COMBUSTI ON AND FLAME 58: 153-162 (1984) 153

Spont aneous Igni ti on Characteristics of Gaseous Hydrocarbon- Ai r

Mixtures
G. FREEMAN and A. H. LEFEBVRE
The Combustion Laboratory, Thermal Sciences and Propulsion Center, School of Mechanical Engineering, Purdue
University, West Lafayette, IN 47907
Measurements of spontaneous ignition delay time are conducted using gaseous fuels and fuel vapors at normal
atmospheric pressure. The apparatus comprises a test section which is constructed from several lengths of 30
mm diameter stainless steel tubing to form a maximum total length of 2.2 m. The method employed to
determine ignition delay times is to establish certain predetermined values of velocity and equivalence ratio
within the test section and then gradually increase the temperature of the mixture until autoignition occurs. All
measurements are taken, at various levels of velocity, with the flame located a few centimeters downstream of
the end of the test section, where it assumes a conical form with the apex pointing upstream.
The results show that ignition delay time can be expressed in terms of mixture temperature, fuel
concentration, and oxygen concentration, by the equation
r~xexp[E/RTm] [Fuel]'[Oxygen] ~,
For the fuels employed in this study, which include propane, aviation kerosine, and n-heptane, the results show
that E is fairly close to 40,000 kcal/kg mol. Ignition delay times are found to be only slightly dependent on fuel
concentration, but strongly dependent on oxygen concentration. For example, for propane n = - 0.59, while
for kerosine n = -0. 65.
I NTRODUCTI ON
Spont aneous i gni t i on is a process whereby a
combust i bl e mi xt ure undergoes chemi cal reac-
t i on l eadi ng to the rapid evol ut i on of heat in the
absence of any concent rat ed source of i gni t i on
such as a flame or spark. In some practical
combust i on devi ces, such as the l ean premi x/
prevapori ze combust or which is now bei ng
act i vel y devel oped for advanced aircraft gas
t urbi ne engi nes, spont aneous i gni t i on must be
avoi ded at all costs, since it coul d damage
combust or component s and produce unaccep-
t abl y high levels of pol l ut ant emi ssi ons [1, 2].
Copyright 1984 by The Combustion Institute
Published by Elsevier Science Publishing Co., Inc.
52 Vanderbilt Avenue, New York, NY 10017
On the other hand, spont aneous i gni t i on is
somet i mes relied upon to provi de the mai n
source of i gni t i on, as in the compr essi on i gni -
tion engi ne.
Spont aneous i gni t i on delay may be defi ned as
the t i me i nt erval bet ween the creat i on of a
combust i bl e mi xt ure, say by i nj ect i ng fuel into
air at high t emperat ure, and the onset of flame.
In vi ew of t hei r pract i cal i mport ance, measure-
ment s of i gni t i on delay t i mes have been con-
duct ed for many fuels over wide ranges of
ambi ent condi t i ons and in a vari et y of test
vehi cl es, i ncl udi ng const ant vol ume bombs,
r api d- compr essi on machi nes, reci procat i ng en-
0010-2180/84/$03.00
154 G. FREEMAN and A. H. LEFEBVRE
gines, shock tubes, and cont i nuous flow devi ces
[ 3- 14] . The test met hods empl oyed and the
results obt ai ned are descri bed in revi ews by
Mullins [3] and, mor e recent l y, by Spadaccini
and Te Vel de [5].
Al t hough the subject of spont aneous ignition
of liquid fuels has recei ved consi derabl e atten-
tion in the past, the role of fuel evaporat i on in
the overal l spont aneous ignition process is still
uncl ear. It was deci ded, t her ef or e, to conduct a
series of exper i ment s using onl y gaseous or
vapor i zed fuels, somet i mes with the injection of
additional oxygen into the fl owi ng air stream, in
or der to obtain mor e accurat e data on chemi cal
del ay times under condi t i ons where the effect s
of fuel evapor at i on are excl uded.
EXPERI MENTAL
The apparat us empl oyed in the measurement of
spont aneous ignition del ay time is shown sche-
mat i cal l y in Fig. 1. Ai r is supplied from a high
pressure bl ower, the ai r flow rate being con-
t rol l ed by an el ect ri cal l y activated pintle valve
fitted into the bl ower inlet duct. Ai r flow rates
are cal cul at ed from the dynami c pressure mea-
sured in the t hroat of a bel l -mout h ori fi ce
t hrough which inlet air enters the bl ower.
Typi cal vel oci t es in the test section range f r om
10 to 40 m/s.
Two separate heat ers are empl oyed to raise
the t emperat ure of the incoming air. A preheat
section contains t wo heat ers which consist of
coiled ni -chrome resistance wi re wound heli-
cally around four cerami c support tubes. Each
of these preheat ers operat es at 3. 5 kW, and can
be t urned on or of f i ndependent l y of the main
heater. The main air heat er consists of t hree
hai rpi n-formed, i ncal l oy-sheat hed, " c a l - r o d "
heating el ement s. These el ement s have a maxi-
mum sheath t emperat ure of 1150K and a maxi-
mum input power of 15 kW. Feedback pr opor -
tional cont rol is used on the main heater. Both
heating sections are heavi l y insulated.
The fuel i nj ect or desi gned for. t he experi ment s
on gaseous fuels and fuel vapors is illustrated in
Fig. 2. For ease of manufact ure and assembl y,
and to ensure structural i nt egri t y, a square tube
mat ri x was const ruct ed to provi de the best
distribution of holes as dictated by the round
cross section of the pipe. The location of each of
the 25 fuel injection points was det ermi ned by
dividing the cross-sect i onal area of the pipe into
25 sections of equal area and locating an
injection point as cl ose as possible to the cent er
of each section. The obj ect i ve was to achi eve
E
E
Preheater - - . . ~
0
Blower
FN2/02
~ System
Fi g. 1. S c h e ma t i c d i a g r a m o f t e s t r i g.
~ S Fuel
ystem
Workino Section
SPONTANEOUS IGNITION CHARACTERISTICS 155
! i i : i i !
Fig. 2. Fuel injector.
rapid mi xi ng of fuel and air and to attain a
uni f or m mi xt ure strength in the fuel / ai r mi xt ure
ent eri ng the test section.
The fuel del i very syst em for vapori zed fuels
is illustrated in Fig. 3. Fuel is pumped f r om a
r eser voi r to the fuel vapor i zer / heat er in the test
cell. The liquid fuel -fl ow rate is moni t ored
using a r ot amet er and is regulated by means of a
t hrot t l e val ve. A back pressure val ve is installed
at the vapor i zer exit to el i mi nat e the t endency of
the vapor i zed fuel flow to surge due to small
pressure fluctuations in the vapor i zer . Si nce the
vapor i zer does not respond well to flow tran-
sients, the fuel cut of f val ve (located j ust up-
stream of the injector) is equi pped with an
exhaust line to allow cont i nuous fuel fl ow, as
well as visual det ermi nat i on of compl et e vapor-
ization.
The test section consists of a single length of
drawn stainless steel tubing, having an internal
di amet er of 6. 22 cm. Vari ous lengths of tubing
are available and can be j oi ned t oget her or
i nt erchanged to vary the length of the test
section. Each segment is j acket ed by a thick
l ayer of insulating material to mi ni mi ze the axial
t emperat ure gradi ent in the fl owi ng mi xt ure.
The test section is i nst rument ed with four
shielded, st agnat i on-t ype t her mocoupl es, lo-
cated along the axis of the tube. The axial
locations of the four t hermocoupl es are as
follows: 1, at the fuel injection plane; 2, 18 cm
downst ream of the fuel injection plane; 3,
hal fway down the test section; and 4, at the end
of the test section. Ther mocoupl es 3 and 4 are
wi t hdrawn when ignition del ay times are being
measured.
Test Procedure
The experi ment al pr ocedur e devel oped to det er-
mine ignition del ay times is as follows. Initially
~ . ~ . ~Sol enot d
Fuel
Tank ~ J
PI Throttl e Valve
Flow
Meter
Electric
Fuel
Vaporizer
~Pump i_1 Back Pressure
' Valve
~. ~ Diverter
Exhouet ~ ~ Solenoid
~ Injector
Fig. 3. Fuel delivery system for liquid fuels.
156 G. FREEMAN and A. H. LEFEBVRE
fl ow condi t i ons are set at pr edet er mi ned values
of vel oci t y, t emperat ure, and equi val ence ratio,
and the mi xt ure t emperat ure is then slowly
i ncreased. The onset of spont aneous ignition is
mani fest ed as a cl earl y visible cool flame,
accompani ed by the odor of al dehydes in the
exhaust gases. (Mullins report ed this same
phenomenon [3]. ) Spont aneous ignition first
appears at a distance of 30- 50 cm downst ream
of the exit of the test section as intermittent
flashes of flame. As the mi xt ure t emperat ure
cont i nues to i ncrease, the fl ame becomes stable
and its l ocat i on moves sl owl y upst ream. The
fl ame assumes the shape of a cone, with its
apex pointing upst ream, and has an attached
fl ame brush ext endi ng downst ream. The mix-
t ure t emper at ur e is al l owed to increase until the
tip of the fl ame is located near the exit of the test
section. At this point the inlet ai r t emperat ure
and the mi xt ure t emperat ure at one or more axial
l ocat i ons are recorded. Fuel flow is abruptly
t ermi nat ed, and t emperat ures are again recorded
at vari ous axial locations in the test section. The
del ay time is then obtained as the length of the
test section di vi ded by the average vel oci t y in
the test section.
The initial mi xt ure t emperat ure, Tm, cannot
be measured di rect l y because mixing takes a
small, but finite length, so some ot her met hod of
det ermi ni ng the initial t emperat ure must be
empl oyed. The met hod that was chosen is to use
a t emperat ure measured at a distance down-
stream of the fuel -i nj ect i on plane where the
results of detailed t emperat ure surveys showed
that mixing is j ust compl et e. Thi s t emperat ure is
then ext rapol at ed back to obtain the true initial
value of Tin, using as a baseline the axial
t emperat ure profi l e as measured at several sta-
tions along the test section with the fuel t urned
off. The pr ocedur e is illustrated in Fig. 4, which
shows that the initial value of Tm is det ermi ned
by fol l owi ng the baseline t emperat ure profi l e
until it passes t hrough Tref. Tm is then taken as
the t emperat ure where the shifted profi l e inter-
sects the t emperat ure axis. I f the test section
were perfect l y insulated, this pr ocedur e would
be superfl uous because Tm would be equal to
Tref. However , as a finite heat loss occurs,
despite the thick l ayer of ext ernal insulation, the
above pr ocedur e is necessary and is consi dered
sat i sfact ory.
One drawback to this met hod is that the
t emperat ure profi l e of the reacting mi xt ure is
not exact l y the same as that for air onl y. By
plotting the actual mi xt ure t emperat ure profi l e
and subtracting from it the " a i r - o n l y " profi l e, a
graph is obt ai ned depi ct i ng the t emperat ure size
due to react i on, as shown in Fig. 5. To mi ni mi ze
er r or s due to this effect it is necessary to keep
,X're f small, although it must be large enough to
T t
Tref
~ ' R e o c t i n g " ~ . ~ .
Mixture " ~ - - , .
I I
0 Xre f L
D O W N S T R E A M D I S T A N C E
Fig. 4. Graphs illustrating method of det ermi ni ng initial mixture temperature.
SPONTANEOUS IGNITION CHARACTERISTICS 157
IO25
T,K ' ~
I00(
975
t I I I I 1 l
3 0 -
0 25 5 75
x/L
F i g . 5 . G r a p h s i l l u s t r a t i n g p r e f l a m e t e m p e r a t u r e r i s e a s a f u n c t i o n o f a x i a l d i s t a n c e .
ensure that the t emperat ure measurement car-
ried out at x,ef is downst ream of the mixing
regi on. It would be desi rabl e to measure the
axial t emper at ur e profi l e for each data point, but
this is i mpract i cal due to the probl ems that
woul d arise f r om insertion of the t her mocoupl e
into the fl owi ng mi xt ure. Insert i on of a t hermo-
coupl e at the upst ream end of the worki ng
sect i on would affect the f uel - ai r mixing proc-
ess, while its presence furt her downst ream
coul d easily induce premat ure autoignition of
the mi xt ure.
In or der to det ermi ne whet her the presence of
the fl ame front can influence ignition del ay
t i mes by suppl yi ng heat or active species to the
i ncomi ng fresh mi xt ure, a ni t rogen quench
syst em was installed. This system includes a
solenoid val ve which can be opened and closed
ver y rapidly to inject a transient flow of cold
ni t rogen gas into the test section. Inj ect i on of
ni t rogen causes the autoignition flame to vanish,
but when the ni t rogen flow is abruptly termi-
nated, the fl ame reappears instantly at its origi-
nal l ocat i on. Thi s suggests that the presence of
the fl ame has no di scerni bl e ef f ect on ignition
del ay times, whi ch is consi st ent with the obser-
vations of Spadaccini [9].
Al t hough the fl ame position tends to remai n
fairly const ant , it occasi onal l y leaps forward a
few cent i met ers and t hen, almost instantane-
ousl y, returns to its original position. This
phenomenon was also noticed by Mullins [3],
who at t ri but ed it to inadequate mixing of fuel
and air, resulting in pocket s of rich mi xt ure in
the flow approachi ng the flame. Thi s expl ana-
tion is consi dered unsat i sfact ory, at least in its
application to the present i nvest i gat i on, part l y
because the results of many det ai l ed t emper at ur e
surveys have shown that mixing is compl et e well
upst ream of the autoignition fl ame, and also
because it is general l y found that ignition del ay
times are fairly insensitive to vari at i ons in fuel /
air ratio. No at t empt has been made to study this
phenomenon because it onl y occurs duri ng the
phase when the mi xt ure t emper at ur e i s being
slowly raised in or der to coax the autoignition
flame t oward the exit of the test section. Cl os e
to the test section the fl ame position usually
remains quite st eady, so that measurement s of
ignition del ay time can be made wi t h good
accuracy.
RESULTS
Fr om global react i on rate consi derat i ons the
chemi cal ignition del ay time can be expressed as
to: exp( E/ R Tm) [Fuel] "[Oxygen] , , ( l )
158 G. FREEMAN and A. H. LEFEBVRE
~, I 0 z
E
>,.-
_1
g
z~
/
PROPANE + ArR
~ = 0 5
0 L ENGT H = t 2 2 m
z~ L E N GT H = 9 2 rn
I~ L E N G T H : 5 3 m
" ~
I 0 ~ 4 0 I I I I I
9 6 0 9 I 0 0 0 1 0 2 0 1 . 0 4 0 1 0 6 0 1 0 5 (
I 0 0 0 / T r n , I / K
Fig. 6. Spontaneous ignition delay times for propane-air mixtures.
wher e
z = ignition del ay t i me (ms),
Tm = initial mi xt ure t emper at ur e (K),
E = gl obal act i vat i on ener gy (kcal / kg
mol ),
R = uni versal gas const ant (kcal / kg
mol K),
[Fuel] --- fuel concent r at i on,
[Oxygen] = oxygen concent rat i on.
The f or m of Eq. (1) suggest s that a pl ot of In r
versus l/Tm shoul d yi el d a st rai ght line with a
posi t i ve sl ope, and this is borne out by the
results shown pl ot t ed in Fig. 6 for pr opane- ai r
mi xt ur es at a const ant equi val ence ratio of 0. 5.
The line di spl ayed in this fi gure is drawn
t hrough t hree sets of dat a poi nt s, cor r espondi ng
to t hree di fferent lengths of test sect i on. The
val ue of act i vat i on ener gy E cal cul at ed f r om the
sl ope of this line is 38, 200 kcal / kg mol .
It is of i nt erest to obser ve that all the data
poi nt s lie in cl ose pr oxi mi t y to the line drawn in
Fig. 6. Thi s is in mar ked cont rast with the
resul t s of a pr evi ous i nvest i gat i on, wher e it was
found that ignition del ay t i me was ver y depen-
dent on the length of the test section empl oyed
[15]. Thi s pr obl em was at t ri but ed to excessi ve
heat l oss f r om the duct walls and was over come
ef f ect i vel y by i ncreasi ng the internal di amet er
f r om 2. 54 to 6. 22 cm and by appl yi ng a thick
l ayer of i nsul at i ng mat eri al to the out er pi pe
wall.
The results obt ai ned using mi xt ures of vapor -
ized kerosi ne with ai r are shown in Fig. 7. The
st rai ght line dr awn t hrough the dat a poi nt s in
this fi gure cor r esponds to a val ue for E of
40, 900 kcal / kg mol .
The equi val ence ratio was vari ed over a range
f r om 0. 2 to 0. 8. For pr opane the results showed
that the equi val ence rat i o has an al most negl i gi -
ble effect on r, al t hough an i ncrease in the
equi val ence rat i o tends to pr oduce a " s t r o n g e r "
tail fl ame. Equi val ence rat i os hi gher t han 0. 8
coul d not be us ed due to pr obl ems of fl ashback.
It was found that as the aut oi gni t i on f l ame
l ocat ed downst r eam of the test sect i on was
SPONTANEOUS IGNITION CHARACTERISTICS 159
O O
i 0 2
J
JET A + AIR
~ 0 5
0 L E N G T H : I 2 2 r n
z~ L E N G T H = 9 2 m
0 L E N G T H : 5 3 r n
I 0 ; / 9 ~ I t , I I
, , 9 8 0 I 0 0 0 1 . 0 2 0 1 0 4 . 0 1 0 , 6 0 1 0 8 0
I O 0 0 / T m , I / K
Fi g. 7. S p o n t a n e o u s i g n i t i o n d e l a y t i me s f or k e r o s i n e - a i r mi x t u r e s .
brought slowly upst ream by gradually increas-
ing the mi xt ure t emperat ure, it would suddenly
flash upst ream and stabilize on the fuel i nj ect or,
t hereby obscuri ng any results and i ncurri ng risk
of damage to the injector.
Mi xt ures of vapori zed n-hept ane and air also
exhi bi t ed onl y a slight dependence of ignition
del ay time on equi val ence ratio. Analysis of the
results showed that r ~ [Fuel] -0.23
The results obt ai ned for mi xt ures in air of
propane, vapori zed n-heptane, and vapori zed Jet
A are shown in Fig. 8. The equi val ence ratio is
0. 5 in all cases. Fr om inspection of this figure it
is apparent that all t hree lines run roughl y
parallel to each ot her, t hereby indicating that all
t hree fuels have about the same value of activa-
tion energy. Mor eover , it is also cl ear that
ignition del ay times for propane are appreci abl y
l onger than those for Jet A.
Fi gures 9 and 10 show for propane and
vapori zed kerosi ne, respect i vel y, the effect of
replacing some of the ni t rogen in the ai r by
oxygen, while maintaining the fuel concent ra-
tion constant. Analysis of the results shows that
for propane r ~ [Oxygen]-0. 59, while for kero-
sine r c t [Oxygen] -'65
In Fig. 1 1 the experi ment al data obt ai ned in
the present i nvest i gat i on for pr opane- ai r and Jet
A- ai r mi xt ures are pl ot t ed, for the purpose of
compari son, al ongsi de the results of previ ous
workers as compi l ed by Chi appet t a and McVey
[6]. It is of interest to note that the results for Jet
A (kerosine) show striking agr eement with those
of Mullins [3], who also conduct ed his experi -
ments at normal at mospheri c pressure. Equal l y
not ewort hy is the cl ose consi st ency bet ween the
propane data obt ai ned by Lezber g [14] and the
results of the present experi ment s.
CONCLUS I ONS
Fr om the r es ul t s of experi ment s conduct ed at
at mospheri c pressure on the i nfl uence of mix-
ture t emper at ur e on the spont aneous ignition
del ay times of mi xt ures with air of propane, n-
160 G. F REEMAN and A. H. LEFEBVRE
J
PROPA
FUEL+ AIR
=05
/
10940 9 ; 0 9 ; 0 I ' I 0 0 0 1020 1040 I ~ 1080
I O00/ Tm, I / K
Fi g . 8. C o m p a r i s o n o f i g n i t i o n d e l a y t i mes ~ r v a r i o u s ~ e l - a i r mi x t u r e s .
.I
i 0 ~
1 0 ,!4 0
PROPANE
VARIED0 2 CONCENTRATION
FUEL CONCENTRATION=2.1%
9 0 9 8 0 1 . 0 0 0
I O00/ Tm, I l K
i I I
1. 020 ).040 1 . 0 6 0 " 1. 080
Fi g. 9. Gr aphs i l l ust rat i ng i nf l uence of oxygen concent r at i on on i gni t i on del ay t i mes.
SPONTANEOUS I GNI TI ON CHARACTERI STI CS 161
o
10 2
///
1 6 %
/
21*
J E T - A
VARIED 0 2 CONCENTRATION
FUEL CONCENTRATION=21%
' 0' 940 9Lo 9~o ' , , i
1000 1020 1.040 1 0 6 0 1 0 8 0
I 0 0 0 / T i n , I / K
Fi g. 10. Gr a phs i l l ust r at i ng i nf l uence of oxyge n concent r at i on on i gni t i on del ay t i mes,
o
IOOC II d b i /
E
I
propone~\
Jel A h
I0 ~ Ri F--JETFUEL A
No2 DIESEL
9 JP 4
1 3 N o 2 DIESEL
I0 I AVTUR
JP 4
g 1 2 KEROSINE
h I0 AVTAG
j 3 K E R O S I N E
k ~4 PROPANE
' ' . . . . . . . " , ~ , ' , ~ ' ~ ' 2 ' ~ ' 2 4 4 6 8 I0 I ~ 14
l I T m XlO 4, K - I
Fi g. 1 1. Compa r i s on of pr es ent dat a wi t h r es ul t s of pr e-
vi ous wor ker s as compi l ed by Chi appet t a and McVey [6].
hept ane vapor , and kerosi ne vapor , the fol l ow-
ing concl usi ons are drawn.
1. Igni t i on delay t i mes can be expr essed in
t er ms of mi xt ure t emper at ur e, fuel concen-
t rat i on, and oxygen concent r at i on, by the
equat i on
ro~exp[E/ R Tin] [ Fuel ] " [ Oxygen] " .
2. For the fuels empl oyed in this study the
val ue of E is fai rl y cl ose to 40, 000 kcal / kg
mol . For exampl e, for pr opane E --- 38, 200
kcal / kg mol , whi l e for kerosi ne E =
40, 900 kcal / kg mol .
3. Over the range of equi val ence rat i os f r om
0. 2 to 0. 8 the dependence of i gni t i on del ay
t i me on fuel concent rat i on is quite smal l ,
i . e. , m = 0. Of the fuel s exami ned the
st rongest dependence on fuel concent r at i on
is exhi bi t ed by n- hept ane, for whi ch m =
- 0 . 2 3 .
4. Igni t i on del ay t i mes are st rongl y dependent
on oxygen concent rat i on. For pr opane n =
- 0 . 5 9 , while for kerosi ne n = - 0 . 6 5 .
162 G. FREEMAN and A. H. LEFEBVRE
. The experimental data obtained in the
present investigation for propane-air and
kerosine-air mixtures are remarkably con-
sistent with the results of previous studies
by Lezberg and Mullins, respectively.
RE F E RE NCE S
1. Lean, Premi xed/ Prevapori zed Combustion, Work-
shop held at Lewis Research Center, NASA CP-2016,
1977.
2. Jones, R. E., DieM, L. A., Petrash, D. A., and
Grobman, J. , NASA TM 79009, 1978.
3. Mullins, B. P., AGARDograph No. 4, 1955.
4. Wentzel, W. , NACA TM 979, 1936.
5. Spadaccini, L. J. , and Te Velde, J. A., NASA CR-
159886, 1980.
6. Chiappetta, L. M., and McVey, J. B., UTRC 81-64
Report, 198 I.
7. Rao, K. V. L. and Lefebvre, A. H., Paper presented
at First Specialist Meeting (International) of the
Combustion Institute, Bordeaux, France, July 1981.
8. Marek, C. J. , Papathakos, L. C., and Verbulecz, P.
W. , NASA TM X-3526, May 1977.
9. Spadaccini, L. J. , Trans. ASME, Vol. 99, Series A,
January 1977.
10. Stringer, F. W. , Clarke, A. E., and Clarke, J. S.,
Proc. Auto. Div. , Institution of Mechanical Engi-
neers, 1970.
I I . Taback, E. D., P&WA TDM-2284, 1971.
12. Mestre, A., and Ducourneau, F,, Combustion Insti-
tute European Symposium, 1973.
13. Spadaccini, L. J. , and Te Velde, J. A. , DOE/ NASA/
0066-2, NASA CR-165315.
14. Lezberg, E. A., NACA TN 4028, 1957.
15. Freeman, G., and Lefebvre, A. H. , Paper presented at
Central States Combustion Meeting, Lexington,
March 1983.
Received 20 March 1984; revised 19 June 1984