Ethylene Decomposition Relief Sizing

High Pressure Polyethylene Industry

David I Shannon
E. I. DuPont de Nemours & Co., Inc.
2695 Old Bloomington Hwy (P.O. Box 526 77902)
Victoria, Texas 77905
Phone: 361-572-1813 E-Mail: david-irvin.shannon@usa.dupont.com
ABSTRACT:
This paper discusses revisions to a method previously used for sizing relief devices
(rupture disks) on vessels in high pressure Polyethylene processes. The Re-evaluation
was forced by an unexpectedly high peak pressure in a product separator (High
Pressure Separator - HPS) when an ethylene decomposition occurred. A method, based
on revised equations for calculating the rate of pressure rise, is presented for
determining relief requirements for an ethylene decomposition in a confined space. The
method applies to both HPSs and Polyethylene Autoclave Reactors. Causes of
decompositions and effect of comonomers are also discussed.
INTRODUCTION:
As a result of an incident at a DuPont facility, ethylene decomposition relief device
sizing was revisited. In the process of doing this, other incidents were identified at
licensee facilities that also had unexpected results. After of the reanalysis of ethylene
decomposition data, a revised method of sizing was developed. This information has
been published in the past at the June 1992 ASME Pressure Vessel and Piping
Conference in New Orleans, La., and at a Society of Polymer Industry safety Conference
in February 1995. In recent years it has been observed that many High Pressure
Polyethylene Facilities have not made changes needed to address the risk identified by
these previous presentations. Additional discussion has been added about causes and
associated changes in decomposition severity, and effect of comonomers (vinyl
acetate).
INCIDENTS:
In January 1987, a DuPont facility experienced an incident where the HPS pressure
exceeded 5000 psig (extrapolated to >6000 psig, instrument maximum scale was
5000). The relief sizing for this vessel indicated that the rupture disks should have
been large enough to keep the event pressure from rising after the disk burst
(3300psig). Technically, even this event would not be a problem for this vessel if it had
a high enough design pressure, but the design pressure of 4500 psig only allowed a
peak pressure of about 5735 psig based on 85% of the hydrostatic pressure. The

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hydro-static test pressure was 6750 psig (designed based on ASME Section VIII, Div.
1). The piping in the off-gas system of this vessel was only designed for 2700 psig.
This piping opened at the joints during this incident. Relief protection for the piping
was sized for process upsets only; the HPS disks are there to protect from a
decomposition. The event itself actually started in the line exit the bottom of the HPS.
The operator involved was unable to establish flow through this 550 psig steam
jacketed line. To break through the perceived plug, pressure was increased and
decreased 3 times in a short period of time, not only increasing the pressure in the line,
but also increasing the temperature in an already hot line (250oC). This resulting
temperature exceeded the ethylene decomposition temperature (see reference 1, 2 and
3 for this temperature(s)) due to adiabatic compression. The temperature increase is
substantial due to poor mixing in the line, essentially acting as a piston compressing the
hot gas at the end of the line which happened to be a broken guard valve.
Two similar events occurred in 1994 at another facility. These resulted from a repair of
the steam condensate drain of the HPS bottom exit (tails) line and a poor but accepted
operating procedure; the line (25 ft long) was pressured up, with steam on the jacket,
against an automatic valve. The poor operating procedure was masked by a
condensate drain that had required flow out the top of the jacket. When flow out the
bottom of the jacket was restored, the poor procedure was exposed by the 2
decomposition events. Each of these incidents resulted from one pressurization of this
line adiabatically compressing 250oC ethylene from less than 10 psig to 2400 psig.
SIZING BASIS:
The original work on ethylene decomposition sizing was done, within DuPont, in 1952
through 1954 to assist in the design of a new High Pressure LDPE Autoclave process.
Based on that work the Reactor and High Pressure Separator (HPS) relief protection
was designed. This design was based strictly on the operating conditions expect while
making polymer. It did not consider start-up or shutdown conditions that might
resulted in different relief protection.
Reactor relief design has resulted in no events on a DuPont Reactor where all of the
disks ruptured, indicating that the available relief area was high enough to handle the
pressure increase generated by the decomposition.
The original HPS rupture design was for a decomposition that started at normal
operating conditions, not low temperature conditions of start-up or shutdown. It was
assumed that decompositions only result from propagation from Reaction or from
external heat input. Based on experience this assumption was invalid.

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DECOMPOSITION CAUSES:
Ethylene decompositions result from ethylene breaking down. The chemical reactions
that are normally proposed for this reaction are below:
C2H4 C + CH4 and C2H4 2C + 2H2.
In reality the result of an ethylene decomposition event is methane, hydrogen, but also
many different oligomers, and possibly some polymer as reported in reference 3, 4, 5
and 6. So, with indefinite complex mixtures, that change with operating conditions and
compositions, an empirical calculation is necessary to get calculable results.
In a Polyethylene Reactor decompositions can be initiated by too much reaction initiator
(oxygen, peroxides and other catalysts if used). They can be initiated by not removing
all of the oxygen from the process during equipment purging. And they can be
catalyzed by impurities such as metal compounds from packing, particular copper.
In the High Pressure Separator (HPS) in a Low Density Polyethylene plant,
decompositions have multiple potential causes. The first one expected is propagation
of a decomposition from reaction. Another is heat input from equipment or pipe
jackets. Equipment purging or plug removal can adiabatically compress gas in heated
downstream piping; e.g., using HPS high pressure gas to quickly pressure up a heated
bottoms line that can be plugged with polymer or may have multiple valves, the
downstream one being closed. Or there can be flow regime problems in the HPS
bottoms line that can adiabatically compress gas to very high temperatures; flow is in
the slug flow regime due to the wrong line pipe diameter for the length of line required.
Decompositions that start in heated lines can, and do, propagate back into the HPS
Original Rupture Disk Sizing Basis:
Work in some unpublished laboratory work done in the 1950s showed development of
equation (1) for the rate of pressure rise during a decomposition. This was developed
from tests run by initiating decomposition in a number of different sized static bombs
and stirred autoclaves. The decompositions were initiated by hot wire, squibs, external
heat, oxygen and peroxide initiators. The equation was developed by fitting the
pressure rise versus time data. It should be recognized that the equations which follow
do not represent a rigorous kinetic model. They are approximations intended strictly for
sizing rupture disks for ethylene decompositions.

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(1)

dP
---- = 2.3 * K * P, where
dt
K = Violence coefficient
P = Pressure, psia.
T = time, sec.

The violence coefficient K for the HPS involved in the 1987 incident was estimated
based on the laboratory data at similar pressures. Violence coefficients for other
vessels, such as the reactor, were estimated the same way.
Equation (2) was also developed for disk venting rate as a function of the pressure, the
vessel volume, and the total rupture disk flow area. This was done by fitting the rate of
pressure decrease after the decomposition reaction was complete.
(2)

dP
---- = - 0.147 * P1.5 * S, where
dt
S = A/V
A = rupture disk area, in2
V = vessel volume, ft3

Note that the available relief area includes the effective capacity of any relief devices
attached to the process lines and the flow through any line that leads to another system
with significant capacity, such as off-gas line with relief valves.
Process vessels are not closed bombs, they have rupture disks so equations (1) and (2)
can be combined to yield a single relationship, equation (3). This equation can only be
used once the vessel pressure actually opens the rupture disks, until then only equation
(1) can be used.
(3)

dP
---- = 2.3 * K * P - 0.147 * P1.5 * S
dt

Ideally, the value of dP/dt in equation (3) is negative. So, when a rupture disk bursts,
the pressure immediately starts back down. Based on the three incidents mentioned
above and a number of incidents on other facilities known to DuPont, this is not
normally the case. The design case for the vessel involved in the 1987 incident used a
K of 0.2.

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With a vessel volume of 355 ft3, rupture disk area of 31.7 in2 and a burst pressure of 33
psig, the value of equation (3) at burst is negative (-550 psi/sec). Since the dP/dt was
greater than zero the data was revisited resulting in the changes discussed below.
Effect of Initial Density
The actual peak pressure experienced in the 1987 incident indicated that something
was not being considered. All DuPont laboratory data and plant incident data were
reviewed to look for variables not accounted for in these equations. This revealed that
the closed bomb pressure (Pmax, psia) and Violence Coefficient (K) are functions of the
mass of ethylene in a vessel at the start of the decomposition as measured by the initial
density (Den0, lb/ft3). Equation (4) shows the closed bomb pressure relationship and
equation (5) the K relationship, as reported in the 1992 ASME Paper (8).
(4)

Ln(Pmax) = 1.3423 * Ln(Den0) 0.4097

(5)

Ln(K) = 2.663 * Ln(Den0) 6.896

The data for the regression that produced equation (4) can be found in Table 1 below.
However, it was later found that the units for the result were in Kpsia, instead of psia,
so the statistics were revisited for this paper and equation (4r) generated as a
replacement.
(4r)

Ln(Pmax) = 1.2273 * Ln(Den0) + 6.807

Table 1 Closed Bomb Data

Init T, C Init P, psia
150
22000
150
22000
250
4500
250
4500
250
2250
250
2250
150
4500
150
4500

Pmax
43000
68300
20100
18700
7500
8570
32900
32300

Init Den, lb/ft3

30.77
30.77
11.82
11.82
6.36
6.36
16.2
16.2

The data for the regression that produced equation (5) can be found in Table 2 below;
includes 13 plant incidents within DuPont, its joint ventures, or its Licensees over a 40
year period.

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Table 2 Violence Coefficient Data

Initial P, Initial Initial Violence Lab or
psig
P,
T, C Coefficient, Plant
barg
K'
Data

9000
12700
14000
22000
22000
22000
27000
26000
13000
24000
11000
3770
3770
4002
3886
3712
3654
3770
2600
9000
9000
2250
2250
12700
14000
22000

621
876
966
1517
1517
1517
1862
1793
897
1655
759
260
260
276
268
256
252
260
179
621
621
155
155
876
966
1517

170
150
150
242
299
283
243
249
215
253
222
142
260
288
280
260
264
254
140
360
276
250
250
350
375
370

2.2
8.3
3.2
9.7
8
10
7
4.8
10
7
5
0.54
0.47
0.63
0.48
0.57
0.51
0.73
0.57
1.18
0.91
0.176
0.143
10.2
3.2
12

Relich- BWR-LK Initial

Kwong
Initial Density,
Initial Density, lb/ft3
Density, lb/ft3
ref 7
lb/ft3

Lab
Lab
Lab
Lab
Lab
Lab
Plant
Plant
Plant
Plant
Plant
Plant
Plant
Plant
Plant
Plant
Plant
Plant
Plant
Lab
Lab
Lab
Lab
Lab
Lab
Lab

23.47
27.4
28.2
29.15
27.73
28.11
30.82
30.37
25.22
29.61
24.98
15.92
10.81
10.62
10.55
10.67
10.41
10.99
11.78
16.99
16.59
6.78
6.78
20.94
21.35
26.11

22.8
26.4
27.1
27.6
26.1
26.5
29.1
28.7
24.2
27.9
22.5
15.9
10.2
10.3
10.2
10.4
10.1
10.7
11.7
16.1
18.6
6.7
6.7
19.8
20.1
24.4

22.944
26.603
27.352
-----24.738
-25.352
16.022
10.87
10.458
10.367
10.703
10.421
11.053
11.871
-18.785
6.698
6.698
----

Additional regression work has been done on this data also to determine the effect of
using different equations of state to determine the initial gas density of the system. In
doing this update it was noticed that regression of the same data could not duplicate
the original equation, the reason for which is unknown. So, four equations were
generated by regressing the data in Table 1, using the different sets of density data
from either actual data tables (from Ref 7), or two equations of state (Relich-Kwong
and Benedict-Webb-Ruben--Lee-Kessler). The results of the regression are shown
below:
Original
RK
BWR-LK
Actual Density7

Ln(K)
Ln(K)
Ln(K)
Ln(K)

=
=
=
=

2.663
2.692
2.735
2.450

*
*
*
*

Ln(Den0)
Ln(Den0)
Ln(Den0)
Ln(Den0)

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6.896
7.060
7.084
6.514

To determine if the difference in these equations is significant, 5 different densities

were input to each equation in the Peak Pressure Estimation method discussed below.
For each case the same rupture disk area of 31.7 in2 and volume of 355 ft3 were used.
The standard deviation for these results was about 5% indicating that the four
equations provide about the same result. So, it is recommended that the equation
regressed on actual density data be used (equation (5r) below, since it is based on
actual data. If the original equation is used, or an equation of state is used to estimate
ethylene density, the results will not change enough to provide an unsafe rupture disk
sizing result.
(5r)

Ln(K) = 2.450 * Ln(Den0) 6.514

To test this peak pressure algorithm, (equations (1) (5)) a computer simulation was
written to solve equation (3) for small time increments, changing the differentials to
differences leading to equation (6) below:
(6)

Pt+1 = Pt + (2.3* K * Pt 0.147* Pt1.5 * S ) * td, where

td = calculation time increment, sec

The results are shown in Figure 1 (1987 incident 140oC, 2600 psia, 355 ft3 vessel,
with 31.7 in2, 3300 psia burst pressure). The graph in Figure 1 indicates a good fit to
the actual event. The plot shows pressure constant until t = 0.0, then rising based on
equation (6) without any venting until t = tr, where the rupture disk bursts. At t = tmax,
the pressure rise portion of equation (6) drops out of the equation since there is no
longer any ethylene to decompose. The pressure at time tmax is the peak pressure.
The times tr and tmax are calculated by equations (7) and (8) below. Simulation of other
events at different operating conditions, not shown, indicate a good match for peak
pressure. Therefore. the equations above provide a good estimate of ethylene
decomposition peak pressure given the initial conditions.

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Figure 1: Ethylene Decomposition Incident - 1987

7000

6000

Pressure, psia

5000

P
HPS Press, psia

4000

3000

2000

1000

0
-5

-3

-1

Time, sec

Peak Pressure Estimation

If the value of equation (3) is greater than zero, a more rigorous calculation has to be
made. This can be done by unsteady state calculations as discussed above (equation
(6)), or by integrating equation (3). In order to estimate the peak pressure during a
decomposition event, the rupture disk burst time and the duration of the event need to
be calculated. To do this, equation (1) is integrated and solved for tmax to get equation
(7).

(7)

tmax

Pmax
Ln(------)
Po
= ------------------ , where
2.3 * K

Pmax = Closed Bomb Pressure, psia,

or pressure at which reaction is completed without a relief device.
Po = Initial pressure, psia
tmax = Decomposition duration, sec

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By substituting the rupture disk burst pressure (Pr) for the closed Bomb Pressure (Pmax),
the time to rupture disk burst (tr) is calculated by equation (8).

(8)

Pr
Ln(------)
Po
tr = -----------------2.3 * K

The amount of time the rupture disks are venting until peak pressure is reached is
calculated by equation (9).
(9)

tv = tmax tr , where
tv = venting time to peak pressure, sec

The times calculated above are then used in an integrated (rearranged) version of
equation (3): equation (10) which is used to calculate the peak vented pressure (Pv).
The integration is done between the rupture disk burst pressure (Pr) and the vented
pressure (Pv), from tr to tmax (or zero to tv, tr is reference). This peak pressure is the
maximum pressure expected in a vessel during an ethylene decomposition.
(10)

X2
Pv = ----- , where
Y2
X = 2.3 * Pr0.5 * K * e0.5*K*2.3*tv
Y = 2.3 * K 0.147 * Pr0.5 * S + Z
Z = 0.147 * Pr0.5 * S * e0.5*K*2.3*tv

For the incident conditions above (1987) equation (10) yields a peak pressure of 6497
psia (K=0.636), which agrees with the unsteady state method results shown in Figure
1.
EFFECT OF COMONOMERS
A small amount of data is available for Vinyl Acetate decompositions from a DuPont
internal report. As shown in Table 4 the violence coefficient for the 80% VA system is
more than 1 order of magnitude lower. A fit to this data combined with the ethylene K'
data gives the following:
Ln(K') = 2.663 Ln(Eth-Deno) - 6.896 - 2.63066 (Wt.Fr.VA)

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This is the ethylene K' as a function of initial density with the addition of a term that
corrects for VA concentration. The effect that this has on an ethylene decomposition is
that K' for 18% VA, for example, is approximately 1/2 of the ethylene K'.
More data is needed to accurately do these calculations for systems with Vinyl Acetate,
or other comonomers, in them. The major limit here is that the effect of VA on the
closed bomb pressure is not known. So, with the significant reduction in K with
increasing vinyl acetate, and no closed bomb pressure data, sizing for ethylene only is
recommended.
Table 4
80% Vinyl Acetate - Ethylene Decomposition
Violence Coefficient Data
Initial
Initial
Press. Temp.
o
Psig
C
3758
272
2420
330
2880
302
2865
329
3085
361

Initial
Initial
Violence Ethylene
Density Eth.Density Coefficient Predicted
lb/ft3
lb/ft3
K'
K'
19.00
10.48
.036
.51
12.49
6.02
.0047
.127
15.06
7.58
.0063
.225
14.22
7.11
.0046
.19
14.15
7.94
.0315
.253

ALTERNATE METHODS:
There are at least two other methods of calculating decomposition required relief area.
One recent paper presented a comparison of the DuPont method, discussed above
(based on ref. 8 equations from 1992) and what was designated as conventional
method, which assumes a steady state mass flow rate that is sufficient to move energy
from the vessel at a rate equal to the maximum rate at which it is input into or released
within the vessel, and a modified DuPont method. See reference 9 for details.
REFERENCES:
1. Neumann, R. and G. Luft (Aug. 1973), Studies of the Thermal Decomposition of
Ethylene under High Pressure, Chemical Engineering Science 28, pp. 1505-1514.
2. Albert, Jens and Gerhard Luft (1998), Runaway phenomena in the
ethylene/vinylacetate copolymerization under high pressure, Chemical Engineering
and Processing 37 (1998) pp. 55-59.
3. Albert, Jens and Gerhard Luft (October 1999), Thermal Decomposition of EthyleneComonomer Mixtures under High Pressure, AICHE Journal Vol. 45, No. 10, pp.
2214-2222.

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4. Bonsel, Harald and Gerhard Luft (1995), Safety Studies on the Explosive
degradation of Compressed Ethene, Chemical Engineering Technology 67, No. 7,
pp. 862-864.
5. Watanabe, Hiromasa and Masaaki Takehisa (1982), Studies on the Explosive
Decomposition of EthyleneMechanism of Ethylene Decomposition under High
Pressure, Koatsu Gasu 19, No. 12, pp. 605-612 (Department of Research, Takasaki
Institute, Japan Atomic Energy Institute).
6. Watanabe, Hiromasa, H. Kurihara and Masaaki Takehisa (1972), The Explosive
Decomposition of Ethylene, Loss Prevention and Safety, Pachec 72, pp. 225-232.
7. (Reference Book) DeReuck, K.M., International Union of Pure and Applied
Chemistry: ETHYLENE International Tables of the Fluid State.
8. Sullivan, J.F. and D.I. Shannon (1992), DECOMPOSITION VENTING IN A
POLYETHYLENE PRODUCT SEPARATOR. PVP, Vol.238, Codes and Standards and
Applications for High Pressure Equipment, ASME, 1992, pp. 191-195.
9. Darby, Ron (2006), Relief Vent Sizing for Deflagrations, Process Safety Progress
(Vol. 25, No. 2), pp. 130-134.

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