Chemical Engineering Research and Design 190 (2023) 220–232

Available online at www.sciencedirect.com

Chemical Engineering Research and Design

journal homepage: www.elsevier.com/locate/cherd

Compact process for cumene manufacture:

Synthesis, design and control
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⁎,1
Prakhar Srivastava, Aayush Gupta, Nitin Kaistha
Department of Chemical Engineering, Indian Institute of Technology, Kanpur 208016, India

a r t i c l e i n f o a b s t r a c t

Article history: A compact single-unit process is developed for continuous cumene manufacture via the
Received 8 September 2022 alkylation of benzene with propylene. The design combines reactive distillation (RD) and
Received in revised form dividing-wall separation in a single column. In terms of the TAC, it is significantly cheaper
10 December 2022 (42%) than the conventional “reaction followed by separation process” and only slightly
Accepted 18 December 2022 more expensive than the RD process. The controllability of the developed compact design
Available online 22 December 2022 is confirmed via rigorous dynamic simulations that demonstrate effective process op­
eration for large production rate and feed composition changes using a simple decen­
Keywords: tralized temperature inferential control system. The developed compact design is
RDWC especially suitable for capacity expansion in space-constrained cumene manufacturing
Cumene facilities.
Compact process © 2022 Published by Elsevier Ltd on behalf of Institution of Chemical Engineers.

reaction is exactly balanced by its consumption via trans­

1. Introduction
alkylation. Commercial cumene plants thus have a near
100% (> 99.7%) benzene utilization efficiency (Luyben, 2010a).
Cumene is an important industrial intermediate used pri­
There are two competing technologies for cumene manu­
marily to produce phenol (Fortuin and Waterman, 1953).
facture: conventional reaction followed by separation and
Phenol and its derivatives are used for manufacturing poly­
catalytic distillation which combines reaction and separation
carbonate and epoxy resins, detergents, nylon, bakelite,
(Pathak et al., 2011). Schematics of the two flowsheets are
herbicides, etc. Almost all of the cumene is produced via
shown in Figs. 1, 2.
benzene (C6) alkylation with propylene (C3= ) over acid cata­
In the conventional process, the C6 C3= mixture, with C6
lyst as.
in excess to suppress the C12 side reaction, is heated and fed
C6 H6 C3 H6 C9 H12
Benzene + Propylene Cumene (main reaction) to a cooled packed bed reactor with near complete conver­
sion (say 99.5%) of C3= . The reactor effluent is condensed and
The cumene can further alkylate to di-Isopropyl benzene then separated in a three-column light-out-first separation
(DIPB) as. train. Any unreacted C3= along with the inert propane (C3)
C9 H12 C3 H6 C12 H18 entering with the C3= feed is discharged as fuel gas vapor
Cumene + Propylene DIPB ( side reaction)
distillate from the first column. The unreacted C6 is re­
The DIPB (C12) formed through side reaction is converted covered up the top of the second column and recycled back
back to cumene via the trans alkylation of benzene as. to the main reactor. The C9 product is drawn as the distillate
C12 H18 C6 H6 2C9 H12 from the third column. Its bottoms are C12, which is mixed
DIPB + Benzene Cumene (transalkyaltion) with a small fraction of the second column C6 distillate
stream, heated, and sent to the transalkylator. The trans­
The transalkylation reaction allows the recycle-to-extinction
alkylator effluent is cooled and fed to the second column for
of the C12 side-product, where its generation via the side
separation.
The more compact catalytic distillation process has only
⁎
Corresponding author. two columns. Reaction and C6 recovery is integrated into the
E-mail address: nkaistha@iitk.ac.in (N. Kaistha). first reactive distillation (RD) column. It consists of a reactive
1
0000-0002-1617-6532
https://doi.org/10.1016/j.cherd.2022.12.026
0263-8762/© 2022 Published by Elsevier Ltd on behalf of Institution of Chemical Engineers.
 Chemical Engineering Research and Design 190 (2023) 220–232 221

Fig. 1 – Nominal Design and Operating Condition of Conventional Process for Cumene Production.

Fig. 2 – Nominal Design and Operating Condition of Reactive Distillation Process for Cumene Production.
222 Chemical Engineering Research and Design 190 (2023) 220–232
Fig. 3 – Input output Structure.
section and a stripping section below it. C6 (heavy reactant) is
fed at the top of the reactive section while C3= (light reactant)
is fed just below it. This ensures the reactants ‘move in’ in
the reactive section ensuring high reactant concentration
and hence reaction rates. Unreacted C3= and inert C3 leave the
RD column as vapor distillate. The RD column stripping
section prevents C6 from leaving down the bottom. The
bottom then is a C9 − C12 binary mixture, which is separated
in the downstream second column. The C9 product leaves as
the distillate and the C12 bottoms is recycled back to the RD
column to recycle the C12 to extinction. Pathak et al. (2011)
have compared the two processes to show that the catalytic
distillation process is economically much cheaper than the
conventional process and is easily controlled using a tem­
perature inferential control system.
Given cumene’s continued importance in the bulk che­
micals industry, it is natural to seek further process in­
tegration for a much more compact and economical cumene
process. In this context, it is pertinent to recall the integra­
tion of the conventional methyl acetate process consisting of
a reactor followed by a 9-column separation section into a
single reactive distillation unit (Agreda and Partin, 1984). This
commercial success story catalyzed the emergence of pro­
cess intensification and integration as a major research area
in the subsequent decades. Is it possible to obtain a single-
unit cumene process, where the various reaction and se­
paration tasks are integrated into the single unit? If yes, how
does the integrated process compare economically with the
existing technologies? Lastly, given that highly integrated
processes are often more difficult to control (Mansouri et al.,
2016; Luyben, 2020), is the integrated single-unit process
easily controllable? These questions are addressed here in
the context of cumene manufacturing.
The primary objective of the work is to synthesize, design,
and operate a compact single-unit process for cumene
manufacture using existing ideas for process integration.
Specifically, in addition to catalytic distillation that combines
reaction and separation, a dividing wall is applied to in­
tegrate all separation tasks into a single unit. Dividing-wall
columns (DWCs) were first proposed more than 5 decades
ago (Kaibel, 1987) for separating an ideal ternary mixture into
its pure constituents in a Petlyuk arrangement. In the last
decade, research interest in DWCs has increased sig­
nificantly due to their energy and capital cost-saving poten­
tial. In addition to the separation of ideal systems, DWCs
have been developed for homogenous and heterogenous
azeotropic distillation systems (Bravo-Bravo et al., 2010;
Murrieta-Dueñas et al., 2011). Research has also shown that
despite the increased complexity due to process integration,
DWCs may be effectively controlled using simple decen­
tralized control systems (Xia et al., 2012; Ling and Luyben,
2010). It is then reasonable to expect that the synthesized
single-unit cumene process should also be easily con­
trollable.
In the following, the single-unit cumene process is syn­
thesized using common sense arguments. An economic
process design is then developed and its economics are
compared with existing processes. A decentralized tem­
perature inferential control system is synthesized for the
design and shown to provide effective regulation for pro­
duction rate and feed composition change disturbances. The
article concludes by summarizing the main contribution of
the work.
2. Compact single-unit cumene process
The compact single-unit cumene process may be synthe­
sized using catalytic distillation and dividing wall concepts.
We shoot for the ideal process material input-output struc­
ture shown in Fig. 3, consisting of C3= (with some inert C3) and
C6 fresh feeds and C9 product and fuel gas exit streams. The
fuel gas allows the inert C3 and any unreacted C3= to exit the
process.
Since the C3 C3= separation is very expensive, near
complete C3= conversion is desired for good process eco­
nomics. The normal boiling points of all the species are noted
in Table 1. The low boiling C3 and unreacted C3= may be re­
moved as vapor distillate from a column for use as fuel gas.
To minimize expensive C6 loss in the fuel gas stream, the
column should be pressurized so that most of the C6 in the
overhead vapor condenses using cheap cooling water. The
pressurization also increases the tray temperatures for
higher reaction rates. Accordingly, as shown in Fig. 4a, a
pressurized reactive section is used for effecting the alkyla­
tion chemistry.
The trays are loaded with alkylation catalyst bales. Fresh
C3= is fed slightly above the bottom of the alkylation section
while fresh C6 is fed towards its top. The relatively heavy C6
moves down while the light C3= moves up thereby delivering
high reactant composition in the reactive zone. The overhead
vapor is condensed and the C6 rich condensate is refluxed.
The uncondensable C3 and unreacted C3= leave as vapor dis­
tillate with some loss of precious C6. The liquid leaving the
Table 1 – Boiling point of Component at atmospheric
pressure.
Component Boiling Point (∘C)
Propylene − 47.6
Propane − 42.0
Benzene 80.1
Cumene 152.4
DIPB 210.0
 Chemical Engineering Research and Design 190 (2023) 220–232 223

Fig. 4 – Formation of Single Pot RDWC Process for Cumene Production.

alkylation zone contains mostly C6, C9, some C12 and negli­
gible C3= or C3.
Further below the alkylation zone, a few reactive trays
with transalkylation catalyst are provided, as shown in
Fig. 4b. For the time being, let us assume a C12-rich recycle
stream is available. This stream (heavy reactant) is fed just
above the transalkylation zone with a C6 rich vapor stream
entering the zone from below for rigorous transalkylation
reactant contact.
The liquid leaving the transalkylation zone contains C6, C9
and some C12. As one moves further down the transalkyla­
tion zone, the next few fractionation trays prevent C6 from
moving down. This section is therefore aptly referred to as
the C6 stripper (see Fig. 4c). The stripping away of C6 results
in a C9 − C12 liquid stream exiting down the bottom of this
section. This stream may be rectified to recover pure C9
product and stripped off C9 to obtain a C12 rich liquid stream
for recycle to the transalkylation zone. The C9 rectifying and
stripping sections are shown in Fig. 4d and 4e, respectively.
The individual operations depicted in Fig. 4(a-e) may be
combined as schematically shown in Fig. 4f to obtain the
compact single unit cumene process flow sheet as in Fig. 5.
At the top, we have the alkylation-translkylation reactive
section. Below it, a dividing wall is provided, with one side
224 Chemical Engineering Research and Design 190 (2023) 220–232
Fig. 5 – Single Pot RDWC Process for Cumene Production.
earmarked for the C6 stripping task and the other side ear­
marked for the C9 rectification task. The trays below the di­
viding wall perform the C9 stripping task to recover the C12
rich recycle stream down the bottoms.
The C9 rectifier is isolated by a solid wall from the reactive
section above it. An external condenser provides liquid to
this section. This single-unit compact design is feasible but
has two major disadvantages. The first one is that the non-
reactive separation sections operate at the high reactive zone
pressure, which adversely affects the key component’s re­
lative volatility making the separation more difficult. Also,
since C12 is the heaviest component and therefore high
boiling, the reboiler temperature at the high pressure is more
than what can be achieved using high-pressure steam. The
reboiler then is a very costly fired furnace, instead of a much
cheaper steam-driven one. To overcome these disadvantages
while retaining the single-unit compact design, the C6 strip­
ping section is isolated from the reactive zone by means of a
solid wall. Liquid from a trap-out tray at the bottom of the
reactive zone is pumped into the C6 stripping zone.
Also, the overhead vapor from the low-pressure C6 stripping
section is forced into the bottom of the high-pressure reactive
zone using a small steam turbine-driven compressor. The re­
sulting single-unit compact process flowsheet is shown in
Fig. 6. Note that it satisfies the material input-output structure
of Fig. 3 with no C12 discharge stream as the C12 is recycled-to-
extinction and only a fuel gas (unreacted C3= and inert C3)
stream and the C9 product stream exiting the process.
3. Process modeling, design and economics
A steady state economic process design is now developed for
the synthesized compact cumene process flowsheet in Fig. 6.
The process model details, the developed design using the
model, and, its economics are now described.
3.1. Process model
Aspen Plus (version 8.8) is used for steady state and dynamic
process modeling. The alkylation and transalkylation ki­
netics are taken from (Pathak et al., 2011) and reproduced in
Table 2 for completeness. Since the system consists of hy­
drocarbons with only C and H elements, the Peng-Robinson
equation of state is used to model the thermodynamic
properties. The process flowsheet has 6 steady state opera­
tion degrees of freedom (DoFs) for an appropriately chosen
number of trays in the reactive and separation sections, feed
locations into the column as well as specified reactive zone
pressure (Pr) and separation section pressure (Ps). These DoFs
are specified as follows.
1. One DoF sets the process throughput. We use the fresh C3=
(limiting reactant) flow rate for the purpose. The C3= feed
contains 5 mol% inert propane (C3) impurity.
2. A design spec-vary is used on the reactive zone column
section with the vapor distillate rate adjusted to hold the
condenser temperature at the specified value.
3. A design spec vary is used on the C9 stripping section that
adjusts the reboiler duty to hold the C12 mol fraction in the
bottom stream at the specified value.
4. On the C9 rectifier, a design spec vary adjusts the rectifier
reflux ratio to hold the C9 product purity.
5. For the C6 stripper, the fraction (1 − f) of vapor going from
below into the stripper is specified.
6. A flowsheet design spec vary is applied that adjusts the
total fresh C6 to hold the C6 C3= ratio in the vapor distillate.
With these specification variables, an appropriate process
design is to be developed for manufacturing 100 kmol/h cu­
mene product that is 99.9 mol% pure.
3.2. Process design and economics
The principal design variables are the reactive section pres­
sure (Pr), the number of reactive trays (Nr), the purity of the
C12 recycle stream (xCBot
12
) and the vapor split fraction (f) into
the C9 rectifier. Common-sense heuristics are used to fix the
other design variables. Thus, the operating pressure of the
divided-wall section of the unit (Ps) is chosen as 1.1 bar to be
only slightly above atmospheric for favorable relative vola­
tility. The condenser temperature is specified as 50∘C, which
is considered the lowest feasible temperature using cooling
water as the cheap cooling utility. This minimizes the C6 loss
in the fuel gas. The number of trays in the fractionation
sections is estimated to be around 3 times the minimum
trays from the Fenske equation. The number of trays in the
C9 rectifying and C6 stripping sections that are separated by
the dividing wall must be the same and therefore set to the
larger of the two calculated values. To calculate the separa­
tion factor for use in the Fenske equation, a reasonable se­
paration section feed composition and product stream key
component impurity level are needed. Table 3 reports the
values along with the calculated minimum and re­
commended trays for the three separation sections. The
fresh C6 to the alkylation is fed on the second tray (top-down
numbering) while fresh C3= is fed 3 trays above the C12 recycle
stream feed tray. The three intervening trays ensure the
 Chemical Engineering Research and Design 190 (2023) 220–232
Fig. 6 – Single Pot RDWC Process with Design and Nominal Operating Condition.
transalkylation zone is C3= free so that only transalkylation
chemistry occurs on the reactive trays below the C12 feed.
Now let us consider the major design variables. The pri­
mary consideration in setting the reactive zone pressure (Pr)
is reducing the loss of C6 in the fuel gas vapor distillate
stream and also ensuring a nearly complete C3= conversion.
The variation in the C6 loss and C3= loss in the fuel gas stream
with Pr for a reasonable Nr = 40 trays is shown in Fig. 7. As Pr
is increased, the law of diminishing returns catches up with
respect to both C6 and C3= loss. Since a high Pr increases the
compression cost, Pr is set at a reasonable value of 4.2 bars
from Fig. 7. The number of reactive trays is adjusted for near
complete C3= conversion of 99.5% to mitigate the loss of pre­
cious C3= in the overhead fuel gas stream. Nr is thus obtained
as 40 with a hold up of 0.28 m3 in the alkylation zone. For the
recommended design, this translates to a reasonable struc­
tured catalyst packing height on a reactive tray that is
slightly under 1 ft assuming a catalyst density of 1000 kg/m3.
The spacing between two reactive trays is then 3 ft for a 2 ft
free space for vapor-liquid disengagement between the trays.
The trans-alkylation zone has 4 reactive trays with a catalyst
225
hold-up of 0.2 m3. A lower hold-up results in the C12 recycle-
to-extinction loop diverging.
The values of f and xCBot
12
are adjusted for minimizing the
Total Annualized Cost (TAC), which is defined as
TCC
TAC = + YOC
PBP
where TCC is the total capital cost, PBP is the payback period
and YOC is the yearly operating cost. The pricing data and
cost correlations used are given in Supporting Information
Table S1. A standard PBP of 3 years is used. The equipment is
sized based on the converged material and energy flows
imported from Aspen Plus. Aspen’s tray sizing utility based
on Fairs’s method (Couper et al., 2005) is used to get the
diameter of the different tray sections in the column. The
condenser and reboiler heat transfer areas are calculated
assuming an appropriate temperature difference. Overall
heat transfer coefficients of 852 and 568 W m−2 K−1 are used
for the reboiler and condenser respectively.
The variation in TAC with xCBot12
and f is plotted in Fig. 8a
and 8b, respectively. The former plots the variation for
226 Chemical Engineering Research and Design 190 (2023) 220–232

translkylation zone catalyst loading of 0.2 and 0.3 m3. From

Table 2 – Reaction Kinetics and other Model Detailsa.
the Figure, xCBot
12
= 0.8 and f = 0.73 is near optimum. The near
Reaction Reaction Kinetics optimum process design and nominal operating conditions
C3H6 + C6H6 ⟶ C9H12 63742 0.96 0.87 thus obtained are shown in Fig. 6. Table 4 summarizes the
r1 = 6.981 × 105 exp RT
CB CP
equipment sizing and cost information of the RDWC design.
C3H6 + C9H12 ⟶ C12H18 79162 0.61 0.92
r2 = 4.000 × 104 exp RT
CC CP The TAC of the proposed design is $2.6930×106 yr−1.
C6H6 + C12H18⇌2 C9H12 100000
rf = 2.529 × 108 exp RT
xB xD

rb = 3.877 × 109 exp

127240 2
RT
xC 4. Plant wide control system design and
performance
a
CB: Benzene Composition. CP: Propylene Composition. CC:
Cumene Composition. CD: DIPB Composition. xB: Benzene mole
The controllability of the proposed RDWC design is to be
fraction. xD: DIPB mole fraction. xC: Cumene mole fraction.
tested using traditional decentralized control shown in
Composition units: kmol ⋅ m−3. Reaction rate units: kmol ⋅ m−3 ⋅ s−1.
R: 8.316 kJ ⋅ kmol−1. Thermodynamic package: Peng-Robinson. Fig. 10. A ± 10% throughput step change and a ± 4 mol% C3=
feed composition change are the principal disturbances for
which the system is to be tested. The control structure is now
synthesized. To the extent possible, temperature inferential
Table 3 – Fenske equation data for Single Pot RDWC.
control is to be used. To facilitate the proper choice of the
Light key
controlled tray temperatures, Fig. 9 plots the column tem­
composition
perature and composition profiles Fig. 10.
Section Light key Top Bottom αav N min N

C9 Rectifier Cumene 0.999 0.8781 4.44 3.30 10 4.1. Control structure synthesis
C6 Stripper Benzene 0.1022 0.0001 23.06 2.26 10
C9 Stripper Cumene 0.7170 0.20 5.51 1.36 3 The first step in synthesizing the control structure is to
choose the throughput manipulator (TPM). In line with

Fig. 7 – Effect of Reaction Section Pressure with a) Propylene (C3= ) loss b) Benzene (C6) loss.

Fig. 8 – Variation in TAC with a) Bottom C12 mole fraction (x CBot

12
) b) vapor split (f).
 Chemical Engineering Research and Design 190 (2023) 220–232 227

Table 4 – Costing and sizing details of RDWC.

Size CC $106 Energy kW OC $106 yr−1 UCC $106 UOC $106 yr−1

Reactive Divided Wall Column (RDWC)

HP Column Height (m) 60.57 1.3137 2.1874 0.0300

Diameter (m) 1.3
Condenser(m2) 250.49 0.5539 3272.44 0.03
Drum(m3) 4.99 0.1332
Tray(m2) 1.19 0.1866
LP Column Height (m) 10.53 0.4936 0.9871 0.9588
Diameter (m) 1.77
Condenser(m2) 21.23 0.1113 1551.0 0.0142
Reboiler (m2) 51.97 0.1993 2059.1 0.9446
Drum(m3) 4.04 0.0822
Tray(m2) 2.21 0.1007
Catalyst Weight (tons) 12.00 0.6000 0.6000
Total 3.7745 0.9888

Miscellaneous

Pump 0.0839 6.21 0.0053 0.0839 0.0053

Compressor 0.6862 401 0.1840 0.6862 0.1840
Grand Total Steam 2460 1.1286 4.5446 * 1.1781#
Cooling Water 4823.44 0.0442
Electricity 6.21 0.0053
TAC $2.6930 × 106 yr−1
−1 −1 −1
Steam cost: $17.70 GJ , Cooling water cost:$0.354 GJ , Electricity:$33.04 GJ . CC = Capital Cost, OC = Operating Cost, UCC = Unit Capital Cost,
UOC = Unit Operating Cost. *TCC = Total Capital Cost, #YOC=Yearly Operating Cost

conventional practice, the TPM is fixed at the C3= (limiting
reactant) fresh feed. The reactive zone pressure is controlled
by manipulating the condenser duty. The vapor distillate is
manipulated to hold the condenser temperature. The reflux
drum level is regulated by manipulating the reflux rate while
the bottom liquid trap-out tray level is controlled by ma­
nipulating the side-draw rate. The fresh C6 feed rate is
maintained in ratio with the fresh C3= feed. To compensate for
any stoichiometric imbalance in the feeds, the output of the
ratio multiplier is biased by a temperature inferential feed­
back controller that maintains the difference between the
temperatures of Tray 39 and Tray 33 in the alkylation zone.
These tray locations have been chosen as they correspond to
a sharp change in the C6 and C9 composition profile. This
additive feedback - ratio feedforward configuration (Luyben,
2022) provides more effective stoichiometric feed balancing
compared to conventional feedback adjustment of the ratio
setpoint (multiplicative feedback). On the fractionator side of
the column, the pressure is maintained by manipulating the
C9 condenser duty. The bottom sump level is maintained by
manipulating the bottom rate. The C9 rectifier reflux drum
level is regulated by manipulating the C9 product rate. The
reflux rate is manipulated to hold the temperature of tray
number 53th in the C9 rectifying section. To ensure C6 does
not leak down the C6 stripping section, Tray 57 temperature
is controlled by adjusting the reboiler duty. To ensure vapor
does not build/deplete in the C6 stripping section, its top
pressure is controlled by manipulating the compressor duty.
4.2. Dynamic simulation and tuning
The steady-state simulation is exported to the aspen dy­
namics after initializing hold-ups and flow resistances must
be initialized for a pressure-driven rigorous dynamic simu­
lation. All surge levels are sized for a 5–10 min residence time
at the nominal design with 50% hold-up. Also, the control
valves are sized for a significant pressure drop at the nominal
design condition for good flow rangeability.

Fig. 9 – Compact RDWC Column Profiles a) Composition Profile b) Temperature Profile.

228 Chemical Engineering Research and Design 190 (2023) 220–232

Fig. 10 – Control Structure of Single Pot RDWC Process.

The temperature measurements are lagged by 30 s to
account for sensor dynamics. The control signals to the
condenser and reboiler duty valves are lagged by 2 min to
account for heat transfer equipment dynamics. All flow
controllers are PI and tuned with Kc = 0.5 (%/%) and τI = 1 min
for a fast and non-oscillatory response. All the pressure
controllers are PI and tuned using the relay feedback test
with Zeigler-Nichols settings for tight pressure control. All
level controllers are P only with Kc = 2 (%/%). The tray tem­
perature controllers are tuned using the relay feedback test
with Tyreus-Luyben settings. First, the T57 (C9 stripping sec­
tion) temperature controller is tuned with all other
temperature controllers on the manual. Next, with the T57
controller on automatic, the T53 (C9 rectifying section) con­
troller is tuned. Then with both T57 and T53 controllers on
automatic, the ΔT (reacting section) controller in tuned. The
tuning parameters thus obtained are noted in Table 5.
4.3. Closed loop performance
The closed-loop performance of the control system is eval­
uated for a ± 10% TPM setpoint step change and a ± 4 mol%
C3= mol fraction step change in the fresh feed. The obtained
dynamic responses are shown in Fig. 11. The TPM change
 Chemical Engineering Research and Design 190 (2023) 220–232 229

Table 5 – Tuning parameters by a TL tuning with corresponding set point.

Controller Gain Reset time (min) Set point (∘C) Sensor span (∘C) MV Span

ΔTC 9.00 18.48 5.82 (0,11.56) (− 10,10) kmol/hr

TC1 5.76 11.88 166.17 (0332.34) (0,14.83) GJ/hr
TC2 5.24 11.10 161.61 (0323.22) (0,12290) kg/hr

Fig. 11 – Plantwide transient response of Single Pot RDWC process to principal disturbances (a) Feed Throughput change:
+ 10%; − 10%. (b) Feed composition change: + 4%; − 4%.
230 Chemical Engineering Research and Design 190 (2023) 220–232
disturbance is effectively handled with smooth flow tran­
sients and the response completing in about 6–8 hrs. The
product purity control is tight with the maximum deviation
being within ± 0.1 mol%. Similarly, the C3= feed composition
disturbance is also handled effectively with the fresh C6 feed
increasing or decreasing to match the altered consumption
rate of C3= in the reactive zone. The response completion time
is about 6–8 hrs. In the transient period, the product quality
control is acceptably tight with the maximum deviation
being within ± 0.1 mol%.
Overall these dynamic results suggest that the developed
process design effectively handles the expected production
rate and feed composition change disturbance using a simple
decentralized control structure. The compact cumene pro­
cess exhibits good controllability.
5. Economic design of conventional and RD
processes
In this section, near minimum TAC steady-state designs of
the conventional (Fig. 1), and the RD (Fig. 2) processes are
obtained and compared with the proposed RDWC design.
Strictly speaking, the optimization is an MINLP problem. It is
however not practical due to the fragility of process simula­
tors that often require manual intervention to converge to a
steady state for reasonable specifications. Thus, as the opti­
mizer updates the flowsheet specifications, one eventually
hits a spec where the steady-state solver fails to converge,
prematurely terminating the optimization iterations. We
then do not obtain a significantly better design than the in­
itial guess. In this situation, we optimize the major design
variables that have a significant effect on the TAC to obtain
near-optimum values for the same and then compare the
design alternative TACs. The approach has been re­
commended by Douglas in his pioneering process design
textbook (Douglas, 1988).
5.1. Conventional process design
We apply heuristics to fix the pressure, the number of trays
as well as some of the split specifications for the three dis­
tillation columns. Column C1 purges C3 as the vapor dis­
tillate. To minimize the C6 loss in the distillate, the
condenser temperature and pressure should be, respectively,
as low and as high as possible. Accordingly, the condenser
temperature is set at 50∘C and the column pressure is set at
9.5 bar for a reboiler temperature of 240∘C, which is the
highest temperature achievable using high-pressure steam
as the heating utility. Columns C2 and C3 are operated
slightly above atmospheric at 1.1 bar. The number of trays in
each column is set to thrice the minimum from the Fenske
equation. On C1, which performs the relatively easy C3 − C6
split, a column design-spec vary holds the bottoms propane
mol fraction at 0.1 mol% for a sharp split. In column C2, the
benzene purity up the top is optimized. A design spec vary
holds the bottoms benzene impurity at 0.01 mol%, which
results in a cumene product benzene impurity of 0.01 mol%,
which is the same as for the RDWC process. In column C3, a
design spec vary holds the distillate cumene product purity
at 99.9 mol%. The bottom C12 purity is optimized. All column
feed locations are chosen to minimize their respective re­
boiler duties.
With the columns thus configured, we focus on the other
remaining design variables. Douglas’ doctrine dictates
minimizing the loss of expensive C3= reactant as it is not re­
covered and recycled. The alkylator is therefore sized for a
high single pass propylene conversion, XC3 = 99.5% (eco­
nomic constraint), the same as for the compact single unit
process. The other design variables are:
1. Reactor pressure (PRX).
2. Alkylator inlet temperature (TRXin ).
3. C6 to C3= ratio to the alkylator [C6 C3=]RX .
4. Recycle C6 purity (xC6 ).
5. Transalkylator inlet temperature (TTAin ).
6. C6 to C12 ratio to the transalkylator ([C6 C12]TA ).
7. Recycle C12 purity (xC12 ).
The alkylator is a pressurized water-cooled shell-and-tube
heat exchanger with catalyst-loaded tubes. The shell-side
pressurized water (coolant) flow rate is kept high for a small
coolant temperature rise. The tubes then ‘see’ a nearly con­
stant shell side temperature, TRXshell. As a balance between
reaction quenching (excessive cooling) and reaction run-away
(limited cooling), TRXshell is chosen to be the same as the al­
kylator inlet temperature, ie TRXshell = TRXin (operational con­
straint) (Luyben, 2010b). Because the main reaction is highly
exothermic, the temperature profile inside the alkylator is
sharp with a hot spot. To prevent catalyst damage, the hot
spot temperature, Thotspot≤ 400∘C (operational constraint). Also
for prolonging catalyst life, the temperature rise in the alky­
lator, TRX = Thotspot TRXin 50°C (operational constraint). Due
to the high exothermicity of the main reaction, satisfying
these operational constraints requires maximizing the heat
transfer area in the shell-and-tube alkylator subject to the
tube pressure drop being reasonable. Accordingly, 2 in. inner
dia tubes are used.
The C6 to C3= ratio to the alkylator (C6 C3=)RX should be > 1 so
that C6 is in excess for suppressing C12 formation. The excess
C6 also acts as a heat carrier and suppresses Thotspot. Now
since the alkylator is the most expensive equipment in the
flowsheet, the TAC gets minimized by minimizing the re­
actor size for the specified single pass conversion of 99.5%.
The reactor size, in turn gets minimized by running the re­
actor at the highest allowed temperature without violating
the hot spot and temperature rise operational constraints as
well as ensuring that the alkylator operation is in the vapor
phase with no liquid condensation. Given that the main re­
action is highly exothermic, TRXin = 350° C with Thotspot
reaching 400∘C, appears to be a good choice for the hottest
possible reactor. To prevent condensation in this tempera­
ture range, we set PRX = 25 bar which gives a dew point
temperature of the reactor exit stream of about 315∘C, which
is sufficiently below 350∘C. Fig. 12a plots the variation in the
TAC with TRXin . At the minimum TAC, TRXin = 350°C. For a
higher TRXin , the Thotspot = 400∘C constraint is active and the
TAC increases due to the increased (C6 C3=)RX required for
MAX
Thotspot at 400∘C. For TRXin < 350∘C, the TRX constraint is ac­
tive and the TAC increases since the reactor is now colder
and therefore longer for 99.5% propylene conversion.
The variation in TAC with the purity of the benzene re­
cycle stream (xC6 ) is plotted in Fig. 12b. The optimum purity is
97 mol%. Above it, the benzene recycle column capital and
operating cost increases substantially. Below it, the TAC in­
creases due to higher C12 formation in the alkylator and the
consequently higher C12 recycle-to-extinction cost.
The transalkylation reaction is only slightly exothermic so
that the transalkylator is adiabatic. The slight exothermicity
 Chemical Engineering Research and Design 190 (2023) 220–232
Fig. 12 – Variation of TAC with a) Reactor inlet temperature b) C6 composition c) C6∕C12 ratio d) C12 composition for
conventional process.
also implies that the decrease in the equilibrium conversion
with temperature is slight. To reduce the transalkylator size
for near-equilibrium conversion, its temperature should be
as high as possible, subject to an operational constraint. We,
therefore set the transalkylator inlet temperature, (TTAin ), to
240∘C, the highest feasible temperature achievable using
high-pressure steam as a cheap heating utility.
The C6 to C12 ratio to the transalkylator ([C6 C12]TA ) affects
the flow rate in the C12 recycle-to-extinction loop and hence
the capital and operating cost of each equipment inside the
loop. Increasing the ratio causes the equilibrium C12 con­
version to increase. The recycle-to-extinction flow rate of C12
in the loop then decreases at the expense of higher C6 re­
cycled per unit C12. We constrain ([C6 C12]TA ) 2 to avoid
processing issues due to recycle of heavies [C12 and higher
poly isopropyl benzenes (PIPBs)] with lower ratios causing
fouling and flow issues. The variation in the TAC with
([C6 C12]TA ) holding the other dominant design variables fixed
at their finally recommended values is shown in Fig. 12c. The
‘best’ ([C6 C12]TA ) is constrained at its minimum allowed value
of 2.
The recycle C12 purity (xC12 ) is the last design variable
studied. Increasing xC12 increases C3 reboiler duty due to the
purer bottoms. Decreasing it results in a higher recycle-to-
extinction loop flow rate since the bottom stream now has
less C12. There then exists an optimum xC12 . Fig. 12d plots the
variation in the TAC with xC12 holding all other specifications
at their finally recommended values. The near op­
timum xC12 = 0.95.
231
The ‘near’ optimum steady-state design and operating
conditions for the conventional process obtained as ex­
plained above are shown in Fig. 1. Using the pricing data, and
equipment cost correlation details in Supporting Information
Table S1, the conventional process TAC is obtained as
$4.6544 × 106 yr−1. The major equipment sizing and cost de­
tails for the recommended design are provided in Supporting
Information Table S2. The RDWC process, with its TAC of
$2.6930 × 106 yr−1 is a significant 42% cheaper than the con­
ventional process. This is directly attributable to the process
integration in the RDWC process.
5.2. RD process design
The RD process has fewer design DoFs. The C3= fresh feed sets
the production rate. The alkylation reactive zone is sized (# of
reactive trays and catalyst hold-up per tray) to ensure near
complete (99.5%) conversion of C3= . Similar to the RDWC
process, the catalytic packing height on each reactive tray is
no more than 0.3 m (∼ 1 ft). The distance between two cat­
alytic trays is 0.9 m (∼ 3 ft). As before, the number of trays in a
non-reactive fractionation section is set to about thrice the
minimum trays from the Fenske equation.
The C6 fresh feed is adjusted to ‘make-up’ for consump­
tion by reaction. This is ensured by a flowsheet design spec
vary that maintains the C6 to C3= ratio in the fuel gas stream at
1.1, which ensures a water-cooled condenser temperature of
50∘C is feasible over the process operation envelopes. We are
then left with the 4 steady-state DoFs for the two columns.
232 Chemical Engineering Research and Design 190 (2023) 220–232
Fig. 13 – Variation of TAC with C12 composition for RD
Process.
The two product impurity mol fractions, xCprod
12
= 0.0009 and
xCprod
6
= 0.0001, take away two DoFs. An RD condenser tem­
perature of 50∘C takes away the third DoF leaving one re­
maining DoF for optimization. This DoF is the C12 purity of
the RD column bottoms stream. Fig. 13 plots the variation in
TAC with the C12 purity. The optimum value obtained is 0.84.
The ‘near’ optimum design and operating conditions for the
RD process are shown in Fig. 2.
The TAC of the optimized RD process is 2.5883 × 106 yr−1.
The equipment sizing and cost details are provided in
Supporting Information Table S3. The proposed RDWC pro­
cess is slightly more expensive (∼ 4%) than the RD process.
The TAC of the RDWC process is slightly higher due to the
significant compression cost (capital and operating), which is
not fully offset by the reduction in equipment capital cost
through process integration into a single unit. Nevertheless,
in our consideration, the more compact RDWC process
should be preferable for capacity expansion in existing
space-constrained facilities.
6. Conclusions
This study synthesizes and compares the compact single-
unit RDWC process to the existing conventional and RD
processes for continuous cumene production. Results show
that in terms of the TAC, the proposed RDWC design is about
42% cheaper than a conventional process and slightly more
expensive than the RD process. Lower capital and energy
costs from process integration may be responsible for cost
savings as compared to conventional process design. The
RDWC process TAC is slightly more expensive than the RD
process as the saving due to fewer columns is offset by the
capital and operating cost for the compressor required for
supplying vapor to the pressurized reactive zone. The plant-
wide control results show that the RDWC process effectively
handles large throughput and feed C3 composition changes.
The RDWC process is therefore a promising alternative to the
conventional process due to significant cost savings. It may
also be preferred over the RD process in scenarios where the
availability of space is a limiting constraint.
Declaration of Competing Interest
The authors declare that they have no known competing fi­
nancial interests or personal relationships that could have
appeared to influence the work reported in this paper.
Acknowledgement
The financial support from the Ministry of Education,
Government of India, is gratefully acknowledged.
Appendix A. Supporting information
Supplementary data associated with this article can be found
in the online version at doi:10.1016/j.cherd.2022.12.026.
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