Explosion Safety in Ethoxylation

Reactors
M Braithwaite
(1)
& A Pekalski
(3)
(1) Imperial College, London, UK
(2) Shell Global Solutions, Chester, UK
EthoxylationReactor Study (1997-2000)
many reactor types/ different bases of safety/
reactor conditions/ products
relievers
containers
Review of EO Hazards
J L Gustin, IChemE Hazards XV (April 2000)
this study solely concerned with reactor issues - ie
excludes EO/air interactions, toxicity, downstream EO handling,
liquid phase EO chemistry, corrosion etc
decomposition flame in the vessel and not detonation or events
external to the reactor is the prime concern
Combustion Characteristics of Ethylene
Oxide
Molecular Weight 44.05
Density (relative to air) 1.5
Boiling Point 10.4 Deg C at 1 ata
Stoichiometric Concentration in air 7.72 % v/v
Heat of Formation at 25 Deg C 52.7 kJ / mole
Heat of Combustion at 25 Deg C 1217 kJ /mole
Autoignition Temperature 429 Deg C at 1 ata
Flash Point Deg C <- 18 Deg C
Lower Explosion Limit 3.6 % v/v
Upper Explosion Limit 100 % v/v
Basis of Safety in EthoxylationReactors
containment
maximum pressure governed by EO concentration. T, P
inerting
use on inert (egN
2
) to render system non-reactive
relief + venting
emergency (via bursting disk)
controlled (via relief valve) - smaller capacity
suppression
rapid release of powder/ inert gas
avoidance of ignition
best practice but not a B o S
Recent Plant Accidents involving Ethylene Oxide
Year Country Company Cause
1987 Switzerland Sandoz External fire
1987 Belgium BP External hot spot
1987 Netherlands DOW Failure of heat exchanger
1989 Belgium BASF Hairline crack, EO distillation column
1989 J apan Asahi Denka EO leakage
1991 China Lu Shun Reactor malfunction
1991 USA Union Carbide Iron oxide impurities
Batch ethoxylators --- generic
chemical engineering
v v v v v v v v v v
EO / PO FEED
SUBSTRATE+CATALYST FEED
VENT TO HEADGEAR
DIFFUSIONAL MASS TRANSFER
(DISSOLUTION OF GASES)
REACTION KINETICS
HEAT TRANSFER
PRODUCT
BULK MASS TRANSFER
MIXING
DIFFUSIONAL MASS TRANSFER
(SOLUTION OF GASES)
VVV
Ethylene oxide reactions
TYPICAL RELATIVE
HEAT OF REACTION MOLAR
CHANGE KCal/Mole
HYDROLYSIS 21.4 CONTRACTION
22.4 CONTRACTION POLYMERISATION
NO CHANGE
28.1 ISOMERISATION
31.0 EXP. 1.5 --->1.75 DISPROPORTIONATION
32.7 EXP. 2.0 --->2.5 DECOMPOSITION (FLAME)
EXP. 1.1 COMBUSTION
291.2
This Study - one component
of complete engineering overview of
ethoxylationreactors (1996-2000)
revisit thermodynamic (conservative) estimates of maximum
overpressures in EO/ EO+N
2
mixtures
assess literature information of gross decomposition rates
develop simple venting model based on above to evaluate :
gaps in current understanding
needs for more experimental data
feasibility of some envisaged engineering solutions
eg N2 dilution
use of relief valves only in existing plant
alternative diluents/ operating conditions
Published EO studies
Author/ Ref GAS

Initial
Pressure
bara
Initial
Temperature
Deg C
Scale of
experiment
(litres)
Flow
conditions &
Vessel type

R Friedman & E Burke EO 0.4 - 2.0 60 140 - Laminar flame
J H Burgoyne & K E Bett
et al
EO 0.3 - 9.3 20 100 2.44 Static/ cylinder
R K J une and R F Dye EO/N
2
1.7 6.5 60 190 2.00 Static/ cylinder
R Siwek & E Rosenberg EO 0.5 4.0 40 200 20 10(3) Various/
Various

T Ogawa, A Miyake & H
Matsuo
EO/
N
2
/PO
1 5 20 180 0.765 Static/
Cylinder
M.Braithwaite, A.Pekalski
& J Zevenbergen
EO/N
2

4 100 20
Static/ turbulent
sphere


15
20
25
30
35
40
45
50
55
20 40 60 80 100 120 140 160 180 200
Initial temperature [C]
P
m
a
x


[
b
a
r
a
]
100%EO
80%EO
60%EO
50%EO
Effect of initial temperature and mixture composition on the maximum equilibrium pressure
Solid line model with soot, dashed line model without soot, Pini=4 bara, Tini=100
o
C
STANJ AN Chemical EquiibriumCode (Stanford University (Reynolds)
a
20 liter explosion sphere
Pressure-time curve:
P
max
, (dP/dt)
max
Cube-root law:
K = (dP/dt)
max
* V
1/3
= constant ?
0
5
10
15
20
25
30
35
0 0.5 1 1.5 2 2.5 3 3.5 4 4.5 5 5.5
Time [s]
P

[
b
a
r
a
]
Ignition
100% EO
80% EO
60% EO
Pressure-time history for EO-nitrogen mixtures of different
initial composition; Pini= 4 bara, Tini = 100 C, IE= 180 J.
Ethylene Oxide: Maximum rate of pressure
rise &
maximum pressures - from 373 K and 4
bara
Composition
EO/N2
[EO%]
Ignition
Energy
[J ]
(dP/dt)max
[bar/s]
Pmax
[bara]
60 180 25.01 17.46
80 180 36.80 25.65
100 0.72 41.98 31.83
100 180 77.80 33.65
100 540 169.6 36.38
Explosion severity data of pure EO, Pini= 4 bara,
Tin = 100
o
C, IE= 250J, V= 0.02 m3 [Bartknecht]
Mixture
status
(dP/dt)
max
[bar / s] K
d
[bar m / s]
Quiescent 96 26
Turbulent 1500 407
EO Decomposition Model -Decomposition
Flame
Laminar Flame velocity (T,P) - experimental
Simple Flamelet Model
S
eff
= S
u
x (Re/Re
c
)

S
u
- laminar burning velocity at T,P
Re
c
, - adjustable constants
Large scale studies - K
D
- experimental
K
D
- reduced maximum rate of pressure rise
EO Decomposition Model - Assumptions
ideal gas (EO, N2: EO gaseous decomposition products)
infinitessimal reaction film - 2 zone model
adiabatic process
mechanical equilibrium throughout
products in chemical equilibrium
flame velocity simulated by simple expression
spherical flame
vented gas either reactant or product - not mixed
no additional turbulence generated by venting process
Typical Pressure-Time History for EO
decomposition in a 5 m
3
vessel: initial
conditions 373 K and 4 bara: confined and
vented explosions
Time (secs)
1 2 3
P
r
e
s
s
u
r
e

(
B
a
r
a
)
0
10
20
30
40
50
Maximum Pressure in 5 m
3
vented EO
vessel: initial conditions - 373 K 4 bara
Ignition (1-base, 2-middle, 3-top)
1 2 3
P
r
e
s
s
u
r
e

(
b
a
r
a
)
30
32
34
36
38
40
Vessel Aspect Ratio
0.2 0.4 0.6 0.8 1.0
P
r
e
s
s
u
r
e

(
B
a
r
a
)
31
32
33
34
No of Relief Valves
0 1 2 3
P
r
e
s
s
u
r
e

(
B
a
r
a
)
10
15
20
25
30
35
40
45
50
EO Analysis (pre-SAFEKINEX) Conclusions
limited rate data
simple turbulence model
20 litre explosion data best available
Conservative design for explosion relief
(Containment preferred anyway for EO)