Presented at ECOS 2000

Gasification of Coal, Biomass and Oil

EUROTHERM Seminar No 65
University of Twente
Enschede, The Netherlands, July 5-7, 2000

Air Separation Units, Design and Future Development

R. J. Allam, H. Castle-Smith
Air Products PLC
Hersham Place, Surrey KT12 4RZ
Great Britain
(1932) 249200

A. R. Smith, J. C. Sorensen and V. E. Stein

Air Products and Chemicals, Inc.
7201 Hamilton Boulevard
Allentown, PA 18195-1501
U.S.A
(610) 481-4911

Abstract
Air separation units (ASUs) have successfully been applied to support gasification projects
worldwide. ASU technology has ranged from traditional, low pressure, standalone facilities
supplying products only to the gasification island, to highly integrated, elevated pressure facilities
that obtain air feed from and inject excess nitrogen into a gas turbine. The near-term direction of
ASUs is increased single unit capacity, process optimizations that will benefit integration with the
new generation of higher pressure ratio and increased capacity gas turbines, and overall ASU
facility optimization for the specialized requirements of shipboard units for remote gas
conversion processes. Longer-term development is proceeding on ion transport membrane
technology to support cost improvements for highly efficient production of oxygen, power, and
steam.

ASU Design Options

The Basic Process

Cryogenic air separation processes (Figure 1) are selected based on an optimization of the capital
cost and power consumption required to meet customer production specifications. Compressed
air is cooled and cleaned prior to cryogenic heat exchange and distillation into oxygen, nitrogen,
and optionally, argon rich streams. Pressurizing these streams for delivery is accomplished by
gas compression, liquid pumping or combinations of pumping followed by compression. Product
storage can be provided as backup or for “peaking” duty, supplying higher than design rates of
product delivery for short periods of time.

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 Air Boost Product Compressed
Compression Compression Compression Products

Cryogenic
Cooling and Pumped
Heat Exchange Products
Pretreatment
and Distillation

Product
Product
Storage
Storage

Figure 1 - Cryogenic Air Separation Process Options

Process Alternatives
Numerous options for the configuration of heat exchange, distillation, pumping and compression
equipment are possible. These process alternatives are driven by the purity and number of
product and byproduct streams to be produced, by tradeoffs between capital and power
consumption, and by the degree of integration between the ASU and other facility units.
Characterizing the types of cryogenic ASU processes, hereinafter referred to as cycles, can be
based on the method of pressurizing the product stream(s) or on the air feed pressure to the ASU.

Compression Cycles
Traditional cycles are based on removing gaseous products from the distillation section, warming
and then compressing the gaseous streams to delivery pressure. Many hundreds of the these
plants have been built worldwide. Oxygen typically leaves the main heat exchangers at fairly low
pressure, resulting in compressors with high inlet volumetric flows and sometimes requiring two
or more compressor casings or bodies to delivery the product at the required pressure.

Pumped Liquid Cycles

Liquid products may be removed from the distillation section and pumped prior to entering the
cryogenic heat exchangers for vaporization and warming. Products may be pumped to their
delivery pressure or pumped to an intermediate pressure and compressed to their final delivery
pressure. Producing a liquid product from the distillation system requires three to five times the
power of producing a gaseous product. Therefore, the refrigeration contained in a pumped
product stream must be efficiently recovered. This is accomplished by condensing an air or
nitrogen feed stream at high pressure against the vaporizing product stream in the cryogenic heat
exchangers. The liquefied air or nitrogen feed returns the refrigeration to the distillation section.
Full or partial pumping of product streams adds another degree of freedom in optimizing
cryogenic cycles, and can eliminate or reduce the size of oxygen compression equipment.

Low and Elevated Pressure Cycles

Low pressure (LP) ASU cycles are based on compressing the feed air only to the pressure
required to reject the majority of the nitrogen byproduct at atmospheric pressure. Feed air
pressures will vary between 3.5 to 6 barg depending on the oxygen purity and the level of energy
efficiency desired. Elevated pressure (EP) ASU cycles produce all product and byproduct
streams at pressures well above atmospheric pressures. An EP cycle is chosen when all or nearly
all of the nitrogen byproduct will be compressed as a product stream. The air pressure of an EP
cycle is optimized based on the tradeoffs between increased air compression power versus

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decreased product compression power. Or, the pressure may be set by air extracted from a gas
turbine and supplied to the ASU.

Compressor Drivers
ASU compression equipment may be driven by electric motors, steam or gas turbines. Steam or
gas turbine drivers will more often be examined for remotely located projects than for projects in
industrial locations with robust electrical distribution systems. The low capital cost of electric
motors is the primary reason for their domination of the ASU market. Both steam and gas turbine
drivers will have significantly higher installed costs, and may have lower availability.

Integration Opportunities
Additional optimization opportunities arise when the integration of gas turbines and ASUs is
investigated. Projects requiring gas turbines and ASUs include integrated gasification combined
cycle (IGCC), partial oxidation routes to alternate fuels and chemicals, and remotely located
facilities where electricity from the grid is not available or costly to procure. Figure 2 depicts
some of the major options for the integration of these units, including: (a) full or partial air
supply to the ASU, (b) pressurized nitrogen supply to the gas turbine as a combustion diluent,
turbine coolant, and for power augmentation, (c) low pressure nitrogen for gas turbine inlet
cooling, or heated for HRSG steam production, and (d) chilled water for gas turbine inlet cooling,
or heated for HRSG feedwater.

GTCC

Air
Extraction
Nitrogen HEAT
Water/N2 Injection RECOVERY

ASU
O2, N2

Figure 2 - Gas Turbine/ASU Integration Opportunities

Air Integration
Air extracted from a gas turbine’s air compressor can be used to partially or fully supply the
requirements of an ASU. Air pressure to the ASU distillation section may or may not be
determined by the pressure of the extracted air from the gas turbine. In a simple configuration,
the ASU distillation feed pressure will be set by the extraction air pressure. If the extracted air
flow is less than the total ASU requirement, a supplemental air compressor will be used and the
discharge pressure will match the pressure of the extracted air. If the extracted air supply is about
a quarter of the total ASU requirement, ASU distillation pressure can be independently
established and a pumped liquid process can be applied. High-pressure extraction air is used to
boil pressurized liquid oxygen and/or nitrogen in the cryogenic heat exchange area. The
supplemental compressed air supply sets the distillation feed pressure to the ASU. Operation at a
pressure independent of the extraction air feed supply can also be achieved by expanding all or a
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portion of the extracted feed and usefully employing the work obtained from the expansion
process. Integrated operation, wherein the ASU’s distillation feed pressure varies with the air
supply pressure from the gas turbine, requires careful attention to the gas turbine’s operating
characteristics during project design. Air, oxygen and nitrogen supply pressures versus turbine
turndown, and variation in ambient conditions, have a major impact on the design of the ASU.

Pressurized Hot Nitrogen

Byproduct nitrogen from the ASU can be compressed and increased in temperature by heat
exchange with extracted air from a gas turbine. Hot nitrogen can also be generated by adiabatic
compression. A primary use for this nitrogen, and one that has been demonstrated commercially,
is to inject it into the gas turbine’s combustor. Nitrogen can be mixed with fuel gas or injected
separately into the combustor. Benefits include NOx reduction and increased power output from
the turbine. An alternative is to use nitrogen as the coolant fluid in a turbine. The nitrogen is an
extremely clean fluid, quite suitable for this duty. A third option would be to introduce
pressurized, but uncompressed nitrogen at a mid-point location in the turbine. This option would
require a specially designed turbine. The benefits of pressurized nitrogen injection options are:
(a) efficient recovery of lower level heat, e.g., from an extracted air supply or from ASU heats of
compression, (b) recovery of the energy contained in the pressurized nitrogen, (c) improved
operation of the gas turbine by reducing NOx formation, and (d) efficient increase in the power
output from the turbine.

Low Pressure Nitrogen

Low pressure nitrogen is routinely used in ASUs to generate chilled water to cool the compressed
air feed stream. Cooling or other near-ambient temperature water enters the top of a
humidification tower and contacts nitrogen flowing upward. As the dry nitrogen is humidified by
contact with water, the water is chilled. The nitrogen exiting the top of the column is saturated
with water and is colder than ambient air. Slightly pressurized nitrogen and chilled water can be
produced from these systems and fed to the air inlet of a gas turbine to reduce the bulk air
temperature and hence increase the mass flow through a gas turbine’s compressor. Cold nitrogen
for gas turbine air cooling can also be produced by expanding pressurized nitrogen. The
temperature of the expanded nitrogen can be controlled by adjusting the inlet pressure and/or
temperature to the expander.

Low-pressure nitrogen can also be used to absorb heat from extracted air, compression heat from
the ASU, or other sources and can be admitted to a heat recovery device, such as a heat recovery
steam generator (HRSG), to increase steam output. The diluting effect of the nitrogen will also
reduce the acid gas dewpoint of the stack gas, and permit deeper heat recovery at the cold end.

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ASU Train Size
A key to the continued reduction in the cost of producing oxygen is to capture the economies of
scale of large single train equipment. Figure 3 demonstrates Air Products’ stepouts in single train
ASU size which have been driven by the needs of the gasification marketplace, culminating in the
world’s largest ASU at Rozenburg, The Netherlands. Of particular note is the 75% increase in
train size between 1996 and 1997. Increased single train size to 5,000 tonne per day is expected
to continue to contribute to reductions in the cost of producing oxygen (Figure 4).
sTPD OXYGEN
ROZENBURG
ROZENBURG
3500 STANDALONE
STANDALONE
3000
BUGGENUM POLK
POLK
2500 AIR/N2 INTEG. N2
N2 INTEG.
INTEG.
PLAQUEMINE
PLAQUEMINE
2000 STANDALONE
STANDALONE

1500
1000
500
0
1987 1993 1996 1997
STARTUP DATE

Figure 3 - ASU Single Train Size History

ASUs have traditionally used multi-stage integral gear or in-line centrifugal compressors for
compressing air. As oxygen production requirements rise above 3,000 tonne per day the air flow
rate may dictate the use of an axial-radial compressor design. The axial inlet stage is needed to
handle large inlet flows, while the radial stages provide the higher discharge pressures required
for air separation. Single machines to produce over 5,000 tonne per day oxygen appear feasible.
Product compression can be performed using centrifugal compressor designs. Frame sizes exist
to support 5,000 tonne per day of oxygen and the equivalent amount of nitrogen. Material
selection and oxygen compressor design philosophy will have to be applied to these larger units,
but this is consistent with past methods used to introduce larger equipment to the market. Air
pretreatment and distillation vessel sizes for single train designs are limited by shop
manufacturing capability and shipping limits. These limits can change between project locations.
Some of the issues that can lead to the decision to use multiple units in place of a single large unit
include: (a) driver size and motor starting voltage drop limits for large compressors, (b) loss of
pricing economies of scale and long delivery times for large pipe and valves, (c) lower shop labor
cost and less risk versus field construction, and (d) shipping cost and size limits to a specific site.

ASU Technology For Gasification Markets

IGCC Power Production

Air Products has successfully implemented a variety of integration schemes between the gas
turbine and ASU, as summarized in Figure 5. Standalone, nitrogen-only integration, and air and
nitrogen integrated applications are in commercial operation. A key to economic IGCC facility
design is the site and project specific optimization of the power block and ASU equipment. In
general, the gas turbine selection will dictate the potential for integration between these units.

5

Main Air Compressor
• < 3,000 t/d: Integral Gear
6
or In-Line
• > 3,000 t/d: Axial-Radial
• > 5,000 t/d feasible
Main Air Compressor
• Two Integral Gear unit price
• Driver size limits
• Motor starting voltage drop
• Spare parts/maintenance
costs
• Turndown with two units
Figure 4 - Large Single Train Air Separation Units Are Practical
Size Considerations
Air Pretreatment Cryogenic Separation Product Compression
• Shop fabricated vessels • Main heat exchangers and • Integral gear > 2,500 t/d
• Shop or field fabricated pipe sub- coolers are modular • In-line units > 5,000 t/d
and valve skids • Shop or field erected
• 2, 3, 4 or more beds columns
• 4,500+ t/d single train
Economic and Site Specific Considerations
Air Pretreatment Cryogenic Separation Product Compression
• Single unit pipe/valve size • Shop versus field labor cost • Driver size limits
and cost and labor availability/quality • Motor starting voltage drop
• Shop versus field labor cost • Shipping constraints • Turndown with two units
• Shipping constraints • Single unit pipe/valve size
and cost
 Standalone, No Integration Nitrogen Integration Air + Nitrogen Integration
Rozenburg, The Netherlands Polk County, FL, USA Demkolec, The Netherlands

GAS TURBINE GAS TURBINE GAS TURBINE

SYNGAS SYNGAS SYNGAS

7

NITROGEN NITROGEN
NITROGEN
TO VENT

AIR OXYGEN/ AIR OXYGEN/ AIR OXYGEN/

AIR NITROGEN AIR NITROGEN NITROGEN
COMPRESSOR COMPRESSOR
ASU GASIFIER ASU GASIFIER ASU GASIFIER

• 3,175 t/d, 99.5% Oxygen, 76 barg • 1,840 t/d, 95% Oxygen, 40 barg • 1,780 t/d, 95% Oxygen, 33 barg
• Single Train • Single Train • Single Train
• Backup Systems: Gas + Liquid • Backup Systems: None • Backup Systems: Gas + Liquid

Figure 5 - Gas Turbine/ASU Integration Examples

Site conditions, however, will also impact the optimum degree of integration. As an example, the
hot and humid conditions at the Polk County IGCC facility resulted in designing the ASU to
inject all the byproduct nitrogen into the gas turbine with no air extraction. The nitrogen from the
ASU provided added diluent to the combustor and allowed more power to be produced by
compensating for the reduced air flow through the gas turbine’s air compressor. In cooler
locations, the amount of required nitrogen diluent would be different, or air extraction from the
gas turbine to the ASU might be employed to optimize the overall system operation.

Future improvements are foreseen through optimization of newer generation gas turbines with the
ASU. Turbines using “G” and “H” technology, sequential combustion turbine designs, advanced
turbine programs and advanced cycle designs such as HAT and CHAT all operate at pressure
ratios that are considerably higher than “F” and similar technology turbines. Gas turbines with
pressure ratios of about 15:1 provide extracted air at nearly optimum pressure for direct use in the
ASU. Mixing extracted air at pressure with separately compressed make-up air permits the ASU
to operate over a range of extracted air flow rates as described in the previous section. With gas
turbine pressure ratios of 23:1 and higher, operation of the ASU’s distillation system at full
extracted air pressure may not be optimum. As the distillation pressure increases, the relative
volatilities between the components of air decrease, thus making the separation process more
difficult. As operating pressure increases, an increasing amount of recycled nitrogen may be
required to produce oxygen and nitrogen streams at reasonable recoveries and at their required
purities.

One approach for using high pressure extracted air is to operate a pumped cycle as described in
the previous section on cryogenic air separation. The high pressure extracted air is heat
exchanged against a pumped liquid oxygen product stream whose pressure is chosen to
thermodynamically balance the flow and pressure of the extracted air. In general, about 30% of
the air feed supplied at high pressure meets the needs of a pumped cycle. The condensed liquid
air is expanded to match the optimum column pressures. The ASU’s main air compressor is sized
to provide the rest of the air requirement at high pressure column conditions. Variation in
extracted air flow and pressure is accommodated by changing the pressure of the pumped oxygen
stream. A small compressor is used to boost the oxygen to the required delivery pressure.
Operated in this manner, the integrated ASU facility achieves operating benefits based on “G or
H” turbine integration.

Gas Conversion
Gas conversion is generically defined as creating transportable products from natural gas. The
chemical route of interest to ASU suppliers is the reforming of natural gas with oxygen to
produce a synthesis gas composed primarily of carbon monoxide and hydrogen. Synthesis gas
can be converted via liquid or vapor phase Fischer-Tropsch reactions and downstream processing
into a variety of transportable end products, including waxes, synthetic crude oil, and middle
distillates (naphtha/kerosene/gas oil). Methanol and dimethyl ether are alternative synthesis
products. Optimum ASU technology varies with the type and location of the conversion process.

The concept of using Floating Production Storage and Offloading (FPSO) approaches for off-
shore gas conversion processes is gaining interest. The FPSO approach may allow development
of marginal natural gas reserves through the reuse of the equipment at a number of locations. Air
Products’ experience in shipboard oxygen units dates to the 1940’s with the production of a range
of small oxygen plants for use on aircraft carriers. Although small in size, the units were
designed for extreme movements of the ship and met very tight height limitations. Designing an

8
ASU for shipboard applications presents some unique challenges: (a) maintaining distillation
column performance under swaying movement of the ship, (b) minimizing footprint, height and
weight, and (c) maintaining safe operation.

Distillation performance using trays is highly susceptible to ship movements due to the
maldistribution of liquid inventory on the tray. Baffles can segment the tray into smaller sections,
but swaying can still cause liquid height variations or even dry areas that significantly decrease
the efficiency of each tray. Adding trays or increasing liquid height to compensate results in
taller columns, which is a drawback for shipboard designs. Structured packing, which is
commonly used by Air Products for land-based ASUs, is much more tolerant of motion. The thin
liquid film on the packing material is much less sensitive to motion. Air Products has carried out
dynamic simulations of packed column performance and is continuing small scale test work to
verify the expected performance of distillation columns for shipboard use.

Air Products has investigated a number of ASU plant arrangements in support of client studies.
Height is a primary concern for both ASU performance and ship design considerations. Taller
columns will be more affected by ship movement, and height restrictions are often set by
helicopter approach and landing requirements. A compact arrangement can be provided by
locating all the cryogenic equipment within a single enclosure, locating air compression
equipment on a lower deck, and locating other compression equipment and the air pretreatment
area on a second deck. A specialized insulation concept has been developed for the cryogenic
area to eliminate weight.

The close proximity of hydrocarbon processing equipment and the limited options for personnel
evacuation have led Air Products to closely examine safety related features of shipboard ASU
designs. A key feature of these design studies is a concept for the containment of cryogenic
liquids within a sealed membrane system and the controlled release of vapor to eliminate
overpressure failure of the cryogenic enclosure. In addition to equipment design studies, a full
CFD model of a conceptual arrangement for the ship was performed to understand atmospheric
dispersion of vented gases from the hydrocarbon processing area, gas turbine drivers and the
ASU. The model was useful in addressing potential problems associated with intake of
hydrocarbons into the ASU through the main air compressor and the impact of vented gases from
the ASU on other shipboard functions.

Ion Transport Membrane (ITM) Oxygen Technology

In partnership with the U.S. Department of Energy (DOE), an Air Products-led team is
developing ITM technology for large-scale oxygen production. The ITM Oxygen process uses
nonporous, mixed-conducting, ceramic membranes that have both electronic and oxygen ionic
conductivity when operated at high temperature, typically 800 to 900ºC. The mixed conductors
are inorganic mixed-metal oxides (e.g., perovskites such as (La,Sr)(Fe,Co,Cu)O3-d) that are
stoichiometrically deficient of oxygen, which creates oxygen vacancies in their lattice structure.
Oxygen from the air feed adsorbs onto the surface of the membrane, where it dissociates and
ionizes by electron transfer from the membrane. The resulting oxygen anions fill vacancies in the
lattice structure and diffuse through the membrane under an oxygen chemical-potential gradient,
applied by maintaining a difference in oxygen partial pressure on opposite sides of the membrane.
At the permeate surface of the membrane, the oxygen ions release their electrons, recombine, and
desorb from the surface as oxygen molecules. An electronic countercurrent accompanies the
oxygen anion transport, eliminating any need for an external circuit. The separation is 100%

9
selective for oxygen, in the absence of leaks, cracks, flaws, or connected through-porosity in the
membrane.

Since ITM is thermally activated, the basic process cycle must include heating the pressurized air
feed to high operating temperatures, either by indirect heat exchange or direct firing. To achieve
acceptable cycle efficiency, the energy associated with the hot, pressurized, non-permeate stream
can be recovered by integrating the process with a gas turbine power generation system. Figure 6
depicts a block flow diagram for the integration of an ITM Oxygen membrane into an IGCC
facility.

COAL COAL GAS COAL GAS

COAL
GASIFIER TREATING
N2
BFW STEAM
STEAM TURBINE
BOTTOMING
CYCLE ELECTRIC POWER

ELECTRIC POWER
GAS TURBINE
TOPPING CYCLE AIR

NON-PERMEATE AIR COAL GAS

ITM

OXYGEN

Figure 6 - ITM Oxygen / IGCC Integration

ITM Oxygen development is a multi-phase program. The overall goal of Phase I is to develop the
ITM Oxygen technology to the point of demonstrating all necessary technical and economic
requirements for further scale-up to the 5-TPD production scale. Phase II activities will focus on
construction and testing of a 1-TPD unit, followed by further scale-up to 5 TPD oxygen
production. The Phase II project will provide the design, engineering, cost, and scale-up data for
a Phase III, 25- to 50-TPD, pre-commercial demonstration unit, fully integrated with a gas turbine
and tested at a suitable field site. By the end of Phase III, sufficient demonstration of all essential
aspects of the technology will have occurred to enable further industrial commercialization in the
2005 to 2007 time frame.
Disclaimer
The ITM sections of this report were prepared by Air Products and Chemicals, Inc. pursuant to a
Cooperative Agreement partially funded by the United States Department of Energy, and neither
Air Products and Chemicals, Inc. nor any of its contractors or subcontractors nor the United
States Department of Energy, nor any person acting on behalf of either: (a) makes any warranty
or representation, express or implied, with respect to the accuracy, completeness, or usefulness of
the information contained in this report, or that the use of any information, apparatus, method, or
process disclosed in this report may not infringe privately-owned rights; or (b) assumes any
liabilities with respect to the use of, or for damages resulting from the use of, any information,
apparatus, method or process disclosed in this report. Reference herein to any specific
commercial product, process, or service by trade name, trademark, manufacturer, or otherwise,
10
does not necessarily constitute or imply its endorsement, recommendation, or favoring by the
United States Department of Energy. The views and opinions of authors expressed herein do not
necessarily state or reflect those of the United States Department of Energy.

Conclusion
Air Products has introduced unique cryogenic ASU designs for integrated and non-integrated
operation with gas turbines at a number of gasification facilities worldwide. The introduction of
higher pressure ratio gas turbine equipment offers the opportunity to explore new ways to
integrate ASU and gas turbine operation for further improvement in project economics. Gas
conversion projects have differing technical and economic criteria from IGCC facilities, including
the potential need for shipboard operation. Future developments in ASU design, integration and
operation will continue to increase single train sizes and reduce the capital and operating costs of
gasification projects. The new ITM Oxygen process uses mixed-conducting, ceramic membranes
to produce high-purity oxygen at a high flux rate from a hot, compressed air stream. By
integrating the energy-rich, vitiated, non-permeate stream with a gas turbine system, the ITM
Oxygen process becomes a highly efficient co-producer of oxygen, power, and steam.

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