----------------------------~~--~------- -

THE PRODUCTION OF LIQUID NITROGEN

FROM ATMOSPHERIC AIR USING
A GAS REFRIGERATING MACHINE

PROEFSCHRIFT
TER VERKRIJGING VAN DE GRAAD VAN
DOCTOR IN DE TECHNISCHE WETENSCHAP
AAN DE TECHNISCHE HOGESCHOOL TE
DELFT OP GEZAG VAN DE RECTOR MAGNI-
FICUS DR. R. KRONlG, HOOGLERAAR IN
DE AFDELING DER TECHNISCHE NATUUR-
KUNDE, VOOR EEN COMMISSIE UIT DE
SENAAT TE VERDEDIGEN OP WOENSDAG
22 JUNI 1960 DES NA MIDDAGS TE 4 UUR

DOOR

JOHANNES VAN DER STER

NATUURKUNDIG INGENIEUR

GEBOREN TE VLAARDINGEN

BIBliOTHEEK
DER
. __._---
/

TECHNISCHE HOGESCHOOL
DELFT
 STELLINGEN:

I. Het is niet mogelijk zuivere vloeibare zuurstof uit atmosferische lucht te winnen
met een installatie analoog aan de in dit proefschrift beschreven installatie voor
vloeibare stikstof.

2. Het is aan te bevelen om in condensor-verdampers, die in luchtsplitsingsapparaten

voorkomen, de vloeistof in de pijpen te laten verdampen en de damp op de buitn-
wand van de pijpen te laten condenseren in tegenstelling met de methode die in
de praktijk wordt toegepast.
(Ru hemann M. The separation of gases. Second edition. Oxford University
Press 1949 blz. 69.)

3. De bedrijfstijd van de in dit proefschrift op blz. 18 beschreven water-en-koolzuur-

afscheider wordt in zeer sterke mate bepaald door de manier waarop in het begin
de sneeuwlaag op het gaas wordt gevormd.

4. Voor het oppompen en regelen van stromen van vloeibare lucht, zuurstof of
stikstof is de dampbellenpomp tot nu toe ten onrechte verwaarloosd. (O.a.
Scott R. B. Cryogenic Engineering. D. van Nostrand Company, Inc. New Yersey
J959 blz. 263.)

5. Naarmate de beschikbare relatieve insteekdiepte bij dampbellenpompen voor

vloeibare gassen kleiner is moet men, als men met n-trapspompen wil volstaan,
gebruik maken van stijgbuizen met kleinere diameter.

6. Voor het bepalen van de zuiverheid van kokende vloeistoffen is om principile

redenen in vele gevallen het gebruik van een areometer te prefereren boven het ge-
bruik van een dampspanningsthermometer.

Tl. Voor het bepalen van de zuiverheid van kokende vloeibare zuurstof is in af-
wijking van stelling 6 het gebruik van een dampspanningsthermometer te pre-
fereren boven het gebruik van een areometer.

8. Het is nadelig voor de industrie dat de salariring in de verschillende vormen van

het technisch onderwijs niet concurrerend is met de salariring in de industrie.

9. Bij het uitvoeren van processen bij lage temperaturen dient men er rekening
mee te houden dat gifstoffen, die in ongevaarlijke concentraties met het te ver-
werken gas worden aangevoerd, bij het opwarmen van de installatie in concen-
traties vrij kunnen komen die wel gevaarlijk kunnen zijn.
Daarom dient men bij het opwarmen het vertrek waarin de installatie is geplaatst,
goed te ventileren.

10. Vergeleken met het land wordt de zee op een zeer primitieve manier als voedsel-
bron gebruikt. In verband met de sterk toenemende wereldbevolking is het ge-
wenst dat naar nieuwe methoden van voedselwinning uit de zee wordt gezocht.
11. Het is gewenst dat de wetenschappelijke medewerker van een research labora-
torium , die zich met "project onderzoek" bezig houdt, aangaande de kosten van
zijn werk op de hoogte wordt gebracht.
(Casimir H. B. G. Philips techno T. 20 (1958), 3, 66.)

12. Het is niet gewenst dat in wetenschappelijke publikaties uitspraken worden gedaan
over nut of onbruikbaarheid van bepaalde processen, zonder dat daarbij argu-
menten naar voren worden gebracht ter ondersteuning van de uitspraak. Dit geldt
vooral wanneer door de uitspraak de ontwikkeling van de techniek kan worden
geremd.
(Plank R. Kltetechnik II (1959), 5, 126.)

13. Ten onrechte wekt Hausen de indruk, dat men met installaties voor vloeibare
lucht volgens Linde, Claude of Heylandt, geen vloeistof kan maken die dezelfde
samenstelling heeft als de lucht waarvan men is uitgegaan.
(Hausen H. Handbuch der Kltetechnik. Achter Band. Springer-Verlag blz. 85.)
THE PRODUCTION OF LIQUID NITROGEN
FROM ATMOSPHERIC AIR USING
A GAS REFRIGERATING MACHINE
Dit proefschrift is goedgekeurd door de promotoren
PROF. DR. ING. L. VHL EN PROF. IR. H. KRAMERS
Aan mijn ouders
Installation for the production of liquid nitrogen from atmospheric air.
 CONTENTS

1. General introduction

2. Theoretical part 2
2.1. Principle of the installation 2
2.2. The reflux ratio of the column . . 4
2.3. The specific power consumption . 8

3. Description of the installation 12

3.1 . Introduction . . . . . . . . 12
3.2. The column. . . . . . . . . 13
3.3. Heat-exchanger and reboiler . 16
3.3.1. Purification of the air. . . . . . . 16
3.3.2. Design of heat-exchanger and reboiler 20
3.4. The condenser . 27
3.5. The reflux pump . . . 29
3.6. Insulation . . . . . 29

4. The automatic control 32

4.1. Introduction . . . . . . . . . . 32
4.2. The air feed. . . . . . . . . . . 33
4.2. The removal of the oxygen . . . . 33
4.4. The removal of the liquid nitrogen . . . . . 34
4.4.1. Description of the control of the reflux 34
4.4.2. Statie properties of the control system . . 36
4.4.3. Dynamic properties of the control system . 46

5. Safeguarding the installation against explosion hazards of acetylene and

other hydrocarbons 55

Appendix 1. Vapour bubble pumps for liquid nitrogen and liquid oxygen 60

Appendix 2. The transfer function of the refiux regulating device 71

Appendix 3. The use of a hydrometer for measuring the purity of liquid

nitrogen 77

List of symbols 85

Bibliography 88

Summary 90

Samenvatting 90
 -1-

THE PRODUCTION OF LIQUID NITROGEN FROM

ATMOSPHERIC AIR USING A GAS
REFRIGERATING MACHINE

1. GENERAL INTRODUCTION

In recent years there has been a marked increase in the use of liquid air and
liquid nitrogen in laboratories and in industry. These extremely cold liquids,
whose bolling points at 'a pressure of 1 atm (105 N/m2) are about -194C
and -196 C, respectively, are primarily employed for purposes of cooling.
They find application, for example, in vacuum technique, in research on the
proper ties of solids at low temperatures, in the making of shrink fits, and
for delaying chemical reactions.
For particulars of the familiar methods by which liquid gases can be made,
the reader is referred to the handbooks 1) and 2) in which these methods are
described in detail. The installations commercially available, and which operate
on conventional principles, are generally rather elaborate, and this has meant
that the user of sm all quantities has hitherto been obliged to obtain liquid
nitrogen and air from third parties.
With the gas refrigerating machine, described by Khler and Jonkers 3), it
has become possible to make small quantities of liquid air simply and economi-
cally. In this machine the Stirling-process is performed with a certain quantity
of hydrogen or helium. The gas is compressed at room temperature and the
heat generated by the compression is removed by cooling-water. The gas
flows through a regenerator, in which it is cooled still further, and thence to a
cold space in which expansion takes place and where the cold is produced.
This cold is transferred in a heat-exchanger to the air which is to be condensed.
The gas then flows back through the regenerator, thereby being raised to
room temperature again. When producing liquid air with a gas refrigerating
machine it is not necessary to compress the air. As a re sult the installation
becomes particularly simple in design and the production of liquid air can be
controlled in a very easy way.
When using liquid air, however, certain precautions are necessary, for it
can be dangerous in certain circumstances if brought into contact with in-
flammabie subsrances. For this reason it is sometimes better to use liquid
nitrogen ins te ad of liquid air; liquid nitrogen is also preferabie if the tem-
perature of a cooling bath is to be kept very constant.
This thesis will deal with a new method of obtaining liquid nitrogen from
 -2-

atmospheric air using a gas refrigerating machine. Particular attention will be

paid to the design and building of an installation employing a gas refrigerating
machine whose refrigerating capacity at -196 C is about 650 W. This instaUa-
tion produces liquid nitrogen at the rate of 0.036 mole per second (4.5 1 h- 1).
In order to make such a small installation as attractive as possible, its opera-
ti on must be made very simpie. Therefore an automatic control system has
been introduced which reduces the manual operations required virtually
to switching the installation on and off.
For separating water and carbon dioxide from the processed air no use has
been made of chemicalor physical absorption methods, but to simplify opera-
tion a new system of purifying the air by cooling is employed. By virtue of
this system, the installation can operatc continuously for a week before it
becomes necessary to defrost the trapped impurities.
In orthodox air-separating installations the air is compressed; one of the
fatures of the system described here is that no compressors are used. This
contributes largely to the simplicity both of the installation and its method of
operation.
In chapter 2 of this thesis the system employed will be analysed , and in
chapter 3 structural details wiU be described. Certain investigations conducted
with a view to making specific designs possible will be discussed , induding
the new method of purifying air by cooling. In regard to the control system
(chapter 4) particular attention will be paid to the stability of the reflux regu-
lation . This system involves the use of a vapour bubble pump for pumping
the reflux to the top of the rectifying column. An investigation has been made
into the behaviour of this type of pump and is described in appendix 1.
A study has been made of the danger of explosions resulting from the accu-
mulation of hydrocarbons in the air. Measures taken to prevent these explosion
hazards are described in chapter 5.
For the purpose of measuring the purity of the liquid nitrogen product by
simple means and with sufficient accuracy, a hydrometer has been developed .
The work on this instrument is described in appendix 3.

2. THEORETICAL PART
2.1. Principle of the installation
With the advent of the gas refrigerating machine it has become possible to
produce liquid nitrogen on a small oscale from atmospheric air. For this purpose
the refrigerating machine must be used in conjunction with a rectifying column
which operates at a pressure of 1 atm. between the boiling l'oints of oxygen
(90 OK) and nitrogen (77 OK).
A column ofthis kind is essentially a vertical tube in which liquid flows from
top to bottom and a vapour flows from the bottom to the top. The flow of
 -3-

vapour and liquid is maintained by heating the column at the base and cooling
it at the top. Moreover, measures are adopted to ensure that intimate contact
is established between the vapour and the liquid. When saturated air is fed into
the column somewhere between top and bottom, the ascending vapour will
become progressively richer in the more volatile component, nitrogen, and the
descending liquid progressively richer in the heavier component, oxygen. With
a sufficiently intensive supply and dissipation of heat it is possible in this way to
extract pure nitrogen at the top and pure oxygen at the bottom.
The flow diagram adopted is shown in fig. 1. In this figure, A denotes the

2 5 4

Liquid nifrog~n

8
--
~ -.--J

1 3

Air OXY'len
Fig. 1. Diagram of an installation with gas-refrigerating machine for producing liquid
nitrogen from air.

gas refrigerating machine, B the column in which the air is separated into its
components and C a heat-exchanger.
Air (1) is fed into the system, and the products extracted are virtually pure
liquid nitrogen (2) and gaseous oxygen (3) which is slightly contaminated with
nitrogen *). The air feed is pre-cooled by the cold bottom product in the heat-

*) Unless otherwise stated, it will henceforth be assumed that both products are completely
pure. It will further be assumed that the air consists of 22 mol % oxygen and 78 mol %
Dtrogen; the presence of argon will thus be disregarded, at least provisionally.
 -4-

exchanger C, where it is also partly dried. By heat exchange with the liquid
oxygen in the reboiler at the base of the column the air is then further cooled,
and at the same time the residu al water vapour and carbon dioxide are removed.
The air then enters the rectifying column B at a suitable point between top and
bottom. The vapour issuing from the top (4) is condensed by the gas refrigerat-
ing machine A. Part of the condensate is taken off as product (2) andAhe
remainder is returned to the column as reflux (5). The descending liquid
becomes increasingly richer in oxygen by virtue of the rectifying action of the
column, and enters the reboi1er at the base in the form of almost pure liquid
oxygen. By beat exchange with the air the liquid oxygen is evaporated bere.
Part of tbe vapour leaves tbe column as gaseous bottom product (3), the re-
mainder is returned to ascend tbe column. The extracted cold oxygen vapour
is raised to room temperature in the heat-exchanger C by heat excbange with
the air to be separated.

2.2 Tbe reDox ratio of the column

First of all we will demonstrate that the required fractionation of the air
can in fact be accomplished by the system described. To tbis end it is necessary,
and sufficient, to show that in the steady state the reflux ratio *) is higher than the
minimum value required for the separation of the components according to
the theory of rectification. It should be added that the separation is more
easily effected the more the reflux ratio exceeds this minimum value.
It can be seen from tbe diagram ofthe system (fig. 1) that after the air (1) has
been pre-cooled in the heat-exchanger C, it is further cooled at tbe base of
column B. The cold needed for this cooling is introduced to the column by
the reflux (5), and therefore the reflux is coupled with tbe cooling of the air.
In order to calculate the reflux ratio we must draw up the heat balance over
the column and the beat-exchanger. In doing so we shall assume in the fust in-
stance that losses are negligible. Tbe heat balance can be readily evaluated on
the basis of tbe block diagram in fig. 2. As in fig. 1, A, Band C here denote
respectively the gas refrigerating machine, the column and the heat-exchanger.
Air of, say, 20 C is fed into the system and oxygen of the same temperature
is extracted from it. The oxygen from the air and the oxygen product balance
each other thermally, and therefore they can be left out of account in calcu-
lating the heat balance. The nitrogen fTOm the air passes, as it were, the heat-
exchanger C without being coo1ed, but it leaves the column as top product
in a saturated state (-196 C). Somewhere between C and A then, the nitro-
gen has been cooled, which involves the extraction of 6390 joules from the va-
pour per mole of nitrogen product. Cold is supplied to the column because liquid

*) The reflux ratio at the top is defined as the number of mols of reflux supplied to the column
per mol of top product.
 -5-

nitrogen is introduced into it as retlux, whilst this nitrogen leaves the column
again as a saturated vapour. For a reflux of r moles liquid per mole product,
this amount of cold is r times the molar heat of evaporation of nitrogen, that
is r X 5600 joules. The heat balance for Band Cis thus :
6390 - r X 5600 = 0
So we find for the retlux ratio the value r = 1.14, which is roughly 1.4 times the
minimum reflux of 0.8 tequired for separating air into 22 mole % oxygen and
78 mole % nitrogen 4). The retlux ratio, which in this case is determined by
the ratio between the sensible and the latent heat of nitrogen, is so large that
it is readily possible to separate air into its components.
The amount of the nitrogen production mayalso be inferred from fig. 2.
, _._ ._ ._ ._._,
.I I.
I I
A I
H=OJ I -rmol
I I
I i
I
1mo lol
liquidn ifrogen
H=5600J H= 5600J H=OJ
I
i
I
I
I
I
I i
I
I
I
I
I
I
I
I
L ___ -.JI I
B
~ -- -

I I
i
I
I
I
I
I
I
i
I
I
I
I
I
I
I
I
IH=H99OJ
I
i I
I c i
i I
I I
L ._. __ ._ . _ .- _.~
H=11990J

Nifrogen Oxygen Oxygen

Air
Fig. 2. Diagram for ca1culating the nitrogen production and the reflux ratio.

The air flows into the region bounded by the dot-dash line. From this region
come the products, liquid nitrogen and gaseous oxygen. The latter is thermally
balanced with the oxygen in the air tlow. Thus it is as if only the nitrogen
 -6-

is supplied to the instaUation, and the cold production of the gas refrigerating
machine is entire1y utilized for cooling and condensing this nitrogen. The pro-
duction is then equal to the production obtained when nitrogen supplied in
boules is cooled and condensed by the refrigerating machine at normal pressure.
It will be evident that the foregoing gives a very idealized picture, since it
takes no account of the cold losses. We shall now caIculate the reflux ratio
taking the losses into account. These losses, with the symbols, are:
Insulation losses
Recuperation losses
Losses arsing fr om the freezing of the impurities out of the air q)water
Losses arising from the reflux pumping by means of a vapour bubble
pump (enabling the machine to be set up at the side ofthe column)
Also taken into account are:
The cold production ofthe gas refrigerating machine q)E
The difference in enthalpy ofN 2 at 20C and liquid N 2 at -196 C per
mole !:l.HN2
The useful cold, i.e. the production of the refrigerating machine after sub-
traction of aH losses, can leave the installation only in the form of liquid
nitrogen. The nitrogen production is therefore :

N = q)E - q)ins - ~~ - q)water-q)vbP mole S- 1 (2.1)

N
2

In the reflux caIculation the correction for the losses is more complicated than
in the caIculation of the production. This is evident as alllosses directed on the
refrigerating machine itself cause a decrease in the cold production; the
reflux ratio remains unaffected. Alllosses directed on the base of the column
increase the reflux ratio, ho wever, because the reflux returned to the top of the
column is not only required to cool the nitrogen of the air feed but also to
cover the above-mentioned losses. The question is therefore important whether
the losses are directed straight on the machine or whether they find their way
via the column to the machine. To the first kind belongs q)vbP and the insula-
tion losses of the refrigerating machine itself; the second sort incIude
q)he and q)water. The insulation losses are distributed over the whole length
of the column, and consequently it is not readily possible to say exactIy to
what extent they influence the reflux. We shall as su me that one part b is purely
directed on the base of the column, and the remainder (1 - b) is directed on
the top of the column. As in the previous section, we caIculate the reflux ratio
as follows:
Per mole of nitrogen product the quantity of heat supplied to the base of the
column is:
Q = 6390 + q)he + q)water + q)ins (2.2)
N
 -7-

This must be absorbed by a flow of liquid consisting of r ' moles of liquid

nitrogen suppling 5600 r' joules of cold to the column. We then find for r' the
value:
, = 1 14 + ct>he + q>water + q>lnS (2.3)
r. 5600 N
Substituting (2.1) in this expres sion gives :
. !::.HN
r' = 1.14 + 560; (2.4)

Obviously the losses are always smaller than the cold production, and there-
fore r' is always greater than 1.14. So we see that rectification of the air is also
possible when the losses are taken into account.
Generally speaking, it will be difficult to operate a liquid-nitrogen installa-
tion of this kind in such a way that exactly 0.78 mole nitrogen and 0.22 mole
oxygen are extracted as top and bottom products, respectively, per mole air
feed . In order to be sure that the top product, the nitrogen, is constantly pure,
it will always be necessary to extract more than 22 % of the air feed as bottom
product, which means of course that the bottom product will be impure oxygen.
It is known from rectification theory that the minimum value of the reflux
ratio at the top does not depend on the purity of the bottom product but
solely on the purity of the top product 4). Thus there is no danger that the
extraction of nitrogen together with the oxygen will cause the reflux to drop
below the minimum value, which might reduce the purity of the top product.
Summarizing, we may conclude that wh en using the system described in fig . 1
for making liquid nitrogen, there is in all cases an ample excess of reflux
to ensure that the air will be properly separated into its components.
We will now calculate the value of r' for the column designed. Measure-
ments have shown that the above-mentioned heat fluxes in the actual installa-
tion have the following values :
q>E 650 W (at an average pres su re of 23 atm in the gas refrigerating
machine).
q>lns 154 W
q>vbP 20 W
q>water 42 W (at a wet bulb temperature of 14 C).
q>he 8W
The available cold for cooling and condensing the nitrogen is thus 426 W.
This gives a producton of 0.035 moles of liquid nitrogen per second (4.4 1 h- 1).
In fig. 3 the distribution of the cold production ct>E in the various parts is
represented by splitting a current of width ct>E into a number of currents each
having a width corresponding to their true magnitude. The shaded currents
re the heat and enthalpy flows flowing via the column and which according-
 -8-

ly determine the reflux ratio. The reflux ratio can be calculated from formula
(2.4). Putting <5 as 0.5, we find r' = 1.78 for the reflux ratio, which is more

~ins=154W=24%

For cooling down and condensafion

ol the nitrogen 421 W = 65 %

Fig. 3. Distribution of the cold-production of the gas-refrigerating machine.

than twice the minimum value. Fig. 4 shows the build-up of the reflux ratio
in a similar manner as in done in fig. 3.

From cooling down

fhe nitrogiM product =64 %

From fH.E.=23%

TM re/lux ratio = 100 %

Fig. 4. Build-up of reflux-ratio.

2.3. Tbe specific power consumption

For the cold production of 650 W the gas refrigerating machine consumes
6.0 kW. The specific power consumption at the production of 4.4 l/h is thus
equal to 1.36 kWh/I.
It might be asked what, in principle, is the minimum work to be performed
in order to produce at normal pressure llitre of liquid nitrogen from air. This
work can be divided into the minimum work required to separate a given
 -9-

quantity of air into oxygen and nitrogen, and the minimum work required
to cool and conden se this nitrogen. In both cases the minimum work is given
by the increase in exergy. For I mol of air this can be written as :

Amin = D.Ex = D.H - To D.S , (2.5)

where To is the ambient temperature and D.H and D.S are respectively the in-
crements in the enthalpy and the entropy per mole upon the transition from the
one state into the other 6).
If the heat of association be disregarded, there will be no change in the
enthalpy upon the separation of oxygen and nitrogen from a mixture, and if
the process is isobaric the internal energy will also remain constant. The
minimum work of separation can therefore be written as :

Amin = - To D.S = -D. U -I PdV = -I PdV (2.6)

When oxygen and nitrogen are separated from air at constant pressure they
are both reduced in volume. The minimum work of separation now is the work
required , to compress each component isothermally to its new volume.
The re sult is the same as that obtained in the hypothetical experiment in which
the air is separated into its components by means of two semi-permeable walls,
followed by isothermal compression of the components 5).
The minimum work is:

AmJn = pv. (-PI In - P + -pz ln - P ) (2.7)

P PI P pz
In this expres sion PI and pz are the partial pressures of the components where
Pis equal to PI plus pz and V is the volume of I mole of the mixture. We can
now calculate the minimum work needed to separate such a quantity of air
of 20 oe into 78 mole % nitrogen and 22 mole % oxygen th at after separation
and following liquefaction I litre of liquid nitrogen is obtained. This minimum
work is:
AmJn = 0.013 kWh/1
In order to calculate the minimum work required for the cooling and the
condensation of the pure nitrogen, we again compute the increase in exergy
(formula 2.5). The results are shown in Table I. Although the decrease in enthalpy
is greater upon cooling than up on condensation, the minimum work is more
than three times smaller. The reason for th is is that in the fust part the cold
must be produced at all temperatures between 293 and 77 oK, whereas in the
second part cold must be produced only at the lowest temperature (77 OK).
The total minimum work needed to obtain liquid nitrogen from air is
0.179 kWh/I, of which 7% is used for the separation, 23% for the cooling and
70% for the condensatjon of the nitrogen.
 -10-

TABLE I
Calculated minimum work required for cooting from 20 C and condensing
nitrogen to obtain llitre ofliquid nitrogen at a pres su re of 105 Nm- 2.

Bin Sin Ex in A min. in

State
J/mole J/mole C J/mole kWh/1

N2 1 atm. 293 oK 11990 111 -20600

0.041
N21 atm. n OK 5600 72 - 15500
0.l25
N2 1 atm. liquid 0 0 0

If the liquid nitrogen were produced without cold losses in a system as shown
in fig. 1, in which the gas refrigerating machine were replaced by a Carnot
process, the minimum work would be 0.269 kWh/ I, which is 1.5 times as much
as with the ideal process. In this temperature range the efficiency of the gas
refrigerating machine is almost 30% of the efficiency of the Carnot process.
The specific power consumption of a system as shown in fig. 1, without losses,
would therefore be 0.89 kWh/I; as stated, this increases to 1.36 kWh/I when
losses are taken into account. The processes mentioned are coUected with their
specific power consumptions in Table Il.

TABLE II
The specific power consumptions of various processes capable of producing
liquid nitrogen fr om air.

Specific power consumptions

Process
compared with
in kWh/1
ideal process

Ideal process 0.179 1.0

As in fig . 1 with Carnot process. 0.269 1.5
I As in fig. 1 with gas refrigerating machine 0.891 5.0
(Without losses in the column and heat-
exchanger).
As in fig. 1 with gas refrigerating machine, 1.36 7.8
taking losses into account.

We shall finally consider where the losses arise in the installation and what
their magnitude is in terms of energy. To this end we first determine the amount
 -11-

of energy expended on each heat and enthalpy flow and we then consider what
each would have cost if it had been produced with an ideal process. The fust
can be done quite simply by distributing the specific power consumption of
1.36 kWhjl proportionally over the various components offig. 3. The minimum
work for each of these components can be found from the increase in exergy.
For the flows of enthalpy, tb is is :

AmJn = /).Ex = /).H - To /).S, and for the heat flows

Tl
AmJn = /).Ex = <P (T - 1).
o
In the latter expres sion <P is the relevant heat flow, To the ambient temperature
and Tl the temperature towards which the heat is flowing. The results of the
calculation are given in Table lIl.

TABLE III
Analysis of the losses in the installation.

Loss
Workin min. work
kWh/1 in kWh/1 in % in % ofthe
in kWh/1
ofwork totalloss

Cooling of N2 0.47 0.041 0.429 91 39.5

Condensation 0.41 0.125 0.285 70 26.2
i <Plns to 77 OK 0.16 0.048 0.112 70 . 10.3
i <Pins to 90 oK 0.16 0.038 0.122 76 11.2
<Pwater 0.09 0.001 0.089 99 8.2
<PvbP 0.05 0.016 0.034 70 3.1
<Pb e 0.02 0.004 0.016 76 1.5

1.36 0.273 1.087 100

Compared with the ideal case the greatest losses occur in the cooling of the
nitrogen and the freezing-out ofthe water. This is evident, since these processes
are carried out with needlessly "expensive cold".
It would be possible to reduce the specific power consumption by precooling
the air feed with an auxiliary machine operating at a higher temperature;
this machine could be used at the same time to freeze out the greater part of
the water. For reasons of economy and simplicity, however, this would only
be worthwhile in installations larger than the one described here.
 -12-

3. DESCRIPTION OF THE INSTALLATION

3.1. Introduction
A greatly simplified drawing ofthe installation built on the principle represent-
ed in fig. lis shown in fig. 5. Here again, A is the gas refrigerating machine, B
the rectifying column and C the heat-exchanger.

column packing

insulation material

B A

Fig. 5. Installation for producing liquid nitrogen from atmospheric air.

 -13-

Owing to the condensation of the nitrogen in the condensor 6 of the machine,

a subatmospheric pressure is produced so that the air to be processed is sucked
in from atmosphere. It enters the instaUation at 1 and flows via the heat-exchan-
ger C, where it is pre-cooled by the oxygen bottom product, to the reboiler 2.
The air is further cooled by heat exchange with the liquid oxygen in the reboiler,
after which it flows through the duct 3 to the air inlet port of the column. It
then rises through the upper part ofthe column, where the oxygen is washed out.
Nitrogen vapour leaving the column flows through pipe 4 and the connecting
tube 5 to the condenser 6, where it is condensed. The condensate flows back
through the tube 5 to the downcorner 7 of a vapour bubble pump. The latter
pumps the reflux through the riser 8 to the top of the column. Via the overflow
9 and the trap 10 the nitrogen product is discharged. The vapour bubble pump
is heated by conduction with the aid of a copper strip 11, one end of which is
fixed to the pump, the other end being held at a temperature of roughly 15 C
by a stream of water.
The liquid arriving at the base of the column is evaporated in the reboiler by
the in-drawn air. Part of the vapour is .eturned to the column and the remainder
is blown off via the heat-exchanger C as bottom product (12). The instaUation
is insulated by three mutuaUy sealed spaces packed with insulating material.
In this chapter we shaU deal at greater length with the design and construction
of the various components and with the experience thereby gained.

3.2. Tbe column

If the reflux ratio of a rectifying column is known, as weU as the composition
of feed, top product and bottom product, it is possible to calculate the number
of theoretical plates required *). F or this purpose, use is made of phase diagrams
of mixtures of the components present in the feed . A phase diagram of this
kind, i.e. a diagram of temperature versus composition, has been made for
oxygen and nitrogen mixtures by Dodge and Dunbar 7).
The simplest method of calculation is that devised by Mc Cabe and Thiele 8),
which assumes that the constituents of the feed have the same molar heat of
evaporation and that no heat is supplied to the column or withdrawn from it
between the top and bottom.
The first assumption is a rather rough one for the design of an air-rectifying
column, the molar heat of evaporation of oxygen and nitrogen being respectively
6.8 and 5.5 kJ mole-1 at a pressure of 105 N m- 2 (1 atm). An essentially more
accurate method, whose only simplifying assumption is the absence of heat
supply and withdrawal between the top and bottom of the column, has been
put forward by Ponchon 9), Merkel 10) and Keesom 11). In this method the

*) A theoretical plate is a plate from which the issuing liquid and vapour are in equilibrium
with each other.
 -14-

number of plates is determined graphically in an enthalpy versus composition

diagram . lts drawback is, however, that the graphical construction is not
particularly accurate. Hausen 12) has indicated a method in which the caloric
unit of mass is used. This unit is chosen such that the heat of evaporation for
each sub stance is exactly equal to unity. The re sult is that, when all flows and
compositions are expressed in these caloric units, the liquid and vapour flow is
constant over the height of the column, as in the Mc Cabe-Thiele method. The
difference, however, is that the molar heats of evaporation are not now assumed
to be equal, and this makes the method more exact. This method is also useful
when it is necessary to calculate the number of plates needed in a rectifying
column in which mixtures of more than two components are to be separated .
Hitherto it has been assumed that the top and bottom products are both pure,
in other words that for every 100 moles of air feed 22 moles of oxygen and
78 moles of nitrogen are extracted from the column. The ratio between the
quantities of bottom product and air feed, which we shall refer to as blow-off
ratio ~, was thus 0.22. Since nitrogen is the principal product of the installation,
it must be as pure as possible. In order to prevent the purity of the nitrogen
from being adversely affected by slight changes in the regulation ofthe column,
the blow-off ratio is always chosen higher than 0.22, viz. between 0.25 and
0.32. The number of plates calculated for the upper part of the column *) is
independent of the blow-off ratio if the latter is greater than 0.22. In that case
the number of plates calculated for the lower part of the column is dependent on
the blow-off ratio, such that as the ratio increases the necessary number of plates
decreases. In the light of the above considerations, a blow-off ratio of 0.25
was chosen when calculating the number of plates for the column in fig . 1.
When air composed of 78 % nitrogen and 22 % oxygen is fed in and when a
purity of the top product of 99.8 % is required it follows from the heat balance
that the bottom product will contain 12% nitrogen. As we have seen, the reflux
ratio is 1.8 (page 8). Calculation with the Mc Cabe and Thiele method then
gives 8 plates for the upper part and slightly more than 2 plates for the lower
part of the column. With the enthalpy-versus-composition diagram of Keesom
one arrives at 7 and 3.5 plates, respectively. The difference between these meth-
ods of calculation is most pronounced in the lower part of the column, where
the greatest changes in concentration occur.
Till now we have disregarded the presence of argon in the air. It is however
known that, in the rectification of air, the argon content of almost 1% has an
appreciabie influence on the process. Since argon has a boiling point of about
-186C it tends to accumulate in the lower part ofthe column, where the tem-
perature at the base is -183C (ifpure oxygen were made) and -191 C at the

*) The upper part of the column is the part between the top and the point of air entry; the
bottom part is that between the boUom and the entry point.
 -15-

entry port. This means that many plates are needed in the lower column in
order to obtain the oxygen free from argon. In the column just described the
bottom product contains as much as 12% nitrogen. It is therefore probable that
the argon is extracted from the column together with the bottom product. To
ascertain whether this really happens the number of plates for the column was
again calculated, this time by the method proposed by Hausen and taking into
account the argon content of the air. In this calculation Weishaupt's ternary
diagram for oxygen-nitrogen-argon mixtures was used 13). Here again, 7 plates
we re calculated for the upper part and 3.5 plates for the lower part of the column.
Obviously, then, the effect ofthe argon in this column is very smal!.
We will now proceed in calculating the dimensions of the column. At the
condensation temperature of nitrogen under a pressure of 1 atm., viz -196 oe,
the refrigerating capacity of the gas refrigerating machine is 650 W. The heat of
condensation of nitrogen at normal pressure being 5600 J mole- 1 we find for
the rate of vapour flow through the upper column 0.11 mole s-1, and through
the lower column 0.06 mole S- l. The rate of liquid flow in the column is 0.08
mole S-l (10 1 h- 1 ).
In columns with such small volumetric flows it is often practi~e to use,
instead of plates, a packing material with which the column is fiUed to the top.
In the installation described, the packing material consists of small pieces of
wire gauze of 8 X 8 mm2 bent into a saddle shape (Mc Mahon packing) 14). The
advantages of this packing material over plates are that it combines efIicient
operation with a low resistance to flow; is simple to intro duce into the column
and is relatively cheap; m oreover its heat capacity is low, resulting in a short
cooling time.
The diameter of the upper column was fixed at 48 mm, making the vapour
velo city 0.4 m S- l (calculated with respect to the empty column). The diameter
of the lower column was fixed at 38 mm, resulting in a vapour velocity of
0.3 m S- l. These veloeities are low, as a result of which the pressure drop over
the column is also low. This is important in connection with the possibility
of extracting the nitrogen product from the installation ; we shall return to this
subject later (page 28).
We calculated above th at the upper column should contain 7 and the lower
column 3t theoretical plates. In the case of columns filled with packing it is
usual to refer to the height ofthe column which, as regards its function, is equiva-
lent to a theoretical plate. This H.E.T.P. (height equivalent to a theoretical
. plate) is not exactly known for the packing material in use; the data available
on nitrogen-oxygen destillation show very considerable disparity. Mc Mahon
himself gives 4 cm 14), but mentions that the measurement was not particularly
exact. Rushton gives 5 cm 15), Haselden 12.5 cm and Schuftan 7.5 cm 16). In
order to make sure of a good product, the figure adopted for our column was
about 9 cm per plate. This made the packing height of the upper column 59 cm,
 -16-

and that of the lower column 36 cm. In this situation, pressure drops were
measured over the upper and lower parts of the column of 600 and 300 N m-2 ,
respectively (6 and 3 cm water column). The measured purity of the nitrogen
was 99.8 to 99.9 %.
At the top ofthe column, and at the air inlet, distributors are fitted to ensure
uniform distribution of the liquid. When conventional distributors were used,
difficulties arose from the fact that the relatively small openings in these dis-
tributors repeatedly became c10gged with pieces of ice or solid carbon dioxide.
Another solution was therefore sought which would prevent this. The dis-
tributors designed for the purpose consist essentially of a conical jacket having
a serrated lower edge with 12 teeth (fig. 6). When the flow of liquid to be dis-

Fig. 6. Liquid distributor.

tributed is directed on to the apex of the cone, the excellent moistening proper-
ties of liquid oxygen-nitrogen mixtures ensure that the surface of the cone is
covered with an almost uniformly thick film of liquid, so that virtually the
same quantity ofliquid flows down over each tooth (approx. 0.81 h- 1). Bending
the teeth inwards does not disturb the individu al streams, thus making it
possible to distribute the liquid uniformly over the surface of the packing by
bending the points. With these distributors there is no danger of blockages
since the liquid flows freely over the surface of the cone, carrying impurities
with it. Oblique positioning of the distributor (up to an angle of 30) is found
to have scarcely any effect on its operation, nor is the directing of the liquid
on to the apex of the cone particularly critica!. These distributors are only
suitable for sub stances that moisten the surface thoroughly. A distributormade
of phosphor bronze works excellently with liquid air but not nearly so weIl
with water, for example.

3.3. Heat-exchanger and reboiler

3.3.1. Purification of the air
Since the air fractionation process takes place at extremely low temperatures
it is necessary to remove all water and carbon dioxide from the air feed, as
 -17-

otherwise blockages would be caused by the formation of ice or solid carbon

dioxide in the low-temperature parts of the installation. The principal methods
of separating water and carbon dioxide from air are :
1. Chemical and physical absorbtion whereby the carbon dioxide forms a
bond with e.g. potassium hydroxide, and the water is absorbed in aluminum
oxide, potassium hydroxide or silicagel.
2. The method whereby water and carbon dioxide are frozen-out by gradual
cooling of the air.
The drawback of the first method is that it makes the operation of the system
complicated, since it means that chemicals have to be supplied or regenerated
at regular intervals.
The second method does not have this disadvantage, but it does mean that the
freezing-out process costs expensive cold, resulting in a decrease in nitrogen
production . In principle, most of the moisture could be frozen-out by means
of an auxiliary refrigerating machine operating at, say, -20 C, but this is too
complicated and therefore unacceptable for an installation as small as the one
described here. Fig. 7 shows the decrease in nitrogen production y as a function
15r------,---------r-----,------~

101-- - - - + - - - - _ _ _ t - - -r-t7<C.-- - _ j

51--~~~~~-___t----+----_j

o 5 10 15 20
TWb(oe )

Fig. 7. Percentage drop y inproduction, due to freezing-out of moisture, as a function of wet

bulb temperature T w b . , for various values of blow-off ratio a.

of air humidity at the blow-off ratios <X = 0.25 and <X = 0.32. Although in
extreme cases the decrease in production may be as much as 15 %, the freezing
out of impurities was nevertheless chosen because of its simplicity. A dis ad-
vantage of the method, however, is that the heat-exchanger must be warmed
up after some time for defrosting.
The manner in which the moisture and carbon dioxide are frozen out of the
air is analogous to the method described by Roozendaal 17) . According to this
method the air to be purified is passed through a piece of wire gauze which is
 -18-

kept at a temperature of about - 170 oe. The air is thereby cooled and a layer
of sn ow forms on the gauze. One might expect that the gauze would soon be-
co me clogged with snow and that consequently the pressure drop over the
gauze would rise very rapidly. If, ho wever, at a given air flow, the surface area
ofthe gauze is made large enough and the temperature ofthe gauze low enough,
a situation can be reached whereby the gauze only becomes c10gged after a
considerable time has eIapsed. It is in fact possible to select the conditions in
such a way that the layer of snow grows counter to the direction of air flow.
The layer becomes progressively trucker and yet the pressure drop over the
snow and the gauze remains remarkably low for a long time.
The physical explanation for this phenomenon is not known in detail, but
in broad lines it may be explained as follows : When the damp air is cooled
down by the cold gauze a layer of snow forms on the gauze. Now if the surface
temperature of this snow is sufficiently low, crystals will form on the surface
as a result of diffusional transfer of the water vapour in the air stream. The
structure of these crystals appears to be fairly coarse. The air flows through the
snow layer and is thereby cooled, and in the process the water vapour still
present in the air settles in the form of fine crystals in the gaps between the

Fig. 8. " Sn ow-cake" formed on the water and carbon-dioxide separator of a gas-refrigerating
machine used for producing liquid air. A section of the 6 cm fully-grown snow cake has been
removed, showing clearly the difference in structure between the surface and the interior
layers.
 -19-

coarser crystals. Finally, these gaps become filled too, and therefore if the layer
is not to cause clogging it is a necessary condition that the growth of the layer
by diffusion should be a continuo us process. This is possible only if the surface
temperature of the snow is sufficiently low. This temperature is determined by
the temperature of the gauze, the thermal conductivity of the snow and the
volume of air flowing per unit area of the gauze. The lower the gauze tempe-
rature, the better the thermal conductivity and the smaller the volume of air
flow, the longer wiU the snow trap remain in operation before the surface tempe-
rature rises to such a value as to cause a blockage.
If the gauze temperature is lower than the sublimation temperature of the
carbon dioxide in the air (-142 C), carbon dioxide will also settle in the snow
layer. In this way a layer can build up close to the gauze consisting of ice crystals
and solid carbon dioxide in roughly equal parts. .
Fig. 8 shows a "snow cake" formed on the ice and sn ow separator of a gas
refrigerating machine used for making liquid air. In this experiment the tem-
perature of the gauze was -170C, the surface of the gauze 0.1 m2 and the
load 1.3 X 10- 2 kg air m-2 S- l. The air velo city was 1.0 X 10- 2 m S- l (at a
temperature of 0 C in the empty cross-section) and the wet-bulb temperature
was 12 C. A section has been removed from the cake, showing clearly that the
structure of the surface is much coarser than that of the parts farther inside.
In this case the thickness of the snow layer is 6 cm and the mass of the snow
5 kg. The density of the snow layer is 400 kg m- 3 , that of the carbon dioxide
layer 900 kg m- 3 .

15~--~~~-------+------~+-------~

o 50 100 150 200

((h)

Fig. 9. Pressure drop ,t",P across the snow cake as a function of time t.
I. Snow trap of liquid air machine.
11. Snow trap of nitrogen installation (cold oxygen coils not insulated).
111. Snow trap of nitrogen installation (cold oxygen coils insulated by glass-wool blanket).
 -20-

In fig . 9, curve I represents the pressure drop over the gauze as a function
of time. During the fust 100 hours from the start the surface temperature is so
low that the snow layer can grow continuously; the pressure drop is therefore
low and shows little increase with time. After about 110 hours a much sharper
increase sets in. This might be thought to be attributable to the blockage of the
sn ow layer owing to inadequate growth. At this stage, however, that is not yet
the case. Measurements have demonstrated that at the end of the operating
period the resistance is offered principally by the COz layer and much less by
the water-snow layer. The latter is found to be primarily responsible for the
increase in resistance only in the case of high humidities. The pressure-versus-
time curve then resembles curve I, but the operating time is shorter.
During the fust hour after starting the machine, when no sn ow layer has yet
formed on the gauze, the water vapour and carbon dioxide in the air is not
completely trapped, and the liquid air produced looks rather cloudy. After
one hour, however, the layer has grown sufficiently to trap virtually all the
impurities, and the liquid air is then crystal-clear.
A sn ow trap built on the principle described combines excellent trapping
properties *) with a low resistance to flow and very compact construction .
Moreover, the trap is inexpensive to build and cannot be contaminated by dust,
which is trapped in the sn ow layer and flushed away when the layer is melted.
The construction of the snow trap designed for the liquid-nitrogen installation
will be discussed in the next section. .

3.3.2. Design of heat-exchanger and reboi/er

The air feed is pre-cooled in the heat-exchanger by the bottom product of
the column, the gaseous oxygen. When this oxygen is raised in temperature
from -183 C to +20 c, its enthalpy increase is 6426 J mole- 1 which, at a
normal load and a blow-off ratio of 0.25, represents a cooling capacity of
56 W. (In that case oxygen is extracted at the rate of 0.088 mole S-I). This is a
considerable percentage of the cold production of the refrigerating machine
and therefore it is necessary to use the cold to pre-cool the air by the oxygen
exhausted. Perfectly dry air of 20 C can be cooled, at a blow-off ratio of 0.25,
to -31 C. If the air is moist, the degree of cooling is considerably less, owing
to the condensation of the water vapour. For example, if the air feed has a wet
bulb temperature of 20C, it is cooled by the oxygen to an average temperature
of 0 C.
In the design of a heat-exchanger in which the air is to be pre-cooled in
counter-flow by the cold oxygen, steps must be taken to ensure that the heat-
. exchanger does not rapidly become blocked by ice and sn ow formation. Even

*) Thls appears not only from the clarity of the liquid air but also from measurements
described in chapter 5, in which the trapping of acetylene is dealt with.
 -21-

at wet buib temperatures higher than 20 C, whereby the air has an average tem-
perature higher than 0 C upon Ieaving the heat-exehanger, these diffieulties
still arise beeause it is virtually impossibie to utilize the coid from the oxygen
without iee and snow settling on the walls of the heat-exehanger ehannels.
Espeeially the requirement that the heat-exchanger has to funetion effieiently
at widely varying air humidities is not easy to fuifil.
The eonstruetion of the heat-exehanger and reboiier is entirely governed by
the new method of purifying the air by cooling, as deseribed in the previous
seetion and whieh is also applied here. Fig. 10 shows the design of the heat-

l388l column paching

I ~ I air

oxygen OiquidJ

insulafion material

w
Fig. 10. The heat-exchanger and reboiler combination.

exehanger and reboiler eombination in simplified form. The gause G, through

whieh the air is passed and on whieh the snow Iayer forms during operation,
is soldered to a round eage eonsisting of a number of vertieally positioned
 -22-

pipes H in which the liquid oxygen is evaporated. The reboiler, of which the
cage is a very important component, is secured to a plate of phenolic laminated
fabric P. Also fixed to this plate is a doubie-walledjacket B filled with insulating
material, thus thermally insulating the space containing the reboiler.
The air enters through a large number of holes 1 uniformly distributed over
the periphery of the plate P. It then fiows to the "snoiW chamber" 3 via a
cylindrical gap formed by the wall of the insulating jacket Band a brass shield
2 fixed to plate P. Mter having been pre-cooled by the oxygen product in the
snow-chamber, the air fiows through the gauze G on which the snowcake will
be built up. After passing the snowcake the air fiows via the filter F and the
pipe 5 to the gap 6 surrounding the lower part of the column. In this gap the
air is further cooled against the wall of the column, where at the same time any
traces of hydrocarbons remaining in the air are removed. *) Thefilter F consists
of a wire-gauze basket which, like the column, is fiHed with Mc Mahon packing.
During the period when no snow has yet formed on the gauze, this filter
intercepts part of the moisture in the air feed and thus prevents blockages
inside the column.
The cold gaseous oxygen fr om the reboiler is passed through a fiat copper
coil4 ofthree turns situated at the top ofthe snow chamber. This coil is shielded
underneath by a glass-wool blanket and a perforated plate in order to insulate
it to some extent from the air. The reason for this insulation wilI be dealt
with on page 23. By free convection of the air (the coil is much lower in tempera-
ture than the air in the snow chamber) the temperature of the oxygen in the
coil is raised from -183 C to -60 C. Mter emerging the coil the oxygen
fiows through a copper pipe which goes down inside the shield 2 in one turn
and goes up outside it in one turn. At the position A, where the air enters the
snow chamber, the temperature ofthe oxygen is -30 C, and is raised to about
+10 C in the length of copper pipe contained in the gap between the shield
and the wall of the jacket. In this construction, then, the major part (75 %)
of the cold contained in the oxygen is transferred to the air in the large snow
chamber, where blockage by ice accretion is not possible. The remainder of the
cold is transferred to the air in the above-mentioned gap. This gap, however,
is wide enough not to become ice-blocked, partly because the oxygen coil
consists of one turn only. Although a thick crust of ice and sn ow does form on
the pipe in a certain humidity range, it has never caused a blockage. Shield 2
is cooled sufficiently by convection in the snow chamber to act as a water
separator at high dew points. Water is then continuously tapped off at W at
wet bulb temperatures higher than 13 oe. Another advantage of this design
is that the air feed, whose temperature is not very much below room temperature,
fiows along the wall of the insulating jacket and thereby shields the jacket

*) Thls part of the installation will be dealt with at greater length in chapter 5.
 -23-

from the extremely cold parts. The insulation losses are therefore lower than
they would be if no shield were present.
Sin ce the load on the gauze is 1.4 X 10- 2 kg m- 2 s-1, the sn ow layer might be
expected to build-up in a manner similar to that described on page 19 in regard
to the water and CO 2 separator, for which the pressure drop over the sn ow
layer is given as a function of time by curve I in fig. 9. Tests showed, however,
that this is by no means the case. The pressure-versus-time plot obtained,
shown by curve 11 in fig . 6, is impermissible in connection with the regulation
of the oxygen extraction. It was obvious that the cause of the rapid increase
in the resistance of the snow layer should be sought in the pre-cooling of the
air by the cold oxygen. It was thought that eddies might occur in the snow
chamber, preventing the build-up of a snow layer with the desired structure.
Eddies might also be caused by the vertical position of the gauze. As the cage
is more than twice as high as the sn ow trap in fig. 8, it may be expected that the
eddies will also be stronger. Various tests were made with the flat coil positioned
at different places in the snow chamber. The pressure variation measured was
in all cases virtually the same as that shown by curve 11. It was noticed, however,
that comparatively little snow had formed on the coldest parts of the coil.
This led to the assumption that, whilst the air flowing along these parts was
certainly cooled, the cooling gave rise to an extra dense mist of fine ice crystals
swirling in the air. This would cause disproportion between the accretion of
the layer of coarse cyrstals and the further filling of this layer, resulting in the
measured rapid increase in flow resistance. The results were indeed much
better when measures were taken to diminish the eddies by insulating the flat
coil with cotton wool. The use of cotton wo ol is not advisable, however, for one
thing because it is inflammabie and for another because its thermal conductivity
is strongly dependent on the moisture content. Other suitable insulation was
therefore sought, and good results were finally obtained by insulating the coil
with a blanket of glass-wool supported by a perforated brass plate. The pressure-
versus-time variation measured on this construction is represented by curve III
in fig. 9. Measurements with a wet glass-wool blanket produced the same results.
Although the pressure curve is not as favourable as that of the snow trap in
fig. 8, the regulation of the blown-off oxygen is no longer upset and therefore
this solution is acceptable. Measurements have proved that the heating of the
oxygen is not reduced when the insulation is applied. The reason is that, al-
though the heat transfer is on the one hand decreased by the insulation, it is
promoted on the other by the increase in surface area. The latter also reduces
the temperature difference between the air and the cold wall - the perforated
plate - thereby diminishing mist formation.
The capacity of this heat-exchanger-reboiler to separate water and carbon
dioxide in the form of snow is such that the installation can normally operate
for a whole week without interruption. The trapped quantity of snow is then
 -24-

8 kg. The behaviour in a very wide range of air humidities is fairly constant. At
wet bulb temperatures higher than 13 oe, condensation water is continuously
tapped oft' during operation.
Inside the insulation of the jacket an electric element is fixed to the base
plate of the snow chamber. When the sn ow chamber is filled up as far as the
brass shield, the gas refrigerating machine is stopped, the electric element is
switched on, the snow melts and the water is drained oft'.
Fig. 11 shows a view of the heat-exchanger and reboiler fr om underneath,

Fig. 11. View of heat-exchanger and reboiler combination from undemeath. The shield 2 and
the insulating jacket B (fig. 10) have been removed.

the insulating jacket and the brass shield having been removed. The space
between the reboiler and the coil entirely fills up with snow during a period of
operation.
We will now describe the innerpart of the reboiler where the liquid oxygen
from the column is evaporated. The construction will further be discussed
with reference to fig. 10. The liquid oxygen flows from the lower part of the
column .t hrough the pipe 7 to the annular pipe 8. To this pipes the boiler
pipes are connected thus constituting the above-mentioned cage, on which the
gauze Gis soldered.
When the air flows through the snow layer and the gauze, heat is trans-
 -25-

ferred to the gauze, in consequence of which the liquid oxygen boils in the
boiler pipes. The boiling causes a circulation of the vapourizing liquid through
the boiler pipes, through vessel 9 and tube 10 back to the annular pipe 8.
The vessel 9 serves as a buffer stage and plays an important role in the control

Fig. 12. Reboiler of liquid nitrogen column. The gauze has not yet been soldered to the boiler
pipes.
 -26-

of the reflux, described in chapter 4. To the bottom of 8 a plate is soldered

that prevents air from flowing along the gauze to the column. In principle,
gauze might also be fitted here, but its cooting would involve constructional
difficulties. The oxygen to be exhausted flows from the vessel 9 through the
pipe 11 to the coil 4, and the remainder of the vapour passes through the pipe
12 to the column. The partition 13 prevents drops of liquid, produced by the
sputtering of the boiler pipes, from being carried along with the gas stream
and causing pressure fluctuations in the column. Such pressure fluctuations
must be avoided, because they would uspet the regulation of the oxygen
product. Fig. 12 shows a photograph of areboiler with the boiler pipes not yet
soldered to the gauze. The components indicated in fig . 10 can clearly be dis-
tinguished. (The large conical plate welded to the reboiler is the base of the
insulation space around the column.)
Sin ce the water and carbon dioxide are more readily frozen out of the air
according as the temperature of the gauze is lower, the aim in designing the
reboiler was to make this temperature as low as possible by ensuring good heat-
conduction of the gauze and good heat-transfer in the boiler pipes.
The cage consists of 32 boiler pipes 20 cm long. The inside and outside
diameters of the pipes are 4 and 6 mm, respectively; The centre-to-centre
distance between the pipes is 15 mmo Soldered to these pipes is a piece of copper-
wiregauze meauring 0.1 m2 The mesh width of the gauze is 0.84 mm, and the
wire thickness is 0.34 mmo Calculations and measurements have shown that the
maximum temperature drop over the gauze is about 2 C at the normal heat
flux of 320 W.
No data have been foundin the literature on theheat transfer to boiling liquid
oxygen in boiler pipes as described above. Measurements made under other
crcumstances have been reported, however; Haselden and Peters, for example,
performed measurements on a pipe of 10 mm diameter the exterior of which
was flushed with oxygen 18). They found that the position of the pipe has a
marked influence on the results, a greater heat transfer being measured in the
horizontal position than in the vertical position. The results for the vertieal and
horizontal positions of the pipe are represented by curves land Il, respectively,
in fig . 13. Haselden and Prosad 19) have investigated the boiling heat transfer
of liquid oxygen in a duct. Their measurements were made on a vertieal pipe
36 em long and having an internal diameter of 10 mm, inside of which a tube
was inserted to form a duet of 4 mmo The liquid pumped up by the vapour
bubbles in this duet flowed .down again through the inner tube. The results are
represented by curve III in fig. 13. It is noticeable that the heat transfer on
boiling in a duct is much better than on boiling on an open surface. The results
of Haselden and Prosad are only applicable, as they themselves state, to those
cases in which the circumstances (duct width,height and liquid flow) are exaetly
the same as those in the experiment. The heat transfer of heated wires to liquid
 -27-

oxygen has been measured by Weil 20). He found that the maximum heat
flux is 15 X 1()4 Wm- 2 and that it occurs at a temperature difference of 11 C.

20
.p
10 ~
8 d
6 I ./
4 /
2
][~;/
10-" ~(Wm~).
1-0
]][ ;j,~
0'8 I ~n
0'6 I III
04 / Ijj
Ij
0'2 /1
o1/jl
o 2 4 6 8 10 12 14
iJ /J(oCJ

Fig. 13. The boling heat transfer of liquid oxygen as a funetion of tbe temperature differenee
between the wall and the liquid.
I. Measurements by Haselden and Peters on a vertieally positioned pipe of 10 mm diameter.
Il. As I. Horizontal position.
111. Measurements by Haselden and Prosad on boiling oxygen in a duet 4 mm wide.
IV. Our measurements on a fin of 5 x 2 x 0.5 em3
P. Maximum heat flux measured by Weil on eleetrieally heated wires.

This is indicated in fig. 13 by the point P. We have performed heat transfer

measurernents on a copper rib of 5 X 2 X 0.5 crn3 . It appeared that the
position of the rib had no effect on the heat transfer. The results are represented
by curve IV in fig . 13; a maximum heat flux of 17 X 104 Wm- 2 was measured
at a temperature difference of 9.5 c.
In the construction adopted, about 10 Ware dissipated per boiler pipe.
The surface load is then 0.4 X 104 Wm- 2 . On a working column a temperature
difference of 1 C was measured between the pipe wall and the liquid. The heat
transfer is thus comparable with the data reported by Haselden and Ptosad.
The maximum gauze temperature was -180 C. At this temperature the
carbon dioxide and water contents are 10-2 p.p.m. and less than 10- 3 p.p.m.,
respectively. For this installation, in which there are no expansion valves to
get blocked up, this content is certainly low enough.

3.4. The condenser

The saturated nitrogen vapour that leaves the column is condensed in the
condensor of the gas refrigerating machine. This gives rise to a subatmospheric
pressure so that the air can be sucked in directly by the installation itself.
 -28-

The air then flows via the heat-exchanger and snow trap to the column, in
which the oxygen is washed out of the air. The pressure in the condensor is
thus equa1 to the pres su re of the outside air minus the pressure 10ss caused by
the flow resistance in the parts of the installation through which the air flows.
This pressure loss, depending on the thickness of the sn ow 1ayer on the gauze,
is (1-3) 103 Nm- 2 (10-30 cm water column). The condensation temperature of
the nitrogen is accordingly about -196 C.
The head of the gas refrigerating machine is provided with 104 recessed fins,
making the tota1 condensing surface 0.2 m 2 The co1d production at the tem-
perature referred to is 650 W. The surface 10ad is thus 3.2 X 103 Wm- 2 .
Hase1den and Prosad showed in their paper mentioned under 19) that Nusselt's
theory on the heat transfer by condensation in the case of 1aminar flow of
the condensation 1ayer is a1so applicable to the condensation of nitrogen.
Calcu1ation indicates that the temperature difference between the vapour and
the wall is 0.4 c, at a 10ad of 3.2 X 103 Wm- 2
Un1ess special precautions are taken the traces of hydrogen a1ways present
in the air, and other gases that cannot be liquefied at -196 C and a pres su re
of 1 atmosphere, will accumu1ate in the condenser and cause appreciable
deterioration of the heat transfer. To prevent this a water-jet pump is used for
extracting gas continuously from the condenser. The gas is extracted after it
has passed the condenser , when the amount of "uncondensable" gas is greatest;
the flow rate amounts to 1 or 2% of the gas to be condensed, and is found to
be sufficient in the cases normally encountered. When this exhaust system was
not operated, a drop in cold production of ab out 50 W in an hours time was
repeated1y ascertained.
After the installation has been started, the parts that operate at 10w
temperature must be cooled down before the normal operating situation is
reached. During this starting period the air cannot be cooled in the reboiler
because the latter as yet contains no liquid. To avoid contamination of the
column during this period, the air is not sucked in via the normal channel
but through a direct communication between the condenser and the outside
air. Before the air enters the condenser, however, it flows through a auxiliary
sn ow trap, of the same type as described above, which is mounted on the head
of the machine. The gauze surface-area (0.025 m 2) and the spa ce around it are
both small, but adequate for the starting period of 1i hours.
The condensate formed must be divided during operation into reflux and
nitrogen product. The way in which this is done is described in chapter 4, where
the regulation of the system is dealt with.
The nitrogen extracted as product is tapped off via a trap. If the negative
pressure in the condenser were very high, the nitrogen oudet wou1d have to
be in a 10w position, which could mean that large vessels could not be placed
under it. Measures were therefore taken to keep the negative pressure in the con-
 -29-

den ser as small as possible, among other things by adopting low gas flow-rates
in the column and in the snowtrap.

3.5. The reftux pump

In the diagram of theinstallation (fig. 1) the gas refrigerating machine is
shown mounted above the column. Since the whole column together with the
heat-exchanger is almost 2 meters high, it is obviously not desirabie to have the
refrigerating machine mounted at such a height. In reality the refrigerating
machine is therefore set up at the side of the column, and the reflux is pumped
to the top by means of a vapour bubble pump. In principle a vapour bubble
pump is a U-shaped tube with limbs ofunequallength. The liquid to be pumped
upwards flows through the short limb, which we shall call the "downcorner"
(see also fig. 35). The long limb, called the "riser" , is heated at its base, causing
the liquid contained in it to boil. The ascending vapour bubbles carry the
liquid upwards. This method of pumping was chosen in order to avoid the
use of moving parts which might become ice-bound. A copper strip connects
the pump to a sm all heat-exchanger through which water flows. The heat
required for operating the pump is withdrawn from the water owing to the
temperature difference over the strip. Given the dimensions of the downcorner
(47 cm), the riser (116 cm) and the diameter of the pump (6 mm) a power of
11 W is required to pump the reflux (0.078 mole S-l = 10 1 h- 1) to the top of
the column. In chapter 4, where the control is discussed, and in appendix 1,
we shall consider at greater length the properties of vapour bubble pumps for
liquid nitrogen.

3.6. Insulation
The entire installation is insulated by a number of mutually sealed-off
spaces filled with insulating material. These are the insulation spaces around the
condenser, the column, the heat-exchanger and the nitrogen outlet pipe.
They are all filled with silica-aerogel, a powdered substance with especially
favourable properties in that it has very low thermal conductivity, is not in-
flammable and moreover can readily be poured, making it a simple matter to
fi11 up the insulation spaces. lts drawbacks are its high price and its dustiness,
which makes it troublesome to handle.
The literature contains various data on the use of silica-aerogel as an insulat-
ing material in the region between -196 oe and room temperature. One ofthe
fust publications was by Katan 21). Curve I in fig. 14 gives his plot of the
therm al conductivity of silica-aerogel as a function of pressure. A paper on the
properties of powdered insulating materials has also been published by Fulk
et al 22). The results of their measurements of thermal conductivity versus
pressure are represented by curve 11 in fig. 14. They also performed measure-
ments on mixtures of silica-aerogel and aluminium powder at a pressure of
 -30-

10- 3 mm Hg. In a range of 15 to 16 percentage by weight of aluminium the

finest powders were found to possess a thermal conductivity 3 to 4 times lower
than silica-aerogel, without admixtures, under the same conditions. This is
denoted by point A in fig. 14.
2-5

B
2-0
102 (Wm- t C-')

1-0 /
/
II/ 0 ~
0-5

f.--- l..-----'
eA
~ /(
o ,.
10 - 10 10li< 10)J 10

Fig. 14. Thermal conductivity of silica-aerogel as a function of pressure P measured between

+20 C and -196 C.
I. After Katan.
IT. After Fulk et al.
A. Silica-aerogel with aluminium powder after FuIk.
B. Our measurements on silica-aerogel.

We have also performed measurements on silica-aerogel and other pourable

insulating materiais. The experimental set-up consisted of a spherical vesse1
filled with liquid nitrogen and surrounded by another spherical vessel which
was held at room temperature. The space between the two vesse1s was packed
with the insulating material. In consequence of the insulation loss the liquid
nitrogen boils; the thermal conductivity of the insulating material is then cal-
culated from the flow rate of the vapour issuing from the inner vessel and from
the dimensions of the inner and outer vessel. The insulation spa ce always
contained nitrogen at normal pressure.
In this way we found for silica-aerogel A. = 2.2 X 10- 2 Wm- l C-I. This is
indicated by point B in fig. 14.
The quality ofthe insulation may suffer considerably if the insulating material
gets wet, owing to the diffusion of water vapour if the space is not complete1y
air-tight, and because the space itself may "breathe" as a result of temperature
variations. There are several methods of keeping the insulation dry:
1. The insulation space can be hermetically sealed.
 -31-

2. The nitrogen drawn from the condenser, which is contaminated with

uncondensable gases and obviously is dry, can be conducted through the
insulation space.
3. An open communication can be made between the top ofthe column and the
insulation space, thereby enabling the latter to breathe dry nitrogen.
4. The insulation space can be connected via a liquid trap to the bottom of
the downcorner of the vapour bubble pump. This pro duces in the insulation
space a pressure higher than atmosphere, as a result of which nitrogen will
constantly be exhausted through any leaks there may be in the insulating
jacket and no damp air can be sucked in.
The fust method was adopted for the column and heat-exchanger insulation
spaces ; with the other methods the high gas-absorption of silica-aeroge1 at low
temperature proved too troublesome, in particular in the case of method 4.
For example the change in the temperatures in the installation caused by re-
adjusting the blow-off ratio seriously disturbed the vapour bubble pump, and
hen ce the reflux control. It was not possible to use the first method also for
the insulation space of the condenser as will be c1ear from the following. When
the column is cooled down, the pressure in the sealed insulation space decreases
to 0.6 atm as a re sult of the temperature drop and gas absorption of the
silica-aerogel. The column now is flexibly connected to the refrigerating
machine in order to prevent the transmission of vibrations, which would be
bad, among other things, for the soldered joints. It was found that, if the
condenser insulation space is sealed, the resultant negative pressure deprives
this coupling of its flexibility, unless measures are taken to counterbalance the
pressure. This, however, involves constructional difficulties. For the sake of
simplicity this insulation space was therefore brought into open communica-
tion with the condenser itself. The volume of the insulation space of the con-
denser is much smaller than that of the column, so that gas absorption presents
no difficulties. Moreover, the condenser is much more constant in tempera-
ture than the column. The insulation space around the nitrogen outlet pipe is
filled with silica-aerogel, after which it is exhausted on the pump to 10- 3 mm Hg.
We will now see what the losses are in the installation designed . The pro-
duction of the gas refrigerating machine, minus the condenser insulation loss,
can easily be measured with a c10sed evaporation-condensation system. In
this way a production of 650 W was measured at a pressure of 23 atm in the
refrigerating machine. During a test of the whole installation, with the refri-
gerating machine operating at .the same pressure, the production measured
was 4.4litres of liquid nitrogen an hour (0.035 mole S- 1). The wet bulb tempera-
ture during the experiment was 16 C. With the aid of these data we can now
draw up the heat balance :
 -32-

1. For cooling and condensing 0.035 mole N2 S-l 421 W

2. For pumping and controlling the reflux 20 W
3. For the heat-exchanger losses 8W
4. For freezing the water out of the air 42 W
491 W
The cold production of the refrigerating machine is 650 W
The insulation losses are therefore : 159 W
The insulation losses can also be calculated from the dimensions, the tem-
perature and the thermal conductivities ofthe insulating material. The following
are the calculated heat-flow figures for the various components :
1. The insulation space around the column.
a) Conduction through the silica-aerogel 45 W
b) Conduction through the measuring leads 6W
c) Conducting through plate P (fig. 10) 8W
d) Conducting through the coupling with the machine 5W
64 W
2. The insulation space around the nitrogen outlet pipe 2 X 20 W = 40 W*)
3. The insulation space around the heat-exchanger and reboiler combination.
a) Conduction through the hardpaper plate 4 W
b) Conduction through the silica-aerogel 10 W
c) Conduction through the measuring leads 6 W
20 W

The total calculated insulation losses are 124 W. The difference between the
calculated and measured values may be due partly to the omissions made in the
calculations with regard to the geometric configuration.

4. THE AUTOMATIC CONTROL

4.1. Introduction
If a small installation like the one described in the previous chapter is to
work economically it should be simple to operate. Therefore the installation
has been built in such a way that it can work practically without attendance.
The only deliberate control operations in the present case are limited to starting
up the installation ; thereafter the control is fully automatic. In principle it is
necessary to regulate the following :

*) The insulation loss of the nitrogen outlet pipe is 20 W, but this must be counted twice
because the cold nitrogen released upon evaporation passes out of the column together
with the liquid, thus increasing the losses. The sensible and latent heats of the nitrogen are
roughly equal, so that the totalloss is twice as high as the insulation loss.
 -33-

1. The air feed .

2. The removal of the oxygen.
3. The removal of the liquid nitrogen.
The methods of control adopted here will be discussed with reference to fig . 15,
which shows the installation in schematic form, omitting all components not
concerned with the control.

Fig. 15. The control of the installation.

4.2. The air feed

The air feed is maintained by the subatmospheric pres su re produced in the
installation owing to the condensation of the saturated nitrogen vapour in the
condens er. The use of liquid traps (see below) makes it impossible for the air
to enter the column in any other way than through the inlet. Since the air
cannot accumulate, it is sucked into the column in the right amount, without
the need for an automatic controller.

4.3. The removal of the oxygen

Since a certain negative pressure pI'evails in the column, the oxygen cannot
simply be blown out if tbe column and reboiler are in open communication. In
order nevertheless to allow this straightforward method of removal to be
adopted, the installation is designed in such a way that the liquid from the
column can only enter the reboiler thtough the standpipe 3. In the second place
 -34-

the fraction of the vaporized oxygen flowing back to the column can only enter
the column through the pipe 4, which contains an adjustable flow-resistance.
This resistance, which is in the form of a valve of comparatively wide cross-
section, is adjusted in such a way tbat the pressure drop across it causes the
pressure in the reboiler to rise above that of the atmosphere so that the oxygen
can be blown off.
Since air contains 78 % nitrogen, at least 22 % of the gas mixture sucked in
must be exhausted ifthe nitrogen product is not to be contaminated with oxygen.
The valve is so adjusted that 25 to 32 % is exhausted, which means that the
vapour so removed consists partly of nitrogen. Thus, for the same production
of liquid nitrogen, more air is sucked in than would be the case if exactly 22 %
we re exhausted. lt might be tbought that this would entail some loss of energy
and adversely affect the efficiency of the installation. This is not the case,
however. The reason is that the air is not compressed (hence there is no loss
due to the work of compression) and that the waste product is reheated to
nearly room temperature. Accordingly, a fairly coarse adjustment of tbe valve
is permissible, which considerably simplifies the operation.
If the installation starts sucking in more air, e.g. because of ncreased pressure
in the working space of the gas refrigerating machine, more oxygen will
evaporate in the reboiler, causing the pressure to rise. The consequence is that
more oxygen will be exhausted, and in fact in such a way that the ratio between
the flows of air and tbe oxygen remains roughly constant. The system described
has proved its efficacy even in the case of considerable variations in the pro-
duction of the refrigerating machine, in air humidity and in the pressure drop
across the snow layer in the heat-exchanger. It has been found in all cases that
it is quite sufficient to check the oxygen blown off and make any necessary
adjustment once every one or two days.

4.4. The removal of the liquid nitrogen

4.4.1 Description ofthe contro! ofthe reflux

The nitrogen leaving the column is condensed in the condenser of the gas
refrigerating machine. The condensate leaving this condenser has to be divided
into nitrogen product and reflux. Controlling the fust quantity thus also amounts
to controlling the quantity of reflux. We can therefore just as well speak of the
reflux control as of controlling the nitrogen product.
The demands made on this control are much higher than those applicable to
removal of the oxygen. This is evident, for if slightly too much nitrogen is
tapped off, the reflux will be too small, and this will cause the level in the reboiler
to drop and finally cause the reboiler to boil dry. Conversely, if not enough is
tapped off, the reboiler will finally overflow and the column will be flooded.
In both cases the installation cannot function properly. This means that an
 -35-

automatic controller must be adopted which has to keep the reflux at the correct
value at all times. This can be done by measuring the level in the reboiler and
by using this to control the splitting of the condensate stream. Both the liquid-
level measurement and the control of the division into reflux and nitrogen
product can be etfected in various ways. The method chosen was preferred
because of its simplicity and reliability, due to the absence of moving parts.
In the previous chapter we have seen that the gas refrigerating machine is
placed at the side of the column, and that it is therefore necessary to pump the
reflux to the top of the column. As already described a vapour bubble pump
is used for that purpose. It has proved possible to let the pump play an active
part in controlling the reflux; its operation will be explained with reference to
fig. 15. In this figure the vapour bubble pump is formed by the tubes 5, 7 and 8.
The riser tube 8 is heated by means of the copper strip 11, one end of which is
fixed to the bottom of tube 8 and over the other end water is allowed to flow.
The system works as follows: The vapour leaving the top of the column
flows to the gas refrigerating machine through the upper part of tube 5 and
through tube 6. The condensate runs back down tube 6 and passes into the
lower part of tube 5. This tube is provided with an overflow 9, which keeps
the liquid level in the tube constant during operation. The reflux delivered by
the vapour bubble pump is now solely a function of the heat flow through the
strip. The liquid which is not pumped up is discharged via the overflow and
the trap 10. By using the vapour bubble pump it is possible to divide the con-
densate into product and reflux simply and automatically by the expedient
of regulating the heat supply. Therefore the copper strip 11 is so designed as
to conduct slightly too much heat to the riser tube. Fixed to this strip at
point 12 is a feeier 13, which passes through the cover of the reboiler into the
liquid oxygen. The position of point 12 on the strip is chosen in such a way
that its temperature is higher than that ofliquid oxygen. Ifthe reflux is ' excessive,
the level in the reboiler-rises. As aresult, the temperature of point 12 drops and
less heat is conducted to the pump. The latter then pumps up less liquid, and
the reflux accordingly decreases until equilibrium is reached.
Fig. 16 shows part of the reflux controller, namely the lower section of the
vapour bubble pump, the copper strip which conducts heat to the pump (11 in
fig. 15), the cover of the reboiler with the lead-in for the feeier 13, the attachment
of the feeier to the strip, and the connections for supplying and carrying off
the water which keeps the end of the strip at the correct temperature. In this
construction the riser tube 8 is placed inside the downcomer 5 in order to
prevent the control from being atfected by insulation losses. The strip is fixed
to the (thin) riser tube by means of a copper block; part ofthe riser tube can be
seen in the photograph above and below the block. One of the two bent thin
pipes is a drainage pipe for removing any water that might enter the vapour
bubble pump.
 ~36-

The following are the demands to be met by the automatic controller of the
reflux:

Fig. 16. Bottom part of vapour bubbie pump, sbowing tbe attacbed conductor strip and the
connection of tbis strip to tbe feeier.

1. The con trol range must be sufficiently wide.

2. The controller must be stabie.
3. The cold losses due to the control must be as low as possible.
The remainder of this chapter will be devoted to the calculation of the static
and dynamic properties of the control system, and the results of the calculation
will be compared with those obtained by experiment.

4.4.2. Static properties of the control system

One of the most important static properties is the control range. lts width
is determined by the properties of the regulating device, in this case the fee Ier
together with the heat-conducting strip, and by the characteristic of the vapour
bubble pump. As regards the latter, however, there are virtually no possibilities
of variation. The relative submergence of the pump, for instance, is fixed by
the required length of the column and height of the gas refrigerating machine,
whilst the diameter is primarily governed by the requirement that the pump
must be insensitive to particles of ice or carbon dioxide that may be present in
the nitrogen. The pump employed has an inside diameter of 6 mm; the lengths of
 -37-

riser and downcomer are 116 cm and 47 cm, respectively. The pump charac-
teristic, measured with a set-up described in the appendix, is shown in fig. 17.
5

10
/
/
/
10 2 f(mol s-'~

o 5
1/ 10
P (W)
15 20

Fig. 17. Delivery F as a function of the heat flow p to the vapour bubble pump used for
controlling the reflux.

This characteristic differs somewhat from the theoretical characteristic which

can be found with the aid of the general formula for vapour bubble pumps,
given in appendix 1. One reason for this is that considerations of structural sim-
plicity made it desirabie to fit a curved section to the top of the pump. Particu-
lars of this modification are also discussed in the appendix.
For the purpose of caIculating the proper ties of the regulating device it is
necessary to make the following simplifying assumptions :
1. The thermal resistance of the strip is independent of temperature in front of
and behind the feeler.
2. The insulation of the strip is in the fust approximation ideaf.
3. The temperature difference between the connection ofthe strip to the vapour
bubble pump and the liquid nitrogen is 1.5 C, irrespective ofthe pump load.
The temperature ofthe end ofthe strip is then -194.5 C.
4. The composition of the liquid in the reboiler is always constant at 84 % 02,
12% N 2 and 4% A, corresponding to a blow-off ratio of 0.25. The tem-
perature of this liquid is then -184.5 C.
5. The temperature of the warm end of the strip is constant at 15 C.
The heat flow through the strip is given by
~
;.S D.-& D.-&
(/> _
-- '---e (4.1)
where:
(/> heat flow,
= thermal conductivity of the strip material,
 -38-

S cross-sectional area of the strip,

/).{} = temperature difference,
= length,
e = thermal resistance.
Thermal flow through conductors can be calculated with the aid of an
e1ectrical analogue if I is substituted for <IJ, U for /).{} and R for e 23). This
method offers particular simplifications in calculating the dynamic behaviour
ofthe control system, and will be used below.
The equivalent e1ectrical circuit of the regulating device is given in fig. 18.
R, K R,

Fig. 18. Equivalent electrical circuit of the reflux regulating device.

The resistances Rl and R3 are determined by the dimensions of the copper

strip, whilst R2 depends on the shape and material of the feeler and on the level
in the reboiler. The potentials UI, U2 and U3 are fixed by the assumptions made
in points 3, 4 and 5 above (see page 37). Since we are only concerned with
UI-U3 and U2-U3, we shall henceforth put U3 = 0. The currents through the
circuit can be calculated with the aid of Kirchhoff's laws. For the current to
the vapour bubble pump we thus find:
Is = UI R2 U2 Rl+ (4.2)
Rl Rz +
Rl R3 +
R 2 R3
The maximum value of this current is reached when R2 is maximum. For
R2 = CO, Is is:
Is ~ UI (4.3)
max RI+R3

The minimum value of Is is obtained when R2 is minimum. For R2 = 0, then,

(4.4)

To obtain the widest possible con trol range, the values of UI and U2 being
fixed, it is therefore necessary that Rl + R3 should be as small and R3 as large
as possible.
 -39-

Let us now consider the current ft through Rl. This quantity represents the
heat flux which enters the installation from the water. This must be kept as
low as possible, because the nitrogen production of the installation is diminish-
ed by this thermal leakage. Since the potentialof the star-point K (fig. 18)
depends on R2, it follows that ft will also be dependent on R2. The maximum
value of ft will occur when R2 is minimum, that is to say equal to zero. The
maximum value of ft is given by :
I _ Ul-U2
lmax - Rl (4.5)

It is necessary to make this quantity as small as possible, but this can only
be done if Rl is as high as possible. The requirements for a wide control range
and a small cold loss are thus diametrically opposed. The control range will
therefore have to be chosen in such a way that it reasonably fulfills the require-
ments without entailing unduly high losses.
In the automatic controller of the installation designed the heat-conductor
is a copper strip of25 X 3 mm 2 The length ofthe warmest part (RI) is 247 mm,
the length of the coldest part (R3) is 188 mmo Since the thermal conductivity of
copper is highly temperature-dependent in the range from +15 oe to -194.5 oe,
it is not possible to use the same values for the two parts. With the aid of data
from the literature 24) and our own measurements an estimate was made of
the average value of lhe thermal conductivity of the two resistances in their -
respective temperature ranges. The values are:
l = 400 Wm- l e- l and 3 = 450 Wm- l e- l
This leads to :
el = 8.2 CjW and e3 = 5.6 CjW
From the data on page 37 it follows that UI = 210 oe and U2 = 10 oe. We
can now calculate the limits of the control range from formulas (4.3) and
(4.4). We have then:
<1>3min = 1.8 Wand <1>3max = 15.2 W
A plot of <1>3 as a function of e2is represented by curve I in fig . 19. The refluxes
corresponding to the extreme values of <1>3 can be read from fig. 17 and amount
to 0 and 0.12 mol of liquid nitrogen per second.
Hitherto we have assumed that it would be possible for R2, and hence for
e2, to vary from zero to infinity. In reality, however, this is not a practical
possibility. In the first place e2 = 0 is not possible because of the finite heat
transfer between the boiling liquid oxygen and the feeIer and because of the
fact that the resistance of the feeIer lead-in through the reboiler cover is not
infinitely small. It is therefore necessary to introduce in the equivalent circuit
a resistance R20 in series with R2; the value of R20 is determined by the resist-
 -40-

ance of the fee1er lead-in and by the boiling resistance. In the second place
(12 = 00 cannot be achieved because it is impossible to insulate the feeier
completely from the liquid oxygen. To correct for this in the equivalent circuit
5

~
.-
If
10 ./

I
o 5 10 15 20 25
112(oCW- 1J

Fig. 19. Plot of <P3 versus (!2.

J. Without losses (diagram fig. 18).
II. With losses (diagram fig. 20).

a resistance R2a is introduced in parallel to R 2; this parallel resistance is

determined by the heat transfer from the feeier to the oxygen vapour in the
reboiler and by the insulation losses of the lead-in. This resistance is actually
a divided parallel resistance which must also be partIy across R2o' With the
feeIer as constructed the simplification adopted is, however, permissible. In
the new equivalent circuit (fig. 20) R2 can now vary from zero to infinity. A
consequence of the presence of R20 and R2a is that Iama.x is smaller and /a mln
is larger, which means that the control range is shorter.
The magnitude of R20 and R2a is governed by structural considerations.

u,

Fig. 20. Improved equivalent circuit of reflux regulating device.

 -41-

The resistance R20 (and hence the value of 13m1n ) can be made small by making
the diameter ofthe feeier lead-in large (the feeier being kept as short as possible).
This meets with difficulties, however, since it is also necessary to make R2a
large. For the latter purpose the feeier lead-in must be weU insulated thermally
from the wall of the reboiler. This is done by fitting a thin stainless-steel dia-
phragm in the reboiler cover where the feeler is led through. Since the size
of this diaphragm is limited by the available space, the diameter of the lead-in
must not be unduly large, as otherwise the conduction losses through the dia-
phragm would be excessive and 13ma.x would accordingly be too small. The
actual design of the feeier and lead-in through the reboiler cover is shown in
fig. 21. The line AB in this figure denotes the highe st level and the line PQ the

5cm
A- -----t-1""""'1-+---- 8

rangt: 8rass
ol
Iiquidlt:Yt:1
o
Fig. 21. The feeier and the lead-in through the reboiler cover.

lowest level of the oxygen in the reboiler. The thermal re~istance, which is
more or less shortcircuited by the liquid level, is contained primarily in the
brass tip of the feeler . The long upper section is determined partly by the
design of the reboiler with its boiler pipes. The pressure fluctuations occurring
during operation are somewhat damped in the vapour space and the liquid and
vapour pumped up through the boiler pipes can be separated there. The upper
section of the feeler is thick and made of copper in order to obtain the smalle st
possible value of R20 . The heat-conducting strip is tightened at soldering tem-
perature against the face C and then soldered to it, thus producing a very good
joint. The shape and dimensions of the brass tip will be dealt with later. The
feeier is surrounded by a shield to protect it from splashes of liquid. The
liquid can flow freely in and out through holes provided at the bottom of the
shield. Larger holes at the top are provided to aUow the vapour to escape.
For the feeier in fig. 21 the thermal resistance of the upper part between the
soldered joint with the brass tip and the connection with conductor strip, can
be approximately calculated. The value arrived at is: {! = 0.6 C/W. A
second resistance governing the value of {!20 is the temperature difference
 -42-

between the feeler and the liquid at the highe st level in the reboiler. The
value of 1/>2, which, together with the available surface area, determines this
temperature difference, can be found from the formula :
fl. __ 1/>3 (!3 - {}2
'P 2 (4.6)
(!2

In the present case 1/>2 is about 20 W at the highest level of the liquid. The
surface area of the brass tip is 10-3 m2 The temperature of this surface, how-
ever, is not the same at all points, owing to the thermal reSistivity of the brass.
It is estimated that half the surface has the maximum temperature difference
with the liquid, and that the remainder does not contribute to the heat transfer.
According to the data from fig. 13 the temperature difference between the wall
and the boiling oxygen is 6 c at this heat flux of 4.104 Wm-2 This temperature
difference corresponds to a resistance of 0.3 C/W. The total value of (!2 0 is
then 0.9 C/W. Calculation of 1/>3min from (4.2) yields 1/>3min = 4.6 W. For
the simplified case we have already mentioned the figure 1.8 W.
Since the temperature of the feeier is higher than its ambient temperature,
heat will also be transferred by conduction and convection. The heat conduction
through the diaphragm is easily calculated, and amounts to 0.02 wtc. The
calculation of the h~at transfer by convection from the feeier to the vapour is
more difficult. Ifthere were free convection, the heat transfer could be estimated
from the known formulas. The loss would then be 0.04 wtc. Howev'er, since
the feeier is surrounded by a shield there can be no question of free con-
vection. On the one hand the shield reduces the heat transfer, and on the
other hand the better contact with the vapour produced upon boiling wiU
increase the heat transfer. Moreover, heat will also be transferred by the sputter-
ing of liquid against the feeier. We shall assume that the increase and decrease
approximately cancel one another out and we then find for the parallel resistance
(!2" = 17 C W- l

From (4.2) we find that in this case 1/>3max reaches a value of 13.0 W.
On the operating column the ends of the control range can be measured
either by emptying the reboiler or by filling it with liquid oxygen. The results of
these experiments are given together with the calculated values in Table IV.

TABLE IV
Calculated and measured values of the upper and lower limits of the reflux
control range.
1/>3min 1/>3max
Without losses (according to diagram in fig. 18) 1.7 W 15.2 W
With losses (according to diagram in fig. 20) 4.6W 13.0W
Measured values :
I 6.0W l3.0W
 -43-

It can be seen that there is reasonable agreement between the results of cal-
culation and experiment.
At various loads on two columns the temperature difference was measured
over (23, from which the heat flow <P3 was calculated at the known value of (23 .
On the other hand the reflux can be calculated from the cold production of the
gas refrigerating machine and the nitrogen production of the installation.
Then, with the aid of fig . 17, <P3 can again be calculated. The results are collect-
ed in Table V.

TABLE V
Comparison of the measured and expected values of <P3.

<P3 (From calibration

Reflux <P3 (Measured) Difference
graph)

2.2 X 10- 6 m3 S- 1 7.1 W 8.2W +1.1W

2.8 8.4 9.6 + 1.2
3.0 9.1 10.2 + 1.1
3.3 10.2 11.3 + 1.1
3.6 11.6 12.5 +1.1
2.8 8.6 9.6 + 1.0
3.3 10.0 . 11.5 +1.3
2.7 8.2 9.3 + 1.1
3.3 10.0 11.2 + 1.2

The average difference between the values of <P3 measured on the column and
the values found from the calibration graph is 1.1 W. Probably this difference
is due to the insulation losses. This follows also from the fact that in a column
in which the insulation space was evacuated, thereby reducing the insulation
losses, the heat flow through (23 rose by about 10%, the reflux remaining con-
stant. For these reasons 1.1 W was applied as a correction to the calculated
values of <P3. In this way <P3 = 1(22) was obtained, which is shown as curve Ir in
fig. 19.
With the aid of the characteristic of the vapour bubble pump (fig. 17) the
pumped reflux can be constructed as a function of (22 (fig. 22). The control
range extends from 2.0 X 10- 2 male S-1 to 11.0 X 10- 2 mole S- 1. A reflux of
2.0 X 10- 2 male S-1 represents a supply of cold to the column of 113 W. Trus
is less than the insulation loss. The cold production of the gas refrigerating
machine can therefore be lowered (by reducing the pressure of the medium in
the machine) until no liquid nitrogen emerges from the column, without the
reflux controller reaching the lower limit of the calculated working range. The
 -44-

upper limit of 11.0 X 10- 2 mole S- 1 is reached in the case that, for example,
the dew point of the air is 20 C and the production of the refrigerating machine

15

----
10

5 I
,
o 5 10 15 20 25
t?2(OCW- I)

Fig. 22. The delivery F of the vapour bubble pump as a function of the resistance 1!2 of the
feeIer.

is about 900 W instead of the norm al cold product ion of 650 W. The con trol
range is thus extremely wide.
The maximum value of CP1 can be calculated with Kirchhoff's laws and
amounts to 22 W. The production drop of the installation as a result of this
heat flow is 1.6 X 10- 3 moles of liquid nitrogen per second (0.2 1 h-1). It is
possible to offset this 10ss by passing the air feed along the beginning of the
strip, thereby precooling the air. This leads to complications, however, which
are undesirable in view of the necessary structural simplicity of the installation.
The losses might also be limited by reducing the con trol range. The wide con-
trol range is chosen in order to avoid under all circumstances difficulties arising
from the unavoidable tolerances due to fabrication.
The variation of the reflux F as a function of the level h in the reboiler should
be uniform over the entire control range in order for the static sensitivity of the
regulation to be constant over the whole control range. From fig. 22 it may be
taken that the F versus (!2 curve is far from being a straight line. It is therefore
necessary to design the feeier in such a way that at high values of (!2 (low level)
the value of d(!2jdh will be much higher than at low values of (!2 (high level).
Moreover, it is necessary to ensure that the boiling resistance does not have
an unduly great influence, since it is not likely that tbis resistance will be readily
reproducible. After experiments with various types of feeiers it was found
th at the tapered feeier in fig . 21 adequately met the specified requirements. Fig.
23 shows the quantity of liquid pumped per unit time as a function of the level
in the reboiler, the level being calculated from the tip of the feeier. Curve I ap-
--- -- ---- --------------------------------~---,

-45-

plies to the case where the resistance {22 consists solely of the thermal resistivity;
curve II represents the case where the boiling resistance amounts to half the
1 5 , - - - - , -- - -,-------,------,-----,-- - -- ,

5r------+------4-----r---~_+~~~~---~

~~1------~O------~------2L-----~3------~4------~5
h (1O- 2mJ

Fig. 23. Tfie delivery F of the vapour bubble pump as a function of the level h in the reboiler.
1. Boiling resistance left out of account.
Il. Boiling resistance is half of thermal resistivity.
111. Boiling resistance is equal to thermal resistivity.

thermal resistivity; in the case of curve III the boiling resistance is equal to the
thermal resistivity.
The measurements reported in Table V were accompanied by readings of the
level in the reboiler. The level was measured with a "Hampson meter" (an
instrument which measures the hydrostatic pressure in the liquid). The accu-
racy of the instrument is not particularly high, nor are the results very' easy to
interprete. What is to be measured is the point at which the tapered fee1er is
moistened by the liquid in the reboiler. On the one hand, this point will be higher
than corresponds to the measurement, owing to the boiling and sputtering of
the liquid inside the shield; and on the other hand the measurements will indicate
too high a point because the fee1er, being warm, is not immediately moistened.
The accuracy of the measurement is estimated 3 mmo The measuring
points are plotted in fig. 23. Because ofthe inadequate accuracy, it is not possible
to determine from the measurements exactly what contribution the boiling
resistance makes to {22. Nor is it possible to calculate this contribution exactly,
because, owing to the temperature gradient in the fee1er, it is not known what
the temperature difference with the Huid will be at each point on the surface
of the feeier. A rough calculation shows that it is improbable that the boiling
resistance will be greater than half the thermal resistivity. If the level in the re-
boiler is high, the boiling resistance according to the estimate on page 42 will
be small (and is moreover already included in (220)' At lower levels the resist-
ance will increase because the surface area decreases. At the lowest levels,
 -46-

however, the effect on the quantity of nitrogen pumped up per unit time
will be very slight, because the thermal resistivity is high and furthermore the
F versus (22 curve is very flat. The effect of the boiling resistance will therefore
be most pronounced in the middle of the con trol range.
From fig. 23 it may be taken that the sensitivity of the regulating device,
given by dF/dh, is not constant. At the highest level this sensitivity is approxi-
mately twice as high as at the lowest level. This difference might be reduced
by using a cone of the same length but with a larger apex angle. Another possi-
bility would be to design a feeier having a bottom part the same as that of the
feeier used, but terminating in a truncated cone with a larger apex angle. Since
the contribution of the boiling resistance in this problem plays a substantial
part it is not possible here, without experiments to give a conc1usive answer.
4.4.3. Dynamic properties of the con trol system
In the preceding section we have seen how it was pos si bIe to improve the
proper ties of the regulating device by giving the feeier a conical shape. By ex-
periments with cones of different length a co ne was found by means of which the
control system could also be given the desired dynamic properties, i.e. stability
and rapid response. These are essential, as otherwise a minor fault in operation
will upset the functioning of the installation. Although this result was obtained
by experiment, subsequent theoretical investigation of the dynamic behaviour
of the automatic controller is called for in order to determine the effect of
various factors. This is important with a view to the possible further deve1op-
ment of th is type of air fractionating system. We shall describe the dynamic
behaviour by the frequency-response method of calculation.

-
Fig. 24 shows a block diagram of the reflux controller. The transfer function

Fi Fu Fu hu
Hl, Hs

f;
~
h;
H3 H2 ~ H1

Name of element.
-
Fig. 24. Block diagram of the automatic refiux controller.
Transfer function.
Feeier Hl = (22Ih,
Regulating device H2 = wal(22
Correcting device Ha = Ft/Wa
Column H4 = FuiF,
Reboiler H5 = h,)Fu
 -47-

on the i th element is denoted by Ht. On the signallines between the elements

the symbols earlier employed are marked, but they now refer to the deviations
with respect to the steady state and not to the value of the relevant quantity
itself. The liquid level ht in the reboiler is converted by the feeier into the
thermal resistance (22 which, in its turn, governs via the regulator the heat
flow (P3 to the correcting device (the vapour bubble pump). The flow of liquid Ft
pumped up by this device is conducted to the column. The liquid flows down
through the column and arrives as Fu in the leboiler. The liquid flow is converted
in the reboiler into the level hu, which closes the controlloop. The product of
the transfer functions will be called H ( = - Hl H2 H3 H4 H5). The control system
is stable if the locus of H intersects the negative part of the real axis to the
right of the point -1. If the real axis is intersected at the point -lor to the
left of it the controller is unstable. The frequency at which the locus of H bisects
the axis is also approximately the frequency at which the controller recovers
after a disturbance; this applies, however, only if the damping is not excessive
and provided the locus does not cut the axis at too sharp an angle 25).

Calcu/ation of the transfer function Hof the contro/loop

Since most of the elements are not linear, the transfer function H will be
calculated for three reflux settings, viz. at 5.1,8.1 and 10.5 X 10- 2 mo1e S-l.
Use will be made ofthe same simplifying assumptions as mentioned on page 37,
and also of the simplest equivalent circuit (fig. 18). We shall now discuss in
turn the calculation of the various transfer functions.

The transfer function Hl

The values of (22 appertaining to the above-mentioned settings can be found
with the aid of figures 17 and 19 (curve I). Hl can now be calculated with the
formula for thermal flow through a cone, on the assumption that the boiling
resistance is halfthe conduction resistance. In the foregoing it could not be shown
quantitatively that this is really the case. It follows fr om rough calculations,
however, that this ratio is reasonable. In the method of calculation employed
the thermal capacity of the brass tip of the feeler is disregarded, and therefore
the transfer function is independent of frequency. This is permissible since the
tip represents only a small part of the mass of the feeier (11 %).

The transfer function H2

The equivalent circuit in fig . 18 cannot be used for calcu1ating the transfer
function H2 because in this case it is necessary to take account of the thermal
capacities of feeier , strip and insulating material. A detailed calculation is
given in appendix 2; the equivalent circuit can be seen in fig . 42. It will suffice to
mention here the fin al result. For small fluctuations we have :
 -48-

H2 = sinh(yj:. La )[1+ 2 { ,hS yj: .coth(yj:. L1) + asyj: .coth(yj: .La) + j wme 2 }]
(4.7)
In this formula the coefficient of thermal diffusivity ai = (Nee)i of both
parts of the conductor strip is not equal. The average values used are al =
1.1 X 10-4 m2 S-l and as = 1.6 X 10- 4 m2 S-l. The quantity $2 can be found
from formulae (4.2) and (4.6).

The transfer funetion Ha

The transfer function ofthe vapour bubble pump can be regarded as indepen-
dent of frequency in that the periods of the frequencies considered are long
in relation to the time the vapour bubbles remain in the riser. Hs can therefore
be constructed and read as the gradient in fig. 17.

The transfer funetion H4

According to assumption number 4 on page 37 the temperature ofthe liquid
in the reboiler is constant. This applies, however, only if the variabie part of the
reflux is small in relation to the average value. We shall con fine ourselves to
such cases. A second assumption is that the "hold up" ofthe column is so small
that the variabie part of the reflux can pass through the column without inter-
ference, i.e. the density of the liquid at the top of the column is equal to that
at the bottom.
The transfer function of a flow of liquid through the column is determined
by the reaction to a discontinuous load. A measurement was therefore made
on the operating column of the change in the reboiler level after c10sing the
nitrogen outlet. It was found that after 20 to 30 seconds the level began to
rise almost linearly. The accuracy of this measurement is not particularly
high. For this reason experiments were carried out at room temperature with
a liquid possessing properties similar to those of liquid air. This consisted of
a mixture of hexane, heptane and octane. This density of this liquid is 0.8 to
0.9 times that of liquid air, whilst its viscosity is half and its surface ten si on 1.8
times as high. The correspondence between the properties of the two liquids is
thus relatively poor, but since the result has only a slight effect on the transfer
function of the control loop, this liquid was quite adequate as a medium of
comparison. With a liquid flow of about 3 cma s-1, corresponding to tbe
actual situation, measurements were made to ascertain the way in which,
and after what interval of time, the liquid leaves the base of the column.
Starting fr om a dry column, a time-lag of 60 seconds was measured; with a .
c01umn filled with wet packing, 30, 32 and 31 seconds were measured successi-
 -49-

ve1y. After this initial period the liquid starts almost immediately to flow at
full force. When the feed is shut off, the liquid flow decreases abruptly after
31 seconds; but the liquid continues to drip for a while from the packing. It is
therefore not entirely correct to assume that the transfer function consists
merely of a time lag, but this simplification seems permissible for the present
purpose.

TABLE VI
Transfer functions of the elements of the automatic reflux controller (fig. 24).
1. Controller with feeier as in fig. 21. The reflux is 5.1 X 10- 2 mole S- l.
2. Controller with fee Ier as in fig. 21. The reflux is 8.1 X 10- 2 mole S-l.
3. Controller with feeier as in fig. 21. The reflux is 10.5 X 10- 2 mole S- l.
4. Controller with lightweight feeier and strip. The reflux is 8.1 X 10- 2mole S- l.
5. As 4. Feeier increased in weight by 200 grams.
6. As 4. Feeier increased in weight by 400 grams.
7. As 4. Feeier with short conical tip (2 cm).

Hl
I -
H 2 H3 H 4 H5

1. -190 C W- l m- l 1.27 Dl W2 C- 1 1.45 x 10- 2 moles- 1W- l e- 31j 46 x 1O- 4 msmole- l

j
-
2. -275 0.73 D2 0.98 e- 3lj 46 x 10- 4

- .i
3. -1250 0.20 D3 0.64 e- 3lj 46 x 10- 4
j
-
4. -225 1.15 D4 1.09 e- 3lj 46 x 10- 4
j
-
5. -225 1.15 D5 1.09 e- 3lj 46 x 10-4
----
j
-
6. -225 1.15 D6 1.09 e- 3lj 46 x 10-4
j
-
7. -530 1.15 D7 1.09 e-3li 46 x 10- 4
.i

The transfer function is now

H4 = e-i "'" where = 31 seconds (4.8)
At a different reflux value the hold-up of the column will have a different
value, and so will . The value of .. was taken as constant, ho wever, in the
calculation. This is permissible since the influence of H4 on H is rather small.
 -50-

I
2
-%.(mol s-'rn-~
1
-~ XF;
1

0'5

10- 10- 3 10- 2 10-~ 10- J 10- 2

o o -.... .
~ W(r 'J

" "
a b

h 6 \
10J /r.(msmor'?
4

1\ \
2

o
~ f...-
o
\
10-* 1O- J 10- 2 1P- 10- J 10- 2

-~
W(r'J W(S-'J

" "
c d
Fig. 25. Example of the construction of the transfer function H of the control loop (case 2
table Vno
a. Amplitude and phase of Hl H2 H 3 as a function of frequency.
b. Amplitude and phase of H4 as a function of frequency.
c. Amplitude and phase of H s as a function of frequency.
d. Amplitude and phase of H as a function of frequency.

The transfer function H5

The reboiler is an integrator. The transfer function is :

where Sr is the surface area of the liquid. In the actual installation, Sr = 75.10- 4
m 2

The transfer function H

The resuIts ofthe calculations are collected in Table VI. The fust part (1 to 3)
refers to the reflux control system described above. The numbers 4 to 7 refer
to modified systems on which experiments were done. The transfer function H2
 -51-

for the second column is written as a constant multiplied by a vector Dt. For
w = Othis vector is equal to theunit vector, but at higher frequencies adamping
and phase shift occur, which can be calculated with the aid offormula (4.7).
Fig. 25 shows how the transfer function H of the control loop is brought
about. By way of example, number 2 is taken from Table VI. It is noticeable
that in this case the phase shift is primarily caused by the action of the reboiler
and regulating device, and to a much lesser extend by the time lag of the
column . It can be seen from fig. 25d that, with a phase shift of n radians, the
amplitude of the transfer function is less than 1, which indicates that the regula-
tion must be stabie.
Fig. 26 shows the transfer functions plotted in a locus. The numbers in the
figure correspond to those in the tabie. Curves 2 and 3 biseet the real axis
between the origin and the point -1; in these cases, then, the controller is
stabie. Curve 1, however, bisects the axis at the point -2, which means that
the controller is unstable in this case. Experiments with areflux value as low
as in case 1 have demonstrated that no instability in fact arises. This lack of
agreement between experiment and theory might be due to the factors neglected

- 1 "" 1

, { -j

Y'
0 2/
I / "al =10-J s- 1
eal=10- 2s- t
V /
I 11

Fig. 26. Locus of reflux controlloop for three points of the con trol range.
1. Controller with feeIer as in fig. 21. The reflux is 5.1 x 10- 2 mole S-l.
2. As 1. The reflux is 8.1 x 10- 2 mole S- l.
3. As 1. The reflux is 10.5 x 10- 2 mole S- l.

in the calculation. lt is possible, for example, that the boiling resistance at

this reflux has a different value from the one assumed. lts effect on the static
sensitivity is considerable. Moreover, particularly at low reflux values the tem-
perature of the reboiler will not be constant.
Fig. 27 shows the temperature fh of the starpoint K (fig. 18) as measured in
a few experiments as a function of time. Fig. 27a represents the behaviour of
 -52-

tbe regulation in an experiment whereby the nitrogen removal was stopped for
5 minutes. Fig. 27b represents (h as a function of time t at the point of transi-
tion from the starting period to the operating condition. At A the feeler comes

100 100

~A
75 75

50
r--
1\ f I'-- 50 \ I ~

V 1/ '-

25 25
\ B

o o 2 5

a b

100

75

50 \
-~ /
25

o 2 3 4 5 6 7

Fig. 27. Some response curves of the reflux control system.

a. Nitrogen ou tiet pipe shut-off for 5 minutes.
b. Transition from starting period to operating state.
c. Cold production of gas refrigerating machine reduced from 800 W to 500 W ; humidity
of air intake reduced from 20 oe dew point to 0 oe dew point.

into contact with the liquid for tbe first time; at B the outlet pipe is opened.
Finally fig. 27c shows the behaviour of the control system when the cold
 -53-

production of the refrigerating machine is suddenly reduced from about 800 W

to about 500 W, and when in addition the wet air feed (20 C dew point) is
replaced by dry air. Mter a disturbance the installation returns to the steady
state with a damped oscillation . The angular frequency of this oscillation is
w = 4 X 10- 3 S- l, which agrees with what might be expected fr om the locus
(approximately between w = 5 X 10- 3 S- l and w = 10 X 10 - 3 S- l) . Aftel a
serious disturbance, as in fig . 27b and 27c the installation returns to complete
equilibrium after 1 hour, although the purity ofthe top product improves much
earlier to more than 99.5%.
In the fust column on wbich the regulation was tried out, the design of the
reboiler differed entirely from that described in the previous chapter. The
feeier was not passed through the cover but through the wall of the reboiler, wbich
made it possible to have a much lighter feeier than that in fig . 21 (C2 = 21 J;oC
instead of C2 = 66 J;aC). Moreover, the conductor strip was more than twice
as light as in cases 1,2 and 3. Finally, owing to the different dimensions of the
vapour bubble pump, the transfer function of tbis pump was, at the same
refiux value, much larger than in the cases described above. The locus for this
case is shown in fig . 28 (curve 4). The reaction of this regulation to a sudden

I -1 1

1 i-i
J
7 6/s 4

J euJ=10-2 s-f

lIJ
I1

Fig. 28. Locus for various versions of the reflux control system, for the middle of the con trol
range (8.1 X 10- 2 mole S- 1) .
4. Controller with lightweight feeier and strip.
5. As 4. FeeIer increased in weight by 200 grams.
6. As 4. FeeIer increased in weight by 400 grams.
7. As 4. FeeIer provided with short conical tip (2 cm).

change in the reboiler level was also measured. For this purpose the reboiler
was abruptly emptied by means of a condenser cooled with liquid nitrogen.
The temperature of the starpoint measured during this experiment is given in
fig. 29a. The frequency of the oscillation at wbich the process returns to the
steady is w = 7 X 10-3 S-l. Tbe frequency at which the locus cuts the real
 -54-

axis is also bigber tban in cases 1, 2 and 3. Calculation and experiment botb
indicate tbat tbe stability of tbe regulation is very bigh.
100 100

75 75
~ f'

).-1
10 ~f-
50
U I Iv\....v----
1\
~ V

25 25

o 4 0 1 2 3 4

a b

10 0

75

[7 ~ Y\l/' -
50
V
25

o 2 5 6

c
Fig. 29. Temperature Ok of the startpoint K as a function of time t, for part of the control
systems of fig. 28. At t = t the reboiler is emptied.
a . 4 [rom fig. 28.
b. 5 [rom fig. 28.
c. 6 [rom fig. 28.

In order to determine whether the feeier could be heavier, experiments were

do ne with feeiers to wbich extra weigbts of 200 and 400 grams, respectively,
were attacbed. Tbe values of C2 are tbereby increased from 21 J;oC to 80
and 137 J;oC. The polar diagrams for these cases are sbown in fig. 28 (nrs. 5
and 6). It appears from the figure that the controller in both cases is not un-
 -55-

stabie, although less stabie than in the previous case. Since the real axis is
bisected at lower frequencies, it is also likely that the inertia of the controller
will be greater. The experiment entire1y comes up to expectations, as appears
from fig. 29b, c which shows the reaction of the controllers to the abrupt
emptying of the re boiler.
Finally, the locus of a controller using a short feeier (2 cm) was
calculated . This system proved to be completely unstable, in agreement with
the fact that the locus bisects the real axis to the left of point -1.
It has appeared from the foregoing that the calculated stability of the
reflux controller shows reasonable agreement with the stability found by ex-
periment, except at low reflux values. The method of calculation can there-
fore be used for predicting the behaviour of the controller after introducing
certain modifications; it will always be necessary, however, to ensure that the
simplifying assumptions are also permis si bie in such cases. The stability of the
controlloop is determined by all elements in the loop. For a given length of
column and a given design of vapour bubble pump, the principal stabilizing
factors are:
1. The surface area of the liquid in the reboiler.
2. The way in which the thermal resistance of the feeier varies as a function of
the liquid level. This is a function of :
a) The shape of the feeier
b) The length of the feeler
c) The thermal conductivity of the feeler material.

5. SAFEGUARDING THE INSTALLATION AGAlNST EXPLOSIONS

HAZARDS OF ACETYLENE AND OTHER HYDROCARBONS

During the early development of air-fractionating technique unaccountable

explosions in rectifying columns were of frequent occurrence. Berger puts the
figure as high as a thousand 26). It later appeared that the cause in most cases
was to be sought in the presence of solid acetylene in the reboiler of the column.
Acetylene, which is normally present in air in only a very small fraction, may
accumulate in appreciable quantities inside the reboiler, p.u ticularly after long
periods of operation. Static e1ectricity produced by the friction of solid acety-
lene partic1es against the wall can give rise to sparks, resulting in an explosion.
A shock or bump mayalso cause explosions, especially if ozone happens to
be dissolved in the liquid oxygen.
The amount of acetylene that may accumulate in the reboiler of an air-
fractionating installation depends on several factors, viz :
1. The acetylene content of the air fed into the installation. Normally this is
no more than 0.01 to 0.1 p.p.m., but in industrial areas it may be as high
as 5 p.p.m. 27).
 -56-

2. The quantity of air processed during the period of operation. The amount
of acetylene that accumulates is proportional to this quantity of air, and
therefore the danger is greater in the case of long periods of operation and
large installations.
3. If the air to be separated is compressed, it may become contaminated with
acetylene due to the cracking of the lubricating oi!. This can be prevented
by adopting low compression ratios, and in addition by using special oi!.
The fact that the air is not compressed in the installation described is a
further attractive feature in regard to the hazards of acetylene accumula-
tion.
4. The type of installation. The chance of acetylene accumulating in an in-
stallation that produces liquid oxygen, for example, is not so great as in
one that produces gaseous oxygen, because in the former type the reboiler
is regularly flushed out.
There are various methods of avoiding the accumulation of acetylene and
other hydrocarbons. In the fust place the air feed should be as pure as possible,
and with this in view the position of the air-intake opening is chosen with
care. Other possible measures are:
1. To flush out the reboiler regularly by tapping of the liquid.
2. To trap impurities by means of absorbers.
3. To freeze out undesired substances at pI aces not accessible to the liquid
oxygen. This removes the danger of explosions.
The data on the maximum permissible concentration of acetylene in the
reboiler show wide disparity, ranging from 1 to 100 p.p.m. It is probable that
apart from the content the total quantity also plays a role. The specification
is often that there should be no solid acetylene present, i.e. that the concentra-
tion should not exceed 3 to 5 p.p.ID.
10' 10

10
/ 0
p(Nm"')
10
/v p ' (Nm 1)
o
V
------
/ .~

,7
'v

10 0" ~
/ ./

10 .....
,
'v

80 90 100 110 0'1 10 10

7(C) {, (p .p. m)

Fig. 30. Vapour pressure p of ;acetylene as Fig. 31. Vapour pressure p' of acetylene
a function of absolute temperature T. above liquid oxygen as a function of the
acetylene content e of the liquid. The
temperature is 90 OK.
 -57-

We shall now consider to what extent the danger of explosion exists in the
installation actually built. For this purpose it is necessary to know the vapour
pressure of acetylene as a function oftemperature and the solubility of acetylene
in liquid oxygen. These quantities are represented in figs. 30 and 31. The data
are taken from Karwat 28). F:rom the vapour pressure curve (fig. 30) it may be
seen that the acetylene content at the top of the column (77 OK) is so low
(about 10- 3 p.p.m.) that the acetylene is virtually unable to leave this end of
the installation. According to fig. 31 the maximum conc;entration in the vapour
above liquid oxygen saturated with acetylene is equal to 0.2 p.p.m. This is a
measure of the maximum amount of acetylene that can leave the bottom end
of the installation. It follows from the value mentioned that at a blow-off
ratio of 0.25 the permissible concentration in the air feed is 0.05 p.p.m. At
higher concentrations, acetylene will accumulate in the reboiler unless coun-
termeasures are taken. The amount of acetylene that might then accumulate
in a given time inside the reboiler depends on the dew point (for acetylene) of
the air fed into the column. For various dew points calculations have been made
of the quantity of acetylene th at might enter the reboiler during a period in
which 600 litres of liquid nitrogen are made. The results are given in fig . 32.

10

V
fa /

O' 1

80
1/
90
/ 100
TD(Ko;
110

Fig. 32. The quantity of acetylene m that might crystallize in the reboiler as a function of the
dew point TD of the air feed into the column. If no countermeasures were taken, this quantity
would accumulate in the time taken by the installation to produce 17.103 mole (600 litres) of
liquid nitrogen.

The maximum concentration of acetylene found in atmospheric air is, accord-

ing to Pollitzer, 5 p.p.m.; the dew point is then 100 oK. It is calculated that in
this case 2.4 grams of acetylene could accumulate in the reboiler. This quan-
tity is not large enough to cause serious explosions; nevertheless, it may cause
damage to parts of the installation.
To prevent the accumulation of acetylene in the reboiler the cage with
boiler pipes is so designed as to keep the temperature of the gauze soldered to
 -58-

the pipes as low as possible. This means that at high concentrations a large
proportion of the acetylene will be taken up in the sn ow trap. In order to re-
duce still further the acetylene content of the air entering the column the air,
after passing through the gauze of the snow trap, is additionally cooled against
the wall of the lower part of the column. For this purpose the gap around this
part of the column through which the air rises is provided with 16 gauze rings.
These rings are soldered to the sides of the column and thus cooled by the
descending liquid. The air flows through .the gauze and deposits thereon a
fraction of its acetylene content. If the air can be cooled in this way to such an
extent as to reduce its dew point to 87 oK or lower, no accumulation of acety-
lene in the reboiler is possible.
Various experiments were carried out on a working installation whereby
the acetylene concentration in the liquid oxygen was measured at regular in-
tervals during a period of operation. The concentration measurements were
made by the colorimetrie method described by Brustier et al 30). In the first
experiment 10 p.p.m. of acetylene were added to the air from the start. The
results are represented in fig . 33. The high concentration at the outs et is due
20

1-5
{Jp.p.mJ

\
0-5
\ ~.
o 2 3 4
t (days)

Fig. 33. Acetylene content e of the oxygen in the reboiler as a function of time. Air feed with
10 p.p.m. acetylene added.

to the fact that the (small) snow trap incorporated in the condensor of the gas
refrigerating machine has a fairly high gauze temperature. Some time after
switching over, the acetylene content of the oxygen decreases sharply and
finally reaches a state of equilibrium at ab out 0.25 p.p.m. A second experiment
was done whereby 10 p.p.m. of acetylene were added to an installation that
had already been in operation for 48 hours. The concentration curve in this case
is shown in fig. 34. Mter some time almost the same state of equilibrium is
reached here as in the preceding experiment. The knee in the curve is pro-
 -59-

bably due to acetylene entering the reboiler in one way or another and there-
upon being dissolved. The acetylene content of the air immediately behind the
gauze was found by measurement to be 1.0 p. p.m.; at the air inlet it had fallen
10',--------.,.----,----------.,.---- r -- - - - . - - - - - - ,

cep.p.m)

051--- - - - I - - - - 1 - - - - - - I - - - - 1 - - - - - + - - ------l
.'-e.._._-----..,_".

o 2 3 5 6
f (days)

Fig. 34. Acetylene content e of the oxygen in the reboiler as a function of time. After 48
hours of operatioD, 10 p.p.ffi. acetylene were added to the air feed (t = 0).

to be below 0.2 p.p.m. (with the set-up used, 0.2 p.p.m. was the smallest
quantity that could be measured. Even at the extreme1y high concentra-
tion of 10 p.p.m. no acetylene accumulates in the reboiler, thanks to the efficient
operation of the sn ow trap and the gauze rings at the base of the column.
As regards the other hydrocarbons the same applies as to acetylene. Here
too, the greatest part will be frozen out. Apart from what has been said,
however, it is necessary to ensure that the air intake is not needlessly contarni-
nated by hydrocarbon vapours. Moreover, in view of the marked effect of
ozone, no ozone-producing equipment must be situated near the air-fractionat-
ing plant.
 -60-

APPENDIX 1. VAPOUR BUBBLE PUMPS FOR LIQUID NITROGEN

AND LIQUID OXYGEN

1.1.Introduction
1.2. Experimental arrangement and metbod of measurement
1.3. Measurements on vapour bubble pumps for liquid uitrogen
1.4. Discussion
1.5. Vapour bubble pumps for liquid oxygen

1.1.lntroduction
In chapter 3 and 4 it was described how a vapour bubble pump is used
for pumping the reflux to the top ofthe column and how the reflux is controlled
by regulating the flow of heat. Since, as far as is known, the literature contains
no data on vapour bubble pumps for liquid nitrogen, an investigation was
initiated to determine the characteristics of these pumps.
The vapour bubble pump much resembles the air-lift pump, about which a
great deal has been written. In his thesis, Behringer describes his experiments
on glass air-lift pumps used for pumping water. He succeeded in devising a
formula for defining the behaviour of these pumps 31).
A simplified air-lift pump is shown in fig. 35. The leng th of the downcomer

Fig. 35. Principle of an air-lift pump.

is Id, the length of the riser Ir + ld, and the diameter of the riser is d. When an
 -61-

air flow qa is introduced, a liquid flow ql is pumped up by the rising air bubbles.
The results of Behringer's work can be summarized as follows :
l. Provided the values of lr/ld are not unduly smalI, the relative liquid content
fP of the ris er is constant and equal to fP = ldj(lr + Id). (1)
This means that the resistance to flow is neglected.
2. Due to 1, the average air velocity Va in the riser is :
qa . fJ
(2)

where fJ is the expansion factor, which is equal to unity if the hydrostatic

pressure at the base of the riser is small in relation to the ambient pressure.
3. The theoretical delivery is defined by Behringer as the quantity of liquid
pumped up per unit time when the average vapour and liquid velocities are
equal. It is given by :
(3)

4. Owing to losses, the actual delivery is smaller than the theoretical. These
losses are:
a) A 10ss A due to the difference in density causing the liquid to flow down-
wards at the sides of the bubbles. This 10ss is dependent only on the dia-
meter d and is proportional to d 2 in the case oflarge diameters.
b) A 10ss B due to the flow through the pipe. This 10ss is dependent on ld,
Ir, Va and d, and is given by:
B = CfP (Va d)5 /3 (4)
where Cis a constant.
5. The delivery ofthe pump is therefore :
qz = q1th - A (d) - B (Id, Ir, Va, d). (5)
After substitution of (3) and (4), the formula for the delivery becomes :

ql = qa _ fP_ _ A - CfP (Va. d)5 /3 (6)

1- fP
In the case of all air-lift pumps used for pumping water and whose riser di-
ameter are smaller than 1 cm, the same value of Capplies ; a different (constant)
value of C applies to pumps having a diameter greater than 1.5 cm. The
loss A depends solely on d. The delivery ql depends solely on fP, and not on
the length of the pump.
If we assume that the pattern of flow in the air-lift pump is the same as that
in the vapour bubble pump, formula (6) can also be used for the latter. In that
case, however, qa must be replaced by:

(7)
 -62-

Ir

I I insulafion maferial
~ rubber

It--~ liquid

Fig. 36. Experimental arrangement for determining the properties of vapour bubble pumps.
 -63-

where <P is the heat flow to the pump, r the heat of evaporation per unit mass,
and ethe density ofthe vapour. The delivery ofthe pump is then given by:

l --
q; - ~ -A- C { 4<P } 5/
3
(8)
q - I-q;r.e q; r.q;(1-q;)nd
In this case, too, the delivery depends only on q; and not on the length of the
pump. Again, C would have to be constant and A dependent only on the
diameter.
With the arrangement described below, measurements were made on vapour
bubble pumps having different values of q;, d, la +
Ir and <P in order to ascer-
tain whether Behringer's formula also applies to vapour bubble pumps for
liquid nitrogen and liquid oxygen.

1.2. Experimental arrangement and method of measurement

The experimental arrangement (fig. 36) consists essentially of a dewar vessel
filled with the liquid to be pumped (length 0.5 m, diameter 6 cm) which
functions as downcomer, together with a copper riser pipe AB which is elec-
trically heated over a leng th CD (0.1 m). To this end the pipe is wrapped in thin
paper and then wound with a heater wire. In view of the importance of measur-
ing the power supplied to the pump with the least possible error, the pump is
carefully insulated. For this purpose the bottom section is surrounded by an
insulation space filled with cotton wo ol and the bottom part of the riser (CA) is
made of stainless steel. The section EB is surrounded by the pumped liquid.
Since differences in hydrostatic pressure inside and outside the pipe might give rise
to temperature differences, causing extra heat to be supplied to the pump, the riser
is also fitted with a rubber sleeve. The space around EB is insulated by cotton
wool. The upper part is surrounded by a space filled with silica-aerogel. The
liquid not evaporating in the space around the riser can escape through the
outlet pipe via a liquid trap. This means that the outlet opening always projects
above the liquid and that no damp air can enter through the outlet pipe. If
this were to happen, the mist that would form would obscure the outlet opening.
The merit of this arrangement is that on the one hand the ris er is very weIl
insulated, and on the other it is a simple matter to introduce modifications.
The arrangement can be used for two kinds of measurement, namely static
and dynamic.

a) Statie measurements
Mter the entire apparatus has been cooled down and filled with, say, liquid
nitrogen, the dewar vessel is placed under the outlet opening of a gas refrigerat-
ing machine with which nitrogen is condensed. Now when a heat flow <P is
generated in the heater element, the level in the dewar vessel will finally adjust
itself in such a way that at the relevant value of q; (calculated in relation to
 -64-

the middle of CD) the pump delivers ju st as much liquid as is supplied to the
vessel by the refrigerating machine. By measuring the output of the refrigerating
machine we then know the delivery of the pump.

b) Dynamic measurements
Mter the whole apparatus has been cooled down and filled with liquid nitro-
gen, a fixed heat flow is used and the liquid level in the dewar vessel is measured
as a function of time. The liquid is thus gradually pumped out of the vessel by
the vapour bubble pump and the value of qJ changes continuously. From a
plot of level versus time and the surface area of the liquid the delivery of the
pump can now be determined by a single measurement at various values of qJ.
Comparative tests, in which statie and dynamic measurements were made
under identical conditions, have shown that both methods of measurement
yield the same results. This is understandable, since the mean velocity of air
is very much higher than the speed at which the value of qJ changes. The great
advantage of the dynamic method is that it is much faster than the static method,
the settling time of the latter being very long. Most of the measurements were
therefore of the dynamic kind; the only exception was the measurement of
the zero delivery.

"""'"'-"k-----\---Yt'I---If-----+-- Id + I r = 116 m --+----1

6
Ap =04 . 1O- mJs- '
~p =120.10-1Zm'l,s-'w-f2~

o 1-0 20 30 40
10"'e,(m*%s-fw- f'liJ
Fig. 37. Example of method of determining the values of A and Cin the A-C plane (no. 2 from
Table VII).

1.3. Measurements on vapour bubble pumps for liquid nitrogen

Measurements have been carried out on pumps having different values of d,
qJ,Id + Ir and W. The data of each measuring point were substituted in formula
(8) producing an equation with the two unknown quantities A and C. *)

*) The value used for the heat of evaporation is r = 199.103 J kg-1 30) and for the density
e = 4.6 kg m- 3 33).
 -65-

For each pump of specific leng th and diameter an average of 14 equations were
obtained in this way. The values of A and C were found by determining the
common point of intersection of the lines in the A - Cplane.
An example of such a constructionis shown in fig. 37. It is not readily possible
to say with certainty whether the fact that the lines do not pass exactly through

TABLE VII
Results of measuremens on vapour bubble pumps for liquid nitrogen.

No d(m) la + lr(m)1 q; rJ>(W) ql (m3 S-l) A(m3 s- 1 ) C(m4"'s-1 W - 1"')

1 3.10- 3 1.16 0.17-0.30 1.5- 5.0 (0.22-0.72) 10- 6 0.05.10- 6 13.5.10- 12

2 4 1.16 0.24-0.36 2.0- 7.0 0.11-1.62 0.40 12.0
3 4 0.95 0.26-0.37 2.0- 6.0 0.55-1.57 0.45 12.0
4 4 0.70 0.23-0.44 2.0- 4.0 0.44-1.80 0.45 10.5
5 4 0.45 0.23-0.64 2.0- 4.0 0.36-2.8 0.60 13.0
6 4 0.25 0.50-0.60 1.0- 4.0 0.40-2.0 0.50 14.5
7 5 1.16 0.26-0.30 3.0-7.0 0.0 -1.1 1.05 13.0
8 6 1.15 0.21-0.30 7.0-20.0 0.2 -2.6 1.7 13.0
9 10 0.70 0.39-0.44 30.0-40.0 0.0 -l.l 8.0 23.0

TABLE VIII
The effect of length on the delivery ofvapour bubble pumps (d = 4 mm).

(f> = 2.0 W rJ> = 4.0 W rJ> = 5.0 W

la + Ir q; = 0.28 q; = 0.28 q; = 0.30

1.16 m 0.29.1O- 6m3 s - 1 0.77.1O- 6m3s- 1 0.98.10- 6m3s- 1

0.95 - 0.61 0.90
0.70 0.30 0.78 1.03
0.45 0.40 0.76 0.94
0.25 0.24 0.60 0.80

one point is due to the error of measurement or to the imperfection of the

formula. For the sake of clarity, not all the measurements are reproduced, but
the results are collected in Table VII. The third, fourth and fifth columns in th is
 -66-

table indicate the ranges within which the quantities f/J, <l> and qz were varied.
The last columns give the constructed values of A and C.

Conclusions :
1. The differences in the C-values are not considerable. The only marked
difference appears where the diameter is 10 mmo
2. The quantity A increases sharply with diameter. In fig. 38 the variation of
A is shown as a function of diameter.
It can c1early be seen that, at large diameters A is approximately prop or-
tional to the square ofthe diameter, aresult also obtained by Behringer.
3. A and C show no marked dependence on the length of the pump. This
also appears from the data in Table VIII, in which the outputs of various
pumps of different lengths are compared.
4. In the region investigated, formula (8) represents the behaviour of vapour
bubble pumps quite weIl. The value of C is 13.0 X 10- 12 m 4'I's- l W - l'/, ;
the value of A can be read from fig . 38. The delivery of vapour bubble
pumps for liquid nitrogen is then given by the equation :

1.4. Discussion
We have seenin theforegoing that it is indeed possible to define the behaviour
of vapour bubble pumps by the Behringer formula for air-lift pumps, at least
within the ranges given in Table VII for f/J, <l> and qz. The values found for A

-
10

V
/

1-0
A=cd 2 -

....-
~v -- -----
/
./"

,
,,
,-'

,,
/
.-"
~ /
0-1 ~ /

2 3 5678910

Fig. 38. Plot of the 10ss A from formula (9) versus the diameter d of the riser of the vapour
bubble pump. The dashed line indicates Behringer's results on an air-lift pump (water in
glass tubes).
 -67-

are greater than in the case of the air-lift pump, as can be seen in fig . 38.
The value of C is 1.8 times the corresponding value for the air-lift pump.
Tbe higher losses are due, among other things, to the fact that the viscosity
of liquid nitrogen is very much lower than that of water. In Table IX the
deliveries calculated with formula 9 are compared with the measured values in
a number of cases. The table also shows the losses A and B in order to give an
impression of their magnitude compared with the measured delivery. The
measurements were done on a pump with Irt + Ir = 1.16 m. The agreement
between measurements and calculations is quite reasonable.
With formula 9 we can calculate the value of $ in which the delivery is
exactly equal to zero in a given case. These values can be measured by reducing
$ untilliquid just stops issuing from the riser. Fig. 39 gives the measured and
calculated values for d = 4 mm and 6 mmo Especially in this region of

6.-----.-----Tr~--._--------__.
. --calculafed curVe
e measured values
\
folWJ ~----r-----+-~~~----~--~
~.v--- d=6.10- m
J

4~----~----+-----~----4---~

~
~~
e

2~----~--~~r---+-----4-----~

~.~
J
d=4 ,10- m

o 0'1 0'2 0'3 0 '4 0 ,5

'f
Fig. 39. The heat flow CPo for various vapour bubble pumps at which the pump only just
yields no liquid as a function of ([J. Comparison between calculated and measured values.

delivery the agreement between calculations and measurements is quite good.

In the formula for the delivery of the vapour bubble pump (9) the third
term on the right-hand side increases more sharply than the first term with
increasing $. This means that, after reaching a maximum value, the delivery
will start to drop again. This maximum value of ql is reached when dqzld$ = O.
Mter differentiation and rearranging, we find for the value of $ at which ql is
maximum:
$m = 11 X 106 d'l' (1 - q;) . (10)
By substitution of (10) in (9) we can calculate q1max itself.
q1max = 5 q; d'l. - A (11)
 -68-

From (11) it may be seen that there is a range of cp values below which the
pump will not regularly pump up liquid at any value of <P. These values can
be found by putting qZmax = O. This gives :
A
CPmin = 5 . d 'l' (12)

In the measurements, <P was always smaller then <Pm. When <P is larger than
about 2/3 <Pm the pumps start to function irregularly and, particularly when the
deliveries are high, the liquid spurts out far above the outlet (order of magnitude
0.1 m). The deviations [rom the formula are then much greater, as already
pointed out by Behringer. Consequently one should not expect unduly high
accuracy from formulas 10, 11 and 12.
As regards the pump used in the nitrogen installation, d = 6.10- 3 mand cp =
0.39. For structural reasons the outlet opening is not straight but is provided

TABLE IX
Comparison of calculated and measured deliveries of vapour bubble pumps for
liquid nitrogen.

ql(m3s- 1) ql(m3s- 1)
cp d(m) <P(W) q1th(m3s- 1) A(m3s- 1) B(m3 s- 1) (cal- (measur-
culated) ed)

0.167 3.0.10- 3 3.0 0.65.10- 6 0.05.10- 6 0.29.10- 6 0.31.10- 6 0.33 .10- 6

4.0 0.87 0.05 0.47 0.35 0.36
5.0 1.09 0.05 0.68 0.36 0.36
4.0 3.0 0.65 0.40 0.18 0.07 0.10
4.0 0.87 0.40 ~ . 29 0.18 0.25
5.0 1.09 0.40 0.42 0.27 0.35
5.0 3.0 0.65 1.05 ~.13 - -
4.0 0.87 1.05 ~.20 - -
5.0 1.09 1.05 ~.29 - -
0.286 3.0 3.0 1.31 0.05 0.62 0.64 0.62
4.0 1.74 0.05 ~.97 0.72 0.68
5.0 2.18 0.05 1.46 0.67 0.68
4.0 3.0 1.31 0.40 ~.39 0.52 0.55
4.0 1.74 0.40 ~.65 0.69 0.78
5.0 2.18 0.40 ~.95 0.83 0.93
5.0 3.0 1.31 1.05 p.27 - -
4.0 1.74 1.05 0.43 0.26 0.26
5.0 2.18 1.05 0.65 0.48 0.45
 -69-

with a curved (semicircular) section. For determining cp the calculation is made

from the middle of the heater block (fig. 16) up to the top point of the curved
section. Fig. 40 shows the deliveries calculated with formula 9 and those
measured on a straight pump and on a pump with a curved section. According
to (10) the applicable value of CPm in this case is 20 W. The difference between the
calculated and measured values is greater the higher the load. The delivery
of the pump with a curved outlet is greater than that of the pump with the straight
outlet at high values of cp and ql and smaller at low values. This may be due
to the fact that, at the load at which the liquid only just "boils over the edge",
a partial separation of vapour and liquid takes place in the curved section,
causing liquid to flow back down the pipe. At the higher loads the pump
becomes increasingly irregular in operation and moreover the liquid tends
to spout upwards. Where the pipe is straight the spouted liquid can return to

" ,O,------,-----.-,--- ----7"'!-------,

3-01--- - - + - - - ------l>'-f....",c---f-------i

2'OI--- -- - I - - - V - - / - - ! - - - -- I - - - ------l

1-01----- ---1Hf--- - - ! - - - - - 1 - - - ------l

o 20
1> (ow)
Fig. 40. The delivery qj of the vapour bubble pump used in the installation as a function of
the heat flow lP.
J. Riser with curved outlet.
11. Riser with straight outlet (measured).
IJL Riser with straight outlet (calculated from (9.

the pipe, but where a curved outlet is used it will not be able to return after
passing the corner, and the delivery will accordingly be higher.

1.5. Vapour bubble pumps for liquid oxygen

With the arrangement shown in fig . 36 experiments were also done on the
pumping of liquid oxygen. The measurements were made on pumps having
diameters of 3,4 and 6 mm. The constants in formula 8 were determined in
the same way as described above; the results are collected in Table X.
 -70-

TABLE X
Results of measurements on vapour bubble pumps for liquid oxygen.

No. d Id + Ir A 1;

1 3.1O- 3m 1.20 m 0.20.1O- 6 m3s- 1 13.0 10- 12m4"'s-IW- 1 ' "

2 3 0.67 0.05 12.0
3 4 1.20 0.40 14.0
4 4 0.70 0.40 13.0
5 6 1.16 1.1 19.0
6 6 0.70 1.5 14.0

With the exception of number 5, th ere are no great differences between the
values of 1;. It is possible that in the case of number 5 the pipe was partly
blocked by a piece of ice; this measurement was therefore not used for deter-
mining the average value of 1;.
The formula giving the delivery of vapour bubble pumps for liquid oxygen is :

3
qz = 0.98 10- 6 cp 1 cp cp - A - 13.0 10- 12 cp { (1 !cp) d }5/ (13)

The coefficient of the first term differs fr om that of the corresponding term in
formula 9 owing to differ'!nces in the heat of evaporation and the density or
nitrogen and oxygen. For the heat of evaporation r = 214.103 J kg- 1 and
for the density ofthe vapour f! = 4.7 kg m- 3 are taken.
 -71-

APPENDIX 2. THE TRANSFER FUNCTION OF THE REFLUX

REGULATING DEVICE
For calculating the transfer function H2, i.e. the heat flow (/>3 to the vapour
bubble pump as a function of the thermal resistance (J2 of the feeler, the equi-
valent circuit in fig. 18 cannot be used. For this purpose it is necessary to
take into account the thermal capacity of the feeler, of the conductor strips
and the insulation. To be able to do this we fust calculate the heat flow through
a bar the temperature of which varies sinusoidally with time at one end and is
constant at the other. The insulation of the bar is assumed to be ideal and the
coefficient of thermal diffusivity a ( = Af (Jc) constant. The temperature () of the
bar, which is a function of the coordinate of position x and the time I , must
satisfy the differential equation :
08 02 8
Ot = a OX2
(1)

The boundary conditions are:

1. For x = 0 8 = 8 0 + -&ei wt (2)
2. For x = L 8 = eL (3)
We try the solution :

8 (X,/) = 8 0 - Tx (8 0 - 8 L) + -&eiWt ePX (4)

Substitution of (4) in (1) yields for p the values :

p=~
so that (4) can be written as : _

e(x,I) ~ 61.- ~ (eo _ 61 + Del.'(,e Vj; . + c,e - ~. x)

x (5)

Both boundary conditions are fulfilled if :

Cl + C2 = O

l/jw
era C2 = O

Solving these two equations and substituting Cl and C2 in (5) gives the following
solution on the differential equation :

(6)
 -72-

The heat flow tP L that leaves the bar at the position x = L can be calculated,
with the above solution, from :

tP L = - },S (Oe)
~ (7)

where Sis the cross-sectional area of the bar.

Differentiation of (6) with respect to x gives :

oe -. cosh {lfja
V
W
(L-X)}
_
Ox
=
eL-eO

. L
_#eiwt
V JW
- . - - - - = = - --
a ~~ { 1V/.iaW
---

L }
(8)

After substitution in (7) we obtain the expression :

The heat flow tPo that enters the bar at the position x = 0 is found in the same
way:

"e e 1/-'-
J; . cosh (VjJ
- . L ))
tPo = S
j ~ 0 -;, ~ L + {}eiwt . V
sinh
.i: -
(Va' L)
(10)

It is known that the differential equation for describing a thermal wave

in a heat-conducting medium (1) is the same as that used describing the

8=fjo~v.Jwt B=8l
+0-+-'-_ _ _ _ _
x=o -x
- 11 Ir-----+---' X=L
1l

-10

I ,
,
:
I
[ T l '

'1 1

T 1 1i 11 1 T
1 1

u"u,
o
x=o -x X=L
Fig. 41. Equivalent circuit of a heat-conducting bar. One end of the bar is kept at a constant
temperature; the temperature of the other end varies sinusoidally with time.
 -73-

behaviour of long electrical transmission lines (without inductance). There-

fore it is possible to use for our problem a long transmission line as an equivalent
electric circuit (fig. 41). For further proof on this analogue, reference may be
made to the relevant literature (e.g. 34).
With the aid of the above calculations it is possible to extend the equivalent
circuit of fig. 18 for the purpose of working out the dynamic behaviour of the
regulating device in more detail. The latter is after all a star circuit consisting
of the feeier and two heat conducting strips, the ends of which are held at a
fixed temperature. The feeier (fig. 21) consists essentially of two conductors in
series, one having a low resistance and high thermal capacity, and the other
having a high varia bie resistance and a low thermal capacity. According to
assumption 4 on page 37, the tip ofthe feeier is kept at a constant temperature.
To simplify the problem we disregard the resistance of the first conductor and
the thermal capacity of the second; this is certainly permissible for angular
frequencies lower than w = 10- 2 S- l. In the one case the long line can be re-
placed by a capacitance, in the other by a resistance. The equivalent circuit is
shown in fig. 42.
So far we have assumed that the strips are ideally insulated. Since this is not
the case, however, thermal waves will penetrate the insulation from the surface
ofthe strip.This will cause an additional damping and phase-shift ofthe thermal
flow through the strip. An exact calculation of the effect of the insulation is
not possible, but a fairly rough correction can be applied. This consists in
adding to the conductor strip the thermal capacity of a layer of insulating
material surrounding the strip.
To determine the thickness of this layer we shall fust work out the behaviour
of a thermal wave that enters the insulation from the strip at right-angles to the

Fig. 42. Equivalent circuit of the reflux regulating device used for ca1culating the dynamic
properties.
 -74-

surface. The method of calculation resembles that used on page 71. The
solution must satisfy the differential equation
08 02 8
M = a, ox2 (11)

where at is the coefficient of thermal diffusivity of the insulating material.

The boundary conditions are:
x = 0 8 = Ooeiwt
x = 00

We again try the solution () = 0. eiwt ePZ

Substitution in (11) gives : p = Vjw!a,
The boundary conditions can only be satisfied by the solution :
lfJW
8 (x,t) = Ooeiwt e -V ----;;; . x (12)
The temperature at a distance x from the strip, with respect to the temperature
ofthis strip, is :

8 (x,t)
Ooeiwt = e
-~ . x
e
-V2:t .jx
(13)

For x = V2a,/w, the amplitude of the temperature fluctuation is exactly e

times smaller than that of the strip. This value of x is called the penetration
depth. The thickness of the insulating layer, which assumed to participate
fully in the temperature fluctuations of the strip, is assumed to be equal to this
penetration depth.
At w = 5.10-3 . S- 1 the correction for the thermal capacity of the strip is 25 % .
We shall discuss the transfer function of the regulating device with respect to
the equivalent circuit (fig. 42) in which the transfer function is represented by
the differential quotient dIa/dR2
For the purposes of the calculation the temperature U" of the starpoint Kis
used as an independent variabie between 13 and R2. The relation between Ia
and U" follows from formula 9, after which dla/dU" can be calculated. From
formula 10 we determine the currents to and from the starpoint (lik, 13" and
their difference h,,). Mter reducing h" by Ic we obtain the current through
the resistance of the feeier (12) . The potential across R2 can be found by apply-
ing Kirchhoff's law to the circuit abc d, after which R2 can be found with
Ohm's law. We can now calculate dR2/dU" from the known relation between
R2 and U", and the desired transfer function then follows from:
dI3
(14)
d R2
 -75-

We shall now continue the calculation by solving the thermal conduction

problem. The symbols used for the electrical quantities I, U and R will be replac-
ed by the corresponding symbols $, () and (J, and the subscripts used in fig . 42
will be retained. We assume that the temperature of point Kis equal to :
ek = e o + {}eiwt (15)
We can then find W3 with the aid of formula 9 :

eo yjW
W3 = A3S
( -L3 + {}e iwt -
a3
.
sinh
(16)

After differentiating (15) and (16) with respect to t we find :

(17)

The currents to and from the cross-over point are found with the aid of formula
10:

W3k = A3S
eo
{-L3 +. {}eiwt
yjW coth (yj: .
- . L3 ) } (18)
a3

coth (yj: . Ll)} ' (19)

The current taken up by the thermal capacity of the feeier is :

Wc = {}e iwt . jwmc2 (20)
where m is the mass of the feeier and C2 the specific heat of the feeier material.
The heat flow through the resistance of the feeier follows from :
W2k = Wlk - /13k - Wc (21)
All terms in (21) are realor products containing {}eiwt .
We can therefore write for W2k :
W 2k = W2 + (A + Bj) {}eiwt (22)
We have stipulated that in the circuit abc d the sum of all temperatures must
be equal to zero, hence:
(23)
Mter substituting (15), (22) and the relation (J 2 = 2 + (J2 (t) we find after some
transposition :
) _ {}e iwt {I - 2 (A + Bj)} (24)
(J2
(
t - W2 + {}eiwt (A + Bj)
 -76-

If the fiuctuations in the current through the feeler are small compared with
the average value, we can write (24) as :

(/2 (t ) =
De1wt {l - 2 (A
--~-';--'-----_---=:"'~
+ Bj)} (25)
rI>2
After differentiating (25) and (15) with respect to t we find :

(26)

Substitution of (18) to (22) in (26) gives :

(~. Ll) + aSalP: coth (Vj: .Ls) + jWmC2}

rI>z
(27)
In this expression rI>2 is the direct current through the feeier ; it can be calculated
from formulas 4.2 and 4.6. The transfer function can now be found from
d rI>a d rI>a de k
(28)
d (/2 - de k . d (/2
Mter substitution of (17) and (27) we finally obtain :
 -77-

APPENDIX 3. THE USE OF A HYDROMETER FOR MEASURING

THE PURITY OF LIQUID NITROGEN

3.1. Introduction
3.2. Theory
3.3. Design of the hydrometer
3.4. Results of measurements
3.5. Discussion

3.1. Introduction
Liquid nitrogen produced by air-fractionating installations will generally
contain oxygen and sometimes argon as contaminants. The density of these
contaminants differs considerably from that of liquid nitrogen *), and it must
therefore be possible to use the density of contaminated liquid nitrogen as a
measure of its purity. In this section we shall describe how the purity of liquid
nitrogen can be determined by measuring the density of the liquid by means
of a hydrometer.

3.2. Theory
Fig. 43 represents schematically a hydrometer floating in a liquid. According
to the fundamentallaw of hydrostatics, in the state of equilibrium the weight

h ./

v e

Fig. 43. Hydrometer floating in a liquid; the symbols are those used in the calculation.

*) (lN2 = 810 kg m- 3 (l02 = 1140 kg m-3 (lA = 1410 kg m-3

 -78-

G of the hydrometer and the upward pressure exerted upon the body in the
liquid should be equal :
G = eg {V + ( 1- h) S} (1)
In a given case G/g, V, 1and S are assumed in the first instance to be constant;
the reading h is thus determined by the density e of the liquid.
The value of e depends not only on the composition but also on the tem-
perature of the liquid and the pressure exerted on it :
h = h (e, T, P) (2)
The temperature T is a function of the composition e and of the pressure P *)
T = T(e, P) (3)
The reading of the hydrometer as a function of these variables can now be
calculated as follows :
From (2) it follows that :

dh = G~) de + (:~) dT +
. T,P e,P
G;) dP
e,T
(4)

From (3) it follows that :

dT = Co~) de + (~~) dP (5)

P e
After substitution of (5) in (4) we obtain the equation :

dh = {(!~) T,P+ (:;). e,P. (!~) P}de + {(:;) T,e+ (:~) e,P. (~~)e} dP (6)

The terms (oT/oe) pand (IJT/IJP)e are known and the partial derivatives of h
with respect to e, Pand T can be determined by differentiating (1) with respect
to e, Pand T.

The partial derivative (oh/IJe)T,p

By differentiating (1) with respect to e, and after manipulation, we obtain the
equation:

~ ~ {V+(l-h)S} +~
Oh)
( IJe
=
T,P S e (IJe)
oe T,P S
(OV) + I-h (OS) (7)
oe T,P S oe T,P
The second and the third terms on the right-hand side are obviously equal to
zero. We thus have:
V+(I-h)S
S
!.(oe)
e
'
IJe
(8)
T,P

*) We are concemed here with boiling liquids, and not with undercooled or superheated
liquids.
 -79-

The partiaf derivative (oh/oT)c,p

By differentiating (1) with respect to T, and after some manipulation we obtain :

Oh) = V + (l-h)S
( oh S
(oe) +
e oT
{! Ol: V + 2/a Ol: (l-h)S}
v + (/ - h) S (9)
~p ~p

In this equation Ol: is the cubic expansion coefficient of the material of which
the hydrometer is made. The second term between the braces is certainly
smaller, than 01: . If we consider the case where a glass or metal hydrometer
f10ats in liquid nitrogen, we can disregard this term in relation to the first term.
The error thereby involved is smaller than 1 %. We thus obtain :

oh ) = V + (f-h)S! (oe) (10)

( oT S e oT
~p ~p

The expansion coefficient mentioned in (10), at constant pressure, is not

known for liquid nitrogen; it is possible, however, to measure the density as a
function oftemperature along the liquid line (L). We can write for this:

u~) L= U~t+ U;t ~~ (11)

Since, in the case of liquid n rogen, the second term on the right-hand side is
only 0.3 % ofthe left-hand side ofthe equation, we can permissibly put (oe/oT)p
equal to (de/dT)L ; equation (10) then becomes:

Oh) = V + (f-h)S ! (de) (12)

( oT c,p S ' e dT L

The partiaf derivative (oh/OP)c,T

By differentiating (1) with respect to P, and after manipulation we obtain:

Oh) = V + (f-h)S
( oP S e
{!
(oe) + ! (OV) + S2(f-h) .! (OS) }
oP c,T v oP T,c V ' S oP T,c
(13)
c,T
With the glass hydrometers made for the measurements the second and third
terms are negligible compared with the compressibility of the liquid. There then
remains:

v + (f-h)S ! (oe) (14)

S e oP c,T
After substituting (8), (10) and (14) in (6) we obtain :

dh = V + (f-h)S {!(oe)' + ! (oe) . (OT)} de +

S e oe T,P e oT c,p oe P

+ V + (/-h)S
S
{!e (oe)
oP
+ ! (oe) . (OT) } dP.
e oT P,c oP c
(15)
T,c
 -80-

The differential quotients from (15) for oxygen and argon as contaminants
in liquid nitrogen are given in Table XI.

TABLE XI
The differential quotients from formula (15) for liquid nitrogen contaminated
by oxygen and argon. The pressure is 105 Nm- 2.

O 2 in N 2 AinN2 O 2 in N2 AinN2

1 (oe) *) 1 (oe)
0.38 1O- 2/mol % 0.63 1O- 2/mol % 1O- 9m2/N 1O- 9m 2/N
e OC T,P e oP T,e

1 (oe)
e oT c,p -0.56 1O- 2;oC -0.56 1O- 2;oC
e1 ee)
oT P,e
-0.56 1O- 2;oC -0.56 1O-2;oC

G~)p 6.510-2 C/mol% 5.0 10- 2 aC/mol %

(::t 8 10- 5 Cm2/N 8 10- 5 C m2/N

Using the data from the table we can write (15) as :

dh = V + (1- h)S {(0.35 10- 2) d CO 2 + (-4.5 10- 7) dP } and (16)

S

dh = V + (I - h)S {(0.60 10- 2) dCA + (-4.510- 7 ) dP} (17)

S
The dependence on pressure is considerable. If the nitrogen is contaminated by
0.1 % oxygen the effect is the same as if the pressure were reduced by 7.8 X 102
Nm-2 (5.8 mm Hg). When measuring the purity of liquid nitrogen with the aid
of a hydrometer it is therefore necessary to measure the pressure on the liquid
at the same time. In most cases this will be the barometric pressure.

3.3. Design of the hydrometer

A hydrometer has been developed for measuring the purity of the liquid
nitrogen produced by the installation described in this thesis. The required
sensitivity is 2.5 cm/mol % 02. The measuring range is required to extend
from 0 to 1 % oxygen. This is a rather small range, but there is no point in

*) It was assumed in calculating this value that the mixture gives rise to no contraction.
Use was made of data reported by Mathias, Kamerlingh Onnes and Crommelin (33)
(35) (36).
 -81-

making it larger because, at higher percentage contaminations, argon as

weIl as oxygen is found in the liquid nitrgeJi. The sensitivity to argon is cal-
culated to be 1.7 times greater than the sensitivity to oxygen, and therefore
where argon is present in addition to oxygen it is not readily possible with the
hydrometer to determine the purity of the nitrogen. One may infer from a
large reading, however, that the liquid is badly contaminated and that the ni-
trogen content is higher than the value read fr om the calibration curve.
In view of the sensitivity of the measuring range the length of the stem could
weIl be 2.5 cm. The requirement, however, that measurements should be
possible up to a maximum of 2000 metres above sea level caUs for an appre-
ciably longer stem. At 2000 metres altitude the minimum pressure is about
79 X l3 Nm- 2, and at sea level the maximum barometric reading is about
106 X l3 Nm- 2. Ifthe hydrometer is to have a measuring range of 1% 02 over
this whole range of pressures the length of the stem must be 11 cm.
After some metal prototypes had been tried, glass was finally chosen as the '
structural material. The drawback of metal hydrometers is that their walls
must be extremely thin; they are thus easily dented, which makes the calibra-
ti on useless. Having regard to vulnerability of introducing scale divisions
inside the stem, the stem was given a diameter of 4.6 mmo
With the known values of dh/de and S, the value of V is found from formula
(16) to be V = 115 X 10- 6 m3 Since in this case volume V is large compared
with the volume IS of the stem, the term (1:- h)S in formula (15) can be
disregarded. A linear scale is then obtained.
The hydrometer is weighted at the bottom by mercury. The usuallead shot
cannot be used for this purpose because the po or thermal contact between
the shot makes the cooling time of the meter too long (15 minutes). The
cooling time of a mercury-weighted hydrometer is very much shorter (2 or 3
minutes), allowing quicker measurements to be made. A further advantage of
using mercury is that the liquid nitrogen does not boil for very long, so that
there is no troublesome lift of the hydrometer.

3.4. Results of measurements

Before the hydrometer discussed above was tested, a met al hydromeret
having the same sensitivity was made (2.5 cm/mol %). This was used for
investigating the reproducibility of the measurement. Twenty successive
readings were taken of the level of the hydrometer in a vessel containing a liquid
of given composition. Between every two measurements the hydrometer was
raised to room temperature, cooled in another vessel of liquid to prevent the
composition of the liquid in the measuring vessel from being affected by the
evaporation, and then returned to the measuring vessel. The following readings
were obtained : 8.0 - 8.0 - 8.0 -7.9 - 7.9 -7.9 -7.8 - 7.8 - 7.8 - 7.7
cm. After refilling the vessel with the originalliquid :
 -82-

8.1 - 8.1 - 8.1 - 8.0 -7.8 -7.7 cm.

After again renewing the liquid :.
8.1- 8.1- 8.0 - 8.0 -7.9 -7.9 - 7.8 cm.
Apart from a drift in the readings the reproducibility is quite satisfactory.
This drift in the readings is probably due to the condensation of oxygen from
the air on the cold surface of the hydrometer when it is transferred from one
vessel to the other. After refilling the vessel the original readings are again
obtained. The measurement is accurate to within 0.05 % of oxygen. Careful
precautions are necessary, however, to achieve this accuracy.
1. A good dewar vessel must be used without an observation slit. In dewar
vessels with observation slits, evaporation gives rise to circular currents in
the liquid, as a results of which the hydrometer is unsteady, at one moment
being drawn down and at another being pushed up.
2. The hydrometer must be carefully cleaned before use.
3. Prior to the measurement the hydrometer and the vessel must be cooled
down to prevent the composition of the liquid from being affected by
evaporation. Moreover, when filling the vessel, the liquid should be poured
in a short stream to avoid air condensing in the stream.
4. No reading must be taken until the liquid is completely steady.
5. After some time, ice forms on the stem and increases the weight of the
hydrometer. A weight of 30 rnilligrams of ice has the same effect as -0.1%
of oxygen. Light icing-up of the stem therefore does not harm, but one should
not wait too long before taking a reading.
Sensitivity and pressure-dependence measurements were performed on
three glass hydrometers. The results of the sensitivity measurements are collect-
ed in Table XII.

TABLE XII
Measured sensitivity of some hydrometers for liquid uitrogen.

Hydrometer Range Sensitivity

1 0.00 - 1.48 % 02 2.6 X 1Q- 2 m/ % 02

I 0.00 -1.52 2.8
I 0.00- 3.00 2.7
2 0.00 -1.48 2.7
2 0.00-1.52 2.7
2 0.00-3.00 2.6
3 0.00 -1.48 2.7
3 0.00-1.52 2.7
3 0.00- 3.00 2.8
 -83-

The differences in sensitivity are not significant. The average sensitivity is

2.7 X 10- 2 m/% 02. The volume of these hydrometers is V = 105 X 10-6 m3
The cross-sectional area of the stem is S = 0.166 X 10-4 m 2 . The sensitivity
calculated from (16) is dh/de = 2.2 X 10- 2 m/mol %. The measured sensitivity
is 23 % higher. One reason for this difference might be the occurrence of con-
traction when the liquid nitrogen and liquid oxygen mix, which is not taken
into account in the calculation.
The pressure-dependence was measured by determining the reading of the
hydrometer as a function of the pressure on the liquid nitrogen in a closed
vessel provided with an observation slit. Series of measurements were made at
decreasing pressure in order to avoid errors due to undercooling. The experi-
ment was done with three hydrometers, two series of measurements being
performed with each hydrometer. The resuIts are plotted in fig. 44. The same

fa

~
I
- calculated curve
measured with
8 hydrometer N? f -
x.~
, measured with
x hydromet., N~ 2
measured with
6 o hydrometer N~ 3

4 ~
2
0

'"~ >

0~
o x

o
07 08 Og f O

Fig. 44. Pressure-dependence of hydrometer for liquid nitrogen. Comparison between measur-
ed and calculated values.

figure shows the theoretioally expected pressure-dependence. In calculating

this curve, (oT/oP)c cou1d not be assumed to be constant as with formula
(16), it being necessary to take into account the curvature of the vapour-pressure
curve. The spread in the resuIts is greater than in the reproducibility experi-
ments. One reason for this may be that the observation slit required for this
measurement affected the results. Moreover, as the pressure decreased it be-
came increasingly difficult to ascertain whether the state of equilibrium had
been reached. At the lowest pressure the liquid also boiled more irregularly,
which made the pressure measurement less accurate.
 -84-

3.5. Discussion
A hydrometer can readily be used to check the purity of liquid nitrogen.
At normal pressure (10 5 Nm- 2) the measurement is accurate to within 0.1 %
oxygen. At lower pressure the accuracy is less owing to the errors involved in
the measurement of the pressure-dependence. The accuracy at pressures in the
region of 0.8 X 105 Nm- 2 is about 0.2% oxygen.
In addition to taking the reading of the hydrometer it is always necessary at
the same time to record the barometric reading, since the re su lts of the measure-
ment depend to a marked degree upon atmospheric pressure.
 -85-

LIST OF SYMBOLS

A Loss in the yield of a vapour bubble pump, which is

dependent on the diameter ofthe riser tube only. m3 S- 1

Amin Minimum work. J

a Coefficient ofthermal diffusivity. m 2 S- 1
c Specific heat. J kg- 1 C-l
C Heat capacity. J C- l
c Concentration. (mole %)
d Diameter. m
D Vector Cb = 1 asw = 0)
Ex Exergy J mole- 1
F Delivery of vapour bubble pump. mole S-1
Ft Liquid flow to the column. m3 s-1
Fu Liquid flow from the column. m3 S- 1

G Weight. N
g Acceleration of free fall. m S-2
H Enthalpy. J mole- 1
H Transfer function.
!:l. HN 2 Difference in enthalpy between 1 mol of N 2 at 20 C
and 1 mol of liquid nitrogen at -196 C. J mole-1
H.E.T.P. Height equivalent to a theoretical plate. m
h Height of liquid level. m
h Reading of hydrometer. m
I Electric current. A
j Imaginary unit.
I Length. m
l Length of the downcomer of an air-lift or vapour
bubble pump. m
Length of the ris.er of an air-lift or vapour-bubble
pump m
m Mass. kg
p.p.m. Parts per million.
p Pressure. Nm- 2
p Partial pressure. Nm-2
p Vapour pressure. Nm-2
p' Vapour pressure above liquid oxygen. Nm-2
!:l.p Pressure drop. Nm- 2
qv Vapour flow. m3 S- 1
ql Liquid flow. m 3 S-1
qZth Yield of vapour bubble pump when there are no
losses.
 -86-

r Reflux ratio calculated without losses.

rI Reflux ratio calculated with losses.
r Heat of evaporation. J kg- 1
R Electrical resistance. Q
S Cross-sectional area. m2
S Entropy. J mole-1C- l
Sr Area of liquid level in reboiler. m2
t Time. s
T Temperature oK
To Ambient temperature oK
TE Dew point. oK
TW.b. Wet bulb temperature. oK
U Voltage. V
U Internal energy. J mole- 1
V Volume. mS
Va Mean gas velocity. m S-1
X Coordination. m
(X Coefficient of cubic thermal expansion. C- 1
(X Blow-off ratio.
{l Coefficient of expansion of bubbles in a riser tube.
y Decrease in liquid production.
15 Part of (])jD8 which works at the lower part of the
column.
e Content of acetylene in liquid oxygen. p.p.m.
g; Relative submergence.
(]) Heat flow. W
(])o Heat flow to vapour bubble pump at which ql = O. W
(])jns Insulation losses. W
(])h. e. Cold losses in heat exchanger. W
(])water Losses due to the freezing out of water from the air
to be separated. W
(])v .bP Losses due to the controlling and the pumping-up of
the reflux. W
(])E Cold production. W
(])m Heat flow to the vapour bubble pump for which ql is
maximum.
Thermal conductivity. Wm- 1 C-1
e Density kgm- S
e Resistance to heat flow. CW-1
T Time lag. s
DJ} Temperature difference. C
() Temperature. C
 -87-

fh Temperature of point K. C
w Angular frequency. S- l
C Constant factor used with vapour bubble pumps.
 -88-

BIBLIOGRAPHY

1) Hausen H., Handbuch der Kltetechnik. Achter Band. Herausgegeben von R. Plank.
Springer Verlag 1957.
2) Ruhemann M., The separation of gases. Second edition. Oxford University Press 1949.
3) Khler J. W. L. and Jonkers C. 0., Fundamentals of the gas refrigerating machine.
Philips tech. Rev. 16 (1954), 69; Construction of a gas refrigerating machine. Philips tech.
Rev. 16 (1954), 105; Die Gaskltemachine von Philips. Kltetechn. 6 (1954),234; K1te-
techno6 (1954),262; Hausen H. 1) S 96.
4) Keesom W. H., Graphical treatment of the thermodynamics of the rectifying column .
Int. Congr. Refrig. Buenos Aires 1932, p. 136; Commun. phys. Lab. Leiden, Supplement
69.
5) Hausen H., 1) S 160.
6) Rant R., Bewertung und praktische Verrechnung von Energien. AUg. Wrmetechn.
8 (1957), 2, 25 ; Hausen H., 1) S 29; Keesom W. H., Thermodynamische theorie van
het rectificatieprocess. D. B. Centen's Uitgevers Mij., N.V. Amsterdam 1933.
7) DodgeB. F. and Dunbar A. K., An investigation of the coexisting liquid and vapor
phases of solutions of oxygen and nitrogen. J. Amer. chem. Soc. 49 (1927), 591.
8) Mc Cabe W.L. and Thiele E. W., Graphical design of fractionating columns. Industr.
Engng. Chem. 17 (1925),605.
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10) Merkel Fr., Die Rektifikation. Arch. Wrmew. 10 (1929), 13.
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Z. Ver. dtsch. Ing.-Beiheft Verfahrenstechnik 1942. S. 17.
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by 1000 Torr. Angew. Chem. 20 (1948), 321.
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39 (1947), 712.
15) RushtOD J. H., Liquid air fractionation. Navy Department Research Contracts on
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march 1957. Bri. J. Appl. Phys. 8 (1957), 436.
17) Laan C. J. M. v. d. and Roozendaal K., Will he published shortly in Philips tech. Rev.
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nitrogen. Trans. Instn. Chem. Engrs. 27 (1949), 201.
19) Haselden J. J. and Prosad G., Heat transfer from condensing oxygen and nitrogen
vapours. Trans. Instn. Chem. Engrs. 27 (1949), 195.
20) Grber- Erk- Grigull, Die Grundgesetze der Wrmebertragung. Dritte Auflage.
Springer Verlag 1955.
21) Katan L. L., Vacuum powder insulation fodow temperatures. Vacuum 1 (1951), 191.
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Conf. Cryogenic Engng. 1956. Boulder Colorado. p. 163.
23) Lawson D. J. and Mc. Guire J. H., The solution of transient heat flow problems by
analogous electrical networks. Proc. lnstn. Mech. Engrs. 167 (1953), 275.
24) Powell R. L. and Blanpied W. A., Thermal conductivity of metals and alloys at low
temperatures. National Bureau of Standards Circular 556.
25) Brown G. S. and Camp bell D. P., Principles of Servomechanisms. J. Wiley and Sons,
New York. Chapman and Hall, London 1948.
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27) Pollitzer F., ber Explosionen an Apparaten zur Verflssigung und Zerlegung von Luft.
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29) Karwat E., Oxygen Plant Safety. Chem. Engng. Progr. 53 (1957), 188.
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Summary
The advent of the gas refrigerating machine has made it possible to produce
small amounts of liquid air in an economical way. The present thesis describes
how liquid nitrogen can be produced from atmospheric air by combining the
refrigerating machine with an air-rectifying column. The author discusses in
particular the design and construction of an installation capable of producing
more than 4 litres of liquid nitrogen an hour. The purity of the product is
99.8 - 99.9 % ; the efficiency is 1.36 kWh/ I.
The most conspicuous feature compared with other air fractionating systems
is th at the air is not compressed. In consequence of tbis, the installation and
its operation are extremely simpie. Water vapour and carbon dioxide are
removed fr om the feed by cooling the air in such a way that, in spite of the
compact design, the installation can operate continuously for a week.
A detailed account is given of the automatic control of the installation,
special attention being paid to the stability ofthe reflux. In the reflux controlling
system a vapour bubble pump is used for returning the liquid nitrogen to the
top ofthe column . An investigation ofvapour bubble pumps for liquid nitrogen
and liquid oxygen is described in the appendix. Also inc1uded in the appendix
are calculations and experiments on a hydrometer specially developed for
simply and accurately measuring the purity of the nitrogen product.
The installation is safeguarded against explosions caused by accumulations
of hydrocarbons; the measures adopted to this end are discussed and various
measurements are described.

Samenvatting
Door bet ter beschikking komen van de koudgaskoe1machine is het mogelijk
om op economische wijze kleine hoeveelheden vloeibare lucht te, maken. In
dit proefschrift wordt beschreven hoe vloeibare stikstof uit lucht kan worden
gewonnen door deze koelmachine te combineren met een luchtsplitsingskolom.
In het bijzonder worden ontwerp en bouw van een installatie beschreven, waar-
mee ruim 4 liter vloeibare stikstof per uur kan worden gemaakt. De zuiverheid
van het produkt is 99,8 - 99,9 %, het rendement is 1,36 kWh/I.
Het meest kenmerkende verschil met bestaande luchtsplitsingsinstallaties is
dat de te verwerken lucht niet wordt gecomprimeerd. Hierdoor is het mogelijk
gebleken om een, ook wat de regeling betreft, zeer eenvoudige installatie te
maken. Door afkoeling van de lucht worden waterdamp en koolzuur eruit
verwijderd. Dit gebeurt op een speciale manier waardoor het mogelijk is om
ondanks de compacte bouw, een week ononderbroken in bedrijf te zijn.
De installatie is voorzien van een automatische refluxregeling, die uitvoerig
wordt behandeld.
In deze reflux regeling is een dampbellenpomp toegepast, waarmee vloeibare
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stikstof wordt opgepompt. Een onderzoek, dat gedaan is aan dampbellenpompen

voor vloeibare stikstof en vloeibare zuurstof, is in de appendix beschreven.
Om de zuiverheid van het produkt, de vloeibare stikstof, op een eenvoudige
wijze te kunnen meten is een areometer ontwikkeld. Berekeningen en metingen
aan deze areometer zijn ook in de appendix opgenomen.
Er zijn maatregelen genomen tegen het gevaar voor explosies van kool-
waterstoffen, die zich in de installatie kunnen verzamelen; metingen daaraan
worden beschreven.