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Economic Design and Optimization of Zeolite-Based Cumene

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ECONOMIC DESIGN AND OPTIMIZATION OF

ZEOLITE-BASED CUMENE PRODUCTION
PLANT
a a a a
H. R. Norouzi , M. A. Hasani , B. Haddadi-Sisakht & N. Mostoufi
a
Process Design and Simulation Research Centre, Oil and Gas
Centre of Excellence, School of Chemical Engineering, College of
Engineering, University of Tehran , Tehran , Iran
Accepted author version posted online: 14 Apr 2014.Published
online: 29 May 2014.

To cite this article: H. R. Norouzi , M. A. Hasani , B. Haddadi-Sisakht & N. Mostoufi (2014) ECONOMIC
DESIGN AND OPTIMIZATION OF ZEOLITE-BASED CUMENE PRODUCTION PLANT, Chemical Engineering
Communications, 201:10, 1270-1293, DOI: 10.1080/00986445.2013.806312

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 Chem. Eng. Comm., 201:1270–1293, 2014
Copyright # Taylor & Francis Group, LLC
ISSN: 0098-6445 print=1563-5201 online
DOI: 10.1080/00986445.2013.806312

Economic Design and Optimization of

Zeolite-Based Cumene Production Plant

H. R. NOROUZI, M. A. HASANI,
B. HADDADI-SISAKHT, AND N. MOSTOUFI
Process Design and Simulation Research Centre, Oil and Gas Centre of
Downloaded by [University of Saskatchewan Library] at 11:34 04 June 2014

Excellence, School of Chemical Engineering, College of Engineering,

University of Tehran, Tehran, Iran

The aim of this work is intensification of an industrial-scale production process of

cumene to obtain higher profitability and reduce the energy requirements of the
process. In the first step, two topological changes were made in the reactor configur-
ation and benzene separation column, which led to a considerable reduction in utility
requirements and equipment sizes in the process. In the second step, parametric
optimization was carried out by a statistical method (full factorial design) to adjust
the process parameters. In the final step, a pinch analysis was done to reduce utility
requirements of the process. A mathematical model was developed based on the
statistical analysis, which was then used to obtain optimized conditions of the process.
The capital investment of the process remained almost intact, around $4.5 million,
and the utility requirements reduced from $2.44 to 1.49 million=yr. These changes
greatly enhanced the profitability of the process, for which the net present value
was increased from $0.82 to 4.53 million.

Keywords Cumene; Economic optimization; Factorial design; Statistical

method; Zeolite catalyst

Introduction
Finding a configuration and operational conditions of a process in which a chemical
is produced in a reliable and economical manner with low energy consumption, low
initial capital investment, low or negligible environmental impact, and high yield is
the goal of plant design engineers. Optimization of a process is conducted when the
flow sheet of the base case and detailed mass and energy balances of the process are
available. Moreover, the economic aspects of the plant, including size of equipment,
capital investment, and utility requirements, must be evaluated (Seider et al., 2010).
It requires a great amount of knowledge, experience, and hard work. In this work,
intensification of the liquid-phase alkylation of benzene with propylene was carried
out to make the process more effective and thus more profitable.

Address correspondence to N. Mostoufi, Process Design and Simulation Research Centre,

Oil and Gas Centre of Excellence, School of Chemical Engineering, College of Engineering,
University of Tehran, P.O. Box 11155=4563, Tehran, Iran. E-mail: mostoufi@ut.ac.ir
Color versions of one or more of the figures in the article can be found online at www.
tandfonline.com/gcec.

1270
 Zeolite-Based Cumene Production Plant 1271

The vast majority of cumene (isopropylbenzene) manufactured worldwide is used

in the production of phenol and acetone (Schmidt, 2005). Reactions occur in the pres-
ence of different catalysts such as solid phosphoric acid (SPA), aluminum chloride
(AlCl3), and zeolites. The first license for cumene production belongs to the corpor-
ation UOP; in this process the reaction occurs in the gas phase in the presence of SPA
catalyst (Stefanidakis and Gwyn, 1977). This catalyst had been originally used for
converting light olefins into gasoline components (Gary and Handwerk, 1994). The
side reactions occurring when using SPA catalyst produce poly-isopropyl-benzenes
(PIPB), which cannot be converted back to cumene by the transalkylation reaction.
These heavy components must be removed in the following separation section. The
problem in this process is the low overall yield, high temperature of the reactor,
and short-life and unregenerable catalyst, which has hazardous environmental effects.
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Another license belongs to Monsanto and Kellogg, which uses a mixture of

AlCl3 and HCl as the catalyst in a homogeneous liquid-phase reaction of benzene
and propylene. The transalkylation of PIPB is also possible in this process. Thus,
this process has a high yield. However, corrosion of pipes and equipment are still
a problem (Canfield et al., 1986).
Liquid-phase and zeolite-based catalytic processes were developed by CDTech
(Pohl and Ram, 2005; Sy et al., 1993), Mobil-Badger, and UOP (Hwang and Chen,
2010). This catalyst is regenerable, and transalkylation reactions also occur over this
catalyst. Among different the zeolite-based processes, the technology developed
by CDTech uses reactive distillation, while the others use two fixed-bed reactors
for performing alkylation and transalkylation reactions.
Many researchers have investigated the optimization of the above-mentioned
processes. Luyben (2010) studied the gas-phase process on the SPA catalyst and econ-
omically optimized the process with a simple model. Total annualized cost (TAC),
which accounts for initial investment with a three-year payback time, operating costs,
and raw material costs, was the objective function to be minimized in that study.
Pathak et al. (2011) studied the vapor-phase and reactive distillation (RD) process
of CDTech for cumene. They also used TAC as the objective function and concluded
that the reactive distillation process is 47% cheaper than the conventional gas-phase
process. Lei et al. (2009) considered a zeolite-based process that uses two fixed-bed
reactors. They started with side stream draw from a distillation column to reduce
energy consumption. They further modified the alkylation reactor and replaced it
with a reactive distillation column and concluded that the energy consumption and
total investment can be reduced in this way. However, they did not include any econ-
omic evaluation in the optimization procedure. Norouzi and Fatemi (2012) studied
gas-phase production of cumene on SPA catalyst and developed an economic model
that comprised initial investment, operating costs, labor costs, raw material costs,
revenue, plant life, and inflation, among other factors. The net present value
(NPV) was chosen as the objective function, and a statistical procedure, response
surface method, was chosen to adjust operational conditions and to find the global
optimum of the process to maximize the NPV.
In the present study, liquid-phase alkylation of benzene on a zeolite catalyst was
investigated. This process corresponds to the process proposed by UOP and Mobil-
Badger (Hwang and Chen, 2010) which uses two fixed-bed reactors and a separation
train to recover the product. A full economic model was developed for optimization.
This model includes grass root capital investment, operating and raw material costs,
revenue, plant life, taxes, and inflation and was adjusted for the year 2011. The
 1272 H. R. Norouzi et al.

optimization procedure was divided into two parts. First, some changes were made in
the topology of the process to reduce the utility requirements and to enhance the NPV
of the process. Second, full factorial design, which is a statistical method, was used to
optimize the operational conditions of the process to obtain a higher NPV.

Process Description
Cumene is produced by alkylation of benzene with propylene on a proper catalyst like
zeolite-based catalysts such as b, Y, ZSM-12, and MCM-22 (Corma et al., 2000;
Dimian and Bildea, 2008; Han et al., 2001; Perego et al., 1996). The reactions occur
in the liquid phase at a temperature range that yields complete conversion of propy-
lene and under a proper pressure to maintain the reactants in the liquid phase
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throughout the reactor. Different licenses that use liquid-phase reactors consider a
series of two reactors. In the first reactor, known as the alkylation reactor, the follow-
ing reactions take place:

k1
C3 H6 þ C6 H6 ! C9 H12
Propylene benzene cumene

k2
C3 H6 þ C9 H12 ! C9 H12
Propylene cumene DIPB

The first reaction yields the main product of the process. The produced cumene may
further react with propylene to produce DIPB or higher propyl-benzenes. Here, for
simplicity, it was assumed that the only by-product is DIPB. The reaction rate
constants are listed in Table I (Dimian and Bildea, 2008). It was shown that the
alkylation reactions follow the Eley-Rideal kinetic model in which the adsorption
of propylene is the rate-determining step (Corma et al., 2000). In the range of operat-
ing conditions of this process, this kinetic law reduces to a first-order reaction, as
shown in Table I (Dimian and Bildea, 2008). The reactor is an adiabatic fixed bed
of catalyst pellets with the inlet temperature range of 150
to 200
C. The pressure
is maintained high enough to ensure that the boiling point temperature of the solution
is at least 20
C higher than the temperature anywhere else in the reactor. Therefore,
the pressure has to be maintained between 2.5 and 3.5 MPa depending on the compo-
sition of the mixture and the temperature of the reactor. The benzene to propylene
mole ratio (B=P) is maintained at more than 4 in the reactor (Perego and Ingallina,

Table I. Kinetics of alkylation and transalkylation reactions (Dimian and Bildea,

2008; Pathak et al., 2011)

Reactor Reaction Rate expression Rate constants

Alkylation Cumene reaction k1Cp k1 ¼ 6510 exp 52564
RT


DIPB reaction K2Cp k2 ¼ 450 exp 55000
RT
100000


Transalkylation Forward k3 xB xD k3 ¼ 2:529  108 exp RT
127240


Backward k4 x2c k4 ¼ 3:877  109 exp RT

E is in kJ=kmol, rate of reaction is in kmol=m3  s, and concentration is in kmol=m3.

 Zeolite-Based Cumene Production Plant 1273

2002). An excess amount of benzene is required in the reactor for the following rea-
sons: to absorb heat generated by exothermic reactions in the rector, to enhance the
selectivity of the cumene reaction over the DIPB reaction, and to suppress the reac-
tion between propylene molecules, which produces higher linear hydrocarbons. The
boiling temperature of these hydrocarbons is close to that of benzene, thus, separating
them from benzene (to avoid accumulation) becomes problematic.
In the second adiabatic reactor, known as the transalkylation reactor, the
produced DIPB is converted back to cumene in a reaction with benzene in the liquid
phase:
k3
C6 H6 þ C12 H18 â 2 C9 H12 ð3Þ
benzene DIPB cumene
k4
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The inlet temperature for this reactor is about 220
–240
C, and the benzene to DIPB
mole ratio is between 5 and 10. The reaction rate constants of these reactions are listed
in Table I (Pathak et al., 2011). Utilization of the second reactor enhances the overall
yield of the alkylation process and hence the profitability of the whole plant.
A typical process flow diagram of cumene production on a zeolite catalyst is
shown in Figure 1. Fresh and pure benzene at the molar rate of 100 kmol=h is fed
to the vessel V-1, mixed with the recycled benzene coming from the separation
section, and pumped to 3.6 MPa. The recycled benzene is utilized to maintain the ben-
zene to propylene mole ratio at the desired value. The refinery-grade propylene at the
molar flow rate of 105 kmol=h (5 kmol=h propane as impurity) is pumped to 3.6 MPa
and mixed with the benzene stream. The mixed feed stream is heated to 170
C by the
hot outlet product stream of the alkylation reactor in the heat exchanger E-1. The pre-
viously mentioned reactions occur (Equations (1) and (2)) in the alkylation reactor
R-1. Both reactions are highly exothermic, thus, the temperature of the reactants
increases gradually along the reactor length. The inlet temperature and B=P must
be maintained in a way that no vapor is generated in the reactor. Complete conversion
of propylene is desired due to two important facts: first, the unreacted propylene
would escape from the process in the propane column (C-1) with propane, which is

Figure 1. Process flow diagram of liquid phase cumene production for the base case.
 Downloaded by [University of Saskatchewan Library] at 11:34 04 June 2014

Table II. Stream table of process flow diagram shown in Figure 1

Fresh Fresh Mixed Alkylation Fuel Benzene C-2 bot- Trans Trans
Stream benzene propylene feed effluents gas C2-feed ovhd toms Cumene DIPB feed effluents
Temperature 25.0 25.0 170.0 257.5 56.7 113.3 81.7 161.3 151.8 213.4 240.0 240.3
[
C]
Pressure 0.10 1.15 3.54 3.54 1.50 0.13 0.10 0.12 0.10 0.11 3.50 3.50
[MPa]
Vapor 0.00 0.00 0.00 0.00 1.00 0.72 0.00 0.00 0.00 0.00 0.00 0.00
fraction

1274
Mole flow 100.0 105.0 605.0 505.0 5.10 532.37 425.00 107.37 99.90 7.47 32.47 32.47
[kmol=h]
Mass flow 7811.4 4428.5 44547.4 44547.4 228.2 47550.4 34327.4 13223.0 12011.2 1211.8 3231.2 3231.2
[kg=h]
Comp. mole flow [kmol=h]
Benzene 100 474.76 378.41 0.099 398.3 398.2 0.144 0.144 0.00 23.42 20.0
Propylene 100 100.0 0.002 0.002 0.0 0.0 0.0 0.0 0.0 0.0 0.0
Propane 5 5.00 5.00 5.00 0.0 0.0 0.0 0.0 0.0 0.0 0.0
Cumene 25.237 117.94 0.0 126.4 26.83 99.54 99.53 0.003 1.580 8.427
DIPBs 0.001 3.649 0.0 7.692 0.001 7.691 0.225 7.466 7.467 4.043
 Zeolite-Based Cumene Production Plant 1275

economically unfavorable; second, benzene and propylene are reacted with a 1:1 mole
ratio and the inlet flow rate of benzene to the process should be reduced in the fresh
benzene stream, which in turn reduces the overall productivity of the plant.
The reactor effluent is passed through the heat exchangers E-1 and E-2 and then
is fed to the propane column in which propane is completely removed from other
components. The condenser E-3 is partial and its pressure is 1.5 MPa. The overhead
stream has fuel value and can be used in the fuel cycle of the process. The bottom
liquid leaving the propane column is mixed with the product stream of transalkyla-
tion reactor R-2 (trans effluents) and is fed to the benzene column C-2 in which
benzene is collected in the overhead and recycled back to both reactors. In this
column, the concentration of benzene in the bottom stream must be negligible to
ensure high purity of cumene in the next column. Bottoms of the benzene column
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are sent to the cumene column C-3 where cumene product is obtained overhead with
a minimum purity of 99.5%. The bottoms of this column, containing mostly DIPB,
are mixed with the recycled benzene from the benzene column (transalkylation
recycle) and fed to the transalkylation reactor R-2. In this reactor, DIPB is converted
back to cumene. The effluent from this reactor is then sent to the benzene column
C-2. A stream table of the base case, described above, is supplied in Table II.
The number of trays and reflux ratios of columns were determined according to
the following procedure:
. The minimum reflux ratio and minimum number of trays were determined using
the shortcut method (Seider et al., 2010).
. The actual number of trays and feed stage were determined based on the actual
reflux ratio, which was chosen to be 1.25 times the minimum reflux ratio.
. Since the shortcut method does not provide the exact solution of the column, an
exact simulation of the column was made using the rigorous distillation method.
After simulating the column with the number of trays and the feed stage, the
reflux ratio was adjusted to achieve the desired purification.

Economic Model
As the main goal of this study is the economic optimization of the cumene production
process, the consideration of a comprehensive economic model that takes into
account all effective parameters is essential. This economic model requires infor-
mation about the fixed capital investment, the annual utility requirements, the raw
material costs, the operating labor costs, and the revenue of the process. The methods
for evaluating all these factors are introduced in the following.

Capital Investment
There are methods for estimating the capital cost of a process at the preliminary
design stage, such as the Lang factor, the six-tenths rule, and the bare module cost
(Turton et al., 1998). The bare module cost is a more detailed cost estimation method
that considers the construction materials, the operating pressure, and the special
configuration of equipment in cost estimation. This technique relates all costs to
the purchased cost of equipment evaluated for some base conditions. The bare
module cost of equipment is determined by the following relation:

0 0
CBM ¼ CP FBM ð4Þ
 1276 H. R. Norouzi et al.

To estimate the bare module cost of all major equipment in the cumene process,
it is necessary to know the size, the construction material, the configuration, and the
operating pressure of all equipment. Detailed information about the construction
materials and the operating conditions of the major equipment in the process
(base case) is listed in Table III. The bare module correlations for estimating the
equipment costs belong to past data on purchased equipment, and they need to be
updated according to changes in economic conditions (such as inflation). The
Chemical Engineering Plant Cost Index (CEPCI) was used to account for the effect
of inflation:
 
0 0 CEPCI2
ðCBM Þ2 ¼ ðCBM Þ1 ð5Þ
CEPCI1
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where subscripts 1 and 2 refer to the base time and the present time of cost
estimation, respectively. The correlations used for estimating equipment costs belong
to 1996 with a CEPCI of 382. The CEPCI for the year 2011 was 585.7, and all costs
were adjusted according to this value.

Utility Cost
The fuel price fluctuates more than equipment costs, and, in fact, it does not follow
a general trend like the CEPCI. The cost of utilities in a plant is greatly influenced by
the price of fuel. In general, the utility cost is linked to two separate variable costs:
inflation (CEPCI) and fuel cost. To reflect this dual dependence, the following
two-factor equation was used (Ulrich and Vasudevan, 2006):

Cu ¼ aðCEPCIÞ þ bðCf Þ ð6Þ

The values of a and b for different utilities are presented by Ulrich and Vasudevan
(2006). The price of fuel is based on the average price of natural gas in 2011 in the
U.S., obtained from the U.S. Department of Energy (2011). The industrial price
for natural gas is $4.9=1000 ft3. Assuming 38.1 MJ=std-m3 heating value for natural
gas (Perry et al., 1999), the price of natural gas was estimated to be $4.54=GJ. Accord-
ing to the price of natural gas as the reference fuel, costs of different utilities were
calculated and are listed in Table IV. This table also includes the values of a and b
for different utilities. Available utilities differ from one process to another. Here,
low pressure (LPS), medium pressure (MPS), and high pressure (HPS) steams at
0.5, 1.0, and 4.1 MPa (gauge), respectively, and cooling water entering at 30
C and
leaving at 45
C were considered as well as electricity for driving pumps.

Raw Material and Product Prices

Prices of raw materials (benzene and propylene) and products (cumene) were
obtained from ICIS (2011). The prices of benzene, propylene, and cumene were
considered as $0.947, $0.970, and $1.050=kg, respectively, for the year 2011. Heat
value of the fuel produced in the ‘‘fuel gas’’ stream was estimated according to the
price of natural gas ($4.54=GJ). The heating values for burning propane, propylene,
benzene, cumene, and DIPB were calculated to be $9.18, $8.68, $14.54, $22.71, and
$30.98=kmol ($0.208, $0.206, $0.186, $0.189, and $0.191=kg), respectively.
 Zeolite-Based Cumene Production Plant 1277

Table III. Operating conditions and sizing data for main equipment in the process

Pressure
Uoveral Material of Utility
(W  m2  K1)b constructionc Tube side Shell side type
Heat Exchangersa
E-1 (Heat ex.) 700 CS=CS 35.5 35.4 None
E-2 (Cooler) 700 CS=CS 35.3 4 CW
E-3 (Condenser) 450 CS=CS 15 4 CW
E-4 (Reboiler) 750 CS=CS 15.2 43 HPS
E-5 (Condenser) 450 CS=CS 1 4 CW
E-6 (Reboiler) 750 CS=CS 1.2 11 MPS
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E-7 (Condenser) 450 CS=CS 1 4 CW

E-8 (Reboiler) 900 CS=CS 1.1 43 HPS
E-9 (Heater) 800 CS=CS 35 43 HPS

Residence Configuration
time (min)d (material)e L=D
Vessels
V-801 10 Horizontal (CS) 3
V-802 10 Horizontal (CS) 3
V-803 10 Horizontal (CS) 3
V-804 10 Horizontal (CS) 3
Towersf
C-1 Reflux ratio ¼ 5, pressure ¼ 1.5 MPa, vessel material:
carbon steel, 12 sieve trays, tray spacing ¼ 61 cm, 80%
active area
C-2 Reflux ratio ¼ 0.25, pressure ¼ 0.1 MPa, vessel material:
carbon steel, 18 sieve trays, tray spacing ¼ 61 cm, 80%
active area
C-3 Reflux ratio ¼ 0.7, pressure ¼ 0.1 MPa, vessel material:
carbon steel, 14 sieve trays, tray spacing ¼ 61 cm, 80%
active area
Reactors
Alkylation reactor Length ¼ 7 m, diameter ¼ 1.3 m, vessel material: carbon
steel
Transalkylation reactor Length ¼ 1.3 m, diameter ¼ 0.7 m, vessel material: carbon
steel
Pumps For all pumps 60% hydraulic efficiency was considered,
construction material: carbon steel
a
20% overdesign.
b
From Gas Processors Suppliers Association (1998).
c
From Stefanidakis and Gwyn (1997).
d
From Branan (1995).
e
From Turton et al. (1998).
f
From Seider et al. (2010).
 1278 H. R. Norouzi et al.

Table IV. Utility cost estimation based on Ulrich and Vasudevan (2006)
for the year 2011

Utility type $=GJ a b

4
Electricity 20 1.30  10 0.010
LP steam (5 MPa (gauge)) 8.21 3.47  106 0.004
MP steam (10 MPa (gauge)) 9.54 3.47  106 0.004
HP steam (42 MPa (gauge)) 12.04 3.47  106 0.004
CW (30 to 45
C) 1.3 7.00  104 0.003
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Other Costs
Other costs of production are operating labor, maintenance cost, and fixed operating
cost. The techniques used to estimate these costs are described by Turton et al.
(1998). The fixed operating costs are independent of changes in the production rate
and include local taxes, insurance, and depreciation, which are charged at a constant
rate even when the plant is not in operation. In the calculation of the fixed operating
costs, an average tax of 30% was assumed and the straight-line depreciation method
for a period of 10 years was used.

Table V. Details of capital investment and utility requirements of different cases in

the optimization procedure

Optimized
Two- case after
Base 4-Bed column Optimized pinch
case reactor case case analysis
Capital investment Total 4.481 3.88 4.26 4.22 4.50
(million $) Heat ex. 1.534 1.405 1.701 1.685 1.965
Towers 0.954 0.738 0.795 0.783 0.783
Reactors 0.483 0.503 0.503 0.511 0.511
Vessels 0.637 0.498 0.503 0.502 0.502
Pumps 0.837 0.735 0.758 0.739 0.739
Utility requirements Total 2.440 1.90 1.75 1.68 1.49
(million $=yr) Steam 2.053 1.597 1.466 1.414 1.25
CW 0.305 0.253 0.232 0.215 0.193
Electricity 0.082 0.048 0.052 0.051 0.051
Catalyst 0.04 0.04 0.04 0.032
Revenue Total 105.348 105.44 105.40 105.42 105.42
(million $=yr) Cumene 104.954 105.05 105.0 105.23 105.23
Fuel prod. 0.394 0.391 0.392 0.393 0.393
Production cost 1.025 1.018 1.017 1.017 1.015
($=kg)
COM (million $=yr) 102.53 101.87 101.7 101.7 101.5
NPV (million $) 0.82 2.95 3.56 4.16 4.53
Present value ratio 1.18 1.76 1.84 1.99 2.01
Payback time (years) 3.3 1.8 1.9 1.9 1.9
 Zeolite-Based Cumene Production Plant 1279

Economic Status of the Base Case

The calculation sequence for economic evaluation of the process is as follows:
. Materials and energy balances were obtained for all operating units in the process
until a final solution was obtained. The results were heat duties, work duties,
stream flow rates, etc.
. The results of materials and energy balances were applied in design equations with
assumptions presented in Table III, and all equipment was sized.
. The results of materials and energy balances as well as sizes of all equipment were
used in the economic model to determine different economic parameters such as
utility costs, equipment costs, and NPV.
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The process described above was considered to be the base case from which the
optimization started. Before proceeding to the optimization of the base case, its
economic status was evaluated to have a criterion for comparison. According to
the material balance of this process and assuming a stream factor of 0.95, the annual
production rate of cumene is 99,960 metric ton. The grass root capital investment of
the process obtained from the economic model was estimated to be $4.48 million=yr
for the year 2011. The utility requirements of the process (based on the energy
balances) were estimated to be $2.44 million=yr. Almost 84.1% of utility requirements
belongs to the steam, followed by the cooling water and the electricity, which are
12.5% and 3.4%, respectively. The net present value and cost of manufacturing
(COM) of the base case are $0.82 million and $102.53 million=yr, respectively. Details
of capital investment, utility requirements, revenue, and economic parameters of the
base case are presented in Table V.
By inspecting the process flow diagram of the process, two loops of materials
and a one-through flow (Main Flow) are distinguishable. The first loop is the

Figure 2. Cost breakdown of utilities requirements in each material processing flow in the
plant, Main flow, Loop1, and Loop2.
 1280 H. R. Norouzi et al.

benzene recycle to the alkylation reactor, and the second loop is the benzene recycle
to the transalkylation reactor. Materials flowing in the first loop (Loop1) are passed
through the following utility-demanding units: P-1, E-2, E-3, E-4, E-5, and E-6.
Also, materials flowing in the second loop (Loop2) are passed through P-6, E-9,
E-5, E-6, and E-8. The cost breakdown of each type of utility, which is required for
processing the materials flowing in each loop, is shown in Figure 2. The main flow
in this figure refers to the stream flow in which materials enter the process once and
leave it as the final product. As can be seen in this figure, the contribution of Loop1
to the utility requirements in the whole process is much greater than that of Loop2 and
Main Flow. This shows that the benzene recycle to the alkylation reactor (Loop1) can
greatly affect the economics of the process. Thus, it is an important variable that
should be adjusted in the process to obtain better profitability. However, adjustment
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of the second benzene recycle (Loop2) seems to be less important. In addition, change
in important parameters of the process, such as reactor inlet temperature and volume
(to achieve higher conversion and selectivity) and separation conditions, can also
change the utility requirement of the main flow in the process.

Economic Optimization Procedure

There are two kinds of optimization procedures, namely topology=configuration
changes and parametric=operating condition changes (Seider et al., 2010; Turton
et al., 1998). Topological changes are carried out prior to the parametric because
they have a greater influence on the profitability of the process. When the topology
of the process is fixed, parametric optimization can be easily carried out by a proper
strategy. Based on the discussion of the utility cost breakdown of the process in the
previous section, Loop1 and Main Flow are the most important parts of the process
that should be considered first in optimization. The optimization procedure starts
with topological changes in the process in which modifications are made to reduce
the utility requirements of Loop1 and Main Flow in the process. The procedure ends
with parametric changes in which the most profitable operating conditions would be
determined. It is worth mentioning that since the overall yield of this process is 100%
(all the entering materials are converted into the desired product), there is no need of
extra space to enhance it by changing either topology or operating conditions. Thus,
the economic condition of the process can be enhanced only through reducing the
utility requirements and capital investment of the process.

Topological Changes
Reactor Topology
As discussed before, to control the reactor temperature and to prevent production of
linear hydrocarbons (reaction between propylene molecules) the B=P should not fall
below a certain threshold. Thus, benzene is recycled back to the alkylation reactor to
achieve such conditions. However, this recycling requires larger equipment and more
utility usage. The calculations above showed that this recycle (Loop1) includes a large
portion in the utility requirement. Thus, the reduction of this stream can greatly influ-
ence both capital investment (smaller equipment) and utility requirements. There are
different configurations proposed for the alkylation reactor in the literature (Hwang
and Chen, 2010; Schmidt, 2005). In one configuration, both propylene and benzene
are premixed, heated, and enter the reactor. In another configuration, the propylene
 Zeolite-Based Cumene Production Plant 1281

stream is divided into several parts (e.g., four) and injected stage-wise along the
reactor. The reactor may have inter-stage cooling to keep the temperature below
the bubble point. When propylene is reduced by one-fourth, the required mole flow
of benzene in the reactor inlet to obtain the same B=P is also reduced. On the other
hand, since the total amount of benzene in the reactor is reduced, the temperature rise
in the reactor is enhanced, and inter-stage cooling is needed to cool down reacting
components.
For the first change, a stage-wise propylene injection was employed to test
whether or not it would change the total profitability of the process. The configur-
ation illustrated in Figure 3 was used instead of the original one. The new configur-
ation consists of four catalytic beds and is called the four-bed reactor hereafter. To
keep the temperature of the reactor below the bubble point, an intercooler was used
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after the second bed. In the four-bed reactor, the flow rate of benzene entering the
reactor was reduced from 500 to 225 kmol=h. However, the B=P was increased from
5 to 9, which is favorable to the process. A minimum value of 225 kmol=h benzene is
required to maintain the temperature below the boiling point throughout the reactor.
Temperature and B=P profiles along the reactor for the base case and the four-bed
reactor are shown in Figure 4(a) and 4(b), respectively. In Figure 4(a), for the base
case, the temperature increases along the reactor as the reactions proceed. In the
four-bed reactor, the temperature increases gradually along the bed and drops at
the end of each bed where the fresh and cold propylene is injected into the bed.
The fresh propylene cannot absorb all the heat generated by the reaction, thus, an
inter-stage cooler is required to reduce the reactor temperature. The boiling
points in the inlet and outlet of each bed are also illustrated in this figure. Figure 4(a)
demonstrates that the temperature is well below the bubble point of the mixture

Figure 3. Alkylation reactor with four catalytic beds and an inter-stage cooler and side feeding
of propylene.
 1282 H. R. Norouzi et al.
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Figure 4. Temperature (a) and B=P ratio (b) profiles along the reactor for the base case and
the four-bed reactor.

throughout the reactor. B=P is shown along the reactor in Figure 4(b); this ratio
increases along the reactor with the consumption of propylene. As can be seen in this
figure, this value is always greater than the minimum allowable B=P in the reactor. The
overall conversion of propylene in both reactor configurations is nearly complete.
The economic condition of the process is enhanced considerably with the above-
mentioned modification to the reactor topology. As expected, the utility consumption
of the process is reduced from $2.44 to 1.9 million=yr. Moreover, due to the
 Zeolite-Based Cumene Production Plant 1283

reduction in the amount of materials processed in Loop1, the size of equipment (P-1,
P-3, E-1, E-2, E-4, E-5, E-6, C-1, C-2, etc.) is reduced. This leads to less total invest-
ment for the process (from $4.48 to 3.88 million) even though an inter-stage cooler is
added in the four-bed reactor configuration. All these effects are reflected in the
profitability of the process: the NPV of the process is increased from $0.82 to 2.95
million and payback time is reduced from 3.3 to 1.8 years. More details about the
capital investment, utility requirements, revenue, and economic parameters of the
new plant are presented in Table V.

Benzene Column Topology

The topology of the flow sheet can still be changed in order to lower the utility
requirement of the process and enhance its economic condition. Hot and cold utilities
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constitute the majority of the utility requirement (more than $1.85 out of $1.9
million=yr). Among the columns in this process, the topology of the benzene column
C-2 can be modified to reduce the utility requirement. A large amount of materials
enters this column (25,000 kg=h), which requires large equipment and large utility
usage. The condenser and reboiler duties are 10.23 and 3.87 GJ=h, respectively, which
impose $450,000=yr utility cost on the process. A reduction in the utility requirement
of this tower can enhance the economic condition of the process. The old and new
configurations for this column are shown in Figure 5(a) and 5(b). The liquid stream
entering the column (C2-Feed) is split into two distinct streams, which are fed to
columns C-2 and C-2þ in the new configuration. The split fraction is defined as:

Flow rate of 00 split 100

SF ¼ ð7Þ
Flow rate of 00 C  2 Feed 00

Figure 5. (a) Original benzene column and (b) the new configuration for benzene column.
 1284 H. R. Norouzi et al.

Operating pressures of C-2 and C-2þ are 1.0 and 8.0 bar, respectively. These
values are selected in a way that the reboiler temperature of C-2 becomes lower (by
at least 10
C) than the condenser temperature of C-2þ. Moreover, since the HP steam
is available at 254
C, the reboiler temperature of C-2þ should not exceed 244
C.
Since the new configuration of the benzene column does not change the operat-
ing conditions and the flow rates of the streams in other parts of the entire process
(and indeed the capital investment and operating cost of the rest of the process),
profitability analysis of the new separation configuration should be focused on the
benzene column alone. It was assumed that both proposed configurations have
the same operating lives as the plant life (i.e., 10 years). However, the operating costs
and the initial investment of these configurations are essentially different. Many cri-
teria are available to evaluate the profitability of the new configuration over the old
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one. Here, the net present value of the benzene separation section was chosen as the
criterion of analysis. The net present value returns all the investments (fixed capital
and operating costs) paid during the plant life converted back to the present time.
Thus, it reflects the effect of time, including plant life and construction periods,
on the value of money. The net present value for the benzene separation section,
assuming 2 years for startup, 10 years plant life, and 10% interest rate, can be
estimated by the following equation (Turton et al., 1998):

NPV ¼ FCITM þ Oprt: Cost  ðP=A; 0:1; 10ÞðP=F ; 0:1; 1Þ ð8Þ

In which FCITM is the total module cost, Optr. Cost is the annual operating cost of the
section. including utility, operating labor, maintenance, etc. The expression in the first
parenthesis of Equation (8) returns the sum of 10 years annual operating cost back to
the year of startup (equal to 6.145), and the expression in the second parentheses
returns this sum to the present time (equal to 0.8264) (Turton et al., 1998).

NPV ¼ FCITM þ 5:08ð1:23 Utility þ 0:18 FCITM þ 2:73 LabourÞ ð9Þ

There are different factors that affect the NPV of the benzene column: the split
fraction of the C-2 Feed (SF), the operating pressure of columns, and the con-
densation rate of C-2þ. The operating pressure of the columns changes the relative
volatility of the components, and the condensation rate changes the vapor and liquid
flows in both columns and the size and utility requirements of both columns. Of
these three, the operating pressures of both columns are kept fixed. According to
the requirements described above, the temperatures of both columns also cannot
be changed noticeably. However, the other two factors, SF and condensation rate,
were tested to find an optimum condition for this column.
The NPV of the new benzene column configuration versus condensation rate at
different split fractions is shown in Figure 6. The NPV of the original benzene column
is $-3.9 million. The shaded rectangle of this figure shows the operating conditions at
which improved economic conditions of the benzene column were obtained. It can be
seen in this figure that better economic conditions are obtained for split fractions 0.5
and 0.6. The proper selection of SF mainly depends on the feed composition and the
place where the product streams are drawn from these columns. When the feed stream
is to be distributed between these two columns, it is better to set a greater value of the
flow rate to the top column (C-2) in which the pressure is lower and relative volatility
is high. Moreover, this column requires cheap cooling water within the condenser,
 Zeolite-Based Cumene Production Plant 1285
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Figure 6. NPV of the new benzene column configuration vs. condensation rate at different
split fractions; shaded rectangle shows the operating conditions at which better economic
condition of benzene column is obtained.

while the bottom column needs expensive steam for evaporation. Better economics
would be obtained if the condensation rate is reduced at constant SF. Reducing the
condensation rate decreases the utility requirements of both the reboiler of C-2þ
and the condenser of C-2. However, a minimum condensation rate exists at which
the two columns can together perform the desired task at each SF, and the con-
densation rate cannot be reduced below this minimum.
For the current case, the condensation rate of 90 kmol=h and SF ¼ 0.6 were
chosen for the new configuration of the benzene column. The operating conditions
and connections between these two columns are shown in Figure 5(b). The required
condenser and reboiler duties are reduced by 54% and 25%, respectively, in the new
configuration. However, it should be noted that the utility type of the reboiler chan-
ged from MPS to HPS, which is 20% more expensive. Details of capital investment,
utility requirements, revenue, and economic parameters of the new plant with new
benzene column configuration are presented in Table V. This table illustrates that
the capital investment is increased while the utility requirement is reduced from
$1.9 to 1.75 million. The final outcome of this change is the enhancement of the
NPV of the process and the reduction of COM.

Operational Conditions Optimization

After performing topological changes to the process, it is necessary to adjust the oper-
ating conditions of the new process at which better profitability is obtained. The selec-
ted operating conditions should have a significant effect on process performance and
hence on the economic status of the process. Here, four parameters were chosen as the
manipulated variables: inlet temperature of the alkylation reactor (T), molar flow rate
of the recycle to the alkylation reactor (B-A), alkylation reactor length (L), and molar
flow of the recycle to the transalkylation reactor (B-T). Statistical methods were used
to find a model that describes the behavior of the process. After that, this model was
used to find the optimum operating conditions. By using a statistical method it is
possible to determine the level of importance of each variable and to find the probable
 1286 H. R. Norouzi et al.

interactions between them (Omidbakhsh et al., 2010; Vining, 1998; Zivorad, 2004).
Moreover, the statistical analysis (regression) can give a mathematical model as a
function of manipulated variables. In this study, the full factorial design was used
to determine the level of significance of each manipulated variable on the objective
function.
Based on the full factorial design, 24 evaluations should be available to deter-
mine the significant effects of the variables and their binary interactions (Zivorad,
2004). Table VI shows the full factorial design of the four variables mentioned
above. The process was simulated at each operating condition and the NPV, capital
investment, and utility requirements were calculated in each case and reported in this
table. In performing these simulations, some constraints were imposed on the
process to accomplish the aim of this process, which is manufacturing cumene with
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a molar purity greater than 99.5%. These constraints are listed below:
. Concentration of benzene in cumene column (C-3) feed must be negligible to
guarantee that highly purified cumene is obtained in the overhead of C-3.
. Temperature of C-2þ bottoms must not exceed 242
C. The reboiler of this column
is derived by HP steam.
. Concentration of benzene recycle does not fall under 94 mol.%.
. Temperature of liquid mixture through the alkylation reactor must be below the
boiling point. If this constraint is not satisfied in each case, additional inter-
coolers have to be added to the reactor to keep the temperature in the range.
Analysis of variance (ANOVA) was carried out on the NPV values to determine the
significance of single-factor and two-way interactions. A significance level of 10%

Table VI. Full factorial design table and NPV of the process as response

Capital
B-A B-T investment Utility NPV
No. (kmol=h) T (
C) (kmol=h) L (m) (million $) (million $=yr) (million $)
1 95 160 20 5 4.100 1.670 4.04
2 150 160 20 5 4.190 1.510 4.18
3 95 180 20 5 4.220 1.690 3.95
4 150 180 20 5 4.200 1.780 3.65
5 95 160 40 5 4.170 1.730 3.84
6 150 160 40 5 4.140 1.550 3.63
7 95 180 40 5 4.220 1.800 2.74
8 150 180 40 5 4.260 1.890 1.23
9 95 160 20 8 4.140 1.720 3.88
10 150 160 20 8 4.240 1.790 3.43
11 95 180 20 8 4.380 1.670 4.00
12 150 180 20 8 4.350 1.850 3.11
13 95 160 40 8 4.280 1.740 4.00
14 150 160 40 8 4.350 1.860 3.04
15 95 180 40 8 4.240 1.730 3.88
16 150 180 40 8 4.350 1.870 3.06
17 122.5 170 30 6.5 4.140 1.780 3.72
 Zeolite-Based Cumene Production Plant 1287

was considered for determining the significant variables. The results are shown in
Table VII. The test values of Fischer and the p-values were considered as the decision
criteria. Those factors with p-values less than 0.1 were considered to have a signifi-
cant effect on the NPV, and the variables with p-values greater than 0.1 were
reported as nonsignificant parameters. In addition, case no. 17, which is the center
point in the full factorial design, was evaluated to test whether or not there is a cur-
vature (second-order functionality rather than linear) in the respond function. The
calculated p-value for the curvature was found to be 0.514 (see Table VII), which
shows that the response (NPV) is linear. Hence, a linear model (two-level factorial
design) is adequate to obtain a mathematical model for the NPV.
The Pareto chart of standardized effects for significant variables is shown in
Figure 7 (nonsignificant variables are not illustrated in this figure). The vertical
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dashed lines indicate the significance limit of each term, which is considered to be
10%. Among the four above-mentioned variables, only the recycle to the transalkyla-
tion reactor (B-T) has a nonsignificant effect on the NPV of the process. As
discussed before, this recycle (Loop2) has the least contribution to the utility require-
ments of the process; hence, any changes in this variable do not have a pronounced
effect on the NPV of the process. However, the recycle to the alkylation reactor
(B-A), Loop1, has a significant and negative effect on the NPV. Although attempts
were made to reduce the contribution of Loop1 to the utility requirement of the pro-
cess, it still possesses a significant effect based on the statistical analysis. Moreover,
the inlet temperature of the reactor (T) and reactor length (L) both have a positive
effect on the NPV of the process. Reducing either the reactor length or the inlet tem-
perature reduces the conversion of propylene in the reactor. In this state, a part of
the fed propylene will leave the process unreacted in the overhead of the propane
column. Therefore, the NPV of the process is reduced as a result of a decrease in
the production rate of cumene.
One of the most interesting capabilities of the statistical analysis used in this
study is determining the binary (two-way) interactions between the variables. The
results in Figure 7 show that (T)  (L) has a negative effect on the NPV. This indi-
cates that the NPV is enhanced when one variable is increased while the other is
decreased. Combined variables (B-A)  (T) and (B-A)  (L) have a positive effect

Table VII. ANOVA analysis of NPV for determining significant variables

Variable Mean sum of squares F-test p-value Significance

(B-A) 26.58 14.5 0.004 Yes
(T) 7.84 4.28 0.069 Yes
(B-T) 0.865 0.31 0.604 No
(L) 17.56 9.58 0.013 Yes
(B-A)  (T) 11.52 6.29 0.033 Yes
(B-A)  (B-T) 0.051 0.02 0.899 No
(B-A)  (L) 12.92 7.05 0.023 Yes
(T)  (B-T) 0.941 0.33 0.589 No
(T)  (L) 8.702 4.75 0.057 Yes
(B-T)  (L) 0.504 0.18 0.690 No
Curvature 1.395 0.49 0.514 No
 1288 H. R. Norouzi et al.
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Figure 7. Pareto chart of standardized effect for significant variables. Dashed lines indicate
statistically significant bond for each term.

on the NPV. In other words, when the benzene recycle to the alkylation reactor
(B-A) is increased, the inlet temperature or the reactor length should be increased
in order to reach higher reaction rate or longer residence time. Hence, the statistical
analysis matches the expected trends of the process, and, therefore, the mathematical
model obtained from this analysis reflects the influence of different variables on
the NPV reliably. The following mathematical model was obtained for the NPV
of the process:

NPV ¼ 19:01  0:7132ðB  AÞ þ 0:0115ðTÞ þ 6:3877ðLÞ þ 0:003086ðB  AÞðTÞ

þ 0:021788 ðB  AÞðLÞ  0:04917ðTÞðLÞ
R2 ¼ 0:95 ð10Þ

Optimized Process
Optimization was performed based on Equation (10) by the Simplex method
(Vining, 1998), and the optimal conditions were determined to be: inlet temperature

Figure 8. Process flow diagram of liquid-phase cumene production for the optimized case.
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Table VIII. Stream table of process flow diagram (optimized case) shown in Figure 8

Fresh Fresh Mixed Alkylation Fuel Benzene C-2 Trans Trans

Stream benzene propylene feed effluents gas C2-feed ovhd bottoms Cumene DIPB feed effluents
Temperature 25 25 160 252.5 44.2 242.5 117.6 158.0 151.8 213.3 240.0 240.3
[
C]
Pressure 0.3 1.15 3.54 3.54 1.5 1.52 0.8 0.11 0.1 0.11 3.5 3.5
[MPa]
Vapor 0 0 0 0 1 0.007 0 0 0 0 0 0

1289
fraction
Mole flow 100 105 221.25 200.01 5.01 227.90 120.00 107.90 100.00 7.90 32.90 32.90
Mass flow 7811.4 4428.5 16571.0 19892.4 221.0 22966.5 9666.2 13300.3 12019.3 1281.0 3295.0 3295.0
Comp. mole flow [kmol=h]
Benzene 100 189.492 93.128 0.003 113.12 113.04 0.074 0.074 0.000 23.550 19.994
Propylene 100 25.000 0.007 0.007 trace trace
Propane 5 1.250 5.000 5.000
Cumene 5.508 98.243 0.000 106.81 6.95 99.861 99.852 0.010 1.459 8.571
DIPB trace 3.629 trace 7.96 trace 7.960 0.074 7.887 7.888 4.332
 1290 H. R. Norouzi et al.

of 160
C, reactor length of 6 m, and benzene recycle to the alkylation reactor of 95

kmol=h. The results indicate that the NPV of the process becomes $4.82 million at
this optimized condition. A simulation was done at the optimized conditions, and
the results of different economic parameters of the process are reported in the last
column of Table V. It can be seen in this table that both capital investment and
utility requirements of the optimized case are less than those of the two-column case,
resulting in an increase in the NPV of the process. The NPV of the optimized process
obtained from the simulation is $4.16 million, which is greater than that of the
two-column case, which is $3.56 million. And the utility cost of the process is
reduced from $1.75 to 1.68 million=yr. The process flow diagram of the optimized
case is illustrated in Figure 8, and the corresponding streams of this process are
shown in Table VIII.
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Utility requirements of the optimized process are 20.7 and 14.1 GJ=h for cold and
hot utilities, respectively. Pinch analysis was carried out for the optimized case to find
out if further process enhancement is possible. The composite curve of the optimized
case is illustrated in Figure 9. Hot and cold pinch temperatures are located at 222
and
212
C, respectively. The results show that minimum cold and hot utility requirements
are 17.5 and 11.2 GJ=h, respectively, if perfect energy targeting is done on the process
(Smith, 2005). This shows that more energy can be recovered through the process. As
can be seen in the flow sheet, there are two heat exchangers that cross the pinch point
(Smith, 2005). The first exchanger is the intercooler, for which the inlet and outlet
temperatures are 243
and 160
C, and the second exchanger is E-1, for which the inlet
and outlet temperatures are 253
and 194
C. These heat exchangers should be
avoided and extra exchangers were added to the process. In this way, cooling is done
in two stages, first the hot stream is cooled to 222
C by a cold stream above the pinch
point (E-8), and then it is further cooled to the desired final temperature by a cold
stream or utility. These changes were made to the process, and simulation was carried
out again. The results showed reductions in both hot and cold utilities. The hot utility
requirement was decreased by 11% (1.6 GJ=h), and the cold utility requirement was
decreased by 13.5% (2.8 GJ=h). The economic state of the process is listed in

Figure 9. Composite curve of optimized case and pinch point.

 Zeolite-Based Cumene Production Plant 1291

Table V. The total annual utility cost was reduced from $1.68 to 1.49 million=yr and
the total investment was increased from $4.22 to 4.50 million due to the addition of
extra exchangers. The NPV of the process in this condition was further enhanced and
increased to 4.53.
Norouzi and Fatemi (2012) studied the vapor phase production process of
cumene on SPA catalyst with the same annual production capacity and the same
economic model as this study. Their optimized process required $10.2 million total
investment and $3.83 million annual utility requirements. These values are consider-
ably greater than those obtained for the optimized case of the zeolite-based process.
NPV of $4.79 million was obtained for the optimized case of the SPA process,
whereas it is $4.53 million for the optimized case of the zeolite-based process. The
higher value of the NPV for the SPA process should be compared to $10.2 million
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total capital investment, which yields 1.42 present value ratio, while the present value
ratio is 2.01 for the zeolite-based process. The investment in a process with a higher
present value ratio and lower capital investment is more tempting.

Conclusion
The zeolite-based production of cumene from propylene and benzene was studied for
intensification of an industrial-scale production process to obtain higher profitability
and reduce the energy requirements of the process. A comprehensive model that
considers all influential factors was established for the profitability analysis. Using
established economic models, the total investment and yearly utility requirements
of the base process were calculated to be $4.48 and 2.44 million, respectively, which
yielded an NPV of $0.82 million.
A multistage procedure was followed to optimize the base process. First,
topological changes were made to the process. The reactor with one catalytic bed
was replaced with a reactor with four catalytic beds with an inter-stage cooling in
which propylene is added through side streams. In addition, the benzene column
was replaced with two columns with operating pressures of 1 and 8 bar. These topo-
logical changes led to a considerable reduction in utility requirements and equipment
sizes in the process and thus to better profitability. After that, the parametric opti-
mization was carried out by a statistical method (full factorial design) to adjust
process parameters at which the profitability is maximized. The analysis of variance
determined the influential parameters on the NPV of the process and showed that
the linear model is adequate to obtain a mathematical model for the NPV.
A mathematical model was developed and utilized to get the optimized
conditions of the process. Comparisons between the base case and optimized case
revealed that the capital investment and the utility requirements of the process were
reduced from $4.481 to 4.22 million and from $2.44 to 1.68 million=yr, respectively.
These greatly enhanced the economic condition of the process for which the net
present value was increased from $0.82 to 4.16 million. Finally, pinch analysis was
done to find the heat flow across the pinch point. Extra exchangers were added to
the process to change hot and cold stream contact pattern; a substantial reduction
in utility cost was obtained and the NPV increased to 4.53. This work can be further
improved by considering poly-alkylation reactions in the process to gain a better
picture of the process. In addition, dynamic simulation can be another option
through which different start-up scenarios can be tested and fault detection and
troubleshooting of the process can be performed.
 1292 H. R. Norouzi et al.

Nomenclature
a utility cost coefficient
b utility cost coefficient
C0BM bare module equipment cost
Cf price of fuel, $=GJ
CP purchased cost for the base condition, $
Cu cost of utilities, $=GJ
CEPCI Chemical Engineering Plant Cost Index
F0BM bare module cost factor
FCITM total module cost, $
k1 first-order reaction constant in Equation (1), 1=s
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k2 first-order reaction constant in Equation (2), 1=s

k3 forward reaction constant in Equation (3), kmol=m3  s
k4 backward reaction constant in Equation (3), kmol=m3  s
NPV net present value, million $
Oprt. Cost operating cost, $=y

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