ASU Course (ENG) PDF

Air separation techniques course
Dear Reader,
This course is strictly for internal use. If you have any questions or need for an ASU
training course, please refer to the Corporate Supply / Production (SUP) team.
Air separation techniques
course
by Anders Lenneskog, SUP
Version
No. Date Made by Approved by
1-Swe 19 March 1995 AL
2-Swe 15 Sept. 1995 AL MR
3-Eng 1 Nov. 1995 ASB / AL MR
4-Eng 20 Feb. 2001 AL PEI
Air separation techniques course
Preface
This course has been developed in AGA during many years and is based on Dr Herreilers course
material from 1970. It is by now classical and has been used for training innumerable operators and
production supervisors. It has been thoroughly revised, but the basic framework is still there. I have
inserted my experience from many Technical Reviews of air separation plants.
Additional work has been carried out to describe current techniques used in an air low pressure
plant with a nitrogen recycle. An overview section on gas properties, thermodynamics and others
has been included, as the education of the operators has increased. Increased electricity costs have
resulted in that economical running and maintenance of the large compressors have become more
important. Therefore, a section has been added which shows the effect on the compressors
electricity consumption. How automatic controllers function has also been included. The section
regarding distillation has been considerably reduced. Start, stop and defrosting has not been dealt
with in this course.
In comparison with the courses already given the text of this material has been considerably
concentrated. Every chapter has been divided into sections with headings of the main topics to be
discussed. With this help the course material can more easily be used as a reference book.
Lidingö, March 1995

Anders Lenneskog
Versions 2 and 3 have been corrected and made clearer./ AL Nov 95
In version 4 is added : process with air cycle, internal compression, QT - diagram for heat
exchangers, orifice plates with flow calculation, output signal from a controller, what is pressure,
spray coolers, Nm3 LOX equivalents and a few corrections and improvements. / AL Sept. 1999
Further corrections (especially 18.2) and clarifications were made. Added hydrocarbon risks. /
AL May 2000
CONTENTS
1. INTRODUCTION ....................................................................................................................................................... 2
2. AIR GASES BOILING POINTS................................................................................................................................. 3
3. MAIN PROCESS FUNCTIONS ................................................................................................................................. 4
4. GENERAL DISTILLATION TECHNIQUES............................................................................................................. 5
4.1 The normal distillation column ........................................................................................................................... 5
4.2 Column types ...................................................................................................................................................... 5
4.3 Columns with sieve trays .................................................................................................................................... 6
4.4 Columns with structured packings ...................................................................................................................... 6
4.5 How single columns function.............................................................................................................................. 7
4.6 Composition at the different trays ....................................................................................................................... 7
4.7 Material balances ................................................................................................................................................ 8
4.8 Controlling the LOX take-out ............................................................................................................................. 9
4.9 Operating a single column, disturbances............................................................................................................. 9
4.10 Increased vapour quantity ................................................................................................................................. 10
4.11 Maximum production........................................................................................................................................ 11
4.12 Minimum production ........................................................................................................................................ 11
4.13 Changed composition in the feed ...................................................................................................................... 11
4.14 Changed air feed ............................................................................................................................................... 12
4.15 Changed cold quantity in the feed..................................................................................................................... 12
4.16 Warning for "over-controlling"......................................................................................................................... 13
5. AUTOMATIC CONTROLLERS AND INSTRUMENTATION.............................................................................. 14
5.1 Controller and instrumentation designations ..................................................................................................... 14
5.2 Flow measurement with orifice plate (New in version 4) ................................................................................. 15
5.3 Function of a controller ..................................................................................................................................... 16
5.4 Output signal from a controller (New in version 4)..................................................................................... 16
5.5 Overview of Normal Controllers....................................................................................................................... 17
5.6 Connected controllers........................................................................................................................................ 17
5.7 Alarms, switches and trips................................................................................................................................. 18
6. LINDES DOUBLE COLUMN (without argon) ........................................................................................................ 19
6.1 Description of the Parts of Double Columns..................................................................................................... 19
6.2 Boiling Point Depends on LOX and LIN Pressure............................................................................................ 19
6.3 How a reboiler - condenser functions................................................................................................................ 20
6.4 Controlling a double column ............................................................................................................................. 21
6.5 Lachmann Outlet (impure nitrogen) .................................................................................................................. 22
6.6 Controlling the Oxygen Purity in the Upper Column ........................................................................................ 23
6.7 Subcooling of Liquid Products, flash of boiling liquids (revised for version 4)............................................. 24
6.8 Increased Reflux Quantity through the GAN Feed............................................................................................ 25
6.9 Summary of the Function of a Double Column Using Material Balances......................................................... 25
6.10 Material Balance Inside the Double Column .................................................................................................... 26
7. HEAT EXCHANGERS AND ENERGY CALCULATIONS ................................................................................... 29
7.1 How a Heat Exchanger Functions ..................................................................................................................... 29
7.2 Temperature Diagram........................................................................................................................................ 30
7.3 Specific Heat, Energy Content and Power ........................................................................................................ 31
7.4 Calculating the Cold Loss in a Heat Exchanger ................................................................................................ 32
7.5 Balancing Stream in Main Heat Exchanger....................................................................................................... 32
7.6 Specific Heat at High Pressure .......................................................................................................................... 33
7.7 Controlling the Balance and Compensation Streams......................................................................................... 34
7.8 Description of Plate Heat Exchangers ............................................................................................................... 34
8. AIR PREPARATION AND PURIFICATION .......................................................................................................... 35
8.1 Contaminants in Air .......................................................................................................................................... 35
8.2 Air Filters .......................................................................................................................................................... 35
8.3 Water Vapour in the Air.................................................................................................................................... 35
8.4 Vapour Content Dependency on Temperature .................................................................................................. 36
8.5 Vapour Content Dependency on Air Pressure................................................................................................... 37
8.6 Condensate Separator........................................................................................................................................ 37
8.7 Dryers - mole sieves .......................................................................................................................................... 37
8.8 Mole Sieves in Combination with Other Drying Media .................................................................................... 38
8.9 Risks with hydrocarbons (New in version 4).................................................................................................... 38
8.10 The Function of Mole Sieve Batteries (Rev. in version 4)................................................................................ 39
9. COMPRESSOR AND COOLING WATER - THE IDEAL GAS EQUATION ....................................................... 41
9.1 Function of a Turbo Compressor....................................................................................................................... 41
9.2 What is pressure? New in version 4 ................................................................................................................. 42
9.3 Calculation of Gas Volume According to the Ideal Gas Equation .................................................................... 42
9.4 Calculation of Normal Cubic Meter (Nm3 ) ...................................................................................................... 43
9.5 Change of Capacity due to altered Suction Conditions ..................................................................................... 44
9.6 Capacity Control ............................................................................................................................................... 45
9.7 Compressor Curves and Surging ....................................................................................................................... 45
9.8 Efficiency .......................................................................................................................................................... 46
9.9 Cooler Temperatures and Dirt in Coolers ......................................................................................................... 47
9.10 Changed Energy Consumption due to Changed Cooling Water Temperature .................................................. 48
9.11 Cooling Water System ...................................................................................................................................... 48
10. REFRIGERATION MACHINES AND SPRAY COOLERS .................................................................................... 50
10.1 Function of Refrigeration Machines.................................................................................................................. 50
10.2 Heat Pump Systems........................................................................................................................................... 51
10.3 Detailed Description of Refrigeration Plant for +5°C....................................................................................... 52
10.4 Contaminants in Ammonia................................................................................................................................ 54
10.5 Overview of Cold Production to -40° C............................................................................................................ 54
10.6 Cooling of Air in a Spray Cooler New in version 4 ......................................................................................... 55
QUESTIONS TO CHAPTER 1 TO 10 ........................................................................................................................... 57
11. CRYOGENIC COLD PRODUCTION...................................................................................................................... 58
11.1 Temperature Drop in an Expansion Valve........................................................................................................ 58
11.2 The Linde Process for Manufacturing Liquid Air ............................................................................................. 58
11.3 Other Historical Processes for Liquid Air......................................................................................................... 59
11.4 Heat Content Diagram for Gases ...................................................................................................................... 60
11.5 Entropy Diagram for Gases............................................................................................................................... 61
12. EXPANSION TURBINES ........................................................................................................................................ 63
12.1 Oil Braked Expanders ....................................................................................................................................... 63
12.2 The Function of a Booster-Expander ................................................................................................................ 63
12.3 Labyrinths, Gap Pressure and Seal Gas ............................................................................................................ 64
12.4 Balancing the Shaft Axial Forces...................................................................................................................... 65
12.5 Efficiency of an Expansion Turbine.................................................................................................................. 65
12.6 A simpler Check of Expander Efficiency.......................................................................................................... 66
12.7 Measuring the Cold Production of the Boosters ............................................................................................... 67
12.8 Cold Requirements for the Production of Liquid .............................................................................................. 68
12.9 LOX equivalents of Nm3 (New in version 4) ................................................................................................. 68
13. COLD PRODUCTION IN THE NITROGEN RECYCLE........................................................................................ 69
13.1 Nitrogen Recycle with -40°C Refrigeration Machine and One Cold Expansion Turbine with Booster............ 69
13.2 Reduction of Cold Production in the Nitrogen Recycle .................................................................................... 71
13.3 Nitrogen Recycle with Warm and Cold Expansion Turbine with Boosters ...................................................... 72
13.4 Feed Compressor to Increase Reflux ................................................................................................................ 73
13.5 Controlling the recycle with warm and cold booster-expander (rev. in version 4)........................................... 74
13.6 Temperature Diagram (QT-diagram) for Recycle Heat Exchangers (New in version 4) .................................. 75
13.7 Balancing the Heat Exchanger with the Help of the QT Diagram (New in version 4)..................................... 76
13.8 An overview of Other Cold Processes .............................................................................................................. 77
13.10 List of different types of recycles or cold production in AGA ..................................................................... 78
14. COLD PRODUCTION IN AIR CYCLE AND INTERNAL COMPRESSION ........................................................ 80
14.1 Outline of the Air Cycle Process....................................................................................................................... 80
14.2 Internal Compression ........................................................................................................................................ 81
15. LINDE DOUBLE COLUMN WITH ARGON, RARE GASES AND IMPURITIES ............................................... 83
15.1 Rare Gases and Hydrogen in the Air................................................................................................................. 83
15.2 Rare Gases in the Pressure Column .................................................................................................................. 84
15.3 Rare Gases in the Condenser............................................................................................................................. 84
15.4 Rare Gases in the Upper Column...................................................................................................................... 84
15.5 Argon Transfer Zone......................................................................................................................................... 86
15.6 Carbon Monoxide and Nitrous Oxide in the Columns (Rev. in version 4) ................................................... 86
16. ARGON PURIFICATION IN THE CRUDE ARGON COLUMN ........................................................................... 87
16.1 Crude Argon Column........................................................................................................................................ 87
16.2 Different ways to control the Crude Argon Column ......................................................................................... 88
16.3 Control of Crude argon Column with the Condenser Level .............................................................................. 88
16.4 Maximising Crude Argon Production, the Double Column .............................................................................. 89
16.5 Maximising the Crude Argon Column, Nitrogen “Sense” ................................................................................ 90
16.6 Controlling the Crude Argon Column with the Condensers Evaporation Flow ................................................ 91
16.7 Crude Argon Column which gives Oxygen free Argon .................................................................................... 92
17. CHEMICAL PURIFICATION OF ARGON ............................................................................................................. 93
17.1 Hydrogen Feed.................................................................................................................................................. 93
17.2 Deoxo - Chemical Reactor ................................................................................................................................ 93
17.3 Dryers ............................................................................................................................................................... 94
17.4 Chemical Purification without Hydrogen and Dryer......................................................................................... 94
18. PURE ARGON COLUMN ........................................................................................................................................ 95
18.1 Function of a Pure Argon Column .................................................................................................................... 95
18.2 Controlling the Pure Argon Column ................................................................................................................. 96
19. AN OVERVIEW OF PRESSURE AND PRESSURE DROPS IN THE PROCESS................................................. 98
19.1 Pressure Drops in Pipes .................................................................................................................................... 98
19.2 Investigation of Pressure Drops ........................................................................................................................ 98
19.3 Pressure Drop in the Air Path ........................................................................................................................... 99
19.4 Carbon Dioxide in the Columns...................................................................................................................... 100
19.5 Pressure Drop of the Outgoing Gases from the Upper Column ...................................................................... 100
19.6 The Pressure in the Pressure Column.............................................................................................................. 101
19.7 Pressure Drop on the Recycle Suction Side .................................................................................................... 102
19.8 Pressure Drop on the Pressure Side in the recycle .......................................................................................... 103
20. SPECIFIC ENERGY CONSUMPTION AND PRODUCTION COSTS ................................................................ 104
20.1 Costs of Increased Specific Energy Consumption .......................................................................................... 104
20.2 Break-down of the Electric Consumption (kW) of Different Machines.......................................................... 104
20.3 Production and Specific Energy...................................................................................................................... 105
20.4 Separation and Liquefaction Energy ............................................................................................................... 105
20.5 Cost of Argon when Running with Surplus Air (New in version 4).............................................................. 106
20.6 Measurement Methods for Production and Energy Consumption (Rev. in version 4) .................................... 107
Questions to chapter 11-20 (New in version 4) ........................................................................................................ 109
Air separation techniques course Version 4
1. INTRODUCTION
This course describes the main principles of plant construction and operating method of a
cryogenic air separation plant. Cryogenic is defined as extreme cold and in this case cooling of
air to its liquid state. Other air separation processes such as PSA or membrane techniques will
not be dealt with by this course.
Air is a mixture of different gases. The three most important are:
Nitrogen 78 % (volume) Chemical symbol: N2

Oxygen 21 % (volume) Chemical symbol: O2
Argon 1 % (volume) Chemical symbol: Ar
Most air separation plants produce these three gases in liquid form. Moreover, some plants
produce oxygen and/or nitrogen in gas form for pipe delivery. Exceptionally some plants
produce only gaseous nitrogen.
Product names:
LOX Liquid Oxygen

LIN Liquid Nitrogen
LAR Liquid Argon
GOX Gaseous Oxygen
GAN Gaseous Nitrogen
Air separation plants are constructed in different forms depending on what products are
produced and production capacity and purity. Moreover process equipment and machinery
from different manufacturers are used. However, the basic principles of construction and
working methods for all these different plants are nearly the same.
When a new plant is to be constructed and the production capacity and purity determined, the
most appropriate process which has the lowest energy consumption and purchase price is
selected. It can be seen that the process equipment and manufacturer can vary widely.
Other components in air:
Dust
Water vapour
Carbon dioxide
Hydrocarbons (e g methane, ethane, propane and acetylene)
Rare gases (helium, neon, krypton, and xenon)
Diverse air contaminants
Most of these components have a disturbing effect on the process and must be removed. The
reasons why they disturb the process and how to remove them is explained later in this course.
It is characteristic of the cryo process that the liquids are close to the boiling point and that heat
is leaking in. The manufacturer of equipment must take this into consideration, such as to
design the suction line of a pump so that no cavitation will occur.
© Linde Gas AG Page 2 (109) 2001-02-20

2. AIR GASES BOILING POINTS
Degrees Degrees
Celsius (°°C) Kelvin (K)
Water (melting point) 0 = 273 K 0 273
Propane -42 = 231 K
Carbon dioxide (melting point) -79 = 195 K

Acetylene -84 = 190 K
Nitrous oxide (N2O) -89 = 185 K
Ethane -89 = 185 K
-100 173
Ethene -104 = 169 K
Xenon -108 = 165 K
Krypton -153 = 120 K

Methane -162 = 112 K
Oxygen -183 = 90 K
Argon -186 = 87 K
Nitrogen -196 = 77 K
-200 73
Neon -246 = 27 K
Hydrogen -253 = 20 K
Helium -269 = 4K
-273 0
These boiling points are measured at atmospheric pressure. As we will see later the boiling
points change with pressure.
In the Kelvin scale, the zero point is at the absolute zero point, which is the lowest temperature
that can exist in the universe. Zero degrees Kelvin = -273,15°C. The Kelvin units are widely
used within cryogenic science and technology as they are much more practical. One can see
much more easily which is colder or warmer, for example that boiling LIN is colder than LAR,
which is colder than LOX.
The differences in boiling points have vital influence on the separation of liquids by
distillation.
© Linde Gas AG Page 3 (109) 2001-02-20

Figure 3.1 Overview of an Air Separation Process
Electrical
Air power
Cooling Cold Distillation

water production columns
LIN
Purification GAN LIN

Air Compressor Heat Air LOX
by mole
with filter
sieves exchanger
GOX LAR
Electrical
power
Coldbox
3. MAIN PROCESS FUNCTIONS
1. Air compressor with filter

Dust free air is compressed to a pressure sufficient to get it through the equipment.
2. Air purifying
Normally mole sieves are used to remove water vapour, carbon dioxide and certain other
contaminants.
3. Cooling down the air

In a heat exchanger the air is cooled down close to the dew point by the cold separated gases,
which come from the distillation column. If a suitably large enough heat exchanger is used the
cold gases can be warmed to a temperature just under that of the incoming air, so that the cold
losses become acceptable.
4. Cold production
Production of liquid products requires cold and moreover cold losses occur through the
equipment insulation and in the heat exchanger. This cold is produced in a recycle by
compressing, cooling and expanding nitrogen to its liquid state. It is a recycle because the gas
which does not condense is warmed up and is fed back to the compressor again.
5. Cooling with cooling water

Compressors and other machines need large amounts of cooling water. A large part of the heat
removal is in fact cold production.
6. Air separation
The liquid air is separated into oxygen, argon and nitrogen in the distillation columns. The cold
gases are fed through the heat exchanger and are warmed-up while the liquids are fed into tank.
See figure 3.1 Overview of an Air Separation Process
The cold equipment demands much insulation in order to get an acceptable cold loss. So
columns, heat exchangers and parts of the cold production equipment are built in a large tower-
like box, the so-called coldbox.
The unique feature of air separation is the great interdependency of the different flows. This is
because it is a cryogenic process, in which the external media such as cooling water and steam
cannot be used. The different products or internal flows are used for boiling and condensing in
the columns, as reflux, for cooling the incoming air and for subcooling the liquid products.
Cold nitrogen gas is used in the recycle for cold production for liquefaction etc.
A changed gas flow gives a different pressure, and a change of pressure can have a
considerable effect on the other flows as their boiling points change with pressure. Also
changed temperatures, for example, in a condenser will change the rate of heat exchange and
therefore change the gas flow in the column which will alter the purity. How all these processes
come together shall be given in overview by this course.
© Linde Gas AG Page 4 (109) 2001-02-20

Condenser
Cooling Water
Top Product
Reflux
Feed
Steam
Reboiler
Bottom Product
Figure 4.1 A Normal Distillation Column

4. GENERAL DISTILLATION TECHNIQUES
Distillation is a common method to manufacture pure products from liquid mixtures within the
chemical and in particular the petroleum industries. This is built around the principle that in a
boiling liquid mixture the component which has the lowest boiling point is the most volatile,
i.e. it will vaporise the most easily.
As an example, take a liquid mixture of alcohol (boiling point 78°C) and water (boiling point
100°C). If we have a boiling mixture with 50 % alcohol, the vapour will contain 80 % alcohol.
To have a yet purer alcohol, the vapour must be separated and condensed to liquid. This liquid
must then be boiled again to obtain vapour, which contains a higher alcohol content. The
boiling liquid which remains contains a reduced amount of alcohol and increased water
content, because more alcohol than water was removed as vapour.
Another example of a liquid mixture is vinegar, which is a mixture of water (bp 100°C) and
acetic acid (bp 118°). In this mixture water has the lowest boiling point and will vaporise the
most easily. Therefore the vapour from boiling vinegar contains a higher percentage of water
than the liquid.
4.1 The normal distillation column
The most common type of distillation apparatus consists of a column with:
• Reboiler in the bottom to produce vapour that rises in the column

• Outlet for the bottom product, in liquid form
• Some column filling material so that vapour can come in intensive contact with the liquid
• Crude product feed in the centre
• Outlet for vapour product at the top
• Condensation of top vapour to liquid
• Feed back to the column of top liquid, which will run downwards and meets the rising
vapour. This liquid is called reflux.
• A part of the top-liquid or top-gas is taken out as product, which is called the distillate.
See figure 4.1 A Normal Distillation Column
4.2 Column types
Within air separation there are two types of column filling. Definitely the most common type is
the sieve tray which is found in all plants. In recent years, structured packing has been
introduced and is used in certain parts or in whole columns. In certain older plants of the revex
type, for GOX production, occasionally the bubble cap tray type can be found.
© Linde Gas AG Page 5 (109) 2001-02-20

Column Diameter
Liquid (B)
Vapour (D)
Liquid Level
C
E
Sieve Trays
Column
Wall
A-E refer to figure 4.4
Figure 4.2 Column with Sieve Trays

4.3 Columns with sieve trays
See figure 4.2 Column with Sieve Trays
Sieve trays are metal discs in which very large amount of small holes have been drilled. The
upwards moving vapour streams through these holes, so that it prevents the liquid from running
down through the same holes. The liquid runs over into a drain, whose pipe goes down into the
liquid (= liquid lock) on the next lower tray. The liquid lock prevents the vapour from
streaming up through the pipe.
The large number of small holes cause a powerful division of the up-flowing vapour into small
bubbles, so that the contact between vapour and liquid becomes very intense.
With this type of tray, the quantity of vapour must be large enough at all times to support the
liquid. If for some reason, the vapour quantity is too small, then the liquid will run down
through the holes and the distillation process will no longer work in the correct way.
4.4 Columns with structured packings
See figure 4.3 Column with Structured Packing
Structured packings comprise corrugated plates, which sit next to each other so that every other
plate is corrugated in the same direction. The corrugation direction of one plate compared to
the direction on the plate next to it forms an "X". The liquid runs downwards and is mixed in
the centre of the "X" with the vapour travelling upwards in the opposite direction through the
same passages. The corrugations ensure that the contact area between liquid and vapour is
large, which is very important. To increase the contact area still further there are lower
corrugations in the other direction on the plates.
Structured packings are often used in cooling towers for cooling water, but here the material is
plastic.
These column types have a very much lower pressure drop than that of a sieve tray column,
which is an advantage as it leads to a reduced compressor work requirement. The pressure drop
in a sieve tray column is higher as the vapour must support the liquid on the upper part of the
trays. The disadvantage with structured packings is that they are much more sensitive to
changes in the gas and liquid flows.
Structured packing also requires very thorough design and installation of the liquid distributors
in the top part of each section, so that the liquid is evenly distributed. All passages through the
corrugation must, in practise, take the same amount of liquid. Otherwise the vapour tends to
find the easiest path, such as the passage which contains less liquid, which results in unsatis-
factory distillation.
See figure 4.3 Liquid Distributors in Column with Structured Packing
© Linde Gas AG Page 6 (109) 2001-02-20

1 . P a ck in gs
2 . S u p p o rts
3 . L iq u id co lle cto rs
4 . R in g ch an n e l
5 . L iq u id d istrib u to r
6 . L oc ating g rid
7 . S u p p o rt grid
8 . S team in let
9. Sum p
1 0 . C ircu latio n to reb oiler
11 . S k irt
1 2 . A nc h o rag e
F igure 4.3 C olum n w ith

S tructu red packing
4.5 How single columns function
We can take as an example the column shown in figure 4.1, and we will separate liquid air at
boiling point. For the moment we will ignore argon, so we say that we have a mixture of
oxygen and nitrogen. As nitrogen has the lowest boiling point, it follows that it will rise to the
top (as vapour) and oxygen moves to the bottom (as liquid). Also we will ignore for now how
the boiling and condensation is carried-out. There exist processes with single columns, and
AGA has such a plant in Nice, France. This equipment was manufactured by SIAD in Italy, but
it is not fed with liquid air but air on the dew point. The pure argon column (chapter 18) is also
a complete single column.
The air runs downwards in the column while it is liquid. For each tray downward, the ratio of
oxygen increases, until in the bottom of the column in the reboiler we find pure LOX, which is
removed through the bottom outlet. In the reboiler GOX is produced and this rises up through
the column, while in each higher tray the nitrogen content increases. Immediately above the
highest LOX-level in the reboiler the pure GOX is removed. When the gas has risen to the air
feed, the mixture is virtually the same as air. For each higher tray the nitrogen content increases
and in the top we will find pure GAN (however, the process in this example, the GAN would
not be as pure as it would be in our plants, as will be explained later). The GAN condenses at
the top of the column, some runs back into the column as reflux and some is taken out as LIN
product.
4.6 Composition at the different trays
See figure 4.4 Temperatures of O2 - N2 Mixtures at Different Compositions. (T-x diagram)
The vertical shows temperature (T), while the horizontal axis shows the O2 - N2 mixture
composition (x) in percent. Two curves have been drawn.
• Dew point curve that shows at which temperature each gas mixture starts to condense.
• Boiling point curve that shows at which temperature each liquid mixture starts to boil.
The end points of each curve represent pure O2 (oxygen) and pure N2 (nitrogen) respectively.
At these points the dew point and boiling point are the same, -183°C for O2 and -196°C for N2.
This applies at atmospheric pressure. In the column the pressure is somewhat higher, therefore
the temperatures are also a little higher. The temperature is higher at the bottom where boiling
takes place. The temperature reduces in even steps with each higher tray towards the top.
Now we will study with the help of diagram 4.4 what, in principle, takes place on a tray. The
gas that mix with the liquid on each tray can be considered as being the same composition. We
will take as an example 40 % O2. The diagram shows a vertical dotted line (a-a) at that O2
content. The liquid is boiling at point B on the boiling point curve. By drawing a horizontal
line from point B we can read off the temperature. The vapour exists at the dew point, because
it comes from the boiling liquid of the tray below, that is at point A on the dew point curve.
This is warmer than the liquid on this tray and with intensive mixing the temperatures will be
levelled out and correspond to point C.
© Linde Gas AG Page 7 (109) 2001-02-20

a Dew Point -183
o
Curve
C
Gas Phase
Boiling
Point
A (gas in) Curve
A'
D (gas out) C (mixture)
E (liquid out)
B'
B (liquid in)
-196 Liquid Phase

a
O2 0 10 20 30 40 50 60 70 80 90 100 %
N2 100 90 80 70 60 50 40 30 20 10 0%
A-E refer to figure 4.2
Figure 4.4 Temperature - Composition (T, X) Diagram

at Constant Pressure
The gas that was cooled and then partly condensed will have a composition, which corresponds
to point D on the dew point curve. The liquid that was warmed up and then partly vaporised
can be compared to the corresponding point E on the boiling point curve. Therefore the gas will
now contain less O2, while the liquid will contain more O2.
Where point C meets line a-a depends on how much liquid there is in proportion to the amount
of gas. If there is a large amount of gas then point C will approach the dew point curve, which
means that the gas formed through the mixing in the liquid will receive a somewhat small
increase in nitrogen content, while there will be a large reduction in the content in the liquid.
Using more intuitive reasoning one can say that the liquid acts as a cleaner of the gas and
"washes" the oxygen downwards, while the gas acts as a "stripper" to the liquid and takes the
nitrogen upwards. Too much gas and too little liquid will result in a small washing effect on the
gas, so that the reduction of oxygen content in the gas is minimal, while the increase of oxygen
content in the liquid will be large, as there is little liquid the change in it will be relatively
large. The reverse situation will happen if there is too much liquid and little gas. This means
that the proportion of gas and liquid quantities in a column also have a crucial importance
for purification. More liquid in proportion to gas will give a purer gas while the reverse will
give purer liquid.
In practice there is less oxygen in the gas than in the liquid, which it meets on a tray depending
on how large the reflux ratio is, so the calculations in the diagram become a little more
complicated.
Of great importance of product purity is the number of trays. More trays give greater purity.
However, in an existing plant the number of trays cannot be altered, so it is important to learn
how to use the process in the best way.
4.7 Material balances
Before we go into how to operate the column, we must first understand what material balance
is. We operate the process continuously, which means stable without interruption. The
condition is what goes into process must go out, as there is no large space available for
storage. Therefore, the quantity of air-in = oxygen + nitrogen-out. It is obvious that it is not
possible to take out more oxygen than is found in the air. Therefore, quantity of air-in • 0,21 =
oxygen-out (0,21 = O2 content in air) and quantity of air-in • 0,78 = nitrogen-out (0,78 = N2
content in air). All flows in Nm3/h.
What happens if we take out too much of one product? Assume that the column is working
stable and we have pure oxygen at the bottom and pure nitrogen at the top. In between there is
a gradual change in the composition between the two products. This can be illustrated by a
diagram.
See figure 4.5 Composition of O2 and N2 in the Column.
The analysis instrument is denoted as QI = Quality (analysis) Indicator. QI-1 is used for pure
oxygen. QI-2 is for mixture above the centre and QI-3 for pure nitrogen. All are analysing the
oxygen concentration, but in different measuring ranges (% or ppm).
© Linde Gas AG Page 8 (109) 2001-02-20

QI-3 Top 0% O2
O2 analysis
N2 QI-2 QI-2 QI-2
Correct Too high N2 Too low
O2
O2
QI-1 Bottom 100% O2
A) Correct quantity B) Too much C) Too little

of top product top product top product
Figure 4.5 Composition of O2 and N2 in the column

Note the difference between purity and concentration. When the O2 concentration is
increasing at QI-1 it means that the LOX purity is increased. But when the O2 concentration is
increasing at QI-3, the LIN purity is decreased.
In figure 4.5a we have the correct composition. If we take out too little nitrogen product, then
more N2 will accumulate at the top of the column because it will be continuously fed with air
and rises up the column. This nitrogen accumulation grows and starts to "press down" the
oxygen. The purity becomes better in the nitrogen, which can be read off as a decrease at QI-3.
The "press down" will propagate downwards through the entire column to the oxygen part and
will go out there. This means that if all of the nitrogen cannot go out of the top outlet, it tries to
go out with the oxygen, therefore the purity of the oxygen worsens, which can be read-off as a
decrease at QI-1. If this has gone too far it will already be to late to save the purity of the
oxygen. Therefore an analyser is installed a number of trays down from the top: QI-2. This can
sense any changes in gas content much earlier than it can do at the column top, as the changes
are greater. The oxygen concentration decreases in the entire column as shown in figure 4.5c.
If we on the contrary take out more of the nitrogen product than is allowed by the material
balance, then the oxygen concentration in the entire column increases, see figure 4.5b. The
nitrogen which enters the column with air, is not enough to replace this, so the oxygen is
drawn-up through the column and worsens the purity of the nitrogen, QI-3 increases. However
the purity of the oxygen improves in the bottom and QI-1 increases.
4.8 Controlling the LOX take-out
In this example we operate a column which is fed with liquid air and produces products in
liquid form. The amount of bottom product (=LOX) which is taken out must therefore be the
same as the amount of oxygen in the air which is fed in. If we take out the right amount of top
product (=LIN), then the right amount of LOX will run down to the reboiler. If we take out the
wrong amount of LOX the level in the reboiler will either rise or sink. Too low levels mean
that the heater elements will not be fully covered by liquid, which reduces its boiling effect and
worsens the distillation. Too high levels will mean that the LOX rises over the first tray and
destroys the purification process there. It can be seen then that we must take out the amount of
LOX that will maintain the liquid level within the specified limits. Therefore, an automatic
controller is situated at the LOX outlet, called a Level Indicator Controller (LIC).
See figure 4.6 Operating a Single Column
The LIC includes a measurement unit, which measures the liquid level and shows how much it
is. There is also a calculator unit that calculates how great the difference is between the desired
level and actual level. This difference is sent to the control unit, which then generates a signal
to the control valve for the LOX outlet to open or close the valve, so that the difference
between the actual and desired levels is less than a pre-determined percentage i.e. the correct
level. More on controllers id described in chapter 5.
4.9 Operating a single column, disturbances
To be able to operate a column, as shown in figure 4.6, we require more measurement

instruments and possibilities to control. We must be able to operate the valves from a control
room and use HIC-control valves, HIC= Hand Indicator Controller.
© Linde Gas AG Page 9 (109) 2001-02-20

Cooling Medium
Top Product
QI-3
Top Product Liquid
Gas Reflux
HIC
QI-2
PDI
Feed
PDI
QI-1 HIC
HIC
Vapour
Bottom
Reboiler Product,
LIC Gas
Bottom Product,
Liquid
Figure 4.6 Operating a Normal Distillation Column

The valve's degree of opening is set by the operator and shown on a control panel. This,
however, is not an automatic controller as that mentioned above, the LOX-level control using a
LIC. This HIC-valve is placed in the heating element of the reboiler and the LIN outlet. In this
example, we run the column only with products in liquid form. Later we will deal also with
operation with products in gaseous form.
To be able to see how much vapour is rising in the column we include a Pressure Difference
Indicator (PDI) in the columns upper and lower parts. This is because to increase the vapour
flow through the column trays, we must increase pressure a little more, i.e. increase the
pressure difference over the trays and vice versa in order to reduce the vapour flow. Therefore,
the pressure difference is a measure of vapour flow.
Vapour quantity in the column can be altered by changing the heat supply effect in the reboiler
using a HIC. Increased boiling means increased vapour quantity that rises in the column,
increasing the pressure difference on both PDI.
We have stable operation with a constant air quantity and the correct LOX and LIN take out,
which is in accordance with the material balance. This can be shown by seeing if the three
analyses (QI) are correct.
4.10 Increased vapour quantity
If we increase the vapour quantity in the column, the whole of this increase will go up to the
condenser. The condenser will condense everything and because the LIN outlet remains
unchanged the reflux quantity into the column will increase. This runs down through the entire
column and more oxygen is washed downwards in the column. The increased boiling strips off
more nitrogen. The purity of both the top products (LIN) and bottom product (LOX) increases
somewhat, and subsequently becomes constant. The reverse occurs for decreased vapour
quantity. In the figure the vapour quantity is chosen to get a normal reflux ratio. Other flows
are calculated with material balance. LA = liquid air, R = reflux.
Figure 4.7 Flows in a Single Column at Different Operating Cases.
When the purity of both products has become less, then the vapour quantity has been reduced
for some reason. The first thing to try is to open the heating valve more. The instrument
calibration can have been altered, so that it can appear that the valve is more open than it
actually is. If this does not help then it could be due to the fact that the reboiler surface is
clogged e g by carbon dioxide, which is deteriorating the heat transfer. Defrosting can cure this,
but if one can wait there is an alternative:
We can begin by trying to improve the top product purity by increasing the reflux, which
demands a reduced LIN-outlet. However, this causes a problem with the material balance, as
nitrogen is being pushed downwards in the column and finally contaminates the oxygen part at
the bottom. We must instead establish a reduced air input so that the LIN withdrawal
corresponds to what is being fed in. This then leads to a reduced oxygen quantity, but this is
automatically controlled, with the bottom liquid level, so that it is not a problem.
© Linde Gas AG Page 10 (109) 2001-02-20

LIN = 790
Reflux ratio =
= 1210/790 = 1,53
2000 R=2000-790=1210
LA=1000
2000 1210+1000=2210
Strip ratio =
= 2000/210 = 9,52
LOX=210
a) Start case
LIN=790+0
Reflux ratio =
= 1310/790 = 1,65
2000+100
R=1210+100
LA=1000+0
2000+100 2210+100
Strip ratio =
= 2100/210 = 10,0
LOX=210+0
b) increased boiling
Figure 4.7 Single column flows at different operating cases

Assume that we have received an increased vapour quantity. This improves purity. The vapour
quantity should then be reduced so that the purity gets somewhat better than has been specified.
Increased purity is more expensive, because of increased heat consumption. Customers shall
have a product with the guaranteed purity, no more or no less.
To be able to increase production capacity the heating capacity must also be increased. If we
increase air quantity and output of both products without increasing heating, then the reflux
quantity is reduced and the purity is degraded.
4.11 Maximum production
When more vapour presses through the holes in the trays, there will be more foam and splashes
over the liquid. When there is a too large quantity of vapour, the foam will rise up to the next
tray. This is serious as far as this tray is concerned because the liquid in the foam will contain a
higher oxygen content than the tray should have. Each higher tray will have gradually more
oxygen and the nitrogen is contaminated. This is called column flooding. On the pressure
difference meters this can be seen as an unstable value. What is the normal pressure drop (PDI)
in the column during stable operation and what is the pressure drop when flooding occurs can
only be learned by experiences.
4.12 Minimum production
When the vapour quantity is reduced too much the vapour in the holes cannot support the
liquid, which then begins to drop through. Because the liquid shall run over the whole tray
before it runs down over the drain outlet, the liquid that drops through the holes leaves far less
time for mixing with the vapour. This means that less quantities of nitrogen will be evaporated.
Consequently the nitrogen content is increased downwards and the oxygen part contaminated.
This is known as a "weeping column".
4.13 Changed composition in the feed
Even if it does not seem possible now, we shall see later than the feed O2 - N2 composition can
change, particularly when we have several columns.
Assume that the nitrogen content increases and the oxygen content is reduced in the feed. This
means that we should produce more top product, but we do not know whether the gas
composition has changed, so we do nothing. Earlier Figure 4.5c described what will happen.
The nitrogen drives the oxygen downward in the column, so that the QI-2 analysis decreases
and continues to decrease. This is a warning to us that we should take out more top product.
The bottom product output is controlled automatically by the level controller.
Conversely, if the nitrogen content decreases in the feed then we must take out less top
product.
© Linde Gas AG Page 11 (109) 2001-02-20

LIN = 790+79
Reflux ratio =
= 1131/869 = 1,30
2000+0 R=2000-790-79=1131
LA=1000+100
2000+0 1210+1000+100-79
=2210+21
Strip ratio =
= 2000/231 = 8,66
LOX=210+21
c) Increased air and production without increasing boiling
LIN=790+0
Reflux ratio =
= 1310/790 = 1,65
2000+100
R=1210+100
LA=900, GA=100
2000+0 1210+100+900
=2210+0
Strip ratio =
= 2000/210 = 9,52
LOX=210+0
d) Unchanged air flow with 10% vapour
Figure 4.8 Single column flows at different operating cases

4.14 Changed air feed
The air feed flow is normally controlled automatically. If some kind of disturbance occurs so
that the flow is altered and the controller cannot re-establish the flow to normal value, the
control loop must be investigated.
If we want to increase production of both top and bottom products, we must increase the
airflow due to material balance. As the air is liquid it runs downwards and there will be no
change of the vapour quantity. This gives unchanged quantity of condensate from the
condensor. If subsequently we increase the LIN output, the purity will deteriorate, because the
reflux quantity will be reduced. We must increase the vapour quantity by an equal value to the
air feed increase. This means that both the production and the reflux flow can be increased
equally. So we must increase reboiling by a sufficient amount, so that we obtain the correct
reflux ratio (= reflux quantity/LIN product) and that will be seen by getting the purities to their
correct level.
Figure 4.8 Flows in the Single Column of Different Operating Cases.
All changes in the column must be carried out in small steps, one change at a time, then wait to
see if the purity level goes in the right direction. It can take up to one hour to increase the air
flow, depending on how large the increase is. Which order the control actions take place is
decided by experience. A safe order is first to increase reboiling so that the purity values
increase. Then increase the airflow and try the correct increase of top product, so that the QI-2
analysis does not increase. When it starts to stabilise, increasing reboiling, airflow etc. occurs.
The airflow and boiling can be increased to a maximum, which results in a pressure difference
over the column, which we will learn, from experience, does not give flooding.
The reasoning gives that the reverse will occur when the air feed is reduced. Then decreased
boiling and decreasing quantity of the top product occurs.
4.15 Changed cold quantity in the feed
So far we have assumed that we have had liquid air at its boiling point as the feed. This implies
that in the bottom part of the column the liquid flow is much larger than in the upper part,
because the reflux liquid has been added. It is sometimes necessary to have a column with
larger distances between the trays in the lower part than those in the upper part to avoid
flooding.
What happens if the feed has for some reason warmed, so that it contains vapour as well? The
vapour will rise and smaller amounts of liquid will run down. There will be an increase in the
vapour quantity in the upper part of the column, which can then be seen on the upper pressure
difference meter. More vapour condenses and if the top output remains unchanged the reflux
increases. This leads to a slight improvement in purity of the top product, which later becomes
constant. However, because we have not increased the air quantity, we will not be able to take
out more nitrogen from the top due to material balance considerations. See figure 4.8d.
© Linde Gas AG Page 12 (109) 2001-02-20

A) Start case B) Increased boiling and reflux
C) Increased air and production D) Unchanged air flow

without increasing boiling with 10% vapour
Figure 4.9 Concentration profiles in different operating cases

There is no reason whatsoever to reduce the boiling in the bottom, as the vapour quantity will
be reduced in both parts of the column. Accordingly, we obtain the correct purity in the top but
possibly it will be too low at the bottom. It is therefore better to accept the new situation with
more vapour in the air feed. If possible, one should ensure that vapour is not present in the
feed, because it is also disturbing the condensor by increasing its load.
However, normally in our air separation plants, which as we will see later, the air is fed as
vapour, some degrees over or at the dew point (the temperature with cooling that the first drops
of liquid appear). If liquid is present in the feed it is a disturbance, which reduces the vapour
flow upwards through the column and the liquid runs down. Reduced vapour means that there
is reduced reflux, therefore reduced purity in the top, so that the top out-take must be reduced.
The best way to solve this problem is to ensure that there is no liquid in the air feed. Liquid in
the air feed can be caused by the wrong distribution of flows in the main heat exchanger and
recycle heat exchanger. More about this later.
Concluding, the concentration profiles of the column are shown for the different cases in 4.10-
11 and 4.14-15.
See figure 4.9 Concentration Profiles of Different Operating Cases.
4.16 Warning for "over-controlling"
We have looked at how distillation can be affected in different ways. Assume that a
disturbance occurs. That leads us to ask when must we do something?
We have a column, which is shown in figure 4.6 and we run the process with the desired purity
and stable production. Yet still there are continually small variations in analysis, pressure
differences and LOX-level, however, these are normal variations and we shall do nothing about
them.
It is not possible to say what are normal variations, due to different conditions in different
processes. We shall look at the process we are running and learn from experience which events
are normal variations.
We shall do nothing as long as those variations are normal, because each time we alter the
setting of a valve we cause a disturbance in the column. Perhaps later this disturbance must be
reversed by a new valve setting etc. To run the process in this manner is called “over-
controlling”.
So the answer to the question "When do we do something?" is:
We must do something when the value read-off an instrument is not normal (out of limits),
which means that it is more than the normal variation which we know from experience.
© Linde Gas AG Page 13 (109) 2001-02-20

5. AUTOMATIC CONTROLLERS AND INSTRUMENTATION
When we shall learn about how the processes function it is very important to understand how
all automatic controllers work. In the instruction manual from the process suppliers there are
lists of them. Study the controller one after the other. Look at the flow diagram (P&ID) and
start at the measurement points.
Measuring what? Look in the ring at the first letter (see 5.3). Which valve does the control
signal go to? Follow the dotted line to the valve. Then follow the process line from the valve
until you come back to the measurement point. Try to determine what to do if you want to
increase the process value. In the measurement point we should expect to the new process
value. What happens down stream of the control valve? What happens up stream of the
measurement point, what happens in the other stream if there is a split up stream?
5.1 Controller and instrumentation designations
A complete list of control designations can be found on the flow diagrams. The following are
the most important:
The first letter in the circle that symbolises a controller is used for the measured process
property. Sometimes there is an additional letter such as D in PD = Pressure Difference.
F = Flow
P = Pressure
T = Temperature
L = Level
H = Hand
Q = Quality
S = Speed
U = multi-variable
K = time schedule
The succeeding letters are used to designate the function of the controller:
A = Alarm
C = Control
E = primary Element
I = Indicating
T = Transmitting
V = Valve
X = computing relay
S = Switch
Z = trip
The primary element, E is not a measuring instrument. It takes some form of signal from the
process line and leads it onto a transmitter. For pressure, PE this is just a tube with a shut-off
valve. For flow, FE it is usually an orifice plate in the process line which gives one pressure
before and one after. For temperature, TE it is an electric resistance in a pocket in the process
line. Measuring instruments are designated PI for example.
© Linde Gas AG Page 14 (109) 2001-02-20

Figure 5.1 Orifice plate for flow measurement
p1 p2
Figure 5.2 Calculation of flow in an orifice plate.

Plant: Porcheville Date: 21 Nov -88
Barometer: 1004 mbar
FLOW CALCULATION
Tag No. FIC 63 GAN
Panel instrument 18000 Nm3/h
Temperature, TI- 63 8 °C = 281,2 °K
Pressure, PI- 63 0,17 barg = 1,174 bara
Precision manometer ….. barg = ......... bara
Precision ∆p meter (U-tube) 236 mm wg = 23,14 mbar
Design pressure 1,039 bara

temperature 282,5 °K
max. flow 25 000 Nm3/h
corresp. ∆p ............. mm wg = 50 mbar
Factor = Max.flow/√∆p = 3536
1,174 282 ,5
Flow = 3536 • √23,14 √( • )= 18 117 Nm3/h
1,039 281,2
Nm3 at 0°C and 760 mm Hg

5.2 Flow measurement with orifice plate (New in version 4)
The most common way of measuring flow rate is by using an orifice plate. This is a disc with
a precision drilled hole, fitted between the flanges of a pipe.
See figure 5.1 Orifice Plate for Flow Measurement.
When a gas or liquid flows through an orifice its velocity increases and a small drop in
pressure occurs, that is proportional to the square of the flow. There are formulas that can be
used to calculate the flow from the measured drop in pressure, depending on the relationship
between the diameter of the pipe and the orifice, pressure, temperature and density. So the
measured drop in pressure, ∆p, gives a signal that is calculated in the process computer
together with the orifice factor, K, to a flow F, Nm3/h.
F = K • √∆p
This applies for design pressure and design temperature. If these deviate the correct flow can
be calculated with the formula:
p Td
F = K • √∆p • √ ( • )
pd T
P = actual pressure (bar abs)
Pd = design pressure (bar abs)
T = actual temperature (K)
Td = design temperature (K)
Due to the dependency on pressure and temperature, the more important flow meters are also
connected to pressure and temperature sensors, so that the flow can be accurately calculated.
This is referred to as compensation of pressure and temperature.
The disadvantage of orifice plates is that they require relatively long straight lengths of pipe
before and after the plate to achieve accurate measuring. This affects the pipe lay out and can
increase costs. Cryogenic liquids are difficult to measure because they are so close to boiling
point and the small ∆p involved can be sufficient to result in boiling. This will disturb
measuring significantly.
Other meters that are based on ∆p are the venturi tube and the V-cone. The venturi is a
constricted throat-like passage, i.e. a piece of pipe that is tapered on each side of a
constriction. The V-cone is a throttle consisting of a cone in a pipe of unchanged diameter.
Both of these require smaller straight stretches before and after.
An example of how one checks and calculates a flow is enclosed. The orifice plate factor is
calculated with the aid of its design data. The flow is read on the panel and ∆p is measured
with a precision gauge. Temperature and pressure are read on the panel (as an alternative the
pressure can be checked using a precision gauge) and converted to absolute values. The real
flow is calculated using the formula and then compared with the panel value. A calibration
should be made if deviation is too great. The formula can also be used to calculate the real
flow through an orifice plate, which is not compensated for pressure and temperature.
See figure 5.2 Calculation of Flow through an Orifice Plate.
© Linde Gas AG Page 15 (109) 2001-02-20

5.3 Function of a controller
Take as an example a pressure controller, PIC. On detailed flow charts not only the PIC but
also all of its components are drawn. The components are a measurement point (PE), a
transmitter (PT) of the measured value, a control unit (PIC), which displays the measured value
and a correction unit (control valve, PCV).
Output signal
PE PT PIC
Process flow PCV
A pressure signal is taken from the measuring point, PE, which is sent to the transmitter (PT).
The pressure value is converted in the transmitter to an electrical signal (4-20mA), which is
sent to the control unit (PIC). There the actual pressure is calculated, the value of which is
indicated and is then compared with the set point pressure value (desired pressure). If the
difference between the two is larger than a pre-determined difference value, then a signal
(output signal) is sent to an actuator on the control valve to open or close by some amount, to
correct the pressure. The valve corrects the pressure value until the difference between the set-
point and actual value is less than the pre-determined value, e.g. +/- 0,1 %. It is not always that
the actual pressure value obtained is exactly that of the set-point value.
A controller that is set at the “Auto” mode works automatically. It may also be set to the
“Man” mode, i.e. manual setting of the valve opening. In this mode the valve works as a HIC
(see below). A good way to quickly get some idea of possible problems when coming for the
first time to an installation is to see if any controllers are in the “Man” mode and then check
why.
There is also indication of how large the output signal from the PIC is (in %) to the actuator on
the control valve. This can be used to see if the valve is operating or not. There is a dis-
advantage with this, which is that the actuator may work poorly but the correct output signal
comes to it. Therefore one must regularly inspect the actuator. The actuator is denoted in the
figure above by a small ring connected with a line to the valve.
5.4 Output signal from a controller (New in version 4)
The output signal is very important for understanding how an automatic controller and also
the actual process works. When you study a controller look how the output signal changes,
especially if some interference has occurred when you have altered the set point. In modern
installations that have computer control one can set the output signal in trend, i.e. its
variations in relation to time are displayed in a diagram. This is recommended when a
problem has occurred in the process or when it is necessary to tune the way in which the
controller is working.
© Linde Gas AG Page 16 (109) 2001-02-20

A control valve in the Auto mode is never completely still and the output signal varies
continually. You will learn by experience what are normal variations. With the help of the
trend you can see if there is any deviation from normal. You can also see when maximum
capacity is obtained at any position, e.g. if a FIC does not attain the set point but the output
signal is 100%, i.e. fully open valve.
The output signal shows you how you should have set the valve, if there had been no
automatic mode. The object of the controllers is to enable running of the process in a smooth
and satisfactory manner so that the enormous flows of material and energy (nowadays often
more than 100,000 kg/h and 10 MW) move forward with small ripples on the surface. The
system can also be run with a smaller margin to the limit values, thus giving smaller losses.
In computerised systems the controllers are controlled by software. This can, in principle, be
modified so that any signal can be used to control any valve. New cascade coupling of
controllers can also be made. Consequently, the initial settings are not at all fixed forever.
5.5 Overview of Normal Controllers
HIC = Hand Indicating Controller. A hand-operated valve (not automatic) that shows how
many percent the valve is open. Often used for reflux to the upper column or LIN to tank in
older plants, however rare in new ones.
FIC = Flow Indicating Controller. Often used for air to a cold box, GAN from cold box and in
combination with a pressure meter for surge protection of the large compressors (see Chapter 9
and below).
PIC = Pressure Indicating Controller. Often used for impure N2 from the upper column and to
the mole sieve regeneration gas.
TIC = Temperature Indicating Controller ("thermostat"). Used for electrical heaters used in
regenerating mole sieves.
QIC = Quality (= analysis) Indicating Controller. Used to control GOX purity by analysing the
argon zone and controlling the GOX valve.
LIC = Level Indicating Controller. Used for the liquid levels in the bottom of the columns,
condensers and liquid separators.
KC = Time Control Timer. Used for mole sieve change sequence, which is opening and closing
valves in a certain order of time.
5.6 Connected controllers
There are a number of controllers that work in co-operation with others. They can vary between
different plants. Here we will look at some common combinations.
See figure 5.3 Connected Controllers
© Linde Gas AG Page 17 (109) 2001-02-20

(a) FCV-3930
GAN Atmosphere
TC5,
feed
Flow more than FIC
approx. 9300 3930
Recycle
Flow less than FIC
approx. 9300 3931
FCV-3931
(b)
Process
PT FT
FX FIC Blow-off
PI HIC
Atmosphere
(c) TC1
After Coldbox
mole sieves
TE PT FT
FIC
2615 FX
Figure 5.3 Connected Controllers

• Split range. This means that a measurement range is split at a certain value. Under this
value, one valve is controlled and above this value another valve is controlled. An example
is a feed compressor in Eggborough, England. The split value is 9300 Nm3/h, which is the
design flow for the compressor. When the flow is more than 9300, the compressor is
operating at its maximum, so that valve FCV-3930 (GAN to atmosphere) is controlled. With
flows of less than 9300 Nm3/h, the feed compressor is not at maximum, so the FCV-3930 is
completely closed and the guide vanes (FCV-3931) on the compressor are controlled,
controlling the flow in the compressor (see Figure 5.3a and 9.5).
• Cascade or remote set point = RSP. This means that the output signal from a controller
does not go to a valve, but to another controller that monitors a valve. This is to obtain a
more stable control. An example is oxygen analysis (QIC) somewhat over the reboiler that
goes to a FIC that monitors the GOX take out valve (See 6.6).
• Compressor surge protection. With certain pressures and flows a compressor can be in an
unstable condition which will damage it (see chapter 9 "Compressor"). Therefore both
pressure and flow at the outlet are measured and in a calculation unit (FX) it is determined
whether the compressor is operating within safe limits. If not, a signal goes to the FIC to
open a valve to discharge to the atmosphere (see Figure 5.3b).
• Pressure and temperature compensation for flow meters. Gas volume depends on both
pressure and temperature. By measuring these, then a calculation unit (FX) can provide the
correct flow value even if the pressure and temperature vary. Figure 5.3c shows flow
measurement of air after a mole sieve, where pressure changes at a sieve change and
temperature changes after the cooling period. See Chapter 8 for more details on sieve
changes.
The automation of the plants is increasing. There are a few which are unmanned in nights and
one (Sept. 98) which is operated from another plant. This demands more configuration of the
process computer and more remote controlled valves. The plant must among others be able to
stop in a safe position. There is also process control for optimum operation in different
operating cases. This is different control loops, which consist of calculation equations which
changes the set point of several controllers. There is e.g. one loop for choosing a certain
LOX/LIN production, one for maximising the reflux to the upper column, one for maintaining
the argon cloud, etc.
5.7 Alarms, switches and trips
The purpose of operating with alarms (A), switches (S) and trips (Z) is safety and protection of
the plant. For each process value is defined a range of permitted values. Outside this, both
below and above, is defined a range for alarm. Outside the alarm range a signal goes to trip or
to a switch which is taking some kind of action.
The large compressors have trips for oil temperature (TIZA) and oil pressure (PIZA), bearing
temperature and shaft vibration. Electrical heaters have trips for temperature (TIZA). Liquid
products to tank have switches for purity (QISA). At impure product the valve to tank is closed
and the valve to evaporation is opened.
© Linde Gas AG Page 18 (109) 2001-02-20

Gaseous Reflux 1
Nitrogen
"Low" pressure
2
Gaseous
Oxygen 3
Liquid Reboiler- Liquid

Oxygen Condenser Nitrogen
"High" pressure
Air
Rich Liquid
Figure 6.1 The Linde Double Column

6. LINDES DOUBLE COLUMN (without argon)
6.1 Description of the Parts of Double Columns
Nearly always in air separation plants are a combination of two columns used. It was the idea
of Dr Carl von Linde, founder of the Linde Company, to build together two columns, as shown
in Figure 6.1.
See figure 6.1 Linde Double Column.
The lower part is a "half" single column with a condenser in the top and an air feed in the
bottom. The upper part is a single column without a condenser but with a reboiler. The
condenser in the lower column acts as the reboiler for the upper column. In the figure a tube
type condenser is shown, which is used in older plants.
Air is fed to the bottom of the lower column, normally at a temperature that is just above the
dew point. Vapour rises up the column to the condenser and forms a reflux. Air cannot be fed
in liquid form to this column, as it does not contain a reboiler that is required to create vapour.
We have seen already that at the top of the column, there is pure nitrogen as it has a lower
boiling point than oxygen. The bottom product will not be pure, however compared with the air
that was fed in, it is oxygen rich as nitrogen has been taken out as top product. The bottom
product, known as "rich liquid", contains approx. 35-40 % oxygen.
The rich liquid is then fed to the centre part of the upper column for further separation. In this
column there is no condenser, but reflux is taken from the pure top product of the lower
column. At the bottom of the column, there is a reboiler, which is heated from the condensing
of nitrogen in the lower column. There, the upper column can also distillate and we have pure
oxygen at the bottom, as oxygen has a higher boiling point than nitrogen.
To be able to take out liquid product, cold (or some liquid) must be supplied. This is usually
carried-out by taking GAN from the top of the lower column to the so called recycle, where
liquid nitrogen is produced and is fed back to the same place in the lower column.
6.2 Boiling Point Depends on LOX and LIN Pressure
For a double column to function the LOX must boil and GAN is condensed to LIN. At
atmospheric pressure this will not happen as LIN is colder (-196°C) than LOX (-183°C). You
cannot heat with something that is colder.
In order to achieve this, the nitrogen pressure must be raised (as this raises the boiling point).
Figure 6.2 shows how the boiling points of LOX and LIN depend on the pressure.
See figure 6.2 Vapour Pressure Curves for O2 and N2.
© Linde Gas AG Page 19 (109) 2001-02-20

Figure 6.2 Nitrogen and oxygen vapour pressures
8,0
7,5
Pressure (bar abs) LIN GAN
7,0
6,5
N2 O2
6,0
5,5
5,0
LOX GOX
4,5
4,0
3,5
3,0
2,5
2,0
∆ T=2,5 K required
1,5 temperature difference
for heat tranfer
1,0
0,5
0,0
76 78 80 82 84 86 88 90 92 94 96 98 100 102 104 106 108 110 112 114 116
Temperature (K)
The vertical axis of the diagram represents pressure from 0 to 7,5 bar absolute. In diagrams and
tables absolute pressure is often used, which implies that 0 bar absolute = vacuum and 1 bar
abs is approximately sea level atmospheric pressure. But in air separation plants, overpressure
is always used, in comparison to atmospheric, where 0 bar = 1 bar abs = atmospheric pressure
and 1 bar = 2 bar absolute. This is used for practical reasons, as it is much easier to
manufacture a pressure meter that measures overpressure. To separate the two units we
sometimes write it as bar g (g = gauge).
The horizontal scale of the diagram represents temperature from 76 K to 116 K. This
corresponds to degrees C: -197°C to -157°C. The curves in the diagram then shows the
relationship between pressure and temperature. Usually these are known as the vapour pressure
curves.
Use the diagram as follows: For example, if you wish to know the boiling point of LIN at 4,5
bar g, you use a ruler and draw a line from 5,5 bar (absolute) on the vertical scale, horizontally
right until you reach the LIN-curve. Then draw a line vertically downwards from that point to
the temperature scale and read off the temperature, slightly more than 95 K = -178°C. You can
now see that this is some degrees warmer than LOX at 1 bar (absolute).
The LOX pressure in the upper column is around 0,5 bar g = 1,5 bar a higher than atmospheric
pressure. How this is determined we will see later. In the diagram a line has been drawn from
this pressure to the LOX curve, where the temperature can be read off as 94 K = -179°C. Often
a temperature difference of 2,5°C (= K) is required so that heat can be transferred from LIN to
LOX. Therefore the LIN temperature must be 94 + 2,5 = 96 K. If you use degrees Celsius you
must be aware of what is warmer and what is colder. It is more evident to use Kelvin.
Now we can read off what pressure LIN has at 96,5 K, by following the line from this
temperature to the LIN curve. From the LIN line we can read off the pressure scale, 6,0 bar
(absolute) = 5,0 bar g. The lower column must therefore operate at this pressure. Because of the
pressures the lower column is often called the pressure column and the upper is called the low-
pressure column.
At the boiling of LOX heat is taken from GAN which is condensed to LIN. If the pressure of a
liquid at the boiling point is decreased, then it starts to boil without supplying heat. This
phenomenon is very common and is called flash. The heat is taken from the remaining liquid
and the temperature decreases until it becomes what the vapour pressure curve predicts and
then the boiling ceases. This is the foundation of cold production in a refrigeration machine
(chapter 10).
6.3 How a reboiler - condenser functions
What must we do to maintain the lower column at the desired pressure? To answer this
question we must study how condensers work. It is a heat exchanger that transfers heat from a
warmer medium to a colder one. More information is given about heat exchangers in chapter 7.
The capacity of a condenser is determined by:
(a) Condensation area of the condenser. The larger the area then more heat transfer takes
place, and vice versa.
© Linde Gas AG Page 20 (109) 2001-02-20

Pure Nitrogen,
GAN QI-6
Reflux
HIC
HIC
Impure
Nitrogen,
QI-5
Lachmann
QIC QI-4
FIC QI-3
GOX
LOX 0,5 bar -179o
-176,5
LIC
LIN
LOX
LIN LIN
QI-2 GAN 5,0 bar
QI-1
Air
LIC
Figure 6.3 The Linde Double Column with Lachmann Exit

(b) Difference in temperature (T) between the LOX and LIN sides. The greater the difference
then more heat transfer takes place, and vice versa. This difference is often called ∆T
(delta t, where delta = difference).
Now if we push in air into the pressure column and we ensure that no gas can escape, thus all
the gas will condense. In your plant the condenser area is determined and you cannot alter it.
The only thing that we can alter is the temperature difference.
The oxygen in the upper columns lower part boils at a determined pressure, and therefore the
temperature is also determined. The condensation temperature of the gas in the top of the
pressure column is the only thing we can alter.
If, however, we increase the quantity of air fed to the column a larger quantity of nitrogen must
condense. The rate of condensation in the condenser is not sufficient for this larger quantity and
if the gas does not condense the pressure rises. Higher pressure means that the condensation
temperature is higher and therefore it follows that the temperature difference ∆T rises, until the
condensation of the condenser is sufficient again to condense all of the nitrogen.
Now we have found the answer to our question. We do not need to do anything to maintain the
desired pressure in the pressure column. It is maintained automatically at the correct pressure,
sufficient so that all nitrogen will condense. We do not need to try to change this pressure,
which is good as we have one less consideration to worry about.
6.4 Controlling a double column
See figure 6.3 The Linde Double Column with Lachmann Outlet.
In the upper part of the lower column there is a container to collect condensed LIN. The LIN
from the container is fed to the upper column as reflux and is taken out as LIN product. The
LIN, which is not taken out of this container, runs over the top edge and becomes reflux in the
lower column. Because the lower column is at a higher pressure than the upper column, the
liquid is easily pushed up to the top of the upper column. However these days there is a
installation, Stenungsund, Sweden with extra high columns, where pressurised cold gas is used
in order to pump liquid up to the upper column.
The reflux in the lower column washes out more and more oxygen and in the bottom there will
be approximately 37 % O2, the rich liquid. This is taken out through a valve, which is
controlled by a level controller (LIC).
The material balance can be shown as air-in = LIN + rich liquid. As we want to control the LIN
outlet and the air feed will be constant, only the rich liquid remains. Therefore the rich liquid is
controlled by its level. This means that if we increase the LIN outlet, then there will be less rich
liquid and vice versa.
From our study of single columns, we know that LIN purity depends on the reflux ratio. As
there is no reboiler in the lower column, and all incoming air is in gaseous form, which
completely condenses, the LIN purity solely depends on how much is taken out from the
lower column.
© Linde Gas AG Page 21 (109) 2001-02-20

Pure Nitrogen,
GAN QI-6
Reflux
HIC
HIC
Impure
Nitrogen,
QI-5
Lachmann
QIC QI-4
FIC QI-3
GOX
LOX 0,5 bar -179o
-176,5
LIC
LIN
LOX
LIN LIN
QI-2 GAN 5,0 bar
QI-1
Air
LIC

A large withdrawal means that there is little reflux remaining in the lower column with
consequently reduced purity and vice versa with a small take out. The correct action is to take
out as much as is possible without the specified LIN purity being exceeded, e g 3 ppm O2
measured by QI-2. This is that as much reflux as possible is fed to the top of the upper column
after producing LIN to the tank.
In older plants there are often two refluxes, one pure and one impure. Sometimes there is only
an impure reflux. In Sweden only Sandviken does not have pure reflux. Here the impure reflux
is taken out some trays down from the top and is sent to the upper column at the Lachmann
outlet (see below). In newer plants with internal compression and a big airflow these refluxes
exist.
It can be difficult to see the changes in the O2 content in the top of the lower column, which
was mentioned earlier for the single column, in 4.7. Many plants have an extra analysis point
QI-1 in the lower parts of columns, where the analysis result is a couple of % or a few 100 ppm
O2 in the upper part. Through this analysis point an earlier warning can be given, if the O2
content rises so much that it prevents the purity at the top from being recovered.
With a maximum amount of reflux in the upper column, as much oxygen as is possible is
washed down to the bottom and can be taken out as LOX and GOX. This includes the loss of
oxygen with the top GAN being as little as possible. Again we can use the material balance for
an explanation. All oxygen, which comes into the lower column with air goes to the upper
column, with the rich liquid and that which goes into the upper column goes out. Therefore the
oxygen which cannot be taken out from the bottom must go out of the top.
6.5 Lachmann Outlet (impure nitrogen)
The main problem with the upper column is reflux deficiency. It is not possible to take out
GAN from the top, which has the same purity as the reflux (e.g. 3ppm O2). Pure GAN can be
delivered by pipeline to nearby customers or can be used in a future liquefier where LIN is
obtained.
It helps the reflux deficiency to reduce the gas quantity in the top. This can be done by taking
out gas from around the centre point between the top and the rich liquid feed. This is called a
Lachmann outlet, after its inventor. As much impure nitrogen is removed from this outlet, as is
sufficient the reflux to achieve the required purity of the GAN at the top.
Using an oxygen analyser QI-5 on this Lachmann gas we get the warning of any change in the
oxygen content below the top, as was mentioned in the description of the single column in 4.7.
We also have pure GAN in the top of the lower column, but it is not good to take this out as
pure GAN product. The GAN, which is taken out there, will reduce the GAN quantity to the
condenser and consequently reduce the quantity of LIN available for reflux in the upper and
lower column. We have already seen that there is a shortage of reflux here. Cold production in
the recycle does not disturb the reflux, as GAN is taken out and LIN sent back which becomes
reflux. But there is always leakage in the recycle, turbo compressors have a small amount of
leakage in labyrinth sealings. Normally, these leakages are not large, but if they increase the
reflux to the upper column will be reduced.
© Linde Gas AG Page 22 (109) 2001-02-20

Pure Nitrogen,
GAN QI-6
Reflux
HIC
HIC
Impure
Nitrogen,
QI-5
Lachmann
QIC QI-4
FIC QI-3
GOX
LOX 0,5 bar -179o
-176,5
LIC
LIN
LOX
LIN LIN
QI-2 GAN 5,0 bar
QI-1
Air
LIC

6.6 Controlling the Oxygen Purity in the Upper Column
LOX is taken out of the bottom of the upper column using LIC-level control. Above the highest
LOX-level GOX is taken out. If, as mentioned earlier in 6.4, the reflux is at its maximum
value, we have the best possibilities to wash down oxygen in the upper parts of the column.
The LOX-purity is influenced by the reflux condition in the lower part. There the reflux flow is
the same as the sum of the rich liquid and reflux quantities from the top. These two are fed
from the lower column and the sum of them is identical to the air fed in minus the LIN
production, according to the material balance. So the reflux flow in the lower part of the upper
column is not affected by changes in the reflux to the upper column, but only by the LIN
production, which for the moment we will not alter. To be able to influence LOX purity we
must be able to affect the reflux condition and this can be affected through the vapour quantity.
The vapour quantity depends on the condensation of GAN, which depends on the air quantity.
As this does not change, the only thing left to do is to change the GOX take out, then the
vapour quantity will change, and consequently the oxygen purity. Compare with 4.6: More
vapour in comparison with liquid means that the liquid becomes purer. The vapour drives out
the N2 impurity from the liquid.
To obtain a high oxygen purity a large quantity of rising vapour is required, i.e. a small GOX
take out as the oxygen pushes the nitrogen upwards and consequently increases purity. The
rising oxygen must go out somewhere. In our case this will be through the Lachmann outlet.
Therefore oxygen is lost there. On the other hand if the purity is decreased then the GOX take
out is increased. This increase of GOX is usually a loss, because it can only be utilised in a
plant with a GOX pipeline client where there is buffer capacity. So, the purity should be set in
accordance to the plant specification, normally 99,6 % GOX and 99,7 % LOX.
Why is the GOX purity less than that of LOX? To answer that question we must go back to the
distillation principles given in chapter 4. LOX is the component that has the highest boiling
point and collects at the bottom of the column. Contaminants in LOX have a lower boiling
point than the LOX and therefore will boil off a little easier, which means that their
concentration in the gas increases.
If we look closely at the reasons for the changed oxygen purity, it is to a great extent that they
depend more on the material balance than on the reflux condition. Changing the oxygen purity
requires changing the GOX take out by only a few hundred m3/h. This gives a small change in
the reflux condition, as the total amount of vapour quantity in the lower part of the column is
the same order of size as the air quantity, i e a couple of 10000 m3/h. A change in order of size
of one percent. This is more important that when we take out oxygen, which it does not
correspond with the material balance (=oxygen quantity in the incoming air, see 4.7), it alters
the concentration of oxygen in the entire column. Oxygen presses up with too little oxygen
withdrawal and is drawn down with too much take out.
© Linde Gas AG Page 23 (109) 2001-02-20

o
GAN -194
HIC
0,26 0,26 bar

LIC bar
PIC
0,1 bar Impure N2

-193o
LIN
-195o
PIC
o
-187
0,1 bar
PIC -183o
0,5 bar
LOX LIN
o
-182 -177
o
-175,5o 4,8 bar
o
GAN -174
Impure N2 -174o
LIC
o
RL -172,5
LOX -178,5o
GOX
Figure 6.4 Double Column, with Subcooler

(Eggborough, England)
The most common control of LOX purity is carried out using an analyser some way up the
column. Here there will be time to alter the control before too many contaminants run down
into the LOX. The analyser controls an automatic valve on the GOX outlet using a QIC. Often
the analyser controls a flow-controlling valve on the GOX outlet using a FIC, as it gives more
stable control. To sum up the GOX valve controls the purity of GOX and LOX. The oxygen
content in the whole column is affected. Reduced GOX withdrawal means higher GOX purity
and higher oxygen content in the whole column. The reverse applies for a larger GOX
withdrawal.
In newer plants, like Tepeji del Rio, Mexico, the O2 purity is not controlled in this way. There
no GOX is taken out when max LOX is produced. The LOX purity is controlled by changing
the concentration profile in the column with the LIN production which changes the reflux. The
LIN valve is controlled by the analysis of the Lachmann gas.
6.7 Subcooling of Liquid Products, flash of boiling liquids (revised for version 4)
The liquid products LOX and LIN are taken out of the columns, boiling at temperatures of
approximately -179°C respectively -177°C. As the pressure in the tanks (both approximately
0,1 bar g) are much lower than in the columns; LOX approx 0,5 bar and LIN approx 5 bar, the
boil-off would be considerable if the products were fed directly to tank. From the vapour
pressure curves at the beginning of this chapter we know that as pressure drops the boiling
point is reduced, so that boiling increases and gas forms which leaves the tanks. The heat is
taken from the liquid and the temperature sinks, until it becomes what the vapour pressure
curve predicts, then the boiling ceases. This boil-off because of reduced pressure is called
flash.
Flash in tanks is a loss of both gas and cold and can be countered by subcooling of the LOX
and LIN. Moreover there will also be boil-off from the tanks due to heat conduction from the
ambient through the insulation, the walls are always somewhat warmer than the liquid. This
depends on the quality of the insulation, its thickness and it is relatively small at approx 50-100
Nm3/h.
Subcooling is carried out in a heat exchanger, where the LOX and LIN meet GAN and impure
nitrogen, which are at -194° C and -193° C respectively. This has the advantage that the GAN
and impure nitrogen are then partly warmed up (to -174° C, or a few degrees colder), so that
when they enter the cold end of the main heat exchanger the ∆t to the outgoing air will only be
a few degrees. The air comes out at the dew point, which at 5 bar is -172°. It is not economic
with large ∆T, as it does not contribute to the heat transfer. The subcooler is sometimes
combined for LOX, LIN reflux and rich liquid, but sometimes separate heat exchangers are
used.
See figure 6.4 Double Column with Subcooling.
LOX can be subcooled to -187°C. As LOX in the tank boils at -182°C the subcooling to -187°
C is adequate, to also compensate for heat leakage in the tanks. This means that with
subcooling the tank boil-off can be reduced to zero. Figure 6.4 shows that the tank pressure
controls the LOX subcooling, using a PIC controlling the LOX flow bypassing the heat
exchanger.
© Linde Gas AG Page 24 (109) 2001-02-20

o
GAN -194
HIC
0,26 0,26 bar

LIC bar
PIC
0,1 bar Impure N2

-193o
LIN
-195o
PIC
o
-187
0,1 bar
PIC -183o
0,5 bar
LOX LIN
o
-182 -177
o
-175,5o 4,8 bar
o
GAN -174
Impure N2 -174o
LIC
o
RL -172,5
LOX -178,5o
GOX
Figure 6.4 Double Column, with Subcooler

(Eggborough, England)
Usually however a TIC control is used, which can be used in the same way: LOX temperature
is set so low that evaporation from the tank is reduced to almost nothing, which means that
tank pressure remains constant. If there is hand control it is not possible to operate with 0 boil-
off, because then there is the risk of under pressure at filling of tankers. Sometimes there is a
pressure build up coil in order to avoid this under pressure.
LIN goes through the subcooler with the pressure of the pressure column and consequently its
temperature will be sufficiently high to be able to be cooled by GAN. The cooling decreases
the boil-off after expansion to tank pressure but not completely. Therefore the gas is separated
in a vessel, the flash vessel, and goes to the GAN pipe from the column top. The temperature
of the boiling liquid is depending on the pressure and is -194° and cannot be cooled further.
LIN is subcooled in order to get as much as reflux possible. Moreover the flash vessel becomes
smaller.
In a few older plants there is a pressure controller on the boil-off of this vessel. This pressure
shall be set as low as possible in order to obtain as small boil-off as possible from the tank. The
boil-off of the vessel goes to heat exchanger and the cold is utilised. In a few plants this vessel
for separation of GAN from LIN is combined with the top of the upper column (see figure 6.6).
In the case where the reflux is cooled in a separate subcooler, it is important that it is cooled
sufficiently as the evaporation caused by the pressure drop will mean a decrease in the
available reflux liquid to the upper column. Without subcooling LIN evaporation is approx. 20
%, with a pressure drop from 5 bar to 0,1 bar.
6.8 Increased Reflux Quantity through the GAN Feed
It is possible to increase the reflux quantity in the lower column, by feeding pure cold GAN at
the top. This GAN rises to the condenser and LIN reflux is obtained, which gives more LOX
boiling. The GAN is taken from the top of the upper column, is warmed up and compressed to
a suitable pressure to be pushed into the lower column, after having been cooled down in a heat
exchanger. More details of this are given in 13.3 and figure 13.2.
Because of this installation the GAN purity in the upper column is important, even if this GAN
will not go to any customer. The purity shall not be any worse than that exists in the top of the
lower column. This is because the impure GAN feed gives a small increase in the oxygen
content in the top of the lower column. This can give the impression that a problem lies in the
lower column and that the quantity of reflux to the upper column must be reduced, so that there
will be more reflux in the lower column, which will worsen the situation.
6.9 Summary of the Function of a Double Column Using Material Balances
We have mentioned what a material balance is (4.7). What goes into the process must go out. If
we measure the airflow and all products, we see that the sum of the products is the same as the
airflow. This applies, of course, also for each one of the air components; O2, N2 and Ar and all
incoming are the same as the output.
© Linde Gas AG Page 25 (109) 2001-02-20

HIC
HIC
LIN
product
RL
Material
Balance
Boundary
LIN
Air in RL
LIC
Figure 6.5 Lower Column, Material Balance

We ignore argon for the moment. Now two material balances can be calculated, for total flow
and oxygen flow respectively. For the oxygen balance one must know the oxygen content in all
flows. In air there is 21 % O2, in LOX 99,7 %, in GOX 99,6 %, in LIN and GAN approx. 1
ppm and in impure nitrogen 50 ppm to 0,3 % depending upon the process. One ppm is an
abbreviation for one part per million, so the oxygen quantity in LIN and GAN can be taken as
being practically nothing and can be ignored. Also 50 ppm O2 can be ignored.
Total balance: Air = LOX + GOX + LIN+ GAN + impure N2 (in Nm3/h)
Oxygen balance: 0,21 • air = 0,997 • LOX+ 0,996 • GOX + 0,003 • impure N2
The total balance should also include gases leaking from the nitrogen recycle for cold
production.
A material balance can also be calculated for smaller parts of the process; for a process vessel,
for a T-pipe, or in fact anywhere the flow splits or mixes. To carry out a correct material the
following aids are available.
Draw a ring around the process vessel or flow splitting for which a material is to be calculated.
Only the flows which cross the ring shall be included in the balance. Flows which are
completely on the outside or inside the ring shall not be included.
Take as an example the lower column where air enters and LIN and rich liquid (RL) go out. We
ignore for the moment nitrogen losses in the recycle and from the GAN-feed.
See figure 6.5 Lower Column, Material Balance.
The airflow is constant. The LIN flow can be changed with a manual valve, but the rich liquid
is controlled by a level controller. This determines the size of the rich liquid take out after the
LIN take out depending on how much is available. So if we increase the LIN take out the rich
liquid is reduced and vice versa.
Total balance: Air = LIN + RL (in Nm3/h)

Oxygen balance: 0,21 • Air = LIN/1 000 000 + X • RL
X is the oxygen content in the rich liquid and is normally 35 to 40 %. We do not need to
calculate the equation, for we see that all oxygen goes out in the rich liquid, as 1 ppm in LIN is
practically nothing. However, if we know the O2 analysis (=X) in the rich liquid, we can
calculate the quantity of LIN and the rich liquid.
In the first equation we can see that if we increase the LIN the RL must be reduced, as the air
feed has not been changed. In the second equation we can see that with the reduced RL the
oxygen content must increase. The oxygen quantity in the air feed is not altered and with
smaller amounts of RL the oxygen content in the RL then takes a larger part of the RL.
Therefore the oxygen content increases with increased LIN take out.
6.10 Material Balance Inside the Double Column
See figure 6.6 Double Column, showing Internal Flows.
The material balance for the gas at the bottom of the lower column is ringed in Fig 6.6 point 1.
© Linde Gas AG Page 26 (109) 2001-02-20

GAN
HIC
GAN-up
3 HIC
Impure N2 6
LIN-Prod.
N2-up Reflux-UC RL
4
GOX-up
GOX 5
Reflux-O2
GOX-Boil
LOX
LIN-
GAN- cond.
cond. 2
GAN- Reflux-LC LIN-UC

-Up
Air
Air in 1 Up RL
LIC
Figure 6.6 Double Column, showing Internal Flows

Air-in = Air-up (Figure 6.6.1)
The air in is somewhat warmer than the dew point, so it is entirely a gas that must keep rising
up in the column. There is, of course, a continuing exchange with the downwards running
liquid (reflux). But the part of the gas that condenses is very similar to that part of the liquid
that vaporises, so the two flows balance each other out. This applies as well for all of the
following material balances inside the column. Air-in is practically equal to the air rising up
from the bottom of the column.
The rising air gradually increases its nitrogen content, until it becomes pure nitrogen at the
column top (GAN-up). The increase is from 78 % to 100 % nitrogen, which is not a
particularly large change, so GAN-up is similar to Air-in. GAN-up depends as well directly on
how much air goes in.
This GAN goes into the condenser and becomes LIN-cond. Material balance: GAN-up = LIN-
cond.
The LIN runs down into an open container from which reflux for the upper column and LIN
product is taken out, LIN-UC. That which is not taken out runs over the edge of the container
and becomes reflux for the lower column (Reflux-LC). Material balance for the container
becomes (ringed in Figure 6.6, point 2):
LIN-cond = LIN-UC + Reflux-LC (see Figure 6.6.2).
LIN-cond depends upon Air-in, via GAN-up and Air-up, so this is not changed. Therefore if
LIN-UC increases, Reflux-LC decreases. Reduced Reflux-LC gives reduced LIN purity. If we
have very pure LIN, we should increase LIN-UC until the purity is close to what has been
specified for the installation, often 1 ppm O2. Using this method we can feed the most possible
reflux to the upper column.
The LIN-UC goes into the top of the upper column into a container, equal to that in the lower
column, from which LIN-product is taken out. This method is used, as much gas is formed
after expansion in the reflux valve (even if the reflux is subcooled). This gas is separated and
goes out of the top of the column as GAN. In certain plants there is a separate separator in
which reflux expands and GAN separated from LIN. Material balance for the container
becomes, ringed in Figure 6.6, point 3:
LIN-UC = LIN-prod + Reflux-UC (see Figure 6.6.3)
The more LIN-prod we take out, reduces Reflux-UC. In other words LIN-prod "steals"
reflux. Following this the oxygen content increases in the Lachmann gas, which is comparable
to oxygen loss.
Around about the centre of the upper column the rich liquid enters the column. The RL mixes
with Reflux-UC. This mixed stream becomes reflux in the lower part of the upper column,
where oxygen is purified so we call this Reflux-O2. Material balance for this mixture becomes
ringed in Figure 6.6, point 4:
© Linde Gas AG Page 27 (109) 2001-02-20

GAN
HIC
GAN-up
3 HIC
Impure N2 6
LIN-Prod.
N2-up Reflux-UC RL
4
GOX-up
GOX 5
Reflux-O2
GOX-Boil
LOX
LIN-
GAN- cond.
cond. 2
GAN- Reflux-LC LIN-UC

-Up
Air
Air in 1 Up RL
LIC
Figure 6.6 Double Column, showing Internal Flows

Reflux-UC + RL = Reflux- O2 (see Figure 6.6.4).
Both these flows come from the lower column and the sum of them is equal to the incoming
air. The difference is that we take out LIN-product from LIN-UC. If LIN-production is not
altered, then the reflux in the lower part of the upper column is not altered either. With
material balance we get following equations, which are solved:
Air-in = LIN-UC + RL (see figure 6.5) and

LIN-UC = LIN-prod + Reflux-UC (see Figure 6.6.3). Therefore:
Air-in = LIN-prod + Reflux-UC + RL but:
Reflux-UC + RL = Reflux-O2 which is put in and we have:
So finally Air-in = LIN-prod + Reflux- O2
If both Air-in and LIN-prod are not changed, then Reflux- O2 is not changed. This means that:
the only way to control oxygen purity is to control how much GOX rises from the reboiler
(GOX-boil). But GOX-boil depends on how much GAN condenses, which cannot be easily
altered, so what is controlled the GOX take out. Material balance for the GOX take out
becomes, ringed in point 5:
GOX-boil = GOX + GOX-up (see Figure 6.6.5).
For example, if we reduce the GOX take out the oxygen gas (GOX-up) increases, which rises
in the column and goes out with the impure nitrogen and becomes a loss. This method
increases the oxygen content in the whole column and the LOX product becomes purer, but at
the cost of an increased oxygen loss in the impure nitrogen. This does not apply to the new
plants like Tepeji, which was mentioned in 6.6.
The GOX that rises in the column gradually increases its nitrogen content, to obtain the
composition of the impure-N2 at its outlet. N2-up is the flow in the column up to this outlet,
and GAN-up is the flow above. Material balance for this outlet becomes, ringed in Figure 6.6,
point 6:
N2-up = Impure-N2 + GAN-up (see Fig 6.6.6).
GAN-up goes out as GAN-product and can be controlled. If we increase the GAN-product,
then GAN-up increases therefore impure-N2 is reduced, as N2-up is not changed. With
increased GAN-up and unchanged reflux, the oxygen content in GAN-up increases. The correct
setting is the specified purity of GAN, often 1 ppm oxygen. Therefore increased GAN-
product, increases oxygen content and reduces the impure nitrogen flow.
© Linde Gas AG Page 28 (109) 2001-02-20

7. HEAT EXCHANGERS AND ENERGY CALCULATIONS
Heat exchangers are equipment to transfer heat between different gas or liquid flows, without
the different flows coming into direct contact with each other. In air separation plants there are
many flows that shall be warmed or cooled, therefore heat exchangers are important and even
are necessary. In compressors the gas leaving each compressor stage must be cooled, this is
carried out in a heat exchanger. We have already studied reboiler-condensers in double
columns, which are heat exchangers. Liquid product subcoolers are also heat exchangers.
7.1 How a Heat Exchanger Functions
The simplest heat exchanger consists of two concentric pipes (a smaller pipe in a larger pipe),
through which heat can be exchanged between a cold gas stream and a warm stream. One
stream is fed through the inner pipe and the other between the inner and outer pipes. Normally
the streams go in the opposite direction to each other, which we call counter current.
Cold stream
Warm stream
Cold stream
The warm gas warms up the metal wall and becomes cooler itself. On the other side of the
metal wall the cold gas gets warmed-up. Heat is transferred therefore through the wall from the
warm gas to the cold gas. The heat given off from the warm gas is equal to the heat gained by
the cold gas. We assume that the heat exchanger is well insulated from the surroundings.
The quantity of heat transferred depends on the factors that we have already discussed for
reboilers/condensers:
• Wall area between the gases. A larger area results in a larger heat transfer and vice versa for
a smaller area which gives a smaller heat transfer.
• Temperature difference between the gases. A bigger difference results in a larger heat
transfer and vice versa for a smaller temperature difference.
There is a law of nature, which says that heat is spontaneously transferred only from a warmer
to a colder object. When there is no longer any difference, the heat transfer ceases and heat
does not go from the cold object to the warmer. One can understand therefore that the
temperature difference is important to be able to transfer heat.
To increase the heat transfer area a number of tubes are laid in parallel. Sometimes plates are
also set onto the pipes at right angles, called fins to give a further increase in heat transfer area.
Tube coolers are used to cool gas with water in a compressor. If one instead uses air for
cooling, then fins are required on the tubes. Within the air separation process so called plate
heat exchangers are used, which are described later in this chapter.
© Linde Gas AG Page 29 (109) 2001-02-20

Warm end Cold end
110
100
Temperature (oC) 80 Air 19 600 Nm /h

3
60
40 Heat
o
Air cooling = 86,9
24 23,1 Tcold end = 6,1o
20
Water 78 700 kg/h 17 Water warming = 7o
a) Design Case
Warm end Cold end
110
100
Temperature (oC)
3
80 Air 19 600 Nm /h
60
40 Heat
o
Air cooling = 87,3
20,5 22,7 Tcold end = 5,7o
20
Water 157 400 kg/h 17 Water warming = 3,5o
b) Double Cooling Water Flow
Warm end Cold end

110
100
Temperature (oC)
3
80 Air 19 600 Nm /h
60
40 Heat
o
30,8 Air cooling = 86,1
23,9 Tcold end = 6,9o
20
Water 39 350 kg/h 17 Water warming = 13,8o
c) Half Cooling Water Flow
Figure 7.1 Coolers - Temperature Diagram

7.2 Temperature Diagram
To show how the temperatures vary in a heat exchanger a diagram has been produced.
See figure 7.1 Cooler Temperature Diagram.
Fig. 7.1a shows an air cooler operating at its designed condition. In Fig. 7.1b we assume that
we double the cooling water flow. This increases the cooling and the air becomes colder. As
the temperature of the cooling water at the inlet is unchanged, the temperature difference at the
cold end becomes smaller. This temperature difference is often referred to as ∆T (delta T,
where delta = difference). This ∆T can never be equal to 0, because the air cannot be cooled so
much that it has the same temperature as the inlet cooling water. The quantity of heat removed
is proportional to the temperature drop and the flow of the air (see the calculations on next
page). As the flow and inlet temperatures are not changed and the temperature drop increases
somewhat, the quantity of heat removed is increased only slightly.
The heat is taken up by the cooling water, which had been doubled. So the temperature rise of
the cooling water, which is proportional to the heat taken-up, will be only half as much. This
means that it will be colder at the warm end, so the ∆T will increase at the warm end.
In a cooler, the gas cannot be cooled to the same temperature as the inlet cold water. Too
much cooling water will only give a slightly colder gas, and also it takes water from the
other coolers. The amount of cooling water must be set at the design value to obtain the
desired temperature rise.
In Fig. 7.1c we assume that we reduce the cooling water flow by half. This reduces the cooling
and the air stream becomes warmer and ∆T is larger at the cold end. As the heat exchanging
area and the warm air stream flow remain unchanged, then the quantity of heat removed is only
slightly reduced. The heat is taken-up by the cooling water flow, which is halved and the
temperature rise in the cooling water will be doubled.
In the main heat exchanger, where air is cooled by the outlet gases from the columns, the cold
streams cannot be varied in proportion to the warm stream as much as in a cooler. It is only the
balance and compensation streams which can be changed, see 7.5-7.7. In this heat exchanger
the temperature curves are situated closely with a small ∆T over the whole heat exchanger. If
the balance stream is adjusted poorly, the ∆T in the cold or warm end will increase
considerably and disturb the column and increase the cold loss respectively. On the other hand
it is all right to overload the cold and warm streams equally. If one doubles both, so the
quantity of heat transferred is also doubled. As the heat exchanging area is not changed, ∆T at
both the cold and warm ends must be doubled.
© Linde Gas AG Page 30 (109) 2001-02-20

7.3 Specific Heat, Energy Content and Power
The heat content in a gas is known as enthalpy (H) and is measured in kJ = kilo Joule. An often
used older unit is kcal = kilo calories and 1 kcal = 4,19 kJ.
Specific heat (c) is the energy required to raise the temperature of 1 kg material by 1°C. For
gases there are two different specific heats: cp for constant pressure (P) and cv for constant
volume (V). These can be physically expressed as:
H = m • cp • (T2 - T1)
Where m = mass (kg)

cp = specific heat (kJ/kg°C)
T2 - T1 = temperature difference (°C)
Now we can calculate how much energy which is given up by air and is taken-up by cooling
water in the cooler, which we have discussed earlier in figure 7.1. Normally, gas flows are not
measured, in the gas industry, in kg/h, but the "normal cubic meter" (Nm3). Using a conversion
table Nm3 can be converted to kg. Air has a density of 1,29 kg/Nm3 so the flow = 25 330 kg/h.
We will use the specific heat at constant pressure (cp) as to great extent the pressure remains
unchanged in a heat exchanger. For air cp = 1,0 kJ/kg,°C and for water cp = 4,2. Sometimes the
specific heat is given in kJ/kg, K; which is equal to that in °C, as it is a temperature difference
and it is equal in degrees C and K. Using the formula above we can calculate the difference in
enthalpy (heat content):
Hair = 25 330 (kg/h) • 1,0 (kJ/kg °C) • (110 -23,1)(°C) = 2 201 000 (kJ/h)
Hwater = 78 700 • 4,2 • (24-17) = 2 303 000 (kJ/h)
The difference in values is because we did not take into consideration the condensing of water
vapour in air. It is easier to perform the correct calculations if we also include the units of each
measurement value. The units can be reduced, if as above the same units of measurements are
used above and below the fraction line (here: /). In the calculation above kg and °C can be
reduced so that we have energy (in kJ) per hour. This becomes energy per hour, as we wanted
to calculate the cooling by a certain number of kg of air per hour.
Energy consumption during a certain time is called power. Conversely power multiplied with
time is equal to energy. For example an electric motor with an effect of 1,000 kW (kilowatt) is
consuming in an hour 1,000 kWh (kilowatt-hour) of energy, and in two hours 2,000 kWh etc.
To get a feeling of the order of magnitude of what 2 300 000 kJ/h is, we can convert this to
kW. One kJ = 1 kWs (kilowatt second) and one hour = 3 600 seconds. Therefore 2 300 000
(kJ/h) = 2 300 000 (kWs/h)/3600 (s/h) = 639 (kW s/h) • (h/s) = 639 kW.
If we use the measurement unit reduction, we have to be aware that a division of 3 600 implies
that the unit s/h is inverted to h/s and then we can see that both s and h cancel each other out.
© Linde Gas AG Page 31 (109) 2001-02-20

7.4 Calculating the Cold Loss in a Heat Exchanger
In the warm end of a main heat exchanger there is a temperature difference, which depends on
the heat exchanging area. In air separators an area is used which is enough to give a difference
of 2-3°C. This difference is a cold loss, as the colder gases go out into the atmosphere and that
cold can not be used elsewhere. Smaller temperature differences demand larger area, so that the
purchase cost of the plant becomes more expensive. This must be set against the decreased
operating cost resulting from the smaller cold losses. A normal temperature difference of 3°C
corresponds to:
10 000 (kg/h) • 1,0 (kJ/kg °C) • 3 (°C) = 30 000 (kJ/h) = 30 000/3600 (kW) = 8,3 kW.
This is an acceptable loss, but if the temperature difference is increased to 6°C, the loss
becomes 16,6 kW. We must do something about this, although we should keep in mind that the
large compressors are also important as they draw thousands of kilowatts and with poor
maintenance we can loose even more in them.
Please note that this calculation can only be done for a heat exchanger with low pressure gases
out and 5 bar air in, because then is cp = 1,0. For internal compression and high pressure air cp
is deviating too much.
Energy can be measured in kJ or kWh and power in kJ/h or kW. Normally kJ is used for heat
energy and kWh for electrical energy. It is not only for historical reasons that we have two
different energy units. It is also because of there are different sorts of energy and that electrical
energy is more high-grade and is more convertible to work than heat is.
7.5 Balancing Stream in Main Heat Exchanger
Because it produces liquid products, the quantity of cold gases coming out through the heat
exchanger will be less than the incoming air. This would lead to that the air will not be cooled
so much and when it goes into the lower column it is too warm. This disturbs the rectification
process by vaporising too much liquid from the lowest column trays. The air shall be cooled to
the dew point.
Therefore another cold stream is fed out through the heat exchanger: Cold nitrogen gas from
the top of the lower column, which is called the balance stream. This is used in the nitrogen
recycle, which we will discuss later. To achieve a balanced heat exchanger the flow must be
about the same as the liquid production.
Air
GOX
GAN
Lachmann
Balance stream
© Linde Gas AG Page 32 (109) 2001-02-20

7.2
7.6 Specific Heat at High Pressure
In the main heat exchanger there is air at 5 bar, which is cooled down by GOX, GAN and
impure GAN at 0,2 - 0,5 bar.
The GOX, GAN and impure GAN together are roughly comparable in composition to the air
and together have the same specific heat 1,0 kJ/kg K. Air at higher pressures has a peculiarity
in that its specific heat (cp) increases at low temperatures. For air at 5 bar its cp is 10-20 %
larger from -140°C to -170°C. This means that air is required to give up a larger quantity of
energy. But as the air meets low pressure gases with lower specific heats, this results in less
cooling down.
To compensate for this, the balance stream is increased in the cold end, where cp is larger. This
means that some of the balance stream must be removed, somewhere around the centre of the
heat exchanger. This stream is called the compensation stream in the figure below. Data from
the Malmö plant.
+8° Air -171°

9800 Nm3/h
+5° GOX -179°
50 “
+5° GAN -175°
4000 “
+5° Lachmann -179°
2965 “
2550 Nm3/h, +5° Balance stream 4715 “ -175°
Liquid production, Compensation stream,

2360 Nm3/h -120°, 2165 Nm3/h
In the nitrogen recycle, there is nitrogen at approx. 50 bar that is cooled by nitrogen at 5 bar,
normally in a separate heat exchanger. Nitrogen at 5 bar has almost exactly the same specific
heat as air at the same pressure. At 50 bar a large change occurs, compared with 5 bar nitrogen.
When it cools down there will be no clear distinction between gas and liquid, except that
density gradually increases. This occurs at pressures greater than 33 bar and temperatures
greater than -147°C, which are called critical pressure and temperature respectively for
nitrogen. When it is colder than -147°C it is a liquid.
A consequence of this is that the specific heat will be much higher in the cold end of the heat
exchanger. At condensation to liquid with low pressures a large quantity of heat is given up at
the boiling point, the so-called heat of evaporation. At pressures over the critical pressure, a
corresponding quantity of heat is given up but this occurs over a relatively large temperature
range. Already at -80°C the specific heat is 30 % larger, and -100°C 50 % larger and at -120°C
120 % larger. At the critical temperature -147°C it is at maximum which is some hundred %.
This means that much more than 5 bar nitrogen is required to be able to cool down 50 bar
nitrogen, which we will see later in the recycle description.
© Linde Gas AG Page 33 (109) 2001-02-20

Figure 7.3 Cryogenic Heat Exchanger
7.7 Controlling the Balance and Compensation Streams
Located on both the balance and compensation streams are control valves, flow- and
temperature meters. They are controlled as follows:
The compensation stream is approx. 20-25 % of the air (according to Malmö, otherwise in
accordance with the operation manual) and is determined so that the air is cooled down, until
its temperature approaches the dew point. This stream is often missing in newer plants and the
air is allowed to become warmer or ∆T will be bigger in the warm end.
The balance stream shall be approximately equivalent to the liquid production. Fine
adjustments are made in the knowledge that too much balance stream will mean that all gases
will become colder at the warm end outlet and that ∆T increases. This means that even the
other outgoing gases (GOX, GAN and Lachmann) become colder and cold is lost. The cold end
will not become cooler, as the air is at dew point so that the quantity of liquid air increases, but
the temperature remains unchanged. This is not satisfactory, as there is reduced quantity of air
rising in the column and a reduced reflux, so that less LIN can be taken out of the top.
Too little balance stream results in a small ∆T in the warm end but a greater ∆T in the cold end,
i.e. the air is not cooled as much, which also disturbs the column. Therefore one has to balance
between the two outer limits, so that ∆T in the warm end becomes not to large, maybe around
2-3°C and the air cools to just over the dew point.
7.8 Description of Plate Heat Exchangers
In existing plants almost only plate heat exchangers are used. These are constructed from a very
large number of corrugated plates, with flat plates fixed in between each corrugated plate, so
that a block is formed. The material is aluminium. In the corrugation between each second
plate a gas is fed. At each end it is distributed and then collected by welded flanges running
diagonally, which run out to a collection pipe.
See figure 7.2 Schematic Drawing of a Plate Heat Exchanger Block.
In the adjoining corrugation another gas is fed, in the next a third etc., then the first gas is fed in
again and so on.
See figure 7.3 Photograph of a Cryogenic Heat Exchanger Block.
The size of the block can be up to 1.2 m wide, 1.2 m high and 6 m long (according to Linde
1986). At least two such blocks are required for the main heat exchangers. These are divided by
temperature between around atmospheric temperature and the air's dew point. Depending upon
capacity required, there may be number of parallel pairs of blocks.
© Linde Gas AG Page 34 (109) 2001-02-20

Diagram 8.1: Moisture content of saturated air
55
50
45
40
Moisture content (g/m3)
35
30
25
20
15
10
0
-10 -5 0 5 10 15 20 25 30 35 40
Temperature (°C)
Water content in air and vapour pressure curve

1200 1200
1000 1013 mbar 1000
800 800
Moisture content (g/m3)
Partial pressure (mbar)
mbar g/m3
600 600
400 400
200 200
0 0
-10 0 10 20 30 40 50 60 70 80 90 100 110
Temperature (°C)
8. AIR PREPARATION AND PURIFICATION
8.1 Contaminants in Air
The air that is used is contaminated with:

• Dust
• Water vapour, the amount of which depends on the weather conditions
• Carbon dioxide, approx. 0,04 %
• Hydrocarbons, e g acetylene, in ppm quantities and less
The contaminants are found in normal fresh air. There are also other contaminants, but in
smaller quantities, e g sulphur dioxide and nitrogen dioxide, which occur from combustion. In
areas around industrial chemical plants or steel works, there can be other contaminants as well.
8.2 Air Filters
An air filter removes dust particles. Normally they comprise two parts: A course filter for the
large particles and a fine filter which take out particles with a size down to a micrometer (=1
millionth of a meter = 1 thousandth of a millimetre).
Dust must be removed or else it accumulates and clogs the process equipment, therefore
increasing resistance and can lead to undesired stoppages. This particularly applies to turbo
compressors, that are very sensitive to dust as they have parts that rotate at very high speeds
and have very small clearances with stationary parts. The dust increases wear, and gas leaks
through the clearances in the compressor reduce its operating efficiency.
A course filter normally comprises a screen that is rolled on automatically. More dust in the
filter increases the pressure drop over the filter, by measuring the pressure drop new screen can
be automatically brought into use. One must always check that the roll is not empty and that the
screen is not damaged, which will indicate that the pressure drop has increased or decreased
respectively by too much.
A fine filter comprises a textile mesh in a cassette. There is a pressure meter that measures the
pressure drop and when a pre-determined value is exceeded, for example 60 mm wc ≈ 6 mbar,
the filter must be changed. This can be viewed as an insignificant drop but its importance is in
the air compressor energy consumption (see 9.5.)
8.3 Water Vapour in the Air
Water vapour must be removed from the air as we have a cryogenic process which means that
the vapour freezes to ice, even if there is as little as 1 ppm vapour in the air.
Atmospheric air will always contain water vapour, the quantity being dependent on
temperature, weather and wind conditions. This is because that over water, even when it is
cold, there is always evaporation taking place with the water vapour rising into the atmosphere.
© Linde Gas AG Page 35 (109) 2001-02-20

Air
Demister
(Droplet capturer)
Manhole
Air
Level indicator
Drain
Figure 8.2 Water separator

At the same time condensation occurs in the form of very small drops, that return to the water.
If there is dry air standing still over water, then in the beginning there will be more evaporation
than condensation. The vapour content increase and therefore condensation increases. Finally,
the maximum vapour content is reached, this is known as the air being saturated with water
vapour. Evaporation and condensation continue but in exactly equal proportions. Equilibrium
has been reached. This is one of natures many recycle.
8.4 Vapour Content Dependency on Temperature
The vapour content in air that is saturated depends on the temperature. The following table
shows how much vapour there is at different temperatures. The table also shows the vapour
pressure, which shows how much pressure that vapour alone has. We can see that at 100°C the
vapour pressure is 1,013 bar, which is identical to atmospheric pressure. Therefore, when we
boil water, the vapour content rises so much that it displaces the air.
Temperature Vapour Content Vapour Pressure

(°C) (g/m3) (mbar)
-10 2,3 2,9

0 4,8 6,1
5 6,8 8,7
10 9,4 12,3
20 17,3 23,4
30 30,3 42,4
40 51,0 123
100 598 1013
It is important to note that the vapour is not lost when the temperature is less than 0°C. Vapour
content reduces gradually with temperature. This explains why it is possible to dry laundry
outdoors in the wintertime.
When air is saturated with vapour, we say that it has 100 % relative humidity. When it rains the
relative humidity is 100 % and on a sunny day it can be 70 %. Despite this there can be more
water vapour in the air on a sunny day than on a rainy, if it is warmer on the sunny day. For
example, if it is 20° and 70% there will be 0.7 • 17,1 = 11,9 g/m3 vapour, whereas at 10° C and
100 % there will be 9,3 g/m3 vapour.
If we cool down air at 20°C and 70 % relative humidity the possible vapour content is reduced
as we can see in the table. This implies that when the air becomes colder the relative humidity
increases. When this approach 100 % the air cannot hold of the vapour so condensation begins.
The dew point is reached. In our example we had 11,9 g/m3 vapour, and this point is reached at
approx. 14°C. This means that air at 20°C and 70 % has the same dew point = 14°C, which can
be read off the tables that are more detailed than the one here.
If we continue to cool the air more water will come out. At 10°C the air will contain 9,3 g/m3
of water. We have cooled out 11,9-9,3 = 2,6 g/m3. If we had cooled air at 20°C and 100 %
relative humidity to 10°C, then we would cool out 17,1-9,3 = 7,8 g/m3, while the vapour
content that remains in the air depends only on the final temperature.
© Linde Gas AG Page 36 (109) 2001-02-20

Manhole/
Sieve Fill
Air
Distributor Regeneration
Gas
Molecular sieves
Sieve
Alumina gel Drain
Bed Support
Air
Distributor
Regeneration
Gas
Drain
Figure 8.3 Mole Sieve Adsorber

8.5 Vapour Content Dependency on Air Pressure
The air pressure has almost no effect on the vapour quantity at saturation. In an air compressor
air is compressed from atmospheric pressure to approx. 5 bar g. If we convert the pressures to
absolute pressures: 1 and 6 bar abs we can calculate the volume ratio according to the ideal gas
equation. More details of this are given in the next chapter. The final volume is 1/6 of the
original volume. Therefore the final volume would contain six times as much water as the
original volume, which means that a lot of water must condense out.
If we compress air at 20°C and 70 % relative humidity to 5 bar g and cool it to 20°C, the water
input vapour content is 11,9 g/m3. However at the outlet the air can only contain 17,1 / 6 = 2,85
g/m3, therefore 11,9-2,85 = 9,05 g/m3 must condense out.
If we compress air at 20°C and 100 % relative humidity in the same way, then more vapour
goes in : 17,1 g/m3, but only the same amount of vapour can come out. Therefore more water
must be condensed out =17,1-2,85 = 14,25 g/m3.
8.6 Condensate Separator
See figure 8.2 Condensate Separator.
The air after the compressor is cooled with water and refrigeration machine to +5°C. Large
amounts of condensate are formed, which have to be separated. A condensate separator is a
container, that has a much larger diameter that the pipe that it is connected to. The larger
diameters make the velocity of the airflow become lower, so that it is possible that the water
droplets are not blown away but fall to the bottom. The water is taken out via a valve that is
designed only to pass water.
To ensure that the very small droplets and mist are separated the container is filled with, many
metallic meshes which are fitted tightly together. The small droplets adhere to the meshes to
form larger droplets, which fall down and are separated. If water droplets enter the drier, then it
will become overloaded. Therefore it is important that the separator is in good working order.
There is an alarm and trip for high water level in the separator (LZAH).
8.7 Dryers - mole sieves
Drying is nowadays carried out using mole sieves. These are manufactured from a man made
mineral of aluminium silicate called zeolite. This comprises crystals that tie in a lot of water to
their molecular structure. When the zeolite is warmed-up the water is evaporated, while the
silicate molecules remain tightly together and pore holes are formed which are all of equal size.
The zeolite is now ready for air drying. The water molecules bind very powerfully to the
surface of the pores. This is called adsorption.
Because of its special molecular structure with pores the mole sieve will pick up other
contaminants such as carbon dioxide, acetylene and most hydrocarbons. Mole sieves manu-
factured from zeolite crystals are bound onto a ceramic material to become beads of around 5
mm diameter. These are put into a cylindrical vessel as a bed on a plate with small holes.
© Linde Gas AG Page 37 (109) 2001-02-20

Break through sequence
1. Methane CH4 6. Carbon dioxide CO2
2. Ethane C2H6 7. Acetylene C2H2
3. Propane C3H8 8. Propylene C3H6
4. Ethylene C2H4 9. Bigger hydro-
5. Nitrous oxide N2O -carbons, C4 +
CH4+
Concentration C2H6 C3H8 C2H4 N2O
Bed height
CH4+C2H6
C3H8
CO2
C2H4
N2O
C2H2
C3H6
C4+
CO2 C2H2
C3H6
C4+
H2O H2O
Direction
of flow
1. Beginning of adsorption 2. End of adsorption
Figure 8.4 Break through sequence of impurities in a mole sieve

There are both standing and lying vessels. Air is fed into the bottom of the vessel, passes over
the mole sieve and goes out from the top. Heated impure nitrogen is fed in the opposite
direction to remove the water, which is called regeneration. Therefore two vessels are
required, one for drying, and the other for regeneration.
See figure 8.3 Mole Sieve Adsorber.
To avoid having large, expensive vessels and large electrical heaters for regeneration, the
vapour quantity in the air is reduced before it goes into the mole sieve. This is done by cooling
the air to +5°C with a refrigeration machine. This temperature is selected in order that there is
no risk of freezing the vapour to ice in the cooler. If the refrigeration is degraded and the
temperature is increased, then the vapour quantity and the load of the mole sieves are
increased.
If overloading occurs in the mole sieve, then carbon dioxide breaks through into the process. It
then freezes out to soft snow in the cold end of the main heat exchanger. This appears as an
increased temperature difference, which cannot be reduced by changing the gas streams, and as
increased pressure drop. Carbon dioxide will continue to be partly blown into the column and
because it has a higher boiling point it is washed down in the rich liquid. Then it will be fed to
the upper column and washed down to the LOX-reboiler and then form a layer on the reboiler
surface. This degrades the heat transfer that raises the pressure of the nitrogen part on the
condenser side (see 6.3). Please note that a break through of CO2 shall be avoided according to
new rules, see 8.9!
8.8 Mole Sieves in Combination with Other Drying Media
Mole sieves are very sensitive to water droplets. When the water binds, energy is released and
when the water droplets come, the temperature rise is so large that there is a risk that the mole
sieve beads can split. So in the bottom part of some mole sieves, where the air enters, there is a
layer of alumina gel, which is a common drying media, manufactured from aluminium oxide,
see figure 8.3.
The quantity of alumina gel used is designed for the amount of water and the quantity of mole
sieve to the amount of carbon dioxide and hydrocarbons. An advantage with alumina gel is
that it requires less energy to remove the water from it.
8.9 Risks with hydrocarbons (New in version 4)
In 1997 powerful explosions occurred in two ASU. As a consequence of this the gas industry
has strengthened the rules of operation. The rules for AGA are available on Lotus Notes, SEQ
service (Safety, Environment, and Quality). The explosions were among others caused by a
big release of ethene in the neighbourhood in one case and by smoke from forest fires for
months in the other case. Other important factors are mentioned as follows.
Most of the hydrocarbons are completely adsorbed in the mole sieves, but ethene and propane
partly, and methane and ethane not at all. Their boiling points are higher than the boiling point
for oxygen (see chapter 2), so they will be washed down to the LOX reboiler and go out to
tank. Ethane, ethene and propane have much higher boiling points, so they will as a matter of
fact go down completely in the LOX. Methane, which has its boiling point closest to LOX,
will to a big part go down into the LOX, but a part goes out with the GOX.
© Linde Gas AG Page 38 (109) 2001-02-20
QI
PC CO2
Figure 8.5 Flow Schematic of a Mole Sieve Battery
Pressure
Build-up
Atmosphere
TIS
Filter PDIS
TI TI TIC
PIS PIS
Electric
PDIS Heater
To
US Cold Box
TIS TIS
KC
Valves
Signals
from
Switches FS
Pressure
Reduction
PIC
Impure N2
for Regenerating
LA
Air from
ref. unit
As oxygen is 21 % in air the concentration of ethane, ethene and propane in LOX will be
approximately 5 times ( 1 / 0,21 ) that of their concentration in air, if all O2 is taken out as
LOX. Their presence in the atmosphere is varying but for methane it can be 1-2 ppm and for
the others less than 0,1 ppm each. The solubility of these hydrocarbons in LOX is several
hundred ppm, which is much less than the explosion limit, so it is normally a small risk. But a
reduced production of LOX means an increased concentration, so new rules of minimum
allowed production must be followed.
Dry boiling of LOX is very dangerous as in this case the hydrocarbons are enriched to a high
concentration. This can occur if you are operating with too low level in the reboiler and a part
is coming up of the LOX bath. Splashes of LOX are then boiled off and the hydrocarbons
remain. Detailed instructions of the dimension of the reboiler in relation to the sample points
of the level indicator are necessary from the manufacturer.
Dry boiling can also occur in a passage in the reboiler block, if it is partly clogged by CO2. A
well operating CO2 analyser is necessary in all plants. The alarm limit shall be 1 ppm CO2 in
the end of an adsorption cycle. Continuous break through of CO2 below 1 ppm but above the
detection limit of the analyser is serious, as this could be an indication of a damage or leak
inside the mole sieve.
Break through of CO2 has also the consequence that the partly adsorbed ethene and propane
are pushed out in the coldbox. At a big break through, but not 1 ppm, even acetylene can be
pushed out. Acetylene is present in the atmosphere with approximately 0,1 ppm and is
especially dangerous, as it is not soluble in LOX above 5 ppm. Above that are formed crystals
(“ice”) which are very explosive.
See figure 8.4 Break through Sequence of Impurities of a Mole Sieve.
Nitrous oxide (N2O or laughing gas) has appeared to be a risk factor in plants with an
uncommon type of LOX reboiler, the falling film type. Approximately 0,35 ppm of it is
present in the atmosphere and it passes to a great extent through the mole sieves. If there is a
big GOX production, then it may crystallise in the falling film reboiler and cause dry boiling
in a spot.
For plants in risk areas, such as in the neighbourhood of oil refineries and petrochemical
complexes and having falling-film reboilers, there are special rules.
8.10 The Function of Mole Sieve Batteries (Rev. in version 4)
See figure 8.5 Flow Schematic of a Mole Sieve Battery.
The pipe work and valves have been arranged so that the following steps will be carried out in
each mole sieve.
Adsorption Out of air at 5 bar from the refrigeration machine at +5°C

Parallel operation Of both vessels at 5 bar
Pressure reduction Of the vessel which was adsorbing
Heating With impure nitrogen at 0,2 bar
Cooling With impure nitrogen at +5°C
Pressure build up With air at 5 bar
© Linde Gas AG Page 39 (109) 2001-02-20

Figure 8.6 Mole sieve regeneration gas curve (Cryoss, Hungary)
250
200 gas out

gas in
150
Temperature (C)
100
water
50
desorbing
CO2
desorbing
0
0 50 100 150 200 250 300
Time (minutes)
In a mole sieve the entire cycle takes 2-12 hours and the switch over of the vessels (adsorption
- regeneration) is automatic. The cycle times can be varied within certain limits, as this can be
necessary if the pre-cooling degrades. This increases the water quantity in air and mole sieve
bed, so the cycle time must be decreased. If this is not sufficient, then the airflow must be
reduced. Else carbon dioxide is pushed out to the cold box. The difficulty is that shorter drying
time gives shorter time for regeneration of the other vessel. If the refrigeration machine
completely fails and there is no reserve machine, then the whole plant must be stopped.
Too rapid pressure drops or rises can damage mole sieves. They rub against each other and
powder is formed. Their distribution can be irregular and the bead level uneven, which will
increase the risk of carbon dioxide break through. Therefore a pressure reduction is carried-out
in steps: First through a small pipe with a small valve and then through a large pipe with a large
valve. In newer plants there is a Pressure Differential Switch (PDISH), which does not allow
the large valves to open if pressure differential is over a certain limit. In a few plants there is a
mechanism for making the bed level even during operation.
The impure nitrogen used for regeneration is warmed in an electric or steam heater to approx.
200°C. The temperature is controlled by a control (TISH), which shuts off the heater if the
temperature is too high. The flow of impure nitrogen must be set according to the manufac-
turers instructions, otherwise the regeneration may not be sufficient even if the temperature is
correct. Normally, there is a flow meter with an alarm (FISL), because if there is too little flow
the electric heater can be damaged through the risk of over heating.
Heating continues until the temperature at the outlet is at a level, that it can be ensured that all
water is removed with the regeneration gas. If this temperature is plotted on a printer, you can
see when this happens as there will be a "notch" in the curve. Please note that there is always
remaining some rest water in the mole sieve and it could slowly increase. If a capacity
reduction has occurred and CO2 is breaking through, it may help to increase the flow of the
regeneration gas or to regenerate at max possible temperature for a couple of hours during a
plant stop.
See figure 8.6 Mole Sieves Regeneration Gas Curves
In mole sieves where is no alumina-gel in the bottom and where part of the mole sieve has
pulverised, the powder can be baked together in clumps with the help of water. These clumps
allow less gas to pass through, so that regeneration takes a longer time. This can be seen on the
temperature plot by the curve being more "drawn-out". The pressure differential in the mole
sieve can be measured which will increase when there is dust in it.
In certain plants there is a 3rd vessel with a stone bed acting as a heat accumulator. The heater is
on continuously and hot regeneration gas is passed through the stone bed. During the regenera-
tion cycle, part of the cold regeneration gas can be heated in the bed. By the heat accumulation
the heater kW capacity can be reduced. This can be important depending on the electricity
tariffs, because the discontinuous heater creates a higher peak power to the whole plant.
© Linde Gas AG Page 40 (109) 2001-02-20

Figure 9.1 Turbo compressor with impellers
9. COMPRESSOR AND COOLING WATER - THE IDEAL GAS EQUATION
In nearly all plants only turbo-compressors are used for air and recycle. However, in certain
small plants, e.g. Reykjavik, Iceland, screw compressors are used. The air and recycle
compressors consume around 90 % of the total plant electricity consumption. Therefore it is
important that they are well maintained to preserve their efficiency.
9.1 Function of a Turbo Compressor
Inside a turbo compressor there are installed a number of bladed wheels called impellers,
which are similar to a propeller or a fan. The normal type of compressor is one where the
impeller sits in a housing, which is in the form of a spiral shell. The impeller and shell are
manufactured to the highest precision, so that there is the smallest possible space between them
without actually making contact. This makes lubrication not necessary, so that the air remains
oil free.
See figure 9.1 Turbo Compressor with Impeller.
The gas enters in an axial direction to the impeller, which is attached to a shaft with a bearing
and rotates at high speed. This causes the gas to rotate. Because of the high rotation speed, the
gas is prevented from leaking back into the space between the impeller and wall. Any gas loss
is small. The gas goes out in a radial direction from the impeller to the spiral shell, which
expands reducing the velocity. As the gases energy is not changed, its kinetic energy is
converted from velocity into higher pressure (Bernoulli’s law), which we desire.
So that gases will not leak out through the shaft, there is a seal, called the labyrinth seal. This
consists of a number of thin plate rings on the shaft and in the wall. These are placed
alternately in the wall and on the shaft, with a little distance between them. Because of the
small gap between the moving and stationary rings leakage becomes small and under control.
See figure 9.2 Labyrinth Seal.
One impeller cannot raise the pressure sufficiently, so it is necessary to use several of them.
Normally, four, or sometimes three, are used. With compression heat is developed and the
temperature of the gas rises. This heat must be cooled out, to achieve an effective compression
in the next stage. Therefore a cooler is situated after each impeller which cools the gases with
water. Because the gas volume reduces with each compression, the first stage spiral shell is the
biggest and each of the successive stages are smaller.
The energy consumption of a turbo-compressor is directly dependent on:
• Flow (Nm3/h)
• Suction temperature (°C) in all stages
• Pressure rise Pout/Pin (bar/bar abs)
With 10 % more flow in Nm3/h, then there is 10 % higher energy consumption, if nothing else
has changed.
© Linde Gas AG Page 41 (109) 2001-02-20

a) Gas labyrinth
b) Oil labyrinth
c) Oil splash ring
d) Leak air
Figure 9.2 Labyrinth seals

9.2 What is pressure? New in version 4
Pressure is force applied to a unit area, in SI it is N/m2, where 1 N/m2 = 1 Pa (Pascal). In the
European gas industry the unit of pressure bar is preferred, where 1 bar = 105 Pa = 100 kPa.
The advantage is that atmospheric pressure is about 1 bar. In Britain, however, the unit of
pressure psi is used, i.e. pounds per square inch. One 1 bar = 14,5 psi.
There are, unfortunately, more units of pressure, for example the older 1 kp/cm2 (also called
ata) = 0,981 bar and 1 atm = 1,013 bar. Atm is the unit of pressure used as standard in
physics. It is used in the definition of the normal cubic metre (Nm3) of gas. The story about
the standard atmosphere, atm, is instructive and is as follows:
The mercury barometer was invented in the 17th

century in Italy by Torricelli. It consists of a Vacuum
vertical glass tube that is sealed at the top and

open at the bottom. The tube is filled with Air pressure
760 mm
mercury and while keeping the open end closed
it is inverted and lowered into a bowl of
mercury. The mercury in the tube falls to some
extent and causes a vacuum in the top of the
tube. The height of the column of mercury over
the free surface of mercury in the bowl depends
on atmospheric pressure. It is actually the air
that forces mercury up in the glass tube. 0
Torricelli observed that the height of the column
of mercury varied from day to day. A standard
atmosphere was defined as 1 atm = 760 mm Hg
(= mercury).
The height (h) of a liquid can be converted to pressure (P) by the formula P = ρ • g • h, where
ρ is the density and g is the acceleration at the earth’s surface due to the force of gravity. So
for 760 mm Hg the result will be P = 0,76 (m) • 9,807 (m/s2) • 13 595 (kg /m3) = 101 328
N/m2 = 1,013 bar. Conversion of the unit to N gives due to force = mass • acceleration
according to Newton’s law, N = kg m/s2 so that P = m • m/s2 • kg/m3 = kg m/s2 • 1/m2 = N/m2.
That pressure corresponds to the height of a column of liquid, is used when stating that a
pump gives a certain height instead of pressure and the same flow. Consequently, for a water
pump 1 bar = 105 N/m2 = h • 9,807 • 1000 => h = 10,19 m. Pressure drop can be measured
using a U-tube containing water (e.g. on the orifice plate in 5.2) stating the pressure
difference in mm of water: 1 mbar = 10,19 mm water column or gauge.
9.3 Calculation of Gas Volume According to the Ideal Gas Equation

m
The Ideal Gas Equation: pV = • RT
M
Where P = Pressure (bar abs)

V = Volume (m3)
m = mass (kg)
© Linde Gas AG Page 42 (109) 2001-02-20

Figure 9.3 Turbo compressor
M = Molecular weight (kg/kmol, for air = 28,96, N2 = 28,02)

R = Gas constant (0,08314 m3 bar/K, kmol)
T = temperature (K)
Using the gas equation, one can calculate the gases state at a certain point, e g its volume at a
certain pressure and temperature. However, one cannot calculate what happens in a process,
e g in compression where the pressure changes. But the condition of the gas can be calculated,
before and after compression. We can take as example, compression of 6 m3 of air to 1 m3 in a
cylinder.
1. Before compression 2. After compression and cooling
3
6 m3
2 20° C
1 m3
1 bar
1 20° C
P2 bar
m m
P1V1 = • RT P2V2 = • RT
M M
Index (1) denotes condition before compression and (2) afterwards. As the mass (m) and
temperature (T) of the air are unchanged, then:
P1V1 = P2V2
Therefore P2 can be calculated: 1 • 6 = P2 • 1; Thus P2 = 6 bara
m
The mass can also be calculated: 6 • 1 = • 0,08314 • 293
29
m = 7,14 kg
9.4 Calculation of Normal Cubic Meter (Nm3)
V (m3) is the real or the so-called effective volume of the gas. It is not practical to measure in
production, as the volume depends on pressure and temperature. Therefore, one has introduced
Nm3, which is 1 m3 at 0°C and 1,013 bar (=760 mm Hg, mercury). But there is unfortunately
m3 at other pressures and temperatures as well.
If we want to calculate a gas volume to Nm3 from another cubic meter, we can use the formula
above:
© Linde Gas AG Page 43 (109) 2001-02-20

P0V0 T0 T0 P1
•
= or V0 = V1 •
P1V1 T1 T1 P0
Where V0 = volume in Nm3

P0 = 1,013 bar a
T0 = 273 K (0°C)
V1 = volume in m3 at pressure P1 and temperature T1.
The volume in Nm3 before and after compression in the example above becomes:
273 1,0
Before: V0 = 6• • = 5,52 Nm3
288 1,013
273 6,0
After: V0 = 1• • = 5,52 Nm3
293 1,013
Calculation of the AGA Gas, Sweden m3 (15°C = 288 K and 1 kp/cm2 = 0,981 bar) to Nm3:
273 0,981
V0 = 1• • = 0,918 Nm3
288 1,013
Where 1 m3 AGA Gas = 0,918 Nm3

or 1 Nm3 = 1,089 m3 AGA Gas.
9.5 Change of Capacity due to altered Suction Conditions
A compressor is said only to "know" the real volume flow (effective volume) on its suction
side. It can take in only a certain effective volume at a certain guide vane setting. But the
effective volume depends on pressure and temperature according to the gas equation, as we
have seen, then the compressor's capacity on suction pressure and temperature.
Assume that we have a compressor with a design capacity 10 000 m3/h effective volume at
20°C (=293 K) and 1 bar a. This can be calculated out to Nm3 according to the gas equation:
273 1,0
V0 = 10 000 • • = 9 198 Nm3/h
293 1,013
A day with high pressure 1,02 bar (=765 mm Hg) and 20°C it becomes:
273 1,02
V0 = 10 000 • • = 9 382 Nm3/h
293 1,013
Or a winter’s day with temperature -10° (= 263 K) and 1,0 bar it becomes:
273 1,00
V0 = 10 000 • • = 10 247 Nm3/h
263 1,013
© Linde Gas AG Page 44 (109) 2001-02-20

Figure 9.4 Compressor guide vanes
Also the air filters pressure drop is important: Assume it has increased by 10 cm water gauge
(=wg) over its design value. As 1 bar = 10,2 m wg this is ≈0,01 bar. The flow then becomes
around 1 % less compared with the design value.
273 (1,0 − 0,01)

V0 = 10 000 • • = 9 106 Nm3/h
293 1,013
Reduction 9198 - 9106 = 92 Nm3/h, and 92/9198 = 0,01 = 1 %.
9.6 Capacity Control
At the inlet to the first impeller (in certain cases all impellers) sit guide vanes, which can be
turned. The vanes alter the angle of the incoming gas stream against the rotating impeller. This
is very significant, as there is kinetic energy imparted to the gas from the impeller and when the
angle changes, then the velocity of the gas changes in relation to the rotating impeller.
See figure 9.4 Guide Vanes.
In normal operation the angle is 0°, because the gas goes straight onto the impeller. If the guide
vanes are turned so that the incoming gas stream goes in the same direction as rotation of the
impeller, then the gas velocity is reduced to the impeller. This reduces the amount of kinetic
energy that is transferred, so reducing the flow. The guide vane angle in this case is positive
and is shown on a scale on the inlet pipe. Normally, it is possible to increase the angle to + 60°,
then the flow is reduced to 60-65 %. Energy consumption of the compressor is reduced, but not
to the same degree as the efficiency is reduced.
Flow can be increased somewhat if the guide vane angle is reduced to approx -15°. Now the
gas flow is directed against the rotation of the impeller. This increases the amount of kinetic
energy and increases the gas flow to approx. 110 %. However the electricity consumption also
increases.
In a few plants there is a simpler type of control, which is a valve on the inlet. In this case
closing the valve somewhat reduces the flow, which reduces pressure and effective volume on
the inlet. This is less efficient (but has cheaper equipment), as we take off pressure which later
the compressor must add.
The best but most expensive capacity controller is the speed control of the compressor motor.
This method maintains the compressor efficiency even at small airflows. Only the plant in
Vienna uses this method and only during the first five years when a reduced air flow was
required.
9.7 Compressor Curves and Surging
The compressor flow depends on the backpressure of the process and guide vane angle. The
manufacturer tests the machine and draws up a diagram for different pressures and guide vane
angles.
© Linde Gas AG Page 45 (109) 2001-02-20

Figure 9.5 Compressor curves
See figure 9.5 Compressor Curves.
On the horizontal scale there is volume flow and the vertical scale the pressure ratio (Pout/Pin).
A curve is drawn for different guide vane angles, e g 0°, 20°, 40° and -10°. The curves are in a
similar form, so that with a large pressure ratio the flow becomes small and with a small
pressure ratio there is a large flow.
It is easier to understand this if you imagine a fan in front of you which is blowing into a pipe
and has a butterfly valve on the far end. When the valve is completely open the air flow is
largest but the pressure in the pipe is low. When we gradually close the valve, the pressure
increases but the airflow is reduced.
Finally, we come to the point where the opposing pressure has increased so much that the fan
can no longer cope, then the air loses contact with the fan blades and the flow dramatically
drops in an instant. Now the pressure reduces and the air can flow again normally in the pipe,
until the pressure rises too much again and the air lets go. If nothing is done about this, the
process will be repeated and the whole fan installation will be damaged by the powerful
vibrations which occur. This is called surging.
This area is shown to the left of the diagram and is called the surging area. To avoid surging it
is the easiest to quickly increase the flow and this is done by opening a blow-off valve on the
compressor discharge pipe, which goes directly to the atmosphere or to the suction side of the
compressor. This is carried-out automatically by a control system, which comprises a flow
controller (FIC), a pressure meter (PI) and a calculation unit. Flow and pressure are measured
at the compressor outlet and the calculation unit determines whether we are within the safe area
of the diagram. If not, a signal is sent to the flow controller, which opens the blow-off valve.
See fig 5.3 in chapter 5, Controllers.
9.8 Efficiency
Efficiency is how much of the energy input is utilised. For a compressor this is how much of
the shaft work is used to raise the pressure of the gas. It has already been stated that at
compression temperature rises, so that heat must be cooled out, which is unutilised energy. The
efficiency depends on how well the compressor is constructed and how many impellers and
inter-coolers there are. A four-stage compressor has four impellers and three inter-coolers and
better operating efficiency than a three-stage compressor with two inter-coolers. Compressors
from the 1970's, have an efficiency of approx. 50 % while modern examples have around 70 %.
There are many reasons for the losses: Friction between moving and stationary machine parts,
friction between moving gas and walls. In itself the compression also causes heat as the gas
molecules become more packed and there will be more friction between them.
Electric motors have a much better efficiency, normally 96-97 %. So only 3-4 % of the input
electric energy must be cooled out.
© Linde Gas AG Page 46 (109) 2001-02-20

TECHNICAL REVIEW
Plant: Cubatão
Date: 19 May 1991
Barometer: 1016 mbar

Air temperature: 21°C
Cooling water temperature: 29°C
Figure 9.6 COMPRESSOR EFFICIENCY CALCULATION
The compressor isothermal work (W) is calculated by the formula:
W = m/M ⋅ R ⋅ [T1 ⋅ ln (P2/P1) + T2 ln (P3/P2) + etc for each compressor stage]
where m = mass flow, kg/s

M = molecular weight of nitrogen: 28,02 and air 28,96 kg/kmol
R = universal gas constant 8,314 kJ/kmol, °K
T = temperature at stage inlet, °K
P = pressure at stage inlet, bara (except Pout)
To get mass flow in kg/s from Nm3/h, multiply with air density 1,29 kg/Nm3 or nitrogen 1,25 kg/Nm3
and divide with 3600 s/h.
The efficiency is the sum of the isothermal work for each stage, or for the whole machine by T1 ln
(Pout/P1), divided by actual power consumption measured at terminal corrected for motor efficiency.
Air compressor
m (FIC-1) = 57441 Nm3/h = 20,58 kg/s

T1 = (tag numbers) 21 °C = 294 °K
T2 = (missing in) 35 °C = 308 °K
T3 = (flow sheet) 31 °C = 304 °K
T4 = 32 °C = 305 °K
P1 = 0 bar g = 1,016 bar a
P2 = 0,56 bar g = 1,576 bar a
P3 = 1,1 bar g = 2,12 bar a
P4 = 2,2 bar g = 3,2 bar a
Pout = 5,34 bar g = 6,356 bar a
Isothermal work = 3279 kW
Measured power = 4875 kW (motor eff. = 97,2 % )
Shaft power = 4739 kW
Efficiency = 69 %
Remarks: W = 20,58 / 28,96 * 8,314 [294 * ln(1,576/1,016) + 308*ln(2,12/1,576) +

304 * ln(3,2/2,12) + 305 * ln(6,356/3,2)] = 3279 kW
_____________________________________________________________________
It is inevitable that heat forms when machines put something into motion. A car motor must
have a cooling system, as do we humans when we work our bodies (a muscle is heated when it
is used).
There are several ways to calculate a compressor’s efficiency. One, which is used within AGA
at Technical Reviews (TR) of air separation plants, is the isothermal efficiency. Isotherm
means constant temperature. The calculation gives the energy consumption if the gas had been
compressed in a large number of impellers, with intercoolers, at the same temperature. This
isothermic compression is in theory the best compression, an important goal for the
manufacturer to try to attain. This means that isothermic compression energy is also the lowest
possible energy consumption for a given pressure, temperature and flow.
See figure 9.6 TR Calculation of a Compressor’s Efficiency.
The attachment explains how the calculation is carried out. The suction temperature, pressure,
flow and delivery pressure are noted. These are used to calculate the isothermic energy. The
kWh-meter reading for the compressor is also noted and the isothermic efficiency can then be
calculated. This is compared with earlier calculations and if there is a reduction of more than 2
% then it is time for inspection and maintenance.
There is an easier way to see if the efficiency is reduced. Increased friction in the bearings
gives higher bearing temperature. Wear on the impeller gives increased leakage of warm gas
back to the suction side, which gives higher suction temperature and consequently a higher
outlet temperature. By calculating the temperature difference between the inlet and outlet and
comparing this with the data from when the compressor was new (at the same load of course),
it is possible to see if any degradation has taken place.
9.9 Cooler Temperatures and Dirt in Coolers
Most often water is used for cooling after each compressor stage. There are however a small
number of plants where the coolant is air from the atmosphere. Water coolers comprise a tube
bundle in a large cylinder, where water and gas go in opposite directions. The cooler is a sort of
heat exchanger and as we saw in Chapter 7 it is the heat exchanging area and temperature
difference which determines how much heat is transferred for a given flow.
Coolers are manufactured with a certain area, which gives a specified temperature of the
outgoing gas at the specified flows, and temperatures of the gas and water. This means that the
cooling water temperature determines the temperature of the gas that goes to the next
compressor stage. This is important as the energy consumption in the compressor depends on
the suction temperature into the compressor stage.
To find out how efficient the coolers are, you take the temperature difference between the
outgoing gas and incoming cooling water.
See figure 9.7 Compressor Cooler.
© Linde Gas AG Page 47 (109) 2001-02-20

Figure 9.7 Compressor cooler
If the cooling water temperature increases, then the outgoing gas temperature increases as well.
Therefore we take the temperature difference between these two to check how the cooler itself
is functioning. To check if the cooling water flow is correctly set, we look at the temperature
rise of the water through the cooler. This should be within the manufacturer’s specification,
normally 5 to 10°C. If there is too little cooling water, the temperature rises more and vice
versa for too much water.
If now the cooling water flow is correctly set, it can be seen that fouling of tubes results in
increased temperature difference between the inlet cooling water and outlet gas
(= ∆tcold end in diagram 7.1). With too large temperature difference the cooler must be cleaned.
9.10 Changed Energy Consumption due to Changed Cooling Water Temperature
If the cooling water temperature increases, the suction temperature also increases to stages 2, 3
and 4 in the compressor and this means that energy consumption increases. This can be
calculated using the isotherm operating efficiency equation, where pressure rises and flow are
unchanged. A simplified calculation can be carried out in a way that the new energy
consumption stands in relation to the design in approximately the same way as the new cooling
water temperature to design.
Example Design cooling water temp 25°C = 298 K, the new = 29°C = 302 K.
Ratio between new and design energy consumption becomes: 302/298 =
1,013 = 101,3 %.
As a rule of thumb a cooling water temperature rise of 4°C gives an electricity consumption
rise of 1 % in a four-stage compressor.
9.11 Cooling Water System
Dirty coolers are a continuing problem within the process industry. It is seldom possible to use
clean water as it is expensive. In some plants direct cooling with river water is used or a closed
system of circulating water, which in its turn is cooled without dirt entering. A few have no
cooling water at all but direct cooling with air.
Most plants use a circulation cooling water system in which the water is cooled in direct
contact with the atmosphere, a so-called open cooling water system.
See figure 9.8 Principle of Operation of an Open Cooling Water System.
Cooling water circulates through the coolers and cooling tower. Heat taken-up by the coolers is
given off by evaporation of the water in the tower. Blowing air through the water falling in the
tower increases the evaporation. To get better contact between water and air there is some
tower filling, sometimes wood bars or often structured packing in plastic.
© Linde Gas AG Page 48 (109) 2001-02-20

TI TI TI
Cooling
Coolers TC1 TC2
Towers
with Fans
FQ LIZ
TI
LIC
QIS
Conductivity,
M
pH
Bleed-off
Pump
Drain
FQ
Clean Chemical
Water Additives
Feed
Figure 9.8 Principle of Operation of an Open Cooling Water System

We have seen in earlier chapters, about operating the reboiler in double columns, that heat is
required for evaporation. In the cooling tower a small part of the water evaporates, taking up
heat from the remaining water, which then becomes cooler. The evaporated water is replaced
by a fresh water feed which is measured by a flow meter giving an accumulated value, FQ.
Even if the water feed is fresh it always contains a little salt and calcium. Because of the
continuous addition to the circulation system, the salt and calcium content will rise, as these
cannot be lost with the evaporated water. Therefore part of the circulating water must be bled
off to avoid having a too high concentration of salt, calcium and even dirt from the atmosphere.
The bleed off is also measured with a accumulating flow meter.
Chemicals are added to prevent the formation of lime deposits and to inhibit (protect against)
corrosion in pipes and coolers. The acidic content (i.e. the pH) is balanced: Too much acidity
pH<6 causes corrosion and too much alkalinity pH>8 gives lime formation.
Further more, diverse bacteria come in from the air, which can survive and grow relatively well
in the warm water. The bacteria will cause formation of slime and algae that must be
prevented. Bacteria-poison is added to the water a few times a week.
© Linde Gas AG Page 49 (109) 2001-02-20

Cooling
Water Heat out
Condenser
NH3 liquid o NH3 gas
+20
7,6 bar g
Control Compressor
Valve NH3 = ammonia
3,3 bar g
o
0
NH3 boiling NH3 gas
Vaporizer
Air Heat in
o
+5C
o
+ 20 C
Figure 10.1 Principle of a One Stage Refrigeration Machine

10. REFRIGERATION MACHINES AND SPRAY COOLERS
We have already said that a large amount of cooling by cooling water is required in the process.
This cooling of gas is usable down to + 20° C, depending on the design of the cooling towers
and the temperature of the ambient air. Normally it is not possible to obtain cooling water
temperatures lower than + 15° C in a normal open cooling tower plant.
Because we are working with cryogenic process, one understands that several types of cooling
are required for cooling at lower temperatures. Mole sieves require, as said earlier, cooling to +
5°C. This is carried out using refrigeration machines of the same type as domestic refrigerators.
Nowadays refrigeration machines are seldom used. They are rather expensive and require a lot
of maintenance. For cooling of air to mole sieves are used so called spray coolers. These
cannot cool down to +5° C but to between +10° and +15°. This demands bigger mole sieves.
However by using a part alumina gel (chapter 8.8), it will not be so big increase of the energy
consumption for the regeneration. Refrigeration machines for -40° C have completely been
replaced by the warm expansion turbine, chapter 13.3.
10.1 Function of Refrigeration Machines
Refrigeration machines consist of, in simple terms, a compressor, a condenser, an expansion

valve and an evaporator, through which runs the cooling media.
See figure 10.1 Principle of Operation of a One-Stage Refrigeration Machine.
The compressor compresses the cooling media, which is either ammonia or freon gas. Heat is
removed from the condenser using cooling water and liquid ammonia forms. This then goes to
an expansion valve, which reduces the pressure so that the ammonia begins to boil. In the
evaporator all of the ammonia boils off and this takes out the heat from e.g. the air after the air
compressor. The ammonia vapour then goes to the suction side of the compressor to complete
the cycle.
Using this method we can remove heat from a point in the process and transfer it out with the
cooling water, i.e. we produce cold. To understand how this works we must look at a vapour
pressure curve of a normally used coolant - ammonia.
Pressure Temperature
bar a bar g °C
0,41 -0,59 -50 At the given pressures and

0,72 -0,28 -40 temperatures it is equilibrium
1,20 0,20 -30 between gas and liquid. At
2,91 1,91 -10 colder temperatures it is liquid
4,29 3,29 0 and warmer it is gas.
6,15 5,15 +10
8,57 7,57 +20
11,7 10,7 +30
© Linde Gas AG Page 50 (109) 2001-02-20

o
+40 +40 C
18 kW
M
+10 100 kW
0 0 oC 65 kW
M
-10
100 kW
- 40oC
-40
800 kW work
M
-100
100 kW
heat
- 175oC
o
-200 Temperature ( C)
Figure 10.2 Heat Pumping from Different Temperatures

In the compressor the ammonia gas is obtained by 7,6 bar, which condenses at +20° C. This
means that cooling water at +17° C is sufficiently cold to condense it. A temperature difference
of 3° C is enough for heat transfer from ammonia to the cooling water in the condenser (=heat
exchanger).
After the ammonia has passed the expansion valve the pressure becomes approx. 3,3 bar and
the temperature 0° C. This is sufficiently cold to cool the air going into the mole sieves at +5°
C. The boiling ammonia takes heat from the air as evaporation requires heat.
For this process to work the compressor must raise the pressure of the ammonia, so that it is
possible to condense it. At higher cooling water temperatures the ammonia pressure becomes
higher. At the suction side the pressure must be sufficiently low to be able to cool the air to
+5°C. This is controlled with the expansion valve. If one closes the valve the pressure is
reduced and therefore the ammonia temperature reduces, and vice versa, if the valve is opened.
We want to hold the cooling to +5°C constant, while the cooling water temperature varies. This
can be a problem with very warm cooling water, where pressure rise and the compressor load
rises.
10.2 Heat Pump Systems
The comparison with a heat pump is useful in the cryogenic process. A refrigeration machine
system is in reality the same as a heat pump system, in that they use the same equipment (but
possibly using a coolant other than ammonia). The same principle of operation diagram applies
(Fig. 10.1), but the condensation temperature is higher so that it can be used for heating.
Cooling takes place at a temperature which depends on what is available, ground heat *, e g can
be taken from +5° C (this means that the ground is cooled to this temperature). Heating takes
place at e.g. +40°C.
In warmer climates it is usual to have air conditioning (or cooling) of buildings. Such systems
are also heat pumps that pump out heat from the building, with evaporators and compressors
out to a condenser in the atmosphere, from for example +18° C to +30°C.
It is important that the term heat pump is explained that heat is pumped up from a colder
temperature to a warmer one and that this costs electrical energy to the compressor motor.
Cold production is actually to remove heat.
See figure 10.2 Heat Pumping from Different Temperatures.
There is an important basic rule in thermodynamics about heat, which also can be observed
with common sense: That heat only transfers spontaneously if there is a temperature difference;
and heat goes from the warmer to the colder and that different temperatures try to even
themselves out. To transfer heat from a colder part to a warmer part requires work.
*
in colder countries during winter the temperature can be let’s say –10° C. However at a certain level below the
surface of the ground there is always +8°. This can utilised by putting down an evaporator there. This cools the
ground to + 5° and the condenser in the house is heating at + 40°.
© Linde Gas AG Page 51 (109) 2001-02-20

PIC PSH
Cooling
Water PSL
2 1
LI 4 V4
TIC
o
+5 C
V1 LIC o
Air +20 C
5
V2
Oil
V3
Figure 10.3 Flow Schematic of a Refrigeration Machine

This is also an answer to a perplexing question: If we shall produce cold, i.e. to remove heat,
why must we feed so much energy to the air separation process compressors?
If one looks on temperature as a level measurement one can understand that it requires
relatively little mechanical energy to pump up heat from +5° C to +40° C. From -40°C it
requires more energy and from -175° C considerably more is required. The well from which we
pump is deeper the colder it is!
10.3 Detailed Description of Refrigeration Plant for +5°C
See figure 10.3 Flow Schematic for a Refrigeration Machine for +5° C.
Ammonia is compressed in a compressor. This is normally a piston* type, sometimes a screw

type. Both types are lubricated, so that a little oil evaporates by the compression heat and goes
out with the ammonia. An oil separator is therefore installed, which is filled with, e g a lot of
metal mesh layers where oil droplets can form. The oil is taken out at the bottom and led to the
oil tank. The oil separator is similar to the construction of the water separator. See figure 8.2 in
8.6.
Ammonia vapour enters the condenser in a very over-heated state on the outside of the tubes in
which the cooling water runs. A large part of the condenser is used to cool down the ammonia
to its condensation temperature. The rest of the condenser condenses to liquid ammonia. To
avoid the risk of liquid rising up in the condenser, it runs down into a collection vessel (called a
receiver), which can hold sufficient liquid to cope with variations in cooling demand.
This is important because if liquid rises in the condenser, it reduces the heat transfer area and
therefore the quantity of transferred heat.
The receiver has a level indicator, so that we are able to know how much liquid is in the vessel.
At the bottom of the vessel there will be some oil which has passed through the oil separator,
so a drain pipe is located there.
Pressure pushes the ammonia liquid from the receiver through the expansion valve to the
evaporator. There the boiling ammonia cools the air to +5° C. Here again the ammonia is on
the outside of the tubes and the air is on the inside of the tubes. To obtain an even cooling the
ammonia level in the evaporation is maintained at a constant level by LIC control of the
expansion valve, which gives a constant heat exchange area.
The ammonia vapour goes to the suction side of the compressor. The temperature of the boiling
ammonia depends, as we know, on the pressure. So by controlling the pressure we can change
the ammonia temperature and so control the temperature of the cooled air. To be able to
maintain the temperature of the ammonia constant, a control valve is installed between the
evaporator and compressor, so that it is possible to control the pressure in the evaporation.
Normally this valve is controlled by a TIC which measures the temperature of the cooled air.
*
This section was written for an old system with simple control and piston compressor. Screw compressors
usually have a slide valve on the suction side for capacity control.
© Linde Gas AG Page 52 (109) 2001-02-20

PIC PSH
Cooling
Water PSL
2 1
LI 4
V6 TIC
o
+5 C
V1 LIC o
Air +20 C
5
V2
Oil
V3
Figure 10.4 Flow Schematic of a Refrigeration Machine

(compressor with bypass)
The compressor is built to operate at full capacity, sometimes even with a certain overcapacity.
If the amount of ammonia evaporated is not sufficient, as e g happens when the airflow is
reduced, the compressor sucks in more ammonia vapour than has been evaporated and passed
through the TIC valve. This causes the suction pressure to drop and therefore the ammonia
flow is reduced, which in turn causes the filling of the cylinders to be reduced (of a piston
compressor). This is a form of capacity control.
However the compression ratio increases as the outlet pressure depends on the cooling water
temperature, which is unchanged. Increased compression ratio leads to a higher outlet
temperature. So as not to put the compressor in danger a limit can be set for the permitted
compressor ratio and also for the suction pressure. On the suction pipe there is a switch for low
pressure (PSL). When this switch closes the pressure increases and the compressor can be
started again.
If the cooling water becomes warmer or the flow reduces, or the fouling of the condenser pipes
increase, the outlet pressure increases which can also put the compressor into danger. On the
pressure side therefore, a high-pressure switch (PSH) is installed. There is also protection for
high outlet temperature (TSH) - see Chapter 5 for a description of the abbreviations.
To have a stable operation with stable condensing pressure one allows this to control the
cooling water flow with a PIC. Even if the cooling water temperature is constant, the outlet
temperature will change with a changed flow. This causes the cooling waters average
temperature to change and therefore change cooling and condensation pressure. If the cooling
water goes in at 20° C and out at 30° C, the average temperature is 25° C. If the water flow is
doubled, the outlet temperature becomes 25° C and average temperature 22,5° C. This is colder
which increases heat transfer (cooling), so that the condensation temperature and therefore
pressure become lower.
This control is important to balance capacity changes. Such a procedure leads to a changed
evaporation, which gives a changed suction pressure and flow to the compressor, which give
changed condensing and changed condensation pressure.
It is important that the condensation pressure is stable as the flow through the expansion valve
depends upon this. A high pressure pushes through more ammonia at a certain valve opening
than a low pressure.
Another way to control refrigeration capacity is to feed hot ammonia vapour to the evaporator.
In this installation the valve on the suction side of the compressor has been removed. Ammonia
gas is taken from the vapour directly after the compressor and is blown into the bottom of the
evaporator. This flow is controlled with a valve, which is controlled by the temperature (TIC)
of the air that leaves the evaporator. In this way the compressor continuously operates and
overcapacity is throttled by expanding the compressed ammonia back to the suction side of the
compressor, via the evaporator. However, this is costly in compressor energy consumption to
be able to control the refrigeration capacity in this way.
See fig 10.4 Flow Diagram for Refrigeration Machine for +5° C (with compressor bypass).
© Linde Gas AG Page 53 (109) 2001-02-20

Cooling
Water
2
HT-
Compressor
1
V1 o
o
+5 C
Vaporizer +5 C o
Air
+20 C
3
LT-
V2 Compressor
5
o
o
Vaporizer -40 C -40 C N2
o
-20 C
4
o
Figure 10.5 Principle of a Refrigeration Machine for -40 C
10.4 Contaminants in Ammonia
The main contaminants in ammonia are: Air, oil and water.
Air can enter through leaks in the suction side of the compressor, but also when parts of the
installation are opened for maintenance. Air will naturally not condense in the condenser,
which causes the pressure to rise, increasing the compressor work. The air can be removed by
tapping off at a high point over the liquid ammonia in the receiver vessel, and it is blown out to
a small container that has water in it. When air is being removed, bubbles in the water show
this and when ammonia comes through the bubbles stop and there is a cracking noise.
Oil is a normal contaminant and is not soluble in liquid ammonia. Some of the oil passes
through the oil separator and collects in low points of the installation with liquid ammonia. In
the bottom of the receiver vessel there is a tap-off connection that goes to an oil collection
vessel.
Water is not a normal contaminant, but it is more difficult to deal with. It enters with the air but
it will be in small quantities, as it is present by only a few percent in air. The water collects in
the evaporator as it has a higher boiling point than ammonia. This reduces the heat exchanging
area and therefore cold production. To remove water one must stop the process, remove the
ammonia from the evaporator and then tap-off the water.
10.5 Overview of Cold Production to -40° C
In older plants up to the middle of the 1980's there is also cooling to -40°C carried out in the
nitrogen recycle as an addition to the liquid production. Nowadays an expansion turbine, a
warm turbine, has replaced this type of cooling, see Chapter 13. But in certain plants there are
both a warm turbine and a cold refrigeration machine.
At this low temperature the evaporation pressure will also be low and the compression ratio
will be too high for one compressor. In this case two compressors are used.
See figure 10.5 Principle of Operation for a Refrigeration Machine for -40° C.
The high-pressure compressor compresses ammonia vapour from the medium pressure
evaporator (+5° C). The compressed vapour (7,6 bar) condenses and the liquid expands to 3,3
bar through a valve back to the medium pressure evaporator. From here liquid is taken which
then expands through another valve to low pressure (-0,3 bar which is 0,3 bar under atmos-
pheric pressure) in the low-pressure evaporator (-40° C). The ammonia vapour is sucked into a
low pressure compressor, which compresses up to medium pressure (3,3 bar), and is fed to the
bottom of the medium pressure evaporator, where it is cooled by liquid ammonia which is
partly evaporated. This cooled vapour goes to the suction side of the high-pressure compressor
to complete the cycle.
© Linde Gas AG Page 54 (109) 2001-02-20

12o Atmos.
Mole sieves
Air Cooler Water Cooler 20o

FIC
10o 22o
FIC
o
22
PDIA PDI
LZA UZ LZA
Air from 5 bar, 74o 0,2 bar, 25o

GAN + WN
Compressor
LICA LIC
10o
UZ
UZ UZ
PIC
Cooling water
System
Figure 10.6 Spray Coolers for Air and Cooling Water (Avesta)
10.6 Cooling of Air in a Spray Cooler New in version 4
The cooling of air to the mole sieves is nowadays most often done with a spray cooler. This
consists of a column of filler medium, where cooling water goes in at the middle and extra-
cooled water at the top. The air enters at the bottom counter current to water and the cooled
air goes out at the top. Consequently, the air is cooled by direct contact with the water and
the unit is therefore called DCAC, i.e. Direct Contact Air Cooler.
In Avesta the spray cooler is designed for 107 000 Nm3/h air at a temperature of +74°C from
the compressor. Since it is to be cooled anyway there is no cooler bundle after the
compressor. Cooling water at 103 m3/h and 22°C enters the column at the middle, and at the
top 45 m3/h and 10°C. It is dimensioned to supply air at 12°C, consequently ∆TCold = 2°C.
See figure 10.6. Spray Cooler and Water Cooler.
The filler medium is randomly distributed 70 mm large plastic “snowflakes” with the
purpose of achieving the best possible mixing and contact between the gas flowing up and
the water flowing down. It is the same principle as sieve trays and structured packing in the
distillation columns.
The extra-cold water is obtained by leading the cooling water at 22°C into the top of another
column with the same filler medium receiving 59 000 Nm3/h, 25°C dry GAN and waste N2
at the bottom. This is called the water cooler or DCWC = Direct Contact Water Cooler. It
works as a cooling tower in that the water vaporises and heat is extracted from the water,
thus cooling it. Because the nitrogen is extremely dry it can absorb a lot of the water vapour,
1100 kg/h, and the water is chilled to 10°C, i.e. 15°C colder than the incoming nitrogen.
Energy balance, water cooler:

Withdrawn heat = water cooling + GAN cooling. Absorbed heat = vaporisation.
Vaporisation = 1100 (kg/h) • 2460 (kJ/kg) = 2706 MJ/h

Water cooling = 45431 (kg/h) • (22-10) (°C) • 4.19 (kJ/kg°C) = 2284
GAN cooling = 73976 (kg/h) • (25-20) (°C) • 1.04 (kJ/kg°C) = 385
Withdrawn heat = 2669

Difference = 37 = 1.6%
The air cooler cannot chill to as low a temperature as a refrigeration machine, but it requires
less power and maintenance. In Avesta there are two 22 kW pumps for the spray cooler and
there are a few kW more in the cooling water pump for a greater flow. One example of a
refrigeration machine is Stenungsund that has cooling at the rate of 75 000 Nm3/h from 30 to
10°C, which requires 210 kW in the HP compressor. The spray cooler is to greater
advantage, i.e. because the dry gas is utilised before being evacuated to the atmosphere. This
assumes accordingly that one does not sell too much GAN.
© Linde Gas AG Page 55 (109) 2001-02-20

12o Atmos.
Mole sieves
o
20
FIC
o o
10 22
FIC
22o
PDIA PDI
LZA UZ LZA
Air from 5 bar, 74o 0,2 bar, 25o

GAN + WN
Compressor
LICA LIC
10o
UZ
UZ UZ
PIC
Cooling water
System
Figure 10.6 Spray Coolers for Air and Cooling Water (Avesta)
With the aid of diagram or table in chapter 8.4, the moisture content in GAN can also be
calculated. For 20°C the moisture content at saturation is 17.3 g/m3. This applies for actual
m3 so 59 000 Nm3 at 20°C and 1 bar is 59 000 • 293/273 = 63 516 m3/h. I.e. the amount of
moisture = 63 516 • 17.3 = 1097 kg/h.
Since the air goes directly on to the mole sieves that are damaged by water, the instrumen-
tation is adapted accordingly. The pressure drop across the column shows whether flooding
occurs. There is an alarm on PDI for this reason. At the water level, LIC, in the bottom there
is both an alarm and two drain pipes with valves. There is a separate trip, LZ, for high level.
The impulse tubes are protected against freezing during the winter by electric heating, i.e.
tracing. Oil filled impulse tubes and diaphragm against the column can also be used.
© Linde Gas AG Page 56 (109) 2001-02-20

QUESTIONS TO CHAPTER 1 TO 10
1. Which is the coldest, at the same pressure, boiling LOX or boiling LIN?
2. Which of oxygen and nitrogen boils off the least from liquid air? Why?
3. We have a distillation column with a reboiler at the bottom and a condenser at the top. It
is fed with liquid air and only LOX and LIN is taken out.
What is taken out from the top and what is taken out from the bottom?
How can we, in this column, increase the purity of both top and bottom product and still
take out the same quantity of product?
4. What is LIC?
5. What are the four important functions of a PIC?
What do they do?
6. In a Linde double column there is a combined reboiler-condenser.
What will boil and what will condens?
Why is the pressure higher at condensing than in boiling?
7. Where from in the lower column in a Linde double column is LIN taken out?
What happens to the LIN analysis if one increases the take out?
Why?
8. Where from the upper column in a Linde double column is LOX and GOX taken out?
What happens to the LOX analysis if we reduce the GOX take-out?
Why?
9. Where from the upper column in a Linde double column is GAN and impure N2 taken out
(Lachmann)?
What happens to the Lachmann flow if we reduce the GAN take-out?
What happens to the O2 analysis in the Lachmann outlet if we reduce the GOX take-out?
10. Air after a compressor stage is cooled with water, going in the opposite direction, in a
heat exchanger (cooler). If we increase the cooling water flow a little, what happens to:
• Water temperature out from the cooler?
• Air temperature out from the cooler?
• Temperature difference in the cold end?
• Temperature difference in the warm end?
11. After air compression the air is cooled to +5°C. If this temperature increases, what
happens to the water vapour content of the air?
12. What happens to a mole sieve if it is operated for too long in the sequence drying of air?
13. What happens to the gas flow in a turbo compressor when the backpressure increases
(downstream pressure)?
14. What happens to the energy consumption of a turbo compressor if the cooling water
temperature increases?
15. Which four important components are found in a refrigeration machine? Which gas is
compressed?
16. Why can't we cool with ammonia to -100° C?
© Linde Gas AG Page 57 (109) 2001-02-20

Boundary for material
and energy balance
6
Cooling
Water Heat Exchanger
1 2 V
3
Compressor
Cold Production, using Expansion Valve

4
Liquid
Air
Refrigerating Machine
T2 T3
T6
T7 Heat
Exchanger
Heat
Air T1 Exchanger
Water
T5
T4
Separator
V1
V2
Liquid Air
Figure 11.1 The Linde Process for Liquid Air

11. CRYOGENIC COLD PRODUCTION
At temperature lower than -50°C ammonia or other cooling media are not adequate to produce
cold. Ammonia, for example, evaporates at a pressure of 0,41 bar abs at -50° C. As
atmospheric pressure is approx. 1 bar this means that evaporation takes place with an
underpressure of 0,59 bar. If a small leak occurs causing air to leak into the system this is hard
to detect as very little ammonia leaks out. The practical difficulties with leak sealing increase
dramatically with larger underpressure. Also the compression ratio in the compressor will rise.
We need to produce cold for other reasons than producing liquid air gases. The process loses
cold through the insulation and through the temperature difference between the incoming air
and outgoing gases in the main heat exchanger.
11.1 Temperature Drop in an Expansion Valve
Within the air separation techniques this is the oldest and the simplest, but it is also the least
efficient method to come down to cryogenic temperatures. Note that it does not produce cold in
the valve itself, only that a temperature drop occurs. We have said that refrigeration machines
require a compressor with water cooling to produce cooling = transport away heat. This is what
the expansion valve is used for, to sink the temperature of the liquid ammonia.
Such an expansion not only of boiling liquids but also of gases, gives a temperature drop. We
know that compression gives a temperature rise and if we expand this gas without cooling back
to the initial pressure, the temperature will sink to the initial temperature (if we had an ideal
process). In practice it will be some degrees warmer, due to various friction heating.
This temperature sinking of an expanded gas is called the Joule-Thomson effect after the
English scientists who discovered this in the 1800's. Thomson was awarded for his discovery
and became Lord Kelvin. Joule’s name is used as designation of the energy unit. In England
and USA the expansion valve is called the Joule-Thomson valve.
11.2 The Linde Process for Manufacturing Liquid Air
At the end of the 1800's, Carl von Linde in Germany was the first to start industrial production
of air gases. His invention as we have seen was the double column and the process for
manufacturing liquid air.
See figure 11.1 The Linde Process for Liquid Air.
He used a compressor that went up to 200 bar, a heat exchanger, and expansion valve and a
collection vessel for liquid air. The heat exchanger was manufactured from thick copper tubes,
which were wrapped in spirals around a pipe, which was covered by a larger pipe. High-
pressure air went through the copper tubes and the expanded air on the outside.
© Linde Gas AG Page 58 (109) 2001-02-20

T7
Water Heat Heat

Compressor Cooler T1 Exchanger 1 T2 Exchanger 2 T3 T4
V
Air
T6
G
T8
Expansion T5
Machine
Liquid
Air
Figure 11.2 The Claude Process for Liquid Air

The air is compressed in the piston compressor to 200 bar and cooled with water to +20° C and
dried. If this air goes directly to an expansion valve, its temperature becomes -16° C at the
outlet pressure of 1 bar. Now the air is fed into a heat exchanger and comes at the start at +20°
C before the expansion valve. As no liquid forms, all air is fed at -16° C back to the heat
exchanger. Then begins cooling down of the high pressure air by the low pressure air, which
itself is heated-up to some degrees colder than +20° C. This feed will be cooler before the
valve and therefore even colder afterwards. Cooling down continues until the dew point of air
-191° C is reached. Then the first drops of liquid air begin to form and they stay in the
collection vessel. Now the process enters a stable and continuous production and the liquid can
be sent to a distillation column. The low-pressure air is dry so if it is sent back to the
compressor, the drier can be dimensioned smaller.
One can easily believe that cold is produced in the expansion valve, as the temperature sinks
there, but this is not the case. A valve neither adds nor takes away heat. Cold production is
carried out at the compressor with the following cooling, which removes the heat from the air.
This process is not so effective, only around 10 % of the compressed air becomes liquid. The
rest of the air is used for cooling down in the heat exchanger. As all of the air is compressed to
200 bar and this demands a great deal of energy, the energy consumption for the liquid
production is relatively large: 3,4 kWh/ Nm3. A small improvement is to install a refrigeration
machine that cools the air from -20 to -40°C. Such a process is also shown in figure 11.1.
11.3 Other Historical Processes for Liquid Air
Shortly after the Linde process, other processes were developed one of which by the
Frenchman, Claude, who was one of the founders of L'Air Liquide. He developed the
expansion machine, which utilised the kinetic energy in the expanding gas to carry out work.
An expansion machine is the opposite of a compressor. Its developed work can be used for
example, to drive an electrical generator. Owing to work is taken out of the air, the total energy
consumption per liquid product produced becomes less. Moreover, the cold production per m3
of high pressure air is larger, so that it is operated with much lower pressures than the Linde
process and still have a good yield. This means that a simpler compressor can also be used.
The difficulties to construct an expansion machine were great. It is a piston machine and it is
not able to produce liquid air, as its metal becomes brittle and the liquid will practically
pulverise the piston. Lubrication is also very difficult, as most lubrication media will solidify.
Selecting an outlet temperature over the dew point and using this gas in the heat exchanger
solved the difficulties, so that liquid is produced in an expansion valve. If one expands air of
100 bar with a temperature of -40° C, to 5 bar its temperature becomes -77° C, after a valve
while it becomes -158°C, after an expansion machine. This means that one must take out the
air to the expansion machine from a point in the heat exchanger where it is -40° C, in order to
get a good margin above the dew point at the outlet of the expansion machine.
See figure 11.2 The Claude Process for Liquid Air.
© Linde Gas AG Page 59 (109) 2001-02-20

(bar)
a-b compression
c-d “
e-f “
b-c water cooling
d-e “
f-g “
g-h valve expansion
j-k “
a-h cold production
g-j heat exchanger
k-h “
Figure 11.3 Pressure heat content diagram for air

Cold production in an expansion machine is proportional to the temperature sink in it and

the flow. A big flow causes lower temperature at the inlet and the sink is reduced. This depends
on the heat exchangers, more on this in 13.1. So increased flow can counteract the desired
increase of cold production. It is vice versa for reduced flow to the expansion machine. So you
have to find a good intermediary position.
Another way to improve cold production is to first cool the air in an ammonia cooler to -40° C.
This means that the air must be taken out from the heat exchanger at around -20° C before it
goes to the ammonia cooler. This cooling uses much less energy as, among other things, one
works at much lower pressure with the cooling media and the cooling media can carry a lot of
heat as it is a liquid which evaporates.
These improvements will reduce the energy consumption to 1,2 kWh/Nm3 of liquid air, which
is somewhat worse than modern turbo machinery can give.
11.4 Heat Content Diagram for Gases
To make the cold process more clear, we shall now go through how the airs heat content
(enthalpy, kJ/kg) changes with pressure and temperature.
See figure 11.3 Heat Content - Pressure Diagram of Air.
The vertical scale shows pressure and the horizontal scale heat content. The whole lines show
heat content for a certain temperature (in K). If we want to know, the heat content at, e.g. 50
bar and 300 K (= +27° C), we start on the vertical scale at 50 bar and go horizontally to the
right until we meet the 300 K line, which we mark. Then we go vertically downwards to the
horizontal scale and read off the heat content 285 kJ/kg. Similarly we can read off the heat
content 265 kJ/kg for 200 bar and 300 K.
One can see that the line for 300 K slopes off at the left for higher pressure, i.e. the heat content
reduces at high pressure if the temperature does not change. Note that the temperature curves
do not describe a working process with condition changes at, for example, compression, but
they are used to know the condition of the gas at a certain point. Compression can be put into
the diagram. Here one must know the pressure and temperature before and afterwards, so that
these two points can be put into the diagram. The succeeding cooling can be obtained by
putting in the point, for the condition after the cooling.
We know that an expansion valve does not change the heat content, so that if we expand the
air, which is at 50 bar and 300 K , to 1 bar, this can be shown on the diagram as a line going
vertically down. It will be colder as we end up on the left of the 300 K line. Using a ruler we
can estimate the temperature to be 292 K, i.e. a reduction of 8 K. In the same way we can
estimate the temperature, for an expansion from 200 bar at 300 K to 1 bar, which will be 264
K, a reduction of 36 K.
One can also see that the line slopes off dramatically at high pressures and low temperature, i.e.
the temperature sink in an expansion valve will be big under such conditions.
© Linde Gas AG Page 60 (109) 2001-02-20

1 6
Expansion
in valve
Real
2 Expansion
in machine
Ideal
s
line
Critical
ure
point
s
Temperature
Pres
Liquid
Gas Enthalpy lines
4 3 5
Gas + liquid
Entropy
Figure 11.4 T-s diagram for N 2

At the left side of the diagram there is a "bubble". This shows the area within which liquid and
gas are found together, i.e. liquid boiling together with gas at the dew point in equilibrium. To
the right of the bubble it is warmer and there is only gas. To the left of the bubble it is colder
and there is only liquid. The top of the bubble is the critical point (see 7.6). At higher pressures
and temperatures than the critical point there is no clear distinction between gas and liquid if
the gas is cooled.
Now we can see what happens if we have very cold gas at 200 bar and for example 150 K (-
123°C) and we expand it in a valve to 1 bar. As the pressure sinks we go vertically downwards
in the diagram and we enter the "bubble" where we will have a mixture of boiling liquid and
gas.
We will go back to the Linde process for liquid air. Let us for simplicity sake say that we start
with air at 200 bar and 300 K into the heat exchanger. We assume that the plant is well
insulated, so that there are no cold losses. As there is no cold production in this cold box the
heat content of the incoming air is equal to that of the outgoing gas + liquid. We read off the
diagram the heat content of in- and out-going gas together with the out-going liquid:
Gas 200 bar, 300 K = 265 kJ/kg

Gas 1 bar, 300 K = 300 kJ/kg
Boiling liquid 1 bar = -130 kJ/kg
Assume that 100 kg/h goes in and X kg/h of liquid goes out. Therefore (100-X) kg/h of air at 1
bar goes out. Now we can make an energy balance:
Energy in = energy out, therefore: 100 • 265 = (100 - X) • 300 + X • (-130)

26 500 = 30 000 - 300X - 130X, which is reduced to 30 000 - 26 500 = 430X and
X = 8,1 kg/h liquid and 100 - 8,1 = 91,9 kg/h air at 1 bar.
Using this equation, one can see that it is the state of the compressed air before the heat
exchanger, which determines how large the production of liquid air will become. High pressure
and low temperature will give a large production.
11.5 Entropy Diagram for Gases
The previous diagram is good to see expansion in a valve. In the diagram there are also dashed
lines for entropy, which is added or removed heat divided by the absolute temperature (K).
Changes in entropy are an important measure of how close to the ideal a process is. If the
entropy change is zero then the process is ideal. This is why entropy diagrams are constructed
and normally the temperature is the vertical scale and entropy is on the horizontal scale.
See figure 11.4 Temperature - Entropy Diagram for N2.
© Linde Gas AG Page 61 (109) 2001-02-20

On this diagram there are lines for different pressures that slope up to the right. Incidentally
these are called isobars, which means that the pressure is the same all along the line. The other
lines, which cross the isobars are the heat content (enthalpy), so that the diagram can also be
used to read off heat content. At the lower left you find the "bubble" for the liquid and gas
mixture. To the right of the bubble there is only gas and to the left only liquid.
This diagram is good to see the expansion in an expansion machine. In fact the theoretically
best, the ideal expansion has no entropy change. This would be in the diagram a line going
straight gown from the inlet point (see the diagram at, for example, 200 bar, 300 K) to the
outlet pressure at, for example, 5 bar. By putting a dot on the actual outlet point (e g 5 bar, 180
K = -93°C), one can compare the actual expansion, with the ideal.
Heat content values can also be read off this diagram, as these lines have been drawn in. We
will deal with these more carefully, when we go through the expansion turbines in the nitrogen
recycle (chapter 12).
It works well to compare expansions in machine and valve with this diagram. If we expand the
same air at 200 bar and 300 K, to 5 bar, then the valve expansion will go along a line for
constant heat content, as this has not changed. The outlet temperature will be 266 K = -7°C.
This means there is a considerably smaller temperature sink than in an expansion machine.
One can also put in the points for an entire liquefaction process, for example the Linde process
(see Fig. 11.1). Point 1 is air at 200 bar and 300 K on the way into the heat exchanger, where it
is cooled with unchanged pressure to point 2 by cold low pressure air, which goes in the
opposite direction. At point 2 the air is expanded on a line at a constant heat content to point 3
at a pressure of 6 bar. We are now in the liquid - gas area and using the dashed lines where it
states X = 0,9 etc., we can read off how big the gas part is, in our case X = 0,9 = 90 % which is
10 % liquid.
This mixture is separated in a collection vessel and the gas is at point 5 on the "bubbles" right
edge. Point 4 is liquid on the "bubbles" left edge. The cold gas from point 5 goes in the heat
exchanger where it cools down the high pressure air and is itself warmed up to approx. 300 K
along the isobar at 6 bar to point 6. Here the air is compressed and cooled to 200 bar and 300
K, but the different compressor stages are not drawn in.
To draw lines in the diagram is a way to form a picture of the process. These can also be drawn
in the pressure - heat content diagram. This may seem difficult at first, but it can simplify
understanding later on. The difficulty with air separation processes is it is cryogenic and that
most of the pipes and apparatus are in-built in the insulated cold box. So there are not so many
pipes and apparatus that can be seen in the machine hall and to feel the temperature of these
parts. This is otherwise a very good way to get to know how the process functions.
11.6 Temperature Diagram of the Heat Exchanger in a Liquefier
Deleted, as it will be gone through in 13.1 and 13.6.
© Linde Gas AG Page 62 (109) 2001-02-20

In
Out In
Out
Figure 12.1 Expander (left) - booster (right)
Closed impeller
Open impeller
Expander impellers with nozzles

12. EXPANSION TURBINES
Expansion turbines are used to produce cold. The difference from the expansion machines
mentioned in Chapter 11 is that the expanded gas sets into motion a turbine wheel (an impeller
of the same type as in a compressor, see Chapter 9). This gives mechanical work that can be
used by an impeller on the same shaft to compress gas, a booster.
In some older plants, for example, the old Stenungsund, Sweden, the work was used instead to
drive an electric generator. Here an interesting comparison can be made with electrical
production in a turbine with a generator in a hydroelectric power station. The falling water,
from high to low, gives work in a turbine. The height from which the water fall corresponds
directly to a pressure, which we can also measure in meter water gauge (=m wg, 10 m wg ≈ 1
bar). Electrical production depends directly on the height and water flow as well as pressure
drop and gas flow (temperature however can also vary).
12.1 Oil Braked Expanders
In plants with little liquid production, for example, Reykjavik, Iceland, with around 800 Nm3/h
LOX, it is not worthwhile to use the expansion work, so the work must be removed using an
oil brake. This increases the temperature of the oil and the heat is taken away in a cooler.
Such a turbine is also found in some older plants, for example, Vienna in Austria as a
complement to a booster-expander. It is used when the booster-expander is shut down in order
to produce sufficient cold to maintain production of GOX, GAN and LAR in the plant, the so-
called gas case. The biggest part of the cold production is required for the production of liquid
air gases, therefore only a small expander is required for the gas case, and this is also oil
braked. In newer plants with relatively large LAR-production, for example, Stenungsund, the
gas case is driven with a booster-expander with significantly reduced pressure and flow.
12.2 The Function of a Booster-Expander
See figure 12.1 Booster-Expander and Expander Wheel with Nozzle.
High-pressure gas goes to the expander through a nozzle, where the pressure is converted to
kinetic energy so that its velocity increases considerably. The pressure sinks to around half. The
gas stream meets the impeller in the same direction as it is rotating at a velocity, which matches
the speed at the outer part of the wheel. The best efficiency is when the wheel velocity is 65-75
% of the gas velocity. The gas is forced to the centre between the blades and is sent out
backwards by the pressure drop. The backward moving gas stream drives the wheel forwards.
From the outlet the gas moves axially in a pipe.
The blades are bent backwards at the outlet in such a way that the rotation of the gas is as little
as possible to hold down losses. Turbines, which can produce some liquid, have the blades at
such an angle from the wheel's radius, that no force is developed that makes droplets drive onto
any of the blade surfaces.
© Linde Gas AG Page 63 (109) 2001-02-20

50 bar
Nozzles
Seal gas Return to Gap pressure, 25 bar
compressor
Blow off to atm.
Bearing
5 bar
Oil ring
Oil out
Figure 12.2 Seal gas to expander
Normal operation, Start-up,

valve 425 and 426 closed valve 425 and 426 open
Figure 12.3 Balancing axial forces

The blades were not manufactured in that way in the 1980's or earlier for these turbines, so they
have strict instructions that the outlet temperature shall be maintained with a margin over the
dew point.
Altering the opening between the nozzles controls the expander’s capacity, which alters the
volume flow. This is the effective volume mentioned in 9.3. This means that it depends on the
inlet pressure and temperature, so if the pressure, for example, increases, the flow in Nm3/h
also increases with the same nozzle setting.
The expander work is used for further compression of the high pressure N2 in the booster,
which after cooling in a heat exchanger goes to the expander (more on this in the next chapter).
The booster is a single stage compressor, so it must be protected against surging (see 9.7). It
takes up exactly the same work as the expander gives out less the bearing losses. This means
that if the flow to the booster is too little, then the shaft revolutions will increase. As there is a
limit for how much the machine can take there is a switch for too high revolutions.
If the flow to the booster is sufficient and one increases the flow to the expander, it may happen
that one reaches the limit for what the booster can "shovel" away. This cause the pressure
before the booster to rise and the pressure uptake must increase to be able to give off the
increased expander work. This means that a outlet pressure increases yet again, so that it can
cause a safety valve to blow.
As the booster and expander are on the same shaft there are many problems with sealing and
balancing etc which must be solved.
12.3 Labyrinths, Gap Pressure and Seal Gas
As half of the pressure drop lies over the expansion wheel, this must be sealed so that the gas
does not pass outside it. There are two types of wheels, open or closed, see Fig 12.1. The
closed wheel has labyrinths, which go into a ring of carbon. The open wheel must be
manufactured with great precision, so that the gap between it and the wall is not too large.
When the flow increases it is harder for the gas to go through the wheel and the pressure after
the inlet nozzles increases. In the gap between the inlet and outlet there is a pressure drop, gap
pressure, which increases. This increases leakage in the gap and the load on the labyrinths.
Therefore often there is a switch for high gap pressure.
Expansion turbines work at very low temperatures. This part of the machine must be
thoroughly insulated. But the turbine shaft bearings are lubricated with warm oil, so they must
be protected against the cold.
See figure 12.2 Seal Gas to the Expansion Turbine.
This is carried out in such a way that beyond the output of oil from the bearing, there is a
labyrinth on the shaft (the same type as in the compressor, see 9.1) to reduce oil leakage to this
part, where the seal gas is blown out to the atmosphere. There is a further labyrinth and the seal
gas feed. There is again a labyrinth to yet another blow out of seal gas. Following this there is
another labyrinth to the expansion turbine itself.
© Linde Gas AG Page 64 (109) 2001-02-20

In : 267 K; 28,3 bar
s
re line
T2
Pressu
In : 176 K; 58,5 bar Out : 179 K; 5,7 bar
Ideal out : 5,7 bar
Critical T1
point
Temperature
Liquid
Gas Enthalpy lines
Out : 96 K; 5,8 bar

1% liquid
Gas + liquid
Entropy
Figure 12.4 T-s diagram for warm and cold expander

The pressure at the inlet of the expansion turbine is around half of the pressure before the
nozzle. The gas leaks behind the impeller towards the shaft through the labyrinth and its
pressure sinks. To prevent the cold gas continuing to the bearing, seal gas at a somewhat
higher pressure than the cold gas is added. The seal gas is blown out in two directions,
towards the cold gas and towards the oil. This holds down the cold process gas leakage by it
own back pressure and possible particles from wearing out as well as the cold gas are blown
out, protecting the bearing. The seal gas, which is blown out at the bearing, carries away the oil
leakage.
12.4 Balancing the Shaft Axial Forces
To prevent movement in the axial direction, an axial bearing is situated on the shaft. As the
outlet gas of the expander goes out axially, then a force occurs in the opposite direction on the
shaft. In normal operation this force is largely balanced out by the force which occurs in the
booster side, as there the gas goes in axially.
See figure 12.3 Balancing the Shaft Axial Forces.
The shaft axial bearing can cope with the resulting force, but with start ups and wear in the
labyrinth too large shaft-forces occur. A piston (disc) on the shaft, which is fed with gas from
the booster inlet, can balance these. The larger the shaft forces become then the larger
consumption of process gas with pressure. The gas can be fed back to the suction side of the
recycle compressor, so that there will only be a pressure loss.
12.5 Efficiency of an Expansion Turbine
Efficiency is the actual cold production (=heat content reduction) divided by the ideal. The
ideal cold production is expansion at constant entropy, which was mentioned in 11.5. This is
called isentropic expansion, so therefore the efficiency is called isentropic. Now we shall see
how this is on a temperature - entropy diagram.
See figure 12.4 Temperature - Entropy Diagram for Cold and Warm Expansion Turbines.
In the diagram a line has been drawn representing expansion in a cold turbine (T1) and a warm
turbine (T2). In plants from the mid 1980's and older, there are no warm turbines, as a -40°C
refrigeration machine is used instead.
The in-and outlet points are marked with knowledge of their pressures and temperatures,
respectively. The ideal outlet point for T2 is obtained by going straight down from the inlet
point to the outlet pressure line. This means that the entropy has not changed, as this is on the
horizontal scale of the diagram.
We can read off the enthalpy (heat content) at the points for T2. The inlet point lies between
the enthalpy lines 7400 and 7600, the outlet point between 5000 and 5200 and the ideal outlet
point between 4800 and 5000 (kJ/kmol). We can find out, using a ruler the enthalpy values: in
= 7575, out = 5110 and ideal out = 4850. Actual cold production = 7575 - 5110 = 2465 and
ideal cold production = 7575 - 4850 = 2725 kJ/kmol (1 kmol N2 = 28 kg).
© Linde Gas AG Page 65 (109) 2001-02-20

Therefore the isentropic efficiency = (7575 - 5110)/ (7575 - 4850) • 100 = 90 %.
This is a relatively complicated work, which you do not need to do. We at AGA have
developed a Lotus PC program, which can carry-out this calculation. You enter the temperature
and pressure for the in- and outlets and get the efficiency instantly. The diagram calculations
are described to give a better understanding of expansion turbines and efficiency.
Unfortunately, it is not possible to calculate the efficiency for the cold turbine T1, as it
produces some liquid that is not measured. The only way is to calculate how much work the
booster has taken up.
12.6 A simpler Check of Expander Efficiency
There is a simpler way to check the efficiency for T2. This is the temperature drop, which
should be compared with the value from earlier operation with the same loading, preferably the
acceptance test. This gives a good indication of efficiency if the flow and pressures are the
same. A change of more than 2°C is significant if the accuracy in the respective temperature
meters is +/- 1°C. You should check the accuracy in the specification for your plant.
In the temperature-entropy diagram one can observe a worsened efficiency, in such a way that
the outlet point is moving upwards along the slope of an isobar (constant pressure line), and the
temperature is increasing. We can also see that the entropy increases which means a less
efficient process. Outlet enthalpy increases resulting in reduced cold production.
This method cannot be used with T1, as liquid forms in it. As the outlet pressure is constant the
temperature will also be constant (according to the vapour-pressure curve, which we went
through in 6.2). So a reduced efficiency does not alter the outlet temperature, but the liquid
flow is reduced, which is not measured.
One can also see in the diagram what happens if the outlet pressure rises, which in itself does
not change the efficiency. If we, for example, increase the outlet pressure at T2 from 5,7 to 6,0
bar, the outlet enthalpy increases from 5110 to 5200 so that the cold production reduces from
2565 to 2475, which is 3,5 %. Such a pressure rise is not impossible. In a process with a
nitrogen recycle this depends on, as we shall go into more detail later, the pressure in the lower
column, which in its turn depends on the air flow and the upper column pressure.
By the same method we can see what happens if the inlet pressure rises….(doubtful, deleted)
It is easy to sit and increase cold production by making simple changes in a diagram. In
practice it is maybe not so easy, for example, to increase the pressure at the T2 inlet, one will
get it to reduce cold production in T1 or reduces the inlet temperature at T2 which is a
counteraction etc. When, at last, one attempts to increase cold production one must test by trial
and error how to get more liquid to the tank.
© Linde Gas AG Page 66 (109) 2001-02-20

Figure 12.5 Nitrogen enthalpy from Vasserman's tables
330
325
320
Enthalpy (kJ/kg)
315
p = 25 bar
310 p = 35 bar
p = 30 bar
305
300
290 295 300 305 310 315 320 325 330
Tem p (K)
12.7 Measuring the Cold Production of the Boosters
To simplify the optimisation of cold production we have developed a method to calculate how
much work the boosters have taken up. These take up all the work that the expanders give out,
except for losses in the bearings, which are a small part of the transmitted work and are as such
rather independent of the loading.
The work which is taken up by a booster is: flow (F) multiplied by the enthalpy increase (hout -
hin) of the gas. The enthalpy depends, which we have seen in the temperature-entropy or
pressure-enthalpy diagrams, only on the pressure and temperature of the gas.
See figure 12.5 Nitrogen Enthalpy from Vasserman’s Tables
To simplify the enthalpy calculation we have calculated with a PC a simple (= linear) enthalpy
equation which depends on pressure (P) and temperature (T) based on a data table. This is
possible within the normal working range of a booster.
Booster work = F (Nm3/h) • d (kg/Nm3) • (hout - hin) (kJ/kg)

of which work becomes in (kJ/h)
Density of N2: d=1,25 kg/Nm3
Enthalpy: hin = -0,205 • P + 1,094 • T - 16,97
hout = - 0.144 • P + 1,094 • T - 19,42
(Calculated for the booster to T2 in the previous example).
These equations give an error less than 0,5% compared to the data table. Using signals; for
flow, pressure in and out, temperature in and out to the process computer and having put in the
calculation equations the cold production can be calculated "on-line".
The same calculation is carried out for the second booster and the sum of cold production is
calculated and shown on the display of the process computer. This gives a good help in
making fine adjustments for maximum cold production.
In plants with refrigeration machine for -40°C the enthalpy equation becomes simpler:
hout - hin = cp • (Tout - Tin)
Where cp is the specific heat, which is taken from tables.
To be able to carry-out the calculation there must be signals from all of the named
measurements points to the process computer, and the equations must be loaded into the
computer. At present this has only been done in Tepeji and Donawitz.
© Linde Gas AG Page 67 (109) 2001-02-20

12.8 Cold Requirements for the Production of Liquid
Using Vasserman’s tables we can calculate how much heat must be removed (cold production)
to produce liquid from pure gases at + 20°C and 1 bar. This includes the enthalpy of cooling
down to the boiling point and the heat of condensation (= heat of evaporation in tables).
LOX : 569 kJ/Nm3

LIN: 529 "
LAR: 479 "
This explains why the production in Nm3/h in the max LIN case is bigger than in the max LOX
case.
Using the calculated cold production in the booster the total liquid production can be estimated,
but this includes all cold losses. We can also calculate what the cold loss in the main heat
exchanger in the example in chapter 7.4 is corresponding to in LOX production.
Cold loss = 30 000 kJ/h
Loss of LOX = 30 000 (kJ/h) / 569 (kJ/Nm3) = 52,7 Nm3/h
12.9 LOX equivalents of Nm3 (New in version 4)
In order to be able to compare production at varying LOX, LIN and LAR quantities but with
same cold production, has been introduced the LOX equivalents. This is a recalculation of LIN
and LAR quantities into LOX based on the table of cold requirements in preceding section.
One Nm3 LIN corresponds to 529/569 = 0,93 Nm3 LOX.
1 Nm3 LIN= 0,93 Nm3 LOX equivalents

1 Nm3 LAR= 0,84 Nm3 LOX equivalents
Certain gas companies use LIN as a reference. Then 1 Nm3 LOX = 1,08 Nm3 LIN equivalents.
© Linde Gas AG Page 68 (109) 2001-02-20

14560 Nm3/h 775 Nm3/h
HC6 13785 Nm3/h

TI TI
PI 11 8 -165
5,4 14
-165 -93
T1 49,0
PI
13
Leak gas
FI TR
E3-4 7 E5 1-11 HC19 Liquid 2945 K1
Gas 655
PI
39,0
11
TC3 49,5 +30
-93 3600 -163
PI TI NS
FI 12 6 HC20 5,4 bar
18500 5 TI -117
Leak gas +27 12 HC8
TI TI
5 4 PI
-26
TC2 8
LIN
C1
TI tank
7
5,1 PI AEV2 TR -120
10 1-12
-40
HC3
TR
NH3 1-8 HC2
FI 2165 -176
HC4 3 3940 Nm3/h
FI TR TR
4 1-4 1-7 4715 Nm3/h
TI
3 2550 +5,5 -175
TR TR
1-3 +5,5 50 Nm /h
3
GOX 1-6 TI
TI
2 +5,5 4000 GAN -175 18
TR TR
1-2 +5,5 2965 Waste N2 -179 1-5
+8,5 9800 Air -171
E1-2 o
T in C
P in bar g
F in Nm3/h
Figure 13.1 Nitrogen recycle with one expander (Malmö) Net liquid production:
2360 Nm3/h
13. COLD PRODUCTION IN THE NITROGEN RECYCLE
The most common way to produce cold to get liquid products is the nitrogen recycle, which we
will go through in more depth here. Moreover, an overview is also given of other processes
existing within AGA.
In principle, the nitrogen recycle is a development of the Claude process, which we discussed
in 11.3. This process was manufactured and installed until the late 1970's and is still in use in
Russia. Piston compressors for high-pressure air and piston type expansion machines were
used. These machines demand much more maintenance than turbo machinery. In 1970, the first
modern installation came in Malmö, Sweden, with a nitrogen recycle where turbo compressors
were used. It became possible to manufacture turbo compressors with higher pressures than the
long existing turbo compressors for air at 6 bar, which are used in plants that produce only
gaseous oxygen. Plate heat exchangers also began to be manufactured for the necessary
pressure at affordable prices.
Sandviken, Sweden continues to use a Malmö type recycle, and in newer plants they are
changed somewhat which is described in the following overview.
13.1 Nitrogen Recycle with -40°C Refrigeration Machine and One Cold Expansion Turbine
with Booster
The basics of the Claude process remain: A compressor (TC2, TC = turbo compressor), two
heat exchangers (E3 - 4 and E5, E= exchanger), an expansion turbine (T1) and an expansion
valve (HC19). In addition there is an ammonia (NH3) refrigeration machine and a booster
compressor (TC3) coupled with the expansion turbine.
See figure 13.1 Nitrogen Recycle with Main Heat Exchanger in Malmö.
There is besides a main heat exchanger (E1-2) and it requires a balance stream and a compen-
sation stream from the recycle, which was described in 7.5 and 7.6. Valve HC4 and
respectively HC3 control these. If HC3 is fully open and the flow is not enough, one can close
HC20 a little, which controls the flow of LP-nitrogen from the turbine through E5. This forces
more flow to E1-2.
Cold nitrogen that shall become liquid is taken from the top of the pressure column (C1)
through the make-up valve HC2. This flow is equal to the liquid production +gas losses in the
compressor and booster. This flow goes through the main heat exchanger as a balance stream,
to balance the reduction of the returning gases in E1-2 because of liquid production. Yet
another stream through the cold end is the compensation stream, which is taken from the outlet
of the expansion turbine, which goes in with the flow from C1 after HC2.
The balance stream becomes heated to around +5° C and goes together with the warmed up
low-pressure nitrogen coming out from E3-4 to go into TC2. There approx. 18 500 Nm3/h is
compressed to 39 bar. TC3 takes up so much work from T1 that it additionally compresses to
49,5 bar. This stream is cooled in E3-4 to -26° C and is taken out to the refrigeration machine
to be cooled to -40° C.
© Linde Gas AG Page 69 (109) 2001-02-20

14560 Nm3/h 775 Nm3/h
HC6 13785 Nm3/h

TI TI
PI 11 8 -165
5,4 14
-165 -93
T1 49,0
PI
13
Leak gas
FI TR
E3-4 7 E5 1-11 HC19 Liquid 2945 K1
Gas 655
PI
39,0
11
TC3 49,5 +30
-93 3600 -163
PI TI NS
FI 12 6 HC20 5,4 bar
18500 5 TI -117
Leak gas +27 12 HC8
TI TI
5 4 PI
-26
TC2 8
LIN
C1
TI tank
7
5,1 PI AEV2 TR -120
10 1-12
-40
HC3
TR
NH3 1-8 HC2
FI 2165 -176
HC4 3 3940 Nm3/h
FI TR TR
4 1-4 1-7 4715 Nm3/h
TI
3 2550 +5,5 -175
TR TR
1-3 +5,5 50 Nm /h
3
GOX 1-6 TI
TI
2 +5,5 4000 GAN -175 18
TR TR
1-2 +5,5 2965 Waste N2 -179 1-5
+8,5 9800 Air -171
E1-2 o
T in C
P in bar g
F in Nm3/h
2360 Nm3/h
It goes back to E3-4 and is cooled to -93°C at the outlet. There the stream is divided: 3600
Nm3/h goes to E5 to be cooled to -163° C and after the expansion valve, HC19, 2945 Nm3/h
LIN and a little gas goes to the column. This is somewhat more than the cold production to the
tank 2360 Nm3/h, as it shall compensate for cold losses as well. The other part of the divided
stream, approx. 14 500 Nm3/h goes to the expansion turbine where gas is obtained at -165° C
and 5,4 bar. The pressure is equal to the pressure in the top of column C1, if valve HC2 is fully
open.
A larger part of this expanded gas goes to E5 to cool the high-pressure nitrogen. A small part
goes together with the feed from column C1, so that it will be sufficient for both the balance
and compensation streams in E1-2.
The low-pressure nitrogen which has gone through E5 and valve HC20, has warmed to almost
the same temperature as the compensation stream from E1-2, these streams are mixed and go
through E3-4. There it is warmed up to approx. 3° C colder than the high-pressure nitrogen at
the warm end and goes to the suction side of TC2. The temperature of the HP-Nitrogen is set
by the cooling water temperature and by how clean the booster cooler is.
So now we are back to where we started. This is the reason why it is called a recycle. Nitrogen
in the recycle can be likened to the ammonia that circulates in refrigeration machines as
cooling media. The difference is that the nitrogen is both the cooling media at approx. 15,500
Nm3/h and that which shall be cooled, approx. 3,000 Nm3/h.
The best way to operate this recycle is to: When TC2 is at maximum and the make-up from
column via HC2 is fully open, the balance and compensation streams are correctly set and the
refrigeration gives -40° C; divide the flow between the expansion valve and turbine. HC19
and the turbine nozzles control this, HC 6. This affects the temperatures in the heat
exchangers E5 and E3-4, as most of the expanding gas is used to cool the high-pressure gas.
More flow to the turbine gives more cold to the heat exchangers and the temperature of the
high-pressure gas sinks, which also goes to the turbine, and vice versa. HC19 is throttled in
order to increase the pressure to T1, but please note that this affects also the temperatures of
E3-4.5.
If too much goes to the turbine this gives a too cold temperature and relatively little cold
production per Nm3, because of the physical properties of the gas (the curve for expansion is
moved in the T-s diagram). Too little to the turbine gives good cold production per Nm3, but a
small flow gives little cold production. An ideal flow to the turbine should be found in between
these extremes. This can be seen from the temperature difference at the cold end of E5 which is
approx. -163° C + 165° C = 2° C and that the temperature to the turbine is approx. -93° C.
There is an advantage of the balance and compensation streams in the main heat exchanger.
This lead to a reduced quantity of LP gas that is returned to the nitrogen heat exchanger and
that the turbine inlet does not get very cold. More cold can then be produced in the turbine.
This process does not disturb the pressure column very much, as GAN is taken out from the top
and LIN is sent back, which means that it functions as a condenser and gives reflux to the
column. This means that no liquid is required to be fed in with the air, as in certain other
processes and all of the air will rise in the column, giving more reflux as the gas condense at
the top. If liquid is fed in with the air, it cannot be separated in the pressure column, but it goes
out with the rich liquid.
© Linde Gas AG Page 70 (109) 2001-02-20

14560 Nm3/h 775 Nm3/h
HC6 13785 Nm3/h

TI TI
PI 11 8 -165
5,4 14
-165 -93
T1 49,0
PI
13
Leak gas
FI TR
E3-4 7 E5 1-11 HC19 Liquid 2945 K1
Gas 655
PI
39,0
11
TC3 49,5 +30
-93 3600 -163
PI TI NS
FI 12 6 HC20 5,4 bar
18500 5 TI -117
Leak gas +27 12 HC8
TI TI
5 4 PI
-26
TC2 8
LIN
C1
TI tank
7
5,1 PI AEV2 TR -120
10 1-12
-40
HC3
TR
NH3 1-8 HC2
FI 2165 -176
HC4 3 3940 Nm3/h
FI TR TR
4 1-4 1-7 4715 Nm3/h
TI
3 2550 +5,5 -175
TR TR
1-3 +5,5 50 Nm /h
3
GOX 1-6 TI
TI
2 +5,5 4000 GAN -175 18
TR TR
1-2 +5,5 2965 Waste N2 -179 1-5
+8,5 9800 Air -171
E1-2 o
T in C
P in bar g
F in Nm3/h
2360 Nm3/h
The disturbances that can occur because of the nitrogen recycle: is increasing compressor
leakage and that the column pressure is affected. When leakage occurs gas is taken from the
top of the column and is not sent back, which reduces the reflux. This cause reduced reflux to
the upper column and increased oxygen loss in the Lachmann gas (see 6.10). We will come
later to see that even the argon loss increases in the Lachmann. A change in cold production
will change the flow to the condenser, which will affect the pressure column's pressure (see
6.3). Reduced cold production gives increased column pressure.
Nitrogen recycle processes with separate recycle and main heat exchangers are flexible in that
liquid production can be varied between 60-100 % independent on the quantity of air, which in
turn can vary between 60-100 %, independently on the liquid production. At small airflows it is
however difficult to achieve 100 % liquid production as the column pressure will become
lower (see 6.3 - Condenser Pressure), which gives reduced suction pressure to TC2 and less
cold production.
13.2 Reduction of Cold Production in the Nitrogen Recycle
At full cold production valve HC2, the make-up from column C1 to the recycle, is fully open.
That what goes through is the same as what leaves the recycle with HC19 expansion valve +
compressor and booster gas leakages. TC2 goes with constant flow and pressure ratio and
sucks in the correct flow from HC2, as the remainder that is sucked in is that which circulates
in the recycle. With HC2 fully open the load on TC2 will be at maximum, which gives max
cold production with right distribution between HC19 and the turbine. This gives right flow to
HC19 and to circulation in the recycle.
If for some reason, there is too little gas coming in through HC2, then TC2 will have too little,
as it needs a constant flow volume. As it "shovels off" gas at the same rate as before, the
pressure drops on the suction side. From what we went through the function of compressors
(9.5), we know that a compressor takes in a constant suction flow in effective m3 and that if its
pressure goes down the flow in Nm3 reduces. The pressure ratio is unchanged so the outlet
pressure will also sink. This means that we cannot produce the same amount of cold in the
expansion turbine, as its cold production depends on flow and pressure.
This means that we can reduce cold production in the recycle by closing the make-up valve
(HC2) from the column a little. This does not apply only to the Malmö type recycles, but also
to modern types with warm turbines instead of -40° C refrigeration machines.
When one using this method reduces the flow Nm3/h through TC2, the flows in the heat
exchangers will be changed, so the turbine inlet nozzle and expansion valve must be adjusted.
This is to achieve the correct inlet temperature to the turbine and the correct ∆T in the cold end
of heat exchanger E5, which was described on preceding page.
We can calculate the new flow to TC2 using the gas equation (see 9.5) at a suction pressure, for
example, of 3 bar g. The calculation is somewhat simplified by setting the suction temperature
to 0°C not +20° C as it is.
© Linde Gas AG Page 71 (109) 2001-02-20

3245-1
Atm.
FIC
Figure 13.2 Flow Schematic of a Nitrogen Recycle with two Turbines
Q-3271
3261
(9 400) F-2615 (17 800)
FIC T-2615 (11)
E3116
PIC P-3930 (0,12)
Air T - (-172)
T-3930 (21)
GAN
Waste N2 P - 3261 (0,32)
Atm. T-3925 (21) Q-3220
F-3925 GOX
3
T-3156 (-177) 15000 Nm /h
QIC T-3935
Q-3935
(21)
N2 Seal T-3401 (-97)
T-3451 (-6) P-(56,2)
P - (27,3)
TIC
P-3211
P-1311 T2 T1 (0,56)
(0,06) (-93) T-3402 D3631
T-3452 (-177)
TC5
S-3451 S-3401 LIC FIC
PIC (28 000) (25 000)
TCV-3401
F-1310
(9 400)
P-(4,65) P-3410 (56,7) F-3455 F-3245 (6987)
F-3405
T-(25) T-(24) TC4 (56 600) TC3 (56 700) P - (4,8)
FIC
Shaft PIC F-3411 Design data within parenthesis
(28 300) o
T in C
F-1410 P in bar g P-3201
(85 000) 3
F in Nm /h Air (4,94)
P-1410 P-1411 (27,6)
(4,65) T-1409 (24)
TC2
Max cold production Reduced cold production

Column pressure (bar g) 5,4 5,4
Compressor suction (bar g) 5,4 3,0
Compressor flow (Nm3/h) 18 500 X
Effective volume (m3/h) 18 500/(5,4 + 1) = X/(3,0 + 1) =
= 2891 = X/4
The effective volume to the compressor is unchanged so:
2891 = X/4 therefore X = 11 563 Nm3/h.
This flow is almost proportional to cold production so it becomes 11 563/18 500 = 63%.
13.3 Nitrogen Recycle with Warm and Cold Expansion Turbine with Boosters
From the mid-1980's the -40°C refrigeration machines were replaced by an additional
expansion turbine, the so-called warm turbine, as it works at higher temperatures than the other
turbine. The process is more efficient and uses less energy, but it is more complicated. There
will be an additional booster, with a different pressure, and an expander, therefore an additional
passage in the heat exchanger. There will also be an additional flow division which must be
carried out by the operator, not only between the expansion valve and turbine, but also between
the warm and cold turbines.
Take as an example the process in Eggborough, England, which was put into operation at the
end of 1993. Here, however, the recycle heat exchanger is combined with the main heat
exchanger, which is not common, so that there are no balance and compensation streams. This
means that the flow to the expansion valve must be controlled in relation to the airflow to
maintain the balance, so the process will be less flexible than with separate heat exchangers.
See figure 13.2 Flow Schematic of a Nitrogen Recycle with two Turbines.
The basic components are also found in this recycle: A turbo-compressor TC2, a cold booster-
expander TC3-T1, an expansion valve TCV-3401, a make-up valve FIC-3245 and parts of the
main heat exchanger E3116. Also there is a warm expander-booster TC4-T2, replacing the -40°
C refrigeration machine and a liquid separator D3631 after the cold expander as it produces
little liquid.
Also there is a feed compressor TC5, which is not there for the cold production, but is used to
improve the reflux in the pressure column.
Eggborough produces 12200 Nm3/h of liquid, so there must be a relatively large flow in
TC2 = 85000 Nm3/h. This flow is around 7-8 times the liquid production in all of the
nitrogen recycles. The pressure rises from 5 to 27,5 bar. After TC2 there is the first division
of the flows. The larger part goes to the cold booster TC3 and the smaller part to the warm
expander T2.
© Linde Gas AG Page 72 (109) 2001-02-20

3245-1
Atm.
FIC
Q-3271
3261
(9 400) F-2615 (17 800)
FIC T-2615 (11)
E3116
PIC P-3930 (0,12)
Air T - (-172)
T-3930 (21)
GAN
Waste N2 P - 3261 (0,32)
Atm. T-3925 (21) Q-3220
F-3925 GOX
3
T-3156 (-177) 15000 Nm /h
QIC T-3935
Q-3935
(21)
N2 Seal T-3401 (-97)
T-3451 (-6) P-(56,2)
P - (27,3)
TIC
P-3211
P-1311 T2 T1 (0,56)
(0,06) (-93) T-3402 D3631
T-3452 (-177)
TC5
S-3451 S-3401 LIC FIC
PIC (28 000) (25 000)
TCV-3401
F-1310
(9 400)
P-(4,65) P-3410 (56,7) F-3455 F-3245 (6987)
F-3405
T-(25) T-(24) TC4 (56 600) TC3 (56 700) P - (4,8)
FIC
(28 300) o
T in C
F-1410 P in bar g P-3201
(85 000) 3
P-1410 P-1411 (27,6)
(4,65) T-1409 (24)
TC2
Approximately 28000 Nm3/h goes to T2 via the heat exchanger E3116, where it is cooled to
-6°. It expands to 5 bar and -93° C and is fed to E3116 to a carefully calculated point, where it
meets the expanded gas from T1 warmed up to the same temperature. This gas mixture is
further warmed-up and leaves E3116 at +21° C, approx. 3° C colder than the incoming high-
pressure nitrogen. This then continues to the suction side of TC2.
The other flow from the division after TC2 is 57000 Nm3/h and it goes to TC3, where the
pressure is raised to 40 bar. It is cooled with water in an aftercooler and goes on to the warm
booster TC4 where the pressure is raised to 58 bar. It is then cooled in an aftercooler to +24° C
and goes into E3116. This temperature controls the temperature of the outgoing low pressure
nitrogen. It is cooled to -97° C and at a carefully calculated point there is the second division of
the flows: Approximately 15000 Nm3/h continues in the heat exchanger and is cooled to -177°
C. Then it goes to the expansion valve where the larger part becomes liquid, which goes to the
pressure column.
The larger part of the divided flow, 41000 Nm3/h from the 2nd division goes to the cold
expander; where the outlet pressure is 5 bar and the temperature -177° C. As liquid forms, the
temperature becomes controlled by the pressure according to the vapour pressure curve (6.2).
The liquid is separated in D3631 and goes to the upper column as reflux. It cannot go back to
the pressure column, as its pressure is somewhat too little. This pressure is set by the gas over
the liquid, which in its turn becomes somewhat lower than the column pressure, as there is a
small pressure drop in the pipe with the control valve FIC-3245 from the column. At this point
the gas from D3631 meets the make-up.
The make-up from the column and the expanding gas from D3631 go into the heat exchanger
and is warmed up as it cools the high pressure nitrogen. At -94° C it meets the low-pressure
nitrogen from T2 (mentioned above). It is warmed up to +21° C at the outlet of E3116 and goes
to the suction side of TC2. The circle is complete in the recycle.
13.4 Feed Compressor to Increase Reflux
The feed compressor takes GAN from the upper column at 0,2 bar, which is warmed up in
E3116 and compresses it to 5 bar and sends it to the suction side of TC2. In this way the
recycle is fed not only from the pressure column but also from the upper column. This means
that more gas will be left in the pressure column, which can rise to the condenser, so that we
will have more reflux.
The feed compressor takes 9000 Nm3/h and 15 000 Nm3/h goes through the expansion valve.
So using a material balance for the whole recycle, we can calculate how large the make-up is:
Make-up + feed = Exp. valve flow + gas leakage in TC2, 3, 4 + T1 liquid

Make-up + 9000 = 15 000 + 200 + 300
Make-up = 6500 Nm3/h
If we do not have a feed, then the make-up must increase to 15500 Nm3/h to balance the liquid
which leaves the recycle in the expansion valve. With more reflux we have a better yield in the
upper column, more oxygen and argon but there is a electrical consumption cost in the feed
compressor.
© Linde Gas AG Page 73 (109) 2001-02-20

3245-1
Atm.
FIC
Q-3271
3261
(9 400) F-2615 (17 800)
FIC T-2615 (11)
E3116
PIC P-3930 (0,12)
Air T - (-172)
T-3930 (21)
GAN
Waste N2 P - 3261 (0,32)
Atm. T-3925 (21) Q-3220
F-3925 GOX
3
T-3156 (-177) 15000 Nm /h
QIC T-3935
Q-3935
(21)
N2 Seal T-3401 (-97)
T-3451 (-6) P-(56,2)
P - (27,3)
TIC
P-3211
P-1311 T2 T1 (0,56)
(0,06) (-93) T-3402 D3631
T-3452 (-177)
TC5
S-3451 S-3401 LIC FIC
PIC (28 000) (25 000)
TCV-3401
F-1310
(9 400)
P-(4,65) P-3410 (56,7) F-3455 F-3245 (6987)
F-3405
T-(25) T-(24) TC4 (56 600) TC3 (56 700) P - (4,8)
FIC
(28 300) o
T in C
F-1410 P in bar g P-3201
(85 000) 3
P-1410 P-1411 (27,6)
(4,65) T-1409 (24)
TC2
From the material balance we can see that if gas leakage from the recycle compressor and
booster increases, this results in that the make-up to the recycle must increase, which then
means that we loose reflux in the pressure column.
In Eggborough the feed compressor consists of two stages which is two impellers on one shaft,
which is driven by a large gear wheel in the recycle compressor. This can be seen as a six-stage
compressor, each with three impeller pairs driven by the large gear wheel. Consequently there
is one impeller pair more than in the compressor shown in 9.6. In some plants there is a
separate feed compressor and in others none at all, particularly in plants dated before 1984.
Feed compressors existed in certain plants in the 60’s.
13.5 Controlling the recycle with warm and cold booster-expander (rev. in version 4)
To achieve maximum cold production you begin by running the maximum amount of air to
get the highest possible pressure in the pressure column. This also gives maximum
separation. If the separated O2 and Ar is not needed, one can increase the pressure on PIC-
3261 for the upper column (see chapter 19.6) and reduce the amount of air. The make-up
valve (FIC-3245) is then opened fully from the pressure column to the recycle to obtain the
greatest possible suction to the recycle compressor, TC2. The capacity can then be increased
on TC2 to maximum with PIC, which controls its guide vanes.
Downstream of TC2 there are two dividing points. The first is between the warm expander,
T2, and the cold, T1, which goes via boosters and heat exchangers. The second is between
the Joule-Thomson (J-T) valve (TCV-3401) and T1. In both of the dividing points the
distribution is set so that design flow and pressure are obtained initially. It is controlled by
the flow (FIC) to T2 through its nozzles, by the pressure (PIC) through high-pressure N2
from TC4 to E 3116 through the nozzles on T1 and by the temperature to T1 (TIC) through
the J-T valve.
Remember when setting FIC that a warm expander gives greater cold production than a cold
one. Design T2: 857 kW cold production and 28300 Nm3/h N2 and T1: 889 kW and 41168
Nm3/h N2, i.e. 3.0 and 2.2 kWh/100 Nm3 respectively.
The TIC on the way to T1 controls the flow to the J-T valve. Accordingly, the temperature
of HP-N2 is also controlled all the way in the heat exchanger from the outlet to T1 and on to
the valve. It is therefore possible to control the valve with the temperature prior to it, which
exists in some installations. The advantage of controlling the temperature to T1 is that it
varies much more than prior to the valve.
All of these three controllers and even PIC on TC2 interact, so it is very difficult to predict
what will happen, even if one alters only one of them. I recommend making tests on the
basis of the design case and that small alterations are made on the regulators one at a time. It
is difficult to determine when greater production of cold is really made by looking at
process data. The only reliable way is to measure the liquid production in the tanks (chap.
20.5) overnight. One can also measure the production of cold in the boosters, as suggested
in chap. 12.7.
© Linde Gas AG Page 74 (109) 2001-02-20

Figure 13.3 Eggborough: QT-diagram för heat exchanger
E-3116
310
290
Air
WN
270
T2 (WE exp) 28 bar
250
Qw N2 57 bar, Air
230
Temperature (K)
210
Qc GAN+ WN
+GOX+N2 5 bar
190
T2 (WE exp) 5 bar

T1 (CE exp) 57 bar
170
150
130
110
T1 (CE exp) 5 bar

90
0 1000 2000 3000 4000 5000 6000 7000
Transferred heat (kW)
An indication of higher production of cold is when the speed of both expanders increase and
that loss of cold at the hot end of the heat exchanger, i.e. ∆Twarm, does not increase. Cold
losses increase if the heat exchanger is not well balanced and you can read this in the QT
diagram.
Reducing the production of cold is done in the same way as in the Malmö recycle in chap.
13.2 using the make-up valve FIC-3245.
13.6 Temperature Diagram (QT-diagram) for Recycle Heat Exchangers (New in version 4)
To achieve maximum cold production the heat exchangers should be balanced and to achieve
this one must know where the bottlenecks are located. The heat exchanger temperature -
diagram, the Q-T diagram, shows this. This diagram has a temperature scale (T) and a scale
for transferred heat (Q). This is designed in that I have taken the enthalpies, i (kJ/Nm3) from
tables for each stream at different temperatures. I have then calculated the enthalpy
difference, ∆i, from the warm end at each temperature level and multiplied it by the flow, F
(Nm3/h). The amount of heat transferred is thus obtained, Q (kJ/h) = F(Nm3/h) • ∆i (kJ/Nm3).
The streams that are cooled down are called the warm stream and the streams that are heated
are called the cold streams. One can say, with great reliability, that the streams moving in the
same direction have the same temperature after the same length of heat exchanger. This is
also how the manufacturer calculates the heat exchanger. This implies that a compound
warm stream, Qw, and cold stream, Qc, respectively can be calculated by adding together the
transferred heat at the different temperatures.
The Q-T diagram can be utilised to analyse operation, but one must be aware that the area of
the heat exchanger is not included. It is, however, useful in connection with small changes
around the design case, because here the heat transfer coefficient is constant. The inter-
mediate inputs and outputs of the expanders have a fixed position with a certain heat
exchanging area from the end points of the heat exchanger. A calculation is made with
altered flow at unchanged temperature, which gives an alteration in the amount of heat. One
can picture the QT curve as an elastic band. It is stretched or slackened depending on
whether Q increases or decreases. The shape of the curve changes negligibly, because it
depends on thermodynamic data and flow. In the actual heat exchanger 100% heat has
always been transferred, when the curve comes to the cold end. I can then estimate the
change in temperature at the intermediate points of the QT curve.
See figure 13.3 Q-T Diagram for Heat Exchanger E-3116
One can also judge in which direction the curve is moving without any calculations. Look at
the diagram. There is a take off to T2 = the expander at the warm end. For the moment we
disregard the control of the process, so there are two possibilities if we increase the flow to
T2:
1. The flow increases upstream the take off in the heat exchanger.
2. The flow decreases downstream the take off in the heat exchanger.
© Linde Gas AG Page 75 (109) 2001-02-20

E-3116
310
290
Air
WN
270
T2 (WE exp) 28 bar
250
Qw N2 57 bar, Air
230
Temperature (K)
210
Qc GAN+ WN
+GOX+N2 5 bar
190
T2 (WE exp) 5 bar

T1 (CE exp) 57 bar
170
150
130
110
T1 (CE exp) 5 bar

90
0 1000 2000 3000 4000 5000 6000 7000
The first results in Qw being cooled less down to the take off, so the curve moves upwards
with the inlet at 297 K as the fixed point. Downstream of the take off there will be no
change, except that the entire curve moves parallel upwards. The second results in no change
upstream of the take off and downstream there will be no reduction in the cooling of Qw. So
the outlet at the cold end will move upwards and the take off to T2 is a fixed point. By
studying the function of the controllers you can determine which alternative will occur.
If you look closer at Qw round the take off to T2, you will observe that its slope has
changed. So Qw has a point here where the curve is “pliant”. Using process control you
bend the curve Qw so that it fits close to Qc, but not too close.
The main object of the QT diagram is to see where the bottle necks are, i.e. the pinches,
places where ∆T has a minimum, see also chap. 14.2. There is one at 150 K and one at 210
K. ∆T may not come close to 0, because the transfer of heat would cease and a “dead zone”
would arise. On the other hand, ∆T may not be allowed to become too great because
efficiency of the process would be reduced. Pinches always occur because HP-N2 is non-
linear at low temperatures. HP-N2 is over critical (p> 34 bar) and the curve is then clearly
non-linear around the critical temperature = 126 K. The curve is “less” non-linear up to 200
K. Low pressure gas, 5 bar is linear except down at dewpoint where it deflects slightly.
13.7 Balancing the Heat Exchanger with the Help of the QT Diagram (New in version 4)
To be able to get anything out of the QT diagram, one must know the net changes of the
flow in the different sections divided by the inlets and the outlets to the expanders.
You can begin by testing an increase of FIC to T2 since it gives the highest production of
cold. There will probably be a corresponding reduction to T1, even if the other regulators
tend to pull in different directions. We assume that they are the same size. There will thus
be no net change in the flow in the warmest section between inlet to heat exchanger and
outlet to T2 on Qw. There will be a reduction in the section between the outlets to T2 and
T1.
Consequently, in the hot section there will be no change of Qw, while in the middle section
Qw tends to creep closer to Qc because Qw is cooled down more. This implies that it will be
colder to T1. The TIC now starts to operate and it increases the flow of HP-N2 in the entire
heat exchanger. This increase in flow will be less than that to T2, because it goes through
the entire heat exchanger and can thus give off much more heat. So due to the TIC, Qw will
remain unchanged, except in the outlet at the cold end of the heat exchanger, where it will
be somewhat warmer.
The outlets from the two expanders go back to the heat exchanger and become part of Qc.
From T1 there comes little liquid, so since the pressure is constant the temperature will be
constant. Consequently, Qc inside the heat exchanger at the cold end is a fixed point. The
flow at the cold end became less, while becoming greater at the middle. This implies that
there will be a net reduction of the flow in the cold section and no change in the warm
section. So Qc at the middle point will creep closer to Qw, i.e. become warmer. In the warm
section there will be no change except just this creeping of Qc towards Qw in the middle
point.
© Linde Gas AG Page 76 (109) 2001-02-20

E-3116
310
290
Air
WN
270
T2 (WE exp) 28 bar
250
Qw N2 57 bar, Air
230
Temperature (K)
210
Qc GAN+ WN
+GOX+N2 5 bar
190
T2 (WE exp) 5 bar

T1 (CE exp) 57 bar
170
150
130
110
T1 (CE exp) 5 bar

90
0 1000 2000 3000 4000 5000 6000 7000
This leads to a reduction of ∆T between Qw and Qc and the pinch at 210 K becomes worse,
with the result that the transfer of heat decreases and Qc becomes colder in the outlet at the
hot end. Consequently, ∆Twarm increases and cold is lost, which can “eat up” a possible
increase in production of cold in T2. It is also possible that the pinch at 150 K deteriorates,
but Qw has however increased in temperature there.
The temperature to T1 is important because it sets the limit for how much work can be
taken out from T1. If it becomes colder, the temperature drop will decrease as the outlet
temperature is fixed by the formation of liquid. By that is reduced the possible production of
cold. So you can test it by raising this temperature with the TIC. The J-T valve will then
open and increase the flow through the heat exchanger. This produces a rise in temperature,
because the increased flow cannot be cooled down as much. However, the increase in flow
will be taken from the flow to T1. The result will be that the production of cold per m3
increases, but the flow decreases. If you move in the other direction then the production of
cold per m3 will decrease, but the flow will increase. The best position is somewhere
between.
In Eggborough, the temperature to the J-T valve was calculated by design as -177°, but in
fact it was evident that it must be -174° to get balancing of the air temperature to the column
right. If temperature to the valve is lower than -174°, there would be too much liquid in the
air, which implies inferior separation in the pressure column.
13.8 An overview of Other Cold Processes
Other processes for cold production use air. We have already discussed the original Linde and
Claude processes. These are called high-pressure processes because of the high pressure of air,
up to 200 bar.
In the mid-1970's, a process was introduced as an alternative to the Malmö type nitrogen
recycle. This is called the medium pressure process with air cycle. This has almost the same
machinery as Malmö, but it is air that is compressed to a highest pressure of 50 bar and all of it
should go to the column for separation and there is no air recycle. The process uses somewhat
less energy than the Malmö process and is somewhat cheaper to purchase as the recycle and
main heat exchanger are combined.
This process was improved with a warm booster-expander of the same type as the nitrogen
recycle in the mid-1980's. As the air is fed back in a recycle this process is called the medium
pressure air recycle. It has low specific electricity consumption and is suitable for plants which
have large GOX-customers supplied by pipeline where GOX is large in relation to the liquid
production. More on this in next chapter.
When relatively cheap plants with little machinery and only small liquid production are
required, 1000 - 2000 Nm3/h, then select a process with air cycle at low pressure, approx. 11
bar. This has a high specific electricity consumption, approx. 2 kWh/ Nm3 of liquid, but it has
not played a big part in the smaller countries in South America where they are used.
13.9 Air Cycle - Medium Pressure
Deleted, old-fashioned process. Next chapter describes modern air cycle processes used.
© Linde Gas AG Page 77 (109) 2001-02-20

13.10 List of different types of recycles or cold production in AGA
1. Nitrogen Recycle, medium pressure
All processes with three exceptions have separate cold production and main heat exchangers.
The highest pressure is approximately 50 bar with two exceptions.
a) -40° C refrigeration machine and cold turbine with booster = 50 bar.
Cartagena (formerly Malmö) Colombia

Cali (formerly Oslo) "
Copenhagen Denmark
Porcheville France Also refrigeration from +17 to +10° C
Sandviken Sweden
Meitingen Germany With internal O2 compression to 7 bar
San Roque Spain
Santa Cruz Brazil
Reykjavik (formerly Bergen) Island Air braked expander
Toulouse France Expander on the same shaft as the
recycle compressor = 20 bar
Recife Brazil Oil braked expander
Nice France Combined recycle and main heat
exchanger, recycle from top of single
column, booster = 15 bar
b) Warm + cold turbine with boosters
Sundsvall Sweden
Oxelösund " With internal O2 compression = 14 bar
in separate heat exchanger.
Stenungsund " With refrigeration also from +15 to
+12° C and -22 to -40° C.
Leirdal Norway
Sköldvik Finland
Harjavalta "
Herne Germany With refrigeration also from +35 to
+10° C and -22 to -40° C.
Botlek (sold) Holland With internal O2 compression = 20 bar
Parkersburg USA
Canton "
Dayton "
Waukesha "
Maracaibo 1 Venezuela
Cubatâo Brazil With internal O2 compression = 50 bar
Eggborough UK Combined recycle and main heat exchanger
Santiago 2 Chile “
Tepeji del Rio Mexico
Alcalá Spain Combined recycle and main heat exchanger
Toulouse 2 France
Bogotá Colombia
Buenos Aires 2 Argentina
© Linde Gas AG Page 78 (109) 2001-02-20

c) Additional liquefiers with nitrogen recycle and cold and warm turbine with boosters
Sundsvall, formerly Sandviken Sweden with nitrogen purification

Canton USA
Ostrava Czechia
Dayton USA
Cubatão Brasil
Copenhagen Denmark
2. Air cycle
All processes have a common cold production and main heat exchanger. Certain ones have
air recycles.
a) Medium pressure air cycle, two air compressors, TC1 = 9 bar, TC2 = 37,5 bar, one booster =
50 bar, -40° C refrigeration machine.
Moscow, formerly Turku Russia

Schwechat Austria + small oil braked expander (air 5 - 0,2 bar)
Mexico City Mexico TC1 + TC2 combined in six stage
compressor, + air braked expander
Buenos Aires Argentina Air recycle to TC2: 4,5 to 26,5 bar,
booster 34,5 bar.
b) Low pressure, one air compressor TC1 = 9 bar, a booster = 11 bar, no -40° C refrigeration
machine.
Callao Peru Air recycle

Santiago 1 Chile Air recycle + nitrogen recycle = 9 bar,
boosters = 11 bar
Maracay Venezuela Expander coupled to third stage of TC1
Rio Negro Columbia Expander coupled to third stage of TC1
Guayaquil Ecuador Air recycle to TC2: 5 to 19 bar,
booster = 24 bar.
Montevideo Uruguay TC1 20 bar (6-stage), booster 1 = 25 bar,
booster 2 = 30 bar.
c) High pressure, TC1 = 200 bar, an oil braked expander, -30°C refrigeration machine.
Moscow Russia
Kaliningrad "
d) Medium pressure air recycle, two air compressors, TC1 = 5 bar, TC2 = 27 bar, booster 1 =
38 bar, booster 2 = 55 bar.
Bremen Germany
Harjavalta 2 Finland
Lausitz Germany Internal O2 compression
Tjeldbergodden Norway “
Avesta Sweden “
Donawitz Austria “
Luleå Sweden “
© Linde Gas AG Page 79 (109) 2001-02-20
Recycle
Waste N2
Bypass
GAN
Mole LP-GOX
sieves
LP-Air
5 bar HP-GOX
HP-Air 50-70 bar
MP-Air 25-35 bar
Gas ==> Liquid
Gas <== Liquid

Via
tank
5 bar
Figure 14.1 General Air Cycle Process with Internal Compression

14. COLD PRODUCTION IN AIR CYCLE AND INTERNAL COMPRESSION

New in version 4
During the nineties, AGA has aimed at building installations near major GOX customers
such as steelworks or chemical industries. If the GOX production is greater than the liquid
production for AGA, then an air cycle process is somewhat more economical than a nitrogen
recycle.
14.1 Outline of the Air Cycle Process
This process has an air compressor that supplies air at 5 bar for separation. After this an
additional compressor is used to achieve compression to the pressure needed in the
expanders for cold production. There is a cold and a warm expander as in new N2 recycles.
The main heat exchanger is combined for cold production and cooling of air for separation.
Figure 14.1. General Air Cycle Process with Internal Compression
If the liquid production is almost as big as the GOX production, then more air will be
needed in the compressor for cold production than that coming from the air compressor.
This is cared for by returning the air not needed for separation to the suction side of the
compressor, thus providing an air recycle.
If the GOX production is much greater than the liquid production, then air recycle is not
needed and even less flow may pass through this compressor. This is taken care of in that
the air at 5 bar that bypasses this compressor goes in via its own passage into the main heat
exchanger. This process is called air cycle.
Giving a name to the compressor for cold production is a bit of a problem. If it is for an air
recycle, then it is all right to call it the recycle compressor. But if it is not, then it is usually
called the high-pressure (HP) compressor or the air booster. This can be mixed up with the
boosters that are connected to the expanders.
The advantage of a major GOX customer is obvious. One has a joint installation instead of
two and thus smaller investment. Furthermore, a bigger plant implies smaller specific
electric power consumption (kWh/Nm3 product). The disadvantage is the mutual dependency.
It is not possible to run GOX only or liquid only and any disruption on one side will affect
the other. Reduced liquid production implies significantly higher specific electric power
consumption (kWh/ Nm3 liquid).
When one is now running the plant for the GOX customer anyway, one can make a further
combination of the process equipment. Instead of compressing GOX in compressors, it can
be done by pumping LOX at the right pressure through the main heat exchanger, i.e.
internal compression.
© Linde Gas AG Page 80 (109) 2001-02-20

Figure 14.2 Temperature curve for MP-LOX and -air
50
-50
Temperature C
MP-air 29,2 bar

a) 7800 Nm3/h
-100
MP-LOX 11,3 bar

6404 Nm3/h -147 C
-150
-151 C -162,6 C
-200
0 500 1000 1500 2000 2500 3000 3500 4000
(Avesta QT-digram för HE-22)

50
-50
Temperature C
MP-air 29,2 bar

b) 7300 Nm3/h
-100
MP-LOX 11,3 bar
6404 Nm3/h
-147 C
-150
-151 C
-173,3 C
-200
0 500 1000 1500 2000 2500 3000 3500 4000
Transferred heat (MJ/h)
14.2 Internal Compression
The traditional way of supplying gas to a customer in the vicinity, is to compress low
pressure gas from the main heat exchanger in a compressor and convey the gas in a pipe to
the customer. A recent development is to replace the compressor with a pump, that pumps
liquid to the right pressure and vaporises it in a heat exchanger. The gas is supplied to the
customer from the main heat exchanger.
The vaporisation occurs at a temperature that depends on the pressure according to the
vapour pressure curves, see chapter 6.2, and it requires a sufficiently warm gas counter flow.
This gas is the high pressure (HP) gas (air or N2), which is to be converted to liquid in the
cycle for cold production. This implies that the flow must increase to absorb the cold. It is
called internal compression.
So, instead of compressing GOX for example, more HP air is compressed and is pumped
LOX. This is the big advantage of internal compression and it is much cheaper to increase
the capacity of a compressor than to buy one more. The pump takes LOX from the storage
tank so it is combined with the backup system, while in external compression there is a
separate pump for backup. Furthermore, a GOX compressor is especially expensive because
of the greater risk with GOX and the appertaining higher safety requirements involved.
Electric power consumption for internal compression is a little higher than for external
compression. The big disadvantage is that the HP compressor must be in operation for HP-
GOX and thus its minimum capacity gives a certain production of liquid whether we want it
or not. It is not possible to run the process without HP-GOX (or HP-GAN), if it is large in
relation to the liquid production because balance in the heat exchanger changes too much.
HP-GOX and liquid production are dependent on each other, so it is not possible to increase
one and decrease the other. Consequently, flexibility in the plant will be smaller. Variations
in the HP-GOX flow result in disruption in the air separation, so it must be avoided.
In Avesta, GOX is compressed internally, 36 bar (HP-GOX) in heat exchanger HE-21 and
GOX, 11 bar (MP-GOX) in HE-22. In HE-22, HP-GAN and GAR are also compressed. It is
mainly 46 bar air that vaporises HP-LOX and 29 bar air MP-LOX. If one were to vaporise
this LOX solely with compressed air, the temperature curves according to the figure would
be given.
See figure 14.2. Temperature Curve for MP-LOX and 29 bar Air.
The horizontal parts of the curves in figure 14.2b indicate boiling, 11 bar O2 at -151° and 29
bar air at -147°. ∆T = 4° and shall be so. If it becomes smaller the heat transfer will
deteriorate, see chap. 7.1, and GOX will then be too cold. ∆T becomes smaller if the O2
pressure is raised or the air pressure is lowered. Such changes in pressure must therefore be
considered very carefully. If ∆T becomes 0, i.e. the horizontal parts move together, a “dead
zone” will arise. The transfer of heat will then cease in that part of the heat exchanger and
GOX becomes too cold.
© Linde Gas AG Page 81 (109) 2001-02-20

Figure 14.3 Temperature curve for HP-LOX and -air
50
HP-air 46,9 bar

-50
Temperature C
a) 8500 Nm3/h
-100
pinch
HP-LOX 36,3 bar
5600 Nm3/h
-127 C
-139,9 C
-150
-200
0 500 1000 1500 2000 2500 3000 3500
(Avesta QT-diagram för HE-21)

50
HP-air 46,9 bar

-50
Temperature C
b) 8000 Nm3/h
-100
HP-LOX 36,3 bar cross-over
5600 Nm3/h
-127 C
-143,7 C
-150
-200
0 500 1000 1500 2000 2500 3000 3500
Transferred heat (MJ/h)
If one uses too little air then the curve in figure 14.2a will apply. As can be seen, the
temperature curves intersect -151° and to the right. This is entirely a theoretical
phenomenon. In reality it does not occur, because before the crossover it is the air that is
hotter and it gives off heat due to ∆T. When this ∆T falls to 0, the transfer of heat ceases and
the air cannot then become colder, in particular not colder than the oxygen. A bigger “dead
zone” arises and GOX will be insufficiently heated and become much colder at the outlet.
If one uses the right amount of air then the curve in figure 14.2b will apply. There the
crossover has changed to a pinch, which is a smallest ∆T. This pinch prevents the air from
being chilled lower than -165°, which is too warm for the column. It is true that this air is
expanded in a valve to the pressure of the lower column and achieves the right temperature,
but the warmer it is the more gas there will be and the column is made for a small proportion
of gas and a large proportion of liquid at this point.
The internal compression of HP-GOX in Avesta occurs at such a high pressure that the air
pressure is above the critical (= 37.7 bar). This implies that the temperature curve will be
different.
See figure 14.3. Temperature Curve for HP-LOX and 46 bar Air.
There is no horizontal part here for condensation of air because a supercritical “gas” does
not condense. On the other hand one can see that the slope of the curve changes strikingly
and this is because the specific heat increases strongly near the critical temperature -141°. In
figures 14.3a and 14.3b it is shown that a change in the airflow affects pinch and crossover.
Here the air cannot be chilled even to -150°.
To enable the heat exchanger to work without getting all too large or small ∆T, several flows
are applied and in this connection the turbines are utilised. They are applied to such places
where they can counteract pinches and balance excessive ∆T (as on the left over -127°).
They also balance differences in specific heat at low temperatures of the high-pressure air.
New in version 4
© Linde Gas AG Page 82 (109) 2001-02-20

He
He
LIN
LIN
GAN GAN
Tube Condenser Block Condenser
Figure 15.1 The Function of a Condenser, the Helium outlet

15. LINDE DOUBLE COLUMN WITH ARGON, RARE GASES AND IMPURITIES
So far we have assumed that the air to the distillation column comprises of oxygen and
nitrogen after we have cleaned it from dust, water, carbon dioxide, diverse hydrocarbons and
contaminants. Now it is time to go through the other components. One of them is argon which
is found in relatively large amounts, while the other components are found in very small
amounts.
15.1 Rare Gases and Hydrogen in the Air
The rare gases are helium (chemical symbol He), neon (Ne), argon (Ar), Krypton (Kr) and
Xenon (Xe). They are called rare gases because they do not react chemically with other
elements. For most applications which argon is used for, this characteristic is important and
makes it a very good protection gas.
Hydrogen (H2) is extremely reactive and burns in oxygen to form water (H2O).
These gases cannot be removed in mole sieves or some other similar method. To see what
happens to these gases in the columns, we must look at their various boiling points compared
with oxygen and nitrogen. From the table in chapter 2 we know the boiling points at 1 bar and
their concentration in air has been added.
Component Concentration Boiling point (°°C)

Nitrous oxide 0,35 ppm -88
Xenon 0,1 ppm -108
Krypton 1 ppm -153
Oxygen 20,9 % -183

Argon 0,93 % -186
Nitrogen 78,1 % -196
Neon 18 ppm -246

Hydrogen 0,5 ppm -253
Helium 5 ppm -269
The gases which are extracted from the columns: O2, N2 and Ar have been separated from the
others in the table. We can see that two gases: Kr and Xe have higher boiling points than
oxygen and three gases; Ne, H2 and He have lower boiling points than nitrogen. Argon's
boiling point lies in between oxygen and nitrogen, closer to oxygen than nitrogen.
15.2 Rare Gases in the Pressure Column
When air is fed to the pressure column, Kr and Xe will become washed down in the rich liquid
as their boiling points are higher than oxygen. However He, H2 and Ne will rise in the column
as their boiling points are lower than nitrogen, none of them will wash down in the rich liquid.
© Linde Gas AG Page 83 (109) 2001-02-20

Figure 15.2 Enrichment in the LOX reboiler
GOX Sum O2 :
LOX ≈ 0,21*Air
Air (1 ppm Kr)
1. LOX = 100%
GOX = 0%
Enrichment in LOX = 1 ppm * Air flow = 4,8 ppm
1*0,21 * Air flow
2. LOX = 1%
GOX = 99%
Enrichment in LOX = 1 ppm * Air flow = 480 ppm

0,01*0,21*Air flow
3. Minimum LOX = 0,5-1,0 % of sum O2

According to IGC Doc 65/99
Argon has a boiling point (b.p.) between oxygen and nitrogen. The rich liquid comprises 35-40
% oxygen and the rest is almost only nitrogen, so that the mixture will be much colder than
oxygen (b. p.) and 5°C colder than argon (b. p.). Consequently the argon is warmer than the
rich liquid and most will be washed down in it. However, the closer the boiling points are to
each other, then the more difficult it is to separate the components. So a small part of the argon
will rise up to the top in the nitrogen. The concentration of argon in the top nitrogen can be
from somewhere under 100 ppm to several hundred ppm, depending on how many trays there
are and how big oxygen concentration one is running for.
15.3 Rare Gases in the Condenser
When He, Ne and H2 come up to the condenser, they cannot condense because their boiling
points are much lower than that of the boiling oxygen. So that when nitrogen condenses to LIN
these gases remain as bubbles.
See figure 15.1 The Function of a Block Condenser.
GAN comes into the top of the condenser and streams downwards. Because the velocity of the
LIN is high the gas bubbles have not got enough time to separate and remain in the condenser,
but they follow the LIN out as product and back to the pressure column. Because of the return
to the pressure column, the rare gases will accumulate and their concentration will rise to many
times higher than in the incoming air. To avoid this a gas separator is situated on the LIN pipe
out from the condenser. This can be, for example, a vertical pipe of larger diameter, with a
collection space at the top with a small tube and a valve to the atmosphere, the so-called
helium outlet.
Hydrogen really is a contaminant which one want wants to remove from nitrogen, but also
helium and neon are contaminants for certain customers (electronic manufacturers). In plants
with 10,000 Nm3/h air there will be 0,18 Nm3/h Ne, 0,05 Nm3/h He and 0,005 Nm3/h H2, so
the helium outlet should be some Nm3/h.
In plants from the 1960's, tube condensers were used, which is also shown in Fig 15.1. This
figure is useful since the tube condensers are still used in pure argon columns.
15.4 Rare Gases in the Upper Column
With the separation of helium, neon and hydrogen after the condenser, there will be only slight
quantities which enter the upper column with the reflux. These will not go downwards in the
column and will largely go directly out with the top GAN.
Argon, krypton and xenon go with the rich liquid to the upper column. Kr and Xe are easily
washed down to the LOX in the reboiler. Because of their high boiling point, there are only
insignificant quantities in the GOX and the largest part will go out with the LOX. They cause
no disturbances in the column and their concentration becomes around five times larger.
© Linde Gas AG Page 84 (109) 2001-02-20

FIG 15.3
Why this concentration rise? In the air there is 21 % oxygen. This implies that the oxygen flow
out from the reboiler = 0,21 • air flow, according to the material balance. In the oxygen flow
there is all of the Kr and Xe. An unchanged krypton flow in a reduced total flow means that the
concentration of krypton has become larger in proportion to the reduction of the total flow.
Krypton flow in LOX (if GOX=0) = 1 millionth • air flow (Nm3/h)

Krypton concentration = 1 millionth • air flow / (0,21 • air flow) =
= 1 millionth / 0,21 = 4,8 millionths (ppm)
See figure 15.2 Enrichment in the LOX reboiler.
The argon is approx. 5°C warmer than the rich liquid. This means that it is washed downward
from the inlet of the rich liquid and it is only 3°C colder than oxygen, which makes it difficult
to separate them. So there is to a large extent only argon as a contaminant in the oxygen at the
bottom of the column. The others are krypton and xenon which are mentioned above, and there
is methane (see 8.9) and nitrogen up to a few ppm. So in an installation with 99,7 % LOX there
is approx. 0,3 % Ar. The following is a calculation of how much argon goes out with oxygen:
Oxygen flow = 0,21 • air (plants with good O2 extraction)

Argon in oxygen = 0,3/100 • 0,21 • air (Nm3/h)
Argon in air = 0,9/100 • air
Ar in O2/Ar in air = 0,3 • 0,21/0,9 = 0,07 = 7 %
The remainder of the argon must rise in the column. This is the same reasoning as used for
oxygen which was presented in 4.7 and Fig 4.5. If we do not take out from the bottom of the
upper column the quantity of oxygen which comes in, then the oxygen must rise in the column
and it is taken out in another place. If there is no outlet for argon production, which is the case
in a few AGA plants, then the argon rises to the impure nitrogen outlet, where most of it goes
out.
Now we shall study the argon concentration at different trays in the column. An example
follows how it can look like.
See figure 15.3 Concentration Profile in the Upper Column.
At the first trays above the reboiler the argon concentration rises slowly from 0,3 % to become
1 % around the 13th tray. Here one can see in this part of the column that changes take place
slowly. If you haven't correctly controlled the column, then the purity is reduced slowly in one
tenth of % steps. On the other hand it takes a relatively long time to correct the purity again.
Higher up the concentration rises more quickly, to be at around the 27th tray (=theoretical tray,
which corresponds to 35th actual tray), it will be 10 % Ar and 90 % O2. At this point the
nitrogen begins to come into the percentage area at 0,15 %. Additionally some trays up there
will be 1 % nitrogen and the argon continues to rise. If we continue upwards the nitrogen
begins to rise dramatically, while both the argon and oxygen parts reduce.
© Linde Gas AG Page 85 (109) 2001-02-20

PI QI FIC
Crude Argon
o
-194 C N2 GAN
LIC
CO
-191,5
Impure
-193 N2
PDI
QIC
90% O2
10% Ar
-186 Ar
GOX (with a small part of the CH4)

-183 O2 LOX
He -269 (at 1 bar)
H2 -253 "
-162 CH4 Ne -246 "
-153 Kr
-108 Xe
-89 C2H6 LIN
N2 -196 (at 1bar)
-88 N2 O
-84 C2H2
-79 CO2
LIC
Figure 15.4 Double Column, with Side Column for Argon

(Distribution of Contaminants, with Boiling Temperatures)
Depending on the construction and production case, the oxygen content in the Lachmann outlet
can vary from some percent down to 50 ppm. The corresponding argon content is in the same
order of magnitude. Where the plants date from the 1970's the oxygen content is some few
percent. At Sundsvall, Sweden, which is specially built for maximum argon it is less than 50
ppm oxygen in the Lachmann. Normally the value is a few tenths of % oxygen.
15.5 Argon Transfer Zone
To produce argon, a gas with high argon content is taken from the upper column to a side
column, where the oxygen and argon are separated. It has already been suggested it is difficult
to separate these two, so many trays and a large reflux ratio is required in the side column.
Nearly all nitrogen in the gas to the side column goes to the top, as nitrogen is much colder
than oxygen and argon.
See figure 15.4 Double Column with Side Column for Argon.
The side column can handle a nitrogen content of approx. 0,1 % in the feed. Therefore the
outlet is situated at the tray in the upper column where this nitrogen content is obtained, which
is at, around the 35th actual tray. This area is called the argon transfer or the argon zone or
cloud. Here the oxygen content is approx. 90 % and the argon content approx. 10 %. This
means that it requires a relatively large number of trays to separate oxygen and argon. In the
whole upper column there can be up to 110 trays. In a pressure column, there are 50 to 60 trays.
15.6 Carbon Monoxide and Nitrous Oxide in the Columns (Rev. in version 4)
In recent years the demand for higher purity has increased, particularly from electronics
manufacturers. Carbon monoxide is an unwanted contaminant. Carbon monoxide occurs when
there is incomplete combustion of carbon and hydrocarbons, for example in car engines. It
exists in the atmosphere at 0,1-0,2 ppm, which varies depending on certain process industries
and motor traffic. It is a poisonous gas that means that it is not a rare gas, but it is taken up here
to see which product it contaminates.
Carbon monoxide goes through the mole sieves and has a boiling point of -191,5°C, which is
4,5°C warmer than nitrogen and 5,5°C colder than argon. So it tends to go out with impure
GAN with around the double concentration that it has in air. In the top CO goes out with GAN
at approximately the same concentration as in air. A slight part goes down to the argon transfer
and continues on to the side column. Because of the large reflux in this column there can be a
measurable concentration (0,1 ppm) in the crude argon at the top. No carbon monoxide goes
down to the LOX.
A simple way to avoid increased amounts of CO in the process is to prohibit idling of cars and
tankers in the neighbourhood of the air intake.
Nitrous oxide (N2O) as mentioned in 8.9 passes to a great extent through the mole sieves.
Having the boiling point -88°, it is washed down to LOX. If there is a great enrichment of
LOX, which occurs at big GOX production, then the nitrous oxide concentration in LOX will
increase considerably. This is also a safety risk in reboilers of falling-film type (8.9).
© Linde Gas AG Page 86 (109) 2001-02-20

PI QI FIC
Crude Argon
2% O2
GAN 97% Ar
1% N2
LIC
Impure
N2
TI PDI
QIC
90% O2
10% Ar
0.03% N2
GOX
LIC
Figure 16.1 Double Column, with Crude Argon Column

16. ARGON PURIFICATION IN THE CRUDE ARGON COLUMN
The traditional method to purify argon is that the gas from the argon transfer in the upper
column is purified in a side column, the so called crude argon column to approx. 2 % O2 and 1
% N2. The remainder of the oxygen part is removed by chemical purification. Then the nitrogen
part is removed in the pure argon column. The reason why not all of the oxygen is removed in
the crude argon column, is that it demands so many trays that the pressure drop will be too
large. But structured packing in the column has been shown to be competitive in recent times,
because of its low-pressure drop. This makes it possible to increase the number theoretical
trays and not to use chemical purification. So the new plants in Santiago, Chile, and Avesta,
Sweden, use this method. This is an advantage for operation and maintenance as chemical
purification contains many apparatus and machinery, as we will see.
16.1 Crude Argon Column
A crude argon column is a column with a condenser but without a reboiler, so it must take in
gas in the bottom. This gas comes from the argon transfer and contain approx. 90 % oxygen, 10
% argon and 0,1 % nitrogen. As there is much oxygen which we want to remove and we know
that it is difficult to separate oxygen and argon, a large number of trays and a large reflux ratio
(=reflux flow/crude argon flow) is required. There is around 50-60 trays and a reflux ratio =
30-40 (i.e. 30-40 times as much column reflux as crude argon production). Crude argon with 2
% oxygen is taken out as gas from the top. Column reflux runs from the bottom of the column
to the argon transfer in the upper column.
See figure 16.1 Double Column with Crude Argon Column
The condenser uses as its cooling media a part of the rich liquid, which after expansion
becomes colder than the condensed crude argon. The evaporated part of the rich liquid is then
fed into the upper column.
Despite the air being cleaned in the mole sieves, certain hydrocarbons pass through and there
can possibly be traces of acetylene and carbon dioxide in the rich liquid. If all rich liquid was to
be evaporated, then these would accumulate in the condenser. Therefore a small liquid line
from the condenser to the gas line for evaporated rich liquid from the condenser is installed.
This is supplied with a valve, which cannot be completely shut as, for example, it has a small
hole drilled in it. This method continuously purges a small amount of liquid from the condenser
and with this liquid are purged the hydrocarbons. Down stream of the valve there is a TI in
order to be able to see that liquid really is passing through it.
There will be a relatively large change in the upper column, due to the crude argon column. A
large quantity of gas is taken from the argon transfer and around half that amount of rich liquid
is used for condensing. This leads to a reduced quantity of gas rises above the argon transfer
and a reduced amount of rich liquid is added. So in the part between the argon transfer and the
rich liquid feed, both the liquid and gas streams have been reduced. To compensate for this
more trays are built in. The most important parts of the column, the top and bottom, are
practically unaffected.
© Linde Gas AG Page 87 (109) 2001-02-20

PI QI FIC
Crude Argon
RL o
2% O2
-186
GAN 0,45 bar 97% Ar
1% N2
o
-184
LIC 0,3 bar
Impure
N2
TI PDI
0,4 bar
QIC
90% O2
10% Ar
0.03% N2
GOX
0,6 bar
LIC
Figure 16.2 Double Column with Crude Argon Column

(with Control of Condenser level)
The evaporated rich liquid is fed to the upper column at a lower point than the liquid with the
same composition. This is so that each feed shall be added where the concentrations are as
alike as is possible. This means that why the rich liquid is added at the tray where the liquid
contains approx. 35 % oxygen and the evaporated part is added above the tray where the gas
has approx. 35 % oxygen, which occurs at a lower point.
16.2 Different ways to control the Crude Argon Column

The level in the condenser (LIC) controls the rich liquid, which is added to the condenser.
There are several ways to control how much shall be condensed. The oldest method from the
1970's is to control the level and to allow the evaporation to go freely to the upper column.
During the 1980's and onwards control was carried out using a valve, which is controlled by the
flow (FIC) of the evaporated quantity from the condenser. By this way the condensation is
altered too, as the heat which is given off by what is being condensed is taken up by what is
evaporated. The level in the condenser remains constant. In recent years there has been a new
variant, which works well in a column with structured packing. The pressure drop, which
occurs over the packing, controls with a PDIC the quantity of evaporation.
16.3 Control of Crude Argon Column with the Condenser Level

This type of control is among others found in the plants in Cartagena (formerly Malmö),
Sandviken and Turku. The rich liquid expands in the condenser to the upper columns pressure
and therefore the temperature becomes constant and 5-6°C colder (depending on the oxygen
content) than the argon that condenses. From chapter 7, Heat Exchanger, we know that the
quantity of transferred heat depends on ∆T and area. Here ∆T is constant and the area can be
varied through the level of the liquid in the condenser. This means that by changing the level
the heat transfer will also change, and therefore the condensation and evaporation.
See figure 16.2 Crude Argon Column (with condenser level control).
See figure 16.3 Vapour Pressure Curves of Ar, N2 and RL *.
As it is the condenser that sucks in gas from the argon transfer, this creates a pressure drop
from the upper column through the crude argon column, and this pressure drop in proportional
to the gas flow. Therefore a pressure drop meter (PDI) over the column measures the gas flow.
This measurement is very important for the control, as it gives an indication on how the reflux
ratio changes in the column. The reflux ratio is the liquid flow in the column divided by the
crude argon production (measured with a FI). The gas flow is equal to the sum of the crude
argon production and liquid flow according to the material balance. So by, for example,
increasing condensation with unchanged crude argon withdrawal (controlled by a FIC) both the
gas flow and liquid flow increase, which is shown on the PDI. Also the reflux ratio will
increase and the crude argon will be purer. One can also say that there will be more "wash
liquid" in the column. Alternatively purer crude argon can be achieved, by reducing the crude
argon flow, so that the reflux ratio also becomes larger.
Example: In a crude argon column with 60 trays the reflux ratio shall be 30 to obtain the design
production of 100 Nm3/h with 2 % oxygen, at the argon transfer there is 90 % oxygen. Then the
liquid flow is = 30 • 100 = 3000 Nm3/h and the gas flow = 3000 + 100 = 3100 Nm3/h (Gas
flow = crude argon + liquid flow).
*
Because of the bleed off of RL from the CAR condenser, the RL will be distilled there so that the O2 concentration in the RL
is 60-70%. So fig 16.3 should have a curve for RL 65% O2. The big increase of O2 is due to the small bleed off flow.
© Linde Gas AG Page 88 (109) 2001-02-20

Figure 16.3 Vapour pressures of N2, Ar and RL (40% O2)
9
6
Pressure (bar a)
3 RL
Ar
N2
2
0
76 78 80 82 84 86 88 90 92 94 96 98 100 102 104 106 108 110 112 114 116
Tem perature (K)
If we increase condensation so that the liquid flow = 3100 Nm3/h, then the reflux ratio =
3100/100 = 31 and gas flow = 3100 + 100 = 3200 Nm3/h. If we reduce crude argon production
to 97 with the original condensation, the reflux ratio becomes = 3000/97 = 30,9. The gas flow
= 97 + 3000 = 3097 Nm3/h. Both changes give the same reduction of oxygen content since the
reflux ratios are practically the same.
16.4 Maximising Crude Argon Production, the Double Column
As argon is an expensive and sought after gas, one wants to extract as much of it as is possible.
This can be tried by increasing condensing until there is too much nitrogen in the crude argon.
But first the double column must be running stable and have the correct composition.
To start with one checks that the pressure column is giving the most possible quantity of reflux
to the upper column, to reduce the argon loss in the impure nitrogen. The reflux out-take from
the pressure column shall be increased until the oxygen content begins to approach the
specified purity, e g 1 ppm oxygen, which will be seen earlier in the analysis point in the lower
part of the column, at a certain couple of % of oxygen (sometimes a few 100 ppm). In certain
cases the argon concentration can be a limitation if it is specified (e g 100 ppm Argon) and can
be measured.
Where there is a feed compressor, then it must have the correct flow to obtain as much reflux
as is possible.
The top GAN from the upper column shall be taken out to as much as the installation has been
constructed for, not less even when there are no customers for it. This step is important in order
to use the rectification capacity of the top section as much as possible and thereby reduce
oxygen and argon losses of the impure nitrogen. More GAN means less impure nitrogen flow
according to the material balance. It can be that the oxygen flow increases in the impure
nitrogen, but the flow reduces so that the oxygen flow (= % oxygen • flow of impure nitrogen)
reduces.
The GAN flow shall be increased until the specified purity, e g 1 ppm oxygen is reached. This
is particularly important when a feed compressor is used as it feeds the pressure column, and
then the purity of the LIN will be wrong if the top GAN is impure. A possible limitation is that
the impure nitrogen flow must not be too small, that it is not sufficient for the regeneration of
the mole sieves.
Finally, the argon transfer must be set for the correct oxygen content: This is controlled by the
valve for the GOX outlet, and as we know from 6.6 that this affects the composition in the
entire upper column. When the oxygen-content in the argon transfer is reduced through
increasing GOX take out, the argon and nitrogen go downwards in the column and increase in
the transfer zone. This can result in too much contaminants in the LOX in the bottom. On the
other hand in the top both GAN and the impure nitrogen become purer and less oxygen and
argon is lost with the impure nitrogen. If the oxygen content in the argon transfer is increased,
the argon and nitrogen climb upwards in the column and reduce in the transfer zone. The purity
of the LOX in the bottom becomes better, while the oxygen content rises in the top and more
oxygen and argon are lost with the impure nitrogen.
© Linde Gas AG Page 89 (109) 2001-02-20

PI QI FIC
Crude Argon
RL o
2% O2
-186
GAN 0,45 bar 97% Ar
1% N2
o
-184
LIC 0,3 bar
Impure
N2
TI PDI
0,4 bar
QIC
90% O2
10% Ar
0.03% N2
GOX
0,6 bar
LIC

(with Control of Condenser level)
So the argon transfer is set so that the correct oxygen purity can be obtained at the bottom, e g
99.7 %. This normally gives around 90 % in the argon transfer and there is 10 % argon and
0.1% nitrogen. If there is too much nitrogen there, you can test with a higher oxygen content in
the transfer and of the LOX. There is no apparatus for the continuous analysis of nitrogen, at
this concentration. Therefore you should test with different oxygen concentrations what the
crude argon column can cope with.
16.5 Maximising the Crude Argon Column, Nitrogen “Sense”
Condensation should be increased as much as possible, to be able to purify as much crude

argon as possible. The pressure drop (PDI) increases when the gas flow in the column
increases. The more gas is sucked into the column, the more nitrogen comes in which is very
difficult to condense. The rich liquid boils at approx. -186°C (0.45 bar g), argon (0.3 bar g) at -
184°C and nitrogen (0.3 bar g) and -194°C. This means that the rich liquid boils 2°C below
argon but at 8°C above nitrogen, so it cannot condense the nitrogen. Nearly all of the nitrogen
that comes into the crude argon column must go out with the crude argon at the top gas outlet.
Take as an example the same column as before with 0,03 % nitrogen in the argon transfer.
With 3100 Nm3/h gas rising comes 0,03/100 • 3100 = 1 Nm3/h nitrogen. With 100 Nm3/h of
crude argon the nitrogen content becomes 1/100 = 1 %. If it is 0,3 % of nitrogen in the transfer,
rises in the column 0,3/100 • 3100 = 9,3 Nm3/h and the nitrogen content in the crude argon
becomes 9,3 %. This will be difficult for the condenser as the temperature sinks, roughly
calculated, to 0,093 • (-194) + 0,907 • (-184) = -184,9°C, and as the rich liquid is -186°C so ∆T
has reduced from 2 to 1,1°C and through this the heat transfer is reduced with 45 % (= 0,9/2 •
100)!
Now the condensation and PDI reduce. This is an unstable situation and if one now tries to
increase condensing to increase the reflux ratio to, for example 31 the reflux becomes 3100 and
the gas stream 3200. Then the nitrogen flow becomes 0,3/100 • 3200 = 9,6 Nm3/h and the
nitrogen content still higher. In a tube condenser (used in Malmö and Turku) there will be so
much nitrogen that not all of it cannot go out with the crude argon, and the tubes fill up from
above with nitrogen. This blocks the heat exchanger area, reducing condensing and the gas
stream decreases so that the column begins to "weep". Finally the gas stream will be so small
that the column "collapses" and we must begin from the beginning, which takes around six
hours.
A column with a block condenser as in Sandviken and newer plants are not so sensitive. They
function as we described for helium in the condenser (see 15.3), so that the non-condensable
goes with the condensate. This means that the nitrogen cannot fill-up a block condenser but its
operation worsens, which is called nitrogen “sense”.
If the PDI sinks after a level rise in the condenser, then you should lower the level. This way
reduces condensing and the suction of nitrogen. That reduces the PDI and the pressure becomes
higher at the top, so that the nitrogen can be blown out of the column. Alternatively the O2
content of the argon transfer shall be increased.
© Linde Gas AG Page 90 (109) 2001-02-20

HIC
PI QI FIC
Crude Argon
GAN 2% O2
o
-186 97% Ar
FIC 1% N2
LIC -184o
TI
Impure
N2
TI PDI
QIC
90% O2
10% Ar
0.03% N2
GOX
LIC

(with Control of Evaporator flow)
To sum up, in order to obtain more crude argon, the level in the condenser should be somewhat
increased. The pressure drop in the column is kept under strict supervision and it should
increase and be stable for a long time. Now the purity of the crude argon will improve and the
valve for the crude argon flow (FIC) can be opened a little more. More product should now
come out. If not then the pressure (PI) of crude argon is too low. This can happen if there is a
too large pressure drop in the column.
If there is more crude argon and the column is stable, then the condenser level shall be
increased until a nitrogen “sense” arrives. At this point we note all operating data and go back
to a safe condition. This procedure is repeated for other concentrations in the argon transfer.
16.6 Controlling the Crude Argon Column with the Condensers Evaporation Flow
This type of control is these days the most common. It is better as the evaporation flow is
measured and controlled with a FIC, which shows more clearly than the pressure difference
over the column with trays. The evaporation flow corresponds directly to the condensation
flow, so it is a direct control of the reflux ratio. Using this type of control the level shall be held
constant.
See figure 16.4 Crude Argon Column (with control of evaporator flow).
A nitrogen sensing occurs when one increases the flow setting, but the flow does not increase.
Then the flow setting shall be taken back. Alternatively the O2 content in the argon transfer
shall be increased. Otherwise, if the flow increases and becomes stable, then the crude argon
flow can be increased if the purity has improved which we have done through previously.
The equipment for this type of control is a little more expensive as it requires a FIC with an
additional orifice plate, which demands a straight pipe, and a controller with a valve. Recently
a cheaper variant has emerged which is used in Eggborough and Santiago. This is control of the
evaporation flow with the pressure drop (PDIC) over the column. This saves the flow
measurement. As the pressure drop is small, approximately 40 mbar, this demands a good
quality controller that is well maintained.
Nitrogen sensing occurs when the PD setting is increased and the PD does not increase.
In plants that have the possibility to take out large quantities of LIN, the pipe of evaporated rich
liquid divides, one part going through the flow control valve to the upper column and one part
going through a manual valve (HIC) to the impure nitrogen. This because that in the max LIN
case the reflux is so small in the upper column, that one would lose more argon in the impure
nitrogen than by reducing the blowing in of evaporated rich liquid into the upper column.
This is found in Stenungsund (FIC even), Eggborough and Herne among others.
© Linde Gas AG Page 91 (109) 2001-02-20

1ppm O2
1% N2
99% Ar
QI FIC
GAN To
Pure Argon
PDIC Column
90% O2
10% Ar
0,03% N2 QI
QIC
GOX
LIC
Figure 16.5 Crude Argon Column with Oxygen free Argon

16.7 Crude Argon Column which gives Oxygen free Argon
To obtain oxygen free (less than 1 ppm) argon, this requires a very large number of trays,
perhaps 200, in the crude argon column. Using sieve trays the pressure drop becomes too big.
But with structured packing the ∆p becomes ≈40 mbar and the increased cost for the column
can compete, because the chemical purification is not needed. In a traditional column with 60
sieve trays which gives an argon purity of only 98%, the ∆p is ≈ 150 mbar.
This is an advantage for operation and maintenance as chemical cleaning contains so much
apparatus: Compressor, chemical reactor with three aftercoolers, dryers with regeneration,
instrumentation (see next chapter). Also, no hydrogen or electricity for compressors and dryers
is required.
As it requires so many theoretical trays the column, with structured packing, must be divided
into two parts, which stand beside each other. The second column has a condenser at the top
with rich liquid which gives oxygen free argon. It is fed with gas from the first column, which
is fed with reflux, using a pump from the other column.
See figure 16.5 Crude Argon Column with Oxygen Free Argon.
There is a big volume of liquid running in these column parts, in the Lausitz plant 30000 litres
(at 940 Nm3/h LAR). So it takes a long time to start up, 1-2 days, because many argon
molecules must be extracted from the low pressure column and the right concentration profile
must be built up in the crude argon column.
© Linde Gas AG Page 92 (109) 2001-02-20

Atm.
FIC QIC
Figure 17.1 Flow Schematic of Chemical Argon Purification
H2
H2 recovery UZ
FIC PIC M
Crude Argon Column
Pure Argon Column

FIC
Stenungsund, Sweden
TIC
TIS
FIC,
H2 feed
Atm.
Electric
TSH Heater QIC
H2 H20
FIC NH3
GAN
17. CHEMICAL PURIFICATION OF ARGON
Crude argon with approx. 2 % oxygen is purified in the chemical purification. This is done by
adding hydrogen, which in a chemical reactor reacts (burns) with the oxygen to form water
vapour. This water is removed in a drier. Chemical purification is not used where the crude
argon column can produce oxygen free argon.
As the crude argon is cold it must be warmed up and this is carried out in a heat exchanger
where it meets the warm oxygen free argon. The pressure is so low that a compressor is
required to put the crude argon through the purification equipment.
See figure 17.1 Flow Schematic of Chemical Argon Purification.
17.1 Hydrogen Feed
Twice as much hydrogen than oxygen is required in the process. This can be seen in the
chemical formula:
H2 + 1/2 O2 ---> H2O
To be sure that there is sufficient hydrogen, so that all of the oxygen will be removed, a surplus
of hydrogen is added, leaving a hydrogen content after the chemical reactor of 1 %. This is
analysed and controlled using a QIC on the hydrogen feed.
A calculation of hydrogen consumption: Assume 100 Nm3/h crude argon with 2,5 % oxygen.
This means that the oxygen flow is 0,025 • 100 = 2,5 Nm3/h. Hydrogen consumption will be 2 •
2,5 = 5 Nm3/h. The hydrogen surplus after the reactor is normally separated in a part of the
pure argon column (see next chapter) and is reused in the crude argon.
Hydrogen is added before or after the compressor. To avoid hydrogen leaks into the purifi-
cation equipment at operation stoppage, there is often not only a shut-off valve on the hydrogen
pipe, but there is also a small valve down stream which opens to the atmosphere.
The compressor normally has a pressure of 4-5 bar, which is much more than what is required
to put the argon through the equipment. The reason for this is to reduce the water content in the
argon before the dryers (see 8.5), which leads to reduced regeneration energy to the dryers. This
saving is bigger than the extra energy, which is required to compress the gas to the higher
pressure. The compressor capacity is controlled with PIC control of a valve on the suction side.
It can also be carried out by bypassing the gas from the pressure side to the suction side.
17.2 Deoxo - Chemical Reactor
The chemical reactor is called "Deoxo" or "De-oxidiser". The reaction between hydrogen and
oxygen require a relatively high temperature to initiate it, so there is a catalyst in the reactor.
This enables the reaction to start at room temperature. The catalyst consists of palladium, a
very noble and expensive metal coated on the surface of small beads similar to those in the
mole sieves. The catalyst will initiate the chemical reaction without itself being consumed.
© Linde Gas AG Page 93 (109) 2001-02-20

Atm.
FIC QIC
Figure 17.1 Flow Schematic of Chemical Argon Purification
H2
H2 recovery UZ
FIC PIC M
Crude Argon Column
Pure Argon Column

FIC
Stenungsund, Sweden
TIC
TIS
FIC,
H2 feed
Atm.
Electric
TSH Heater QIC
H2 H20
FIC NH3
GAN
The chemical reaction develops a great amount of heat, which raises the gas temperature. If the
reactor is well insulated the temperature would be 230°C for each percent oxygen. But the
reactor is not insulated as the heat must be removed before the gas goes to the drier.
To protect the Deoxo against overheating there is a temperature switch (TSH). Sometimes
there is TIC control of an oxygen free argon bypass to the suction side of the compressor. This
means that the oxygen content goes down and therefore the temperature of the Deoxo.
The Deoxo easily reduces the oxygen content to less than 1 ppm. Besides this, there is approx.
1 % nitrogen, 1 % hydrogen and 4-6 % water vapour in the argon. To remove as much water as
possible the gas is cooled.
First there is an air cooler, which is a tube bundle with fins and sometimes there is a fan to
improve the cooling. There also is a water cooler with water from the cooling water system.
Finally there is an ammonia cooler which cools to +5°C. This is used to reduce the water
content so that the regeneration energy of the dryers can be reduced.
17.3 Dryers
The dryers contain mole sieves and function as those described in 8.7, except CO2 adsorption.
They are regenerated with either dry argon or GAN. The advantage in using argon is that it can
be returned and fed to the suction side of the compressor. The disadvantage is that this
recycling can cause certain contaminants, e.g. methane, to accumulate and reach a too high
concentration. The advantage of using GAN is that this accumulation is avoided, but the
disadvantage is the losses through purging with argon. If besides the purging is not properly
done, there will be to much nitrogen to the pure argon column which will disturb it.
17.4 Chemical Purification without Hydrogen and Dryer
In Eggborough, England, the crude argon column has structured packing and is so high that it
can be left without being divided. It can give crude argon, with less than 0,1 % oxygen (=1 000
ppm). This low oxygen content means that it is possible to use a chemical reactor with nickel in
metallic form. The crude argon is warmed up by the returned oxygen free argon and goes to the
reactor.
The nickel is coated onto the surface of beads as in the palladium catalyst. This is not however
a catalyst as the nickel itself is consumed and forms nickel oxide. Regeneration is carried out
with hot nitrogen with some few % of hydrogen. This recreates the metallic nickel from the
oxide and water is formed, which goes out to the atmosphere, so no drying is required. Then
purging of the nickel is carried out with dry GAN at room temperature.
As the crude argon column has structured packing the pressure drop is small and there is a
relatively large pressure left for chemical purification (approx. 0,3 bar). Thus, no compressor is
required. The oxygen free argon goes in the heat exchanger and is cooled down to the dew
point then goes into the pure argon column which does not require a hydrogen separator.
© Linde Gas AG Page 94 (109) 2001-02-20

FI TI
H2 to Crude Ar
Rest gas
before compressor
FI TI
Ar from drier
Low pressure
GAN, 0,2 bar
5 bar 0,3 bar, -193

LIN
H
LIC
PIC 0,1-0,2 bar

HIC
PDI
Pressure -185
GAN, -177
PI
LIC
QI
TIC
4 bar
-167
LIC
LAR
Figure 18.1 Pure Argon Column

(Sundsvall, Sweden)
18. PURE ARGON COLUMN
When we have the dry oxygen free argon from the chemical cleaning, the last thing to do is to
separate the nitrogen and hydrogen from it. Separating argon from nitrogen is relatively simple
compared with separating oxygen and argon and the separation of argon and hydrogen is very
simple because of the temperature differences.
The separation takes place in the pure argon column, which is the only normal distillation
column in the plant. This means that it has both a reboiler and a condenser and the feed is in
the middle.
18.1 Function of a Pure Argon Column
See figure 18.1 Pure Argon Column.
The cold argon gas with hydrogen and nitrogen first goes to the reboiler at the bottom where it
boils off the pure LAR, while itself is condensed. This is possible because the gas has a higher
pressure than the LAR. The reboiler is often of the tube type and the impure argon gas rises in
the tubes and then condenses. The hydrogen is separated here as no hydrogen and little nitro-
gen condenses. The hydrogen rises to the top and goes out to the heat exchanger and is recycled
in the crude argon to the compressor. For a picture of the tube condenser, see Fig 15.1. Because
of the risk of leaks of hydrogen in the coldbox, this pipe in certain plants runs within a larger
pipe. A pressure meter is connected to the mid space, to give warning of a hydrogen leak. In
other plants a hydrogen detector is used on the gas in the coldbox insulation.
In certain plants there is only condensing of impure argon gas in the reboiler. Separation of
hydrogen takes place in a separator outside of the column. In plants without chemical
purification hydrogen separation is not required.
The condensed argon goes via a level valve to the centre of the column and runs downwards to
meet the boiled off gas from the bottom, so that we obtain rectification. To be able to increase
boiling there is an additional reboiler, which uses GAN from the pressure column. Due to its
pressure it is sufficiently warm for boiling off the LAR. This GAN condenses to LIN and is
sent via a hand valve (HIC), where the pressure is decreased, to the condenser. There it can
condense argon due to its low pressure. This LIN is not sufficient so more must be added from
the pressure column through a level controlled valve (LIC).
The main purpose with this column is to obtain pure LAR in the bottom. Therefore pay great
attention to the lower part of the column. The nitrogen content shall reduce from approx. 10000
ppm to 1 ppm in the bottom. This is necessary with a relatively large amount of vapour from
the reboiler, which is 2,5-3 times the LAR-production. If this content reduces too much, we can
be sure that there will be much nitrogen in the LAR. Therefore the pressure difference (PDI)
over the column, which is a measure of vapour quantity is important.
To take LIN and GAN from the pressure column is a loss of reflux. Therefore, in the newest
plants (Tepeji, Santiago 2) is used rich liquid. In order to be able to condense, the pressure of
the rich liquid must be as low as possible and the argon content of the rest gas (see below) must
be raised to approximately 75 % or the column pressure is raised somewhat.
© Linde Gas AG Page 95 (109) 2001-02-20

FI TI
H2 to Crude Ar
Rest gas
before compressor
FI TI
Ar from drier
Low pressure
GAN, 0,2 bar
5 bar 0,3 bar, -193

LIN
H
LIC
PIC 0,1-0,2 bar

HIC
PDI
Pressure -185
GAN, -177
PI
LIC
QI
TIC
4 bar
-167
LIC
LAR
Figure 18.1 Pure Argon Column

(Sundsvall, Sweden)
The vapour rises to the top and the nitrogen content increases (also possible rests of the
hydrogen). Nearly all condenses and goes back as reflux. It is difficult to get pure nitrogen at
the top, as it has nearly the same pressure as the LIN that condenses, so that there will be a
small temperature difference. Normally it should be around 15-25 % Ar in the top nitrogen,
which goes out as the so-called residual gas. This may seem a large loss. But if the nitrogen
content in the crude argon is 1 % it becomes, according to the material balance for 100 Nm3/h
crude argon, 1 Nm3/h N2. If the argon content is 25% in the top nitrogen, the nitrogen content is
75%. Assume that the residual gas flow is X, then 0,75 • X=1 Nm3/h, which means that X =
1,33 Nm3/h and the argon flow = 0,25 • 1,33 = 0,33 Nm3/h. If the argon content is 50 % the
loss rises to 1 Nm3/h of argon.
It is also worthwhile to note that if the nitrogen content increases in the crude argon, then the
argon loss increases in the pure argon column. If the nitrogen content = 2 % the nitrogen flow
will be 2 Nm3/h. With 25 % argon in the top, the residual gas flow = 2/0,75 = 2,66 Nm3/h and
the argon loss = 0,25 • 2,66 = 0,66 Nm3/h.
If we get oxygen in the column it washes down into the reboiler and contaminates the LAR.
Oxygen has a warmer boiling point than argon so it is not boiled off from the LAR, but must be
drained.
18.2 Controlling the Pure Argon Column
The residual gas valve controls the argon concentration at the top of the column. Too much
residual gas flow gives increased argon content and too little gives a reduction. When the argon
content reduces, so the condensation temperature and ∆T in the condenser is reduced, which
reduces the heat transfer. The result of this is that the condensing will be reduced and the
pressure rise in the same way as for helium in the condenser in the double column (see 15.3).
This pressure increase can be used as a signal to open the residual gas valve more. To have the
correct control the level must be constant, as a changed level signifies changed area and heat
transfer. For the same reason the temperature of the boiling LIN must be unchanged. In certain
plants (Sandviken, Stenungsund and Malmö) this is solved by having a pressure controller
(PIC) on the boiled off LIN. In newer plants the boiling off goes to the impure nitrogen from
the upper column, which has constant pressure.
This means that pressure control of the residual gas valve is a little uncertain. Too much blow
off gives an argon loss and too little gives impure LAR (from the material balance reasons
nitrogen is forced down in the column). Fig 18.1 shows the pure argon column in Sundsvall.
In this plant the column pressure is controlling the LIN feed and the condenser level the
residual gas valve. Both these, PIC and LIC, are co-operating. When the N2 concentration in
the top is increasing, the condensation is decreasing and the pressure wants to increase. Then
the PIC is increasing the LIN feed. But since the condensation has decreased, the level wants to
rise. Then the LIC opens the rest gas valve and more gas blows out. N2 is decreasing in the
column top, the condensation increases and the LIN level does not increase.
© Linde Gas AG Page 96 (109) 2001-02-20

The HIC on pressure GAN is used in order to get the correct purity of the LAR in the bottom.
The HIC increased until the N2 concentration < 1 ppm. This is increasing the boiling and the
pressure wants to increase in the column. Then the PIC increases the LIN feed to the
condenser. Depending on the N2 concentration in the top, the LIC starts to work according to
the above.
The condenser works with nearly no level at all. This means that the LIN spurts in over the
condenser and boils away before it becomes a level. In this way not all of the condenser will be
at -194°C as boiling LIN at 0,2 bar, but it will be a little warmer so avoiding the risk for
forming argon ice. This forms at -189°C for pure argon but in mixtures with nitrogen the risk is
less. At 80 % argon and 20 % nitrogen argon ice forms at -196°C.
© Linde Gas AG Page 97 (109) 2001-02-20

TECHNICAL REVIEW 1 Enclosure
CRYOTON, Holland Page
PRESSURE MEASUREMENTS
TAG NO. PANEL BEAMEX Pressure

(bar) (bar) drop (bar)
Air measured Jan. 23
Suction filter U-tube 8 mm WG
After air compressor PI-0228 5,18 5,16 0
Before spray cooler PI-2401 5,16 5,10 --
Before MS 5,03 -- --
After MS 1 4,98 -- --
Before MS 2 4,97 -- --
After MS 2 4,95 -- --
Box inlet PI-5810 5,03 4,97 --
Column bottom PI-3201 4,94 4,96 0,20
MS 1 diff. pressure 0,044 *

MS 2 diff. Pressure 0,048 *
Columns measured Jan. 24

Under, bottom PI-3201 4,87 4,82 --
Under, difference PDI-3202 0,12 + 4,82 0
- 4,68 0,14
Upper, bottom PI-3211 0,56 0,56 --
Upper, difference PDI-3212 0,24 + 0,56 0
- 0,32 0,24
Crude argon PDI-401 0,212 0,210
Products measures Jan. 24

GOX from column PI-3211 0,56 0,56 0
after heat ex. PI-5820 0,58 0,55 0,01
GAN from column PDI-3212- 0,32 0
after heat ex. PI-5835 0,26 0,25 0,08
Waste N2 after heat ex. PI-5880 0,28 0,28 0
before MS PI-2632 0,08 0,06 0,22
Measured with Beamex PC 125 precision manometer except * MS diff. measured with Druck DPI
601 precision diff. pressure manometer.
Comment to waste N2 pressure: operating high to get 107% recycle load at 77% of design air.
Figure 19.1 Pressure drop measurements

19. AN OVERVIEW OF PRESSURE AND PRESSURE DROPS IN THE PROCESS
To move gas around in the process as pressure drop, ∆P is required. This is the same physical
principle that lies behind the need for a temperature difference to transfer heat. Compressor
work is required, so that the necessary pressure can be obtained and this means that there is
electricity consumption.
The main task for the air compressor is that it gives sufficient pressure to the air that shall be
separated as gaseous products. The pressure is determined mainly by the evaporation of LOX
with GAN in the double column, which we have dealt with previously. The biggest part of the
air compressors electric consumption goes to separating the gases, so the consumption is
determined by how much we want to produce. But a small part of the consumption depends on
the pressure drops in the process, which can increase if you have not paid attention to them.
The main task for the recycle compressor is to give sufficient pressure to the nitrogen recycle
for it to be able to produce cold in the booster-expanders. This cold makes liquid products of
the gases that are separated with the help of the air compressor. So the electric consumption in
the recycle is determined by how much liquid we want to produce. Again a small part of the
electric consumption also depends on the pressure drop.
19.1 Pressure Drops in Pipes
The pressure drop in pipes depends on diameter, flow, pressure and temperature. The
connection between the three latter is the same as we discussed in 9.5 for the dependency of
compressor capacity on effective volume. Here the same effective volume applies again and
gives the same pressure drop in the same pipes. For example 12 000 Nm3/h of air at 5 bar (g)
and +5°C has an effective volume of 12 000 • 1/6 • 278/273 = 2036 m3/h, and 100 000 Nm3/h
of nitrogen at 49 bar (g) and +5°C the effective volume becomes 100 000 • 1/50 • 278/273 =
2036 m3/h.
For this flow the process manufacturer can select the same pipe diameter (naturally the inner
diameter, as the pipe wall thickness will be different due to the pressure). With a larger dia-
meter the pressure drop becomes less, but larger pipes cost more. During construction the
process manufacturer makes a compromise choice of pipe diameters (and the corresponding for
valves and heat exchangers etc). A certain pressure drop must be accepted and that this
selection means a price in pipes etc, which is a compromise with energy loss due to pressure
drop.
19.2 Investigation of Pressure Drops
In the guarantee test all measurement data is collected for the process. All instruments are
calibrated and checked. This data is important for comparison, when the installation has run for
several years when wear and dirt accumulations have increased. One should compare if the
pressure drops have increased. The air separation process is really a very clean process, but
there are a few possibilities for dirt accumulation. Normally this is a long-term problem and it
can take up to one year for a significant difference to be noticeable. This can make it difficult
for the personnel to see any changes. One becomes blinkered. So it is recommended, every now
and then, to go and look back at the original process data.
© Linde Gas AG Page 98 (109) 2001-02-20

Silencer
Cooling
Water
PI
Check
valve
QI FIC
Ammonia
Water LI
separator
QE
PI
Figure 19.2 Pressure Drop in Air Path

Pressure drops are examined in a logical order in the flow direction of a stream from higher
pressure to lower pressure. We always go downstream, so to say. The pressure always sinks
downstream, if not the pressure meter showing is either a wrong or a new little compressor is
installed.
The important streams to examine are:
• Air from compressor to pressure column

• GOX, GAN and impure nitrogen from upper column to atmosphere
• Nitrogen recycle suction side from pressure column to compressor
• Nitrogen recycle pressure side from compressor to expander.
If you follow the streams in this way it will also be easier to see how the process is connected
together.
Make a table for each stream, one column showing where the measurement took place, one for
the number of the measurement point (tag No.), one for process measurement values, possibly
one for a measurement value using a precision instrument, and one column for pressure drop.
Figure 19.1 Measurement of Pressure Drop in a Technical Review
To be able to make a comparison with another test, it is important that it is the same production
case with the same flows, pressure and temperatures. If you find a significant change in
pressure drop, you should examine it more closely and try to find out where it has occurred.
The existing pressure measurements are possibly not adequate for a more exact determination
of where the fault is. There you can use local measurement points with shut-off valves and
connect a portable precision pressure meter. You can also if you are careful use other
measurement points : An analysis outlet, an outlet for level measurement or what else is
available. If this is not sufficient you can as the next stop install a pipe with a shut-off valve at
the relevant point on the pipe network.
When you are surer that you know where the problem is, you take the appropriate corrective
actions at the next stop. For example, opening the plant part in question and repairing or
cleaning it, or defrosting it.
19.3 Pressure Drop in the Air Path
After the air compressor a pressure drop occurs in the silencer, aftercooler, check valve, +5°C
cooler, water separator, mole sieves with filter, shut-off valve, main heat exchanger and the
trays in the pressure column. These can vary so you must check the flow schematic of your
installation.
See figure 19.2 Flow Schematic for Air to the Column.
Abnormal pressure drops can occur if there is a fault in the check valve, dirt and corrosion in
the coolers and water separator, dust from the mole sieves in the filter, dust in the mole sieve
bed that has baked in (see 8.10), ice or frozen carbon dioxide (CO2) in the heat exchanger.
© Linde Gas AG Page 99 (109) 2001-02-20

Atm.
Set Point= 0,10
FI PIC Set Point = 0,3 + 0,1
PIC
GAN
0,15 + 0,1
0,25
FIC
0,05 + 0,1 FIC

0,3 +0,1
0 + 0,1 Waste
N2
MS
Atm.
GOX 0,5 +0,1
5,0 +0,3
5,5 + 0,3
5,2 +0,3
Figure 19.3 Double Column and Air Compressor Pressures

Carbon dioxide comes from "break through" from the mole sieves. It forms a frost in the cold
end of the main heat exchanger. The frost is relatively loose so a part of it will continue into the
column. If there is a CO2-analyzer, a "break through" will be detected at the end of an
adsorption cycle, as a rapid increase in the concentration. Water break through is less plausible,
as the CO2 is already fully breaking through.
19.4 Carbon Dioxide in the Columns
Carbon dioxide has a melting point of -79°C (actually it is the so-called sublimation point, as it
transfers directly from solid state to gas), so that it is washed down in the rich liquid and to the
LOX in the upper column. There it forms a coating on the reboiler surface, which worsens the
heat transfer. This leads to that it becomes harder to condense GAN, so that the pressure on the
GAN side and the temperature difference increase (see 6.3).
To find out if there is CO2 in the reboiler we measure the pressure of both LOX and LIN sides
and calculate the respective temperatures with the help of vapour pressure curves (see fig 6.2).
The temperature difference is compared with that measured in the guarantee test and if the
difference is significant, then the installation must be defrosted.
Carbon dioxide can also be noticed by disturbances in the level of the rich liquid. The reason is
possibly that there is CO2 in the lower impulse tube for level measurement, which gives false
signals to the level controller.
19.5 Pressure Drop of the Outgoing Gases from the Upper Column
In the upper column there is a pressure drop over the trays. Therefore the GOX pressure out
from the column will be the highest, then comes the impure nitrogen and the lowest is the GAN
at the top. The GOX has its pressure drop in the main heat exchanger, while the GAN and
impure nitrogen have a pressure drop in the subcooler and the impure nitrogen also in the mole
sieves. In these pipes there are hardly any increases in pressure drop, except for the impure
nitrogen in the mole sieve as we have mentioned. It is important to know the pressure drop if
you have a gas customer and you want to increase production over the design, as the pressure
drop increases and this can make it difficult to take out product from the coldbox. If the ∆P for
the impure nitrogen in the mole sieve would increase, this can affect the whole process, which
we shall discuss.
See figure 19.3 Double Column Pressures and Air Compressor.
The process manufacturer designs the plant, so that the pressure drop will be so large that the
pressure of the GOX and GAN before the control valve after the heat exchanger is as small as
possible, minimum approx. 0,05 bar for all specified operational cases. It is designed also so
that the impure nitrogen will have a smaller ∆P and higher pressure, approx. 0,15 bar after the
heat exchanger. GOX and GAN have a flow controller (FIC). The impure nitrogen flow is
determined by the material balance = what remains when GOX and GAN is taken out, so this
cannot be flow controlled, but there the pressure out from the column is controlled (PIC). This
pressure is set in so that is sufficient to obtain a sufficient pressure on the GOX and GAN. For
example Schwechat was designed for 4.000 Nm3/h GAN and its customers wanted 4.500
Nm3/h. This presented no difficulties to increase the rectification, but the pressure went down
to zero after the heat exchanger. This was solved by rising the pressure, approx. 0,1 bar at the
PIC for the impure nitrogen from the column.
© Linde Gas AG Page 100 (109) 2001-02-20

Atm.
Set Point= 0,10
FI PIC Set Point = 0,3 + 0,1
PIC
GAN
0,15 + 0,1
0,25
FIC
0,05 + 0,1 FIC

0,3 +0,1
0 + 0,1 Waste
N2
MS
Atm.
GOX 0,5 +0,1
5,0 +0,3
5,5 + 0,3
5,2 +0,3
Figure 19.3 Double Column and Air Compressor Pressures

Down stream of this valve there is another control valve (PIC) for the regeneration gas. This is
set at the pressure, which gives a sufficient regeneration gas flow through the mole sieves. If
this pressure becomes less than the pressure upstream of the control valve for the upper
column, nothing is affected. If this becomes higher the control valve for the upper column will
fully open and the column pressure rises, which is controlled by the regeneration gas valve.
19.6 The Pressure in the Pressure Column
If one raises the pressure in the upper column it is raised in the pressure column. This increases
the air compressor’s pressure and its energy consumption. To show this we will go step by step
up stream from the PIC for the regeneration gas.
The process data in the figure is taken from Eggborough. The pressure of the regeneration gas
is set as low as possible, approx. 0,15 bar, to have an adequate flow. The valve of the surplus
regeneration gas, which goes out to the atmosphere, maintains the pressure. Upstream of the
impure N2 out from the main heat exchanger there is a control valve, which shall control the
upper column’s pressure where the impure N2 leaves it. If this valve is fully open, it has a slight
pressure drop and the pressure rises from 0,15 bar through the main heat exchanger and
subcooler to approx. 0,30 bar in the column.
This gives the GOX a pressure of approx. 0,5 bar (∆P = 0,2 bar over the trays) and GAN 0,25
bar at the top (∆P = 0,05 bar). This should be sufficient to get a pressure > 0,05 bar out from
the main heat exchanger. If not then the pressure shall be increased of the impure nitrogen PIC
from the column. This results in slight closing of the control valve and ∆p increases over it.
The pressure downstream of the valve is not increased, because that is controlled by the
regeneration valve. So the pressure is increased upstream all the way to the column and further
on.
With a pressure of 0,5 bar for the GOX the LIN pressure in the condenser becomes approx. 5,0
bar according to the vapour pressure curves. The pressure at the bottom of the pressure column
becomes 5,2 bar (∆P = 0,2 over the trays) and the compressor pressure 5,5 bar (∆P = 0,3 from
compressor to column). In other words the upper column's pressure controls the air
compressor's pressure.
If one raises the upper column pressure by 0,1 bar the GOX pressure rises by the same amount.
But the LIN pressure rises by approx. 0,3 bar (according to the vapour pressure curves)! As the
air compressor's pressure and electricity consumption increase, the pressure of the upper
column should not be increased unnecessarily. Also, the rectification is worsened at higher
pressures.
With reduced airflow this reduces the pressure drop to the pressure column, the condensing in
the condenser and the pressure drop of the gases out from the upper column, so the pressure
reduces in the pressure column and air compressor. One can then reduce the pressure of the
regeneration gas, for the mole sieves require less flow and reduce the upper column's pressure,
if neither the GOX nor the GAN pressure out from the heat exchanger is too low.
© Linde Gas AG Page 101 (109) 2001-02-20

3245-1
Atm.
FIC
Q-3271
3261
(9 400) F-2615 (17 800)
FIC T-2615 (11)
E3116
PIC P-3930 (0,12)
Air T - (-172)
T-3930 (21)
GAN
Waste N2 P - 3261 (0,32)
Atm. T-3925 (21) Q-3220
F-3925 GOX
3
T-3156 (-177) 15000 Nm /h
QIC T-3935
Q-3935
(21)
N2 Seal T-3401 (-97)
T-3451 (-6) P-(56,2)
P - (27,3)
TIC
P-3211
P-1311 T2 T1 (0,56)
(0,06) (-93) T-3402 D3631
T-3452 (-177)
TC5
S-3451 S-3401 LIC FIC
PIC (28 000) (25 000)
TCV-3401
F-1310
(9 400)
P-(4,65) P-3410 (56,7) F-3455 F-3245 (6987)
F-3405
T-(25) T-(24) TC4 (56 600) TC3 (56 700) P - (4,8)
FIC
(28 300) o
T in C
F-1410 P in bar g P-3201
(85 000) 3
P-1410 P-1411 (27,6)
(4,65) T-1409 (24)
TC2
19.7 Pressure Drop on the Recycle Suction Side
Here there are several streams meeting so a consequential list as for the air stream cannot be
made. From the pressure column to the suction side of the recycle compressor there will be a
pressure drop in the make-up valve to the recycle (if it is not fully open), heat exchanger, shut-
off valve, silencer and suction filter of the compressor.
The streams which go through the main heat exchanger for balancing and compensation are
flow controlled, so usually it is the control valves that take the pressure drop. It is only if both
valves are fully open that the heat exchanger's pressure drop has some significance. See figure
13.1 Malmö recycle.
The cold expansion turbine outlet goes through a silencer (this applies to Eggborough, which is
an outdoor installation with accompanying noise demands) and together with the make-up from
the column to the heat exchanger. In the heat exchanger after a small pressure drop it meets the
outlet from the warm turbine. The stream continues with a pressure drop in the heat exchanger
to the suction inlet of the compressor. In addition there is the feed compressor's pressure line,
which goes together with the recycle compressor suction before the filter. So there is a pressure
drop over a check valve. See figure 13.2, Eggborough recycle.
The lowest pressure in the suction line will be at the inlet to the recycle compressor. If we go
back up stream, the pressure increases and the warm turbine has a lower outlet pressure than
the cold one. The latter's pressure is controlled by the make-up valve from the pressure column.
If the valve is fully open the pressure will be almost as high as that in the column.
Normally ∆P from the cold turbine to the compressor suction side is 0,2-0,3 bar. This may
seem insignificant. But if the compressor's pressure ratio (out/in) = 28,6/5,7 = 5,0 this means
that an increased ∆P = 0,2 bar on the suction side results in 5 • 0,2 = 1,0 bar less on the
pressure side.
Possible reasons of an increased pressure drop are: The shut-off valve is not fully open, fault in
the check valve or dirt in the filter. The nitrogen is dry and clean so there is little risk of dirt,
but there can be welding debris left from the construction. There is a possibility that the
insulation material of the silencers, normally mineral wool, is loose and gets caught in the filter
or in the heat exchanger. There is also a small possibility that the feed compressor after-cooler
leaks and that with wrong starting routines water leaks into the nitrogen side. This water
freezes solid in the heat exchanger on the pressure side and can only be removed by defrosting.
The make-up valve controls the pressure on the suction side. When the valve is fully open, the
flow through the compressor reaches its maximum and cold production is at maximum, which
we discussed in 13.1. This means that abnormal pressure drops on the suction side give
reduced cold production. In 13.2 it was shown how we reduce cold production by lowering the
suction pressure to 3,0 bar. If the suction pressure by some reason does down 0,2 bar, then the
flow for the same reason becomes in the compressor: 2891 = X/ (5,4-0,2+1), X=17 924 Nm3/h.
Capacity = 17 924/18 500 = 97 %.
© Linde Gas AG Page 102 (109) 2001-02-20

3245-1
Atm.
FIC
Q-3271
3261
(9 400) F-2615 (17 800)
FIC T-2615 (11)
E3116
PIC P-3930 (0,12)
Air T - (-172)
T-3930 (21)
GAN
Waste N2 P - 3261 (0,32)
Atm. T-3925 (21) Q-3220
F-3925 GOX
3
T-3156 (-177) 15000 Nm /h
QIC T-3935
Q-3935
(21)
N2 Seal T-3401 (-97)
T-3451 (-6) P-(56,2)
P - (27,3)
TIC
P-3211
P-1311 T2 T1 (0,56)
(0,06) (-93) T-3402 D3631
T-3452 (-177)
TC5
S-3451 S-3401 LIC FIC
PIC (28 000) (25 000)
TCV-3401
F-1310
(9 400)
P-(4,65) P-3410 (56,7) F-3455 F-3245 (6987)
F-3405
T-(25) T-(24) TC4 (56 600) TC3 (56 700) P - (4,8)
FIC
(28 300) o
T in C
F-1410 P in bar g P-3201
(85 000) 3
P-1410 P-1411 (27,6)
(4,65) T-1409 (24)
TC2
19.8 Pressure Drop on the Pressure Side in the recycle
There are two paths: From the compressor to the warm expander and to the cold expander via
both the boosters. After the compressor there are a check valve and a silencer. To the warm
turbine there is a filter and a shut-off valve. To the cold turbine there is the same and a filter
before and a check valve after the respective booster. See figure 13.2.
Here there are the same possibilities for abnormal ∆P as on the suction side.
To show the influence of ∆P on the pressure side an example is shown from Meitingen,
Germany. There was no dirt in the filters, but ∆P was high because of a less good construction:
∆P (booster-filter) = 0,87 bar, ∆P (expander-filter) = 0,48 bar (only one booster-expander). In
the sister plant in Buenos Aires the filters had been changed so that ∆P = 0,22 + 0,35 bar. What
will it serve the Meitingen plant to change the filters to this ∆P?
The recycle compressor can work with a lower pressure = 1,35 - 0,57 = 0,78 bar, which means
less electric consumption. This can be calculated by using the isotherm efficiency formula
given in 9.8. One calculates with the help of operating data the efficiency. Then this efficiency
is used to calculate electric consumption for a 0,78 bar lower outlet pressure. For such a small
change one can assume that the efficiency is not changed.
Measured electric consumption = 3716 kW
Calculation of isothermal work =

41472 • 1,25 • 8,314 • 296,5 • ln 33,7 = 2 364 kW
3600 28,02 5,20
Isothermal efficiency = 2364/3716 = 63,6 %
Isothermal work for lower outlet pressure =

41472 • 1,25 • 8,314 • 296,5 ln 32,92 = 2 338 kW
3600 28,02 5,20
Electric consumption for lower outlet pressure = 2338/0,636=3676 kW
Electricity saving = 3716-3676 = 40 kW
Electricity consumption per year = 8400 h • 40 kW = 336 000 kWh
Cost saving, for electricity price = 0,114 DM/kWh = 38 300 DM
This cost saving can motivate the purchase of better filters, which have a price similar to that of
the saving.
© Linde Gas AG Page 103 (109) 2001-02-20

Figure 20.1 Cryogenic air separation, Coldbox
nitrogen recycle
9
Cooling LAR
water
8
7
5
6 LOX
GAN
Air in 1 2 3 Air LIN
GOX
M
20. SPECIFIC ENERGY CONSUMPTION AND PRODUCTION COSTS
The specific energy consumption, the so-called specific energy, is the most important measure
of the plant and how well it is operated. This is the total electricity consumption, minus any
pipe delivery compressors, divided with the total liquid production to the tanks: kWh/Nm3
liquid. This figure should not be too much bigger or be preferably identical to that measured
during the guarantee test. Good plant maintenance, first of all the air and recycle compressors
holds down energy consumption and good operation of the process gives a lot of production.
The electricity consumption is the dominant operating cost of an air separation installation.
Other costs such as water and hydrogen are of minor significance.
See Fig. 20.1 Overview of the Air Separation Process
20.1 Costs of Increased Specific Energy Consumption
As an example we will take Sandviken. If the specific energy has increased by 5 % from 1,25
kWh/Nm3, then the increased electric consumption for a years production of 65 million Nm3 of
liquid products will be 0,05 • 1,25 (kWh/ Nm3) • 65 (million Nm3) = 4,06 million kWh. The
electricity cost is approx. 0,21 SEK/kWh, which leads to an increased electricity cost = 0,21
(SEK/kWh) • 4,06 (million kWh) = 0,853 million SEK = 853 000 SEK.
20.2 Break-down of the Electric Consumption (kW) of Different Machines
Sandviken Sundsvall Stenungsund Eggborough
Recycle compressor 4400 2800 5375 6100

Air compressor 2250 530 5650 1500
Feed compressor - 700 * Incl.
Regeneration of mole sieves 120 270 195 130
Cold Machine 210 - 380 50
Cooling water pump 170 - 230 135
Cooling tower fans 60 - - 92
Crude argon compressor 55 110 114 -
Regeneration of argon dryers 7 20 20 6
TOTAL 7500 9150 11800 8470
The total includes ventilation, lighting, tank pumps, oil pumps, heating, computers,
instrumentation, transformer losses etc.
The GOX and GAN product compressors to the delivery pipe are handled separately.
* In Stenungsund part of one GAN compressor is used for feed.
As seen above the air and the recycle compressors constitute a very large amount of the total
consumption.
© Linde Gas AG Page 104 (109) 2001-02-20

20.3 Production and Specific Energy
Start-up year 1976 1984 1990 1994
LOX (Nm3/h) 4900 4000 5000 3300

LIN 760 5000 8800
LAR 178 550 615 125
GOX 350 9000 10000 200
Air 26 000 62 000 74 000 18 000
Specific energy 1,28 2,01 1,11 0,69

(kWh/Nm3 liquid)
The production is given in the design case. One can change freely between LOX and LIN, but
in certain older plants like Sandviken one cannot reach 100% LIN. Moreover one cannot
decrease LOX to zero, because of the risk of hydrocarbon accumulation in the reboiler. When
LIN is increased LAR will decrease somewhat because decreased reflux.
The differences in specific energy depend on machinery efficiency, production capacity and
GOX-quantity. Efficiencies have gradually improved since the 1970's. Malmö, from 1970 has
less than half of Sandviken's capacity, has a specific energy of 1,50 kWh/Nm3. In plants with
larger capacity the machines have better efficiencies. The GOX-quantity has a big effect, as it
requires air, which demands electricity consumption in the air compressor. For Sundsvall this
specific energy becomes not completely fair. The GOX is blown off to obtain LAR, which
means operation with surplus air. In 1995 a liquefier was installed. The following division of
specific energy is better.
20.4 Separation and Liquefaction Energy
The main task of the air compressor is to feed the column with air, which shall be separated. So
the air compressors electricity consumption is used to separate the gases. For separation mole
sieves, +5°C refrigeration machine and cooling water are also required. A plant for GOX
delivery by pipe has this equipment and a small expansion turbine to compensate for cold
losses. For this can be calculated separation energy, which is the electricity consumption
divided by GOX production: kWh/Nm3 GOX. The separation energy can also be calculated in
a plant which produces liquid. This is calculated as kWh/Nm3 GOX + LOX.
The main task of a recycle compressor is to produce cold to produce liquid from the gaseous
products. So the electricity consumption of a recycle compressor goes to the liquefaction of the
gases. Also required is cooling water and possibly a -40°C refrigeration machine. Liquefaction
energy is the recycle compressor’s electricity consumption divided by the total liquid
production: kWh/Nm3 liquid.
Electricity consumption in argon purification is distributed to the LAR production.

Additionally there is the hydrogen consumption.
© Linde Gas AG Page 105 (109) 2001-02-20

Separation energy 0,43 0,41 0,38 0,43

(kWh/Nm3 oxygen)
Liquefaction energy 0,75 0,62 0,51 0,50
(kWh/Nm3 liquid)
Argon purification 0,35 0,24 0,22 0,05
(kWh/Nm3 LAR)
This is used as a check of the efficiency of the separation and liquefaction and for the
production cost calculation, which is important for price setting. For GOX this will be the
separation energy. For LOX it will be the separation and liquefaction energy. For GAN
normally the separation energy is not calculated, as it is a by-product which goes to the
atmosphere. If GAN is delivered by pipe the separation energy is calculated depending on the
local conditions. So for LIN it becomes only the liquefaction energy. For LAR it becomes the
separation, liquefaction and purification energy. Hydrogen consumption and possible surplus
air must also be considered.
GOX 0,43 0,41 0,38 0,43

LOX 1,18 1,03 0,89 0,93
GAN 0 0 0 0
LIN 0,75 0,62 0,51 0,50
LAR 1,53 1,27* 1,11 0,98
* to be added kWh for surplus air, special calculation is required. See below.
20.5 Cost of Argon when Running with Surplus Air (New in version 4)
This is a calculation of the marginal cost, i.e. the change in cost if one changes from the
current operational mode to another. One estimates how much more argon one receives for a
certain increase of air and this results in an increase in electric power consumption by the air
compressor. The marginal production cost is:
Increase in electric power consumption (kW) = (kWh/Nm3 Ar)

Increased argon production (Nm3/h)
This requires operational data from the plant in both modes of operation. If only the data for
100% air is known, the normal case for the guarantee test, then the marginal cost can be
calculated as follows:
Total electric power consumption air compressor (kW)

Total argon production (Nm3/h)
For Sundsvall it will be 5300/550 = 9,6 kWh/Nm3 Ar. This is the marginal cost of a small
change near the operational mode for 100% air.
© Linde Gas AG Page 106 (109) 2001-02-20

If the normal operational mode is 65% air, which is minimum, and one wishes to increase to
100% for argon it will be with an example from Maracaibo:
Test 65% air Test 100% air

Air (Nm3/h) 12520 19220
Power air compressor (kW) 1571 1950
Argon yield (%) 94 94
Increased argon prod. = (19220-12520) • 0,00932 • 0,94 = 59 Nm3/h

Increased power = 1950 - 1571 = 379 kW
Marginal argon cost = 379/59 = 6,4 kWh/Nm3 Ar
Note that the result will be different if one goes from 65 till 80% or 80 to 95% air, because
the efficiency of the air compressor is lowest at minimum flow. In this range the increase of
electric power consumption per m3 air is not so great. As a comparison the cost of argon
calculated at 100%:
1950/(19220 • 0,00932 • 0,94) = 11,6 kWh/Nm3 Ar.
The change in efficiency does not enter here. Compared to Sundsvall it is more due to the
compressor and its efficiency is lower.
When the Sundsvall plant was being planned the scarcity of argon was acute. At that time
the marginal cost was calculated before the plant was ordered. What will be the cost for
argon by surplus air if a bigger air compressor and greater separation capacity are ordered?
This was weighed against the import cost of argon. For 9000 Nm3/h GOX the surplus air is =
9000/0,21 = 42900 Nm3/h. This gives 0,00932 • 0,95 • 42900 = 380 Nm3/h Ar. Power
consumption by the air compressor for 62000 Nm3/h air is 5300 kW and for the surplus air
42900 Nm3/h it is 3670 kW.
Marginal cost for argon: 3670/380 = 9,7 kWh/Nm3 Ar.
20.6 Measurement Methods for Production and Energy Consumption (Rev. in version 4)
Electricity consumption is relatively easy to measure. In all plants there is a kWh-meter for the
incoming electricity consumption and where there are product compressors these normally
have separate meters. Electricity meters measure consumption in kWh and give an accumulated
value, so by comparing the reading at the end of the period to that at the start, the difference is
the consumption. One has to be aware that often the value is multiplied by a certain factor e.g.
100, so that the consumption can be given in kWh (sometimes the reading is in MWh =
megawatt hour, mega=1 million). This measurement factor shall be clearly indicated on the
meter.
Production measurement is a little more complicated. It is difficult to get good measurement

accuracy of the production to the tanks. It is cryogenic liquids boiling or lying close to the
boiling point. Orifice plates for flow measuring have a pressure drop in order to be able to
measure, which make them very sensitive to boiling. Micro-motion type flow meters, which
have improved in recent years, are difficult to calibrate in operation especially the setting of the
zero.
© Linde Gas AG Page 107 (109) 2001-02-20

Technical Review
Plant : Forel, Moscow
MATERIAL BALANCE
Stream Tag No. Flow O2 Conc. O2 Flow

(Nm3/h) (%) (Nm3/h)
Air FIC 1 19250 20,95 4033
GOX FIC 101) 16 16

FIC 2 1270 1270
LOX by tank level 2736 99,9 2736

Estimated losses 50 50
GAN FIC 3 2100 0 0
LIN 0 0 0
Estimated losses
and flash
Crude Ar FIC 401 140 1 1
Leak gas2) 0 0
Waste N2 by balance* 12988 0,26 34
TOTAL OUT 19250* 4107
Difference 0* +74
= 1,8%
Nm3 at 0°C and 760 mm Hg
Oxygen yield = (1270+2736)/4033 = 99,3% Argon yield =
1) FIC 10 controlling between 0-120 Nm3/h. Est’d average from trend

2) No leaks because FIC 1 is measured after compressors and boosters
Figure 20.2 Material balance for an air separation plant

The best measurement accuracy can be obtained by measuring the rise of the tank level under a
certain period, e g one day. This is done during the guarantee test and in AGA Technical
Reviews. The good quality in this measurement depends on that the inner tank has been
constructed with good accuracy; in a diameter of 10 m the diameter may vary by some mm.
This is normally checked and measured before the tank roof is welded on.
The latest development is ultra sonic flow meters from Danfoss. They have been verified in the
Donawitz plant for LOX and LIN with tank level measurements and the accuracy was found
better than 1 %. A key factor is that they have the same diameter as the pipe and insignificant
pressure drop. And LIN, which is the most difficult to measure, is produced at boiling point
high up in the coldbox. So there are many meters liquid column above the flow meter, which
makes that boiling can be avoided.
The level is measured with a measurement device, made by Enraf, and it is a float suspended
on a piano wire. A tension meter measures the tension in the wire and a small motor adjusts
automatically the position of the float, so that there is always the same tension in the wire. The
winding up of wire is measured and gives the level in mm with an error less than +/- 1 mm.
The problem with this method is that the accuracy is reduced if the measurements are only
taken over a short time. For example, if the level rise is 100 mm the error becomes +/- 2 mm =
2 % but with 50 mm the error is 4 %. The rise in the tank level depends on tank diameter and
production. Over 24 hours the change is normally more than 100 mm. As unloading to tankers
is carried out many times per day it is difficult to get 24 hours with an undisturbed tank.
Where there are no Enraf meters, level indicators (pressure difference type) of highest class
should be used. Nowadays there are such ones with an accuracy better than 0,1% of the
measuring range (≈20 m wg). This becomes +/- 20 mm, thus significantly worse than the Enraf.
Then unloading to tankers is weighed on a scale, which usually has an accuracy of +/- 100 kg.
As the vehicle is weighed both before and after the error becomes +/- 200 kg, which
corresponds to around 1 %. The problem is with transfer losses. The pump must be cooled
down and boiled off gas from the tanker must be blown off. This is some % in losses in all,
which depends on how well the operator does his job and if the tanker is not cold etc.
Measurement of gaseous products is much easier. The orifice plate can be used for example,
see 5.2.
In order to check the accuracy of the production measurement, especially during guarantee test,
the material balance is an important aid. In 6.9 it is described how it is done. It consists of one
total balance and one oxygen balance. The total balance is that incoming air shall equal all
products and the O2 balance is the same for O2 in air and in products.
See figure 20.2 Material Balance for an Air Separation Plant
The 2nd column shows the total flows and the 4th the O2 flows. Gas flows are measured in the
process computer, but are checked as described in 5.2. In this plant there is no meter for waste
N2, so that is calculated by balance. By the analysis of the waste N2 is obtained its O2 flow.
More O2 goes out than goes in, which is rare. The difference was 1,8 %, which however is
acceptable. There are many measured values included in the balance. We suspected that the
airflow was indicated too small. It was checked with precision instrument as of 5.2. But as it is
50 bar in the measuring point, it is difficult to do an exhaustive check.
© Linde Gas AG Page 108 (109) 2001-02-20

Questions to chapter 11-20 (New in version 4)
Chapter 11:
1. For cold production in the Claude process is needed 2 machines and 4 apparatus.
Which are they ?
What do they do ? ( Increasing/decreasing/unchanged: pressure, temperature or heat contents.
Changing gas/liquid state)
Chapter 12:
1. A booster-expander consists of one impeller for expansion of cryogenic gas and one for
compression of warm gas and they are connected on the same shaft,
How is the leak gas minimized ?
How is the bearing protected for cold leak gas ?
2. The cold production in an expander depends on the flow, the temperature sink and the pressure
drop of the gas passing it.
On which of the three is it possible to see an efficiency reduction without calculation ?
How ?
3. Which of O2, N2 and Ar demands most resp. least cold/m3 to become liquid ?
Chapter 15:
1. The first stage in the recovery of argon is to take a gas stream from the upper column to feed the
crude argon column.
What is the composition of this gas stream ? (% O2, N2 and Ar)
What is this part of the upper column called ?
Chapter 16:
1. Which gases are separated from each other in the crude argon column ? (O2, N2 and Ar)
2. Describe the function of this column, where is the feed, product withdrawal, condenser, reboiler ?
condensing and boiling with what ?
3. The crude argon production is limited by N2 , the so-called nitrogen sense. Describe this shortly.
Chapter 18:
1. Which gases are separated from each other in the pure argon column ? (O2, N2 and Ar)
2. Describe the function of this column, where is the feed, product withdrawal, condenser, reboiler ?
condensing and boiling with what ?
Chapter 19:
1. The pressure of the upper column is controlled by a PIC. How is increased pressure affecting the
air compressor ?
2. How is this affecting the energy consumption of the air compressor ?
3. In figure 19.1 there is a comment in the bottom of the page : operating with high waste N2
pressure to get max recycle load at reduced air flow. Explain how and why.
Chapter 20:
1. How is calculated the plant specific energy (kWh/Nm3) ?
© Linde Gas AG Page 109 (109) 2001-02-20

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Air separation techniques course

by Anders Lenneskog, SUP

Lidingö, March 1995

Versions 2 and 3 have been corrected and made clearer./ AL Nov 95

Air is a mixture of different gases. The three most important are:

Nitrogen 78 % (volume) Chemical symbol: N2

LOX Liquid Oxygen

Other components in air:

© Linde Gas AG Page 2 (109) 2001-02-20

2. AIR GASES BOILING POINTS

Water (melting point) 0 = 273 K 0 273

Propane -42 = 231 K

Carbon dioxide (melting point) -79 = 195 K

Krypton -153 = 120 K

© Linde Gas AG Page 3 (109) 2001-02-20

Cooling Cold Distillation

Purification GAN LIN

3. MAIN PROCESS FUNCTIONS

1. Air compressor with filter

3. Cooling down the air

5. Cooling with cooling water

See figure 3.1 Overview of an Air Separation Process

© Linde Gas AG Page 4 (109) 2001-02-20

Figure 4.1 A Normal Distillation Column

4. GENERAL DISTILLATION TECHNIQUES

4.1 The normal distillation column

The most common type of distillation apparatus consists of a column with:

• Reboiler in the bottom to produce vapour that rises in the column

See figure 4.1 A Normal Distillation Column

4.2 Column types

© Linde Gas AG Page 5 (109) 2001-02-20

A-E refer to figure 4.4

Figure 4.2 Column with Sieve Trays

4.3 Columns with sieve trays

See figure 4.2 Column with Sieve Trays

4.4 Columns with structured packings

See figure 4.3 Column with Structured Packing

See figure 4.3 Liquid Distributors in Column with Structured Packing

© Linde Gas AG Page 6 (109) 2001-02-20

F igure 4.3 C olum n w ith

4.5 How single columns function

4.6 Composition at the different trays

See figure 4.4 Temperatures of O2 - N2 Mixtures at Different Compositions. (T-x diagram)

© Linde Gas AG Page 7 (109) 2001-02-20

-196 Liquid Phase

A-E refer to figure 4.2

Figure 4.4 Temperature - Composition (T, X) Diagram

4.7 Material balances

See figure 4.5 Composition of O2 and N2 in the Column.

© Linde Gas AG Page 8 (109) 2001-02-20

Correct Too high N2 Too low

QI-1 Bottom 100% O2

A) Correct quantity B) Too much C) Too little

Figure 4.5 Composition of O2 and N2 in the column

4.8 Controlling the LOX take-out

See figure 4.6 Operating a Single Column

4.9 Operating a single column, disturbances

To be able to operate a column, as shown in figure 4.6, we require more measurement

© Linde Gas AG Page 9 (109) 2001-02-20

Figure 4.6 Operating a Normal Distillation Column

4.10 Increased vapour quantity

Figure 4.7 Flows in a Single Column at Different Operating Cases.

© Linde Gas AG Page 10 (109) 2001-02-20