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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
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.
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.
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.
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.
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.
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.
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.
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.
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.
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
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.
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%.
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.
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
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.
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.
Stage 3: Compression
Figure 2-3: Schematic of Compression Section
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 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
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. .
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.
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:
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.
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.
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.
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
The chart below was taken from the PRO/II output file. This depicts
the summary of RX-7,7, the ammonia converter.
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
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
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
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
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.
Reactor Feeds
Table 3-2:Reactor Feed Stream Compositions.contains the
reactor feed composition used in this model.
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
Component Data
All components in the simulation are available in the PRO/II
databanks.
UOM K K K K
UOM K K K K
Figure 3-4 illustrates the data Entry Window to use for entering this
data.
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
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
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.
$
$ ---- 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
RETURN
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.
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.
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
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.
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
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
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
STREAM ID 11 15
NAME C4'S FLARE GAS
PHASE LIQUID VAPOR
THERMO ID SRKM_VLLE SRKM_VLE
STREAM ID 11 15
NAME C4'S FLARE GAS
PHASE LIQUID VAPOR
THERMO ID SRKM_VLLE SRKM_VLE
STREAM ID 11 15
NAME C4'S FLARE GAS
PHASE LIQUID VAPOR
THERMO ID SRKM_VLLE SRKM_VLE
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
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
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
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.
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
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.
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]
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.
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.
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
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.
4-2 Unzelman, G.H., "U.S. Clean Air Act Expands Role for Oxygen-
ates", Oil & Gas Journal, April 15, 1991.
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).
4-7 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).
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
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.
$ MAKE-UP
PROP STREAM=3,TEMP=100,PRES=400,RATE(LV)=45, &
COMP(LV)=4,80 / 5,20
$ 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
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
HX UID=FB2
OPERATION CTEMP=170
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
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
STCALC UID=F1X,NAME=3_PHASE
FEED 24X
OVHD V=24A,L=25A
BTMS STREAM=25AX
FOVHD 1,23,1.0/24,0.0
STCALC UID=F1Z,NAME=3_PHASE
FEED 24Z
OVHD V=24C,L=25C
BTMS STREAM=25CX
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
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
$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$
$ REFRIGERATION CIRCUIT
$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$
$ PRODUCT PURIFICATION CIRCUIT
PUMP UID=P2,NAME=EFFL_PUMP
FEED 25
PROD L=251
OPERATION PRES=120
$
$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$
$ After first run, substitute first insert in Appendix 4-B for Column DIC4
COLUMN UID=DIC4, NAME=ISO-STRIPPER
PARA SURE=20, TRAYS=42
FEED 253X, 1
PROD OVHD=30, BTMS=31, 1300
DUTY 1, 42
$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$
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
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
PUMP UID=P3
FEED 11
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
$ -----------------------------------------------------
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
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
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
A-7 Gary, J.H. and Handwerk, G.E. (1984). Petroleum Refining Technol-
ogy and Economics (2nd Edition ed.). Marcel Dekker, Inc. ISBN
0824771508.
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
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
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.
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
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.
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.
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:
j=1
where:
xj
x j = ------------------- ji (5-5)
N
x
j
j = 1
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
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.
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.
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
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)
Term Units
G velocity
Kg, constant velocity
SSRATIO, supersaturation dimensionless
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
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.
Feeds 21
Products Liquid 22
Mixed 23
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
Cake Properties
Feeds 26
Products Liquid 27
Mixed 28
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
Cake Properties
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
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
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
SLURRY PROPERTIES
KINETICS DATA
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
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
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
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
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
STREAM ID 1 2 3 4
NAME NH3FD CO2FD
PHASE LIQUID VAPOR LIQUID LIQUID
THERMO ID NRTL01 NRTL01 NRTL01 NRTL01
STREAM ID 5 6 7 8
NAME
PHASE LIQUID MIXED LIQUID LIQUID
THERMO ID NRTL01 NRTL01 NRTL01 NRTL01
STREAM ID 9 10 11 12
NAME DECGS1 DECGS2
PHASE VAPOR LIQUID MIXED VAPOR
THERMO ID NRTL01 NRTL01 NRTL01 NRTL01
STREAM ID 13 14 15 16
NAME FLGS1 FLGS2
PHASE LIQUID VAPOR LIQUID VAPOR
THERMO ID NRTL01 NRTL01 NRTL01 NRTL01
STREAM ID 17 18 19 20
NAME CRYGS1
PHASE LIQUID LIQUID VAPOR MIXED
THERMO ID NRTL01 NRTL01 NRTL01 NRTL01
STREAM ID 21 22 23 24
NAME CRYGS2
PHASE MIXED LIQUID MIXED VAPOR
THERMO ID NRTL01 NRTL01 NRTL01 NRTL01
STREAM ID 25 26 27 28
NAME
PHASE MIXED MIXED LIQUID MIXED
THERMO ID NRTL01 NRTL01 NRTL01 NRTL01
STREAM ID 29 30 31
NAME DRYGS UREAPROD
PHASE VAPOR MIXED MIXED
THERMO ID NRTL01 NRTL01 NRTL01
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
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.
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.
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
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.
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)
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).
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
Simulation
The process flow diagram for this section of the plant is shown in
Figure 6-1.
EDC Purification
Figure 6-2 and 5 show a process flow diagram for the EDC
purification section of the plant.
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
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.
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.
Technical Results
The main feeds to a plant producing 154 MTPD of 99.9+% pure
VCM product are summarized below.
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.
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.
PC 21, 807.668 /*
33, 1190.567
STREAM DATA
$ REFERENCE STREAMS:
$ ---------------------------------------------------------------$
$ 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
$ ---------------------------------------------------------------$
RECYCLE DATA
ACCEL TYPE=WEGS
END