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Cryogenics 46 (2006) 825830

www.elsevier.com/locate/cryogenics

Determination of the pressurising period for stored cryogenic uids


A. Hofmann

*,1

Gartenstr. 51, 82515 Wolfratshausen, Germany

Abstract
It is a normal operating condition for a lot of cryogenic storage vessels that no boil-o gas is vented over long periods, which leads to a
simultaneous pressure increase of the stored uid. One main reason therefore is to avoid product losses during transport or between withdrawals. At transport conditions the mixing of the uid can be assumed to be ideally, which results in a maximum reachable pressurising
period. At stationary conditions the pressurising period is expected to be shorter, because a stratication is rising up, so that the heat
capacity of the stored uid cannot be used completely.
In a thermodynamic view, an isochore change of state takes place and the heat ux into the vessel rises the internal energy of the uid.
For the representation of the isochore change of state a new developed Du/vv-diagram with the 1 105 Pa reference as a basis line is
introduced. The basis line is linear for the lling rate and functionally connected with the specic volume.
For the uids He and H2 e.g., Du/vv-diagrams are pointed out, using the u- and v-values on the saturation lines for the two phase
region and those of some isobar lines for the region above the critical pressure.
 2006 Elsevier Ltd. All rights reserved.
Keywords: Storage vessel; Pressurising period; Isochore change of state

1. Introduction
A classical example for the operating condition with a
closed venting valve is the transport of liquid helium from
the USA to Europe. Thereby, the complete transport
period from charging to discharging the storage vessel
can reach a space up to 30 days. During this period no
boil-o gas should be vented, because this would mean a
partial loss of the expensive product.
Another example is the transport of liquid hydrogen
from the liquefaction plant to a sometimes very far customer. The transport shall be carried out with a closed
venting valve too, especially regarding safety considerations, in order to avoid uncontrolled hydrogenairmixtures, which are explosive within wide boundaries.
There are still many more examples for other uids and
applications.
*

Tel.: +49 8171 29438.


E-mail address: mn.hn@t-online.de
Formerly Linde AG, Geschaftsbereich LE.

0011-2275/$ - see front matter  2006 Elsevier Ltd. All rights reserved.
doi:10.1016/j.cryogenics.2006.06.003

The maximum pressurising period or the one way travel


time is dened as the period, in which at a xed lling rate
the pressure rises up from 1 105 Pa start-pressure to the
maximum allowable working pressure, caused by the heat
ux into the vessel during this time.
For storage vessels under transport conditions it is
assumed that any stratication in the liquid phase and at
the boundary layer to the gas phase is not durable and will
be destroyed by swashing motions of the uid. The uid
then is ideally mixed and the pressurising period is maximum and theoretically calculable.
The heat ux into the vessel causes an increase of the
pressure as well as of the temperature of the stored uid.
Referred to the conditions of helium and hydrogen as a
stored uid, the temperature increase is negligible as against
the temperature dierence of the uid to the surroundings,
so that the heat ux into the vessel can be assumed to be
constant during the whole pressurising period.
For other uids with a greater temperature dierence
between start- and end-pressure, reactions to the heat ux
are not excluded, e.g. by a non-negligible decrease of the

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A. Hofmann / Cryogenics 46 (2006) 825830

temperature dierence between uid and surroundings or


by increase of the absolute temperature of the uid, which
reacts on the mean thermal conductivity of the insulation
and on the capacity of the adsorption material in the insulation space. A pressure increase in the insulation space
then cannot be excluded, which leads to an increase of
the heat ux with a simultaneous decrease of the pressurising period.
If such a feedback process becomes eective, it can be
determined experimentally by continually recording the
pressure of the uid as a function of time and by comparison of this curve with a theoretical one, using the heat ux
at the beginning of the pressurising period.
The heat capacity of the bulk of the storage vessel and of
the insulation material normally can be neglected as
against the heat capacity of the stored uid. This is valid
for helium and hydrogen at low absolute temperatures,
but not more for LNG at a small storage volume.
2. Thermodynamic change of state
From the thermodynamic view, an isochore change of
state takes place, at which the specic volume v of the stored
uid remains constant and the incoming heat ux rises
its internal energy u, whereby the pressure as well as the
temperature increase. For the representation of this process,
therefore an uv-diagram [1] or better the new developed
Du/vv-diagram is suitable, which contains the two phase
region including lines of constant pressures, constant temperatures and constant lling rates. The lling rate is
dened as the portion of the liquid volume of the stored
uid, referred to the total geometric volume of the vessel.
If the specic volume at the start-pressure is smaller
than that at the critical point, then the liquid level in the
vessel is rising up, till the total volume of the vessel is lled
with liquid. The saturation line in the Du/vv-diagram will
be crossed on the left side of the critical point. After that,
the pressure rises up very quickly in the compressed liquid.
At the following cross of the critical temperature, the compressed liquid changes, as dened, in a compressed gas
without a change of phase.
If the specic volume at the start-pressure is greater than
that at the critical point, then the liquid level in the vessel
sinks down, till the last drop of liquid is evaporated. The
saturation line in the Du/vv-diagram will be crossed on
the right side of the critical point. After that, the pressure
rises up in the compressed vapour. At the following cross
of the critical temperature, the compressed vapour changes,
as dened, in compressed gas.
High lling rates are settled on the left and low ones on
the right of the critical point. High lling rates shall be
reached for the liquid transport and low ones for the transport back after discharge of the uid.
The pressurising period is, an equal start-pressure supposed, a function of the lling rate. At very high lling
rates the pressurising period decreases, because the saturation line is reached quickly and then the isobar lines are

near together. At very low lling rates it decreases too,


because the incoming heat ux is distributed to a smaller
uid mass. The maximum pressurising period can be
reached at a lling rate of about 60%.
3. Determination of the pressurising period
The determination of the pressurising period at a xed
lling rate and at known start- and end-pressure, or respectively the determination of the lling rate for a xed pressurising period and at known start- and end-pressure, are the
most frequent questions. For treating this questions one
diers between the uid related terms and the vessel related
terms. The vessel related ones are already xed by the realities of the construction.
The uid related terms are:
M (g)
MG (g)
ML (g)
V (m3)

total mass of the uid lling


mass of the portion of gas of the uid lling
mass of the portion of liquid of the uid lling
total volume of the uid lling or geometrical volume of the storage vessel
VG (m3) volume of the portion of gas of the uid lling
VL (m3) volume of the portion of liquid of the uid lling
p1 (Pa) reference-pressure 1 105 Pa
p (Pa) pressure of the uid
Dt (s) pressurising period between start- and end-pressure
u (W s/g) specic internal energy of the total uid lling at
the end-pressure
uG (W s/g) specic internal energy of the portion of gas of
the uid lling at the end-pressure on the saturation line
uL (W s/g) specic internal energy of the portion of liquid
of the uid lling at the end-pressure on the saturation line
v (m3/g) specic volume of the total uid lling at the endpressure
vG (m3/g) specic volume of the portion of gas of the uid
lling at the end-pressure on the saturation line
vL (m3/g) specic volume of the portion of liquid of the
uid lling at the end-pressure on the saturation
line
x ()
portion of volume gas related to the total volume
of the uid lling
(1  x) () portion of volume liquid related to the total
volume of the uid lling (lling rate)
Remark: Corresponding terms at the reference-pressure
p1 = 1 105 Pa are additionally marked with the
index 1.
The vessel related terms are:
pmax (Pa) maximum allowable working pressure
Q (W) heat ux into the storage vessel
V (m3) geometrical volume of the storage vessel

A. Hofmann / Cryogenics 46 (2006) 825830

A supposition for the determination of the pressurising


period is the assumption that the uid is ideally mixed.
For vessels under transport conditions this assumption is
fullled. The pressurising period then has the maximum
value, which is equal to theoretical one.
For the determination of the pressurising period, the following relation is valid:
Dt

u  u1 V
Qv

or newly arranged
Dt

Du=v
Q=V

In Eq. (2), the term Du/v means the volume related specic
heat capacity of the total uid lling between start- and
end-pressure. This is a characteristic value of the uid.
The term Q/V means the heat ux, related to the geometrical volume, or the specic heat ux into the vessel. This a
characteristic value of the vessel.
By division of these terms, the determination of the
pressurising period, according to Eq. (2), becomes very
transparent and one can see that it is advantageous to have
a diagram for the uid, in which the Du/v-values are
exposed immediately.
From Eq. (2), one can see additionally that vessels with
a smaller volume have a shorter pressurising period,
because at equal quality of the insulation or constant heat
ux density the characteristic value of the vessel increases.
For p = pmax the maximum allowable working pressure
is utilised as end-pressure, which leads to the maximum
pressurising period. At passing over this limit, a special
overow device should become active, whose capacity is
designed for the normal heat ux into the vessel with the
corresponding mass ow rate. The additionally installed
safety relief device should become active at a higher pressure, e.g. at the vessel test pressure, which has a sucient
distance to the maximum allowable working pressure.
The capacity of this safety relief device has to be designed
for the maximum failure, i.e. the loss of vacuum in the insulation space.
4. Development of a Du/vv-diagram
From Eq. (2), one can see that the internal energy
always is used as dierence between start- and end-pressure. Additionally, in the most normal cases, the start-pressure can be assumed to be identically with the 1 105 Pa
reference-pressure, so that the 1 105 Pa line can be used
as a basis for making the dierence of the internal energies.
By division of this dierence through the actual specic
volume of the total uid lling, one obtains the specic
heat capacity per volume unite. If this characteristic value
of the uid between start- and end-pressure and for xed
lling rates can be checked immediately, using a special
Du/vv-diagram, is that much more comfortable than using
a conventional uv-diagram.

827

For the horizontal axis, the specic volume v now as


before is the suitable term, because it remains constant during the isochore change of state. The specic volume v however is functionally connected with the portion of volume
gas x1. By choosing a linear scale for x1 on the horizontal
axis, therefore a non-linear scale for v1 is valid, according
to Eq. (12).
A linear scale for x1 means that the whole length of
every isobar line between the saturation lines corresponds
to a linear scale of the portion of volume gas from zero
to one. By connecting points of equal portion of volume
gas, one obtains in a simple manner lines of constant
portion of volume gas x or with (1  x) lines of constant
portion of volume liquid, i.e. lines of constant lling rates.
The isobar lines within the two phase region in this representation become strait lines. Therefore, it is sucient to
determine the points on the saturation lines, which can
directly calculated, using thermodynamic table values.
4.1. Fundamentals for preparing a Du/vv-diagram
For preparing a Du/vv-diagram in the two phase region
as well as in the supercritical region, a mass balance and an
energy balance are taken as a basis.
From the mass balance one obtains
M MG ML

V
VG VL

v
vG
vL

1 V G =V V L =V

v
vG
vL

or with the portion of volume gas x and the portion of volume liquid (1  x)
1
x
1  x

v vG
vL

Solved for the specic volume of the total uid lling at the
end-pressure, Eq. (6) can be written as
vG vL
v
7
xvL 1  xvG
x can be chosen freely in the range between zero and one.
From the energy balance one obtains
uM uG M G uL M L

V
VG
VL
uG
uL
v
vG
vL

For the specic internal energy of the total uid lling at


the end-pressure one can write, using Eq. (9) and the portions of volume gas x and volume liquid (1  x):


uG
uL
u v x 1  x
10
vG
vL
Because of the specic uid lling remains constant at an
isochore change of state, for the specic volume at the reference-pressure p1 = 1 105 Pa it is valid:

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A. Hofmann / Cryogenics 46 (2006) 825830

v1 v

11

With the specic volume v1 now the lling rate x1 at the reference-pressure 1 105 Pa has to be determined. Therefore,
Eq. (7) is solved for x1, using values on the saturation lines
at the reference-pressure. With x1 the value on the horizontal axis is xed.
x1

vG1 vL1  v1
v1 vL1  vG1

12

Table 2
x1- and Du/v-values of helium-4 for the p = 2 105 Pa isobar line in the
two phase region
x-values

x1 ()
Du/v
(W s/cm3)

0.2

0.4

0.6

0.8

1.0

0.233
0.441

0.340
0.425

0.448
0.409

0.556
0.393

0.663
0.377

0.771
0.361

Subsequently, with Eq. (10) the specic internal energy u1 is


calculated, using the values on the saturation lines at the
reference-pressure 1 105 Pa.


uG1
uL1
u1 v 1 x 1
1  x1
13
vG1
vL1

For freely chosen x-values, the resulting x1- and Du/


v-values are shown in Table 2 and Fig. 1.
According to this method, complete Du/vv-diagrams
for the uids He (Fig. 1) and H2 (Fig. 2) has been developed, using tabulated values from [2,3].

Therewith, the Du/v-value for the vertical axis can be


determined.

4.3. Examples for the application of the Du/vv-diagram

Du u  u1

v
v1

14

By application in series of Eqs. (7), (10)(14), the isobar


lines in the two phase region of a Du/vv-diagram can be
determined.
The above described method can be applied to every
point in the eld, as long as the specic volume of this point
lays between dened boundaries. The range of the specic
volume is dened by the chosen basis. For p1 = 1 105 Pa
e.g., it is valid vL1 < v < vG1.
According to this method, the isobar lines in the supercritical or single phase region can be transferred too into
the Du/vv-diagram. This is of interest, when the heat
capacity of the uid shall be utilised in this region, because
the critical pressure lies very low, e.g., for the uids He and
H 2.
Using a Du/vv-diagram, immediately the lling rate can
be determined, at which for a chosen end-pressure, the
maximum pressurising period is reached, corresponding
to the highest Du/v-value at this pressure.

Du=v 0:355 W s=cm  0:355  106 W s=m

For He as a uid, the Du/v- and x1-values in the two


phase region for the isobar line p = 2 105 Pa with the reference-pressure p1 = 1 105 Pa shall be determined. The vand u-values at p = 2 105 Pa and at p1 = 1 105 Pa on the
saturation lines are taken over from [2], see Table 1. With
this calculation it shall be conrmed that the isobar lines in
the two phase region are strait lines with a linear scale,
referring to the Du/v- and x1-values.
Table 1
v- and u-values of helium-4 at p1 = 1 105 Pa and at p = 2 105 Pa on the
saturation lines
vL (cm3/g)

vG (cm3/g)

uL (W s/g)

uG (W s/g)

7.99
10.01

60.22
24.11

9.15
14.17

24.72
22.66

For the characteristic value of the vessel one obtains


Q=V 5=40 0:125 W=m

Therewith, the pressurising period can be calculated by


using Eq. (2):
Dt

4.2. Demonstration of the calculation method

p1 = 1 105 Pa
p = 2 105 Pa

Example 1. A transport vessel for liquid helium has a


geometrical volume of V = 40 m3. The end-pressure, corresponding to the maximum allowable working pressure, is
set to p = 4 105 Pa and the heat ux into the vessel,
equipped with a nitrogen cooled shield, is set to Q = 5 W.
The vessel is lled up at p1 = 1 105 Pa with a lling rate of
95%.
Which pressurising period can be expected under the
above conditions?
From the Du/vv-diagram for He (Fig. 1) at x = 0.05
and p = 4 105 Pa, a value for the characteristic heat
capacity of the uid can be found:

Du=v 0:355  106

2; 840; 000 s  788:8 h


Q=V
0:125

32:8 d
Example 2. A liquid hydrogen fuel tank for a car has a
geometrical volume of V = 0.12 m3. The end-pressure is
set to p = 5 105 Pa and the heat ux into the vessel to
Q = 1.5 W. The car will be parked with a lling rate of
60% at 2 105 Pa pressure in the tank.
How long is the pressurising period, till the hydrogen
starts venting?
Here the start-pressure is dierent from the referencepressure. From the Du/vv-diagram for hydrogen (Fig. 2)
at x = 0.4 and p = 2 105 Pa a value of the characteristic
heat capacity of the uid of Du/v = 1.2 W s/cm3 can be
found and one of Du/v = 3.8 W s/cm3 at 5 105 Pa vertical
above and therewith one between 5 105 Pa and
2 105 Pa:

A. Hofmann / Cryogenics 46 (2006) 825830

829

Fig. 1. Du/vv-diagram for helium-4 with 1 105 Pa reference pressure as basis line. The linear scale from x1 = 0 ! 1 corresponds, according to Eq. (12),
to v1 = 7.99 ! 60.22 (cm3/g).

Fig. 2. Du/vv-diagram for para-hydrogen with 1 105 Pa reference pressure as basis line. The linear scale from x1 = 0 ! 1 corresponds, according to
Eq. (12), to v1 = 14.12 ! 754.54 (cm3/g).
3

Du=v 3:8  1:2 2:6 W s=cm  2:6  106 W s=m

Therewith, the pressurising period can be calculated by


using Eq. (2):

For the characteristic value of the vessel one obtains


Q=V 1:5=0:12 12:5 W=m

Dt

Du=v 2:6  106

208; 000 s  57:78 h 2:4 d


Q=V
12:5

830

A. Hofmann / Cryogenics 46 (2006) 825830

References
[1] Kropschot RH, Birmingham BW, Mann DW. Technology of liquid
helium. NBS Monograph 111; 1968.
[2] Arp VD, Mc Carty RD, Friend DG. Thermophysical properties of
helium-4 from 0.8 to 1500 K with pressures to 2000 MPa. NIST
Technical Note 1334; 1998.

[3] Mc Carty RD. Hydrogen technological survey thermophysical


properties. NASA Special Publication SP-3089; 1975.