Moderate-pressure cryogenic air

separation process
Hare Cheung

Union Carbide Industrial Gases Inc., Linde Division, 175 East Park Drive, Tonawanda, NY
14151, USA

Received 11 December 1990; revised 9 April 199 1

A new cryogenic air separation process has been developed which complements the traditional double
column low pressure air separation cycle’,2. The process, designated the M-Plant cycle (for moderate
pressure), focuses upon high fractional recovery of argon and production of moderate pressure
gaseous nitrogen. The M-Plant cycle distillation system inverts product pressures and provides crude
argon and high purity nitrogen at about 200 kPa pressure with high purity oxygen slightly above
atmospheric pressure. The traditional T-Plant cycle uses a standard low pressure double column
distillation system which furnishes the oxygen at about 140 kPa pressure and crude argon and high
purity nitrogen at slightly above atmospheric pressure. Since nitrogen and argon comprise the larger
part (79%) of the processed air, the M-Plant cycle conserves product pressure energy and results in a
physically smaller upper column and nitrogen piping which reduces capital cost. Customers requiring
large amounts of gaseous nitrogen at about 200 kPa pressure and above can realize as much as 10%
energy savings and up to 5% greater argon recovery over the traditional T-Plant.

Keywords: distillation; cryogenics; air separation

Introduction processes ensure availability and competitive sources of

argon. The M-Plant cycle is viewed first as a nitrogen
Small-scale commercial production of argon began in
process with argon co-product. and can be assessed
1916 in Cleveland. 0hio4. Initially. argon was used to till
economically against nitrogen-only plant cycles such as
incandescent lamps with argon-nitrogen mixtures. and in
those given in Refs 3 and 7.
1939. in fluorescent lamps. After 1943. demand for argon
increased greatly with the advent of inert-gas-shielded
welding. More recently. metallurgical applications such Traditional argon recovery
as argon-oxygen-decarburization (AOD) of stainless and Argon has traditionally been a by-product of oxygen
other steels. blanketing and stirring usages, and electronic product-based cryogenic air separation processes. Typical
applications at ultrahigh purity have increased annual early processes in the 1940’s are illustrated by Ruhemann”
domestic argon production from 135 million Nm3 in 1975 and Simpson’ for gaseous oxygen and liquid oxygen
to 338 million Nm3 in 1988. At the same time. on-site production. respectively. Most argon is produced from
oxygen production, which is essentially the sole source of large-tonnage oxygen processes, such as a T-Plant cycle.
argon, has increased only 22.4%.. On the other hand, on- The state-of-the-art for argon production from such a
site nitrogen production has increased by > 300% from T-Plant cycle in the 1960’s has been reported by Latimes.
1975 to 1988. The 1988 total domestic oxygen production Essentially, no basic process changes have occurred to the
was 13 820 million Nm3 compared with the total nitrogen T-plant cycle separation column system in the last four
production of 21 934 million Nm’. These statistics point decades. There have been many revolutionary improve-
out the desirability for argon recovery from nitrogen- ments in equipment and machinery as well .as the use of
product-based air separation plants. more column system separation stages to increase argon
The new process. designated as the M-Plant cycle, recovery and enhance separation performance. Also. a
focuses upon high-recovery argon and moderate-pressure preference has developed to prepurify the feed air using
gaseous nitrogen production and is. for practical purposes. molecular sieve adsorption to remove water vapour.
a nitrogen-product-based ternary air separation process carbon dioxide. acetylene and higher hydrocarbons
(oxygen. nitrogen, argon). This M-Plant cycle complements before cryogenic processing.
the conventional T-Plant cycle which is an oxygen- A standard modem nitrogen/oxygen T-Plant process
product-based air separation process. Together, the two with argon recovery typically involves filtering of the feed
air to remove particulate matter and compressing the
“1989 Union Carbide Industrial Gases Technology Corp. filtered air to supply the energy required for the separation

0950-4214/91/010025-04 Gas Separation & Purification 1991 Vol 5 March 25

Cryogenic air separation process: H. Cheung

oxygen. Self-sustaining air separation plant refrigeration

Figure 1 Moderate pressure nitrogen/argon M-plant with oxygen
production
of air at a compressor discharge pressure of z 640 kPa.
This high-pressure feed air is prepuritied by chilling it to
278 K and then removing water vapour, carbon dioxide,
acetylene and higher hydrocarbons in a 13X molecular
sieve adsorption system.
The chilled, clean feed air then is inserted into the
process portion ofthe cold box as shown in Figure 1. In the
cold box, the feed air is first cooled against returning cold
effluent product and waste streams in the primary heat
exchanger. It is then fed into the bottom of the lower
column of the conventional triple-column distillation
system comprising a double column, each with lower and
upper columns, and a crude argon column which often is
designated as the low ratio column (LRC). The feed air is
separated into a high-purity nitrogen (shelf liquid) stream
at the top of the lower column and an oxygen-rich liquid
stream at the bottom of the lower column. These two
liquid streams are further cooled in the superheater and
throttled to about the same low pressure as the upper
column.
The throttled high-purity nitrogen reflux liquid is
directed to the top of the upper column to provide liquid
nitrogen reflux at 114 kPa and 78.4 K. The throttled.
subcooled, oxygen-rich kettle liquid is transferred to the
crude argon column (LRC) condenser where liquid argon
reflux is generated and kettle liquid is partially vaporized
into a kettle vapour fraction and an oxygen-enriched
kettle liquid fraction. These two kettle fractions are
intermediate upper column feeds, along with a small
turbine air stream taken from a midpoint of the primary
heat exchanger and expanded in the turbine and further
cooled against oxygen product. These streams to the low-
pressure upper column are separated into a high-purity
vapour nitrogen product at the top of the column. a small
vapour nitrogen-rich waste stream located a few trays
below the top, and a high-purity vapour oxygen product at
the bottom.
Liquid oxygen is reboiled at the bottom of the upper
column in a main reboiler/condenser which condenses
high-pressure nitrogen from the lower column to supply
high-purity nitrogen for lower column reflux and shelf
liquid. A low ratio column vapour feed (containing
1 l-13% argon in oxygen with traces of nitrogen) is taken
from an upper column location between the kettle liquid
feed and oxygen product take-off. This stream is fed into
the bottom of the low ratio column and is separated into a
liquid return stream to the upper column and a small
crude product argon stream overhead with nominal
composition of 97.5% argon, 1.0% nitrogen, and 1.5%
is generated by the turbine with turbine airflow of
z 8-10% ofthe cold box air. This refrigeration compensates
for warm end losses, heat leak and liquid nitrogen used to
operate the argon refinery.
To maximize argon recovery in the described T-Plant
cycle, the upper column top is operated at z II4 kPa, the
lowest practical pressure. This low pressure enables the
relative volatilities between argon and oxygen and
between nitrogen and argon to be as large as possible, thus
maximizing the separation of the air into the three major
components. The process arrangement results in high-
purity nitrogen production at the lowest pressure. The
nitrogen contains essentially no pressure energy and can
be discarded without an energy penalty if only product
oxygen, or product oxygen and product argon are desired.
This versatility. along with cycle operating flexibility. has
made the T-Plant cycle the ‘work-horse’ of cryogenic air
separation for many decades. At the 114 kPa upper
column top pressure. oxygen recovery is 99.9% at 99.5+%
oxygen purity: argon recovery is near 90%; and nitrogen
recovery is 90% at =: 1 ppm oxygen in the product
nitrogen.
However, if moderate-pressure nitrogen is desired. the
T-Plant cycle is less efficient. The T-Plant cycle is very
sensitive to top upper column pressure. For example.
applying the same number of separation stages as the
114 kPa top upper column pressure illustration given
above and raising the top upper column pressure to a
moderate pressure of 191 kPa results in decreasing the
oxygen recovery to 96.4%, argon recovery to 60% and
nitrogen recovery to 67%. for the same purity products.
M-Plant cycle
A new moderate-pressure cryogenic air separation
process has been developed to complement the T-Plant
cycle. The patented process, designated as the M-Plant
cycle, focuses upon high recovery of argon and moderate-
pressure gaseous nitrogen production. This M-Plant cycle
features an innovative air separation distillation system
arrangement which uniquely inverts conventional
oxygen/nitrogen product pressures and allows favourable
operating conditions for high argon recovery. For practical
purposes the pressure inversion makes the M-Plant cycle
a nitrogen-based ternary air separation process. The cold
box portion of the M-Plant cycle is shown in Figure2.
wherein a top upper column pressure of 191 kPa is chosen
for comparison purposes with the T-Plant cycle moderate
pressure illustration previously cited.
Figure 2 Standard nitrcgen/oxygen.T-plant with argon production

26 Gas Separation & Purification 1991 Vol 5 March

 Cryogenic air separation process: H. Cheung

Filtered feed air is compressed to 855 kPa, chilled to
278 K. prepurified by adsorption to remove water vapor,
carbon dioxide, acetylene, and higher hydrocarbons, and
inserted into the cold box. In the cold box, the feed air is
first cooled against returning effluent product and waste
streams in the primary heat exchanger and then fed into
the bottom of the lower column. The triple column
distillation system comprises a double column, with lower
and upper columns. and the crude argon low ratio
column. The feed air is separated into a high-purity
nitrogen shelf transfer stream at the top of the lower
column and an oxygen-rich kettle liquid stream at the
bottom of the lower column. Both high-pressure liquid
streams are further cooled in the superheater and throttled
into the moderate pressure upper column. The throttled
high-purity nitrogen shelf liquid is inserted at the top of
the upper column to provide liquid nitrogen reflux at
191 kPa and 83.2 K. The single-throttled kettle liquid is fed
to an intermediate upper column location which is also
fed by a small air stream. This stream is taken from a
midpoint of the primary heat exchanger. expanded in the
turbine, and further cooled against oxygen product.
These two feeds to the moderate-pressure upper
column are separated into a high-purity vapour nitrogen
product at the top ofthe column. a small vapour. nitrogen-
rich waste stream located a few trays below the top, and a
high-purity liquid oxygen product stream at the bottom.
This liquid oxygen product stream is directed into the low
ratio column condenser at an appropriate pressure to be
vaporized to gaseous oxygen product. The vaporized
liquid oxygen refrigeration provides low ratio column
liquid argon reflux. Liquid oxygen is reboiled at the
bottom of the upper column. in the main reboiler/
condenser. which condenses high-pressure and high-
purity nitrogen from the top of the lower column for lower
column reflux and shelf liquid.
A low ratio column vapour feed. containing 12-16%
argon in oxygen with traces of nitrogen, is taken from an
upper column location between the kettle liquid feed and
upper column bottom. The moderate-pressure. low ratio
column vapour feed is fed into the bottom of the low ratio
column where it is separated into a liquid return stream to
the upper column and a small. moderate-pressure, crude
argon product stream overhead with a nominal com-
position of 97.5% argon, 1.O% nitrogen, and 1.5% oxygen.
As in the T-Plant cycle, self-sustaining air separation
plant refrigeration is generated by the turbine. An
example of the column system operating conditions for
the M-Plant cycle are given in Table 1.
Lower column air is 92.7% of the feed air, and turbine
air is 7.3% of the feed air. The low ratio column feed is
20.2% of the feed air compared with the oxygen product of
21%. The low ratio column feed composition of 15.45%
argon is considerably higher than for the T-Plant cycle.
Nitrogen recovery is z 94%. and argon recovery is r 93%.
Oxygen recovery is identical with the T-Plant cycle of
99.9% at the low 114 kPa pressure at the top of the upper
column.
As described previously, the T-Plant cycle, operating
with the same number of theoretical stages in the column
system, and at the same uppercolumn pressure of 191 kPa
recovered only 60% of the argon as compared with the
M-Plant cycle, which recovered 93%. This marked improve-
ment is the result of not producing kettle vapour in the low
ratio column condenser. The T-Plant cycle kettle vapour
bypasses the lower portion of the upper column. The
M-Plant cycle. by omitting the rather large kettle vapour
upper column feed stream, experiences slightly higher
loadings in the lower portion of the upper column, since
the liquid equivalent to the kettle vapour is vapourized in
the reboiler or main condenser. Effectively, rather than
bypassing T-Plant cycle kettle vapour, its equivalent is run
down and up again in the lower portion of the M-Plant
cycle upper column. This technique reduces the internal
reflux ratio in the lower portion of the upper column and
favours argon stripping in that critical portion of the
upper column which conducts the difficult argon-oxygen
separation. The upper portions of the upper column are
less affected because the relative volatility of nitrogen/
argon is much larger. In effect. the novel M-Plant column
system arrangement allows enrichment to higher argon
compositions at the upper column take-off point for the
low ratio column feed. as demonstrated by the 15.45%
argon composition given in Table 1. A comparison of the
ability of both cycles for separating air into its three major
components of oxygen. nitrogen. and argon is presented
in Table?.
The M-Plant cycle is a better air separator with upper

Table 1 Example of column system operation in M-plant cycle

Stream Flow (% of Pressure Temperature Composition (%)

feed air) (kPa) (K)
Oxygen Argon Nitrogen

Lower column air 92.7 813 109.3

Turbine air 7.3 210 95.3
Feed air 100.0 21.0 0.9 89.1
LRC feed 20.2 217 97.6 84.50 15.45 0.05
Nitrogen 73.9 191 83.2 1 ppm 99.98
Crude argon 0.9 188 93.6 9z5 97.3 0.8
Oxygen 21.0 126 92.6 0.25 0

Table 2 Air separation capability with same number of theoretical stages in column system

Cycle Upper column top Temperature Product recovery (%)

pressure (kPa) (K)
Oxygen Nitrogen Argon

T-Plant 114 78.4 99.9 90

T-Plant 191 83.2 96.4
M-Plant 191 83.2 99.9 93

Gas Separation & Purification 1991 Vol 5 March 27

Cryogenic air separation process: H. Cheung
column reflux furnished at 83.2 K than the T-Plant cycle
with upper column reflux furnished at 78.4 K. The
M-Plant cycle is strikingly superior to the T-Plant cycle at
moderate pressures, and offers limited pressure versus
recovery trade-offs.
Physically, the M-Plant cycle offers the oppo~uni~ to
reduce the diameter of both nitrogen piping and the upper
column. Using the 114 kPa T-Plant case and the 191 kPa
M-Plant case given in Table2. and applying the piping
pressure drop approximation method at high Reynolds
numbers given by Lydersen”, the pipe diameter ratio is
approximated by the reciprocal of the vapour density for
the same pressure drop. mass velocity and pipe length.
This formula gives a pipe diameter ratio of the M-Plant
cycle to the T-Plant cycle at the top of the upper column of
0.62. Using the F-factor criteria of Latimeg for the top of
the upper column, the upper column diameter ratio at this
point equals 0.89. In terms ofgreater capacity for the same
column diameter, the upper column throughput can be
increased z 25% with the M-Plant cycle. Since the upper
column is the largest component in the cold box, and the
nitrogen low-pressure piping is the largest piping in the
cold box, cold box size reduction possibilities exist. The
oxygen piping is slightly larger; but fortunately. there is
less oxygen volume flow than nitrogen. By comparison,
the M-Plant cold box is slightly more compact than the
T-Plant cold box and through its use, capital savings as
well as performance benefits can be realized.
Conclusions
Conceptually, the new M-Plant cycle is a nitrogen-based
ternary air separation process focused upon high argon
recovery. The M-Plant cycle is created by the innovation
of utilizing liquid oxygen to operate the crude argon
column condenser rather than conventional oxygen-
enriched kettle liquid. This innovation provides a
favourable argon/oxygen stripping reflux ratio in the
lower portion of the upper column and also inverts
product pressures so that product pressure energy is
28 Gas Separation Et Purification 1991 Vol 5. March
retained in the larger nitrogen fraction of the separated
compressed air. The favourable upper column operating
conditions result in up to 5% greater argon recovery over
the traditional T-Plant cycle, and the nitrogen product
pressure inversion can result in up to 10%energy savings
and some cold box capital savings due to compactness.
The M-Plant cycle commercialy complements the
traditional T-Plant cycle, which is an oxygen-product-
based air separation process. Together, the two processes
ensure availability and competitive sources of argon. The
M-Plant cycle is preferred when nitrogen is the major
product, and the T-Plant cycle is preferred when oxygen is
the major product. When all the air separation elements
are considered as products, the choice of cycles is less
certain. The M-Plant cycle is a better air seaparator
providing higher argon recovery. low energy consumption.
and compactness; but the T-Plant cycle is more versatile
with more operating flexibili~.
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