Explosions in Methane O2 N2 Mixtures in Vessels

Course of explosions in Propene/O2/N2 and Methane/O2/N2
mixtures in vessels of 20 l to 2500 l

and load on the walls
Dr. Hans-Peter Schildberg

BASF-AG
GCT/S - L511
D-67056 Ludwigshafen
Email: hans-peter.schildberg@basf.com
Tel: +49 621 60-56049
H.-P. Schildberg, 41st UKELG meeting, 13 May 2008, Shell Technology Centre Thornton
Outline of talk
Introduction
Explosion characteristics
Course of explosion in 20 l sphere
Pressure load Pdet on the wall of the vessel
- quantification of Pdet for four scenarios occuring in a pipe (no precompression)

- quantification of Pdet for four scenarios occuring in a pipe (with precompression)
- quantification of Pdet for Propene/O2/N2 in vessel at Pinitial = 5 bar abs, Tinitial = 20 C
Comparison: detonative regimes

in 20 l vessels
100, 500, 2500 l vessels
Predetonation distances of Propene/O2 in tubes

Did ignition source directly trigger a spherical detonation?
Information available in literature on explosive gas

mixtures of type combustible/O2/N2
0
(explosion limits, pex, (dp/dt)ex)
explosive range of
10
combustible/air/O2
explosion limits
--
pex, (dp/dt)ex
--
--
l. - %
]
[vo
70
40
60
50
50
pex, (dp/dt)ex
30
60
]
l.- %
[vo
++
80
O2
combustible / air /O2
explosion limits
90
20
pinitial 1 bara pinitial > 1 bara

combustible / air /N2
100
40
70
30
80
Course of explosion
(deflagrative, detonative, heat explosion)
90
pinitial 1 bara pinitial > 1 bara

combustible / air /N2
combustible / air /O2
20
pipe (L/D > 100)
++
vessel (L/D 1)
--
pipe (L/D > 100)
--
vessel (L/D 1)
--
--
comb
ustible
/air
100
0
10
0
10
20
30
40
50
60
70
combustible [vol.-%]
explosive range of
combustible/air/N2
=> Much work needed to better understand combustible/air/O2 mixtures

mixtu
res
80
90
100
Motivation for this work

Trend in partial oxidation reactions:
- replacing air or diluted air as oxidant by oxygen enriched air or by pure oxygen
Advantages:
- increase of yield in space and time
- lower operating pressures
Critical Issue when dealing with combustible/air/O2-mixtures: Process Safety

- vessel-like geometry
- explosion characteristics
- course of explosion (deflagration, detonation)
Focus of
this work
- bubble column geometry (explosive gaseous bubbles dispersed in liquid)

- mechanisms of flame propagation
- course of explosion (deflagration, detonation)
Gaseous mixtures investigated
Propene / O2 / N2,
very detailed exp. investigations
Methane / O2 / N2
Hydrogen / O2
Cyclohexane / NO
only for one value of Pinitial and Tinitial
Cyclohexane / N2O
Cyclohexane / NO2
Introduction


in 20 l vessels
100, 500, 2500 l vessels

Experimental setup
Test vessel:
20 l sphere
20 l sphere, Pmax=600 bar, Tmax=500C
Ignition source:
exploding wire according to EN1839,
Bomb method, section 4.2.3.3.3
(arc discharge, ca. 200 A over ca. 3 ms)
Ignition energy:
ca. 20 J
Mixture preparation:
partial pressure method,
ideal gas characteristics assumed
References for complete documentation of

explosion characteristics
H.P. Schildberg in deliverables no. 8 and no. 13 of EU-Research Project SAFEKINEX,
Contract No. EVG1-CT-2002-00072; download possible from www.safekinex.org
Explosion characteristics of Propene/O2/N2 at 1, 5, 10 and 30 bar abs, 25 C and 200 C,

Hans-Peter Schildberg in Process Safety and Industrial Explosion Protection,
editor: ESMG European Safety Management Group e. V. , Hamm, Germany (2005), ISBN 3-9807567-4-2
(proceedings of the International ESMG Symposium 2005 in Nrnberg, Germany, 32 pages )
Determination of the Explosion Behaviour of Methane and Propene in Air or Oxygen at Standard and
Elevated Conditions,
A.A. Pekalski, H.-P. Schildberg, P.S.D. Smallegange, S.M. Lemkowitz, J.F. Zevenbergen, M. Braithwaite,
H.J. Pasman, 11th International Symposium Loss Prevention and Safety Promotion in the Process
Industries (2004), Praha Congress Centre 31st May-3rd June 2004;
Thematic Section B, page 2118-2138 (ISBN 80-02-01574-6)
Determination of the Explosion Behaviour of Methane and Propene in Air or Oxygen at Standard and
Elevated Conditions,
A.A. Pekalski, H.-P. Schildberg, P.S.D. Smallegange, S.M. Lemkowitz, J.F. Zevenbergen, M. Braithwaite,
H.J. Pasman, Process Safety and Environmental Protection, Volume 83, issue B5, 421-429 (2005)
Introduction


in 20 l vessels
100, 500, 2500 l vessels

Questions to be raised when considering explosions of

combustible/air/O2 mixtures in vessel-like geometry
What compositions will undergo a transition from Deflagration to
Detonation (DDT) after ignition with a thermal ignition source?
What is the largest conceivable pressure load on the vessel wall?
How does the volume of the vessel affect the detonative range?
How about the obscure effects reported mostly only in non-public
communication?
(Vessels believed to be explosion pressure proof did sometimes
rupture, but when repeating the experiment at same initial pressure
with even the worst case mixture (i.e. what one believed to be worst
case), a mechanically identical vessel did withstand the load).
Will combustible/air mixtures remain deflagrative for higher values of

Tinitial and Pinitial?
10
Literature data on deflagrative and potentially detonative

explosion regime of n-Butane/O2/N2 at 1 bar abs, 20 C
0
Characteristic values of the explosive range [1]:

Lower explosion limit in O2: 1.4 vol.-%
Upper explosion limit in O2: 51 vol.-%
Lower explosion limit in air: 1.4 vol.-%
Upper explosion limit in air: 9.4 vol.-%
Limiting oxygen concentration: 9.4 vol.-%
100
10
90
Characteristic values of the potentially detonative range [2,3]:
.5
20
Lower detonation limit in O2: 2.05 vol.-%

Upper detonation limit in O2: 38 vol.-%
Lower detonation limit in air: 1.98 vol.-%
Upper detonation limit in air: 6.18 vol.-%
:6
80
:O
30
ne
nBu
ta
l.- %
]
at
io
[Vo
ric
r
sto
ich
iom
et
50
[3] M. A. Nettleton in Gaseous Detonations, p. 76, Chapman and Hall Ltd, New York (1987)
]
l.-%
[2] M. A. Nettleton, Fire Prev. Sci. and Tech. No 23, p.29 (1980)
[Vo
50
[1] E. Brandes and W. Mller, Sicherheitstechnische Kenngren - Band 1:

Brennbare Flssigkeiten und Gase, Wirtschaftsverlag NW, Bremerhaven
(2003), ISBN: 3-89701-745-8;
UEL in O2 is an estimate, basis is measured value of 56 Vol-% at 200 C,
ZET-report no. 197.0390.3N
O2
40
60
70
e
er e to le
h
b
v
i
i
, w at ss
es agr po
r
u l s
60
ixt def n i
m
o
i
of m s
e n fro xplo
g
n
e
of losion
ra sitio ive
ge
ran e exp
t
n
t iv
tra ona
gra
t
efla
d
e
d
40
70
30
80
20
binary
m
90
ixture
n-
100
0
10
Butane
/air
0
10
20
30
40
50
60
70
80
90
100
n-Butane [Vol.-%]
11
What does potentially detonative regime mean?

If a mixture lies outside the potentially detonative regime, an explosion
will under all circumstances (e.g. type of ignition source, geometry) only be
deflagrative
If the mixture lies inside the potentially detonative regime and a
detonative ignition source triggers an explosion, the flame front will
propagate as detonation right from the beginning
If the mixture lies inside the potentially detonative regime and a thermal*
ignition source triggers an explosion, the flame front will initially propagate
as deflagration and the transition to detonation (DDT) will not necessarily
occur!
There are further conditions that have to be fullfilled to enable the DDT (e. g.
geometry of the containment must support flame acceleration).
However, in practical applications it is mostly hard to assess to which degree
these conditions are satisfied.
There are absolutely no simulation tools (e.g. reactive CFD codes) available
which could predict the DDT in vessels at least to some rudimentary extent.
*: in process plants almost all ignition sources are thermal. The initial stage of the explosion they
can trigger is always deflagrative
12

explosion regime of Propen/O2/N2 at 1 bar abs, 20 C
0
Characteristic values of the explosive range [1,2]:

Lower explosion limit in O2: 2 vol.-%
Upper explosion limit in O2: 58 vol.-%
Lower explosion limit in air: 2 vol.-%
Upper explosion limit in air: 11 vol.-%
100
10
90
20
Characteristic values of the potentially detonative range [3]:
:4
.5
80
30
:O
tio
ra
st
oic
hi
om
et
ric
50
40
ativ
agr
defl
70

(2003), ISBN: 3-89701-745-8;
[2] H.P. Schildberg in Process Safety and Industrial Explosion Protection,
editor: ESMG European Safety Management Group e. V. , Hamm,
Germany (2005), ISBN 3-9807567-4-2 (proceedings of the International
ESMG Symposium 2005 in Nrnberg, Germany, 32 pages )
]
l.-%
[Vo
e
er e to le
h
w tiv ib
60
s, gra oss
e
ur fla is p
t
ix e
m m d sion
f
o ro lo
ge on f exp
n
ra siti ve
n ti
tra ona
f
on
t
losi
ge o
de
ran e exp
Pr
op
en
e
-%
]
70
O2
[Vo
l.
40
50
60
Lower detonation limit in O2: 2.50 vol.-%

30
80
20
binary
m
90
ixture
P
100
0
ropene
10
/air
0
10
20
30
40
50
60
70
80
90
100
Propene [Vol.-%]
13

explosion regime of H2/O2/N2 at 1 bar abs, 20 C
0
Characteristic values of the explosive range [1,2]:

Lower explosion limit in O2: 4 vol.-%
Upper explosion limit in O2: 95.2 vol.-%
Lower explosion limit in air: 4 vol.-%
Upper explosion limit in air: 77 vol.-%
100
10
90
Characteristic values of the potentially detonative range [3]:
20
de
fla rang
gra e
t iv e o f
ex
p lo
s io
n
60
50
range of mixtures, where

transition from deflagrative to
detonative explosion is possible
70
80
iome
h
c
i
o
st
atio
tric r
=
H 2:O 2
40
2:1
30
20
90
binary
m
100
0
[2] V. Schrder in Process Safety and Industrial Explosion Protection,

editor: ESMG European Safety Management Group e. V. , Hamm, Germany (2005),
ISBN 3-9807567-4-2 (proceedings of the International ESMG Symposium 2005 in
Nrnberg, Germany)
]
-%
60

(2003), ISBN: 3-89701-745-8
l.
[Vo
50
70
O2
[Vo
l.-%
]
30
40
Lower detonation limit in O2: 15 vol.-%

80
ixture
H2 /air
10
0
10
20
30
40
50
60
70
80
90
100
H2 [Vol.-%]
14
Experimental setup to determine the potentially

detonative range of explosive gas mixtures
Booster-mixture, Acetylene/O2,
stoichiometric with respect to formation of
CO and H2O. It transits to detonation after a
few millimeters and acts upon the mixture to
be tested with a stronger detonation front
than the one that occurs in the mixture when
it undergoes a detontive explosion
mixture to be tested for potential detonability (i.e.

ability to propagate a detonation which was once
initiated either by an external source or by an
initially deflagrative explosion in the mixture to
be tested, which succeeded in running up to a
detonation)
ca. 15*pipe diameters

location of thermal
ignition source for
booster mixture
thin membrane or nothing

(after injecting the mixture
to be tested the booster
mixture is injected close to
the ignition source and
propagates almost as plug
flow into the pipe)
Signals of pressure and/or flame sensors give

evidence whether a stable detonation could be
triggered in the mixture
Note:
Pipe must be long enough for to allow that the initial state of the overdriven detonation can
pass over to a stable final state, which can be either a stable detonation or a deflagration in
the mixture to be tested.
15
Different explosion regimes (deflagration, heat explosion, detonation)

found for Propene/O2/N2 in a 20 l sphere at 5 bar abs, 25 C
0
10
100
90
80
50
l. -
m
hio
c
i
sto
ere -%)
d h ol.
me 69 v
for
is up to
ot
so l.-%
vo
%]
70
ve
ati
n
o
60
et
f d ion
o
H2
ge plos
3
ran ex
+
CO
3
->
2
O
5
1.
range of
+
6
H
deflagrative
explosion,
3
cC
i
r
5
bar
abs,
25 C
et
(43
40
70
[Vo
[Vo
30
50
60
80
O2
l. - %
]
yellow range:
possibly heat
explosion
st
oi
ch
io
m
et
st
ric
oi
ch
C
io
3H
m
6 +
et
4.
ric
5
O
C
2 3H
>
6 +
3
CO
3
O
2 +
2 >
3
H
3
CO
2O
+
3
H
2O
20
40
30
20
90
prope
ne/air-
mixtur
10
es
100
0
0
10
20
30
40
50
60
70
Propene C3H6 [Vol.-%]
80
90
100
16
Different explosion regimes (deflagration, heat explosion, detonation) of

Propene/O2/N2 in a 20 l sphere at Pinitial = 1, 5 and 10 bar abs, 25 C
10
5 bar abs
90
l.-%
]
[Vo
60
50
50
3
->
2
range
of
5 O explosion,
deflagrative
1.
+
6 bar abs, 25 C
1
H
C3
ric
et
-%
]
[Vo
l.
2
H2
60
40
70
30
80
80
20
90
prope
ne/air-m
100
0
0
10
20
30
40
50
60
70
10 bar abs
.5
20
30
40
50
60
70
80
90
100
:4
0
10
:O
e
tiv
na
eto
f d ion pene y
o
s
ge plo t pro onl
a .- %
ran ex
(Heat explosion range and

detonative range were not
determined. It might be
that the detonative range
even extends down to the
air line)
70
60
ry vol d)
da
un 10 ate
(bo nc. > stim
e
co
50
40
30
20
90
10
ixtures
80
range of
deflagrative explosion,
10 bar abs, 25 C
80
30
30 bar abs
90
op
en
e
Pr
tio
ra
et
ric
st
oi
ch
io
m
70
]
-%
60
40
100
l.
[Vo
50
100
prope
ne/air-m
O2
[Vo
l.-%
]
40
90
100
10
20
yellow range:
possibly heat
30
explosion
80
iom
ich
50
20
90
10
ixtures
sto
70
ve
ati
60
ton
de on
f
o
i
H2
ge xplos
n
3
a
r
e
+
CO
3
->
2
5O
1.
range of
+
H6
deflagrative
explosion,
3
C
5 bar abs, 25 C
ric
et
l. -
iom
ich
sto
40
[Vo
70
80
30
ere -%)
d h ol.
me 69 v
for
is up to
ot
so l.-%
vo
%]
70
90
(43
60
CO
yellow range:
possibly heat
explosion
]
l.-%
[Vo
50
80
e
tiv
na
eto
f d ion
o
s
ge plo
ran ex
100
O2
yellow range:
30
possibly heat
explosion
40
10
20
O2
st
oi
ch
st
io
oi
m
ch
et
io
ric
m
C
et
3H
ric
6 +
C
4.
3H
5
6 +
O
2 3
>
O
3
2 CO
>
3
2 +
C
3
O
H
+
2O
3
H
2O
20
1 bar abs
100
st
oi
ch
io
m
et
st
ric
oi
ch
C
io
3H
m
6 +
et
4.
ric
5
O
C
2 3H
>
6 +
3
CO
3
O
2 +
2 >
3
H
3
C
2O
O
+
3
H
2O
prope
ne/air
-mixtu
res
10
100
0
40
50
60
70
80
90 100
0
10
20
30
17

Propene/O2/N2 in a 20 l sphere at 1, 5 and 10 bar abs, 200 C
0
100
10
20
30
40
50
60
70
0
10 bar abs
O
O
2
H
3
+
C
O
->
2
+
6
H
3
prope
10
20
20
30
40
50
60
70
80
90
100
H
3
+
2
CO
3
->
2
+
6
H
3
ric
et
et
ric
st
oi
ch
io
m
oi
ch
iom
st
40
30
ne/air
-mixtu
res
10
0
40
50
60
70
80
90 100
0
0
10
(Heat explosion range and

detonative range were not
determined. It might be
that the detonative range
even extends down to the
air line)
70
20
100
10
ixtures
80
st
90
30
30 bar abs
ve
a ti
60
to n
de
of sion
H2
e
3
g xplo
n
+
a
r
e
50
CO
3
->
O2
5
1.
+
H6
C3
c
range of
ri
et
iom
h
c
10
bar
abs, 200 C
oi
4.
[Vo
l.-%
]
40
80
l.-%
[Vo
70
prope
ne/air-m
100
O2
60
100
40
range of
5 bar abs, 200 C
90
30
50
90
100
10
20
yellow range:
possibly heat
explosion
80
st
oi
ch
io
m
et
st
ric
oi
ch
C
io
3H
m
6 +
et
4.
ric
5
O
C
2 3H
>
6 +
3
CO
3
O
2 +
2 >
3
H
3
C
2O
O
+
3
H
2O
l.-%
]
[Vo
2
st
oi
ch
io
m
et
st
ric
oi
ch
C
io
3H
m
6 +
et
4.
ric
5
C
O
3H
2 >
6 +
3
CO
3
O
2 +
2 >
3
3
H
C
2O
O
+
3
H
2O
l.-%
]
[Vo
2
10
50
l.
iom
ich
H6
60
20
90
10
res
sto
C
ric
et
70
ve
ati
ton
de on
f
i
o s
H2
ge plo
3
+
ran ex
CO
3
->
2
5O
1.
+
[Vo
100
60
80
20
prope
ne/air
-mixtu
50
70
30
40
80
)
re
he l.-%
ed 5 vo
orm 7
is f up to
ot
so l.-%
]
vo
-%
40
30
(41
50
->
90
90
O2
]
l.-%
80
io
ich
60
3H
[Vo
sto
range of detonative
explosion
+
O
3C
n,
of
sio
e
O
g
plo
ran e ex 0 C
1. 5
0
v
+
i
rat s, 2
H6
flag ab
C3
de bar
5
tric
me
2
70
70
40
yellow range:
possibly heat
explosion
O2
60
100
20
80
30
50
10
90
20
yellow range:
possibly heat
explosion
5 bar abs
1 bar abs
30
18

Methane/O2/N2 in a 20 l sphere at 1 and 5 bar abs, 25 C and 200 C
1 bar abs, 25 C
0
10
[Vo
l.-%
]
50
40
20
90
10
20
30
40
50
60
70
Methane CH4 [Vol.-%]
80
90
2
2O
->
+
4
1.5
O
2
2H
O2
->
CO
10
20
30
50
40
50
60
70
0
5 bar abs, 200 C
40
30
20
10
80
70
40
90
2
2O
->
+
4
1.5
O
2
2H
O2
->
CO
2H
60
50
4
CH
CH
ric
ri c
et met
m
o
io
hi
of
range plosion,
ich toic
2H 2
ex
sto s
O+
rative
deflag abs, 200 CO 2 -> C
0.5
5 bar
+
CH 4
etric
hiom
stoic
ts
tar
ns
ti o
4
ma CH
for l.-%
ot
o
so 55 v
at
80
2
CO
range of detonative
explosion
]
l.-%
[Vo
70
40
30
20
metha
ne/air-m
ixtures
100
100
90
20
50
60
90
O2
[Vo
l.-%
]
yellow range:
possibly heat
30
explosion
80
100
10
60
2H
metha
ne/air-m
ixtures
100
100
4
CH
CH
ric
ri c
et met
m
io
hio
of
range plosion,
ich toic
2H 2
ex
sto s
O+
rative
deflag abs, 25 C O 2 -> C
.5
0
5 bar
+
CH 4
etric
hiom
stoic
80
0
10
70
30
metha
ne/air-m
ixtures
60
2
CO
ts
->
->
2
O2
2O
1.5
+
4
4
CH
CH
ric etric
et
m iom
o
i
h
of
ich toic
2
range plosion,
+ 2H
ex
sto s
CO
rative
deflag abs, 25 C .5O 2 ->
0
1 bar
+
CH 4
etric
hiom
stoic
50
range of detonative
explosion
tar
ns
ti o
4
ma CH
for l.-%
ot
o
so 55 v
at
60
70
40
]
l.-%
[Vo
100
0
2H
80
30
O2
90
ts
80
CO
tar
ns
4
tio
m a CH
for l.-%
ot
o
so 55 v
at
70
O
2
2H
]
l.-%
[Vo
60
yellow range:
possibly heat
explosion
mixture reacts sometimes

detonative and sometimes
as heat explosion
O2
[Vo
l.-%
]
70
40
2
CO
90
20
80
30
50
100
10
90
20
yellow range:
possibly heat
explosion
5 bar abs, 25 C
100
10
0
10
20
30
40
50
60
70
80
90
100
19
Pressure-time traces of Propene/O2 at 5 bar, 25 C (1)

top
center
bottom
Propene = 2.25 vol.-%

25 O2 = 97.75 vol.-%,
5 bar abs, 25 C
20
10
15
5
File: PROP76-2.25%.DAT
500
1000
1500
Time [ms]
2000
2500
100
60
100
25
File: PROP08A;Propene=3, O2=97
Vol.%; 5bar abs; 25C.DAT
100
Time [ms]
200
300
70
0
171 171.5 172 172.5 173 173.5 174 ic
Time [ms]
sto
150
100
Propene = 4 vol.-%
O2 = 96 vol.-%,
5 bar abs, 25 C
sto
Pressure [bar abs]
50
ve
ati
n
60
eto
f d sion
o
2
ge plo
3H
ran ex
+
O
3C
>
O2
5
.
1
range of
+
6
H
deflagrative
explosion,
3
C
ic
r
5
bar
abs,
25 C
t
me
o
i
h
50
40
30
80
20
125
90
propen
100
e/air-m
ixtures
10
10075
50
50
25
25
File: PROP142A-4%.DAT
70
]
l.-%
[Vo
50
200
40
80
O2
300
Propene = 3 vol.-%
O2 = 97 vol.-%,
75 5 bar abs, 25 C
Pressure [bar abs]
30
3000
[Vo
l.-%
]
0
0
75
90
20
10
100
ich
iom
et
st
r ic
oi
ch
C
3H
io
m
6 +
et
4.
ric
5
O
C
2 3H
>
6
3
+
CO
3
O
2 +
2
->
3
H
3
2O
CO
+
3
H
2O
Pressure [bar abs]
30
20
40
Time [ms]
60
0
26
0
10
26.5
20
27 27.5 28
Time [ms]
30
28.5
40
50
60
70
29
20
80
90
100

100
Pressure [bar abs]
75
250
Propene = 5 vol.-%
O2 = 95 vol.-%,
5 bar abs, 25 C
200
10
150
50
50
30

20
25
30
Propene = 6 vol.-%,
O2 = 94 vol.-%,
5 bar abs, 25 C
15 15.5 16
Time [ms]
400
25
0
0
100
2.5
7.5
Time [ms]
10
12.5
100
70
7
80
40
7.5
8
8.5
Time [ms]
9.5 sto
ic
70
ve
ati
n
60
eto
f d sion
o
2
ge plo
3H
ran ex
+
O
3C
>
O2
5
.
1
range of
+
6
H
deflagrative
explosion,
3
C
ic
r
5
bar
abs,
25 C
t
me
o
i
h
50
40
30
20
500
Propene = 7 vol.-%,
O2 = 93 vol.-%,
5 bar abs, 25 C
125
0
6.5
15
150
90
propen
400
e/air-m
ixtures
10
100300
75
200
50
0
10
20
30
100
25
0
0
60
200
17
sto
50
16.5
50
300

Pressure [bar abs]
14.5
Pressure [bar abs]
15
Time [ms]
]
l.-%
[Vo
75
10
80
O2
100
[Vo
l.-%
]
0
0
0
14
90
ich
iom
et
st
r ic
oi
ch
C
3H
io
m
6 +
et
4.
ric
5
O
C
2 3H
>
6
3
+
CO
3
O
2 +
2
->
3
H
3
2O
CO
+
3
H
2O
25
100
20
100
top
center
bottom

10
Time [ms]
15
20
0
5
5.5
6.5
7
Time [ms]
7.5
40
50
60
70
8
21
80
90
100

150
125
400
100
10
300
75
200
50
25
20
10
Time [ms]
100
0
3
3.5
4.5
5
Time [ms]
400
50
300
75
60
200
100
25
70
0
0
10
Time [ms]
15
20
150
0
1
1.5
80
40
sto
50
30
5.5
2.5
3
Time [ms]
3.5
sto
ic
70
ve
ati
n
60
eto
f d sion
o
2
ge plo
3H
ran ex
+
O
3C
>
O2
5
.
1
range of
+
6
H
deflagrative
explosion,
3
C
ic
r
5
bar
abs,
25 C
t
me
o
i
h
]
l.-%
[Vo
Propene = 13 vol.-%,
O2 = 87 vol.-%,
5 bar abs, 25 C
125
Pressure [bar abs]
20
80
O2
150
15
[Vo
l.-%
]
0
0
top
center
bottom
90
100
Pressure [bar abs]
100
ich
iom
et
st
r ic
oi
ch
C
3H
io
m
6 +
et
4.
ric
5
O
C
2 3H
>
6
3
+
CO
3
O
2 +
2
->
3
H
3
2O
CO
+
3
H
2O
Pressure [bar abs]
500
Propene = 8 vol.-%,
O2 = 92 vol.-%,
5 bar abs, 25 C
50
40
30
20
500
125
400
90
propen
100
e/air-m
ixtures
10
300
100
75
25
200
Propene = 18.18 vol.-%,

O2 = 81.82 vol.-%,
5 bar abs, 25 C
50
100
10
20
30
File:PROP130A-18.2%.DAT
0
0
10
Time [ms]
15
20
0
0
0.5
1.5
2
Time [ms]
2.5
40
50
60
70
22
80
90
100

150
200
150
100
75
100
O2 = 77 vol.-%,
5 bar abs, 25 C
50
10
20
10
Time [ms]
0
0
15
0.5
1.5
2
Time [ms]
50
600
100
400
O2 = 72 vol.-%,
5 bar abs, 25 C
60
200
70
25
File: Prope132a.dat, 28 vol.-%
10
Time [ms]
0
0
15
0.5
80
40
sto
75
Pressure [bar abs]
125
30
1.5
2
Time [ms]
2.5
sto
ic
70
ve
ati
n
60
eto
f d sion
o
2
ge plo
3H
ran ex
+
O
3C
>
O2
5
.
1
range of
+
6
H
deflagrative
explosion,
3
C
ic
r
5
bar
abs,
25 C
t
me
o
i
h
]
l.-%
[Vo
[Vo
l.-%
]
800
2.5
top
center
bottom
80
O2
150
50
90
50
25
0
100
ich
iom
et
st
r ic
oi
ch
C
3H
io
m
6 +
et
4.
ric
5
O
C
2 3H
>
6
3
+
CO
3
O
2 +
2
->
3
H
3
2O
CO
+
3
H
2O
Pressure [bar abs]
125
50
40
30
20
800
90
Pressure [bar abs]
150
propen
600
10
100400
100
50
0
0
e/air-m
ixtures
0
200
Propene = 33 vol.-%
O2 = 67 vol.-%,
5 bar abs, 25 C
File:PROP137A-33%.DAT
10
Time [ms]
15
20
0
2
0
10
2.5
20
3
3.5
4
Time [ms]
30
4.5
40
50
60
70
5
23
80
90
100

400
100
10
Time [ms]
15
30
0
4
20
4.5
5.5
6
Time [ms]
[Vo
l.-%
]
300
200
Propene = 38 vol.-%
O2 = 62 vol.-%,
5 bar abs, 25 C
50
10
15
Time [ms]
20
70
0
11
25
11.5
40
12 12.5 13
Time [ms]
80
13.5
14
ic
ve
ati
n
60
eto
f d sion
o
2
ge plo
3H
ran ex
+
O
3C
>
O2
5
.
1
range of
+
6
H
deflagrative
explosion,
3
C
ic
r
5
bar
abs,
25 C
t
me
o
i
h
50
40
30
20
400
90
propen
e/air-m
ixtures
10
300
100
100
200
50
10
20
30
100
File: Prope11A;Propene=39, O2=61
vol.-%, 5 bar abs, 25C
0
15
sto
70
500
O2 = 61 vol.-%,
5 bar abs, 25 C
150
60
100
Pressure [bar abs]
50
]
l.-%
[Vo
Pressure [bar abs]
150
6.5
top
center
bottom
80
O2
400
100
90
ich
iom
et
st
r ic
oi
ch
C
3H
io
m
6 +
et
4.
ric
5
O
C
2 3H
>
6
3
+
CO
3
O
2 +
2
->
3
H
3
2O
CO
+
3
H
2O
100
File:PROP10A;Propene=35.5, O2=64.5
100
20
200

O2 = 64.5 vol.-%,
5 bar abs, 25 C
50
10
300
sto
Pressure [bar abs]
500
150
20
25
Time [ms]
30
35
0
17
17.5
18 18.5 19
Time [ms]
19.5
40
50
60
70
20
24
80
90
100

0
500
O2 = 60 vol.-%,
5 bar abs, 25 C
400
100
10
300
100
20
25
Time [ms]
30
35
30
0
22
22.5
23 23.5 24
Time [ms]
300
100
60
200
70
100
25
30
Time [ms]
35
40
O2 = 58 vol.-%,
5 bar abs, 25 C
150
0
26
500
26.5
27 27.5 28
Time [ms]
80
28.5
29
sto
ic
ve
ati
n
60
eto
f d sion
o
2
ge plo
3H
ran ex
+
O
3C
>
O2
5
.
1
range of
+
6
H
deflagrative
explosion,
3
C
ic
r
5
bar
abs,
25 C
t
me
o
i
h
50
40
30
20
90
propen
400
e/air-m
ixtures
10
300
100
100
200
50
35
40
Time [ms]
45
10
20
30
100

0
30
sto
50
0
20
Pressure [bar abs]
50
Pressure [bar abs]
400
40
70
top
center
bottom
]
l.-%
[Vo
O2 = 60 vol.-%,
5 bar abs, 25 C
25
80
O2
500
150
24.5
[Vo
l.-%
]

90
20
200
50
0
15
100
ich
iom
et
st
r ic
oi
ch
C
3H
io
m
6 +
et
4.
ric
5
O
C
2 3H
>
6
3
+
CO
3
O
2 +
2
->
3
H
3
2O
CO
+
3
H
2O
Pressure [bar abs]
150
50
0
34
34.5
35 35.5 36
Time [ms]
36.5
40
50
60
70
37
25
80
90
100
Pressure [bar abs]
150
O2 = 57 vol.-%,
5 bar abs, 25 C
150
0
100
100
10
50
50
70
75
0
61
61.5
62 62.5 63
Time [ms]
63.5
30
sto
70
sto
80
ic
70
ve
ati
n
60
eto
f d sion
o
2
ge plo
3H
ran ex
+
O
3C
>
O2
5
.
1
range of
+
6
H
deflagrative
explosion,
3
C
ic
r
5
bar
abs,
25 C
t
me
o
i
h
top
]
l.-%
[Vo
40
80
O2
50
60
64
ich
iom
et
st
r ic
oi
ch
C
3H
io
m
6 +
et
4.
ric
5
O
C
2 3H
>
6
3
+
CO
3
O
2 +
2
->
3
H
3
2O
CO
+
3
H
2O
65
Time [ms]
[Vo
l.-%
]
60
90
20
0
55
100
50
40
30
20
90
propen
e/air-m
ixtures
10
100
0
0
10
20
30
40
50
60
70
26
80
90
100
Pressure-time traces of stoich. Propene/O2/N2 at 5 bar, 25 C (1)

40

O2 = 24.75 vol.-%,
N2= 69.75
5 bar abs, 25 C
0
10
30
20
20
30
Time [ms]
40
150
(first test)
50
File: PROP208A-27%O2(erster Test).DAT
10
20
Time [ms]
30
40
0
18
18.5
19 19.5 20
Time [ms]
20.5
21
Pressure [bar abs]
75
60
center
top
40
70
sto
80
100
Propene = 6 vol.-%
O2 = 27 vol.-%,
N2 = 67
5 bar abs, 25 C
50
bottom
100
25
0
0
[Vo
l.-%
]
Pressure [bar abs]
50
200
Propene = 6 vol.-%
O2 = 27 vol.-%,
N2 = 67
5 bar abs, 25 C
100
90
(second test)
25
10
20
30
File: PROP209A-27%O2(zweiter Test).DAT
0
0
10
20
Time [ms]
30
40
0
20
e/air
100
50
25
ic
tiv
na
o
t
de
of osion
e
g pl
ran ex
+
O
C
3
->
2
O
1.5
ran
+
H6
deflagrati
3
C
5 bar a
tric
e
m
o
i
h
propen
75
50
30
50
sto
10
100
75
90
ich
iom
et
st
r ic
oi
ch
C
3H
io
m
6 +
et
4.
ric
5
O
C
2 3H
>
6
3
+
CO
3
O
2 +
2
->
3
H
3
2O
CO
+
3
H
2O
File: PROP15A; Propen=5.5, O2=25,

N2=69.5 Vol.%;5bar abs;25C.DAT
0
0
100
20
10
Pressure [bar abs]
50
20.5
21 21.5 22
Time [ms]
22.5
23
27
40
50
60
Propene C3H6 [Vol.-

250
75

O2 = 31 vol.-%,
N2 = 62.1
5 bar abs, 25 C
10
150
50
100
File:PROP16A;Propen=6.9, O2=31,
50
15
20
0
12
12.5
13 13.5 14
Time [ms]
14.5
150
(first test)
25
50
10
Time [ms]
15
20
Pressure [bar abs]
100
75
50
7.5
8.5
9
Time [ms]
9.5
File: PROP17A;Propen=7.8, O2=35,

10
Time [ms]
15
20
sto
90
200
100
100
0
7
70
80
300
(second test)
40
10
400
O2 = 35 vol.-%,
N2 = 57.3
5 bar abs, 25 C
25
0
0
0
7
60
center
top
File: PROP207A-35%O2.DAT
0
0
50
bottom
100
7.5
8.5
9
Time [ms]
9.5
80
30
15
200

O2 = 35 vol.-%,
N2 = 57.3
5 bar abs, 25 C
ich
iom
et
st
r ic
oi
ch
C
3H
io
m
6 +
et
4.
ric
5
O
C
2 3H
>
6
3
+
CO
3
O
2 +
2
->
3
H
3
2O
CO
+
3
H
2O
75
10
Time [ms]
sto
100
90
20
[Vo
l.-%
]
0
0
100
50
25
Pressure [bar abs]
200
Pressure [bar abs]
100
ic
ve
ati
n
eto
f d sion
o
ge plo
3
ran ex
+
O
3C
->
O2
1.5
range
+
H6
deflagrative
3
C
5 bar abs
tric
e
m
o
i
h
propen
10
20
30
e/air-m
40
50
60
Propene C3H6 [Vol.-%
10
28

400

O2 = 40 vol.-%,
75 N2 = 51.2
5 bar abs, 25 C
300
10
50
200
25
100
bottom
10
Time [ms]
15
20
5.5
6
6.5
Time [ms]
7.5
center
300
250
top
75
150

O2 = 60 vol.-%,
N2 = 26.7
5 bar abs, 25 C
60
100
70
50
File: PROP216A-60%O2.DAT
0
0
10
Time [ms]
15
20
150
0
1
1.5
2.5
3
Time [ms]
3.5
40
sto
50
25
sto
80
90
400
100
300
100
200
75
Propene = 18.18 vol.-%,
O2 = 81.82 vol.-%,
5 bar abs, 25 C
50
25
100
propen
10
20
30
10
Time [ms]
15
20
0
0
0.5
1.5
2
Time [ms]
2.5
e/air-m
40
50
60
Propene C3H6 [Vol.-%
File:PROP130A-18.2%.DAT
0
0
ic
ve
ati
n
eto
f d sion
o
ge plo
3
ran ex
+
O
3C
->
O2
1.5
range
+
H6
deflagrative
3
C
5 bar abs
tric
e
m
o
i
h
500
125
Pressure [bar abs]
50
200
Pressure [bar abs]
100
80
30
[Vo
l.-%
]
0
4.5
90
20
File: PROP18A;Propen=8.9, O2=40,

0
0
100
ich
iom
et
st
r ic
oi
ch
C
3H
io
m
6 +
et
4.
ric
5
O
C
2 3H
>
6
3
+
CO
3
O
2 +
2
->
3
H
3
2O
CO
+
3
H
2O
Pressure [bar abs]
100
29

Methane/O2/N2 in a 20 l sphere at 1 and 5 bar abs, 25 C and 200 C
1 bar abs, 25 C
0
10
[Vo
l.-%
]
50
40
20
90
10
20
30
40
50
60
70
80
90
2
2O
->
+
4
1.5
O
2
2H
O2
->
CO
10
20
30
50
40
50
60
70
0
5 bar abs, 200 C
40
30
20
10
80
70
40
90
2
2O
->
+
4
1.5
O
2
2H
O2
->
CO
2H
60
50
4
CH
CH
ric
ri c
et met
m
o
io
hi
of
range plosion,
ich toic
2H 2
ex
sto s
O+
rative
deflag abs, 200 CO 2 -> C
0.5
5 bar
+
CH 4
etric
hiom
stoic
ts
tar
ns
ti o
4
ma CH
for l.-%
ot
o
so 55 v
at
80
2
CO
range of detonative
explosion
]
l.-%
[Vo
70
40
30
20
metha
ne/air-m
ixtures
100
100
90
20
50
60
90
O2
[Vo
l.-%
]
yellow range:
possibly heat
30
explosion
80
100
10
60
2H
metha
ne/air-m
ixtures
100
100
4
CH
CH
ric
ri c
et met
m
io
hio
of
range plosion,
ich toic
2H 2
ex
sto s
O+
rative
deflag abs, 25 C O 2 -> C
.5
0
5 bar
+
CH 4
etric
hiom
stoic
80
0
10
70
30
metha
ne/air-m
ixtures
60
2
CO
ts
->
->
2
O2
2O
1.5
+
4
4
CH
CH
ric etric
et
m iom
o
i
h
of
ich toic
2
range plosion,
+ 2H
ex
sto s
CO
rative
deflag abs, 25 C .5O 2 ->
0
1 bar
+
CH 4
etric
hiom
stoic
50
range of detonative
explosion
tar
ns
ti o
4
ma CH
for l.-%
ot
o
so 55 v
at
60
70
40
]
l.-%
[Vo
100
0
2H
80
30
O2
90
ts
80
CO
tar
ns
4
tio
m a CH
for l.-%
ot
o
so 55 v
at
70
O
2
2H
]
l.-%
[Vo
60
yellow range:
possibly heat
explosion
mixture reacts sometimes

detonative and sometimes
as heat explosion
O2
[Vo
l.-%
]
70
40
2
CO
90
20
80
30
50
100
10
90
20
yellow range:
possibly heat
explosion
5 bar abs, 25 C
100
10
0
10
20
30
40
50
60
70
80
90
100
30
20
30
20
600
700
100
75
50
40
10
15
Time [ms]
20
25
30
0
23
23.5
24 24.5 25
Time [ms]
25.5
ch
om
ri
et
H
cC
2
2O
->
CO
2H
26
200
150
100
20
0
0
oi
st
25
Methane = 12 vol.-%,
O2 = 88 vol.-%,
5 bar abs, 25 C
Pressure [bar abs]
60
[Vo
125
10
0
0
l.-%
]
500
Pressure [bar abs]
40
300
400
Time [ms]
l. -%
[Vo
50
200
O2
60
100
0
0
top
center
bottom
yellow range:
possibly heat
explosion
10
O2 = 90 vol.-%,
5 bar abs, 25 C
Pressure [bar abs]
30
Methane = 7 vol.-%,
O2 = 93 vol.-%,
5 bar abs, 25 C
Pressure-time traces of Methane/O2 at 5 bar, 25 C (1)
50
10
Time [ms]
15
20
0
13
13.5
14
14.5
Time [ms]
15
31
40
200
20
11
[Vo
2
100
oi
st
50
10
Time [ms]
15
20
0
5
5.5
6.5
7
Time [ms]
7.5
ch
om
ri
et
H
cC
2
2O
->
CO
2H
800
2nd test:
O2 = 85 vol.-%,
5 bar abs, 25 C
20
10.5
30
9.5 10
Time [ms]
l. -%
[Vo
40
150
70
50
8.5
200
20
60
0
8
l.-%
]
15
O2 = 85 vol.-%,
5 bar abs, 25 C
10
Time [ms]
O2
40
0
0
Pressure [bar abs]
yellow range:
possibly heat
explosion
100
60
Pressure [bar abs]
300
20
0
0
top
center
bottom
400
Pressure [bar abs]
60
O2 = 86 vol.-%,
5 bar abs, 25 C
500
600
400

200
10
0
0
10
Time [ms]
15
20
0
6
6.5
7.5
8
Time [ms]
8.5
9
32
40
30
150
20
50
10
0
0
2.5
7.5
10
30
20
[Vo
300
200
2.5
oi
st
5
Time [ms]
7.5
10
0
3
3.5
4.5
5
Time [ms]
ri
et
->
2nd test:
O2 = 80 vol.-%,
5 bar abs, 25 C
400
300
200
100
25
0
3
3.5
4
4.5
5
5
7.5
10
Time [ms]
Time [ms]
0
0
5.5
ch
om
H
cC
2
2O
CO
2H
500
125
50
100
0
0
75
5.5
400
10
100
4.5
5
Time [ms]
500
O2 = 80 vol.-%,
5 bar abs, 25 C
40
Pressure [bar abs]
50
3.5
l. -%
[Vo
60
0
3
O2
5
Time [ms]
70
Pressure [bar abs]
yellow range:
possibly heat
explosion
100
l.-%
]
50
top
center
bottom
200
Pressure [bar abs]
60
250
Methane = 17.5 vol.-%,

O2 = 82.5 vol.-%,
5 bar abs, 25 C
70
2.5
5.5
6
33

125
O2 = 75 vol.-%,
5 bar abs, 25 C
100
75
50
200
10
50
2.5
3
Time [ms]
3.5
[Vo
2
200
150
100
oi
st
50
2.5
3rd test:
O2 = 75 vol.-%,
5 bar abs, 25 C
75
250
25
100
1.5
300
2nd test:
O2 = 75 vol.-%,
5 bar abs, 25 C
50
0
1
l.-%
]
7.5
7.5
10
0
1
1.5
2.5
3
Time [ms]
3.5
ri
et
->
800
600
400
200
25
0
0
5
Time [ms]
ch
om
H
cC
2
2O
CO
2H
75
0
0
Pressure [bar abs]
5
Time [ms]
l. -%
[Vo
100
Pressure [bar abs]
2.5
O2
125
125
yellow range:
possibly heat
explosion
100
25
0
0
top
center
bottom
300
Pressure [bar abs]
400
0
1
1.5
2
2.5
3
5
7.5
10
Time [ms]
Time [ms]
2.5
3.5
4
34

125
300
250
200
75
150
50
O2 = 65 vol.-%,
5 bar abs, 25 C
50
0
0
0.5
1.5
2
Time [ms]
500
O2 = 60 vol.-%,
5 bar abs, 25 C
75
10
2.5
400
300
200
ch
oi
st
100
25
0
0
2.5
5
Time [ms]
7.5
10
0
2
2.5
3.5
4
Time [ms]
4.5
io
ri
et
cC
+
4
2O
->
CO
2H
Pressure [bar abs]
100
75
50
O2 = 55 vol.-%,
5 bar abs, 25 C
150
125
900
800
700
600
500
400
200
25
0
0
300
100
2.5
5
Time [ms]
7.5
10
0
3
3.5
4.5
5
Time [ms]
5.5
top
center
bottom
Pressure [bar abs]
100
7.5
l. -%
[Vo
125
5
Time [ms]
O2
150
2.5
[Vo
0
0
50
l.-%
]
25
yellow range:
possibly heat
explosion
100
Pressure [bar abs]
100
6
35

150
75
50
400
300
yellow range:
possibly heat
explosion
200
100
25
15
Time [ms]
20
25
0
14
14.5
15 15.5 16
Time [ms]
O2 = 45 vol.-%,
5 bar abs, 25 C
Pressure [bar abs]
oi
st
ch
om
ri
et
H
cC
2
2O
->
CO
O
2
2H
20
0
0
25
50
75
Time [ms]
100
125
150
top
bottom
40
17
l. -%
[Vo
80
60
16.5
[Vo
10
O2
0
5
l.-%
]
100
500
O2 = 50 vol.-%,
5 bar abs, 25 C
Pressure [bar abs]
125
36
l.-%
]
bottom
10
0
0
60
40
200
Time [ms]
300
oi
st
ch
om
ri
et
H
cC
2O
->
CO
2H
80
60
40
20
20
0
0
top
400
O2 = 30 vol.-%,
N2 = 55 vol.-%,
5 bar abs, 25 C
Pressure [bar abs]
80
100
[Vo
20
30
40
yellow range:
possibly heat
explosion
O2 = 20 vol.-%,
N2 = 70 vol.-%,
5 bar abs, 25 C
Pressure [bar abs]
Pressure-time traces of stoich. Methane/O2/N2 at 5 bar, 25 C (1)
10
15
Time [ms]
20
25
30
0
16
16.5
17 17.5 18
Time [ms]
18.5
19
37
O2 = 40 vol.-%,
N2 = 40 vol.-%,
5 bar abs, 25 C
40
40
20
15
20
4.5
5.5
6
Time [ms]
6.5
bottom
top
[Vo
150
100
50
50
0
0
0
4
100
10
Time [ms]
O2 = 50 vol.-%,
N2 = 25 vol.-%,
5 bar abs, 25 C
150
yellow range:
possibly heat
explosion
l.-%
]
20
0
0
Pressure [bar abs]
60
Pressure [bar abs]
60
10
Time [ms]
15
20
0
3
oi
st
3.5
4.5
5
Time [ms]
5.5
ch
om
ri
et
H
cC
2
2O
->
CO
2H

38

Pressure [bar abs]
25
20
15
10
O2 = 90 vol.-%,,
5 bar abs, 200 C
30

O2 = 87.5 vol.-%,,
5 bar abs, 200 C
30
20
10
10
Time [ms]
15
20
0
12
o
st
12.5
13 13.5 14
Time [ms]
14.5
i
i ch
om
et
C
ric
+
H4
2O
->
CO
2H
15
40
30
20
10
0
0
l.-%
]
20
O2 = 86 vol.-%,,
5 bar abs, 200 C
40
[Vo
30
Pressure [bar abs]
40
10
0
0
Pressure [bar abs]
40
20
30
l.-%
[Vo
30
20
Time [ms]
O2
40
10
yellow range:
possibly heat
explosion
0
0
top
center
bottom
10
10
Time [ms]
15
20
0
8
8.5
9.5 10
Time [ms]
10.5
11
39
100
7.5
10
o
st
2.5
5
Time [ms]
7.5
10
O2 = 80 vol.-%,,
5 bar abs, 200 C
Pressure [bar abs]
0
4
4.5
5.5
6
Time [ms]
6.5
i
i ch
om
et
C
ric
+
H4
2O
->
400
100
300
200

100
25
0
0
l.-%
]
200
CO
2H

O2 = 82.5 vol.-%,,
5 bar abs, 200 C
300
100
0
0
50
6.5
400
10
75
0
6
l.-%
[Vo
20
5
Time [ms]
O2
30
2.5
yellow range:
possibly heat
7
7.5
8
8.5
9
explosion
Time [ms]
[Vo
0
0
Pressure [bar abs]
200
10
40
top
center
bottom
20
300
30
400
O2 = 85 vol.-%,,
5 bar abs, 200 C
Pressure [bar abs]
40
2.5
5
Time [ms]
7.5
10
0
3
3.5
4.5
5
Time [ms]
5.5
40

400
200
100
25
2.5
5
Time [ms]
7.5
10
100
200
2.5
5
Time [ms]
7.5
10
100
O2 = 55 vol.-%,,
5 bar abs, 200 C
Pressure [bar abs]
0
2
o
st
2.5
3.5
4
Time [ms]
4.5
i
i ch
om
et
C
ric
+
H4
2O
->
2H
500
400
300
200
25
0
0
l.-%
]
O2 = 60 vol.-%,,
5 bar abs, 200 C
300
2
CO
100
2.5
5
Time [ms]
7.5
10
0
4
4.5
5.5
6
Time [ms]
6.5
center
bottom
]
Pressure [bar abs]
400
100
0
0
50
3.5
Time [ms]
500
25
75
l.-%
[Vo
50
2.5
top
O2
75
0
2
[Vo
0
0
yellow range:
possibly heat
explosion
4
4.5
5
50
300
Pressure [bar abs]
75
O2 = 75 vol.-%,,
5 bar abs, 200 C
100
41

100
50
O2 = 50 vol.-%,,
5 bar abs, 200 C
Pressure [bar abs]
75
250
200
150
100
25
50
0
0
10
Time [ms]
15
20
0
10
10.5
yellow range:
possibly heat
11 11.5 12 12.5 13
Time [ms]
explosion
30
10
oi
st
0
0
20
200
Time [ms]
300
200
400
Time [ms]
600
800
top
center
bottom
10
0
0
et
+
H4
->
400
O2 = 38 vol.-%,,
5 bar abs, 200 C
Pressure [bar abs]
30
100
ch
om
C
ric
20
2O
CO
2H
l.-%
[Vo
[Vo
l.-%
]
O2 = 45 vol.-%,,
5 bar abs, 200 C
40
O2
Pressure [bar abs]
50
42
20
10
10
15
Time [ms]
20
25
30
20
20
2.5
20
10
12.5
15
0
6
6.5
7.5
8
Time [ms]
8.5
cC
2O
CO
2H
40
30
20
10
0
0
7.5
Time [ms]
io
ri
et
->
50
2nd test:
O2 = 40 vol.-%,,
N2 = 40 vol.-%,
5 bar abs, 200 C
Pressure [bar abs]
30
ch
oi
st
10
50
40
center
top
30
10
0
0
bottom
40
10
0
6
6.5
7
7.5
8
7.5
10
12.5
15
Time [ms]
Time [ms]
2.5
8.5
43
30
O2 = 40 vol.-%,,
N2 = 40 vol.-%,
5 bar abs, 200 C
40
50
O2
Pressure [bar abs]
50
l.-%
]
[Vo
0
0
yellow range:
possibly heat
explosion
Pressure [bar abs]
30
O2 = 30 vol.-%,,
N2 = 55 vol.-%,
5 bar abs, 200 C
40
25
25
0
0
50
5
Time [ms]
7.5
10
4.5
5
Time [ms]
5.5
center
bottom
top
75
50
25
0
0
2.5
5
Time [ms]
7.5
10
100 Note:This is not on the

stoichiometric line!!
75 O2 = 55 vol.-%,,
N2 = 30 vol.-%,
5 bar abs, 200 C
50
Pressure [bar abs]
3.5
100
25
0
1
oi
st
1.5
2.5
3
Time [ms]
3.5
ch
io
ri
et
cC
7.5
Time [ms]
2O
CO
2H
75
50
25
2.5
+
4
->
100
25
0
0
0
3
yellow range:
possibly heat
explosion
10
12.5
15
0
7.5
8.5
9
9.5
Time [ms]
10
10.5
44
O2
75
2.5
O2 = 60 vol.-%,,
N2 = 10 vol.-%,
5 bar abs, 200 C
100
Pressure [bar abs]
50
l.-%
]
50
75
[Vo
75
100
Pressure [bar abs]
100
O2 = 50 vol.-%,,
N2 = 25 vol.-%,
5 bar abs, 200 C
Summary of the differences in the pressure time diagrams between

explosions in vessels that were triggered by a thermal ignition and
ended up as deflagration, heat explosion or detonation
presence of pressure
pulse
width of pressure pulse
at half height [s]
height of pressure pulse
divided by pressure in
mixture just before its
occurrence
deflagration
no
(not
applicable)
(not
applicable)
precompression ratio at
the moment when
pressure pulse occurs
(not
applicable)
"oscillations" in
reaction gases after
occurrence of pressure
pulse
no oscillations
anyway
acoustic sound heard

outside the vessel
course of explosion
heat explosion
yes
detonation
yes
100 - 200
< 50
typically 4 to 7
typically 15 to 50
(equals deflagration
pressure ratio of the
precompressed unreacted
mixture)
(due to too small

sampling rate the true
maximum was
presumably mostly
missed)
5 10
1 20
(largest value equals

pex/pinitial of the
corresponding gas
mixture)
(largest value equals

pex/pinitial of the
corresponding gas
mixture)
no oscillations
massive
oscillations (due to
shock front bouncing
backwards and forwards in reaction
gases)
nothing
click
prolonged whistle
45
Heat explosion tentative explanation of the course of events

Before heat explosion:
12
10
8
6
4
2
0
0
hot reaction
gases
flame front
precompressed
unreacted mixture
Pressure as function of radial position in

20 l sphere (pinitial = 1 bar abs) just
before heat explosion occurs in the
precompressed, unreacted mixture
(R0 = 17 cm)
pressure/pinitial
Reaction rate sufficiently slow to allow for pressure equilibrium over entire sphere
radial position r/R0
At heat explosion:
Immediate temperature rise and hence also pressure rise in the shell so far unreacted, but
heated by adiabatic compression. The induction time must be of the order of 0.1 ms or
even less, otherwise the flame front of the initial deflagration would have run through the
thin shell of unreacted mixture before the heat explosion could develop.
After heat explosion:

reaction gases flow to the central part of the sphere and pressure equilibrium is attained
46
Temperatures obtainable by adiabatic compression

pfinal/pinitial
1,5
2
3
4
5
6
7
8
9
10
12
14
16
18
20
Tfinal [C] resulting for differrent values

Tfinal [C] resulting for different values
of in case that Tinitial = 35 C = 308 K
of in case that Tinitial = 200 C = 473 K
= 1,4
= 1,3
= 1,2
= 1,1
= 1,4
= 1,3
= 1,2
= 1,1
72,8
65,2
56,5
46,6
258,1
246,4
233,1
217,8
102,5
88,4
72,7
55,0
303,6
282,0
257,9
230,8
148,6
123,9
96,9
67,3
374,4
336,5
295,0
249,7
184,7
151,1
115,1
76,4
429,9
378,3
322,9
263,5
214,8
173,5
129,8
83,5
476,1
412,7
345,5
274,5
240,9
192,7
142,2
89,5
516,2
442,2
364,6
283,7
264,0
209,6
153,0
94,6
551,7
468,1
381,2
291,5
284,9
224,7
162,6
99,1
583,8
491,3
395,9
298,4
304,0
238,4
171,2
103,1
613,1
512,4
409,2
304,6
321,7
251,0
179,1
106,7
640,2
531,7
421,3
310,1
353,5
273,5
193,0
113,1
689,1
566,3
442,7
319,9
381,7
293,3
205,2
118,5
732,4
596,7
461,3
328,2
407,1
311,0
215,9
123,3
771,5
623,9
477,8
335,6
430,4
327,1
225,6
127,6
807,2
648,6
492,7
342,1
451,9
341,9
234,4
131,4
840,2
671,3
506,3
348,1
Temperatures may well lie above the ignition temperatures the

mixtures presumably have in the precompressed state!
Formula for temperature increase due to adiabatic compression: T final = Tinitial
final
p
initial
( 1)
47
Autoignition temperatures of Propene/O2/N2

10
Autoignition Temperature (AIT)

[C]
90
20
2
80
30
N2
[Vol.%]
O2
[Vol.%]
100
H
3
->
4.
5
+
6
H
3
st
80
40
30
20
90
propen
e/air-m
ixtures
10
100
0
0
10
20
AIT [C] at Pinitial = 5 bar abs for stoichiometric (with respect to CO2 and H2Oformation) Propene/O2 mixtures, i.e. Propene:O2 = 1 : 4.5
4.46
20.07
75.47
280
7
31.5
61.5
270
10
45
45.0
270
30
40
50
60
70
AIT [C] at Pinitial = 1 bar abs for stoichiometric (with respect to CO2 and H2Oformation) Propene/O2 mixtures, i.e. Propene:O2 = 1 : 4.5
4.46
20.07
75.47
485 (CHEMSAFE, DIN-method in open Erlenmeyer
flask)
7.0
31.5
61.5
410
10.0
45.0
45.0
310
15.5
70.0
14.5
290
50
ich
io
m
et
r ic
hio
m
et
r ic
sto
ic
st
o
70
CO
->
ve
ati
60
ton
de on
f
i
o
2
H
ge xplos
n
3
ra e
+
O
3C
->
O2
1.5
range of
+
H6
C3
c
5 bar abs, 25 C
tri
me
hio
c
i
o
]
l.-%
[Vo
50
60
40
70
O2
AIT [C] at Pinitial = 5 bar abs for Propene/O2 mixtures

4.46
95.54
0
280
7
93
0
270
10
90
0
270
20
80
0
260
30
70
0
260
40
60
0
250
50
50
0
250
60
40
0
250
[Vo
l.-%
]
CO
Propene
[Vol.-%]
48
80
90
100
Induction times of two mixture compositions lying in the yellow

range of the explosion diagram at 5 bar abs
Propene= 5 vol.-%,
O2 = 95 Vol.-%
C3H6-O2-N2=20-40-40
C3H6-O2-N2=5-95-0
10
90
[Vo
l.-%
]
1100
1200
60
Temperature, K
sto
1000
900
70
Calculation by A.A. Konnov,

Department of Mechanical Engineering
Vrije Universiteit Brussel (VUB),
based on the rate coefficients for all elementary reactions
sto
80
ic
70
tive
na
o
60
t
e
f d sion
o
2
ge plo
3H
ran ex
+
O
3C
->
O2
1.5
range of
+
H6
3
C
ic
5 bar abs, 25 C
etr
m
o
i
h
O2
800
50
40
Propene= 20 vol.-%,
O2 = 40 vol.-%,
80 N2 = 40 vol.-%
]
l.-%
[Vo
ich
iom
et
st
r ic
oi
ch
C
3H
io
m
6 +
et
4.
r ic
5
O
C
2 3H
>
6 +
3
CO
3
O
2 +
2 >
3
H
3
2O
CO
+
3
H
2O
30
1
0
700
100
20
Induction time, ms
50
40
30
20
90
propen
e/air-m
ixtures
10
100
0
10
20
30
40
50
60
70
49
80
90
100
Is heat explosion a realistic assumption for what

happens in yellow range of the explosion triangle ?
- temperatures achieved by adiabatic compression lie well above
the autoignition temperature, i. e. heat explosion is possible in
principle
- but: induction times calculated on the basis of the rate coefficients
of the elementary reactions are still far too long
(The induction time would have to be of the order of 0.1 ms or even less,
otherwise the flame front of the initial deflagration would have run already
through the thin shell of unreacted mixture before the heat explosion can
develop).
- including the influence of thermal radiation from the cental part of the sphere
does not give a substancial reduction in induction times either (calculation of
Hans Pasman)
Not really clear what happens in the

yellow range of the explosion triangle
50
Summary on explosion regimes of combustible/air/O2 mixtures

ignited with a thermal ignition source in vessel-like geometry
There are three explosion regimes: deflagration, heat explosion, detonation
The detonative range in the 20 l sphere is discernibly smaller than the
potentially detonative range
What really happens in the heat explosion regime is not yet really understood,
maybe the pressure time curves are just due to failed DDTs
The heat explosion regime becomes much smaller with increasing initial
pressure
Mixtures of type combustible/air seem to remain deflagrative even at elevated
pressures and temperatures.
However, the data collected so far do not allow to exclude that the detonative
regime will expand down to the air line when going to extremely high initial
pressures and large vessel volumes.
51
Introduction


in 20 l vessels
100, 500, 2500 l vessels

52
Schematic pressure-time trace of a detonative pressure pulse

hot reaction products
flamefront coupled
with shockfront, v >> vsoundl
unburned gas mixture
pressure sensor, flush

with inner surface of wall
von Neumann spike, about twice as high as PCJ

50
width < 1 s => much less than cycle time of any
eigenfrequency of the containment
=> not noticed by the containment and not
registered by the fastest available pressure sensors
45
Pressure/Pinitial
40
35
30
PCJ , about twice the deflagration pressure ratio of the gas mixture
25
20
15
10
5
0
width of Taylor expansion fan: ca. 20 s 50 s in laboratory

scale containments, longer in structures of larger dimensions
Leading edge of
detonation peak
has almost infinite
slope (rise time < 1s)
(less than one quarter of the time interval over which the peak has already propagated)
deflagration pressure ratio

of gas mixture
Pinitial
time
53
Pressure-time diagrams recorded during a detonation in

a long pipe at different locations (1/2)
Example: Propane/O2, stoichiometric, Pinitial = 6 bar abs, Tinitial = 20 C, pipe 25x2, L = 5 m, side-on pressure
Pdet 35*Pinitial
(same value at all sensors)
v = s/t
= 0.945m/0.375ms
= 2519 m/s
location of ignition
1025 mm
pipe: 25 x 2
P1
P2
P3
P4
1970 mm
2915 mm
3855 mm
5000 mm
54
Pressure-time diagrams recorded during a detonation in

a long pipe at different locations (2/2)
300
Pressure [bar abs]
Experiment:
Ethylene/air stoichiometric,14 bar abs,
20 C, side-on pressure,
pipe: i = 44.3 mm, o = 48.3 mm,
L = 8 m,
turbulence enhancer in front of ignition
source to reduce run-up distance
250
P3
200
150
100
50
0
22
23
24
Time [ms]
25
26
Pressure [bar abs]
300
P2
200
s = 2 m
t = 1.033 ms
vdet=s/t=1936 m/s
100
22
23
24
Time [ms]
25
26
Pressure [bar abs]
500
P1
400
300
s = 1.5 m
t = 0.796 ms
vdet=s/t=1883 m/s
200
100
0
location of ignition
22
P3
23
24
Time [ms]
2m
26
P1
P2
25
1.5 m
0.5 m
55
Qualitative consideration: differences between the pressures

produced in a long pipe by a deflagration and by a detonation (2/2)
Example: Propane/air, stoichiometric, Tinitial = 20 C, explosion pressure ratio: 9.5 (simplification: no heat loss to wall)
Detonative Explosion (predetonation stage necglected)
flamefront coupled
with shockfront, v >> vsoundl
unburnt gas mixture
Pex/Pinitial
Location of
ignition
25
20
15
10
5
0
Pdet = 2*9.5*Pinitial
P = 9.5*Pinitial
extension:
in space ca. 10 20 cm
In time ca. 20 50 s
P = Pinitial
distance from left pipe end
P is different at different locations in the pipe:

- behind shockfront: P = 9.5*Pinitial (9.5 is explosion pressure ratio of mixture)
- at shockfront:
P = 2*9.5*Pinitial (i.e. about twice as high as behind shockfront)
- in front of shockfront: P =
Pinitial
(reason: reaction gases would like to expand into region ahead of shockfront, but speed of sound in
hot reaction gases only about 1000 m/s whereas shockfront propagates with about 1700 m/s)
56
Detonation pressures Pdet in long pipes (L >> Lpredet, no precompression)
Stable Detonation, side-on pressure (i. e. in plane perpendicular to shockfront)
detonation
front
Pdet = Pinitial * PCJ
pressure sensor,
flush with inner
surface of wall
PCJ is the so-called

Chapman-Jouguet-pressure ratio
of the explosive gas mixture
Stable Detonation, reflected pressure (i. e. in plane parallel to shockfront, e. g. blind flange)
pressure sensor,
flush with inner
surface of flangel
detonation
front
Pdet = Pinitial * PCJ * Freflec
2 Freflec 2.5
Important:
The pipe directly ahead of the blind flange
experiences the reflected pressure as well. The
length of this section corresponds to the axial
extension of the taylor expansion fan.
(In lab-scale equipment of up to 5 m length a
section of about 3 pipe diameters from the blind
flange back into the pipe is affected, in longer
pipes this section increases).
57
Detonation pressures Pdet in long pipes (L >> Lpredet, no precompression)

(continued)
Side-on pressure at location where Deflagration-to-Detonation transition (DDT) occurs
Pdet = Pinitial * PCJ * FDDT
location of
ignition
1.5 FDDT 2
flame front of initial first occurrence of ignition

deflagration has accelerated by adiabatic compression
to a very high speed in precompressed mixture;
generation of shock front
coupled with flame front,
propagating leftwards
Reflected pressure, if DDT occurs directly in front of blind flange (a very rare case!)
1.5 FDDT 2
Pdet = Pinitial * PCJ * FDDT * Freflec

flame front of initial
deflagration has accelerated
to a very high speed
first occurrence of ignition

by adiabatic compression
in precompressed mixture;
2 Freflec 2.5
Important:
The pipe directly ahead of the blind flange
experiences the reflected pressure as well. The
length of this section corresponds to the axial
extension of the taylor expansion fan.
(In lab-scale equipment of up to 5 m length a
section of about 3 pipe diameters from the blind
flange back into the pipe is affected, in longer
pipes this section increases).
58
25
40
20
30
15
20
10
Pcj/Pinitial at 5 bar abs, 25 C

Pcj/Pinitial at 5 bar abs, 200C
measured defl. pr.-ratios Pex/Pinitial at 5 bar abs, 25C
measured defl. pr.-ratios Pex/Pinitial at 5 bar abs, 200C
10
pex/pinitial (deflagration pressure

ratio)
50
Solid lines:
Calculated Chapman-Jouguet
pressure ratios for pinitial = 5 bar abs
(by Prof. M. Braithwaite with
software package STANJAN)
Symbols:
Measured deflagration pressure
ratios (scale on right side of plots)
The values are just about half of the

Chapman-Jouguet pressure ratios!!
pcj/pinitial
P
CJ
(Chapman-Jouguet
pressure
80
40
20
30
15
20
10
10
5
calculated Pcj/Pinitial at 5 bar abs, 25C
measured defl. pr.-ratios Pex/Pinitial at 5 bar abs, 25 C
0
0
2
4
6
8
10
12
14
16
18
20
Propene conc. in stoich. Propene/O2/N2-mixture [vol.-%]
59
ratio)
10
20
30
40
50
60
70
Propene concentration in Propene/O2-mixture [vol.-%]
(Chapman-Jouguet
ratio)
divided by ppressure
initial)
pex /pinitial (deflagration pressure
pcj /pinitial
CJ pressure
(Chapman-Jouguet
(Chapman-Jouguet
ratio)
divided by p pressure
initial )
Chapman-Jouguet pressure ratios PCJ calculated by STANJAN

Example: Propene/O2/N2
17,5
30
15
25
12,5
20
10
15
7,5
5
10
calculated Pcj/Pinitial at 5 bar abs, 25 C
calculated Pcj/Pinitial at 5 bar abs, 200 C
2,5
measured defl. Pr.-ratios Pex/Pinitial at 5 bar abs, 25C
pex /pinitial (deflagration pressure

ratio)
35
p cj /p initial
CJ pressure
(Chapman-Jouguet
divided by Ppressure
initial )
(Chapman-Jouguet
ratio)

Example: Methane/O2/N2
measured defl. Pr.-ratios Pex/Pinitial at 5 bar abs, 200C
0
10
20
30
40
50
60
70
Methane concentration in Methane/O2-mixture [vol.-%]
80
20
15
10
CJ
PCJ Chapman-Jouguet
detonation
pressure ratio
(Chapman-Jouguet
pressure ratio)
5 bar abs, 25 C
5 bar abs, 200 C
0
0
5
10
15
20
Methane concentration in Methane/air-mixture [vol.-%]
60
20
10
15
7,5
10
calculated deto natio n pr.-ratio s P CJ/P initial at 1bar abs, 20C
pex/pinitial deflagration pressure

ratio)
pcj /pinitial
(Chapman-Jouguet pressure
divided by p initial )

Example: H2/O2/N2
2,5
calculated deto natio n pr.-ratio s P CJ/P initial at 5 bar abs, 20C

10
20
30
40
50
60
70
80
90
H2 concentration in H2/O2-mixture [vol.-%]
p cj /p initial
(Chapman-Jouguet pressure
divided by p initial )
0
100
20
10
15
7,5
10
calculated deto natio n pr.-ratio s P CJ/P initial at 1bar abs, 20C

measured pex/pinitial at 1bar abs, 20 C
measured pex/pinitial at 5 bar abs, 20 C
measured pex/pinitial at 5 bar abs, 200C
0
0
10
20
30
40
50
60
70
H2 concentration in H2/Air-mixture [vol.-%]
2,5
p ex/p initial deflagration pressure

ratio)
measured pex/pinitial at 1bara bs, 20 C
0
80
61
Chapman-Jouguet pressure ratios PCJ calculated on basis of

detonation velocity
PCJ = pdet /pinitial = ( *M2+1)/(+1)
( * M2)/(+1)
= (D2 * MW)/(R*Tinitial*(+1))
= /pinitial * D2/(+1)
meaning of symbols: M = D/c
D
c = ( * pinitial /)0.5
MW
R=8.314
Tinitial , pinitial
pdet
Mach number
propagation speed of detonation [m/s]
speed of sound in the unreacted gas mixture [m/s]
density of unreacted gas mixture [kg/m3]
mean molar mass of unreacted gas mixture [kg/mol]
universal gas constant [J/(mol*K)]
cp/cv, for diatomic gases = 1.4
initial temperature [K], initial pressure [Pa] of gas mixture
side on pressure of stable detonation
Remarks:
For using STANJAN various thermodynamic parameters of the reaction components
must be known. If these are not available, the detonation velocity is experimentally
easily aminable with high precision by recording the side-on pressure of the
propagating detonation at different axial locations in the pipe with piezoelectric
pressure sensors. Since the absolute signal value, which is actually the quantity one
is looking for, is often prone to errors, one has to use the bypass over the speed.
62
General remarks on Chapman-Jouguet pressure ratios PCJ

Chapman-Jouguet pressure ratios can be calculated by e.g. STANJAN
(freeware, STANJAN Chemical Equilibrium Solver v4.01, Stanford University 2003)
If thermodynamic quantities required by STANJAN are not available for all
components of the considered explosive gas mixture, PCJ can be calculated on
the basis of the experimentally determined detonation speed.
Chapman-Jouguet pressure ratios are with good precision twice as high

as the explosion pressure ratio found for deflagrative explosion:
- stoichiometric combustible/air- mixtures at 20C:
- stoichiometric combustible/O2-mixtures at 20 C:
16 PCJ 20
30 PCJ 50
Chapman-Jouguet pressure ratio is inversely proportional to the absolute initial

temperature. (Propagation speed of detonation is almost independent of Tinitial !)
63
Example: bulging out of a pipe end due to reflected pressure

Experiment:
Acetylene, 8 bar abs, 20 C, pipe
220.9 x 8.2, i.e. i = 204.5 mm,
material: St35.8, Rp0.2 = 230 N/mm2,
PRp0.2=184 bar, L = 8 m, detonative
ignition source to reduce run-up
distance;
side-on pressure ca. 400 bar,
reflected pressure ca. 800 bar
Increase of tube diameter
directly in front of blind
flange to 117 % of original
value
no increase in diameter in
the section that has only
been exposed to the sideon pressure
64
Example: Rupture of pipe end due to reflected pressure

Experiment:
Ethylene/air stoichiometric, 17 bar
abs, 20 C, pipe 76.1 x 2.6, i.e. i =
70.9, material: 1.4541, Rp0.2 = 210
N/mm2, PRp0.2=154 bar, L = 8 m;
side-on pressure ca. 340 bar,
reflected pressure ca. 765 bar
increase in diameter to
105 % of original value in
the section that has only
been exposed to the sideon pressure
end of tube, which was
exposed to the reflected
pressure, is fragmented
65
Example: bulging out of a pipe wall due to the

extra pressure at the point where the DDT occurs
Experiment:
Acetylene, 24 bar abs,
20 C, pipe 3.17 x 0.5,
i = 2.17 mm, material:
1.4541, Rp0.2 250 N/mm2,
PRp0.2 1152 bar,
kaltgezogen, L = 10 m
Localized bulging of tube is

attributed to the location of
the deflagration to detonation
transition
66
Introduction


in 20 l vessels
100, 500, 2500 l vessels
67
How does precompression (pressure piling) come

into existence?
During the initial deflagrative stage of the explosion each volume element that
reacts through expands by a factor equal to the explosion pressure ratio at the
expense of the volume available for the yet unreacted mixture.
If this volume is large compared to the volume occupied by the reaction gases
formed during initial deflagrative stage, the pressure in the yet unreacted
mixture will almost stay the same as at the moment of ignition (P = Pinitial).
However, if this volume is small, the yet unreacted mixture will be
precompressed. When the deflagration to detonation transition then occurs, the
detonation will not propagate in a mixture at pressure P = Pinitial, but at P =
Fprecomp * Pinitial
Fprecomp may attain any value between 1 and the explosion pressure ratio of the
gas mixture (up to 10 for combustible/air-mixtures, up to 24 for combustible/O2mixtures).
The temperature rise that comes along with the fast and hence adiabatic
compression will slightly alleviate the detonative pressure Pdet. This is
accounted for by the Factor Ftemp (details see next slide)
In the formulae given beforehand for Pdet, Fprecomp and Ftemp will appear as
additional factors
68
Temperature factor Ftemp

The temperature factor Ftemp accounts for the reduction of the Chapman-Jouguet
pressure ratio due to the rise in temperature of the unburned mixture brought
about by the precompression during the initial deflagrative stage of the explosion.
I: Temperature Tfinal of unburned mixture attained by adiabatic compression:
T final = Tinitial
final
pinitial
( 1 )
= Tinitial F precomp
( 1)
with: = cp/cv ( = 1.4 for ideal gases)

Tinitial = temperature at moment of ignition
II: Chapman-Jouguet pressure ratio is inversely proportional to the temperature the

gas mixture exhibits at the moment of detonation (here denoted by Tfinal).
Ftemp results from the combined effect of I: and II:
Ftemp
Tinitial 1
=
=
T final F precomp
( 1)
69

Tinitial = 25 C = 298 K
Pfinal/Pinitial
Tfinal [C] for different values of = cp/cv

= 1,4
= 1,3
= 1,2
= 1,1
1,2
40,9
37,8
34,2
30,0
1,5
61,6
54,2
45,8
90,3
76,7
169,8
Pfinal/Pinitial

= 1,4
= 1,3
= 1,2
= 1,1
1,2
225,3
220,3
214,6
207,9
36,2
1,5
258,1
246,4
233,1
217,8
61,5
44,4
303,6
282,0
257,9
230,8
137,3
102,5
65,0
429,9
378,3
322,9
263,5
224,2
177,6
128,7
77,7
516,2
442,2
364,6
283,7
266,8
208,5
148,4
87,0
583,8
491,3
395,9
298,4
10
302,3
234,0
164,4
94,4
10
640,2
531,7
421,3
310,1
12
333,1
255,8
177,9
100,5
12
689,1
566,3
442,7
319,9
14
360,4
274,9
189,6
105,8
14
732,4
596,7
461,3
328,2
16
385,0
292,1
200,0
110,4
16
771,5
623,9
477,8
335,6
18
407,6
307,6
209,4
114,6
18
807,2
648,6
492,7
342,1
20
428,4
321,9
218,0
118,3
20
840,2
671,3
506,3
348,1
25
474,5
353,4
236,6
126,3
25
913,5
721,2
535,8
360,8
30
514,5
380,3
252,3
133,0
30
977,0
763,9
560,8
371,4
35
550,0
403,9
266,0
138,7
35
1033,2
801,4
582,5
380,5
40
582,0
425,1
278,1
143,7
40
1084,0
835,1
601,7
388,5
45
611,2
444,3
289,0
148,2
45
1130,5
865,6
619,1
395,6
50
638,2
462,0
299,0
152,3
50
1173,4
893,6
634,9
402,0

final
pinitial
( 1)
70
Example 1: precompression in a pipe

P3
P1
P2
deflagration
first occurrence
detonation front
precompressed
unburned gas mixture
If the pipe is only slightly longer than the predetonation distance, the unburned
gas which is remaining at the moment when the DDT occurs may have been
precompressed by a factor Fprecomp by the initial deflagrative stage of the
combustion.
Fprecomp may attain any value between 1 and the explosion pressure ratio of the
gas mixture (up to 10 for combustible/air-mixtures, up to 24 for combustible/O2mixtures).
The temperature rise that comes along with the fast and hence adiabatic
compression will slightly alleviate the detonative pressure Pdet. This is
accounted for by the Factor Ftemp
71
Example 2: precompression in the vessel-pipe configuration
vessel
pipe, slightly longer than Lpredet
Location
of ignition
hot, gaseous
reaction products
Precompressed, unburned gas mixture
deflagrative
flamefront
If in the vessel the DDT does not happen because of the unfavourable L/D-ratio
and if the volume of the pipe is small compared to the volume of the vessel, the
precompression factor may come close to the highest possible value, i. e. the
explosion pressure ratio.
The highest possible value is usually not attained, because the available time is
too short to pressurize the pipe up to the same pressure as in the vessel.
This configuration occurs frequently in practical applications, because vessels
often have nozzles onto which short pipe segments with a block valve are
welded.
72
Example 3: precompression in empty vessels

(i.e. without packing inside)
vessel (here spherical, L/D = 1)
Location of
ignition
hot reaction
products
Precompressed, unburned mixture
First occurrence of detonation front

Flamefront of initial deflagration
If there is a transition from deflagration to detonation in the vessel,

precompression will almost always occur, because the diameter is usually not
much larger than the predetonation distance. The precompression factor
may attain the highest possible value, i. e. the explosion pressure ratio.
Reference: GCT report 105.0428.3N, 106.0104.3I

73
Detonation pressures Pdet in pipes with precompression (1/2)
Side-on pressure (i. e. in plane perpendicular to shockfront)
detonation
front
Pdet = Pinitial * PCJ* Fprecomp * Ftemp
pressure sensor,
flush with inner
surface of wall
Reflected pressure (i. e. in plane parallel to shockfront, e. g. blind flange)

pressure sensor,
flush with inner
surface of flangel
detonation
front
Pdet = Pinitial * PCJ * Freflec* Fprecomp * Ftemp

Important:
about 3 pipe diameters from the blind flange
back into the pipe this higher pressure also
acts on the wall of the pipe!
74
Detonation pressures Pdet in pipes with precompression (2/2)
Side-on pressure at location where Deflagration-to-Detonation transition (DDT) occurs
Pdet = Pinitial * PCJ * FDDT * Fprecomp * Ftemp
location of
ignition
flame front of initial first occurrence of ignition

deflagration has accelerated by adiabatic compression
to a very high speed in precompressed mixture;
Reflected pressure, if DDT occurs directly in front of blind flange (a very rare case!)
Pdet = Pinitial * PCJ * FDDT * Freflec * Fprecomp * Ftemp

deflagration has accelerated
to a very high speed
first occurrence of ignition

by adiabatic compression
in precompressed mixture;
Important:
about 3 pipe diameters from the blind flange
back into the pipe this higher pressure also
acts on the wall of the pipe!
75
Detonation pressure Pdet acting on the wall of a vessel (almost

always with precompression)
Pdet =
Initial pressure in vessel at moment of ignition (Pinitial)

x Chapman-Jouguet pressure ratio of the mixture at the temperature
the mixture exhibits at the moment of ignition (PCJ)
x Precompression factor (FPrecomp)
x Temperature factor (FTemp)
x Factor accounting for reflection of stable detonation at wall (Freflec )
x Factor accounting for extra pressure if DDT happens directly
before wall (FDDT), otherwise factor is 1
Pdet = Pinitial * PCJ * Fprecomp * Ftemp * Freflec * (FDDT or 1, depending on where DDT happened)
76
Example: Rupture of the wall of a pipe installed in the

vessel-pipe configuration due to precompression
detonation in this
section,
outer diameter
is 102 % to 110 %
of original value
closed Valve
(to vacuum pump)
10x2 pipe (1.4541)
rupture pressure in hydraulic test: 3480 bar
rupture at location
of DDT in
precompressed
mixture
only deflagration
in this section,
outer diameter
is not increased
Rest of the bend
has been burned
off by outflowing
hot reaction gases
20 l sphere
Pinitial = 25 bar abs,

Tinitial = 250 C
99.5 vol.-% N2O
0.5 vol.-% Tetradecane
Ignition in center of sphere
77
Introduction


in 20 l vessels
100, 500, 2500 l vessels
78
Precompression factors Fprecomp in the heat explosion and

detonative range of explosion diagrams of Propene/O2/N2
at 5 bar abs, 25 C and 200 C
Propene/O2-mixture
stoichiometric Propene/O2/N2-mixture
(Propene:O2=1:4.5)
15
5 bar abs, 25 C
20
pheat_initial /pF
initial or pdet_initial /pinitial
5 bar abs, 200 C
15
5 bar abs, 25 C
5 bar abs, 200 C
10
precomp
Fprecomp
pheat_initial /pinitial
or pdet_initial /pinitial
25
10
5
0
0
10
20
30
40
Propene concentration in Propene/O2-mixture [vol.-% ]
50
0
0
10
15
Propene conc. in (Propene:O2=1:4.5)/N2-mixture [vol.-% ]
orange filled symbols: heat explosion

blue and red symbols: detonation
Note: on stoichiometric line at 200 C only deflagration for one test with 7.8 vol.-% Propene
79
20
Upper limit for precompression factors

The precompression factors attain at maximum
the deflagration pressure ratio!
Example for Propene/O2-mixtures:

25
1 bar abs, 25 C
5 bar abs, 25 C
20
10 bar abs, 25 C
1 bar abs, 200 C
5 bar abs, 200 C
0
0
10
40 vol.-%: stoichiometric
composition for
C 3H6 + 1.5 O2 -> 3 CO + 3 H 2
10
10 bar abs, 200 C

25 vol.-%: stoichiometric composition
for C3H6 + 3 O2 -> 3 CO + 3 H 2O
18.18 vol.-%: stoichiometric composition

for C3H6 + 4.5 O2 -> 3 CO2 + 3 H 2O
pex/pinitial
15
20
30
40
50
60
70
80
90
80
Example: Detonative pressure pulses Pdet acting on the wall of a 20 l

sphere in case of Propene/O2/N2, Pinitial = 5 bar abs, Tinitial = 25C
(1.4 1)
sto
ic h
io
m
et
st
ric
oi
ch
C
3H
io
m
6 +
et
4.
ric
5
O
C
2 3H
>
6 +
3
CO
3
O
2 +
2 3
>
H
3
CO
2O
+
3
H
2O
-%
]
[Vo
l.
2
50
Pressure at border line of

detonative range about factor
6 to 17 larger than in center
because of precompression.
80
H
C3
O2
CO
l.-%
ic
st o
ric
et
m
hio
+
6
1 .5
3
->
+3
[Vo
70
ex
ra
O2
50
60
1.4
1
Pdet = 5barabs 20 10
2.25 1.75 = 2039barabs
10 (1.41)
1.4
1
Pdet = 5barabs 32 1.1
2.25 1 = 385barabs
0
1
.
1
100
(1.4 1)
1.4
1
10
Pdet = 5barabs 37 1
2.25 1 = 416barabs
90
1
(1.41)
1.4
1
20
Pdet = 5barabs 44 1
2.25 1 = 495barabs
80
(1.4 1)
1
1.4
1
30
Pdet = 5barabs 47 4
2.25 1 = 1627barabs
70
(1.4 1)
4
1.4
40
ve
1
ati
n
o
=
P
5
barabs
40
20
2.25 1.75 = 6692bara

60
et
det
f d i on
o
20

s
e
H
ng plo
range of
5 bar abs, 25 C
40
30
20
90
propen
e
/a ir-mi
xture s
100
0
The highest value attainable

by Pdet/Pinitial is about 1300 !!
10
0
10
20
30
40
50
60
70
Propene C 3H 6 [Vol.-%]
(1.4 1)
80
90
100
1.4
1
Pdet = 5barabs 27 13
2.25 1.75 = 3320barabs
13

81
Summary concerning pressure load

Pressures acting on the wall may be a factor 1300 higher than the initial
pressure in the mixture. The main reason is that in vessels the highest
theoretically possible precompression factors (=deflagration pressure ratios)
actually do occur !!
Pressure at the border line of detonative range about factor 6 to 17 larger
than in center because of precompression!
(I.e. in the detonative regime the lowest pressure load on the wall is
generated by mixtures in the vicinitiy of the stoichiometric combustible/O2mixtures)
The obscure effects talked about in non-public communication seem to be
explainable with precompression
Since in the empty vessel the static equivalent pressure Pstat of the
detonative pressure pulse Pdet is at least 0.5*Pdet, the lower limit for the
required pressure resistance of a detonation pressure proof empty vessel is
known.
Since this lower limit is extremely high,it is questionable whether the design
of a detonation pressure proof empty vessel is economically justifiable.
82
Introduction


in 20 l vessels
100, 500, 2500 l vessels

83
Vessels used for the experiments

Characteristic parameters of all vessels:
100 l vessel: L = 1309 mm; i = 327.2 mm; L/ i =4.0; distance P1-P3 = 1343 mm
500 l vessel: L = 2146 mm; i = 570 mm;
L/ i =3.76; distance P1-P3 = 2309 mm
2500 l vessel: L = 3644 mm; i = 956 mm;
L/ i =3.8; distance P1-P3 = 3866 mm
Sketch of 2500 l vessel (the others are alike, only smaller):

4021
weld neck flange

NW150, PN160
P1
1938
1928
3866
H.-P. Schildberg, 41st UKELG meeting, 13 May 2008, Shell Technology Centre
P2Thornton
s=4
0
L = 3644
346
torospherical head
175
P3
weld neck flange
NW300, PN160
wall
thickness
s = 30
34
outer diameter o = 1016
location
of ignition
3718
3040 (cylindirical section)
332
torospherical head
inner diameter i = 956
128
84
Examples for pressure/time recordings by sensor P3

in 100 l and 500 l vessel
500
Pressure [bar abs]
400
Experiment:
v = s/t
Ethane=22.2 vol.-%,
= (2*1.343m)/2 ms O2=77.8 vol-%,
= 1343 m/s
300
t = 2ms
Tinitial = 25 C,
100 l vessel, L/D = 4
File: EFOV108K.DAT
200
100
0
65
Pressure [bar abs]
1000
750
500
70
75
80
Time [ms]
85
90
Experiment:
v = s/t
= (2*2.309m)/3.66msEthane=11.4 vol.-%,
O2=40 vol.-%, N2=48.6 vol.-%,
= 1261m/s
t = 3.66ms

Tinitial = 25 C,
500 l vessel, L/D = 3.8
The peaks are due to

the shockwave of the
detonation which after
having reached the
one end of the vessel
is reflected backwards
into the hot reaction
gas, travels until
reaching the opposite
torospherical head of
the vessel, is again
reflected and so on
File: EFOV150K.DAT
250
0
65
70
75
80
Time [ms]
85
90
85
Results of tests with stoichiometric Ethane/O2/N2mixtures in vessels ranging from 20 l to 2500 l

Tests with Pinitial = 4 bar abs
O2-conc. in
stoichiometric
mixture [vol.-%]
course of explosion
20 l sphere
30
deflagrative
35
heat explosion
40
detonative
2500 l cylinder,
L/D=3.8
deflagrative
detonative
Tests with Pinitial = 8 bar abs

O2-conc. in
stoichiometric
mixture [vol.-%]
course of explosion
20 l sphere
30
deflagrative
35
detonative
40
detonative
100 l cylinder,
L/D=4
500 l cylinder,
L/D=3.76
deflagrative
deflagrative
detonative
detonative
86
Summary of comparison of explosive regimes of

combustible/O2/N2 mixtures in vessels of different
volume
For stoichiometric mixtures there is - within experimental accuracy no change in the critical composition (transition from deflagrative to
detonative combustion) when varying the vessel volume over two
orders of magnitude !!!
For combustible/O2 mixtures the potential change of the critical

compositions with vessel volume could not yet be studied.
87
Introduction


in 20 l vessels
100, 500, 2500 l vessels

88
Experimental setup to determine predetonation distances

of Propene/O2-mixtures in a i = 76.3 mm pipe at pinitial = 5
bar abs, 25C
1000
2000
2000
2000
7000 mm, PN160, DN80, o = 88.9 mm, i = 76.3 mm, s = 6.3 mm

location of
thermal ignition (the lengths of the tube segments are specified as from centre of gasket to centre of gasket,
i. e. the actual tubes are slightly less than 1000 mm or 2000 mm, respectively)
source
89
Position of pressure sensors in the i = 76.3 mm pipe

location of
thermal ignition source
P1
P2
100
200
300
400
P3
P4
P5
100
P6
100
100
P7
P8
100
P9
250
100
P10
P11
P12
P13
P14
P15
P17
P16
P17
1000
500
1000
750
2000
1000
1000
2000
1250
1500
1750
2000
Enlarged section of first two pipe segments:

location of
P1
P2
100
200
300
400
P3
P4
P5
100
100
P6
100
P7
100
P8
100
P9
P10
250
P11
P12
P13
P14
P15
P16
500
750
1000
1000
1250
1500
1750
2000
Pressure sensors used (all piezoelectric, supplied by PCB):

PCB M112A05, 0 - 345 bar, ca. 16 pC/bar
PCB M113A03, 0 - 1034 bar, ca. 5 pC/bar
PCB M119A11, 0 - 5520 bar, ca. 3.6 pC/bar
90
Predetonation distances of Propene/O2 in a i = 76.3 mm

pipe at 5 bar abs, 20 C
100
Predetonation distances of Propene/O2
at 5 bar abs, 20C; in 7 m long tube,
76.3 mm internal diameter.
80
70
60
50
40
30
20
10
25 vol.-% is stoichiometric
for CO and H2O formation
18.18 vol.-% is stoichiometric

for CO2 and H2O formation
Predetonation distance
[length/diameter]
90
0
0
10
15
20
25
30
35
40
Propene concentration in Propene/O2- mixture [vol.-% ]
45
50
Course of explosion in 20 l sphere, i = 340 mm:

defl.heat expl. (?)
10
DDT
15
20
deflagration
25
30
35
40
45
50

Note: in 7 m long pipe with i = 76.3 mm no DDT for Propene conc. 4 vol.-% (i.e. predet.distance > L/D=92)
in 11 m long pipe with i = 86 mm no DDT for Propene conc. 50 vol.-% (i.e. predet.distance > L/D=127)
91
Predetonation distance [length/diameter]
Predetonation distances of stoichiometric Propene/O2/N2

in a i = 76.3 mm pipe at 5 bar abs, 20 C
100
Predetonation distances of stoich. Propene/O2/N2
(for CO2- and H2O-formation) at 5 bar abs, 20C;
in 7 m long tube, 76.3 mm internal diameter.
90
80
70
60
50
40
30
20
10
0
0
3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20
Propene concentration in stoich. Propene/O2/N2- mixture [vol.-% ]
Course of explosion in 20 l sphere, i = 340 mm:

deflagration heat expl. (?)
DDT
10 11 12 13 14 15 16 17 18 19 20
Propene concentration in stoichiometric Propene/O2-mixture [vol.-%]

92
Example for how to determine the predetonation distance

in pipes from pressure/time diagrams
Example: Propene/O2, 5 bar abs, 20 C, 41 vol.-% Propene, i=76 mm, L = 7 m, ignition at t = 0 ms
location of
300 1500 mm
200
100
0
11
11.5
800
600 1750 mm
400
200
0
11
11.5
800
600 2000 mm
400
200
0
11
11.5
400
300 6000 mm
200
100
0
11
11.5
1500
P5
1750
P6
P7
2000
4000
12
12
12
5000
6000
7000
13,5
12.5
12.5
12.5
13
13
13
13.5
13.5
13.5
14
14
14
Time of arrival of retonation or detonation wave [ms]
200
150 500 mm
100
50
0
11
11.5
200
150 800 mm
100
50
0
11
11.5
300
250 1250 mm
200
150
100
50
0
11
11.5
1250
P4
ards
800 1000
P3
reto
nati
on p
eak
prop
aga
ting
Pressure [bar abs]
500
P2
bac
kw
P1
13,25
Detonation wave, v = 2591 m/s
13
Retonation wave, v = 1612 m/s
12,75
12,5
12,25
12
11,75
11,5
12
12.5
13
13.5
14
1000
2000
3000
4000
5000
6000
Distance of pressure sensor from ignition source (left blind flange) [mm]
12
12.5
13
13.5
14
pressure sensor
defect
12
12.5
13
13.5
14
13.5
14
v = s/t=0.25m/0.1ms=2500m/s
Predetonation distance is given by

intersection of distance-time curve of
retonation and detonation wave.
(in this example: Lpredet = 156050 mm)
v = s/t=4.25m/1.64ms=2591m/s
12
12.5
Time [ms]
13
93
7000
Clarification of an apparent contradiction with respect

to predetonation distances
Lean mixtures that require up to 760 mm (L/D 10) predetonation distance in a pipe and
rich mixtures that require up to 1500 mm (L/D 20) predetonation distance in a pipe
manage to run up to detonation in a sphere with radius 170 mm !!!
At first glance this is an unexpected result:
In the pipe the unburnt gas is made stream turbulent between rigid walls by expansion of the
reaction products. This should encourage flame acceleration.
Hence, if for some mixture the predetonation distance in a pipe is larger than the radius of the
sphere, one would not expect this mixture to run up to detonation in the sphere.
Possible reasons that mixture detonates in sphere although in pipe lpredet >> radius of sphere:
- In the sphere there is massive precompression (up to factor of 12 on lean side and up to
a factor of 20 on rich side of detonative range) which is absent in long pipes.
Predetonation distances reduce with increasing pressure (see next slide).
- Based on the precompression difference between lean and rich side it qualitatively makes
sense that on the rich side mixtures which exhibit about twice the predetonation distance
in a pipe as mixtures on the lean side, still run up to detonation in the sphere
- Because precompression in the sphere is adiabatic, the temperature of the mixture rises
substantially (see next slide). Possibly this also contributes to reducing the predetonation
distance (????)
- In sphere sonic pressure waves of initial deflagration are reflected backwards and
interfere with combustion zone, which might accelerate the flame. In long pipes this effect
should almost be absent.
94
Predetonation distances as function of initial pressure

C2 H4 + air, 20 C, stoic
hiom., i = 50 mm
predetonation distance sD [m]
2C
O+
+N
O2 ,
O,
CH
1
2
0.5
+O
2
0.3
0.2
C
2
0.1
H
2
,2
0.5
,4
C
i
00
C
,3
,
7 .7
i =
C
15
,
m
m
i =
15
mm
,3
7.
7
=1
m=
5m
m
m=
m
15
m
m
Empirical law for the

pressure dependence of
the predetonation distance:
0.5
sD =
const.
m
(Pini)
=0
0.4
=0
.61
C
,
0.03
0.2 0.3
=1
5m
m
i =
79
mm
i
0.05
38
C,
+5
.67
O
40
C,
m = 0.057
.76
=0
.7 6
1
2 3
5
10
20 30
initial pressure Pinitial [bar abs]
50
C2H4 + air, 20 C, stoichiom., i = 50 mm, L = 22 m (I. Ginsburg and W. L. Bulkley, Chemical Engineeri
ng Progress,
Vol.
59,
no.
2,
p.
82
86
(1963)
= 15 mm, L = 2.94 m
2 CO + O , 40 C,
2
CH4 + 5.67 O2 , 40 C i = 15 mm, L = 2.94 m
H2 + O2, 200 C,
i = 15 mm, L = 2.94 m
H2 + O2, 37.7 C,
i = 15 mm, L = 2.94 m
C2H2 + 4 O2, 37.7 C, i = 15 mm, L = 2.94 m
L.E. Bollinger, M. C. Fong and R. Edse, American Rocket Society:

ARS Journal (Easton, Pa) 31, p. 588 - 595 (1961)
H2 + N2O, 37.7 C, i = 79 mm , L = 2.94 m (L.E. Bollinger, J. A. Laughrey and R. Edse, American RocketSociety:
Pa) 32,p. 81 - 82 (1962)
H.-P. Schildberg, 41st UKELG meeting, 13 May 2008, Shell Technology

Centre Thornton
ARS Journal
(Easton,
95

Pfinal/Pinitial

= 1,4
= 1,3
= 1,2
= 1,1
1,2
40,9
37,8
34,2
30,0
1,5
61,6
54,2
45,8
90,3
76,7
169,8
Pfinal/Pinitial

= 1,4
= 1,3
= 1,2
= 1,1
1,2
225,3
220,3
214,6
207,9
36,2
1,5
258,1
246,4
233,1
217,8
61,5
44,4
303,6
282,0
257,9
230,8
137,3
102,5
65,0
429,9
378,3
322,9
263,5
224,2
177,6
128,7
77,7
516,2
442,2
364,6
283,7
266,8
208,5
148,4
87,0
583,8
491,3
395,9
298,4
10
302,3
234,0
164,4
94,4
10
640,2
531,7
421,3
310,1
12
333,1
255,8
177,9
100,5
12
689,1
566,3
442,7
319,9
14
360,4
274,9
189,6
105,8
14
732,4
596,7
461,3
328,2
16
385,0
292,1
200,0
110,4
16
771,5
623,9
477,8
335,6
18
407,6
307,6
209,4
114,6
18
807,2
648,6
492,7
342,1
20
428,4
321,9
218,0
118,3
20
840,2
671,3
506,3
348,1
25
474,5
353,4
236,6
126,3
25
913,5
721,2
535,8
360,8
30
514,5
380,3
252,3
133,0
30
977,0
763,9
560,8
371,4
35
550,0
403,9
266,0
138,7
35
1033,2
801,4
582,5
380,5
40
582,0
425,1
278,1
143,7
40
1084,0
835,1
601,7
388,5
45
611,2
444,3
289,0
148,2
45
1130,5
865,6
619,1
395,6
50
638,2
462,0
299,0
152,3
50
1173,4
893,6
634,9
402,0

final
pinitial
( 1)
96
Summary on predetonation distances of Propene/O2

Predetonation distances change drastically (about 2 orders of
magnitude) over a relatively narrow range of compositions
Above result corroborates the so far preliminary conclusion drawn
from the comparisons of the detonative regimes found in 20, 100,
500 and 2500 l vessels (detonative range in 20 l sphere about the
same as in 2500 l vessel)
Above statements are compatible with the well established
observation that combustible/air mixtures do not run up to detonation
in empty vessels ->>>> see next slide ->>>>>
97
Tentative generalisation of the results found for the course of the

explosion of Propene/O2/N2 in the 20 l sphere and in tubes (thermal
ignition presumed!)
0
Combustible/air-mixtures
do not detonate in vessels
of any practical size.
Combustible air mixtures with

L/D 100 do not detonate in
vessels of any practical size
[Vo
l.- %
]
30
50
4.46 vol.-% Propene

in Propene/air
(stoichiometric)
70
ich
st o
80
(typical for
stoichiometric
hydrocarbon/air)
iom
70
e
ti v
na
o
t
60
e
f d ion
o
ge plos
H2
ran ex
+3
CO
>3
O2
1.5
range of
+
H6
3
C
ric
5 bar abs, 25 C
et
Detonative range in larger vessels

seems to be about the same as in
20 l vessel
Propene/O2-mixtures with
L/D 100 do not detonate in
vessels of any practical size
45 vol.-% Propene
in Propene/O2
50
60
80
l.-%
[Vo
sto
ic h
io
m
et
st
ric
oi
ch
C
3H
io
m
6 +
et
4.
ric
5
O
C
2 3H
>
6 +
3
CO
3
O
2 +
2 >
3
H
3
C
2O
O
+
3
H
2O
20
40
L/D = 64
90
O2
Predetonation distance of
combustible/air-mixtures
is about L/D 100
L/D ca. 100
100
10
Propene/O2 mixtures with

predetonation distances L/D 100
do not detonate in 20 l vessel
4.5 vol.-% Propene

in Propene/O2
L/D = 70
40
30
20
90
propen
e/a ir-m
ixture
s
10
100
0
0
10
20
30
40
50
60
70
Propene C 3H 6 [Vol.-%]
80
90
100
98
Introduction


in 20 l vessels
100, 500, 2500 l vessels

99
Did our the ignition source directly trigger a spherical detonation?
Ignition source used is fusing wire according to EN 1839, section 4.2.3.3.3 :

- wire of 0.2 mm diameter, ca. 5 mm long, clamped between two electrodes
- by a thyristor the wire is connected for a fraction of a half wave with
the secondary coil of an insulation transformer
(thyristor typically opens between 0 and 150 and closes at 180)
- wire melts in about first millisecond
- just when first contact breaks apart between the electrodes by the melting of the wire
an arc discharge emerges and keeps on burning until the voltage between the pole
tips falls back to 0.
This ignition source must be rated as purely thermal, since the shock wave
associated with the first occurrence of the arc discharge is negligible (see
next slides)
100
Current/time, Voltage/time and Pressure/time diagrams of ignition

source melting wire with subsequent arc discharge (1/5)
Thyristor opens for 3.33 ms (120-180 of
one half wave of 50 Hz mains supply)
Heating of wire until
melting occurs
Pressure [bar abs]
Example:
ignited in 1 bar N2
at 20C,
thyristor switched on
from 120 to 180
of one half cycle
of mains supply
1.15
1.1
1.05
1
0.95
0.9
0.85
-3
-2
-1
Arc discharge
is burning
In about 50% of all

ignitions conducted
Pressure at sensor in 1 cm distance of arc discharge
1 bar N2 at 20C
there was not at all
any pressure
detected by the
piezoelectric sensor
File: v001_hwz-1_zw120_1bar-n2.sbs
(irrespective of the
duration the thyristor
0
1
2
3
4
5
6
7 was switched on)
Current [A]
300
Current through wire and current of arc discharge
200
100
0
-3
-2
-1
Voltage [V]
300
Voltage at output pin of Halbwellenzuendgeraet

(about factor 7 larger than at electrode tips)
200
100
0
-3
-2
-1
2
Time [ms]
7
101

Pressure [bar abs]
Example: ignited in 1 bar N2 at 20C, thyristor switched on from 5 to 180 of one half cycle of mains supply
1.15
1.1
1.05
1
0.95
0.9
0.85
-3
-2
-1
Current [A]
300
200
100
0
-3
-2
-1
300
Voltage [V]

200
100
0
-3
-2
-1
2
3
Time [ms]
8
102

Pressure [bar abs]
For all ignitions
conducted at 20 bar N2
and at 20C there was
a pressure signal
detected by the
piezoelectric sensor of
the order of
p = 0.4 to 0.7 bar
20.5
20.25
20
19.75
-3
300
Current [A]
19.5
-2
-1
200
100
0
-3
-2
-1

300
Voltage [V]
200
100
0
-3
-2
-1
2
Time [ms]
7
103
Current/time, Voltage/time and Pressure/time diagrams of ignition source

melting wire with subsequent arc discharge (4/5)
Pressure [bar abs]
20.5
20.25
20
19.75
19.5
Current [A]
-3
300
-1
200
100
0
-3
300
Voltage [V]
-2
-2
-1

200
100
0
-3
-2
-1
2
Time [ms]
7
104
-2
-1

200
100
1.15
1.1
1.05
1
0.95
0.9
0.85
-3
-2
-1
2
Time [ms]
-1
300
200
100
0
-3
-2
-1
300

200
100
0
-3
-2
-1
2
3
Time [ms]
-1
100
0
-3
-2
-1

300
200
100
0
-3
-2
200
-2
-3
300
Current [A]
Current [A]
Voltage [V]
Pressure [bar abs]
100
0
-3
Current [A]
300
1 bar N2, 5 - 180
200
0
-3
Voltage [V]
Pressure [bar abs]
19.5
-2
-1
20.5
2
Time [ms]
20.25
20
19.75
19.5
-3
300
Current [A]
-1
20
19.75
-2
-1
200
100
0
-3
300
Voltage [V]
-2
300
20.5
20.25
Voltage [V]
20 bar N2, 120 - 180
20 bar N2, 5 - 180
1 bar N2, 120 - 180
Pressure [bar abs]
1.15
1.1
1.05
1
0.95
0.9
0.85
-3
Pressure [bar abs]

-2
-1

200
100
0
-3
-2
-1
2
Time [ms]
105
Summary of talk
Abundant set of explosion characteristics in the important

but so far mostly unexplored combustible/air/O2 region of
the explosive range
Detonative range in empty vessels is determined
Pressure load on the wall is understood quantitatively
The link between detonation in pipes and in vessels is
established
106

Explosions in Methane O2 N2 Mixtures in Vessels

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Course of explosions in Propene/O2/N2 and Methane/O2/N2

mixtures in vessels of 20 l to 2500 l

Dr. Hans-Peter Schildberg

- quantification of Pdet for four scenarios occuring in a pipe (no precompression)

Comparison: detonative regimes

100, 500, 2500 l vessels

Predetonation distances of Propene/O2 in tubes

Information available in literature on explosive gas

combustible / air /O2

pinitial 1 bara pinitial > 1 bara

pinitial 1 bara pinitial > 1 bara

combustible / air /O2

pipe (L/D > 100)

pipe (L/D > 100)

=> Much work needed to better understand combustible/air/O2 mixtures

Motivation for this work

Critical Issue when dealing with combustible/air/O2-mixtures: Process Safety

- bubble column geometry (explosive gaseous bubbles dispersed in liquid)

Gaseous mixtures investigated

- quantification of Pdet for four scenarios occuring in a pipe (no precompression)

Comparison: detonative regimes

100, 500, 2500 l vessels

Predetonation distances of Propene/O2 in tubes

20 l sphere, Pmax=600 bar, Tmax=500C

References for complete documentation of

Explosion characteristics of Propene/O2/N2 at 1, 5, 10 and 30 bar abs, 25 C and 200 C,

- quantification of Pdet for four scenarios occuring in a pipe (no precompression)

Comparison: detonative regimes

100, 500, 2500 l vessels

Predetonation distances of Propene/O2 in tubes

Questions to be raised when considering explosions of

Will combustible/air mixtures remain deflagrative for higher values of

Literature data on deflagrative and potentially detonative

Characteristic values of the explosive range [1]:

Characteristic values of the potentially detonative range [2,3]:

Lower detonation limit in O2: 2.05 vol.-%

[1] E. Brandes and W. Mller, Sicherheitstechnische Kenngren - Band 1:

What does potentially detonative regime mean?

Literature data on deflagrative and potentially detonative

Characteristic values of the explosive range [1,2]:

Characteristic values of the potentially detonative range [3]:

[1] E. Brandes and W. Mller, Sicherheitstechnische Kenngren - Band 1:

Lower detonation limit in O2: 2.50 vol.-%

Literature data on deflagrative and potentially detonative

Characteristic values of the explosive range [1,2]:

Characteristic values of the potentially detonative range [3]:

range of mixtures, where

[2] V. Schrder in Process Safety and Industrial Explosion Protection,

[1] E. Brandes and W. Mller, Sicherheitstechnische Kenngren - Band 1:

Lower detonation limit in O2: 15 vol.-%

Experimental setup to determine the potentially

mixture to be tested for potential detonability (i.e.

ca. 15*pipe diameters

thin membrane or nothing

Signals of pressure and/or flame sensors give

Different explosion regimes (deflagration, heat explosion, detonation)

Different explosion regimes (deflagration, heat explosion, detonation) of

(Heat explosion range and

Different explosion regimes (deflagration, heat explosion, detonation) of

(Heat explosion range and

Different explosion regimes (deflagration, heat explosion, detonation) of

5 bar abs, 200 C

mixture reacts sometimes