COMPARATIVE

STUDY

OF

AND

ETHYLENE

MIXTURES

AT

OF

SELF-IGNITION

POLYPROPYLENE

ATMOSPHERIC

OXYGEN

PRESSURE

T. I. Ts'olkovskti, M. P. M u l y a v a ,
G. V. S h c h e m e l e v , and V. U. S h e v c h u k

There is great interest in obtaining olefln oxides by direct oxidation of unsaturated hydrocarbons. A
number of methods are described inthe literature for obtaining oxides with the interaction of ethylene and propylene with oxygen at temperatures of 350-6000C and contact times of 2-15 sec [1, 2]. Under these conditions, it
is possible that the mixture will self-ignite. The self-ignition temperature is one of the technical parameters
that determines many of the requirements for the technological realization of the process. It is of interest to
study self-ignition of hydrocarbon and oxygen mixtures from the point of view of establishing the mechanisms
for their oxidation, a knowledge of which permits choosing the optimal region for realizing the technological
process. Data on the ignition of ethylene and propylene with oxygen and air are contained in [3-7]. However,
in most cases, the limits to self-ignition of ethylene and propylene and the limits on their concentrations for
igniting them with a spark in oxygen and air were studied.
In what follows, we present the results of an investigation of the dependence of the self-ignition temperature on the composition of the e t h y l e n e - and propylene -oxygen mixtures at atmospheric pressure and the time
periods for inducing self-ignition of these mixtures at different temperatures.
Experimental Technique: The self-ignition temperatures of premixed ethylene and propylene oxygen mixtures were determined by injection into a heated evacuated vessel using the technique described in iS]. Reaction vessels with a diameter of 50 mm and a length of 330 mm, made of Khl8N10T steel, were used. In a
number of the experiments, the walls of the reactor were coated with B203.
The presence of self-ignition was determined from the sharp expansion (rupture) of a rubber balloon or
visually through a thick plastic observational window. The temperature was measured by a Chromel - C opel
thermocouple at the center of the furnace. The boundary (lower) temperature was determined to within 9 3-5 ~
The mixtures were prepared from gases with the following purities: ethylene with an admixture of ethane
(mass content) 0.05%, nitrogen 0.07%~ oxygen 0.05%; propylene with an admixture of ethylene 0.1%, propane
0.05~, nitrogen 0.07%, oxygen 0.05%; oxygen with a nitrogen content up to 0.7%.
Experimental Results. The curves showing the dependence of the limiting self-ignition temperature on
the composition of the ethylene and propylene oxygen mixtures in a steel reactor (reactor t) and in a reactor
with walls coated with B203 (reactor 119 are presented in Fig. 1. Curves showing the dependence of the limiting
self-ignition temperature f o r propylene in both reactors have the usual U-like shape with a minimum for oxygen content of 30-50%.
The curves showing the dependence of the limiting self-ignition temperature on the composition of ethylene-oxygen mixtures have a very unusual shape. The concentration curves for self-ignition for both reactors
have a W-like shape, i.e., they have two self-ignition temperature minima: for rich and lean mixtures. The
coating on the reactor walls affects the self-ignition temperature: the limiting self-ignition temperature for
ethylene-oxygen mixtures in reactor I is 30-40 ~ higher than in reactor H. For propylene-oxygen mixtures,
this temperature difference is less and constitutes 15-20 ~.
Self-ignition of ethylene oxygen mixtures was first determined for an oxygen content of 5.7%. The minimum self-ignition temperatures for rich mixtures in both reactors occur with oxygen concentration of 18-40%.
As the oxygen content in the mixture increases further, the self-ignition temperature (approaching the stbichiometi-ic composition) increases sharply. The maximum self-ignition temperature of ethylene l i e s in the range
70'85% oxygen (about 475~C in reactor I and about 445"C in reactor II) and 60 ~ higher than the minimum temperatures in rich mixtures. In comparison with propylene under analogous conditions, the minimum self-ignition
temperature of rich ethylene-oxygen mixtures is ~100 ~ higher (first minimum).
Borislav. T r a n s l a t e d f r o m F i z i k a G o r e n i y a i .Vzryva, Vol. 17, No. 1, pp. 42-46, Jaunary-February, 1981.
Original article submitted December 6, 1979.
0010-5082/81/1701-0033 $07.50 9 1981 Plenum Publishing Corporation

33

II : ;,:+
9 9

Ib!

[_.

356 1

25

50

75

02,%

Fig. 1. Dependence of the self-ignitiontemperature on

the composition of ethylene- {a) and propylene-oxygen
(b) mixtures and on the wall coating; Kh18N10T steel,d =
50 m m .
Wtth further increase in the oxygen content, the self-ignition t e m p e r a t u r e of e t h y l e n e - o x y g e n mixtures
d e c r e a s e s once again. The second minimum occurs in the region of 95-98% oxygen for both r e a c t o r s ; but,
according to the absolute value of the t e m p e r a t u r e , it is higher than the minimum for rich mixtures. Selfignition of propylene oxygen mixtures first occurs with an oxygen content of about 20%. The minimum for rich
p r o p y l e n e - o x y g e n mixtures lies at a t e m p e r a t u r e of 290-310~
As the oxygen content in the mixtures inc r e a s e s further, the self-ignition t e m p e r a t u r e i ncreases,
It may be assumed that the unusual behavior of the curves showing the composition dependence of the
limiting self-ignition t e m p e r a t u r e for e t h y l e n e - o x y g e n mixtures is related to different mechanisms for selfignition of rich and lean mixtures. The considerable time intervals for inducing self-ignition of p r o p y l e n e oxygen and rich ethylene--oxygen m i xt ur es , which reach tens of seconds at the limiting temperature, indicate
the initial p r e s e n c e of a chain reaction with degenerate branches. Self-ignition of lean e t h y l e n e - o x y g e n m ix t u res (80% oxygen) occurs over a time less than 0.1 sec even at the limiting t em perat ure. For this reason, it
is fully possible that in a given case continuously branching chains occur. In ethylene mixtures with an oxygen
content 45 to 95%, self-ignition is accompanied by a loud sound characteristic of a detonation. For propylene-oxygen mixtures, this limit is somewhat m o r e narrow.
The p r es en ce of long time intervals for inducing self-ignition of p r o p y l e n e - o x y g e n and rich e t h y l e n e oxygen mixtures permits determining the effect of the activation energy for self-ignition. Fig. 2 presents the
logarithms of the induction periods as a function of the inverse self-ignition temperatur~ for ethylene mixtures
with different oxygen compositions. For r e a c t o r ! (Fig. 2a), for all mixtures, it is possible to draw two straight
l i n e s which intersect at different t e m p e r a t u r e s . As the oxygen content in the mixture increases, the point of
intersection is displaced toward higher t e m p e r a t u r e s . The effective activation energies, determined from the
angle of inclination of the straightlines, a r e 16.5 ~-1.5 and 90 +10 kcal/mole for high and ~ow t em perat u re s,
respectively.
The dependence of log T on 1/ T for mixtures in which self-ignition was studied in r e a c t o r II has a similar c h a r a c t e r (Fig. 2b). The effective activation energy for self-ignition at high t em perat ures is practically
the same as for r e a c t o r I (17.0
kcal/mole). However, at low t e m p e r a t u r e s , it constitutes 36.5 ~1.5 k c a l /
mole, which differs significantly from the value obtained in r e a c t o r I.
Comparing the activation energies f o r self-ignition obtained for ethylenes-oxygen mixtures at atmospheric
p r e s s u r e in both r e a c t o r s with different values of the t e m p e r a t u r e , it may be concluded that as the t e m p e r a t u r e d e c r e a s e s , reactions involving the loss of active centers on the surface of the reacting wall begin to play
an increasing role in the self-ignition p r o c e s s for rich mixtures and, in addition, for the steel r e a c t o r this
role becomes dominant.
Figure 3 shows the logarithms of the induction times as a function of the inverse self-ignition t e m p e r a ture for p r o p y l e u e - o x y g e u mixtures. As in the case of ethylene, the effective activation energies a r e different

34

45--

x 2

09

e* 5

O tO
z~ l l

m 4

/
#if!

///

o,~'

1,g-~F .......T - .

0,5

.......

;,50

1,35

t,40

;',45

I,~50 l / r ' f o ~

Fig. 2. Logarithm of the time period for [nducing self-ignition of

ethylene-oxygen mixtures as a function of the inverse temperature
for reactor T (a) and TT (b). The oxygen content in the mixtures in
%is: 1) 13.9, 2) 18.1, 3) 25.0, 4) 29.6, 5) 40.5, 6) 52.5, 7) 10.5, 8)
14o0, 9) 18.0, 10) 20.0, 11) 22.2, 12) 30.1, 13) 44o0, 14) 51~
....

/],

,/

I
AX

1,0~-

..'

1,2

&

t,4

t,6

1,2

1,4

,5

3
~

6
7

1,6

l/TqO 3

Fig. 3. Logarithm of the time for inducing self-ignition for propylerie--oxygen mixtures as a function of the inverse temperature for
reactors I (a) and IT 6). The oxygen content in the mixture in % is:

1) 31.7, 2) 39.0, 3) 44.7, 4) 56.3, 5) 61.7, 6) 88.4, 7) 19.6, 8) 23.9, 9)

35.2, 10) 43.7, 11) 54.5, 12) 7.4.3, 13) 84.6, 14) 89.9, 15) 94.0.

35

at high and low temperatures, although this difference is not as significant. However, in the case of propylene,
the low- and high-temperature regions are separated by an intermediate zone, the so-called negative temperature rate coefficient region. In this zone, the induction period for self-ignition is either independent of t e m p e r a t u r e or increases with increasing temperature. For reactor I, this zone is observed in the temperature
range from 370 to 510~ and for reactor II from 350 to 480~
The effective activation energies, determined in
reactors I and H, are close to each other both for low and high temperatures. At high temperatures, the effective activation energy of the self-ignition process for propylene constitutes 18.8 ~1.5 and 22.4 -~5 kcal/mole
and at low temperatures 27.6 "1.5 and 30.2 ~-2.5 kcal/mole for reactors I and II, respectively~ ~
l~ should be noted that with significa~t depletion of the mixtures in both reactors the negative temperature coefficient region disappears. Thus, in a mixture with an oxygen content of 88.4%, in reactor I, the logarithm of the induction time is a linear function of the inverse temperature over.the entire temperature interval. In reactor II, the narrowing of the negative coefficient region (mixture with 84.6 and 89.9% O2) and its disappearance in a mixture with 94% 02 can be easily observed.
1~ is known [4] that oxidation of ethylene at a temperature above 420"C is accompanied by luminescence.
Such a phenomenon also occurs with self-ignition of ethylene-oxygen mixtures. In rich mixtures (6-12% 02)
at 400-420"C there appears a blue luminescence, which at high temperatures can become a yellow flame. In
mixtures with an ethylene content of 2.5-4.0%, a yeUow flame, which later becomes a blue flame, appears with
self-ignition. With self-ignition of rich and lean propylene-oxygen mixtures, a blue luminescence, which
changes into a yellow flame as the temperature increases, appears.
Thus, the concentration limits for self-ignition of ethylene- and propylene-oxygen mixtures at atmospheric p r e s s u r e and the self-ignition temperature in the entire range of concentrations have been determined
for the first time. The effect of coating the walls of the reactor on the limiting self-ignition temperature has
been determined. An unusual W-shaped curve was obtained for the self-ignition temperature for e t h y l e n e Oxygen mixtures as a function of their composition. The region in which the negative temperature coefficient
occurs with self-ignition of propylene oxygen mixtures was determined.
LITERATURE
1.

2.
3~
4.
5.
6.
.

8.

36

CITED

P. V. Zimakov and O. N. Dyment, Ethylene Oxide [Russian translation], Khimiya, Moscow (1967).
N. M. Emanuel t, O. N. Dyment, and ]~. A. Blyumberg, Zh. Vses. Khim. Ob-va ira. D..I. Mendeleeva,
248 (1969).
G. P. Kane and D. T. A. Townend, Proc. R. S.c., A160~ 174 (1937).
V. Yost, Explosions and Combustion in Gases [Russian translation], IL, Moscow (1952).
B. Lewis and G. Von Elbe, Combustion, Flames, and Explosions of Gases, Academic P r e s s (1961).
A. I. Rozlovs~i, Scientific Foundations of Safety in Working with Combustible Gases and Vapors [in
Russian], Ehimiya, Moscow (1972).
S.A. Yankovskii, in: Self-Ignition of Gases and Vapors [in Russian], Proceedings GIAP, Moscow (1966).
G. P. Churik, V, U. Shevchuk, et al., Gazov. Prom-st, 1, 42 (1973).