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SimSci

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May 2014
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Table of Contents

Case 1:
Air Separation Plant
Abstract . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .1-1
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .1-2
Process Overview. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .1-5
Process Simulation. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .1-9
Results . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .1-28
PRO/II Simulation PDF: . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .1-31
Column Section . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .1-32
Inter-Column Heat Transfer. . . . . . . . . . . . . . . . . . . . . . . . . . . . .1-33

Case 2:
Ammonia Synthesis Plant
Abstract . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .2-1
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .2-1
Process Overview. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .2-3
Process Simulation. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .2-10
Unit Operations for Stage 1 - Catalytic Reforming . . . . . . . . . . .2-17
Unit Operations for Stage 2 - Catalytic Shift and Methanation. .2-20
Unit Operations for Stage 3- Compression . . . . . . . . . . . . . . . . .2-23
Unit Operations for Stage 4 Conversion . . . . . . . . . . . . . . . . . .2-24
Use of the Model in Process Control . . . . . . . . . . . . . . . . . . . . . .2-30

Case 3:
Methyl Tertiary Butyl Ether (MTBE) Plant
Abstract . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .3-1
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .3-2
Process Overview. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .3-4
Process Simulation. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .3-8
Technical Results . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .3-36
Results Analysis. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .3-37
Appendix 3-A: Complete MTBE Plant Flowsheet . . . . . . . . . . .3-38
Appendix 3-B: PRO/II Selected Output . . . . . . . . . . . . . . . . . . .3-40
Appendix 3-C: PRO/II INPUT FILE. . . . . . . . . . . . . . . . . . . . . .3-50

PRO/II Case Book Table of Contents-1


Case 4:
Sulfuric Acid Alkylation
Abstract . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4-1
Sulfuric Acid Alkylation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4-2
Simulation Scope and Objectives . . . . . . . . . . . . . . . . . . . . . . . . . 4-4
Reactor Modelling . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4-5
Sulfuric Acid Alkylation Flowsheet . . . . . . . . . . . . . . . . . . . . . . . 4-7
RUN #1 Auto-Refrigeration and Iso-Stripper Operation . . . . . 4-10
Runs #2 and #3 - Deisobutanizer with Auto-thermal Refrigeration
and Deisobutanizer with effluent Refrigeration . . . . . . . . . . . . . 4-13
Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4-16
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4-17
Keyword Input File Inserts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4-29

Case 5:
Urea Plant
ABSTRACT . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5-1
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5-2
Process Outline . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5-3
Process Simulation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5-5
Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5-21

Case 6:
Vinyl Chloride Monomer (VCM) Plant
Abstract . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6-1
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6-1
Process Outline . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6-4
Process Description and Simulation Model. . . . . . . . . . . . . . . . . . 6-5
Technical Results . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6-17
Input File . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6-19
Feeds Summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6-27
Recycle and Product Streams . . . . . . . . . . . . . . . . . . . . . . . . . . 6-28
HCL Column (COL3) Summary . . . . . . . . . . . . . . . . . . . . . . . . . 6-29
VCM Column (COL4) Summary . . . . . . . . . . . . . . . . . . . . . . . 6-30

Table of Contents-2
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.

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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.

PRO/II Case Book Air Separation Plant 1-3


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.

1-4 Air Separation Plant February 26, 2014


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.

PRO/II Case Book Air Separation Plant 1-5


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.

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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

PRO/II Case Book Air Separation Plant 1-7


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.

1-8 Air Separation Plant February 26, 2014


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.

PRO/II Case Book Air Separation Plant 1-9


Figure 1-2: Representation of Air Plant Flowsheet

1-10 Air Separation Plant February 26, 2014


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

PRO/II Case Book Air Separation Plant 1-11


Figure 1-4: Report Options dialog.

1-12 Air Separation Plant February 26, 2014


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

PRO/II Case Book Air Separation Plant 1-13


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

1-14 Air Separation Plant February 26, 2014


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.

PRO/II Case Book Air Separation Plant 1-15


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

1-16 Air Separation Plant February 26, 2014


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.

PRO/II Case Book Air Separation Plant 1-17


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.

1-18 Air Separation Plant February 26, 2014


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

PRO/II Case Book Air Separation Plant 1-19


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

1-20 Air Separation Plant February 26, 2014


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

PRO/II Case Book Air Separation Plant 1-21


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

1-22 Air Separation Plant February 26, 2014


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

PRO/II Case Book Air Separation Plant 1-23


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

1-24 Air Separation Plant February 26, 2014


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

PRO/II Case Book Air Separation Plant 1-25


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.

1-26 Air Separation Plant February 26, 2014


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

PRO/II Case Book Air Separation Plant 1-27


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%.

1-28 Air Separation Plant February 26, 2014


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.

PRO/II Case Book Air Separation Plant 1-29


1-30 Air Separation Plant February 26, 2014
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

PRO/II Case Book Air Separation Plant 1-31


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

1-32 Air Separation Plant February 26, 2014


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

PRO/II Case Book Air Separation Plant 1-33


1-34 Air Separation Plant February 26, 2014
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

PRO/II Case Book Air Separation Plant 1-35


Figure 1-25: Selective Stream Summary

1-36 Air Separation Plant February 26, 2014


Compressor Results
Figure 1-26: Report of Compressor Operations

PRO/II Case Book Air Separation Plant 1-37


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

1-38 Air Separation Plant February 26, 2014


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

PRO/II Case Book Air Separation Plant 1-39


Figure 1-29: High Pressure (HP) Column Composition Profile

Figure 1-30: Low Pressure (LP) Column Feeds and Products

1-40 Air Separation Plant February 26, 2014


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

PRO/II Case Book Air Separation Plant 1-41


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

1-42 Air Separation Plant February 26, 2014


Figure 1-33: Argon Column Composition Profile

PRO/II Case Book Air Separation Plant 1-43


1-44 Air Separation Plant February 26, 2014
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
PROPERTY STREAM=12_R1, REFSTREAM=12
PROPERTY STREAM=3_R1, REFSTREAM=3
PROPERTY STREAM=2_R1, REFSTREAM=2
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

PRO/II Case Book Air Separation Plant 1-45


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
PARAMETER TRAY=69,IO
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
PSPEC PTOP=1.17, DPCOLUMN=0.404
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
PARAMETER TRAY=55,IO
FEED 15,55
PRODUCT OVHD(M)=17,100, BTMS(M)=16, SUPERSEDE=ON
CONDENSER TYPE=PART
DUTY 1,1,-3,CONDENSER
PSPEC PTOP=1.15, DPCOLUMN=0.17
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

1-46 Air Separation Plant February 26, 2014


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, &
DNAME(KC/H)=CONDENSER
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, &
DNAME(KC/H)=CONDENSER
END

PRO/II Case Book Air Separation Plant 1-47


1-48 Air Separation Plant February 26, 2014
Case 2:
Ammonia Synthesis Plant

Abstract
Over 140 million tons of ammonia is produced worldwide each
year. The rewards for reducing costs, increasing efficiency and
improving the profitability of ammonia plants are enormous.
Computer simulation of the plant is the first step towards
identifying which parameters control the conversion rate, product
purity, energy usage, and the production rate of an existing facility.
This casebook demonstrates the use of PRO/II in the simulation of
an ammonia synthesis process. The entire plant is modeled, from
the reforming of the hydrocarbon feedstream to synthesis gas
through its purification to its conversion to ammonia in a synthesis
reactor. This casebook also outlines the use of the simulation for
parametric studies in the evolution of a control strategy.
The ammonia synthesis loop involves a large recycle compared to
the feed and product rates. In addition there are several thermal
recycles and two control loops. Special thermodynamics are used to
ensure the accurate prediction of the separation of ammonia from
the other materials.

Introduction
Chemically combined nitrogen is essential for the growth of all
living organisms. Animals and plants (with one or two exceptions)
are unable to assimilate free nitrogen from the air, so they depend
upon nitrates, ammonium salts or other nitrogen compounds found
in the soil.
The natural supplies of fixed nitrogen were adequate for many
centuries to satisfy the normal processes of nature. However, by the

PRO/II Case Book Ammonia Synthesis Plant 2-1


beginning of the 19th century, the increase in world population
along with the growth of big cities created a demand from the more
industrialized countries for supplemental sources of fixed nitrogen.
This supplement was first found in imported guano and sodium
nitrate and later in ammoniacal solutions and ammonium sulphate
by-products from the carbonization of coal in gas-works and coke
ovens.
By the start of the 20th century the demand for fertilizer nitrogen
again outstripped supply. Three different processes for the fixation
of nitrogen were designed and put in commercial operation to
ensure adequate supplies of fertilizer nitrogen.
One of those three was the direct synthesis of ammonia from
nitrogen and hydrogen by the Haber-Bosch process. This was
developed in Germany between 1905 and 1913 and virtually all
fixed nitrogen is now produced by this process.
The total world production in 2005 was over 140 million tons of
fixed nitrogen. Global demand for ammonia is expected to increase
about 2% per year for the foreseeable future. More than 90% of this
is produced as ammonia and about 85% of the total fixed nitrogen
production is used in fertilizers.

Alternative Routes to Ammonia


There are several licensors of ammonia synthesis processes. All
produce ammonia from hydrocarbon feedstocks and air. The
hydrocarbon feedstock is usually a natural gas although others, such
as naphtha, are used where natural gas is not locally available. The
processes are all fundamentally similar: the feed hydrocarbon gas is
desulfurized then converted to synthesis gas in a reforming process
followed by a CO shift and methanation reactors. The resulting
syngas, after purification, is a mixture of hydrogen and nitrogen in
stoichiometric quantities (3:1). This is converted to ammonia in a
synthesis reactor which is located in a recycle loop, because of a
low conversion per pass.
Kellogg Brown & Root (KBR) is the largest licensor of Ammonia
Synthesis Technology with over 170 Kellogg plants and over 25
Braun (now owned by KBR) plants. These plants have accounted
for more ammonia capacity worldwide than any other licensor.1

1.1 "Ammonia", by Kellogg Brown & Root, 2000

2-2 Ammonia Synthesis Plant February 26, 2014


The Kellogg Process
At over 170 units worldwide, the Kellogg process has been installed
in more ammonia plants than any other process. The simulation
considered in this Casebook is a generic Kellogg process.
Schematic diagrams of the full flowsheet may be found in
Appendix 2-A:.
Although the Kellogg process is a licensed process, operational
benefits can be gained from changing a number of the variable
parameters: temperatures, recycle rates, air and steam quantities and
so on. Recently there has been some work on lowering the steam to
carbon ratio to the primary reformer and modifying the catalysts
used in the shift converters.The emphasis in ammonia plants today
is for lower energy usage. New Kellogg plants claim 6.85Gcal/short
ton for all energy requirements over one year.

Process Overview
The Kellogg Ammonia process is a single train process, divisible
into four stages, which operate sequentially. In stage 1 the natural
gas undergoes catalytic reforming to produce hydrogen from
methane and steam. The nitrogen required for the ammonia is
introduced at this stage. In stage 2, the resulting syngas is purified
by the removal of carbon monoxide and carbon dioxide in a MEA
plant or similar process. Stage 3 consists of compression of the
syngas up to the pressure required in stage 4, the ammonia loop.

Feedstocks and Products


Main Feeds
The main feedstock for this ammonia process is 6 million SCFD of
natural gas at a temperature of 60oF and a pressure of 340 psig. Its
composition is shown in
Table 2-1: Main Feed Composition
Component Mole%
Carbon Dioxide 2.95
Nitrogen 3.05
Methane 80.75
Ethane 7.45
Propane 3.25
Butane 2.31
Pentane 0.24

PRO/II Case Book Ammonia Synthesis Plant 2-3


Before entering the primary reformer, the natural gas is mixed with
superheated steam at 334 psig and 950 F. Nitrogen is supplied from
the air which is fed to the secondary reformer at 289 psig and 330 F.
The composition of air is displayed in Table 2-2:Air Composition.
Table 2-2: Air Composition
Component Mole %
Oxygen 21.00
Nitrogen 78.05
Argon 0.95
There is also a water feed which is used to saturate the syngas in the
MEA plant.

Products
The main product of an ammonia plant is, of course, ammonia. The
ammonia product stream must have a purity greater than 99.5%.
The major impurities are hydrogen, nitrogen, argon and methane.
The other product streams are:
letdown gas from the final separator consisting of
approximately 45% ammonia, 30% hydrogen with the rest
being nitrogen, argon and methane
purge gas from the ammonia loop consisting of approximately
8% ammonia, 57% hydrogen plus nitrogen, argon and methane
Ammonia is recovered from the letdown and purge gases in an
absorber.
Detailed descriptions of the product streams may be found at the
end of the Simulation section in Table 2-5.

2-4 Ammonia Synthesis Plant February 26, 2014


Stage 1: Catalytic Reforming
Figure 2-1: Schematic of Catalytic Reforming Section

Following sulfur removal, the primary steam reformer converts


about 70% of the hydrocarbon feed into raw synthesis gas in the
presence of steam using a nickel catalyst.
The main reforming reactions are:
CH4 + H2O <> CO + H2 (2-1)
CO + H2O <>CO2 + H2 (2-2)
In the secondary reformer, air is introduced to supply the nitrogen.
The heat of combustion of the partially reformed gas raises the
temperature and supplies the energy to reform most of the
remaining hydrocarbon feed.
The reformer product stream is used to generate steam and to
preheat the natural gas feed.

PRO/II Case Book Ammonia Synthesis Plant 2-5


Stage 2: Shift and Methanation
The shift conversion is carried out in two stages. The first uses a
high temperature catalyst and the second uses a low temperature
one. The shift converters remove the carbon monoxide produced in
the reforming stage by converting it to carbon dioxide by the
reaction:
CO + H2O <> CO2 + H2 (2-3)
This reaction also creates additional hydrogen for the ammonia
synthesis.

Figure 2-2: Schematic of Shift and Methanation Section

Shift reactor effluent is cooled and the condensed water is


separated. The gas is then passed to the purification section where
carbon dioxide is removed from the synthesis gas in any one of a
number of systems such as hot carbonate, MEA, Selexol etc.
After the purification stage, the last traces of carbon monoxide and
carbon dioxide are removed in the methanation reactions:

2-6 Ammonia Synthesis Plant February 26, 2014


CO + 3H2O <> CH4 + H2 (2-4)
CO2 + 4H2 <> CH4 + 2H2O (2-5)
The methanation reaction is necessary not only to remove the
carbon monoxide and carbon dioxide, but also to create water
which can then be removed in the compression stage. This will add
efficiency to the process in that any water that is removed will not
have to be circulated in the large recycle loop in the ammonia
synthesis stage.

Stage 3: Compression
Figure 2-3: Schematic of Compression Section

The purified synthesis gas is cooled and the condensed water is


removed. The gas is then compressed in a three stage unit. The
centrifugal compressors are driven by steam turbines using steam
generated in the plant itself, reducing overall power consumption.

PRO/II Case Book Ammonia Synthesis Plant 2-7


Stage 4: Conversion
Figure 2-4: Hydrogen Gas Conversion Section

The compressed synthesis gas is dried, mixed with a recycle stream


and introduced into the synthesis loop after the recycle compressor.
The gas mixture is chilled and liquid ammonia is removed from the
secondary separator. The vapor is heated and passed to the
ammonia converter. The feed is preheated inside the converter
before entering the catalyst bed.
The ammonia synthesis reaction is:
N2 + 3H2 <> 2NH3 (2-6)
Very high pressures (typically in excess of 300 atmospheres) are
required in order to obtain a reasonable conversion. The conversion
of hydrogen per pass is still less than 30% and so a large recycle of
unreacted gases is necessary.
The converter vapor product is cooled by ammonia refrigeration in
the primary separator to condense the ammonia product.
A purge is removed from the remaining gases to prevent the build
up of inerts in the loop. The molar concentration of inerts (argon
and methane) in the converter feed is maintained at 12%.

2-8 Ammonia Synthesis Plant February 26, 2014


Energy Integration
The process features a high level of energy integration. Nearly all
the power and heating requirements of the process are met by the
heat available elsewhere in the process.

In the Reformer
The primary reformer passes the natural gas and steam mixture
through catalyst-packed tubes in a furnace. The furnace exhaust
gases are used to generate steam in a series of boilers. This steam is
then used to drive the compressors.
The effluent from the secondary reformer is used in a waste heat
boiler and then to preheat the feed to the desulfurizer.

In the Shift and Methanators


The methanator feed is preheated by exchanging with the
methanator product and then further heated by exchange with the
high temperature shift reactor effluent. Energy from this effluent is
further recovered in a waste heat boiler.
The effluent from the low temperature shift reaction is used in
another reboiler.

In the Conversion
The products from the ammonia converter are mixed with the
synthesis gas from the compressors and cooled for ammonia
separation by exchange with the converter feed. The converter feed
is preheated by the products inside the converter vessel.

Material Recycle
The final stage, the Synthesis Loop, is a recycle operation. The
conversion of nitrogen and hydrogen to ammonia in the converter is
very low - less than 30% of the hydrogen is converted per pass.
Therefore there has to be a large recycle in order to convert all the
feed and ensure that the final ammonia product reaches the required
purity.
The ratio of recycle to ammonia product is of the order of 3:1

PRO/II Case Book Ammonia Synthesis Plant 2-9


Process Simulation
The PRO/II input for the simulation may be found in PRO/II
Keyword Input File. This section explains the details of the
simulation used in this case study. The screen shots are meant to
illustrate specific data entry for points of interest.

General Data
Because stage 4 of this process involves a loop which has a large
recycle rate in comparison to the product rates, it is essential that
the flowsheet is in mass balance. The normal stream component
recycle convergence tolerance must therefore be tightened - in this
case to 0.05%. The stream Temperature and Pressure recycle
tolerances were also tightened to 0.1 and 0.001 respectively. The
Wegstein acceleration option is used to help speed up convergence.
The graphic below shows the data entry window for the recycle
convergence and acceleration options. .

2-10 Ammonia Synthesis Plant February 26, 2014


The threshold mole fraction limit for trace components in the
recycle is also reduced to 0.0001 in order to ensure that all
components are checked for the loop convergence. The maximum
allowed number of recycle trials is increased to 150 to ensure that
the number of recycle trials is sufficient to converge the flowsheet.
PRO/II is also asked to report the overall flowsheet mass balance in
the Miscelleous Report Options menu.
.

PRO/II Case Book Ammonia Synthesis Plant 2-11


Component Data
All the components in the simulation are available in the PRO/II
data bank.

Thermodynamic Data
For most of the units in the flowsheet the Soave-Redlich-Kwong
(SRK) equation of state is an excellent predictor of phase
equilibrium and thermal properties. However, in stage 4 where the
ammonia is being separated from the recycle gas in flash units, a
more accurate prediction is needed to represent the interaction
between ammonia and the other components in the streams. For
this, a second method is used with user-defined SRK binary
interaction parameters. Figure 2-5 illustrates the Data Entry
Window.
Figure 2-5: Entering Binary Interaction Data

The data used in this case study is defined in Table 2-3 below.

2-12 Ammonia Synthesis Plant February 26, 2014


Table 2-3: SRK Binary Interaction Parameters
Comp i H2 H2 H2 N2 H2 N2 Argon C1
Comp j N2 Argon C1 C1 NH3 NH3 NH3 NH3
kija 0.085 0.0004 -0.2079 0.0204 0.276 0.31 0.3383 0.18
kijb 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0
kijc 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0
UOM R R R R R R R R

Invoking the second thermodynamic set for the ammonia separators


is as simple as selecting the second thermodynamic set from the
Thermodynamic System drop-down window in the Flash drum data
entry window. Figure 2-6 depicts this drop down list with the
available thermodynamic methods.

Figure 2-6: Selecting A Thermodynamic METHOD Set

PRO/II Case Book Ammonia Synthesis Plant 2-13


Stream Data
Feed Streams
The main feed streams - natural gas, steam, and air - are defined in
the normal way by rate, composition, temperature, and pressure. In
addition there is a water feed to the MEA plant which ensures that
the syngas leaves the plant saturated.

Recycle Streams
There is a recycle stream in stage 4. The large flowrate of this
recycle stream relative to the flowsheet feeds and products along
with the fact that the ammonia species is created in the recycle,
necessitates an initial estimate of the rate and composition of the
recycle stream. The stream initial estimates are entered into stream
31R below:

2-14 Ammonia Synthesis Plant February 26, 2014


Other Streams
There are several thermal recycles in this flowsheet. These may be
simulated in one of several different ways:
They can be input as they are and allowed to converge naturally
They can be replaced by simpler units and solved rigorously
after the flowsheet has solved
Or
They may be circumvented by using the REFERENCE
STREAM facility
The reference stream option was chosen in this simulation to
circumvent the thermal recycles. Thermal recycles can be broken
using reference streams because the composition of the stream
remains the same through the thermal recycle loop. The only thing
that changes within the thermal recycle loop is temperature and
pressure. If the temperature an pressure is know elsewhere in the
loop, a reference stream can be used to break the thermal recycle
loop. This will speed up the convergence time of the simulation
without sacrificing accuracy in the results.
In stage 2, the feed to the low temperature shift reactor (stream 13)
is referenced to the high temperature shift product (stream 11). This
defines all the properties of stream 13 as the same as stream 11.
Temperature and pressure are over-written and defined as 400 oF
and 274 psig. Similarly, stream 21 is referenced to stream 19 with a
temperature of 675 oF and a pressure of 254 psig. These reference
streams allow the heat exchangers to be solved separately after
converging the air flowrate controller loop.
Stream 13 is not defined as a product from a unit operation.
However, in stage 4, stream 38B is a unit operation product.
Nevertheless, in order to eliminate a thermal recycle around the
Ammonia Converter, it is referenced to stream 38.

PRO/II Case Book Ammonia Synthesis Plant 2-15


Figure 2-7: Configuring Referencing Streams

This means that stream 38B takes its composition and rate at all
times from stream 38 but its temperature and pressure are calculated
by the heat exchanger from which it is a product.

2-16 Ammonia Synthesis Plant February 26, 2014


Unit Operations for Stage 1 - Catalytic Reforming
Input
Since there is no sulfur in the input, the Desulfurizer RX1 is
modeled as an isothermal flash to set the temperature and pressure
of the reformer feed.
Both the reformers, RX2 and RX3, are modeled as Gibbs Free
Energy reactors with typical temperature approaches specified.
The rate of air feed to the secondary reformer must be such that the
syngas product from stage 2 has the correct nitrogen:hydrogen
ratio. This is achieved by putting a controller on the stage 2
Methanator product and varying the air feed rate to the secondary
reformer. This means that stages 1 and 2 are in a controller loop.

Figure 2-8: Stage 1 Unit Operations - Catalytic Reformng

To satisfy the primary reformer, the molar ratio of steam (stream 5)


to natural gas (stream 1) should be 6:1. The flow rate of the steam
could be set to the correct value in the Stream Data Section.
However, that would involve calculating the molar rate of natural
gas (the stream is known only in volume units) before the
simulation begins. It is much easier to let PRO/II perform that

PRO/II Case Book Ammonia Synthesis Plant 2-17


calculation. Furthermore, allowing PRO/II to perform this
calculation allows the natural gas stream to be changed at any time
(for a turndown case or a different design case) and the steam rate to
be automatically recalculated.

The secondary reformer product (stream 8) is used to preheat the


desulfurizer feed (stream 2). This thermal recycle is not a simple
one in that the process demands a fixed temperature for both the
products from exchanger X-1. This is achieved by dividing the
exchanger into two halves: the cold side is X-1A and is solved
before the desulfurizer; the secondary reformed product is cooled in
H-1, a combination of waste heat boiler WHB1 and the hot side of
X-1.
After stages 1 and 2 have solved, H-1 is divided into WHB1 and the
hot side of X-1 (X-1B). This can be achieved because PRO/II
allows the use of reference streams to link two streams. The define
feature is similar to reference stream feature except that it links unit
operation parameters. The define feature was used to link the duties
from one exchanger to another. In this case stream 8_R1 was

2-18 Ammonia Synthesis Plant February 26, 2014


referenced to stream 8 and the duties for X1-B and WHB1 were
defined as the duties for X-1A and H-1 respectively.
The graphics below illustrate the use of the define feature to line the
duties together.

WHB1's duty is calculated as the difference between the duties of


H-1 and X-1A. X1-B's duty is simply the same as that for X1-A
except with the opposite sign.

PRO/II Case Book Ammonia Synthesis Plant 2-19


Results
The stream calculator determines the steam flowrate as 3952.7 lb
mole/hr which is six times the natural gas flowrate.
Virtually all of the C2 and higher hydrocarbons are broken down in
the primary reformer and converted to hydrogen, carbon monoxide
and carbon dioxide. 58% of the methane in the feed is also
converted. 95% of the residual methane is converted in the
secondary reformer along with the remaining traces of ethane and
propane. All of the oxygen is consumed in the secondary reformer.
The duties of WHB1 and X-1 are 53.62 and 4.17 MM Btu/hr
respectively.

Unit Operations for Stage 2 - Catalytic Shift and


Methanation
Figure 2-9: Stage 2 Unit Operations: Catalytic Shift & Methanation

2-20 Ammonia Synthesis Plant February 26, 2014


Input
Both the High Temperature Shift Reactor (RX4) and the Low
Temperature Shift Reactor (RX5) are modeled by an equillibrium
reactor unit operation using the built-in shift reaction equilibrium
data. They operate adiabatically and the products are assumed to be
at equilibrium.
The MEA plant removes the bulk (99.92%) of the carbon dioxide
from the shift reactor product and is modeled as a stream calculator
(T-1). The treated gas is saturated with water in flash unit SAT and
excess water discharged.
The final part of stage 2 is the Methanator (RX6), modeled by an
equillibrium reactor unit operation using the built-in methanator
and shift reaction equilibrium data. The reactor operates
adiabatically and equilibrium is assumed to be achieved.
The syngas must have a hydrogen:nitrogen molar ratio of 3:1 to
satisfy the stoichiometry of the ammonia reaction. This is
accomplished by inserting a controller to measure that ratio in the
Methanator product and vary the air feed to the Secondary
Reformer until the required ratio is achieved. Thus there is a
significant loop involving most of the units of stages 1 and 2. This
makes it more important for any thermal recycles within that loop to
be eliminated if at all possible.
The thermal recycle in stage 2 of the plant is a complex one,
involving preheating the Methanator feed first with its own product
and then with the RX4 product. This recycle is eliminated by
referencing streams 13 and 21 to bypass these exchangers
completely.
Stream 13 is the same as stream 11 except for its temperature and
pressure, both of which are known. Therefore stream 13 is set in the
Stream Data Section and referenced to stream 11. It gets its rate and
composition from stream 11 and its conditions from the Stream
Data Section.
In the same way, stream 21 is referenced to stream 19.
After the control loop has solved, exchangers X-2, WHB2 and X-3
are solved in the normal way.

PRO/II Case Book Ammonia Synthesis Plant 2-21


Results
The controller solves after 3 trials with an air flowrate of 1008 lb
mole/hr. This produces the required hydrogen:nitrogen ratio in the
product from the methanator.
85% of the carbon monoxide is converted in RX-4 and 93% of the
remainder is converted in RX-5. This gives a concentration of
0.055% carbon monoxide and 11.1% carbon dioxide in the exit gas
from RX-5. The concentration of carbon dioxide is reduced to
0.02% in the MEA Plant.
The final removal of all the carbon monoxide and carbon dioxide is
carried out in the methanator reactor.

2-22 Ammonia Synthesis Plant February 26, 2014


Unit Operations for Stage 3- Compression
Input
The Condensate Separator (D-2) is modeled as a flash unit,
decanting water in a declared water stream and using the PRO/II
built-in water solubility data.

Figure 2-10: Stage 3: Compression Unit Operations

The compressors are modeled as single stage isentropic


compressions with a specified adiabatic efficiency of 95%. Each
one has an aftercooler reducing the product temperature to 95 F.
The first and second compressors also have water decantation
streams to knock out any liquid water that may have condensed in
the aftercoolers. Finally, all the remaining water is removed in a
drying unit (SEP1), modeled as a stream calculator.

Results
The compressor work for the three stages is 1752, 1831 and 1776
HP respectively. The corresponding aftercooler duties are 4.73, 4.70
and 4.35 MM Btu/hr.
Most of the water is removed after the first compressor with a small
amount removed after the second compressor. The final separator
removes all remaining water from the synthesis loop feed.

PRO/II Case Book Ammonia Synthesis Plant 2-23


Unit Operations for Stage 4 Conversion
Figure 2-11: : Unit Operations for Stage 4 Conversion

Input
The fourth compressor (CP-4) is in the ammonia recycle loop. The
loop starts at that unit, stream 31R being the main recycle stream.
An initial estimate for this stream is needed, as discussed in the
Stream Data Section above.
The Ammonia Converter feed is preheated by exchanging inside the
converter with its product stream. This exchanger is modeled
separately in the flowsheet as FDEF. The exchangers before the
separators do not appear on the simulation flowsheet as they are
combined with the separators.
There are two thermal recycles in the loop. The loop involving the
convertor and feed preheater is split by referencing the convertor
feed (stream 38B) to the product from exchanger X-4 (stream 38) in
the Stream Data Section. FDEF is then solved after the convertor
when both feed streams have been calculated.
The loop involving exchanger X-4 is solved explicitly as it appears
in the flowsheet. This involves introducing an inner loop within the
ammonia recycle loop. This loop could also be eliminated by using
the devices mentioned above.

2-24 Ammonia Synthesis Plant February 26, 2014


The Ammonia Converter (RX-7) is modeled using an equilibrium
reactor model with supplied equilibrium data. The Data Entry
Windows (DEWs) that follow were reformatted slightly to fit the
page size of this manual.

Figure 2-12: Ammonia Converter (Reactor) Main Input DEW

PRO/II Case Book Ammonia Synthesis Plant 2-25


Figure 2-13: Ammonia Synthesis Reaction Definitions

Figure 2-14: Reaction Equilibrium Input Data

2-26 Ammonia Synthesis Plant February 26, 2014


The reference condition for heat of reaction data is given as vapor at
800 F and the stoichiometry represents the well-known ammonia
synthesis reaction. The heat of reaction is given as -45.18 thousand
energy units per mole of base component reacted, in this case
nitrogen. The equilibrium constant is a function of temperature
according to the Arrhenius equation:

Ln (Keq) = A + B/T (2-7)


The equilibrium constant is computed at the reaction temperature
minus the approach temperature difference given.
The reactor feed has to contain 12 mole % inerts (argon and
methane). This is achieved by varying the rate of the recycle stream
31R using a controller (CTL1). This action of the controller could
conflict with the recycle convergence because this stream is also the
recycle stream for the main loop. This is avoided by solving the
recycle before the controller is invoked.
To maintain the inerts material balance, a purge is taken off the
recycle stream. Calculator BD-1 computes the purge draw rate.

Figure 2-15: Computing the Recycle Purge Rate

PRO/II Case Book Ammonia Synthesis Plant 2-27


This acts similar to a valve on the purge stream regulating the flow.
The calculator builds a dummy stream 31X consisting of stream 28,
the dry syngas feed to the loop, minus the products from the loop,
streams 32 and 37. The splitter SP1 operates such that the argon rate
in the purge stream 31P is equal to the argon rate in the dummy
stream 31X - in other words equal to the net argon coming in to the
loop. Thus there is an exact argon balance in the loop and there will
be no build up of inerts as the flowsheet recycle solves.

Figure 2-16: Splitter SP1 Material Balance Specification

2-28 Ammonia Synthesis Plant February 26, 2014


Results
The synthesis loop solves with a production of 1539.72 lb mole/hr
of 99.7% purity ammonia. The product compositions are shown in
Table 2-4:Product Stream Compositions. The overall conversion to
ammonia is 98% with a reactor conversion per pass of 27.4% based
on Nitrogen. The recycle stream rate is 10654 lb mole/hr giving a
recycle:feed ratio of 3.3:1. The purge stream is 74.1 lbmol/hr which
is 0.7% of the total recycle flowrate.
Table 2-4: Product Stream Compositions
Component NH3 Product Let Down Gas Purge
Hydrogen 1.69 21.45 42.39

Nitrogen 0.43 6.15 14.38

Argon 0.56 4.05 4.97

Methane 1.92 7.68 6.11

Ammonia 1535.03 33.3 6.27

Rate (lb_mole/hr) 1539.72 72.65 74.12

Temperature (F) 79.4 79.4 85

Pressure (psig) 350 350 4660

PRO/II Case Book Ammonia Synthesis Plant 2-29


Use of the Model in Process Control
Very clear benefits of using a computer model of a Kellogg
Ammonia plant were demonstrated in a paper published in
Hydrocarbon Processing, November 1980. The paper focuses on
the design of control strategies and uses a simulation model to
derive the responses of the plant to different settings of various
parameters.
The parameters that were examined were:
The ratio of synthesis loop recycle rate to fresh syngas
In many plants the fresh syngas feed to the synthesis loop is limited
by front-end restrictions such as insufficient synthesis compressor
power or absorber capacity.
The ratio of nitrogen to hydrogen in the syngas
At constant syngas make-up rates, ammonia production increased
as H/N decreased, but synthesis compressor loadings increased.
Synthesis loop pressure
Production of ammonia increases with increased loop pressure. The
design pressure, constrained by mechanical considerations, is the
limiting factor and the purge system should be operated the keep the
operating pressure just below the design pressure.
The temperature of the synthesizer feed
Production is extremely sensitive to this parameter and an optimum
temperature can be found. The control of this parameter is critical to
the profitability of the plant.
Methane content in syngas
Ammonia production decreases with increasing methane. Improved
primary reformer temperature control can alleviate this problem.
The results of these simulations have been put into practice in a
number of installations and these have consistently led to improved
productivity and higher conversion efficiency.

2-30 Ammonia Synthesis Plant February 26, 2014


Appendix 2-A: Complete Ammonia
Plant Flowsheets

Graphical Representation: Complete Ammonia Plant Flowsheets

PRO/II Case Book Ammonia Synthesis Plant 2-31


Figure 2-17: PRO/II Flowsheet: Processng Sections

Figure 2-18: : Catalytic Reforming

2-32 Ammonia Synthesis Plant February 26, 2014


Figure 2-19: Catalytic Shift and Methanation

Figure 2-20: : Compression Stages

PRO/II Case Book Ammonia Synthesis Plant 2-33


Figure 2-21: Schematic of Conversion Section

2-34 Ammonia Synthesis Plant February 26, 2014


Appendix 2-B: PRO/II Selected Output

The chart below was taken from the PRO/II output file. This depicts
the overall plant mass balance as calculated by PRO/II:
Table 2-5: Product Stream Summary t
Overall Plant Mass
Balance lb/hr lb/hr
Component Feed +Reaction -Product =Deviation % dev

1 h2o 200171.24 -19308.08 180863.16 0.00 0.00


2 o2 6773.16 -6773.16 0.00 0.00 0.00
3 co 11110.16 0.00 11110.16 0.00 0.00
4 co2 51686.75 32899.52 84586.27 0.00 0.00
5 h2 23765.16 124.05 23896.18 0.00 0.00
6 n2 135607.21 -22050.76 113588.40 -6.96 -0.03
7 a 2295.14 0.00 2295.14 -31.95 -0.30
8 c1 9501.45 -8284.17 1219.00 0.00 0.00
9 c2 1475.82 -1475.81 0.01 -1.71 -0.14
10 c3 944.14 -944.14 0.00 0.00 0.00
11 nc4 884.53 -884.53 0.00 0.00 0.00
12 nc5 114.08 -114.08 0.00 0.00 0.00
13 nh3 0.00 26811.15 26817.75 -6.60 0.02

total 444328.83 0.00 444376.06 -47.23 -0.01

The chart below was taken from the PRO/II output file. This depicts
the summary of RX-7,7, the ammonia converter.

Overall Operating Conditions


Reactor Type Adiabatic
Duty, MM Btu/hr 7.08086E-
Total Heat of Reaction at 800.00 F, MM Btu/ 05
hr -35.5038
Inlet Outlet
feed 38b
Vapor Product 29A
Temperature, F 571.29 926.82
Pressure, psig 4760.00 4730.00

PRO/II Case Book Ammonia Synthesis Plant 2-35


Reaction Data
Rates, lb_mole/hr
Fraction
Component Feed Change Product Converted
2 o2 6.14596E-09 0.0000 6.14596E-09
3 co 1.04160E-05 0.0000 1.04160E-05
4 co2 9.67314E-08 0.0000 9.67314E-08
5 h2 8516.0375 -2361.2530 6154.7844 0.2773
6 n2 2875.2775 -787.0843 2088.1931 0.2737
7 a 723.2566 0.0000 723.2566
8 c1 892.0648 0.0000 892.0648
9 c2 1.23713E-03 0.0000 1.23713E-03
10 c3 1.21410E-08 0.0000 1.21410E-08
11 nc4 4.63078E-09 0.0000 4.63078E-09
12 nc5 3.02841E-09 0.0000 3.02841E-09
13 nh3 525.0477 1574.1687 2099.2164

Total 13531.6852 -1574.1687 11957.5165


Base lb_mole/hr Converted
Component reaction converted Fraction(1)

6 n2 1 787.0843 0.2737
Reactor Mass Balance Fraction
Converted
Rates, lb_mole/hr
2 o2 1.96663E-07 0.0000 1.96663E-07
3 co 2.91756E-04 0.0000 2.91756E-04
4 co2 4.25713E-06 0.0000 4.25713E-06
5 h2 17167.3105 -4760.0030 12407.3075 0.2773
6 n2 80546.5254 -22048.9708 58497.5546 0.2737
7 a 28892.6554 0.0000 28892.6554
8 c1 14311.1818 0.0000 14311.1818
9 c2 0.0372 0.0000 0.0372
10 c3 5.35374E-07 0.0000 5.35374E-07
11 nc4 2.69157E-07 0.0000 2.69157E-07
12 nc5 2.18500E-07 0.0000 2.18500E-07
13 nh3 8941.8560 26808.9734 35750.8294

Total 149859.5666 0.0000 149859.5662

2-36 Ammonia Synthesis Plant February 26, 2014


The following pages show selected parts of the stream information
exported to Excel.

Component Rates
Stream ID nat gas 5 7 3IP 39 40
Description nat gas steam air purge LetDwn NH3Prod
Phase vapor vapor vapor vapor vapor liquid
Temperature, F 60.00 950.00 330.00 85.00 79.42 79.42
Pressure, psig 340.00 334.00 289.00 4660.00 350.00 350.00
Molecular Wt. 20.30 18.02 28.96 12.03 14.70 17.00

Component Molar Rates, lb_mole/hr


H2O 3952.7
O2 211.67 0.00 0.00 0.00
CO 0.00 0.00 0.00
CO2 19.43 0.00 0.00 0.00
H2 42.39 21.45 1.69
N2 20.09 786.70 14.39 6.15 0.44
A 9.58 4.97 4.05 0.56
c1 531.97 6.11 7.68 1.92
c2 49.08 0.00 0.00 0.00
c3 21.41 0.00 0.00 0.00
nc4 15.22 0.00 0.00 0.00
nc5 1.58 0.00 0.00 0.00
NH3 6.27 33.28 1535.03

Total, lb-mor/hr 658.79 3952.74 1007.95 74.12 72.61 1539.64


component mole fractions
H2O 1.00
O2 0.21 0.00 0.00 0.00
CO 0.00 0.00 0.00
CO2 0.03 0.00 0.00 0.00
H2 0.57 0.30 0.00
N2 0.03 0.78 0.19 0.08 0.00
A 0.01 0.01 0.06 0.00
c1 0.81 0.11 0.00
c2 0.07 0.00 0.00
c3 0.03 0.00 0.00
nc4 0.02 0.00 0.00
nc5 0.00 0.00 0.00
NH3 0.46 1.00

PRO/II Case Book Ammonia Synthesis Plant 2-37


Stream ID nat gas 5 7
Description nat gas steam air
Phase vapor vapor vapor
Total Stream Properties
Mole Rate LB-MOL/HR 658.79 3952.74 1007.95
Weight Rate lb/hr 13371.05 71209.75 29194.01
Std Liq Rate FT3/HR 607.71 1141.79 536.33
Temperature f 60.00 950.00 330.00
Pressure psig 340.00 334.00 289.00
Molec. weight 20.30 18.02 28.96
Enthalpy MM BTU/HR 1.34 106.60 1.83
btu/lb 100.14 1497.06 62.55
Mole Frac.Liq. n/a n/a n/a
Reduced Temp 1.36 1.21 3.31
Reduced Pres 0.53 0.11 0.56
Acentric Factor 0.03 0.34 0.03
Watson K (UOPK) 17.48 8.76 6.00
Std Liq Density lb/ft3 22.00 62.37 54.43
Spec. Grav. 0.35 1.00 0.87
API gravity 269.59 10.00 30.62
Vapor Phase Properties
rate, mole LB-MOL/HR 658.79 3952.74 1007.95
Rate, Wt. LB/HR 13371.05 71209.75 29194.01
Std. Liq. Rate FT3/HR 9627.93 168399.02 28355.77
Std. vap.Rate FT3/HR 250000.00 1500000.13 382500.00
Spec Gravity
(Air=1.0) 0.70 0.62 1.00
Molec. wt. 20.30 18.02 28.96
Enthalpy BTU/LB 100.14 1497.06 62.55
cp BTU/LB-F 0.51 0.53 0.25
Density LB/FT3 1.39 0.42 1.03
thermal
conductivity BTU/HR-FT-F n/a 0.04 n/a
viscosity cp n/a 0.03 n/a
Liquid Phase Properties n/a n/a n/a

2-38 Ammonia Synthesis Plant February 26, 2014


Stream ID 3IP 39 40
Name purge LetDwn Gas NH3 Prod
phase vapor vapor liquid
Total Stream Properties
Mole Rate LB-MOL/HR 74.12 72.61 1539.64
Weight Rate lb/hr 891.78 1067.09 26211.19
Std. Liq. Rate FT3/HR 37.68 36.41 682.83
temperature f 85.00 79.42 79.42
pressure psig 4660.00 350.00 350.00
Molec. weight 12.03 14.70 17.02
Enthalpy MM BTU/HR 0.07 0.34 1.54
btu/lb 76.90 319.43 58.89
Mole Frac.Liq. n/a n/a 1.00
Reduced Temp 2.92 1.27 0.74
Reduced Pres 10.49 0.38 0.22
Acentric Factor -0.09 0.06 0.25
Watson K 11.88 12.29 12.26
(UOPK)
Std Liq Density lb/ft3 23.67 29.31 38.39
Specific Grav. 0.38 0.47 0.62
API gravity 241.36 169.61 98.40
Vapor Phase Properties
Rate lb_mole/hr 74.12 72.61 n/a
lb/hr 891.78 1067.09 n/a
ft3/hr 105.55 1087.83 n/a
Std. vapor Rate ft3/hr 28127.78 27552.61 n/a
Sp. Gravity n/a
(Air=1.0) 0.42 0.51 n/a
Molec. wt 12.03 14.70 n/a
Enthalpy Btu/lb 76.90 319.43 n/a
cp Btu/lb-F 0.68 0.57 n/a
Density lb/ft3 .45 0.98 n/a
therm conduct. Btu/hr_ft_F n/a n/a n/a
viscosity cp n/a n/a n/a
Liquid Phase Properties n/a n/a n/a

PRO/II Case Book Ammonia Synthesis Plant 2-39


Appendix 2-C:
PRO/II Keyword Input File

TITLE DATE=NH3 SYN


DESC This is the PRO/II simulation file corresponding to the
DESC PRO/II Casebook on Ammonia Synthesis.
DESC For more information on this model
DESC please contact Technical Support DESC
PRINT INPUT=ALL, STREAM=COMPONENT, RATE=M, MBALANCE, ION=NONE
TOLERANCE STREAM=0.0005,-0.1,0.0001,0.001
DIMENSION ENGLISH, PRES=PSIG
SEQUENCE DEFINED=GASHEATER,

X-1A,RX-1,S1,RX-2,RX-3,H-1,RX-4,RX-5, & REB1,CW-1,D-1,T-
1,SAT,RX-6,CT1,X-3,X-2,WHB2,WHB1,X1-B,CW2, & D-2,CP-1,CP-2,CP-
3,SEP1,REFC,CP-4,X-4,M1,D-7,DM2,DM1,RX-7, & FDEF,D-
6,DM3,DM4,BD1,SP1,DUM1,CAL1,DUM2,CTL1,D-8

CALCULATION TRIALS=150, RECYCLE=ALL, COMPCHECK=CALC, DVARI-
ABLE=ON, &

FLASH=DEFAULT, MAXOPS=1000000, CDATA=FIX
COMPONENT DATA
LIBID1,H2O/2,O2/3,CO/4,CO2/5,H2/6,N2/7,A/8,C1/9,C2/10,C3/
11,NC4/ & 12,NC5/13,NH3, BANK=SIMSCI,PROCESS
THERMODYNAMIC DATA
METHOD SYSTEM=SRK, TRANSPORT=NONE, DENSITY(L)=RCK1, &
SET=1, DEFAULT
METHOD SYSTEM=SRK, DENSITY(L)=RCK1, SET=2
KVAL(VLE)
SRK(R) 5,6,0.085,0,0
SRK(R) 5,7,0.0004,0,0
SRK(R) 5,8,-0.2079,0,0
SRK(R) 7,8,0.0204,0,0
SRK(R) 5,13,0.276,0,0
SRK(R) 6,13,0.31,0,0
SRK(R) 7,13,0.3383,0,0
SRK(R) 8,13,0.18,0,0
STREAM DATA
PROPERTY STREAM=1, TEMPERATURE=60, PRESSURE=340, &
PHASE=M, RATE(GV)=250000, &
COMPOSITION(M)=4,2.95/6,3.05/8,80.75/ & 9,7.45/10,3.25/ &
11,2.31/12,0.24
PROPERTY STREAM=5, TEMPERATURE=950, PRESSURE=334, PHASE=M, &

2-40 Ammonia Synthesis Plant February 26, 2014


COMPOSITION(M,LBM/H)=1,1000
PROPERTY STREAM=7, TEMPERATURE=330, PRESSURE=289, PHASE=M, &
RATE(GV)=375000, COMPOSITION(M)=2,21/6,78.05/7,0.95
PROPERTY STREAM=WAT, TEMPERATURE=100, PRESSURE=271, PHASE=M, &
COMPOSITION(M,LBM/H)=1,1000
PROPERTY STREAM=31R, TEMPERATURE=85, PRESSURE=4660, PHASE=M, &
COMPOSITION(M,LBM/H)=5,6000/6,2000/7,300/8,1000/13,700
PROPERTY STREAM=31X, TEMPERATURE=85, PRESSURE=4660, PHASE=M, &
COMPOSITION(M,LBM/H)=7,7
PROPERTY STREAM=36A, TEMPERATURE=40, PRESSURE=4840, PHASE=M, &
COMPOSITION(M,LBM/H)=5,8514.13/7,724.309/2,6.16216E-9/ &
3,1.04288E-5/4,9.6746E-8/6,2874.7/8,893.043/9,0.00123812/&
10,1.21531E-8/11,4.64927E-9/12,3.04016E-9/13,525.107
PROPERTY STREAM=S1, TEMPERATURE=93.719, PRESSURE=4950, &
PHASE=M, &
COMPOSITION(M,LBM/H)=5,8517.75/7,724.917/2,6.18542E-9/ &
3,1.04418E-5/4,1.01574E-7/6,2875.69/8,894.384/9,0.00124165/&
10,1.21867E-8/11,4.65563E-9/12,3.04603E-9/13,902.201
PROPERTY STREAM=13, TEMPERATURE=400, PRESS=274, REFSTREAM=11
PROPERTY STREAM=21, TEMPERATURE=675, PRESS=254, REFSTREAM=19
PROPERTY STREAM=38B, TEMP=571.14, PRESSURE=4760, REFSTREAM=38
PROPERTY STREAM=8_R1, REFSTREAM=8
NAME 1,NAT GAS/5,STEAM/7,AIR/31R,RECYCLE/11,HTS OUT/ &
19,TRTD GAS/ 38,RX FEED/8,SEC REF OUT/6,PR REF OUT/ &
14,LTS OUT
NAME 17,MEA FEED/22,METH PROD/25,SYN GAS/31P,PURGE/ &
31,PRI SEP/ & 36,SEC SEP/39,LETDWN GAS/40,NH3 PROD
RXDATA
RXSET ID=1
REACTION ID=1
STOICHIOMETRY 5,-3/6,-1/13,2
HORX HEAT=-45.108, REFCOMP=6, REFTEMP=800
EQUILIBRIUM A=-32.975, B=22930.4
UNIT OPERATIONS
HX UID=GASHEATER
COLD FEED=1, M=2
OPER DUTY=1.6
HX UID=X-1A
COLD FEED=2, V=3, DP=2
OPER CTEMP=750
FLASH UID=RX-1, NAME=DESULFURIZER
FEED 3
PRODUCT V=4 ISO
TEMPERATURE=740, DP=2
CALCULATOR UID=S1, NAME=STM-GAS FLOW
SEQUENCE STREAM=1,5
PROCEDURE
R(1) = 6.0 * SMR(1) $ CALCULATE STEAM RATE

PRO/II Case Book Ammonia Synthesis Plant 2-41


CALL SRXSTR(SMR,R(1),5) $ SET STEAM TO CALCULATED RATE
RETURN
GIBBS UID=RX-2, NAME=PRI REFORMER
FEED 4,5
PRODUCT V=6
OPERATION DP=45,
TEMPERATURE=1360, ISOTHERMAL
ELEMENTS REACTANTS= 1/3/4/5/8/9/10/11/12
CONVERSION APPROACH=-35
GIBBS UID=RX-3, NAME=SEC REFORMER
FEED 6,7 PRODUCT V=8
OPERATION DP=5, ADIABATIC
ELEMENTS REACTANTS= 1/2/3/4/5/8/9/10/11/12
CONVERSION APPROACH=-35
HX UID=H-1, NAME=COOL REFGAS
HOT FEED=8, M=10, DP=4
OPER HTEMP=675
EQUREACTOR UID=RX-4, NAME=H T SHIFT
FEED 10
PRODUCT V=11
OPERATION ADIABATIC, DP=2 RXCALCULATION MODEL=SHIFT
REACTION SHIFT
EQUREACTOR UID=RX-5, NAME=L T SHIFT
FEED 13
PRODUCT V=14
OPERATION ADIABATIC, DP=2
RXCALCULATION MODEL=SHIFT
REACTION SHIFT
FLASH UID=REB1, NAME=REBOILER
FEED 14
PRODUCT V=15
ADIABATIC DP=4, DUTY=-45
HX UID=CW-1
HOT FEED=15, V=16, DP=2
OPER HTEMP=100
FLASH UID=D-1, NAME=COND SEP
FEED 16
PRODUCT V=17, W=18
ADIABATIC
STCALCULATOR UID=T-1, NAME=MEA COLUMN
FEED 17,1
OVHD V=CO2, DTAD=0
BTMS L=19A, DP=12, TEMPERATURE=100
FOVHD(M) 1,3,0
FOVHD(M) 4,4,0.9992
FOVHD(M) 5,13,0
OPERATION STOP=ZERO
FLASH UID=SAT, NAME=H2O SAT

2-42 Ammonia Synthesis Plant February 26, 2014


FEED 19A,WAT
PRODUCT V=19, W=XS
ISO TEMPERATURE=100
EQUREACTOR UID=RX-6, NAME=METHANATOR
FEED 21
PRODUCT V=22
OPERATION ADIABATIC, DP=2
RXCALCULATION MODEL=METHANATION
REACTION METHANATION
REACTION SHIFT
CONTROLLER UID=CT1
SPEC STREAM=22, RATE(LBM/H), COMP=5,WET, DIVIDE, 7
STREAM=22, RATE(LBM/H), COMP=6,WET, VALUE=3
VARY STREAM=7, RATE(LBM/H)
CPARAMETER IPRINT, NOSTOP
HX UID=X-3
HOT FEED=22, M=23, DP=2
COLD FEED=19, V=20, DP=2
CONFIGURE COUNTER, U=90, AREA=1025
HX UID=X-2
HOT FEED=11, V=12, DP=2
COLD FEED=20, V=21X, DP=2
CONFIGURE COUNTER
OPER CTEMP=675
HX UID=WHB2
HOT FEED=12, V=13X, DP=2
OPER HTEMP=400
HX UID=WHB1
HOT FEED=8_R1, V=9, DP=2
DEFINE DUTY(BTU/HR) AS HX=H-1, DUTY(BTU/HR), MINUS, &
HX=X-1A, DUTY(BTU/HR)
HX UID=X1-B
HOT FEED=9, V=10X, DP=1
DEFINE DUTY(BTU/HR) AS HX=X-1A, DUTY(BTU/HR), TIMES,-1
FLASH UID=CW2
FEED 23
PRODUCT M=24
ISO TEMPERATURE=100
FLASH UID=D-2, NAME=COND SEP
FEED 24
PRODUCT V=25, W=24W
ADIABATIC
COMPRESSOR UID=CP-1, NAME=1ST STAGE
FEED 25
PRODUCT V=26, W=WA1
OPERATION CALCULATION=GPSA, PRES=700, EFF=95
COOLER ACDP=5, ACTEMP=95
COMPRESSOR UID=CP-2, NAME=2ND STAGE

PRO/II Case Book Ammonia Synthesis Plant 2-43


FEED 26
PRODUCT V=27, W=WA2
OPERATION CALCULATION=GPSA, PRES=1950, EFF=95
COOLER ACDP=5, ACTEMP=95
COMPRESSOR UID=CP-3, NAME=3RD STAGE
FEED 27 PRODUCT V=28A
OPERATION CALCULATION=GPSA, PRES=4960, EFF=95
COOLER ACDP=5, ACTEMP=95
STCALCULATOR UID=SEP1, NAME=WATER REMOVL
FEED 28A,1
OVHD L=WA3, TEMPERATURE=95
BTMS V=28, TEMPERATURE=95
FOVHD(M) 1,1,1
FOVHD(M) 2,13,0
OPERATION STOP=ZERO
CALCULATOR UID=REFC, NAME=REF_RATE
SEQUENCE STREAM=31R
DEFINE P(1) AS STREAM=31R, RATE(LBM/H),TOTAL,WET
PROCEDURE
IF (R(1) .GT. 0) GOTO 100
R(1) = P(1)
100 CALL SRXSTR(SMR,R(1),31R)
RETURN
COMPRESSOR UID=CP-4, NAME=RECYCLE COMP
FEED 31R
PRODUCT V=33
OPERATION CALCULAT=GPSA, PRES=4950, EFF=95, WTOL=1E-5
HX UID=X-4
HOT FEED=S1, M=34, DP=50
COLD FEED=36A, V=38, DP=50
CONFIGURE COUNTER
OPER CTEMP=84.999
MIXER UID=M1
FEED 33,28
PRODUCT M=S1
FLASH UID=D-7, NAME=SEC SEP
FEED 34
PRODUCT V=36, L=37
ISO TEMPERATURE=39.999, PRESSURE=4840
METHOD SET=2
FLASH UID=DM2
FEED 36
PRODUCT V=36A
ISO TEMPERATURE=39.999
FLASH UID=DM1
FEED 37
PRODUCT L=37A
ISO TEMPERATURE=39.999

2-44 Ammonia Synthesis Plant February 26, 2014


EQUREACTOR UID=RX-7, NAME=CONVERTER
FEED 38B
PRODUCT V=29A
OPERATION ADIABATIC, PHASE=V, DP=30, TEMP=900
RXCALCULATION MODEL=STOIC
RXSTOIC RXSET=1
REACTION 1
BASE COMPONENT=6
APPROACH DT=20
HX UID=FDEF, NAME=RX EFFL EXCH
HOT FEED=29A, V=29, DP=30
COLD FEED=38, V=38B, DP=30
CONFIGURE COUNTER
OPER HTEMP=430
FLASH UID=D-6, NAME=PRI SEP
FEED 29
PRODUCT V=31, L=32
ISO TEMPERATURE=84.999, PRESSURE=4660 METHOD SET=2
FLASH UID=DM3
FEED 31
PRODUCT V=31A
ISO TEMPERATURE=84.999
FLASH UID=DM4
FEED 32
PRODUCT L=32A
ISO TEMPERATURE=84.999
CALCULATOR UID=BD1, NAME=PURGE RATE
SEQUENCE STREAM=31X
DEFINE P(1) AS STREAM=28, RATE(LBM/H), COMP=7,WET
DEFINE P(2) AS STREAM=32A, RATE(LBM/H), COMP=7,WET
DEFINE P(3) AS STREAM=37A, RATE(LBM/H), COMP=7,WET
PROCEDURE
V(1) = P(1) - P(2) - P(3)
IF (V(1) .LE. 0.001) V(1) = 0.001
CALL SRXSTR(SMR, V(1), 31X)
RETURN
SPLITTER UID=SP1, NAME=PURGE
FEED 31A
PRODUCT M=31P, M=31RA
OPERATION OPTION=FILL
SPEC STREAM=31P, RATE(LBM/H), COMP=7,WET, DIVIDE, &
STREAM=31X, RATE(LBM/H), COMP=7,WET, &
VALUE=1, RTOLER=1E-5
FLASH UID=DUM1
FEED 31RA
RODUCT M=31RB
ADIABATIC
CALCULATOR UID=CAL1, NAME=SET_RATE

PRO/II Case Book Ammonia Synthesis Plant 2-45


SEQUENCE STREAM=31RB
DEFINE P(1) AS CALCULATOR=REFC, R(1)
PROCEDURE
CALL SRXSTR(SMR,P(1),31RB)
RETURN
FLASH UID=DUM2
FEED 31RB
PRODUCT M=31R
ADIABATIC
CONTROLLER UID=CTL1
SPEC STREAM=38,FRACTION, COMP=7,8,WET, VALUE=0.12, &
ATOLER=0.001
VARY CALCULATOR=REFC, R(1), STEPSIZE=10, EST2=10500
CPARAMETER NOPRINT, NOSTOP, ITER=39
FLASH UID=D-8, NAME=LETDOWN
FEED 32A,37A
PRODUCT V=39, L=40
ADIABATIC PRESSURE=350
RECYCLE DATA
ACCELERATION TYPE=WEGSTEIN, STREAM=36A,31R
LOOP NUMBER=1, START=X-4, END=DM2,WEGSTEIN, TOLE=2E-6
LOOP NUMBER=2, START=CP-4, END=DUM2,WEGSTEIN, TOLE=0.0015
END

2-46 Ammonia Synthesis Plant February 26, 2014


Case 3:
Methyl Tertiary Butyl Ether
(MTBE) Plant

Abstract
This casebook demonstrates the use of PRO/II in the simulation of
the synthesis of methyl tert-butyl ether (MTBE). MTBE is used as
an octane enhancer for reformulated gasolines, and is becoming
increasingly important as stricter air pollution control measures are
implemented. A PRO/II simulation model of a typical MTBE plant
is presented here. The process plant includes a reactor along with an
azeotropic distillation column for separation of the MTBE product.
A reactive distillation section is added to the MTBE azeotropic
column in order to increase the overall conversion to MTBE. This is
followed by the methanol recovery section which includes a liquid-
liquid extractor. SIMSCI's SRKM thermodynamic method provides
a good simulation of the VLE fractionators and the VLLE extractor.
The thermodynamics successfully predicts the azeotropic removal
of methanol from the MTBE product stream.

Casebook Highlights
Petrochemicals Application
Stoichiometric Reactor Units
Multi-tray Reactive Distillation Column
Complex Reaction Kinetic Models
Liquid-liquid Extraction Column Using VLLE
Thermodynamics
Column Condenser Modeled as an Attached, Rigorous Heat
Exchanger
Column Tray Rating
Recycle Acceleration Techniques

PRO/II Case Book MTBE Synthesis Plant (Rev. 3) 3-1


Introduction
Methyl tertiary butyl ether (MTBE) is an octane enhancing agent
for unleaded motor gasoline. MTBE is produced from the butylenes
in the product streams of liquid feed ethylene crackers and fluid
catalytic crackers. In some plants, raffinates from butadiene
extraction or catalytic butane dehydrogenation are used to produce
MTBE. MTBE synthesis also offers a method of selectively
removing isobutylene from mixed C4 streams. This enables the
recovery of high purity 1-butene and 2-butene which are superior
sulfuric acid alkylation feedstocks.
MTBE has several desirable properties that makes it a suitable
gasoline additive. The first desirable property is that MTBE has a
low boiling point and an RVP of 8-10 psi. This causes the gasoline
enhanced with MTBE to have a lower vapor pressure. The lower
vapor pressure results in reduced emissions. The second desirable
property is that MTBE has an octane number of approximately 109.
When MTBE is mixed with gasoline, it increases combustion,
without reducing engine power. The third desirable property is that
MTBE increases the front-end octane number which reduces engine
knocking during acceleration. The addition of MTBE to gasolines
also generally implies a reduced aromatic and butane content which
leads to reduced carbon monoxide and hydrocarbon emissions.
The current and future demand for MTBE and other oxygenates for
reformulated gasoline stems from environmental legislation and
restrictions on air pollutant levels. Most US refiners have elected to
use MTBE (and other esters) rather than ethanol (and other
alcohols) as their main oxygenate for reformulated gasoline. Recent
environmental legislation has resulted in an increased demand for
MTBE and other octane-enhancing agents. In Europe, lead-based
gasolines are being phased out, resulting in increasing use of MTBE
and other octane-enhancing agents. MTBE is being phased out in
some areas of the world due to a negative environmental impact.
Ethanol, another octane-enhancing agent, is becoming more
common and is replacing MTBE as the octane-enhancing agent of
choice.

3-2 MTBE Synthesis Plant (Rev. 3) February 26, 2014


Manufacture
There are two principal processes for MTBE synthesis currently in
use. These two processes both produce MTBE by reacting
isobutylenes with methanol using sulfonic ion-exchange resins as
the catalyst. The MTBE product is separated in an azeotropic
distillation column, and the unreacted methanol is recovered and
recycled to the MTBE reactor.

Standard (Hls) Process


The key feature of this process is the fixed bed MTBE reactor used
prior to the azeotropic distillation column. Conversions of
isobutylene to MTBE are in the range 85-95%. It is common that
two reactors are used in tandem, along with a recycle, in order to
increase the overall conversion closer to 99%.

Ethermax Process1
The Ethermax process, developed jointly by UOP Corporation,
Koch Engineering, and Hls AG utilizes a single fixed-bed reactor
followed by a reactive distillation column. In this process, tower
packing that holds the resin catalyst is placed in a section of the
MTBE azeotropic distillation tower. The MTBE reaction is
completed in the column and the product is separated at the same
time. The overall conversion of isobutylene to MTBE can be
improved to 99% or greater with this process, with almost no
increase in capital expenditure. The Ethermax process is the process
that is modeled in this casebook.

Catalyst
A common catalyst for the MTBE synthesis process is the
Amberlyst 15 polymeric catalyst developed by Rohm and Haas.
Approximate properties of the commercial form of this catalyst,
along with suggested operating conditions are provided in Table 3-
1:Approximate Catalyst Properties of Amberlyst 15. For exact
catalyst properties, please contact the manufacturer.
Table 3-1: Approximate Catalyst Properties of Amberlyst 15
Physical form Spherical beads
Ionic form Hydrogen
Acid site concentration 1.8 meg/ml (4.9 meg/g)
Moisture content 53%
Apparent density 770 g/l
Particle size 0.35-1.2 mm

PRO/II Case Book MTBE Synthesis Plant (Rev. 3) 3-3


Shrinkage: Wet to methanol 4%
Wet to MTBE 12%
Porosity 0.30 cc/g
Average pore diameter 250 A
Surface area 45 m2/g
Bulk density 48 lb/ft3
Maximum operating 120 C
temperature
Minimum bed depth 0.61 m
Flowrate, LHSV 1-5 hr-1
Chemical Enginneering Progress, p.15, Aug.1991

Process Overview
There are numerous variations on MTBE plant designs. In general,
an MTBE plant is comprised of the three sections, a reactor section,
a MTBE recovery section, and a methanol recovery section. For the
Ethermax process, the MTBE recovery section includes a second
reaction zone in the distillation column. The complete process flow
diagram for the MTBE reactive distillation plant model used in this
simulation is shown in Figure 3-1.

Reactor Section
MTBE is manufactured by catalytically reacting isobutylene and
methanol in a fixed-bed reactor at a moderate temperature and
pressure. The reaction is exothermic and reversible, and is carried
out in the liquid phase over a fixed bed of ion-exchange resin-type
catalyst. It is highly selective since methanol reacts preferentially
with the tertiary olefin.
In the Ethermax MTBE process, modeled here, an isobutylene-rich
mixed C4 stream is mixed with fresh methanol along with a small
amount of recycle methanol and fed to the reactor section. The
reactors are cooled to under 200 F to prolong catalyst life and to
minimize the undesirable side reactions such as dimerization of
isobutylene.

3-4 MTBE Synthesis Plant (Rev. 3) February 26, 2014


Figure 3-1: Overall MTBE Flowsheet

Reactor Feeds
Table 3-2:Reactor Feed Stream Compositions.contains the
reactor feed composition used in this model.

PRO/II Case Book MTBE Synthesis Plant (Rev. 3) 3-5


Table 3-2: Reactor Feed Stream Compositions.
Stream Name C4 Methanol Methanol
Stream Number Feed 2 Feed 1 Recycle 20
Flowrate (kg-mol/hr) 850 277.5 4.3
Temperature (C ) 16 16 44
Pressure (kPa) 1620 1620 1724
Component Mole %
N-butane 9.0 0.0 0.0
Isobutane 41.0 0.0 0.0
1-butene 7.0 0.0 0.0
Cis 2-butene 4.0 0.0 0.0
Trans 2-butene 6.0 0.0 0.0
Isobutylene (IBTE) 33.0 0.0 0.0
MTBE 0.0 0.0 0.0
Tert-butanol (TBA) 0.0 0.0 0.0
Water 0.19 0.0 6.98
Di-isobutylene (DIB) 0.0 0.0 0.0
Methanol (MEOH) 0.0 100 93.02
The methanol-to-isobutylene ratio in the reactor feed is kept low to
minimize the costs of recovering unreacted methanol, and to
facilitate the operation of the MTBE column which will be
discussed later. Generally, this ratio is maintained close to 1:1.
An isobutylene conversion to MTBE of 90 to 93% is easily
achieved in the reactor. Overall isobutylene conversions higher than
those obtained in the standard process can be achieved by either
recycling a portion of the MTBE column overhead product, or by
providing a second reactor unit and MTBE column downstream of
the first MTBE column. The cost-effectiveness of these options
vary from plant to plant, but both require greater capital
expenditure. In the reactive distillation process, no major increase
in capital expenditure is required and overall isobutylene
conversions of over 99% are easily obtained.
Any water in the reactor feed (from recycle methanol) is instantly
converted to t-butanol. Another impurity, di-isobutylene, is formed
by the dimerization of isobutylene. While the formation of di-
isobutylene and t-butanol should be minimized, their presence in
small concentrations in the MTBE product is acceptable since these
byproducts also have very high octane numbers.

3-6 MTBE Synthesis Plant (Rev. 3) February 26, 2014


Table 3-3:Primary Reactions shows the three main reactions used
in the stoichiometric reactor model. The base component and the
fraction converted are also shown.
Table 3-3: Primary Reactions
Base
Reaction Component Conversion %
2 (IBTE) = DIB IBTE 0.25
H2O + IBTE = TBA H20 100.00
IBTE + MEOH = MTBE MEOH 93.0

MTBE Recovery Section


In the Hls process, the reactor products are processed in the MTBE
column where MTBE, along with t-butanol, dimerized butylene,
and a trace amount of methanol, are removed as the bottoms
product. In the Ethermax process, further reaction of the
isobutylene to MTBE takes place in a section of the distillation
column containing the catalyst resin in tower packing. The MTBE
is removed as the bottoms product in a manner similar to the
standard process. The MTBE product is greater than 99.5% pure
and requires no further purification.
The key to operating the MTBE column is to have a sufficient
amount of C4s in the column feed to form azeotropes with the
methanol in the feed. Conversely, if a proportionately large amount
of methanol is present in the column feed, it may result in
breakthrough of methanol with the MTBE bottoms product.
Therefore, suitable azeotrope formation is possible only when a
limited excess of methanol is used in the reactor feed. In this
manner, unreacted methanol, which has a higher boiling point than
MTBE, is fractionated away from the MTBE bottoms. The
overhead product containing non-reactive linear butenes, iso and
normal butanes, and unreacted methanol and isobutylene, is sent to
the methanol recovery section.

Methanol Recovery Section


In the methanol recovery section, the MTBE column overhead
product is water washed to extract methanol. This unit is simulated
as a liquid-liquid extraction column. The raffinate, which contains
less than 10 ppm methanol, is suitable for recovering high purity C4
isomers, or as a feed to an alkylation unit.

PRO/II Case Book MTBE Synthesis Plant (Rev. 3) 3-7


The extract phase which contains water, methanol and small
amounts of dissolved hydrocarbons is warmed and flashed to
remove the hydrocarbons. The resultant methanol-water mixture is
fractionated to recover methanol as the overhead product. The
methanol (with a trace of water) is recycled to the MTBE reactor.
The wash water stream from the bottoms, along with a small
amount of makeup water, is returned to the water wash column.

Process Simulation
General Data
SI units are used in this simulation. The total calculation sequence
is specified, as shown in Figure 3-2. The calculator CAL0 is
processed before the MTBE column in order to set the reaction
factor equal to 1.0 on the first pass through the flowsheet.
Figure 3-2: Specifying Calculation Sequence

3-8 MTBE Synthesis Plant (Rev. 3) February 26, 2014


PRO/II includes a summary of the overall flowsheet mass balance
when that option is activated in the Miscellaneous Report Options
menu. Figure 3-3 illustrates the Miscellaneous Options DEW.
Figure 3-3: Including Material Balance in Report

Component Data
All components in the simulation are available in the PRO/II
databanks.

PRO/II Case Book MTBE Synthesis Plant (Rev. 3) 3-9


Thermodynamic Data
The VLE fractionators are simulated well with PRO/II's modified
Soave-Redlich-Kwong (SRKM) equation of state method. For this
method, PRO/II contains extensive, built-in databanks that
encompass binary interaction parameter data for the majority of
component pairs present in this simulation. In this casebook,
however, binary interaction data (kijs) are directly supplied for 8
component pairs to improve the accuracy of the separations in the
columns. The binary interaction parameters are listed in Table 3-
4:Binary Component Interaction Data .. The thermodynamic set
used for VLE thermodynamics is referred to as SRKM_VLE
Table 3-4: Binary Component Interaction Data .
Comp i NC4 1BUTENE BTC2 BTT2
Comp j TBA MEOH MEOH MEOH
kija 0.046993 0.136 0.136 0.136

kjia 0.12603 -0.0323 -0.0323 -0.0323

kijb 0.0 0.0 0.0 0.0

kjib 0.0 0.0 0.0 0.0

UOM K K K K

Binary Component Interaction Data (continued) .


Comp i IBTE MEOH TBA MTBE
Comp j MEOH TBA H20 DIB
kija 0.13553 -0.073971 -0.145 0.05785

kjia -0.032271 -0.055222 -0.253 -0.0093

kijb 0.0 0.0 0.0 -10.144

kjib 0.0 0.0 0.0 6.17

UOM K K K K

Figure 3-4 illustrates the data Entry Window to use for entering this
data.

3-10 MTBE Synthesis Plant (Rev. 3) February 26, 2014


Figure 3-4: PRO/II Binary Interaction Data Entry Window

Transport properties are needed in order to use the rigorous heat


exchanger model in the MEOH recovery section. Transport
property calculations are set to pure-component averages by default
and can be modified by modifying the thermodynamic method of
choice. Modification is not required in this simulation, as pure-
component averages should be used.
The liquid extraction unit is simulated using the SRKM method for
VLLE thermodynamics with binary interaction data again supplied
as part of the input. The thermodynamic set used for VLE
thermodynamics is referred to as SRKM_VLLE. Note that the
L1KEY component (i.e., the predominant component in the L1
liquid phase) is specified as n-butane. The L2KEY component is
specified to be water.
Figure 3-5 illustrates explicitly specifying the light and heavy key
components for determining liquid phases. This eliminates the need

PRO/II Case Book MTBE Synthesis Plant (Rev. 3) 3-11


for PRO/II to find an appropriate immiscible pair, reducing the
computation time. All the azeotropes are properly predicted.
Figure 3-5: Specifying LLE Key Components

3-12 MTBE Synthesis Plant (Rev. 3) February 26, 2014


Stream Data
Feed Stream
The mixed C4 feed stream, and the methanol feed stream are
specified in the normal manner, using the compositions and stream
conditions given in Table 3-2:Reactor Feed Stream
Compositions..

Recycle Stream
The composition of the recycle methanol-water stream from the
MEOH recovery section is estimated initially for the first run
through the flowsheet (see Table 3-2:Reactor Feed Stream
Compositions.)
Figure 3-6: Typical Stream Input Data

The amount of wash water in stream 10 (the feed to column T-2) is


provided. The temperature and pressure of the cooling water stream
(CW) for the condenser for column T-3 is provided, along with an
estimate of the flowrate. An estimated value is given for the
flowrate of the make-up water stream, MKUP.

PRO/II Case Book MTBE Synthesis Plant (Rev. 3) 3-13


Unit Operations
MTBE Reaction
The MTBE reaction section of the plant is shown in With reference
to the previous figure, mixed C4s (stream 2) are combined with
fresh methanol (stream 1) and recycle methanol (stream 20) and
pre-heated in a heat exchanger (HX-1) to 43.5 C. The heated feed
(stream 3) is then sent to a conversion reactor (RX-1) which is
maintained at 55 C by circulating a coolant. A pressure drop of 69
KPa through the reactor is also specified..
Figure 3-7: MTBE Reaction Section

With reference to the previous figure, mixed C4s (stream 2) are


combined with fresh methanol (stream 1) and recycle methanol
(stream 20) and pre-heated in a heat exchanger (HX-1) to 43.5 C.
The heated feed (stream 3) is then sent to a conversion reactor (RX-
1) which is maintained at 55 C by circulating a coolant. A pressure
drop of 69 KPa through the reactor is also specified.
Since this is a conversion reactor, the three reactions defined in
Table 3-3 on page 3-7 take place in this reactor at the specified
conversion levels. The extents of reaction are defined based on the
values in Table 3-3. Figure 3-8 illustrates the Data Entry Window
used to enter the extent of reaction data.

3-14 MTBE Synthesis Plant (Rev. 3) February 26, 2014


Figure 3-8: Extent of Reaction Data Entry Window

Figure 3-9 illustrates the Data Entry Window available to enter the
stoichiometries of the major and minor reactions in the process.
Figure 3-9: Reactrion Definition Data Entry Window

PRO/II Case Book MTBE Synthesis Plant (Rev. 3) 3-15


MTBE Distillation and Recovery
The MTBE distillation and recovery section of the plant is shown in
Figure 3-10: : MTBE Distillation and Recovery Section.
Figure 3-10: : MTBE Distillation and Recovery Section

The reactor product (stream 4) exchanges heat with the MTBE


column bottoms product in exchanger HX-2. Normally, this would
create a thermal calculation loop. To avoid the loop, this simulation
models it using two separate heat exchangers, HX-2A and HX-2B,
as shown in Figure 3-10. Stream 4 (from the reactors) is heated in
HX-2A to produce stream 5. Since the temperature of stream 5 is
known to be to 72 C, it is used as the performance specification of
exchanger HX-2A. Specifically, the cold-side outlet temperature is
specified to be 72 C.
The product of column T-1, stream 7, is cooled in exchanger HX2-
B to produce the MTBE product stream 8. Since this physically is
the hot side of exchanger HX-2, The duty of exchanger HX-2B is
defined to be equal to the duty in HX-2A, as shown in Figure 3-11.
Figure 3-11: Applying HX-2A Duty to Exchanger HX-2B

3-16 MTBE Synthesis Plant (Rev. 3) February 26, 2014


This approach avoids an unnecessary calculation loop since the
temperature of stream 5 is fixed at 72 C.The heated stream 5 is fed
to tray 15 of the 30 tray MTBE column (T-1).

MTBE Distillation Column


The MTBE column is simulated with the CHEMDIST algorithm.
The main column DEW is illustrated in Figure 3-12. Additional
Data Entry Windows for specific data are accessible by clicking the
mouse on the various buttons that comprise the column schematic.
Not all the DEWs are illustrated in this description.
Figure 3-12: Main Data Entry Window for A Column

This simulation uses the SIMPLE initial estimate generator (IEG).


A top pressure of 621 KPa and a column pressure drop of 76.5 KPa
are given. The condenser is operated at a fixed temperature of 43.5
C and pressure of 621 KPa.
The control specifications are a bottoms flowrate of 278 kgmoles/hr
and a reflux ratio of 1.1. The condenser and reboiler duties are
varied to achieve these specifications. Figure 3-13 illsatrates the
data entry window used to enter these specifications anc variables.

PRO/II Case Book MTBE Synthesis Plant (Rev. 3) 3-17


Figure 3-13: \MTBE Column Specifications & Variables

The next step is to provide all the information required for


specifying the reaction trays in the distillation column.

Implementing Reactive Distillation


One way to visualize the reaction zone of a distillation column is as
a series of boiling-pot reactors. On each reaction tray sits a bed of
solid catalyst. Each tray is connected to the next in the forward
direction (down the column) by the flow of liquid from one tray to
the next, and in the reverse direction by the vapor flow moving up
from one tray to the previous tray.
For the reactive distillation process, the reaction zone (trays 8
through 13) is specified in the column data entry window
illustrated in Figure 3-14.

3-18 MTBE Synthesis Plant (Rev. 3) February 26, 2014


Figure 3-14: Assigning Reactions to Column Trays

Additionally, the liquid volume of each of the reaction trays is


specified using the Reaction Volumes button to open the Tray
Effective Reaction Volumes DEW shown in Figure 3-15.
Figure 3-15: Specifying Tray Reaction Volumes

PRO/II Case Book MTBE Synthesis Plant (Rev. 3) 3-19


Also, the concentration of the dry catalyst (GCAT, in g/l) may be
specified. This simulation uses a value of 360.0 (g/l). To do this:
Press the Subroutine/Procedures ... button in the Options
section of the Reaction Selection DEW (see Figure 3-14). This
opens the User Subroutine and Procedure data entry window
shown in Figure 3-16.
Figure 3-16: Specifying Concentration of Dry Catalyst

3-20 MTBE Synthesis Plant (Rev. 3) February 26, 2014


In the Procedure Data group, press the DEFINE ... button to
open the Definition DEW shown in Figure 3-17.
Figure 3-17: Setting Catalyst Concentration Using Define

A value of 360 g/l is given for GCAT to represent commercial


catalyst loadings (corresponding to a wet catalyst density of 770 g/l
at 53% moisture content - see Table 3-1:Approximate Catalyst
Properties of Amberlyst 15).
The reaction factor, RXFACT, is used to demonstrate how the
reaction rate in the simulation model can be varied to match data
from an actual plant. For this casebook, RXFACT is set equal to
1.0, indicating that the reaction rate has not been adjusted. Refer to
Figure 3-18.
Figure 3-18: Define Reaction Factor

PRO/II Case Book MTBE Synthesis Plant (Rev. 3) 3-21


MTBE Kinetic Model
The algorithm used for the reactive distillation column model is a
Newtonian-based algorithm. Therefore, in order to accurately
model the MTBE reaction in the distillation column, we need to
determine not only the reaction rate of the reaction, but also the
temperature and composition derivatives of the rate. These
derivatives may be generated numerically by an estimation method,
or analytically by an expression based on the reaction rate equation.
PRO/II automatically generates numerical estimates for the reaction
rate derivatives. In many cases, this is sufficient. However, certain
reactions require the use of more accurate analytical derivatives that
provide better solutions. Reactions requiring these more accutate
analytical derivatives include: reversible reactions, exothermic
reactions, and/or reactions where the equilibrium is sensitive to
temperature.
The MTBE reactions fit all three of the reaction types, requiring the
use of analytical derivatives. The reaction rate expression and its
analytical derivatives can be easily and readily entered by the user
in the Procedure Data category of input. The MTBE reaction rate
expression used in this simulation model is based on the rate
expression described in a paper by Al-Jarallah1. In this casebook,
we will detail how to enter the reaction rate and the associated
analytical derivatives for the MTBE reaction.
First, in the Reaction Data category of input, the stoichiometry of
the forward reaction is given (IBTE + MEOH = MTBE). This is
represented as equation 3 in Figure 3-9, Reactrion Definition Data
Entry Window on page 3-15. The equation is:
C 4 H 8 + CH 4 O = C 5 H 12 O (3-1)
The kinetic data is provided later, in the Procedure Data category of
input using FORTRAN-like language as the procedure named
ALJD.
The reaction rate equation described by Al-Jarallah takes into
account the forward and the reverse reaction. We have modified Al-
Jarallah's rate equation for this casebook to simulate the effect of
catalyst loading on the reaction rate. This was achieved by

1.Adnan M. Al-Jarallah, Mohammed A. B. Siddiqui, and A. K. K. Lee, "Kinetics


of Methyl Tertiary Butyl Ether Synthesis Catalyzed by Ion Exchange Resin
Canadian Journal of Chemical Engineering (66) pp. 802-807

3-22 MTBE Synthesis Plant (Rev. 3) February 26, 2014


removing the catalyst terms from the concentration terms. The
modified reaction rate is given by:
C C1.5
C A C B0.5 --------- -
K eq
:r s = k s K a -------------------------------------------------------- (3-2)
1 + K A C A + K B C b 1.5

where:
ks = surface reaction rate constant = 1.2x1013 exp(- 87900/RT)
in (gmole/g catalyst)1.5/hr, (1a)
Ka = equilibrium adsorption constant = 5.1x10-13 exp(97500/
RT) in g catalyst/gmole, (1b)
KC = equilibrium adsorption constant = 1.6x10-16
exp(119000/RT) in g catalyst/gmole , (1c)
Keq = equilibrium constant
CA = IBTE concentration in mole/l
CB = MEOH concentration in mole/l
CC = MTBE concentration in mole/l

Kinetic Data
The procedure data used in the reactive distillation column model is
entered in the Kinetic Procedure data entry window shown below.
Figure 3-19: User-Defined Kinetics Calculation Procedure.

PRO/II Case Book MTBE Synthesis Plant (Rev. 3) 3-23


The entire code will be shown below along with a description of
purpose. The first portion of the defines real and integer variables.
REAL KS, KA, KC, KALJ, KREH1, KREH2, KIZQ, KEQREF
INTEGER IBTE , MEOH , MTBE
Next, the indices for the components are set, a value is given for the
gas constant in J/gm-mole K, and the basis for the temperature
values in the procedure is set to an absolute basis. In addition, the
temperature and composition rate derivatives are initially set equal
to zero.
$ INITIALIZE DATA:
$ SET INDEXES FOR COMPONENTS
$ DEFINE GAS CONSTANT IN JOULES/GM-MOLE K
$ NOTE: R COULD HAVE BEEN RETRIEVED IN INPUT UNITS BY R=RGAS.
$ HOWEVER, SINCE THE REACTION BASIS WON'T CHANGE, AND
$ RGAS WILL CHANGE WITH THE DEFAULT UNITS, THIS
$ ELIMINATES ONE POSSIBLE SOURCE OF ERROR..
$ INITIALIZE THE LOCAL VARIABLE TK TO THE ABSOLUTE TEMPERATURE.
$ NOTE: THE TEMPERATURE BASIS FOR THE FLOWSHET MUST BE
$ CELSUIS or KELVIN.
$ SET TEMPERATURE AND COMPOSITION DERIVATIVES TO ZERO.
$
IBTE = 6
MTBE = 7
MEOH = 8
$
R = 8.314
$
TK = RTABS
$
DO 1000 I1 = 1,NOR
DRDT(I1) = 0.0
DO 1000 I2 = 1,NOC
1000 DRDX(I2,I1) = 0.0
The surface reaction rate constant, ks, and the equilibrium
adsorption constants, KA, and KB, are calculated using the
expressions given previously as (1a), (1b), and (1c).
$
$CALCULATE THE SURFACE REACTION RATE CONSTANT, KS, AND THE
$EQUILIBRIUM ADSORPTION CONSTANTS KA AND KB. THE ACTIVATION
$ENERGY IS IN J/GM-MOLE.
$UNITS: KS - (GM-MOLE / GM CATALYST)**1.5 /HOUR
$KA - GM-CATALYST / MOLE
$KC - GM-CATALYST / MOLE
$
KS = 1.2E+13*EXP(-87900.0/(R*TK))
KA = 5.1E-13*EXP( 97500.0/(R*TK))
KC = 1.6E-16*EXP(119000.0/(R*TK))

3-24 MTBE Synthesis Plant (Rev. 3) February 26, 2014


Next, the derivatives of these constants are computed and are used
later on in calculating the rate derivatives.

DKSDT = KS * 87900.0 / R / (TK*TK)


DKADT = KA * (-1.0) * 97500.0 / R / (TK*TK)
DKCDT = KC * (-1.0) * 119000.0 / R / (TK*TK)

Then the bulk concentration of components A, B, and C per gram


of catalyst (RHOA, RHOB, and RHOC) are determined from the
liquid mole fractions of the components (XLIQ), the density of the
liquid, and the catalyst loading (GCAT) in g/l. Note that the liquid
density, DENS, obtained directly from PRO/II using the predefined
variables, RLMRAT and RLVRAT, is in the user-specified units of
kg-moles/m3 (SI units). Our basis for calculations is gm-moles/l
and the conversion factor between these kg-moles/m3 and gm-
moles/l is 1.0. Also, note that the value of GCAT used here is 12.4
g/l. This value is used because it is the catalyst loading at which
data for the Al-Jarallah rate equation was collected.
$
$ ---- CALCULATE THE EQUILIBRIUM CONSTANT.
$
$ UNITS - (GM-MOLES/GM-CATALYST)/HOUR
$ PHASE - LIQUID PHASE REACTION
$ CATALYST - ION EXCHANGE RESIN AMBERLYST 15,
$ THE EQUILIBRIUM SHOULD BE INDEPENDANT OF THE CATALYST
$
$ -- METHOD 1.0: ADNAN M. AL-JARALLAH, MOHAMMED A. B. SIDDIQUI, AND
$ A. K. K. LEE, "KINETICS OF METHYL TERTIARY BUTYL
$ ETHER SYNTHESIS CATALYZED BY ION EXCHANGE RESIN"
$ CANADIAN JOURNAL OF CHEMICAL ENGINEERING (66)
$ PP. 802-807
Expressions for the equilibrium constant and its derivative as
functions of temperature are provided based on equilibrium data
published by Al-Jarallah et al.
$
KALJ = EXP(-17.31715+(7196.776/TK))
$
DKALJDT = - KALJ * 7196.776 / (TK*TK)
Then the reaction rate and rate derivatives with respect to
temperature and composition are determined.
$
$ BULK CONCENRATIONS OF COMPONENTS PER GRAM OF CATALYST,
$ XLCONC IS IN MOLES/FLOW VOLUME.
$ XLCONC WILL BE PASSED TO THE PROCEDURE

PRO/II Case Book MTBE Synthesis Plant (Rev. 3) 3-25


$ IN USER INPUT UNITS. INTERNALLY TO PRO/II, IT IS IN SI UNITS
$ (KG-MOLE/CUBIC METER). THE BASIS FOR THESE REACTION EQUATIONS
$ IS GM-MOLES/LITER. THE CONVERSION FACTOR FROM INPUT UNITS OF
$ KG-MOLES/CUBIC METER TO THE REACTION BASIS OF GM-MOLES/LITER
$ IS ONE. THEREFORE, XLCONC CAN BE USED WITH NO CONVERSION.
$
$ RHOA=(XLCONC(MEOH)/GCAT) |-THIS SHOULD BE EQUIVALENT TO BELOW.
$ RHOB=(XLCONC(IBTE)/GCAT) | IT HAS BEEN WRITTEN EXPLICITLY BELOW
$ RHOC=(XLCONC(MTBE)/GCAT) | TO MAKE IT OBVIOUS HOW TO DO THE
$ ANALYTICAL DERIVATIVES.
$
$ CALCULATE DENSITY IN MOLES / VOLUME
$
GCATX = 12.4
DENS=RLMRAT/RLVRAT
RHOA=(XLIQ(MEOH)*DENS/GCATX)
RHOB=(XLIQ(IBTE)*DENS/GCATX)
RHOC=(XLIQ(MTBE)*DENS/GCATX)

$
$ ---- CALCULATE REACTION RATE AND DERIVATIVES BY TERMS
$ ---- UNITS - RATE - GRAM-MOLE / GRAM CATALYST / HR.
$
$ DENOMINATOR & DERIVATIVES.
$
RDEN = 1.0 + (KA*RHOA)+ 0.0 +(KC*RHOC)
DRDDT = RHOA*DKADT + 0.0 + RHOC*DKCDT
DRDDME = KA/GCATX*DENS
DRDDIB = 0.0
DRDDMT = KC/GCATX*DENS
$
$ FIRST FACTOR IN RATE EQUATION.
FACT1 = KS *KA/RDEN
DFAC1DT = DKSDT*KA/RDEN + KS*DKADT/RDEN - KS*KA/RDEN**2 * DRDDT
$
$ SECOND FACTOR IN RATE EQUATION.
FACT2 = RHOA*RHOB**0.5 - RHOC**1.5/KALJ
DFAC2DT = 0.0 + RHOC**1.5/KALJ**2 * DKALJDT
$
$ COMBINE TERMS TO CALCULATE RATE AND DERIVATIVES.
$
$ -- RATE EQUATION (RATE PER ONE GRAM OF CATALYSIS).
RATE = FACT1 * FACT2
$
$ -- RATE TEMPERATURE DERIVATIVE.
DRDT(1) = DFAC1DT * FACT2 &
+ FACT1 * DFAC2DT

$ -- RATE COMPOSITION DERIVATIVES.


DRDX(MEOH,1) = -KS*KA/RDEN**2 * DRDDME * FACT2 &
+ FACT1 * (RHOB**0.5/GCATX*DENS)
DRDX(IBTE,1) = -KS*KA/RDEN**2 * DRDDIB * FACT2 &
+ FACT1 * (RHOA/2.0/RHOB**0.5/GCATX*DENS)

3-26 MTBE Synthesis Plant (Rev. 3) February 26, 2014


DRDX(MTBE,1) = -KS*KA/RDEN**2 * DRDDMT * FACT2 &
- FACT1 * (1.5* RHOC**0.5/GCATX/KALJ*DENS)
It is important to note, however, that the rate and rate derivatives
calculated above are computed on a basis of 1 gram of catalyst.
The reactive distillation algorithm requires that these values
(RRATES, DRDT, and DRDX) be supplied on a unit reaction
volume basis. Therefore, the rate and rate derivatives are multiplied
by the grams of catalyst per unit volume, GCAT.
$
$ ---- CONVERT RATE EQUATION AND DERIVATIVES TO A STRAIGHT
$ VOLUME BASIS BY MULTIPLING THE BASE RATE BY THE GRAMS OF
$ CATALYST/UNIT VOLUME.
$ ---- THE RATE IS RETURNED IN INPUT UNITS, KG-MOLES/CUBIC METER/
$ HOUR.
$
RRATES(1) = GCAT * RXFACT * RATE
DRDT(1) = GCAT * RXFACT * DRDT(1)
$
DRDX(MEOH,1) = GCAT * RXFACT * DRDX(MEOH,1)
DRDX(IBTE,1) = GCAT * RXFACT * DRDX(IBTE,1)
DRDX(MTBE,1) = GCAT * RXFACT * DRDX(MTBE,1)

RETURN

Once the column converges, the top and bottom product


compositions are known. Exchanger (HX-2B) then is simulated for
heat exchange between the column feed (see HX-2A) and the
bottom product (stream 7). The duty in this exchanger is set equal to
the duty in exchanger HX-2A. The cooled hot side fluid is the
MTBE product (stream 8).
Pump P-1 pumps the liquid distillate (stream 6) at a pressure of 827
KPa to the methanol recovery section.
A calculator (CONVERSION) is set up to compute the conversions
of IBTE and MEOH to MTBE in the reactive distillation column
itself. Figure 3-20 and Figure 3-21 illustrate some of the data Entry
Windows for the calculator.

PRO/II Case Book MTBE Synthesis Plant (Rev. 3) 3-27


Figure 3-20: Conversion Calculator Procedure

Figure 3-21: Declaration of Results From Conversion Calculator

3-28 MTBE Synthesis Plant (Rev. 3) February 26, 2014


Methanol Recovery
The methanol recovery section of the process is shown in Figure 1:
MTBE Distillation and Recovery Section.

Figure 1: MTBE Distillation and Recovery Section


The methanol-C4s azeotrope (stream 6P) is delivered by pump P-1
to heat exchanger HX-3 where it is cooled to 38 C against cooling
water (CW). The exchanger also calculates the utility (CW)
requirement given a CW delivery temperature of 16 C and a return
temperature of 32 C. The cooled process stream is fed to the
bottom of the water wash column (T-2).

PRO/II Case Book MTBE Synthesis Plant (Rev. 3) 3-29


Column T-2 is simulated as a liquid-liquid extractor with 5
theoretical trays. Recirculating wash water is fed to the top of the
column. A top pressure specification of 792 KPa is given. This
column uses the VLLE SRK thermodynamic set (SRKM_VLLE)
defined previously in the Thermodynamic Data Category of the
input file.
The raffinate leaves the top of the column (stream 11) and contains
the unreacted and non- reactive C4s. The extract phase (stream 12)
exits at the bottom. It enters the cold side (HX4A) of the feed-
bottoms heat exchanger where it is warmed to 99 C against the
recycle wash water (stream 21) which in turn is cooled (in unit HX-
4B described later on).

Valve V-1 drops the pressure of the heated methanol-water stream


(13) to 241 KPa generating a mixed phase stream (14) which is
adiabatically flashed in unit D-1. The vapor phase (stream 15)
containing the dissolved hydrocarbons which have been released is
vented as a flare gas; the liquid phase (stream 16) is pumped (P-2)
to the methanol column to recover methanol.
The methanol column (T-3) is simulated with 20 theoretical trays.
The feed (stream 17) enters on tray 10. Figure 3-22 illustrates the
main data entry window for this column. The column top pressure
is 138 KPa, and the pressure drop through the column is 34.5 KPa.

3-30 MTBE Synthesis Plant (Rev. 3) February 26, 2014


Figure 3-22: Column T-3 Main Data Entry Window

The column has asub-cooled, fixed temperature condenser that


operates at 30 C and 103.5 kPa. Figure 3-23 illustrates supplying
the condenser data.
Figure 3-23: Column T-3 Condenser DEW

PRO/II Case Book MTBE Synthesis Plant (Rev. 3) 3-31


The separation of methanol from water is readily solved using the I/
O algorithm and conventional IEG. The performance specifications
are 99.5% recovery of methanol in the overhead product and
99.95% recovery of water in the bottoms product. Tray rating
calculations are done for this column for 610 mm diameter sieve
trays throughout the column. Note in Figure 3-24 that one variable
is required for each of the two specifications.
Figure 3-24: Column T-3 Performance Specifications

Make-up Water Calculations


A calculator (CAL1) computes the total loss of water as a result of
carry over with the C4s (stream 11), the vent gas (stream 15) and by
consumption in the reactor. This total quantity is the amount of
make-up water required. The flowrate of the make-up water stream
(MKUP) is established through a procedure call to the PRO/II
stream function SRXSTR. The main data window that specifies this
calculator appears in Figure 3-25.

3-32 MTBE Synthesis Plant (Rev. 3) February 26, 2014


Figure 3-25: Data Entry for Make-up Water Calculator

Pump P-4 pumps the recovered wash water from the methanol
column bottoms combined with make-up water as stream 21 to heat
exchanger HX4B. This unit represents the hot side of the exchanger
HX-4 (see HX-4A described previously) and calculates the exit
temperature for stream 22.
Trim cooler (HX-5) further cools the wash water (stream 22) to the
desired temperature of 38 C before it (stream 10) goes back to the
water wash column. At this stage, the first recycle loop between
unit T-2 (water wash column) and HX-5 (trim cooler) is closed.
The second recycle loop between unit HX-1 (feed heater) and P-3
(recycle pump) is closed when the pump P-3 recycles the overhead
(stream 19) from the top of the methanol column (T-3) to the reactor
section.

PRO/II Case Book MTBE Synthesis Plant (Rev. 3) 3-33


Rating the Methanol Column (T-3) Condenser
As an illustrative example, a rigorous heat exchanger (RC-1) is
used to rigorously rate the methanol column condenser. This
rigorous heat exchanger is modeled as an attached heat exchanger
to column T-3. Figure 3-26 illustrates the main data entry window
of this exchanger.
Figure 3-26: Rigorous Heat Exchanger RC-1 Main DEW

This unit takes as its input the exchanger's mechanical data such as
shell and tube dimensions, tube layout pattern, the baffle cut and
shell and tube side nozzle sizes. A fouling factor of 0.00035 m2-K/
kW is used for the condenser cooling water side.

3-34 MTBE Synthesis Plant (Rev. 3) February 26, 2014


Figure 3-27: setting Heat Exchanger RC-1 Fouling Factors

ZONES analysis is requested to determine where phase changes


occur in the exchanger. An extended data sheet is printed in the
output. ZONES options for tabular data and for plots are available
on the Print Options DEW shown in Figure 3-28.
Figure 3-28: Requesting Zones Analysis in HX RC-1

PRO/II Case Book MTBE Synthesis Plant (Rev. 3) 3-35


Technical Results
The overall mole balance for a 200,000 metric tonne per day MTBE
plant using the reactive distillation process is shown in Table 3-5.
Table 3-5: Summary of Resulting Product Streams
Stream Name 1 2 MKUP
Stream Description MEOH Feed OLEFINS Makeup Water
Phase Liquid Liquid Liquid
Temperature, C 16.00 16.00 38.00
Pressure kPa 1620.00 1620.00 350.00
Component Flowrates, kg_mol/hr
NC4 0.00 0.09 0.00
IC4 0.00 0.41 0.00
1BUTENE 0.00 0.07 0.00
BTC2 0.00 0.04 0.00
BTT2 0.00 0.06 0.00
IBTE 0.00 0.33 0.00
MTBE 0.00 0.00 0.00
MEOH 1.00 0.00 0.00
TBA 0.00 0.00 0.00
H2O 0.00 0.00 1.00
DIB 0.00 0.00 0.00

Stream Name 8 11 15
Stream Description MTBE C4S Flare Gas
Phase Liquid Liquid Liquid
Temperature, C 88.5844 38.1654 99.0981
Pressure kPa 663.00 792.00 241.00
Component Flowrates, kg_mol/hr
NC4 0.00 0.1337 0.1229
IC4 0.00 0.6091 0.4223
1BUTENE 0.00 0.1040 0.0046
BTC2 0.00 0.0594 0.0051
BTT2 0.00 0.0891 0.0048
IBTE 0.00 0.0039 0.0001
MTBE 0.9977 0.00 0.00
MEOH 0.0004 0.00 0.0321
TBA 0.0007 0.00 0.00
H2O 0.00 0.0007 0.4081
DIB 0.0013 0.00 0.00

3-36 MTBE Synthesis Plant (Rev. 3) February 26, 2014


Results Analysis
The results of this simulation shown above indicate that the overall
conversion of IBTE is 99.2% with a selectivity to MTBE of 99.7%.
In the reactive distillation column itself, 87.2% of the IBTE fed to
the column is converted to MTBE. The MTBE product is 99.77%
pure and needs no further purification.
There are a number of factors that affect the overall conversion rate
of IBTE. Some of these are:
Methanol to IBTE ratio
Number of reaction trays
Type of catalyst used
Note, however, that while the IBTE conversion in the conversion
reactors increases as the MEOH:IBTE ratio is increased, the overall
IBTE conversion reaches a maximum, then decreases as the
MEOH:IBTE ratio is increased. This is due to the fact that more
MTBE product is carried upward through the column stripping
section into the reaction trays. This promotes the reverse reaction of
MTBE to methanol and IBTE, thus reducing the overall conversion
of IBTE.

Additional References
1. Hydrocarbon Processing, Vol. 61, No. 9, p.177, Sept. 1982.
2. Bitar, L.S., E. A. Hazbun, and W. J. Piel, MTBE Production and
Economics, Hydrocarbon Processing, Vol. 63, No. 10, pp. 63-68,
Oct. 1984.
3. Hutson, T., et al., in ``Handbook of Chemicals Production Processes'',
Ed. Robert A. Meyers, McGraw-Hill Book Company, New York,
Chap. 1.12, 1986.
4. Friedlander, R.H., in ``Handbook of Chemicals Production
Processes'', Ed. Robert A. Meyers, McGraw-Hill Book Company,
New York, Chap. 1.13, 1986.
5. Jacobs, R., and R. Krishna, 1993, Multiple Solutions in Reactive
Distillation of Methyl tert-Butyl Ether Synthesis, Ind. Chem Res.,
32(8).
6. Hydrocarbon Processing, Vol. 69, No. 10, pp.29,31,33,44, Oct. 1990.
7. Oil & Gas J., Mar. 25, 1991, pp.26-29.
8. Shah, V.B., D. Bluck, J. W. Kovach III, R. Parikh, and R. Yu, 1994,
The Sensitivity of the Design and Operability of the MTBE Processs
with Respect to Changes in Reaction Parameters and Process
Configurations, paper presented at the Refining LNG and
Petrochemasia 94 Conference in Singapore, December 7-8 1994.

PRO/II Case Book MTBE Synthesis Plant (Rev. 3) 3-37


Appendix 3-A: Complete MTBE Plant Flowsheet
Figure 3-29 is a graphic representation of the flowsheet.
Figure 3-29: MTBE Plant Graphical Representation

The PRO/II PDF of the simulation flowsheet appears in Figure


3-30. The PDF has been arranged to fit the physical dimensions of
one page in this manual. The default laydown of the flowsheet in
PRO/II is different from the figure presented here. It may be useful
to compare the graphical representation (above) to the PFD
(below).

3-38 MTBE Synthesis Plant (Rev. 3) February 26, 2014


Figure 3-30: MTBE Plant PRO/II Flowsheet

PRO/II Case Book MTBE Synthesis Plant (Rev. 3) 3-39


Appendix 3-B: PRO/II Selected Output
The following pages show selected parts of the stream and unit
operation information exported to Excel.
SIMULATION SCIENCES INC. R PAGE P-54
PROJECT MTBECASEBOOK PRO/II VERSION 9.3 ELEC V7.0
PROBLEM MTBE PLANT OUTPUT SIMSCI
USER DEFINED PROPERTIES SET 04/08/10
==============================================================================

STREAM ID 1 2 MKUP 8
NAME MEOH FEED OLEFINS MKUP WATER MTBE
PHASE LIQUID LIQUID LIQUID LIQUID
THERMO ID SRKM_VLE SRKM_VLE SRKM_VLE SRKM_VLE

*** TOTAL STREAM ***


RATE, KG-MOL/HR 277.5000 850.0000 0.5988 278.0000
RATE, KG/HR 8891.6994 48548.1421 10.7869 24505.6969
RATE, M3/HR 11.1348 83.0507 0.0108 32.8873
COMP. MOLE RATES,
KG-MOL/HR
1 NC4 0.0000 76.5000 0.0000 2.6022E-04
2 IC4 0.0000 348.5000 0.0000 4.1515E-05
3 1BUTENE 0.0000 59.5000 0.0000 5.9105E-05
4 BTC2 0.0000 34.0000 0.0000 3.9284E-04
5 BTT2 0.0000 51.0000 0.0000 2.0465E-04
6 IBTE 0.0000 280.5000 0.0000 1.3594E-06
7 MTBE 0.0000 0.0000 0.0000 277.3590
8 MEOH 277.5000 0.0000 0.0000 0.1013
9 TBA 0.0000 0.0000 0.0000 0.1881
10 H2O 0.0000 0.0000 0.5988 0.0000
11 DIB 0.0000 0.0000 0.0000 0.3506
TEMPERATURE, C 16.00 16.00 38.00 88.58
PRESSURE, KPA 1620.000 1620.000 350.000 663.000
MOLECULAR WEIGHT 32.0422 57.1155 18.0153 88.1500
ENTHALPY, M*KJ/HR 0.2085 1.9112 1.8217E-03 4.6415
ENTHALPY, KJ/KG 23.4516 39.3678 168.8762 189.4070
MOLE FRAC LIQUID 1.0000 1.0000 1.0000 1.0000
REDUCED TEMPERATURE 0.5640 0.6950 0.4808 0.7276
REDUCED PRESSURE 0.2001 0.4201 0.0159 0.1932
ACENTRIC FACTOR 0.5640 0.1908 0.3449 0.2664
WATSONK 10.5990 13.3631 8.7576 11.2523
STD.DENS (LV), KG/M3 798.5532 584.5605 999.0140 745.1415
STD. SPGR, (H2O,60F), SPGR 0.7993 0.5851 1.0000 0.7459
STD. SPGR, (AIR,60F) N/A N/A N/A N/A

3-40 MTBE Synthesis Plant (Rev. 3) February 26, 2014


SIMULATION SCIENCES INC. R PAGE P-55
PROJECT MTBECASEBOOK PRO/II VERSION 9.3 ELEC V7.0
PROBLEM MTBE PLANT OUTPUT SIMSCI
USER DEFINED PROPERTIES SET 04/08/10
==============================================================================

STREAM ID 1 2 MKUP 8
NAME MEOH FEED OLEFINS MKUP WATER MTBE
PHASE LIQUID LIQUID LIQUID LIQUID
THERMO ID SRKM_VLE SRKM_VLE SRKM_VLE SRKM_VLE

*** VAPOR PHASE ***


RATE, KG-MOL/HR N/A N/A N/A N/A
RATE, KG/HR N/A N/A N/A N/A
RATE, M3/HR N/A N/A N/A N/A
RATE, K*M3/HR N/A N/A N/A N/A
COMP. MOLE RATES,
KG-MOL/HR
1 NC4 0.0000 0.0000 0.0000 0.0000
2 IC4 0.0000 0.0000 0.0000 0.0000
3 1BUTENE 0.0000 0.0000 0.0000 0.0000
4 BTC2 0.0000 0.0000 0.0000 0.0000
5 BTT2 0.0000 0.0000 0.0000 0.0000
6 IBTE 0.0000 0.0000 0.0000 0.0000
7 MTBE 0.0000 0.0000 0.0000 0.0000
8 MEOH 0.0000 0.0000 0.0000 0.0000
9 TBA 0.0000 0.0000 0.0000 0.0000
10 H2O 0.0000 0.0000 0.0000 0.0000
11 DIB 0.0000 0.0000 0.0000 0.0000
STD. SPGR, (AIR,60F) N/A N/A N/A N/A
MOLECULAR WEIGHT N/A N/A N/A N/A
ENTHALPY, K*KJ/KG-MOL N/A N/A N/A N/A
CP, KJ/KG-MOL-C N/A N/A N/A N/A
DENSITY, KG/K*M3 N/A N/A N/A N/A
THERMAL CONDUCTIVITY,
W/M-K N/A N/A N/A N/A
VISCOSITY, PAS N/A N/A N/A N/A

PRO/II Case Book MTBE Synthesis Plant (Rev. 3) 3-41


SIMULATION SCIENCES INC. R PAGE P-56
PROJECT MTBECASEBOOK PRO/II VERSION 9.3 ELEC V7.0
PROBLEM MTBE PLANT OUTPUT SIMSCI
USER DEFINED PROPERTIES SET 04/08/10
==============================================================================

STREAM ID 1 2 MKUP 8
NAME MEOH FEED OLEFINS MKUP WATER MTBE
PHASE LIQUID LIQUID LIQUID LIQUID
THERMO ID SRKM_VLE SRKM_VLE SRKM_VLE SRKM_VLE

*** LIQUID PHASE ***


RATE, KG-MOL/HR 277.5000 850.0000 0.5988 278.0000
RATE, KG/HR 8891.6994 48548.1421 10.7869 24505.6969
RATE, M3/HR 11.1348 83.0507 0.0108 32.8873
COMP. MOLE RATES,
KG-MOL/HR
1 NC4 0.0000 76.5000 0.0000 2.6022E-04
2 IC4 0.0000 348.5000 0.0000 4.1515E-05
3 1BUTENE 0.0000 59.5000 0.0000 5.9105E-05
4 BTC2 0.0000 34.0000 0.0000 3.9284E-04
5 BTT2 0.0000 51.0000 0.0000 2.0465E-04
6 IBTE 0.0000 280.5000 0.0000 1.3594E-06
7 MTBE 0.0000 0.0000 0.0000 277.3590
8 MEOH 277.5000 0.0000 0.0000 0.1013
9 TBA 0.0000 0.0000 0.0000 0.1881
10 H2O 0.0000 0.0000 0.5988 0.0000
11 DIB 0.0000 0.0000 0.0000 0.3506
STD. SPGR, (H2O,60F), SPGR 0.7993 0.5851 1.0000 0.7459
MOLECULAR WEIGHT 32.0422 57.1155 18.0153 88.1500
ENTHALPY, KJ/KG 23.4516 39.3678 168.8762 189.4070
CP, KJ/KG-MOL-C 78.6347 132.0747 78.6807 204.0637
DENSITY, KG/M3 798.9136 586.4964 979.7484 663.1786
SURF. TENS, N/M 0.0229 0.0122 0.0702 0.0120
THERMAL CONDUCTIVITY,
W/M-K 0.2024 0.1054 0.6235 0.1179
VISCOSITY, PAS 6.0863E-04 1.8057E-04 6.9743E-04 1.8513E-04

3-42 MTBE Synthesis Plant (Rev. 3) February 26, 2014


SIMULATION SCIENCES INC. R PAGE P-57
PROJECT MTBECASEBOOK PRO/II VERSION 9.3 ELEC V7.0
PROBLEM MTBE PLANT OUTPUT SIMSCI
USER DEFINED PROPERTIES SET 04/08/10
==============================================================================

STREAM ID 11 15
NAME C4'S FLARE GAS
PHASE LIQUID VAPOR
THERMO ID SRKM_VLLE SRKM_VLE

*** TOTAL STREAM ***


RATE, KG-MOL/HR 572.1370 0.0294
RATE, KG/HR 32942.7334 1.2037
RATE, M3/HR 57.0388 1.9353E-03
COMP. MOLE RATES,
KG-MOL/HR
1 NC4 76.4962 3.6181E-03
2 IC4 348.4875 0.0124
3 1BUTENE 59.4998 1.3480E-04
4 BTC2 33.9995 1.4874E-04
5 BTT2 50.9996 1.4078E-04
6 IBTE 2.2475 4.2432E-06
7 MTBE 3.9890E-03 6.8776E-08
8 MEOH 3.5771E-03 9.4405E-04
9 TBA 3.2985E-10 6.5264E-15
10 H2O 0.3994 0.0120
11 DIB 5.4450E-11 6.2376E-23
TEMPERATURE, C 38.17 99.10
PRESSURE, KPA 792.000 241.000
MOLECULAR WEIGHT 57.5784 40.8884
ENTHALPY, M*KJ/HR 3.0354 1.1435E-03
ENTHALPY, KJ/KG 92.1413 950.0048
MOLE FRAC LIQUID 1.0000 0.0000
REDUCED TEMPERATURE 0.7496 0.7279
REDUCED PRESSURE 0.2085 0.0213
ACENTRIC FACTOR 0.1893 0.2628
WATSONK 13.5205 12.7278
STD.DENS (LV), KG/M3 577.5494 621.9588
STD. SPGR, (H2O,60F), SPGR 0.5781 0.6226
STD. SPGR, (AIR,60F) N/A 1.4117

PRO/II Case Book MTBE Synthesis Plant (Rev. 3) 3-43


SIMULATION SCIENCES INC. R PAGE P-58
PROJECT MTBECASEBOOK PRO/II VERSION 9.3 ELEC V7.0
PROBLEM MTBE PLANT OUTPUT SIMSCI
USER DEFINED PROPERTIES SET 04/08/10
==============================================================================

STREAM ID 11 15
NAME C4'S FLARE GAS
PHASE LIQUID VAPOR
THERMO ID SRKM_VLLE SRKM_VLE

*** VAPOR PHASE ***


RATE, KG-MOL/HR N/A 0.0294
RATE, KG/HR N/A 1.2037
RATE, M3/HR N/A N/A
RATE, K*M3/HR N/A 6.5983E-04
COMP. MOLE RATES,
KG-MOL/HR
1 NC4 0.0000 3.6181E-03
2 IC4 0.0000 0.0124
3 1BUTENE 0.0000 1.3480E-04
4 BTC2 0.0000 1.4874E-04
5 BTT2 0.0000 1.4078E-04
6 IBTE 0.0000 4.2432E-06
7 MTBE 0.0000 6.8776E-08
8 MEOH 0.0000 9.4405E-04
9 TBA 0.0000 6.5264E-15
10 H2O 0.0000 0.0120
11 DIB 0.0000 6.2376E-23
STD. SPGR, (AIR,60F) N/A 1.4117
MOLECULAR WEIGHT N/A 40.8884
ENTHALPY, K*KJ/KG-MOL N/A 38.8442
CP, KJ/KG-MOL-C N/A 82.3064
DENSITY, KG/K*M3 N/A 3258.8043
THERMAL CONDUCTIVITY,
W/M-K N/A 0.0246
VISCOSITY, PAS N/A 1.0319E-05

3-44 MTBE Synthesis Plant (Rev. 3) February 26, 2014


SIMULATION SCIENCES INC. R PAGE P-59
PROJECT MTBECASEBOOK PRO/II VERSION 9.3 ELEC V7.0
PROBLEM MTBE PLANT OUTPUT SIMSCI
USER DEFINED PROPERTIES SET 04/08/10
==============================================================================

STREAM ID 11 15
NAME C4'S FLARE GAS
PHASE LIQUID VAPOR
THERMO ID SRKM_VLLE SRKM_VLE

*** LIQUID PHASE ***


RATE, KG-MOL/HR 572.1370 N/A
RATE, KG/HR 32942.7334 N/A
RATE, M3/HR 57.0388 N/A
COMP. MOLE RATES,
KG-MOL/HR
1 NC4 76.4962 0.0000
2 IC4 348.4875 0.0000
3 1BUTENE 59.4998 0.0000
4 BTC2 33.9995 0.0000
5 BTT2 50.9996 0.0000
6 IBTE 2.2475 0.0000
7 MTBE 3.9890E-03 0.0000
8 MEOH 3.5771E-03 0.0000
9 TBA 3.2985E-10 0.0000
10 H2O 0.3994 0.0000
11 DIB 5.4450E-11 0.0000
STD. SPGR, (H2O,60F), SPGR 0.5781 N/A
MOLECULAR WEIGHT 57.5784 N/A
ENTHALPY, KJ/KG 92.1413 N/A
CP, KJ/KG-MOL-C 144.1388 N/A
DENSITY, KG/M3 548.9739 N/A
SURF. TENS, N/M 9.4520E-03 N/A
THERMAL CONDUCTIVITY,
W/M-K 0.0974 N/A
VISCOSITY, PAS 1.4705E-04 N/A

PRO/II Case Book MTBE Synthesis Plant (Rev. 3) 3-45


COLUMN T-1 SUMMARY
---------- NET FLOW RATES ----------- HEATER
TRAY TEMP PRESSURE LIQUID VAPOR FEED PRODUCT DUTIES
DEG C KPA KG-MOL/HR M*KJ/HR
------ ------- -------- -------- -------- --------- --------- ------------
1C 43.5 621.00 633.5 575.9L -23.6635
2 50.6 621.00 661.6 1209.5
3 51.3 623.73 659.7 1237.5
4 51.7 626.46 658.4 1235.6
5 52.1 629.20 657.3 1234.4
6 52.4 631.93 655.6 1233.3
7 52.8 634.66 651.7 1231.5
8 53.5 637.39 636.1 1227.6
9 54.5 640.13 614.6 1214.6
10 56.2 642.86 583.0 1195.7
11 59.1 645.59 540.3 1166.8
12 63.5 648.32 494.8 1127.3
13 68.6 651.05 463.1 1085.1
14 73.4 653.79 445.5 1054.5
15 76.9 656.52 1207.1 1036.8 869.4M
16 91.0 659.25 1180.4 929.1
17 105.4 661.98 1202.0 902.4
18 115.4 664.71 1237.2 924.0
19 121.0 667.45 1264.5 959.2
20 123.9 670.18 1281.7 986.5
21 125.5 672.91 1292.3 1003.7
22 126.5 675.64 1299.1 1014.3
23 127.1 678.38 1303.7 1021.1
24 127.5 681.11 1307.0 1025.7
25 127.9 683.84 1309.6 1029.0
26 128.2 686.57 1311.8 1031.6
27 128.4 689.30 1313.6 1033.8
28 128.6 692.04 1315.3 1035.6
29 128.8 694.77 1316.7 1037.3
30R 129.1 697.50 1038.7 278.0L 23.7857

COLUMN T-2 SUMMARY


---------- NET FLOW RATES ----------- HEATER
TRAY TEMP PRESSURE L2 L1 FEED PRODUCT DUTIES
DEG C KPA KG-MOL/HR M*KJ/HR
------ ------- -------- -------- -------- --------- --------- --------
----
1 38.2 792.00 375.0 375.0L 572.1L
2 38.2 792.00 375.1 572.2
3 38.2 792.00 375.2 572.2
4 38.2 792.00 375.8 572.3
5 38.2 792.00 572.9 575.9L 378.8H

3-46 MTBE Synthesis Plant (Rev. 3) February 26, 2014


COLUMN T-3 SUMMARY
---------- NET FLOW RATES ---------- HEATER
TRAY TEMP PRESSURE LIQUID VAPOR FEED PRODUCT DUTIES
DEG C KPA KG-MOL/HR M*KJ/HR
----- ------- -------- -------- -------- -------- -------- --------
1C 30.0 103.50 96.9 4.4L -4.0726
2 74.1 138.00 105.9 101.3
3 76.5 139.92 103.7 110.3
4 81.8 141.83 99.4 108.1
5 93.0 143.75 95.8 103.7
6 104.7 145.67 95.9 100.1
7 108.8 147.58 96.2 100.2
8 109.9 149.50 96.3 100.6
9 110.4 151.42 96.4 100.7
10 110.8 153.33 483.1 100.7 378.8L
11 111.6 155.25 483.6 108.7
12 112.2 157.17 484.0 109.2
13 112.8 159.08 484.4 109.6
14 113.3 161.00 484.8 110.0
15 113.8 162.92 485.1 110.4
16 114.2 164.83 485.4 110.7
17 114.6 166.75 485.8 111.0
18 114.9 168.67 486.1 111.3
19 115.3 170.58 486.3 111.6
20R 115.7 172.50 111.9 374.4L 4.5073

PRO/II Case Book MTBE Synthesis Plant (Rev. 3) 3-47


Shell and Tube Exchanger Data Sheets
EXCHANGER NAME T-3 COND UNIT ID RC-1
SIZE 381 - 5750 TYPE AES HORIZONTAL CONNECTED 1 PARALLEL 1 SERIES
AREA/UNIT 37.0M2 (28.3M2 REQUIRED) AREA/SHELL 37.0M2
Performance of one unit Shell-side Tube-side
FEED STREAM ID CW
FEED STREAM NAME (ATTACHED)
TOTAL FLUID KG/HR 3188. 174827.
VAPOR (IN/OUT) KG/HR 3188. / /
LIQUID KG/HR / 3188. 174827. / 174827.
STEAM KG/HR / /
WATER KG/HR / /
NON CONDENSIBLE KG/HR
TEMPERATURE (IN/OUT) DEG C 74.1 / 30.0 21.0 / 26.3
PRESSURE (IN/OUT) KPA 138.00 / 88.76 690.00 / 428.42

SP. GR., LIQ (4C / 4C H2O) / 0.803 1.000 / 1.000


VAP (4C / 4C AIR) 1.087 / /
DENSITY, LIQUID KG/M3 / 787.363 994.441 / 989.867
VAPOR KG/M3 1.538 / /
VISCOSITY, LIQUID PAS / 5.2E-04 1.0E-03 / 8.9E-04
VAPOR PAS 1.1E-05 / /
THRML COND,LIQ W/M-K / 0.2000 0.6006 / 0.6081
VAP W/M-K 0.0202 / /
SPEC.HEAT, LIQUID KJ/KG-K / 2.6389 4.4975 / 4.4538
VAPOR KJ/KG-K 1.5195 / /
LATENT HEAT KJ/KG 1164.32
VELOCITY M/SEC 0.16 5.23
dP /SHELL KPA 49.24 262.06
FOULING RESIST M2-K/KW 0.35222( 0.65987 REQD) 0.00035
TRANSFER RATE KW/M2-K SERVICE 1.00 ( 0.77 REQD) CLEAN 1.55
HEAT EXCHANGED M*KJ/HR 4.073
MTD(CORRECTED) 39.9
FT 0.911
Construction of One Shell Shell-side Tube-side
DESIGN PRESSURE KPA 2068. 2068.
NUMBER OF PASSES 1 2
MATERIAL CARB STL CARB STL
INLET NOZZLE ID MM 152.0 102.0
OUTLET NOZZLE ID MM 102.0 102.0

TUBE: NUMBER 109 OD 19.000 MM BWG 14 LENGTH 5.8 M


TYPE BARE PITCH 25.4 MM PATTERN 90 DEGREES
SHELL: ID 381.00 MM SEALING STRIPS 0 PAIRS
BAFFLE: CUT 0.180
SPACING (IN/CENT/OUT): MM 98.80/ 76.20/ 98.80, SINGLE
RHO-V2: INLET NOZZLE 1548.5 KG/M-SEC2
TOTAL WEIGHT/ SHELL,KG 2053.5(1) FULL OF WATER 3701.5
BUNDLE 1062.8
(1) TOTAL WEIGHT/SHELL DOES NOT INCLUDE BUNDLE WEIGHT

3-48 MTBE Synthesis Plant (Rev. 3) February 26, 2014


Shell and Tube Extended Data Sheet for Exchanger 'RC-1'
EXCHANGER NAME T-3 COND UNIT ID RC-1
SIZE 381 - 5750 TYPE AES HORIZONTAL CONNECTED 1 PARALLEL 1 SERIES
AREA/UNIT 37.0 M2 ( 28.3 M2 REQUIRED)

Performance of one unit Shell-side Tube-side

FEED STREAM ID
FEED STREAM NAME (ATTACHED)
WT FRACTION LIQUID (IN/OUT) 0.000 / 1.000 1.000 / 1.000
REYNOLDS NUMBER 46389.15 80107.92
PRANDTL NUMBER 4.154 7.127
WATSON K,LIQUID / 10.561 8.758 / 8.758
VAPOR 10.561 / /
SURFACE TENSION N/M / 0.024 0.074 / 0.073
FILM COEF(SCL) KW/M2-K 1.9 (1.000) 15.6 (1.000)
FOULING LAYER THICKNESS MM 0.000 0.000

THERMAL RESISTANCE
UNITS: (M2-K/KW) (PERCENT) (ABSOLUTE)
SHELL FILM 51.72 0.51515
TUBE FILM 8.27 0.08235
TUBE METAL 4.61 0.04593
TOTAL FOULING 35.41 0.35267
ADJUSTMENT 30.89 0.30765

PRESSURE DROP Shell-side Tube-side


UNITS: (KPA) (PERCENT) (ABSOLUTE) (PERCENT) (ABSOLUTE)
WITHOUT NOZZLES 98.42 48.47 89.15 233.62
INLET NOZZLES 1.57 0.77 6.77 17.74
OUTLET NOZZLES 0.01 0.00 4.08 10.70
TOTAL /SHELL 49.24 262.06
TOTAL /UNIT 49.24 262.06
DP SCALER 1.00 1.00

CONSTRUCTION OF ONE SHELL

TUBE: OVERALL LENGTH 5.8 M EFFECTIVE LENGTH 5.68 M


TOTAL TUBESHEET THK 66.0 MM AREA RATIO (OUT/IN) 1.285
THERMAL COND 51.9 W/M-K DENSITY 7862.00 KG/M3

BAFFLE: THICKNESS 4.762 MM NUMBER 73

BUNDLE: DIAMETER 327.0 MM TUBES IN CROSSFLOW 92


CROSSFLOW AREA 0.010 M2 WINDOW AREA 0.012 M2
WINDOW HYD DIA 40.63 MM
TUBE-BFL SHELL-BFL
LEAK AREA 0.002 M2 LEAK AREA 0.001 M2

PRO/II Case Book MTBE Synthesis Plant (Rev. 3) 3-49


Appendix 3-C: PRO/II INPUT FILE
TITLE PROJECT=MTBECASEBOOK, PROBLEM=MTBE PLANT, USER=SIMSCI
DESC This is a PRO/II simulation file corresponding to the
DESC PRO/II Casebook on a MTBE Plant.
DESC For more information on this model
DESC please contact Technical Support
DESC
DESC
PRINT INPUT=ALL, STREAM=COMPONENT, MBALANCE
DIMENSION SI, TEMP=C
SEQUENCE DEFINED=HX-1,RX-1,HX-2A,CAL0,T-1,CONVERSION,HX-2B,P-1, &
HX-3,T-2,HX4A,V-1,D-1,P-2,T-3,CAL1,P-4,HX4B,HX-5,P-3,RC-1
COMPONENT DATA
LIBID 1,NC4/2,IC4/3,1BUTENE/4,BTC2/5,BTT2/6,IBTE/7,MTBE/ &
8,MEOH/9,TBA/10,H2O/11,244TM1P,,DIB, BANK=SIMSCI,PROCESS
THERMODYNAMIC DATA
METHOD SYSTEM=SRKM, SET=SRKM_VLE, DEFAULT
KVAL(VLE)
SRKM 1,9,0.046973,0.126027,0,0,0,0,1,1
SRKM 3,8,0.136,-0.0323,0,0,0,0,1,1
SRKM 4,8,0.136,-0.0323,0,0,0,0,1,1
SRKM 5,8,0.136,-0.0323,0,0,0,0,1,1
SRKM 6,8,0.135525,-0.032271,0,0,0,0,1,1
SRKM 8,9,-0.073971,-0.055222,0,0,0,0,1,1
SRKM 9,10,-0.145,-0.253,0,0,0,0,1,1
SRKM 7,11,0.05785,-0.0093,-10.144,6.17,0,0,1,1
METHOD SYSTEM(VLLE)=SRKM, L1KEY=1, L2KEY=10, SET=SRKM_VLLE
KVAL(VLE)
SRKM 1,9,0.046973,0.126027,0,0,0,0,1,1
SRKM 3,8,0.136,-0.0323,0,0,0,0,1,1
SRKM 4,8,0.136,-0.0323,0,0,0,0,1,1
SRKM 5,8,0.136,-0.0323,0,0,0,0,1,1
SRKM 6,8,0.135525,-0.032271,0,0,0,0,1,1
SRKM 8,9,-0.073971,-0.055222,0,0,0,0,1,1
SRKM 9,10,-0.145,-0.253,0,0,0,0,1,1
SRKM 7,11,0.05785,-0.0093,-10.144,6.17,0,0,1,1
STREAM DATA
PROPERTY STREAM=1, TEMPERATURE=16, PRESSURE=1620, PHASE=M, &
COMPOSITION(M,KGM/H)=8,277.5
PROPERTY STREAM=2, TEMPERATURE=16, PRESSURE=1620, PHASE=M, &
RATE(M)=850, COMPOSITION(M)=1,9/2,41/3,7/4,4/5,6/6,33, &
NORMALIZE
PROPERTY STREAM=10, TEMPERATURE=38, PRESSURE=793, PHASE=M, &
COMPOSITION(M,KGM/H)=10,375
PROPERTY STREAM=20, TEMPERATURE=44, PRESSURE=1724, PHASE=M, &
COMPOSITION(M,KGM/H)=8,4/10,0.3
PROPERTY STREAM=CW, TEMPERATURE=21, PRESSURE=690, PHASE=M, &
RATE(LV)=175, COMPOSITION(M)=10,100
PROPERTY STREAM=MKUP, TEMPERATURE=38, PRESSURE=350, PHASE=M, &
COMPOSITION(M,KGM/H)=10,500
NAME 1,MEOH FEED/2,OLEFINS/20,MEOH RECYC/MKUP,MKUP WATER/ &
6,T-1 OVHD/8,MTBE/11,C4'S/15,FLARE GAS

3-50 MTBE Synthesis Plant (Rev. 3) February 26, 2014


RXDATA
RXSET ID=ST1
REACTION ID=1
STOICHIOMETRY 6,-2/11,1
REACTION ID=2
STOICHIOMETRY 6,-1/9,1/10,-1
REACTION ID=3
STOICHIOMETRY 6,-1/7,1/8,-1
RXSET ID=ALJX
REACTION ID=ALJ0
STOICHIOMETRY 6,-1/7,1/8,-1
PROCEDURE DATA
PROCEDURE(KINETIC) ID=ALJD, NAME=ALJD lah
PDATA GCAT,RXFACT
CODE
REAL KS, KA, KC, KALJ, KREH1, KREH2, KIZQ, KEQREF
INTEGER IBTE , MEOH , MTBE
$
$ INITIALIZE DATA:
$ SET INDEXES FOR COMPONENTS
$ DEFINE GAS CONSTANT IN Joules/gm-mole K
$ Note: R could have been retrieved in input units by R=RGAS.
$ However, since the reaction basis won't change, and
$ RGAS will change with the default units, this
$ eliminates one possible source of error..
$ Initialize the local variable TK to the absolute temperature.
$ Note: The temperature basis for the flowsheet must be Celsius
$ or Kelvin.
$ Set temperature and composition derivatives to zero.
$
IBTE = 6
MTBE = 7
MEOH = 8
$
R = 8.314
$
TK = RTABS
$
DO 1000 I1 = 1,NOR
DRDT(I1) = 0.0
DO 1000 I2 = 1,NOC
1000 DRDX(I2,I1) = 0.0
$
$ Calculate the surface reaction rate constant, ks, and the
$ equilibrium adsorption constants Ka and Kb. The activation
$ energy is in J/gm-mole.
$ units: ks - (gm-mole / gm catalyst)**1.5 /hour
$ Ka - gm-catalyst / mole
$ Kc - gm-catalyst / mole
$
KS = 1.2E+13*EXP(-87900.0/(R*TK))
KA = 5.1E-13*EXP( 97500.0/(R*TK))
KC = 1.6E-16*EXP(119000.0/(R*TK))

PRO/II Case Book MTBE Synthesis Plant (Rev. 3) 3-51


$
DKSDT = KS * 87900.0 / R / (TK*TK)
DKADT = KA * (-1.0) * 97500.0 / R / (TK*TK)
DKCDT = KC * (-1.0) * 119000.0 / R / (TK*TK)
$
$ ---- Calculate the equilibrium constant.
$ Units - (gm-moles/gm-catalyst)/hour
$ Phase - Liquid Phase Reaction
$ Catalyst - Ion Exchange Resin Amberlyst 15,
$ equilibrium should be independant of the catalyst
$
$ -- METHOD 1.0:
$ Adnan M. Al-Jarallah, Mohammed A. B. Siddiqui, A. K. K. Lee;
$ "Kinetics of Methyl Tertiary Butyl Ether Synthesis Catalyzed
$ by Ion Exchange Resin"
$ Canadian Journal of Chemical Engineering (66) pp. 802-807
$
KALJ = EXP(-17.31715+(7196.776/TK))
DKALJDT = - KALJ * 7196.776 / (TK*TK)
$
$ Bulk concenrations of components per gram of catalyst, XLCONC is
$ in moles/flow volume. XLCONC will be passed to the procedure
$ in user input units. Internally to PRO/II, it is in SI units
$ (kg-mole/cubic meter). The basis for these reaction equations
$ is gm-moles/liter. The conversion factor from input units of
$ kg-moles/cubic meter to the reaction basis of gm-moles/liter
$ is one. Therefore, XLCONC can be used with no conversion.
$
$ RHOA=(XLCONC(MEOH)/GCAT)|-This should be equivalent to below.
$ RHOB=(XLCONC(IBTE)/GCAT)| It has been written explicitly below
$ RHOC=(XLCONC(MTBE)/GCAT)| to make it obvious how to do the
$ analytical derivatives.
$
$ Calculate density in moles / volume
$
GCATX = 12.4
DENS=RLMRAT/RLVRAT
RHOA=(XLIQ(MEOH)*DENS/GCATX)
RHOB=(XLIQ(IBTE)*DENS/GCATX)
RHOC=(XLIQ(MTBE)*DENS/GCATX)
$
$ ---- Calculate reaction rate and derivatives by terms
$ ---- Units - RATE - gram-mole / gram catalyst / hr.
$ Denominator & derivatives.
RDEN = 1.0 + ( KA*RHOA ) + 0.0 + ( KC*RHOC )
DRDDT = RHOA*DKADT + 0.0 + RHOC*DKCDT
DRDDME = KA/GCATX*DENS
DRDDIB = 0.0
DRDDMT = KC/GCATX*DENS
$
$ First factor in rate equation.
FACT1 = KS *KA/RDEN
DFAC1DT = DKSDT*KA/RDEN + KS*DKADT/RDEN - KS*KA/RDEN**2 * DRDDT

3-52 MTBE Synthesis Plant (Rev. 3) February 26, 2014


$
$ Second factor in rate equation.
FACT2 = RHOA*RHOB**0.5 - RHOC**1.5/KALJ
DFAC2DT = 0.0 + RHOC**1.5/KALJ**2 * DKALJDT
$
$ Combine terms to calculate rate and derivatives.
$ -- Rate equation (rate per one gram of catalysis).
RATE = FACT1 * FACT2
$
$ -- Rate temperature derivative.
DRDT(1) = DFAC1DT * FACT2 + FACT1 * DFAC2DT
$ -- Rate composition derivatives.
DRDX(MEOH,1) = -KS*KA/RDEN**2 * DRDDME * FACT2 &
+ FACT1 * (RHOB**0.5/GCATX*DENS)
DRDX(IBTE,1) = -KS*KA/RDEN**2 * DRDDIB * FACT2 &
+ FACT1 * (RHOA/2.0/RHOB**0.5/GCATX*DENS)
DRDX(MTBE,1) = -KS*KA/RDEN**2 * DRDDMT * FACT2 &
- FACT1 * (1.5* RHOC**0.5/GCATX/KALJ*DENS)
$
$ ---- Convert rate equation and derivatives to a straight volume
$ ---- basis by multipling the base rate by the grams of
$ ---- catalyst/unit volume.
$ ---- The rate is returned in input units, kg-moles/cubic
$ meter/hour.
$
RRATES(1) = GCAT * RXFACT * RATE
$
DRDT(1) = GCAT * RXFACT * DRDT(1)
$
DRDX(MEOH,1) = GCAT * RXFACT * DRDX(MEOH,1)
DRDX(IBTE,1) = GCAT * RXFACT * DRDX(IBTE,1)
DRDX(MTBE,1) = GCAT * RXFACT * DRDX(MTBE,1)
RETURN

UNIT OPERATIONS
HX UID=HX-1, NAME=FEED HEAT
COLD FEED=1,2,20, L=3, DP=34.5
OPER CTEMP=43.5
CONREACTOR UID=RX-1, NAME=REACTORS
FEED 3
PRODUCT L=4
OPERATION ISOTHERMAL, TEMPERATURE=55, DP=69
RXCALCULATION MODEL=STOIC
RXSTOIC RXSET=ST1
REACTION 1
BASE COMPONENT=6
CONVERSION 0.0025
REACTION 2
BASE COMPONENT=10
CONVERSION 1
REACTION 3
BASE COMPONENT=8
CONVERSION 0.93

PRO/II Case Book MTBE Synthesis Plant (Rev. 3) 3-53


HX UID=HX-2A, NAME=FEED-BTMS-A
COLD FEED=4, L=5, DP=34.5
OPER CTEMP=72
CALCULATOR UID=CAL0, NAME=COPY RXFACT
PROCEDURE $Set RXFACT TO 1 on first call.
IF (R(2) .NE. 1.0) R(1) = 1.0
R(2) = 1.0
RETURN
COLUMN UID=T-1, NAME=MTBE COLUMN
PARAMETER TRAY=30,CHEMDIST=35
FEED 5,15
PRODUCT OVHD(M)=6, BTMS(M)=7,280, SUPERSEDE=ON
CONDENSER TYPE=TFIX, PRESSURE=621, TEMPERATURE=43.5
DUTY 1,1,,CONDENSER
DUTY 2,30,,SIDEHC2
PSPEC PTOP=621, DPCOLUMN=76.5
PRINT COMPOSITION=M, PROPTABLE=ALL
ESTIMATE MODEL=SIMPLE, RRATIO(L)=1.1
SPEC ID=COL1SPEC1, STREAM=7, RATE(KGM/H),TOTAL,WET, &
VALUE=278
SPEC ID=COL1SPEC2, RRATIO, PHASE=L, VALUE=1.1
DEFINE GCAT AS 360
DEFINE RXFACT AS 1
VARY DNAME=CONDENSER,SIDEHC2
PLOT LOG, XCOMPONENT=6,6/8,8/7,7/1,1
TSIZE SECTION(1)=2,29,VALVE, DMIN=381, FF=80, DPCALC=0
VLLECHECK CHECK=OFF
LVOL 8,5/9,5/10,5/11,5/12,5/13,5
RXTRAY REFERENCE=ALJX, LOCAL=L_ALJX, KPROCEDURE=ALJD, &
TRAY=8, & 13
RXSET LOCAL=L_ALJX
REACTION ID=ALJ0, COPTION=KINETICS
KINETICS PEXP(C,KG,M3,KPA,HR)
CALCULATOR UID=CONVERSION, &
NAME=CONVERSION OF IBTE-MEOH TO MTBE
RESULT 1,IN - MEOH/2,IN - IBTE/3,IN - MTBE/ &
4,OUT - MEOH/5,OUT - IBTE/6,OUT - MTBE/ &
20,IBTE CONV/21,MEOH CONV
DEFINE P(1) AS STREAM=4, RATE(KGM/H), COMP=8,WET
DEFINE P(2) AS STREAM=4, RATE(KGM/H), COMP=6,WET
DEFINE P(3) AS STREAM=4, RATE(KGM/H), COMP=7,WET
DEFINE P(4) AS STREAM=6, RATE(KGM/H), COMP=8,WET
DEFINE P(5) AS STREAM=6, RATE(KGM/H), COMP=6,WET
DEFINE P(6) AS STREAM=6, RATE(KGM/H), COMP=7,WET
DEFINE P(7) AS STREAM=7, RATE(KGM/H), COMP=8,WET
DEFINE P(8) AS STREAM=7, RATE(KGM/H), COMP=6,WET
DEFINE P(9) AS STREAM=7, RATE(KGM/H), COMP=7,WET
PROCEDURE
$ --- LOAD RATES
R( 1) = P( 1)
R( 2) = P( 2)
R( 3) = P( 3)
R( 4) = P( 4) + P( 7)

3-54 MTBE Synthesis Plant (Rev. 3) February 26, 2014


R( 5) = P( 5) + P( 8)
R( 6) = P( 6) + P( 9)
$ --- CALCULATE CONVERSION
R(20) = ( R(2) - R(5) ) / R(2)
R(21) = ( R(1) - R(4) ) / R(1)
$ --- DISPLAY RESULTS
DISPLAY R( 1: 9 )
DISPLAY R( 20:21 )
RETURN
HX UID=HX-2B, NAME=FEED-BTMS-B
HOT FEED=7, L=8, DP=34.5
DEFINE DUTY(KJ/HR) AS HX=HX-2A, DUTY(KJ/HR)
PUMP UID=P-1, NAME=T-1 OVHD
FEED 6
PRODUCT L=6P
OPERATION EFF=65, PRESSURE=827
HX UID=HX-3, NAME=COOLER
HOT FEED=6P, L=9, DP=34.5
UTILITY WATER, TIN=16, TEMPERATURE=32
CONFIGURE COUNTER
OPER HTEMP=38
COLUMN UID=T-2, NAME=WATER WASH
PARAMETER TRAY=5,LLEX=25
FEED 9,5/10,1
PRODUCT OVHD(L1,M)=11, BTMS(M)=12,185, SUPERSEDE=ON
PSPEC PTOP=792
PRINT PROPTABLE=PART
ESTIMATE MODEL=SIMPLE
METHOD SET=SRKM_VLLE
HX UID=HX4A, NAME=FEED-BTMS
COLD FEED=12, L=13, DP=34.5
OPER CTEMP=99
VALVE UID=V-1, NAME=VALVE
FEED 13
PRODUCT M=14
OPERATION PRESSURE=241
FLASH UID=D-1, NAME=SEPARATOR
FEED 14
PRODUCT V=15, L=16
ADIABATIC
PUMP UID=P-2, NAME=FEED PUMP
FEED 16
PRODUCT L=17
OPERATION EFF=65, PRESSURE=690
COLUMN UID=T-3, NAME=MEOH COLUMN
PARAMETER TRAY=20,IO=10
FEED 17,10
PRODUCT OVHD(M)=19, BTMS(M)=18,182, SUPERSEDE=ON
CONDENSER TYPE=TFIX, PRESSURE=103.5, TEMPERATURE=30
DUTY 1,1,,CONDENSER
DUTY 2,20,,SIDEHC2
PSPEC PTOP=138, DPCOLUMN=34.5
PRINT PROPTABLE=PART

PRO/II Case Book MTBE Synthesis Plant (Rev. 3) 3-55


ESTIMATE MODEL=CONVENTIONAL, RRATIO=10
SPEC ID=COL3SPEC1, STREAM=19, RATE(KGM/H), COMP=8,WET, &
DIVIDE, &
STREAM=17, RATE(KGM/H), COMP=8,WET, VALUE=0.995
SPEC ID=COL3SPEC2, STREAM=18, RATE(KGM/H), COMP=10,WET, &
DIVIDE, &
STREAM=17, RATE(KGM/H), COMP=10,WET, VALUE=0.9995
VARY DNAME=CONDENSER,SIDEHC2
TRATE SECTION(1)=2,19,SIEVE, PASSES=1, DIAM(TRAY)=610, &
DIAMETER(SIEVEHOLE,IN)=0.5, WEIR=50.8, DCC=38.1
CALCULATOR UID=CAL1, NAME=MAKEUP
SEQUENCE STREAM=MKUP
DEFINE P(1) AS STREAM=11, RATE(KGM/H), COMP=10,WET
DEFINE P(2) AS STREAM=15, RATE(KGM/H), COMP=10,WET
DEFINE P(3) AS STREAM=19, RATE(KGM/H), COMP=10,WET
PROCEDURE
R(1) = P(1) + P(2) + P(3)
CALL SRXSTR(SMR,R(1),MKUP)
RETURN
PUMP UID=P-4, NAME=WATER PUMP
FEED 18,MKUP
PRODUCT L=21
OPERATION EFF=65, PRESSURE=862
HX UID=HX4B, NAME=FEED-BOTS
HOT FEED=21, L=22, DP=34.5
DEFINE DUTY(KJ/HR) AS HX=HX4A, DUTY(KJ/HR)
HX UID=HX-5, NAME=COOLER
HOT FEED=22, L=10, DP=34.5
OPER HTEMP=38
PUMP UID=P-3, NAME=RECYCLE PUMP
FEED 19
PRODUCT L=20
OPERATION EFF=65, PRESSURE=1724
HXRIG UID=RC-1, NAME=T-3 COND
TYPE TEMA=AES
TUBES FEED=CW, L=WOUT, LENGTH=5.75, OD=19, BWG=14, &
PASS=2,PATTERN=90, PITCH=25.4, FOUL=0.00035, &
METHOD=SRKM_VLE
SHELL DPUNIT=49.244, METHOD=SRKM_VLE, ID=381
BAFFLE CUT=0.18
SNOZZLE TYPE=CONV, ID=152,102
TNOZZLE ID=102,102
PRINT EXTENDED, ZONE
ATTACH COLUMN=T-3, TYPE=CONDENSER
RECYCLE DATA
ACCELERATION TYPE=WEGSTEIN
LOOP NUMBER=1, START=T-2, END=HX-5,WEGSTEIN
LOOP NUMBER=2, START=HX-1, END=P-3,WEGSTEIN
END

3-56 MTBE Synthesis Plant (Rev. 3) February 26, 2014


Case 4:
Sulfuric Acid Alkylation
Abstract
Computer flowsheet simulation of plant processes has become a
widely accepted design and optimization tool in today's refinery.
Because most refinery processes have a high degree of thermal
integration and material recycle, process simulation is often the
only way to quantify how different unit operations interrelate in the
overall flowsheet environment.
The H2SO4 alkylation plant is used in this paper as a vehicle to
demonstrate how a modern flowsheet simulator, PRO/II, may be
used to evaluate process alternatives, which include parametric
studies of flowsheet variables and changes in flowsheet
configuration. Three flowsheet variables are perturbed to study the
effect on economically sensitive flowsheet parameters. Two key
flowsheet configuration design decisions are explored:
Effluent refrigeration vs. auto refrigeration, and
De-isobutanizer vs. iso-stripper operation.
This work does not make definitive judgments on the merits of
these options, but rather demonstrates how these design choices
may be evaluated by the process engineer using modern simulation
technology.

PRO/II Case Book Sulfuric Acid Alkylation 4-1


Sulfuric Acid Alkylation
Market Position
Alkylate is a high octane component in gasoline blends. It is
composed primarily of iso-octanes and iso-heptanes which make a
very small contribution to the overall vapor pressure, and no
contribution to the aromatic or olefin content. These have become
key issues in refinery planning since implementation of the Clean
Air Act Amendments of 1990.[4-1],[4-2].Increasing alkylate
production can partially offset the need to reduce reforming
severities to meet aromatic targets. Alkylation can also be used to
reduce olefin content in gasoline.
Table 4-1 shows the octane and vapor pressure characteristics of the
principal reactants and products of an alkylation plant. This
demonstrates that, although the octane numbers of alkylation feeds
are suitable for gasoline production, the vapor pressures are
excessive.
Table 4-1: Octane and Vapor Pressure Characteristics of
Alkylate Reactants and Products[4-3]
Vapor Pressure
Octane at 100F
Reactants Motor Research psia
Isobutane 97.6 100.1 72.6
Propylene 84.9 100.2 227.6
Isobutylene na na 64.6
* *
2-Butylenes 83.5 100.0 47.8*
1-butylene 80.8 97.4 63.2
2-Methylbutylenes 83* 99* 16.4*
Products (partial list) 20.4
Isopentane 90.3 92.3 3*
Dimethylpentanes 88* >100
*
Trimethylpentanes 98 >100 1*
C9s 98* 100* >0.5
* approximate average

Reactor products have excellent octane as well as vapor pressure


characteristics. Sulfuric acid alkylation is a highly complementary
process for refineries that are considering on-site MTBE
production.[4-4] The MTBE process selectively reacts isobutylene

4-2 Sulfuric Acid Alkylation February 26, 2014


from the olefin stream, permitting 1- and 2-butylene to pass through
for alkylation. Isobutylene produces lower quality alkylate, while 1-
and 2-butylene produce superior alkylate.

Comparison to HF Alkylation
The relative advantages of hydrofluoric acid (HF) to H2SO4
alkylation have been vigorously debated in the open literature and
in the marketplace for years.[4-5] From about 1960 through the
1980s, HF alkylation was preferred to H2SO4 alkylation in new
plants. The advantages of HF include superior product when the
olefin content is high in propylene and isobutylene, and reduced
catalyst cost. Also, HF alkylation does not require refrigeration or
acid regeneration so it is marginally better in that respect.
More recently, preferences have shifted toward H2SO4 alkylation.
This is due in part to the high corrosive nature of the HF acid, which
requires exotic materials of construction. The process is also much
more hazardous due to the HF acid, and is not readily acceptable
environmentally. Safety and liability considerations, together with a
reduction in isobutylene content in the olefin feed (due to the
MTBE plant), are additional factors. Also, the more recent
development of the wet sulphuric acid process (described briefly
in Appendix 4-C) ameliorates may of the disadvantages previously
incurred by H2SO4 alkylation. Together, all these factors are
changing the economics to favor H2SO4 alkylation. Several
refiners, particularly those near major population centers, are
considering revamping their HF alkylation facitlities to H2SO4
alkylation.

Chemistry
The primary purpose of the alkylation reactor is to join isobutane
and a light olefin to form branched alkylates.[4-6]
acid
iC 4 + C 3 C 7 + heat
(4-1)
acid
iC 4 + C 4 C 8 + heat

Disproportionation reactions contribute to a distribution of alkylate


products from iC5 to C12+; e.g.,
2C 8 C 7 + C 9 (4-2)

PRO/II Case Book Sulfuric Acid Alkylation 4-3


Olefin polymerization is undesirable and is usually minimized by
proper mixing, low reaction temperatures and high isobutane
concentrations.

2C 3 H 6 C 6 H 12
(4-3)
C n H 2n + C m H 2m C n + m H 2 m + n

The polymers form acid-soluble oils that foul the sulfuric acid
catalyst, resulting in excessive purge and makeup requirements. As
the acid strength weakens, an acid runaway, characterized by low
octane and increased acid consumption, may occur.

Simulation Scope and Objectives


The objective is to model the overall basic sulfuric acid alkylation
process in a manner that permits the process engineer to analyze
virtually all flowsheeting issues. The flowsheet models presented
here allow the following questions to be answered with few or no
changes to the input description:
How is the process affected if more propane is circulated in the
depropanizer-refrigeration recycle?
How is the process affected if more isobutane is recycled from
the de-isobutanizer?
What are the optimum feed tray locations for each of the four
distillation columns?
How do the utility requirements change for changes in
feed-stock?
What are the total reboiler steam requirements for all four
distillation columns?
What is the total refrigeration duty?
If supplemental isobutane is available, where is the optimum
place in the flowsheet to introduce this feed?
For a given reactor volume, what is the space velocity?
What are the differences if the deisobutanizer is operated as an
isostripper instead of a conventional tower?
How is the refrigeration duty affected if effluent regrigeration
rather than autorefrigeration is chosen?

4-4 Sulfuric Acid Alkylation February 26, 2014


How much reboiler duty is saved if the debutanizer is
elimi-nated by drawing a normal butane?rich side stream off of
the deisobutanizer? How is the isobutane recycle affected?
The simulation makes the following simplifying assumptions:
Feed pretreatment is not included. When the amine towers
are working correctly, their operation has no effect on the
flowsheet.
Caustic treatment is not considered. The reactor products
generally run through a caustic wash to neutralize acid
carry-over and ester formation. When the acid settler is
working correctly, the caustic wash has little effect on the
heat or hydrocarbon balance, so it may be safely deleted
from the simulation.
The stoichiometry is fixed for each isobutane-olefin
reaction pair, and each olefin reacts to extinction. The
REACTOR MODEL section clarifies this further.
Sulfuric acid is assumed to be 100% pure and totally
immiscible with the process hydrocarbon. In reality,
circulating sulfuric acid is generally maintained at 85 to 96
weight percent.
The trace amount of hydrocarbon absorbed by the acid is
disposed of by the acid purge and may usually be ignored in
the hydrocarbon balance. Acid entrained or absorbed in the
reactor hydrocarbon effluent is neutralized by caustic wash,
and does not normally have a significant effect on the
hydrocarbon balance. For flowsheet simulation purposes,
the only effect of having a sulfuric acid circulation is to
correctly account for the flowing heat capacity.

Reactor Modelling
Reaction Stoichiometry
A fixed stoichiometry for each pair of reacting components is
derived from the work of Cupit, et al.[4-7] This reference provides
reaction yields on a volumetric basis. PRO/II was used to normalize
the products to mass balance with the feeds. Note that, although it is
necessary to adjust the stoichiometry to mass balance, it is not
necessary to normalize the stoichiometry to integer coefficients.
Table 4-2 lists the coefficients used in this simulation. Heat of

PRO/II Case Book Sulfuric Acid Alkylation 4-5


reaction data need not be supplied. PRO/II automatically accounts
for reaction enthalpy via pure component heat of formation data
adjusted for temperature and pressure.
Table 4-2: Stoichiometric Coefficients for Alkylating
Pairs of Components
Olefin Propylene Isobytylene 2-Butylenes 1-Butylene
Reactant
olefin 12.3008 8.5683 10.9924 11.5763
isobutane 12.3461 10.5445 11.3223 9.9587
Products
isopentene 0.5541 1.2706 0.6346 0.6877
2,3-dimethylbutane 0.5553 0.5925 0.6261 0.5870
2,4-dimethylpentane 2.3756 0.3827 0.2832 0.3016
2,2,4-trimethylpentane 5.9539 0.2638 0.1703 0.1730
2,4-dimethylhexane 0.4574 2.5703 3.3018 3.1778
2,3-dimethylhexane 0.0731 0.3627 0.4360 0.5271
2,3,4-trimethyl pentane 0.3969 2.1523 4.6514 4.2314
2,2,5-trimethylhexane 0.0821 0.3998 0.1852 0.1686
C9s (nbp=280, mw=128) 0.0594 0.2074 0.0782 0.0984
C10s (nbp=325, mw=142) 0.6688 0.2754 0.0891 0.0720
C11s (nbp=365, mw=156) 0.4325 0.2134 0.799 0.0761
C12s (nbp=395, mw=170) 0.0468 0.5173 .02831 0.2674
C13+ (nbp=425,mw=184) 0.0315 0.0239 0.0000 0.0079

Reactor Configurations
In the auto-refrigeration flowsheets considered by this paper, the
reaction vessel is divided into four reaction chambers. Flashing
occurs in each chamber to balance the exothermic heat of reaction.
In the flowsheet where effluent refrigeration is considered, the
reaction takes place in a single reaction chamber under sufficient
pressure to suppress vapor flashing. This work assumes the reaction
is maintained at 45 F. Temperatures significantly above 45 F result
in excessive acid consumption and lower octane. Temperatures
significantly below 45 F increase the refrigeration load. Liquid
hydrocarbon and acid phases coexist in the reactor.

4-6 Sulfuric Acid Alkylation February 26, 2014


The reactor could be modeled with a reactor unit operation using
conventional two phase equilibrium models, followed by a three
phase flash. This has one disadvantage in that the reactor is nested
two levels deep in controller and recycle loops, and rigorous three
phase flashes add to the calculation overhead. In this paper, a
stream calculator unit operation replaces the three-phase flash. This
allows the user to mathematically manipulate stream separation.
One other solution for modeling a three phase reactor is to declare
the acid as a solid component. It thus carries with it a fixed heat
capacity, but no vapor pressure. This strategy is not used in the
simulations presented here, but has been proven in preliminary runs
for this work.

Thermodynamic Models
The Soave modification to the Redlich?Kwong equation of state is
used for all unit operations in the flowsheet for the calculation of
equilibrium, enthalpy and entropy. [4-8]

Sulfuric Acid Alkylation Flowsheet


The flowsheet for the sulfuric acid alkylation plant with auto-
refrigeration and isostripper design is shown in Figure 4-1.
Treated saturated feed is combined with recycle from the
refrigeration circuit and depropanized in column DEC3. The
overhead enters the deethanizer DEC2 and leaves the flowsheet as
fuel gas and HD5 propane product. The bottoms are cooled to 100 F
and enter the economizer together with condensed propane rich
re-frigeration and supplemental isobutane feed. Evaporation in the
economizer cools the stream to 55 F. The pressure is then let down
to 30 psia as it enters the first reaction chamber together with
sulfuric acid and recycle isobutane.
Acid and hydrocarbon are cascaded into each of four reaction
chambers in sequence. Olefin feed enters the tube side of the
economizer where it is cooled to 65 F.
The stream is split into four equal parts, each of which enters a
separate reaction chamber. Olefin reacts to extinction with
isobutane in each chamber to form alkylate.

PRO/II Case Book Sulfuric Acid Alkylation 4-7


Figure 4-1: H2SO4 Alkylation Plant

Vaporization in each chamber approximately compensates for the


heat of reaction to maintain the reactor at about 45 F throughout.
All of the vapor is collected and recycled to the refrigeration circuit.
Acid is settled and decanted. Part of the acid is purged for on?site or

4-8 Sulfuric Acid Alkylation February 26, 2014


off?site regeneration. The hydrocarbon enters the isostripper DIC4
where normal butane and alkylate product is separated from the
isobutane rich recycle. The alkylate is then stabilized to an RVP of
12 psi in the debu-tanizer DEC4. The hydrocarbon feeds to the
flowsheet are shown in Table 4-3.
Table 4-3: Feed Hydrocarbon Conditions
Component Rates, standard liq. vol, bbl/hr
Saturated Olefin Supplemental
Feed Feed Isobutane
Stream ID 1 2 3
methane 2.0 - -
ethane 10.1 - -
propane 100.0 9.0 -
Isobutane 187.5 95.0 36.0
normal butane 100.0 50.0 9.0
propylene - 9.0 -
isobutylene - 14.0 -
2-butylene - 75.0 -
2-butylene - 56.0 -
Isopentane - 5.0 -
Total 399.5 413.0 45.0
Temperature, F 100 100 100
Pressure, psia 400 215 400

The supplemental isobutane feed has been included here to


demon-strate that alternate sources of isobutane with varying
compositions and thermal conditions may be processed.
Table 4-4: Acid Feed to Reactor
Stream Property Property Value
Feed Stream ID SA1
Stream ID SA1
Acid rate, 106 lb/hr 1.00
Temperature, F 45
Pressure, psig 40

The optimum flowsheet feed location for this stream may or may
not be the same as for the bulk of the isobutane feed. The effects of
alternate feed locations may be quickly tested via simulation.

PRO/II Case Book Sulfuric Acid Alkylation 4-9


RUN #1 Auto-Refrigeration and Iso-Stripper Operation
Simulation Strategy
The success of the simulation convergence depends on which
flow-sheet variables have assumed values, and which are calculated
by the program. Assumed values may be investigated through
sensitivity analyses and optimization techniques. Referring to the
flowsheet in Figure 4-1, convergence stability is enhanced by fixing
flowrates at least once in each of the recycle circuits. Thus, the
bottoms of depropanizer DEC3 is specified to contain a fixed value
of 50 mole/hr of propane, and the overhead rate from
deisobutanizer is fixed at 1000 bbl/hr.
The economizer H2 is operated in a manner that fixes the outlet
temperature of both sides of the exchanger. Normally, there are only
enough degrees of freedom to specify one outlet temperature of a
heat exchanger; however, the upstream pressure on the saturates
side is varied by controller C1 until both temperature specifications
are met. This control loop is embedded in another control loop as
well as a recycle loop. It is thus essential that the tolerance is
tightened, enabling the external loops to see clean derivatives. Since
this is the innermost loop, a good practice is to set this tolerance just
barely loose enough to ensure convergence on each pass. An
absolute tolerance of 0.0001 F is used in this demonstration.
The reactor RX1A effluent temperature is controlled at 45 F by
adjusting splitter S1. This has the effect of circulating more or less
refrigerant through the autorefrigeration circuit and thus cooling the
reactor to a greater or lesser extent. The number of control iterations
is limited to 5 as it is not necessary to solve this recycle to
completion on each recycle pass. This permits the recycle and
control loop to converge simultaneously, reducing CPU time. An
absolute tolerance of 0.0002 F is used.
Effluent processing includes two-stage compression followed by an
after-cooler condenser. To speed up recycle calculations, all these
unit operations are replaced by single flash drum MCOM.
Following the successful convergence of all recycle loops, detailed
effluent calculations are performed once by solving two
compressors and a heat exchanger (see Figure 4-2). Although the
compressors do not require excessive amounts of CPU, the number
of passes through this loop make it well worthwhile to reduce the
two P-S (constant pressure - constant entropy) compressors and one

4-10 Sulfuric Acid Alkylation February 26, 2014


P-T (constant pressure - constant temperature) heat exchanger to the
single P-T flash unit MCOM.

Figure 4-2: Detailed Effluent Processing Model of Flash MCOM

The case study feature of PRO/II may used to study the effects of
increased propane to the refrigeration circuit, increased isobutane
recycle, and a change in feed composition to include more normal
butane. However, this must be run as a batch execution because the
PROVISION Graphical User Interface still does not fully support
all features of Casestudy.

Input Description
Appendix 4-A lists the PRO/II keyword input file for the auto-
refrigeration/isostripper batch run. This is revision 2 that is
compatible with PRO/II versions 8 and 9. An electronic copy of the
file is available in the %P2Install% \manual\casebook\inputs\
directory, where %P2Install% is the directory where PRO/II is
installed.

Results
Key operating conditions for the base case and case studies are
summarized in Table 4-5, including total reboiler duties, reactor
effluent flowrates and isobutane content, refrigeration loads, and
product flows. These parameters form the basis for calculating
operating expenses.

PRO/II Case Book Sulfuric Acid Alkylation 4-11


Table 4-5: Key Flowsheet Parameters
Run #1 - Auto-refrigeration and Isostripper Operation
Base More C3 More iC4 More nC4
Case Recycle Recycle in Feed
Input Flow Parameters
C3 in de-propanizer
50 100 50 50
bottoms, moles/hr
Recycle from
2525 2525 2600 2525
isostripper, bbl/hr
Additional normal
butane in saturates 0 0 0 50
feed, bbl/hr
Calculated Flow Parameters
Reboiler duties, 106 Btu/hr
De-ethanizer DEC2 1.00 1.00 1.00 1.00
De-propanizer DEC3 28.24 29.02 28.40 28.46
Iso-stripper DIC4 80.69 80.69 82.73 80.36
De-butanizer DEC4 9.09 9.08 9.10 11.73
Total reboiler duties 119.02 119.79 121.23 122.05

HC liquid reactor effluent
Hot volume rate, gpm 2180 2180 2232 2214
isobutane content, liq
64.0 64.0 64.0 58.4
vol %

Compressor shaft power, hp


Stage 1 996 995 977 1044
Stage 2 2005 2005 2005 2069
Total compressor duty 3001 3000 2982 2113

Product flowrates at standard conditions


Gas products, mscfh
Fuel gas 17.42 17.41 17.42 17.44
Liquid products, bbl/hr
Liquid propane 111.1 111.1 111.0 110.8
Normal butane 118.9 118.6 118.9 168.7
12 RVP alkylate 522.3 522.3 522.3 522.6

4-12 Sulfuric Acid Alkylation February 26, 2014


Table 4-6 illustrates one approach to summarizing the results.

Table 4-6: Significance of Simulation Results for Run #1


Case Observation Conclusion
More C3 in Profitability is improved when
Increases depropanizer reboiler
depropanizer propane in depropanizer bottoms
duty
bottoms is minimized.
Increase in octane and decrease
Increases isobutane in acid consumption due to iso-
concentration in reactor. butane content, together with
Reduces reactor and settler reduced compressor loading,
residence time due to increased more than compensates for
More iC4 reactor throughput. increase in reboiler duty. If the
recycle
Increases isostripper reboiler iso-stripper hydraulics and
duty. reactor residence time
Reduces first stage compressor requirements are not limiting,
load. profitability improves as iso-
butane recycle increases.
Reactor iso-butane concentration Although normal butane is an
decreases. inert copmponent in the reactor,
Reactor throughput increases. it adversely affects plant
More nC4 in The debutanizer reboiler rate profitability. In particular, the
feed increases in proportion to decrease in reactor iso-butane
increases in product butane. concentration translates to a
The refrigeration load significant drop in octane and
requirement decreases. increase in acid consumption.

Runs #2 and #3 - Deisobutanizer with Auto-thermal


Refrigeration and Deisobutanizer with
effluent Refrigeration
Appendix 4-B provides listings of differences in key word files
from run 1 to runs 2 and 3. Figure 2-3 illustrates the difference in
configuration between the isostripper and the deisobutanizer in the
flowsheet.

PRO/II Case Book Sulfuric Acid Alkylation 4-13


Figure 4-3: Iso-stripper vs. De-butanizer Configuration

The deisobutanizer overhead constitutes the isobutane rich recycle


to the reactor. Based on the recycle rate chosen, the reflux and feed
tray location is optimized in a separate run constrained by an 80
percent of flood specification. The larger the recycle, the smaller
the reflux with the limiting case being the isostripper design
demonstrated by Run #1.
In the flowsheet for the effluent refrigeration process, the reactions
occur under pressure with cooling coils sufficient to keep all
hydrocarbons in the liquid state.
After decanting the acid, the hydrocarbon reactor effluent is let
down and passed through the tube side of the reactor. A 10 F hot-
out/cold-out approach is assumed to be sufficient to cool the
reactor, thus the tube side outlet is assumed to be at 35 F.

4-14 Sulfuric Acid Alkylation February 26, 2014


Input Description
The changes required in the input file are shown in Appendix 4-B.

Results
Key operating conditions for all three configurations studied are
summarized in Table 4-7.
Table 4-7: Comparison of Key Flowsheet Parameters for Alternate Configurations
Refrigeration circuit Auto- Auto- Effluent
Refrigeration Refrigeration Refrigeration
Deisobutanizer Isostripper Deisobutanize Deisobutnaize
configuration r r
Calculated Flow Parameters
Reboiler duties, 106 Btu/hr
De-ethanizer DEC2 1.00 1.00 1.00
De-propanizer DEC3 28.24 27.11 27.20
Iso-stripper DIC4 80.69 80.03 80.03
De-butanizer DEC4 9.09 9.10 9.10
Total reboiler duties 119.02 117.24 117.33

HC liquid reactor effluent


Hot volume rate, gpm 2180 1131 1120
isobutane, liq vol % 64.0 50.7 50.2
Compressor shaft power, hp
Stage 1 996 1454 1706
Stage 2 2005 2016 2086
Total compressor duty 3001 3470 3792
Product flowrates at standard conditions
Gas products, mscfh
Fuel gas 17.42 17.46 17.48
Liquid products, bbl/hr
Liquid propane 111.1 111.0 110.9
Normal butane 118.9 119.0 119.0
12 RVP alkylate 522.3 522.3 522.3

PRO/II Case Book Sulfuric Acid Alkylation 4-15


The significance of these results can be summarized as follows:

Table 4-8: Significance of Results for Runs #2 and #3


Comparison Observation Conclusion
Isostripper vs. Debutanizer operation decreases The isostripper operation
deisobutanizer substantially the isobutane requires a substantially larger
content in the reactor. capital investment for increased
The deisobutanizer operation reactor and settler volumes. The
substantially decreases the benefit to this is a substantially
reactor volumetric throughput. improved octane and lower acid
The deisobutanizer operation consumption due to the higher
decreases the depropanizer duty, reactor isobutane concentration.
but increases refrigeration load.
Auto vs. effluent Autorefrigeration requires less Based on the operating
refrigeration refrigeration. parameters considered here,
autorefrigeration operation is
more economical.
Licensors of autorefrigeration alkylation point out that the lower
temperatures required on the tube side of effluent refrigeration
reactors accounts for the higher compression requirements.[4-9] Note,
however, that the two reactor designs are fundamentally different.
Other considerations, not included here, such as capital costs and
mixing utilities, have an important impact.

Conclusions
Steady state process simulation technology has matured to the point
where large scale highly integrated process plants are simulated
routinely to answer "what if" questions ranging from small
parametric changes to changes in plant configuration. PRO/II has
been used to demonstrate this capability in solving a sulfuric acid
alkylation flowsheet which has a high degree of recycle and thermal
integration. Typical process questions regarding this flowsheet have
been posed and answered.

4-16 Sulfuric Acid Alkylation February 26, 2014


References
4-1 Masters, K.R., "Alkylation's Role in Reformulated Gasoline", pre-
sented at 1991 Spring National Meeting AIChE.

4-2 Unzelman, G.H., "U.S. Clean Air Act Expands Role for Oxygen-
ates", Oil & Gas Journal, April 15, 1991.

4-3 API, Technical Data Book ? Petroleum Refining, Volume 1 (1987).

4-4 Chapin, L.E., Liolios, G.C. and Robertson, T.M., "Which Alkyla-
tion? HF or H2SO4?", Hydrocarbon Processing, September 1985,
pg. 67?71.

4-5 Myer, D.W., Chapin, L.E. and Muir, R.F., "Cost Benefits of Sulfuric
Acid Alkylation," Chem. Eng. Progress, 79, 8, pg. 59?65 (1983).

4-6 Lee, L. and Harriott, P., "The Kinetics of Isobutane Alkylation in


Sulfuric Acid," I&EC Process Design Dev., 16, 3 (1977).

4-7 Cupit, C.R., Gwyn, J.E. and Jernigan, E.C., "Special Report Cata-
lytic Alkylation", Petroleum and Chemical Engineering, 33, 47,
1961 and 34, 49, (1962).

4-8 Soave, G., "Equilibrium Constants from a Modified Redlich?Kwong


Equation of States," Chem. Eng. Sci., 27, 1177?1203 (1972).

4-9 Lerner, H. and Citarella, V.A., "Exxon Research and Engineering


Sulfuric Acid Alkylation Technology", presented at 1991 NPRA
Annual Meeting.

PRO/II Case Book Sulfuric Acid Alkylation 4-17


4-18 Sulfuric Acid Alkylation February 26, 2014
Appendix 4-A Keyword Input

Input File
TITLE PROJ=CaseBook, PROB=H2SO4 ALKY,USER=SIMSCI
DESC 12,000 BPSD H2SO4 Alkylation plant.
PRINT RATE=M,LV,STREAM=PART,INPUT=ALL
CALC TRIALS=40 ,RECYCLE=TEAR
DIME LIQV=BBL,XDENS=SPGR
OUTD SI
SEQU FX,HT3 ,FB2,DEC3, FB2X &
PC1,S1,V1, H2,C1, &
OLSP,RX1A,F1X,RX1B,F1Y,RX1C,F1Z,RX1D, &
F1ZZ,SETL,VAPR,C2,MCOM, P2, &
DIC4,FT1, P1,DEC4,FB4,CL4, &
P3,DEC2,FB1,CL1, &
SCTN,CMP1,CMP2,AFTR
tole duty=0.005,misc=0.01

COMP DATA

LIBID 1,C1 /2,C2 /3,C3 /4,IC4 /5,NC4 /&


6,PROPENE/7,ISOBUTENE/8,T2BUTENE,,2BUTENE /9, 1BUTENE / &
10,IC5 /11,23DMB /12,24MP /13,23MP /&
14,224MPN /15,24HX /16,23HX /17,234MP /18,225MHX
PETRO 19,C9s, 128.26, 0.73, 280 / &
20,C10s, 142.28, 0.74, 325 / &
21,C11s, 156.31, 0.75, 365 / &
22,C12s, 170.34, 0.76, 395 / &
23,C13s, 184.36, 0.77, 425
LIBID 24,H2SO4,BANK=SIMSCI
TC(K) 24,924
PC(BAR) 24,64
$ VISC(L) CORR=1,DATA=24,,,1
VISC(V) CORR=1,DATA=24,,,1
COND(V) CORR=1,DATA=24,,,1
$ COND(L) CORR=1,DATA=24,,,1

THERMODYNAMIC DATA

METHOD SYSTEM=SRK,TRANSPORT=PURE,SET=SRK
ENTHALPY ALPHA=SIMSCI
SA06 24,1.81341,1.25196,0.566576

STREAM DATA

$ SATURATE FEED
PROP STREAM=1,TEMP=100,PRES=400, &
COMP(LV)=1,2 / 2,10 / 3,100 / 4,187.5 / 5,100.

PRO/II Case Book Sulfuric Acid Alkylation 4-19


$ OLEFIN FEED
PROP STREAM=2,TEMP=100,PRES=215, &
COMP(LV)=3,9 / 4,95 / 5,50 / 6,9 / 7,14/ 8,175 /9,56 / 10,5

$ MAKE-UP
PROP STREAM=3,TEMP=100,PRES=400,RATE(LV)=45, &
COMP(LV)=4,80 / 5,20

$ MAKEUP N-BUTANE FOR CASE STUDY ANALYSIS


PROP STREAM=1NB,TEMP=100,PRES=400,COMP(LV)=5,1,RATE=0.00001

$ ACID FEED
PROP STREAM=SA1, TEMP=45, PRES=40, COMP(WT,LB/HR)=24,1000000

$ DEIC4 FEED
PROP STREAM=253X,TEMP=110,PRES=115,REFSTREAM=251

$ DEC2 FEED
PROP STREAM=11B,TEMP=140,REFSTREAM=11A

$ RECYCLE STREAM DATA ESTIMATES

PROP STREAM=27P,NAME=RCY_SAT,PHASE=L,PRES=400, &


COMP=3,80 / 4,280 / 5,50

PROP STREAM=26,NAME=SRG_DRUM,PHASE=L,PRES=73, &


COMP=3,1100 / 4,3500 / 5,620

PROP STREAM=30R,NAME=RCY_IC4,TEMP=62,PRES=200, &


COMP=3,210 / 4, 3000 / 5,300

NAME 1,SATURATED FEED/2,OLEFIN FEED/3,MAKEUP IC4/ &


10,DEC3 FEED/11,PROPANE TO DEC2/12,DEC3 BOTTOMS/ &
20, OLEFIN TO RXN/21,IC4 TO RXN/24, RXN VAPORS/&
25, RXN LIQUIDS/26, COMP SURGE DRUM LIQ/27, RCY TO DEC3/&
30, DEIC4 OVHD/ 30R, IC4 RCY/32, BUTANE/332,ALKYLATE/&
40, FUEL GAS/41B, HD5 PROPANE

OUTPUT FORMAT=VOLSUM, STREAMS=1,2,3,DESCRIPTION=FEED


STREAMS
OUTPUT FORMAT=VOLSUM, STREAMS=40,41B,32,332, &
DESCRIPTION=PRODUCT STREAMS
OUTPUT FORMAT=VOLSUM, STREAMS=25, &
DESCRIPTION=REACTOR EFFLUENT

FORMAT ID=VOLSUM, NAME, LINE, TEMP, PRES, LINE, &


LRATE(LV,1,2,BBL/DAY)=C2+, LRATE(LV,3,BBL/DAY)=PROPANE,&
LRATE(LV,4,BBL/DAY)=I-BUTANE, LRATE(LV,5,BBL/DAY)=N-BUTANE,&
LRATE(LV,6,BBL/DAY)=PROPENE, LRATE(LV,7,9,BBL/DAY)=BUTENES,&
LRATE(LV,10,BBL/DAY)=PENTANE, LRATE(LV,11,23,BBL/DAY)=C6+,LINE,&
RATE(LV,BBL/DAY), RATE(LV,BBL/HR), &

4-20 Sulfuric Acid Alkylation February 26, 2014


RATE(LV,M3/HR), LINE, &
ARATE(LV,GAL/MIN), ARATE(LV,L/MIN), LINE, &
RATE(GV,FT3/HR), RATE(GV,M3/HR), LINE, CPCT(LV,4)
RXDATA

RXSET ID=RS1
REACTION ID=RX1
$ PROPENE - ISOBUTENE REACTION
STOIC 4, -12.3461/ 6, -12.3008/ &
10, 0.5541/ 11, 0.5553/ 12, 2.3756/ 13, 5.9539/ 14, 0.4574/ &
15, 0.0731/ 16, 0.1062/ 17, 0.3969/ 18, 0.0821/ 19, 0.0594/ &
20, 0.6688/ 21, 0.4325/ 22, 0.0468/ 23, 0.0315

REACTION ID=RX2
$ ISOBUTENE - ISOBUTANE REACTION
STOIC 4, -8.5683/ 7, -10.5445/ &
10, 1.2706/ 11, 0.5925/ 12, 0.3827/ 13, 0.2638/ 14, 2.5703/ &
15, 0.3627/ 16, 0.5101/ 17, 2.1523/ 18, 0.3998/ 19, 0.2074/ &
20, 0.2754/ 21, 0.2134/ 22, 0.5173/ 23, 0.0239

REACTION ID=RX3
$ 2-BUTENE - ISOBUTANE REACTION
STOIC 4,-10.9924/ 8, -11.3233/ &
10, 0.6347/ 11, 0.6261/ 12, 0.2832/ 13, 0.1703/ 14, 3.3018/ &
15, 0.4360/ 16, 0.5566/ 17, 4.6514/ 18, 0.1852/ 19, 0.0782/ &
20, 0.0891/ 21, 0.0799/ 22, 0.2831

REACTION ID=RX4
$ 1-BUTENE - ISOBUTANE REACTION
STOIC 4,-11.5763/ 9, -9.9587/ &
10, 0.6877/ 11, 0.5870/ 12, 0.3016/ 13, 0.1730/ 14, 3.1778/ &
15, 0.5271/ 16, 0.6466/ 17, 4.2314/ 18, 0.1686/ 19, 0.0984/ &
20, 0.0720/ 21, 0.0761/ 22, 0.2674/ 23, 0.0079

UNIT OPERATION

FLASH UID=FX,NAME=OLEFIN FD
$ THIS SIMULATES THE OLEFIN FEED FROM THE BOTTOM OF THE
$ OLEFIN DEPROPANIZER (WHICH WILL BE ADDED AT A LATER DATE
FEED 2
PROD L=2A
BUBB TEMP=200

FLASH UID=HT3, NAME=PRECHILLER


$ PRECOOLS OLEFIN FEED TO 100 F
FEED 2A
PROD L=2B
ISO TEMP=100,DP=5

HX UID=FB2
OPERATION CTEMP=170

PRO/II Case Book Sulfuric Acid Alkylation 4-21


COLD FEED=1,1NB,27P,L=10

COLUMN UID=DEC3, NAME=SAT DEC3


FEED 10,20
PROD OVHD=11,60,BTMS=12
CONDENSER TYPE=BUBB,PRES=310
PARA TRAY=40
SPEC REFLUX,VALUE=4000
SPEC STREAM=12,COMP=3,RATE,VALUE=50.0
ESTI MODEL=CONVENTIONAL,RRATIO=9.0
DUTY 1,1/2,40
VARY DUTY=1,2
PSPEC PTOP=315,DPCOL=10
PRINT PROP=BRIEF
TRATE SECTION=2,39,SIEVE,PASSES=2, &
SPACING(TRAY,IN)=24, DIAMETER(TRAY,FT)=10.0

HX UID=FB2X
HOT FEED=12,L=121,DP=5
OPERATION
COLD FEED=1,1NB,27P,L=10X
CONFIG U=80
DEFINE DUTY AS HX=FB2, DUTY

HX UID=PC1, NAME=ECON PRECOOL


HOT FEED=121,L=122,DP=5
OPERATION HTEMP=100
CONFIG U=100
UTIL WATER TIN=70,TEMP=80

SPLITTER UID=S1
FEED 26
PROD L=27,L=28
SPEC STREAM=27,RATE(LV),VALUE=75

VALVE UID=V1
FEED 28
PROD M=28V
OPERATION DP=30

HX UID=H2, NAME=ECONOMIZER
HOT FEED=2B,L=20,DP=3
COLD FEED=122,3,28V,DP=1,L=21,V=29
CONFIG U=80
OPERATION HTEMP=65

CONTROLLER UID=C1
SPEC STREAM=21,TEMP,VALUE=55,ATOL=0.0001
VARY VALVE=V1,DP,MAXI=70

4-22 Sulfuric Acid Alkylation February 26, 2014


$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$
$ REACTOR SECTION
SPLITTER UID=OLSP,NAME=OLEFIN_SPLITTER
FEED 20
PROD V=20A, V=20B, V=20C, V=20D
SPEC STREAM=20A,RATE,RATIO, REFF, VALUE=0.25
SPEC STREAM=20B,RATE,RATIO, REFF, VALUE=0.25
SPEC STREAM=20C,RATE,RATIO, REFF, VALUE=0.25

CONREACTOR UID=RX1A, NAME=1ST_STAGE


FEED 20A,21,30R,SA1
PROD M=24X
OPERATION PRES=30,ADIABATIC
RXCALC MODEL=STOIC $,REFPHASE=L,REFTEMP=45
RXSTOIC RXSET=RS1
REACTION RX1
BASE COMPONENT=6
CONVERSION 1
REACTION RX2
BASE COMPONENT=7
CONVERSION 1
REACTION RX3
BASE COMPONENT=8
CONVERSION 1
REACTION RX4
BASE COMPONENT=9
CONVERSION 1

STCALC UID=F1X,NAME=3_PHASE
FEED 24X
OVHD V=24A,L=25A
BTMS STREAM=25AX
FOVHD 1,23,1.0/24,0.0

CONREACTOR UID=RX1B, NAME=2ND_STAGE


FEED 20B,25A,25AX
PROD M=24Y
OPERATION PRES=29,ADIABATIC
RXCALC MODEL=STOIC $,REFPHASE=L,REFTEMP=45
RXSTOIC RXSET=RS1
REACTION RX1
BASE COMPONENT=6
CONVERSION 1
REACTION RX2
BASE COMPONENT=7
CONVERSION 1
REACTION RX3
BASE COMPONENT=8
CONVERSION 1
REACTION RX4
BASE COMPONENT=9

PRO/II Case Book Sulfuric Acid Alkylation 4-23


CONVERSION 1

STCAL UID=F1Y, NAME=3_PHASE


FEED 24Y
OVHD V=24B,L=25B
BTMS STREAM=25BX
FOVHD 1,23,1.0/24,0.0

CONREACTOR UID=RX1C, NAME=3RD_STAGE


FEED 20C,25B,25BX
PROD M=24Z
OPERATION PRES=28,ADIABATIC
RXCALC MODEL=STOIC $,REFPHASE=L,REFTEMP=45
RXSTOIC RXSET=RS1
REACTION RX1
BASE COMPONENT=6
CONVERSION 1
REACTION RX2
BASE COMPONENT=7
CONVERSION 1
REACTION RX3
BASE COMPONENT=8
CONVERSION 1
REACTION RX4
BASE COMPONENT=9
CONVERSION 1

STCALC UID=F1Z,NAME=3_PHASE
FEED 24Z
OVHD V=24C,L=25C
BTMS STREAM=25CX
FOVHD 1,23,1.0/24,0.0

CONREACTOR UID=RX1D, NAME=4TH_STAGE


FEED 20D,25C,25CX
PROD M=24ZZ
OPERATION PRES=27,ADIABATIC
RXCALC MODEL=STOIC $,REFPHASE=L,REFTEMP=45
RXSTOIC RXSET=RS1
REACTION RX1
BASE COMPONENT=6
CONVERSION 1
REACTION RX2
BASE COMPONENT=7
CONVERSION 1
REACTION RX3
BASE COMPONENT=8
CONVERSION 1
REACTION RX4
BASE COMPONENT=9
CONVERSION 1

4-24 Sulfuric Acid Alkylation February 26, 2014


STCALC UID=F1ZZ,NAME=3_PHASE
FEED 24ZZ
OVHD V=24D,L=25D
BTMS L=25DX
FOVHD 1,23,1.0/24,0.0

STCALC UID=SETL,NAME=ACID_SETTLER
FEED 25D/25DX
OVHD V=24E,L=25,PRES=26
BTMS STREAM=SA2,PRES=26
FOVHD 1,23,1.0/24,0.0

MIXER UID=VAPR, NAME=RXN_VAPORS


FEED 24A,24B,24C,24D,24E
PROD V=24

CONTROLLER UID=C2
SPEC STREAM=25,TEMP,VALUE=45,ATOL=0.0002
VARY SPLITTER=S1,SPEC,MINI=1,MAXI=1000,STEP=20
CPARAMETER ITER=5

$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$
$ REFRIGERATION CIRCUIT

FLASH UID=MCOM $ SIMULATED IN DETAIL OUTSIDE THE


FEED 24,29 $ RECYCLE LOOPS WITH CMP1, CMP2 AND AFTR
BUBB TEMP=100 $ PRES=73
PROD L=26

$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$
$ PRODUCT PURIFICATION CIRCUIT

PUMP UID=P2,NAME=EFFL_PUMP
FEED 25
PROD L=251
OPERATION PRES=120

$
$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$
$ After first run, substitute first insert in Appendix 4-B for Column DIC4
COLUMN UID=DIC4, NAME=ISO-STRIPPER
PARA SURE=20, TRAYS=42
FEED 253X, 1
PROD OVHD=30, BTMS=31, 1300
DUTY 1, 42

$ The next line sets the iC4 recycle rate


SPEC STREAM=30, RATE(LV),VALUE=2525

PRO/II Case Book Sulfuric Acid Alkylation 4-25


VARY DUTY=1
ESTIMATE MODEL=CONVENTIONAL
PRESSURE 1,90 / 42,95
PRINT PROP=BRIEF
TRATE SECTION=2,42,SIEVE,PASSES=4, &
SPACING(TRAY,IN)=24, DIAMETER(TRAY,FT)=13

$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$

HX UID=FT1,NAME=EFFL_RECL
COLD FEED=251,L=252,DP=5
HOT FEED=30,L=30R,DP=5
OPER HTEMP=62
CONFIG U(BTU/HR)=90

PUMP UID=P1
FEED 27
PROD L=27P
OPER PRES=400

$ THE DEBUTANIZER CIRCUIT IS SOLVED OUTSIDE THE LOOP

COLUMN UID=DEC4,NAME=DEBUTANIZER
PARA TRAYS=30,ERRINC=1.05
FEED 31,15
PROD OVHD=32,350,BTMS=33
COND TYPE=TFIX,TEMP=100,PRES=80
DUTY 1,1/2,30
SPEC STREAM=33, RVP,VALUE=12.0
SPEC STREAM=32, COMP=10, PERCENT(LV), VALUE=2.0
VARY DUTY=1,2
ESTIMATE MODEL=CONVENTIONAL
PRESSURE 2,85/30,90
PRINT PROP=BRIEF
TRATE SECTION=2,29,SIEVE,PASSES=1, &
SPACING(TRAY,IN)=24, DIAMETER(TRAY,FT)=5

HX UID=FB4,NAME=EFFL_ALKY
COLD FEED=252,L=253,DP=5
HOT FEED=33,L=331,DP=5
OPER CTEMP=110

HX UID=CL4,NAME=ALKY_CLR
HOT FEED=331,L=332,DP=5
UTIL WATER TIN=70,TEMP=80
OPER HTEMP=100

$ THE DEETHANIZER IS SOLVED OUTSIDE THE LOOP

PUMP UID=P3
FEED 11

4-26 Sulfuric Acid Alkylation February 26, 2014


PROD L=11A
OPERATION PRES=600

COLUMN UID=DEC2, NAME=DEETHANIZER


FEED 11B,5
PROD OVHD=40,40,BTMS=41
CONDENSER TYPE=PART,PRES=420
PARA TRAY=20
SPEC TRAY=1,TEMP,VALUE=100.0
SPEC STREAM=41,TVP(PSIG),VALUE=203 $ HD5 SPEC IS 208 MAX
ESTI MODEL=CONVENTIONAL,RRATIO=2.0
DUTY 1,1/2,20
VARY DUTY=1,2
PSPEC PTOP=425,DPCOL=10
PRINT PROP=BRIEF
TSIZE SIEVE

HX UID=FB1
COLD FEED=11A,L=11B,DP=5
HOT FEED=41,L=41A,DP=5
OPERATION HOCO=5

HX UID=CL1
HOT FEED=41A,L=41B,DP=5
UTIL WATER TIN=70,TOUT=80
OPERATION HTEMP=100

$ THE COMPRESSOR REQUIREMENTS CAN BE CALCULATED AFTER


$ THE RECYCLE LOOPS ARE SOLVED

VALVE UID=SCTN, NAME=SUCTION


FEED 24
PROD V=240
OPERATION PRES=23

COMPRESSOR UID=CMP1, NAME=1ST STAGE


FEED 240
PROD V=241
OPERATION CALC=GPSA,EFF=80
DEFINE PRESSURE AS STREAM=29 PRESSURE MINUS 1

COMPRESSOR UID=CMP2, NAME=2ND STAGE


FEED 241,29
PROD V=260
OPER CALC=GPSA
DEFINE PRESSURE AS STREAM=26,PRESSURE,PLUS 5.0

FLASH UID=AFTR, NAME=AFT_COOL


FEED 260
PROD L=261
BUBB DP=5

PRO/II Case Book Sulfuric Acid Alkylation 4-27


$ -----------------------------------------------------
RECYCLE

LOOP NO=1, START=FB2, END=P1, TOLE=0.0025


LOOP NO=2,START=DEC2,END=FB1, WEGS, TOLE=0.0005

$ -----------------------------------------------------

CASESTUDY OLDCASE=BASECASE,NEWCASE=MORE_C3
CHANGE COLUMN=DEC3,SPEC(2),VALUE=100
DESC INCREASE C3 IN THE BOTTOMS OF THE
DESC SATURATE DEPROPANIZER.

CASESTUDY OLDCASE=BASECASE,NEWCASE=MORE_IC4
CHANGE COLUMN=DIC4,SPEC,VALUE=2600
DESC INCREASE IC4 RECYCLE

CASESTUDY OLDCASE=BASECASE,NEWCASE=MORE_NC4
CHANGE STREAM=1NB,RATE(LV),VALUE=50
DESC INCREASE NC4 IN SATURATE FEED

END

4-28 Sulfuric Acid Alkylation February 26, 2014


Appendix 4-B
Input Changes for Runs 2 and 3

Keyword Input File Inserts


Run 2 (De-isobutanizer Configuration) and
Run 3(Effluent Refrigeration Configuration)
Substitute these file inserts for the corresponding sections if input
listed in Appendix 4-B.

Insert 1: Debutanizer
Original input to discard:
COLUMN UID=DIC4, NAME=ISO-STRIPPER
PARA SURE=20, TRAYS=42
FEED 253X, 1
PROD OVHD=30, BTMS=31, 1300
DUTY 1, 42

$ The next line sets the iC4 recycle rate


SPEC STREAM=30, RATE(LV),VALUE=2525

VARY DUTY=1
ESTIMATE MODEL=CONVENTIONAL
PRESSURE 1,90 / 42,95
TRATE SECTION=2,42,SIEVE,PASSES=4, &
SPACING(TRAY,IN)=24, DIAMETER(TRAY,FT)=13
PRINT PROP=BRIEF

Changed input to insert:


COLUMN UID=DIC4, NAME=Debutanizer
PARAMETER TRAY=43
FEED 253X, 20
PROD OVHD=30, BTMS=31, 1300
DUTY 1, 1 / 2, 43
SPEC STREAM=30, RATE(LV), VALUE=1000

$ The next statements set the IC4 recycle


SPEC REFLUX(LV), VALUE=1600
VARY DUTY=1, 2
ESTIMATE MODEL=CONVENTIONAL
PRESSURE1, 85 / 2, 90 / 43, 95
TRATESECTION=2,42 SIEVE, PASSES=4, &
SPACING(TRAY, IN)=24, DIAMETER(TRAY, FT)=13

PRO/II Case Book Sulfuric Acid Alkylation 4-29


PRINT PROP=BRIEF

Insert 2: Effluent Refrigeration


Changed input to be inserted.
Replace CONREACTOR RX1A with:
PUMP UID=P4, NAME=Sats Pump
FEED 21
PROD L=21X
OPERATION PRES=80

REACTOR UID=RX, NAME=1st_stage


FEED 20, 21X, 30R, SA1
PROD M=25X
OPERATION PRES=80, ISPTHERMAL, TEMP=45
RXCALC CONV $ RefPhase=L, RefTemp=45
$ PROPENE - ISOBUTENE REACTION
REACTION RX1
BASE COMPONENT=6
CONVERSION 1
$ ISOBUTENE - ISOBUTANE REACTION
REACTION RX2
BASE COMPONENT=7
CONVERSION 1
$ 2-BUTENE - ISOBUTANE REACTION
REACTION RX3
BASE COMPONENT=8
CONVERSION 1
$ 1-BUTENE - ISOBUTANE REACTION
REACTION RX4
BASE COMPONENT=9
CONVERSION 1

STCALC UID=ACST, NAME=Acid Settler


FEED 25X
OVHD L=25Y, DP=2
BTMS STREAM=SA1, DP=0
FOVHD 1,23, 1.0 / 24, 0.0
$
$ Simulates
$ dP across valve,
$ dP across tubes,
$ heat exchange and separation in one unit
$
$FLASH UID=TUBE, NAME=Cooling Tubes
FEED 25Y
PROD V=24, L=25
ADIA TEMP=35, PEST=20
DEFINE DUTY AS REACT=RX, DUTY, MULTIPLY, -1.0

4-30 Sulfuric Acid Alkylation February 26, 2014


Appendix 4-C :
Wet Sulfuric Acid Process

The availability of a suitable catalyst is also an important factor in


deciding whether to building an alkylation plant. When sulfuric
acid is used, significant volumes are needed. Access to a suitable
plant is required for the supply of fresh acid and the disposition of
spent acid. If a sulfuric acid plant must be constructed specifically
to support an alkylation unit, such construction will have a
significant impact on both the initial requirements for capital and
ongoing costs of operation.
Alternatively it is possible to install a WSA Process unit to
regenerate the spent acid. The WSA process is the ideal choice for
regeneration of spent sulphuric acid. No drying of the gas takes
place. This means that there will be no loss of acid, no acidic waste
material and no heat is lost in process gas reheating. The selective
condensation in the WSA condenser ensures that the regenerated
fresh acid will be 98% w/w even with the humid process gas. It will
be possible to combine spent acid regeneration with disposal of
hydrogen sulphide by using hydrogen sulphide as fuel.[A-5].
The wet sulfuric acid process (WSA process) is one out of many gas
desulfurization processes on the market today. Since its
introduction in the 1980s, where it was patented by the Danish
catalyst company Haldor Topse A/S, it has been recognised as an
efficient process for recovering sulfur from various process gasses
in the form of commercial quality sulfuric acid (H2SO4). The WSA
process is applied in all industries where removal of sulfur is an
issue.
Wet catalysis processes differ from other contact sulfuric acid
processes in that the feed gas still contains moisture when it comes
into contact with the catalyst. The sulfur trioxide formed by
catalytic oxidation of the sulfur dioxide reacts instantly with the
moisture to produce sulfuric acid in the vapour phase to an extent
determined by the temperature. Liquid acid is subsequently formed
by condensation of the sulfuric acid vapour and not by absorption of
the sulfur trioxide in concentrated sulfuric acid, as is the case in
contact processes based on dry gases. The concentration of the

PRO/II Case Book Sulfuric Acid Alkylation 4-31


product acid depends on the H2O/SO3 ratio in the catalytically
converted gases and on the condensation temperature. [A-5] [A-6]
The wet catalysis process is especially suitable for processing the
wet gasses obtained by the combustion of hydrogen sulfide (H2S)
containing off-gasses.[A-7] The combustion gasses are merely
cooled to the converter inlet temperature of about 420-440 C. To
process these wet gasses in a conventional cold-gas contact process
(DCDA) plant would necessitate cooling the gas to an economically
unacceptable extent to remove the large excess of moisture.
Therefore in many cases Wet catalysis processes is a more cost-
efficient way of treating hydrogen sulfide containing off-gases.
Description of the wet sulfuric acid process (WSA)
In the first step, sulfur is burned to produce sulfur dioxide.
S (s) + O2 (g) --> SO2 (g) (4-4)
or Hydrogen sulfide H2S gas is incinerated to SO2 gas.
H2S + 3/2O2 --> H2O + SO2 + 518KJ/mole (4-5)
This is then oxidized to sulfur trioxide using oxygen in the presence
of a vanadium (V) oxide catalyst.
2 SO2 + O2 --> 2 SO3 + 99KJ/mole (in presence of V2O5) (4-6)
The sulfur trioxide is hydrated into sulfuric acid H2SO4.
SO3 + H2O --> H2SO4 (g) + 101 KJ/mole (4-7)
The last step is the condensation of the sulfuric acid to liquid 97-
98% H2SO4
H2SO4 (g) + 0.17H2O (g) --> H2SO4(l) + 69 KJ/mole

Appendix 4-C References


A-5 Sulphur recovery; (2007) The Process Principles, details advances
in sulphur recovery by the WSA process. Denmark: Jens Kristen
Laursen, Haldor Topse A/S. Reprinted from Hydrocarbon Engi-
neering August 2007

A-6 U.H.F Sander, H. Fischer, U. Rothe, R. Kola (1984). Sulphur, Sul-


phur Dioxide and Sulphuric Acid (1st Edition ed.). The British Sul-
phur Corporation Limited. ISBN 0902777645.

A-7 Gary, J.H. and Handwerk, G.E. (1984). Petroleum Refining Technol-
ogy and Economics (2nd Edition ed.). Marcel Dekker, Inc. ISBN
0824771508.

4-32 Sulfuric Acid Alkylation February 26, 2014


Case 5:
Urea Plant

ABSTRACT
This case book demonstrates the use of PRO/II in the simulation
of a chemicals processing plant manufacturing 1000 tons per day of
urea from ammonia and carbon dioxide. Urea is widely used as a
solid fertilizer, as a protein supplement for livestock, as well as a
feedstock for the manufacture of plastics and adhesives. The
process plant simulated here includes a reactor, an NH3 recovery
distillation column, and a series of crystallizers. SIMSCISM's NRTL
databank, along with urea/water solubility data, provide a good
simulation of the system's vapor-liquid and solid-liquid equilibria.
Urea growth and nucleation rate crystallization data obtained from
the literature are provided for the crystallizer units.

Feature Highlights
Solids-Handling Application
User-supplied Solubility Data
Stoichiometric Reactor Units
Filtering Centrifuge Units
Solids Dryer and Freezer Units
Crystallizer Units with User-supplied Nucleation and Growth
Rates

PRO/II Case Book Urea Plant 5-1


Introduction
What is Urea?
Urea is a source of fixed nitrogen used primarily as a crop fertilizer
and as a protein food supplement for livestock. Urea is particularly
desirable for this use as it is readily soluble in water. A secondary
use for urea is as a feedstock for the manufacture of adhesives,
plastics and resins.
Urea is manufactured by the high pressure reaction of ammonia and
carbon dioxide to form ammonium carbamate, followed by the
decomposition of the carbamate to yield urea and water. With
recycle and a stoichiometric excess of feed components, about 99%
of the CO2 and NH3 is converted to urea. The major contaminant is
a dimer of urea called biuret (NH2CONHCONH2.H2O). The biuret
concentration should not exceed 0.2-0.3% when the urea is to be
used for feed supplements or as feedstock for plastics production.
For fertilizer use, the biuret content may be up to 1%.

Relevance
Urea has a maximum nitrogen content of 46% and, among major
nitrogenous fertilizers, is second only to ammonia. It also has the
highest nitrogen content of any solid fertilizer and can be easily
manufactured as granules. Worldwide, in 2002 a total of about 108
million metric tons (108Mt) of urea were produced in more than 70
countries. This production delivered about 51.4Mt of contained
nitrogen. China was the largest producer with about 28%, and all of
asia accounted for about 46% of the total. The United States
produced about 13%, or about 14Mt. Capacity in North America
and Western Europe is expected to decline due to fluctuating natural
gas prices. It is expected that production will continue to shift
toward world regions that have abundant natural gas, lower-cost
raw materials, and cheaper labor.

Routes to Urea
The production of urea may be divided into two separate parts:
Synthesis
Finishing
The synthesis loop produces a concentrated 70-80% urea solution.
The finishing step produces either granular urea or crystalline urea.
Spherical granules or flakes are formed by evaporation followed by

5-2 Urea Plant February 26, 2014


passing the molten solid product countercurrent to a flow of hot air
(known as prilling). Crystallization is used to produce virtually pure
crystalline urea. The type of finishing process determines the final
form of urea required (i.e., the biuret content, grain size, and
moisture content).
Once-through urea processes, now rare, were once common. In
these plants, unconverted ammonia would be recovered and
undergo downstream conversion to other ammonium compounds.
Nowadays, partial and total recycle processes are used, with total
recycle plants being more commonplace.
Two types of urea manufacturing process obtained from the open
literature are outlined below.
Table 5-1: Types of Urea Manufacturing Processes
Process Description Reference
Toyo Koatsu Total recycle process using medium operating Chao1 and
conditions (synthesis loop at 3500 psia, high Dente2
pressure decomposer at 325 psia, low pressure
decomposer at 25 psia). Produces prilled urea with
0.4 wt% biuret, and 0.3 wt% moisture.

Snamprogetti Total recycle process using mild operating Hydrocarbon


conditions (synthesis loop at 2500 psia, high Processing6
pressure decomposer at 260 psia, low pressure
decomposer at 65 psia).

In the United States, urea is produced mainly in the form of


spherical prills or granules between 20 and 50 US. mesh in size,
although the use of purer, crystalline urea is increasing rapidly.

Process Outline
The urea process described in this case book produces a crystalline
product, and is based on information obtained from Chao1 and
Dente2. The urea process presented is intended as a generalized
example of a urea flowsheet and does not represent any specific
licensed technology. The urea flowsheet presented here is based on
the plant described by Chao1 for the Toyo Koatsu process, which is
a total NH3 recycle process. The urea synthesis plant modeled here
is a partial NH3 recycle process. A schematic of the process is
shown in Figure 5-1.

PRO/II Case Book Urea Plant 5-3


Figure 5-1: Urea Plant Schematic

U
r
e
a

i
s

f
o
r
med by reacting CO2 and NH3 at high temperature and high
pressure to form ammonium carbamate urea, and water:
3NH 2 COONH 4 + NH 2 COONH 4
8NH 3 + 4CO 2 (5-1)
+3H 2 O
This highly exothermic reaction goes almost to completion under
reactor conditions of about 365 F and 3515 psia. The reactor
product stream pressure is let down through a pressure control valve
on the exit of the reactor. The reactor exit stream then enters the
NH3 recovery column where recovered NH3 is recycled back to the
reactor. The bottoms of the NH3 recovery column then enter the
high pressure decomposer where a small fraction of the ammonium
carbamate is decomposed and excess NH3 is removed as a vapor
stream:
NH 2 COONH 4 NH 2 CONH 2 + H 2 O (5-2)
This equilibrium endothermic decomposition reaction does not go
to completion under normal reaction conditions of 302 F and 325

5-4 Urea Plant February 26, 2014


psia. The exiting liquid then enters the low pressure decomposer
where the majority of ammonium carbamate decomposes at 150 F
and 25 psia, and a mixed NH3/H2O vapor is removed as a vapor
stream. The liquid stream then enters a flash drum followed by an
evaporator where additional NH3/H2O is removed as a vapor. The
remaining liquid urea/H2O stream then enters the crystallization
section.
The crystallization scheme used involves the use of a vacuum,
forced recirculation configuration. This concentrates the solution to
supersaturation resulting in urea crystal formation. The first
crystallizer operates at 130 F and 1.5 psia, while the second
crystallizer operates at 130 F and 1.335 psia. Following each
crystallization stage is a centrifuge which separates the crystal
product from the mother liquor. The two stage crystallizer is then
followed by a dryer to remove<%0> most of the <%-2>remaining
water. This type of crystallization scheme requires significantly less
energy compared to atmospheric configurations.

Process Simulation
The complete input file for this simulation can be found in
Appendix 5-B. Selected portions of the input file are shown here.
For detailed explanations of the keywords used in the input file,
please refer to the PRO/II Keyword Manual, available from
Invensys.
KWM n appears beside some examples of keyword input. KWM indicates the
PRO/II Key Word Manual, Thermo indicates the PRO/II
Thermodynamic Data Input Manual, etc. n indicates the chapter
that provides detailed explanation of the keyword entries.

PRO/II Case Book Urea Plant 5-5


Simulation Model
Figure 5-2 shows a block diagram of the simulation flowsheet.

Figure 5-2: Urea Plant Simulation Flowsheet

5-6 Urea Plant February 26, 2014


General Data
English units of measure are used throughout the simulation for
input and output report data. The density units are changed from the
default API gravity units to DENSITY units (lb/ft3). The
FLENGTH keyword is used to specify the fine length units of
microns. The MBAL keyword specifies that an overall mass
balance be reported in the final output.
KWM 5 DIMEN ENGLISH, XDEN=DENSITY, FLENGTH=MIC
PRINT RATE=W, STREAM=COMPONENT, MBAL

Component Data
All components except the intermediate, ammonium carbamate, are
in the SimSci databank. Ammonium carbamate is specified to be a
non-library component (using the NONLIB keyword). The particle
size distribution intervals for urea are given using the ATTRIBUTE
statement. The component urea is specified to exist in the vapor,
liquid, and solid phases using the PHASE statement.
KWM 6 COMPONENT DATA
LIBRARY 1, UREA / 2, WATER / 4, AMMONIA / 5, CO2 / &
6, N2 / 7, O2 / 8, H2, BANK=SIMSCI
NONLIBRARY 3, AMCA
PHASE VLS=1
ATTR COMP=1, PSD(MIC) 0, 20, 50, 100, 200, 500, 1000.

Literature data1,4 and the property estimation facilities of the


Thermodynamics Data Manager (TDM program) are used to obtain
physical property data for the intermediate compound ammonium
carbamate. A portion of the physical property data input for this
compound is shown below.
$ PRO/II physical property insert for:
$ Name: AMMONIUM CARBAMATE
$ Formula: CH6N2O2
$ Created: 08/24/93
$ Source: User File: urea
$
$ Thermo methods available for use:
$ Library
$ EOS Methods
$
PHASE VLS = 3
MW 3, 0.7807092E+02
SPGR 3, 1.2
ACENTRIC 3, 0.5942138E+00
TC(K) 3, 0.6590952E+03
PC(PA) 3, 0.6740707E+07
FORMATION(S,J/KG,MOLE) 3, -.6450466E+09, -.4480641E+09

PRO/II Case Book Urea Plant 5-7


NMP(K) 3, 0.4061500E+03
HFUS(J/KG,MOLE) 3, 0.6903593E+08
VP(L,PA,K) CORR=20, LN, DATA= 3, &
0.4261500E+03, 0.3031500E+03, -.2929800E+02, -
.3908196E+04, &
0.9295685E+01, -.1620786E-04, 0.2000000E+01, 0.1162653E-
07

Thermodynamic Data
The NRTL liquid activity coefficient method is used to predict the
vapor-liquid equilibria, while the Soave-Redlich-Kwong equation
of state is used to calculate the liquid and vapor phase entropies.
Transport properties are calculated using the LIBRARY method.
User-supplied solubility data are used to predict solid-liquid
solubilities.
KWM 8 THERMODYNAMIC DATA
METHOD SYSTEM=NRTL, ENTROPY(V)=SRK, ENTROPY(L)=SRK,
&
KVALUE(SLE)=SOLDATA, TRANSPORT=LIBRARY

Solubility Data
With many inorganic systems, ideal solubility does not adequately
describe the solution behavior. For these cases solubility data can be
fitted to the following equation:

ln x i = A + B
---- + C ln T (5-3)
T
The above equation provides a good fit to much of the solubility
data reported in the literature. For systems containing more than
one solvent, the solubility of the solute in the multi component
solvent is calculated using the following relationship:

x i mix = xj xij ji (5-4)

j=1

where:
xj
x j = ------------------- ji (5-5)
N
x
j
j = 1

The solubility expression and the mixing rule described in the


above equations provide a great deal of flexibility in matching data

5-8 Urea Plant February 26, 2014


reported in the literature and obtained in the plant. Solubility data
for the urea/water solute/solvent pair are provided as shown below.
Thermo 7 KVALUE(SLE)
SOLUTE 1
SOLDATA(K) 1,2, 0., -1310.37, 0.533619

Stream Data
Feed Streams
Data for the ammonia feed stream and the carbon dioxide feed
stream are provided as shown below.
KWM 9.1 STREAM DATA
PROP STRM=1, TEMP=-28, PRES=320, COMP(W)=4,105049
PROP STRM=2, TEMP=100, PRES=300, COMP(W)=5,93408

Recycle Streams
The composition, temperature, and pressure of the recycle stream
from the NH3 recovery column are estimated initially for the first
run through the simulation.
$ INITIAL GUESS FOR TEAR STREAMS
$
KWM 9.1 PROP STRM=7, TEMP=126, PRES=320, COMP(W)=2, 0.5 / 4, 58667.0

Reaction Data
The stoichiometry of the two reactionsthe primary urea reaction
and the decomposition reaction<%-2>is provided in the Reaction
Data category of input.
KWM 10.8 RXDATA
RXSET ID=RST1
REACTION ID=RXC1
STOICHIOMETRY 4,-8 / 5,-4 / 1,3 / 2,3 / 3,1
$
$ DECOMPOSITION REACTION
$
RXSET ID=RST2
REACTION ID=RXC2
STOICHIOMETRY 3,-1 / 4,2 / 5,1

PRO/II Case Book Urea Plant 5-9


Unit Operations
Urea Synthesis
As shown in Figure 5-2, fresh NH3 feed (stream 1) is mixed with
recycle NH3 (stream 7) from the NH3 recovery column (COL1).
The combined NH3 feed is raised to the operating pressure of
reactor RX1 of 3515 psia in pump P1. Fresh CO2 feed (stream 2) is
raised to the operating pressure of reactor RX1, 3516 psia, in
compressor COM1. The primary urea reaction occurs in a high
pressure, high temperature reactor. Reactor (RX1) is modeled as a
conversion reactor unit, with 100% conversion. This reactor uses
the reaction set RSTI previously defined in the Reaction Data
category of input.
Note that the heat of reaction may be optionally input for the urea
reaction. However, PRO/II can calculate the heat of reaction from
the heat of formation of the components if a value is not input.

KWM 14.2 CONREACTOR UID=RX1


FEED 3, 4 PRODUCT L=5
OPERATION ISOTHERMAL, PHASE=L, TEMP=365.
RXCALC MODEL=STOIC
RXSTOIC RXSET=RST1
REACTION RXC1
BASE COMPONENT=5
CONVERSION 1.0
High pressure reactor effluent is reduced in pressure to 320 psia
through a valve (VL1) before entry into the NH3 recovery column
(COL1). The column is simulated with the SHORTCUT column
model. The column product specifications are 65% of the NH3 are
recovered in the overhead product (stream 7), which is 99.995%
ammonia. A bubble condenser is used for the overhead product.

KWM 12.8 SHORTCUT UID=COL1


FEED 6
PRODUCT STREAM=7, PRES=320, PERCENT(W)=23
PRODUCT STREAM=8, PRES=325
SPEC STREAM=7, COMP=4, FRACTION(W), VALUE=.99995
SPEC STREAM=7, COMP=4, RATE(W), RATIO, &
STREAM=6, COMP=4, RATE(W), VALUE=0.65
CONDENSER TYPE=BUBBLE
EVALUATE MODEL=CONVENTIONAL, KEYL=4, KEYH=2, RRMIN=2.5
The bottoms product from column COL1 (stream 8) is then sent to
the high pressure and low pressure decomposers (RX2, RX3)
modeled as conversion reactors. Both reactors use reaction set

5-10 Urea Plant February 26, 2014


RST2 previously defined in the Reaction Data category of input. In
the high pressure (325 psia) reactor, 88% of the carbamate is
decomposed to urea under isothermal conditions at 302 F. An off
gas of CO2 and NH3 is generated in streams 9 and 12. In the low
pressure (25 psia) reactor, 99.95% of the remaining carbamate is
converted to urea at 252 F.
KWM 14.2 CONREACTOR UID=RX2
FEED 8
PRODUCT V=9, L=10
OPERATION ISOTHERMAL, PHASE=L, TEMP=302.
RXCALC MODEL=STOIC
RXSTOIC RXSET=RST2
REACTION RXC2
BASE COMPONENT=3
CONVERSION 0.88
$
$ HIGH PRESSURE DECOMPOSER BOTTOMS COOLER
$
KWM 11.1 FLASH UID=FL2
FEED 10
PRODUCT M=11
ISO TEMP=158, PRES=25
$
$ LOW PRESSURE DECOMPOSER
$
KWM 14.2 CONREACTOR UID=RX3
FEED 11
PRODUCT V=12, L=13
OPERATION ISOTHERMAL, PHASE=L, TEMP=252.
RXCALC MODEL=STOIC
RXSTOIC RXSET=RST2
REACTION RXC2
BASE COMPONENT=3
The reaction product stream 13 is then sent into a flash drum (FL3)
and evaporator (FL4), both modeled as flash units, where H2O and
NH3 are taken off as a vapor in streams 14 and 16.

Finishing
The bulk urea solution from the urea synthesis section is then sent
into the first stage (CR1) of a two stage vacuum evaporative
crystallization purification process. The crystallizer is operated at
130 F and 1.5 psia, and a design specification is made that 85% of
the urea in the feed crystallizes. Growth and crystal nucleation rate
data are provided using information obtained from the literature.
See the Kinetic Data section later in this case book for more
information on how these parameters were derived.

PRO/II Case Book Urea Plant 5-11


Following the first crystallizer unit, the slurry is sent into a
centrifuge (CEN1) to separate the crystal product from the mother
liquor. The diameter of the centrifuge is specified to be 3 feet, and
operates at a speed of 1000 RPM.
KWM 15.6 CRYSTALLIZER UID=CR1, NAME=CSTAGE1
FEED 18
PRODUCTS OVHD=19, BTMS=20
PRINT CSD
OPERATION SOLUTE=1, SOLVENT=2, TEMP=130, PRES=1.5
DESIGN PFRAC=0.85
GROWTH KG=2.952E-8, GEXP=0.
NUCLEATION KB=8.7417, BEXP=-3.87, 0., -1.75, 0.
$
$ PUMP INTO FIRST CENTRIFUGE
$
KWM 11.2 PUMP UID=P3, NAME=PUMP3
FEED 20
PRODUCT L=21
OPERATION PRES=20
$
$ FIRST STAGE CENTRIFUGE
$
KWM 15.3 FCENTRIFUGE UID=CEN1, NAME=CENT1
FEED 21
PRODUCT FILTRATE=22, CAKE=23
RATING DIAMETER=3, RPM=1000
The mother liquor (stream 22) is then sent to the second stage
crystallizer (CR2) and centrifuge (CEN2). The second crystallizer
operates at the same temperature as the first, 130 F, but at a lower
pressure, 1.335 psia.
KWM 15.6 CRYSTALLIZER UID=CR2, NAME=CSTAGE2
FEED 22
PRODUCTS OVHD=24, BTMS=25
PRINT CSD
OPERATION SOLUTE=1, SOLVENT=2, TEMP=130, PRES=1.335
DESIGN PFRAC=0.95
GROWTH KG=2.952E-8, GEXP=0.
NUCLEATION KB=8.7417, BEXP=-3.87, 0., -1.75, 0.
$
$ PUMP INTO SECOND CENTRIFUGE
$
KWM 11.2 PUMP UID=P4, NAME=PUMP4
FEED 25
PRODUCT L=26
OPERATION PRES=20
$
$ SECOND STAGE CENTRIFUGE
$
KWM 15.3 FCENTRIFUGE UID=CEN2, NAME=CENT2

5-12 Urea Plant February 26, 2014


FEED 26
PRODUCT FILTRATE=27, CAKE=28
RATING DIAMETER=3, RPM=1000
Both crystal product streams 23 and 28 are then sent to a dryer
(DR1) where the final crystal product, containing 0.1% moisture by
weight, is produced (stream 30).
$
$ FINAL DRYING OF SOLID PRODUCT
$
KWM 15.1 DRYER UID=DR1, NAME=DRYER
FEED 23, 28
PRODUCT OVHD=29, BTMS=30
OPERATION PRES=15
DESIGN BTMS, MOISTURE(W)=0.001
Finally, the solid urea crystals from the dryer are cooled to 200 F
prior to prilling.
$MAKE SURE THAT ANY REMAINING UREA IS CONVERTED TO A SOLID
$PRIOR TO CONVERSION TO A GRANULAR PRODUCT
$
KWM 15.7 FREEZER UID=FRZ1, NAME=FREEZER
FEED 30
PRODUCT M=31
OPERATION TEMP=200., DP=0.
The prilling section of the urea flowsheet, which converts the urea
into a granular product, is not simulated in this case book.

Kinetic Data
It is important to accurately determine growth and nucleation
kinetic parameters. The article by Bennett3 is a good source of urea
crystallization data. The articles by Bennett3 and Perry4 provide
good discussions on calculation of crystallization kinetic
parameters from crystal size distribution data.
Crystal size distribution data obtained from the Bennett3 article for
sample number 192 are used to demonstrate how to calculate both
growth and nucleation rates. First, the crystal size distribution data
in Tyler screen size are converted to average particle diameter.

Table 5-2: Tyler Screen Sizes


Screen Length Average Diameter
Range range (mm) (mm)
14-20 1.168-0.833 1.000
20-28 0.833-0.589 0.711

PRO/II Case Book Urea Plant 5-13


Table 5-2: Tyler Screen Sizes
Screen Length Average Diameter
Range range (mm) (mm)
28-35 0.589-0.417 0.503
35-48 0.417-0.295 0.356
48-65 0.295-0.208 0.251
65-100 0.208-0.147 0.178

Next the cumulative screen collection data must be converted into


actual weight percent for each interval range.
Table 5-3: Screen Collection Data
Avg Diameter, Screen Weight
Dav (mm) Accumulation Percent
1.000 4.4 4.4
0.711 18.8 14.4
0.503 43.0 24.2
0.356 74.6 31.6
0.251 90.1 15.5
0.178 97.5 7.4
-0.178 100.0 2.5

The number density (nL) as defined here is the number of crystals in


a specified size range up to size L per liter of volume. The formal
definition for n is:
N
nL = lim -------- (5-6)
where: l 0 L

N = number of crystals retained on the screen in the


specified size range
L = difference between the screen size of the retaining sieve
and its immediate predecessor.
As an example, the number density for screen size 14-20 (n20) is
calculated directly using the following slurry properties and the
above screen data.
Slurry density, MT = 450. g/L

5-14 Urea Plant February 26, 2014


Crystal density, rc = 1.335 g/cm3 = 1.335x10-3 g/mm3
Retention time, t = 3.38 h
L = 1.168-0.833 = 0.335 mm
Crystal volume, Vc = Dav3
Now, nL is given by:
M T x wt
n L = -------------------
- (5-7)
c V c L
where:
xwt = weight fraction retained on screen
So for example, the number of crystals / mm L
450 0.044
n 20 = ----------------------------------------------------------------------------------- = 44273 (5-8)
3
1.335 10 1.168 0.833 1.0
ln(n20) = 10.698
Similar calculations for the other screen sizes yield the following
table.

Table 5-4: Crystal Number Density


Avg Diameter, Number Density
Dav (mm) ln(n)
(n)
0.178 72492960 18.099
0.251 37958350 17.452
0.356 19346070 16.778
0.503 3726570 15.131
0.711 553490 13.224
1.000 44773 10.698

A plot of the natural log of number density versus the average


particle diameter is known as a Population Density Plot. An
example is shown in) as shown in Figure 3.
The intercept of this plot, n0, is known as the nuclei population
density. When using the following relationships, both the nucleation
and growth rates are calculated.
D av 0
ln n = -----------
- + ln n
Gt
0
B = Gn (5-9)

PRO/II Case Book Urea Plant 5-15


where:
Dav= average crystal diameter
G= growth rate over the time interval t
t= crystallizer time interval
n0= number density of crystal nuclei
B = nucleation rate

Figure 5-3: Population Density Plot

From Figure 5-3, the intercept is 19.78 and the slope is -9.13. The
following calculations then are performed.
Since Dav= 1 mm and slope = -Dav/Gt
It follows that: Slope = -1/Gt = -9.13

5-16 Urea Plant February 26, 2014


Therefore:
G = 1/(-9.13)(3.38) = 0.0324 mm/h
The growth rate calculated using equation Equation 5-9 is:
B = (0.0324) * exp(19.78) = 12.65x106 crystals / L-h
The nuclei number density is also given by:
0 k i1
n = Kb MT G (5-10)
where:
Kb = a constant
i, k = exponents (constants)
Table 5-5 lists a group of samples reported by Bennettt3 that
characterizes observed growth and nucleation rates.

Table 5-5: Growth Versus Nucleation Rate

Sample No. ln(n0) G ln G


191 18.18 0.0330 -3.41
192 19.71 0.0338 -3-39
193 18.70 0.0317 -3.45
194 20.51 0.0200 -3.91

Using the natural logarithms of growth vs. nuclei number, densities


are plotted as shown in Figure 5-4. Using the following expression
and the resulting slope of the plot, the exponent for the power law
nucleation rate equation is determined. Calculation of the i
exponent assumes the slurry density (MT) is constant.

PRO/II Case Book Urea Plant 5-17


Figure 5-4: Growth vs. Nucleation Rate

The slope (-2.75) of the plot shown in Figure 5-4 yields a value of
-1.75 for the exponent i. The nucleation rate, B, then is obtained
from Equation 5-11 as:
k 1.75
B = Kb MT G (5-11)

Similar data at constant growth rate is required to calculate the k


exponent in the final form of the nucleation equation. For urea
crystallization, a value of -3.87 is recommended for the k exponent
by Bennett3. In addition, a value of -1.66 is recommended for the i
exponent, compared to -1.75 calculated here. The paper by Garside
and Shaw5 is a recommended source of nucleation and growth
kinetic data. The following is the final recommended form of the
nucleation equation as reported by Garside and Shaw5.
3.87 1.66
B = 0.548M T G (5-12)

The units of the nucleation rate, B, are Number of crystals/L-s. The


constants of this equation must be converted to be consistent with
input units (refer to Table 4.1 of the PRO/II Keyword Input Manual
for default dimensional units). The following summarizes the

5-18 Urea Plant February 26, 2014


default dimensional units used in the growth and nucleation
expressions.
PRO/II Growth Rate Expression:
G exp onent
G = K a SSRATIO (5-13)

Term Units
G velocity
Kg, constant velocity
SSRATIO, supersaturation dimensionless

PRO/II Nucleation Rate Expression


i j K 1
B = K b M T SSRATIO G RPM (5-14)

Term Units
B No. / [(time) (liquid volume)]
Kb, constant No. / [(time) (liquid volume)]
MT liquid density
RPM revolutions per minute
The GEXPONENT term in Equation 5-13 is set to zero. The
following are converted growth and nucleation rates.
0.0324mm m ft h
G = K a = -------------------------- ---------------------- 3.28 ---- -------------- (5-15)
h 1000mm m 3600s
8 ft
= 2.952 10 ----
s

6 number of crystals L
B = 12.65 10 ----------------------------------------------- 28.32 -----3-
L-h ft
(5-16)
number of crystals-
8
= 3.582 10 ----------------------------------------------
3
ft h
Next, the Kb constant in the nucleation expression, Equation 5-14,
must be converted to be consistent with input units in the following
manner.
3 i
i g i i g 0.0624262lb ft
M T --- = M T --- -----------------------------------------
L L gL
(5-17)
lb i
M T -----3-
i i
= 0.0624262

ft
PRO/II Case Book Urea Plant 5-19
i m k k m 3.28ft k k ft k
G ---- = G ---- -------------- = 3.28 G ----
k
(5-18)
s s m s

No No L s
K b ------------ = K b ------------ 28.32 -----3- 3600 ---
L s L s h
ft (5-19)
3
= 101952K b Number of crystals/ft h

Now, using equation (13):

3.87 1.66 3.87 1.66


B = 0.548 101952 0.0624262 3.28 M T G
3.87 1.66
= 8.7417 M T G
(5-20)
where units of measure are:
B (Number of crystals/ft3-h)
G (ft/s)Ncx = abbreviation for number of crystals
MT (lb/ft3)
This newly formulated equation can now be tested to check that it
fits the published nucleation rate data using the reported slurry
density of 450 g/L and calculated growth rate of 2.952x10-8 ft/s.
3 3.87
g N cx ft 8 1.66
B = 8.74172 450 --- 0.0624262 ------------------- 2.952 10
L g L (5-21)
7 Number of crystals
= 6.842289 10 ---------------------------------------------
-
3
ft h

There is a large deviation in nucleation rate compared to the value


of 3.582x108 number of crystals/ft3-h calculated from the published
data. However, if the calculated growth rate exponent of -1.75 is
used in place of the suggested value of -1.66, the nucleation rate is
calculated to be 3.258x108 number of crystals/ft3-h. This value
compares closely with the value calculated from the data. The final
form of growth and nucleation rate equations used in this simulation
then are: 8
G = 2.952 10
(5-22)
3.87 1.75
B = 8.741M T G

5-20 Urea Plant February 26, 2014


Technical Results
The overall mass balance for the partial NH3 recycle urea plant is
summarized in the output report of the simulation:
OVERALL PLANT MASS BALANCE

------------------ LB/HR ------------------ PERCENT


COMPONENT FEED +REACTION -PRODUCT =DEVIATION DEV
--------------------- ---------- ---------- ---------- ---------- -------
1 UREA 0.00 95598.21 95598.21 0.00 0.00
2 WATER 0.00 28677.21 28677.21 0.00 0.00
3 AMCA 0.00 3542.12 3542.55 -0.43 -0.01
4 AMMONIA 105049.00 -55764.79 49269.20 15.01 0.03
5 CO2 93408.00 -72052.75 21355.25 0.00 0.00
6 N2 0.00 0.00 0.00 0.00 0.00
7 O2 0.00 0.00 0.00 0.00 0.00
8 H2 0.00 0.00 0.00 0.00 0.00

TOTAL 198457.00 0.00 198442.42 14.58 0.01

Conclusion
The 1000 tons/day urea process discussed in this case book
demonstrates the use of many chemicals and solids capabilities in
PRO/II. This example also highlights those features of PRO/II that
make it easy to incorporate available literature data.

Output Results
The keyword input file appears in Appendix 5-A. Appendix 5-B is a
listing of selected results. These include the urea reactor RX1 and
the decomposers RX2 and RX3, the filtering centrifuge units CEN1
and CEN2, the dryer DR1, the crystallizers CR1 and CR2, the
solids freezer FRZ1, and stream weight component rates for
selected streams.

PRO/II Case Book Urea Plant 5-21


References
1. Chao, George Tsei-Yu, Urea: Its Properties and Manufacture,
Chao's Institute, 1967.
2. Dente, M., S. Pierucci, A. Sogaro, G. Carloni, E. Rigolli, Simulation
Program For Urea Plants, Comput. Chem. Eng. Vol 12, No. 5, pp.
389-400, 1988.
3. Bennett, R.C., M. VanBuren, Commercial Urea Crystallization,
Crystallization From Solutions and Melts, Chem. Eng. Prog. Symp.
Ser., No. 95(7), Vol. 65, 1969.
4. Perry, R.H., D. Green, Perry's Chemical Engineers' Handbook,
Sixth Edition, pp. 19-32 - 19-33, McGraw Hill, 1984.
5. Garside, J., M.B. Shah, Crystallization Kinetics From MSMPR
Crystallizers, Ind. Eng. Chem. Process Des. Dev., Vol 19, No 4, pp.
509-514, 1980.
6. Hydrocarbon Processing, Nov. 1985, pp. 172.
7. Austin, G.T., Shreve's Chemical Process Industries, Fifth Edition,
pp.311-13, McGraw-Hill, 1984.
The following are additional sources of information related to using
PRO/II with solids and electrolytes:
8. Goldfarb, S., J. Coon, J. Tanger, K.M. Ng, C.F. Chu, Crystallization
Process Optimization Using PRO/II, Presented at: November 1990
AIChE Meeting.
9. Goldfarb, S., J. Coon, J. Tanger, A. Harvey, Rigorous Simulation of
Aqueous Electrolyte Flowsheets With Special Emphasis on Solids
Processing Capabilities, Presented at: Fourth International
Symposium on Process Systems Engineering (PSE 91).
10. Goldfarb, S., Continuous Sugar Crystallization Process With
Applications in the Agri-Chemical Industry, Presented at: August
1993 AIChE Meeting.

5-22 Urea Plant February 26, 2014


Appendix 5-A: Input Data File
The keyword input file for this example is UreaPlnt.inp. It normally
is installed with the PRO/II Casebook manual in the folder:
%ProIIInstall%\Manual\Casebook\Inputs\

where %ProIIInstall% represents the root directory where PRO/II is


installed. The following is a listing of that keyword input file.
$ UREA PLANT FLOWSHEET
$
TITLE PROJ=CaseBook, PROBLEM=UreaPlant, USER=SimSci,
DATE=Apr_2010
DIMEN ENGLISH, XDEN=DENSITY, FLENGTH=MIC
PRINT RATE=W, STREAM=COMPONENT, MBAL
CALCULATION TRIALS=50
TOLERANCE STREAM=0.001
$
COMPONENT DATA
LIBRARY 1, UREA / 2, WATER / 4, AMMONIA / 5, CO2 / 6, N2 / &
7, O2 / 8, H2, BANK=SIMSCI
NONLIBRARY 3, AMCA
PHASE VLS=1
ATTR COMP=1, PSD(MIC) 0, 20, 50, 100, 200, 500, 1000.
$
$ Fill in missing data for UREA and AMMONIUM CARBAMATE from the Thermo-
dynamic Data Manager.
$
$ PRO/II physical property insert for:
$ Name: UREA
$ Formula: CH4N2O
$ Created: 05/10/95
$ Source: User File: urea
$
ACENTRIC 1, 0.5973908E+00
SURFACE(L,N/M,K) CORR= 1, DATA= 1, 0.5000000E+03, &
0.2000000E+03, 0.1565836E+00, -.2684714E-03, &
0.1951699E-07, 0.9796545E-10, -.1376130E-12, &
0.1206885E-15
VISC(V,PAS,K) CORR= 1, DATA= 1, 0.5000000E+03, &
0.2000000E+03, -.1111774E-05, 0.2164776E-07, &
0.2485747E-14, -.8143611E-17, 0.1319303E-19, &
-.8382776E-23
VISC(L,PAS,K) CORR=20, DATA= 1, 0.5000000E+03, &
0.2000000E+03, -.1761028E+03, 0.1244212E+05, &
0.2315481E+02, 0.0000000E+00, 0.0000000E+00, &
0.0000000E+00
COND(V,W/MK,K) CORR= 1, DATA= 1, 0.5000000E+03, &
0.2500000E+03, -.1894533E-01, 0.7768554E-04, &

PRO/II Case Book Urea Plant 5-23


-.8991741E-11, 0.2449163E-13, -.3284755E-16, &
0.1733994E-19
COND(L,W/MK,K) CORR= 1, DATA= 1, 0.5000000E+03, &
0.2000000E+03, 0.2532868E+00, -.1769604E-03, &
-.1309749E-06, 0.0000000E+00, 0.0000000E+00, &
0.0000000E+00
$
$ PRO/II physical property insert for:
$ Name: AMMONIUM CARBAMATE
$ Formula: CH6N2O2
$ Created: 05/10/95
$ Source: User File: urea
$
$ Thermo methods available for use:
$ Library
$ EOS Methods
$
PHASE VLS = 3
MW 3, 0.7807092E+02
SPGR 3, 1.2
ACENTRIC 3, 0.5942138E+00
TC(K) 3, 0.6590952E+03
PC(PA) 3, 0.6740707E+07
FORMATION(S,J/KG,MOLE) 3, -.6450466E+09, -.4480641E+09
NMP(K) 3, 0.4061500E+03
HFUS(J/KG,MOLE) 3, 0.6903593E+08
VP(L,PA,K) CORR=20, LN, DATA= 3, 0.4261500E+03, &
0.3031500E+03, -.2929800E+02, -.3908196E+04, &
0.9295685E+01, -.1620786E-04, 0.2000000E+01, &
0.1162653E-07
LATENT(J/KG,K,MOLE) CORR= 1, DATA= 3, 0.6000000E+03, &
0.4000000E+03, 0.5178937E+09, -.4814254E+07, &
0.2047703E+05, -.4408357E+02, 0.4744715E-01, &
-.2057343E-04
VISC(L,PAS,K) CORR=20, DATA= 3, 0.5000000E+03, &
0.2500000E+03, -.4705848E+02, 0.4595930E+04, &
0.4787454E+01, 0.0000000E+00, 0.0000000E+00, &
0.0000000E+00
SURFACE(L,N/M,K) CORR= 1, DATA= 3, 0.5000000E+03, &
0.2000000E+03, 0.8006542E-02, -.1452831E-04, &
0.2243716E-10, 0.9652577E-11, -.1462233E-13, &
0.1190758E-16
ENTH(L,J/KG,K,MOLE) CORR=1, DATA= 3, 0.2955000E+03, &
0.1255000E+02, -.1765825E+08, -.6685015E+04, &
0.3085568E+03, -.1735744E+00, -.1174778E-08, &
0.1799982E-11
ENTH(V,J/KG,K,MOLE) CORR=1, DATA= 3, 0.1500000E+04, &
0.1500000E+03, 0.9131459E+08, 0.2351811E+05, &
0.7600609E+02, 0.7937258E-02, -.2484022E-04, &
0.7275022E-08
DENS(L,KG/M3,K,MOLE) CORR=1, DATA=3, 0.4775945E+03, &
0.3664834E+03, 0.2375940E+02, -.4553412E-01, &
0.1678109E-03, -.4529840E-06, 0.6004568E-09, &

5-24 Urea Plant February 26, 2014


-.3358131E-12
VISC(V,PAS,K) CORR= 1, DATA= 3, 0.5000000E+03, &
0.2000000E+03, -.1917443E+00, 0.3993549E-02, &
0.3461876E-09, -.1233446E-11, 0.2128086E-14, &
-.1416680E-17
COND(V,W/MK,K) CORR= 1, DATA= 3, 0.5000000E+03, &
0.2500000E+03, -.1232028E+00, 0.1417707E-02, &
-.6673806E-05, 0.1653591E-07, -.2039134E-10, &
0.1002095E-13
COND(L,W/MK,K) CORR= 1, DATA= 3, 0.5000000E+03, &
0.2000000E+03, 0.2532868E+00, -.1769604E-03, &
-.1309749E-06, 0.0000000E+00, 0.0000000E+00, &
0.0000000E+00
CP(S,J/KG,K,MOLE) CORR=1, DATA= 3, 0.4731500E+03, &
0.2931500E+03, 0.9867493E+06, -.1073353E+05, &
0.4725547E+02, -.8751843E-01, 0.5856834E-04, &
0.0000000E+00
DENS(S,KG/M3,K,MOLE) CORR=1, DATA=3, 0.2931500E+03,&
0.2931500E+03, 0.2222994E+02, 0.0000000E+00, &
0.0000000E+00, 0.0000000E+00, 0.0000000E+00, &
0.0000000E+00
SVTB 3, -.1348239E+02
SLTB 3, 0.9952457E+02
SLTM 3, 0.1659695E+02
HVTB 3, -.1246233E+02
HLTB 3, 0.4591732E+05
HLTM 3, 0.8994148E+04
$
THERMODYNAMIC DATA
METHOD SYSTEM=NRTL, ENTROPY(V)=SRK, ENTROPY(L)=SRK, &
KVALUE(SLE)=SOLDATA, TRANSPORT=LIBRARY
KVALUE(SLE)
SOLUTE 1
SOLDATA(K) 1,2, 0., -1310.37, 0.533619
$
STREAM DATA
PROP STRM=1, TEMP=-28, PRES=320, COMP(W)=4,105049
PROP STRM=2, TEMP=100, PRES=300, COMP(W)=5,93408
$
$ INITIAL GUESS FOR TEAR STREAMS
$
PROP STRM=7, TEMP=126, PRES=320, COMP(W)=2,0.5 / 4,58667.
NAME 1, NH3FD / 2, CO2FD / 9, DECGS1 / 12, DECGS2 / &
14, FLGS1 /16, FLGS2 /19, CRYGS1 / 24, CRYGS2 / &
29, DRYGS /31, UREAPROD
$
$ REACTION DATA
$
RXDATA
$
$ MAIN UREA REACTION
$
RXSET ID=RST1

PRO/II Case Book Urea Plant 5-25


REACTION ID=RXC1
STOICHIOMETRY 4,-8 / 5,-4 / 1,3 / 2,3 / 3,1
$
$ DECOMPOSITION REACTION
$
RXSET ID=RST2
REACTION ID=RXC2
STOICHIOMETRY 3,-1 / 4,2 / 5,1
$
UNIT OPERATIONS
$
$ CO2 COMPRESSOR
$
COMPRESSOR UID=COM1
FEED 2
PRODUCT V=4
OPERATION PRES=3516, EFF=75
COOLER ACDP=1, ACTOUT=100
$
$ NH3 RECYCLE & FEED PUMP
$
PUMP UID=P1
FEED 1, 7
PRODUCT L=3
OPERATION PRES=3515
$
$ HIGH PRESSURE REACTOR
$
CONREACTOR UID=RX1
FEED 3, 4
PRODUCT L=5
OPERATION ISOTHERMAL, PHASE=L, TEMP=365.
RXCALC MODEL=STOIC
RXSTOIC RXSET=RST1
REACTION RXC1
BASE COMPONENT=5
CONVERSION 1.0
$
$ PRESSURE REDUCTION VALVE
$
VALVE UID=VL1
FEED 5
PRODUCT M=6
OPER PRES=320
$
$ AMMONIA SEPARATOR
$
SHORTCUT UID=COL1
FEED 6
PRODUCT STREAM=7, PRES=320, PERCENT(W)=23
PRODUCT STREAM=8, PRES=325
SPEC STREAM=7, COMP=4 , FRACTION(W), VALUE=.99995
SPEC STREAM=7, COMP=4 , RATE(W), RATIO, &

5-26 Urea Plant February 26, 2014


STREAM=6, COMP=4, RATE(W), VALUE=0.65
CONDENSER TYPE=BUBBLE
EVALUATE MODEL=CONVENTIONAL, KEYL=4, KEYH=2, RRMIN=2.5
$
$ HIGH PRESSURE DECOMPOSER
$
CONREACTOR UID=RX2
FEED 8
PRODUCT V=9, L=10
OPERATION ISOTHERMAL, PHASE=L, TEMP=302.
RXCALC MODEL=STOIC
RXSTOIC RXSET=RST2
REACTION RXC2
BASE COMPONENT=3
CONVERSION 0.88
$
$ HIGH PRESSURE DECOMPOSER BOTTOMS COOLER
$
FLASH UID=FL2
FEED 10
PRODUCT M=11
ISO TEMP=158, PRES=25
$
$ LOW PRESSURE DECOMPOSER
$
CONREACTOR UID=RX3
FEED 11
PRODUCT V=12, L=13
OPERATION ISOTHERMAL, PHASE=L, TEMP=252.
RXCALC MODEL=STOIC
RXSTOIC RXSET=RST2
REACTION RXC2
BASE COMPONENT=3
CONVERSION 0.9995
$
$ FLASH DRUM
$
FLASH UID=FL3
FEED 13
PRODUCT V=14, L=15
ISO TEMP=250, PRES=15
$
$ EVAPORATOR
$
FLASH UID=FL4
FEED 15
PRODUCT V=16, L=17
TPSPEC TEMP=230
SPEC STREAM=17, FRAC(W), COMP=4, VALUE=0.001

PRO/II Case Book Urea Plant 5-27


$
$ PUMP INTO FIRST CRYSTALLIZER
$
PUMP UID=P2, NAME=PUMP2
FEED 17
PRODUCT L=18
OPERATION PRES=20
$
$ FIRST STAGE CRYSTALLIZER
$
CRYSTALLIZER UID=CR1, NAME=CSTAGE1
FEED 18
PRODUCTS OVHD=19, BTMS=20
PRINT CSD
OPERATION SOLUTE=1, SOLVENT=2, TEMP=130, PRES=1.5
DESIGN PFRAC=0.85
GROWTH KG=2.952E-8, GEXP=0.
NUCLEATION KB=8.7417, BEXP=-3.87, 0., -1.75, 0.
$
$ PUMP INTO FIRST CENTRIFUGE
$
PUMP UID=P3, NAME=PUMP3
FEED 20
PRODUCT L=21
OPERATION PRES=20
$
$ FIRST STAGE CENTRIFUGE
$
FCENTRIFUGE UID=CEN1, NAME=CENT1
FEED 21
PRODUCT FILTRATE=22, CAKE=23
RATING DIAMETER=3, RPM=1000
$
$ SECOND STAGE CRYSTALLIZER
$
CRYSTALLIZER UID=CR2, NAME=CSTAGE2
FEED 22
PRODUCTS OVHD=24, BTMS=25
PRINT CSD
OPERATION SOLUTE=1, SOLVENT=2, TEMP=130, PRES=1.335
DESIGN PFRAC=0.95
GROWTH KG=2.952E-8, GEXP=0.
NUCLEATION KB=8.7417, BEXP=-3.87, 0., -1.75, 0.
$
$ PUMP INTO SECOND CENTRIFUGE
$
PUMP UID=P4, NAME=PUMP4
FEED 25
PRODUCT L=26
OPERATION PRES=20

5-28 Urea Plant February 26, 2014


$
$ SECOND STAGE CENTRIFUGE
$
FCENTRIFUGE UID=CEN2, NAME=CENT2
FEED 26
PRODUCT FILTRATE=27, CAKE=28
RATING DIAMETER=3, RPM=1000
$
$ FINAL DRYING OF SOLID PRODUCT
$
DRYER UID=DR1, NAME=DRYER
FEED 23, 28
PRODUCT OVHD=29, BTMS=30
OPERATION PRES=15
DESIGN BTMS, MOISTURE(W)=0.001
$
$ ENSURE ANY REMAINING UREA IS CONVERTED TO A SOLID
$
FREEZER UID=FRZ1, NAME=FREEZER
FEED 30
PRODUCT M=31
OPERATION TEMP=200., DP=0.
$
END

PRO/II Case Book Urea Plant 5-29


Appendix 5-B: Output Report File
Selected PRO/II output is shown below. The output selected
highlights solids capabilities.
SIMULATION SCIENCES INC. R PAGE P-4
PROJECT CaseBook PRO/II VERSION 9.3 ELEC V7.0
PROBLEM UreaPlant OUTPUT SimSci
PLANT MATERIAL BALANCE Apr_2010
==============================================================================
FEED STREAMS: 1 2
PRODUCT STREAMS: 9 12 14
16 19 24
29 31 27

OVERALL PLANT MOLAR BALANCE


---------------- LB-MOL/HR ---------------- PERCENT
COMPONENT FEED +REACTION -PRODUCT =DEVIATION DEV
--------------------- ---------- ---------- ---------- ---------- -------
1 UREA 0.000 1591.827 1591.827 0.000 0.00
2 WATER 0.000 1591.827 1591.827 0.000 0.00
3 AMCA 0.000 45.371 45.376 -0.006 -0.01
4 AMMONIA 6168.265 -3274.396 2892.988 0.881 0.03
5 CO2 2122.436 -1637.198 485.239 0.000 0.00
6 N2 0.000 0.000 0.000 0.000 0.00
7 O2 0.000 0.000 0.000 0.000 0.00
8 H2 0.000 0.000 0.000 0.000 0.00

TOTAL 8290.701 -1682.568 6607.257 0.876 0.01

OVERALL PLANT MASS BALANCE


------------------ LB/HR ------------------ PERCENT
COMPONENT FEED +REACTION -PRODUCT =DEVIATION DEV
--------------------- ---------- ---------- ---------- ---------- -------
1 UREA 0.00 95598.21 95598.21 0.00 0.00
2 WATER 0.00 28677.21 28677.21 0.00 0.00
3 AMCA 0.00 3542.12 3542.55 -0.43 -0.01
4 AMMONIA 105049.00 -55764.79 49269.20 15.01 0.03
5 CO2 93408.00 -72052.75 21355.25 0.00 0.00
6 N2 0.00 0.00 0.00 0.00 0.00
7 O2 0.00 0.00 0.00 0.00 0.00
8 H2 0.00 0.00 0.00 0.00 0.00

TOTAL 198457.00 0.00 198442.42 14.58 0.01

5-30 Urea Plant February 26, 2014


SIMULATION SCIENCES INC. R PAGE P-13
PROJECT CaseBook PRO/II VERSION 9.3 ELEC V7.0
PROBLEM UreaPlant OUTPUT SimSci
FILTERING CENTRIFUGE SUMMARY Apr_2010
==============================================================================

UNIT 14, 'CEN1', 'CENT1'

Feeds 21

Products Liquid 22
Mixed 23

Type of Operation Rating

Operating Conditions

Temperature, F 130.0609
Pressure, PSIA 20.0000
Average Particle Diameter, MIC 648.4185
Average Solid Density, LB/FT3 83.3434
Total Solid Feed Mass Flow Rate, LB/HR 6.429E+04
Surface tension, DYNE/CM 69.3608
Volume Flow Rate of Filtrate, FT3/HR 589.9697
Particle Sphericity 0.7500

Physical Configuration

Bowl Diameter, FT 3.0000


Radius of Liquid Surface / Radius of Bowl 0.7380
Radius of Cake / Radius of Bowl 0.7900
Height of Bowl / Radius of Bowl 0.9545
RPM 1000.0000
Basket Height, FT 1.4317
Selected Bowl Radius, FT 1.5000
Centrifuge Type Not Specified

Cake Properties

Mass Fraction of Solid in Cake 0.9523


Cake Thickness, MIC 9.601E+04
Cake Resistance, FT/LB 2.976E+06
Filter Medium Resistance, 1/FT 6.096E+05
Porosity if Cake 0.4500

PRO/II Case Book Urea Plant 5-31


SIMULATION SCIENCES INC. R PAGE P-14
PROJECT CaseBook PRO/II VERSION 9.3 ELEC V7.0
PROBLEM UreaPlant OUTPUT SimSci
FILTERING CENTRIFUGE SUMMARY Apr_2010
==============================================================================

UNIT 17, 'CEN2', 'CENT2'

Feeds 26

Products Liquid 27
Mixed 28

Type of Operation Rating

Operating Conditions

Temperature, F 130.0768
Pressure, PSIA 20.0000
Average Particle Diameter, MIC 567.6160
Average Solid Density, LB/FT3 83.3434
Total Solid Feed Mass Flow Rate, LB/HR 1.576E+04
Surface tension, DYNE/CM 69.4362
Volume Flow Rate of Filtrate, FT3/HR 257.6413
Particle Sphericity 0.7500

Physical Configuration

Bowl Diameter, FT 3.0000


Radius of Liquid Surface / Radius of Bowl 0.7380
Radius of Cake / Radius of Bowl 0.7900
Height of Bowl / Radius of Bowl 0.9545
RPM 1000.0000
Basket Height, FT 1.4317
Selected Bowl Radius, FT 1.5000
Centrifuge Type Not Specified

Cake Properties

Mass Fraction of Solid in Cake 0.9482


Cake Thickness, MIC 9.601E+04
Cake Resistance, FT/LB 2.976E+06
Filter Medium Resistance, 1/FT 6.096E+05
Porosity if Cake 0.4500

5-32 Urea Plant February 26, 2014


SIMULATION SCIENCES INC. R PAGE P-15
PROJECT CaseBook PRO/II VERSION 9.3 ELEC V7.0
PROBLEM UreaPlant OUTPUT SimSci
DRYER SUMMARY Apr_2010
==============================================================================

UNIT 18, 'DR1', 'DRYER'

Feeds 23 28

Products Vapor 29
Mixed 30
TEMPERATURE, DEG F 369.532
PRESSURE, PSIA 15.000
PRESSURE DROP, PSI 5.000
MOLE FRAC VAPOR 0.04528
MOLE FRAC TOTAL LIQUID 0.03534
MOLE FRAC H/C LIQUID 0.03534
MOLE FRAC FREE WATER 0.00000
MOLE FRAC MW SOLID 0.91937
MOISTURE CONTENT 9.99999E-04
DUTY, MM BTU/HR 10.55778
DRYER OPERATION MOISTURE-P

PRO/II Case Book Urea Plant 5-33


SIMULATION SCIENCES INC. R PAGE P-16
PROJECT CaseBook PRO/II VERSION 9.3 ELEC V7.0
PROBLEM UreaPlant OUTPUT SimSci
CRYSTALLIZER SUMMARY Apr_2010
==============================================================================
UNIT 12, 'CR1', 'CSTAGE1'
Feeds 18
Products Vapor 19
Mixed 20
OPERATING CONDITIONS
TEMPERATURE, F 130.00
PRESSURE, PSIA 1.50
HEAT EXCHANGER DUTY, MM BTU/HR -11.9173
VOLUME, FT3 10745.9867
RESIDENCE TIME, HR 7.6394
CRYSTAL PRODUCTION RATE, LB/HR 64294.794
TEMPERATURE CHANGE IN HEAT EXCHANGER, F N/A
SLURRY RECIRCULATION RATE, FT3/HR N/A
AGITATOR RPM 100.000

CRYSTALLIZER DATA
CRYSTAL COMPONENT 1 UREA
SUPERSATURATION 5.9605E-10
CRYSTAL SHAPE FACTOR 1.000

SLURRY PROPERTIES
FEED SLURRY LIQUID VOLUME FRACTION 1.000
FEED SLURRY VOLUMETRIC RATE, FT3/HR 1494.103
PRODUCT SLURRY LIQUID VOLUME FRACTION 0.452
PRODUCT SLURRY VOLUMETRIC RATE, FT3/HR 1406.645
PRODUCT SLURRY MAGMA DENSITY, LB/FT3 45.708

KINETICS DATA
GROWTH RATE, FT/SEC 2.9520E-08
NUCLEATION RATE, NUMBER/HR/FT3 4.9515E+07

PARTICLE SIZE DISTRIBUTION


---- NUMBER DENSITY ----
------- DIAMETER, MIC -------- --- WT FRAC ---- /MIC/FT3
RANGE AVERAGE FEED PRODUCT FEED PRODUCT
------------------ ---------- ------- ------- ----------- -----------
0.000 - 20.00 10.00 0.0000 0.0000 0.0000E+00 6.6295E+05
20.00 - 50.00 35.00 0.0000 0.0001 0.0000E+00 5.9924E+05
50.00 - 100.0 75.00 0.0000 0.0012 0.0000E+00 5.0980E+05
100.0 - 200.0 150.0 0.0000 0.0136 0.0000E+00 3.7651E+05
200.0 - 500.0 350.0 0.0000 0.2314 0.0000E+00 1.6779E+05
0.500 - 1.000 E+03 0.750 E+03 0.0000 0.7537 0.0000E+00 3.3323E+04

5-34 Urea Plant February 26, 2014


SIMULATION SCIENCES INC. R PAGE P-18
PROJECT CaseBook PRO/II VERSION 9.3 ELEC V7.0
PROBLEM UreaPlant OUTPUT SimSci
CRYSTALLIZER SUMMARY Apr_2010
==============================================================================

UNIT 15, 'CR2', 'CSTAGE2'

Feeds 22

Products Vapor 24
Mixed 25

OPERATING CONDITIONS

TEMPERATURE, F 130.00
PRESSURE, PSIA 1.34
HEAT EXCHANGER DUTY, MM BTU/HR 5.5558
VOLUME, FT3 2318.0340
RESIDENCE TIME, HR 5.0517
CRYSTAL PRODUCTION RATE, LB/HR 15763.480
TEMPERATURE CHANGE IN HEAT EXCHANGER, F N/A
SLURRY RECIRCULATION RATE, FT3/HR N/A
AGITATOR RPM 100.000

CRYSTALLIZER DATA

CRYSTAL COMPONENT 1 UREA


SUPERSATURATION 1.7764E-17
CRYSTAL SHAPE FACTOR 1.000

SLURRY PROPERTIES

FEED SLURRY LIQUID VOLUME FRACTION 1.000


FEED SLURRY VOLUMETRIC RATE, FT3/HR 589.970
PRODUCT SLURRY LIQUID VOLUME FRACTION 0.588
PRODUCT SLURRY VOLUMETRIC RATE, FT3/HR 458.865
PRODUCT SLURRY MAGMA DENSITY, LB/FT3 34.353

KINETICS DATA

GROWTH RATE, FT/SEC 2.9520E-08


NUCLEATION RATE, NUMBER/HR/FT3 1.4952E+08

PRO/II Case Book Urea Plant 5-35


SIMULATION SCIENCES INC. R PAGE P-19
PROJECT CaseBook PRO/II VERSION 9.3 ELEC V7.0
PROBLEM UreaPlant OUTPUT SimSci
CRYSTALLIZER SUMMARY Apr_2010
==============================================================================

UNIT 15, 'CR2', 'CSTAGE2' (Cont)

PARTICLE SIZE DISTRIBUTION


---- NUMBER DENSITY ----
------- DIAMETER, MIC -------- --- WT FRAC ---- /MIC/FT3
RANGE AVERAGE FEED PRODUCT FEED PRODUCT
------------------ ---------- ------- ------- ----------- -----------
0.000 - 20.00 10.00 0.0000 0.0000 0.0000E+00 2.5525E+06
20.00 - 50.00 35.00 0.0000 0.0003 0.0000E+00 2.1909E+06
50.00 - 100.0 75.00 0.0000 0.0035 0.0000E+00 1.7158E+06
100.0 - 200.0 150.0 0.0000 0.0353 0.0000E+00 1.0849E+06
200.0 - 500.0 350.0 0.0000 0.3966 0.0000E+00 3.1958E+05
0.500 - 1.000 E+03 0.750 E+03 0.0000 0.5643 0.0000E+00 2.7730E+04

SIMULATION SCIENCES INC. R PAGE P-20


PROJECT CaseBook PRO/II VERSION 9.3 ELEC V7.0
PROBLEM UreaPlant OUTPUT SimSci
MELTER/FREEZER SUMMARY Apr_2010
==============================================================================
UNIT 19, 'FRZ1', 'FREEZER'
Feeds 30

Products Mixed 31

OPERATING CONDITIONS

TEMPERATURE, F 200.00
PRESSURE, PSIA 15.00
PRESSURE DROP, PSI 0.00
DUTY, MM BTU/HR -7.0614
MOLE FRAC VAPOR 0.0000
MOLE FRAC TOTAL LIQUID 0.0032
MOLE FRAC MW SOLID 0.9968

MELTING/FREEZING DATA
DUTY NMP
COMPONENTS FROZEN FRACTION MM BTU/HR F
--------------------- -------- ----------- -------
1 UREA 1.0000 -0.2976 270.86

5-36 Urea Plant February 26, 2014


SIMULATION SCIENCES INC. R PAGE P-21
PROJECT CaseBook PRO/II VERSION 9.3 ELEC V7.0
PROBLEM UreaPlant OUTPUT SimSci
CONVERSION REACTOR SUMMARY Apr_2010
==============================================================================
UNIT 3, 'RX1'
OPERATING CONDITIONS
REACTOR TYPE ISOTHERMAL REACTOR
DUTY, MM BTU/HR -34.7104
TOTAL HEAT OF REACTION AT 77.00 F, MM BTU/HR -38.0197

INLET OUTLET
----------- -----------
FEED 3
4
LIQUID PRODUCT 5
TEMPERATURE, F 60.14 365.00
PRESSURE, PSIA 3515.0000 3515.0000

REACTION DATA
--------- RATES, LB-MOL/HR ---------- FRACTION
COMPONENT FEED CHANGE PRODUCT CONVERTED
------------------ ----------- ----------- ----------- -----------
1 UREA 5.38249E-24 1591.8273 1591.8273
2 WATER 4.33234E-05 1591.8273 1591.8273
3 AMCA 1.7863 530.6091 532.3954
4 AMMONIA 9718.5395 -4244.8727 5473.6667 0.4368
5 CO2 2122.4364 -2122.4364 0.0000 1.0000

TOTAL 11842.7622 -2653.0455 9189.7167

LB-MOL/HR FRACTION
BASE COMPONENT REACTION CONVERTED CONVERTED(1)
------------------ ----------- ----------- ------------
5 CO2 1 2122.4364 1.0000
(1) FRACTION CONVERTED BASED ON AMOUNT IN FEED

REACTOR MASS BALANCE


----------- Rates, LB/HR ------------ Fraction
Component Feed Change Product Converted
-------------------- ----------- ----------- ----------- -----------
1 UREA 3.23249E-22 95598.2077 95598.2077
2 WATER 7.80483E-04 28677.2137 28677.2145
3 AMCA 139.4570 41425.1400 41564.5970
4 AMMONIA 165512.1650 -72292.5579 93219.6071 0.4368
5 CO2 93408.0000 -93408.0000 0.0000 1.0000
TOTAL 259059.6228 0.0000 259059.6263

PRO/II Case Book Urea Plant 5-37


SIMULATION SCIENCES INC. R PAGE P-22
PROJECT CaseBook PRO/II VERSION 9.3 ELEC V7.0
PROBLEM UreaPlant OUTPUT SimSci
CONVERSION REACTOR SUMMARY Apr_2010
==============================================================================
UNIT 6, 'RX2'
OPERATING CONDITIONS
REACTOR TYPE ISOTHERMAL REACTOR
DUTY, MM BTU/HR 63.1751
TOTAL HEAT OF REACTION AT 77.00 F, MM BTU/HR 32.0677
INLET OUTLET
----------- -----------
FEED 8
VAPOR PRODUCT 9
LIQUID PRODUCT 10
TEMPERATURE, F 233.07 302.00
PRESSURE, PSIA 325.0000 325.0000

REACTION DATA
--------- RATES, LB-MOL/HR ---------- FRACTION
COMPONENT FEED CHANGE PRODUCT CONVERTED
------------------ ----------- ----------- ----------- -----------
1 UREA 1591.8272 0.0000 1591.8272
2 WATER 1591.8272 0.0000 1591.8272
3 AMCA 530.6146 -466.9409 63.6738 0.8800
4 AMMONIA 1922.5107 933.8817 2856.3924
5 CO2 0.0000 466.9409 466.9409
TOTAL 5636.7797 933.8817 6570.6614

LB-MOL/HR FRACTION
BASE COMPONENT REACTION CONVERTED CONVERTED(1)
------------------ ----------- ----------- ------------
3 AMCA 1 466.9409 0.8800
(1) FRACTION CONVERTED BASED ON AMOUNT IN FEED

REACTOR MASS BALANCE


----------- Rates, LB/HR ------------ Fraction
Component Feed Change Product Converted
-------------------- ----------- ----------- ----------- -----------
1 UREA 95598.2050 0.0000 95598.2050
2 WATER 28677.2129 0.0000 28677.2129
3 AMCA 41425.5706 -36454.5021 4971.0685 0.8800
4 AMMONIA 32741.4323 15904.5281 48645.9604
5 CO2 0.0000 20549.9736 20549.9736

TOTAL 198442.4209 0.0000 198442.4204

5-38 Urea Plant February 26, 2014


SIMULATION SCIENCES INC. R PAGE P-23
PROJECT CaseBook PRO/II VERSION 9.3 ELEC V7.0
PROBLEM UreaPlant OUTPUT SimSci
CONVERSION REACTOR SUMMARY Apr_2010
==============================================================================
UNIT 8, 'RX3'
OPERATING CONDITIONS
REACTOR TYPE ISOTHERMAL REACTOR
DUTY, MM BTU/HR 17.7914
TOTAL HEAT OF REACTION AT 77.00 F, MM BTU/HR 1.2566

INLET OUTLET
----------- -----------
FEED 11
VAPOR PRODUCT 12
LIQUID PRODUCT 13
TEMPERATURE, F 158.00 252.00
PRESSURE, PSIA 25.0000 25.0000

REACTION DATA
--------- RATES, LB-MOL/HR ---------- FRACTION
COMPONENT FEED CHANGE PRODUCT CONVERTED
------------------ ----------- ----------- ----------- -----------
1 UREA 1591.7928 0.0000 1591.7928
2 WATER 1385.2013 0.0000 1385.2013
3 AMCA 18.3068 -18.2977 9.15342E-03 0.9995
4 AMMONIA 619.4463 36.5954 656.0417
5 CO2 23.1057 18.2977 41.4034
TOTAL 3637.8529 36.5954 3674.4483
LB-MOL/HR FRACTION
BASE COMPONENT REACTION CONVERTED CONVERTED(1)
------------------ ----------- ----------- ------------
3 AMCA 1 18.2977 0.9995
(1) FRACTION CONVERTED BASED ON AMOUNT IN FEED

REACTOR MASS BALANCE

----------- Rates, LB/HR ------------ Fraction


Component Feed Change Product Converted
-------------------- ----------- ----------- ----------- -----------
1 UREA 95596.1349 0.0000 95596.1349
2 WATER 24954.7892 0.0000 24954.7892
3 AMCA 1429.2311 -1428.5165 0.7146 0.9995
4 AMMONIA 10549.5170 623.2394 11172.7564
5 CO2 1016.8772 805.2771 1822.1543

TOTAL 133546.5494 0.0000 133546.5494

PRO/II Case Book Urea Plant 5-39


SIMULATION SCIENCES INC. R PAGE P-24
PROJECT CaseBook PRO/II VERSION 9.3 ELEC V7.0
PROBLEM UreaPlant OUTPUT SimSci
STREAM WEIGHT COMPONENT RATES Apr_2010
==============================================================================

STREAM ID 1 2 3 4
NAME NH3FD CO2FD
PHASE LIQUID VAPOR LIQUID LIQUID
THERMO ID NRTL01 NRTL01 NRTL01 NRTL01

FLUID RATES, LB/HR


1 UREA 0.0000 0.0000 0.0000 0.0000
2 WATER 0.0000 0.0000 7.8048E-04 0.0000
3 AMCA 0.0000 0.0000 139.4570 0.0000
4 AMMONIA 105049.0000 0.0000 165512.1650 0.0000
5 CO2 0.0000 93408.0000 0.0000 93408.0000
6 N2 0.0000 0.0000 0.0000 0.0000
7 O2 0.0000 0.0000 0.0000 0.0000
8 H2 0.0000 0.0000 0.0000 0.0000
TOTAL FLUID, LB/HR 105049.0000 93408.0000 165651.6228 93408.0000

MW SOLID RATES, LB/HR


1 UREA 0.0000 0.0000 0.0000 0.0000
2 WATER 0.0000 0.0000 0.0000 0.0000
3 AMCA 0.0000 0.0000 0.0000 0.0000
4 AMMONIA 0.0000 0.0000 0.0000 0.0000
5 CO2 0.0000 0.0000 0.0000 0.0000
6 N2 0.0000 0.0000 0.0000 0.0000
7 O2 0.0000 0.0000 0.0000 0.0000
TOTAL MW SOLID, LB/HR 0.0000 0.0000 0.0000 0.0000

TOTAL RATE, LB/HR 105049.0000 93408.0000 165651.6228 93408.0000

TEMPERATURE, F -28.0000 100.0000 44.6511 100.0000


PRESSURE, PSIA 320.0000 300.0000 3515.0000 3515.0000
ENTHALPY, MM BTU/HR -6.7624 4.7133 2.2745 4.7133
MOLECULAR WEIGHT 17.0306 44.0098 17.0418 44.0098
WEIGHT FRAC VAPOR 0.0000 1.0000 0.0000 0.0000
WEIGHT FRAC LIQUID 1.0000 0.0000 1.0000 1.0000
WEIGHT FRAC MW SOLID 0.0000 0.0000 0.0000 0.0000

5-40 Urea Plant February 26, 2014


SIMULATION SCIENCES INC. R PAGE P-25
PROJECT CaseBook PRO/II VERSION 9.3 ELEC V7.0
PROBLEM UreaPlant OUTPUT SimSci
STREAM WEIGHT COMPONENT RATES Apr_2010
==============================================================================

STREAM ID 5 6 7 8
NAME
PHASE LIQUID MIXED LIQUID LIQUID
THERMO ID NRTL01 NRTL01 NRTL01 NRTL01

FLUID RATES, LB/HR


1 UREA 95598.2077 95598.2077 0.0000 95598.2050
2 WATER 28677.2145 28677.2145 7.7806E-04 28677.2129
3 AMCA 41564.5970 41564.5970 139.0253 41425.5706
4 AMMONIA 93219.6071 93219.6071 60478.1766 32741.4323
5 CO2 0.0000 0.0000 0.0000 0.0000
6 N2 0.0000 0.0000 0.0000 0.0000
7 O2 0.0000 0.0000 0.0000 0.0000
8 H2 0.0000 0.0000 0.0000 0.0000
TOTAL FLUID, LB/HR 259059.6263 259059.6263 60617.2026 198442.4209

MW SOLID RATES, LB/HR


1 UREA 0.0000 0.0000 0.0000 0.0000
2 WATER 0.0000 0.0000 0.0000 0.0000
3 AMCA 0.0000 0.0000 0.0000 0.0000
4 AMMONIA 0.0000 0.0000 0.0000 0.0000
5 CO2 0.0000 0.0000 0.0000 0.0000
6 N2 0.0000 0.0000 0.0000 0.0000
7 O2 0.0000 0.0000 0.0000 0.0000
TOTAL MW SOLID, LB/HR 0.0000 0.0000 0.0000 0.0000

TOTAL RATE, LB/HR 259059.6263 259059.6263 60617.2026 198442.4209

TEMPERATURE, F 365.0000 292.4821 127.9653 233.0678


PRESSURE, PSIA 3515.0000 320.0000 320.0000 325.0000
ENTHALPY, MM BTU/HR 77.4783 77.4783 6.5832 26.9806
MOLECULAR WEIGHT 28.1902 28.1902 17.0612 35.2049
WEIGHT FRAC VAPOR 0.0000 0.4585 0.0000 0.0000
WEIGHT FRAC LIQUID 1.0000 0.5415 1.0000 1.0000
WEIGHT FRAC MW SOLID 0.0000 0.0000 0.0000 0.0000

PRO/II Case Book Urea Plant 5-41


SIMULATION SCIENCES INC. R PAGE P-26
PROJECT CaseBook PRO/II VERSION 9.3 ELEC V7.0
PROBLEM UreaPlant OUTPUT SimSci
STREAM WEIGHT COMPONENT RATES Apr_2010
==============================================================================

STREAM ID 9 10 11 12
NAME DECGS1 DECGS2
PHASE VAPOR LIQUID MIXED VAPOR
THERMO ID NRTL01 NRTL01 NRTL01 NRTL01

FLUID RATES, LB/HR


1 UREA 2.0701 95596.1349 95596.1349 2.4577
2 WATER 3722.4238 24954.7892 24954.7892 8909.5732
3 AMCA 3541.8374 1429.2311 1429.2311 0.6093
4 AMMONIA 38096.4434 10549.5170 10549.5170 10493.9902
5 CO2 19533.0964 1016.8772 1016.8772 1802.8394
6 N2 0.0000 0.0000 0.0000 0.0000
7 O2 0.0000 0.0000 0.0000 0.0000
8 H2 0.0000 0.0000 0.0000 0.0000
TOTAL FLUID, LB/HR 64895.8710 133546.5494 133546.5494 21209.4698

MW SOLID RATES, LB/HR


1 UREA 0.0000 0.0000 0.0000 0.0000
2 WATER 0.0000 0.0000 0.0000 0.0000
3 AMCA 0.0000 0.0000 0.0000 0.0000
4 AMMONIA 0.0000 0.0000 0.0000 0.0000
5 CO2 0.0000 0.0000 0.0000 0.0000
6 N2 0.0000 0.0000 0.0000 0.0000
7 O2 0.0000 0.0000 0.0000 0.0000
TOTAL MW SOLID, LB/HR 0.0000 0.0000 0.0000 0.0000

TOTAL RATE, LB/HR 64895.8710 133546.5494 133546.5494 21209.4698

TEMPERATURE, F 302.0000 302.0000 158.0000 252.0000


PRESSURE, PSIA 325.0000 325.0000 25.0000 25.0000
ENTHALPY, MM BTU/HR 25.0732 24.0578 13.5648 15.9134
MOLECULAR WEIGHT 22.1276 36.7103 36.7103 18.4149
WEIGHT FRAC VAPOR 1.0000 0.0000 0.0565 1.0000
WEIGHT FRAC LIQUID 0.0000 1.0000 0.9435 0.0000
WEIGHT FRAC MW SOLID 0.0000 0.0000 0.0000 0.0000

5-42 Urea Plant February 26, 2014


SIMULATION SCIENCES INC. R PAGE P-27
PROJECT CaseBook PRO/II VERSION 9.3 ELEC V7.0
PROBLEM UreaPlant OUTPUT SimSci
STREAM WEIGHT COMPONENT RATES Apr_2010
==============================================================================

STREAM ID 13 14 15 16
NAME FLGS1 FLGS2
PHASE LIQUID VAPOR LIQUID VAPOR
THERMO ID NRTL01 NRTL01 NRTL01 NRTL01

FLUID RATES, LB/HR


1 UREA 95593.6772 0.2755 95593.4017 0.0973
2 WATER 16045.2159 989.5365 15055.6794 512.6611
3 AMCA 0.1053 0.0422 0.0632 0.0153
4 AMMONIA 678.7662 441.1092 237.6570 127.4104
5 CO2 19.3149 17.7209 1.5940 1.4026
6 N2 0.0000 0.0000 0.0000 0.0000
7 O2 0.0000 0.0000 0.0000 0.0000
8 H2 0.0000 0.0000 0.0000 0.0000
TOTAL FLUID, LB/HR 112337.0796 1448.6843 110888.3952 641.5867

MW SOLID RATES, LB/HR


1 UREA 0.0000 0.0000 0.0000 0.0000
2 WATER 0.0000 0.0000 0.0000 0.0000
3 AMCA 0.0000 0.0000 0.0000 0.0000
4 AMMONIA 0.0000 0.0000 0.0000 0.0000
5 CO2 0.0000 0.0000 0.0000 0.0000
6 N2 0.0000 0.0000 0.0000 0.0000
7 O2 0.0000 0.0000 0.0000 0.0000
TOTAL MW SOLID, LB/HR 0.0000 0.0000 0.0000 0.0000

TOTAL RATE, LB/HR 112337.0796 1448.6843 110888.3952 641.5867

TEMPERATURE, F 252.0000 250.0000 250.0000 230.0000


PRESSURE, PSIA 25.0000 15.0000 15.0000 8.7834
ENTHALPY, MM BTU/HR 13.8352 1.3812 13.3529 0.6619
MOLECULAR WEIGHT 44.5306 17.8329 45.4190 17.8357
WEIGHT FRAC VAPOR 0.0000 1.0000 0.0000 1.0000
WEIGHT FRAC LIQUID 1.0000 0.0000 1.0000 0.0000
WEIGHT FRAC MW SOLID 0.0000 0.0000 0.0000 0.0000

PRO/II Case Book Urea Plant 5-43


SIMULATION SCIENCES INC. R PAGE P-28
PROJECT CaseBook PRO/II VERSION 9.3 ELEC V7.0
PROBLEM UreaPlant OUTPUT SimSci
STREAM WEIGHT COMPONENT RATES Apr_2010
==============================================================================

STREAM ID 17 18 19 20
NAME CRYGS1
PHASE LIQUID LIQUID VAPOR MIXED
THERMO ID NRTL01 NRTL01 NRTL01 NRTL01

FLUID RATES, LB/HR


1 UREA 95593.3044 95593.3044 3.6000E-03 31298.5069
2 WATER 14543.0183 14543.0183 629.8924 13913.1259
3 AMCA 0.0479 0.0479 9.0884E-03 0.0388
4 AMMONIA 110.2466 110.2466 78.2450 32.0015
5 CO2 0.1914 0.1914 0.1862 5.2651E-03
6 N2 0.0000 0.0000 0.0000 0.0000
7 O2 0.0000 0.0000 0.0000 0.0000
8 H2 0.0000 0.0000 0.0000 0.0000
TOTAL FLUID, LB/HR 110246.8085 110246.8085 708.3363 45243.6784

MW SOLID RATES, LB/HR


1 UREA 0.0000 0.0000 0.0000 64294.7938
2 WATER 0.0000 0.0000 0.0000 0.0000
3 AMCA 0.0000 0.0000 0.0000 0.0000
4 AMMONIA 0.0000 0.0000 0.0000 0.0000
5 CO2 0.0000 0.0000 0.0000 0.0000
6 N2 0.0000 0.0000 0.0000 0.0000
7 O2 0.0000 0.0000 0.0000 0.0000
TOTAL MW SOLID, LB/HR 0.0000 0.0000 0.0000 64294.7938

TOTAL RATE, LB/HR 110246.8085 110246.8085 708.3363 109538.4722

TEMPERATURE, F 230.0000 230.0511 130.0000 130.0000


PRESSURE, PSIA 8.7834 20.0000 1.5000 1.5000
ENTHALPY, MM BTU/HR 11.9853 11.9884 0.7478 -0.6767
MOLECULAR WEIGHT 45.8314 45.8314 17.9039 46.2984
WEIGHT FRAC VAPOR 0.0000 0.0000 1.0000 0.0000
WEIGHT FRAC LIQUID 1.0000 1.0000 0.0000 0.4130
WEIGHT FRAC MW SOLID 0.0000 0.0000 0.0000 0.5870

5-44 Urea Plant February 26, 2014


SIMULATION SCIENCES INC. R PAGE P-29
PROJECT CaseBook PRO/II VERSION 9.3 ELEC V7.0
PROBLEM UreaPlant OUTPUT SimSci
STREAM WEIGHT COMPONENT RATES Apr_2010
==============================================================================

STREAM ID 21 22 23 24
NAME CRYGS2
PHASE MIXED LIQUID MIXED VAPOR
THERMO ID NRTL01 NRTL01 NRTL01 NRTL01

FLUID RATES, LB/HR


1 UREA 31298.5069 29069.4643 2229.0426 0.0399
2 WATER 13913.1259 12922.2495 990.8763 7003.5393
3 AMCA 0.0388 0.0360 2.7628E-03 0.0310
4 AMMONIA 32.0015 29.7224 2.2791 29.2626
5 CO2 5.2651E-03 4.8901E-03 3.7497E-04 4.8848E-03
6 N2 0.0000 0.0000 0.0000 0.0000
7 O2 0.0000 0.0000 0.0000 0.0000
8 H2 0.0000 0.0000 0.0000 0.0000
TOTAL FLUID, LB/HR 45243.6784 42021.4772 3222.2012 7032.8776

MW SOLID RATES, LB/HR


1 UREA 64294.7938 0.0000 64294.7938 0.0000
2 WATER 0.0000 0.0000 0.0000 0.0000
3 AMCA 0.0000 0.0000 0.0000 0.0000
4 AMMONIA 0.0000 0.0000 0.0000 0.0000
5 CO2 0.0000 0.0000 0.0000 0.0000
6 N2 0.0000 0.0000 0.0000 0.0000
7 O2 0.0000 0.0000 0.0000 0.0000
TOTAL MW SOLID, LB/HR 64294.7938 0.0000 64294.7938 0.0000

TOTAL RATE, LB/HR 109538.4722 42021.4772 67516.9950 7032.8776

TEMPERATURE, F 130.0609 130.0609 130.0609 130.0000


PRESSURE, PSIA 20.0000 20.0000 20.0000 1.3350
ENTHALPY, MM BTU/HR -0.6734 2.6376 -3.3109 7.8496
MOLECULAR WEIGHT 46.2984 34.9282 58.0622 18.0111
WEIGHT FRAC VAPOR 0.0000 0.0000 0.0000 1.0000
WEIGHT FRAC LIQUID 0.4130 1.0000 0.0477 0.0000
WEIGHT FRAC MW SOLID 0.5870 0.0000 0.9523 0.0000

PRO/II Case Book Urea Plant 5-45


SIMULATION SCIENCES INC. R PAGE P-30
PROJECT CaseBook PRO/II VERSION 9.3 ELEC V7.0
PROBLEM UreaPlant OUTPUT SimSci
STREAM WEIGHT COMPONENT RATES Apr_2010
==============================================================================

STREAM ID 25 26 27 28
NAME
PHASE MIXED MIXED LIQUID MIXED
THERMO ID NRTL01 NRTL01 NRTL01 NRTL01

FLUID RATES, LB/HR


1 UREA 13305.9443 13305.9443 12709.6529 596.2914
2 WATER 5918.7102 5918.7102 5653.4697 265.2405
3 AMCA 5.0685E-03 5.0685E-03 4.8413E-03 2.2714E-04
4 AMMONIA 0.4598 0.4598 0.4392 0.0206
5 CO2 5.2985E-06 5.2985E-06 5.0611E-06 2.3745E-07
6 N2 0.0000 0.0000 0.0000 0.0000
7 O2 0.0000 0.0000 0.0000 0.0000
8 H2 0.0000 0.0000 0.0000 0.0000
TOTAL FLUID, LB/HR 19225.1195 19225.1195 18363.5667 861.5528

MW SOLID RATES, LB/HR


1 UREA 15763.4801 15763.4801 0.0000 15763.4801
2 WATER 0.0000 0.0000 0.0000 0.0000
3 AMCA 0.0000 0.0000 0.0000 0.0000
4 AMMONIA 0.0000 0.0000 0.0000 0.0000
5 CO2 0.0000 0.0000 0.0000 0.0000
6 N2 0.0000 0.0000 0.0000 0.0000
7 O2 0.0000 0.0000 0.0000 0.0000
TOTAL MW SOLID, LB/HR 15763.4801 15763.4801 0.0000 15763.4801

TOTAL RATE, LB/HR 34988.5996 34988.5996 18363.5667 16625.0329

TEMPERATURE, F 130.0000 130.0768 130.0768 130.0768


PRESSURE, PSIA 1.3350 20.0000 20.0000 20.0000
ENTHALPY, MM BTU/HR 0.3437 0.3451 1.1523 -0.8072
MOLECULAR WEIGHT 43.0572 43.0572 34.9468 57.8998
WEIGHT FRAC VAPOR 0.0000 0.0000 0.0000 0.0000
WEIGHT FRAC LIQUID 0.5495 0.5495 1.0000 0.0518
WEIGHT FRAC MW SOLID 0.4505 0.4505 0.0000 0.9482

5-46 Urea Plant February 26, 2014


SIMULATION SCIENCES INC. R PAGE P-31
PROJECT CaseBook PRO/II VERSION 9.3 ELEC V7.0
PROBLEM UreaPlant OUTPUT SimSci
STREAM WEIGHT COMPONENT RATES Apr_2010
==============================================================================

STREAM ID 29 30 31
NAME DRYGS UREAPROD
PHASE VAPOR MIXED MIXED
THERMO ID NRTL01 NRTL01 NRTL01

FLUID RATES, LB/HR


1 UREA 14.6664 2810.6676 0.0000
2 WATER 1176.0587 80.0582 80.0582
3 AMCA 2.9791E-03 1.0834E-05 1.0834E-05
4 AMMONIA 2.2917 7.9784E-03 7.9784E-03
5 CO2 3.7480E-04 4.1472E-07 4.1472E-07
6 N2 0.0000 0.0000 0.0000
7 O2 0.0000 0.0000 0.0000
8 H2 0.0000 0.0000 0.0000
TOTAL FLUID, LB/HR 1193.0202 2890.7338 80.0662

MW SOLID RATES, LB/HR


1 UREA 0.0000 80058.2739 82868.9415
2 WATER 0.0000 0.0000 0.0000
3 AMCA 0.0000 0.0000 0.0000
4 AMMONIA 0.0000 0.0000 0.0000
5 CO2 0.0000 0.0000 0.0000
6 N2 0.0000 0.0000 0.0000
7 O2 0.0000 0.0000 0.0000
TOTAL MW SOLID, LB/HR 0.0000 80058.2739 82868.9415

TOTAL RATE, LB/HR 1193.0202 82949.0077 82949.0077

TEMPERATURE, F 369.5322 369.5322 200.0000


PRESSURE, PSIA 15.0000 15.0000 15.0000
ENTHALPY, MM BTU/HR 1.4214 5.0183 -2.0431
MOLECULAR WEIGHT 18.1697 59.9207 59.9207
WEIGHT FRAC VAPOR 1.0000 0.0000 0.0000
WEIGHT FRAC LIQUID 0.0000 0.0348 9.6525E-04
WEIGHT FRAC MW SOLID 0.0000 0.9652 0.9990

PRO/II Case Book Urea Plant 5-47


SIMULATION SCIENCES INC. R PAGE P-32
PROJECT CaseBook PRO/II VERSION 9.3 ELEC V7.0
PROBLEM UreaPlant OUTPUT SimSci
SOLID ATTRIBUTES Apr_2010
==============================================================================

STREAM ID 20 21 23 25
NAME
PHASE MIXED MIXED MIXED MIXED
THERMO ID NRTL01 NRTL01 NRTL01 NRTL01

1 UREA
PSD, MIC
0.000 - 20.00 1.422E-06 1.422E-06 1.422E-06 4.925E-06
20.00 - 50.00 8.265E-05 8.265E-05 8.265E-05 2.719E-04
50.00 - 100.0 1.153E-03 1.153E-03 1.153E-03 3.492E-03
100.0 - 200.0 0.0136 0.0136 0.0136 0.0353
200.0 - 500.0 0.2314 0.2314 0.2314 0.3966
0.500 - 1.000 E+03 0.7537 0.7537 0.7537 0.5643

STREAM ID 26 28 30 31
NAME UREAPROD
PHASE MIXED MIXED MIXED MIXED
THERMO ID NRTL01 NRTL01 NRTL01 NRTL01

1 UREA
PSD, MIC
0.000 - 20.00 4.925E-06 4.925E-06 2.112E-06 2.112E-06
20.00 - 50.00 2.719E-04 2.719E-04 1.199E-04 1.199E-04
50.00 - 100.0 3.492E-03 3.492E-03 1.614E-03 1.614E-03
100.0 - 200.0 0.0353 0.0353 0.0179 0.0179
200.0 - 500.0 0.3966 0.3966 0.2639 0.2639
0.500 - 1.000 E+03 0.5643 0.5643 0.7164 0.7164

5-48 Urea Plant February 26, 2014


Case 6:
Vinyl Chloride Monomer
(VCM) Plant

Abstract
This case book presents and analyzes a PRO/II simulation of a
Vinyl Chloride Monomer (VCM) synthesis plant. It includes 31 unit
operations, including four columns, three reactor systems, and 6
recycle streams. An enhanced version of the SRK equation of state
(SRKM) is used to model the system thermodynamics. After
reaching solution, the simulation satisfies all required product
purity specifications. The model can be used for economic
evaluations, set point selections for achieving product quality, and
as a tool for control system design/revamp.

Introduction
A typical vinyl chloride monomer (VCM) plant, represented in
Figure 6-1, is comprised of five sections. Each flowsheet section
was first simulated separately (as described later in the Process
Outline section). Once the flowsheet model of each section has
been finalized, they were combined into an overall plant simulation.

PRO/II Case Book VCM Synthesis Plant (Rev. 3) 6-1


Figure 6-1: Overall Vinyl Chloride Monomer (VCM) Plant

The final overall plant simulation has only one recycle loop that
solves relatively quickly in about 5 iterations. However, simulation
of individual sections may be desirable for various needs, such as
training or localized troubleshooting during operations. It is,
however, useful to have a tool to investigate interactions between
different parts of the plant. For that purpose, this application
simulates the entire plant. Within the context of the total plant
flowsheet, this application emphasizes the purification trains for
1,2-dichloroethane (EDC) and VCM. Simple models have been
used for the three reactor systems. This provides a tool for the
realistic assessment of VCM plant operations.
This application demonstrates PRO/II's capability to rigorously
simulate a flowsheet processing a large number of species in a wide
range of concentrations. The chemical species in a VCM plant are
generally non-ideal and somewhat polar. The SRKM equation of
state (developed at SimSci) has been used to simulate this
flowsheet. All of the desired separation efficiencies are achieved.

6-2 VCM Synthesis Plant (Rev. 3) February 26, 2014


Relevance of Modelling VCM Plants
There are several possible objectives for the simulation of a VCM
plant. For example:
Tighten VCM product purity specifications for downstream
polymerization to PVC;
Improve heat integration and energy efficiency;
Establish on-line optimization and control philosophies;
Debottlenecking;
Establish emission levels for comparison with environmental
targets.
It is necessary to have a simulation model of the plant for
assessment of advanced process control applications and
improvements. On the basis of this model, it is possible to establish
a base case from which achievable improvements in performance
can be estimated. The resulting economic benefits can then be
evaluated and compared against
the cost of implementing the changes. In a similar way, plant
bottlenecks and constraints may be investigated.

Background
Commercial processes for the production of vinyl chloride from
ethylene and chlorine have been operating successfully since the
1950s. These processes include direct chlorination of ethylene to
produce EDC followed by pyrolysis of EDC to produce vinyl
chloride. Commercial EDC cracking furnaces operate in the 480-
550 C range with pressures up to 30-40 atmospheres. Single pass
conversion of EDC is in the 50-60% range. This conversion level
optimizes costs between coking cycles, utilities and yields. The
resulting HCl is recycled to oxychlorination reactors where fresh
ethylene reacts with HCl in the presence of oxygen to produce more
EDC. Since HCl is totally consumed within the plant and is not a
product, this process is often referred to as the balanced
oxychlorination process.
Pyrolysis of EDC is very selective towards VCM. Typical yields of
VCM are greater than 95% at EDC conversion levels in the 50-60%
range. The by-products include acetylene, ethylene, methyl
chloride, butadiene, vinyl acetylene, benzene, chloroprene and

PRO/II Case Book VCM Synthesis Plant (Rev. 3) 6-3


various other chlorinated hydrocarbons in trace amounts. Many of
these chlorinated species are environmentally harmful.
The pyrolysis reactor establishes the yield slate and raw VCM
product composition. While there is a high selectivity towards vinyl
chloride, the correct prediction of impurities in the reactor feed and
by-product formation in the effluent is important. Some trace
species in the feed inhibit the cracking reactions; others serve as
promoters. Ninety-nine percent EDC feed purity is desirable. At the
other end of the process, a purity of 99.9+% is specified for
polymer grade VCM. This is achieved by two means:
First, by controlling the cracking process to minimize by-product
formation;
Second, by proper operation of the VCM purification section to
reduce the concentration of various trace contaminants to low ppm
levels.
High purity VCM product is necessary for subsequent
polymerization to polyvinyl chloride (PVC) and other co-polymers.
For example, the presence of methyl chloride and butadiene as
impurities in the VCM product interferes with its polymerization to
PVC. The typical upper limit to acceptable methyl chloride content
in VCM is in the 60-150 ppm range.

Process Outline
An overview of the VCM plant is shown above in Figure 6-1. The
process is comprised of these 5 sections (or blocks):
Direct chlorination of ethylene to form EDC. Figure 6-2.
Oxychlorination section where ethylene is reacted with
recycled HCl and O2 to form more EDC. Figure 5-3.
Purification of EDC. Figure 5- 4.
Thermal cracking of EDC to form VCM and HCl. The raw
VCM product is quenched and cooled. Figure 5-5.
Purification of VCM. The HCl formed is recycled to the
oxychlorination reactor. Unreacted EDC is recycled to the EDC
purification system. Figure 6.
Each of the five major sections of the plant is shown and discussed
individually in the text that follows.

6-4 VCM Synthesis Plant (Rev. 3) February 26, 2014


Process Description and Simulation Model
Direct Chlorination
A process flow diagram for this section of the plant is shown below
in Figure 6-2.

Figure 6-2: Direct Chlorination Section

Reaction
Direct chlorination of ethylene to EDC is conducted in a liquid
phase reactor by intimately mixing ethylene and chlorine in liquid
EDC. The operating conditions are 120-150 C and 0-30 psig
pressure.
C 2 H 4 + Cl 2 C 2 H 4 Cl 2 + Heat (6-1)

PRO/II Case Book VCM Synthesis Plant (Rev. 3) 6-5


The heat of reaction is removed by circulating cooling water or by
recirculating the liquid EDC through external coolers. In most
commercial processes ferric chloride is used as a catalyst. The
reactions often run with a small excess of ethylene to maintain fuel-
rich vent gases for incineration. Conversion of the lean component
usually is 100%, with selectivity for EDC greater than 99%.

EDC Product Treatment


There are two major design variations for recovering the EDC
product. In some designs, EDC is withdrawn as a liquid. In others,
the heat of reaction is utilized to boil off sufficient EDC as a vapor
product. In the simulation being discussed here, product EDC is
removed as a vapor phase which also contains unreacted ethylene
and chlorine. Liquid EDC is recovered by two stage condensation.
Any HCl and Cl2 remaining in the vent gas are removed in a caustic
scrubber. The liquid EDC goes to a caustic wash vessel where
dissolved chlorine and by-product HCl are removed. EDC
overflows from the caustic wash to a decanter where it combines
with the oxychlorinator product.

Simulation
As shown in Figure 6-2, the main feeds to the plant are ethylene and
chlorine. The flow of ethylene (C2F1) is set by the desired VCM
production rate (154 tpd). Calculator CAL1 adjusts the flow of
chlorine (CL2F) such that the chlorine-to-ethylene ratio in the
reactor feed is 0.99.
In actual operations, the reaction takes place in a liquid EDC
medium in the presence of ferric chloride as the catalyst. The
conversion of the lean component (chlorine) is nearly 100% with
99% selectivity for EDC. Therefore, this reaction system has been
modeled by two reactors functioning in parallel. The combined total
feed (FDIR) is split (SPL1) such that a 0.985 fraction goes to the
first reactor (RX1) and the remaining to the second reactor (RX2).
Unit RX1 is a Gibbs reactor where most of the EDC forms. Unit
RX2 uses a stoichiometric model. A reaction stoichiometry has
been balanced and fitted to expected yields of by-products. The
reaction conditions for both the reactors are 120 C and 15 psig
pressure.
The resulting product streams from the reactors are combined
(MIX2). The effluent stream (EDCD) is cooled and flashed (FLS1)
to separate a vent stream (VNT1) and a raw product stream
(EDCE).

6-6 VCM Synthesis Plant (Rev. 3) February 26, 2014


The raw product stream EDCE is then washed and scrubbed with
caustic to remove any HCl and unconverted chlorine. This process
is highly efficient in practice and is modeled with a stream
calculator (STC2) to remove all of the HCl and Cl2.

Oxychlorination
Reaction
The reaction between ethylene, hydrogen chloride and oxygen
occurs at temperatures between 225-325C, with pressure in the
range of 15-225 psig.
C 2 H 4 + 2HCl + O 2 C 2 H 4 Cl 2 + H 2 O + Heat (6-2)
In a balanced oxychlorination plant, dry hydrogen chloride gas is
produced mainly from the thermal cracking of EDC. Compressed
air supplies the oxygen. This reaction is conducted in either a fixed
bed or a fluidized bed reactor containing a catalyst. It is highly
exothermic and good temperature control is essential for the
successful production of EDC. Temperatures above 325 C
deactivate the catalyst, increase by-product formation and burn
ethylene to carbon monoxide and carbon dioxide. The heat of
reaction is removed by circulating boiler feed water (BFW) through
coils embedded in the reactor and generating steam.
Typical results from this operation are 93-97% ethylene conversion,
94-97% HCl conversion and 93-96% EDC selectivities. This
reaction yields more by-products than the direct chlorination step.
These by-products must be minimized and removed in the EDC
purification step. Some of the by-products (chloral, for example)
readily polymerize and tend to foul operating lines and controls.
One way to reduce by-product formation is to provide feeds of good
purity. For example, the recycle HCl stream from the VCM
purification section should contain less than 0.1% of acetylene.
Presence of acetylene leads to the formation of highly chlorinated
by-products and tars.
Production control is related to HCl mass flow established by the
pyrolysis reactor severity and HCl column operation. Air and
ethylene flow rates are then ratioed in slightly greater than
stoichiometric amounts.

EDC Recovery
EDC, nitrogen and other gases from the oxychlorination reactor
first pass through a caustic scrubbing tower where unreacted HCl is
removed. The vapor then passes to a refrigerated condensation

PRO/II Case Book VCM Synthesis Plant (Rev. 3) 6-7


system to recover EDC and water. The crude EDC mixed with
water flows to the decanter where it combines with the direct
chlorination product. Uncondensed nitrogen passes to atmosphere
through a venting system.

Simulation
The process flow diagram for this section of the plant is shown in
Figure 6-1.

Figure 6-1: Oxy-Chlorination Section

For the oxychlorination section shown in Figure 6-1, the controlling


flow is that of the recycle HCl stream from the top of the HCl
column (of the VCM Purification Section). Therefore, when
simulating the complete flowsheet, this section is solved as part of a
recycle loop. This means initial estimates of the recycle HCl stream
temperature, pressure, composition and flow rate are required.

6-8 VCM Synthesis Plant (Rev. 3) February 26, 2014


Calculator CAL2 fixes the ethylene feed flow rate (C2F2) at 3% in
excess of stoichiometric requirement. In a similar fashion, the flow
rate of air (for oxygen) is fixed.
In the absence of a specific two-phase catalytic model for
oxychlorination, this simulation uses available qualitative
information on the oxychlorination product composition.
Accordingly, the reaction system is modeled as two Gibbs reactors
in parallel. The first reactor (RX3) converts a majority of the feed to
produce the desired products. The second one (RX4) processes a
small fraction of the feed to yield the by-products.
The reaction system model begins with the feed streams being
combined (MIX3) and then split (SPL2) into stream FOXA (96%)
and FOXB (4%). Since it is known that selectivity for EDC is about
96%, stream FOXA reacts in a Gibbs reactor (RX3) where the
reaction is limited to the main reacting and product species:
ethylene, EDC, HCl, O2 and water. Typical operating conditions for
units RX3 and RX4 are 290 C at 90 psig, with an approach of about
25 C.
The product streams from the two reactors (OXYA and OXYB) are
combined by MIX4 into combined stream OXC before entering the
caustic scrubber. The caustic wash unit that removes unreacted HCl
is a stream calculator (STC3) that simulates ideal removal of HCl.
The washed product stream (OXYD) is cooled and flashed to
remove all non-condensables (mainly nitrogen and unreacted
oxygen) as a vent stream (VNT2). The final product from this
section, stream EDC2, feeds the EDC purification section.

EDC Purification
Figure 6-2 and 5 show a process flow diagram for the EDC
purification section of the plant.

Process Feed Pre-treatment


Figure 5-4 illustrates the feed-processing portion of the EDC
purification section. Trace amounts of impurities in the pyrolysis
feed can inhibit the cracking reactions and cause fouling. In
addition, EDC must also be dry to prevent excessive corrosion
downstream of the reactor. Therefore, the combined EDC from
three different sources must be purified to 99%: EDC from direct
chlorination, EDC from oxychlorination and EDC recovered and
recycled from the cracking step.

PRO/II Case Book VCM Synthesis Plant (Rev. 3) 6-9


Figure 6-2: EDC Purification Feed Pre-treatment

The combined EDC from both direct chlorination and


oxychlorination sections is washed with water and scrubbed with
caustic. This removes chlorine, HCl, and other water-extractable
impurities such as chloral. Free water is decanted.

EDC Purification Process


The crude EDC and unconverted recycle EDC from the VCM
column are combined into stream EDC5 and fed to the two columns
shown in Figure 5-5.

6-10 VCM Synthesis Plant (Rev. 3) February 26, 2014


Figure 6-3: EDC Purification Columns

Stream EDC5 is dried and purified in two distillation columns. In


the first column (the lights column), water and lower boiling point
impurities (light ends) are separated as the overhead product. The
bottoms product of the light ends column is mixed with a purge
stream from the feed vaporizer and fed to the second (heavies)
column.
Another purge stream (QSP) from the quench system, downstream
of the cracker, is also directed to the bottom of the heavies column.
Pure EDC of around 99% purity is taken as the overhead product
(TOP2) while the heavy impurities leave the column as the bottoms
product BTM2 (heavy ends).
The bottoms product from the heavies column may be processed
further, normally via batch distillation, to provide distilled
heavies by-product, consisting mainly of recovered EDC, and
residual heavy tar.

PRO/II Case Book VCM Synthesis Plant (Rev. 3) 6-11


Simulation
As illustrated in Figure 6-2, this EDC purification section begins
with a simulation of a saturator/decanter unit to accomplish the feed
pre-treatment. Streams EDC1 and EDC2 are brought together in a
mixer (MIX5). The resultant EDC3 stream is combined with a large
excess of water (WTR1) and flashed in a three-phase flash unit
(FLS3) that serves as both a saturator and a decanter. The SRK
equation of state with DECANT=ON is used for thermodynamics
and is a non-rigorous simulation of VLLE equilibrium.
While the water phase is decanted as pure water, the amount of
water dissolved in the hydrocarbon phase is predicted based on
solubility data. The free-water decant model reduces the
computational time required to solve this unit and does not
adversely impact the overall flowsheet model.
Three streams exit unit FLS3: a small vent stream (VNT3), aqueous
decant (WTR2), and a crude, wet EDC stream (EDC4). This EDC
stream is mixed with a recycle EDC stream (BTM4) from the
bottoms of the VCM column (see VCM Purification Section).
The combined feed (EDC5) is fed to the lights column (COL1).
Refer to Figure 6-3. The IO distillation algorithm is used to
simulate both columns in this section. Column COL1 has 12
theoretical trays. The bottom product is specified to contain 99.9%
of the EDC entering the column in stream EDC5. This limits the
water content to 0.1% water, effectively specifying at least 99.9%
dehydration. The other specification sets the condenser reflux ratio
at 24.5 : 1. A partial condenser is used for this column. The top
vapor product (TOP1) removes most of the water and other light
species with some loss of EDC. The remaining EDC and heavies
(BTM1) pass on to the heavies column (COL2).
Usually a surge tank is placed between the two columns to allow
monitoring of the moisture content. Before being fed to the heavies
column, the partially dehydrated EDC is mixed with a recycle
liquid purge stream (VAPP) from the pyrolysis reactor feed
vaporizer.
The combined feed (HVYF) goes to COL2 which has 30 theoretical
trays. The stripping section of the column also receives another
recycle purge stream (QSP) from the quench separator. This purge
prevents collections of heavy cracking by-products in the quench
system. The specifications for COL2 are a fixed reflux ratio of 0.6
and a maximum EDC loss of 3% in the bottoms product (BTM2).

6-12 VCM Synthesis Plant (Rev. 3) February 26, 2014


When solved, the top product (TOP2) is about 99.9% pure dry
EDC.

EDC Cracking and Quench


A typical flowsheet for the EDC cracking and quench section is
shown below in Figure 6-4.

Figure 6-4: EDC Thermal Cracking Section

Process
Pure EDC is preheated and vaporized before being fed to the
cracking furnace, where it is thermally cracked at about 500 C and
200 psig by the following reaction.
C 2 H 4 Cl 2 C 2 H 3 Cl + HCl
(6-3)
About half of the EDC
EDC entering the
VCM reacts. The product
furnace
stream then contains roughly equimolar proportions of EDC, VCM
and HCl. This stream is quenched by recycled liquids and cooled to
about 25-50 C before being fed as both liquid and vapor to the HCl
column.
There are two purges in this section of the plant. A liquid purge to
prevent iron buildup and fouling of the EDC vaporizer. A quench

PRO/II Case Book VCM Synthesis Plant (Rev. 3) 6-13


separator purge to remove <169>tarry<170> by-products of the
cracking reaction. Both of these purges are recycled to the heavies
column.
EDC furnaces are typically operated up to a maximum of 55%
conversion of EDC. This optimizes conversion per pass, column
tray loadings and balances the load between direct chlorination and
oxychlorination reactors.

Simulation Model
The pyrolysis reactor is simulated as a stoichiometric reactor.
Stoichiometry of three of the major molecular reactions
representing the overall reaction system is defined. For trace
species in the feed and the effluent, a reaction fitted to typical plant
data is specified. This simplified approach to the overall pyrolysis
process is appropriate for the overall modeling of the VCM plant. If
desired, a more detailed model of this reactor system could be
achieved using in-line Fortran reaction data or by implementing the
reactions as a user-added subroutine.
The top product (TOP2) from the heavies column (COL2) of the
EDC purification section is sent to a pure EDC surge tank. The
pyrolysis furnace receives its feed from this tank. The feed is heated
and flashed (FLS4) to recover a liquid purge stream (VAPP). The
balance is a vapor stream (PYRF) which is fed to the pyrolysis
reactor (PYRO). The reactor effluent (EFF1) is quenched by
recirculating liquid streams (Q1 and Q2) to yield a quenched
product (EFF2). This stream passes to a quench separator (FLS5)
where the liquid phase containing heavy by-products is removed. A
small portion is sent to the EDC purification section as purge. The
remaining liquid phase constitutes the Q1 quench stream. The vapor
phase (VF5) is further cooled in one or more heat exchangers and
flashed (FLS6) to recover a liquid stream (Q2) that constitutes the
other circulating quench stream.

Vinyl Chloride Monomer Purification


Process
VCM is separated from HCl and EDC in two distillation columns.
The first column, called the HCl column, receives mixed phase
feeds containing mainly EDC, VCM and HCl with small amounts
of reaction by-products.

6-14 VCM Synthesis Plant (Rev. 3) February 26, 2014


HCl distills off at the top; with half of it is recycled directly to the
oxychlorinator, and the other half condensed against propane
refrigerant for reflux to the column.
The bottom product is fed to the VCM column for final separation
of the purified VCM product as the overhead. EDC is recycled to
the lights column for re-purification.
The flow diagram for this section is illustrated in Figure 6-1.

Figure 6-1: VCM Purification Section

Control and Specification


The HCl column is operated to achieve impurity specs of less than
100 ppm VCM in the distillate and less than 5 ppm HCl in the
bottoms. Any VCM in the overhead will be converted to more
highly chlorinated by-products in the oxychlorinator, representing a
decreased product conversion efficiency.

PRO/II Case Book VCM Synthesis Plant (Rev. 3) 6-15


A breakthrough of HCl into the bottoms results in out-of-spec VCM
that must be rerun, reducing VCM production rates. Proper
simulation can help establish better set points and improve the
control system for a more stable operation.

Simulation
The HCl column in this simulation has 32 theoretical trays,
including the condenser and the reboiler. The feed to this column
comes from the flash unit (FLS7) upstream of the column. The
vapor (VF7) is fed to tray 8 while the liquid (LF7) is fed to tray 12.
One of the control specifications is for the reflux ratio to be
maintained at 1.0. The other control specification is a suitable tray
temperature. In this example, the temperature of tray 1 (the
condenser) is maintained at -31.2C. This stabilizes high purity in
the overhead product.
A top pressure of 135 psig is maintained by using a partial
condenser using refrigerant propane. The column top temperature is
around -31C. Simulation results show that both the top product
(TOP3) and the bottom product (BTM3) purity requirements are
achieved. In this simulation, the top product (TOP3) is recycled to
the oxychlorination section, while the bottoms feed the VCM
column (COL4). Other versions of the process may route the
recycle differently.
The VCM column has 16 theoretical trays and a top pressure of 65
psig. The control specifications are the reflux ratio of 0.45 and tray
13 temperature of 140 C. The column converges with ease and
provides high purity VCM (greater than 99.9%) as the distillate
product (TOP4). The bottoms product (BTM4) is unreacted EDC
that recycles to the EDC purification section.
The two columns in the VCM purification section exhibit similar
behavior as the columns in the EDC purification section. Both
columns successfully converge with the IO algorithm and the
SRKM equation of state.

Methods and Data


All of the components are available in the pure component data
bank, along with pure component properties.
The SRKM equation of state is chosen for its excellent handling of
light polar compounds. Binary interaction parameters for many
component pairs are already present in PRO/II's thermodynamic

6-16 VCM Synthesis Plant (Rev. 3) February 26, 2014


data base. Additional pairs have been regressed for this simulation
and entered in the Thermodynamic Data Category of input.

Technical Results
The main feeds to a plant producing 154 MTPD of 99.9+% pure
VCM product are summarized below.

Ethylene 7326 lb/hr


Chlorine 10009 lb/hr
Air 7970 lb/hr (23.29% Oxygen = 1856 lb/hr)

The main product is VCM. Various vent gas, decant water and
purge streams containing heavies and other by-products of reaction
are also removed from the process.
PRO/II automatically determined the calculation sequence, the
recycle loops and the recycle streams. The flowsheet converged in
five iterations of the outermost loop. The PRO/II input file for this
simulation is attached.
Selected results, mainly related to the HCl column, are presented
after the keyword input listing. Examination of the results shows
that all product purity specifications are achieved. Electronic copies
of the input files and the complete output file are available in the
Casebook\Inputs directory of the documentation installed with
PRO/II.

Benefits and Economics


The VCM plant model may be used for optimization, improved
product quality through set point selection, and as a simple control
system design/revamp tool.

Commercial Information
In 2005, world VCM capacity was approximately 35 million metric
tons. About 99.5% of production in the United States is used to
manufacture PVC. There are roughly 125 to 150 VCM plants world
wide. About 90% of these plants use the balanced oxychlorination
process described here. The technology for these plants is available
from about 15 different licensors, each specializing in one or more
sections of the VCM plant. Some of the leading licensors are B. F.
Goodrich, Hoechst, Stauffer, ICI, Dow, PPG, and Tosoh.

PRO/II Case Book VCM Synthesis Plant (Rev. 3) 6-17


6-18 VCM Synthesis Plant (Rev. 3) February 26, 2014
Appendix 6-A: Keyword Input
Input File
TITLE PROJECT=Casebook, PROBLEM=VCM Plant, USER=SIMSCI, DATE=APR01
DIMEN ENGLISH, TEMP=C, PRES=PSIG
CALCU TRIALS=10
TOLER STREAM=0.03,-1.0,0.01,0.01
PRINT INPUT=ALL, STREAM=PART, RATE=WT, MBAL
SEQUENCE PROCESS
COMPONENT DATA
LIBID 1, ETHYLENE / 2, CHLORINE /*
3, EDC / 4, CCL4 /*
5, CHCL3 , , CHLOROFORM /*
6, CH3CL , , METHYL CHLORDE /*
7, CH4 , , METHANE /*
8, DCLMETHN , , DICHLORO METHN / *
9, CO / 10, CO2 /*
11, C2CL4 , , TET-CHLOR ETHL / *
12, C2CL6 , , HEX-CHLOR ETHN / *
13, C2HCL3 , , TRI-CHLOR ETHL / *
14, C2HCL5 , , PNT-CHLOR ETHN / *
15, C2H2 , , ACETYLENE /*
16, 12DCLETT , , t-12-C2H2CL2 / *
17, 11DCLETE , , 11-C2H2CL2 / *
18, 12DCLETC , , c-12-C2H2CL2 / *
19, C2H2CL4 , , 1112-C2H2CL4 / *
20, H2C2CL4 , , 1122-C2H2CL4 / *
21, VCM /*
22, 112TCLET , , 112-C2H3CL3 / *
23, 111TCLET , , 111-C2H3CL3 / *
24, 11DCLETH , , 11-C2H4CL2 / *
25, C2HCL3O , , DCLACTCL /*
26, VAC /*
27, CLETHANE /*
28, PROPDIEN /*
29, PROPENE /*
30, 2CL13BD , , CHLOROPRENE / *
31, 13BUTD , , 13-BUTADIENE / *
32, BENZENE /*
33, HCL /*
34, O2 /*
35, N2 /*
36, WATER, *
BANK=PROCESS, SIMSCI

PC 21, 807.668 /*
33, 1190.567

PRO/II Case Book VCM Synthesis Plant (Rev. 3) 6-19


THERMODYNAMIC DATA

METHOD SET=2, SYSTEM=SRKM, DENSITY(L)=RACKETT, DEFAULT


KVALUE(VLE) BANK=SIMSCI
SRKM &
3, 4, 0.017072, 0.147482, 8.7493, -40.8568, 0.0, 0.0, 1.0, 1.0 / &
3, 5, 0.097254, -0.010004, -29.4815, 2.9565, 0.0, 0.0, 1.0, 1.0 / &
3, 13, -0.045421, 0.047496, 24.2198, -6.5592, 0.0, 0.0, 1.0, 1.0 / &
3, 21, 0.047535, -0.029720, -6.5876, 11.4526, 0.0, 0.0, 1.0, 1.0 / &
3, 24, 0.0, 0.000433, 0.0, -4.1170, 0.0, 0.0, 1.0, 1.0 / &
3, 32, 0.014733, 0.039946, -5.0258, -13.9200, 0.0, 0.0, 1.0, 1.0 / &
3, 33, -0.093415, -0.095866, 16.8146, 11.1944, 0.0, 0.0, 0.965, 0.916 / &
4, 5, 0.019164, 0.004298, -3.2167, 0.6711, 0.0, 0.0, 1.17385, 0.07978 / &
4, 8, 0.072803, -0.146358, -15.0106, 52.9615, 0.0, 0.0, 1.44081, 0.10411 / &
4, 32, -0.004987, 0.007738, 3.3921, -0.3973, 0.0, 0.0, 1.0, 1.0 / &
5, 24, 0.051741, -0.061022, -18.7303, 18.4166, 0.0, 0.0, 1.0, 1.0 / &
5, 32, -0.089119, -0.031971, 21.2937, 4.1652, 0.0, 0.0, 1.14492, 1.17331 / &
8, 13, 0.005434, -0.018618, -0.3390, 5.0332, 0.0, 0.0, 1.0, 1.0 / &
21, 33, -0.008752, 0.011038, 1.7890, -4.3071, 0.0, 0.0, 1.10530, 0.93789

METHOD SET=3, SYSTEM(VLE)=SRK, DENSITY(L)=RACKETT


KVALUE(VLE) BANK=SIMSCI
WATER DECANT=ON

STREAM DATA

$ VARIOUS FEED STREAMS:

PROP STREAM=C2F1, PHASE=V, PRES(PSIG)=15, TEMP=75, &


COMP(W)=1,100, NORMALIZE, RATE(W)=4000

PROP STREAM=CL2F, PHASE=V, PRES(PSIG)=15, TEMP=75, &


COMP(W)=2,100

PROP STREAM=C2F2, PHASE=V, PRES(PSIG)=105, TEMP=75, &


COMP(W)=1,100

PROP STREAM=AIRF, PHASE=V, PRES(PSIG)=105, TEMP=75, &


COMP(M)=34,21/35,79, NORMALIZE

PROP STREAM=WTR1, PHASE=L, PRES(PSIG)=12, TEMP=40, &


COMP=36,100, NORMALIZE, RATE(W)=1000

$ RECYCLE STREAMS (STARTING GUESS):

PROP STREAM=Q1, PHASE=L, PRES(PSIG)=165, TEMP=160, &


COMP(W)=3,56133/4,33/5,30/6,0.2/13,121/15,0.3/ &
18,14.9/21,3800/24,49/26,0.02/27,0.7/ &
30,20/31,0.02/32,298/33,576/ &
NORMALIZE, RATE(W)=62000

PROP STREAM=Q2, PHASE=L, PRES(PSIG)=150, TEMP=90, &


COMP(W)=3,42944/4,31/5,29/6,0.25/13,92/15,0.4/ &

6-20 VCM Synthesis Plant (Rev. 3) February 26, 2014


18,14.7/21,5207/24,49/26,0.03/27,0.97/ &
30,19/31,0.03/32,240/33,829/ &
NORMALIZE, RATE(W)=50000

PROP STREAM=VAPP, PHASE=L, TEMP=200, PRES(PSIG)=200, &


COMP(W)=1,5.4295E-04/ 3,9889.6846/ 4,20.3888/ &
5,6.3502/ 6,0.0281/ 8,0.0280/ 9,5.4295E-04/ &
10,5.4295E-04/ 11,0.3703/ 12,2.9903E-06/ &
13,11.3615/ 14,1.3128E-03/ 15,0.0286/ &
16,0.1162 / 17,0.0272/ 18,3.8722/ 19,0.2392/ &
20,0.0270 / 21,21.2816/22,0.5113/ 23,1.9886/ &
24,8.3884/ 25,1.0862/ 26,0.0110/ 27,0.0261/ &
29,5.4348E-03/ 30,2.5708/ 31,5.5609E-03/ &
32,28.6818/ 33,2.9158/ 34,5.4295E-04/ &
35,5.4295E-04/ 36,1.6774E-03, &
NORMALIZE, RATE(W)=10000

PROP STREAM=TOP3, PHASE=L, TEMP=-31, PRES(PSIG)=135, &


COMP(W)=33,100, NORMALIZE, RATE(W)=9865

PROP STREAM=BTM4, PHASE=LIQUID, TEMP=155, PRES(PSIG)=74, &


COMP(W)=3,19555 / 4,120 / 5,22 / 13,40 / &
18,11 / 21,9 / 24,39 / 30,15 / 32,120, &
NORMALIZE, RATE(W)=19932

$ REFERENCE STREAMS:

PROP STREAM=C2F0, REFSTREAM=C2F1


$----------------------------------------------------------------
$ Reaction Data Section
$----------------------------------------------------------------
RXDATA
RXSET ID=RX2
REACTION ID=CNV1
STOICHIOMETRY 1,-0.5/ 2,-0.5/3,0.021/4,0.015/5,0.018/&
6,0.04 / 8,0.02/ 11,0.012/ 12,0.0115/ 13,0.019/ &
14,0.012/ 15,0.05/ 16,0.021/ 17,0.023/ 18,0.022/ &
19,0.016/ 20,0.014/ 21,0.0348/ 22,0.015/23,0.0183/&
24,0.02/ 25,0.015/ 26,0.037/ 27,0.03/ 33,0.0599
RXSET ID=PYRO
REACTION ID=CNV1
STOICHIOMETRY 3,-1/21,1/33,1
REACTION ID=CNV2
STOICHIOMETRY 1,-1/15,-1/31,1
REACTION ID=CNV3
STOICHIOMETRY 15,0.2251/21,-0.2251/33,0.2251

PRO/II Case Book VCM Synthesis Plant (Rev. 3) 6-21


UNIT OPERATIONS DATA
$ ---------------------------------------------------------------$
$ DIRECT CHLORINATION REACTOR SECTION
$ ---------------------------------------------------------------$

CALC UID=CAL1, NAME=RATIO CALC 1


SEQU STREAM=C2F0,CL2F
PROCEDURE
R(1) = 0.99 * SMR(C2F0)
CALL SRXSTR(SMR,R(1),CL2F)
RETURN

MIXER UID=MIX1, NAME=FEED MIXER 1


FEED C2F1, CL2F
PROD V=FDIR

SPLIT UID=SPL1, NAME=FD SPLT 1


FEED FDIR
PROD V=DIRA, V=DIRB
SPEC STREAM=DIRA, RATE, RATIO, REFFEED, VALUE=0.985

GIBBS UID=RX1, NAME=DIR CL RX 1


FEED DIRA
PROD M=EDCA
OPER ISOTHERMAL, PRES(PSIG)=15, TEMP=120
ELEM REACTANTS(M)=1,2/2,0/3,722/22,1

CONREACTOR UID=RX2, NAME=DIR CL RX 2


FEED DIRB
PRODUCT M=EDCB
OPERATION ISOTHERMAL, TEMPERATURE=120, PRESSURE=15
RXCALCULATION MODEL=STOIC
RXSTOIC RXSET=RX2
REACTION CNV1
BASE COMPONENT=2
CONVERSION 0.995

MIXER UID=MIX2, NAME=RX MIX 1


FEED EDCA,EDCB
PROD M=EDCD

FLASH UID=FLS1, NAME=D-CLO OV FLS


FEED EDCD
PROD L=EDCE, V=VNT1
ISOT TEMP=25, PRES(PSIG)=13

STCALC UID=STC2, NAME=CAUSTIC WASH


FEED EDCE
OVHD L=EDC1
BTMS L=WST1
FOVHD 1,1.0/3,32,1.0/34,36,1.0
FBTMS 2,1.0/33,1.0

6-22 VCM Synthesis Plant (Rev. 3) February 26, 2014


$ ---------------------------------------------------------------$
$ OXY CHLORINATION REACTOR SECTION
$ ---------------------------------------------------------------$

CALC UID=CAL2, NAME=RATIO CALC 2


SEQU STREAM=TOP3,C2F2,AIRF
PROCEDURE
R(1) = 1.03 * 0.5 * SMR(TOP3)
CALL SRXSTR(SMR,R(1),C2F2)
R(2) = 0.30 * (100/21) * SMR(TOP3)
CALL SRXSTR(SMR,R(2),AIRF)
RETURN

MIXER UID=MIX3, NAME=FEED MIXER 2


FEED C2F2,AIRF,TOP3
PROD V=FDOX

SPLIT UID=SPL2, NAME=FD SPLT 3


FEED FDOX
PROD V=FOXA, V=FOXB
SPEC STREAM=FOXA, RATE, RATIO, REFFEED, VALUE=0.96

GIBBS UID=RX3, NAME=OXY CL RX1


FEED FOXA
PROD M=OXYA
OPER ISOTHERMAL, PRES(PSIG)=90, TEMP=290
ELEM REACTANTS(W)=1/3/33/34/36
CONV APPROACH=25 $$, *
$$ PERCENT=1,95/33,96

GIBBS UID=RX4, NAME=OXY CL RX2


FEED FOXB
PROD M=OXYB
OPER ISOTHERMAL, PRES(PSIG)=90, TEMP=290
ELEM REACTANTS(W)=1/3/4/5/6/8/9/10/13/16/ *
18/21/24/25/27/33/34/36
CONV APPROACH=25

MIXER UID=MIX4, NAME=OXY EDC MIX


FEED OXYA, OXYB
PROD M=OXYC

STCALC UID=STC3, NAME=OXY NAOH WSH


FEED OXYC
OVHD V=OXYD
BTMS L=WST2
FOVHD 1,32,1.0/34,36,1.0
FBTMS 33,1.0

FLASH UID=FLS2, NAME=OXY REFRIG


FEED OXYD
PROD L=EDC2, V=VNT2
ISOT TEMP=25, PRES(PSIG)=60

PRO/II Case Book VCM Synthesis Plant (Rev. 3) 6-23


$ ---------------------------------------------------------------$
$ EDC PURIFICATION SECTION
$ ---------------------------------------------------------------$

MIXER UID=MIX5, NAME=RAW EDC MIX


FEED EDC1, EDC2
PROD L=EDC3

FLASH UID=FLS3, NAME=SATURATOR


FEED EDC3, WTR1
PROD L=EDC4, V=VNT3, W=WTR2
ADIA DP=1.0
$ ISOT TEMP=-5, PRES(PSIG)=6.5
$ METHOD SET=1B $$ RIGOROUS NRTL (VLLE) FLASH
METHOD SET=3 $$ DECANT WATER USING SRK

MIXER UID=MIX6, NAME=EDC FD MIX


FEED EDC4, BTM4
PROD L=EDC5

COLUMN UID=COL1, NAME=EDC LT COL


PARA TRAY=12, IO=35 , DAMP=0.7
FEED EDC5,3
PROD OVHD=TOP1,5, BTMS=BTM1
ESTI MODEL=CONV, RRATIO=24.5
PSPE PTOP(PSIG)=185, DPCOL=22
COND TYPE=PART
DUTY 1,1/2,12 $ 17
VARY HEAT=1,2
SPEC RRATIO, VALUE=24.5
SPEC STREAM=BTM1, COMP=3, RATE, RATIO, *
STREAM=EDC5, COMP=3, VALUE=0.999
METH SET=2

MIXER UID=MIX7, NAME=HVY FD MIX


FEED BTM1, VAPP
PROD M=HVYF

COLUMN UID=COL2, NAME=HVY COL


PARA TRAY=30, IO = 35
FEED HVYF,17 / QSP,29 $ SECOND FEED NOT IGNORED
PROD OVHD=TOP2,460, BTMS=BTM2
ESTI MODEL=CONV, RRATIO=0.6
PSPE PTOP(PSIG)=60, DPCOL(PSIA)=15
COND TYPE=BUBB
DUTY 1,1/2,30
VARY HEAT=1,2
SPEC RRATIO, VALUE=0.6
SPEC STREAM=BTM2, COMP=3, RATE, RATIO, *
STREAM=HVYF, COMP=3, VALUE=0.03
METH SET=2
$ PRINT ITER=ALL

6-24 VCM Synthesis Plant (Rev. 3) February 26, 2014


FLASH UID=FLS4, NAME=PYRO FD FLSH
FEED TOP2
PROD V=PYRF, L=VAPP
TPSP PRES(PSIG)=200, TEST=200
SPEC STREAM=VAPP, RATE(W), VALUE=10000

$ ---------------------------------------------------------------$
$ PYROLYSIS SECTION ( EDC ---> VCM + HCL )
$ ---------------------------------------------------------------$
CONREACTOR UID=PYRO, NAME=CRACKER
FEED PYRF
PRODUCT V=EFF1
OPERATION ISOTHERMAL, TEMPERATURE=500, PRESSURE=175
RXCALCULATION MODEL=STOIC
RXSTOIC RXSET=PYRO
REACTION CNV1
BASE COMPONENT=3
CONVERSION 0.55
REACTION CNV2
BASE COMPONENT=1
CONVERSION 1
REACTION CNV3

$ ---------------------------------------------------------------$
$ REACTOR EFFLUENT QUENCH SECTION
$ ---------------------------------------------------------------$

MIXER UID=MIX8, NAME=QUENCH MIXER


FEED EFF1, Q1, Q2
PROD M=EFF2
OPER PRES(PSIG)=170

FLASH UID=FLS5, NAME=QUENCH FLASH


FEED EFF2
PROD V=VF5, L=LF5
TPSPEC PRES(PSIG)=165, TEST=160
SPEC STREAM=LF5, RATE(W), VALUE=64125

SPLIT UID=SPL3, NAME=QUENCH SPLIT


FEED LF5
PROD L=Q1, L=QSP
SPEC STREAM=QSP, RATE(W), VALUE=2000

FLASH UID=FLS6, NAME=POST FLASH 1


FEED VF5
PROD V=VF6, L=Q2
TPSPEC PRES(PSIG)=150, TEST=90
SPEC STREAM=Q2, RATE(W), VALUE=50000

PRO/II Case Book VCM Synthesis Plant (Rev. 3) 6-25


$ ---------------------------------------------------------------$
$ VINYL CHLORIDE MONOMER (VCM) PURIFICATION SECTION
$ ---------------------------------------------------------------$

FLASH UID=FLS7, NAME=POST FLASH 2


FEED VF6
PROD V=VF7, L=LF7
ISOT PRES(PSIG)=140, TEMP=25

COLUMN UID=COL3, NAME=HCL COLUMN


PARA TRAY=32, IO=35 $ Actual number of trays = 73 + 2
FEED VF7,8 /LF7,12
PROD OVHD=TOP3,270, BTMS=BTM3
ESTI MODEL=CONV, RRATIO=1.0
$ TEMP 1,-31/6,-31/9,-25/11,0/13,20/17,20/24,22/ *
$ 27,40/35,78/40,80/42,90
PSPE PTOP(PSIG)=135, DPCOL=10
COND TYPE=PART
DUTY 1,1/2,32 $ 42
SPEC RRATIO, VALUE=1.0
$ SPEC TRAY=34, TEMP, VALUE=73
SPEC TRAY=1, TEMP, VALUE=-31.2 $CHANGE FOR PV1.01
VARY HEAT=1,2
METH SET=2
$ PRINT ITER=ALL

COLUMN UID=COL4, NAME=VC COLUMN


PARA TRAY=16, IO
FEED BTM3,7
PROD OVHD=TOP4,270, BTMS=BTM4
ESTI MODEL=CONV, RRATIO=0.45
PSPE PTOP(PSIG)=65, DPCOL=10
COND TYPE=BUBB
DUTY 1,1/2,16 $20
SPEC RRATIO, VALUE=0.45
$ SPEC TRAY=17, TEMP, VALUE=140
SPEC TRAY=13, TEMP, VALUE=140
VARY HEAT=1,2
METH SET=2
$ PRINT ITER=ALL

RECYCLE DATA
ACCEL TYPE=WEGS

END

6-26 VCM Synthesis Plant (Rev. 3) February 26, 2014


Appendix 6-B: Selected Results
Feeds Summary

PRO/II Case Book VCM Synthesis Plant (Rev. 3) 6-27


Recycle and Product Streams

6-28 VCM Synthesis Plant (Rev. 3) February 26, 2014


HCL Column (COL3) Summary

PRO/II Case Book VCM Synthesis Plant (Rev. 3) 6-29


VCM Column (COL4) Summary

6-30 VCM Synthesis Plant (Rev. 3) February 26, 2014


Invensys Systems, Inc.
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United States of America
http://iom.invensys.com

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