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May 2014
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Case 1:
Air Separation Plant
Abstract
The production of nitrogen and oxygen is an essential step in many
chemical processes. These two gasses are the first and second most
used industrial gases respectively.1 Nitrogen is commonly used as a
blanket gas while Oxygen is used in various processes because of it
reactivity. Argon can also be recovered in air separation plants and
Argon is commonly used as an inert filler gas. Due to high demand
for these three gasses industrially, separating these components
from air can be quite profitable if the plant is designed and operated
efficiently.
Computer simulation is an essential tool in the design of new air
separation plants and in modifying existing designs to meet new
operating requirements. This casebook demonstrates the use of
PRO/II in the simulation of an air separation process with Nitrogen,
Oxygen and Argon products. This simulation includes pre-cooling
the air and the use of a turbo- expander to produce the refrigerant.
This process contains one material recycle and a number of thermal
recycles.
Since this process involves separating components with relatively
close boiling points at very low temperatures. Special
thermodynamics will need to be used to predict the separations
accurately.
PRO/II Case Book Air Separation Plant 1-1

Introduction
Air separation is a commercially important process because both
Oxygen and Nitrogen are essential materials in today's process
industries. The main constituents of air are Nitrogen and Oxygen
with a small amount of Argon. There are also traces of other rare
gases but these are only present in ppm.
Oxygen
The steel industry is the largest consumer of industrially produced
Oxygen. Oxygen is injected into furnaces allowing more efficient
combustion than air. The manufacture of chemicals is the second
largest use of industrially produced Oxygen. The manufacture of
ethylene oxide, acetylene, titanium dioxide, propylene oxide and
vinyl acetate all require Oxygen. The chemical industry also uses
industrial Oxygen for partial oxidation processes such as ammonia
and methanol production.
Other uses for the industrially produced Oxygen include: coal
gasification and liquefaction; oxy-acetylene welding; non-ferrous
metallurgical processes; waste water treatment; and medical
applications.
Nitrogen
Most of industrially produced Nitrogen is used as a gaseous blanket
to exclude Oxygen and moisture. This may be to reduce explosion
hazards in hydrocarbon liquid storage or to avoid corrosion with
liquids such as sulfuric acid.
In the metals industry, Nitrogen is used as a blanket to prevent
oxidation of the metal during smelting and to cool and purge molds
of Oxygen before pouring in the metal. Nitrogen is also used in the
oil exploration industry to enhance oil recovery by maintaining the
pressure in the wells, while liquid Nitrogen is used to fracture the
production section of oil wells.
A rapidly growing area for the use of Nitrogen is the electronics
industry which uses about 15% of current production. Very high
purity Nitrogen is used to provide an inert, dust-free, environment
for the production of complex miniature components.
Liquid Nitrogen is widely used in cryogenic applications such as:
food freezing and refrigeration; low temperature metal treatment;
shrink fitting of parts; the storage of biological materials such as
blood and organs; and in cryosurgical procedures.
1-2 Air Separation Plant March 5, 2014

The Nitrogen must be dry and have low Oxygen content. The
amount of Oxygen allowed depends on the application and some
typical values are shown in Table 1-1.
Table 1-1: Nitrogen Purities for Various Applications
Application Phase Purity
(ppm Oxygen)
Refineries, hydrogen storage Gas 500
blanketing
Pharmaceuticals, food and drink Gas & Liquid 1 200
Electronics Gas & Liquid 0.5 100

Well fracturing Liquid 1 10
Argon
The steel industry is probably the largest user of Argon because of
its inert properties. It is used to remove Oxygen from molds in
pressure die-casting and to protect the molten metal in continuous
casting.
Argon is also widely used as a high-grade inerting medium in
welding in order to prevent oxidation at the welded joint. It must be
used in preference to Nitrogen in high quality aluminum welding to
avoid the formation of nitrides.
Other uses of Argon include: fill gas for light bulbs; gas
chromatography; and as an inert medium or carrier gas in the
production of semiconductors.
Manufacture
The vast majority of Nitrogen, Oxygen, and Argon are produced by
the cryogenic separation of air. Nitrogen may also be separated
from Oxygen by the combustion of hydrocarbons in air. This
process, which also produces carbon dioxide, does not produce the
same high purity Nitrogen as cryogenic separation and is much less
common today. Oxygen can also be obtained by the electrolytic
dissociation of water but this is expensive and virtually all Oxygen
is produced from air separation. A small amount of medium purity
(90-95%) Oxygen is produced by pressure swing adsorption
processes but cryogenic separation is the predominant method. This
is because, in addition to allowing the production of large quantities
of high purity Oxygen, cryogenic processes can produce Oxygen as
a liquid.

Virtually all Argon is produced from the cryogenic separation of air
processes. A small amount of Argon is also produced as a by-
product from ammonia synthesis. The purge drawn from the
synthesis loop contains up to 6.5 mole % Argon which may be
recovered by cryogenic technology.
The configuration of a cryogenic separation process depends on
which products are to be made together with the phases and purities
required. In small plants which supply only Nitrogen or Oxygen,
the separation is usually carried out in a single distillation column.
However, in larger plants, the use of a single column is generally
inefficient.
Large plants must produce both Nitrogen and Oxygen in order to be
economically viable, necessitating a double column configuration.
Double column processes employ pressure difference to allow
energy integration between the columns.
Argon has a boiling point between those of Nitrogen and Oxygen;
therefore, it can build up within the distillation columns. It is
removed as a side draw into another distillation column where it is
removed as an overhead product. The remaining gases are returned
to the Nitrogen/Oxygen separation column. Because of the
increasing demand for Argon, more and more air separation plants
now incorporate Argon recovery.
Most air separation plants can produce only small amounts (0-10%)
of the products as liquid. If more liquid products are required,
additional refrigeration must be supplied. If the plant is to produce
predominantly liquid products, a liquefier can be integrated into the
process at the design stage. Alternatively, a separate liquefier may
be added later to liquefy Oxygen or Nitrogen products in the future
as market conditions require.
The size of separation plants can vary considerably. Small plants
will produce less than 0.1x106 kg/day of Oxygen whereas large
plants may produce up to 2.2x106 kg/day.

Process Overview
The separation process in this casebook produces gaseous Nitrogen,
Oxygen and Argon products. Part of the Oxygen is also produced as
liquid. The plant produces approximately 1.5x106 kg/day of
Oxygen between the liquid and gaseous phases. The flowsheet is
illustrated below in Figure 1-1.
Figure 1-1: Air Separation Flowsheet
The separation of Oxygen and Nitrogen is carried out in a double

distillation column. This consists of two separate columns which
are physically placed one on top of the other. The bottom column
(HP column) operates at higher pressure and its condenser is the
reboiler for the upper, lower pressure, column (LP column). The HP
column bottom product is fed to the LP column as feed and the
reflux to the LP column is provided by the liquid top product from
the HP Column.
The Argon column takes a vapor side draw from the LP column and
returns its bottom product to the tray below the draw. The Argon
product is drawn overhead.

Feedstocks and Products
Feed
Ignoring the impurities and traces of rare gases, the composition of
dry air feed is listed below in Table 1-2.
Table 1-2: Air Composition
Component Mole %
Nitrogen 78.11
Argon 0.93
Oxygen 20.96
Products
Since the main use of Nitrogen is to exclude Oxygen, the Nitrogen
produced in the air separation plant must contain very little Oxygen.
This can range between 0.5 to 5000 ppm depending on the intended
use of the Nitrogen. In this study, the amount of Oxygen in the
Nitrogen product must not exceed 10ppm. Impurities in the Oxygen
product are not as tightly controlled but the purity must be greater
than 99.5%.
Argon, which is also used to exclude Oxygen, is also limited in the
amount of Oxygen that it can contain. However, the relative
volatility of Argon to Oxygen is about 1.1 at the top of the Argon
column making it impractical to remove all the Oxygen by
distillation. If the columns are efficient, the Argon product contains
0.5-1% Nitrogen with an Oxygen content of 1-2%. The Argon is
then further treated by catalytic deoxygenation where the remaining
Oxygen is burned with hydrogen.
Feed Pretreatment
The air used in the separation process must first be dried and other
impurities removed. The impurities will include carbon monoxide,
methane, ethane, ethylene and acetylene. Other impurities may be
present depending on the location of the plant.
There are two basic methods for removing the impurities before the
separation process:
Chilling with Freon followed by molecular sieve adsorption;
Using reversing exchangers to alternately freeze and sublime
the impurities.

Molecular sieves are generally used in small plants while large
plants (over 0.5x106 kg/day) generally use reversing exchangers as
these have a lower pressure loss. However, molecular sieves are
now becoming more common in larger plants.
Air Refrigeration
The normal boiling points of Nitrogen and Oxygen are 77K and
90K respectively. This means that the air must be cooled to very
low temperatures for the separation. The air feed is cooled as much
as possible by exchange with the gaseous product streams but
additional refrigeration is required to compensate for heat loss and
the production of liquid products.
Small plants provide the refrigeration by compressing the air to
high pressure (typically 150 atmospheres) and using the Joule-
Thomson effect to cool it as it expands through a valve. In large
plants, the compression costs become too high for this to be
economic. These plants only compress the feed air to about 6-8
atmospheres. The feed is split and about 10% is compressed, cooled
and passed through a turbo-expander. The work produced by the
expander is used to drive the compressor.
High Pressure Column

The main air feed enters the HP column which operates at a
pressure of approximately 6 atmospheres. The column separates
Nitrogen from Argon and Oxygen, producing a pure liquid Nitrogen
product overhead. This product contains a few ppm Oxygen with
less than 0.2% Argon. If a liquid Nitrogen product is required from
the process, it is drawn from the top of the HP column.
The flowrate of the bottom product from the HP column is about
60% of the feed rate and it contains about 35% Oxygen, 1% Argon
with the remainder being Nitrogen.
Low Pressure Column

The LP column operates at about 1.5 atmospheres and separates the
Nitrogen and Oxygen to give pure products of each. The lower
pressure gives better separation as it increases the relative volatility
between the Nitrogen and Oxygen. The overhead product is
gaseous Nitrogen with the same purity as the liquid Nitrogen
product from the HP column. Both liquid and gaseous Oxygen are
drawn from the bottom of the column. The Oxygen product stream

will be better than 99.5% pure because the Argon is removed from
the side draw.
The main Oxygen feed to the LP column is the bottom product from
the HP column. It is subcooled by exchange with the low pressure
Nitrogen product and is used to provide the cooling in the Argon
column condenser. It then enters the LP column with a liquid
fraction in the region of 50%.
The air from the turbo-expander is fed a few trays below the main
feed.
The reflux in the LP column is supplied by the liquid Nitrogen
product from the HP column. This stream is subcooled by exchange
with the low pressure Nitrogen product and flashed through a valve
to give a 90% liquid reflux.
Argon Column
The Argon column feed is a vapor side draw from the bottom
section of the LP column and the Argon vapor is removed
overhead. Because Nitrogen is more volatile than Argon, any
Nitrogen in the feed will leave in the Argon product. It is therefore
essential that the feed contains very little Nitrogen. In order to
ensure this, the draw from the LP column is taken a few trays below
the maximum Argon concentration. The draw rate is about 20% of
the air feed rate to the plant and only about 4% of the draw stream is
removed as Argon product.
Energy Integration
The process has a high level of energy integration as all the cooling
is supplied from the feed pressure. There is no other refrigeration in
the process. The main air feed is cooled to its dew point by
exchange with the product streams. These streams are also heated
by the product from the compressor. The compressor is driven by
the expander and so its work also derives from the feed stream
pressure.
The pressures in the LP and HP columns are set to ensure that the
HP column condenser can provide heat for the LP column reboiler.
This means that the pressure in the HP column must be sufficient to
raise the overhead temperature 2-3K above that of the LP column
bottoms.

The cooling in the Argon column condenser is provided by the HP
column bottom product. The pressure is let down to ensure that its
temperature is below the Argon column top temperature.
The HP column products are both liquid and supply the reflux in the
LP column. As the pressures are reduced, they will vaporize thereby
reducing the available reflux. The LP column overhead product is
used to subcool these products to reduce the vaporization, and
subsequent loss of available reflux.
Material Recycle
This flowsheet contains only one material recycle - between the LP
and Argon columns. The flow in these streams is large compared to
the product produced in the Argon column. It consists of about 90%
Oxygen with the remainder mostly Argon. The draw from the LP
column contains approximately 0.01% Nitrogen.
Process Simulation
The flowsheet illustrated in Figure 1-2 was adapted from the
flowsheet PFD generated by PRO/II for the air plant simulation. It
was edited only to fit the size and aspect ratio restrictions of this
manual while still displaying readable labels. It differs from the
process flowsheet in Figure 1-1 in that it includes stream identifiers
and shows the unit operation icons actually used to simulate and
solve the flowsheet. Screen shots of the PRO/II PFD are in
Appendix 1-A. Selected results are listed in Appendix 1-B.
The full input file for the simulation may be found in Appendix 1-
C. Screenshots of the important data entry windows that were
entered in the graphical user interface appear within the text below.

Figure 1-2: Representation of Air Plant Flowsheet

General Data
There is a recycle between the LP column and the Argon column.
The threshold mole fraction limit for trace components is reduced to
1.0 x 10-5 because the Nitrogen concentration in the recycle is
small. Using the default setting of 0.0, the Nitrogen balance would
not be checked in the convergence test.
Figure 1-3: Recycle and Acceleration Dialog
By default, PRO/II includes the overall flowsheet mass balance in

the output report. This may be controlled from the Miscellaneous

Figure 1-4: Report Options dialog.

Component Data
All the components in the simulation are available in the PRO/II
databanks. Note PRO/II includes several component data libraries
including the Process and Simsci libraries that contain different
versions of data for many components. The libraries are search in a
user-specified order, so different daa may be used depending upon
the search order. Starting with version 8.0, the default search order
is Simsci then Process. To obtain the same results as earlier
versions of PRO/II, change this order to Process then Simsci.
Figure 1-5: Changing Component Bank Search Order

Thermodynamic Data
The importance of accurate thermodynamic calculations for this
simulation can not be overemphasized. The product purities are
specified in terms of parts per million and product temperature
differences are only a few degrees. Any inaccuracies in the
thermodynamic calculations will, therefore, have a significant
effect on the results.
The Soave-Redlich-Kwong equation of state is suitable for the
equilibrium, enthalpy and vapor density calculations for light gases
such as those in this simulation. Ideal liquid densities are used as
they give better results for these components than the default API
method.
The boiling points of Nitrogen and Oxygen are only 13K apart and
those of Nitrogen and Argon are only separated by 3K. It is
therefore essential to use binary interaction parameters obtained
near process conditions for each pair of components in order to
obtain an accurate simulation model.
Figure 1-6: Low Pressure Binary Interaction Coefficients
The SIMSCI databank provides interaction parameters which cover

a wide range of temperatures and pressures. For more accurate
results, parameters should be derived for the specific temperature
and pressure ranges in the simulation. The best source of these

parameters is always in-house data, if available. Most companies
who work with these plants will have derived interaction
parameters in the past. If data is not available in-house, parameters
may be obtained from the literature or by regressing experimental
vapor-liquid equilibrium data.
This simulation uses separate interaction data for the high and low
pressure sections of the process. The Nitrogen/Oxygen and the
Argon/Oxygen interactions were obtained by regressing data for the
specific pressure range from Gmehling & Onken1. The low
pressure Nitrogen/Argon parameter is the Gmehling & Onken
regressed values. The binary interaction parameters used in the low
pressure thermodynamic method, LOWP, are shown above in
Figure 1-6.
Figure 1-7: High Pressure Binary Interaction Coefficients
For the high pressure column, the Nitrogen/Argon interaction is

assumed ideal and is set to zero. The high pressure binary
interaction parameters used in the high pressure thermodynamic
method, HIGHP, are shown in Figure 1-7.
1.Recommended Data of Selected Compounds and Binary Mixtures, Parts
1 and 2, 1987, DECHEMA Chemistry Data Series, Vol, IV, Stephan, K.,
ed., DECHEMA, Germany.

Stream Data
There is only one feed stream to the process which is the air feed. It
comes from the purification stage where the water and carbon
dioxide are removed. The temperature is 278K.
There is a recycle (stream 16) between the Argon column and the
LP column. The recycle is named ARG BTMS. Figure 1-8 shows
the initial estimate data input for this stream.
Figure 1-8: Initial Estimate Data for Recycle (Stream 16)
An initial estimate must be supplied because the Argon product

flowrate is low compared to the return stream - about 4% of the

feed. If the return stream is not known, then its flowrate can be
estimated as 20% of the feed air flowrate and it is about 90%
Oxygen with the rest consisting of Argon. Streams in this old
simulation all are assigned numeric IDs. For more convenient
identification, they also have been assigned descriptive names. The
preferred approach in modern versions of PRO/II is to assign
streams descriptive (rather numeric) identifiers, and not bother with
descriptive names. For example:
Older approach:
PROP STRM=16
NAME 16,ARG BTMS
Newer approach:
PROP STRM=ARG BTMS
Calculation Sequence
PRO/II handles the calculation sequence automatically by using the
Minimum Tear Stream method. PRO/II solves this flowsheet by
starting with the distillation columns rather than following the air
feed stream through the process because the cold stream
temperatures into the exchanger are unknown. However, the feed to
the HP column is set at its dew point and the air feed to the LP
column is 5K above its dew point.
The calculation starts at the HP column. After it is solved, the
products streams are set to the correct pressures and liquid fractions
for the LP column feeds and the LP and Argon columns are solved
along with the recycle. After the recycle is solved, all of the other
units can be solved.
Column Section
The column section includes not only the three distillation columns,
but also the feed splitter and the exchangers to set the feed
conditions for the feed streams to both the HP and LP columns. The
flowsheet is shown in Figure 1-9.

Figure 1-9: Column Section of Simulatin Flowsheet
Feed Temperatures
Ten percent of the pretreated air feed goes to the LP column via the
compressor and expander. The remaining 90% goes to the HP
column. The splitter divides the air feed and the products are set to
the column inlet conditions. The feed to the HP column is set to its
dew point at the inlet pressure in a flash. Heat exchanger DTAD sets
the air fed to the LP column at 5 Kelvins above its dew point at a
pressure of 1.4 atmospheres.

Figure 1-10: HP Feed Specification in Heat Exchanger DTAD
High Pressure Column

The HP column has a total condenser and no reboiler. The air fed to
the base of the column acts as the reboiler. The only variable is the
condenser duty , and it is varied to meet the 10 ppm Oxygen
specification in the overhead product. A slightly edited image of the
specification Data Entry Window is shown in Figure 1-11.
Figure 1-11: High Pressure Column Specifications

If the overhead product rate is not known, it can be estimated as 40-
50% of the feed. The thermodynamic method for this column is the
high pressure method, HIGHP.
Low Pressure Column

The products from the HP column are cooled by exchange with the
overhead product before being fed to the LP column. The bottom
product from the HP column also provides the condenser duty in the
Argon column. When the LP column is calculated, the overhead
product and the Argon condenser duty are not known and so the
exchangers cannot be modeled at this time. Instead, the column
feeds are simply set to the desired pressure and liquid fraction in
heat exchanger models. The detailed exchangers are modeled later
when the distillation columns have been solved. The
thermodynamic method for this column is the low pressure method,
LOWP. The slightly edited LP column specifications DEW is
shown in Figure 1-12
Figure 1-12: Low Pressure Column Specifications

Heat Exchanger E1 specifications are shown in Figure 1-13: Similar
data is supplied for exchanger E2, with pressure drop set at 4.55 atm
and hot liquid product fraction set at 0.450.
Figure 1-13: Heat Exchanger E1 Specifications
The pure Nitrogen product from the HP column acts as the reflux
and there is no condenser. This stream should be the same purity as
the required product from the LP column. The HP column bottom
(Oxygen) product enters in the top section of the column with the
air feed from the turbo-expander a few trays lower down.
The Argon column draw and return are in the bottom section of the
column. The products are Nitrogen overhead and Oxygen from the
base. The Oxygen is mainly gaseous but a small amount of liquid
Oxygen is also produced.
The reboiler for the LP column is the condenser for the HP column
and its duty has already been calculated in the HP column to meet
the Nitrogen purity specification. It is, therefore, specified as equal
to the LP condenser duty but with a different sign to indicate that it
is heating rather than cooling.
The most important specification on the LP column is the Nitrogen
product purity which is set at 10 ppm Oxygen. There are two side

draws which could be varied in order to meet performance
specifications - the feed to the Argon column and the gaseous
Oxygen product. This means that specified.
In practice, it is not a good idea to specify the Oxygen purity as this
constrains the material balance very tightly. There is then a very
high probability that the specifications will conflict. The best
procedure is to allow the Oxygen purity to vary and fix the Argon
column draw stream. The gaseous Oxygen product is then varied in
order to reach solution.
Argon Column
The Argon column is modeled with a bubble point condenser and
no reboiler. The vapor draw from the LP column enters the base of
the column and acts as the reboiler. Because the Argon product
purity is controlled by the operation of the LP column, a recovery
specification is used on the Argon column. The Data Entry Window
is illustrated in Figure 1-14.
Figure 1-14: Argon Tower Specifications and Variables
A third of the Argon in the feed is typically recovered overhead and

the condenser duty can be varied in order to meet this. The expected
Argon product purity is in the region of 98%. The Argon column

specification is shown above.The thermodynamic method for this
column is the low pressure method, LOWP.
Inter-column Heat Exchangers

Once the distillation columns have solved, the exchangers between
the HP and LP columns can be calculated. Figure 1-15 is a
schematic of the heat exchanger simulation. Exchangers E1 and E2
(in the column section of the flowsheet) are combined into the
LNGHX unit E1E2. The valves are modeled separately. Steam 18 is
the Nitrogen product from the LP column, while streams 12 and 8
are the HP column products.
Figure 1-15: Inter-column Heat Exchangers
Exchangers E3 and E4 are the Argon and HP column condensers.

The streams AV1 and HPV are created from the vapor flow into the
condensers using the PRO/II psuedo-product stream feature. This
feature models a pseudo stream that does not actually exist on the
column. LPL is created from the liquid flow into the LP Column
reboiler which is the other side of the HP Column condenser. These
exchangers are modeled in order to enable PRO/II to check that the
temperature levels are correct; i.e., there are no crossovers.
The duty on the first stream in LNG exchanger E1E2 is set equal to
the duty calculated in E1 when setting the LP column feed
condition. The duty on the second stream in E1E2 is defined as the
duty of E2 minus the duty of the Argon column condenser. The

condenser duty is actually negative, so it is added to the E2 duty on
the DEFINE statement to specify the cooling duty in E1E2.
The duties of E3 and E4 are simply defined as the same as that of
the corresponding column condenser. If temperature crossovers
occur, PRO/II automatically prints an error message.
Figure 1-16 is a composite that illustrates DEFINE-ing duties for
cells of exchanger E1E2. As the red highlights indicate, place the
cursor in the DUTY field of one cell and click DEFINE on the tool
bar. That action displays the Definition DEW for the selected cell.
Figure 1-16: Define DEWs for Exchanger E1E2

Figure 1-17 illustrates the DEW to DEFINE the temperature
specification of cell 1 in exchanger LNG. Here the Temperature
field of cell 1 is highlighted while pressing the Define button on
the tool bar.
Figure 1-17: DEFINE DEW for Exchanger LNG

Heat Recovery Section
The heat recovery section consists of the LNGHX exchanger and
the compressor and turbo-expander. The simulation flowsheet is
shown in Figure 1-18.
Figure 1-18: Heat Recovery Simulation Schematic
Streams 2 and 3 are the air feeds. 5A and 7A correspond to the

column feed streams 5 and 7 in the column section of the flowsheet.
Streams 19 and 22 are the cold gaseous Nitrogen and Oxygen
products which cool the air feed.

Controller
There is an energy recycle round the three units in this section of the
flowsheet and a controller is used to calculate the temperature of
stream 6 leaving the LNGHX exchanger. The controllers data entry
window is shown in Figure 1-19:
Figure 1-19: Controller Specification

Compressor/Expander
As shown in Figure 1-20, the compressor work is defined as 90% of
that produced in the expander.
Figure 1-20: Specifying Compressor Work Using DEFINE
However, when the compressor is first calculated, the expander

work has not been determined. It is not possible to calculate the
expander first because the inlet pressure is determined by the
compressor. This means that an iterative procedure is required and
it is automatically converged by PRO/II.
The temperature of stream 5A leaving the LNGHX is defined as the
same as the column feed stream 5. The temperature of stream 6 is
not known. However, the temperature of stream 7A leaving the
expander is known. The controller is therefore used to vary the
temperature of stream 6 in order to set stream 7A at the same
temperature as stream 7.
Results
Column Section
The HP column solves with a condenser duty of 10.46 MKCal/hr.
The overhead product is 99.83% Nitrogen with the remainder
mostly Argon. The LP column reboiler duty is the same as that of
the HP column condenser. The Nitrogen product contains slightly
more Argon than the HP column product and is 99.72% pure. The
Oxygen content is the same in both column products at the specified
10 ppm.
7.6% of the Oxygen is produced as liquid. The purity of the liquid
and gas products are 99.7% and 99.6% respectively. These are both
above the desired value of 99.5%.

The Argon product is 97.5% pure with 1.9% Oxygen and 0.6%
Nitrogen. The product rate is 3.2% of the feed from the LP Column.
The condenser duty is 2.96 MKCal/hr.
Inter-Column Exchangers
All the exchangers solve correctly which confirms that there are no
temperature crossovers. The Nitrogen into the HP column
condenser is at a temperature of 96.2K and the Oxygen into the LP
column reboiler is at 94.8K. Because the streams are changing
phase, there is very little temperature change through the exchanger.
The Argon entering the Argon column condenser is at 88.9K and is
exchanging with the LP Column Oxygen product. This Oxygen
stream is heated from 84.0K to 85.5K within the condenser.
The LP column Nitrogen product is heated from 79.1K to 96.3K in
LNGHX unit E1E2.
Heat Recovery Section

The work recycle between the expander and compressor is solved
automatically within the controller loop. The controller solves in
three iterations. The compressor increases the air pressure from 6 to
9 atmospheres with an exit temperature of 320K. This is cooled in
the LNGHX unit to 142K before entering the expander. It is then let
down to the defined feed condition of 89.5K and 1.4 atmospheres.

Appendix 1-A: Simulation Flowsheet
PRO/II Simulation PDF:
Figure 1-21 is a representation of the complete flowsheet taken
from the Piping and Flow Diagram (PFD) of PROVISION.
Figure 1-21: Air Separation Plant PDF

Column Section
Figure 1-22 illustrates the connections of streams to the three major
separation unit operations in this simulation.
Figure 1-22: Connectivbity of distillation units

Inter-Column Heat Transfer
Figure 1-23 shows the details of exchanging energy between
streams that interconnect the major separation unit operations.
Figure 1-23: Heat Exchange Configuration Between Columns

Appendix 1-B: Selected Output
The listings presented here typically are generated using the
Spreadsheet tool located on the PRO/II Tools menu.
Selected Stream Results

Figure 1-24: Overall Feed and Product Material Flows

Figure 1-25: Selective Stream Summary

Compressor Results
Figure 1-26: Report of Compressor Operations

Column Condenser Summary
Figure 1-27: Summary of Top-Tray Column Condensers

HP Column Summary
Figure 1-28: High Pressure Column Tray Operating Profile

Figure 1-29: High Pressure (HP) Column Composition Profile
Figure 1-30: Low Pressure (LP) Column Feeds and Products

Figure 1-31: Low Pressure (LP) Column Summary

Figure 1-32: Low Pressure (LP) Column Composition Profile

Figure 1-33: Argon Column Composition Profile

Appendix 1-C: Keyword Input File
$ Generated by PRO/II Keyword Generation System <version 9.3>
$ Generated on: Fri Jul 24 2009
TITLE PROJECT=CASEBOOK, PROBLEM=AIR PLANT, USER=SIMSCI
PRINT INPUT=ALL, STREAM=COMPONENT, RATE=M, FRACTION=M, &
MBALANCE=ON
TOLERANCE STREAM=,,1E-5
DIMENSION METRIC, TEMP=K, PRES=ATM
SEQUENCE SIMSCI
COMPONENT DATA
LIBID 1,NITROGEN/2,ARGON/3,OXYGEN, BANK=SIMSCI,PROCESS
ASSAY CONVERSION=API94, CURVEFIT=CURRENT, KVRECONCILE=TAILS
THERMODYNAMIC DATA
METHOD SYSTEM=SRK, DENSITY(L)=IDEAL, SET=1-LOWP, DEFAULT
KVAL(VLE)
SRK 1,3,-0.00694,0,0
SRK 1,2,0.0056,0,0
SRK 2,3,0.01574,0,0
METHOD SYSTEM=SRK, DENSITY(L)=IDEAL, SET=2-HIGHP
KVAL(VLE)
SRK 1,3,-0.01089,0,0
SRK 1,2,0,0,0
SRK 2,3,0.01697,0,0
STREAM DATA
PROPERTY STREAM=1, TEMPERATURE=278, PRESSURE=6, PHASE=M, &
RATE(M)=9385.99, COMPOSITION(M)=1,78.11/2,0.93/3,20.96
PROPERTY STREAM=16, TEMPERATURE=92.78, PRESSURE=1.32, PHASE=M, &
COMPOSITION(M,KGM/H)=1,0.0194303/2,108.081/3,1712.1
PROPERTY STREAM=8_R1, REFSTREAM=8
NAME 1,AIR FEED/16,ARG BTMS/8,HP BTMS/12,HP OVHD/15,ARG FEED/ &
17,AR PRODUCT/20,N2 PRODUCT/23,O2 GAS/21,O2 LIQUID
UNIT OPERATIONS
SPLITTER UID=SPL1, NAME=FEED SPLIT
FEED 1
PRODUCT M=2, M=3
OPERATION OPTION=FILL
SPEC STREAM=3, RATE(KGM/H),TOTAL,WET, DIVIDE, STREAM=1, &
RATE(KGM/H),TOTAL,WET, VALUE=0.1
METHOD SET=2-HIGHP
FLASH UID=DEW
FEED 2
PRODUCT V=5
DEW DP=0
COLUMN UID=HP, NAME=HP COLUMN
PARAMETER TRAY=44,IO
FEED 5,44
PRODUCT OVHD(M)=12,4000, BTMS(M)=8, SUPERSEDE=ON
CONDENSER TYPE=BUBB, TEST=96.3

DUTY 1,1,,CONDENSER
PSPEC PTOP=5.8, DPCOLUMN=0.16
PRINT PROPTABLE=PART, ITERATION=ALL, PROFILE=ALL
ESTIMATE MODEL=CONVENTIONAL, REFLUX=6500, CTEMP=96.3, &
TTEMP=96.3, BTEMP=100.7
TEMPERATURE 1,96.3/2,96.3/44,100.7
SPEC ID=COL1SPEC1, STREAM=12,PPM, COMP=3,WET, VALUE=10
VARY DNAME=CONDENSER
TFLOW NET(V)=HPV,2
METHOD SET=2-HIGHP
HX UID=E1
HOT FEED=12, M=14, DP=4.6
OPER HLFRAC=0.9
HX UID=E2
HOT FEED=8, M=11, DP=4.55
OPER HLFRAC=0.45
HX UID=DTAD
HOT FEED=3_R1, M=7, DP=4.6
OPER HDTADEW=5
COLUMN UID=LP, NAME=LP COLUMN
FEED 14,1/11,28/7,32/16,45
PRODUCT OVHD(M)=18,7800.01, VDRAW(M)=22,69,1800, VDRAW(M)=15, &
44,1875, BTMS(M)=21, SUPERSEDE=ON
DUTY 1,69,8,SIDEHC1
PRINT PROPTABLE=PART
ESTIMATE MODEL=CONVENTIONAL, REFLUX=3500
SPEC ID=COL2SPEC1, DNAME(KC/H)=SIDEHC1, DIVIDE, COLUMN=HP, &
DNAME(KC/H)=CONDENSER, VALUE=-1
SPEC ID=COL2SPEC2, STREAM=18,PPM, COMP=3,WET, VALUE=10
VARY DNAME=SIDEHC1
VARY DRAW=22
PLOT PROFILE, XCOMPONENT=1,1/2,2/3,3, YCOMPONENT=1,1/2,2/3,3
TFLOW NET(L)=LPL,68
METHOD SET=1-LOWP
COLUMN UID=ARG, NAME=ARGON COLUMN
FEED 15,55
PRODUCT OVHD(M)=17,100, BTMS(M)=16, SUPERSEDE=ON
CONDENSER TYPE=PART
DUTY 1,1,-3,CONDENSER
PRINT PROPTABLE=BRIEF
ESTIMATE MODEL=CONVENTIONAL, REFLUX=1500
SPEC ID=COL3SPEC1, STREAM=17, RATE(KGM/H), COMP=2,WET, DIVIDE, &
STREAM=15, RATE(KGM/H), COMP=2,WET, VALUE=0.3333
VARY DNAME=CONDENSER
TFLOW NET(V)=AV1,2
METHOD SET=1-LOWP
LNGHX UID=E1E2
HOT FEED=12_R1, M=13, NUMBER=1, CELL=CELL1
HOT FEED=8_R1, M=9, NUMBER=2, CELL=CELL2

COLD FEED=18, M=19, NUMBER=3, CELL=CELL3
DEFINE DUTY(1,KC/H) AS 1, TIMES, HX=E1, DUTY(KC/H)
DEFINE DUTY(2,KC/H) AS HX=E2, DUTY(KC/H), PLUS, COLUMN=ARG, &
DNAME(KC/H)=CONDENSER
COMPRESSOR UID=COM
FEED 3
PRODUCT V=4
OPERATION CALCULATION=GPSA, EFF=82
DEFINE WORK(KW) AS EXPANDER=EXP, WORK(KW), TIMES,0.9
METHOD SET=2-HIGHP
LNGHX UID=LNG
HOT FEED=2_R1, M=5A, NUMBER=1, CELL=CELL1
HOT FEED=4, M=6, TEMP=160, NUMBER=2, CELL=CELL2
COLD FEED=19, V=20, NUMBER=3, CELL=CELL3
COLD FEED=22, V=23, NUMBER=4, CELL=CELL4
DEFINE TEMP(1,K) AS STREAM=5, TEMPERATURE(K)
METHOD SET=2-HIGHP
EXPANDER UID=EXP
FEED 6
PRODUCT V=7A
OPERATION PRES=1.4, EFF=85
CONTROLLER UID=CON
SPEC STREAM=7A, TEMPERATURE(K), DIVIDE, STREAM=7, &
TEMPERATURE(K), VALUE=1, ATOLER=0.01
VARY LNGHX=LNG, TEMP(2,K)
CPARAMETER IPRINT, SOLVE
VALVE UID=V2
FEED 9
PRODUCT M=10
OPERATION DP=4.55
HX UID=E3, NAME=AR CONDENSER
HOT FEED=AV1, L=AL1
COLD FEED=10, M=11A
CONFIGURE COUNTER
DEFINE DUTY(KC/H) AS -1, TIMES, COLUMN=ARG, &
HX UID=E4, NAME=HP CONDENSER
HOT FEED=HPV, L=HPV1
COLD FEED=LPL, M=LPL1
CONFIGURE COUNTER
DEFINE DUTY(KC/H) AS -1, TIMES, COLUMN=HP, &
END

Invensys Systems, Inc.
26561 Rancho Parkway South
Lake Forest, CA 92630
United States of America
http://iom.invensys.com
Global Customer Support

Inside U.S.: 1-866-746-6477
Outside U.S.: 1-508-549-2424 or contact your
local Invensys Representative.
Email: [email protected]
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PRO/II Case Book Air Separation Plant 1-1

1-2 Air Separation Plant March 5, 2014

Pharmaceuticals, food and drink Gas & Liquid 1 200

Electronics Gas & Liquid 0.5 100

PRO/II Case Book Air Separation Plant 1-3

1-4 Air Separation Plant March 5, 2014

Figure 1-1: Air Separation Flowsheet

The separation of Oxygen and Nitrogen is carried out in a double

PRO/II Case Book Air Separation Plant 1-5

1-6 Air Separation Plant March 5, 2014

High Pressure Column

Low Pressure Column

PRO/II Case Book Air Separation Plant 1-7

1-8 Air Separation Plant March 5, 2014

PRO/II Case Book Air Separation Plant 1-9

1-10 Air Separation Plant March 5, 2014

Figure 1-3: Recycle and Acceleration Dialog

By default, PRO/II includes the overall flowsheet mass balance in

PRO/II Case Book Air Separation Plant 1-11

1-12 Air Separation Plant March 5, 2014

Figure 1-5: Changing Component Bank Search Order

PRO/II Case Book Air Separation Plant 1-13

Figure 1-6: Low Pressure Binary Interaction Coefficients

The SIMSCI databank provides interaction parameters which cover

1-14 Air Separation Plant March 5, 2014

Figure 1-7: High Pressure Binary Interaction Coefficients

For the high pressure column, the Nitrogen/Argon interaction is

PRO/II Case Book Air Separation Plant 1-15

Figure 1-8: Initial Estimate Data for Recycle (Stream 16)

An initial estimate must be supplied because the Argon product

1-16 Air Separation Plant March 5, 2014

PRO/II Case Book Air Separation Plant 1-17

1-18 Air Separation Plant March 5, 2014

High Pressure Column

Figure 1-11: High Pressure Column Specifications

PRO/II Case Book Air Separation Plant 1-19

Low Pressure Column

Figure 1-12: Low Pressure Column Specifications

1-20 Air Separation Plant March 5, 2014

Figure 1-13: Heat Exchanger E1 Specifications

PRO/II Case Book Air Separation Plant 1-21

Figure 1-14: Argon Tower Specifications and Variables

A third of the Argon in the feed is typically recovered overhead and

1-22 Air Separation Plant March 5, 2014

Inter-column Heat Exchangers

Figure 1-15: Inter-column Heat Exchangers

Exchangers E3 and E4 are the Argon and HP column condensers.

PRO/II Case Book Air Separation Plant 1-23

Figure 1-16: Define DEWs for Exchanger E1E2

1-24 Air Separation Plant March 5, 2014

Figure 1-17: DEFINE DEW for Exchanger LNG

PRO/II Case Book Air Separation Plant 1-25

Figure 1-18: Heat Recovery Simulation Schematic

Streams 2 and 3 are the air feeds. 5A and 7A correspond to the

1-26 Air Separation Plant March 5, 2014

Figure 1-19: Controller Specification

PRO/II Case Book Air Separation Plant 1-27