Spontaneous Fires in Insulation: Understanding Causes and Preventing Risks

Spontaneous Fires in Insulation
Laurence G . Britton
Central Research and Engineering Technology Department
Union Carbide Chemicals and Plastics Company Inc.,
P.O. Box 8361, South Charleston, WV 25303
~
-_
~-
~~
~-
~-
Combustible liquids may self-heat in porous insulation yielding smoldering or flaming

combustion. In Part I the problem is reviewed and practical measures discussed. Using
t wo-inch cubes of insulation and a standardized procedure, Spontaneous Ignition
Temperatures (SITS)ranging from 55-184 C are reported for a series of combustible
liquids. The application of a selj-heating parameter Z = ( A I T ) / ( A I T - F P ) ,where AIT is
autoignition temperature and FP is closed cup flash-point (both in Celsius), is examined.
The 2parameter gives some indication of materials that will self-heat and those that
will evaporate, For Z > 1.61 ignition occurred for all the liquids tested. Evaporation
usually occurred for materials with Z < 1.35. It was found that some water-reactive or
peroxide-forming materials can ignite where only evaporation would be predicted from Z
value considerations. An important example of a water-reactive material is ethylene oxide
( E O ) ; the importance of EO insulation fires is that under certain conditions explosive
decomposition of EO contained in the equipment can be initiated.
It was previously determined that ethylene oxide reacts in porous, refractory insulations
forming low molecular weight polyethylene glycols. The formation rate depends on
temperature and the type and condition (particularly water content) of the insulation.
Unlike EO the glycols have low volatility and may accumulate over time to several times
the mass of some insulations. Under certain conditions the glycols can ignite
spontaneously. In Part 11 experiments carried out to examine this phenomenon are
discussed.
Whereprocess temperatures are above the SIT (but below the A I T ) . cellular glass
insulation will minimize the risk of insulation fires. One disadvantage, especially for
thermally unstable materials such as EO, is that cellular glass has poor fire endurance
properties. The use of a realistic fire endurance test to specify insulation thickness and
additional measures such as stainless steel jackets are described.
Alternatives to the use of cellular glass are discussed. When selecting an insulation system,
it should be determined whether an insulation fire might occur and the loss potential from
such an event should be evaluated.
Introduction
Spontaneous insulation fires occur when a combustible liquid leaks into porous insulation at a sufficiently high temperature for runaway self-heating to take place. The insulation
provides a large contact surface for reaction and a lower heat
loss environment than for vapor-air mixtures of equal volume.
PlantlOperations Progress (Vol. 10, No. 1)
Slow oxidative self-heating is favored for liquids of low volatility that will not quickly evaporate from the hot regions.
The spontaneous ignition temperature (SIT) of a particular
system depends on the liquid, the type and geometry of the
insulation, plus various factors influencing the heat generation
and loss rates. Under favorable conditions of liquid loading
January, 1991
27
and air ingress the system temperature will increase sufficiently

for autoignition to take place, although only smoldering is
usually produced. Sudden ingress of air during efforts to uncover and remove smoldering insulation is often the cause of
a fire.
SITs decrease as insulation thickness increases, just as vapor
autoignition temperatures (AITs) decrease with increased vapor volume. AITs are measured in a 0.5 liter glass flask using
a standard technique (ASTM E 659-78). For each vapor o r gas
the AIT provides a snapshot of the range of ignition temperatures possible under different conditions. AITs by the
standard method are measured with ignition delays not exceeding ten minutes. Similarly, SITs can be measured and
compared under a set of standardized test conditions. However, at the lower temperatures needed for spontaneous ignition
the ignition delays may be hours or even days. As will be shown,
there is no direct correlation between SITs and ATTs. An important property of SITSis that they are very much lower than
AITs and are often less than the flash-points of the liquids
involved. This has led to the misconception that insulation can
lower the AIT of a material.
In Part I of this paper AITs and flash-points are compiled
for a range of combustible liquids and compared to the SITs
measured under standardized conditions. A self-heating criterion proposed in 1967 by Lindner and Seibring [ 6 ] is ex-
amined. The earlier work [6] established a minimum value for

the term Z = AIT/(AIT-FP), where FP is the flash-point, at
which self-heating would occur rather than evaporation. At
large values of the denominator, evaporation should attenuate
any heating due to slow oxidation, making the attainment of
the AIT unlikely.
Exceptions to a single Z demarcation for evaporation
include water-reactive liquids or vapors that can re.act exothermically with the insulation producing an accumulation of
less volatile combustible products. In Part I1 attention is given
to the most important of thesc exceptions, ethylene oxide (EO).
The mechanism and limiting conditions for EO insulation fires
are discussed and countermeasures described. While it may be
desirable to use a non-porous insulation system such as cellular
glass to avoid insulation fires of most combustibles handled
above their SITs, in the case of EO it can be essential. This is
because EO inside the equipment may be heated to its autodecomposition temperature by an external insulation fire. Since
1987 there have been at least two incidents suspected to have
been initiated in this way, with tens of millions of dollars in
losses from the resulting EO decomposition explosions. The
merits of different insulation systems are discussed with attention both to the avoidance of insulation fires and to the
need for fire endurance in the event of external flame impingement on chemical equipment.
Part I: General Considerations

Theory
Predictive techniques for insulation fires on pipelines have
been developed using Frank-Kamenetskii approximations [2,
41 and precise solutions using finite difference methods (41.
However, not only are the techniques time-consuming, but
comparisons with very careful experiments have not shown
good agreement owing to the complicating effects of realistic
liquid loadings. Full-scale tests using insulated pipes with simulated leaks have been used directly to address the problem
[2]but these are also very time-consuming, especially if a range
of test liquids and insulation thicknesses is involved. Bowes
[2] comments that It would not be unreasonable t o regard
predictions based on the results of ignition tests for cubes as
providing the most conservative estimates of the minimum pipe
temperatures for ignition of liquids in lagging of given thickness. Leaks often occur at flanges. Owing to layered application of insulation, the effective thickness on either side of
the flange may significantly exceed the nominal thickness on
the pipe. Also many practical situations involve trace heating,
which causes the insulation adjacent to the tracing to be hotter
than the inner pipe wall. Such complications support the use
of cube tests to address the general problem.
For isothermally heated cubes of liquid-soaked insulation
(at constant surrounding temperature To) a simple relationship
holds between SIT and the half-side of the cube [2]:
where
log,(S,T~/?) = - E/RT,+M
(1)
= critical ignition parameter (-2.53 for
a cube)
T
= mean SIT (K)
r
= half-side of cube (m)
E, M
= constants
R
= Gas Constant
6,
By determining SITs for a series of at least three sizes of cube

with equal liquid loadings the constants E and M can be found
28
January, 1991
from a plot of the logarithmic term against reciprocal absolute

SIT as given by To. After substitution of constants, equation
(1) gives estimates of SIT for any size of cube. As shown by
Bowes [2] a similar relationship can be derived for the case of
insulation on a pipe (Equation 2). A series of SIT tests on a
pipe with at least three thicknesses of insulation should enable
a predictive model to be generated for any pipi: diameter and
insulation thickness:
l0g,(46,*T~/(r,-r~)~) =
where
6,
8,
- E / R T,+M
(2)
6,*(@,, Z,)
(3)
(4)
E / R T , ~ ( T , -q,:~
The pipe of radius r , is covered with (r, -- r , ) meters of insulation. The pipe wall has temperature T 3and the outer insulation surface (or weather barrier) has temperature 7,.The
calculation for T, used in [2] involves solution of the surface
heat balance equation:
where h is the surface heat transfer coefficient, To is the temperature of the surroundings and h is the thermal conductivity
of the insulation. In practice X may be increased by the liquid
loading and, as shown in Part 11, solar radiation might determine T, in some cases. For evaluation of some existing
systems, T, might be taken as 140 F (60 C) or other pre-specified
maximum temperature used for personnel protection.
Knowing E from cube tests (or from an initial estimate of
say 25 kcal/mol), the dimensionless parameter 8, is first determined using equation (4). From graphical solutions [2]shown
in Figure 1 the dimensionless parameter 6, is then Sound from
the known values of Z, and 8,. After plotting the log term in
equation 2 against l / T p values found from pipe SIT test<, E
is found from the slope and compared with the initial value.
If different, it is used to recalculate 8, and obtain a new plot.
Trial-and-error gives a rapid convergence [9]of K (and M ) .
Plantloperations Progress (Vol. 10, No. 1)
Lindner and Seibring Criterion
loot
60
lot
es=b r
9u
0
2
10
Lindner and Seibring [6]believed the flash-point (FP) and

the autoignition temperature (AIT) should be important parameters influencing spontaneous ignition. Substances with
low flash-point, that is, with high volatility, were found to
have little tendency to spontaneously ignite in their test apparatus. The apparatus comprised a heated 20 cm diameter
tube containing liquid-soaked insulation samples 6 cm thick,
covered on both sides with 6 cm thick layers of the dry insulation. Temperature was ramped at about 10 C/hr while air
pre-heated to the same temperature was passed through the
samples at flow rates of 20, 40, 80 and 120 Iiters/hr. The
temperature inside the soaked insulation sample was compared
with that of the heated air flowing into it. No self-heating was
observed in cellular glass but otherwise the type of insulation
had little influence on the self-heating onset temperature. All
substances tested having a relatively low AIT had a tendency
to spontaneously ignite below the AIT, while if the AIT was
above 500 C no self-heating was observed. To group AIT and
FP a dimensionless parameter Z was defined as:
Z = AIT/(AIT - FP)
(8)
The experimental data indicated that substances with a Z
parameter less than 1.55 did not self-ignite, and the product
evaporated without self-heating. At greater Z values spontaneous ignition was observed. Lindner and Seibring called for
further studies to prove the validity of this empirical guideline,
since systematic evaluation of a wide range of materials had
not been made.
=S
FIGURE 1.
Critical Ignition Parameter Relationships.
Equation (2) can then be solved iteratively to predict SITs for

other pipe diameters and insulation thicknesses.
For insulation on large equipment Z, approaches unity. As
reported in [2] for the case of a slab of insulation in contact
with a hot surface, for example large equipment:
6c* = (l9,l + 1.4)*/8

(7)
Bowes [2]applied these techniques using both cube tests and
pipe tests of transformer uil-soaked insulations (resin bonded
mineral wool or calcium silicate/asbestos). A plot of the log
terms given in equations (1) and (2) against reciprocal temperature was made. It was found that while the cube tests gave
straight lines as predicted, two out of three pipe tests did not
fall on the same lines but deviated by up to 30 C. This was
blamed on the difficulty in achieving uniform oil distribution
and the effects of oil distillation down the steep temperature
gradient in the insulation on the pipe. It was concluded that
the agreement was about as good as could be expected; while
tests run on pipes could probably be used to predict SITs for
other pipe diameters and insulation thicknesses, it was doubtful
whether direct substitution of E and M data obtained from
cube tests into equation ( 2 ) would yield useful predictions of
pipe SITs. However, SIT data obtained in cubes would be most
conservative compared to the same thickness of insulation on
pipes, which unlike the cubes used for testing are not isothermally heated. This was verified by test data in [2].
Gugan [ 4 ] used finite difference methods to solve the precise
heat balance equation, without using the Frank-Kamenetskii
approximation. The variation of h with temperature and other
parameters was precisely established. It was found that using
thermal analysis techniques such as TGA and DTA good predictive ability was shown so long as very low liquid loadings
were used. At realistic and more hazardous liquid loadings,
complications due to liquid effects (vaporization, diffusion and
effect on h) plus air diffusion effects made the approach impractical.
Standardized SIT Test Method

The test method is similar to that developed for addressing
spontaneous heating of solids as described in [q.It was adopted
by Bowes [Z] for testing liquid-soaked insulations. Gugan [4
reported that the lowest SlTs are observed when the wetting
liquid occupies 6-12% by volume of the void spaces, corresponding to weight loadings of about 150-300% for a typical
insulation soaked with mineral oil. Bowes [2]reported that the
optimum liquid content corresponds to 30-50% of the void
volume and is not very critical owing to the dominant effect
of temperature.
In this study it was found that the lowest SITs were observed
using between 150-350 wt% of test liquid applied uniformly
to dried cubes of insulation. A two-inch cube of dried insulation is weighed then sectioned either into a number of equal
slices (mineral wools) or half-inch cubes (calcium silicates).
The test liquid is applied in equal aliquots to each section to
give the required total loading, then the sections are compressed
together into a 2 x 2 x 2 inch light steel mesh basket. The
basket is equipped with wire loops to suspend it in an air
Cube of Liquid-Soaked Insulation in Steel Mesh Basket
FIGURE 2.
Schematic of SIT Test Apparatus.
January, 1991
29
4 00
Epitherm Mineral Wool

Oven Temperature 120 C jf
2
W
v
c
700
- 600
300
edge
200
center
__t_
5 00
L
W
E
W
c)
100
200
300
time (min)
FIGURE 3.
Temperature History for T4EG ignition in Two-Inch Cube.
convection oven controlling to within 1-2 C of the set temperature. During placement of the sample cube a fine thermocouple is pushed into the center of the test cube and a second
pushed between the insulation and the mesh side (Figure 2).
The edge thermocouple should read within a couple of
degrees of the oven set temperature, although at temperatures
much above the minimum SIT, significant self-heating can
occur at the edge. Bowes [2] reported that owing to variability
in behavior several tests at a given cube size and temperature
might be necessary to establish whether ignition is possible.
For this reason a temperature increase of 50 C or more at the
center of the cube was to be regarded as evidence of an ignition
risk. Similar findings were found in this study for tetralin
(Table 5) but other combustible liquids gave well defined ignitions marked by temperature increases of at least 130 C and
usually considerably greater values (up to about 700 C).
Samples are heated at constant temperature and their internal temperatures monitored for exotherm. After several tests,
two temperatures can be identified which separate ignition
from no ignition by a few degrees Celsius. The mean of
these is cited as the SIT for the particular size of cube and
liquid loading. Figure 3 shows a typical temperature history
leading to ignition of tetraethylene glycol (T4EG) in a twoinch cube of Epitherm 1200 mineral wool (oven temperature
120 C). This figure shows the edge self-heating that often
occurs at temperatures above the minimum SIT, which for
T4EG was found to be 85-90 C in two-inch cubes.
For specific applications t o other types of inwlation or insulation thicknesses, the test can be modified accordingly. The
type of porous insulation can have a significant effect on SIT
although this is usually much less important than the type of
liquid and the insulation thickness. Often, empirical use of the
test method is all that is required to determine the cause of a
fire. In the following example, a substantial fire developed
and the cause of ignition was not immediately obvious.
Case History: MDEA Insulation Fire (1989)

A corrosion leak on an elbow of a carbon steel suction pipe
going to a vacuum still led to hot methyldiethanolamine (MEDEA) at about 185 C soaking into Kaylo-I0 (calcium silicate)
insulation. Problems were first experienced with the vacuum
at 2:OO. At 5:41 smoke and fire were observed at the suction
pump. After extinguishing the fire with a fire extinguisher
(5:50)the fire reignited almost immediately. More water was
used to put the fire out (5:56). The next day the insulation
removed from the affected area was found t o be warm and
showed signs of internal smoldering. The hot amine corrosion
problem was corrected by replacing the carbon stelsl suction1
discharge pipe with stainless steel. The action <)f the pump in
drawing air through the insulation (causing the observed loss
of vacuum) may have contributed to the incidence of a fire
rather than just smoldering.
TABLE 1 METHYLDIETHANOLAMINE IN TWO-INCH CUBES OF KAYLO-10 CALCIUM SIIJCATE

Liquid
Result
Loading
t
(wtrrio)
(C)
(C)
(min)
--___ (min)
150
104
1 04
70
6900
methyldiethanolamine
No exotherm
No exotherm
150
1 I7
1I7
115
2940
No exotherm
150
122
122
286
5400
150
125
125
I45
3320
No exotherm
Ignition
150
129
297
86
184
methyldiet hanolamine
Ignition
150
132
447
105
-___ 60
No exotherm
No exotherm
methyldiethacolamine
Ignition
30
January, 1991
Ignition
Ignition
Ignition
100
100
100
100
100
200
132
135
142
147
I53
162
132
135
465
262
425
578
n/a
41
75
42
40
41
5760
2790
121
68
30
89
TABLE 2 AMINES (IN DELTA WRAP MINERAL WOOL)

Liquid
ethylenediamine
diethylenetriamine
diethylenetriamine
diethylenetriamine
diethylenetriamine
triethylenetetramine
tetraethylenepentamine
tetraet hylenepentamine
polyamine
polyamine
polyamine
polyamine
HPA
HPA
HPA
HPA
monoethanolamine
monoethanolamine
monoethanolamine
monoethanolamine
monoethanolamine
diethanolamine
diethanolamine
diet hanolamine
diethanolamine
triethanolamine
triethanolamine
triethanolamine
triethanolarnine
triethanolamine
triethanolamine
aminoethylethanolamine
aminoet hylethanolamine
aminoethylet hanolamine
aminoethvlethanolamine
n-aminoethyl piperazine
n-(2-hydroxyethyl) piperazine
To
Result
Loading
(wt%)
(C)
Evaporated
No exotherm
Ignition
Ignition
Ignition
No exotherm
No exotherm
No exotherm
No exotherm
Ignition
Ignition
Ignition
Ignition
Ignition
Ignition
No exotherm
No exotherm
Ignition
Exotherm
Ignition
No exotherm
Exotherm
Exotherm
Ignition
No exotherm
N o exotherm
Ignition
Ignition
Ignition
No exotherm
Ignition
Ignition
Ignition
No exotherm
Exotherm
Exotherm
Borderline ignition
Ignition
Ignition
Evaporated
Evaporated
EvaDorated
Exotherm
Ignition
Ignition
Ignition
Ignition
Exo therm
Ignition
Ignition
150
150
150
150
150
123
59
65
67
125
123
59
721
398
379
250
350
250
150
150
150
150
150
150
150
150
150
150
150
150
54
54
54
54
No exotherm
Exotherm
Ignition
SIT experiments were conducted on two-inch cubes of Kayloloinsulation soaked with various loadings of MDEA. As shown
in Table 1 the minimum SIT for the two inch cube was found
to be 127 C (plus or minus 2 C) at a loading of 150 wt%
MDEA. This confirmed that the process location was operating
well above the ignition temperature for two inches or more of
calcium silicate insulation. Table 2 shows further MDEA test
results using Delta Wrap (average density 8 Ib/cubic foot)
t*,
Tmax
*O
(C)
(min)
(min)
90
58
41
31
1125
1410
723
136
14
8775
8772
5730
1200
297
21 1
53
36
23
21
1340
1574
410
630
389
n/a
55
55
56
61
69
79
89
99
109
63
67
70
75
87
56
678
780
688
347
336
346
63
67
48 1
98
45 1
105
108
120
n/a
255
110
111
79
51
36
40
46
71
60
62
150
350
350
350
350
350
66
76
81
86
48
53
58
70
80
66
108
87
418
81
108
86
116
70 1
856
465
313
48
53
170
329
292
48
50
24
81
90
3327
5125
74 1
264
180
150
150
150
150
100
108
124
130
100
n/a
859
428
2880
605
289
78
350
350
150
350
350
350
105
105
125
135
170
515
152
119
138
39
135
138
150
150
150
150
150
150
150
150
150
I50
150
110
115
120
125
138
133
144
152
>
500
133
144
152
150
150
150
81
87
94
80
378
664
352
313
91
460
511
150
150
150
117
122
127
117
137
513
70
76
85
96
110
144
120
93
63
46
125
82
77
44
82
102
5490
9987
4890
2547
1635
n/a
5247
1080
3927
1150
685
205
68
38
686
188
108
177
80
85
4140
765
91
120
153
154
n/a
mineral wool, in which the MDEA evaporated with no exotherms.

Tables 1-5 list two time variables. The first (to)is the
time taken for the center of each cube to heat to the oven
temperature. This quantity was found to be highly variable
since it depended on operational factors such as the initial oven
temperature and how long the oven door was open while
mounting the sample cube. Thus, to1was subtracted from
January, 1991
31
TABLE 3 GLYCOL ETHERS, TERGITOLS AND ORGANOSILANE ESTERS IN DELTA WRAP (DI OH KAYLO10 (K)
Result
Loading
(wtV0)
T*
(C)
TI,
(C)
(min)
t,,,,,
(min)
ethoxytriglycol
ethoxytriglycol
ethoxytriglycol
No exotherm
Ignition
Ignition
150 (D)
150 (D)
150 (D)
113
117
122
113
243
246
96
137
106
1064
33
112
bu toxytriglycol
butoxytriglycol
butoxytriglycol
No exotherm
Ignition
lgni tion
Evaporated
Evaporated
Evaporated
No exotherm
N o exotherm
Ignition
Ignition
Ignition
Evaporated
Evaporated
150 (D)
150 (D)
150 (D)
150 (D)
150 (D)
350 (K)
150 (D)
150 (D)
150 (D)
150 (D)
150 (D)
150 (D)
150 (D)
98
106
118
92
132
134
85
92
99
105
98
267
248
73
98
91
92
132
134
52
4067
260
51
2302
5445
6231
Liquid
butyl CELLOSOLVE (1)

TERGITOL
TERGITOL
TERGITOL
TERGlTOL
TERGITOL
15-S-5 (2)
15-S-5 (2)
153-5 (2)
15-S-5 (2)
1 5 3 - 5 (2)
n-propyltrimethoxysilane
f,
75
144
42
110
85
92
65 1
60 1
47 8
I1
60
6738
I0020
870
304
950
115
133
115
133
34
40
9000
5625
62
14
( I ) ethylene glycol monobutyl ether

(2) alkyloxypolyethyleneoxvethanol:Molecular Weight 420
the total run time to give the second parameter tmax, the
run duration after the center of the cube had reached oven
was equivalent
temperature. For runs yielding ignition, tmaX
to the isothermal ignition delay time, and was measured from
to to the time at which maximum temperature was recorded.
If no ignition was recorded (either no exotherm or observed
exotherm less than 50 C) tmmwas measured from to, to
the time the run was terminated. Observed SIT limits (the
nearest temperatures respectively below and above the SIT)
are shown in bold type.
Amines
Table 2 shows the SIT results for alkyleneamines, alkanolamines and piperazines. These all gave ignition with the exception of the volatile ethylenediamine; monoethanolamine
and the alkyleneamines otherwise gave the lowest SITs of any
liquids studied. Monoethanolamine (MEA) and iron form the
complex trisethanolamino-iron [ l a ] ,which is thermally unstable and has been suspected of causing fires in process facilities.
Since insulation will contain some iron, this might explain why
MEA was found to have a much lower SIT than the other
al kanolamines. Among the alkyleneamines there was expected
to be a variation of SIT with increasing chain length, but since
commercial samples of the higher members contained significant concentrations of cyclic material no trends were apparent
in the data. GC analysis was carried out. In brief:
ethylenediamine (99.9 + Vo), diethylenetriamine (97,9To),
diethanolamine
(99.65%),
(99.9 + %I), aminoethylethanolamine (99.9 To), n-aminoethyl piperazine (97.6@Io), n-(2-hydroxyethyl) piperazine
(99.9 + Yo), triethylenetetramine (98% triethylenetetramines), tetraethylenepentamine (90% tetraethylenepentamines), polyamine HPA (complex mixture of linear,
branched, cyclic and bicyclic heavy polyamines).
Compared with Table 1 it is seen that methyldiethanolamine
(MDEA) ignited in calcium silicate but evaporated in mineral
wool insulation. The SIT of MDEA is close to its flash-point
and it appears that the more open structure of mineral wool
allowed faster evaporation and heat loss during the heat-up
time to test temperature than did the more closed structure of
highly sorptive calcium silicate. The type of insulation can
32
January, 1991
therefore determine whether self-heating or evaporation occurs

under these test conditions.
Glycol Ethers, TERGITOLS and Organosilane Esters

Only a small number of these materials have been studied,
as shown in Table 3. They were selected principally t o test the
Lindner and Seibring criterion and have not given spontaneous
insulation fire problems in the field. Table 3 shows that spontaneous ignition is possible for the TERGITOL and the less
volatile glycol ethers tested, and helps explain a fire that occurred when a TERGITOL-soaked vermiculite was dumped
into a large container during the summer. The large volume
of material reduced the SIT to that attainable by solar heating.
Volume/shape effects can be predicted using Equation (1) and
other methods given in [q.
Glycols
Part I1 shows that the SITs of glycols are of particular
importance in addressing the limiting conditions for spontaneous ethylene oxide insulation fires. For this reason an extended series of glycols was studied as shown in Table 4, ranging
from monoethylene glycol up to CARBOWAX II3.C;-600. Thls
polyethylene glycol has a molecular weight of 600 and has a
melting point of about 25 C. High purity low moleculdr weight
PEGS were available up to tetraethylene glycol (T4EG). To
represent pentaethylene glycol (TSEG) a crude mixture of low
molecular weight PEGS was obtained from a plant tank. Its
weight analysis was 67.82% pentaethylene glycol, 21.40% tetraethylene glycol (T4EG), 8.53% hexaethylene glycol, 0.61 070
water, 0.55% ethylene glycol, 0.16% diethylene glycol,
0.0009% NaOH, and 0.0000% triethylene glycol. T4EG yielded
an SIT as low as, or lower than, any of the glycols studied.
Spontaneous fires of high molecular weight polyethylene
glycols have been reported. In one case a smoldering fire of
PEG 3350 occurred on a steam-traced line at 120 C. I n another
a fire occurred with PEG 1350 in a traced unloading line at
150 C. Both lines were insulated with mineral wool. One method
for minimizing the risk of insulation fires involves use of nonporous cellular glass insulation on rigid lines; for flexible lines
TABLE 4 GLYCOLS IN DELTA WRAP (D), EPITHERM 1200 (E) OR KAYLO-10 (K)
Liquid
Result
monoethylene glycol
monoethylene glycol
monoethylene glycol
monoethylene glycol
monoethylene glycol
monoethylene glycol
diethylene glycol
diethylene glycol
diethylene glycol
diethylene glycol
diethylene glycol
diethylene glycol
triethylene glycol
triethylene glycol
triethylene glycol
tetraethylene glycol
crude
crude
crude
crude
pentaethylene
pentaethylene
pentaethylene
pentaethylene
polyethylene glycol
polyethylene glycol
polyethylene glycol
polyethylene glycol
glycol
glycol
glycol
glycol
600
600
600
600
Evaporated
Evaporated
Evaporated
Evaporated
Evaporated
Evaporated
Evaporated
Evaporated
Evaporated
Evaporated
Evaporated
Evaporated
Loading
(wt To)
150 (D)
250 (D)
350 (D)
250 (D)
350 (D)
350 (K)
350 (E)
350 (E)
250 (E)
250 (K)
250 (E)
250 (K)
47
99
99
99
I10
110
110
90
95
107
121
122
132
Tm,
(C)
99
99
99
110
110
110
90
95
107
121
122
132
(rnin)
114
164
107
102
107
n/a
105
120
141
105
150
180
(min)
2248
5009
5066
5578
5473
6381
4455
5850
6834
5610
2450
2460
tlnax
No exotherm
Ignition
Ignition
No exotherm
Ignition
Ignition
No exotherm
No exotherm
Ignition
Ignition
Ignition
Ignition
Ignition
No exotherm
No exotherm
No exotherm
Ignition
350 (E)
350 (E)
350 (D)
86
91
110
86
30 1
242
144
150
224
5625
4125
I66
350 (E)
350 (E)
350 (D)
150 (D)
150 (D)
350 (E)
350 (E)
350 (E)
350 (E)
350 (E)
350 (D)
350 (D)
350 (D)
350 (D)
85
90
92
94
102
108
120
130
155
190
85
91
96
102
85
40 1
635
94
102
296
613
252
263
330
85
91
96
28 1
n/a
1524
83
60
105
810
140
102
67
42
162
132
150
138
2250
3120
7567
5460
5790
456
114
99
60
25
5238
9638
5250
1812
No exotherm
Ignition
Exotherm
Ignition
350 (E)
350 (E)
350 (D)
350 (D)
86
91
96
102
86
28 1
123
277
120
5400
3525
5310
5147
a wrap-around blanket insulation with an impervious skin can

be used to keep liquid away from the porous insulation inside.
Heat Transfer Fluids

Green and Dressel [I] gave an excellent introduction to the
problem of heat transfer fluid (HTF) fires and made an analysis
of types of fire incident for particular types of fluid. Eight
out of twenty-three fires investigated were due to spontaneous
ignition in insulation, described as punking type (intermittently flaming) fires. It should be noted that, for HTFs used
above their normal boiling points, the smoke often seen
following a leak may be condensed vapor rather than evidence
of a fire. Combustible HTFs can be classified into one of seven
groups. Typical examples given in [ I ] are shown:
(1) alkylated aromatics
(2) highly aromatic
hydrocarbons
(3) diphenyl-diphenyl oxide
(DP:DPO)
(4) highly aromatic ethers
(5) polyalkylene glycols
(6) silicon based oils
(7) highly aliphatic mineral oils
Tll
(C)
(Dowtherm J, Therminol 55)

(Dowtherm HT, tetralin)
(Dowtherm A, Therminol VP-I)
(Dowtherm G, Dowtherm 1-F)
(UCON HTF-500)
(Therminol 44, Syltherm 800)
(Chevron HT, Essotherm 500)
The fire incident analysis in [ I ] showed that insulation fires

of groups (1) and (7) had occurred at system temperatures in
the range 204-315 C. These fluids had H / C ratios above about
1.75. While spontaneous fires of highly aromatic HTFs had
been known to occur, the analysis suggested that these fluids
Plantloperations Progress (Vol. 10,
No. 1)
1 50
150
138
are less prone to the phenomenon. Least prone should be

DP:DPO types, which have very high AITs (above 500 C) and
relatively low flash-points of around 130 C.
Table 5 shows SIT test results for tetralin (tetrahydronaphthalene) and a series of Dowtherm HTFs. Tetralin was
selected since it has been involved in several insulation fires in
EO Units, where it was used as a coolant for reactors operating
at about 260 C. Perlites and asbestos-based insulations were
usually involved. The Dowtherms were selected to represent
HTFs in groups 2-4, and to exhibit a range of Lindner and
Seibring Z values. With tetralin at 126 C or more in mineral
wool, exotherms were exhibited almost immedititely the cube
had heated to oven temperature (the t,,, values listed are isothermal run times). Owing to its high volatility the tetralin
quickly evaporated and the heat-up time of the cube caused
significant material loss which might not represent worst-case
practical conditions. The largest exotherm observed was about
60 C. Since tetralin has ignited in plant situations, this exotherm
is clearly significant and the corresponding test temperature
of 165 C is listed as the approximate SIT in Table 6. It is
assumed that in plant situations involving a continuous leak
source of hot tetralin into hot insulation, a local hot spot
develops at some favorable location close to the leak. Tetralin
initially forms tetralin hydroperoxide on contact with air at
elevated temperature (50-100 C) and this unstable material
decomposes rapidly at about 120 C. This mechanism might
explain why exotherms were quickly produced in mineral wool
(open structure) but not in calcium silicate, which would hinder
the air convection needed for peroxide formation; instead, the
calcium silicate would contain almost exclusively tetralin va-
January, 1991
33
TABLE 5 HEAT TRANSFER FLUIDS IN DELTA WRAP (D) OR KAYLO-10 (K)

Liquid
tetralin
tetralin
tetralin
tetrah
tetralin
tetralin
tetralin
tetrah
tetralin
(97%)
(97%)
(97%)
(97%)
(97%)
(97%)
(97%)
(97%)
(97%)
Dowtherm A
Dowtherm A
Dowtherm A
Dowtherm
Dowtherm
Dowtherm
Dowtherm
Dowtherrn
Dowtherm
Dowtherm
Dowtherm
Dowtherrn
Dowtherm
Dowtherm
Dowtherm
Dowtherm
G
G
G
HT
HT
HT
HT
HT
HT
HT
HT
HT
HT
No exotherm
No exotherm
Exotherm
Evaporated
Borderline ignition
Borderline ignition
Evaporated
Exotherm
Exotherm
250 (D)
250 (D)
250 (D)
350 (K)
250 (D)
350 (D)
350 (K)
250 (D)
350 (D)
Evaporated
Evaporated
Evaporated
No exotherm
No exotherm
Evaporated
No exotherm
Exotherm
Exotherm
Exotherm
Exotherm
Borderline ignition
Ignition
Ignition
Ignition
Ignition
88
105
126
134
165
165
170
200
200
88
105
135
134
216
228
170
220
215
120
105
120
70
48
48
YO
33
33
250 (D)
250 (D)
250 (D)
187
209
250
187
209
250
111
78
66
350 (D)
350 (D)
350 (D)
350 (D)
350 (D)
350 (D)
350 (D)
350 (D)
350 (D)
350 (D)
350 (D)
150 (D)
350 (D)
130
209
248
130
140
152
162
172
183
185
193
270
270
130
209
248
130
150
172
199
220
26 1
397
> 500
> 600
> 600
90
114
195
162
6909
3000
690
2495
see text
see text
3375
4137
3137
4155
6852
41 82
____
2547
2136
3825
___
2475
225
40
60
570
275
141
I20
24
45
YO
114
93
90
I05
54
42
24
45
TABLE 6 RANKED SITS FOR TWO-INCH CUBES (IN DELTA WRAP EXCEPT AS NOTED)
~~
vo
Liquid and Insulation Used

monoethanolamine
diethylenetriamine
tetraethylenepentarnine
aminoethylethanolarnine
polyamine HPA
triethylene glycol (Epitherm 1200)
tetraethylene glycol (Epitherm 1200)
polyethylene glycol 600 (Epitherm 1200)
TERGITOL 15-S-5
crude pentaethylene glycol
butoxytriglycol
diethanolamine
ethoxytriglycol
triethanolamine
methyldiethanolamine (Kaylo-10)
tetralin
Dowtherm H T
wt
butyl CELLOSOLVE
butyl CELLOSOLVE (Kaylo-10)
diethylene glycol (Epitherm 1200)
diethylene glycol (Kaylo-10)
Dowtherm A
Dowtherm G
ethylenediarnine
monoethylene glycol
monoethylene glycol (Kaylo-10)
tetralin (Kaylo-10)
150
350
250-350
250
250-350
350
150
150-350
150-250-350
350
I50
350
34
January, 1991
350
150
150
150
150
150
150
350
3 50
350
150
350
150
150
150
350
150
150
350
350
Mean SIT (C)

55
58
62
68
73
83
84
88
88
89
95
99
102
104
115
122
124
128
- 165
184
Evaporated
Evaporated
Evaporated
Evaporated
Evaporated
Evaporated
Evaporated
Evaporated
Evaporated
Evaporated
Evaporated
Evaporated
SIT Limits (C)

53-58
56-61
59-65
67-70
70-76
81-86
81-87
85-91
85- 30
86-31
92-99
96-1 02
98- f 06
100- 108
113-117
120 125
122 127
125 129
see text
183-185
< 132 C
< 134 C
< 122 C
< 132 C
< 250 C
<248 C
< 123 C
< 152 C
< I10 C
< 110 C
< 133 C
< 134 C
Plantloperations Progress (Vol. 10, No. 1 )
~~
TABLE 7 EXAMINATION OF LINDNER & SEIBRING CRITERION (IN DELTA WRAP MINERAL WOOL EXCEPT
AS NOTED)
Liquid
dichlorosilane [W]
trichlorosilane [W]
ethylene oxide [W]
SIT (C)
*
:
:
et hyienediamine
n-propyltrimethoxysilane [W]
tetralin [PI
tetralin [PI (Kaylo-10)
Dowtherm A
monoethanolamine [R]
2-ethyl hexaldehyde [PI
monoethylene glycol
monoethylene glycol (Kaylo- 10)
Dowtherm G
diethylenetriamine
butyl CELLOSOLVE
butyl CELLOSOLVE (Kaylo-10)
diethylene glycol
diethylene glycol (Kaylo-10)
Evaporated
Evaporated
Evaporated
62
Evaporated
Evaporated
84
73
Evaporated
Evaporated
ethoxytriglycol
Dowtherm HT
methyldiethanolamine (Kaylo-10)
polyamine H P A
TERGITOL 153-5
triethylene glycol
tetraethylene glycol (Epitherm 1200)
butoxytriglycol
crude pentaethylene glycol
diet hanolamine
triethanolamine
polyethylene glycol 600
124
115
58
I84
Evaporated
128
83
95
68
88
88
102
99
104
122
89
[W]
[PI
[K]
Evaporated
Evaporated
165
Evaporated
Evaporated
55
*
Tma,
(C)
228
-
329
-
721
-
511
664
-
513
246
7 80
> 600
-
578
418
65 1
48 1
301
613
267
28 1
859
> 500
28 1
AIT (C)
FP (C)
Z Parameter
44 (36)
182
445
402 (385)
245
382 (385)
382 (385)
532
391 (410)
195
427 (398)
427 (398)
502
350 (358)
228 (238)
228 (238)
324
354 (368)
364 (224)
364 (224)
311
279
325 (338)
381
285
285
350
365
349 (321)
349 (371)
358
274
365
338 (662)
320
385
- 52
28
- 29
41
27
77
77
111
85
48
111
111
130
98
66
66
102
129
138
138
0.46
0.87
0.94
1.11
1.12
1.25
1.25
1.26
1.28
1.33
1.35
1.35
1.35
1.39
1.41
1.41
1.46
1.57
I .61
1.61
124
124
149
179
136
136
168
178
171
172
177
I36
182
169
196
- 246
I .66
1.80
1 .85
1.89
1.91
1.91
1.92
1.95
1.96
1.97
1.98
1.99
1.99
2.00
2.58
2.77
reacts exothermically with water: might form less volatile products in the insulation
material readily forms peroxides in air
reacts with iron forming thermaliy unstable complex trisethanolamjno-iron
not tested by standardized method: see text
por. Dowtherms A and G gave no exotherms under the test

conditions and spontaneous ignition is improbable in the temperature range studied. Dowtherm HT gave increasingly larger
exotherms above 140 C and ignited above 183 C.
Examination of Lindner and Seibring Ignition Criterion

Table 7 shows the SIT data from cube tests, the maximum
observed temperatures during self-heating, the sample AITs
measured according to ASTM E 659-78, the flash-points given
on the sample material safety data sheets, and the calculated
Z parameter values.
The measured AITs in some cases differ from published
values (NFPA 325M) by more than the 5 % of the Celsius
value reproducibility given as acceptable by ASTM. Values
from NFPA 325M (1984 Edition) are given in parenthesis.
Fahrenheit-for-Celsius errors compounded by the use of obsolete AIT test methods account for some discrepancies (diethylene glycol and diethanolamine). Another source of discrepancy is the use of lowest published values by NFPA,
often those measured in a one-liter test vessel by the Bureau
of Mines. AITs supplied by Dow Chemical Company for
Dowtherms A, G and HT are significantly higher than those

measured for sealed, as-received samples (Table 7). After discussions with Dow Chemical, plus checks of the test equipment,
the reason for this is unclear since the same ASTM test method
was used. Just 50% of the AIT values in Table 7 are in acceptable agreement with those listed in NFPA 325M.
There are no significant correlations of SIT with AIT, flashpoint or Z. However, both FP and Z provided some indication
of tendency to evaporate. Figure 4(a) shows a plot of the SIT
against Z data from Table 7. All the liquids with Z values
greater than 1.61 gave spontaneous ignition in at least one
insulation used. Liquids with Z values equal to or less than
1.35 evaporated except in cases where exceptional reactivity
could be identified. Tetralin (Z = 1.25) forms peroxides in air
and 2-ethyl hexaldehyde forms per-acids. In separate experiments using forced air flow, it proved possible t o ignite cotton
wool soaked with 2-ethyl hexaldehyde. As discussed earlier,
monoethanolamine might react with iron in insulation forming
an unstable complex. Dichlorosilane can ignite at ambient temperature owing to its very low AIT (44 C) and reactivity with
water [5]. As suggested in [ 5 ] ,tricholorosilane (water-reactive)
might also ignite at ambient temperature in large thicknesses
of insulating material (including vermiculite and absorbent
January, 1991
35
0.4
0.6
0.8
1.0
1.2
1.4
FIGURE 4a.
1.6
1.8
2.0
2.2
2.4
2.6
2.8
Z Parameter
Variation of SIT with Z Parameter.
pillows used for spill control). Ethylene oxide is discussed in

detail in Part 11.
Owing to compounded AIT and FP errors in calculating
Z, a grey region (where ignition or evaporation might
occur) should be expected even were Z derived from rigorous
theory instead of being empirical. The usefulness of the Z
approach lies in the availability of data needed for its calculation and the probability that exceptions may be identified
using information on material safety data sheets (water reactive, forms peroxides or unstable complexes). Figure 4(b)
shows that a flash-point less than 85 C also gives a good
indication of tendency to evaporate, and a flash-point greater
than 138 C indicates a tendency to self-heat. However, there
is a larger grey region when flash-point is used rather than
Z. Observed T,,, values varied widely for successive tests of
the same material due to small differences in test conditions.

Insufficient repetitive tests were made to determine the highest
possible T,,, values for each liquid and make realistic comparisons. While Lindner and Seibring [6] concluded that in
some cases the oxidation runaways failed due to fast evaporation as the reactions proceeded, it if reasonable to assume
that in practical situations involving a continuous leak, all
liquids tested giving greater than a 50 C exotherm might ignite,
yielding maximum temperatures as high as 600-800 C or more.
In summary, it is seen that SITS vary significanily for different chemicals over a range from ambient up to at least 185
C. As will be seen in Part 11, temperatures of 55 C or more
can be achieved by solar heating of Some weather barriers.
While high Z values (above 1.61) are a good indication of
tendency to self-heat, low values (less than 1.35) do not always
u
W
5;0
Flash Point (C)

FIGURE 4b.
36
Variation of SIT with Flash-Point.
January, 1991
c
a
a,
silicate insulations, which are normally made from diatoma8o

*
ceous earth. G
The appearance of acetaldehyde not only corre-
(r
60
200
300
400
500
Reactor Temperature (C)

FIGURE 5.
EO lsomerization to Acetaldehyde in
Tubular Reactor.
exclude the phenomenon. The type of porous insulation soaked

with liquid can influence whether evaporation or self-heating
occurs in some cases, but usually its effect is of secondary
importance. Non-porous insulation such as cellular glass or
other measures to prevent liquid from entering the insulation
are required to prevent self-heating at above the SIT. The test
method described is conservative for two inches of porous
insulation. Owing to a small dependence of SIT on liquid
loading, a wide range of concentrations does not need to be
tested. While the tests are time-consuming, they involve a minimum of oversight after loading the sample.
Part 11: Ethylene Oxide Insulation Fires

Introduction
In 1953 Jefferson Chemicals communicated results of a test
they were using to evaluate insulation for EO service. It had
been found that EO would spontaneously ignite in hot insulation and that the type of insulation had a large effect o n the
SIT. Union Carbide subsequently adopted a similar test. Essentially, EO or EO-air mixtures were passed through small
cubes of test insulation packed into a reactor held a t constant
wall temperature. Thermocouples were used to monitor the
center of the insulation for exotherm. Until recently, this test
was used in conjunction with a fire endurance test (see later)
to qualify insulation for EO service. The range of SITSfound
for different insulations was at a relatively high temperature
and varied from about 250 C for the worst types to about 470
C for the best types. Only one (Jefferson) test from the 1950s
had given an ignition below 250 C; moistened 85% magnesia
insulation gave a n ignition at 145 C after agitation of the
material. Failure to reproduce this result discouraged further
investigation and magnesia insulation was simply not used in
EO service after the mid-1950s.
The mechanism for the high temperature insulation fires
was shown to be the isomerization of EO to acetaldehyde as
described in [3]. Since this isomerization is quite exothermic
(about 27.6 kcal/mol) the heat accumulation can drive a thermal runaway. Figure 5 shows the result of passing EO through
a heated tubular reactor filled with insulation. Residence time
was nominally 25 seconds. At about 200 C significant quantities
of acetaldehyde were detected with Johns-Manville NA calcium
silicate while with Careytemp expanded perlite detection was
at about 280 C. In general, SITS were found to be lower with
calcium silicate than with either perlite or mineral wool, and
this was believed due to the high surface area typical of calcium
sponds to the release of isomerization energy but admixture

of acetaldehyde to EO also greatly reduces its AIT as shown
in Figure 6. When the degree of conversion approaches 20%
the corresponding temperature may be sufficient to cause autoignition of the hot vapor mixture. This phenomenon in particular gave rise to the concept of AIT lowering by insulation.
EO fires were occasionally reported a t much lower temperatures than those identified by tests of the type described, and
these were blamed on catalysis by rust. To address this, realistic
tests were carried out simulating a flange leak on a three-inch
i.d. pipe. Using expanded perlite, fires were produced only at
wall temperatures of 298 C or greater with corresponding ignition delays of about two hours or less. While it was known
131 that large amounts of rust dispersed through insulation
lowers the SIT significantly, the addition of realistic amounts
of rust during- the Diue simulation studies had no significant
Typical examples of the unexplained fires included:
__
Two fires (1969 and 1979) on distillation column reboiler heads. Temperature 90-100 C on process side.
No internal EO decomposition. In the first incident the
leak was due t o a small dent in a reboiler flange gasket
which had been present since installation.
An insulation fire (1980) in the feed line between an
EO compressor and distillation column at the flow
measuring orifice flange. Temperature about 150 C or
less. No internal EO decomposition.
case of the distillation column fires the probability of
external ignition was remote and this suggested that a-low
temperature route to spontaneous EO insulation fires had to
exist.
Low Temperature Reaction of EO with Porous Refractory Insulation (No Air)

An Accelerating Rate Calorimeter (ARC) was modified t o
allow samples of insulation to be exposed t o pure EO vapor
at close to atmospheric pressure. About 2.2 g of insulation
sample was placed in a titanium ARC bomb and degassed at
100 C (three cycles each of nitrogen purging and vacuum).
After cooling, EO vapor from a reservoir was delivered to the
bomb. Pressure was kept close t o atmospheric using a mercury
blow-off set at 10 mmHg. The ARC was then run in standard
heat-wait-search mode while any polymerization reactions
caused fresh EO to flow t o the test bomb. At the 0.02 C/min
detection threshold, exotherms were observed at 87 C with
expanded perlite, 95 C with calcium silicate, and 125 C with
glass wool. With n o insulation, detection was at 313 C. Oils
u,
500
L
W
m
L
400
i:
300
200
0
20
40
60
80
100
Acetaldehyde in Mixture (wt%)
FIGURE 6. Effect of Acetaldehyde Admixture on the

Autoignition Temperature of Ethylene Oxide Vapor in a
125 ml Glass Flask.
January, 1991
37
.
.E
E
finally decomposition of the polymer to carbonaceous solids

plus gas.
Corrected test results for EO plus distilled water are shown
in Figure 7, where the ordinate represents reaction threshold
in Celsius. It is seen that the adiabatic reaction threshold is
greatly reduced as water is added (reference [8] gives a graphic
account of the importance of these glycol-forming reactions).
These reactions are catalyzed both by acids and bases, hence
the thresholds shown in Figure 7 may be significantly reduced
by changes in p H . This is also relevant to the effect of insulation, since as shown in Table 8 insulations are usually basic
in character.
250
V
f-4
200
150
8
EaJ
53
100
u
.g
50
.-Um
d
Types of Insulation
10
20
30
40
Watcr ( l i t
FIGURE 7.
50
7c
60
70
80
90
Some measured properties of insulation samples are given
in l<O)
Adiabatic Reaction Thresholds of EO

Distilled Water in the ARC.
were produced in the insulation samples. These were analyzed

as tetraethylene glycol and other low molecular weight polyethylene glycols. Owing to the small mass of EO, the thermal
inertia (or +factor) was large and exotherms were weak with
poorly-defined starting temperatures. For this reason the test
was not selective enough to differentiate between the activities
of different insulations. However, a low temperature exothermic reaction path was now identified. Since polyethylene
glycols with chains of general description:
H O - CH2 - CH, - (0- CH2 - CH,-),
- 0 -CHI - CHI - OH
were formed rather than polyethylene oxide ( ( - 0

- CH2- CH2-) I , it was considered that the water content
of the insulation should be an important factor. The heat of
such reactions is about 20 kcal/mol. It remained to discover
whether the reaction would contribute significantly to selfheating in insulation, and the conditions (insulation type,
thickness, water content, temperature) under which this could
occur. Also, the appearance of the much less volatile glycols
opened the way for oxidative self-heating in temperature regimes where EO would otherwise evaporate.
Benchmark Tests of Liquid EO and EO-Water Mixtures

in the ARC (No Air)
To increase ARC response, further tests of insulation activity
were carried out using liquid EO rather than vapor. To establish
benchmarks, tests were also made with EO alone and with EO
mixtures with distilled water. The test results for pure E O were
reported in [3].It was found that the corrected adiabatic threshold for detectable self-heating (heat rate 0.02 C/min @ C#J =
1) was between 199-205 C in different bombs. The reaction is
believed to involve isomerization to acetaldehyde (plus some
polymerization, possibly heterogeneous), followed by condensation to acetaldol, cracking to crotonaldehyde plus water,
further condensation to croton oils plus solid polymer, and
in Table 8. Calcium silicate insulations such as Kaylo-10 are

generally based on diatomaceous earth with various proprietary binders and fillers. The specific surface area and water
content are typically high owing to the diatom-based structure.
(Diatoms are a class of microscopic unicellular algae with flinty
shells in two halves, fitting like a box and lid. The earth is
a powdery deposit of diatom frustules.) Upon equilibration
with air at 50% relative humidity (ASTM C870-77), the armospheric water uptake was 7.5 wt%, but this might increase
to about 25 wt% under humid conditions. Upon shaking in
distilled water, small cubes of pre-dried material rapidly took
up 340 wt% of water and sank, giving a final water pH of
9.7. Expanded perlites are made by expanding a ground and
classified volcanic rock in a furnace. The rock melts and pops
into glassy bubbles which are not closed cell, but have a low
surface area. The water of hydration is lost. The finished
product is made by adding various binders (Goodtemp 1500
uses binders of clay, sodium silicate and about 1 wtTo of
polyester fibers). The liquid water uptake of perlivs depends
on whether silicone water repellants have been added. The
latter greatly reduce water uptake and can also repel many
combustible liquids with beneficial effect. Mineral wool insulations, such as low density Rockwool 850 and high
density Rockwool 851 or Epitherm 1200, are spun from slag.
While specific surface area and atmospheric water uptake are
relatively small they can soak up liquid water like a sponge.
Mineral wools with added moisture repellants are far less effective in repelling liquids than are similarly treated perlites,
since wicking still occurs. Expanded vermiculites such as Pumica have a high density and are made by expanding vermiculite
(an altered mica) in a furnace and binding it with a vitrified
binder. Vermiculite (from the Latin verrnis, a worm) is
named after its tendency to curl and expand in a high temperature flame. The sample tested had a relatively high water
uptake and pH.
Liquid EO Plus Insulation Samples in the ARC (No Air)

As discussed in [3] tests were initially done in the ARC on
as received insulation samples to determine the relative rates
of reaction with liquid EO. Further tests were done on samples
conditioned according to ASTM C870-77, which involves pre-
TABLE 8 MEASURED PROPERTIES OF INSULATIONS SAiMPLES

Insulation
Type
Goodtemp lS00
Epitherm 1200
Kaylo-10
Rockwool 850
Rockwool 851
Pumica
38
January, 1991
Liquid Water
Uptake (wt%)
127
129
342
295
73
143
Water Vapor
Uptake (wt%)
2.06
0.21
7.53
0.26
0.39
3.58
Density
PH
Wee)
0.287
0.168
0.199
0.138
0.157
0.402
10.8
9.73
9.73
10.2
7.63
11.2
Surface
Area (m2ig)
1.31
1.0s
75
0.63
0.91
2.36
Exotherm
(C)
132
122
63
129
132
98
Sla>-Shut Relay
glycols under real conditions. After long periods of

- - _ _ _ _ _ _ _ _ _ _ _ . _ _ _ _ _ _ _ _ _ _ _ _ _ _cumulate
.
exposure
the glycols might accumulate even at atmospheric
I n Flare
temperature.
Insulation Plus EO Vapor in Large Isothermal Reactor

(With or Without Air)
30
<c
-1:"
Control loop
LO
healer element
FIGURE 8. 16 Liter Isothermal Test Vessel for

Exposing Hot Insulation to EO Vapor.
drying, weighing, equilibration with air at 73 F and 50% relative humidity, then reweighing. Table 8 shows some specimen
results for 1.60 g. of conditioned sample added to 1.60 g. EO
in the ARC. The "exotherm" values are uncorrected initiation
temperatures (heat rate 0.02 C/min) at an approximately constant 4 factor of 3.2. The lowest exotherm initiation temperatures were observed with asbestos (73 C) and calcium silicate
(63 C for Kaylo-10). Repeatability was found to be poor.
Repeat tests with Goodtemp 1500 perlite gave exotherms at
122 and 132 C. Epitherm 1200 mineral wool gave 97 and 122
C. Rockwool 850 mineral wool gave 143, 126, 92 and 129 C.
This could be blamed in part on the difficulties in obtaining
representative samples of the non-homogeneous materials. As
a final test, Goodtemp 1500 was soaked with rainwater and
retested. The sample took up 127 wt% of its dry weight of
water and gave an elevated pH (Table 8). When 1.60 g. of the
wetted material was added to 1.60 g. liquid EO in the ARC
(4 = 3.29), the exotherm started at 47 C (40 C @ 4 = 1). If
the presence of the insulation is neglected except for its thermal
inertia, and the corrected result compared with Figure 7, the
0.895 g. of water present (36 wt%) lowered the initiation temperature some 34 C more than was observed for distilled water
alone. Thus wet insulation can be more reactive than due simply
to the water it contains. This may be simply due to its elevated
pH but could involve surface effects. In any case, it was seen
that if insulation for EO service is specified partly on the basis
of this type of test it should be recognized that all porous
refractory insulations might react with EO to form and ac-
Heats of combustion of glycols are more than an order of

magnitude greater than their heats of formation from EO and
water. Glycol oxidation is therefore potentially far more important as a heat source than the EO-water reaction. However,
at temperatures well below the SITs given in Table 4 the heat
of glycol formation might be significant should the reaction
proceed at a fast enough rate. In the presence of a continued
EO leak the heat inputs from glycol formation and oxidation
could be additive leading to a reduction in effective SIT. To
address this, experiments were carried out [3] in the approximately spherical 16 liter vessel shown in Figure 8. Liquid EO
in a 30 C water bath was vaporized and passed via a regulator
set at 1-2 psig to a distributor in the reactor. The reactor (about
1 ft. diameter) was filled with half-inch cubes of insulation
and immersed in an oil bath held at constant temperature.
Eight tests were carried out using different insulation samples
or test procedures. Facilities were provided for delivery of air
to the reactor during the tests.
It was found that perlite, mineral wool and calcium silicate
all formed glycols during exposure to EO vapor. Most reactive
was calcium silicate. A 1.702 kg sample of Kaylo-10 (10-11
wtoio of removable water) held at 125 C in the closed system
took up 5.90 kg of EO over a ten-day period and pulled a
vacuum on the depleted EO reservoir. A 40-50 C exotherm
was maintained during reaction. A sample of this exposed
insulation containing about 350 wt% of glycols was subsequently tested for SIT (Table 9). No runaway reactions were
observed in the isothermal reactor under any test conditions
although local charring occurred after admission of air. This
was observed even for perlite. For dry perlite and mineral wool,
no exotherms were observed at temperatures less than 140 C
unless air was added.
Application of Theory to T4EG Cube Test Data

SITs were measured for tetraethylene glycol (T4EG) in oneinch, two-inch and four-inch cubes (Table 9). They were found
to be 108, 88 and 75 C respectively. A further test using an
eight-inch cube showed no exotherm after about 1200 hours
TABLE 9 SIT TEST RESULTS FOR T4EG IN MINERAL WOOL AND CELLULAR GLASS. ALSO EO REACTION
PRODUCTS IN CALCIUM SILICATE
To
T,,,
t*
Lax
Result
Liquid
Insulation
Loading
(C)
(min)
(min)
(cube side)
(wtV0)
(C)
1185
Exotherm
350
103
130
105
1 " Epitherm Wool
5514
Exotherm
350
106
127
75
1 " Epitherm Wool
2065
Ignition
246
150
1 " Epitherm Wool
350
111
2" Epitherm Wool
3 50
85
85
n/a
>2250
No exotherm
2 " Epitherm Wool
3 50
90
40 1
1524
3120
Ignition
EO reaction products
2" Kaylo-10
350
96
469
940
1355
Ignition
3 50
108
296
810
456
Ignition
2" Epitherm Wool
2" Epitherm Wool
350
120
613
140
114
Ignition
Ignition
2" Epitherm Wool
350
130
252
102
99
n/a
I46
186
30
69
Exotherm Only
2 " Cellular Glass
2" Epitherm Wool
350
155
263
67
60
Ignition
2" Epitherm Wool
350
190
330
42
25
Ignition
tetraethylene
tetraethylene
tetraethylene
tetraethylene
glycol
glycol
glycol
glycol
4" Epitherm
4" Epitherm
4 " Epitherm
8 " Epitherm
Wool
Wool
Wool
Wool
350
350
350
350
73
77
90
65
73
692
797
65
n/a
5520
2417
110
6000
2100
814
71950
No exotherm
Ignition
Ignition
Cube shrank
January, 1991
39
200
220
h
0,
180
200
a2
L
180
160
.-ma
L
W
+E
140
p.
140
20
120
100
60
40
80
10
1000
100
10000
Isothermal Ignition Delay (min)
of isothermal heating at 65 C. However, it was found that

shrinkage and drainage of the cube had occurred during this
time and an effect of the shrinkage was to significantly open
up the structure. Thus, increased heat losses due to this effect
probably invalidated the result.
Table 9 shows a result with a two-inch cube of cellular glass
soaked with T4EG (after subdivision into half-inch cubes to
simulate some breakage). The amount of liquid uptake was
too small to give sustained combustion even at 146 C and only
a 40 C exotherm was produced. A sample of Kaylo-10 soaked
with 350 wt% of glycols after exposure to EO vapor in the 16
liter reactor behaved very similarly to cubes of mineral wool
with the same weight loading of T4EG. The comparative isothermal ignition delay times are shown in Figure 9.
Equation (1) in Part 1 was used to correlate test data for
the one, two and four-inch cubes. Figure 10 shows a plot of
the logarithmic term in Equation 1 against reciprocal temperature, plus interpolated and extrapolated SITS for other sizes
of cube. The plot is linear with the simple regression fit and
error indicated on the figure. The constant terms are:
= 52.486 K2-m-2
M
E/R = 11764 K
From Equation (1) the SIT prediction for an eight-inch cube
is 60 C, which supports the idea that the experimental test had
been invalidated by the observed cube shrinkage. Since application of Equations (2-6) will result in higher predicted SITS
for the same thicknesses of insulation o n pipes, the important
result is that since T4EG seems to typify the glycols formed
by the reaction of E O in insulation, spontaneous ignition of
the deposited glycols should not occur at less than about 60
C even with exceptional thicknesses of insulation.
y = 52 486 - 1.1 764e+4x R2 = 0 992

22
21
20
19
18
17
0 0026
0 0027
00028
0 0029
0 0030
I I To
FIGURE 11.
Autodecomposition Temperature of
Vapor.
January, 1991
20
450
FIGURE 9. Ignition Delay Times for T4EG in Twolnch

Cubes of Mineral Wool Versus (single point) EO Reaction
Products in Calcium Silicate.
40
160
EO
460
470
480
490
Autodecomposition Temperature (1)
FIGURE 10.
Regression Fit of T4EG Cube SIT Data to

Equation (1).
Discussion of Two EO Spontaneous Insulation Fire Incidents

In addition to the unexplained incidents described earlier,
two major incidents have recently been attributed to the glycol mechanism. Both (BP Antwerp, 07:00, July 3, 1987 and
BASF Antwerp, 17:36, March 7, 1989) involvud distillation
column explosions reportedly due to EO decompositions initiated by external insulation fires. In the first incident the fire
reportedly originated on a manhead nozzle and in the second
on piping associated with a sight-glass. In both cases stagnant
EO vapor would have been present inside the equipment concerned, but the maximum initial EO tempera1 lire ~ r o u l dhave
been in the range 55-60 C. For the small thicknesses of mineral
wool insulation concerned, spontaneous glycol fires have not
been shown to occur in this temperature range, and heat is
unlikely to accumulate via glycol forming reactions.
To be consistent with the findings in this paper, the following
modified scenarios are suggested for the two incidmts. In the
BP incident the insulation fire might have originated elsewhere
such as the reboiler head, where temperatures would have been
above 90 C . No direct evidence of a leak was discovered during
the accident investigation owing to the extent of the damage.
The reboiler head was fitted with a pressure-test n o d e of small
diameter (small thermal mass) which would have contained
stagnant EO. On the day of the BASF incident there had been
maintenance work on the sight-glass in the morning. Also, it
was established that a small but long-term leak (weld crack)
had been present on the upper nozzle of the sight-glass piping.
If the small EO leak was ignited by static (or other ignition
source) during the maintenance work a flame might have
flashed back into the insulation and heated glycol-soaked mineral wool to above its SIT. Owing to the limited supply of
glycols and the several hour delay between maintenance and
the explosion, it must be assumed in this case that heat transfer
to the bulk of deposited glycols was slow. EO has a very small
minimum ignition energy in air of 0.06 mJ [ 3 ] and is prone to
ignition by imperceptible static sparks from people or ungrounded objects. A small ignited EO leak which would not
by itself heat equipment sufficiently to cause dwomposition
of the contained EO still has the potential to signilicantly raise
the insulation temperature. A long-term leak may deposit significant quantities of glycols in the insulation. If the temper
ature exceeds the SIT for the geometry concerned, the glycol.;
may ignite spontaneously. At temperatures less than the SIT
the glycols may represent a hazardous accumulation of fuel
that may ignite once the EO leak ignites.
TABLE 10 SPECIMEN FIRE ENDURANCE TEST RESULTS

Test
50
54
56
58
61
62
63
64
65
76
77
19
80
82
93
94
Specimen
Thickness
Goodtemp 1500*
Goodtemp 1500*
Goodtemp 1500
Celotemp
Epitherm 1200*
Sproule WR1200
Paroc 1600*
Paroc 1200*
Foamglas
Foamglas + SS jacket
Foamglas
SS jacket
Foamglas + Paroc 1200
Foamglas + Goodtemp *
Foamglas StrataFab
SS jacket
Knauf Temperlite
Foamglas + SS jacket
(Hydrocal undercoat)
2.5 single
2.5 single
2.5 single
2.5 single
2.5 single
2.5 single
2.5 single
2.5 single
2.5 single
2 . 5 single
2 x 1.5 layers
1 + 1.5 layers
1 + 1.5 layers
2 x 1.5 layers
1 + 1.5 layers
2 x 1 layers
Temperature
at 1 hr (F)
Notes
431
expanded perlite
formulation change?
> 1000 @ 46 rnin

> 1000 @ 42 min
410
590
> 1000 @ 42 min
40 1
806
>lo00 @ 33 min
> 1000 @ 48 rnin
946
> 1000 @ 58 rnin
> 1000 @ 31 min
987
expanded perlite
high density mineral wool
expanded perlite
high density mineral wool
low density mineral wool
cellular glass
just passed test
lost hexane feed @ 48 min
Goodtemp melted
just passed test
288
908
expanded perlite
passed test
Fire Endurance Test
Equation (9) shows the results of a criticality analysis of the

data in [3]:
This laboratory has for some years performed a fire endurance test on candidate insulations for EO service. The test
is more severe than that described in NFPA 251 (ASTM E119) and is designed to simulate a fast-developing external fire.
A three-inch diameter steel pipe with thermocouples peened
into the wall from inside is placed 28 inches above a two-foot
square pan containing a hexane pool fire. The hexane is fed
at 0.41 gpm onto two inches of water in the pan. Single or
multiple layers of insulation with or without jackets can be
tested. The criterion for acceptability is that the pipe wall must
remain below 1000 F (538 C) for one hour of fire exposure.
The pass temperature is arbitrary and rather higher than the
minimum autodecomposition temperature of EO (Figure 11).
Table 10 shows typical test results for expanded perlites, mineral wool, cellular glass (with and without stainless steel jackets) and cellular glass-refractory composites (see next section).
An asterisk denotes mastic insulation cover only.
It is believed that changes in formulation (sodium silicate
binder used instead of resin) caused the change in Goodtemp
perlite performance shown in tests 50-56. Samples tested before 1980 all passed the test, and Knouf perlite (test 93) with
a different formulation did very well. High density mineral
wools gave greater fire resistance than low density types. It is
seen from test 65 that cellular glass alone has very poor fire
endurance, and two staggered 1-1/2 inch layers plus a stainless
steel jacket (tests 77 and 82) were required to pass the test.
Limited tests using Pittsburgh-Corning Hydrocal B- 11 undercoat on the pipe suggest that this coating is beneficial, since
as shown in test 94 only two one-inch layers of Foamglas plus
a stainless steel weather barrier passed the test. Composite
insulation comprising cellular glass (1 inch) plus high density
mineral wool (1.5 inch) would probably pass the test even
without a steel jacket, but low density wool (test 79) and Goodtemp perlite (test 80) were unsuccessful. In test 80 the perlite
melted and peeled away from the cellular glass.
Figure 11 adapted from [3] shows the locus of minimum
autodecomposition temperatures (ADTs) found for EO vapor
in a spherical 550 ml stainless steel test vessel. The curve has
been fitted as a simple exponential with the error indicated on
the figure. The ADTs are lower than the value of 560 C often
cited, which was measured for EO at atmospheric pressure in
a small glass flask. In addition to pressure, ADTs are affected
by container surfaces, volume and geometry.
If surFace effects are neglected, estimates for the critical
ADT locus might be made for vessels of other sizes and shape.
log,{P*?/( T3=Ac)) -42876/T= - 80.940

(9)
where P
= pressure (psia)
r
= vessel radius (m)
T = ADT(K)
Ac = constant (3.2 for sphere, 2.0 for cylinder)
For example at 60 psia, iterative solution of equation (9) predicts (and Figure 11 shows) an ADT of 465 C in the 550 ml
(4 inch i.d.) spherical test vessel, for which r = 0.0508 m. The
ADT decreases as Lr increases, and is slightly less for cylinders than for spheres of equal diameter. Also at 60 psia,
equation (9) predicts ADTs of 497 C and 478 C for 1 inch and
2 inch i.d. pipes. These predicted ADTs are increased to 518
C and 497 C respectively at atmospheric pressure. Exact predictions should not be expected owing to model limitations
and possible surface effects.
Composite Insulation Systems and Solar Radiation

It has been suggested [2] that composite insulation comprising a cellular glass inner layer with an outer layer of cheaper
insulation might be used for combustibles handled above their
SITS. The principle is that sufficient thickness of cellular glass
can be used to keep the temperature of the outer porous layer
below the SIT of the combustible involved. An outer layer of
high density mineral wool or equivalent would also increase
the fire endurance of the composite and provide a cushion
against impact breakage. Decreasing the insulation thickness
required to provide fire endurance would facilitate retrofit of
existing insulation in areas such as pipe racks, where spacing
might be a limiting factor. Composites with mineral wool are
commercially available. The main advantages involve improved thermal insulation, cushioning, and retrofit in situations where insufficient space exists to provide the thickness
of 100% cellular glass needed for fire endurance.
InsuIated EO lines are typicaIly provided with stainless steel
weather barriers. Calculations were made to determine the
outer insulation temperature for various thicknesses of cellular
glass insulation on pipes of different diameters and wall temperatures. July Gulf Coast conditions were assumed, with the
sun high in the sky and radiation normal to the weather barrier.
The air temperature was assumed to be 35 C with a 5 mph
breeze. Solar flux was 300 Btu/hr-ft2 (946 W/mZ). Weathered
stainless steel was assumed to have a solar absorptivity of 0.75
January, 1991
41
(for water-reactive vapors and volatile liquid.;) or forced

air flow (for peroxide-forming volatile liquitls). A technique using forced air flow is described in 161, A drawback of isothermal techniques is the significant time
taken to heat the pre-wetted cube to the test temperature.
This enables volatile liquids to evaporate diuring t.he heatup time, whereas in a practical situation they would leak
into insulation already hot. Uniform addiriori of hot
liquid to a hot cube is impractical. Of the liquids tested
this drawback was of practical importaim only with
tetralin, whose SIT was inferred from the rapid appearance of more than a 50 C exotherm during evaporat ion.
SITS are affected by the type of insulation. Calcium
silicate has strong sorptive properties, a high specific
surface area and a dense structure that tends t o impede
evaporation. More volatile liquids or those whose SITS
are near their flash-points may be more likely to selfheat in this insulation than in mineral wools. Air ingress
is favored by open insulation structures such as mineral
wools. This appeared to assist the self-heating oftetralin.
One method to minimize the risk of spontaneous insulation fires is to use a suitable non-porous insulation or
insulation fitted with an impermeable skin. Cellular glass
is an example of non-combustible, non-porous insulation suitable for a wide range of system temperatures.
its non-porous structure can reduce the effects of moisture on heat loss and corrosion. Its disadvantages include
brittleness and sensitivity to vibration, which can be
mitigated using a primary layer of glass fiber tape on
piping (this also reduces the scratching of corrosionprotective paint on equipment). Other disadvantages are
cost and difficulties in fabrication for complex equipment items. For flexible lines, such as heat-traced load/
unload lines for liquids of high melting porxir, a practical
alternative to cellular glass is a wrap-around jacketed
insulation with a suitable impermeable plastic or siliconized fabric cover. In some cases loacl/unload lines
can be left uninsulated where the heat loss is tolerablc
and personnel protection criteria can be met. For high
maintenance items a wrap-around jacketed insulation
might be fitted locally, provided that fire endurance is
not a critical concern; otherwise a snap-on boxed insulation (Part I1 Conclusions) might be used.
Perlites containing water repellants are commercially
available and these can greatly reduce the uptake of
combustible liquid following a leak. For example, a silicone-treated perlite sample diced into half-inch cubes
took up only 30 wt% of tetraethylene glycol after several
weeks of total immersion, which was less Ehan one-tenth
the uptake in other porous insulations. If the liquid is
repelled there is less probability of approaching optimum
liquid loadings, less lateral spread of thc liquid, and a
better chance of early leak detection. Should a spontaneous fire develop, the amount of insulation affected
will be decreased. These advantages alniost disappear
for mineral wools containing water repellants, since
wicking can still occur. Mineral wool also has an open
structure conducive to air ingress and chimney effects
in vertical pipe runs. To assess effectiveness it is recommended that specific tests be made to measure the
weight percentage increase of water repellant insulations
after immersion in the liquid concerned. For high temperature applications (above about 230 (1) the decomposition of the repellant over time must be considered.
and an emissivity of 0.5 at weather barrier temperatures. The

absorptivity and emissivity had to be estimated for weathered
stainless steel and might be conservative. The other primary
factors (wind speed, air temperature and solar radiation) are
not worst-cases.
The predicted surface temperatures (those of the weather
barrier and contacted insulation) were relatively uninfluenced
by pipe diameter, wall temperature or insulation thickness,
since heat conduction through the insulation was small compared with radiation and convection at the surface. For pipes
and equipment of diameter 2-128 inches, cellular glass thicknesses from 1-4 inches and inner wall temperature at 38 C,
surface temperatures varied from 72-75 C. For an inner wall
temperature of 150 C the surface temperatures varied from
78-83 C. These high predicted temperatures made it difficult
to justify the practical problems that a composite insulation
system would introduce. They also made it questionable that
a safe temperature existed below which 100% porous insulation could be used and brought into question the relevance
of personnel protection standards for stainless steel jackets
during the summer. Finally, the temperature effects introduced
an EO thermal expansion concern for valved-in lines and selfheating concerns for lines containing EO and water.
Stainless steel when severely weathered becomes almost a
black body absorber of solar radiation, and is normally a poor
emitter of long wavelength infrared (at the weather barrier
temperature). Certain paints such as zinc oxide will change the
absorptivity to 0.18 and long wavelength emissivity to 0.95,
and would in principle solve the radiation problem. I1 composite insulation is used for EO service it is necessary to take
account of the possibility that an EO leak might ignite and
flash back into the outer porous insulation layer. If this layer
contains previously deposited glycols additional heat will be
generated when these ignite. The equipment could be exposed
to high temperatures especially if the underlying cellular glass
is in poor condition.
Part 1 Conclusions: General

The conditions under which spontaneous insulation fires
are likely to occur are predictable from test data. Simple
isothermal SIT tests of liquid-soaked cubes of insulation
give conservative predictions for equal thicknesses of
insulation on pipes, This has been demonstrated theoretically and experimentally [2]. The effect of insulation
thickness is adequately described by a theoretical model.
While SIT data obtained from pipe simulations may be
scaled to other pipe diameters and insulation thicknesses,
direct use of cube SIT test data to predict SITS for pipes
may give inaccurate results.
SIT data were generated for a series of combustible
liquids using two-inch cubes of pre-dried insulation and
liquid loadings in the range 150-250-350 wt%. Tests
were made primarily with mineral wools while some were
made with calcium silicate. The SITSare generally lower
than reported previously and vary with the type of liquid
from about 55 C t o more than 183 C. The tabulated SIT
data form the widest currently available database. This
provides benchmarks for assessing the results of future
testing by this method.
For a wide range of combustible liquids, spontaneous
ignition always took place for Z > 1.61 and evaporation
usually took place for Z < 1.35. However, water-reactive volatile liquids and vapors having low Z values
may react with moisture in insulation generating heat
plus less volatile products. These products may accumulate and self-heat. Also, peroxide-forming materials
such as tetralin and 2-ethyl hexaldehyde appear to form
a second group of exceptions. Special techniques may
be required to address self-heating of reactive liquids
and vapors. These may involve long periods of exposure
January, 1991
Part I1 Conclusions: EO Insulation Fires

(1)
Refractory insulation materials such as calcium silicate,

mineral wool, vermiculite and perlitc. naturally contain
PlantlOperations Progress (Vol. 10,
No. 1)
significant quantities of water derived from ambient air.

The amount depends o n the type of insulation, temperature and relative humidity. Insulations will soak up
much larger quantities of water if they are wetted.
Insulation provides a basic medium for reaction of EO
with this water to form tetraethylene glycol and other
low molecular weight polyethylene glycols. Analysis of
reaction products after exposing several types of insulation to EO vapor showed IR spectra consistent with
these glycols, The reaction is exothermic but is normally
too slow by itself to accumulate significant heat in typical
thicknesses of insulation.
All porous refractory insulations will accumulate glycols
after extended periods of exposure t o EO vapor. The
rate of glycol formation is faster with calcium silicate
and asbestos than with mineral wools or expanded perlites. Insulations containing moisture repellants also accumulate glycols. The reaction can proceed over the
course of weeks or even years, and a large accumulation
of glycols can build up. This represents a significant
accumulation of fuel which at a sufficiently high temperature might ignite spontaneously. If the insulation is
wetted, the rate of glycol formation is increased and this
could lead to a spontaneous combustion hazard upon
start-up of heated equipment.
Isothermal tests with tetraethylene glycol-soaked cubes
of mineral wool insulation showed that when uniformly
heated in air for extended periods, SITs were 108 C ir,
a one-inch cube, 88 C in a two-inch cube and 75 C in a
four-inch cube. These temperatures can be exceeded in
practical EO handling situations. The SIT data were well
correlated by theory and extrapolation indicated that to
reduce the SIT to 60 C an eight-inch cube would be
required. Since SITs measured in cubes are conservative
in relation to the same thickness of insulation on pipes,
spontaneous ignition of this glycol should not occur at
less than 60 C even for exceptional thicknesses of insulation.
Further tests with lower and higher glycols showed no
reductions of the SIT found for tetraethylene glycol.
Also, a sample of calcium silicate that had been exposed
to EO vapor and taken u p 350 wt% of glycols gave a
self-heating temperature history indistinguishable from
that of mineral wool soaked with 350 wt% of tetraethylene glycol. Tetraethylene glycol appears t o adequately
represent the glycols produced by EO reaction with insulation. Thus, spontaneous EO fires should not occur
at temperatures less than 60 C.
Temperatures obtained during runaway self-heating of
glycols in two-inch cubes could exceed 600 C. In the
presence of a continued EO leak, temperatures exceeding
1000 C could be reached. These temperatures are sufficient to cause autodecomposition of EO contained in
some items of equipment. Since the heat input is limited,
the heat capacity of the equipment is an important factor. Most prone are small diameter items such as pipes
and instrument tubing, which can rapidly be heated to
above 450 C. Autodecomposition is most likely to occur
for stagnant vapor-phase EO, although liquid-phase decomposition might also be possible [3].High rates of
material flow inside the equipment will help convect the
heat away.
At temperatures greater than 250 C an important source
of heat is isomerization of EO t o acetaldehyde. The
admixture of acetaldehyde to EO reduces the vapor autoignition temperature to much less than that of pure EO.
For large EO leaks isomerization followed by combustion will be the principal heat sources after initiation by
glycol self-heating.
EO has a very smali minimum ignition energy in air of
0.06 mJ [3]and a very wide flammable range from 3-
100 mol%. This enables external ignition of a leak by

sources such as static to occur easily. Spark sources might
be people or ungrounded objects introduced during
maintenance operations, ungrounded steel weather jackets, or faulty electrical equipment. Atmospheric electricity could be important, particularly in conjunction
with ungrounded steel jackets on pipelines, which might
attain very high potentials by induction from storm systems. If an external ignition source ever became available, an EO leak couId ignite and flash back to its source
within the insulation. While the leak itself might be too
small to cause significant heating of the equipment, it
could be an effective ignition source for glycols previously deposited in the insulation. Hence, given the event
that an external source might ignite the EO leak, there
is no completely safe temperature for avoiding EO insulation fires in porous refractory insulation.
(9) Cellular glass insulation does not accumulate glycols on
exposure to EO. Even when samples of cellular glass
were deliberately soaked with tetraethylene glycol, the
quantity of liquid absorbed was too small to give sustained combustion. Because the structure is non-porous,
an externally-ignited EO leak will not burn within the
body of the insulation but will be restricted to inter-layer
gaps and the open air. Increased resistance to lateral
convection and diffusion should help with leak detection
and, if the EO is externally ignited, it is likely to give a
visible external ffame rather than burn inside the insulation.
(10) A disadvantage of cellular glass is its relatively poor fire
endurance properties. In the event of a n external fire,
a n important consideration is the time available for fire
control before equipment is heated to the decomposition
temperature of the contained EO. If cellular glass is used,
sufficient thickness should be applied and additional
measures such as a stainless steel jacket should be considered. T o pass a proprietary one hour fire endurance
test, one brand of cellular glass with no undercoat required two staggered layers each 1-1/2inches thick under
a stainless steel jacket (by comparison, a high density
mineral wool outperformed this system when applied as
a single 2-112 inch layer with mastic coating). Limited
tests of cellular glass with Hydrocal undercoat suggested
that the coating might improve fire endurance. For high
maintenance items pre-formed snap-on boxes of cellular
glass enclosed in stainless steel might be used.
(1I ) The fire endurance of cellular glass might be increased
by using an inner cellular glass layer plus an external
layer of insulation with good fire endurance properties,
such as high density mineral wool. In principle this would
allow smaller total insulation thicknesses than for cellular glass alone. If the outer porous insulation is kept
below the SIT of glycols by using a sufficient thickness
of cellular glass, spontaneous fires should be avoided.
To reduce the effect of solar heating of stainless steel
jackets, external paint application could be used. However, where there is the chance of external ignition of
an EO leak it might be possible for the flame to flash
back and burn in the porous outer layer. Heat from this
flame plus that of glycol combustion might expose the
equipment to high temperatures.
(12) UCC&P makes use of leak detectors on flanges, comprising a tight band around the flange and a 1/4 tube
directing any leaked vapor or liquid downwards to the
open air. This is done principally to increase the sensitivity of portable gas analyzers. While leak detectors also
decrease vapor permeation into the insulation, the system is not completely gas tight and vapor can still migrate
through small openings such as in bolt holes.
(13) The following insulation system might be considered for
equipment containing sufficient EO concentrations to
January, 1991
43
represent a decomposition risk (nominally about 50%

E O or greater by weight): minimum thickness of 2 inches
of cellular glass on pipes and 3 inches on vessels, installed
in two layers with staggered joints, using Hydrocal (or
equivalent) bore coating and stainless steel jackets.
Equipment operating at 60 C or greater (plus certain
vapor lines) with existing porous insulation might be
retrofitted on an accelerated basis according to the anticipated risk of insulation fires in the systems concerned.
Certain equipment might be exempted owing to special
considerations, such as lines run underground, lines in
temporary use, and transportation vessels such as railcars.
Acknowledgements
Bill Schwartz carried out the ARC and fire endurance tests
under the direction of Glenn Synder. Bob Litton performed
the SIT tests and experiments on glycol formation from EO.
Solar radiation calculations were made by George Schwarz.
The test program was sponsored by the Industrial Chemicals
Division of Union Carbide Chemicals and Plastics Company
Inc.
Literature Cited
1. Green, R. L., and Dressel, D. E., Heat Transfer Fluid
Fires and their Prevention in Vapor Thermal Liquid Systems, Paper 9d, AlChE 1989 Spring National Meeting,
Houston, Texas.
44
January, 1991
2. Bowes, P. C., Fires in Oil Soaked Lagging, Building

Research Establishment Current Paper CP S5/74, Fire
3.
4.
5.
6.
7.
8.
9.
10.
Research Station, Borehamwood, England, February

(1974).
Britton, L. G., Thermal Stability and Deflagration of
Ethylene Oxide, paper 62d, AIChE Spring National
Meeting, New Orleans, LA, March 8 (1988). Also Planr/
Operations Progress, Vol. 9, No. 2 , April (1990).
Gugan, K., Lagging Fires: The Present Position, Paper
C , Symp. on Chemical Process Hazards with Special Reference to Plant Design, Institution of Chemica! Engineers,
Symposium Series 39, .4pril (1974).
Britton, L. G., Combustion Hazards o f Silane and its
Chlorides, Plant/Operations Progress, Vol. 9, No. I ,
January (1990).
Lindner, H., and Seibring, H . , Self-lgnition of Organic
Substances in Lagging Material, Chemie-lng. -Techn,
Vol. 39, No. 1 1 , pp. 667-671 (1967). [in German].
Beever, P. F., and Thorne, P. F . , Isothermal Test Methods for Assessing Combustible Powders, Building Research Establishment Current Paper CP5/82, Fire Research
Station, Borehamwood, England, July ( I 982).
Vanderwater, R. G., Case History of an Ethylene (Oxide)
Tank Car Explosion, Chemical Engineerin,y Progress,
Vol. 85, No. 12, December (1989).
Bowes, P. C., and Langford, B . , Sponraneous Ignition
of Oil-Soaked Lagging, Chemical and Process Engineering, May (1968).
Dixon, B. E., and Williams, R. A., Reaction of Iron
with Monoethanolamine, J . SOC. Chem. h i . (Land.),
Vol. 69, No. 69 (1950).

Spontaneous Fires in Insulation: Understanding Causes and Preventing Risks

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Spontaneous Fires in Insulation

Combustible liquids may self-heat in porous insulation yielding smoldering or flaming

PlantlOperations Progress (Vol. 10, No. 1)

and air ingress the system temperature will increase sufficiently

amined. The earlier work [6] established a minimum value for

Part I: General Considerations

By determining SITs for a series of at least three sizes of cube

from a plot of the logarithmic term against reciprocal absolute

Plantloperations Progress (Vol. 10, No. 1)

Lindner and Seibring Criterion

Lindner and Seibring [6]believed the flash-point (FP) and

Critical Ignition Parameter Relationships.

Equation (2) can then be solved iteratively to predict SITs for

6c* = (l9,l + 1.4)*/8

Plantloperations Progress (Vol. 10, No. 1)

Standardized SIT Test Method

Cube of Liquid-Soaked Insulation in Steel Mesh Basket

Schematic of SIT Test Apparatus.

Epitherm Mineral Wool

Temperature History for T4EG ignition in Two-Inch Cube.

Case History: MDEA Insulation Fire (1989)

TABLE 1 METHYLDIETHANOLAMINE IN TWO-INCH CUBES OF KAYLO-10 CALCIUM SIIJCATE

Plantloperations Progress (Vol. 10, No. 1)

TABLE 2 AMINES (IN DELTA WRAP MINERAL WOOL)

PlantlOperations Progress (Vol. 10, No. 1)

mineral wool, in which the MDEA evaporated with no exotherms.

butyl CELLOSOLVE (1)

( I ) ethylene glycol monobutyl ether

therefore determine whether self-heating or evaporation occurs

Glycol Ethers, TERGITOLS and Organosilane Esters

PlantlOperations Progress (Vol. 10, No. 1)

a wrap-around blanket insulation with an impervious skin can

Heat Transfer Fluids

(Dowtherm J, Therminol 55)

The fire incident analysis in [ I ] showed that insulation fires

Plantloperations Progress (Vol. 10,

are less prone to the phenomenon. Least prone should be

TABLE 5 HEAT TRANSFER FLUIDS IN DELTA WRAP (D) OR KAYLO-10 (K)

Liquid and Insulation Used

Mean SIT (C)

SIT Limits (C)

Plantloperations Progress (Vol. 10, No. 1 )

por. Dowtherms A and G gave no exotherms under the test

Examination of Lindner and Seibring Ignition Criterion

Plantloperations Progress (Vol. 10, No. 1)

Dowtherms A, G and HT are significantly higher than those

Variation of SIT with Z Parameter.

pillows used for spill control). Ethylene oxide is discussed in

the same material due to small differences in test conditions.

Flash Point (C)

Variation of SIT with Flash-Point.

Plantloperations Progress (Vol. 10, No. 1)

silicate insulations, which are normally made from diatoma8o

Reactor Temperature (C)

exclude the phenomenon. The type of porous insulation soaked

Part 11: Ethylene Oxide Insulation Fires

Plantloperations Progress (Vol. 10, No. 1)

sponds to the release of isomerization energy but admixture

Low Temperature Reaction of EO with Porous Refractory Insulation (No Air)

Acetaldehyde in Mixture (wt%)

FIGURE 6. Effect of Acetaldehyde Admixture on the

finally decomposition of the polymer to carbonaceous solids

Some measured properties of insulation samples are given