Blowdown of hydrocarbons pressure vessel

arXiv:1101.0969v1 [physics.chem-ph] 5 Jan 2011

with partial phase separation

A. Speranza
Industrial Innovation Through Technological Transfer, I2T3 Onlus
V.le Morgagni 67/a
50134 Firenze
E-mail: alessandro.speranza@i2t3.unifi.it
A. Terenzi
Snamprogetti S.p.A.
Via Toniolo 1
61032 Fano (PU)
E-mail: alessandro.terenzi@snamprogetti.eni.it
Abstract
We propose a model for the simulation of the blowdown of vessels containing two-
phase (gas-liquid) hydrocarbon fluids, considering non equilibrium between phases.
Two phases may be present either already at the beginning of the blowdown process
(for instance in gas-liquid separators) or as the liquid is formed from flashing of the
vapor due to the cooling induced by pressure decrease. There is experimental evidence
that the assumption of thermodynamic equilibrium is not appropriate, since the two
phases show an independent temperature evolution. Thus, due to the greater heat
transfer between the liquid phase with the wall, the wall in contact with the liquid
experiences a stronger cooling than the wall in contact with the gas, during the blow-
down. As a consequence, the vessel should be designed for a lower temperature than
if it was supposed to contain vapor only.
Our model is based on a compositional approach, and it takes into account internal
heat and mass transfer processes, as well as heat transfer with the vessel wall and the
external environment.
Numerical simulations show a generally good agreement with experimental measure-
ments.

1 Introduction
The problems related to the blowdown of pressure vessels containing mixtures of hy-
drocarbons are well known amongst industries involved in plant designing and hydro-
carbons extraction. In particular, the pressure and thermal stress to which the vessel

1
1 Introduction 2

is exposed during the blowdown can present a number of consequences such as cracks
in the walls, that have to be predicted by an accurate simulation of the blowdown
process. Problems are highly enhanced when some liquid is present in the vessel either
already at the start of the depressurisation, or as a result of condensation of heavier
hydrocarbons, induced by the cooling caused by the expansion. Clearly, being the
depressurisation usually caused by security alerts, the blowdown process is often very
rapid. Typically the pressure can fall by 100 bar in a few hundreds seconds. Depend-
ing on the concentration of the mixture of hydrocarbons, the fluid temperature can
fall of as much as 100 K in the same time. In the case of presence of condensed liquid,
the vessel wall in contact with it, as an effect of the higher thermal conductivity of
the liquid, compared to the one of the gas, can be exposed to a temperature drop of
almost as much as the liquid itself, i.e., 50-100 K in a few minutes [7]. With these
extreme working conditions, the modeling of the blowdown process have to be made by
taking into account as many factors as possible. These include heat transfer with the
external environment, the presence of many components in the vessel and the possi-
bility of situations in which the assumption of phase equilibrium are not appropriate.
In fact, in particular this aspect, which is comforted by experimental evidence [7],
is usually not considered in thermodynamic commercial programs. Furthermore, the
complexity of the thermodynamic behavior caused by the presence of many different
hydrocarbons, rather than one pure fluid, often induce authors to neglect it in first
approximation [11]. As far as we know, the only complete model analysed in the past
is the one described by Haque et al. [8]. There, the authors claim their model to allow
for a multicomponent system, non-equilibrium conditions between the gas and the liq-
uid within the vessel, and possibility of having separate water as well as gas and liquid
phase. Also all the heat transfers, except for the one between the two fluids, are taken
into account of. However, despite the numerical results obtained by the authors show
a good agreement with some experiments [7], the model is completely undocumented.
A full understanding of the actual process and the mathematics involved is therefore,
at present, beyond reach.
For these reasons, and with the financial and technical support of ENI S.p.A., a
leading company involved in pipelines and fuels, we develop a complete model taking
into account of all the factors above. Being interested in the evolution of the pressure
within the vessel and the temperature of the fluids and the walls in contact with them,
we neglect all the spatial variations of the thermodynamic quantities and concentrate
on their evolution in time. The assumption of homogeneous fluid is consistent with
what is actually measured experimentally during the blowdown, and therefore a priori
justified by the necessity to focus on average quantities, rather than on their local
variations. Furthermore, even a rapid blowdown process, occurs at a time-scale which
is generally much longer than the time needed for the pressure within the vessel to
rearrange. Therefore, local variations of the pressure should generally be neglected
in a vessel. This is not as clear for the rearrangement of the temperature within the
fluids. However, given the violence of the pressure drop, especially in the early stages
of the depressurisation, the liquid, if present, will quickly start boiling strongly. This
justifies, through a strong convection, the homogeneity of its temperature. For the
gas, on the other hand, assuming a rapid motion induced by the acceleration of the
gas far upstream the orifice towards the exit, we can imagine it to get mixed and
homogenized at all the time, especially in the early stages of the blowdown, while the
pressure is dropping steeply.
Our model is only partially based on the description of the model by Haque et
al. in [8]. In fact, it differs from it rather deeply in the treatment reserved to the
2 The model for mixtures of hydrocarbons 3

energy balance. Furthermore, we neglect the presence of separate water and take into
account the heat exchanged at the interface between the fluids. Here we underline
the assumptions made, the basic equations, and the numerical scheme used to solve
the model. In order to account for the mass exchanged between the gas and the
liquid phase, in conditions away from the thermodynamic equilibrium, we introduce
the “partial phase equilibrium assumption” that we describe in Sec. 2.

2 The model for mixtures of hydrocarbons

As we mentioned in the introduction, in spite of the observed the non-equilibrium
conditions between the two phases (gas and liquid), possibly present in the vessels
during the blowdown process, we have mass exchange between them. This means we
have phase transition in one or both senses. In reality, being a globally non-equilibrium
problem, it will be just the material at the interface between the two phases actually
exhibiting the phase transition in either senses. However, since, as we mentioned, we
neglect spatial variations of temperature and pressure, we will have to assume some
kind of phase equilibrium between the two phases, in order to solve the problem of
mass exchange. In order to do this, besides the two bulk phases gas “G” and liquid
“L”, we will introduce two intermediate phases, present instantly only in traces in the
vessel, which are responsible for the phase transition between the two bulk phases. We
will call these two phases, drops “l”, i.e., the liquid that condenses from the gas and
that, immediately after condensation falls into the bulk liquid, and vapor “g”, which
is the gas that vaporizes from the bulk liquid phase, and that migrates into the bulk
gas region, immediately after forming.
Since the two bulk phases are in non-equilibrium conditions, i.e., at different tem-
peratures T G and T L , while the two incipient phases “l” and “g” has to be in equi-
librium with their respective parent phases “G” and “L”, we will assume T l = T G
and T g = T L . Thus, as the incipient phases move into their respective bulk phases (g
moves into L and l moves into G) they slightly influence their temperatures, as they
mix with them. On the other hand, the two incipient phases mix with the two bulk
phases, and thus, they homogenize with them.
We will call the assumption above, “partial phase equilibrium”, since we assume
that the two incipient (daughter) phases are instantly in equilibrium with their respec-
tive parents. However, as soon as they move into their bulk phases, they mix with
them and disappear. This process is repeated all the time, as long as phase transition
occurs, in either sense. Clearly, not necessarily the transition will be present in both
senses. In fact, likely only vaporization will occur in most of the cases. Then, only
“g” will be present in the vessel. However, as temperature drops due to expansion,
the heavier components of the gas might condense, making the phase transition run
in both directions.
Let us then proceed to the underline of the full model for a multicomponent sys-
tem. Since it would lead us beyond the scope of the present work, here we will not
derive the form of basic equations of the model. However, for a clear derivation and
general considerations on the basic assumptions made, we will refer the reader to
good descriptions of the experimental setting and the basic model, by Dutton and
co-workers [3, 2].
2 The model for mixtures of hydrocarbons 4

2.1 Polydisperse mass and energy balance

Our model, is based on the mass and energy balance equations, between the two bulk
phases G and L. Since the two daughter phases appear and disappear all the time,
and are instantly present just in traces in the vessel, we will not consider them in the
global balance, but they will appear as source terms for the balance equations.
Let us introduce nai , the number of moles of component i in each phase (G and
L) and ψiout , the function describing the discharge [1] of component i. Let us also
introduce ψivap and ψicond , as the functions describing the rate of vaporization (i.e. the
number of moles of component i moving from L to g per unit time) and condensa-
tion (i.e. the number of moles of component i passing from G to l per unit time) of
component i, respectively.
Since the internal energy and enthalpy are written for the phase, and not for the
single species, we will write just two energy balance equations, while we will write one
equation for each species and each phase (G and L) for the number of moles (mass
balance). Assuming we have M components, we will therefore have

dnG
i
= −ψiout + ψivap − ψicond (1)
dt
dnLi
= −ψivap + ψicond (2)
dt
for i = 1...M
From the 2M equations above we will get the evolution of nG L
i and ni due to the
discharge and the net balance between condensation and vaporization.
The energy balance is, on the other hand, simply
d  G G  
n u = −hG ψ out − hG ψ cond − hl − hG ψ cond + hg ψ vap
dt
+λLG SLG (T L − T G ) + λWG SWG (T WG − T G ) (3)
d    
nL uL = hl ψ cond − hL ψ vap − hg − hL ψ vap
dt
−λLG SLG (T L − T G ) + λWL SWL (T WL − T L ) (4)

where the global quantitiesPare simply obtained by summing the single species quanti-
ties; for instance, ψ vap = i ψivap . Here SLG is just the area of the interface between
the two phases and SWL and SWG is the area of interface between the phases and
the wall in contact with them, while the λ coefficients are just the thermal exchange
coefficients between the two phases and the phases and the walls in contact with
them [9, 6, 4, 5].
To the 2M+2 above equations, we will add the obvious total volume conservation

V0 = nG v G + nL v L (5)

and the four equations of state, one for each phase (see below), for a total of 2M+7
equations in the 2M+7 unknowns nG G L L G L l g G L
1 . . . nM , n1 . . . nM , v , v , v , v , P, T , T .
The two quantities T WL and T WG are obtained by solving the two Fourier equations
across the wall, coupled with the system above.
3 Numerical results 5

2.2 Polydisperse phase equilibrium

Since the hydrocarbons have different molecular weight, the rate of condensation and
vaporization will be different from species to species, as different different is their
tendency to be in the gas or liquid phase (expressed in formal terms by their chemical
potentials). Different will also be the discharge rate, ψiout , since as we can imagine,
generally the lighter components will tend to stay in the top part of the vessel and thus
closer to the orifice. Especially in the early stages of the blowdown, we can therefore
imagine the gas phase to lose part of its lighter components. However, we willPneglect
this aspect and we will assume simply that ψiout = xG i ψ
out
, where xai = nai / j naj is
the mole fraction of species i in the phase a (the sum is extended to M) and ψ out is
the total discharge rate. In other words, we will assume the gas to be perfectly mixed,
assumption which is actually consistent with the neglect of spatial variation of P and
T.
The values of ψicond and ψivap will be then obtained by solving the phase equilibrium
conditions for the two sub-systems G↔l and L↔g, in which, in fact, we have split our
system. Since we now have a multicomponent system, we will need to solve
g
µG l
i = µi µL
i = µi

for i = 1...M
From the solution of the phase equilibrium conditions above, we will get nli and ngi as
functions of P, T G , T L and the composition of the two parent phases1 (nL G
i and ni ).
G L
At fixed t and thus at fixed P (t) and T (t) and T (t), we will therefore need to solve
the above phase equilibria to get ngi , nli . The rate of condensation and vaporization
are thus:
dnli
ψicond = (6)
dt
dngi
ψivap = (7)
dt

3 Numerical results
Here we will present just the results obtained with our model, relatively to two exper-
iments (I1 and S9) reported in [7]. However, these are just two preliminary results,
while we will apply our model to far more complex environments. In any case, it is
useful to use our model in these two particular situations, since there Haque and co-
workers describe the experimental apparatus and give some experimental results that
can be directly compared with what we obtain from our model.

3.1 Experiment I1
The experiment consists on the blowdown of a cylindrical steel vessel, with base diam-
eter 0.273 m, length 1.524 m, wall thickness 2.5 cm and top choke of diameter 0.635
cm. The vessel contains only N2 at 150 bar and 290.15 K. The vessel is immersed in
stagnant air at 290.15 K, thus everything is in equilibrium before opening the valve.
1 Note here that the parent depends on time, since there is some fractionation which is

induced by the discharge of gas only. Since presumably the most volatile hydrocarbons will
mainly be in gas phase, the discharge of gas only will leave only the heavier hydrocarbons in
the vessel.
3 Numerical results 6

In Fig. 1(a) we report the value of the pressure inside the vessel during the blow-
down, predicted and experimental. The agreement is rather good, besides a small
deviation from the experimental data, roughly at half process. As can easily be seen
on a logarithmic scale, the blowdown is almost exactly exponential. This is hardly
surprising, being the conditions inside the vessel comparable to the ideal gas.
160 300
blow
exp
140
280
Wall
120
260
100
P (bara)

T (K)
80 240

60
220 Gas

40
200
20

0 180
0 20 40 60 80 100 0 20 40 60 80 100

t (s)
t (s)
a
b

Fig. 1: a):Pressure behavior during experiment I1 obtained by our model blow

and experimental results from Haque and co-workers. The agreement
is rather good. b):Temperature of the gas and the wall in contact with
it, obtained by our model, compared with the experimental results. Ex-
perimental results are contained between the two discontinuous curves.
Again our numerical results lie between the two experimental curves.

In Fig. 1(b) we show the behavior of the temperature of the gas inside the vessel,
and the internal wall in contact with it, obtained with our model, compared to the
experimental results reported in [7]. Once again our result lies within the region
spanned by the two experimental curves (the two discontinuous curves) and thus in
excellent agreement with them. The plot in Fig. 1(b) shows that the temperature is
driven by the cooling due to the expansion in the first stage of the depressurisation,
up to c.ca 30 s. Later the heat coming in from the outside becomes important and the
gas is heated up by the walls. For large t, the temperature goes back to equilibrium
with the external environment and the pressure stops dropping.
The numerical results obtained by our model, of the temperature evolution of the
wall surface in contact with the gas (see Fig. 1b), are again in excellent agreement with
the experimental data, as our prediction lies between the two experimental curves.

3.2 Experiment S9
In this experiment, we model a cylindrical vessel of 1.130 m diameter, 3.240 m length,
5.9 cm wall thickness and top choke of 1 cm diameter. The initial composition is of
85.5 mole % methane, 4.5 mole % ethane, 10.0 mole % propane, at 120 bara and 290.15
K. The vessel is immersed in stagnant air at 290.15 K.
3 Numerical results 7

The pressure evolution predicted by our model is reported in Fig. 2(a). As we

120 310
gas
liq
300
100

290
80

280
P (bara)

60

T (K)
270

40
260

20
250

0 240
0 200 400 600 800 1000 1200 0 200 400 600 800 1000 1200

t (s) t(s)
b
a

Fig. 2: a): Pressure evolution of experiment S9 against time. The pressure de-
crease is again almost exponential and rather close to the results reported
in the paper by Haque and co-workers. b): T evolution of the wall in
contact with the two fluids. After the liquid appears (see text), the wall
in contact with it cools much more rapidly than the wall in contact with
the gas as is expected.

can observe from Fig. 2(a), the pressure drop is rather slower than in experiment I1.
This is probably due to the less efficient expansion of the heavier hydrocarbons in the
parent, and the lower value of the initial pressure. As a consequence, the temperature
of the wall in contact with the gas (see below), although slowly, drops rather more
significantly than in the previous example.
In Fig. 3(a), we show the temperature evolution of the fluid inside the vessel.
Liquid appears after about 165 s from the start of the blowdown, with some delay,
after the crossing of the phase boundary. This delay is probably due to the rapidity of
the blowdown process, that makes the phase transition occur in the “spinodal region”,
i.e., where the parent becomes unstable [10], rather than at the “cloud point”, i.e.,
where the two phases actually start to coexist. However, this delay, although confirmed
by the experimental results reported in [7], could as well be just a numerical effect.
In fact, our program does not include any stability check of the free energy and the
phase equilibrium equations are only solved without looking for a globally more stable
solution [10]. It could well be that the liquid actually appears earlier than we found
with our model. However, this aspect, although interesting, lies beyond our present
scope.
Note the jump of the gas temperature after about 200 s, immediately after the
appearance of the liquid phase. This abrupt increase in the temperature is due to the
heat of condensation transmitted to the gas by a finite quantity of material passing into
the liquid phase. Correspondingly, there is a small decrease of the liquid temperature,
due to the influence of this quantity of drops at temperature T G < T L falling into the
liquid bulk phase. Note also the appearance of some numerical noise in later stages.
These oscillations are probably due to some errors in the evaluation of the internal
3 Numerical results 8

310 120
gas gas
liq liq
300
100
290
80
280

P (bar)
T (K)

270 60

260
40
250
20
240

230 0
0 200 400 600 800 1000 1200 230 240 250 260 270 280 290 300 310
t(s)
T (K)
a b

Fig. 3: (a) – Evolution of the temperature of the fluid in experiment S9. Liquid
appears after about 165 s from the start of the depressurisation. The
liquid is immediately heated up by the wall, due to its larger thermal
conductivity, compared to the one of the gas. For large t, after the
depressurisation is complete, the two fluids tend to have the same tem-
perature.
(b) – P against T evolution of experiment S9, together with the two
phase coexistence region. During the blowdown, the system enters the
phase coexistence region, but only after some time, the liquid (dashed
line) actually appears. Clearly, being the compositions of the two phases
different and different from the parent, after that point, the phase enve-
lope does not correspond to the phase envelope of either phase.

energy of the liquid, when the quantity of liquid becomes small due to vaporization.
The temperature of the liquid appears to be rather sensitive to changes in the value
of the internal energy.
The delay after which the liquid phase appears, is more evident when we plot the P
against T evolution, together with the phase diagram relative to the initial composition
(see Fig. 3(b)). The two phase coexistence region is bordered by the phase envelope
(thick continuous curve in Fig. 3(b)). The P vs. T evolution predicted by our model
during the depressurisation correctly cross the envelope (phase boundary) and the
liquid appears after some delay, well inside the coexistence region.
There is also to notice, that when the liquid solution is found, we do not actually
have an incipient liquid phase and a parent gas phase. In fact, the first solution with
the two phases, already consists of a macroscopic presence of liquid and therefore the
cloud point is already far behind and has actually been missed by our algorithm. It
is possible that a more precise investigation of the onset of the phase coexistence,
e.g., by reversing and reducing the step to look for the point at which the liquid
actually appears, would lead us closer to the phase envelope. However, again despite
being scientifically an interesting point, we decided to overlook this phenomenon, and
concentrate on the temperature evolution of the vessel walls.
In Fig. 2(b) we plot the temperature of the wall portions in contact with the
two fluids against time. As it can be seen, the whole surface is at a certain uniform
temperature when the liquid appears, as it should be, since the vessel is up to that
point filled with gas only. Furthermore, since we apply “partial phase equilibrium
4 Conclusions 9

assumption”, the liquid, when it’s formed, is instantly in phase equilibrium with the
gas. However, due to the abrupt change of the thermal conductivity (higher for the
liquid), the liquid absorbs much more heat from the wall, and the wall in contact with it
cools much more rapidly than the wall in contact with the gas. This result is expected,
and confirmed by the experiments in [7]. On the other hand, the liquid is immediately
heated up by the wall and its temperature rises abruptly after its formation, above
the temperature of the gas.
Furthermore, the strong cooling of about 50 K experienced by the wall in contact
with the liquid is again excellent agreement with the experimental and numerical
results shown in [7]. Finally, at present, we have no physical explanation for the
sudden change in the steepness of the temperature in contact with the liquid at about
700 s, and corresponding to a similar change in the temperature of the liquid. This
jump in the derivatives corresponds to a big discontinuity of the viscosity of the liquid
phase, that suddenly jumps down of two orders of magnitude to become similar to
the viscosity of the gas. This is probably a non physical behavior, induced simply by
the model for the viscosity, which based on the description of the models by Ely and
Hanley [4, 5]. Further investigations are being carried out.

4 Conclusions
We presented a model for the blowdown of pressure vessels containing a mixture of
hydrocarbons. Our model is based on a global mass and energy balance between
the phases, gas and occasionally liquid, present in the vessel, at every stage of the
blowdown. The strong cooling to which the vessel wall may be exposed, especially in
presence of some liquid, requires an accurate modelling which takes into the account
as many phenomena as possible, in order to avoid cracks in the vessel. Our model,
which is based on a compositional approach, allows for the presence of many different
hydrocarbons within the vessel, as well as non-equilibrium conditions between the
phases. All the heat exchanged between the fluids and with the external environment,
via heat diffusion across the vessel walls are also considered. In order to account
for the mass and energy exchanged between the phases, a partial phase equilibrium
assumption has been made. Within this approximation, we assume that the phase
formed by condensation and/or vaporization, remains instantly in equilibrium with
its parent phase, before moving into the corresponding bulk phase and homogenizing
with it.
The numerical results show a rather good agreement with some experimental re-
sults, both qualitatively and quantitatively. In particular, in the case of a mixture of
methane, ethane and propane, the appearance of a liquid phase after some time from
the start of the depressurisation is correctly predicted. The blowdown is estimated
to be complete in about 1200 s, in line with the experiments. Also the temperature
drop of the fluids and the wall in contact with them is quite well estimated by our
model. Similarly, for experiment I1, consisting on the blowdown of a vessel containing
N2 only, the drop of the pressure and temperature of the gas and of the wall in contact
with it are all in excellent agreement with the experimental results.

Acknowledgments
AS wishes to thank Prof. A. Fasano and Prof. M. Primicerio from Università degli
Studi di Firenze for their advice, ENI S.p.A. and I2 T3 Onlus, for funding this research,
4 Conclusions 10

Snamprogetti S.p.A., for providing technical and bibliographical support and Enitec-
nologie in the person of Dr. D. Bersano, for providing the subroutines upon which the
phase equilibrium calculation is based.

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