it was decided that the consideration of the various results given in Table I
simplest possible formula which could take into and a few experimental results which were available
account the inlet conditions and fuel variables would to the Laval laboratories. The results of Roffe et
be of the form [10] - al.[11] showed some inconsistencies in that pressure

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 effects noted at one inlet temperature seemed to be
different to those found at other inlet temperatures. General verification.
Because of this (although the effects of inlet
temperature will be discussed again later) other Fuel effects. A theoretical examination of
experimental evidence was sought, and that of Norster possible effects due to the use of alternative fuels
et al.:121 was used to test the validity of the quickly establishes that for hydrocarbon fuels,
present exponent (0,56). The resultant correlation of providing there is no fuel-bound nitrogen, the
Norster's results is given in Fig. 2 and appears to effects will be limited to those due to the small
be very satisfactory. changes in flame temperatures.
As an example of the effects of fuels within a
pressure-jet atomized combustor, the results for the
J 79 engine were analysed [13]. Estimates for other
combustors suggested that the NO x formation time
30 I I for conventional "diffusion-flame" combustors was of
0 the order of 1 ms. Assuming this time, the values
lo -9 calculated for the various fuels are given in Fig. 3.
pa 0,6 6 p As a check on the accuracy obtainable, for each
00,44 MPa operating condition, the value of the apparent
[NOr] 0,93 MPa residence time was calculated using the experimental
p,00'66
)6 A0
❑ 1,38 MPa data for the base fuel. The actual residence times
20 determined in this way ranged from 0,85 ms (Take Off)
0 to 1,14 ms (Idle). These times were then used to
predict the new values for the other fuels. They do
40
A \
10 0
9
EINOx —
** Dash -

TO
10
9
0
Cruise
0
40 60 80 100 120 140
(c• 0 oc
A/F o—
Idle _
Fig.2 NOx Emissions from a Tubular Combustor
Effect of pressure and overall air/fuel ratio
Inlet temperature 873 K, dual orifice atomizer
Data fro [12] 1 11 12 13 14 56 15

30 Fig.4 Effect of Hydrogen content Upon NOx

J-79 combustor, Data from [13]
Lines are predictions using Eqn.(12)

40
4_
Ddsh

EIN0 10 EINOx TO
x

10 x
7.=
Cruise =

02 Cc,
Idle
30

Fig.3 Predicted vs. Experimental NOx 111 12 13 14 % 15

J-79 combustor, Data from [13]
Open areas are predictions using t = 1 ms, solid
areas predictions using T as determined for each Fig.5 Effect of Hydrogen Content Upon NOx
condition from the data for the base fuel. F 101 combustor, Data from [14]
Lines are predictions using Eqn.(12)

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 indicate some slight improvement over the previous
swirler) was not uniform. Yet a third possibility is
ones. Figure 4 expresses the results in terms of fuel
that the fuel and water droplets interact/react with
hydrogen content at each condition. The predictions
each other to supress the local temperature. Wilkes et
are within the experimental scatter.
al suggest that some of the effects of water are
Similar predictions were made for a pseudo-
dependent upon the presence of fuel-bound-nitrogen
premixed combustor (F101) [14] with very similar
and that, as this latter increases, the effectiveness
results. In this case the base fuel was used to
of water decreases. For whatever reasons, there is no
establish the apparent NO x formation time due to
correlation with Eqn.(12).
lack of data. The apparent residence time would
appear to be of the order of 0,9 ms (cf 1 ms above).
The effects of fuel vaporization. In [17]
The results are given in Fig. 5. Again the predicted
Cooper examined the combustion of "partially"
and measured values are in satisfactory agreement.
vaporized fuel/air mixtures in a premixing -
Both sets of data appear to confirm all the
prevaporizing combustor. Equation (12) was used to
terms in Eqn.(12), since changes occur in
calculate the equivalence ratios ( 9N0x) needed
temperature, pressure, and residence time.
to obtain emissions equal to his experimental values
(T = 2 ms, p3 = 10 atm) from completely premixed
Effects of steam and water. Singh et al.[15]
combustion. These apparent "effective" equivalence-
examined the effects of steam addition to the air
ratios are plotted against the fraction of fuel
upstream of the combustor. Figure 6 illustrates the
evaporated in Fig.7. The results present several
comparison between the experimental values and those
interesting phenomena -
predicted by Eqn.(12). A single experimental point
(a) As the fraction of fuel vaporized decreases
(indicated in Fig.6) was used to establish the
for a constant value of 6, the NO x formed
apparent NO x formation time. This was assessed as
increases until, for vaporized fractions < 0,5,
1,48 ms; the remaining values were estimated using
the NO x emissions approach values which would
this value for the reaction time. The agreement is
need stoichiometric conditions in a premixed
good but not perfect. However, it must be remembered
combustor.
that any error in the arbitrarily chosen base point
(b) For the fully vaporized fuel, the real
must be reflected in subsequent predictions.
equivalence ratio should be close to the
"effective" premixed value. This is true for low
values of 6. However, as the equivalence ratio
is increased (still at fully vaporized
condition), the NO actually produced
increases above that given by a premixed flame
of the same equivalence ratio, this being
indicated by the fact that the effective
equivalence ratio is higher than the true
mixture 6.
(c) Again for the fully vaporized case, an
effect similar to the above mentioned (but to
a smaller degree occurs as the inlet
temperature (for a value of 6 - 0,6) is
increased from 600 K to 1000 K.

(1)
800 overall T3
0,9
al 1
1200 T4K 1400 'NO x

Fig.6 Effect of Steam Upon NOx Formation

0,9
Data from [15], T 3 = 555 K, p 3 = 408 kPa
Number 2 Fuel Oil -

Lines are predictions using Eqn.(12) 0,8 ca 800

Following this success, attention was turned to

the prediction of the effects of water within the
primary zone. The data were taken from a publication 0,7 . 00,6 1000
by Wilkes et al.[16]. Initially, a single point was
0,6 800
selected (dry air) to obtain the time constant, and
L• 0,6 600
this yielded a value of T = 2,5 ms. Using this value, 6 -

satisfactory agreement (±20 %) was obtained for the

dry air data. No success was attained in trying to
predict the effect of water injected directly into '0,5 800
the primary zone, not even when the air flow into the 0,5
primary zone was estimated, and the water/air ratio 0,5 0,6 (),7 0,8 0,9 1
adjusted accordingly. One possible explanation is Fraction of fuel evaporated
that the effective NOx reaction zone contains much
less air than that suggested by the aerodynamic Fig.7 Fuel Vaporization Effects Upon Apparent (1)
survey. Another possibility is that the distribution Data from [17]
of the water droplets (via the fuel nozzle axial

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 Item (a) is in accord with general theory, but
the reasons for the behaviour (b) and (c) are not
clear. One possible explanation for (b) is that the
fuel was actually not as completely vaporized as
stated. A more likely explanation is that, though the
fuel is completely vaporized, the mixing quality
decreases with increasing equivalence ratio, this
creating pockets richer than average with a
corresponding increase in NO x formation. As far as
the behaviour (c) is concerned, no explanation is
apparent. Nevertheless, the diagram (Fig.7) does
indicate the value of NO x measurements as a measure
of vaporization/mixing for incompletely "premixed"
systems, such as air-blast, vaporizers, etc.
AN ALTERNATIVE CORRELATION BASED ON SIMPLE THEORY
In an attempt to shed some light on the time
dependence of NO x formation, it was decided to
approach the question using simple reaction rate
theory. it is obvious that the model is over-
simplified, but this is justified by the experimental
scatter generally observed.
The simplest reaction expressing the formation
of nitric oxide from oxygen and nitrogen is-
N + 0 2 NO
2 2
The generalized rate may be expressed as -
d[N0] e-B/T
A EN ][0 ] - A
dm l 2 2 2
or, if [N2] and [02] are assumed constant-
d[NO]
e-B/T -C/T
- A2 e [NO]
K1
which integrated can be expressed as
-B/T
[NO] = a e tanh ( Y e)
However, T is not instantaneously achieved
T = f(T, ID3, 13, (p)
Equation (16) may be approximated by -
A-B/T
EINO = e tanh (C p T .
x 3
In this form, the data from [11] were analysed
to determine the constants for Eqn.(18). The values
obtained were : A = 10,5 B = 17 752 K
C = 9,081x10 - ' 4 D = 0,8687
E = 3,96 F = - 0,7038
As previously indicated, some of the data in [11]
appear to be experimentally inconsistent. Eliminating
such points yields data which are summarized in
Table III. It will be noted that the rms deviation
given by Eqn.(18) is considerably less than that
given by Eqn.(12).
Plotting the predicted values of the NO x
emission index versus the experimental ones sheds
some light on this (Unfortunately, due to the number
and complexity of the data involved and the necessary
use of colour, the diagrams cannot be reproduced
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here). The points from Eqn.(12) show distinct trends.
The values for the 600 K data, especially at low
pressures, are greatly overpredicted; those at 800 K
are very slightly underpredicted; those at 1000 K are
considerably underpredicted. This represents the
influence of the inlet temperature upon the reaction
rate. In order to achieve the high temperatures
required for NO x formation, at 600 K more time is
required than at 800 K or 1000 K. Thus, the effective
NO x formation time is much less for the experiments
at 600 K. In fact, at this latter condition and at a
pressure of 5 atm the calculated NO x residence time
was only 0,25 ms, compared with a cited combustion
residence time of 3 ms. These observations
demonstrate the inadequacy of Eqn.(12), which uses
the actual NO x formation time, but at the same time
they offer an explanation for its accuracy once a
base point has been used to determine the effective
residence time and thereby obviate the effects of
inlet temperature etc. In Eqn.(18) it is the
combustion residence time which is used, a factor
which is much easier to estimate than the NO x
formation time. As more data become available to
certify the constants of Eqn.(18), the latter should
become a more-than-adequate replacement.
(13)
TABLE III
ANALYSIS OF DATA FROM [11]
[NO]2
, e-C/T
(14)
Total number of points considered 172
Range of inlet pressures p3 5 - 30 atm
Range of inlet temperatures 73 800 - 1000 K
dm (15)
Range of NO x formation times T 1 - 3 ms
2
Range of equivalence ratios ¢ 0,34 - 0,86
Range of flame temperatures T 1620 - 2395 K
Range of EI N0 (experimental) 0,19 - 56,5 g/kg
(16)
Predictions made using Eqn.(18) 55,3 % rms
Predictions made using Eqn.(12) 173 % rms
(17)
The derivation of the constants for Eqn.(18)
involved only the use of measurements made using a
D E F premixed, prevaporized system. Most aircraft and
x T) (18)
industrial engines utilize liquid fuels. Since
combustion cannot be completed until after
evaporation of the liquid, it follows that the
available time for NO x formation will be a
function of the droplet evaporation time. To test
this supposition, it was decided to apply Eqn.(18)
to the J 79 combustor results reported in [13]. For
the "standard" fuel the actual residence time was
calculated assuming the experimental values to be
correct. The results were -
Condition: Idle Cruise Take-Off Dash
ms 26,5 7,40 2,72 1,31
The above times are much longer than those
calculated for the NO x formation times using
Eqn.(12), but it must be remembered that the former
times are combustion times whereas the latter are
formation times. Although there were insufficient
 data to enable the absolute values of drop size (and P3 combustor inlet pressure Pa
hence evaporation times) to be calculated, P4 combustor outlet pressure Pa
comparative values could be assessed for each of the T flame temperature K
four conditions above. These times were found to be T3 combustor inlet temperature K
in accord with the relative times based upon T4 combustor outlet temperature K
Eqn.(18) above. a a constant
a constant
As an additional check, the procedure was AT temperature rise T - T3 K
repeated using the data presented for the F 101 a constant
engine [14]. The results were - 9 an equivalence ratio
410x ¢ calculated from the NO x data
condition: Idle Cruise Take-Off Dash • time
T ms 13,0 2,87 1,43 1,31 • water to dry air mass ratio

For the future developement of Eqn.(18) current REFERENCES

thoughts are (a) to try to obtain published data of a
sort suitable to confirm the equation, (b) to attempt
to assess the effects of water/steam injection both
upstream and within the primary zone of the combustor
and (c) to try to design a series of experiments to
enable the equation to be fully assessed.
[1] N.R.Marchionna, L.A.Diehl, & A.M.Trout; Effect
of Inlet Air Humidity, Temperature, Pressure
and Reference Mach Number on the Formation of
Oxides of Nitrogen in a Gas Turbine Combustor,
NASA TN D - 7396, Oct. 1973

CONCLUSIONS [2] L.B.Davis, R.J.Murad, & C.F.Wilhelm; Emission

and control of NOx in Industrial Gas Turbine
A simple formula for NO predictions has been Combustors; Experimental Results, presented at
established together with its uses and restrictions - the 66th Annual AIChE Meeting, 11-15 Nov 1973

EI NO x = 29 e -21670/T e3
,0,66 (1 _ e - 250i)
This equation functions well providing that a set of
base data are available to establish the apparent
NO x formation time. If no such base exists, then
for aircraft combustors a formation time of 1 ms
(pressure jet atomizers) or 0,8 ms (air-blast
atomizers) may be used. For industrial combustors the
time for liquid fuels will range from 1,5 to 2,5 ms.
A new formula having a more theoretical basis
has been derived, and preliminary indications are
that this formula should be more satisfactory than
the empirical one cited above. The new equation has
the form -
EI NO = e A - B/T tanh ( C p D3 . T E3 . ¢ F
x E.J.Mularz, J.D.Wear, & P.W.Verbulecz;
G.Vermes; A NOx Correlation Method for Gas
Turbine Combustors Based Upon NOx Formation
Assumptions, ASME Paper No. 74-WA/GT-10, 1974
R.L.Marshall; presented in ANSI letter written
by W.L.McGaw to D.Goodwin (EPA), 9 Jan 1975
J.D.Cohen; NOx Emissions at High Power Settings
/ Engine Data Correlation, General Electric Co.
TM 74 AEG 1448, Nov 1974
L.A.Diehl & J.A.Biaglow; Measurements of
Gaseous Emissions from a Turbofan Engine at
Simulated Altitude Conditions, NASA TM X-3046,
Apr 1974
)
Pollution Emissions from Single Swirl Can
-

where : A = 10,5 B 17 752 K Combustor Module Arrays at Parametric Test

C 9,081.10 -1 " D 0,8687 Conditions, NASA TM X-3237, June 1975
E = 3,96 F -0,7038
D.A.Sullivan; A Simple Gas Turbine Combustor
ACKNOWLEDGEMENT NOx Correlation Including the Effect of
Vitiated Air, ASME Paper No. 75 - GT - 5, 1976
The authors are indebted to the Canadian
National Science and Engineering Research Council D.Kretschmer & J.Odgers; Modelling of
for the financial support of this work. Combustors: The Effects of Ambient Conditions
Upon Performance, ASME Paper No. 73 - WA/GT - 6,
NOMENCLATURE 1973

A a constant [10] J.Odgers & D.Kretschmer; The Effects of Fuel

Al a constant Properties Upon Pollutants Present in Gas
A2 a constant Turbine Aero Engines, Proc. 6" Intern.
B a constant Symp. on Air Breathing Engines, AIAA, 1983
C a constant
• a constant [11] G.Roffe & K.S Venkataramani; Experimental Study
• a constant of the Effect of Cycle Pressure on Lean
EINOx NO x emission index g/kg Combustion Emissions, NASA Contractor Report
F x a constant 3032, July 1978
f/a fuel to air mass ratio
h fuel hydrogen content (mass fraction) [12] E.R.Norster & A.H.Lefebvre; "Effects of Fuel
K1 a constant Injection Method on Gas Turbine Combustor
k a constant Emissions", Emissions from Continuous
;71 combustor air mass flow kg/s Combustion Systems, Cornelius & Agnew Ed.,
n a constant Plenum Press, New York, 1972

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 [13] C.C.Gleason, T.L.011er, M.W.Shayerson, &
D.W.Bahr; Evaluation of Fuel Character Effects
on the J 79 Combustion System, Report No. AFAPL
TR-79 2015 (CEEDO TR 79-06), General Electric
- - - -

Co., Aircraft Group, Cincinnati OH, June 1979

[14] C.C.Gleason, T.L.011er, M.W.Shayerson, &

D.W.Bahr; Evaluation of Fuel Character Effects
on the F101 Engine Combustion System, Report
No. AFAPL-TR 79-2018 (CEEDO-TR-79 07), General
- -

Electric Co., Aircraft Engine Group, Cincinnati

June 1979

[15] P.P.Singh, W.E.Young, & M.J.Ambrose; Formation

and Control of Oxides of Nitrogen Emissions
from Gas Turbine Combustion Systems, ASME Paper
No. 72 GT-22, 1972
-

[16] C.Wilkes & R.C.Russel; The Effects of Fuel

Bound Nitrogen Concentration and Water
Injection on NOx Emissions from a 75 MW Gas
Turbine, ASME Paper No. 78-07-89, 1978

[17] L.P.Cooper; Effect of Degree of Fuel

Vaporization Upon Emissions for a Premixed
Partially Vaporized Combustion System, NASA
Technical Paper 1582, Jan 1980

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