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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.
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0011-2275/$ - see front matter 2006 Elsevier Ltd. All rights reserved.
doi:10.1016/j.cryogenics.2006.06.003
826
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
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
828
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
Du u u1
v
v1
14
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
p1 = 1 105 Pa
p = 2 105 Pa
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:
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
Dt
830
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.