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www.elsevier.com/locate/cryogenics

A. Hofmann

*,1

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.

*

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

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

826

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

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)

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

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

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

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:

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

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

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].

determined.

Du u u1

v

v1

14

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.

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

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

using Eq. (2):

Dt

p1 = 1 105 Pa

p = 2 105 Pa

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:

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:

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

using Eq. (2):

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

Dt

Q=V

12:5

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.

properties. NASA Special Publication SP-3089; 1975.

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