FM Global

Property Loss Prevention Data Sheets 7-35R

January 2012
Page 1 of 14

AIR SEPARATION PROCESSES

Table of Contents
Page

1.0 SCOPE ................................................................................................................................................... 2

1.1 Changes .......................................................................................................................................... 2
1.2 General ............................................................................................................................................ 2
2.0 CRYOGENIC PROCESSES ................................................................................................................... 3
2.1 General ............................................................................................................................................. 3
2.2 Process Description ......................................................................................................................... 3
2.3 The Cold Box ................................................................................................................................... 3
2.4 Argon Purification ............................................................................................................................ 4
2.5 Hydrocarbon Hazards ...................................................................................................................... 4
2.6 Regeneration Schedules ................................................................................................................. 7
2.7 Heat Exchanger Technology ............................................................................................................ 8
2.8 Other Hazards ................................................................................................................................. 9
2.8.1 Air Filters ............................................................................................................................... 9
2.8.2 Compressors and Drivers .................................................................................................... 10
2.8.3 Oxygen Piping ..................................................................................................................... 10
2.8.4 Cooling Towers .................................................................................................................... 10
2.8.5 Transformers ....................................................................................................................... 10
2.8.6 Refrigeration Systems ......................................................................................................... 10
2.8.7 Cryogenic Liquid Entrapment .............................................................................................. 11
3.0 NON-CRYOGENIC PROCESSES ........................................................................................................ 11
3.1 Adsorption Processes ..................................................................................................................... 11
3.1.1 Process Description ............................................................................................................. 11
3.2 Membrane Processes .................................................................................................................... 12
3.2.1 Process Description ............................................................................................................ 12
3.3 Hazards ......................................................................................................................................... 13

List of Figures
Fig. 1. Generic air separation plant flow diagram. Adsorbers labeled 1 through 4 may or may not appear
in a particular plant depending on design requirements. (Source: CGA P-8) ................................... 4
Fig. 2. Air separation plant (pre-1960 technology) ........................................................................................ 5
Fig. 3. Plate/fin heat exchanger ..................................................................................................................... 8
Fig. 4. Main condenser, thermosyphon design ............................................................................................ 9
Fig. 5. Main condenser, falling-film design. Shows feed by either direct flow from the low-pressure
column packing (left) or pumped recirculation from the LOX sump (right). ....................................... 9
Fig. 6. Pressure swing adsorption (PSA) ..................................................................................................... 11
Fig. 7. Vacuum swing adsorption (VSA or VSA/PSA) ................................................................................. 12
Fig. 8. Adsorption process skid ................................................................................................................... 13
Fig. 9. Membrane process skid .................................................................................................................... 14
Fig. 10. Membrane process schematic ........................................................................................................ 14

List of Tables
Table 1. Typical Air Composition .................................................................................................................... 2
Table 2. Adsorption of Air Contaminants ....................................................................................................... 6
Table 3. PSA—VSA Process Comparison ................................................................................................... 12

©2007 Factory Mutual Insurance Company. All rights reserved. No part of this document may be reproduced,
stored in a retrieval system, or transmitted, in whole or in part, in any form or by any means, electronic, mechanical,
photocopying, recording, or otherwise, without written permission of Factory Mutual Insurance Company.
7-35R AIR SEPARATION PROCESSES
Page 2 FM Global Property Loss Prevention Data Sheets

1.0 SCOPE
The purpose of this document is to present an overview of the three processes available for the recovery
of oxygen, nitrogen, argon, and rare gases from air (Table 1). The description of each process will highlight
major operating features as well as indicate areas where property loss exposures could exist.

Table 1. Typical Air Composition

Component Volume Percent
Nitrogen 78.1
Oxygen 20.9
Argon 0.9
Rare Gases1 0.002
Carbon Dioxide 0.03
Hydrocarbons 0.001-0.03
1
Neon, Helium, Krypton, Xenon

1.1 Changes
January 2012. Terminology related to ignitable liquids has been revised to provide increased clarity and
consistency with regard to FM Global’s loss prevention recommendations for ignitable liquid hazards.

1.2 General
The three commercial processes for separating oxygen, nitrogen, and other gases from air are a cryogenic
process, an adsorption process using molecular sieves, and a separation process using membrane
technology.
The cryogenic process has been used for over 80 years and is capable of recovering trace gases from
atmospheric air as well as oxygen and nitrogen. Product gases or cryogenic liquids can be of very high purity,
as much as 99.999% or better. This process is capital- and power-intensive and reportedly is economically
justified only in capacities over 50 T/D (tons/day) of oxygen. Many plants are capable of 500 to 1,000 T/D
and facilities handling up to 3,000 T/D have been built. These large plants usually supply nearby customers
with gas by pipeline, and more distant customers with bulk liquid in tank trucks .
In the last year reported, production of industrial gases in the United States totaled about 940 billion ft3 (27
billion m3) of nitrogen, 724 billion ft3 (21 billion m3) of oxygen and 24 billion ft3 (0.7 billion m3) of argon. (U.S.
Department of Commerce, Washington D.C., 2004. This data is no longer collected by the U.S. government.)
Adsorption processes have become commercially available only in relatively recent years. These processes
produce lower purity oxygen (typically 92% to 95%) and nitrogen (typically 95% to 99.9%). Only gaseous
products can be provided. Trace gases in air (argon and the rare gases) cannot be economically recovered
by this method. Adsorption processes are advantageous for small users, as systems can be as small as 5
SCFH (0.13 NM3/Hr) up to 40,000 SCFH (1070 NM3/Hr — 40 T/D) and larger (Note: SCFH is cubic feet/hour
at specified standard pressure/temperature conditions). One manufacturer’s 40-T/D, skid-mounted unit would
be about 8 × 15 × 12 ft high (2.4 × 4.6 × 3.7 m). Advantages include small to moderate capacity, lower capital
and operating costs, and relatively unsophisticated operations requirements.
The membrane process is similar to adsorption in cost and ease of operation but, in general, the plants are
smaller than adsorption plants. This technology also has only recently been commercialized. This process,
however, is only capable of producing nitrogen in the range of 95 to -99.9% purity.
The small units are beginning to replace customer systems based on liquid or gas storage filled by trucks.
Potential applications are diverse, such as heat treating in metal working, controlled atmospheres for food
storage, and semiconductor, circuit board, and chemical manufacturing.
It is estimated that approximately 2% to 5% of U.S. production of nitrogen and oxygen respectively, is provided
by non-cryogenic methods. (U.S. Dept. of Commerce, Washington, D.C., 2004.)
Any process producing high-purity oxygen, or even waste streams enriched in oxygen (above 21% normally
found in air), presents a hazard of accelerated combustion if the gas is involved in a fire.
In contrast, streams that are inert gases (nitrogen, argon, etc.) or are reduced in oxygen content present
potential personnel hazards due to inadequate oxygen for breathing.

©2007 Factory Mutual Insurance Company. All rights reserved.

AIR SEPARATION PROCESSES 7-35R
FM Global Property Loss Prevention Data Sheets Page 3

2.0 CRYOGENIC PROCESSES

2.1 General
The cryogenic process for the recovery of oxygen, nitrogen, argon, and rare gases from air has been in use
since the early 1900s. The process has been modified to improve the economics of the process and to reduce
the potential for accumulation of hydrocarbons that are in the air as contaminants. The quantity and
composition of the hydrocarbons varies depending on location, as they are affected by the presence of
refineries, chemical plants, steel mills, etc. In addition to hydrocarbons, other troublesome materials include
water, sulfur oxides, nitrogen oxides, and dust. Hydrocarbons of concern include methane, ethane, propane,
acetylene, ethylene, and propylene.

2.2 Process Description

The cryogenic process involves compressing and cooling the air, removing troublesome materials via
scrubbing, freezing, or adsorption and then distilling the liquefied air to separate the components. Distillation
process temperatures are around -320°F (-195°C). Products can be recovered as liquids or gases and they
can either be stored (usually as liquids for later delivery) or piped directly to customers (usually as gas).
Figure 1 shows the basic equipment and flow arrangement for a modern large-tonnage air separation plant
that uses pre-purification units (PPU) for front-end removal of contaminants, such as water, carbon dioxide
(CO2), and hydrocarbons. The air is compressed to a nominal 100 psig (700 kPa) pressure in the compressor;
the main exchanger pre-cools the air against intermediate and product streams; the expander provides the
process refrigeration; high-pressure and low-pressure columns separate the oxygen and nitrogen primary
components, and concentrate the argon and other rare gases. Argon or other gas processing is not shown.
Two types of distillation columns are used; either tray or packed bed. Neither method produces any unusual
property loss exposure.
Figure 1 also shows four possible locations of contaminant adsorbers for further removing contaminants.
Various plants will have different combinations of these adsorbers. Locations 1 and 2 are not common in large
oxygen plants, though they have been widely used in small-scale nitrogen generators with reversing heat
exchangers. Location 3 is often called the ‘‘guard adsorber’’ while location 4 can be called the ‘‘hydrocarbon
adsorber’’ or ‘‘rich liquid filter’’.
Older plants use reversing exchangers (REVEX) instead of PPU for front-end removal of contaminants.
REVEX plants are rarely built now, but some continue to operate.
Where REVEX technology is used, as the air is cooled in the main exchanger, moisture and CO2 are
condensed and solidified. If not removed, they will eventually plug the exchanger. On a regular schedule,
typically about every 15 minutes, the air passages and the waste nitrogen vent passages are switched so the
air flows through clean passages and begins to build up a deposit of moisture and CO2. At the same time,
the waste nitrogen revaporizes the deposited water and CO2, thereby cleaning the passageways in
preparation for the next switch.
Some plants are limited to nitrogen production only. The process is simplified in that the high-pressure column
is not needed, and the purity of oxygen in the low-pressure column sump, for the main condenser, is in the
50% to 90% oxygen range. This essentially eliminates the hazard of a large decomposition/explosion event
involving hydrocarbons.

2.3 The Cold Box

Due to the low temperatures used, the process equipment (main exchangers, high- and low-pressure
columns, and related adsorbers and exchangers) is enclosed in a structure called a cold box. It is usually
steel-frame and steel-panel construction with perlite or mineral wool filling the spaces between the equipment.
Typically, dimensions are 10 ft x 10 ft and 75 ft high (3.3 m x 3.3 m × 23 m high). It is usually purged with
dry nitrogen at 1 to 2 in Hg (3 to 7 kPa) to prevent condensation and freezing of water from the atmospheric
air.
Frost accumulation on the cold box is an indication of poor insulation or failure of equipment containing
cryogenic liquid. These leaks could cause structural failure (from extreme cold) or ignition or explosion if small
oil leaks or combustible residues are present in the oxygen-enriched atmosphere. Materials of construction
should be suitable for the expected temperatures.

©2007 Factory Mutual Insurance Company. All rights reserved.

7-35R AIR SEPARATION PROCESSES
Page 4 FM Global Property Loss Prevention Data Sheets

Fig. 1. Generic air separation plant flow diagram. Adsorbers labeled 1 through 4 may or may not appear in a particular
plant depending on design requirements. (Source: CGA P-8)

2.4 Argon Purification

Crude argon needs to be further processed to remove trace oxygen. Two primary processes are currently
used. The most recent technology employs further distillation stages contained in columns either within or
directly attached to the main cold box. Very pure argon product, down to below 1 ppm/v (parts per million by
volume) of single contaminants, can be produced in this way.
The more traditional process is to pass the crude argon, with added hydrogen gas, through a small (typically
about 6 in. diameter by 4 ft long [15 cm × 120 cm]) catalyst-filled reactor, where the trace oxygen is burned.
The resulting water vapor is removed from the argon in simple dryers. In other cases, the resulting
oxygen-free intermediate stream is re-cooled and distilled in a separate column to remove trace nitrogen
impurities. Some suppliers install the nitrogen stripper column in the main cold box.
The catalytic reactor could be located indoors. Because of the small hydrogen use rates (only a few cfm
[L/min]), and the high reactor temperature, special precautions for electrical equipment and construction
(where indoors) are rarely practical. Proper attention to location of the hydrogen supply, natural ventilation
at roof level, and proper arrangement of supply piping with an easily accessible shutoff valve are all needed.

2.5 Hydrocarbon Hazards

Historically, air separation processes without reliable front-end purification techniques have experienced
frequent explosions in the cold box. The explosions were caused by an accumulation of hydrocarbons in the
oxygen-rich liquid phase in the low-pressure distillation column. With new technology for front end purification
and close attention to monitoring hydrocarbon levels in various parts of the system, the frequency of these
events has been reduced but the hazard cannot be eliminated.
Hydrocarbon contaminants, although present in incoming air at levels as low as 10 ppm/v, can concentrate
in the liquid oxygen phase. Without steps to control hydrocarbon buildup, the hydrocarbon level in the main
condenser (low-pressure column reboiler) where product (LOX) is produced could easily reach 200 ppm/v or
more. When total hydrocarbon levels build up, acetylene may exceed its solubility limits and begin to
precipitate out.

©2007 Factory Mutual Insurance Company. All rights reserved.

AIR SEPARATION PROCESSES 7-35R
FM Global Property Loss Prevention Data Sheets Page 5

Acetylene has a solubility limit of 5 ppm, after which solid acetylene particles settle out, either floating on
the LOX surface or accumulating in the exchanger passages. Acetylene in LOX can readily detonate, although
the actual mode of initiation is not clearly established. Other hydrocarbons have solubility limits exceeding
1000 ppm/v so incidents attributed to these are simply due to the high oxidation rates of hydrocarbons in LOX.
Accumulations of propane and ethylene have also been responsible for explosions. Other hydrocarbons
commonly present are not easily ignited.
There are three significant periods in the development of front-end purification technology. The following
briefly discusses the main components of the processes, but other components also contribute to the overall
safety of the operation.
Prior to approximately 1960, incoming air typically went through processing as shown in Figure 2, sometimes
called the high-pressure or split-cycle process. Water and CO2 were effectively removed prior to entering
the distillation process but hydrocarbons were not. Silica gel adsorbers were used to remove hydrocarbons
from the cold, oxygen-rich liquid from the reboiler of the high-pressure distillation column. Caustic scrubbers
were used to remove acidic compounds such as H2S and carbon and nitrogen oxides.
About 1960, the next step in front-end purification technology, reversing exchangers (identified as ‘‘main
exchangers’’ in Fig. 1), were used to ‘‘freeze out’’ the impurities, mostly water and CO2 and small amounts
of heavier hydrocarbons, prior to entering the distillation process. Silica gel adsorbers were also needed
as in the older process.
Approximately 1975, packed bed vessels with molecular sieves (PPU) were introduced for front end
purification. These were effective not only with water and CO2, but also removed much (though not all) of
the hydrocarbons. This eliminated the silica gel adsorbers on the oxygen-rich liquid in most cases. The
process air continued through exchangers for the liquefaction process, but reversing to vaporize the frozen
solids was no longer needed since the water and CO2 were already removed.

Fig. 2. Air separation plant (pre-1960 technology)

Some designs include silica gel hydrocarbon adsorbers for either the rich liquid from the high-pressure column
or the LOX from the main condenser. Either will reduce the likelihood of a damaging incident, but there is
no industry agreement that they are required for safe operation. Plants producing liquid product usually do
not have these adsorbers because the high liquid removal rate removes the hydrocarbons also.

©2007 Factory Mutual Insurance Company. All rights reserved.

7-35R AIR SEPARATION PROCESSES
Page 6 FM Global Property Loss Prevention Data Sheets

Table 2 shows typical adsorption materials, their service use, and how successfully they remove typical air
contaminants.

Table 2. Adsorption of Air Contaminants

No Adsorption Partial Adsorption1 Total Adsorption
Alumina Methane Carbon Dioxide2 Ozone3
Pre-purification unit Ethylene Nitrous oxide Oxides of Nitrogen
Ethane Acetylene Moisture
Propylene
Propane
Nitric oxide
n-butane
Molecular Sieve Methane Ethylene Carbon Dioxide
Pre-purification unit Ethane Propane Acetylene
Nitric oxide4 Nitrous oxide Propylene
Ozone3
Oxides of Nitrogen
n-butane
Moisture
Oxygenates
Chlorinated hydrocarbons
Silica Gel Methane Carbon Dioxide Acetylene
Rich liquid adsorbers Ethane Ethylene Ozone
Vapor phase adsorbers Propylene Dienes
LOX adsorbers Propane
Nitrous oxide
Source: CGA P-8.4
Assumptions: Contaminant at less than 10 ppm/v; CO2 at 400 ppm/v
Total adsorption of heavy hydrocarbons (C4+)
1
Degree of removal is dependent on design and operating parameters. Total removal may be possible with adequate design.
2
Molecular sieve is normally designed to removed CO2
3
By decomposition
4
Nitric oxide is oxidized by air to Nitrous Oxide and subsequently trapped.

Pre-purification units usually involve a combination of alumina and molecular sieve materials to achieve
effective removal of individual contaminants. As can be seen from the table, PPUs typically can remove 100%
of water, oxides of nitrogen, ozone, acetylene, propylene, and C4+ components. They can effectively remove
greater than 99% of CO2. They are ineffective for removal of methane and ethane but due to their high
solubility in LOX, they don’t present the level of hazard in the main condenser that other hydrocarbons do.
To control the contamination level, it is best practice to monitor PPU performance by tracking CO2 levels at the
PPU outlet with a continuous analyzer. Levels of 1 ppm/v CO2 are typically recognized as an alarm/
unacceptable level. A continuous slip of CO2 at levels as low as 0.2 to 0.5 ppm/v is also a danger sign as
contaminants such as acetylene, moisture and hydrocarbons would also be bypassing the adsorber beds and
corrective actions need to be taken.
Many hydrocarbons that are partially removed will break through before CO2. However, experience has shown
that trace contaminants are removed to safe levels if the PPU is operated to the CO2 breakthrough point.
Another step taken to control hydrocarbon accumulation, implemented in the 1960s, was continuous
monitoring of total hydrocarbon content of the liquid oxygen in the main condenser. Levels of 150 to 200 ppm/v
(reported as methane equivalent) were typical safe limits. Regular sampling (once per shift) of the reboiler
liquid and testing for acetylene was also needed.
In plants with no liquid product, a constant LOX bleed, amounting to at least 0.1% to 0.2% of the incoming
airflow rate (0.5% to 1% of oxygen production rate), is drawn from the low-pressure column to reduce
hydrocarbon accumulations. This withdrawal rate is a small factor in preventing hydrocarbon accumulation,
along with other processes and procedures. Plants with liquid product are less likely to have hydrocarbon
accumulations, which are removed with the LOX product outflow.

©2007 Factory Mutual Insurance Company. All rights reserved.

AIR SEPARATION PROCESSES 7-35R
FM Global Property Loss Prevention Data Sheets Page 7

Excessive acetylene or total hydrocarbon levels would cause the plant operators to draw off more of the
oxygen-rich liquid to waste to reduce the accumulation. If this was unsuccessful, plant shutdown would be
initiated.
Incoming process air could be continuously monitored for total hydrocarbons where normal amounts in the
air were high, for example, in or near a refinery or oil producing area. Since even high levels of hydrocarbons
are only a few ppm, monitoring of incoming air may not be practical except in extreme cases.
The design of air separation plants to limit hydrocarbon accumulations in the cold box extends beyond the
front-end purification processes. Prior to construction of a plant, air samples are taken at the proposed
location, the hydrocarbon content is analyzed, and the plant’s hydrocarbon removal system is tailored to
the air’s content and weather conditions likely in the area.
In addition, the following design criteria are applied to the equipment:
a) The distillation column liquid sumps are designed and constructed to eliminate crevices in the materials
of construction.
b) Ledges or shelves within the distillation column sumps where hydrocarbon crystals could accumulate
are eliminated by design.
No method is capable of completely eliminating the unwanted materials, especially if the incoming stream
should exceed the design limits. Hydrocarbon accumulation is still possible and the potential consequences
of an event remain the same. Unwanted materials build up slowly, however, so operators have time to take
corrective action.
The existing filtration and contaminant removal technology is not capable of completely controlling smoke
and carbonaceous aerosol (very small particle size) materials. These contaminants may not show up in normal
analysis devices. Under these conditions, it may be appropriate to shut down the plant.
Explosion hazards will continue to exist at cryogenic air separation plants due to the nature of the operation.
However, the probability of an explosion can be significantly reduced to acceptable levels by the installation
of proper purification equipment, as detailed above, and by the implementation of proper safety control
procedures.

2.6 Regeneration Schedules

Reversing exchangers will switch as often as every two or three minutes, but more commonly every
15 minutes. Timing is strictly based on design capacity to accept plugging of the passages by frozen CO2
or water. It is set in the early design stages and controlled by the process computer.
Molecular sieve beds (PPU) need regular regeneration to remove accumulated contaminants. Regeneration
is usually accomplished by heating waste nitrogen in a fuel-fired, steam or electrically heated auxiliary heater.
There are usually two parallel beds: one on line, one regenerating. Regeneration frequency is set in the
design phase and can range from every 15 minutes to every 12 hours and is initiated by the process control
system, or manually. CO2 levels are monitored downstream of the molecular sieves. This is the first
contaminant to break through and is an auxiliary indication of a need for regeneration.
This regeneration method may be referred to as temperature swing adsorption (TSA). Pressure swing
adsorption (PSA) regeneration methods at ambient temperatures can also be employed, but mostly at plants
smaller than 200 TPD of oxygen. This should not be confused with the PSA nitrogen production process
discussed in section 3.0.
Silica gel filters in the rich liquid or LOX circuit need regeneration based on monitoring of total hydrocarbons.
Typically, the regeneration frequency is anywhere from 1 week to 1 month. Regeneration frequency could
be shorter due to units designed for a smaller hydrocarbon capacity but with two units in parallel. Such a
system would have one off line (regenerating) and one on line. Where there are single units, taking the unit
offline for regeneration does not present an undue hazard due to the long time for hydrocarbon buildup.
Deriming is the process of completely warming up the entire plant. The main purpose is to remove
contaminants that may be present throughout the plant in exchangers and columns. Frequency is determined
by the loss of efficiency in the exchangers or other indicators. In the past, use of oil-lubricated reciprocating
main air compressors required an annual deriming. Centrifugal main air compressors are now commonly
used that introduce no lubricant into the process gas and their design permits a more positive separation of

©2007 Factory Mutual Insurance Company. All rights reserved.

7-35R AIR SEPARATION PROCESSES
Page 8 FM Global Property Loss Prevention Data Sheets

oil-lubricated bearings from the process gas stream. Units with reversing exchangers can go 2 to 3 years
between deriming while PPU-based plants can go somewhat longer.

2.7 Heat Exchanger Technology

Since heat exchange with small temperature differences between exchanged streams is so critical to process
economics, the heat exchangers are a major component of the process. In the distant past, standard shell
and tube exchangers were the primary vehicle. Newer technology uses plate/fin units.
These units (Fig. 3) have corrugated flow passages separated by thin metal sheets. Each block may have
two or more separate process streams being exchanged, and several blocks may make up one exchanger.
There are many variations of the basic features to provide specific efficiency improvements.

(Courtesy of ALTEC International, Inc.)

Fig. 3. Plate/fin heat exchanger

Compared to most shell and tube exchangers, the fluid flow passages are much smaller, with the result that
they can be more readily blocked, for example by ice accumulation (CO2 or water) with resulting dead ends.
These dead ends provide ideal points where hazardous amounts of hydrocarbons can accumulate and
precipitate out even though overall accumulations remain well above dangerous levels. The plugged passage
could also lead to boiling without replenishment and eventual dry spots. The main preventive measure is
control of accumulation amounts and removal of CO2 and water early in the process. Other design features
of the exchanger can limit the effects of dead-end boiling.
Heat exchanger design in the main condenser (reboiler/condenser) located in the liquid sump of the low-
pressure distillation column is of basically two types: thermosyphon or flooded (Fig. 4), and falling film or down
flow (Fig. 5). Most plants use thermosyphon technology where circulation is maintained by temperature
differentials within the exchanger. The LOX boils and vaporizes so it rises through the exchanger. It is
important to keep the LOX levels in the low-pressure column high enough to maintain submergence of the
exchanger. Low levels could create dry spots and potentially increased and hazardous hydrocarbon levels in
the LOX.
Newer technology is the falling-film type, where both condensing and boiling occurs in falling films on the
walls of the exchanger passes. The exchanger could be external to the low-pressure column sump, so LOX
distribution is important to maintain exchanger efficiency and continuous film on the exchanger walls.

©2007 Factory Mutual Insurance Company. All rights reserved.

AIR SEPARATION PROCESSES 7-35R
FM Global Property Loss Prevention Data Sheets Page 9

Fig. 4. Main condenser, thermosyphon design

Fig. 5. Main condenser, falling-film design. Shows feed by either direct flow from the low-pressure column packing (left)
or pumped recirculation from the LOX sump (right).

Liquid-level control is not as important. It is possible that this technology could present reduced potential
for hydrocarbon accumulation hazard in the exchanger, although the two major ASU explosions in 1997
involved each style main condensers.

2.8 Other Hazards

2.8.1 Air Filters

In the past, oil bath filters were used before the main air compressor to remove dust, particulates, etc. That
design presents some possibility of fire exposure and has not been used in many years. Most pre-filters
are large fiberglass filters similar to a home heater air filter and present no significant fire protection exposure.

©2007 Factory Mutual Insurance Company. All rights reserved.

7-35R AIR SEPARATION PROCESSES
Page 10 FM Global Property Loss Prevention Data Sheets

2.8.2 Compressors and Drivers

Large compressors are used in this process. Drivers are nearly always electric motors and some are of the
synchronous type. These will typically include the main air compressor, and oxygen and nitrogen compressors
for pipeline delivery. Both centrifugal and reciprocating machines are used. Basic design and operational
safeguards are addressed in Data Sheets 7-95, Compressors, 5-13, Synchronous Motors, and 5-17, Large
Electric Motors.
A recent study showed that oxygen compressors were responsible for only two fires at air separation plants.
Even though centrifugal machines with large external lubrication system are present, the oil is almost never
involved in the incident, probably due to the lack of hot surfaces or other ignition sources. Past study periods
had indicated a higher frequency of fire. Most likely, improved design and maintenance are responsible for the
reduction.
Oxygen compressor fires are almost always initiated by metal-to-metal friction that results in ignition of the
metal in the oxygen atmosphere. Once the oxygen supply is shut off, the fire self-extinguishes. A good
preventive maintenance program and complete operational interlocks are the keys to reducing the hazard.
Separation from other equipment by distance or noncombustible barriers is the best way to keep the damage
localized.
Nitrogen compressors present a unique problem. Fires have occurred in oil-lubricated reciprocating
compressors pumping high purity nitrogen when the oxygen content has suddenly increased due to plant
upset conditions. Ignition can occur in centrifugal compressors pumping nitrogen as a result of interference
of rotating parts and in reciprocating compressors through ring or valve failure, but only in the presence of
sufficient oxygen. Fuel for the reaction can be lubricating oil or accumulated organic material that has normally
been exposed only to an inert atmosphere. Control of oxygen in the nitrogen stream provides the necessary
protection to reduce the risk of an ignition due to increasing oxygen content.

2.8.3 Oxygen Piping

High-velocity flow of oxygen gas in a pipeline is a recognized source of ignition energy. Any dirt, metal scale,
or other particle traveling with the high-velocity flow represents an energy source (impact) capable of starting
a reaction.
When oxygen is transported in steel pipelines, its velocity is typically limited to 200 ft/s (60 m/s). Normally,
pipeline velocities are kept considerably lower to limit pressure drop and power consumption.
At valves, orifices, or where the velocity can exceed 200 ft/s (60 m/s), copper, brass, or nickel alloys should
be used. Monel tees or impact plates should be used at points of abrupt change in flow direction.
In general, oxygen gas pipelines should be kept free of contaminants and all valves in the system should
be operated slowly to avoid sudden changes in flow and pressure.

2.8.4 Cooling Towers

Cooling towers supplying water mainly for the compressors are important to facility operation. The cooling
towers are often of combustible construction. Use of noncombustible designs would minimize the potential for
interruption of cooling water supply. Sprinklers may be needed in towers of combustible construction. (See
Data Sheet 1-6, Cooling Towers.)

2.8.5 Transformers
Transformers are needed for providing reliable supplies of the large amounts of electric power needed. These
are usually located so as not to present an exposure to, or be exposed by, the process or storage tanks.
Loss experience in this service is good. (See Data Sheet 5-4, Transformers.)

2.8.6 Refrigeration Systems

Most process cooling is provided by the process itself. Some designs require an auxiliary method of cooling
the air in the initial stages of the process. In the past, these refrigeration systems were Freon-based (CFC-
chlorofluorocarbons).

©2007 Factory Mutual Insurance Company. All rights reserved.

AIR SEPARATION PROCESSES 7-35R
FM Global Property Loss Prevention Data Sheets Page 11

Some new systems will have hydrochlorofluorocarbons (HCFC) and a few may have ammonia. Again, loss
experience is favorable, although use of ammonia would introduce new hazards. (See Data Sheet 7-13,
Mechanical Refrigeration.)

2.8.7 Cryogenic Liquid Entrapment

A hazard exists in a process system whenever cryogenic liquid can be trapped between closed valves. As
the liquid vaporizes through normal heat leaks, the pressure generated may cause the trapped section of
piping or equipment to fail. Pressure relief valves, not designed to handle full process flows, are provided
in these sections of the system to relieve the pressure generated by trapped liquid.

3.0 NON-CRYOGENIC PROCESSES

3.1 Adsorption Processes

3.1.1 Process Description

These processes are based on the fact that molecular sieves (a different type from that in the cryogenic
process) can be designed to adsorb and desorb a selected component from a gas stream.
The basic process involves sending compressed air through one of two parallel molecular sieve beds. The
unwanted component is adsorbed on the molecular sieve, leaving the other component as a product gas
stream. After the adsorption cycle, the operating beds are switched. The first bed is desorbed of the unwanted
component (regenerated) while the second bed goes into the adsorption cycle.
This bed switching can take place as often as every minute. In this technology, regeneration/desorption is
caused by a pressure reduction. There are two adsorption-based processes called pressure swing adsorption
(PSA) and vacuum swing adsorption (VSA, sometimes also called VSA/PSA). Figures 6 and 7 show
simplified schematics of each process, while Figure 8 shows a typical equipment configuration. A brief
comparison of the two processes is shown in Table 3.

Fig. 6. Pressure swing adsorption (PSA)

©2007 Factory Mutual Insurance Company. All rights reserved.

7-35R AIR SEPARATION PROCESSES
Page 12 FM Global Property Loss Prevention Data Sheets

Fig. 7. Vacuum swing adsorption (VSA or VSA/PSA)

Table 3. PSA—VSA Process Comparison

PSA VSA
Product Nitrogen Oxygen
Purity range 95% to 99.9% 92% to 95%
Molecular sieve type Carbon Zeolite
Operating pressure, psig, (bar) 70–120 (4.8–8.3) 2–3 (0.1–0.2)
Regeneration Drop pressure Pull vacuum or drop pressure

3.2 Membrane Processes

3.2.1 Process Description

Membrane processes are only capable of providing nitrogen from ambient air. Already widely accepted for
liquid separation (water desalination), semi-permeable membranes are just beginning to expand into the gas
separation area. The semi-permeable membranes involved are in the form of fine hollow tubes about the
thickness of a human hair. Thousands of membrane fibers are bundled together in a module. Compressed
air is forced down the length of the fibers and the unwanted components (oxygen, CO2 and water) selectively
diffused through the fiber walls of the permeable, polymer-coated membrane and are vented as waste. The
remaining nitrogen-rich stream concentrates inside each fiber and is collected as product at the end of the
vessel. Figure 9 shows equipment on a typical membrane process skid, while Figure 10 shows a simplified
schematic of the process.
Membranes provide nitrogen of 95% to 99.9% purity. Higher purity (99.999%) can be achieved by a catalytic
de-oxygenation unit. Using catalyst, the de- oxygenation unit combines trace oxygen in the nitrogen stream
with hydrogen to form water.

©2007 Factory Mutual Insurance Company. All rights reserved.

AIR SEPARATION PROCESSES 7-35R
FM Global Property Loss Prevention Data Sheets Page 13

(Courtesy of Permea, Inc.)

Fig. 8. Adsorption process skid

3.3 Hazards
Since these are package units, often with small capacities, the potential for fire or explosion is negligible.
Where nitrogen is the product, the possibility of excessive residual oxygen presents some concern where the
gas is being used for inerting or purging. The solution is proper attention to required maintenance and the
product quality instrumentation that comes with the unit.
Where oxygen is the product, the concern is related to the strong oxidizing characteristics of high-purity
oxygen in the distribution piping. These hazards are addressed in Data Sheets 7-50, Compresses Gases
in Cylinders, and 7-52, Oxygen.
The hazard of hydrocarbon accumulation associated with cryogenic processes and liquid oxygen does not
exist in membrane processes. There is no liquefaction of the oxygen, and these processes do not increase
the concentration of any trace hydrocarbons in the incoming air.

APPENDIX A GLOSSARY OF TERMS

Ignitable Liquid: Any liquid or liquid mixture that is capable of fueling a fire, including flammable liquids,
combustible liquids, inflammable liquids, or any other reference to a liquid that will burn. An ignitable liquid
must have a fire point.

APPENDIX B DOCUMENT REVISION HISTORY

October 2011. Terminology related to ignitable liquids has been revised to provide increased clarity and
consistency with regard to FM Global’s loss prevention recommendations for ignitable liquid hazards.

©2007 Factory Mutual Insurance Company. All rights reserved.

7-35R AIR SEPARATION PROCESSES
Page 14 FM Global Property Loss Prevention Data Sheets

(Courtesy of Permea, Inc.)

Fig. 9. Membrane process skid

Fig. 10. Membrane process schematic

©2007 Factory Mutual Insurance Company. All rights reserved.