You are on page 1of 0

PRO/II CASEBOOK

Methyl Terti ary Butyl


Ether (MTBE) Pl ant
Abstract
This casebook demonstrates the use of PRO/II

in the simulation of the synthesis


of methyl tert-butyl ether (MTBE). MTBE is of current interest 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 an MTBE
plant is presented here. The process plant includes a reactor and 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. SimScis
SM
SRKM bank provides a good simulation of the
VLE fractionators and the VLLE extractor. All product specifications are achieved.
The thermodynamics successfully predicts the azeotropic removal of methanol from
the MTBE product stream.
Feature Hi ghl i ghts
M Petrochemicals Application
M Stoichiometric Reactor Units
M Multi-tray Reactive Distillation Column
M Complex Reaction Kinetic Models
M Liquid-liquid Extraction Column Using VLLE Thermodynamics
M Column Condenser Modeled as an Attached, Rigorous Heat Exchanger
M Column Tray Rating
M Recycle Acceleration Techniques
Casebook #4, Rev 1. Methyl Tertiary Butyl Ether (MTBE) Plant, March 1995
PRO/II is a registered mark of SIMULATION SCIENCES INC.
SIMSCI is a service mark of SIMULATION SCIENCES INC.
Amberlyst is a trademark of Rohm & Haas
Copyright 1995, SIMULATION SCIENCES INC. ALL RIGHTS RESERVED
Customer Servi ce and Support
Customer Servi ces Address and Phone Numbers
The telephone numbers of Customer Support are given below:
Support Center Tel ephone Facsi mi l e
USA and Canada
Simulation Sciences Inc.
601 S. Valencia Ave
Brea, California 92621
(800) SIMSCI1 (714) 579-0354
(714) 579-0412
Paci fi c Ri m
Simulation Sciences Inc.
601 S Valencia Ave
Brea, California 92621
(800) 827-7999 (714) 579-7468
(714) 579-0412
Japan
SIMSCI Japan K.K.
Towa Hamamatsucho Building #203
2-6-2 Hamamatsucho
Minato-ku, Tokyo 105, Japan
81-3-3432-4631 81-3-3432-4633
Europe/Indi a
SIMSCI International
High Bank House, Exchange Street
Stockport, Cheshire
United Kingdom SK3 OET
44-161-429-6744 44-161-480-9063
South Ameri ca
SIMSCI Latinoamerica C.A.
Centro Banaven (Cubo Negro)
Torre A, PH A-2
Av. La Estancia, Chuao
Caracas, 1060, Venezuela
58-2-959-8033 58-2-993-2717
Introducti on
What i s MTBE?
Methyl tertiary butyl ether (MTBE) is an octane enhancing agent for unleaded motor gasoline.
Suitable feedstocks for the manufacture of MTBE are mixed butylenes from liquid feed ethylene
crackers and from fluid catalytic crackers. In some plants, raffinates from butadiene extraction
or catalytic butane dehydrogenation are used as feed. 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.
Why i s MTBE an Important Commodi ty?
MTBE has a number of desirable properties that makes it a suitable gasoline additive:
Tabl e 1: Desi rabl e Properti es of MTBE
Property Advantage
RVP of 8-10 psi
Low boiling point
Low vapor pressure results in reduced
emissions
RON+MON/2 octane number of ~109 More complete combustion without
reducing engine power
Increases front-end octane number (FON)
of gasoline
Reduces knocking during acceleration
Also, the addition of MTBE to gasolines generally implies a reduced aromatic and butane content.
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. Future US demand for MTBE is expected to grow at a rate
of over 10% per year for the next 5 years. Recent environmental legislation in the Far East
(especially Japan and Korea) has resulted in an increased demand for MTBE in those markets.
In Europe, lead-based gasolines are being phased out, resulting in increasing use of MTBE and
other octane-enhancing agents.
Al ternati ve Routes to MTBE Synthesi s
There are two principal processes for MTBE synthesis currently in use. 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 (Hl s) 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%. In many plants,
two reactors are used in tandem, along with recycle, in order to increase the overall conversion
closer to 99%.
Ethermax Process
1
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.
1
Chemical Engineering Progress, p. 15, Aug. 1991.
1
Catal yst
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. For exact catalyst properties,
please contact the manufacturer.
Tabl e 2: Approxi mate Properti es of Amberl yst 15 Catal yst
Properti es
Physical Form Spherical beads
Ionic Form Hydrogen
Acid Site Concentration 1.8 meq/ml (4.9 meq/g)
Moisture Content 53 %
Apparent Density 770 g/l
Particle Size 0.35-1.2 mm
Shrinkage: Wet to methanol
Wet to MTBE
4%
12%
Porosity 0.30 cc/g
Average Pore Diameter 250 A
Surface Area 45 m2/g
Bulk Density 48 lb/ft3
Operati ng Condi ti ons
Maximum Temperature 120 C
Minimum Bed Depth 0.61 m
Flowrate, LHSV 1-5 hr-1
2
Process Outl i ne
There are numerous variations on MTBE plant designs. In general, an MTBE plant is comprised
of the following sections:
M Reactor section
M MTBE recovery section
2
M Methanol recovery section
The complete process flow diagram for the MTBE reactive distillation plant model used in this
simulation is given in Figure 1. The full PRO/II input file for the Ethermax process is given in
Appendix A.
Figure 1: MTBE Plant Flowsheet
2
For the Ethermax process, the MTBE recovery section includes a second reaction zone in the distillation column.
3
Process Descri pti on
Reactor Secti on
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 this MTBE process, an isobutylene-rich mixed C4 stream is mixed with fresh methanol and a
small amount of recycle methanol and fed to the reactor section. The reactors are cooled to
prolong catalyst life and to minimize the undesirable side reactions such as dimerization of
isobutylene. Temperatures below 94 C (200 F) are recommended.
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 (discussed
later). Generally, this ratio is maintained close to the stoichiometic (molar) value of unity. Table
3 contains the reactor feed composition used in this model.
Tabl e 3: Reactor Feed
Stream Stream No Fl owrate (kgmol e/hr)
C4 Feed 2 850
Temperature 16 C
Pressure 1620 kPa
Component Li brary Name Mol e Percent
N-butane NC4 9.0
Isobutane IC4 41.0
1-butene 1BUTENE 7.0
cis 2-butene BTC2 4.0
trans 2-butene BTT2 6.0
Isobutylene IBTE 33.0
MTBE MTBE 0.0
tert-butanol TBA 0.0
Water H2O 0.19
Di-isobutylene (DIB) 244TM1P --------
Stream Stream No Fl owrate (kgmol e/hr)
Methanol Feed 1 277.5
Temperature 16 C
Pressure 1620 kPa
Component Li brary Name Mol e Percent
Methanol MEOH 100.0
Stream Stream No Fl owrate (kgmol e/hr)
Methanol Recycle 20 4.3
Temperature 44 C
Pressure 1724 kPa
Component Li brary Name Mol e Percent
Methanol MEOH 93.02
Water H20 6.98
4
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 (TBA).
Another impurity, di-isobutylene (DIB), is formed by the dimerization of isobutylene. While the
formation of di-isobutylene and t-butanol should be minimized, their presence in small concen-
trations in the MTBE product is acceptable since these byproducts also have very high octane
numbers.
Table 4 shows the three main reactions used in the stoichiometric reactor model. The base
component and the fraction converted are also shown.
Tabl e 4: Reacti on Stoi chi ometry
Reacti on Base Component Conversi on %
2 (IBTE) =DIB IBTE 0.25
H2O +IBTE =TBA H2O 100.0
IBTE +MEOH =MTBE MEOH 93.0
MTBE Recovery Secti on
In the Hls process, the reactor products are processed in the MTBE column where MTBE, along
with t-butanol (TBA), dimerized butylene (DIB) 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 sufficient amounts 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 Secti on
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.
5
Process Si mul ati on
The full input for the process simulated here may be found in Appendix A. Fragments of the input
are shown here to illustrate points of interest.
Symbol s Used
The symbol
n
is used beside the highlighted fragments of the keyword input file. The number n refers to the
chapter in the PRO/II Keyword Input Manual where detailed explanations of the input data may
be found. The PRO/II Keyword Input Manual may be obtained from SimSci.
General Data
SI units are used. 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. The MBAL keyword on the PRINT statement specifies that an overall mass
balance be reported in the final output.
5
Keyword
Syntax
DIMENSION SI, TEMP=C
PRINT INPUT = ALL, STREAM = COMPONENT, MBAL
SEQUENCE 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
All the components in the simulation are in the PRO/II databank.
Thermodynami c Data
The VLE fractionators are simulated well with SimScis 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 and to demonstrate
the input syntax.
Transport property calculations are selected by specifying the TRANSPORT keyword in order
to use the rigorous heat exchanger model in the MeOH recovery section. The liquid extraction
unit is simulated using the SRKM method for VLLE thermodynamics with binary interaction data
again supplied as part of the input. Note that the L1KEY component (i.e., the predominant
component in the L1 liquid phase) is specified as component 1, n-butane. The L2KEY component
is specified to be component 10, water. Explicitly specifying the key components eliminates the
need for PRO/II to find an appropriate immiscible pair, and reduces computation time. Note also
that each thermodynamic set is given a unique set id number. All the azeotropes are properly
predicted.
23. 3
Keyword
Syntax
METHOD SYSTEM=SRKM, TRANSPORT=PURE, SET=S1
KVAL
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,-0.145000,-0.253000,0,0,0,0,1,1
SRKM 7,11, 0.05785, -0.0093,-10.144,6.17,0,0,1,1

6
METHOD SYSTEM(VLLE)=SRKM, L1KEY=1, L2KEY=10, SET=S2
KVAL
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,-0.145000,-0.253000,0,0,0,0,1,1
SRKM 7,11, 0.05785, -0.0093,-10.144,6.17,0,0,1,1
Stream Data
Feed Streams
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.
Recycl e 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).
31
Keyword
Syntax
$ RECYCLE STREAM ---- INITIAL GUESS
PROP STRM=20, TEMP=44, PRES=1724, COMP=8,4.0/10,0.3
Other Streams
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.
31
Keyword
Syntax
PROP STRM=10, TEMP=38, PRES=793, COMP=10,375
PROP STRM=CW, TEMP=21, PRES=690, COMP=10,100, RATE(V)=75
PROP STRM=MKUP, TEMP=38, PRES=350, COMP=10,500
Uni t Operati ons
MTBE Reacti on
The MTBE reaction section of the plant is shown in Figure 2 below.
Figure 2: MTBE Reaction Section
7
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. The three reactions defined in Table 4 take place in this reactor
at the specified conversion levels. A pressure drop of 69 KPa through the reactor is also specified.
The stoichiometries of the major and minor reactions in the MTBE process are provided In the
RXDATA Category of input:
48
Keyword
Syntax
$ Reaction Data for Reactors
$

RXSET ID=ST1
REACTION ID=1
STOIC 6,-2 / 11,1 $ IBTE + IBTE = DIB
REACTION ID=2
STOIC 10,-1 / 6,-1 / 9,1 $ H2O + IBTE = TBA
REACTION ID=3
STOIC 6,-1 / 8,-1 / 7,1 $ IBTE + MEOH = MTBE
The unit is modeled as a conversion reactor in the Unit Operations Category of input:
92
Keyword
Syntax
CONREACTOR UID=RX-1, NAME=REACTORS
FEED 3
PROD L=4
OPER TEMP=55, DP=69
RXCALC MODEL=STOIC
RXSTOIC RXSET=ST1
REACTION 1
BASE COMP=6
CONV 0.0025
REACTION 2
BASE COMP=10
CONV 1.00
REACTION 3
BASE COMP=8
CONV 0.93
MTBE Di sti l l ati on and Recovery
The MTBE distillation and recovery section of the plant is shown in Figure 3 below.
Figure 3: MTBE Distillation and Recovery Section
8
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-2A 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.
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 (TFIX) of 43.5 C and pressure of 621 KPa. The control
specifications are a bottoms flowrate of 278 kgmoles/h and a reflux ratio of 1.1. The condenser
and reboiler duties are varied to achieve these specifications.
The next step is to provide all the information required for specifying the reaction trays in the
distillation column.
How i s Reacti ve Di sti l l ati on Impl emented i n PRO/II?
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. See the PRO/II
Reference Manual (obtainable from your SimSci representative) for detailed information on the
Reactive Distillation column algorithm.
For the reactive distillation process, the reaction zone (trays 8 through 13) is specified using the
RXTRAY keyword. Note that the liquid volume of each of the reaction trays is also specified
using the LVOL keyword, and that the concentration of the dry catalyst (GCAT, in g/l) is specified
using a DEFINE statement. 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
2). 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.
75
Keyword
Syntax
COLUMN UID=T-1, NAME=MTBE COLUMN
PARA TRAY=30, CHEM=35
FEED 5, 15
PROD OVHD=6, BTMS=7,280
PSPEC TOP=621, DPCOL=76.5
COND TYPE=TFIX, PRES=621, TEMP=43.5
DUTY 1,1 / 2,30
VARY DUTY=1,2
SPEC STRM=7,RATE,VALUE=278.0
SPEC RRATIO, VALUE=1.1
PRINT PROP=ALL , COMP=M
PLOT LOG XCOMP=6,6/ 8, 8/ 7, 7/1,1
ESTI MODEL=SIMPLE
RXTRAY ALJX, 8 , 13
LVOL(M3) 8 , 5.0 / 13, 5.0
DEFINE GCAT AS 360.0
DEFINE RXFACT AS 1.0
9
MTBE Ki neti c 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 by one of two methods:
1. Numerically, by an estimation method
or
2. Analytically, by an expression based on the reaction rate equation.
The PRO/II program can automatically generate numerical estimates of the reaction rate
derivatives. In many cases, this is sufficient. However, for certain types of reactions, the more
accurate analytical derivatives provide better solutions. These are:
M Reversible reactions
or
M Exothermic reactions
or
M Reactions where the equilibrium is sensitive to temperature
The MTBE reaction satisfies all three criteria. 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-Jarallah et al
3
. 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) and the base component is defined to be MEOH. The kinetic data will
be provided later on in the Procedure Data category of input using FORTRAN-like language as
the procedure named ALJD.
75
Keyword
Syntax
RXSET ID=ALJX
REACTION ID=ALJ0
STOICH 6, -1/8, -1/7, 1
BASE COMP=8
KINETIC PROCEDURE=ALJD, POSITION=1
The reaction rate equation described by Al-Jarallah takes into account the forward and the
reverse reaction. We have modified Al-Jarallahs 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:
(1)
rs = ksKa

CACB
0.5

C
C
1.5
K
eq
(1 +K
A
C
A
+K
B
C
b
))
1.5

where:
ks = surface reaction rate constant = 1.2x10
13
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
3
Al-J arallah, 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.
10
Ki neti c Data
In the Procedure Data category of input, the PROCEDURE type of RXKINETIC is selected to
denote that the procedure will be used in the Reactive Distillation column model. In addition,
process data, and real and integer variables are defined:
47
Keyword
Syntax
PROCEDURE DATA

PROCEDURE(RXKINE) ID=ALJD,NAME=Al-Jarallah
PDATA GCAT , RXFACT
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.
CODE
$
$ 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 wont 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 Centigrade
$ 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).
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-speci-
fied units of kg-moles/m
3
(SI units). Our basis for calculations is gm-moles/l and the conversion
factor between these kg-moles/m
3
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.
11
GCATX = 12.4
DENS=RLMRAT/RLVRAT
RHOA=(XLIQ(MEOH)*DENS/GCATX)
RHOB=(XLIQ(IBTE)*DENS/GCATX)
RHOC=(XLIQ(MTBE)*DENS/GCATX)
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.
$
$ -------- 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.
12
$
$ -------- Convert rate equation and derivatives to a straight volume basis
$ -------- by multiplying 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.
81
Keyword
Syntax
HX UID=HX-2B, NAME=FEED-BTMS-B
HOT FEED=7, L=8, DP=34.5
DEFINE DUTY AS HX=HX-2A DUTY
52
Keyword
Syntax
PUMP UID=P-1, NAME=T-1 OVHD
FEED 6
PROD L=6P
OPER PRES=827, EFFI=65
A calculator (CONVERSION) is set up to compute the conversions of IBTE and MEOH to MTBE
in the reactive distillation column itself.
121
Keyword
Syntax
& Calculate RXDIST conversions.
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(M) COMP=8 $ MEOH
DEFINE P(2) AS STREAM=4 RATE(M) COMP=6 $ IBTE
DEFINE P(3) AS STREAM=4 RATE(M) COMP=7 $ MTBE
DEFINE P(4) AS STREAM=6 RATE(M) COMP=8 $ MEOH
DEFINE P(5) AS STREAM=6 RATE(M) COMP=6 $ IBTE
DEFINE P(6) AS STREAM=6 RATE(M) COMP=7 $ MTBE
DEFINE P(7) AS STREAM=7 RATE(M) COMP=8 $ MEOH
DEFINE P(8) AS STREAM=7 RATE(M) COMP=6 $ IBTE
DEFINE P(9) AS STREAM=7 RATE(M) COMP=7 $ MTBE
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
13
Methanol Recovery
The methanol recovery section of the process is shown in Figure 4.
Figure 4: Methanol 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).
81
Keyword
Syntax
HX UID=HX-3, NAME=COOLER
HOT FEED=6P, L=9, DP=34.5
OPER HTEMP=38
UTIL WATER, TIN=16, TOUT=32

79
Keyword
Syntax
COLUMN UID=T-2, NAME=WATER WASH
PARA TRAY=5, LLEX=25
FEED 9,5 / 10,1
PROD OVHD=11, BTMS=12,185
PSPEC TOP=792
ESTI MODEL=SIMPLE
METHOD SET=S2
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 (S2) 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).
81
Keyword
Syntax
HX UID=HX4A, NAME=FEED-BTMS
COLD FEED=12, L=13, DP=34.5
OPER CTEMP=99
14
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.
53
Keyword
Syntax
VALVE UID=V-1, NAME=VALVE
FEED 13
PROD M=14
OPER PRES=241

51
Keyword
Syntax
FLASH UID=D-1, NAME=SEPARATOR
FEED 14
PROD L=16, V=15
ADIA

52
Keyword
Syntax
PUMP UID=P-2, NAME=FEED PUMP
FEED 16
PROD L=17
OPER EFFI=65, PRES=690
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 TFIX type condenser 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.
72
Keyword
Syntax
COLUMN UID=T-3, NAME=MEOH COLUMN
PARA TRAY=20, IO=10
FEED 17,10
PROD OVHD=19, BTMS=18,182
PSPEC TOP=138, DPCOL=34.5
DUTY 1,1 / 2,20
COND TYPE=TFIX, PRES=103.5, TEMP=30
VARY DUTY=1,2
ESTI MODEL=CONV, RRATIO=10
SPEC STRM=19, COMP= 8, RATE, DIVIDE, &
STRM=17, COMP= 8, RATE, VALUE=0.995
SPEC STRM=18, COMP=10, RATE, DIVIDE, &
STRM=17, COMP=10, RATE, VALUE=0.9995
TRATE SECTION(1)=2,19, SIEVE, DIAMETER=610
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.
121
Keyword
Syntax
CALC UID=CAL1, NAME=MAKEUP
SEQUENCE STREAM=MKUP
DEFINE P(1) AS STRM=11, COMP=10, RATE $ H2O IN C4S
DEFINE P(2) AS STRM=15, COMP=10, RATE $ H2O IN FLARE GAS
DEFINE P(3) AS STRM=19, COMP=10, RATE $ H2O TO REACTOR
PROCEDURE
R(1) = P(1) + P(2) + P(3)
CALL SRXSTR(SMR,R(1),MKUP)
RETURN
Pump P-4 pumps the recovered wash water from the methanol column bottoms combined with
make-up water as stream 21 to heat exchanger HX4B. This unit represents the hot side of the exchanger
HX-4 (see HX-4A described previously) and calculates the exit temperature for stream 22.
15
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, an HXRIG module 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 exchangers 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 m
2
-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.
52
Keyword
Syntax
PUMP UID=P-4, NAME=WATER PUMP
FEED 18,MKUP
PROD L=21
OPER EFFI=65, PRES=862

81
Keyword
Syntax
HX UID=HX4B, NAME=FEED-BOTS
HOT FEED=21, L=22, DP=34.5
DEFINE DUTY AS HX=HX4A, DUTY

81
Keyword
Syntax
HX UID=HX-5, NAME=COOLER
HOT FEED=22, L=10, DP=34.5
OPER HTEMP=38

52
Keyword
Syntax
PUMP UID=P-3, NAME=RECYCLE PUMP
FEED 19
PROD L=20
OPER PRES=1724, EFFI=65

82
Keyword
Syntax
HXRIG UID=RC-1, NAME=T-3 COND
TYPE TEMA=AES
SHELL ID=381
TUBES OD=19, BWG=14, LENGTH=4.75, PASS=2, &
PATTERN=90, PITCH=25.4, FOUL=0.00035, FEED=CW, L=WOUT
BAFFLE CUT=0.18
TNOZZLE ID=102, 102
SNOZZLE ID=152, 102
PRINT EXTENDED , ZONES
ATTACH COLUMN=T-3, TYPE=CONDENSER
Finally, the beginning and ending units for the two recycle loops are defined, and the Wegstein
recycle acceleration method is chosen to speed up the convergence.
134
Keyword
Syntax
RECYCLE DATA

ACCEL TYPE=WEGS
LOOP NO=1, START=T-2, END=HX-5
LOOP NO=2, START=HX-1, END=P-3
16
Techni cal Resul ts
The overall mole balance for a 200,000 metric tonne per day MTBE plant using the reactive
distillation process is shown in Table 5.
Tabl e 5: Overal l Mol e Bal ance for a 200, 000 TPY MTBE Pl ant (Ethermax Process) (kg-mol /hr)
Materi al FEEDS PRODUCTS
C4s Feed Methanol Water
Makeup
MTBE
Product
Unreacted
C4s
Fl are Gas
N-butane
76.50
----- ----- trace
76.50 0.003
Iso-butane
348.50
----- ----- -----
348.49 0.012
1-butene
59.50
----- ----- -----
59.50
trace
cis 2-butene
34.00
-------- -------- trace
34.00
trace
trans 2-butene
51.00
-------- -------- trace
51.00
trace
Isobutene (IBTE)
280.50
-------- -------- --------
2.26
--------
MTBE -------- -------- -------- 277.35 trace --------
Methanol -------- 277.5 -------- 0.11 trace
0.001
tert-butanol -------- -------- -------- 0.19 -------- --------
Water -------- -------- 0.61 --------
0.41 0.011
Di-isobutylene -------- -------- -------- 0.35 -------- --------
TOTAL
850.00
277.5 0.61 278.00
572.16 0.03
Resul ts Anal ysi s
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:
M Methanol to IBTE ratio
M Number of reaction trays
M Type of catalyst used
Note, however, that while the IBTE conversion in the conversion reactors increase 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.
Output Resul ts
Selected results are attached. These include reactor RX-1, rigorous exchanger RC-1 zones
analysis, MTBE column T-1 (reactive distillation), tray rating results for methanol column T-3,
and stream molar component rates for selected streams.
17
Addi ti onal 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 Petro-
chemasia 94 Conference in Singapore, December 7-8 1994.
18
Appendi x A
Keyword Input File ---- Reactive Distillation (Ethermax) Process
TITLE PROJECT = MTBECASEBOOK , &
PROBLEM = MTBE PLANT , &
USER = SIMSCI , &
DATE = Mar95

DIMENSION SI, TEMP=C
PRINT INPUT = ALL , &
STREAM = COMPONENT , &
MBAL
SEQUENCE 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

COMP DATA

LIBID 1,NC4 / & $ N-BUTANE
2,IC4 / & $ I-BUTANE
3,1BUTENE / & $ BUTENE-1
4,BTC2 / & $ CIS BUTENE-2
5,BTT2 / & $ TRANS BUTENE-2
6,IBTE / & $ ISO BUTENE
7,MTBE / & $ METHYL TERTIARY BUTYL ETHER
8,MEOH / & $ METHANOL
9,TBA / & $ TERT BUTYL ALCOHOL
10,H2O / & $ WATER
11,244TM1P,,DIB $ DI-ISO BUTYLENE & ISOMERS


THERMO DATA


METHOD SYSTEM=SRKM, TRANSPORT=PURE, SET=S1
KVAL
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,-0.145000,-0.253000,0,0,0,0,1,1
SRKM 7,11, 0.05785, -0.0093,-10.144,6.17,0,0,1,1

METHOD SYSTEM(VLLE)=SRKM, L1KEY=1, L2KEY=10, SET=S2
KVAL
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,-0.145000,-0.253000,0,0,0,0,1,1
SRKM 7,11, 0.05785, -0.0093,-10.144,6.17,0,0,1,1


STREAM DATA

19
PROP STRM= 1, TEMP=16, PRES=1620, COMP=8,277.5
PROP STRM= 2, TEMP=16, PRES=1620, COMP=9/41/7/4/6/33, &
RATE=850, NORMALIZE
PROP STRM=10, TEMP=38, PRES=793, COMP=10,375
PROP STRM=20, TEMP=44, PRES=1724, COMP=8,4.0/10,0.3
$
$ INCREASE MTBE COLUMN CONDENSER COOLING WATER FLOWRATE
$
$ PROP STRM=CW, TEMP=21, PRES=690, COMP=10,100, RATE(V)=75
PROP STRM=CW, TEMP=21, PRES=690, COMP=10,100, RATE(V)=175
PROP STRM=MKUP, TEMP=38, PRES=350, COMP=10,500

NAME 1, MEOH FEED / 2, OLEFINS / 20, MEOH RECYC / &
6, T-1 OVHD / 8, MTBE / 11, C4S / &
15, FLARE GAS / MKUP,MKUP WATER


RXDATA
$
$ Reaction Data for Reactors
$

RXSET ID=ST1
REACTION ID=1
STOIC 6,-2 / 11,1 $ IBTE + IBTE = DIB
REACTION ID=2
STOIC 10,-1 / 6,-1 / 9,1 $ H2O + IBTE = TBA
REACTION ID=3
STOIC 6,-1 / 8,-1 / 7,1 $ IBTE + MEOH = MTBE

$
$ ======================================================================
$ = =
$ = Reaction Data =
$ = =
$ = Column Reaction Data =
$ ======================================================================
$
$
$ ==================================================
$
$ MTBE REACTION SET - Supplemented Al-Jarallah
$
$ Iso-butane+Methanol - MTBE
$
RXSET ID=ALJX
REACTION ID=ALJ0
STOICH 6, -1/8, -1/7, 1
BASE COMP=8
KINETIC PROCEDURE=ALJD, POSITION=1

$
20
$ ======================================================================
$ = =
$ = PROCEDURE DATA =
$ = =
$ ======================================================================
$

PROCEDURE DATA

$ ======================================================================
$ = =
$ = PROCEDURE DATA for RXKINETIC REACTIONS =
$ = (Column Reaction PROCEDURES) =
$ = =
$ ======================================================================
$
$ ==================================================
$ ==================================================
$ ==================================================
$
$ Al-Jarallah MTBE Column Reaction Kinetics.
$
$ ==================================================
$ ==================================================
$ ==================================================
$
$
$
$ Also modified to remove catalyst based concentration
$ from reaction expression. To revert to paper, set
$ GCATX = GCAT. This will drop the reaction rate to
$ way below what seems realistic based on literature
$ data. As is, it is still low.
$
PROCEDURE(RXKINE) ID=ALJD,NAME=Al-Jarallah
$
$ Reference: 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
$
PDATA GCAT , RXFACT
REAL KS , KA , KC , KALJ , KREH1 , KREH2 , KIZQ , KEQREF
INTEGER IBTE , MEOH , MTBE
CODE
$
$ 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 wont 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 = 6
MTBE = 7
MEOH = 8
$
R = 8.314
21
$
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,
$ 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
RHOA=(XLIQ(MEOH)*DENS/GCATX)
RHOB=(XLIQ(IBTE)*DENS/GCATX)
RHOC=(XLIQ(MTBE)*DENS/GCATX)

22
$
$ -------- 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 OPS

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
PROD L=4
OPER TEMP=55, DP=69
RXCALC MODEL=STOIC
RXSTOIC RXSET=ST1
23
REACTION 1
BASE COMP=6
CONV 0.0025
REACTION 2
BASE COMP=10
CONV 1.00
REACTION 3
BASE COMP=8
CONV 0.93
$
$ Provide storage location (RESULT(1))
$ Note: RXFACT is not varied in this casebook,
$ but is set equal to 1.0 always
$
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

HX UID=HX-2A, NAME=FEED-BTMS-A
COLD FEED=4, L=5, DP=34.5
OPER CTEMP=72

$
$ Reactive Distillation.
COLUMN UID=T-1, NAME=MTBE COLUMN
PARA TRAY=30, CHEM=35

FEED 5, 15
PROD OVHD=6, BTMS=7,280

PSPEC TOP=621, DPCOL=76.5
COND TYPE=TFIX, PRES=621, TEMP=43.5
DUTY 1,1 / 2,30
VARY DUTY=1,2
SPEC STRM=7,RATE,VALUE=278.0
SPEC RRATIO, VALUE=1.1

PRINT PROP=ALL , COMP=M
PLOT LOG XCOMP=6,6/ 8, 8/ 7, 7/1,1
ESTI MODEL=SIMPLE

RXTRAY ALJX, 8 , 13
LVOL(M3) 8 , 5.0 / 13, 5.0
DEFINE GCAT AS 360.0
DEFINE RXFACT AS 1.0
TSIZE VALVE FF=80.0 DPCALC=0.0

$
$ Calculate RXDIST conversions.
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(M) COMP=8 $ MEOH
DEFINE P(2) AS STREAM=4 RATE(M) COMP=6 $ IBTE
DEFINE P(3) AS STREAM=4 RATE(M) COMP=7 $ MTBE
DEFINE P(4) AS STREAM=6 RATE(M) COMP=8 $ MEOH
DEFINE P(5) AS STREAM=6 RATE(M) COMP=6 $ IBTE
DEFINE P(6) AS STREAM=6 RATE(M) COMP=7 $ MTBE
DEFINE P(7) AS STREAM=7 RATE(M) COMP=8 $ MEOH
DEFINE P(8) AS STREAM=7 RATE(M) COMP=6 $ IBTE
DEFINE P(9) AS STREAM=7 RATE(M) COMP=7 $ MTBE
24
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 AS HX=HX-2A DUTY

PUMP UID=P-1, NAME=T-1 OVHD
FEED 6
PROD L=6P
OPER PRES=827, EFFI=65

HX UID=HX-3, NAME=COOLER
HOT FEED=6P, L=9, DP=34.5
OPER HTEMP=38
UTIL WATER, TIN=16, TOUT=32

COLUMN UID=T-2, NAME=WATER WASH
PARA TRAY=5, LLEX=25
FEED 9,5 / 10,1
PROD OVHD=11, BTMS=12,185
PSPEC TOP=792
ESTI MODEL=SIMPLE
METHOD SET=S2

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
PROD M=14
OPER PRES=241

FLASH UID=D-1, NAME=SEPARATOR
FEED 14
PROD L=16, V=15
ADIA

PUMP UID=P-2, NAME=FEED PUMP
FEED 16
PROD L=17
OPER EFFI=65, PRES=690

COLUMN UID=T-3, NAME=MEOH COLUMN
PARA TRAY=20, IO=10
FEED 17,10
PROD OVHD=19, BTMS=18,182
PSPEC TOP=138, DPCOL=34.5
DUTY 1,1 / 2,20
25
COND TYPE=TFIX, PRES=103.5, TEMP=30
VARY DUTY=1,2
ESTI MODEL=CONV, RRATIO=10
SPEC STRM=19, COMP= 8, RATE, DIVIDE, &
STRM=17, COMP= 8, RATE, VALUE=0.995
SPEC STRM=18, COMP=10, RATE, DIVIDE, &
STRM=17, COMP=10, RATE, VALUE=0.9995
TRATE SECTION(1)=2,19, SIEVE, DIAMETER=610

CALC UID=CAL1, NAME=MAKEUP
SEQUENCE STREAM=MKUP
DEFINE P(1) AS STRM=11, COMP=10, RATE $ H2O IN C4S
DEFINE P(2) AS STRM=15, COMP=10, RATE $ H2O IN FLARE GAS
DEFINE P(3) AS STRM=19, COMP=10, RATE $ H2O TO REACTOR
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
PROD L=21
OPER EFFI=65, PRES=862

HX UID=HX4B, NAME=FEED-BOTS
HOT FEED=21, L=22, DP=34.5
DEFINE DUTY AS HX=HX4A, DUTY

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
PROD L=20
OPER PRES=1724, EFFI=65

HXRIG UID=RC-1, NAME=T-3 COND
TYPE TEMA=AES
$
$ SIZE FOR UNFINNED TUBES
$
SHELL ID=381
TUBES OD=19, BWG=14, LENGTH=5.75, PASS=2, &
PATTERN=90, PITCH=25.4, FOUL=0.00035, FEED=CW, L=WOUT
BAFFLE CUT=0.18
TNOZZLE ID=102, 102
SNOZZLE ID=152, 102
PRINT EXTENDED , ZONES
ATTACH COLUMN=T-3, TYPE=CONDENSER


RECYCLE DATA

ACCEL TYPE=WEGS
LOOP NO=1, START=T-2, END=HX-5
LOOP NO=2, START=HX-1, END=P-3
26
APPENDIX B
Output File ---- Reactive Distillation (Ethermax) Process
The following are selected exerpts from the PRO/II output report. The complete output is
available from SimSci on floppy disk.
SIMULATION SCIENCES INC. R PAGE P-50
PROJECT MTBECASEBOOK PRO/II VERSION 4.02 386/EM
PROBLEM MTBE PLANT OUTPUT SIMSCI
CONVERSION REACTOR SUMMARY Mar95
==============================================================================

UNIT 2, RX-1, REACTORS

OPERATING CONDITIONS

REACTOR TYPE ISOTHERMAL REACTOR
DUTY, M*KJ/HR -12.3321
TOTAL HEAT OF REACTION AT 25.00 C, M*KJ/HR -19.6827

INLET OUTLET
--------------------- ---------------------
FEED 3
LIQUID PRODUCT 4
TEMPERATURE, C 43.50 55.00
PRESSURE, KPA 1585.5000 1516.5000


REACTION DATA

----------------- RATES, KG-MOL/HR -------------------- FRACTION
COMPONENT FEED CHANGE PRODUCT CONVERTED
------------------------------------ --------------------- --------------------- --------------------- ---------------------
1 NC4 76.5019 .0000 76.5019
2 IC4 348.5030 .0000 348.5030
3 1BUTENE 59.5000 .0000 59.5000
4 BTC2 34.0001 .0000 34.0001
5 BTT2 51.0000 .0000 51.0000
6 IBTE 280.5000 -262.8161 17.6839 .9370
7 MTBE 2.22240E-05 261.9277 261.9277
8 MEOH 281.6427 -261.9277 19.7150 .9300
9 TBA 4.49482E-13 .1871 .1871
10 H2O .1871 -.1871 .0000 1.0000
11 DIB .0000 .3506 .3506

TOTAL 1131.8350 -262.4655 869.3694

KG-MOL/HR FRACTION
BASE COMPONENT REACTION CONVERTED CONVERTED(1)
------------------------------------ --------------------- --------------------- ------------------------
6 IBTE 1 .7013 2.50000E-03
10 H2O 2 .1871 1.0000
8 MEOH 3 261.9277 .9300

(1) FRACTION CONVERTED BASED ON AMOUNT IN FEED
27
SIMULATION SCIENCES INC. R PAGE P-51
PROJECT MTBECASEBOOK PRO/II VERSION 4.02 386/EM
PROBLEM MTBE PLANT OUTPUT SIMSCI
CONVERSION REACTOR SUMMARY Mar95
==============================================================================

UNIT 2, RX-1, REACTORS (CONT)

REACTOR MASS BALANCE

--------------------- RATES, KG/HR ------------------------ FRACTION
COMPONENT FEED CHANGE PRODUCT CONVERTED
------------------------------------ --------------------- --------------------- --------------------- ---------------------
1 NC4 4446.5970 .0000 4446.5970
2 IC4 20256.3900 .0000 20256.3900
3 1BUTENE 3338.4280 .0000 3338.4280
4 BTC2 1907.6760 .0000 1907.6760
5 BTT2 2861.5090 .0000 2861.5090
6 IBTE 15738.2900 -14746.0800 992.2104 .9370
7 MTBE 1.95902E-03 23088.6700 23088.6700
8 MEOH 9024.3950 -8392.6870 631.7076 .9300
9 TBA 3.33174E-11 13.8712 13.8712
10 H2O 3.3712 -3.3712 .0000 1.0000
11 DIB .0000 39.3450 39.3450

TOTAL 57576.6600 -.2617 57576.4000
28
SIMULATION SCIENCES INC. R PAGE P-14
PROJECT MTBECASEBOOK PRO/II VERSION 4.02 386/EM
PROBLEM MTBE PLANT OUTPUT SIMSCI
RIGOROUS HEAT EXCHANGER SUMMARY Mar95
==============================================================================

UNIT 21, RC-1, T-3 COND

HEAT EXCHANGER IS ATTACHED TO COLUMN T-3, UNIT 15 AS A CONDENSER
OPERATING CONDITIONS OVERALL
---------------------
DUTY, M*KJ/HR 3.9720
LMTD, C 42.683
MTD, C 36.858
F FACTOR, (FT) .864
U*A, KW/K 29.935
U, KW/M2-K .876 .809 (REQD)
A, M2 36.981 34.160 (REQD)

SHELL SIDE CONDITIONS INLET OUTLET
--------------------- ---------------------
STREAM IS FROM COLUMN T-3 , UNIT 15
VAPOR, KG-MOL/HR 98.803 N/A
K*KG/HR 3.109 N/A
CP, KJ/KG-C 1.520 N/A
LIQUID, KG-MOL/HR N/A 98.803
K*KG/HR N/A 3.109
CP, KJ/KG-C N/A 2.538
TOTAL, KG-MOL/HR 98.803 98.803
K*KG/HR 3.109 3.109
CONDENSATION, KG-MOL/HR 98.803
L/F .0000 1.0000
TEMPERATURE, C 74.079 27.217
PRESSURE, KPA 138.000 91.775

TUBE SIDE CONDITIONS INLET OUTLET
--------------------- ---------------------
FEED(S) CW
PRODUCTS LIQUID WOUT
VAPOR, KG-MOL/HR N/A N/A
K*KG/HR N/A N/A
CP, KJ/KG-C N/A N/A
LIQUID, KG-MOL/HR 9700.201 9700.201
K*KG/HR 174.749 174.749
CP, KJ/KG-C 4.499 4.457
TOTAL, KG-MOL/HR 9700.201 9700.201
K*KG/HR 174.749 174.749
VAPORIZATION, KG-MOL/HR N/A
L/F 1.0000 1.0000
TEMPERATURE, C 21.000 26.164
PRESSURE, KPA 690.000 318.172
29
SIMULATION SCIENCES INC. R PAGE P-15
PROJECT MTBECASEBOOK PRO/II VERSION 4.02 386/EM
PROBLEM MTBE PLANT OUTPUT SIMSCI
RIGOROUS HEAT EXCHANGER SUMMARY Mar95
==============================================================================

SHELL AND TUBE EXCHANGER DATA SHEET FOR EXCHANGER RC-1
I--------------------------------------------------------------------------------------------------------------------------------------------------------I
I EXCHANGER NAME T-3 COND UNIT ID RC-1 I
I SIZE 381 - 5750 TYPE AES, HORIZONTAL CONNECTED 1 PARALLEL 1 SERIES I
I AREA/UNIT 37. M2 ( 34. M2 REQUIRED) AREA/SHELL 37. M2 I
I--------------------------------------------------------------------------------------------------------------------------------------------------------I
I PERFORMANCE OF ONE UNIT SHELL-SIDE TUBE-SIDE I
I--------------------------------------------------------------------------------------------------------------------------------------------------------I
I FEED STREAM ID CW I
I FEED STREAM NAME (ATTACHED) I
I TOTAL FLUID KG/HR 3109. 174749. I
I VAPOR (IN/OUT) KG/HR 3109. / / I
I LIQUID KG/HR / 3109. 174749. / 174749. I
I STEAM KG/HR / / I
I WATER KG/HR / / I
I NON CONDENSIBLE KG/HR I
I TEMPERATURE (IN/OUT) DEG C 74.1 / 27.2 21.0 / 26.2 I
I PRESSURE (IN/OUT) KPA 138.00 / 91.78 690.00 / 318.17 I
I--------------------------------------------------------------------------------------------------------------------------------------------------------I
I SP. GR., LIQ (4C / 4C H2O) / .800 1.000 / 1.000 I
I VAP (4C / 4C AIR) 1.087 / / I
I DENSITY, LIQUID KG/M3 / 787.360 993.997 / 989.495 I
I VAPOR KG/M3 1.538 / / I
I VISCOSITY, LIQUID PAS / 5.5E-04 9.8E-04 / 8.7E-04 I
I VAPOR PAS 1.1E-05 / / I
I THRML COND,LIQ W/M-K / .2003 .6051 / .6121 I
I VAP W/M-K .0192 / / I
I SPEC.HEAT,LIQUID KJ/KG-K / 2.5378 4.4992 / 4.4567 I
I VAPOR KJ/KG-K 1.5205 / / I
I LATENT HEAT KJ/KG 1157.83 I
I VELOCITY M/SEC .16 5.23 I
I DP/SHELL KPA 46.25 371.85 I
I FOULING RESIST M2-K/KW .35222 ( .44648 REQD) .00035 I
I--------------------------------------------------------------------------------------------------------------------------------------------------------I
I TRANSFER RATE KW/M2-K SERVICE .88 ( .81 REQD), CLEAN 1.27 I
I HEAT EXCHANGED M*KJ/HR 3.972 MTD(CORRECTED) 36.9 FT .864 I
I--------------------------------------------------------------------------------------------------------------------------------------------------------I
I CONSTRUCTION OF ONE SHELL SHELL-SIDE TUBE-SIDE I
I--------------------------------------------------------------------------------------------------------------------------------------------------------I
I DESIGN PRESSURE KPA 2068. 2068. I
I NUMBER OF PASSES 1 2 I
I MATERIAL CARB STL CARB STL I
I INLET NOZZLE ID MM 152.0 102.0 I
I OUTLET NOZZLE ID MM 102.0 102.0 I
I--------------------------------------------------------------------------------------------------------------------------------------------------------I
I TUBE: NUMBER 109 OD 19.000 MM BWG 14 LENGTH 5.8 M I
I TYPE BARE PITCH 25.4 MM PATTERN 90 DEGREES I
I SHELL: ID 381.00 MM SEALING STRIPS 0 PAIRS I
I BAFFLE: CUT .180 SPACING (IN/CENT/OUT): MM 93.70/ 76.20/ 93.70,SINGLE I
I RHO-V2: INLET NOZZLE 1473.0 KG/M-SEC2 I
I TOTAL WEIGHT/SHELL,KG 1007.4 FULL OF WATER 2655.4 BUNDLE 1062.8 I
I--------------------------------------------------------------------------------------------------------------------------------------------------------I
30
SIMULATION SCIENCES INC. R PAGE P-16
PROJECT MTBECASEBOOK PRO/II VERSION 4.02 386/EM
PROBLEM MTBE PLANT OUTPUT SIMSCI
RIGOROUS HEAT EXCHANGER SUMMARY Mar95
==============================================================================

SHELL AND TUBE EXTENDED DATA SHEET FOR EXCHANGER RC-1
I--------------------------------------------------------------------------------------------------------------------------------------------------------I
I EXCHANGER NAME T-3 COND UNIT ID RC-1 I
I SIZE 381 - 5750 TYPE AES, HORIZONTAL CONNECTED 1 PARALLEL 1 SERIES I
I AREA/UNIT 37. M2 ( 34. M2 REQUIRED) I
I--------------------------------------------------------------------------------------------------------------------------------------------------------I
I PERFORMANCE OF ONE UNIT SHELL-SIDE TUBE-SIDE I
I--------------------------------------------------------------------------------------------------------------------------------------------------------I
I FEED STREAM ID CW I
I FEED STREAM NAME (ATTACHED) I
I WT FRACTION LIQUID (IN/OUT) .000 / 1.000 1.000 / 1.000 I
I REYNOLDS NUMBER 52994. 81759. I
I PRANDTL NUMBER 5.045 6.936 I
I WATSON K,LIQUID / 10.599 8.762 / 8.762 I
I VAPOR 10.599 / / I
I SURFACE TENSION N/M / .024 .072 / .072 I
I FILM COEF(SCL) KW/M2-K 1.9 (1.000) 15.6 (1.000) I
I FOULING LAYER THICKNESS MM .000 .000 I
I--------------------------------------------------------------------------------------------------------------------------------------------------------I
I THERMAL RESISTANCE I
I UNITS: ( M2-K/KW ) (PERCENT) (ABSOLUTE) I
I SHELL FILM 52.00 .52123 I
I TUBE FILM 8.24 .08260 I
I TUBE METAL 4.58 .04593 I
I TOTAL FOULING 35.18 .35267 I
I ADJUSTMENT 8.26 .08280 I
I--------------------------------------------------------------------------------------------------------------------------------------------------------I
I PRESSURE DROP SHELL-SIDE TUBE-SIDE I
I UNITS: (KPA) (PERCENT) (ABSOLUTE) (PERCENT) (ABSOLUTE)I
I WITHOUT NOZZLES 97.00 44.87 76.94 286.11 I
I INLET NOZZLES 2.95 1.36 8.46 31.48 I
I OUTLET NOZZLES .05 .02 14.59 54.27 I
I TOTAL /SHELL 46.25 371.85 I
I TOTAL /UNIT 46.25 371.85 I
I DP SCALER 1.00 1.00 I
I--------------------------------------------------------------------------------------------------------------------------------------------------------I
I CONSTRUCTION OF ONE SHELL I
I--------------------------------------------------------------------------------------------------------------------------------------------------------I
I TUBE:OVERALL LENGTH 5.8 M EFFECTIVE LENGTH 5.33 M I
I TOTAL TUBESHEET THK 66.0 MM AREA RATIO (OUT/IN) 1.285 I
I THERMAL COND 51.9 W/M-K DENSITY 7862.00 KG/M3I
I--------------------------------------------------------------------------------------------------------------------------------------------------------I
I BAFFLE: THICKNESS 4.762 MM NUMBER 74 I
I--------------------------------------------------------------------------------------------------------------------------------------------------------I
I BUNDLE: DIAMETER 327.0 MM TUBES IN CROSSFLOW 92 I
I CROSSFLOW AREA .010 M2 WINDOW AREA .012 M2 I
I WINDOW HYD DIA 40.63 MM I
I TUBE-BFL LEAK AREA .002 M2 SHELL-BFL LEAK AREA .001 M2 I
I--------------------------------------------------------------------------------------------------------------------------------------------------------I
31
SIMULATION SCIENCES INC. R PAGE P-17
PROJECT MTBECASEBOOK PRO/II VERSION 4.02 386/EM
PROBLEM MTBE PLANT OUTPUT SIMSCI
RIGOROUS HEAT EXCHANGER SUMMARY Mar95
==============================================================================

ZONE ANALYSIS FOR EXCHANGER RC-1

TEMPERATURE - PRESSURE SUMMARY

---------------- TEMPERATURE, C ------------- ---------------- PRESSURE, KPA -------------
SHELL-SIDE TUBE-SIDE SHELL-SIDE TUBE-SIDE
ZONE IN OUT IN OUT IN OUT IN OUT
-------- ------------- ------------- ------------- ------------- ------------- ------------- ------------- -------------
1 74.1 69.6 21.6 26.2 138.0 122.6 643.4 318.2
2 69.6 65.0 21.4 21.6 122.6 107.2 658.7 643.4
3 65.0 60.5 21.4 21.4 107.2 91.8 663.8 658.7
4 60.5 27.2 21.0 21.4 91.8 91.8 690.0 663.8

HEAT TRANSFER AND PRESSURE DROP SUMMARY

------------ HEAT TRANSFER --------- PRESSURE DROP (TOTAL) - FILM COEFFICIENT -
MECHANISM KPA KW/M2-K
ZONE SHELL-SIDE TUBE-SIDE SHELL-SIDE TUBE-SIDE SHELL-SIDE TUBE-SIDE
-------- ------------------------ ------------------------ -------------------- ----------------- -------------------- -----------------
1 CONDENSATION LIQ. HEATING 15.408 325.273 2.998 15.917
2 CONDENSATION LIQ. HEATING 15.408 15.245 1.405 15.310
3 CONDENSATION LIQ. HEATING 15.408 5.090 .656 15.179
4 LIQ. SUBCOOL LIQ. HEATING .000 26.220 .478 15.088
-------------------- -----------------
TOTAL PRESSURE DROP 46.225 371.828

HEAT TRANSFER SUMMARY (CONT)

------------ DUTY ------------- U-VALUE AREA LMTD FT
ZONE M*KJ/HR PERCENT KW/M2-K M2 C
-------- ----------------- ------------- ------------------------ -------------------- ----------------- ----------------
1 3.47 87.48 1.23 18.96 47.91 .864
2 .16 4.10 .84 1.37 45.71 .864
3 .05 1.37 .50 .85 41.32 .864
4 .28 7.05 .39 12.98 17.89 .864
----------------- ------------- ------------------------ -------------------- ----------------- ----------------
TOTAL 3.97 100.00 34.16
WEIGHTED .88 42.68 .864
OVERALL 20.42 .864
INSTALLED 36.98

TOTAL DUTY = (WT. U-VALUE) (TOTAL AREA) (WT. LMTD) (OVL. FT)
ZONE DUTY = (ZONE U-VALUE) (ZONE AREA) (ZONE LMTD) (OVL. FT)
32
SIMULATION SCIENCES INC. R PAGE P-19
PROJECT MTBECASEBOOK PRO/II VERSION 4.02 386/EM
PROBLEM MTBE PLANT OUTPUT SIMSCI
COLUMN SUMMARY Mar95
==============================================================================

UNIT 5, T-1, MTBE COLUMN

TOTAL NUMBER OF ITERATIONS

CHEM METHOD 38


COLUMN 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 -23.5395
2 50.8 621.00 661.3 1209.5
3 51.5 623.73 659.0 1237.2
4 52.0 626.46 657.6 1235.0
5 52.3 629.20 656.4 1233.6
6 52.7 631.93 654.5 1232.3
7 53.1 634.66 650.4 1230.5
8 53.8 637.39 633.1 1226.3
9 54.8 640.12 610.5 1211.6
10 56.5 642.86 578.0 1191.6
11 59.4 645.59 534.9 1161.9
12 63.8 648.32 489.4 1121.9
13 68.7 651.05 458.5 1079.8
14 73.3 653.79 441.1 1049.8
15 76.7 656.52 1202.6 1032.5 869.4M
16 90.4 659.25 1170.9 924.6
17 104.8 661.98 1188.8 892.9
18 114.9 664.71 1223.4 910.8
19 120.6 667.45 1251.4 945.4
20 123.7 670.18 1269.5 973.4
21 125.4 672.91 1280.7 991.5
22 126.4 675.64 1287.8 1002.7
23 127.0 678.37 1292.7 1009.8
24 127.5 681.11 1296.2 1014.7
25 127.8 683.84 1298.9 1018.2
26 128.1 686.57 1301.1 1020.9
27 128.4 689.30 1303.0 1023.1
28 128.6 692.04 1304.7 1025.0
29 128.8 694.77 1306.2 1026.7
30R 129.1 697.50 1028.2 278.0L 23.5465
33
SIMULATION SCIENCES INC. R PAGE P-20
PROJECT MTBECASEBOOK PRO/II VERSION 4.02 386/EM
PROBLEM MTBE PLANT OUTPUT SIMSCI
COLUMN SUMMARY Mar95
==============================================================================

UNIT 5, T-1, MTBE COLUMN (CONT)

FEED AND PRODUCT STREAMS

TYPE STREAM PHASE FROM TO LIQUID FLOW RATES HEAT RATES
TRAY TRAY FRAC KG-MOL/HR M*KJ/HR
--------- ------------------------ ------------ -------- -------- ------------ ------------------------ ------------------------
FEED 5 MIXED 15 .9471 869.37 9.8626
PROD 6 LIQUID 1 575.94 3.4055
PROD 7 LIQUID 30 278.00 7.1853

OVERALL MOLE BALANCE, (FEEDS - PRODUCTS) 15.43
TOTAL HEAT OF REACTION AT STANDARD CONDITIONS -1.1572
TOTAL HEAT OF REACTION AT PROII ENTHALPY BASIS CONDITIONS -.7213
OVERALL HEAT BALANCE, (H(IN) - H(OUT) ) -6.6467E-06


SPECIFICATIONS

PARAMETER TRAY COMP SPECIFICATION SPECIFIED CALCULATED
TYPE NO NO TYPE VALUE VALUE
--------------------------------- -------- ------------ ------------------------- -------------------- --------------------
STRM 7 30 MOL RATE 2.780E+02 2.780E+02
UNIT T-1 1 RRATIO 1.100E+00 1.100E+00


REFLUX RATIOS

---------------- REFLUX RATIOS ----------------
MOLAR WEIGHT STD L VOL
----------------- ----------------- -----------------
REFLUX / FEED STREAM 5 .7287 .6318 .6974
REFLUX / LIQUID DISTILLATE 1.1000 1.1000 1.1000
34
SIMULATION SCIENCES INC. R PAGE P-36
PROJECT MTBECASEBOOK PRO/II VERSION 4.02 386/EM
PROBLEM MTBE PLANT OUTPUT SIMSCI
COLUMN SUMMARY Mar95
==============================================================================

UNIT 5, T-1, MTBE COLUMN (CONT)

MOLAR REACTION RATES KG-MOL/HR

COMPONENT TRAY 1 TRAY 2 TRAY 3 TRAY 4
-------------------- -------------------- -------------------- --------------------
1 NC4 .0000 .0000 .0000 .0000
2 IC4 .0000 .0000 .0000 .0000
3 1BUTENE .0000 .0000 .0000 .0000
4 BTC2 .0000 .0000 .0000 .0000
5 BTT2 .0000 .0000 .0000 .0000
6 IBTE .0000 .0000 .0000 .0000
7 MTBE .0000 .0000 .0000 .0000
8 MEOH .0000 .0000 .0000 .0000
9 TBA .0000 .0000 .0000 .0000
10 H2O .0000 .0000 .0000 .0000
11 DIB .0000 .0000 .0000 .0000

TEMPERATURE, DEG C 43.500 50.775 51.471 51.952
PRESSURE, KPA 621.000 621.000 623.732 626.464


COMPONENT TRAY 5 TRAY 6 TRAY 7 TRAY 8
-------------------- -------------------- -------------------- --------------------
1 NC4 .0000 .0000 .0000 .0000
2 IC4 .0000 .0000 .0000 .0000
3 1BUTENE .0000 .0000 .0000 .0000
4 BTC2 .0000 .0000 .0000 .0000
5 BTT2 .0000 .0000 .0000 .0000
6 IBTE .0000 .0000 .0000 -2.5733
7 MTBE .0000 .0000 .0000 2.5733
8 MEOH .0000 .0000 .0000 -2.5733
9 TBA .0000 .0000 .0000 .0000
10 H2O .0000 .0000 .0000 .0000
11 DIB .0000 .0000 .0000 .0000

TEMPERATURE, DEG C 52.319 52.657 53.069 53.759
PRESSURE, KPA 629.196 631.928 634.661 637.393
VOLUME, M3 5.000
35
SIMULATION SCIENCES INC. R PAGE P-37
PROJECT MTBECASEBOOK PRO/II VERSION 4.02 386/EM
PROBLEM MTBE PLANT OUTPUT SIMSCI
COLUMN SUMMARY Mar95
==============================================================================

UNIT 5, T-1, MTBE COLUMN (CONT)

COMPONENT TRAY 9 TRAY 10 TRAY 11 TRAY 12
-------------------- -------------------- -------------------- --------------------
1 NC4 .0000 .0000 .0000 .0000
2 IC4 .0000 .0000 .0000 .0000
3 1BUTENE .0000 .0000 .0000 .0000
4 BTC2 .0000 .0000 .0000 .0000
5 BTT2 .0000 .0000 .0000 .0000
6 IBTE -2.5327 -2.8062 -3.1954 -3.2871
7 MTBE 2.5327 2.8062 3.1954 3.2871
8 MEOH -2.5327 -2.8062 -3.1954 -3.2871
9 TBA .0000 .0000 .0000 .0000
10 H2O .0000 .0000 .0000 .0000
11 DIB .0000 .0000 .0000 .0000

TEMPERATURE, DEG C 54.763 56.481 59.417 63.760
PRESSURE, KPA 640.125 642.857 645.589 648.321
VOLUME, M3 5.000 5.000 5.000 5.000


COMPONENT TRAY 13 TRAY 14 TRAY 15 TRAY 16
-------------------- -------------------- -------------------- --------------------
1 NC4 .0000 .0000 .0000 .0000
2 IC4 .0000 .0000 .0000 .0000
3 1BUTENE .0000 .0000 .0000 .0000
4 BTC2 .0000 .0000 .0000 .0000
5 BTT2 .0000 .0000 .0000 .0000
6 IBTE -1.0336 .0000 .0000 .0000
7 MTBE 1.0336 .0000 .0000 .0000
8 MEOH -1.0336 .0000 .0000 .0000
9 TBA .0000 .0000 .0000 .0000
10 H2O .0000 .0000 .0000 .0000
11 DIB .0000 .0000 .0000 .0000

TEMPERATURE, DEG C 68.742 73.285 76.662 90.407
PRESSURE, KPA 651.053 653.785 656.518 659.250
VOLUME, M3 5.000


COMPONENT TRAY 17 TRAY 18 TRAY 19 TRAY 20
-------------------- -------------------- -------------------- --------------------
1 NC4 .0000 .0000 .0000 .0000
2 IC4 .0000 .0000 .0000 .0000
3 1BUTENE .0000 .0000 .0000 .0000
4 BTC2 .0000 .0000 .0000 .0000
5 BTT2 .0000 .0000 .0000 .0000
6 IBTE .0000 .0000 .0000 .0000
7 MTBE .0000 .0000 .0000 .0000
8 MEOH .0000 .0000 .0000 .0000
9 TBA .0000 .0000 .0000 .0000
10 H2O .0000 .0000 .0000 .0000
11 DIB .0000 .0000 .0000 .0000
36
SIMULATION SCIENCES INC. R PAGE P-38
PROJECT MTBECASEBOOK PRO/II VERSION 4.02 386/EM
PROBLEM MTBE PLANT OUTPUT SIMSCI
COLUMN SUMMARY Mar95
==============================================================================

UNIT 5, T-1, MTBE COLUMN (CONT)

TRAY 17 TRAY 18 TRAY 19 TRAY 20
-------------------- -------------------- -------------------- --------------------
TEMPERATURE, DEG C 104.758 114.861 120.615 123.696
PRESSURE, KPA 661.982 664.714 667.446 670.178


COMPONENT TRAY 21 TRAY 22 TRAY 23 TRAY 24
-------------------- -------------------- -------------------- --------------------
1 NC4 .0000 .0000 .0000 .0000
2 IC4 .0000 .0000 .0000 .0000
3 1BUTENE .0000 .0000 .0000 .0000
4 BTC2 .0000 .0000 .0000 .0000
5 BTT2 .0000 .0000 .0000 .0000
6 IBTE .0000 .0000 .0000 .0000
7 MTBE .0000 .0000 .0000 .0000
8 MEOH .0000 .0000 .0000 .0000
9 TBA .0000 .0000 .0000 .0000
10 H2O .0000 .0000 .0000 .0000
11 DIB .0000 .0000 .0000 .0000

TEMPERATURE, DEG C 125.389 126.389 127.035 127.493
PRESSURE, KPA 672.910 675.642 678.374 681.107


COMPONENT TRAY 25 TRAY 26 TRAY 27 TRAY 28
-------------------- -------------------- -------------------- --------------------
1 NC4 .0000 .0000 .0000 .0000
2 IC4 .0000 .0000 .0000 .0000
3 1BUTENE .0000 .0000 .0000 .0000
4 BTC2 .0000 .0000 .0000 .0000
5 BTT2 .0000 .0000 .0000 .0000
6 IBTE .0000 .0000 .0000 .0000
7 MTBE .0000 .0000 .0000 .0000
8 MEOH .0000 .0000 .0000 .0000
9 TBA .0000 .0000 .0000 .0000
10 H2O .0000 .0000 .0000 .0000
11 DIB .0000 .0000 .0000 .0000

TEMPERATURE, DEG C 127.845 128.136 128.389 128.620
PRESSURE, KPA 683.839 686.571 689.303 692.035
37
SIMULATION SCIENCES INC. R PAGE P-39
PROJECT MTBECASEBOOK PRO/II VERSION 4.02 386/EM
PROBLEM MTBE PLANT OUTPUT SIMSCI
COLUMN SUMMARY Mar95
==============================================================================

UNIT 5, T-1, MTBE COLUMN (CONT)

COMPONENT TRAY 29 TRAY 30
-------------------- --------------------
1 NC4 .0000 .0000
2 IC4 .0000 .0000
3 1BUTENE .0000 .0000
4 BTC2 .0000 .0000
5 BTT2 .0000 .0000
6 IBTE .0000 .0000
7 MTBE .0000 .0000
8 MEOH .0000 .0000
9 TBA .0000 .0000
10 H2O .0000 .0000
11 DIB .0000 .0000

TEMPERATURE, DEG C 128.841 129.067
PRESSURE, KPA 694.767 697.500
38
SIMULATION SCIENCES INC. R PAGE P-48
PROJECT MTBECASEBOOK PRO/II VERSION 4.02 386/EM
PROBLEM MTBE PLANT OUTPUT SIMSCI
COLUMN SUMMARY Mar95
==============================================================================

UNIT 15, T-3, MEOH COLUMN (CONT)

TRAY RATING MECHANICAL DATA

SECTION TRAY DIAM TRAY SPACE SF ------------- TRAY ----------------
NUMBERS MM PASSES MM TYPE METAL THK, MM
------------- ----------------- -------- ------------ --------- -------- --------- --------- -------------
1 2 - 19 610. 1 610. 1.00 SIEVE SS 1.880



SECTION NO VALVES VALVE CAP TO SIEVE UNIT ++ WEIR HT DC CLEAR
OR CAPS THK,MM CAP, MM PCT DIA, MM MM MM
------------- ----------------- ------------ ------------- --------- ------------- ------------- ----------------
1 N/A N/A N/A 12.00 12.700 50.800 38.100

++ DIAMETER OF VALVES, SIEVE HOLES, OR BUBBLE CAPS


SECTION DOWNCOMER WIDTHS, MM SLOPED DC WIDTHS, MM
SIDE CENTER OFF-CTR OFF-SIDE SIDE CENTER OFF-CTR OFF-SIDE
------------- --------- ------------ ------------- ---------------- --------- ------------ ------------- ----------------
1 N/A N/A N/A N/A N/A N/A N/A N/A


TRAY RATING RESULTS

PRES DOWNCOMER
TRAY VAPOR LIQUID VLOAD DIAM FF DROP GPM/LWI BACKUP, PCT
CFS HOTGPM CFS MM KPA GPM/IN TRAY SPACING
-------- --------- ------------ --------- ------------ -------- ------------ ---------------- ------------------------
2 21.45 18.73 .968 610.0 81.0 .847 1.5 30.18
3 21.08 17.00 .915 610.0 76.7 .793 1.4 28.51
4 20.66 13.57 .813 610.0 68.7 .705 1.2 25.54
5 20.38 9.72 .688 610.0 59.2 .627 .9 22.46
6 20.38 8.44 .644 610.0 55.9 .611 .8 21.51
7 20.25 8.24 .634 610.0 55.1 .607 .8 21.33
8 20.04 8.22 .630 610.0 54.7 .604 .8 21.27
9 19.81 8.22 .627 610.0 54.3 .601 .8 21.22
10 21.18 42.11 .670 610.0 71.1 .795 2.6 27.45
11 21.06 42.06 .666 610.0 70.7 .791 2.6 27.37
12 20.92 42.04 .663 610.0 70.4 .788 2.6 27.31
13 20.78 42.04 .661 610.0 70.1 .785 2.6 27.26
14 20.62 42.05 .659 610.0 69.8 .782 2.6 27.21
15 20.47 42.07 .657 610.0 69.5 .780 2.6 27.17
16 20.31 42.10 .655 610.0 69.2 .778 2.6 27.14
17 20.15 42.13 .653 610.0 68.9 .776 2.6 27.11
18 20.00 42.17 .652 610.0 68.7 .774 2.6 27.08
19 19.85 42.20 .650 610.0 68.4 .772 2.6 27.05


39
SIMULATION SCIENCES INC. R PAGE P-49
PROJECT MTBECASEBOOK PRO/II VERSION 4.02 386/EM
PROBLEM MTBE PLANT OUTPUT SIMSCI
COLUMN SUMMARY Mar95
==============================================================================

UNIT 15, T-3, MEOH COLUMN (CONT)

ESTIMATED TRAY MECHANICAL DETAILS

SECTION TRAY ------------ DOWNCOMER WIDTHS, MM -------------------- NO VALVES
SIDE CENTER OFF-CTR OFF-SIDE OR CAPS
------------- -------- ------------- -------------------- ----------------- ----------------- -----------------
1 2 47.32 N/A N/A N/A N/A
1 3 44.31 N/A N/A N/A N/A
1 4 38.05 N/A N/A N/A N/A
1 5 30.39 N/A N/A N/A N/A
1 6 27.63 N/A N/A N/A N/A
1 7 27.19 N/A N/A N/A N/A
1 8 27.14 N/A N/A N/A N/A
1 9 27.15 N/A N/A N/A N/A
1 10 82.22 N/A N/A N/A N/A
1 11 82.15 N/A N/A N/A N/A
1 12 82.13 N/A N/A N/A N/A
1 13 82.12 N/A N/A N/A N/A
1 14 82.14 N/A N/A N/A N/A
1 15 82.17 N/A N/A N/A N/A
1 16 82.21 N/A N/A N/A N/A
1 17 82.25 N/A N/A N/A N/A
1 18 82.29 N/A N/A N/A N/A
1 19 82.34 N/A N/A N/A N/A


* NOTE THIS VALUE WAS NOT CALCULATED
40
SIMULATION SCIENCES INC. R PAGE P-52
PROJECT MTBECASEBOOK PRO/II VERSION 4.02 386/EM
PROBLEM MTBE PLANT OUTPUT SIMSCI
STREAM MOLAR COMPONENT RATES Mar95
==============================================================================

STREAM ID CW MKUP WOUT 1
NAME MKUP WATER MEOH FEED
PHASE LIQUID LIQUID LIQUID LIQUID

FLUID RATES, KG-MOL/HR
1 NC4 .0000 .0000 .0000 .0000
2 IC4 .0000 .0000 .0000 .0000
3 1BUTENE .0000 .0000 .0000 .0000
4 BTC2 .0000 .0000 .0000 .0000
5 BTT2 .0000 .0000 .0000 .0000
6 IBTE .0000 .0000 .0000 .0000
7 MTBE .0000 .0000 .0000 .0000
8 MEOH .0000 .0000 .0000 277.5000
9 TBA .0000 .0000 .0000 .0000
10 H2O 9700.2010 .6086 9700.2010 .0000
11 DIB .0000 .0000 .0000 .0000

TOTAL RATE, KG-MOL/HR 9700.2010 .6086 9700.2010 277.5000

TEMPERATURE, C 21.0000 38.0000 26.1637 16.0000
PRESSURE, KPA 690.0000 350.0000 318.1725 1620.0000
ENTHALPY, M*KJ/HR 12.2424 1.5901E-03 16.2145 -.0626
MOLECULAR WEIGHT 18.0150 18.0150 18.0150 32.0420
MOLE FRAC VAPOR .0000 .0000 .0000 .0000
MOLE FRAC LIQUID 1.0000 1.0000 1.0000 1.0000


STREAM ID 2 3 4 5
NAME OLEFINS
PHASE LIQUID LIQUID LIQUID LIQUID

FLUID RATES, KG-MOL/HR
1 NC4 76.5000 76.5019 76.5019 76.5019
2 IC4 348.5000 348.5030 348.5030 348.5030
3 1BUTENE 59.5000 59.5000 59.5000 59.5000
4 BTC2 34.0000 34.0001 34.0001 34.0001
5 BTT2 51.0000 51.0000 51.0000 51.0000
6 IBTE 280.5000 280.5000 17.6839 17.6839
7 MTBE .0000 2.2224E-05 261.9277 261.9277
8 MEOH .0000 281.6427 19.7150 19.7150
9 TBA .0000 4.4948E-13 .1871 .1871
10 H2O .0000 .1871 .0000 .0000
11 DIB .0000 .0000 .3506 .3506

TOTAL RATE, KG-MOL/HR 850.0000 1131.8350 869.3694 869.3694
41
SIMULATION SCIENCES INC. R PAGE P-53
PROJECT MTBECASEBOOK PRO/II VERSION 4.02 386/EM
PROBLEM MTBE PLANT OUTPUT SIMSCI
STREAM MOLAR COMPONENT RATES Mar95
==============================================================================

STREAM ID 2 3 4 5
NAME OLEFINS
PHASE LIQUID LIQUID LIQUID LIQUID

TEMPERATURE, C 16.0000 43.5000 55.0000 72.0000
PRESSURE, KPA 1620.0000 1585.5000 1516.5000 1482.0000
ENTHALPY, M*KJ/HR 1.6339 7.4660 7.4127 9.8625
MOLECULAR WEIGHT 57.1160 50.8702 66.2278 66.2278
MOLE FRAC VAPOR .0000 .0000 .0000 .0000
MOLE FRAC LIQUID 1.0000 1.0000 1.0000 1.0000


STREAM ID 6 6P 7 8
NAME T-1 OVHD MTBE
PHASE LIQUID LIQUID LIQUID LIQUID

FLUID RATES, KG-MOL/HR
1 NC4 76.5017 76.5017 1.5980E-04 1.5980E-04
2 IC4 348.5029 348.5029 4.4492E-05 4.4492E-05
3 1BUTENE 59.5000 59.5000 6.1355E-05 6.1355E-05
4 BTC2 33.9996 33.9996 4.6748E-04 4.6748E-04
5 BTT2 50.9997 50.9997 3.0621E-04 3.0621E-04
6 IBTE 2.2556 2.2556 1.4575E-06 1.4575E-06
7 MTBE 4.4354E-03 4.4354E-03 277.3516 277.3516
8 MEOH 4.1771 4.1771 .1096 .1096
9 TBA 3.2699E-10 3.2699E-10 .1871 .1871
10 H2O .0000 .0000 .0000 .0000
11 DIB 1.4317E-12 1.4317E-12 .3506 .3506

TOTAL RATE, KG-MOL/HR 575.9411 575.9411 278.0000 278.0000

TEMPERATURE, C 43.5000 43.7245 129.0674 89.5676
PRESSURE, KPA 621.0000 827.0000 697.5000 663.0000
ENTHALPY, M*KJ/HR 3.4055 3.4249 7.1853 4.7355
MOLECULAR WEIGHT 57.4214 57.4214 88.1477 88.1477
MOLE FRAC VAPOR .0000 .0000 .0000 .0000
MOLE FRAC LIQUID 1.0000 1.0000 1.0000 1.0000
42
SIMULATION SCIENCES INC. R PAGE P-54
PROJECT MTBECASEBOOK PRO/II VERSION 4.02 386/EM
PROBLEM MTBE PLANT OUTPUT SIMSCI
STREAM MOLAR COMPONENT RATES Mar95
==============================================================================

STREAM ID 9 10 11 12
NAME C4S
PHASE LIQUID LIQUID LIQUID LIQUID

FLUID RATES, KG-MOL/HR
1 NC4 76.5017 3.5071E-15 76.4964 5.3472E-03
2 IC4 348.5029 3.5079E-16 348.4884 .0146
3 1BUTENE 59.5000 9.5072E-18 59.4998 1.5195E-04
4 BTC2 33.9996 2.1428E-16 33.9994 1.9789E-04
5 BTT2 50.9997 6.0544E-18 50.9996 1.0287E-04
6 IBTE 2.2556 3.3171E-15 2.2556 5.1219E-06
7 MTBE 4.4354E-03 4.7170E-15 4.4129E-03 2.2466E-05
8 MEOH 4.1771 .0210 3.6309E-03 4.1942
9 TBA 3.2699E-10 2.0917E-15 3.2802E-10 2.9373E-13
10 H2O .0000 374.9998 .4101 374.5899
11 DIB 1.4317E-12 .0000 4.6466E-12 5.6091E-24

TOTAL RATE, KG-MOL/HR 575.9411 375.0208 572.1573 378.8045

TEMPERATURE, C 38.0000 38.0000 38.7285 38.8592
PRESSURE, KPA 792.5000 793.0000 792.0000 792.0000
ENTHALPY, M*KJ/HR 2.9436 .9829 2.9184 1.0081
MOLECULAR WEIGHT 57.4214 18.0158 57.5782 18.1725
MOLE FRAC VAPOR .0000 .0000 .0000 .0000
MOLE FRAC LIQUID 1.0000 1.0000 1.0000 1.0000


STREAM ID 13 14 15 16
NAME FLARE GAS
PHASE LIQUID MIXED VAPOR LIQUID

FLUID RATES, KG-MOL/HR
1 NC4 5.3472E-03 5.3472E-03 3.4358E-03 1.9115E-03
2 IC4 .0146 .0146 .0116 2.9666E-03
3 1BUTENE 1.5195E-04 1.5195E-04 1.2109E-04 3.0860E-05
4 BTC2 1.9789E-04 1.9789E-04 1.2642E-04 7.1469E-05
5 BTT2 1.0287E-04 1.0287E-04 8.2306E-05 2.0563E-05
6 IBTE 5.1219E-06 5.1219E-06 4.1733E-06 9.4868E-07
7 MTBE 2.2466E-05 2.2466E-05 7.1040E-08 2.2395E-05
8 MEOH 4.1942 4.1942 8.9556E-04 4.1934
9 TBA 2.9373E-13 2.9373E-13 6.0438E-15 2.8769E-13
10 H2O 374.5899 374.5899 .0112 374.5787
11 DIB 5.6091E-24 5.6091E-24 4.0613E-28 5.6087E-24

TOTAL RATE, KG-MOL/HR 378.8045 378.8045 .0274 378.7771
43
SIMULATION SCIENCES INC. R PAGE P-55
PROJECT MTBECASEBOOK PRO/II VERSION 4.02 386/EM
PROBLEM MTBE PLANT OUTPUT SIMSCI
STREAM MOLAR COMPONENT RATES Mar95
==============================================================================

STREAM ID 13 14 15 16
NAME FLARE GAS
PHASE LIQUID MIXED VAPOR LIQUID

TEMPERATURE, C 99.0000 99.0991 99.0991 99.0991
PRESSURE, KPA 757.5000 241.0000 241.0000 241.0000
ENTHALPY, M*KJ/HR 2.7497 2.7497 1.0558E-03 2.7487
MOLECULAR WEIGHT 18.1725 18.1725 40.9009 18.1708
MOLE FRAC VAPOR .0000 7.2406E-05 1.0000 .0000
MOLE FRAC LIQUID 1.0000 .9999 .0000 1.0000


STREAM ID 17 18 19 20
NAME MEOH RECYC
PHASE LIQUID LIQUID LIQUID LIQUID

FLUID RATES, KG-MOL/HR
1 NC4 1.9115E-03 3.5071E-15 1.9115E-03 1.9115E-03
2 IC4 2.9666E-03 3.5079E-16 2.9666E-03 2.9666E-03
3 1BUTENE 3.0860E-05 9.5072E-18 3.0860E-05 3.0860E-05
4 BTC2 7.1469E-05 2.1428E-16 7.1469E-05 7.1469E-05
5 BTT2 2.0563E-05 6.0544E-18 2.0563E-05 2.0563E-05
6 IBTE 9.4868E-07 3.3171E-15 9.4868E-07 9.4868E-07
7 MTBE 2.2395E-05 4.7170E-15 2.2395E-05 2.2395E-05
8 MEOH 4.1934 .0210 4.1724 4.1724
9 TBA 2.8769E-13 2.0917E-15 2.8559E-13 2.8559E-13
10 H2O 374.5787 374.3913 .1873 .1873
11 DIB 5.6087E-24 .0000 .0000 .0000

TOTAL RATE, KG-MOL/HR 378.7771 374.4123 4.3647 4.3647

TEMPERATURE, C 99.1817 115.7024 30.0000 30.5274
PRESSURE, KPA 690.0000 172.5000 103.5000 1724.0000
ENTHALPY, M*KJ/HR 2.7539 3.1838 4.6134E-03 5.0499E-03
MOLECULAR WEIGHT 18.1708 18.0158 31.4703 31.4703
MOLE FRAC VAPOR .0000 .0000 .0000 .0000
MOLE FRAC LIQUID 1.0000 1.0000 1.0000 1.0000
44
SIMULATION SCIENCES INC. R PAGE P-56
PROJECT MTBECASEBOOK PRO/II VERSION 4.02 386/EM
PROBLEM MTBE PLANT OUTPUT SIMSCI
STREAM MOLAR COMPONENT RATES Mar95
==============================================================================

STREAM ID 21 22
NAME
PHASE LIQUID LIQUID

FLUID RATES, KG-MOL/HR
1 NC4 3.5071E-15 3.5071E-15
2 IC4 3.5079E-16 3.5079E-16
3 1BUTENE 9.5072E-18 9.5072E-18
4 BTC2 2.1428E-16 2.1428E-16
5 BTT2 6.0544E-18 6.0544E-18
6 IBTE 3.3171E-15 3.3171E-15
7 MTBE 4.7170E-15 4.7170E-15
8 MEOH .0210 .0210
9 TBA 2.0917E-15 2.0917E-15
10 H2O 374.9998 374.9998
11 DIB .0000 .0000

TOTAL RATE, KG-MOL/HR 375.0208 375.0208

TEMPERATURE, C 115.7115 54.0512
PRESSURE, KPA 862.0000 827.5000
ENTHALPY, M*KJ/HR 3.1933 1.4516
MOLECULAR WEIGHT 18.0158 18.0158
MOLE FRAC VAPOR .0000 .0000
MOLE FRAC LIQUID 1.0000 1.0000
45