NASA Contractor Report 175064

Spontaneous Ignition Delay Characteristics

of Hydrocarbon Fuel/Air Mixtures

(NASA-CR- 1750_)

CHARACTERISTICS

MIXTUBES _ _tlal

HC AOb/MI: AO I

SPONTANEOUS IGNITION DELAY

Of HYOROCA_BCh _UEL-AIR

_£port [_urdn_ Univ.) 102 p

CSCL 21E

G3/07

N86-2 15_5

Unclas

05804

Arthur Lefebvre, W. Freeman, and L. Cowell

Purdue University

West Lafayette, Indiana

February 1986

Prepared for

Lewis Research Center

Under Grant NAG 3-226

National Aeronautics and

Space Administration

CONTENTS

i. INTRODUCTION

2. BACKGROUND

3. EXPERIMENTAL 22

4. DATA REDUCTION AND RESULTS 44

5. CONCLUSIONS AND RECOMMENDATIONS 88

6. REFERENCES 96

INTRODUCTION

Autoignition is the spontaneous combustion of a fuel

and oxidizer mixture in the absence of any external ignition source. This ignition occurs in a finite time after

the fuel and oxidizer are combined. In homogeneous mixtures the time necessary for ignition depends on the temperature, pressure, fuel concentration, and oxygen concentration. The ef[ect of pressure on autoignition delay time

is the focus of this study.

The characteristics of autoignition have been studied

for several different reasons over the past century. Studies have been completed examining the effect of autoigniengines, the knocking phenomena in spark

flame stabilization in gas turbine

presently

in gas

tion on diesel

iqnited engines,

engines, and

combustor concept

pr em} x ing,

for the premixed/prevaporized

turbine engines. The lean,

and prevaporiz]ng (LPP) combustor technology is

the motivation for this study.

Concern over the depletion of the ozone layer in the

stratosphere due to nitric oxides has prompted NASA to initiate the Stratospheric Cruise Emission Reduction Program
(SCERP). One method of reducing the formation of nitric

oxides in gas turbine engines is by mixinq the fuel and air

prior to combustion, alJowing complete evaporation of the

fuel drops, and mixing of the fuel vapor with the air. The

resultant, homogeneous mixture can be burned leaner without

the local hot spots associated with combustion of heterogeneous mixtures. Fig. ].I illustrates typical reductions

found between LPP combustors and conventional combustors

[1].

Among the problems associated with this concept are

autoignition and flashback in the premixing tube. Autoignition occurs in the premixinq tube when the residence time

25-

15

,0

g

X

o

z 0

CONVENTIONAL CLEAN

TECHNOLOGY

JT9D-7 CYCLE

[] CF6-50 CYCLE

APPROXIMAT E RECOMMENDED

EVEL

COMBUSTOR

TECHNOLOGY

FORCED PREVAPORIZIN6

CIRCULATION PREMIXED

l"iqur_; 1.| NO c,missior,._; For" conventional and advanced

x

combustor t_:,ch_o]ogies [1].
of the fuel and air mixture is greater than the delay time.

Flashback is the propagation of the flame upstream from the

combustor to the injector,

speed is greater than

these problems can cause

which occurs when the flame

the mixture velocity. Either of

structural damage as well as

higher pollutant formation. Temperatures and pressures at

the exit of compressors in modern gas turbine engines are

sufficiently high for autoignJtion to occur in one tenth of

a second or less. Designing a premixing passage requires

allowing enough time for complete evaporation while precl_,ding the possibility of autoignition.

The autoignition delay time is composed of two overlapping components: the physical and chemical delay times.

The physical delay time dominates the early stages of the

auto_gnition process. This delay time consists of the time

for the fuel drops to form, heat up, and evaporate; and the

time for the fuel vapor to mix with the air. The chemical

delay time dominates after this mixing has occurred and is

dependcrlt on the chemical kinetics.

The autoignitlon delay time is measured

t tnuous flow apparatus. In this device

injected into a flowing air stream at high

with a conthe fuel is

temperatures,

and ignites at some distance downstream depending on the

air velocity. This concept is illustrated in Fig. 1.2,

where the delay is defined as the length, L, divided by the

fluid velocity, U. Several other devices exist to measure
the delay time, such as: constant volume bombs, compression

engines, and shock tubes.

control of pressure is

method also most closely

tube.

However, in all these methods

impossible. The continuous flow

simulates flow in a premixing

Hot

Air

Fuel

U

S. I. Flame Front__,_.

Fuel/Air _

Mixture _ "_<_

Delay Length, L

Figure, J..2. Basis of igr_it:[on delay times measurement

techn:ique.

4
BACKGROUND

The characteristics of autoignition delay time have

been subjected to considerable study. A review of previous

work is presented here. The major focus is on continuous

flow experiments of homogeneous mixtures of hydrocarbon

fuels in air. In the majority of these studies the delay

time is corre]ated with temperature, pressure, fuel concentration, and oxygen concentration using global reaction

theory. This theory is presented prior to the review. The

chapter concludes with a brief review of flashback theory,

since flashback has been a considerable problem in premixln(] tubes and also in I.his ._tudy.

Aut_o Lgqitj.9!? Ki_[leti_c Th_eo_y

reactitlg f l_ws

between fuel,

Descr iblng the

The chemica[ proces_{es governing the ignition of

are composed of many interwoven reactions

air, intermediate species, and products.

entire overa]l reaction in one step is a

common simplification ()f the problem and has been proven as

a pratt, lea] solution [2].

The reaction between fuel and air can be represented

by fuel and air going to combustion products.
The forward reaction rate equation is

rr = K [oxygen] ] [fuel]m pn (2.1)

where.n=j+m, is the global reaction order, P is the pressure in atmospheres, and the fuel and oxygen concentrations

are based on volume. The reaction rate constant, K, is

expressed from the modified Arrehenius expression as

(2.2)

Here E is the global activation energy, R u is the universal

gas constant, and A is the Arrehenius constant.

The delay time is proportional to the inverse of the

reaction rate and can be expressed as

T _ _ exp [oxygen] J [fuel]-m p-n T-0.5

This corre]ation indicates that plotting the log of delay

time against the inverse of temperature should result in a

stralght line if the other vaYiables are held constant and

-0.5

T is ignored. This is the most common method of correlating autoignition data.

Previous Work

The results of earlier workers have been studied and

compi]ed by the physical variables which influence ignition
delay time in homogeneous mixtures. For a review of the

physical variables influencing the delay time in heterogeneous mixtures, literature surveys have been completed by

Chiappetta and McVey [3] and Freeman [4].

Pressure

Pressure influences lhe autoiqnition delay time

through the reactants conccr, tration. Pressure is inversely

related to delay time as

7- ot p-n (2.4)

To include the pressure term the fuel and oxygen concentrations must be based on volume. The exponent n varies from

0.5 to 2.5 in the literature. The ]og of delay time versus

the log of pressure of previous workers' results for homoger_eous mixtures is shown in Fig. 2.1. The slopes of the

lines, shown in parentheses, represent the pressure

exponent, (n). On]y Burwe] ] and Olson [5], using vaporized

isoL-octane, took measurements at pressures greater than one

atmosphere. Mullins [6] found the value of the pressure

expc_n_:nt to be fuol- ty[_e dependent at pressures below

atmospherlc for a vitiated _ir supply.

Fig. 2.2 illustrates the delay time versus pressure

relationship for heterogeneous mixtures, as compiled by

Chiappetta and McVey [3]. For these aircraft fuels the

pressure exponent varies f rc,m 0.8 to 2.0. In heterogeneous
0

E

°m

0

£]

I0 Im

5-

I--

°_

J

05 -

.01 --

.005 -

.001

.I

e (74)

57)

Key Ref.

a 6

b 6

c 6

d 5

e 7

Fuel

Methane

Ethane

Acetylene

Iso- Octane

Propane

(i.7)

I !

.5 I

r oc p-n (n)

I I

!M(i!)

I000

I000

8OO

655

615

5 I0

Pressure, atmos

F'i,jur{, "2.1. .%ummuYy o1 r(,:;t_] t _ sh()winfl the effect of pressure

on jgn]Lioll (](_i,ly times for homogeneous mixtures.
I000

E

w"

I-

_1

LIJ

0

5OO

200

I00

5C

2O

I0

I

J

m

I

5-

2--

I'

2

KEY REE FUEL

o 20 No. 2 Diesel

b 13 Kerosine

c I I Jet- A

d 2:5 JP- 4

e 16 Jet-A/Diesel

f :52 JP-4

g I0 No. 2 Diesel

h I0 Jet-A

i I0 JP-4

\\ c(i.o)

h(2.0)< \ e (0.9)

1 I I

5 I0 20 50 I00

PRESSURE, atm.

F i(jl,lF'(2 _;_imm,=ry of results showin9 the effect of

pr(_ssuv(' or_ iunitJon d(_]ay times for heterogen(;ou:; mixtllres. Compiled by Chiapetta and

McV(_y 131 .

9
mixtures pressure also influences the evaporation rate of

the fuel drops. Anderson [8] found this dependence to be

small, while Chin and Lefebvre [9] found the effect of

pressure on evaporation rate to increase with increasing

temperature. The lack of understanding of the effect of

pressure on evaporation rate may explain some of the variations in the results of workers using the same fuel. For

example both SpadaccinJ [23] and Taback [32] used JP-4

fuel, but SpadaccJni round n=l.8 while Taback found n=0.9.

Still the results in Fig. 2.2 are similar enough to suggest

that the effect of pressure is more dominant in the chemical delay time than in the physical delay time.

Temperature

According to the global reaction theory temperature

affects the delay time through the Arrehenius expression.

1

-0.5

The term T comes from molecular collision theory, and

has generally been neglected by most previous researchers.

Both Miller [15] and Mullins [6] correlated their data with

the collision term, an(] [ound a negligible effect over a

200°C temperature range. They concluded that its effect

could only be realized over a very large temperature range.

Ignoring the collision term, the log of delay time

versus the reciprocal of temperature should yield a

i0
straight line. Fig. 2.3 shows previous workers' results as

compiled by Chiappetta and McVey [3] and updated by Freeman

[4] as the log of pressure times the delay time versus the

reciprocal of temperature. Chiappetta chose a pressure

exponent of ].0 as being the most representative for all

the stndies available. The majority of work with heterogeneous mixtures was performed at pressures greater than

atmospheric. The slopes of the lines represent the global

activation energy, but since the pressure exponent was set

for comparison the activation energies determined from this

graph may be misleading. Only Freeman [4], Lezberg [12],

and Mu]lins [6] found the activation energy in the range of

40.0 - 50.0 kcal/kg-mol, whic|l

range for gas turbine fuels.

their studies at atmospheric pressure

explain their good correlations.

is the commonly accepted

These researchers performed

only, which could

The initial mixture [emperature was used to correlate

thu data. However, in a reacting flowing mixture the temperature will not remain constant. Variations in temperature along the flow path have been reported from a 200°C

drop by Mestre and Ducourneau [13] to a 200°C rise by

Burwell and Olson [5]. Burwell and Olson used a nearlyadiabat, ic flow channel, and their temperature rise reflects

that of reacting mixtures. Mestre and Ducourneau [13] used

a variably heated channel and found only a minor difference

between adiabatic conditions and flow with heat loss.

ii
41,,--

0

E

4000 -

3OO0 -

2OOO -

I000 --

500 -

400-

500-

200-

I00 --

50-

40-

3oi20-

I0--

5-

4-

:.'5-

2-

I

4

l

6

1

8

b

| d

m

a

Key Ref. Fuel

a II Jet-A

b I0 No. 2 Diesel

c 23 JP4

d I0 No. 2 Diesel

e 16 AVTUR

f 32 JP4

g 13 Kerosine

h 16 AVTAG

j 6 Kerosine

k 12 Propane

4 Jet-A

m 4 Propane

1 1 1 I I I I I

IO 12 14 16 18 20 22 24

I/T m x IO4, K -I

F i qure 2o_. Summary o1: results showing the effect

of temperature on ignition delay times.

Compiled I)y Ch[apetta and McVey [3].

12
Chang 9_ _- [14] also operated an essentially adiabatic

flow scheme using propane, and found a 25°C increase

between his results and Freeman's [4], who employed propane

with a 50°C drop along the test section length.

Oxygen Concentration

The oxygen concentration influences the delay time by

changing the probability of reaction. Oxygen concentration

is related to the delay time via

T _ [oxygen] -j (2.6)

The oxygen concentration exponent ,j, has been found to

vary from 0.25 by Brokaw and Jackson [7] to 2.0 by Mullins

[6] for a vitiated air snpply. Freeman [4], Chang et al.

[14], and Miller [15] found better agreement with values of

0.59, 0.74, and 1.0 burning propane, propane, and calor gas

respectively at atmospheric pressure. Most recent work has

not investigated the effect of oxygen concentration on

delay time in premixing tubes because there the oxygen concentratJon does not va[y strongly in the inlet air.

Fuel Concentration

Fuel concentration affects the delay time in an identical manner to oxygen concentration. Its influence on the

reaction is given by

13
-m T _ [fuel] (2.7)

However, only Burwell and Olson [5] (m=l.O) burning vaporized iso-octane, and Brokaw and Jackson [7] (m=.74) burning

propane, have found a strong influence. Freeman [4], Mulfins [6], Spadaccini [I0], Miller [15], and Stringer et al.

[16] found little influence for lean mixtures. Mestre and

Ducourneau [13] found a strong effect for rich mixtures.

Tacina [17] noticed no effect using a simplex nozzle in

heterogeneous mixtures, but found an increasing effect as

the number of fuel injection points in an airblast atomizer

was increased. Improving the atomization shortens the mixing time and provides a more uniform fuel-air mixture.

This trend illustrates the difficulty of determining fuel

concentration in heterogeneous mixtures, since large variations in fuel cor:centration occur locally around fuel

drops.

Fuel Type

The vol.atility and _t ructure of a fuel have been found

to influence the delay time. In global reaction theory

thls is reflected through changes in pressure, fuel, and

oxygen exponents. Stringer et a_!_- [16] observed a decrease

in ignition delay time with an increase in cetane number, a

decrease in octane number, and in changing fuel type from

aromatics to branching paraffins to napthenes to straight

paraffins. They also found a slight reduction in delay

14
time with increasing number of carbon atoms. In liquid

fuel sprays the effect of fuel type on evaporation rate has

also been noted. Yoshizawa [18] performed shock tube studies with n-butane, n-hexane, and n-octane and noticed no

d_fference Jn delay time belweeI_ these fuels. He concluded

that., with the exception of lighter hydrocarbon fuels, such

as methane and ethane, fuel chemistry has no influence on

delay time.

A number of investigators have suggested mechanisms

for the autoignition process which follow the findings of

Stringer et al. [16]. Edelmen [19] and Henein and Bolt

[20] propose that the heavier hydrocarbon fuels decompose

to paraffins such as methane and ethane, which then react

to autoignition. Hauptman et al. [21] suggests a four-step

mechanism whereby the heavier hydrocarbons are reduced to

intermediate olefinic specles, such as ethene and propene,

which then react to form carbon monoxide and hydrogen. The

carbon monoxide and hydrogen then react with oxygen to the

point, of ignition producing carbon dioxide and water.

Hauptman has demonstrated good correlation between his

theory and the data he obtained in a shock tube study.

Turbulence

Turbulence influences delay time in several contradictory ways. First, air turbulence enhances mixing which

decreases delay time. Secondly, Lefebvre and Ballal [22]

15
suggest that turbulence hinders ignition by more efficiently dissipating the thermal energy. Ballal and

Lefebvre are referring to external sources of ignition, but

their theory applies here because in reacting flows the

temperature profile is flattened by turbulence.

The influence of turbulence on delay time has not

received much attention. Chang et al. [14] placed 4, I0,

and 20 mesh screens upstream of the fuel injector to vary

turbulence intensity and found no effect. Likewise,

Stringer et al. [16] used screens to vary the turbulence

intensity from 3 to 17 percent, and found no effect. Mull. ins [6] put baffles downstream of the injector to increase

the turbulence scale, and found a slight increase in delay

time for liquid fuels.

Fuel Temperature

In all previous work surveyed the inlet fuel temperature was always less than the inlet air temperature. In

heterogeneous mixtures fuel temperature determines the evaporation rate of fue] sprays, and thereby influences the

delay time [6,10]. However, in homogeneous mixtures fuel

temperature only alters the mixture temperature locally,

downstream of the fuel injector, until the fuel and air are

comp]ete].y mixed. If mixing is completed quickly compared

to the delay time no effect_ should be noticed [4].

16
Test Section

Brokaw and ,Jackson [7] varied the test section surface

material between vycor, stainless steel, and potassium

chloride, and observed no effect on delay time at atmospheric pressure. They concluded that three-body reactions

have no effect on delay time. Freeman [4] found varying

the test section length had no effect, while Spadaccini

[10] observed a noticeable increase in delay time with

length, especially at low equivalence ratios. Spadaccini

used a test section w[t_i water-cooled walls, whereas

Freem_n's test section was heavily insulated.

Remarks

All the results preserlted in this section were correlated using global react ion theory, which models only the

chemical delay time. The variations of results obtained in

studies using heterogeneol_s mixtures indicates the influence of the physical delay on the overall delay time.

Since the results of previous workers are of the same magnitude, the autoignit ion delay time must be dominated by

the chemical delay component.

Flashback Theory

Aside from autoignition another problem encountered in

premixing fuel-air passages is flashback of the flame from

the combustor to the injector. Flashback occurs when the

17
flame speed is greater than the fluid velocity.

The first studies of flashback were made in connection

with burner tubes. Lewis and Von Elbe [24] proposed the

classical theory of flashback in laminar flows. They

defined that for flashback to occur in the boundary layer

the velocity gradient must be less than the flame speed

divided by the quenching distance as shown below

SL

(2.8)

OU 1 _

r=R qD

where U is the fluid velocity, S L is the laminar flame

speed, and qD is the quenching distance. This concept is

illustrated in Fig. 2.4 where the velocity profile is

approximated as a straight line. The velocity profile that

intersects the flame speed profile at only one point is the

flashback limit, and represents the smallest fluid velocity

for a given flame speed profile at which flashback will

occur. Putnam and Jensen [25] used the Peclet number to

relate the flame speed and fluid velocity in the Lewis and

Von Elbe model.

pe 2 = k Pe (2.9)

Su U

The Peclet number

transfer number

Prandtl number. The subscr ipt SL or U indicate

city used in the Peclet number. Khitrin et al.

18

is a dimensionless independent heat

equal to the Reynolds number times the

the velo-

[26] found
>:

-JFiii

n

(f)

I,I

_J --

\\

\-,,

,'<

\ \

\ \

_J

_J

<

Iii

m

D

I--

\\

\\

\\

\\

\\

\\

\\

\\

%. \

\x.41

\ \

O

NO FLASHBACK

U

FLASHBACK LIMIT

U

FLASHBACK

U

S

L

QUENCHING DISTANCE, qD

DISTANCE FROM WALL

FLgure 2.4. Flashback Lheory of Lewis and von Elbe [24].

19
in turbulent tube flows that flashback still occurs primarily in the laminar boundary layer and applied a similar

Peclet number criteria.

Forsythe and Garfield [28] examined the factors which

influence the size of the dead space between the burner rim

and flame base. They found that dead space decreases with

increase in pressure, temperature, and equivalence ratio to

stoichiometric conditions. Forsythe also found a decrease

in dead space with a decrease in wall conductivity.

Plee and Mellor [28] conducted a literature survey of

flashback and concluded that flashback from the combustor

was rarely the cause of combustion in the premixing tubes.

Rather a flow disturbance in the passage creates a recirculation zone where autoignition occurs. They used a loading

factor as defined by Lefebvre [29] to set the limits of

flashback with equivalence ratio. The loading factor is

based on turbulent burning velocity theory and indicates

that the tendency to flashback increases with increase in

tube diamete,, equivalence ratio, pressure, temperature, or

decrease in flow rate.

Marek and Baker [30] examined flashback in a heterogeneous flow syst.em over different shaped plates. They

were able to photograph the flame as it propagated up the

plate' s boundary layer from the trailing edge. They

related flashback to the biJ]k fluid velocity and found that

20
inlet temperature and

"flashback velocity"

pressure have no influence over

These studies suggest that to eliminate flashback the

velocity gradient at the wall should be increased, the

flame speed should be decreased, or the quenching distance

increased. The velocity gradient can be increased by

increasing the bulk fluid velocity. Flame speed can be

decreased by decreasing the fluid temperature or fuel concentr,_tion.

increasing

The quenching distance can be increased by

the temperat_2re gradient at the wall, which

occurs with an increase in wall conductivity and with lower

pressure.

21
EXPERIMENTAL

To measure the autoignition delay time at high pressures a continuous flow apparatus was designed and built.

A description of this apparatus and the procedure for its

operation follow.

Experimental Apparatus

The system for establishing autoignition and controlllng mixture temperature, pressure, and fuel concentration

has three main components. This section describes each of

these components: the high pressure air supply, the fuel

delivery system, and the instrumented test section.

High Pressure Air System

The high pressure air supply at The Thermal Science

and Propulsion Center is provided by three Ingersoll Rand

Compressors. The system is illustrated in Fig. 3.1.

The air flow rate is measured with a 9.91 mm ASME

standard orifice plate located in a 4.44 cm containment

pipe. The flow rate is controlled by two valves in parallel. A quarter-inch needle valve provides fine control,

22
0

(9

1.4

u?

t_

"OJ

,._

,,,_

E_

,-4

23
while a quarter-inch ball valve extends the range of the

flow rate.

A twenty atmosphere heater is used to preheat the air.

The heater consists of a three inch stainless steel coiled

pipe located inside of a silo lined with fire bricks. In

the center of the heater are three natural gas burners each

with its own spark-ignited pilot burner. A heater control

throttles the fuel flow to the main burners to achieve a

set output temperature. A fuel throttling valve can also

be set to a constant opening. Due to the low air flow

rates required for this study the throttle valve was always

set at a constant opening. Typically, the heater is

operated at twenty percent of its capacity. At this setting the heater can provide air at 600°C as measured by the

heater exit thermocoup]e.

air to the test cell

because of its length

occurs.

a

The pipe transporting the hot

is heavily insulated. However,

100°C temperature drop still

Fuel Delivery System

The fuel system is capable of handling both liquid and

gaseous fuels, as illustrated in Fig. 3.2. Technical grade

gases are stored in type IK cylinders. Commercial propane

is stored outdoors in a 800 gallon LP tank. The liquid

fuels are stored in a spherical fuel tank in the fuel room.

The pressure of the liquid fuels and propane are regulated

24
"E

"6 o _ _ .._

(D (1)

00 a. a. rr o I-_'

b

(1)

Z r_

e

0

U_'T"

"I] t

09

_n

o

-r'- ::;"

0

_._u_

0

._.11._

@

>

-,-I

(9

,.-t

0",

25
with a blanket of nitrogen on top of the fuel. Each of the

three supplies are separated with check valves and manual

valves.

The flow rate of the fuel is metered with a Oilmount

rotameter. For liquid fuels a Gilmount size #2 rotameter,

with an eighth-inch stainless steel float, is used. Gaseous fuels are measured with a size #3 rotameter with a

quarter-inch stainless steel float. To determine the densJty and viscosity of the fuel a pressure gauge and thermocouple are located near the flow meter. The fuel temperature is measured just upstream of the flow meter using a

thermocouple located in the center of the fuel line. The

pressure is monitored downstream of the flow meter with a

500 psig pressure gauge. The flow rate is controlled with

a quarter-inch needle valve located just downstream of the

pressure gauge

A fuel heater is located just upstream of the fuel

injector. The heater serves two purposes. First, heating

the fuel lowers the required inlet air temperature for

achieving autoignition. Secondly, for liquid fuels the

heater serves as a fuel vaporizer to insure that the combustible mixture remains homogeneous.

* Note: unless indicated otherwise all thermocouples are

sixteenth-inch, stainless steel sheathed, and made of

chromel/alumel.

26
Because of the large volume of expanding gas inside

the fuel heater, flow surging can be a problem when the

path to the fuel in3ector is opened. Flow surging can

cause premature autoignition. To alleviate this problem

the fuel vent, see Fig. 3.2, is normally left open. A

check valve located upstream of the injector requires an

opening pressure great enough to prevent fuel from entering

the test section while the fuel vent is opened. The fuel

vent valve is an electrically-controlled pneumatic ball

valve located downstream of the fuel heater far enough to

allow the fuel vapor to cool. To introduce fuel to the

test section the fuel vent is closed so that the pressure

rises continuously until the resistance pressure of the

check valve is overcome.

Another source of premature autoignition is the temperature rise associated with initial fuel flow through the

hot fuel injector. Without fuel flow through the injector

its temperature is that of the flowing air - typically

600°C. The fuel that first passes through this hot injector is heated to a temperature higher than its steady state

value of between 300 ° and 400°C. This hot fuel mixes with

the air yielding a higher mixture temperature, possibly

autoigniting with subsequent flashback. To prevent this

problem from occurring, a nitrogen purge system was connected between the fuel heater and fuel injector, as illustrated Jn Fig. 3.2. Before fuel is injected a jet of cold

27
nitrogen is forced through the injector, cooling the injector below its steady state temperature with fuel flow.

Test Section

The continuous flow apparatus used to achieve autoignition is illustrated in Fig. 3.3. The main feature of the

design is the concentric tube arrangement to minimize heat

loss.

Air Preparation. Before the air reaches the inlet of the

inner tube it is heated by a 15 kW immersion heater and

passes through flow-straightening tubes and screens. The

heater is used in addition to the twenty-atmosphere heater

to provide sensitive temperature control. The heater controls are similar to those used in the fuel heater.

Downstream of the air heater are flow-straightening

tubes and screens. The resultant velocity profile produced

at the test section inlet is shown in Fig. 3.4. The flow

straighteners also flatten the inlet temperature profile as

illustrated in Fig. 3.5.

The static pressure in the test section is measured

upstream of the fuel injector on a Statham strain gauge

pressure transducer. The transducer output is connected to

a digital millivolt meter and is linear with pressure.

Test Length.

is contained

As illustrated in Fig. 3.3 the test length

inside a larger pipe. The inner pipe is

28
Q_ Q-

_0

r-

.__._

0

(_)

a_

0

0

0

E

X

I I

i

'i_I e"

Ir--7_

t--

.O_

(.)

O0

A

00

"I"

29

0

u_

0

4n

u}

0

_d

(D

u E

-_ .,..4

c¢3

.,-4
30

28

26

24

-_ 22

E

20

"_ 18

>

t6

14

12

I0 | i I

I/2 0 I/2

r/R

[,_igure 3.4. Th(.' velocity profile at the inlet

of the inner pipe.

55O

54O

(.9

o

wrr 530

I--

<

¢r

W

a_ 520

W

I--

510

5OO

v = I0 m/s

1 1 I

I/2 0 I/2

r/R

Figure 3.5. The temperature profile at the inlet

of the inner pipe.

3O
supported in the center of the three-inch diameter outer

pipe using two sets of three, circumferentially symmetric,

legs. Along the length of the inner pipe are three wallmounted thermocouples. These thermocouples are used to

detect flashback and/or flame stabilization on the fuel

injector. Originally they were located in the midstream of

the inner pipe, but this led to premature autoignition and

flashback in the flow recirculation zone created in the

wake of the thermocouples.

The critical portions of the test section are the

inlet, where the fuel is injected; and the exit, where the

flame is detected. A cross-sectional cut at the injector

is illustrated in Fig. 3.6. An enlargement of the test

section is drawn in Fig. _.7. The inner pipe is not drawn

to scale, but the figure does indicate the geometries associated with the inlet and exit.

Fig. 3.6 shows the position of the blockage ring over

the annulus between the inner and outer pipes. As illustrated, a slight gap between the blockage ring and the

outer wail still allows flow in the annulus. The actual

flow in the annulus is only twenty percent of the total

flow. Originally the intention was to maintain the same

bulk velocity on both sides of the inner pipe, and the

inlet end of the inner pipe was flared to compensate for

the blockage of the fuel in3ector. The blockage ring was

installed after it became evident that to reduce the

31
likelihood of flashback some heat loss was necessary at the

inner pipe surface. Greater blockage also aids in overcoming heater limitations since less flow is necessary to

achieve the same velocity in the inner pipe.

The inlet air temperature is monitored using two

shielded thermocouples. As illustrated in Fig. 3.6, one

thermocouple is located at the tube axis while the other is

0.7 of the radius from the center. To determine the inlet

air temperature the readings from the two thermocouples are

averaged. The inlet fuel temperature is measured using a

thermocouple pushed down inside of the fuel injector.

Figure 3.6. Cross-sectional view of test length inlet

just downstream of fuel injector.

32
The exit end of the test section was designed to

reduce the possibility of premature autoignition and flashback, as shown in Fig. 3.7. The water-cooled nozzle acts

as a barrier against flashback in the boundary layer. It

is 5.7 cm long, with diameter reducing from 3.4 to 2.2 cm.

The nozzle acts to block flashback in two ways. First, it

is made of copper with a water-cooled jacket, which lowers

the wall temperature and increases the heat transfer from

the fluid in the boundary layer. Lowering the boundary

layer temperature in this manner increases the quenching

distance and reduces the flame speed. Secondly, by raising

the fluid velocity, the nozzle increases the velocity gradient at the wall.

The nozzle's abrupt expansion at the exit was frequently inspected visually for possible flame stabilization. At no time was any form of stabilization or autoignition in the recJrculation zone detected. This is attributed to the large heat transfer associated with the copper

end piece that seals the nozzle with the water cooling

jacket. Also, the air entrained in the recirculation zone

from the annulus is significantly cooler, thus acting as a

quench.

The water l]sed to cool the nozzle also serves to

quench the combustible mixture downstream. Fig. 3.3 indi--

cates that the water enters 20 cm downstream from the end

of the inner pipe. It tr_vels upstream through a quarter33
la_

',,,,,

',,,,,

',,,,

',,,.,,

',,,,,

',,,,,,

',,,.,

r,,,,,,

',.,,,,

1,

\\\i _ I

'l

JO,l::)a Ul T

i

,,j

',,1

x,l

'xi

'xl

',4

",,1

',4

NI

',,1 \\\\\\\\\\\\\\\\\\\\\\\

0

.r.t

4-1

4J

4-40

_4

r_

-,'4

'IJ

.,-4

4J

,el

U?

r¢3©

-,-I

34
inch tube to the nozzle, cools the nozzle, and is then conveyed downstream in more tubing to the quench ring. The

stainless steel ring is made of a loop of quarter-inch tubing with eight 1.54 mm holes drilled symmetrically around

the ring. The water quenches the autoignition flame and

also cools the back pressure valve.

The pressure in the test section is controlled with a

pneumatically-operated Annin globe valve, which can withstand a maximum pressure of 1440 psig at 100°F. A i0 to 50

psig signal will open the valve under all operating conditions. The signal is controlled by a manual pressure regulator located in the control room.

Fl____am__ee Dtector. Autoign]tion is monitored with an ultraviolet sensitive phototube. The phototube and its housing

are illustrated in Fig. 3.8. The detector is located

direct[ y above the end of t}_e inner tube. The phototube is

a Hamamatsu-type R334M UVtron. The tube requires a 350 to

490 V DC power source and emits a small signal when exposed

to ultraviolet radiat*on at wavelengths between 160 and 290

nm. The signal is amplified with a LM 308 operational

amplifier and is read on an Analogic digital DC mV meter

located in the control room.

The detector is located six inches above

line of the test section.

protect the phototube from

the center -

The housing is water-cooled to

the heat. The phototube is

35
b

Ultraviolet

Phototube

Sapphire

Nitrogen

i

I

I

I

Water

I

I

Fuel/Air _ I

Figure 3.8. The ultra-violet phototube flame detector.

36
separated from the flame by a sapphire window with a

transmissivity of 60% in ultraviolet radiation. Two nitrogen jets keep the sapphire clear and prevent the housing

tube from filling with combustible mixture which might

ignite.

The flame detector works only in the on/off mode. If

the phototube "sees" a flame the mV meter jumps to a nonsteady value between 20 and 200 mV. At the test section

centerline the detector can see a length of approximately

two inches. This range does introduce some error in determining the actual position of the autoignition flame.

Fuel Ingector. The fuel injector, as illustrated in Fig.

3.6, was designed to keep the mixing time as short as possible. It comprises a ring-shaped piece of 4.76 mm stainless steel tubing of 2.02 cm mean diameter. Drilled

through its downstream face are eight evenly-spaced 1.52 mm

holes. The inlet stem of the injector is attached to the

fuel supply with an AN fitting welded to the outer pipe.

The mixing characteristics of the fuel injector were

tested by studying the thermal diffusion of warm air issuing from the injector into a cooler air stream. Temperature profiles were taken at different axial locations and

the standard deviation factor (SDF) was calculated.

37
SDF is defined as indicated below

] 2

SDF \I_(TL-TM) - (3.1)

(TH-T M )

where T L is the local temperature, T M is the mean temperature of the profile, and T H is the temperature of the warm

air issuing from the injector. As the temperature profile

flattens with axial distance SDF goes to zero. Fig. 3.9 is

a graph of SDF versus axia] distance taken with this injector at the indicated conditions. Here the fuel to air

ratio (F/A) is the mass ratio of warm air from the injector

to the cool air in the main air stream. The flow conditions were selected to be representative of those during

actual test runs. The standard deviation factor does not

fall to zero as predicted because of non-adiabatic conditions at the tube wall. The key factor in this graph is

that the slope of the curve drops to zero. The slopes in

Fig. 3.9 reduce to zero in one to two pipe diameters from

the injector, indicating that the fluids are effectively

mixed in less than 6 % of the total test length.

For fuel injected into air, thermal diffusion is not

as important as is mass diffusion. Work has been done by

Forestall and Shapiro [31] on the mixing of a jet in a

coaxial

helium.

velocity

stream. The jet contained small concentrations of

Concentration profiles were determined at various

rat ios. They concluded that temperature and

38
0

4J

O0 0

I| I! I!

o

/

/

t

I

/

/

>

_3

_D

x_

@

@

4J

0

U

'44 -,q

@ 0

xS

0 _q

0

0

-,q 4-)

l

oJ

I

0

I

00

0

I

0

L

Q

0

0

-lOS

39
concentration profiles have the same shape, and

bulent

number.

number s

that turSchmidt number is equal to the turbulent Prandtl

They also noted that turbulent Prandtl and Schmidt

are independent of experimental conditions. Their

results suggest that the concentration

the temperature profile with axial

source in a coaxial stream. Thus, it

profile varies as

distance from a jet

is considered that

the injector provides complete thermal and mass mixing in

less than 6% of the total test length.

Experimqnt,[_ Procedure

Successful operation of the test apparatus described

in the previous section requires setting the pre-calculated

flow conditions, establishing a pre-heat period,

attainment of an autoignition flame. Each

requirements are described in this section.

and the

of these

Pr e- c_._alculat ions

With so many independent variables, acquiring useful

data requires the calculat ion of flow conditions before the

test rig i.'_operated. Autc)iqnition delay time is sensitive

to fluid velocity, pressur,., fuel concentration, and temperature. The experiment,_[ procedure adopted was to set

the pressure, Fluid velocity, and fuel concentration; and

then measure the mixture temperature at which autoignition

occurred. A computer program was written to perform the

calculations needed to det_'rmine the test conditions.

4O
The calculatJorls performed in the program provide orifice plate pressure drop in inches of water and the fuel

flow meter scale readings over a range of equivalence

ratios. The program is run for each rig pressure at which

data are to be taken. The inputs required are the pressure

and temperature at the orifice plate, the fuel density and

viscosity at the flowmeter, the stoichiometric fuel/air

ratio based on mass, and an approximate inlet air temperature to calculate the fluid velocity.

Pre-Heating

Depending on the type of fuel used and the air flow

rate required, the test apparatus can require up to three

hours to attain the desired temperature. This long heating

period is necessary because of the thermal lag of the piping and insulation connecting the twenty-atmosphere heater

to the test cell. The 15 kW electric heater is limited by

an S60°C sheath temperature at low flow rates, and by the

15 kW maxlmum power rating at high flow rates. Typically,

the electric heater can raise the air temperature no more

than 200°C above the temperature of the air supplied from

the twenty-atmosphere heater. The piping, flanges, and

insulation around the test section require an hour to heat

to steady state temperature. The fuel heater requires

thirty minutes to reach a steady temperature.

41
Establishing Autoignition

After the air flow rate and test pressure have been

set, the fuel may be introduced in an attempt to establish

autoignition. The inlet air temperature is set below the

anticipated autoignition temperature, and the fuel injector

is cooled with a nitrogen purge for ten to thirty seconds.

The fuel is then injected and allowed to flow for about one

minute to allow its temperature to stabilize. As the temperature is below the autoignition value flame is not

detected anywhere. The fuel flow is then terminated and

the inlet air temperature

cedure is continued until an

increased by lO°C. This proautoignition flame occurs

somewhere along the test length.

The combustible mixture can ignite anywhere along the

97 cm length from the fuel injector to the water quench

ring. As mentioned earlier, the flame detector is located

81 cm downstream of the fuel injector at the exit of the

inner pipe. This is the desired poir_t of autoignition, and

the temperature is adjusted until autoignition occurs here.

If the mixture temperature is too high, autoignition

will occur inside the inner pipe; and the flame will flashback along the boundary layer to the fuel in]ector. Should

a flame stabi]ize on the injector the temperature indications from the wall--mounted thermocouples along the inner

pipe rise drastically, and the flame detector no longer

42
indicate_ flame because all lh_' fuel has been consumed

upstream. Thus, a flame stabilized on the injector is

detected by the wall-mounted thermocouples only. When this

occurs the fuel flow is terminated and the temperature

decreased by 10°C.

Autoignition can occur downstream of the inner pipe

exit, but *t cannot be detected unless it is seen by the

flame detector. Whenever an aut.oignition flame is detected

by the flame detector it is considered a valid data point.

When the, temperature of ti_e fuel-air mixture is known

to be within 10°C of the autoignition temperature, the fuel

ts injected continuously and the air temperature gradually

increased. The autoignlt_on flame moves upstream with

rise in air temperature until the flame is beneath the

f lame det_._ctor. At t his c:ond it ion the inlet air temperafur,,, tnlet fuel ttem[,eratlJre_, a,r flow rate, the air pressure, and fue[ flow rat_. ar_ recorded. The autoignition

flame in this posit*on is usually unstable and flashback

general [y follows.

Ti, is test procedure w,_.'_used to collect data for different fuels over mixture temperatures from 400 ° to 750°C,

pressures from 1 to I0 atmospheres, bulk fluid velocities

from 6 to 30 m/s, and equivalence ratios of 0.2 to 0.7.

The procedure employed for data reduction, and the results

obtained, are described in t.he following chapter.

43
DATA REDUCTIONAND RESULTS

Autoignition delay times were measured for propane,

ethylene, methane, acetylene, vaporized n-heptane, and

vaporized Jet-A. The influence of pressure, temperature,

and fuel concent-.ration on d_lay t ime were the main focus of

the experimentat.ion. Wh_rl possible, visual observations of

the autoiqnitlon flame w_re made and are reported for each

fuel. The procedure for data reduction is presented prior

to the results.

Da[a Reduction

Once an autoignition flame has been established, the

mlxture velocity and t esr section length are all that are

needed to determine the delay time. The test length

remains constant at 8].26 cm. The mixture velocity is

dependent on the air [low rate, the mixture temperature,

and the static pressure. The pressure is the only property

that is recorded directly.

The air flow rate is determined using standard orifice

plate calibration equations taken from Holman [33]. The

orifice plate pressure, temperature, and pressure drop are

recorded to determine the air flow rate. The fuel flow

44
rate is calculated using calibration equations provlded by

the Gllmount Company. The fuel temperature and pressure at

the flow meter are recorded dur,ng the experiment. Using

these properties the viscosity and density are obtained

from Vargaftik [34] for c_]l fuels except Jet-A.

As the mixture temperature along the test length is

not constant, the question arises as to what temperature

shc)uld be used to correlat.e the delay time. Using the mixLure temperature at. the fuel injector provides the most

consistent result'._, and has been the approach adopted by

mo.'_! prey ioii.'_w_rker._. 'l'hJ._ !_tmp_:rature may be calculated

at I he inl)ector plane, usinq a thermodynamic energy balance.

The prlnr:iple l:_ th,._l l_,e erlergy cont_Ined in the inlet

fuel and air is equal t.o the energy in the exiting mixture,

assuming no heat loss across the injector. This energy

balance ('an be so]ved for i he initial mixture temperature

T A CpA _ FAR T F CPF

(4.1)

T m = ----]_A]_--CpF + Cp A

where the subscrLpt A denotes air, the subscript F denotes

fuel, and FAR is the fuel-air ratio. Specific heats are

calculated with empirical expressions that are a function

of inlet fuel temperature 1116] .

45
The mixture velocity may be calculated from

gas assumption and contlrluity as

an ideal

where the subscript

m R T m m m

U - P A (4.2)

P

m denotes mixture,

cross-sectional area of the inner pipe.

stant of the mixture, Rm'

for the fuel and air.

quite simply as

and A is the

P

The ideal gas conis a mass averaged gas constant

The delay time is then calculated

_J

7 - U (4.3)

where L is the length of the test section.

Results

Results are presented for each of the fuels studied to

show the effect of temperature, pressure, and fuel concentration on delay time. Comparisons between the various

fuels are made, followed by a comparison between the

results of this _tudy and those of previous workers.

'['he relat ]on._hJps for ! emperature, pressure, and fuel

concentration with delay t Jme are based on global reaction

theory. The temperat,_re dependence is expressed graphically as the ].og of delay time versus the reciprocal of

mixture temperature for different pressures and fuel concent.rations. The correlat ion should be a straight line

whose slope is proportJor1,_] tc_ activation energy.

46
The activation energy is dt_termined as

T

1

L.98hH in---

7-

2 (4.41

E .... -]_ I

T T

m I m 2

Pressure dependence is obtained as the log of delay

time versus the log of pressure in atmospheres. The slope

of the line represents the pressure exponent.

The fuel concentration effect ]s presented as the log

of delay time versus the ]oq of equivalence ratio. The

slope of this line is the fuel concentration exponent. As

in the case of pressure, the data points shown in these

graphs are extrapolaLed from the temperature dependence

graphs at constant temperature with varyJng fuel concentrat ions.

In all test runs the fuel temperature was maintained

at between 30() ° and 400°C. Visual observations of the

autoignition flame were made at equivalence ratios of 0.3

and 0.4. All observation:_ were made by removing the flame

detector and looking down through the sapphire window to

the end of the test section. A distance of approximately 5

cm was visible from the nozzle exit along the center line

of the

tent when

increased

through several centimeters around a mean position.

inner pipe. For ,_l] fuels the flame was intermitflrst observed, but as the temperature was

it became more stable. Usually it oscillated

These

47
fluctuations are

velocity, temperature, and

none could be detected.

inside the nozzle of the inner pipe,

injector would ensue. Observat _ons

equivalence ratios, but the flame was

attributed to slight irregularities in

fuel concentration, although

When the flame started to jump

flashback to the

were made at higher

very short-lived.

Flame stability worsened as the pressure was increased.

It should be kept in mind that an autoignition flame

does not stabilize on any flow disturbance, as is normally

associated with flame stabilization. Rather, it is constantly re-lighting at the same point. This consistent

ignition at (_ne point denotes the autoignition flame's stability.

Propane

Propane was used as the baseline fuel mostly because

of the large quantity available, but also because its

behavior was known from previous work at atmospheric pressure (see Freeman [4]). As the baseline fuel, propane was

used to calibrate the flame detector and refine the experimental technique.

Autoignition flames were observed at all pressures.

The flame was pale blue and burned slightly brighter at

higher pressures. Prior to the autoignition flame a cool

flame was observed. Cool flames are characterized by a

faint luminosity and re]at ively low temperature rise.

48
The temperature dependence of propane is illustrated

in Fig. 4.1. The test runs were conducted with a variation

in mixture velocity from 7 to 27 m/s, temperatures from

560 ° to 727°C, and pressures from i to i0 atmospheres. The

activation energy is estimated as 3£.2 kcal/kg-mol and is

constant with pressure.

Delay time is inversely related to pressure, as illustrated in Fig. 4.2. For this figure the data points were

extrapolated from Fig. 4.1 at a mixture temperature of

635°C. The pressure exponent is 1.21.

Fig. 4.3 shows the fuel concentration effect of propane. The fuel concentration exponent is 0.3 and is constant with pressure from 2 to 5 atmospheres.

As expected from global reactlon theory, temperature

has the strongest in[luence on delay time. Pressure exerts

a moderately strong influence on delay time, while the fuel

co_,centration ef[ect is telat ]vely weak.

Ethylene

Ethylene requires much lower temperatures for autoignitJon than does propane. The ethylene autoignition flame

is less stable. Velocity was varied between 7 and 30 m/s,

and pressures from 1 to I0 atmospheres to give autoignition

temperatures from 670 ° to 540°C. As pressure is increased

the stability worser, s, as it. did with propane, but the

49
300

2OO

I00 E

20

I0

I.(

I C

:/

2

Propane-Air Mixtures

¢=04

0

/

3 5 7 I0 Pressure, atmos.

, I 1 I I I

)0 1.04 1.08 1.12 1.16 1.20

I000/T m, Ki:Z4

Figure 4.1. [nflucnc:_ ot: __'m}, ,r,_l.urc: r)r_ ignition delay times of

50
I000

I/)

E

I--

>-

<[

_J

LU

db

500

4OO

300

200

I00

50

4O

3O

2O

I0

m

m

m

Propane- Air

Tm = 908 K

T C_P -1"21

Mixtures

I I I,, I I I I I I I

I 2 :5 4 5 I0

PRESSURE, ATMOS.

2O

Figure 4.2. tllf]uenc_, o! t_l,':;_;t_l_' {)n ignition dc_']ay times

pro[)ar)(,/a J r mixl_t _'_;.

51

of
I00

I/)

E

L,J"

I,--

W

n

90

80

70

60

50

40

5C

20

Pressure, atmos

_2

Propane-Air Mixtures

Tm =9:53 K

r OE(_ -0"3

' I

1%15 .2

I 1 I I I I !

.3 .4 .5 .6 .7 .8 .9

EQUIVALENCE RATIO, ,#

1.0

t"J gur_ 4.3. Jnf.l.t}clic{, of ILl(.' I (T(]|l_.:('li[ _,]t ic)n

of propane/air mLxtllt(,s.

52

on ignition delay times
difference in stability _ver the pressure range is

noticeable.

pane flames.

ignition.

not as

Ethylene flames are slightly bluer than proAgain a cool flame was observed prior to

The temperature dependence for ethylene is illustrated

in Fig. 4.4. The activation energy is estimated as 37.2

kcal/kg-mol and is independent of pressure.

The pressure dependence is shown in Fig. 4.5. The

points were extrapolated from Fig. 4.4 at a temperature of

589°C. A scatter between the data and global reaction

theory is indicated at pressures of 9 and i0 atmospheres.

At these pressures the flame is very unstable, but the

results were repeatable. At_ lower pressures the theory

applies very well and the pressure exponent was determined

to be 0.75. PressiJre exerts less of an influence on

ethylene than on propane.

The m_st surprising results are shown in Fig. 4.6.

The plot of fuel concentration versus delay time illustrates an influence of pressure on the fuel concentration

exponent, which increases from 0.2"7 at 1 atmosphere to 0.55

at 5 atmospheres. The sharpest increase [s between 1 and 2

atmospheres, with decreasing difference in exponent between

subsequent pressure levels. This suggests that the fuel

exponent attains a constant value wlth pressure. The best

explanation for these results is a change in the dominant

53
I00

E

u.i

I-

>..

_I

laJ

£3

90--

80--

70-

60--

50--

40--

30--

20

06

I

0

/

2

3 5 7 9 I0

Ethylene- Air

_f =0.4

I i I

1.08 1.10 1.12

Mixtures

I I

1.14 1.16

IO00/Tm, K -_

0

Pressure, atm,

i I I

1.18 1.20 1.22

FJ gure 4.4. Influence of

ethylene/aJ r

tleml_(,r,_t_lr,, {,rl

m i.x tu r{':4.

54

[_ln.ition delay times of
3OO

2OO

I00

¢t)

E

- 70

UJ

I- 50

4O

_J

W

2O

N

n

m

Ethylene-Air Mixtures

Tm=862 K

.r ocp-O,75

t0 0.6 I 2 3 4 5 7 I0

PRESSURE, arm

Figure 4.5. Infl_le_rc_ of l_r,,r_;;_I<< , on iqnition (]olay times of

ot.hy],"ll_/,li_ mi,xtlir,,:_.

55
I00

9O

8O

7O

60

5O

40

•_ 3c

2O

,,I I I I

I00.15 0.2 0.3 Q4 Q5 Q7

m

0 I=l'essure,atm

Exponent (m)

I

(0.27)

2

(o.4ol

0 3

5 (0501

(0.55)

Ethylene-Air Mixtures

Tm= 909 K

.r _-m

I I I i

I.O

EQUIVALENCE RATIO, @

Figure 4.6. influence of fuel c'(_n{:_,_Itration on iqnition delay times

of ethylene/air nlixtLJr_._.

56
reactions with pressure of the reacting ethylene-air mixture. If this is true, Fig. 4.4 becomes more interesting

owing to the absence of change in activation energy with

pressure that might be expected as the dominant reactions

change. This would suggest that the dominant reactions at

high pressures have nearly the same activation energy as

those occurring at lower pressures.

Methane

Methane has a higher autoignition temperature than

other fuels. Due to temperature limitations on the heater

sheath, data could only be taken over pressures from 7 to

i0 atmospheres, mixture temperatures from 727 ° to 650°C,

and velocities from 5 t:o 13 m/s. A very faint cool flame

was observed for methane, even though previous workers have

never reported any. This cool flame may be due to the

other

4.3.

pane

methane appear to be very stable, even at a pressure of

atmospheres.

alkanes present in the fuel, as indicated in Table

The autoignition flame was paler than for both proand ethyler_e flames. The autoignition flames of

i0

The delay time-temperature dependence is illustrated

in Fig. 4.7. The activation energy for methane is

estimated as 25.0 kcal/kg-mol, which is considerably lower

than for either propane or ethylene. The activation energy

is independent of pressure.

57
The pressure relationship is shown in Fig. 4.8. The

data was extrapolated at a mixture temperature of 690°C.

The methane pressure exponent is 0.99, which is closer to

the value exhJbitted for propane than for ethylene.

Fig. 4.9 illustrates the fuel concentration influence

on delay time. The stability of the methane autoignition

flame at high pressures made it possible to record data up

to ]0 atmospheres at equivalence ratios greater than 0.4.

The effect of fuel concerlt+ration is very weak with an

exponent of 0.19 and no variation with pressure.

Acetylene

Acetylene is the least stable, and most easily ignited

of the fuels examined. Tests were conducted for mixture

temperatures from 514 ° to 546°C, velocities from ii to 20

m/s, and pressures from I to 3 atmospheres. The tests were

conducted at a base]ine equivalence ratio of 0.2. The

equivalence rat io was lowered

also to prevent coking inside

Attempts to take data at an

to improve stability, and

of the fuel injector.

equivalence ratio of 0.4,

clogged the _uel in3ector with coke after only eight hours

of operation. Stability was also improved by not preheating acetylene in the _uel heater. However, acetylene

was still heated to between 150 ° and 250°C when it passed

through the fuel supply tubing adjacent to the test section.

58
2OO

E

II00

i,i

Q

Methane-Air Mixtures

_=0.4

I0

701.00

I I I I

1.02 104 1.06 108

I000/Tin, K-'

I.I0

Figure 4.7. Influcn(:,, of( tcml_ r,_tur_; c_n iqnit [on delay times of

methane/air m i xt_u]-_,_.

59
200

Fioo

m

Methane-Air Mixtures

70-

50 z'

T m = 963 K

_-o[ p-i.o

i _ i i I I

5 6 7 8 9 I0

PRESSURE, aim

Figure 4.8. Inf]u(_nc<; o[ l)_(,:{stlv_, on i{Inition delay times of

met-han_.,/air mixl_u_,,_.

60
I00

9O

uJ" 70

I--

60

_J

I,I

o 50

40

Pressure, otto

7

8

- _ I0

0

Methane- Air Mixtures

Tm= I000 K

T _ _-0.19

, 1, I I I I

Q2 0.3 0.4 0.5 0.7

EOUIVALENCE RATIO,

Figure 4.9. :Influence o_ rue] c:{_n('onLration on jqnition delay times

of methane/air mixtur_,s.

61
Intermittent pale blue flashes of flame appeared just

before the occurrence of flashback. Due to the low

equivalence ratio, the flame could not always be detected

until the flame flashed back. Observations made at

eguivalence ratios of 0.3 and 0.4 revealed no blue flame.

Instead a brief cool flame followed by a bright yellow

flash was observed, and then a flame stabilized on the fuel

injector. To correlate the effect of fuel concentration on

delay time these flashes were assumed to occur at the end

of the test length.

Fig. 4.10 illustrates the temperature and delay time

relationship for acetylene. The activation energy is

estimated at 30.6 kcal/kg-mol and is constant with pressure. The scatter illustrated is attributable to the two

points made earlier. First, acetylene is a very unstable

fuel; and secondly, the flame detector loses sensitivity at

low equivalence ratios.

The pressure and delay time relation illustrated in

Fig. 4.11 shows considerably less scatter. The data points

shown were extrapolated from Fig. 4.10 at a mixture temperature of 533°C. The pressure exponent is lower than for

other fuels, having a value of 0.66.

Fig. 4.12 illustrates the influence of fuel concentration on delay time. The fuel concentration exponent of

0.75 is the highest of all fuels tested. Although at

62
8O

E

I-

>-

..J

uJ

Q

7O

6O

5O

4O

3O

2O

0

0

0

0

0

0

2 3

Acetylene-Air

¢ =o.2

Pressure, arm

Mixtures

i I I I I 1

.18 1.20 1.22 1.24 1.26 1.28

IO00/Tm, K-I

Figure 4.10. Influence of t(,ml,,,_-alllr-_, on i_ rl[tiom dolay times of

acetylene/air mixtu _-<,s.

63
I00

¢;)

E

FJ

w

0

90-

80-

70-

60-

50-

40-

5(3-

200'.7

Acetylene- Air Mixtures

Tm = 806 K

r _ P- 0.66

PRESSURE, otm

Figure 4. t t. In[lug,itch, c_I- i,t{,,{.,-{ql_,., otl icinition delay times of

acety ] _,nc/a i ) m i x I-tl i-, ':_.

64
It)

E

I-

>-

_l

LIJ

C3

I00

9O

8O

70

6O

5O

4O

3O

2O

I0

DE.POORQUALi__r

ure,otm

Acetylene- Air

Tm " 806 K

•t_ -0.75

Mixtures

I

0.15 0.2

1 I I

0.5 0.4 0.5

EQUIVALENCE RATIO,

I

0.6 07

Figurt_ 4.12. [nf]uellc(' (>f: fu_'l

_>F ac:cryl(,rlc/ai r

('_)tl{'¢,n 1 Y_l tii ()n

Ill i :<_ IIl,','_ .

65

on ignition delay times
equivalence ratios from 0.3 to 0.4 stable autoignition

flames were not achieved, the data points seem reliable and

consistent.

Acetylene was the only fuel tested for which the

influence of fuel concentration on delay time is greater

than that of pressure. Acetylene exhibits characteristics

very similar to those of ethylene, with a slightly smaller

pressure influence and a stronger fuel concentration

effect. Acetylene flames are much less stable.

n-Heptane

The n-heptane was supplied by Phillips

This gasoline is rated as g9% pure n-heptane.

fuel was vaporized in the fuel heater prior to

Petroleum Co.

The liquid

injection.

This process could only be successfully accomplished at

pressures below 2 atmospheres. At higher pressures and

c - O

vapor temperatures of 3._u C, n-heptane should still be in

the vapor state, but the results obtained were erratic.

Also, when flashback occurred the flame burned as a heterogeneous flame with a yellow streaky appearance and glowing

carbon particles.

The autoignition flames observed were extremely intermittent and could be detected a long time before the flame

became consistent enough to be considered for a data point.

The flames were pale blue and quite stable at low pressures. Cool flames were again observed.

66
As expected, n-heptane has

in the same range as propane.

levels of 1 and 2 atmospheres,

autoignition temperatures

Data were taken at pressure

mixture temperatures from

636° to 707°C, and velocities between 12 and 24 m/s.

The temperature dependence for n-heptane is illustrated in Fig. 4.13. The data were taken at an equivalence

ratio of 0.3, which is lower than for most other fuels, in

an attempt to obtain data at pressures above 2 atmospheres.

The activation energy is estimated as 37.8 kcal/kg-mol,

regardless of pressure.

The pressure and delay time relationship is shown in

Fig. 4.14. The points were extrapolated at a mixture temperature of 670°C. The pressure exponent is equal to 0.85.

This value lies between the values of the exponents for

methane and ethylene.

tion

value of 0.425, thus n-Heptane exhibits the

effect of fuel concentration for all the alkanes.

concentration exponent is independent of pressure.

Fig. 4.]5 illustrates the influence of fuel concentraon delay time. The fuel concentration exponent has a

strongest

The fuel

With its large fuel concentration

pressure exponent, n-heptane behaves

manner to the alkenes than the alkanes.

exponent and low

in a more similar

67
I00

9O

8O

7O

60

I/)

E

-50

LU

I--

>-

<_

40

W

Q

3O

2O L I

1.020

0

0

2 Pressure, arm

Vaporized n-Heptane-Air Mixtures

=0.3

I I I ! I ! I I

1.040 1.060 1.080 1.100

IO00/T m , K -I

Figure 4.13. Influence of temperature on ignition delay

times of vaporized n-heptane/air mixtures.

68
I00

E

>-

<t

_]

W

C]

0 N

80-

70-

60-

50-

40-

:5(-

ZOos

Vapor ized

T m = 945 K

_-o: p-O.e5

i i I I

n- Heptane-Air Mixtures

I

PRESSURE, atm

I

2

I'_iqur(_ 4.I4. Influ(_nce of pressure on ignition delay

times of vaporized n-heptane/air mixtures.

69
6O

E

w"

F-

_J

W

0

5O

4O o

atm

0

0

2

Vaporized n-Heptane-Air Mixtures

i

0.2

i I ! I

0.5 0.4 0.5 Q6

EQUIVALENCE RATIO,

0.7

F'igur(, 4.15. [nf]uoncc of [uel concentration on ignition

delay times of vaporized n-heptane/air

mixtures.

7O
Jet-A

Jet-A was obtained from the Rock Tsland Refinery in

Indianapolis, IN. This company produces fuel that follows

the ASTM specifications for aviation gas turbine fuels

listed in ASTM D 1655. Unfortunately, data could only be

taken at pressures up to 2 atmospheres, while still insuring a homogeneous mixture. The velocity was varied from 13

to 21 m/s at mixture temperatures from 620 ° to 690°C.

Jet-A autoignition f]ames a_e more stable than nheptane flames and are pale blue. Flames are observable

over a range of 6°C between the first sighting and the

onset of flashback. Cool flames are observed at temperatures around 10°C below the autoignition temperature.

The temperature dependence of delay time is shown in

Fig. 4.16. The activation energy is estimated at 29.6

kcal/kg-mol and is constant with pressure. This value is

well below the commonly accepted value associated with gas

turbine fuels of around 40 kcal/kg-mol. The effect of fuel

vaporization on the ,_uto_gn]t]on characteristics of such a

complicated fuel are unkr_wn. ,]et-A has a distillation

range of lO0°C, so the lif_ht fractlons boil off first, possibly producing sLlghtly different fuel characteristics.

Of course, for fuel vapor to actually differ from the

liquid fuel, some component wol]Id have to be left behind in

the fuel heater. The heater [s mounted vertically and fuel

71
@t)

E

w"

I--

_1

LLI

O

80'--

70-

60-

50-

40-

30-

1.02

0 0

/' /

I0 1.6 2.0 Pressure, otto

Vaporized

:0.4

Jet A- Air Mixtures

I I I I I

1.04 1.06 1.08 1.10 1.12

IO00/Tm, K-I

l"i_gurc 4. 16. ]J_fiuenc(, ol t(,mp(_,raturc on i(_nition delay times

of vaporJ_z_>d Jet A/air mixtures.

72
enters from the bottom and exits at the top. So, a small

portion of the fuel may not pass through, although no evidence was found to support this hypothesis.

Fig. 4.17 illustrates the pressure-delay time relationship. The data points were extrapolated at a temperature of 670°C. The pressure exponent is 0.98.

The influence of fuel concentration on delay time is

illustrated in Fig. 4.18. The fuel concentration exponent

is 0.37 and is constant with pressure.

Effect of Fuel Chemistry

The fuels tested in this study can be divided into

three groups: the paraffins - methane, propane, and nheptane; the olefins - acetylene and ethylene; and a commercial kerosine - Jet-A.

The fuels are listed in order of decreasing autoignition flame stability in 'Fable 4.1, with their respective

carbon to hydrogen ratios (C/H) and maximum laminar flame

speeds [34].

73
I00

£

g

w

£3

90

8O

7O

6O

50-

40-

30-

200.8 _ 1.0I

Vaporized Jet A- Air Mixtures

T m =926 K

-roC P -0.98

I I

2D

PRESSURE, arm

3.0

Figure 4.17. Influence of pressure on ignition delay

times of vaporized Jet-A/air mixtures.

74
I00 '"

90

8O

70

It)

E60

_- 5O

d

d] 40

3O

0

Pressure, arm

I

0

Vaporized JetA-Air Mixtures 2

- T m = 926 K

r 0£ _ -0.37

20 I I I I I 1 I I

0.15 0.2 0.5 0.4 0.5 0.7 Q9

EOUIVAL ENCE RATIO

Figure 4.18. ]influence of fuel concentration on ignition delay

times of vaporized Jet-A/air mixtures.

75
Table 4.1 Fuels Listed by Decreasing Flame Stability,

C/H Ratio, and Laminar Flame Speed

Fuel C/H SL(Cm/s) i

!

Methane 0.25 34 I

I

Jet-A - 38 I

I

Propane 0.38 39 I

I

n-Heptane 0.44 39 I

I

Ethylene 0.50 68 I

I

Acetylene 1.00 158 I

I

Table 4.1 suggests autoignition flame stability is a

strong function of flame speed. Methane exhibits the most

stable characteristics with the lowest flame speed, while

acetylene has a flame speed five times higher and is very

unstable. This observation is not surprising, since the

stability of autoignition f].ames depends on its flashback

character Jstics, and f l,lshbac:k is a function of flame

speed. A similar relation can be made between C/H ratio

and autoignition stability. Fuels with lower C/H ratios

exhibit greater stability.

Fig. 4.19 illustrates the temperature-delay time relatlonship for all the fuels tested. For purpose of comparison the methane data has been multiplied by pressure

with an exponent of 0.99. This is the value of the

exponent determined rot methane. All the data shown are at

one atmosphere for each fuel except methane, which is at 7

76
atmospheres. By using the pressure exponent for methane

and comparing it with the other fuel's relationships at one

atmosphere, the variation in pressure exponent with fuel

type is made inconsequential.

As illustrated in Fig. 4.19, Olefins exhibit lower

auto ign it ion temperatures than paraffins over this range of

temperatures. This is because the carbon to carbon double

bond makes olefins more reactive. As C/H ratio increases

the autoignit ion temperature decreases. The activation

energies of the fuels are expected to behave in a similar

manner. The olefins, t)e]rlq more reactive, should also have

lower activation energies than the paraffins. However,

methane and Jet-A exl_ibit the lowest values, and propane

shows the highest. With these results no correlations

between fuel type and actlvatlon energy can be made.

Fig. 4.20 provides a summary of the pressure and delay

time data for a]I tile fuels tested. The relationships were

transferred (iirect.ly Iron the pressure versus delay time

fiqures presented earl ier for various fuels, and are at the

same mixture temperatl,res .,_ilown there. Olefins exhibit a

smaller pressure depend(.,r_ce than paraffins. Of the two

olefin._ listed, acetylene has the lowest pressure exponent

and the highest C/H ratio. No relation can be drawn

between C/H ratio and pressure influence within the paraffins. Jet-A exhibits a pressure influence similar to the

par af f ins.

77
900

700

5OO

4OO

300

2oo

0

a_ I00 --

I_

80-

50-

40--

300.95

Key

a

b

C

d

e

f

(P) =

Fuel E,

Methane

Propane

n- Heptane

Jet A

Ethylene

Acetylene

Pressure, atm

kcal/kg-mol

25.0

58.2

:57.8

29.6

3Z2

:50.5

b(I)/ c(I

! I

e

!

(I)

I

1.00 1.05 1.10 1.15 1.20

-I

IO00/Tm, K

1.25

Figure 4.19. Comparison of temperature effect on ignition delay

times foe all fuols.

78
A summary of the fuel concentration influence on delay

time is contained in Fig. 4.21. The influence of fuel concentration is generally weak. Ethylene shows a pressure

influence on the fuel concentration exponent. As the C/H

ratio increases so does the fuel concentration exponent for

all fuels except ethylene.

Comparison with Previous Work

Most of the previous work using continuous flow systems employed heterogeneous mixtures. Results are available for comparison for all the fuels studied except

ethylene.

In past work Muffins [6] took the most data employing

homoaeneous mixtures. Fie found an activation energy for

methane of 29 kcal/kg-mol and for acetylene of 31 kcal/kgtool, which compares very w_l[ with the values found in this

study of 25 and 30.6 k_-al/kq tool, respectively.

Fig. 4.22 is a summary of the results obtained by previous researchers for gas turbine fuels. Results for propane and vap_rized Jet-A are inc]tlded from this study.

Propane data were obtained by L,ezberg [12] and Freeman [4].

Both estimated activation energies of 38 kcal/kg-mol, which

is the same value found in this study. The slight shift

between their ignition delay times and those of the present

study might be attributable to differences in flame detection. They conducted experiments at atmospheric pressures

79
E

W

>-

<

_J

W

0

I000

500

400

300

200

I00

50

40

D

m

i

30

20-

0.5

a

b

C

d

e

f

Fuel

Methane

Ethylene

Propane

n-Heptane

Acetylene

Jet A

\

I t I i I I !

I 2 3

n

0.99

0.75

1.21

0.85

0.66

0.98

C

I I I I I II

4 5 I0

PRESSURE, otm

b

2O

Figure 4.20. Comparison of pressure effect on ignition delay

tI:imes fVor all t:ue[s.

8O
150

I00

90

8O

7O

6o

_ 5o

_ 4o

a

30

2O

150.15

Key Fuel P, atm m

--I

a,a Ethylene 1,5 0.27, Q55

b Methane I0 O.19

c Propane 3 0.50

-- d n-Heptane 2 0.43

e Jet A 2 0.57

-b f Acetylene 2 0.75

a_

e

C

i

d

I I I I I I

0.2 0.:3 0.4 Q5 0.7

EQUIVALENCE RATIO, V:)

! I

1.0

Figure 4.21. Comparison of fuel concentration effect on ignition

delay times [or a] ] fuels.

81
only with visual flame detection.

Correlations for Jet-A were made by Freeman and Marek

et al. [ii]. Marek studied heterogeneous mixtures and

found an activation energy of 16.5 kcal/kg-mol, while Freeman used vaporized fuel and obtained a value of 40.9

kcal/kg-mol. The activation energy measured in this study

of 29.6 kcal/kg-mol lies between these two findings. The

temperature relationship also lies between their values,

but closer to Freeman's results. This shift and change in

activation energy may be attributed to two possible causes.

First, it might be an effect of pressure on the activation

energy. More likely, the shift might be caused by differences in experimental technique and flame detection.

Fig. 4.23 is a summary of the pressure and delay time

results of previous work on homogeneous mixtures. The

relationships obtained in this study are labeled directly.

The numbers in parentheses are the corresponding pressure

exponents. As different temperatures were used, the pressure exponents should be compared rather than the positions

of the relationships.

Mullins tested methane and acetylene at subatmospheric pressures. For acetylene good agreement exists

between his study and the present work, but for methane a

larger discrepancy is found. The difference between Brokaw

and Jackson's [7] pressure exponent for propane and the

82
I/)

4-'-

E

4000 -

3000 -

2000 -

I000 --

5OO -

400 -

300 -

200-

I00 -

1

l

50 _

40-

30-

20-

lO--

m

5-

4-

3

2-

I

4

Propane

k

I I

6 8

b

a

Key Ref. Fuel

a II JetlA

b I0 No. 2 Diesel

c 23 JP4

d I0 No. 2 Diesel

e 16 AVTUR

f 32 JP4

g 13 Kerosine

h 16 AVTAG

j 6 Kerosine

k 12 Propane

4 det-A

m 4 Propane

1 I 1 I I I I I

I0 12 14 16 18 20 22 24

I/T m x 104, K-I

P

Figure 4.22. Summary of results obtained by different

workers on the effect of temperature on

ignil]on delay times for gas turbine fuels.

83
value obtained irl this study is appreciable. This difference Js attributed to differences in experimental technique. Brokaw and Jackson used the pressure rise associated with autoignition to detect ignition and measured the

time directl F from fuel injection to ignition. Correlations for n-heptane and ethylene also appear in Fig. 4.23.

The exponents for these fuels are within the range of

values obtained in other studies.

A summary of the pressure dependence of ignition delay

time for gas turbine fuels appears in Fig. 4.24. The pressure correlations for propane and vaporized Jet-A from this

research are labeled. The propane pressure exponent is

within the range of exponents shown in this figure.

The pressure exponent obtained

agrees very well with

Stringer et al. [16].

correlated

exponents.

this study

the values

Spadacclni and

for vaporized Jet-A

of Marek et al. and

TeVelde [10] have

their data using two different pressure

The smaller pressure exponent (i.0) agrees with

very well. All those studies employed heterogeneous mixtures.

The effect of fue] concentration is contested between

d]fforent workers. In this study a weak fuel concentration

dependence (m < 0.5) was observed for all fuels except acetylene. Many previous researchers concluded that fuel concentration exerts Jlo influence on ignition delay

84
I0

m

O._ -

0

w" 01-

m

>_ 005-

._1

ILl

a

QOI --

0.OO5 -

00010. I

d(2.57)_ KEYObc REF666

e(0.74) d 5

Propane (I.21)

• b (I.7)

I ,I

0.5 I

FUEL

Methane

Ethane

Acetylene

iso-Octane

Propane

(0.99)

I I i

5 I0 50 I00

PRESSURE, otto.

Figure 4.23. Summary of results obtained by different

workers on the effect of pressure on ignition

delay times for homogeneous mixtures.

85
I000

E

I--

J

Ld

Q

5OO

2OO

Propane (I.2)

KEY

0

b

C

d

e

f

g

h

i

REE FUEL

20 No. 2 Diesel

15 Kerosine

I I Jet- A

2:5 JP- 4

16 Jet-A/Diesel

32 JP-4

I0 No. 2 Diesel

I0 Jet-A

I0 JP-4

c(I.O)

b (I.9)

\l (2.0)

q (0.9)

h _'_ e (0.9)

h(l.O) .0)_1.0) _

(,.5)

I I I I

5 I0 20 50 I00

PRESSURE, atm.

Figure 4.24. Summary of results obtained by different

workers on the effect of pressure on

ignition delay times for gas turbine fuels.

86
[4,6,10,15,16]. Freeman found no effect for propane and

vaporized Jet-A, but recorded a small fuel concentration

effect for n-heptane. He found an exponent of 0.23 compared to the value of 0.4 obtained in this work.

In general, good agreement with recent studies was

observed for most fuels. In particular, the propane and

n-heptane data agrees well with those of Freeman. The

vaporized Jet-A data taken in these two studies also agrees

quite well. Agreement between these studies is important

since one is building on the work of the other.

87
CONCLUSIONS AND RECOMMENDATIONS

Conclusions

The apparatus described earlier provided consistent

and repeatable autoignition data for the six fuels studied.

Delay times were successfully correlated with pressure,

temperature, and fuel concentration for homogeneous mixtures using global reaction theory whereby

T a exp [ fuel ]-m p-n. (5.l)

Table 5.1 presents a summary of the global activation energles, fuel concentration exponents, and pressure exponents

for all fuels tested.

tion

trations. All autoignition

variations between fuels

observed for all fuels.

Autoignltion flames were located in a controlled posifor all fuels except acetylene at higher fuel concenflames were pale blue, and

were slight. Cool flames were

Olefins are more reactive and have lower autoignition

temperatures than paraffins. They are influenced more

strongly by differences in fuel concentration than are the

88
paraffins, but show a smaller pressure effect on delay

time. The paraffins show a weak fuel concentration influence on delay time.

Table 5.1 A Summary of the Ignition Delay Time Parameters

I uel

I Methane

E (kcal/kg-mol) n

25.0 0 99

mI

0.19 I

I

I Propane 38.2

n-Heptane 37.8

[ Acetylene 30.5

Ethylene 37.2

I

Jet-A 29.6

1 21

0 87

0 66

0 75

0 98

0.30 i

0.40 I

075 I

0.27-0.55 I

I

0.37 1

The global activation energy is

for Jet-A, but

previous workers.

lower than expected

lies in the range of results obtained by

The agreement between Freeman and this

study for propane and vaporized n-heptane is very good,

while the results for vaporized Jet-A agree slightly less

well. Such good agreement suggests that for homogeneous

mixtures apparatus effects are not so great as to preclude

the possibility of describing the autoignition characteristics with a delay time equation derived from global reaction theory.

89
Recommendations

Recommendations are made on designing an apparatus for

studying autoignition, and suggested for further studies on

autoignition characteristics of hydrocarbon fuels.

Test Apparatus

The test apparatus used in this study provided reliable data, but several improvements could be made. These

improvements apply to both homogeneous and heterogeneous

studies.

The temperature limitations on the system decrease the

range of data that can be taken. The maximum sheath temperature of the electric heater is 860°C. At lower flow

rates this temperature is reached quite rapidly, while providing an outlet temperature of less than 750°C. One reason for this inefficient, heating is that the diameter of

the pipe currently housing the heater is too large. A

smaller pipe would increase the heat transferred to the air

providing an outlet temperature of 800°C. The procurement

of a heater with a higher sheath temperature would be even

more advantageous.

Another way to increase the range of data would be by

increasing the length of the test section. The current

test section is 81 cm long. A length of 120 cm would

increase the residence time and lower the temperature

90
reguirements. The only concern with a longer test

is the effect of additional heat loss.

section

In Fig. 5.1 are two schematics of alternate test

apparatus designs. Both designs feature the ability to

control the test section wall temperature. Such control is

advantageous in two ways. A relatively cool wall deters

flashback, while a warm wall minimizes the temperature drop

along the test length. Obviously there is an optimum

compromise temperature, but this temperature changes

depending on the fuel type, flow rate, fuel concentration,

and static pressure. An uninsulated, electrically-heated

wall with a variable power supply would provide sensitive

control of wall temperature. Electrical "strap-on" heaters

are available in the temperature ranges of interest.

Also common to the two designs are windows located at

the fuel injector. For heterogeneous mixtures windows at

the injector plane are required for drop sizing. In homogeneous mixtures these windows could be used for mixing

J

studies, and examining flashback at the injector.

The difference in the two illustrations in Fig. 5.1

lies in the method of flame detection. Fig. 5.1(a) shows a

flame detector scheme similar to that used in these studies. It provides a strong signal and is very sensitive.

The sensitivity is limited by the transmissivity of the

sapphire window. Sapphire only transmits 60% of the

91
O_

0

W n_

_- w

W

c_

D T

w FF-N-_

_ODZ

wWw

-r-I--__

_J

W

0

Z

\\ \ --

v

I

"-r,_

L

112

W

Z

o_ /

W_ O

1

,1

(.gnr

z__

I

0

Z

W

0

0

£3

Z

_J

W_._C---

LL

_" \ \ W

_, \ \ l--

w_-

.... WW

"l"_1

rN \ \ J

_I \',I]I ]

I

@

0

O_

0

4_

0

0

@

0

O_

0 0

-,-.I -_

4J -IJ

@ (D

.IJ .1_

r.--t

0

(D -,-I

-,--I -,_

92
ultra-violet radiation. Using a window made of lithium

fluoride with a transmissivity of 90% would increase the

sensitivity. The detector provides a very erratic signal,

and determining

detector's range

averaging signal

intensity, which would increase as the flame moved

to the test section exit and became more consistent.

the precise flame location within the

of "sight" is impossible. A timeprocessor could be used to measure flame

closer

Another method for flame detection is illustrated in

Fig. 5.1(b). In this design the end of the test section is

fitted with an observation window. Visual observations of

autoignition flames have several advantages. Most important is the additional knowledge acquired on the characteristics of autoignition flames at higher pressures.

Direct observations would also provide greater accuracy

over the current design. The window would be cooled and

kept clean with nitrogen jets. The recirculation zone at

the sudden expansion of the test section would be quenched

with either nitrogen or cool air preferably in coaxial flow

with the air fuel mixture. A video camera may be used for

flame monitoring in the control room during experiments.

Either design in Fig. 5.1 represents an improvement on

the current design. The apparatus illustrated in Fig.

5.1(a) is less expensive, but provides less information on

autoignition than the alternate design.

93
Autoignition Characteristics

The next step in these studies is to add the physical

effects to the autoignition model. In heterogeneous mixtures the additional physical variables that influence

delay time are initial drop size, fuel temperature, and

fuel evaporation rate. Once the effects of these properties are defined, a complete model of the delay time can be

developed including both the physical and chemical components.

Several characteristics of the autoignition phenomenon

have received little or no attention, such as the effect of

mixing time and turbulence on the delay time. The influence of mixing could be studied by using homogeneous mixtures and varying the mixing length with different injector

configurations. This would involve first measuring the

characteristic mixing length at certain flow conditions,

and then measuring the autoignition delay time at the same

flow conditions.

The effect of turbulence influences delay time by

changing mixing time as well as temperature and velocity

profiles. Experiments would also be conducted using homogeneous mixtures, and autoignition delay times measured for

various values of turbulence intensity and scale while

maintaining other Elow conditions constant.

94
These are just two areas that require more study.

Previous workers have assumed that these effects are small.

Until the proposed studies are carried out the validity of

that assumption is questionable.

95
REFERENCES

[i]

[2]

[3]

14]

[5]

[6]

[/I

[_1

[9]

[10]

"Lean Premixed/Prevaporized Combustion; A Workshop

Held at Lewis Research Center," NASA CP-2016, 1977.

Longwell, J.P., E.E. Frost and M.A. Weiss, "Flame

Stability in Bluff-Body Recirculation Zones," Ind.

Eng. Chem., Vol. 45, No.8, 1953.

Chiappetta, [,.M. and J.B. McVey, "Literature Survey

Conducted in Support of the Development of a Model

for Autoignition," UTRC 81-64, 1981.

Freeman, W.G., "The Spontaneous Ignition Characteristics of Gaseous Hydrocarbon Fuel-Air Mixtures at

Atmospheric Pressure," M.S. thesis, School of Mechanical Engineerinq, Purdue University, 1984.

Burwell, W.G. and D.R. Olson, "The Spontaneous Ignition of Iso-Octane Air Mixtures Under Steady Flow

Conditions," SAE 650510, 1965.

Mullins, B.P., "Studies on the Spontaneous Ignition

of Fuels Injected Into a Hot Airstream," Parts I-V,

Fuel, No. 32, 1953.

Brokaw, R.S. and J.I,. Jackson, "Effect. of Temperature, Pressure, and Composition on Ignition Delays

for Propane Flames," F ift:h Symposiom (International)

on Combustion, Heir,hold, New York, 1955.

Anders_,n, O ........ M. Chiappetta, D.E. Edwards and

J.B. McVey, "Analytical Modeling of Operating

(:har,lcterist](:s (_t P_emLxing-Prevaporizing Fuel-Air

Mixir,g Passaq_:_, Vol. I - Analysis and Results,"

[;TRC80- I02, IgR0.

Chin, J.S. and A.H. Lefebvre, "Steady-State Evaporation Character ist Jcs of Hydrocarbon Fuel Drops," AIAA

Journal, Vol. 21, No. I0, 1983.

Spadacc]ni, L.J.

Characteristics of

159866, 1980.

and J.A.

Aircraft

TeVelde, "Autoignition

Type Fuels," NASA CR96
[ii]

[12]

[13]

[14]

[15]

[16]

[17]

[]8]

[19]

[2O]

[21]

Marek, C.J., L.C. Papathakos and P.W. Verbulecz,

"Preliminary Studies on Autoignition and Flashback in

a Premixing-Prevaporizing Flame Tube Using Jet-A at

Lean Equivalence Ratios," NASA TM-X-3526, 1977.

Lezberg, E.A., "Preliminary Investigation of Propane

Combustion in a Three Inch Diameter Duct at Inlet Air

Temperatures of 1400 ° to 1600°F, " NACA TN-4028, 1957.

Mestre, A. and F. Ducourneau, "Recent Studies on the

Spontaneous Ignition of Rich Air-Kerosene Mixtures,"

European S[mp_qsi__ um, The Combustion Institute, 1973.

Chang, C.J., A.L. Thompson and R.D. Winship, "Ignition Delay of Propane in Air Between 725-880°C Under

Isothermal Conditions," Seventh Symposium (International) onn Co mbustig_Q, Academic Press, New York,

1959.

Miller, R.E., "Some Factors Governing the Ignition

Delay of a Gaseous Fuel," Seventh Symposium (International) on Combustion, Academic Press, New York,

1959.

Stringer, F.W., A.E. Clarke and J.S. Clarke, "The

Spontaneous Ignition of Hydrocarbon Fuels in a Flowing System," Proc. Auto. Div., Institute of Mechanical Engineers, 1970.

Tacina, R.R., "Autoignition in a PremixingPrevaporizing Fuel Duct Using Three Different Fuel

Injection Systems at Inlet Air Temperatures to

1250K," NASA TM-82938, ]983.

YoshJzawa, Y., H. Kowada, K. Shigihara, K. Yamada and

Y.Takagishi, "A Shock Tube Study of the Combustion

Process of Hydrocarbon Fuels," Bulletin JSME, Vol.

2], No. 153, 1978.

Edelman, R., C. Economous and O. Fortune, "Research

on Methods of Improving the Combustion Characteristics of Liquid Hydrocarbon Fuels, Vol. II - Kinetics

Modeling and Supersonic Testing," General Applied

Science Laboratories, TR AFAPL-72-24, Vol. If, 1972.

Henein, N.A. and J.A. Bolt, "Ignition Delay in Diesel

Engir, es," SAE Paper 620007, 1976.

Hauptman, D.J.,F.L. Dryer, K.P. Schug and I. Glassman, "A Multiple Step Overall Kinetic Mechanism for

the Oxidat*on of Hydrocarbons," Combustion Science

and Technology, Voi.25, 1981.

97
[22]

[231

[24]

[25]

[2h ]

[2i]

[28]

[29]

[30]

[3L]

[32l

[33]

Ballal, D.R. and A.H. Lefebvre, "Ignition and Flame

Quenching of Flowing Fuel-Air Mixtures," Combustion

and Flame, Vol. 35, 1979.

Spadaccini, L.J., "Autoignition Characteristics of

Hydrocarbon Fuels at Elevated Temperatures and Pressures," UTRC75-78, 1975.

Lewis, B. and G. Von Elbe, Combustion, Flames, and

Explosions of (;a_!es, 2d ed., Academic, New York,

]961.

Putnam, A.A. and R.A. Jensen, "Application of Dimen-

_ion]ess Numbers to Flashback and Other Combustion

Phenomena," Third S_mposium (International) o n

Combustion, Williams and Wilkens, Baltimore, 1949.

Khitrin, L.N., P.B. Moin, D.B Smirnov and V.U.

Schevchuk, "Peculiar ities of Laminar- and TurbulentFlame Flashbacks," [Fe_h Symbosium (International) onn

Combustion, The Combustion Institute, Pittsburgh,

]965

Forsyth, J.S. and J.E. Garside, "The Mechanism of

F/ash-Back of Aerated Flames," Third Symposium

(International) on Combustion, Williams and Wilkens,

Baltimore, 1949.

P/ee, S.L. and A.M. Mellor, "Review

Reported in Pr evapor iz ing/Pr emixing

Flame, Vol. 32, No. 2, 1978.

of Flashback

Combustion and

Lefebvre, A.II., CoA Note Aero. Report No. 163, The

College of Aer:onautics, Department of Propulsion,

Cranfi_,]d InsLitute nf Technology, Bedford, England,

1966.

Mar ek, C.J. and C.E. Baker, "High-Pressure Flame

Visualization of Autoignition and Flashback Phenomena

WiLh a Liquid-Fuel Spray," NASA TM-83501, 1983.

Forestall, W. and A.H. Shapiro, "Momentum and Mass

Transfer in Coaxial Gas Jets," Journal of Applied

Mechanicn, Vo[. 72, 1(950.

Taback, E.D. ,

JP-4 at. High

2284, [971.

"The AuLoignition Characteristics of

Temperatures and Pressures," P&WA TDMHolman, J.P., Exp_ej_lmental Methods for Engineers,

McGraw-Hill, St Gouts, 1978.

98
[34]

[35]

[36]

Vargaftik, N.B., Tables on the Thermophyslcal Properties of Licluids and Gases, Halstead Press, New York,

1975.

Gaydon, A.G. and H.G. Wolfhard, Flames: Their Structure, Radiation, and Temperature, 4th ed., John Wiley

& Sons, New York, 1975.

Van Wylen, G.J. and R.E.

Classical Thermodynamics,

York, 1978.

Sonntag, Fundamentals o_ff

John Wiley & Sons, New

99
1. Report No,

NASA CR-]75064

2. Government Accession No,

4, Title and Subtitle

Spontaneous Ignltlon Delay Characteristics of

Hydrocarbon Fuel/Air Mixtures

7. Author(s)

Arthur H. Lefebvre, William G. Freeman, and

Luke H. Cowell

9. Pe_orming Organization Name and Address

Purdue University

School of Mechanical Engineering

West Lafayette, Indiana 47907

12. Sponsoring Agency Name and Address

National Aeronautics and Space Administration

Washington, D.C. 20546

3. Recipient's Catalog No.

5. Rel_rt Date

February 1986

6. Pedorming Organization C_e

8. Performing Organization Report No.

None

10. Work Unit No.

11. Contract or Grant No.

NAG 3-226

13. Type of Report and Period Covered

Contractor Report

14. Sponsoring Agency Code

505-3] -42

15. Supplementaw Notes

Final report. Project Manager, Robert Tactna, Aerothermodynamtcs and Fuels

Division, NASA Lewis Research Center, Cleveland, 0hiD 44]35.

16. Abstract

The influence of pressure on the autolgnltlon characteristics of homogeneous

mixtures of hydrocarbon fuels In air Is examined. Autolgnltlon delay times are

measured for propane, ethylene, methane, and acetylene In a continuous flow apparatus featuring a multl-polnt fuel injector. Results are presented for mixture

temperatures from 670K to 1020K, pressures from ] to 10 atmospheres, equivalence

ratios from 0.2 to 0.7, and velocities from 5 to 30 m/s. Delay ttme Is related

to pressure, temperature, and fuel concentration by global reaction theory. The

results show variations In global activation energy from 25 to 38 kcal/kg-mol,

pressure exponents from 0.66 to 1.21, and fuel concentration exponents from 0.19

to 0.75 for the fuels studied. These results are generally In good agreement

with previous studies carried out under similar conditions.

17. Key Words (Suggested by Authods))

Autolgnltlon

Ignttlon delay

Spontaneous ignition

18. Distribution Statement

Unclassified - unlimited

STAR Category 07

I.

19. Security Classif. (of this report)

Unclassified

_. Security Classlf. (of this page)

Unclassified

21. No. of pages

101

r22.Price*

A06

*For sale by the National Technical Information Service, Springfield, Virginia 22161