PRO/II CASEBOOK

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-ESSCORs 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
MTBE Plant Rev. 2
PRO/II is a registered mark of Invensys plc.
Copyright 2006, all rights reserved
Amberlyst is a trademark of Rohm & Haas

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SIMSCI-ESSCOR OFFICE LOCATIONS:

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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.

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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 below in Table 1.
For exact catalyst properties, please contact the manufacturer.
Table 1. Approximate Catalyst Properties of Amberlyst 15
Physical form
Ionic form
Acid site concentration
Moisture content
Apparent density
Particle size
Shrinkage: Wet to methanol
Wet to MTBE
Porosity
1

Spherical beads
Hydrogen
1.8 meg/ml (4.9 meg/g)
53%
770 g/l
0.35-1.2 mm
4%
12%
0.30 cc/g

Chemical Engineering Progress, p. 15, Aug. 1991

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Average pore diameter

Surface area
Bulk density
Maximum operating temperature
Minimum bed depth
Flowrate, LHSV

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250 A
45 m2/g
48 lb/ft3
120 C
0.61 m
1-5 hr-1

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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 given in
Figure 1.
FIGURE 1. MTBE Plant Flowsheet

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Process Description
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 resintype 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.
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. Table 2
contains the reactor feed composition used in this model.
Table 2. Reactor Feed
Stream Name
Stream Number
Flowrate (kg-mol/hr)
Temperature (C )
Pressure (kPa)
Component
N-butane
Isobutane
1-butene
Cis 2-butene
Trans 2-butene
Isobutylene (IBTE)
MTBE
Tert-butanol (TBA)
Water
Di-isobutylene (DIB)
Methanol (MEOH)

C4 Feed
2
850
16
1620
9.0
41.0
7.0
4.0
6.0
33.0
0.0
0.0
0.19
0.0
0.0

Methanol Feed
1
277.5
16
1620
Mole %
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
100

Methanol Recycle
20
4.3
44
1724
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
6.98
0.0
93.02

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

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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.
Table 3 shows the three main reactions used in the stoichiometric reactor model. The
base component and the fraction converted are also shown.
Table 3. Approximate Catalyst Properties of Amberlyst 15
Reaction
2 (IBTE) = DIB
H2O + IBTE = TBA
IBTE + MEOH = MTBE

Base Component
IBTE
H20
MEOH

Conversion %
0.25
100.00
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 nonreactive 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

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raffinate, which contains less than 10 ppm methanol, is suitable for recovering high
purity C4 isomers, or as a feed to an alkylation unit.
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.

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Process Simulation
General Data
SI units are used in this simulation. The total calculation sequence is specified. 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.

In order to check the overall material balance, PRO/II is instructed to print out an overall
flowsheet mass balance in the Miscellaneous Report Options menu.

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Component Data
All the components in the simulation are available in the PRO/II databank.
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 below in Table 4.
The thermodynamic set used for VLE thermodynamics is referred to as SRKM_VLE.

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Table 4. Binary Interaction Parameters for SRKM_VLE

Comp i
Comp j
kija
kjia
kijb
kjib
UOM

NC4
TBA
0.0469973
0.12603
0.0
0.0
K

1BUTENE
MEOH
0.136
-0.0323
0.0
0.0
K

BTC2
MEOH
0.136
-0.0323
0.0
0.0
K

BTT2
MEOH
0.136
-0.0323
0.0
0.0
K

IBTE
MEOH
0.13553
-0.032271
0.0
0.0
K

MEOH
TBA
-0.073971
-0.055222
0.0
0.0
K

TBA
H20
-0.145
-0.253
0.0
0.0
K

MTBE
DIB
0.05785
-0.0093
-10.144
6.17
K

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. Explicitly

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specifying the key components eliminates the need for PRO/II to find an appropriate
immiscible pair, reducing the computation time. All the azeotropes are properly
predicted.

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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 2.
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 2).

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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.

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Unit Operations
MTBE Reaction
The MTBE reaction section of the plant is shown in Figure 2 below.
FIGURE 2.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.

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Since this is a conversion reactor. The three reactions defined in Table 3 take place in this
reactor at the specified conversion levels. The extent of reaction are defined based on the
values in Table 3.

The stoichiometries of the major and minor reactions in the MTBE process are provided
in the reaction definitions data entry window.

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MTBE Distillation and Recovery

The MTBE distillation and recovery section of the plant is shown in Figure 3 below.
FIGURE 3. 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. However,
since the temperature of stream 5 is known, this process is modeled by two separate heat
exchangers, HX-2A and HX-2B as shown in Figure 3. Stream 4 from the reactors is
heated to 72 C in HX-2A to produce stream 5. The product of column T-1, stream 7, is
cooled in exchanger HX2-B to produce the MTBE product stream 8. The duty of
exchanger HX-2B is defined to be equal to the duty in HX-2A. This approach avoids an
unnecessary calculation loop since the temperature of stream 5 is fixed at 72 C.

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The heated stream 5 is fed to tray 15 of the 30 tray MTBE column (T-1). The MTBE
column is simulated with the CHEMDIST algorithm using 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.

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The next step is to provide all the information required for specifying the reaction trays in
the distillation column.
Implementing Reactive Distillation
You can visualize the reaction zone of a distillation column 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.

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Note that the liquid volume of each of the reaction trays is also specified using the
Reaction Volumes button in the Options section of the data entry window, and that the
concentration of the dry catalyst (GCAT, in g/l) is specified using a DEFINE statement
specified using the Subroutine/Procedure Data button in the Options section of the data
entry window.

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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
1). 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.
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-Jarallah2. 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). The kinetic data will be provided later on in the
2

Al-Jarallah, A.M., M.A.B. Siddiqui, and A.K.K. Lee, 1988, Kinetics of Methyl Tertiary Butyl Ether
Synthesis Catalyzed by Ion Exchange Resin, Can. J. Chem. Eng., 66, 802-807.

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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
removing the catalyst terms from the concentration terms. The modified reaction rate is
given by:

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

(1a)
(1b)
(1c)

Kinetic Data

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The procedure data used in the reactive distillation column model is entered in the
Kinetic Procedure data entry window shown below.

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/gmmole 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 CENTIGRADE

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$
$
$

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))

Next, the derivatives of these constants are computed and are used later on in calculating
the rate derivatives.
$
DKSDT =
DKADT =
DKCDT =

KS
KA
KC

*
87900.0 / R / (TK*TK)
* (-1.0) * 97500.0 / R / (TK*TK)
* (-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)

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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
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.

PRO/II CASEBOOK

MTBE PLANT

Page 28

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)

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 is converged, the top and bottom product compositions are known.
Exchanger (HX-2B) is now 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.

PRO/II CASEBOOK

MTBE PLANT

Page 29

PRO/II CASEBOOK

MTBE PLANT

Page 30

Methanol Recovery
The methanol recovery section of the process is shown in Figure 4.
FIGURE 4. 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).
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).

PRO/II CASEBOOK

MTBE PLANT

Page 31

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. The column top pressure is 138 KPa; the pressure drop through the
column is 34.5 KPa. A Subcooled, Fixed Temperature condenser type operating at 30 C
and 103.5 KPa is specified. 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.

PRO/II CASEBOOK

MTBE PLANT

Page 32

PRO/II CASEBOOK

MTBE PLANT

Page 33

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.

PRO/II CASEBOOK

MTBE PLANT

Page 34

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.
Then, 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. 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. The ZONES option is selected to determine where phase
changes occur in the exchanger. An extended data sheet is printed in the output.

PRO/II CASEBOOK

MTBE PLANT

Page 35

PRO/II CASEBOOK

MTBE PLANT

Page 36

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 5.

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.

PRO/II CASEBOOK

MTBE PLANT

Page 37

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 CASEBOOK

MTBE PLANT

Page 38

This page left blank intentionally

PRO/II CASEBOOK

MTBE PLANT

Page 39

Appendix A: COMPLETE MTBE PLANT FLOWSHEET

Graphical Representation

PRO/II CASEBOOK

MTBE PLANT

Page 40

PRO/II Flowsheet

11

2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29

CW

RC-1
WOUT

6
1
P-1

6P
3

10
4

1
15

T-1

T-2

30

6
13

12

HX-2A

HX-1

P-3

4
HX-3

19

2
5

14

V-1
RX-1

HX4A

D-1

10
8

11
16

HX-5

HX-2B

12
17

13
14
15

CONVERSION

CAL0

16

CAL1

17

22

18

P-2

HX4B

19

T-3

21

MKUP
18

P-4
20

PRO/II CASEBOOK

MTBE PLANT

Page 41

20

Appendix B: PRO/II SELECTED OUTPUT

The following pages show selected parts of the stream and unit operation information
exported to Excel.
Component Rates
1
Name
Description
MEOH FEED
Phase
Liquid
Temperature
C
16.000
Pressure
KPA
1620.000
Molecular Weight
32.042
Component Molar Rates KG-MOL/HR
NC4
IC4
1BUTENE
BTC2
BTT2
IBTE
MTBE
MEOH
277.500
TBA
H2O
DIB
Total
KG-MOL/HR
277.500
Component Mole Fractions
NC4
IC4
1BUTENE
BTC2
BTT2
IBTE
MTBE
MEOH
1.0000
TBA
H2O
DIB

Stream

PRO/II CASEBOOK

2
MKUP
OLEFINS MKUP WATER
Liquid
Liquid
16.000
38.000
1620.000
350.000
57.115
18.015
76.500
348.500
59.500
34.000
51.000
280.500

0.599

0.0900
0.4100
0.0700
0.0400
0.0600
0.3300

MTBE PLANT

11
15
C4'S FLARE GAS
Liquid
Vapor
38.165
99.098
792.000
241.000
57.578
40.888

0.000
0.000
0.000
0.000
0.000
0.000
277.358
0.102
0.188
0.599

850.000

8
MTBE
Liquid
88.584
663.000
88.150

76.496
348.487
59.500
33.999
51.000
2.248
0.004
0.004
0.000
0.399
0.351
0.000
278.000 572.138

0.004
0.012
0.000
0.000
0.000
0.000
0.000
0.001
0.000
0.012
0.000
0.029

0.0000
0.0000
0.0000
0.0000
0.0000
0.0000
0.9977
0.0004
0.0007

0.1229
0.4223
0.0046
0.0051
0.0048
0.0001
0.0000
0.0321
0.0000
0.4081
0.0000

1.0000
0.0013

0.1337
0.6091
0.1040
0.0594
0.0891
0.0039
0.0000
0.0000
0.0000
0.0007
0.0000

Page 42

Stream

Name
1
Description
MEOH FEED
Phase
Liquid
Total Stream Properties
Rate
KG-MOL/HR
277.500
KG/HR
8891.699
Std. Liquid Rate
M3/HR
11.135
Temperature
C
16.000
Pressure
KPA
1620.000
Molecular Weight
32.042
Enthalpy
M*KJ/HR
0.209
KJ/KG
23.452
Mole Fraction Liquid
1.0000
Reduced Temp.
0.5640
Pres.
0.2001
Acentric Factor
0.5640
Watson K (UOPK)
10.599
Standard Liquid Density KG/M3
798.553
Specific Gravity
0.7993
45.521
API Gravity
Vapor Phase Properties
Rate
KG-MOL/HR
n/a
KG/HR
n/a
M3/HR
n/a
Std. Vapor Rate
M3/HR
n/a
Specific Gravity (Air=1.0)
n/a
Molecular Weight
Enthalpy
KJ/KG
n/a
CP
KJ/KG-C
n/a
Density
KG/M3
0.000
Thermal Conductivity
W/M-K
0.00000
PAS
0.00000
Viscosity
Liquid Phase Properties
Rate
KG-MOL/HR
277.500
KG/HR
8891.699
M3/HR
11.130
Std. Liquid Rate
M3/HR
11.135
Specific Gravity (H2O @ 60 F)
0.7993
Molecular Weight
32.042
Enthalpy
KJ/KG
23.452
CP
KJ/KG-C
2.454
Density
KG/M3
798.914
Surface Tension
N/M
0.0229
Thermal Conductivity
W/M-K
0.20245
PAS
0.00061
Viscosity

PRO/II CASEBOOK

2
MKUP
OLEFINS MKUP WATER
Liquid
Liquid

8
MTBE
Liquid

11
C4'S
Liquid

850.000
48548.141
83.051
16.000
1620.000
57.115
1.911
39.368
1.0000
0.6950
0.4201
0.1908
13.363
584.560
0.5851
110.324

0.599
10.786
0.011
38.000
350.000
18.015
0.002
168.876
1.0000
0.4808
0.0159
0.3449
8.758
999.014
1.0000
10.000

n/a
n/a
n/a
n/a
n/a

n/a
n/a
n/a
n/a
n/a

n/a
n/a
n/a
n/a
n/a

n/a
n/a
n/a
n/a
n/a

n/a
n/a
0.000
0.00000
0.00000

n/a
n/a
0.000
0.00000
0.00000

n/a
n/a
0.000
0.00000
0.00000

n/a
n/a
0.000
0.00000
0.00000

850.000
48548.141
82.777
83.051
0.5851
57.115
39.368
2.312
586.496
0.0122
0.10537
0.00018

0.599
10.786
0.011
0.011
1.0000
18.015
168.876
4.367
979.748
0.0702
0.62348
0.00070

MTBE PLANT

278.000
572.138
24505.658 32942.770
32.887
57.039
88.584
38.165
663.000
792.000
88.150
57.578
4.642
3.035
189.407
92.141
1.0000
1.0000
0.7276
0.7496
0.1932
0.2085
0.2664
0.1893
11.252
13.520
745.142
577.549
0.7459
0.5781
58.210
113.259

278.000
572.138
24505.658 32942.770
36.952
60.008
32.887
57.039
0.7459
0.5781
88.150
57.578
189.407
92.141
2.315
2.503
663.179
548.974
0.0120
0.0095
0.11786
0.09735
0.00019
0.00015

15
FLARE GAS
Vapor
0.029
1.204
0.002
99.098
241.000
40.888
0.001
950.005
0.0000
0.7279
0.0213
0.2628
12.728
621.959
0.6226
95.783
0.029
1.204
0.369
0.660
1.412
40.888
950.005
2.013
3.259
0.02464
0.00001
n/a
n/a
n/a
n/a
n/a
n/a
n/a
0.000
0.0000
0.00000
0.00000

Page 43

Column T-1 Summary

Tray
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30

Temp. Pressure
C
KPA
43.5
621.00
50.6
621.00
51.3
623.73
51.7
626.46
52.1
629.20
52.4
631.93
52.8
634.66
53.5
637.39
54.5
640.13
56.2
642.86
59.1
645.59
63.5
648.32
68.6
651.05
73.4
653.79
76.9
656.52
91.0
659.25
105.4
661.98
115.4
664.71
121.0
667.45
123.9
670.18
125.5
672.91
126.5
675.64
127.1
678.38
127.5
681.11
127.9
683.84
128.2
686.57
128.4
689.30
128.6
692.04
128.8
694.77
129.1
697.50

PRO/II CASEBOOK

Liquid
633.5
661.6
659.7
658.4
657.3
655.6
651.7
636.1
614.6
583.0
540.3
494.8
463.1
445.5
1207.0
1180.4
1202.0
1237.2
1264.4
1281.7
1292.3
1299.1
1303.7
1307.0
1309.6
1311.8
1313.6
1315.3
1316.7

Net Flow Rates

Vapor
Feed
KG-MOL/HR
1209.5
1237.5
1235.6
1234.4
1233.3
1231.5
1227.6
1214.6
1195.6
1166.8
1127.3
1085.1
1054.4
1036.8
929.0
902.4
924.0
959.2
986.4
1003.7
1014.3
1021.1
1025.7
1029.0
1031.6
1033.8
1035.6
1037.3
1038.7

MTBE PLANT

Product
575.9

Duties
M*KJ/HR
-23.6636

278.0

23.7858

869.4

Page 44

Column T-2 Summary

Tray
1
2
3
4
5

Temp. Pressure
C
KPA
38.2
792.00
38.2
792.00
38.2
792.00
38.2
792.00
38.2
792.00

Liquid
947.2
947.2
947.3
948.1

Net Flow Rates

Vapor
Feed
KG-MOL/HR
375.0
0.0
0.0
0.0
0.0
575.9

Product

Duties
M*KJ/HR

572.1

378.8

Column T-3 Summary

Tray
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20

Temp. Pressure
C
KPA
30.0
103.50
74.1
138.00
76.5
139.92
81.8
141.83
92.9
143.75
104.7
145.67
108.8
147.58
109.9
149.50
110.4
151.42
110.8
153.33
111.6
155.25
112.2
157.17
112.8
159.08
113.3
161.00
113.8
162.92
114.2
164.83
114.6
166.75
114.9
168.67
115.3
170.58
115.7
172.50

PRO/II CASEBOOK

Liquid
96.9
105.9
103.7
99.4
95.8
95.9
96.2
96.3
96.4
483.1
483.6
484.0
484.4
484.8
485.1
485.4
485.8
486.1
486.3

Net Flow Rates

Vapor
Feed
KG-MOL/HR
101.3
110.3
108.0
103.7
100.1
100.2
100.6
100.7
100.7
108.7
109.2
109.6
110.0
110.4
110.7
111.0
111.3
111.6
111.9

MTBE PLANT

Product
4.4

Duties
M*KJ/HR
-4.0726

374.4

4.5072

378.8

Page 45

SHELL AND TUBE EXCHANGER DATA SHEET

Exchanger Name
T-3 COND
Unit ID
Size
381 - 5750
Type
AES, Horizontal
Connected
Area/Unit
36.981 M2
28.258 Reqd Area/Shell
Performance of One Unit
Shell-Side
Feed Stream ID
Connected to T-3 Condenser
Feed Stream Name
Total Fluid
KG/HR
3187.93
In
Out
Vapor
KG/HR
3187.93
Liquid
KG/HR
3187.93
Steam
KG/HR
Water
KG/HR
Non-Condensible
KG/HR
Temperature
C
74.1
30.0
Pressure
KPA
138.00
88.76
Sp. Gr.
Density
Viscosity
Thermal Cond.
Spec. Heat

Liquid
Vapor
Liquid
Vapor
Liquid
Vapor
Liquid
Vapor
Liquid
Vapor

Latent Heat
Velocity
DP/Shell
Fouling Resistance
Transfer Rate
Heat Exchanged
MTD (Corrected)
FT
Construction of One Shell
Design Pressure
Number of Passes
Material
Inlet Nozzle ID
Outlet Nozzle ID
Tube:
Number
OD
Thick
Length
Shell:
ID
Baffle:
Cut
RHO-V2:
Inlet Nozzle
Total Weight/Shell
Full of Water
Bundle

PRO/II CASEBOOK

0.000
1.087
0.000
1.538
0.000
0.000
0.0000
0.0202

0.000

RC-1
1 Parallel, 1 Series
36.981 M2
Tube-Side
CW

In

174827.44
Out

174827.44

174827.44

21.0
690.00

26.3
428.42

0.000

0.000

KG/M3
787.365
994.440
989.867
KG/M3
0.000
0.000
0.000
PAS
0.001
0.001
0.001
PAS
0.000
0.000
0.000
W/M-K
0.2000
0.6006
0.6081
W/M-K
0.0000
0.0000
0.0000
KJ/KG-C
2.6389
4.4975
4.4538
KJ/KG-C
1.5195
KJ/KG
1164.3084717
0.00
M/SEC
0.16
5.23
KPA
49.24
262.06
M2-K/KW
0.35222 0.6597 Reqd 0.00035 0.3079 Reqd
KW/M2-K Service 1.00
Reqd.
0.77
Clean 1.55
M*KJ/HR
4.073
C
39.9
0.911
Shell-Side
Tube-Side
KPA
2068.43
2068.43
1
2
CARB STL
CARB STL
MM
152.0
102.0
MM
102.0
102.0
109
Type
Bare
19.000 MM
Pitch
25.4 MM
2.1082 MM
Pattern
90 Degrees
5.8 M
381.00 MM
Sealing Strips
0 Pairs
0.180
Spacing, MM (In/Cent/Out) 98.80 / 76.20 / 98.80
Single
1548.5 KG/M-SEC2
2053.5 KG
3701.5 KG
1062.8 KG

MTBE PLANT

Page 46

SHELL AND TUBE EXCHANGER DATA SHEET

Exchanger Name
T-3 COND
Unit ID
RC-1
Size
381 - 5750
Type
AES, Horizontal
Connected
1 Parallel, 1 Series
Area/Unit
36.981 M2
Area/Shell
36.981 M2
Performance of One Unit
Shell-Side
Tube-Side
Feed Stream ID
Connected to T-3 Condenser
CW
Feed Stream Name
In
Out
In
Out
Weight Fraction Liquid
1.00
1.00
1.00
Reynolds Number
46385.39
80107.67
Prandtl Number
2.656
7.127
Watson K
Liquid
10.561
8.758
8.758
Vapor
10.561
Surface Tension
N/M
0.000
0.024
0.074
0.073
Film Coefficient (Scaling)
KJ/HR-M2-C
1.9
1.000
15.6
1.000
Fouling Layer Thickness
MM
0.0000
0.0000
Percent
Absolute
Thermal Resistance
M2-K/KW
Shell Film
51.72
0.51520
Tube Film
8.27
0.08235
Tube Metal
4.61
0.04593
Total Fouling
35.40
0.35267
Adjustment
30.87
0.30750
Percent
Absolute
Percent
Absolute
Pressure Drop
KPA
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
Tubesheet Thk
66.0 MM
Area Ratio
1.285
Thermal Cond.
51.9 W/M-K
Density
7862 KG/M3
Baffle:
Thickness
4.7625 MM
Number
73
Bundle:
Diameter
327.0 MM
Tubes in crossflow
92
Crossflow Area
0.010 M2
Window area
0.012 M2
Window Hyd Diameter
40.63 MM
Tube Baffle Leak Area
0.002 M2
Shell Baffle Leak Area
0.001 M2

PRO/II CASEBOOK

MTBE PLANT

Page 47

Appendix 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
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

PRO/II CASEBOOK

MTBE PLANT

Page 48

$
$
$
$
$
$
$
$
$
$

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 Centigrade
or Kelvin.
Set temperature and composition derivatives to zero.
IBTE
MTBE
MEOH

= 6
= 7
= 8

= 8.314

TK

= RTABS

$
$
$

1000
$
$
$
$
$
$
$
$

DO 1000 I1 = 1,NOR
DRDT(I1)
= 0.0
DO 1000 I2 = 1,NOC
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
KA
KC

= 1.2E+13*EXP(-87900.0/(R*TK))
= 5.1E-13*EXP( 97500.0/(R*TK))
= 1.6E-16*EXP(119000.0/(R*TK))

$
DKSDT =
DKADT =
DKCDT =
$
$ ---$
$
$
$
$
$
$
$ -$
$
$
$
$

KS
KA
KC

*
87900.0 / R / (TK*TK)
* (-1.0) * 97500.0 / R / (TK*TK)
* (-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,
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
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

PRO/II CASEBOOK

MTBE PLANT

Page 49

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
DRDDT
DRDDME
DRDDIB
DRDDMT

$
$

= 1.0 + ( KA*RHOA
) +
=
RHOA*DKADT
+
=
KA/GCATX*DENS
=
=

0.0
0.0

+ ( KC*RHOC
)
+
RHOC*DKCDT

0.0
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

$
$
$
$

--

Rate equation (rate per one gram of catalysis).

RATE
=
FACT1
*
FACT2

$
$

--

Rate temperature derivative.

DRDT(1) = DFAC1DT
*
+
FACT1
*

Combine terms to calculate rate and derivatives.

--

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

Rate composition derivatives.

DRDX(MEOH,1) = -KS*KA/RDEN**2
+
FACT1
DRDX(IBTE,1) = -KS*KA/RDEN**2
+
FACT1
DRDX(MTBE,1) = -KS*KA/RDEN**2
FACT1

FACT2
DFAC2DT

&

* DRDDME *
FACT2
&
* (RHOB**0.5/GCATX*DENS)
* DRDDIB *
FACT2
&
* (RHOA/2.0/RHOB**0.5/GCATX*DENS)
* DRDDMT *
FACT2
&
* (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
HX
UID=HX-2A, NAME=FEED-BTMS-A
COLD FEED=4, L=5, DP=34.5

PRO/II CASEBOOK

MTBE PLANT

Page 50

OPER CTEMP=72
CALCULATOR UID=CAL0, NAME=COPY RXFACT
PROCEDURE
IF (R(2) .NE. 1.0) R(1) = 1.0 $Set RXFACT TO 1 on first call.
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)
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

PRO/II CASEBOOK

MTBE PLANT

Page 51

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
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, DIAMETER(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

PRO/II CASEBOOK

MTBE PLANT

Page 52