In May 1895, Carl von Linde performed an experiment in his laboratory in Munich that
led to his invention of the first continuous process for the liquefaction of air based on the
Joule-Thomson refrigeration effect and the principle of countercurrent heat exchange. This
marked the breakthrough for cryogenic air separation.
For his experiment, air was compressed Linde based his experiment on findings
from 20 bar [p₁] [t₄] to 60 bar [p₂] [t₅] in discovered by J. P. Joule and W. Thomson
the compressor and cooled in the water (1852). They found that compressed air
cooler to ambient temperature [t₁]. The pre- expanded in a valve cooled down by approx.
cooled air was fed into the countercurrent 0.25°C with each bar of pressure drop. This Carl von Linde in 1925.
heat exchanger, further cooled down [t₂] proved that real gases do not follow the
and expanded in the expansion valve Boyle-Mariotte principle, according to which
(Joule-Thomson valve) [p₁] to liquefaction no temperature decrease is to be expected
temperature [t₃]. The gaseous content of the from expansion. An explanation for this effect
air was then warmed up again [t₄] in the heat was given by J. K. van der Waals (1873), who
exchanger and fed into the suction side of discovered that the molecules in compressed
the compressor [p₁]. The hourly yield from gases are no longer freely movable and
this experiment was approx. three litres of the interaction among them leads to a
liquid air. temperature decrease after decompression.
N₂
Water cooler
Compressor p₂t₁
p₂t5
Heat exchanger
Ar
p₂t₂
O₂ Nitrogen 78.08%
Oxygen 20.95%
Argon 0.93%
p₁t3 Neon 0.0018%
Expansion valve Helium 0.0005%
Krypton 0.00011%
Xenon 0.000009%
t₃ Separator
Liquid air
04 History and technological progress of air separation
Boiling points To enable air to be separated into its The vapour pressure curve illustrates the
constituents by means of rectification – the temperatures and pressures at which a gas
0°C Water freezes
actual separation process – a large part condenses or a liquid evaporates.
of the air volume used must be liquefied.
–107°C Xenon A gas can only be transformed into a →→ Air below atmospheric pressure (1 bar)
liquid state at temperature and pressure must be chilled to –192ºC (81.5 K) before it
conditions below those of its critical point. starts to condense
–152°C Krypton →→ Air below a pressure of 6 bar must be
–183°C Oxygen The critical point of air is Tcrit = –140.7ºC chilled to –172ºC (101 K) before it starts to
(132.5 K) and Pcrit = 37.7 bar. In other words, condense
–186°C Argon
air can be liquefied only at temperatures
–196°C Nitrogen
below –140.7ºC (132.5 K). The boiling point and condensation conditions
of gas mixtures such as air are not identical.
–246°C Neon A condensation line and a boiling point line
delineate the boiling point range.
–273°C Absolute zero
50
N₂ Ar O₂
Liquid
Air
10
6
5
Pressure in bar
V K
Vapour
0.5
81.5 101
60 80 100 120 140 160
Temperature in K
90
Condensation
temperature
TS at PS = 1 bar
Vapour
Temperature in K
Boiling point
temperature
TS at PS = 1 bar
77
Liquid
0 20 40 60 80 100
O₂ concentration in O₂/N₂ mixture % by volume
06 History and technological progress of air separation
Using his air liquefaction principle as a basis, Carl von Linde constructed the first air separation
plant for oxygen production in 1902 using a single-column rectification system.
In 1910, he established the basis for cryogenic air separation with the development of a double-
column rectification system. Now it was possible to produce pure oxygen and pure nitrogen
simultaneously.
This involves installing a pressure column below the low-pressure column. At the top of this
pressure column, pure nitrogen was drawn off, liquefied in a condenser and fed to the top
low-pressure column as reflux. At the top of the low-pressure column, pure gaseous nitrogen
was withdrawn, while liquid oxygen evaporated at the bottom of this column to deliver pure
gaseous oxygen. This principle of double-column rectification combining the condenser and
evaporator to form a heat exchanger unit is still used today.
Pure nitrogen
Liquid N₂
Nitrogen
with 7% O₂
Low-pressure column
1.5 bar
Condenser
Pure
oxygen
Pure oxygen
5.6 bar
Process air
Condenser Condenser/reboiler
1.5 bar
Condenser
5.6 bar
9.0
8.0
N₂ O₂
7.0
6.0
5.6
Pressure in bar
5.0
4.0
3.0
2.0
1.5
1.0
dT=1.4K
94.1 95.5
0
70 75 80 85 90 95 100 105 110 115 120
Temperature in K
08 History and technological progress of air separation
Structured packings
1991
Significant progress in air separation Liquid flowing down becomes increasingly
technology was made in the mid-1980s. For richer in oxygen, whereby the ascending
the first time, structured packings were used vapour is enriched with nitrogen. The main
World’s largest in cryogenic rectification. Packed columns benefits of packed columns compared with
air separation plant with work in a similar way to sieve trays. The sieve trays are a lower pressure drop and
intensive contact between liquid and vapour consequently a lower power consumption for
packed columns required for the rectification takes place on the air separation process. Another important
the huge surface area of the packing material. advantage of packed columns is the possible
loading range including a very high turn down
to nearly 30%. This also forms the basis for a
new process for argon separation.
Downflow of liquid O₂
Rising N2 gas
Packed column.
10 History and technological progress of air separation
1 Air compression 2 Air cooling and purification 3 Cold production and internal product compression
Air booster
compressor
Coldbox Heat
exchanger
Molecular sieve
unit
Expansion
turbine
Sub
Evaporation cooler
cooler
Direct
contact
cooler
Air compressor
Water pump
Cryo pump for
int. compression
→→ Compression of ambient air by a multi-stage turbo compressor with →→ Cooling of process air in heat exchangers down to nearly
intercoolers at a supply pressure of approx. 6 bar. liquefaction temperature by means of countercurrent with gas
→→ Removal of dust particles by a mechanical air filter at the inlet of streams from the rectification process.
the compressor. →→ Further compression of a sidestream of process air by an air booster
compressor. Expansion and cold production of the boosted air
2 Air cooling and purification stream in an expansion turbine.
→→ Cooling of process air with water in a direct contact cooler and →→ Expansion and liquefaction of a sidestream of the boosted air in a
removal of water soluble air impurities. liquid separator.
→→ Chilling of cooling water in an evaporation cooler against dry →→ Evaporation and warming to ambient temperature of the pumped
nitrogen waste gas from the rectification process. oxygen and nitrogen product in high-pressure heat exchangers.
→→ Removal of CO₂, water and hydrocarbons from the process air in
periodically loaded/regenerated molecular sieve adsorbers.
History and technological progress of air separation 11
LIN
Coldbox
ATM
Crude argon
column
Low-pressure
column
LAR
→→ Pre-separation of the cooled and liquefied air within the pressure →→ Argon-enriched gas from the low-pressure column is transformed
column into oxygen-enriched liquid in the column sump and pure into oxygen-free crude argon by means of separation within the
nitrogen gas at the column top. crude argon column.
→→ Liquefaction of the pure nitrogen gas in the condenser/reboiler →→ Pumping back liquid oxygen from the crude argon column sump into
against boiling oxygen in the sump of the low-pressure column. the low-pressure column. Removal of the remaining nitrogen in the
Liquefied nitrogen provides the reflux for the pressure column and pure argon column.
(after sub-cooling) for the low-pressure column.
→→ Different types of condenser are described in detail on page 16.
→→ Further separation of the oxygen-enriched liquid within the low-
pressure column into pure oxygen in the sump and nitrogen waste
gas at the top.
12 History and technological progress of air separation
filled reactors
Internal compression
1978
The internal compression (or liquid pumping)
Booster compressor
75 bar process allows for oxygen, nitrogen as well as
argon to be compressed within the coldbox by
Internal compression HPGAN 100 bar means of liquid pumps, to be evaporated and
of oxygen warmed up in heat exchangers, and finally to
be supplied to the end user at the required
HPGOX 100 bar
pressure.
2012
The ambient air is compressed by a state-of- required with this process design, leading
the-art multi-stage turbo compressor with to a reduction of investment cost. A further
intercoolers at a supply pressure of approx. advantage is the improved energy efficiency
Flexible high air pressure 20 bar. A booster air compressor is no longer of the main air compressor for small plants.
1990
Conventional process
The area in the low-pressure column where
the argon concentration is at a maximum
(approx. 10%) is known as the argon belly. Pure argon production
From there, the gas stream is fed into the by rectification
raw argon column for further rectification.
The remaining oxygen in this gas stream
is completely removed in the packed raw
argon column. Due to the very low pressure
drop in the packings, it is possible to install
a sufficient number of “theoretical trays”
required for the rectification. In the adjoining
pure argon column, the remaining nitrogen is
removed by rectification and the pure argon is
liquefied.
Pure liquid
argon (LAR)
1ppm nitrogen
1ppm oxygen
Condenser
Low-pressure column
Pressure column
→→ Energy-saving solution
Liquid oxygen
Low-pressure column
Gaseous nitrogen
Pressure column
History and technological progress of air separation 17
Condenser fabrication.
18 History and technological progress of air separation
5 ⨯ 10,000 t
N2 per day for
Cantarell, Mexico
1997
Largest ASU
for nitrogen
production
20 History and technological progress of air separation
2006
Largest EPC
contract in the
history of
air separation
History and technological progress of air separation 21
8 ⨯ 3,800 t
O2 per day in
Ras Laffan, Qatar
Air separation units at the Pearl GTL complex in Ras Laffan, Qatar.
22 History and technological progress of air separation
6 ⨯ 3,600 t
O2 per day for a plant
near Yinchuan City, China
2016
Engineering
masterpiece
in China
24 History and technological progress of air separation
2017
Start-up of
largest ASU
in the world
History and technological progress of air separation 25
5 ⨯ 5,250 t
O2 per day for
Jamnagar, India
Delivery of world’s largest coldbox weighing 800 tonnes for Jamnagar, India.
26 History and technological progress of air separation
Linde Engineering.
150
O₂ 20.95 –183.0°
N₂ 78.08 –195.8°
Ar 0.93 –185.9°
Ne 0.0018 –246.1°
new air
He 0.0005 –268.9°
separation
Kr 0.00011 –153.2°
patents in last
Xe 0.000009 –108.0°
5 years
O₂
air separation
plants have
air separation
units owned and 5,250 tpd
been built
by Linde
operated by The
Linde Group
oxygen
19%
Read more:
Heat exchanger linde-engineering.com/air_separation_plants
1,700 m²/m³
TCO
(Total Cost of
max. surface
10
Ownership)
–15%
savings in past
YEARS 10 years
90
Linde air separation units
built in more than
Biggest
pre-fabricated coldbox:
Published by:
Height 70 m Linde AG
Engineering Division, Dr.-Carl-von-Linde-Strasse 6–14
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