25.

Solving a Highly Constrained Cumene Production Problem with A+

A waste water stream with 50 mol% benzene is to be treated to remove impurities so it could be
used to produce cumene (isopropyl benzene). The waste water first enters a flash to remove light
gases. The liquid from the flash then enters a distillation column to separate out high-purity
benzene in the bottom stream. After that, this liquid benzene is pre-heated to a super-heated state
and combined with propylene (100% pure at 200 °F and 14.7 psia). Benzene and propylene are
then allowed to react to form cumene in an isothermal plug flow reactor. The reactor effluent is
cooled in a heat exchanger by the liquid distillate from the first column. A second distillation
column is used to purify cumene which exits as the bottom product.

The cumene reaction is as follows:

C3 H 6 + C6 H 6 → C9 H12
propylene benzene cumene (gas phase reaction)

F LASH-V OVRHEAD
W AST-GAS
CUM-COL

MIXER-1

F LASH CUMENE
V-DISTL HOT-OUT

W ASTE-F

L-DISTL COLD-OUT

F LASH-L
COOLER

BZ-COL

PRE-HTR

BZ-F EED HEATED-B

REACT-IN REAC-OUT

MIXER-2

PP-F EED

REACTOR

The following additional data are known about the process:

1
1. The temperature of the waste water feed is 100 °F and its pressure is 20 psia. Its composition
is: 15% acetone, 50% benzene, 15% methanol, 10% methane, 6% acetylene (C2H2), 3%
nitrogen, and 1% oxygen (all molar basis), and the total flow rate is 200 lbmol/hr.
2. The waste water stream is flashed at 0 °F with negligible pressure drop.
3. The first column (BZ-COL) has 20 theoretical stages, which include a partial condenser
(Pcondenser = 14 psia) and a reboiler (Preboiler = 15 psia). The feed tray location is 15. The
column operates with a molar reflux ratio of 3 and takes out 90 lbmol/hr in the bottom stream.
4. The pre-heater vaporizes the benzene stream and superheats it to 30 °F above its dew-point
temperature. The pressure drop inside the pre-heater is 0.3 psia.
5. The waste gas stream (WAST-GAS) has a total flow rate of 37.0 lbmol/hr.
6. The plug flow reactor has a diameter of 1.2 ft with negligible pressure drop. The kinetics for
the cumene reaction follows the power-law expression and is given as:

rpropylene = kC propylene C benzene

 − 5500 
k = 1.5 × 10 4 exp 
 RT 

where the unit of the activation energy is Btu/lbmol and Ci is molar concentration. The
conversion of the cumene reaction is maintained at 99%.
7. The plug flow reactor is operated isothermally at the same temperature as that of the inlet to
the reactor (REAC-IN). Note that although the cumene reaction occurs in the gas phase, you
must specify Valid Phases = Vapor-Liquid in RPLUG because the generation of cumene
may cause liquid to form inside the reactor.
8. The exit temperature of the cold side in the cooler is 100 °F. This cooler has negligible
pressure drop.
9. The cumene column (CUM-COL) consists of 10 theoretical stages, which include a total
condenser (Pcondenser = 14 psia) and a reboiler (Preboiler = 14.5 psia). The feed tray location is
5. The column takes out 20 mol% of the feed as the overhead distillate and operates with a
molar reflux ratio of 3.
10. The cumene product stream from the second column must contain a purity of 99.5 mole%
cumene (product spec).

Use ASPEN PLUS to simulate this cumene production process. You must use the same block
IDs and stream IDs as given in the figure. For properties, use NRTL-RK and declare nitrogen
and oxygen as Henry’s law components. Also, remember to select APV732 HENRY-AP as a
databank to search in Methods  Binary Interaction  HENRY-1 folder; otherwise, these
Henry’s law binary parameters between the two light gases and the solvents will not be loaded.

Hint: Try to converge the base-case model without design-specs first. Then, slowly add a design-
spec one at a time. Whether you are able to converge this problem depends on the initial guesses
and the range of the manipulated variables in the design-specs.

2
Solution:

Answer the following questions:

1. Temperature of the condenser in BZ-COL = ____6.92____ °F

2. Molar ratio of propylene to benzene in the reactor inlet (REAC-IN) = ____1.194_____

3. Reactor length = ____11.93____ feet

A+ Input Summary:

;
;Input Summary created by Aspen Plus Rel. 26.0 at 12:01:00 Wed Jul 4,
2012
;Directory F:\HMKu\ChEPS\ChEPS Courses\CHE656-16thYear\Midterm Filename
C:\Users\NBPC\AppData\Local\Temp\~ap96d7.txt
;

3
IN-UNITS ENG

DEF-STREAMS CONVEN ALL

DESCRIPTION "
Chemical Simulation with English Units :
F, psi, lb/hr, lbmol/hr, Btu/hr, cuft/hr.

Property Method: NRTL

Flow basis for input: Mole

Stream report composition: Mole flow

"

DATABANKS 'APV732 PURE26' / 'APV732 AQUEOUS' / 'APV732 SOLIDS' &

/ 'APV732 INORGANIC' / NOASPENPCD

PROP-SOURCES 'APV732 PURE26' / 'APV732 AQUEOUS' / &

'APV732 SOLIDS' / 'APV732 INORGANIC'

COMPONENTS
ACETONE C3H6O-1 /
BENZENE C6H6 /
METHANOL CH4O /
CH4 CH4 /
C2H2 C2H2 /
N2 N2 /
O2 O2 /
PROPYLEN C3H6-2 /
CUMENE C9H12-2

HENRY-COMPS HC-1 N2 O2

FLOWSHEET
BLOCK FLASH IN=WASTE-F OUT=FLASH-V FLASH-L
BLOCK BZ-COL IN=FLASH-L OUT=V-DISTL L-DISTL BZ-FEED
BLOCK MIXER-1 IN=FLASH-V V-DISTL OUT=WAST-GAS
BLOCK REACTOR IN=REACT-IN OUT=REAC-OUT
BLOCK PRE-HTR IN=BZ-FEED OUT=HEATED-B
BLOCK MIXER-2 IN=HEATED-B PP-FEED OUT=REACT-IN
BLOCK COOLER IN=REAC-OUT L-DISTL OUT=HOT-OUT COLD-OUT
BLOCK CUM-COL IN=HOT-OUT OUT=OVRHEAD CUMENE

PROPERTIES NRTL-RK HENRY-COMPS=HC-1

PROPERTIES NRTL

PROP-DATA HENRY-1
IN-UNITS ENG PRESSURE=psi PDROP=psi
PROP-LIST HENRY

4
 BPVAL N2 ACETONE 46.12675261 -1426.986036 -5.586500000 &
3.45055556E-3 -108.5800000 105.9800000 0.0
BPVAL O2 ACETONE .6510994089 -188.5680036 1.963100000 &
-5.3538889E-3 -108.9400000 104.0000000 0.0
BPVAL N2 BENZENE -67.23225245 3450.240088 12.54900000 &
-.0142838888 44.78000000 140.0000000 0.0
BPVAL O2 BENZENE 25.72240855 -787.4279838 -2.341200000 &
4.84444444E-4 50.00000000 140.0000000 0.0
BPVAL N2 METHANOL 1.184200177 -71.18280180 1.951700000 &
-4.4888889E-3 -76.00000000 122.0000000 0.0
BPVAL O2 METHANOL 31.12266143 -1381.626013 -2.977400000 &
1.21777778E-3 -13.00000000 122.0000000 0.0
BPVAL N2 PROPYLEN 111.7115357 -3701.519824 -16.01100000 0.0 &
-317.3800000 -296.7700000 0.0
BPVAL O2 CUMENE 9.267484411 0.0 0.0 0.0 77.00000000 &
77.00000000 0.0

PROP-DATA NRTL-1
IN-UNITS ENG
PROP-LIST NRTL
BPVAL ACETONE BENZENE -.1015000000 550.9193400 .3000000000 &
0.0 0.0 0.0 77.00000000 176.1800000
BPVAL BENZENE ACETONE .4224000000 -431.8216200 .3000000000 &
0.0 0.0 0.0 77.00000000 176.1800000
BPVAL ACETONE METHANOL 0.0 183.3946200 .3000000000 0.0 0.0 &
0.0 131.0000000 148.3700000
BPVAL METHANOL ACETONE 0.0 205.4424600 .3000000000 0.0 0.0 &
0.0 131.0000000 148.3700000
BPVAL BENZENE METHANOL 11.58010000 -5908.597200 .4000000000 &
0.0 0.0 0.0 131.0000000 176.1800000
BPVAL METHANOL BENZENE -1.708600000 1606.032720 .4000000000 &
0.0 0.0 0.0 131.0000000 176.1800000
BPVAL ACETONE PROPYLEN 0.0 -52.94376000 .3000000000 0.0 &
0.0 0.0 77.00000000 77.00000000
BPVAL PROPYLEN ACETONE 0.0 760.7433600 .3000000000 0.0 0.0 &
0.0 77.00000000 77.00000000
BPVAL BENZENE PROPYLEN 0.0 272.6013600 .3000000000 0.0 0.0 &
0.0 77.00000000 77.00000000
BPVAL PROPYLEN BENZENE 0.0 -6.830460000 .3000000000 0.0 &
0.0 0.0 77.00000000 77.00000000
BPVAL METHANOL PROPYLEN 0.0 373.6848600 .3000000000 0.0 &
0.0 0.0 77.00000000 77.00000000
BPVAL PROPYLEN METHANOL 0.0 1188.933120 .3000000000 0.0 &
0.0 0.0 77.00000000 77.00000000
BPVAL ACETONE CUMENE -2.747460000 1825.866000 .3000000000 &
0.0 0.0 0.0 68.00000000 260.6000000
BPVAL CUMENE ACETONE 4.597280000 -2331.000000 .3000000000 &
0.0 0.0 0.0 68.00000000 260.6000000
BPVAL BENZENE CUMENE 0.0 98.06436000 .3000000000 0.0 0.0 &
0.0 178.8800000 277.5200000
BPVAL CUMENE BENZENE 0.0 -80.40420000 .3000000000 0.0 0.0 &
0.0 178.8800000 277.5200000

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STREAM PP-FEED
SUBSTREAM MIXED TEMP=200. PRES=14.7
MOLE-FLOW PROPYLEN 100.

STREAM WASTE-F
SUBSTREAM MIXED TEMP=100. PRES=20. MOLE-FLOW=200.
MOLE-FRAC ACETONE 0.15 / BENZENE 0.5 / METHANOL 0.15 / &
CH4 0.1 / C2H2 0.06 / N2 0.03 / O2 0.01

BLOCK MIXER-1 MIXER

PARAM

BLOCK MIXER-2 MIXER

PARAM

BLOCK PRE-HTR HEATER

PARAM PRES=-0.3 DEGSUP=30.

BLOCK FLASH FLASH2

PARAM TEMP=0. PRES=0.

BLOCK COOLER HEATX

PARAM T-COLD=100. CALC-TYPE=DESIGN U-OPTION=PHASE &
F-OPTION=CONSTANT CALC-METHOD=SHORTCUT
FEEDS HOT=REAC-OUT COLD=L-DISTL
PRODUCTS HOT=HOT-OUT COLD=COLD-OUT
HOT-SIDE DP-OPTION=CONSTANT
COLD-SIDE DP-OPTION=CONSTANT

BLOCK BZ-COL RADFRAC

PARAM NSTAGE=20 ALGORITHM=NONIDEAL INIT-OPTION=STANDARD
COL-CONFIG CONDENSER=PARTIAL-V-L
FEEDS FLASH-L 15
PRODUCTS BZ-FEED 20 L / L-DISTL 1 L / V-DISTL 1 V
P-SPEC 1 14. / 20 15.
COL-SPECS MOLE-RDV=0.05 MOLE-B=90. MOLE-RR=3.

BLOCK CUM-COL RADFRAC

PARAM NSTAGE=10
COL-CONFIG CONDENSER=TOTAL
FEEDS HOT-OUT 5
PRODUCTS CUMENE 10 L / OVRHEAD 1 L
P-SPEC 1 14. / 10 14.5
COL-SPECS D:F=0.2 MOLE-RR=3.

BLOCK REACTOR RPLUG

PARAM TYPE=T-SPEC LENGTH=10. DIAM=1.2 NPHASE=2
BLOCK-OPTION FREE-WATER=NO
REACTIONS RXN-IDS=R-1

DESIGN-SPEC DS-1

6
 DEFINE BZOUT MOLE-FLOW STREAM=REAC-OUT SUBSTREAM=MIXED &
COMPONENT=BENZENE
DEFINE BZIN MOLE-FLOW STREAM=REACT-IN SUBSTREAM=MIXED &
COMPONENT=BENZENE
SPEC "BZOUT/BZIN" TO "0.01"
TOL-SPEC "0.0001"
VARY BLOCK-VAR BLOCK=REACTOR VARIABLE=LENGTH SENTENCE=PARAM
LIMITS "10" "15"

DESIGN-SPEC DS-2
DEFINE XCUMENE MOLE-FRAC STREAM=CUMENE SUBSTREAM=MIXED &
COMPONENT=CUMENE
SPEC "XCUMENE" TO "0.995"
TOL-SPEC "0.00001"
VARY STREAM-VAR STREAM=PP-FEED SUBSTREAM=MIXED &
VARIABLE=MOLE-FLOW
LIMITS "80" "120"

DESIGN-SPEC DS-3
DEFINE WASTEGAS STREAM-VAR STREAM=WAST-GAS SUBSTREAM=MIXED &
VARIABLE=MOLE-FLOW
SPEC "WASTEGAS" TO "37.0"
TOL-SPEC "0.0001"
VARY BLOCK-VAR BLOCK=BZ-COL VARIABLE=MOLE-RDV &
SENTENCE=COL-SPECS
LIMITS "0.01" "0.10"

EO-CONV-OPTI

STREAM-REPOR MOLEFLOW MOLEFRAC

REACTIONS R-1 POWERLAW

REAC-DATA 1 PHASE=V
RATE-CON 1 PRE-EXP=15000. ACT-ENERGY=5500.
STOIC 1 MIXED PROPYLEN -1. / BENZENE -1. / CUMENE 1.
POWLAW-EXP 1 MIXED PROPYLEN 1. / MIXED BENZENE 1. / &
MIXED CUMENE 0.
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