Ammonia Storage Tank Study

The pressure and venting dynamics model was developed by adding superheated
liquid to the cryogenic ammonia storage tank. It is useful in that it farces to consider
all the processes during feed to a tank and gives a feel for the behavior to expect
when variables are varied.

James N. Tilton
Du Pont Engineering, Newark, DE 19714

Richard H. Squire, Connie S. Saffie, and C. Riek Atkins

Du Pont Agricultural Products, Belle, WV

BACKGROUND B. The vapor returned to the tank at the maximum

The Belle Plant of the Du Pont Company handles
ammonia in a 20,000 ton cryogenic storage tank as a
terminal operation receiving ammonia by barge since
the Kellogg ammonia plant was shut down in 1976.
The double-walled and insulated tank operates between
0.3-0.5 psig. Ammonia is used on the site for
refrigeration and in the Amines processes. The
ammonia distribution system consists of the 20,000
ton storage tank, compressor, natura! gas assisted flare
stack, and two distribution pumps with heat
exchangers.
The ammonia storage tank is rated at l psig and
has normal and emergency venting capacity. The
normal vent allows the bank to be controlled at a
given set point and the emergency conservation vents
begin opening at the design rating. The vent line from
the storage tank goes to the suction of the compressor
and to the flare stack. Several internal and external
factors were analyzed in the design of the normal and
emergency vents.
l. Internal Factors
A. The heat duty associated with vapor
displacement while loading into the tank.
rate due to a malfunction of the vapor
replacement heater.
C. The rate that the ammonia is pumped out of
the tank. This consideration is for vacuüm
relief.
D. The amount of vapor normally going to the
compressor. This is also for vacuüm relief.
2. External Factors
A. An external fïre of 817 °C completely
engulfing the tank.
B. The rate of drop of outside barometric
pressure.
C. The maximum rate of heat input with the
insulation.
A more than 2x margin of safety was added to the
calculations resulting in the specification of two 10 inch
emergency conservation vents. Thermal overload
resulting from addition of warm ammonia was not
considered in the design basis for the vents. Thermal
overload is defined as the accumulation of sufficient
enthalpy in the tank, either through heat leakage from

63
insulation loss, to cause vaporization rates which
exceed the capacity of the normal vent, or worse, that
of the emergency vents. Ammonia is unloaded from
barges into the bottom of our storage tank where the
addition of warm ammonia is critica!. To determine
the venting requirements for thermal overload events,
a model was developed to predict the dynamics of
tank pressurization and venting behavior when warm
ammonia is added to the tank.
INTRODUCTTON
Large quantities of ammonia are typically stored
cryogenically. Du Pont has three large ammonia
tanks, located at its Beaumont, TX, Victoria, TX and
Belle, WV plants. The Belle tank has a 20,000 ton
capacity and is rated for l psig. It typically operates
at 0.3-6.5 psig. The tank is double-walled and
insulated to minimize heat leakage to the ammonia,
which boils at -33.4°C.
Out of a process hazards review of ammonia
handling and storage at the Belle plant came a concern
over the possibility of venting ammonia to the
environment through the tank emergency vents, or,
worse yet, overpressuring the tank, as a result of
thermal overload. For the present purposes, thermal
overload is defined as the accumulation of sufficient
enthalpy in the tank, either through feeding warm
ammonia or through heat leakage from insulation loss,
to cause vaporization rates which exceed the capacity
of the normal vent, or, worse, that of the emergency
vents.
An obvious situation where thermal overload could
occur is when warm ammonia is fed into an initially
empty tank. More subtle possibilities involve feeding
warm ammonia into a tank partially filled with cold
ammonia. Were the warm ammonia to mix slowly
with the initial liquid so that the liquid surface
temperature and vapor space pressure rise only very
slowly during the feeding, then excessive
accumulation of warm ammonia could go undetected.
During or after this accumulation, three events of
increasing severity are conceivable.
1. The submerged warm ammonia eventually mixes
completely with the cold ammonia, bringing the
entire tank to a uniform bulk temperature that is
higher than it was prior to the warm feed. This
will increase the heat flux through the boundary
layer at the surface and increase the vaporization
rate.
2. Due to the buoyancy of the warm ammonia, it
rises toward the liquid surface as it mixes with the
cold initial liquid. This brings the bulk liquid
temperature near part or all of the surface
64
boundary layer to a temperature less than the warm
feed temperature, but higher than the completely
mixed temperature. This results in greater rates of
vaporization.
3. An extreme version of the preceding case would
yield the greatest rate of vaporization. This would
be an assumed condition where no mixing of the
warm feed into the cold ammonia occurred, and
the warm ammonia then rose to completely cover
the surface. With the bulk temperature just below
the surface boundary layer suddenly raised to the
warm feed temperature, potentially very large
vaporization rates would occur.
The latter two events are related to a phenomenon
described as "rollover". In principle, a rollover can
occur whenever thermal stratification results in a
density inversion. Rollovers are often observed
seasonally in lakes, and have been reported in oil
storage tanks. In principle they can also occur in
cryogenic storage tanks. For liquids stored under their
own vapor pressure, rollovers may be dangerous not
only beause of the stresses exerted on the tank by the
moving liquid, but also because of the sudden increase
in vaporization when superheated liquid is brought to
the surface. For saturated liquid storage, the
possibility of vaporization, and its resultant drastic
increase in destabilizing buoyancy, must be considered
when the superheat of a submerged layer is large.
In 1989, a 10,000 ton capacity ammonia tank
failed in Lithuania, releasing 7000 tons of ammonia,
resulting in 7 deaths, 57 injuries and the evacuation of
32,000 people over a 400 km2 area [2]. Thermal
overload has been suspected as one possible cause of
the accident.
For a given mass of a warm submerged layer, the
consequences of a rollover become more severe as its
temperature is increased above the surface
temperature. At the same time, the buoyancy force
driving the rollover increases. However, the
increasing destabilizing force probably also reduces
the mass of warm material which can accumulate
before the rollover occurs, and also increases the rate
of mixing of the warm feed with the cold initial fluid.
While it is possible to imagine enormous rates of
vaporization when a large mass of very warm
ammonia erupts to the surface of an ammonia tank,
the likelihood of such an accumulation developing in
the first place may be quite small. This poses a rather
difficult problem in fluid mechanics and heat transfer.
It involves both natural convection and forced
convection because the feed velocity contributes to
mixing.
 A future paper will report on a computational fluid
dynamical study of mixing and heat transfer in
ammonia tanks. If successful, it will establish bounds
on the rollover mechanism. In the meantime, a model
has been developed of thermal overload in which flow
and mixing behavior may be assumed, and the
dynamic pressure and venting behavior of the tank
calculated. With this model, it is possible to assume
various behaviors, such as the rate of mixing between
warm and cold ammonia, whether, when and how
rapidly the warm layer flows to the surface, and what
fraction of the surface becomes covered by the warm
fluid. For the assumed behavior, consequences for the
vapor space pressure and venting rates are then
determined.
PROBLEM DESCRIPTION
Figure l schematically depicts the key features of
the tank included in the model. There is a normal
process vent from the vapor space to refrigeration to
maintain normal operating pressure, and a pair of
emergency vents to protect against overpressuring the
tank. The feed nozzle is near the bottom of the tank.
Before filling starts, there is an initial charge of
liquid ammonia with uniform temperature exerting its
equilibrium vapor pressure. For a perfectiy insulated
tank at steady state there would be no vaporization,
and the normal and emergency vents would be closed.
If heat gain is taken into account, there would be
some venting through the normal vent. Then, warm
ammonia is fed from a barge or other source for a
period of time and stopped. The variables of primary
interest to calculate are the pressure in the vapor
space and the venting rates through the normal and
emergency vents as functions of time, both during the
barge unloading and after the unloading.
SIMPLIFIED VENTING EQUATION
Before presenting the dynamic model, a short-cut
venting calculation is described. This short-cut, by
ignoring numerous mitigating effects, provides a
conservative upper bound to which the more careful
dynamic calculations may be compared. Assume that
the warm ammonia is either fed to an initially empty
tank, or rises instantaneously to the surface,
completely covering the vapor-liquid interface without
mixing or exchanging heat with the cold ammonia.
Neglect the reduction of the warm ammonia
temperature as vaporization occurs while the pressure
is increasing from the initial pressure to the maximum
allowed pressure. In reality, some ammonia has to
vaporize to bring the pressure up to the vent set
pressure. Then, an additional amount must vaporize
65
after the vent opens as the pressure continues to rise
from the set pressure to the maximum allowed
overpressure. Take no credit for the cooling this
produces.
For superheats of the order of a few degrees or
less, vaporization should be limited to the liquid
surface, and there should be no boiling in the bulk of
the üquid. This means that the rate of vaporization
should be proportional to the cross-sectional area of
the tank. It will be determined by the rate of heat
transfer from the bulk liquid to the interface divided
by the latent heat of vaporization, if convective heat
transfer on the vapor side is neglected. At the peak
overpressure, this rate is equal to the venting rate, if
the difference between the interface temperature and
the vapor temperature, and the rate of increase of the
vapor space volume are neglected.
Wv
(D
A
where T,-T;, the difference between the warm
ammonia temperature and the temperature at the
interface, is the degrees of superheat above the
saturation temperature corresponding to the maximum
allowed overpressure. The heat of vaporization is
taken at the saturation temperature. It is about 320
PCU/lb for small overpressures. The venting rate Wv
is a mass flow rate; A is the cross-sectional area of
the tank, and h, is the liquid heat transfer coëfficiënt
at the interface. This last variable is the most
uncertain. Because natural convection is an important
contribution to the heat transfer, the coëfficiënt hl is
not independent of the degrees of superheat.
Uncertainty in h, is the only aspect which could
render Eq. (1) non-conservative.
Equation (1) is based on the premise that
vaporization occurs at the surface, and therefore the
rate is proportional to the surface area, and not the
mass of the warm ammonia. This in contrast to some
previous calculations of venting rate requirements
which hold that the required venting rate is
proportional to the mass of warm ammonia. Such a
behavior would be reasonable for very high
superheats, where boiling would occur throughout the
volume of warm ammonia. A useful figure to keep in
mind is that near the liquid surface the saturation
temperature increases at about 0.4 °C per ft of depth
below the surface. Considering the increased
saturation temperature at depth, and the need for
several degrees of superheat of saturation for
homogeneous boiling, it is evident that quite large
superheats are needed for boiling at any significant
depth below the surface.
 Maher and Van Gelder of Chicago Bridge & Iron
[2] in this discussion of rollover and thermal overfill
in LNG storage tanks reported the following empirical
equation for the venting rate as a function of the
depression of the pressure at the liquid surface below
the vapor pressure of the underlying warmer liquid.
(2)
where Wv is in Ib/hr, APS is in inches of water, and
the tank diameter D is in ft. Using methane as an
approximation for LNG and employing the Clausius-
Clapeyron equation, the following estimate can be
derived for the heat transfer coëfficiënt by comparing
Eq. (1) and Eq. (2).
/z;=105(r(-7;.)'/3
where temperature is measured in degrees Celsius and
ht is in PCU/hr ft2 °C. For a l °C superheat, the
heat transfer coëfficiënt is 105 PCU/hr ft2 C and for
5 °C of superheat it is 180 PCU/hr ft2 C. These
fïgures may help give a feel for the expected values of
h, for ammonia tanks, hearing in mind of course that
physical property differences will influence /z;.
Ammonia has a greater thermal conductivity, but a
smaller coëfficiënt of thermal expansion than liquid
methane. A heat transfer coëfficiënt of A ; = 1000
PCU/hr ft2 °C is probably a very conservative
estimate for superheats of a few degrees or less.
DYNAMIC MODEL
The model, illustrated in Fig. 2, uses lumped
average temperatures in two liquid zones and one
vapor zone. One liquid zone, the "hot" zone, consists
of the ammonia which has been fed warm from the
barge, and the other is the "cold" ammonia which
was initially present in the tank. Mixing between the
two zones is important because it reduces their
temperature difference. This effect is modelled by a
"heat transfer" coëfficiënt h^ and a contact area A^
between the two zones. Heat transfer coefficients are
usually used to describe the rate of heat transfer
across a phase interface. In this case, there is no
phase interface, and h^ really describes a rate of
mixing within a single phase. It includes the exchange
of enthalpy by mixing of fluid across the imaginary
boundary between the rather arbitrarily defined "hot"
and "cold" zones. The limit h^ ~* O corresponds to
no mixing or heat exchange between the zones, and
hfc ~* oo corresponds to a single well-mixed liquid
zone. An order-of-magnitude estimate for the area A^
is taken as A^V^s^. The product h^^ is the
mixing rate of enthalpy per degree of temperature
difference.
66
Vaporization can occur from either or both zones.
During a rollover, each zone occupies a fraction of
the vapor/liquid interfacial area. At the interface, with
temperature 7), heat transfer from the bulk liquid to
the interface is described by a liquid side heat transfer
coëfficiënt, h,, and from the interface to the bulk
vapor by a vapor side heat transfer coëfficiënt hv. The
difference in heat flux between the phases determines
the rate of vaporization through the latent heat. The
fraction ƒ of the interface occupied by the hot zone
can be any arbitrarily specified function of time, so
that all the scenarios described in the Introduction can
be studied.
The tank is equipped with two types of vent. One
is the normal vent used to keep the tank at its normal
operating pressure. The other is a pair of conservation
vents to keep the tank within a maximum allowed
overpressure beyond the design pressure in an
emergency. The emergency vents begin opening at a
set pressure Ps (l psig for the Belle tank) and are fully
open at a higher pressure P0 (taken as 1.4 psig). The
fully open capacity is obtained from an orifice
equation with the effective orifice area computed from
the actual manufacturer's capacity curve. Between Ps
and P0, the capacity variation with pressure is assumed
linear.
The normal vent line is branched. One branch goes
to the refrigeration compressor, and the other to the
plant flare stack. For simplicity, the conservative
choice is made to neglect flow to the compressor. All
the flow is assumed to go to atmosphere via the flare.
This path is a 6-inch line with an equivalent resistance
estimated at about 16.7 velocity heads with the vent
valve wide open. Rather than simulate the actual
control scheme for the vent, it is assumed that the
valve for normal venting begins opening at a set
pressure (Psn) and is fully open at a higher pressure
(Pai) with a linear variation of flow rate in between.
In the calculations, the values POT=0.5 and Pon=0.6
psig are taken.
Time-dependent material and energy balances are
written on the vapor and on each of the liquid zones,
giving six differential equations. Along with these are
various algebraic relations among the variables in
these differential balance equations.
The warm ammonia feed rate may be any specified
function of time. Rollover phenomena are included by
specifying the surface fraction ƒ as a function of time.
For example, a rapid rollover of a large mass of
warm liquid could be specified by ramping ƒ from
zero to unity over a small period of time, such as one
minute.
 The temperature at the vapor/liquid interface is No energy can accumulate at the interface. All the
determined by the requirement that the pressure in the heat reaching the interface from the liquid and vapor
vapor space equal the vapor pressure of the liquid at is absorbed by vaporization.
the interfacial temperature. This is the only place a) Vapor/Cold Liquid Interface
where vapor and liquid coexist in equilibrium.
(l -flAh^- T)WJ(Cpv- Cp)(T- T) + A J+(1 -f)Ahv(T-Tv)
Tank insulation is assumed perfect in these (12)
calculations. The effect of loss of insulation is also
under investigation, but will not be reported here. b) Vapor/Hot Liquid Interface
fAhl(Tlh-T:) = Weh[(CpyCl,!)(T-Tr)+ \r]+fAhv(T-Tv)
The following equations constitute the (13)
mathematica! model.
The interface temperature establishes the vapor
Vapor Mass Balance pressure. Pressure is in psia and temperature in
Keivin.
dM„
(3) lnP=17.694826-3237.4292/r.-0.006267012ir.
UI
(14)
Cold Liquid Mass Balance Ideal Gas Law
dM
lc
—— W
Wec (ft
W (15)
dt
Liquid Volume
Hot Liquid Mass Balance a) Cold M
dM
lH = W-W
l eh x (5)
/ (16)
dt b) Hot '
Vapor Internal Energy l/ ——
' lh
Ih
(17)
Uv=MJCpv(Tv-Tr) + \r]-PVv (6) Venting Rate.
Vapor Energy Balance
(18)
^=(Weh+ WJ[Cpv(T-Tr+ \r] +Ahv(T-Tv) Emergency
dt For — Paan < PS,
W\C (T
H'vlSvUv
T)+ M
*r)+ A rJ rP
^
v (?)
(19a)
For P, ^ P-Pam<P0,
Liquid Internal Energy
a) Cold l2PM„(P-Paan)
ve \ p p ^ ^(/^oe *\ (m
1 RTV
S
b) Hot For P-PoJ > P0,
^lh~"^lh^p^lh •*(•) ""tl W w -r A I2PMJ. """' ( \f\f\
Liquid Energy Balances KI
Normal
a) Cold P-Paan < PS„,
dU,£ r-Tr)- -MT^-TÏ-P^- (20a)
=-
dt Psn < Paan < P„n,
(10)
b) Hot i P-Paan-P \
Wm =\
\ D_D
-IA
/ «a (20è)
on sn NRT
düilh =
J
= WlCp{,Tfl-Tr)-WehCpl(T-Tr)-Ahlf(Tlh-Ti-)
'™ v vJ

P-Paan > P ,
~dt
•"- •"- - Oi lef (l 1)
(20c)
NRTV
where ƒ is the fraction of the vapor-liquid interface The total volume in the tank is fixed.
occupied by the hot liquid. V
Y
ta =V
r +V
lh^ v H-F
lc^ v
v (21)

67
MODEL BEHAVIOR
A commercially available equation-based chemical
process simulator was used to solve the set of
simultaneous differential and algebraic equations. The
simulator reads the equations and writes the Fortran
coding necessary to solve them. Gear's method is
used for the integration. To illustrate the behavior of
the model, several test calculations and sensitivity
studies are made.
The uncertain parameters in the model are the
coefficients hv, h, and h^. In order to investigate the
sensitivity of the model to these uncertain parameters,
a "base case" set of values hv = 1.0, ht = 1000 and
hhc = 10 PCU/hr ft2 °C is chosen. The base case also
includes the design parameters for the Belle tank and
an initial charge of 5000 tons at -33 °C. A 2500 ton
barge load of ammonia is fed at a uniform rate for 8
hrs. The simulation starts one-hour before the feed
begins, to demonstrate the initial steady-state
behavior. One hour after the barge unloading is
complete, at t = 10 hr, a rollover is assumed. Over a
1-minute interval, the vapor-liquid surface area
fraction is ramped linearly from all cold liquid to all
hot liquid.
Setting the initial condition Mlh = O would cause
divide-by-zero errors in the numerical solution of the
balance equations on the hot zone. Rather than
complicate the model with various conditional
instructions to modify the equations during the first
hour while the hot zone does not exist, the initial
value of Mlh is set to a negligible mass; the value
Mlh= l Ib is chosen. Then hot zone equations can be
solved from time zero.
Figures 3-5 plot time-dependent results for the
base case. At time t = l hr, unloading commences.
Figure 3 shows the pressure transient. Pressure is
constant for the first hour before barge unloading
begins. Then during the 8 hour period from t = l to
t = 9 hr the pressure rises as warm ammonia is fed.
The pressure rise is largely from compression of the
vapor as liquid volume is increased. Vapor
compression and condensation raise the vapor and
interface temperatures. The liquid feed coincidentally
stops just at the time when the tank pressure reaches
the set pressure of the normal vent. Once the liquid
feed stops, the pressure drops briefly before a new
steady state is reached. Then, at t = 10 hr, the time
arbitrarily selected for the rollover, the hot liquid is
brought to the surface over the assumed l minute
interval. Both normal and emergency vents open as
the pressure surges to 15.79 psia (1.03 psia). At the
peak pressure, the emergency vent is barely open; it
would be fully open at 16.1 psia. The pressure
diminishes steadily for about an hour while the
68
emergency vent is closing. After the emergency vent
is fully closed, the pressure begins to drop rapidly.
This is because the diminishing vaporization rate is no
longer partially offset by a diminishing vent area as it
was while the emergency vent was still open. Several
hours after the rollover, the pressure has dropped
back to nearly the normal vent set pressure.
Figure 4 shows the normal, emergency and total
venting rates. The total rate quickly reaches a peak
after the rollover. In the time scale of the process, the
one-minute rollover time is effectively instantaneous.
The peak total venting rate is 24,255 Ib/hr, of which
about 17% goes to the flare and the remainder goes
directiy to the atmosphere. It is interesting to compare
the peak total venting rate to that which would be
computed from Eq. (1). At 15.79 psia, the saturation
temperature at the interface is —32.0 °C. With a bulk
liquid temperature of -33 °C, a heat transfer
coëfficiënt h, = 1000 PCU/hr ft2 °C, a tank cross-
sectional area of A = 9677 ft2, and a heat of
vaporization of about 327 PCU/lb, Eq. (1) gives a
venting rate of 29,600 Ib/hr. The peak rate in the
dynamic calculation is nearly as great as the simplified
calculation result. This happens because for the
parameters chosen, there is very little interchange
between the hot and cold liquid before the rollover
event, because the rollover happens quickly, and
because the mass of hot liquid is very large compared
to the mass required to vaporize in bringing the vapor
space up to the peak pressure.
Inspection of Figure 5 shows that the small value
of hhc used in the base case gives very slow mixing
between the zones, so that the hot liquid is still very
near its feed temperature when it rolls to the surface.
This extreme case of rapid rollover after virtually no
mixing is worse than what would happen if the warm
liquid had been fed directiy on top of a small heel of
cold liquid, so that venting could occur continuously
throughout the barge unloaded. Figure 6 shows the
pressure and total vent rate history when the barge is
unloaded on top of a shallow heel (165,000 Ib) of
cold ammonia. There is no rollover because the warm
fluid is on the top from the outset. Otherwise, the
conditions are identical to the base case. From a
starting pressure of 0.31 psig, the pressure rises very
rapidly over the first hour of feeding, and then
gradually approaches a peak of 0.75 psig. The peak
venting rate is an order of magnitude lower than in
the base case, but it remains near its peak throughout
the 8-hour barge unloading. Of course, once the
pressurization and excessive venting began, the tank
operator would quickly discontinue the unloading. The
conditions of Figure 6 correspond to an actual
experience at Belle, where it was attempted to unload
ammonia with 2 °C superheat on top of less than a
foot of cold ammonia. After adding only one or two As expected, there is an increase in peak pressure
hundred tons, the pressure had risen from 0.3 to 0.7 and venting rate with an increase in the liquid-side
psig and unloading had to be stopped. heat transfer coëfficiënt h,. The peak venting rate is
not directly proportional to ht because of dynamic
Sensitivity studies with respect to the model effects, and, more importanüy, because the peak
parameters reveals their importance and shows that a pressure also changes with h„ which in turn influences
better understanding of the fluid mechanics is needed the superheat. Over the reasonable range of hv, the
for accurate calculations. Table n shows the results are rather insensitive. The transfer coëfficiënt
sensitivity of peak pressure and venting rates to model hhc reflecting interchange between the hot and cold
parameters and operating conditions. In each section, liquids has a substantial effect on peak pressure and
the parameter value corresponding to the base case venting rates. For small values, the asymptotic limit
condition of Table I is highlighted. When the of no mixing/heat transfer is approached. This gives
parameter in question is changed from the base-case the greatest peak values of P and Wv. For large
value, all the remaining ones retain their base-case values, the asymptotic limit of a single well-mixed
values. liquid phase is approached. This limit gives the least
Table H. Sensitivity Studies values of P and Wv. Note that when hhc is increased
beyond some value between 100 and 1000 PCU/hr ft2
P(max) ÏFv„(max) Wve (max) Wv(max) C, the emergency vent no longer opens.
Base Case* The effect of the initial cold liquid mass is minor
(psig) Ib/hr as long as the feed liquid is submerged beneath it and
mixing is slow before a rollover. As the initial cold
1,091 4,240 20,020 24,260 liquid mass increases, there is a small increase in peak
pressure and venting rate because of the diminishing
Effect of fy (PCU/hr ft2 °C) volume of the vapor space.
100 0.771 3,540 O 3,540
Liquid feed temperature is extremely important. If
500 1.043 4,140 9,140 13,280
the feed temperature is reduced from the base case
1000* 1.091 4,240 20,020 24,260
-31°C to -32°C (1°C superheat above the cold
Effect of /iv (PCU/hr ft2 °C) liquid at — 33 °C), the peak pressure is only 0.9 psig,
the emergency vent does not open, and the peak
0.1 1.091 4,240 20,050 24,280 venting rate is 3,830 Ib/hr. If the superheat is
l* 1.091 4,240 20,020 24,260 increased to 5°C (Tfl= -28°C) the peak pressure is
10 1.089 4,240 19,630 23,870 1.38 psig and the peak total venting rate is 98,400
Ib/hr. The peak pressure is more than 10% above the
Effect of hhc (PCU/hr ft2 °C) tank design pressure and tank damage would be
l 1.095 4,250 21,040 25,290 expected. At Tfl= -23 °C, the calculated peak
10* 1.091 4,240 20,020 24,260 pressure is 3.05 psig and the peak total vehting rate is
100 1.054 4,160 11,720 15,890 161,800 Ib/hr. At this pressure, tank failure would be
1000 0.699 3,360 O 3,360 likely.
10,000 0.620 3,160 O 3,160
Reduction of the mass of ammonia unloaded from
Effect of Initial Cold Liquid Mass (tons) the barge over the 8-hour period by a factor of five
(from the base case 2500 to 500 tons) reduces the
2500 1.091 4,240 20,020 24,260 peak pressure from l .09 to l .04 psig, and the peak
5000* 1.091 4,240 20,020 24,260 total venting rate by about half (from 24,260 to
10,000 1.097 4,250 21,310 25,560 12,840 Ib/hr). Increasing the barge mass to 5000 tons
15,000 1.098 4,250 21,720 25,980 increases the peak pressure to 1.1 psig and the peak
venting rate to 26,190 Ib/hr. While the increase 'm
Effect of Tfl(°C) venting rate is modest, the large venting rate lasts for
-32 0.899 3,830 O 3,830 a much longer time than in the base case. For large
-31* 1.091 4,240 20,020 24,260 feed mass, the hot liquid temperature changes very
-28 1.376 4,800 93,640 98,440 little either before or during the rollover. However,
-23 3.047 7,430 154,400 161,800 for small feed mass, the heat lost to the cold üquid or
to vaporization is enough to drop the hot liquid
Effect of Barge Mass (tons) temperature and cause a substantial reduction in the
2500* 1.091 4,240 20,020 24,260 peak venting rate. This effect would not be picked up
500 1.041 4,130 8,700 12,840 by the simple analysis of Eqn. (1).

69
 Figures 7-18 illustrate the transient tank behavior
for several of the sensitivity study cases. In the
temperature plots, the hot liquid temperature variation
during the first hour shows the cooling of the l pound
of warm ammonia placed in the tank at time zero.
Figures 9, 12, 15 and 16 show the approach of the
hot and cold liquid toward a uniform temperature as
the mixing rate coëfficiënt h^ is increased. The
corresponding pressure profiles show the diminishing
danger as hhc increases.
Recycle of warm ammonia is another possible
cause of thermal overload. Unless plant design
precludes the possibility, it is conceivable that
ammonia with much more than a few.degrees of
superheat could be recycled to a storage tank. It has
been reported [2] that in the Lithuanian tank incident,
14 tons of ammonia at 10 °C was fed into the tank
over a three-hour period prior to the tank faüure
which released 7000 tons. (There is some cause to
suspect that much more than 14 tons were recycled.)
Figures 19 and 20 show model results using the base-
case parameters for the Belle tank, with an initial cold
liquid mass of 7000 tons rather than 5000 tons, and
with 14 tons of 10 °C ammonia fed at a uniform rate
over the three hour period from t = l to t = 4
hours, followed by a rollover of the warm ammonia
to the surface immediately after the recycle was
concluded. The pressure spikes to 1.43 psig, which is
more than 40% beyond the design pressure of the
tank, and the total venting rate reaches the
extraordinary value of 108,000 Ib/hr. At the peak
pressure, some deformation of the tank might be
expected. The vent capacity of the Lithuanian tank
was less than 20,000 Ib/hr.
DISCUSSION
The model development and results are useful from
more than one perspective. First, they force
consideration of all the processes which are going on
during feed to a tank. It gives a feel for the ranges of
behavior to expect as a result of variations of both
known (e.g., initial liquid mass, tank volume) and
unknown (e.g., heat transfer coefficients) variables.
The uncertainties in the model parameters, and the
sensitivity of the results to these parameters, motivates
the development of a more careful computational fluid
dynamic analysis. This analysis should give a better
feel for these parameters, and indeed show whether
the rollover phenomenon is a realistic expectation at
all.
If any provisional conclusions are to be drawn
from the current study, they are the following. When
feeding warm ammonia of a few degrees superheat or
70
less beneath a large mass of cold ammonia,
overpressuri/ation of the Belle tank is not a likely
event in the absence of rollover, or if a rollover
occurs following significant mixing between the warm
feed and cold initial fluid. If mixing is poor and a
rollover occurs with a large degree of superheat, then
overpressurization could occur. Addition of warm
ammonia on top of a small quantity of cold ammonia
could cause very large venting rates, and given
sufficient superheat, could overpressure a tank if
operators faüed to discontinue feed despite the onset
of high pressure and venting. However, at reasonably
small superheats, less than a few degrees Celsius,
venting rates will be large but the pressure will be
controlled at safe levels. Recycle of highly
superheated ammonia is to be avoided.
In Du Pont there is no known evidence that a
rollover bringing significantly superheated ammonia to
the surface of a tank has ever happened. However,
this does not prove that it cannot happen. Should such
an event occur, this study shows that the consequences
are potentially severe, given sufficient superheat.
Limiting operating procedures to ensure the safety of
the tank even under the assumption of poor mixing
followed by a rapid rollover is prudent. A more
careful fluid mechanical study of mixing of warm feed
into the cold initial ammonia is needed to establish the
credibility of the assumed worst-case events.
REFERENCES
1. J. B. Maher and L.R. Van Gelder, "Understanding
Roll-Over and Thermal Overfül in Flat Bottom
LNG Tanks," Amer. Gas Assoc. Distribution
Conf., Atlanta (1972).
2. B. O. Andersson, "The Lithuanian Ammonia
Accident, March 20, 1989," AIChE Ammonia
Symposium, Paper 96A, November 1989.
NOTATION

A tank cross-sectional area

Afc contact area between hot and cold liquid
Aoe emergency vent area
Am normal vent area
C0 orifice coëfficiënt
Cpl liquid heat capacity
Cpv vapor heat capacity
f fraction ofsurface occupied by hot zone
hhc exchange coëfficiënt between hot and cold zones
hL liquid-side heat transfer coëfficiënt
hv vapor-side heat transfer coëfficiënt
Mlc mass of cold liquid
Mlh mass of hot liquid
Mv mass of vapor
Mv molecular weight
N vent line resistance
R gas constant
P pressure
Patm atmospheric pressure
Pa emergency vent juli open pressure
Pon normal vent Juli open pressure
Ps emergency vent set pressure
Psn normal vent set pressure
A Ps depression below bulk liquid vapor pressure
t time
7j interface temperature
Tf bulk liquid temperature
Tlc cold liquid bulk temperature
Tlh hot liquid bulk temperature
Tr reference temperature
Ufc cold liquid intemal energy
Uth hot liquid internal energy
Uv vapor internal energy
Vlc cold liquid volume
Vft hot liquid volume
Vtot total tank volume
Vv vapor volume
Wec vaporization rate from cold liquid
Weh vaporization rate from hot liquid
Wf hot liquid feed rate
Wv total venting rate
Wve venting rate through emergency vent
Wm venting rate through normal vent
A heat of vaporization
\r heat of vaporization at Tr
Pt liquid density

71
OPERATING PARAMETERS FOR
BELLE STORAGE TANK
Du Pont at Belle believe for our application, a
bulk cryogenic storage tank is the safest, most
economical and environmentally sound method of
storing anhydrous ammonia. However, operating
guidelines and parameters must be understood and
closely monitored to maintain this desired state. A
clear understanding of the tank desigo basis is critical
to our operation. The 20,000 ton storage tank at Belle
was originally part of a 1000 ton/day Kellogg plant
which is no longer in operation. The main feed
streams into our tank are the barge unloading pipe
line, recycle from our distribution pumps, and the
return stream from the compressor.
The barge unloading line is the greatest concern
for introducing large amounts of heat into the bottom
of the tank therefore, operating instructions include
guidelines to follow during barge unloading transfers.
There are several ammonia storage tanks that have
flash nozzles at the top of the tank that take 10% of
the unloading flow into the top layer of the tank. This
will indicate the barge is warm due to the pressure
increase. It is critical to keep these on line during
transfers and not valve them out so the unloading
rates may be increased. Since the Belle tank is not
equipped with this configuration, other guidelines are
in place to insure safe operation.
1. Assure the barge pressure is at most O psi and
the liquid mass is at most at -33.4°C upon
arrivsl at the doek.
2. Closely monitor the unloading line
temperature and not allow it to be above
-32 °C.
6. Inform the barge companies of the expectations
that the ammonia should be -33.4°C and at O
psi.
7. Maintain detailed data sheets in order to
monitor each transfer.
8. Operating personnel have been educated to the
importance of keeping within the operating
parameters and changed old mentalities of
hurrying to unload barges to reduce demurrage
costs. There is also the understanding that the
storage tank is not a flash vessel.
These operating parameters are all adrninistrative
procedures. Therefore it is imperative that each person
unloading barges fully understands the results of
operating outside of these guidelines. Barge unloading
personnel are currently being certified with the U.S.
Coast Guard as tankermen to allow them to be more
involved in the unloading. This practice has proven
most effective.
Du Pont at the Belle Plant are extremely proud of
our recent upgrades to the 20,000 ton storage tank
and distribution system and desire to maintain its
current status and integrity. Many people have
provided guidance, support, and input to our efforts to
maintain safety and environmental performance.
Dr. Richard Squire and Dr. Richard Knowles, plant
manager, for supporting continuous improvement.

3. Unload at a maximum rate of 300 tons/hr.

4. Assure the normal vent to the flare stack does

not exceed 30% valve opening during the
barge transfer.

5. Cool down the empty barge unloading lines

prior unloading, especially in the case of long
piping systems that could introducé large
amounts of heat into the tank bottom during
the initial transfer.

72
 Normal Vent |NH3 Tonk F i U i n g goUover |

1Q"BreatherVents

Figure 4. Venting rates during base-case

simulation.
Liquid Feed

Figure 1. Belle ammonia storage tank.

w v,

|NH3 Tank FlUing Rollover |

215- 215, 215.

Tv, P, Mv

Tfc,

-W,

Figure 5. Zone and interface temperatures

Figure 2. Key features modelled. In the smaller during base-case simulation.
figures, hot liquid zone has risen to first
partially, and then completely, cover the surface.
(NH3 Tank F i LI ing Rol lover |

INH3 Tonk FilUnql

VIT
Wfc(0)=16S,000 B)
£ 1=6. Mfc(G)=74aOO kg

£
g 150.

Figure 3. Pressure transient during base-case Figure 6. Pressure and total venting rate for
simulation. unloading into a nearly empty tank.

73
 lNH3 Tank Fullnq Rouovprl |NH3 Tank F J U i n q Rot lover |

Figure 7. Pressure transient with A;reduced to

100 PCU/hr ft2 °C.
Figure 10. Pressure transient with khe increased
to 100 PCU/hr ft 2 °C.

JNH3 Tank F i t t i n g Rol l over | JNH3 Tank F u t ing Rot lover |

39000 30000., 30000

Figure 8. Venting rate with fyreduced to 100

PCU/hr ft 2 °C.
Figure 11. Venting rates with hhc = 100 PCU/hr
ft 2 °C.

|NH3 Tank FiUing Rol lover | |NH3_Tonk Rilling RoUover j

213. 215. 215.

h
*~l*tT-

210J 210J 210.

Figure 9. Temperatures with fc/(creduced to 1 Figure 12. Temperatures with hhc = 100 PCU/hr
PCU/hr ft2 ° C. ft2 °C.

74
 |NH3 Tank FiUing RoUover | JNH3 Tank FtUing RoUover |

fc
" hr ft! *C

^56.700-£-

I' 5
s

Figure 13. Pressure transient with hllc Figure 16. Temperatures with hhc = 10,000
increased to 1,000 PCU/hr ft 2 °C. PCU/hr ft 2 °C.

|NH3 Tonk FiUing RoUover | |NH3 Tonk Ft H ing RoUover |

Figure 14. Venting rate with hhc = 1,000 Figure 17. Pressure transient with initial cold
PCU/hr ft 2 °C. mass increased to 15,000 tons.

|NH3 Tonk FiUing RoUover | [NH3 Tank FiU ing Rot Lover |

£
S 211
g

(hours >

Figure 15. Temperature with hhc = 1,000 Figure 18. Venting rate with Mu = 15,000
PCU/hr ft 2 °C. tons.

75
 |W3 Tank War» Recycle !•( Lons 10 C | |NH3 Tor*. Worm Recycle 11 Lons 10 C
12.700 kg 12.700 kg
xio5
X1Q-
iB5 vfi XI O5
1.50 l. 50

l .20 1.20 1.20

3 è S
0.90 0.90 0,90

155

V z
O.EO
S
0.60 O.GO

j'»
i°-3°
z
|o.30
ï f030

0.00 0.00
t i 2 3 * S B
0.00
( 1 2 3 4 5 6
Tinp (hours > Tin* (hours

Figure 19. Pressure transient with warm Figure 20. Venting rate with warm recycle
recycle and assumed rollover. and assumed rollover.

D1SCUSSEON
Rudolph Frey, M. W. Kellogg Company. Houston, TX: l
would like to know first of all whether this is a doublé
integrity tank or full containment as deflned by the EEMUA in
Europe?
Saffle: Yes, this tank is a doublé walled, doublé integrity
tank.
Frey: The outer wall is able to contain the full fluid, full
hydrostatic pressure at the cold temperature.
Saffle: Yes.
Frey: That was one of my concerns with regards to practice in
ammonia storage here, vis-a-vis European practice. An LNG
tank is very common to provide top loading to get the vapor
dispersion immediately. I think one of the graphs in this study
showed that. Was there any consideration in providing this?
Or, was this a situation where you didn't want to make any
mechanical modifications up there?
Saffle: Basically, this was just for our tank design and we put
the ammonia into the bottom of the tank. So, this study is
just for our tank.
Frey: You couldn't put a sparger or a top loading system in?
Saffle: No.
Frey: This is very effective in preventing rollover. The other
thing done is providing a recirculation system to avoid the
accumulation of a rollover cell in the tank. In terms of the
mathematical modeling, there has been some work done in
LNG relative to the convection cells, which build up in the
tank and provide the incubation period for the rollover. I was
wondering if that work was addressed in setting up your model.
Guy Legendre, Monsanto, Luling, LA: You mentioned that
you don't allow the temperature to get above -32 °C. If it does,
do you have an interlock which shuts down the unloading and
at what temperature is that interlock set?
Saffle: There is no interlock on that system. There is a
thermocouple on the unloading line. It is monitored
continuously. It is completely administrative when that
temperature is exceeded and it is shut down.

76