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Case 3:
Methyl Tertiary Butyl Ether
(MTBE) Plant
Abstract
This casebook demonstrates the use of PRO/II in the simulation of
the synthesis of methyl tert-butyl ether (MTBE). MTBE is used as
an octane enhancer for reformulated gasolines, and is becoming
increasingly important as stricter air pollution control measures are
implemented. A PRO/II simulation model of a typical MTBE plant
is presented here. The process plant includes a reactor along with an
azeotropic distillation column for separation of the MTBE product.
A reactive distillation section is added to the MTBE azeotropic
column in order to increase the overall conversion to MTBE. This is
followed by the methanol recovery section which includes a liquid-
liquid extractor. SIMSCI's SRKM thermodynamic method provides
a good simulation of the VLE fractionators and the VLLE extractor.
The thermodynamics successfully predicts the azeotropic removal
of methanol from the MTBE product stream.
Casebook Highlights
Petrochemicals Application
Stoichiometric Reactor Units
Multi-tray Reactive Distillation Column
Complex Reaction Kinetic Models
Liquid-liquid Extraction Column Using VLLE
Thermodynamics
Column Condenser Modeled as an Attached, Rigorous Heat
Exchanger
Column Tray Rating
Recycle Acceleration Techniques
PRO/II Case Book MTBE Synthesis Plant (Rev. 3) 3-1

Introduction
Methyl tertiary butyl ether (MTBE) is an octane enhancing agent
for unleaded motor gasoline. MTBE is produced from the butylenes
in the product streams of liquid feed ethylene crackers and fluid
catalytic crackers. In some plants, raffinates from butadiene
extraction or catalytic butane dehydrogenation are used to produce
MTBE. MTBE synthesis also offers a method of selectively
removing isobutylene from mixed C4 streams. This enables the
recovery of high purity 1-butene and 2-butene which are superior
sulfuric acid alkylation feedstocks.
MTBE has several desirable properties that makes it a suitable
gasoline additive. The first desirable property is that MTBE has a
low boiling point and an RVP of 8-10 psi. This causes the gasoline
enhanced with MTBE to have a lower vapor pressure. The lower
vapor pressure results in reduced emissions. The second desirable
property is that MTBE has an octane number of approximately 109.
When MTBE is mixed with gasoline, it increases combustion,
without reducing engine power. The third desirable property is that
MTBE increases the front-end octane number which reduces engine
knocking during acceleration. The addition of MTBE to gasolines
also generally implies a reduced aromatic and butane content which
leads to reduced carbon monoxide and hydrocarbon emissions.
The current and future demand for MTBE and other oxygenates for
reformulated gasoline stems from environmental legislation and
restrictions on air pollutant levels. Most US refiners have elected to
use MTBE (and other esters) rather than ethanol (and other
alcohols) as their main oxygenate for reformulated gasoline. Recent
environmental legislation has resulted in an increased demand for
MTBE and other octane-enhancing agents. In Europe, lead-based
gasolines are being phased out, resulting in increasing use of MTBE
and other octane-enhancing agents. MTBE is being phased out in
some areas of the world due to a negative environmental impact.
Ethanol, another octane-enhancing agent, is becoming more
common and is replacing MTBE as the octane-enhancing agent of
choice.
3-2 MTBE Synthesis Plant (Rev. 3) March 5, 2014

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

The key feature of this process is the fixed bed MTBE reactor used
prior to the azeotropic distillation column. Conversions of
isobutylene to MTBE are in the range 85-95%. It is common that
two reactors are used in tandem, along with a recycle, in order to
increase the overall conversion closer to 99%.
Ethermax Process1
The Ethermax process, developed jointly by UOP Corporation,
Koch Engineering, and Hls AG utilizes a single fixed-bed reactor
followed by a reactive distillation column. In this process, tower
packing that holds the resin catalyst is placed in a section of the
MTBE azeotropic distillation tower. The MTBE reaction is
completed in the column and the product is separated at the same
time. The overall conversion of isobutylene to MTBE can be
improved to 99% or greater with this process, with almost no
increase in capital expenditure. The Ethermax process is the process
that is modeled in this casebook.
Catalyst
A common catalyst for the MTBE synthesis process is the
Amberlyst 15 polymeric catalyst developed by Rohm and Haas.
Approximate properties of the commercial form of this catalyst,
along with suggested operating conditions are provided in Table 3-
1:Approximate Catalyst Properties of Amberlyst 15. For exact
catalyst properties, please contact the manufacturer.
Table 3-1: Approximate Catalyst Properties of Amberlyst 15
Physical form Spherical beads
Ionic form Hydrogen
Acid site concentration 1.8 meg/ml (4.9 meg/g)
Moisture content 53%
Apparent density 770 g/l
Particle size 0.35-1.2 mm

Shrinkage: Wet to methanol 4%
Wet to MTBE 12%
Porosity 0.30 cc/g
Average pore diameter 250 A
Surface area 45 m2/g
Bulk density 48 lb/ft3
Maximum operating 120 C
temperature
Minimum bed depth 0.61 m
Flowrate, LHSV 1-5 hr-1
Chemical Enginneering Progress, p.15, Aug.1991
Process Overview
There are numerous variations on MTBE plant designs. In general,
an MTBE plant is comprised of the three sections, a reactor section,
a MTBE recovery section, and a methanol recovery section. For the
Ethermax process, the MTBE recovery section includes a second
reaction zone in the distillation column. The complete process flow
diagram for the MTBE reactive distillation plant model used in this
simulation is shown in Figure 3-1.
Reactor Section
MTBE is manufactured by catalytically reacting isobutylene and
methanol in a fixed-bed reactor at a moderate temperature and
pressure. The reaction is exothermic and reversible, and is carried
out in the liquid phase over a fixed bed of ion-exchange resin-type
catalyst. It is highly selective since methanol reacts preferentially
with the tertiary olefin.
In the Ethermax MTBE process, modeled here, an isobutylene-rich
mixed C4 stream is mixed with fresh methanol along with a small
amount of recycle methanol and fed to the reactor section. The
reactors are cooled to under 200 F to prolong catalyst life and to
minimize the undesirable side reactions such as dimerization of
isobutylene.

Figure 3-1: Overall MTBE Flowsheet
Reactor Feeds
Table 3-2:Reactor Feed Stream Compositions.contains the
reactor feed composition used in this model.

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

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

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

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

The extract phase which contains water, methanol and small
amounts of dissolved hydrocarbons is warmed and flashed to
remove the hydrocarbons. The resultant methanol-water mixture is
fractionated to recover methanol as the overhead product. The
methanol (with a trace of water) is recycled to the MTBE reactor.
The wash water stream from the bottoms, along with a small
amount of makeup water, is returned to the water wash column.
Process Simulation
General Data
SI units are used in this simulation. The total calculation sequence
is specified, as shown in Figure 3-2. The calculator CAL0 is
processed before the MTBE column in order to set the reaction
factor equal to 1.0 on the first pass through the flowsheet.
Figure 3-2: Specifying Calculation Sequence

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

Thermodynamic Data
The VLE fractionators are simulated well with PRO/II's modified
Soave-Redlich-Kwong (SRKM) equation of state method. For this
method, PRO/II contains extensive, built-in databanks that
encompass binary interaction parameter data for the majority of
component pairs present in this simulation. In this casebook,
however, binary interaction data (kijs) are directly supplied for 8
component pairs to improve the accuracy of the separations in the
columns. The binary interaction parameters are listed in Table 3-
4:Binary Component Interaction Data .. The thermodynamic set
used for VLE thermodynamics is referred to as SRKM_VLE
Table 3-4: Binary Component Interaction Data .
Comp i NC4 1BUTENE BTC2 BTT2
Comp j TBA MEOH MEOH MEOH
kija 0.046993 0.136 0.136 0.136
kjia 0.12603 -0.0323 -0.0323 -0.0323
kijb 0.0 0.0 0.0 0.0
kjib 0.0 0.0 0.0 0.0
UOM K K K K
Binary Component Interaction Data (continued) .

Comp i IBTE MEOH TBA MTBE
Comp j MEOH TBA H20 DIB
kija 0.13553 -0.073971 -0.145 0.05785
kjia -0.032271 -0.055222 -0.253 -0.0093
kijb 0.0 0.0 0.0 -10.144
kjib 0.0 0.0 0.0 6.17
UOM K K K K
Figure 3-4 illustrates the data Entry Window to use for entering this
data.

Figure 3-4: PRO/II Binary Interaction Data Entry Window
Transport properties are needed in order to use the rigorous heat

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

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

Stream Data
Feed Stream
The mixed C4 feed stream, and the methanol feed stream are
specified in the normal manner, using the compositions and stream
conditions given in Table 3-2:Reactor Feed Stream
Compositions..
Recycle Stream
The composition of the recycle methanol-water stream from the
MEOH recovery section is estimated initially for the first run
through the flowsheet (see Table 3-2:Reactor Feed Stream
Compositions.)
Figure 3-6: Typical Stream Input Data
The amount of wash water in stream 10 (the feed to column T-2) is

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

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

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

Figure 3-8: Extent of Reaction Data Entry Window
Figure 3-9 illustrates the Data Entry Window available to enter the
stoichiometries of the major and minor reactions in the process.
Figure 3-9: Reactrion Definition Data Entry Window

MTBE Distillation and Recovery
The MTBE distillation and recovery section of the plant is shown in
Figure 3-10: : MTBE Distillation and Recovery Section.
Figure 3-10: : MTBE Distillation and Recovery Section
The reactor product (stream 4) exchanges heat with the MTBE

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

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

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

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

Figure 3-13: \MTBE Column Specifications & Variables
The next step is to provide all the information required for

specifying the reaction trays in the distillation column.
Implementing Reactive Distillation

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

Figure 3-14: Assigning Reactions to Column Trays
Additionally, the liquid volume of each of the reaction trays is

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

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

In the Procedure Data group, press the DEFINE ... button to
open the Definition DEW shown in Figure 3-17.
Figure 3-17: Setting Catalyst Concentration Using Define
A value of 360 g/l is given for GCAT to represent commercial

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

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

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

removing the catalyst terms from the concentration terms. The
modified reaction rate is given by:
C C1.5
C A C B0.5 --------- -
K eq
:r s = k s K a -------------------------------------------------------- (3-2)
1 + K A C A + K B C b 1.5
where:
ks = surface reaction rate constant = 1.2x1013 exp(- 87900/RT)
in (gmole/g catalyst)1.5/hr, (1a)
Ka = equilibrium adsorption constant = 5.1x10-13 exp(97500/
RT) in g catalyst/gmole, (1b)
KC = equilibrium adsorption constant = 1.6x10-16
exp(119000/RT) in g catalyst/gmole , (1c)
Keq = equilibrium constant
CA = IBTE concentration in mole/l
CB = MEOH concentration in mole/l
CC = MTBE concentration in mole/l
Kinetic Data
The procedure data used in the reactive distillation column model is
entered in the Kinetic Procedure data entry window shown below.
Figure 3-19: User-Defined Kinetics Calculation Procedure.

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

Next, the derivatives of these constants are computed and are used
later on in calculating the rate derivatives.
DKSDT = KS * 87900.0 / R / (TK*TK)

DKADT = KA * (-1.0) * 97500.0 / R / (TK*TK)
DKCDT = KC * (-1.0) * 119000.0 / R / (TK*TK)
Then the bulk concentration of components A, B, and C per gram

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

$ IN USER INPUT UNITS. INTERNALLY TO PRO/II, IT IS IN SI UNITS
$ (KG-MOLE/CUBIC METER). THE BASIS FOR THESE REACTION EQUATIONS
$ IS GM-MOLES/LITER. THE CONVERSION FACTOR FROM INPUT UNITS OF
$ KG-MOLES/CUBIC METER TO THE REACTION BASIS OF GM-MOLES/LITER
$ IS ONE. THEREFORE, XLCONC CAN BE USED WITH NO CONVERSION.
$
$ RHOA=(XLCONC(MEOH)/GCAT) |-THIS SHOULD BE EQUIVALENT TO BELOW.
$ RHOB=(XLCONC(IBTE)/GCAT) | IT HAS BEEN WRITTEN EXPLICITLY BELOW
$ RHOC=(XLCONC(MTBE)/GCAT) | TO MAKE IT OBVIOUS HOW TO DO THE
$ ANALYTICAL DERIVATIVES.
$
$ CALCULATE DENSITY IN MOLES / VOLUME
$
GCATX = 12.4
DENS=RLMRAT/RLVRAT
RHOA=(XLIQ(MEOH)*DENS/GCATX)
RHOB=(XLIQ(IBTE)*DENS/GCATX)
RHOC=(XLIQ(MTBE)*DENS/GCATX)
$
$ ---- CALCULATE REACTION RATE AND DERIVATIVES BY TERMS
$ ---- UNITS - RATE - GRAM-MOLE / GRAM CATALYST / HR.
$
$ DENOMINATOR & DERIVATIVES.
$
RDEN = 1.0 + (KA*RHOA)+ 0.0 +(KC*RHOC)
DRDDT = RHOA*DKADT + 0.0 + RHOC*DKCDT
DRDDME = KA/GCATX*DENS
DRDDIB = 0.0
DRDDMT = KC/GCATX*DENS
$
$ FIRST FACTOR IN RATE EQUATION.
FACT1 = KS *KA/RDEN
DFAC1DT = DKSDT*KA/RDEN + KS*DKADT/RDEN - KS*KA/RDEN**2 * DRDDT
$
$ SECOND FACTOR IN RATE EQUATION.
FACT2 = RHOA*RHOB**0.5 - RHOC**1.5/KALJ
DFAC2DT = 0.0 + RHOC**1.5/KALJ**2 * DKALJDT
$
$ COMBINE TERMS TO CALCULATE RATE AND DERIVATIVES.
$
$ -- RATE EQUATION (RATE PER ONE GRAM OF CATALYSIS).
RATE = FACT1 * FACT2
$
$ -- RATE TEMPERATURE DERIVATIVE.
DRDT(1) = DFAC1DT * FACT2 &
+ FACT1 * DFAC2DT
$ -- RATE COMPOSITION DERIVATIVES.

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

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

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

Figure 3-20: Conversion Calculator Procedure
Figure 3-21: Declaration of Results From Conversion Calculator

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

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

Column T-2 is simulated as a liquid-liquid extractor with 5
theoretical trays. Recirculating wash water is fed to the top of the
column. A top pressure specification of 792 KPa is given. This
column uses the VLLE SRK thermodynamic set (SRKM_VLLE)
defined previously in the Thermodynamic Data Category of the
input file.
The raffinate leaves the top of the column (stream 11) and contains
the unreacted and non- reactive C4s. The extract phase (stream 12)
exits at the bottom. It enters the cold side (HX4A) of the feed-
bottoms heat exchanger where it is warmed to 99 C against the
recycle wash water (stream 21) which in turn is cooled (in unit HX-
4B described later on).
Valve V-1 drops the pressure of the heated methanol-water stream

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

Figure 3-22: Column T-3 Main Data Entry Window
The column has asub-cooled, fixed temperature condenser that

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

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

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

Figure 3-25: Data Entry for Make-up Water Calculator
Pump P-4 pumps the recovered wash water from the methanol
column bottoms combined with make-up water as stream 21 to heat
exchanger HX4B. This unit represents the hot side of the exchanger
HX-4 (see HX-4A described previously) and calculates the exit
temperature for stream 22.
Trim cooler (HX-5) further cools the wash water (stream 22) to the
desired temperature of 38 C before it (stream 10) goes back to the
water wash column. At this stage, the first recycle loop between
unit T-2 (water wash column) and HX-5 (trim cooler) is closed.
The second recycle loop between unit HX-1 (feed heater) and P-3
(recycle pump) is closed when the pump P-3 recycles the overhead
(stream 19) from the top of the methanol column (T-3) to the reactor
section.

Rating the Methanol Column (T-3) Condenser
As an illustrative example, a rigorous heat exchanger (RC-1) is
used to rigorously rate the methanol column condenser. This
rigorous heat exchanger is modeled as an attached heat exchanger
to column T-3. Figure 3-26 illustrates the main data entry window
of this exchanger.
Figure 3-26: Rigorous Heat Exchanger RC-1 Main DEW
This unit takes as its input the exchanger's mechanical data such as
shell and tube dimensions, tube layout pattern, the baffle cut and
shell and tube side nozzle sizes. A fouling factor of 0.00035 m2-K/
kW is used for the condenser cooling water side.

Figure 3-27: setting Heat Exchanger RC-1 Fouling Factors
ZONES analysis is requested to determine where phase changes

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

Technical Results
The overall mole balance for a 200,000 metric tonne per day MTBE
plant using the reactive distillation process is shown in Table 3-5.
Table 3-5: Summary of Resulting Product Streams
Stream Name 1 2 MKUP
Stream Description MEOH Feed OLEFINS Makeup Water
Phase Liquid Liquid Liquid
Temperature, C 16.00 16.00 38.00
Pressure kPa 1620.00 1620.00 350.00
Component Flowrates, kg_mol/hr
NC4 0.00 0.09 0.00
IC4 0.00 0.41 0.00
1BUTENE 0.00 0.07 0.00
BTC2 0.00 0.04 0.00
BTT2 0.00 0.06 0.00
IBTE 0.00 0.33 0.00
MTBE 0.00 0.00 0.00
MEOH 1.00 0.00 0.00
TBA 0.00 0.00 0.00
H2O 0.00 0.00 1.00
DIB 0.00 0.00 0.00
Stream Name 8 11 15
Stream Description MTBE C4S Flare Gas
Phase Liquid Liquid Liquid
Temperature, C 88.5844 38.1654 99.0981
Pressure kPa 663.00 792.00 241.00
Component Flowrates, kg_mol/hr
NC4 0.00 0.1337 0.1229
IC4 0.00 0.6091 0.4223
1BUTENE 0.00 0.1040 0.0046
BTC2 0.00 0.0594 0.0051
BTT2 0.00 0.0891 0.0048
IBTE 0.00 0.0039 0.0001
MTBE 0.9977 0.00 0.00
MEOH 0.0004 0.00 0.0321
TBA 0.0007 0.00 0.00
H2O 0.00 0.0007 0.4081
DIB 0.0013 0.00 0.00

Results Analysis
The results of this simulation shown above indicate that the overall
conversion of IBTE is 99.2% with a selectivity to MTBE of 99.7%.
In the reactive distillation column itself, 87.2% of the IBTE fed to
the column is converted to MTBE. The MTBE product is 99.77%
pure and needs no further purification.
There are a number of factors that affect the overall conversion rate
of IBTE. Some of these are:
Methanol to IBTE ratio
Number of reaction trays
Type of catalyst used
Note, however, that while the IBTE conversion in the conversion
reactors increases as the MEOH:IBTE ratio is increased, the overall
IBTE conversion reaches a maximum, then decreases as the
MEOH:IBTE ratio is increased. This is due to the fact that more
MTBE product is carried upward through the column stripping
section into the reaction trays. This promotes the reverse reaction of
MTBE to methanol and IBTE, thus reducing the overall conversion
of IBTE.
Additional References
1. Hydrocarbon Processing, Vol. 61, No. 9, p.177, Sept. 1982.
2. Bitar, L.S., E. A. Hazbun, and W. J. Piel, MTBE Production and
Economics, Hydrocarbon Processing, Vol. 63, No. 10, pp. 63-68,
Oct. 1984.
3. Hutson, T., et al., in ``Handbook of Chemicals Production Processes'',
Ed. Robert A. Meyers, McGraw-Hill Book Company, New York,
Chap. 1.12, 1986.
4. Friedlander, R.H., in ``Handbook of Chemicals Production
Processes'', Ed. Robert A. Meyers, McGraw-Hill Book Company,
New York, Chap. 1.13, 1986.
5. Jacobs, R., and R. Krishna, 1993, Multiple Solutions in Reactive
Distillation of Methyl tert-Butyl Ether Synthesis, Ind. Chem Res.,
32(8).
6. Hydrocarbon Processing, Vol. 69, No. 10, pp.29,31,33,44, Oct. 1990.
7. Oil & Gas J., Mar. 25, 1991, pp.26-29.
8. Shah, V.B., D. Bluck, J. W. Kovach III, R. Parikh, and R. Yu, 1994,
The Sensitivity of the Design and Operability of the MTBE Processs
with Respect to Changes in Reaction Parameters and Process
Configurations, paper presented at the Refining LNG and
Petrochemasia 94 Conference in Singapore, December 7-8 1994.

Appendix 3-A: Complete MTBE Plant Flowsheet
Figure 3-29 is a graphic representation of the flowsheet.
Figure 3-29: MTBE Plant Graphical Representation
The PRO/II PDF of the simulation flowsheet appears in Figure

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

Figure 3-30: MTBE Plant PRO/II Flowsheet

Appendix 3-B: PRO/II Selected Output
The following pages show selected parts of the stream and unit
operation information exported to Excel.
SIMULATION SCIENCES INC. R PAGE P-54
PROJECT MTBECASEBOOK PRO/II VERSION 9.3 ELEC V7.0
PROBLEM MTBE PLANT OUTPUT SIMSCI
USER DEFINED PROPERTIES SET 04/08/10
==============================================================================
STREAM ID 1 2 MKUP 8
NAME MEOH FEED OLEFINS MKUP WATER MTBE
PHASE LIQUID LIQUID LIQUID LIQUID
THERMO ID SRKM_VLE SRKM_VLE SRKM_VLE SRKM_VLE
*** TOTAL STREAM ***

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

==============================================================================
*** VAPOR PHASE ***

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

==============================================================================
*** LIQUID PHASE ***

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

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

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

==============================================================================
STREAM ID 11 15
NAME C4'S FLARE GAS
PHASE LIQUID VAPOR
*** VAPOR PHASE ***

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

==============================================================================
STREAM ID 11 15
NAME C4'S FLARE GAS
PHASE LIQUID VAPOR
*** LIQUID PHASE ***

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

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

---------- NET FLOW RATES ----------- HEATER
TRAY TEMP PRESSURE L2 L1 FEED PRODUCT DUTIES
------ ------- -------- -------- -------- --------- --------- --------
----
1 38.2 792.00 375.0 375.0L 572.1L
2 38.2 792.00 375.1 572.2
3 38.2 792.00 375.2 572.2
4 38.2 792.00 375.8 572.3
5 38.2 792.00 572.9 575.9L 378.8H

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

Shell and Tube Exchanger Data Sheets
EXCHANGER NAME T-3 COND UNIT ID RC-1
SIZE 381 - 5750 TYPE AES HORIZONTAL CONNECTED 1 PARALLEL 1 SERIES
AREA/UNIT 37.0M2 (28.3M2 REQUIRED) AREA/SHELL 37.0M2
Performance of one unit Shell-side Tube-side
FEED STREAM ID CW
FEED STREAM NAME (ATTACHED)
TOTAL FLUID KG/HR 3188. 174827.
VAPOR (IN/OUT) KG/HR 3188. / /
LIQUID KG/HR / 3188. 174827. / 174827.
STEAM KG/HR / /
WATER KG/HR / /
NON CONDENSIBLE KG/HR
TEMPERATURE (IN/OUT) DEG C 74.1 / 30.0 21.0 / 26.3
PRESSURE (IN/OUT) KPA 138.00 / 88.76 690.00 / 428.42
SP. GR., LIQ (4C / 4C H2O) / 0.803 1.000 / 1.000

VAP (4C / 4C AIR) 1.087 / /
DENSITY, LIQUID KG/M3 / 787.363 994.441 / 989.867
VAPOR KG/M3 1.538 / /
VISCOSITY, LIQUID PAS / 5.2E-04 1.0E-03 / 8.9E-04
VAPOR PAS 1.1E-05 / /
THRML COND,LIQ W/M-K / 0.2000 0.6006 / 0.6081
VAP W/M-K 0.0202 / /
SPEC.HEAT, LIQUID KJ/KG-K / 2.6389 4.4975 / 4.4538
VAPOR KJ/KG-K 1.5195 / /
LATENT HEAT KJ/KG 1164.32
VELOCITY M/SEC 0.16 5.23
dP /SHELL KPA 49.24 262.06
FOULING RESIST M2-K/KW 0.35222( 0.65987 REQD) 0.00035
TRANSFER RATE KW/M2-K SERVICE 1.00 ( 0.77 REQD) CLEAN 1.55
HEAT EXCHANGED M*KJ/HR 4.073
MTD(CORRECTED) 39.9
FT 0.911
Construction of One Shell Shell-side Tube-side
DESIGN PRESSURE KPA 2068. 2068.
NUMBER OF PASSES 1 2
MATERIAL CARB STL CARB STL
INLET NOZZLE ID MM 152.0 102.0
OUTLET NOZZLE ID MM 102.0 102.0
TUBE: NUMBER 109 OD 19.000 MM BWG 14 LENGTH 5.8 M

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

Shell and Tube Extended Data Sheet for Exchanger 'RC-1'
EXCHANGER NAME T-3 COND UNIT ID RC-1
SIZE 381 - 5750 TYPE AES HORIZONTAL CONNECTED 1 PARALLEL 1 SERIES
AREA/UNIT 37.0 M2 ( 28.3 M2 REQUIRED)
Performance of one unit Shell-side Tube-side
FEED STREAM ID
FEED STREAM NAME (ATTACHED)
WT FRACTION LIQUID (IN/OUT) 0.000 / 1.000 1.000 / 1.000
REYNOLDS NUMBER 46389.15 80107.92
PRANDTL NUMBER 4.154 7.127
WATSON K,LIQUID / 10.561 8.758 / 8.758
VAPOR 10.561 / /
SURFACE TENSION N/M / 0.024 0.074 / 0.073
FILM COEF(SCL) KW/M2-K 1.9 (1.000) 15.6 (1.000)
FOULING LAYER THICKNESS MM 0.000 0.000
THERMAL RESISTANCE
UNITS: (M2-K/KW) (PERCENT) (ABSOLUTE)
SHELL FILM 51.72 0.51515
TUBE FILM 8.27 0.08235
TUBE METAL 4.61 0.04593
TOTAL FOULING 35.41 0.35267
ADJUSTMENT 30.89 0.30765
PRESSURE DROP Shell-side Tube-side

UNITS: (KPA) (PERCENT) (ABSOLUTE) (PERCENT) (ABSOLUTE)
WITHOUT NOZZLES 98.42 48.47 89.15 233.62
INLET NOZZLES 1.57 0.77 6.77 17.74
OUTLET NOZZLES 0.01 0.00 4.08 10.70
TOTAL /SHELL 49.24 262.06
TOTAL /UNIT 49.24 262.06
DP SCALER 1.00 1.00
CONSTRUCTION OF ONE SHELL
TUBE: OVERALL LENGTH 5.8 M EFFECTIVE LENGTH 5.68 M

TOTAL TUBESHEET THK 66.0 MM AREA RATIO (OUT/IN) 1.285
THERMAL COND 51.9 W/M-K DENSITY 7862.00 KG/M3
BAFFLE: THICKNESS 4.762 MM NUMBER 73
BUNDLE: DIAMETER 327.0 MM TUBES IN CROSSFLOW 92

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

Appendix 3-C: PRO/II INPUT FILE
TITLE PROJECT=MTBECASEBOOK, PROBLEM=MTBE PLANT, USER=SIMSCI
DESC This is a PRO/II simulation file corresponding to the
DESC PRO/II Casebook on a MTBE Plant.
DESC For more information on this model
DESC please contact Technical Support
DESC
DESC
PRINT INPUT=ALL, STREAM=COMPONENT, MBALANCE
DIMENSION SI, TEMP=C
SEQUENCE DEFINED=HX-1,RX-1,HX-2A,CAL0,T-1,CONVERSION,HX-2B,P-1, &
HX-3,T-2,HX4A,V-1,D-1,P-2,T-3,CAL1,P-4,HX4B,HX-5,P-3,RC-1
COMPONENT DATA
LIBID 1,NC4/2,IC4/3,1BUTENE/4,BTC2/5,BTT2/6,IBTE/7,MTBE/ &
8,MEOH/9,TBA/10,H2O/11,244TM1P,,DIB, BANK=SIMSCI,PROCESS
THERMODYNAMIC DATA
METHOD SYSTEM=SRKM, SET=SRKM_VLE, DEFAULT
KVAL(VLE)
SRKM 1,9,0.046973,0.126027,0,0,0,0,1,1
SRKM 3,8,0.136,-0.0323,0,0,0,0,1,1
SRKM 4,8,0.136,-0.0323,0,0,0,0,1,1
SRKM 5,8,0.136,-0.0323,0,0,0,0,1,1
SRKM 6,8,0.135525,-0.032271,0,0,0,0,1,1
SRKM 8,9,-0.073971,-0.055222,0,0,0,0,1,1
SRKM 9,10,-0.145,-0.253,0,0,0,0,1,1
SRKM 7,11,0.05785,-0.0093,-10.144,6.17,0,0,1,1
METHOD SYSTEM(VLLE)=SRKM, L1KEY=1, L2KEY=10, SET=SRKM_VLLE
KVAL(VLE)
SRKM 1,9,0.046973,0.126027,0,0,0,0,1,1
SRKM 3,8,0.136,-0.0323,0,0,0,0,1,1
SRKM 4,8,0.136,-0.0323,0,0,0,0,1,1
SRKM 5,8,0.136,-0.0323,0,0,0,0,1,1
SRKM 6,8,0.135525,-0.032271,0,0,0,0,1,1
SRKM 8,9,-0.073971,-0.055222,0,0,0,0,1,1
SRKM 9,10,-0.145,-0.253,0,0,0,0,1,1
SRKM 7,11,0.05785,-0.0093,-10.144,6.17,0,0,1,1
STREAM DATA
PROPERTY STREAM=1, TEMPERATURE=16, PRESSURE=1620, PHASE=M, &
COMPOSITION(M,KGM/H)=8,277.5
RATE(M)=850, COMPOSITION(M)=1,9/2,41/3,7/4,4/5,6/6,33, &
NORMALIZE
COMPOSITION(M,KGM/H)=10,375
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
RXSET ID=ALJX
REACTION ID=ALJ0
PROCEDURE DATA
PROCEDURE(KINETIC) ID=ALJD, NAME=ALJD lah
PDATA GCAT,RXFACT
CODE
REAL KS, KA, KC, KALJ, KREH1, KREH2, KIZQ, KEQREF
INTEGER IBTE , MEOH , MTBE
$
$ INITIALIZE DATA:
$ SET INDEXES FOR COMPONENTS
$ DEFINE GAS CONSTANT IN Joules/gm-mole K
$ Note: R could have been retrieved in input units by R=RGAS.
$ However, since the reaction basis won't change, and
$ RGAS will change with the default units, this
$ eliminates one possible source of error..
$ Initialize the local variable TK to the absolute temperature.
$ Note: The temperature basis for the flowsheet must be Celsius
$ or Kelvin.
$ Set temperature and composition derivatives to zero.
$
IBTE = 6
MTBE = 7
MEOH = 8
$
R = 8.314
$
TK = RTABS
$
DO 1000 I1 = 1,NOR
DRDT(I1) = 0.0
DO 1000 I2 = 1,NOC
1000 DRDX(I2,I1) = 0.0
$
$ Calculate the surface reaction rate constant, ks, and the
$ equilibrium adsorption constants Ka and Kb. The activation
$ energy is in J/gm-mole.
$ units: ks - (gm-mole / gm catalyst)**1.5 /hour
$ Ka - gm-catalyst / mole
$ Kc - gm-catalyst / mole
$
KS = 1.2E+13*EXP(-87900.0/(R*TK))
KA = 5.1E-13*EXP( 97500.0/(R*TK))
KC = 1.6E-16*EXP(119000.0/(R*TK))

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

$
$ Second factor in rate equation.
FACT2 = RHOA*RHOB**0.5 - RHOC**1.5/KALJ
DFAC2DT = 0.0 + RHOC**1.5/KALJ**2 * DKALJDT
$
$ Combine terms to calculate rate and derivatives.
$ -- Rate equation (rate per one gram of catalysis).
RATE = FACT1 * FACT2
$
$ -- Rate temperature derivative.
DRDT(1) = DFAC1DT * FACT2 + FACT1 * DFAC2DT
$ -- Rate composition derivatives.
DRDX(MEOH,1) = -KS*KA/RDEN**2 * DRDDME * FACT2 &
+ FACT1 * (RHOB**0.5/GCATX*DENS)
DRDX(IBTE,1) = -KS*KA/RDEN**2 * DRDDIB * FACT2 &
+ FACT1 * (RHOA/2.0/RHOB**0.5/GCATX*DENS)
DRDX(MTBE,1) = -KS*KA/RDEN**2 * DRDDMT * FACT2 &
- FACT1 * (1.5* RHOC**0.5/GCATX/KALJ*DENS)
$
$ ---- Convert rate equation and derivatives to a straight volume
$ ---- basis by multipling the base rate by the grams of
$ ---- catalyst/unit volume.
$ ---- The rate is returned in input units, kg-moles/cubic
$ meter/hour.
$
RRATES(1) = GCAT * RXFACT * RATE
$
DRDT(1) = GCAT * RXFACT * DRDT(1)
$
DRDX(MEOH,1) = GCAT * RXFACT * DRDX(MEOH,1)
DRDX(IBTE,1) = GCAT * RXFACT * DRDX(IBTE,1)
DRDX(MTBE,1) = GCAT * RXFACT * DRDX(MTBE,1)
RETURN
UNIT OPERATIONS
HX UID=HX-1, NAME=FEED HEAT
COLD FEED=1,2,20, L=3, DP=34.5
OPER CTEMP=43.5
CONREACTOR UID=RX-1, NAME=REACTORS
FEED 3
PRODUCT L=4
OPERATION ISOTHERMAL, TEMPERATURE=55, DP=69
RXCALCULATION MODEL=STOIC
RXSTOIC RXSET=ST1
REACTION 1
BASE COMPONENT=6
CONVERSION 0.0025
REACTION 2
BASE COMPONENT=10
CONVERSION 1
REACTION 3
BASE COMPONENT=8
CONVERSION 0.93

HX UID=HX-2A, NAME=FEED-BTMS-A
COLD FEED=4, L=5, DP=34.5
OPER CTEMP=72
CALCULATOR UID=CAL0, NAME=COPY RXFACT
PROCEDURE $Set RXFACT TO 1 on first call.
IF (R(2) .NE. 1.0) R(1) = 1.0
R(2) = 1.0
RETURN
COLUMN UID=T-1, NAME=MTBE COLUMN
PARAMETER TRAY=30,CHEMDIST=35
FEED 5,15
PRODUCT OVHD(M)=6, BTMS(M)=7,280, SUPERSEDE=ON
CONDENSER TYPE=TFIX, PRESSURE=621, TEMPERATURE=43.5
DUTY 1,1,,CONDENSER
DUTY 2,30,,SIDEHC2
PSPEC PTOP=621, DPCOLUMN=76.5
PRINT COMPOSITION=M, PROPTABLE=ALL
ESTIMATE MODEL=SIMPLE, RRATIO(L)=1.1
SPEC ID=COL1SPEC1, STREAM=7, RATE(KGM/H),TOTAL,WET, &
VALUE=278
SPEC ID=COL1SPEC2, RRATIO, PHASE=L, VALUE=1.1
DEFINE GCAT AS 360
DEFINE RXFACT AS 1
VARY DNAME=CONDENSER,SIDEHC2
PLOT LOG, XCOMPONENT=6,6/8,8/7,7/1,1
TSIZE SECTION(1)=2,29,VALVE, DMIN=381, FF=80, DPCALC=0
VLLECHECK CHECK=OFF
LVOL 8,5/9,5/10,5/11,5/12,5/13,5
RXTRAY REFERENCE=ALJX, LOCAL=L_ALJX, KPROCEDURE=ALJD, &
TRAY=8, & 13
RXSET LOCAL=L_ALJX
REACTION ID=ALJ0, COPTION=KINETICS
KINETICS PEXP(C,KG,M3,KPA,HR)
CALCULATOR UID=CONVERSION, &
NAME=CONVERSION OF IBTE-MEOH TO MTBE
RESULT 1,IN - MEOH/2,IN - IBTE/3,IN - MTBE/ &
4,OUT - MEOH/5,OUT - IBTE/6,OUT - MTBE/ &
20,IBTE CONV/21,MEOH CONV
DEFINE P(1) AS STREAM=4, RATE(KGM/H), COMP=8,WET
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
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
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, DIAM(TRAY)=610, &
DIAMETER(SIEVEHOLE,IN)=0.5, WEIR=50.8, DCC=38.1
CALCULATOR UID=CAL1, NAME=MAKEUP
SEQUENCE STREAM=MKUP
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
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
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

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Invensys Systems, Inc.

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

3-2 MTBE Synthesis Plant (Rev. 3) March 5, 2014

Standard (Hls) Process

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

3-4 MTBE Synthesis Plant (Rev. 3) March 5, 2014

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

3-6 MTBE Synthesis Plant (Rev. 3) March 5, 2014

MTBE Recovery Section

Methanol Recovery Section

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

3-8 MTBE Synthesis Plant (Rev. 3) March 5, 2014

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

kjia 0.12603 -0.0323 -0.0323 -0.0323

kijb 0.0 0.0 0.0 0.0

kjib 0.0 0.0 0.0 0.0

Binary Component Interaction Data (continued) .

kjia -0.032271 -0.055222 -0.253 -0.0093

kijb 0.0 0.0 0.0 -10.144

kjib 0.0 0.0 0.0 6.17

3-10 MTBE Synthesis Plant (Rev. 3) March 5, 2014

Transport properties are needed in order to use the rigorous heat

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

3-12 MTBE Synthesis Plant (Rev. 3) March 5, 2014

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

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

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

3-14 MTBE Synthesis Plant (Rev. 3) March 5, 2014

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

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

3-16 MTBE Synthesis Plant (Rev. 3) March 5, 2014

MTBE Distillation Column

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

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The next step is to provide all the information required for

Implementing Reactive Distillation

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

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

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

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

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

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$ -- RATE COMPOSITION DERIVATIVES.

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Once the column converges, the top and bottom product

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Figure 3-21: Declaration of Results From Conversion Calculator

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Figure 1: MTBE Distillation and Recovery Section

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

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The column has asub-cooled, fixed temperature condenser that

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* TOTAL STREAM *

* VAPOR PHASE *

* LIQUID PHASE *

* TOTAL STREAM *

* VAPOR PHASE *

* LIQUID PHASE *