Production of Oxygen from Cryogenic Air Separation:

In the late 1800s, various attempts were made to separate oxygen from air on a commercial
scale. These all relied on chemical processes employing thermal cycling [7]. The most successful
processes involved heating barium oxide in air at 590 ◦C under pressure, so that it accumulated
oxygen to form barium peroxide. The peroxide, in turn, was heated to ca. 870 ◦C, at which point
it released half of its oxygen, which was collected at ca. 95% purity. This was subsequently
improved by maintaining the barium oxide at 600 ◦C, while oxygen was absorbed from air
supplied at 170 kPa and subsequently desorbed under vacuum. At this time, successful
experiments in air liquefaction were being conducted, which eventually led to the separation of
oxygen via distillation. Because the percentage of oxygen in the gas phase that is in equilibrium
with liquid air (containing 21% oxygen) is only 6%, separation of oyygen by distillation is
convenient. In 1901, Carl von Linde (Germany) demonstrated the first practical method for
controlling the distillation of liquid air: rectification. Early columns were inefficient, but by 1910,
Linde had introduced a double column, one above the other, with a condenser – evaporator in
between. This remains the concept employed for producing oxygen by cryogenic air separation.
Over the years, oxygen production plants have continued evolving into larger, more efficient
process systems. To date, the largest modular plant is capable of producing 2250 t/d [8].
Cryogenic air separation involves three steps:

1) Purification of the incoming air to remove particles, carbon dioxide, and water

2) Refrigeration and economization of refrigeration values contained in the product and waste
streams

3) Separation by distillation

Figure 1 shows a schematic of a process embodying these steps to produce oxygen. Filtered air
compressed to 600 – 700 kPa is cooled and scrubbed in a direct-contact water wash tower (a)
and then directed into a plate-fin reversing heat exchanger (b), where it is cooled further in
counterflow to product oxygen and waste nitrogen. Carbon dioxide and water are removed
from the air stream by condensation and solidification in this heat exchanger. Every few
minutes, the paths of the incoming air and the waste nitrogen streams are reversed (hence the
name reversing heat exchanger) so that deposited impurities can be purged from the
exchanger. In this way, the process is able to operate continuously on a cyclic basis. State-of-
the-art plants are, however, being constructed with molecular sieve adsorption units, in place
of the reversing heat exchangers. After carbon dioxide and water have been removed by the
sieve, the incoming air is then cooled by cold waste gas in counter flow heat exchangers.
Refrigeration for this process is achieved primarily by the Claude principle of conversion of
energy into work by the expansion of a compressed gas in a turbine. Some of the cooled air is
returned through the cold end of the heat exchanger before expansion to ca. 120 kPa in a
turbine (c), and then introduced at an appropriate point in the upper, low-pressure column of
the double column rectifier (d). The remainder of the air passes into the lower, high-pressure
column

Figure 1. Cryogenic oxygen plant (schematic)

a) Water wash cooler; b) Reversing heat exchanger; c) Expansion turbine; d) Double column
rectifier; e) Condenser; f) Subcooler; g) Adsorber; h) Compressor; i) Filter

at 500 – 600 kPa where it is separated into nitrogen gas at the top and oxygen-enriched liquid

(38% O2) at the bottom. Gaseous nitrogen is condensed by liquid oxygen (which is vaporized) in
the condenser – reboiler (e). Part of this liquid nitrogen is returned as reflux to the lower
column, and part is expanded into the top of the upper column as reflux liquid. The oxygen-
enriched liquid (rich liquid) from the sump of the lower column is expanded as feed into an
appropriate point in the upper column. The reflux liquids used are subcooled by returning
nitrogen in the heat exchanger (f ), to reduce the amount of liquid vaporized on expansion. In
the upper column, the feed is separated into pure oxygen (99.6%) at the bottom and waste
nitrogen with 1–2% oxygen at the top. The adsorber (g), packed with silica gel, removes trace
hydrocarbon matter from liquid oxygen in the condenser – reboiler and from the rich liquid,
ensuring that unsafe hydrocarbon concentrations do not accumulate in the process.(1)
(2)AIR SEPARATION:

Nitrogen and oxygen are, respectively, the second and third most produced chemicals. They are
used in numerous chemical processing, refinery, metal production, and other industrial
operations. For example, high-purity nitrogen is used for purging, blanketing, and providing
atmosphere for metal treating and other purposes; while high-purity or enriched oxygen is used
in chemical processing, steel and paper-making applications, wastewater treatment, and lead
and glass production. Nitrogen and oxygen have been produced since 1907 when Carl von Linde
built the first cryogenic distillation column for air separation in Buffalo, NY. Cryogenic processes
are highly efficient, particularly for large-volume production. Cryogenics account for
approximately 70% of the nitrogen and oxygen produced today (about 20% by adsorption and
10% by membrane and hybrid systems). The polarizabilities of N2, O2, and Ar are nearly the
same (1.74, 1.58, and 1.63 in units of 10−24 cm3, respectively), and are all nonpolar.
Consequently, they adsorb nearly the same on all sorbents except zeolites. The fact that
zeolites can distinguish between N2 and O2 was observed as early as 1938 (Barrer, 1937; 1938).
Barrer reported values for heats of adsorption of N2 on chabazite as high as 8 kcal/mol. The
high heats of adsorption were subsequently explained quantitatively in terms of the
quadrupole–electric field gradient interactions (Drain, 1953; Kington and Macleod, 1959). The
unique adsorption properties of zeolites derive from the fact that their surfaces are composed
of negatively charged oxides with isolated cations that are located above the surface planes.
Despite the finding of N2/O2 selectivity by zeolites, no effort was made to separate air by
adsorption until the 1960’s, after the invention of synthetic zeolites types A and X, and the
pressure-swing adsorption (PSA) cycles. The invention of types A and X zeolites by Milton
(1959) made it possible for these zeolites to be available at controlled quality and guaranteed
supply. The inventions of PSA cycles by Skarstrom (1960) and by Guerin de Montgareuil and
Domine (1964) have been discussed in detail by Yang (1987). Inspired by these inventions,
dreamers in industry began contemplating the possibility of separating air at ambient
temperature (as opposed to 77 K for cryogenic processes) by adsorption. 5A (CaA) and 13X
(NaX) zeolites were used (and are still being used in some instances) as the sorbents. The PSA
technology development encountered some challenges that were unexpected from small-
diameter laboratory column experiments, for example, the “cold spot” problem (large
temperature depression near the feed end, Collins, 1977; Yang, 1987) and the “creeping death”
of beds (due to accumulation and freezing of water). The history of the PSA technology
development may be reflected by the decline in the cost of O2 from PSA as shown in Figure
10.1. Prior to ca. 1980, PSA systems were used with both adsorption and desorption pressures
well above atmospheric. These systems were low in capital (due to simplicity) but high in power
consumption (since both N2 and O2 in the feed are compressed compared with vacuum swing
adsorption (VSA) where only the waste gas is evacuated). The availability of improved sorbents
and lower cost vacuum equipment led to the development of VSA, which is typically operated
with adsorption pressure slightly above atmospheric and desorption pressure of typically 0.2
atm. A further breakthrough occurred in 1989, with the invention of LiLSX zeolite (low silica X,
with Si/Al = 1) (Chao, 1989). The LiLSX is currently the best commercial sorbent for air
separation and will be discussed

in some detail in this chapter. With the advances made in both sorbents and PSA/VSA cycle
technology, PSA/VSA accounts for ∼20% of the oxygen and nitrogen, and the size of a single
PSA/VSA unit is approaching 250 tons/day oxygen, while these numbers continue to grow
steadily. The sorbent productivity (or bed inventory), often expressed as “bed-size factor”
(Leavitt, 1992), is well below 1000 lb of zeolite for per ton/day O2 product (Notaro et al., 1999).
The total power consumption is below 250 kWh per ton O2.