Accepted Manuscript

Title: Economic and environmental analysis of the cumene

production process using computational simulation

Authors: Pedro G. Junqueira, Patrick V. Mangili, Rafael O.

Santos, Lizandro S. Santos, Diego M. Prata

PII: S0255-2701(18)30319-2
DOI: https://doi.org/10.1016/j.cep.2018.06.010
Reference: CEP 7312

To appear in: Chemical Engineering and Processing

Received date: 14-3-2018

Revised date: 9-6-2018
Accepted date: 11-6-2018

Please cite this article as: Junqueira PG, Mangili PV, Santos RO, Santos LS,
Prata DM, Economic and environmental analysis of the cumene production process
using computational simulation, Chemical Engineering and Processing - Process
Intensification (2018), https://doi.org/10.1016/j.cep.2018.06.010

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 Economic and environmental analysis of the cumene
production process using computational simulation

Pedro G. Junqueira1, Patrick V. Mangili1, Rafael O. Santos1, Lizandro S. Santos1*, Diego M.

Prata1

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Department of Chemical and Petroleum Engineering, Universidade Federal Fluminense,
24210-240, Niterói, RJ – Brazil.

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*Corresponding author: Lizandro S. Santos (E-mail: lizandrosousa@id.uff.br)

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Highlights

• Simulation of five different cumene production processes.

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• Simulation of utility plants for more realistic results.
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• Development of six different categories of eco-indicators.
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• Eco-indicators lumping in a single index for global eco-efficiency comparison.
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• Economic analysis by estimating the processes’ gross annual profits.

• The heat integrated process proved to be the most economical and sustainable.
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Abstract
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The need for mitigating environmental impacts has been heading towards the development of
new technologies that could lead the industries to a greater ecological efficiency. Countless
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methodologies for evaluating processes’ efficiency in relation to their respective ecological

footprint have been employed, among which the concept of eco-efficiency has stood out. In this
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context, this work aims to compare six different cumene production plants, namely
conventional, transalkylation, heat-integrated, dividing wall column, reactive distillation and
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double-effect distillation technologies, with regard to their economics and environmental

efficiencies. The economic analysis was performed by estimating their respective Gross Annual
Profit (GAP) and determining the specific production costs indicator, whereas the
environmental assessment was carried out by calculating six eco-indicators, namely raw
materials consumption, fuel consumption, energy use, CO2 emissions, water consumption and
wastewater generation. The processes’ environmental performances were then compared
 2

through the Eco-efficiency Comparison Index (ECI) method. The study showed that the
intensified processes are not only more economically attractive but also more environmentaly
friendly.

Keywords: Computational Simulation, Cumene, Eco-efficiency, Process Economics, Process

Intensification.

1. Introduction

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The man-nature relationship has significantly changed as a result of the manufacturing activities
derived of the first industrial revolution in the 18th century. Greenhouse gases emissions have

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increased due to the exploitation of natural energetic resources and, as the years went by, the

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records concerning the global annual mean temperature have increased. In fact, the World
Meteorological Organization (WMO)’s report1 indicated that 2016 was not only the warmest
year ever recorded but also presented the higher concentration of carbon dioxide in the

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atmosphere. The European Commission2 has released a global list of the countries with the
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greatest CO2 emissions, with China being its top emitter with over 10 million kilotons in 2015,
almost twice as much as the United States (second major contributor).
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Governments have established sustainable development politics with restrict environmental
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laws as an effort to mitigate the ecological impacts resulting mainly from industrial activities.
Hence, industries have been developing more energy-efficient plants, with reduced atmospheric
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emissions, raw materials consumption and waste generation in order to minimize their
ecological footprint. In this regard, Stankiewicz and Moulijn3 stated that new design techniques
are being developed with the intention of increasing production, reducing energy demand and
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minimizing costs, which is the case of process intensification approaches such as reactive
distillation columns, ultrasound assisted equipment and multifunctional reactors, among others.
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In addition, Wang and coworkers4 pointed out that such approach represents an advantageous
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strategy not only in terms of profit and sustainability but also regarding safety, since more
compact process configurations provide smaller volumes of toxic and flammable inventories.

For these reasons, process intensification has gained more and more attention of the industrial
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sector. For instance, the European Comission5 has been fomenting the development of solutions
for sustainably improving the production of chemical goods. The U.S. Department of Energy 6,
in turn, has recently announced the plan of developing novel and breakthrough technologies in
process intensification with the purpose of enhancing energy efficiency through the Rapid
Advancement in Process Intensification Deployment (RAPID) Institute.
 3

In this context, the purpose of this paper is to demonstrate the relevance of process
intensification to the chemical industry by quantitatively and qualitatively comparing the
economics and environmental impacts of six different cumene production plants. To the best of
our knowledge, cumene processes have only been studied in terms of either their economics or
single environmental impacts. Therefore, their ecological performance was evaluated by
considering several impacts in order to provide the scientific community with more relevant
data. In fact, the environmental analysis was performed by determining the raw materials
consumption, fuel consumption, energy use, CO2 emissions, water use and wastewater

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generation eco-indicators. The economic evaluation, in turn, was carried out by estimating the

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Gross Annual Profits (GAPs) of each technology, as well as the specific production costs
indicators. The ecological and economic indicators were subsequently normalized and plotted in

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a radar-type chart in order to determine the most environmentally friendly process by means of
the Eco-efficiency Comparison Index (ECI) method.

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In the next section, a brief revision regarding the cumene manufacturing processes is presented.
In Section 3, we describe the method for calculating the eco-indicators, whereas the

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assumptions to estimate the costs and the economic indicator are provided in Section 4. In
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Section 5, we discuss the methodology required to establish the comparison between the six
technologies. Finally, in Section 6, we summarize the main results and provide some suggestion
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for future works.
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2. Cumene Production
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Cumene is mostly used as an intermediate for the production of acetone and phenol, used in the
manufacture of several products such as bisfenol-A, polycarbonate and epoxy resins, nylon 6,
among others. Due to such aspects, the global demand for cumene has increased significantly,
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being the Asia-Pacific the leading with appoximately 43% of the overall market revenue7,8.

The cumene production technology was originally developed during World War II to meet the
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demand for aviation gasoline, with which it was blended to improve octane rating8,9. Cumene is
currently among the world’s five biggest large-scale productions, along with ethylene,
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propylene, benzene and ethylbenzene10.

Cumene is produced by the Friedel-Krafts alkylation of benzene with propylene, an irreversible

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and exothermic reaction, as represented by Eq. (1). Further alkylation may happen due to the
reaction conditions and result in the undesirable formation of p-diisopropyl benzene (DIPB), as
shown in Eq. (2). Nevertheless, Pathak et al.11 stated that the formation of DIPB can be partially
overturned by using a transalkylation reactor in which DIPB is converted back to cumene, as
shown in Eq. (3). Industrially, cumene is obtained in a gas-phase packed bed reactor under high
temperature and pressure over an acid catalyst12.
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C6 H 6  C3 H 6  C9 H12 (1)

C9 H12  C3 H 6  C12 H18 (2)

C12 H18  C6 H 6  2C9 H12 (3)

In the literature, the cumene production process was originally proposed by Turton et al.13 and
has been optimized by several authors in order to improve its economics and sustainability.
Numerous studies regarding, for instance, the use of different catalysts14, the reduction of raw
materials flow rates15, the increase in overall conversion by using a transalkylator16 and the

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implementation of dividing wall column17, as well as reactive11,18 and double-effect distillation19

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technologies are currently available.

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The cumene production plants studied in this paper were simulated in AspenTech’s Aspen

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Plus® V8.8 software under steady state conditions. In order to obtain consistent results, the
same feed conditions (temperatures, pressures, compositions and flow rates), equipment
specifications (sizes, reaction kinetics and efficiencies) and thermodynamic model (Peng-

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Robinson Equation of State) used by the reference authors were considered. The simulation of
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all processes could be performed since said authors provided sufficient information for
reproduction of their respective works and results.The following sections briefly describe each
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process, whereas a more detailed description regarding equipment parameters and stream
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conditions is provided by the referenced papers.

2.1 Conventional Technology

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Turton et al.13’s design had a significant amount of raw materials that were eliminated in a
purge column with the objective of aiding further separation and avoiding build-up at
subsequent steps. Aiming to reduce such raw materials waste, Luyben15 investigated the
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advantages of increasing both the temperature of the reactor inlet stream (to improve the
reaction rates) and the reactor’s size (to obtain higher propylene conversion) as well as adjusting
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benzene recycle to the feed section. The author found that larger reactors not only increased
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propylene conversion but also required lower temperatures for almost complete (99%)
conversion of propene, thus improving process’ economics, despite the expenditures with higher
reaction vessel costs. Figure 1 illustrates the optimized process studied in this work, as well as
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the results obtained from simulation.

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Figure 1. Cumene conventional production process’ flow diagram.
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In this process, pure benzene at 98.8 kmol/h is mixed with a propylene stream (containing 0.5
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mol % propane, at 101.9 kmol/h). The resulting mixture is vaporized in vessel V1 and preheated
firstly in heat exchanger FEHE and then in the fired heater H1 prior to being sent to a tubular
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reactor R1, in which the reactions described by Eqs. (1) and (2) take place. The reactor has 1500
tubes (0.0763 m diameter and 6 m length) filled with a solid catalyst of 0.5 void fraction and
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2000 kg/m3 density. The reaction kinetics are presented in Table 1.

Table 1. Reaction kinetics for the conventional processa.

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Reaction Rate expression

Reaction 1 – Eq. (1) r1 = 2.80 x 107 exp(-104181/RT) Cbenzene Cpropylene
Reaction 2 – Eq. (2) r2 = 2.32 x 109 exp(-146774/RT) Ccumene . Cpropylene
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a
Cbenzene: Benzene composition. Cpropylene: Propylene composition. Ccumene: Cumene composition.
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Composition units: kmol . m-3. Reaction rate units: kmol . m-3 . s-1. R: 8.316 kJ . kmol-1.

The highly exothermic characteristic of the benzene/propylene conversion requires a boiler

feedwater (bfw) cooling system, thus generating high pressure steam (hps) to be exported.
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Nonetheless, the process would be expected to have surplus heat after heat integration in heat
exchanger FEHE. Therefore, the reactor product is subsequently cooled down in cooler HE1
prior to being sent to a flash vessel V2, in order to separate the fuel gas (containing mainly
propane and non-reacted benzene at 9.9 kmol/h) from the process stream, which is sent to the
separation/purification section that comprises two distillation columns. The first column (C1)’s
top product, containing 94.8 mol % benzene at 106.1 kmol/h, is recycled via pump P1 to the
 6

feed section. Cumene is obtained as top product in the second column (C2) at 93.7 kmol/h with
a purity of 99.9 mol %, while DIPB is retrieved at the bottom at 2.9 kmol/h as by-product.

Both terms “HE” and “HX” were used for heat exchangers in order to distinguish coolers (HE)
from heaters (HX) since they are considered for the calculation of different indicators.

2.2 Transalkylation Technology

Based on Luyben15’s work regarding an overall optimization of Turton et al.13’s design, Pathak
and coworkers11 proposed two other process configurations, namely transalkylation technology

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and reactive distillation technology (discussed later). In the former, a transalkylation reactor was
added with the objective of recovering cumene loss over its further alkylation. Pathak et al.11

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investigated a few key process variables that, when modified, presented significant outcomes in

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terms of capital and operating costs. The first trade-off was associated with the relationship
between reaction conversion and reactor size, since although reducing the latter may result in a

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decrease in capital costs, the fomer would be undesirably lowered. The second parameter
studied was the increase in the reactor temperature, as analyzed by Luyben15, aiming at a higher

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propylene conversion but with the downside of further alkylation. In this design scenario, DIPB
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formation should be as low as possible in order to minimize the transalkylator costs. Finally,
both the benzene feed and recyle were deemed critical for the process’ economics, since higher
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benzene concentrations favor higher propylene conversions.
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Maity and coworkers16 further optimized Pathak et al.11’s transalkylation design with the aid of
a built-in Aspen Plus’s V7.2 optimizer. The authors fixed some variables such as, for instance,
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the mole fractions of benzene/DIPB in the final product and propane mole fraction in the purge
column’s bottom product (to guarantee non-accumulation in further steps). Figure 2 illustrates
the transalkylation process studied in this work, as well as the simulation results.
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Figure 2. Cumene transalkylation production process’ flow diagram.

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In the process, pure benzene at 98.8 kmol/h and a 0.5 mol % propane-containing propylene
stream at 105.3 kmol/h are mixed, vaporized in vessel V1 and preheated (in heat exchanger
FEHE and then in fired heater H1) prior to being sent to a tubular reactor R1, in which the
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reactions described by Eqs. (1) and (2), whose kinetic data are present in Table 1, take place.
The reactor has 150 tubes (0.05 m diameter and 1.764 m length) filled with a solid catalyst of
0.5 void fraction and 2000 kg/m3 density. Similarly to the conventional process, bfw is used to
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cool down the reactor, which generates hps to be exported. Here again, surplus heat would be
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expected after heat-integrating the reactor’s feed and product in heat exchanger FEHE and,
therefore, the reactor product is cooled down in cooler HE1 prior to being fed to column C1.
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From this column fuel gas containing mainly propane and propylene is removed at the top at 6.9
kmol/h. The bottom product is subsequently mixed with the transalkylator’s product and fed at
161.8 kmol/h to two distillation columns for product purification. The first column (C2)’s top
product, containing 95.3 mol % benzene is recycled at 55.7 kmol/h via pump P1 to the feed
section. Cumene is obtained as top product in the second column (C3) at 103.5 kmol/h with a
purity of 99.9 mol %, while the bottom product is pre-heated in heater HX1 and sent at 2.6
 8

kmol/h via pump P3 to a transalkilation reactor R2 where the reaction described by Eq. (3) takes
place. The transalkylator has 100 tubes of 0.05 m diameter and 1.764 m length. The reaction
kinetics for the transalkylation are presented in Table 2. The use of a transalkylator is aimed at
converting DIPB back to cumene and thus increasing the overall conversion. The transalkilator
product is recycled back to the purificication section.

Table 2. Transalkylator reaction kineticsb.

Reaction Rate expression

Reaction 3 – Eq. (3), direct r1 = 2.53 x 108 exp(-100000/RT) xBz xDIPB

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Reaction 3 – Eq. (3), reverse r2 = 3.877 x 109 exp(-127240/RT) xCu

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b
xBz: Benzene molar fraction. xCu: Cumene molar fraction. xDIPB: DIPB molar fraction. Reaction
rate units: kmol . m-3 . s-1. R: 8.316 kJ . kmol-1.

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2.3 Two-Flash Energy-Integrated Technology

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The energy use in the industrial sector represents a critical burden in regard to greenhouse gases
emissions, since it contributes to approximately 21% of the total CO2 emitted20. Balancing

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energy consumption and environment preservation is a continuous challenge to the industries in
order to maximize their economic benefit. In this context, thermal integration of processes
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stands out as a useful technique for improving energy efficiency.
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Flegiel et al.12, for instance, based their process design on Sharma et al.21’s work to apply
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energy integration in the cumene production process. The former authors implemented a Multi
Objective Optimization (MOO) to explore the trade-offs among economic (total capital and
utility costs), environmental (material loss) and safety objectives. Flegiel et al.12’s integration
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was based on the recompression of the product column’s top stream, in order to generate
enough heat duty so it could be used to heat the recycle column’s reboiler, and the use of a gas
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expander in the reactor product stream to generate electricity to be used as partial energy source
for the compressor.
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Sharma and coworkers21 suggested a change in the conventional process’ purge column by
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replacing it by one flash vessel, which resulted in great losses due to the high amount of gas in
the vent (off-gas) stream. Flegiel et al.12 then proposed the use of two flash tanks in series, with
a cooler in between. Such modification resulted in a substantial reduction of material losses and
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therefore, propylene conversion increased from 95.97% to 97.91%. The example studied in this
work, as well as the simulation results, are illustrated in Figure 3.
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Figure 3. Cumene two-flash energy-integrated production process’ flow diagram.
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In the process shown in Figure 3, pure benzene at 350.0 kmol/h is mixed with a propylene
stream (containing 0.5 mol % propane, at 325.9 kmol/h) and the resulting mixture is preheated
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in heat exchanger FEHE prior to being sent to a tubular reactor R1, in which the reactions
described by Eqs. (1) and (2) occur. The reactor has 13,500 tubes (0.0763 m diameter and 7.315
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m length) filled with a solid catalyst of 0.5 void fraction and 2000 kg/m3 density. Said reactions
kinetic data are present in Table 1. Most of the energy generated in the reactor is consumed by a
bfw cooling system, which generates hps that is also assumed to be exported. Part of the
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reactor’s product remaining energy is depleted in expander E1 before it is heat-integrated with

the reactor’s feed in heat exchanger FEHE. The amount of energy converted to electricity is
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sufficient to avoid surplus heat. The reactor product is then sent to a series of two flash vessels
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(V1 and V2, with a cooler HE1 in between) in order to separate fuel gas (containing mainly
propane and benzene at 20.9 kmol/h) from the process stream, which is sent at 482.6 kmol/h to
the separation/purification section that comprises two distillation columns. The first column
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(C1)’s top product, containing 75.4 mol % non-reacted benzene is recycled at 158.1 kmol/h via
pump P1 to the feed section. The second column (C2)’s top product (containing 99.78 mol %
cumene at 319.1 kmol/h) is pressurized in compressor K1 and used to heat the reboiler of the
first column, while DIPB (99.9 mol %) is retrieved as side product at the bottom at 5.4 kmol/h.

2.4 Dividing Wall Column Technology

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Broadly present in chemical plants, distillation columns are responsible for the largest fraction
(up to 80% total) of energy consumption in process industries22. Efforts have been made to
enhance process sustainability, such as finding optimal separation sequences, compacting
multiple columns into one shell (dividing wall columns) and merging different unit operations
in a single equipment (e.g. reactive distillation) - aiming at reduced ground space use and lower
energy requirements11,23.

In this context, dividing wall columns (DWCs) have gained more and more attention in the last
years due to their evident advantages regarding energy and capital costs, sustainability and

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operating flexibility24. In the literature, DWCs have been studied by taking into consideration

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different approaches such as design and control25,26, process expenditures17, and ecological
footprint22, among several others.

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With regard to cumene production, Zhai and coworkers17 proposed a dividing wall column

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design in order to reduce the process energy requirements. The authors replaced both the purge
and product columns by a single DWC. With the purpose of reducing the total annualized costs

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(TACs), the process parameters were optimized by manipulating certain variables such as the
conventional column’s reflux ratio, the DWC’s feed tray location, the number of stages in both
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columns and the liquid/vapor interconnection flow rates. A sensitivity analysis was carried out
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to determine the optimum conditions and, as a final result, the process with the DWC operating
at 3.2 bar was deemed ideal for achieving the minimum TAC. Figure 4 illustrates the example
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studied in this paper, as well as the results obtained from simulation.

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Figure 4. Cumene dividing-wall column production process’ flow diagram.

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In this process, pure benzene at 107.3 kmol/h is sent to a conventional distillation column C1
that is also fed by a stream resulting from the mixture of the products from a tubular reactor R1
and a transalkilator R2. The distillation column’s top product is divided into fuel gas, mainly
comprised of propane at 2.9 kmol/h, and condensate, consisting mainly in cumene and benzene
at 1.0 kmol/h. The column’s bottom product is fed to a dividing wall distillation column (DWC)
C2 via pump P1 in order to separate cumene as top product, at 100.7 kmol/h with a purity of
99.9 mol %, from DIPB (bottom product, at 0.6 kmol/h with a purity of 99.6 mol %). The
distillation column’s intermediate product, containing mainly benzene at 496.3 kmol/h, is

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divided into two streams that are fed via pump P2 to each reactor, while the DWC’s

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intermediate product, containing mainly DIPB at 21.1 kmol/h, is pre-heated in heater HX2 and
recycled via pump P3 to the transalkilator in order to increase the overall conversion. The

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reactions kinetic data for the both tubular reactor and transalkylator are present in Tables 1 and
2, respectivelly. The reactor has 150 tubes (0.05 m diameter and 1.764 m length) filled with a

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solid catalyst of 0.5 void fraction and 2000 kg/m3 density, whereas the transalkylator has 100
tubes of 0.05 m diameter and 1.764 m length. Since the benzene/propylene conversion is highly

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exothermic, the reactor is cooled through a bfw system, thus generating high pressure steam,
which is interpreted as being exported. Any surplus heat present is depleted in cooler E1 prior to
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column C1.
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2.5 Reactive Distillation Technology
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As previously stated, Pathak and coworkers11 proposed two cumene production plant
configurations, namely transalkylation technology and reactive distillation (RD) technology.
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The former focused on increasing the overall conversion by recovering cumene loss due to its
further alkylation in the tubular reactor. Nevertheless, such design strategy resulted in high
energy duties and equipment costs. In view of such drawback, the authors suggested the
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implementation of a catalyst-packed RD column, acting as both a purge column and a reactor

(that involves both alkylation and transalkylation), followed by a conventional distillation
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column. With such design, top fed benzene encounters propylene along the column and the
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unreacted benzene is reboiled, forced back to the reactive zone.

The most significant variable investigated was the RD column’s operating pressure. Higher
values resulted in a higher reactive zone temperature due to the higher bubble point on the
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reactive tray, resulting in higher reaction rates. For this reason, both catalyst costs and benzene
losses in the vent could be reduced. On the other hand, since higher operating pressures may
reduce the benzene-cumene relative volatility, higher reboiler duties are required to avoid
benzene contamination at the bottoms. For optimization, a built in Aspen optimizer was used,
fixing the product purity at 99.9% and 0.09 benzene mole fraction in the RD distillate vent. For
a better understanding of the influence of the operating pressure, Pathak et al.11 compared
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different designs at 2 atm, 3 atm and 4 atm, confirming that higher pressures result in more
attractive economics. The example studied in this work, as well as the simulation results, are
shown in Figure 5.

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Figure 5. Cumene reactive distillation production process’ flow diagram.

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In this process, a pure benzene stream at 100 kmol/h and a propylene stream (containing 0.5
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mol % propane, at 105.3 kmol/h) are fed to a reactive distillation column C1, in which the
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reactions described by Eqs. (1), (2) and (3) occur. The reaction kinetics are shown in Table 3.
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Table 3. Reaction kinetics for the RD processc.

Reaction Rate expression

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Reaction 1 – Eq. (1) r1 = 6.98 x 105 exp(-63742/RT) Cbenzene

0.96 0.87
C propylene
Reaction 2 – Eq. (2) r2 = 4.00 x 109 exp(-79162/RT) Ccumene
0.61 0.92
C propylene
Reaction 3 – Eq. (3) Keq = 6.52 x 10-3 exp(27240/RT)
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c
Cbenzene: Benzene composition. Cpropylene: Propylene composition. Ccumene: Cumene composition.
Composition units: kmol . m-3. Reaction rate units: kmol . m-3 . s-1. R: 8.316 kJ . kmol-1.
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The use of reactive distillation is particulary interesting in this scenario due to the highly
exothermic reactions that take place in the column. The main advantage relates to the direct heat
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integration between reaction and separation, that is, the reaction heat is used to evaporate ligh
ends and hence reduce the total energy requirements for separation. From the RD column fuel
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gas (containing mainly propane) is retrieved at the top at 6.3 kmol/h, while the reaction products
(comprised mainly of cumene) leave at the bottom. Such products are fed at 133.5 kmol/h to a
distillation column C2 in order to separate cumene (at the top) at 99.7 kmol/h, with a purity of
99.9 mol %, from the unreacted components, which are retrieved at the bottom at 33.8 kmol/h
(comprising 20.8 mol % cumene and 79.2 mol % DIPB) and recycled via pump P1 to the RD
column.
 13

2.6 Double-effect Distillation Tehcnology

In Nourouzi et al.19’s design, the liquid-phase alkylation of benzene on a zeolite catalyst was the
object of study, using a four-bed reactor configuration and a separation train to recover the
product, similarly to Hwang and Chen27’s work. The design optimization was based on an
economic model involving grass root capital investment, operating and raw materials costs,
revenue, plant life span, taxes and inflation. The optimization was performed by firstly
minimizing the process’ utility requirements through topological changes and by secondly using
a statistical method to increase the net present value (NPV).

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As the first change, Norouzi and coworkers19 proposed the injection of propylene in four

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different spots along the reactor, in order to decrease the utilities consumption and maintain
benzene/propylene proportion. This is an important factor for controlling the reactor’s

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temperature and also for preventing the formation of linear hydrocarbons. The authors found

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that, when propylene flow rate is reduced by one fourth, the benzene is also reduced to keep the
same proportion, thus expressively increasing the NPV.

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As the second modification, Norouzi et al.19 aimed their efforts toward changing the benzene
column’s configuration by proposing a double-effect distillation system. The previous single
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large column was divided into two columns, C-2 and C-2+. The operating pressures were fixed
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at 1 bar and 8 bar respectively, such that the C-2’s reboiler temperature is at least 10° C lower
than C-2+’s condenser temperature, for energy integration purposes. Double-effect distillation
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refers to a system in which the feed stream is evenly split into two streams that are fed to two
columns operating at different pressures. The overhead product from the high-pressure column
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supplies heat for the low-pressure column’s reboiler. This heat integration has the main
advantage of considerably reducing utilities requirements and, therefore, the operating costs.
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Depending on the feed compositions and the components’ volatilities, such strategy may halve
the overall heat duty28. For this reason, double-effect distillation has been studied for several
applications such as n,n-dimethylacetamide-water separation29, ethanol production30, bioethanol
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distillation31, acetone-methanol separation32, among others.

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After establishing said topological changes, Norouzi et al.19 used statistical models for
analyzing the interactions of the economic function NPV with several variables, such as the
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alkylation reactor’s length, inlet temperature and recycle flow rate, as well as the flow rate of
the recycle to the transalkylation reactor. A full factorial design and an analysis of variance
(ANOVA) were used to find a NPV model that better described the process’ behaviour. The
optimization was then performed by the Simplex method33 and a pinch analysis was carried out
to further improve the process in regard to reducing utilities requirements. Figure 6 illustrates
the example studied in this work, as well as the simulation results.
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Figure 6. Cumene double-effect distillation production process’ flow diagram.

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In the process, pure benzene at 100.0 kmol/h is mixed with part of a benzene recycle stream,
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which is subsequently pressurized. A 0.5 mol % propane-containing propylene stream at 105.0
kmol/h is pressurized and then evenly divided into four streams. The first stream is mixed with
A
the benzene feed and heated in heat exchanger FEHE prior to being fed to the first bed of a 1.3-
M

m diameter, 7 m length four-bed reactor R1, while the second stream is fed to the second bed.
The first product is mixed with the third propylene stream and cooled in an intercooler HE1 in
order to keep the reactor’s temperature below the bubble point. The resulting cooled mixture is
ED

fed to the third bed, while the fourth propylene strem is fed to the fourth bed. The kinetics for
the reactions (1) and (2) that take place in the four-bed reactor are shown in Table 1. The
PT

reactor’s final product is cooled in FEHE. Once again, surplus heat would be expected after
integrating the reactor’s feed and product in FEHE. Thus, the product is subsequently cooled in
cooler HE2 prior to being sent to a distillation column C1, from which fuel gas containing
E

mainly propane is removed at the top at 5.0 kmol/h. The bottom product is mixed with the
CC

transalkylator’s product and split into two streams. The first, at 136.7 kmol/h, and the second, at
91.2 kmol/h, are fed to the low (C2a) and high (C2b) pressure sections of the double-effect
distillation system, respectively. From C2a most of the benzene is retrieved at the top, at 60.1
A

kmol/h, whereas the bottom product is sent at 106.2 kmol/h to the cumene column C3, from
which cumene is retrieved at the top, at 99.9 kmol/h, and DIPB is obtained at the bottom, at 6.3
kmol/h. From C2b, in turn, benzene is retrieved as distillate at 61.6 kmol/h and mixed with the
C2a’s benzene product, while the bottom product is fed to C2a at 29.6 kmol/h. The benzene
stream from the double-effect distillation system is split into a 88.8 kmol/h stream, which is
recycled to the feed section, and a 32.9 kmol/h strean, which is pressurized and pre-heated prior
 15

to being fed to a 0.7-m diameter, 1.3 length transalkylator R2 where the reaction described by
Eq. (3) takes place. The kinetics are disclosed in Table 2. The transalkilator product is mixed
with C1’s bottom product.

3. Environmental Analysis
Global warming, excessive use of raw-materials and inefficient water distribution are some of
the most recurring subjects in recent days. Farming-related activities and energy generation are
the main responsible sectors to be pointed out in terms of global warming, which can be

T
observed from the increase of 20% in nitrous oxide (N2O), 40% in carbon dioxide (CO2) and
150% in methane (CH4) emissions between 1970 and 201434. The scenario becomes even more

IP
obnoxious when it comes to water distribution, since the numbers indicate that almost 1 billion

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people lack access to safe water and more than 2 billion people do not have access to
appropriate sanitation35.

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In light of this context, numerous discussions regarding the world’s current climate situation
have been raised. The need for mitigating environmental impacts has been heading towards the

U
development of new technologies that could lead the industries to a greater ecological
N
efficiency. In this regard, several methodologies to assess the environmental performance of
chemical processes have been developed. Jia et al.36 applied a Process Environmental
A
Performance Assessment (PEPA) to characterize and quantify the environmental impacts of two
M

ethanol production routes. Koroneos et al.37 and Brito and Martins38 used a Life Cycle
Assessment (LCA) approach to evaluated the ecological effects of biomass-derived hydrogen
ED

production processes and butanol production technologies, respectivelly. In fact, LCA is

broadly applied to the sustainability assessment of industrial processes since it provides a wide
range of ecological indicators to estimate environmental impacts. Vaskan et al.39 applied the
PT

Eco-indicator 99 framework to address the optimization of utility plants. Such indicator was
also used by Guillén-Gozálbez et al.40 for selecting the optimal process flowsheet in order to
balance economics and environmental impacts. Jacquemin et al.41 reviewed how several LCA
E

assessment methodologies (e.g. Eco-indicator 99, CML 2001, IMPACT2002, etc.) are used to
CC

evaluate sustainability of the processing industry. Ruiz-Mercado and coworkers42, in turn,

provided 66 ecological indicators useful to the analysis of the ecological performance of
A

chemical processes, being most of them expressed per either sales revenue or product mass.

Countless methodologies for evaluating processes’ efficiency in relation to their respective

environmental burdens have been employed and, therefore, a noticeable absence of a standard
approach would be necessary. In this regard, the international standard ISO 14045:201243 was
formulated with the purpose of providing the guidelines required to carry out eco-efficiency
assessments. The document defines eco-efficiency as an “aspect of sustainability relating the
 16

environmental performance of a product system to its product system value” and proposes its
quantification through the determination of eco-indicators. Such strategy was also suggested by
the Economic and Social Commission for Asia and Pacific (ESCAP)44, which pointed out the
significance of eco-indicators for assisting decision-making tasks (e.g. selecting a particular
plant configuration or technological route with basis on its environmental impacts).

3.1 Eco-indicators

Eco-efficiency indicators are defined as a measure of the ecological performance of a process in

relation to its product or service value, which is given by a relationship between an

T
environmental variable and an economic variable45,46. They are conveniently useful due to their

IP
potential to establish a realistic basis for defining objectives and thus assisting in the
identification of process areas where improvements are conceivable. Particularly for the

R
industrial sector, the main eco-indicators are related to water and raw material consumption,

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greenhouse gases emissions, energy consumption and waste generation47.

Eco-indicators have been used by numerous authors for the analysis of the ecological footprint

U
of different chemical processes. Silalertruksa and coworkers48 assessed the sustainability of
N
sugar cane biorefinery by estimating total output value and greenhouse gas emission indicators,
whereas Chen et al.49 determined the global warming potential (GWP) of ethylene production
A
processes. Wang et al.50 applied the concept of eco-indicators to estimate both resource
M

productivity and emission efficiency of the cement industry. For biorefirenies, Sacramento-
Rivero51 described several sustainability indicators such as land use (SLU), raw materials cost
ratio (RCR), health and safety ccomliance (HSC) and biotechnological-valorization potential
ED

(BVP), among others. For the petrochemical industry, Al-Sharrah and coworkers52 presented a
methodology for evaluating the toxicity potential of processes through the determination of the
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median lethan concentration (LC50), median lethal dose (LD50) and threshold limit value (TLV)
indicators. Mangili et al.45, in turn, used such metrics to compare two acetone-methanol
separation technologies with regard to their environmental performance.
E

The eco-efficiencies of the previously described cumene production technologies are compared
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here through the determination of six indicators, namely raw materials consumption, fuel
consumption, energy use, CO2 emissions, water use and wastewater generation eco-indicators.
A

The indicators applied in this work are conveniently useful when compared to the traditional
LCA metrics (e.g. CML, Eco-indicator 99, ESEERCO, IMPACT2002, LIME, etc.) due to the
latter’s drawbacks regarding the dependence on available, quality data and time-consuming
methodologies. LCA methods are limited to the data that may not be readily available53 and,
hence, gathering sufficient information can be quite arduous. Furthermore, some endpoint
 17

methodologies such as Eco-indicator 99, for instance, rely on relatively narrow frameworks that
are based on specific territories, which may lead to imprecise results54.

In this paper, however, the indicadors can be determined from simulation results without undue
work and take into account different territories, since the parameters used in the calculations
(e.g. CO2 emission factors, utilities conditions, etc.) take the plants location into consideration.
In addition, the metrics applied in this work consider economic aspects (i.e. production rate and
production costs), which are usually neglected by LCA indicators55. The calculation procedures
are described below.

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3.1.1 Raw Materials Consumption

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Raw materials consumption is of great significance to the industry since it contributes to a major

R
portion of the overall process’ expenditures. According to Park and Behera56, it refers to the
total amount of materials (either used for conversion or pre-fabricated) acquired by the

SC
company. Hence, the calculation of the raw materials consumption eco-indicator (RMCi) for the
processes studied was carried out by summing up the feed streams’ flow rates and dividing the

U
result by the total production rate (i.e. flow rate of cumene produced).
N
3.1.2 Fuel Consumption

Intertwined to energy use – and therefore to CO2 emissions, due to the greenshouse gases
A
(GHGs) emissions resulting from combustion – the fuel consumption of process equipment
M

must be taken into account when designing new processes. For the production plants analyzed
in this paper, the total amount of fuel (natural gas) used in the process is determined by Eq. (4).
ED

1 E
mng   i (4)
NCVng ni
Where ṁng corresponds to the natural gas mass flow rate, NCVng refers to the natural gas net
PT

calorific value (approximately 0.048 GJ/kg according to the International Energy Agency57) and
Ei and ni correspond to the required energy and the thermal efficiency of equipment i (fuel
E

consumer), respectively. In this work we considered that only the utility plant’s boiler and the
CC

fired heaters consume natural gas. Both equipment were assumed to operate with 80% thermal
efficiency58,59.

The fuel consumption (FCi) eco-indicator was then determined by dividing ṁng by the total
A

production rate of each process.

3.1.3 Energy Use and CO2 Emissions

Energy consumption is a frequent topic raised by experts when it comes to global warming,
since it is directly associated with GHG emissions. Notwithstanding the current concerns, the
world has headed towards an alarming situation due to the projections for world population
 18

growth, which will result in a significant increase in energy consumption. For this reason,
industrial energy use has gained more and more attention of specialists who study possible ways
of reducing processes’ energy requirements.

The energy use (EUi) and CO2 emissions (CO2Ei) eco-indicators represent a means to estimate
the main energy consumption sources in a chemical process, thus allowing the implementation
of energy-related optimization approaches in order to minimize such environmental burdens.
These indicators were estimated in this paper with basis on the methodology described by
Mangili et al.45. The former was calculated by adding up the energy demands of all heating

T
sources for each process and subsequently dividing the result by their respective production

IP
rate. The latter was determined by converting the respective equipment’s energy requirements
into CO2 emissions. Pumps and compressors were interpreted as electricity consumers operating

R
at 75% efficiency, whereas heaters and reboilers operate with steam generated in the utility

SC
plant’s boiler, which has an efficiency of 80%45. The energy requirements for the cooling tower
fan stacks were calculated from the procedures available in Perry60’s book. The convertion
factors for electricity and natural gas thermal energy were 0.0227 tCO2/GJ61 and 0.0561 tCO2/GJ62,

U
respectively. The lower electricity-CO2 emissions factor for Brazil is due to the fact that the
N
country’s energy mix is predominantly comprised of hydroelectric plants. This value may vary
significantly depending on the country, thus influencing the calculation of the above-stated
A
indicators. In Section 6.1.3 the CO2 emissions are later evaluated by considering conversion
M

factors from different countries with different conversion factors for electricity

One should note that the CO2 indicator applied in this work differs from the GWP since the
ED

latter corresponds to a “from cradle to grave” LCA indicator and, therefore, also includes the
CO2 equivalent emissions due to other environmental burdens such as hydrofluorocarbons,
perfluorocarbons, etc. The detailed description regarding the guidelines and procedures required
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for the calculations is provided by Mangili et al.45.

3.1.4 Water Consumption

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Energy and water are directly related since the use of water/steam in cooling/heating
CC

applications are associated with energy requirements by the respective consumers. This inter-
dependency tends to increase in the coming years, which is mainly due to the increase in the
A

global energy demand and expansion of the energy sector. For this reason, several
methodologies, such as eco-efficiency evaluation, have been applied to the industry in an effort
to estimate possible solutions to minimize energy consumption of industrial processes.

The water consumption eco-indicators (WCi) for the cumene processes were estimated
according to the procedure described by Mangili et al.45. All cooling/condensing equipment
were considered to use cooling water, with the exception of both cooler HE1 and C1’s
 19

condenser from Flegiel et al.12’s process, which were assumed to use chilled water (5° C – 15°
C) due to their lower temperature requirements as described by said authors. The total cooling
water demand from the coolers and condensers, as well as the total amount of water required to
generate low, medium and high pressure steams in the boiler, and the total heating steam
requirements in heaters and reboilers were estimated through simulation. The utility plant,
illustrated in Figure 7, was designed with basis on both such calculations and heuristics
provided by the authors. Cooling water was assumed to be supplied at 30° C and return at 45°
C13. Deaerator was assumed to receive water from the feed tank at 30° C and dispatch it to the

T
boiler feed pump at 90° C, whereas the high pressure heater was considered to operate with
boiler’s bleed steam to heat up water to 160° C prior to sending it to the boiler63. The parameters

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used for low (LPS), medium (MPS) and high pressure (HPS) steams were retrieved from Seider

R
et al.64 and are disclosed in Table 4. Cooling water tower evaporative losses and deaerator vent
were assumed to be 1%39 and 0.2%65 of the water inlet flow rate, respectively. Other losses and

SC
blowdown heuristics are detailed in the next section. To simplify, solids from the ion beds and
chemical injection were neglected in the simulation.

Table 4. Steam conditions.

U
N
Class Temperature, ° C Pressure, bar
A
LPS 254.0 43.4
MPS 185.5 11.4
M

HPS 135.0 3.1

ED
E PT
CC
A

Figure 7. Utility plant flow sheet.

 20

In Figure 7, LPS, MPS, HPS, BFP and CW stand for low pressure steam, medium pressure
steam, high pressure steam, boiler feed pump and cooling water, respectively.

3.1.5 Wastewater Generation

The costs associated with waste treatment correspond to an important drawback for industrial
activities due to strict environmental laws of waste management and nature protection. Waste
streams require complex treatment processes, since toxic compounds cannot be irresponsibly
discharged to the environment due to the harmful effects in several biosystems. Catalyst-packed
ionic columns and electricity-powered aeration are some examples of equipment that contribute

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to higher capital (CAPEX) and operating (OPEX) expenditures in industrial processes66. In this

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regard, the minimization of waste generation is a common objective among the industries.

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The total wastewater flow rate produced by each process was determined by summing up the
process losses and equipment blowdown, according to Figure 8. The respective eco-indicator

SC
(WGi) was then calculated by dividing the result by the total production rate of each process.

U
N
A
M
ED
E PT
CC
A

Figure 8. Wastewater discharge schematic diagram (adapted from the Smith’s book67).

Condensate losses were assumed to be 20% of the total steam flow rate (80% condensate
return), while losses in the boiler feed water treatment were considered to be 2% of the boiler
feed water (BFW) flow rate. Boiler and cooling water blowdowns were assumed to be 3% of the
circulating flow rate. All values stated above were retrieved from Mangili et al.45’s work, with
the exception of cooling water losses (considered to be 1%68 of the total water flow rate required
 21

by the consumers). To simplify, wastewater from freshwater consumers and rain water were
assumed to be the same for all processes and, thus, were neglected in the calculations.

4. Economic Analysis
The development of processes must undergo continuous economic evaluations in order to
determine whether they are financially feasible or impracticable. Nevertheless, Silla69 stated that
although estimations may show a potential profitability, it is possible that the capital
requirements for investment and operation “strain the financial capabilities” of the company.

T
Therefore, the evaluation of the economic feasibility of a process must take into account the
total capital (CAPEX) and operating (OPEX) expenditures.

IP
CAPEX and OPEX correspond to the costs associated with initial expenses (e.g. purchasing and

R
installing industrial equipment, acquiring land for construction, etc.) and operational

SC
investments (e.g. raw material, utilities supply, etc.), respectively70. Thus, the estimation of such
expenses is conveniently useful for assisting in decision-making tasks, especially with regard to
the selection of different production routes and plant configurations.

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The economic analysis was carried out by calculating both the respective processes’ CAPEX
N
and OPEX and specifying a hypothetical payback period of 3 years11,15,17. The TAC for each
A
technology was then determined from Eq. (5).

CAPEX
M

TAC   OPEX (5)

Payback period
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The CAPEX for each process was calculated with the aid of AspenTech’s Process Economic
Analyzer (PEA) V8.8 with basis on the equipment specifications provided by the reference
authors and updated currencies. Moreover, as exercized by Zhai et al.17, a penalty of 10% to
PT

both the DWC and RD column was assumed since the construction and installation of such
equipment may be more complex than the conventional columns.
E

For the utility plant, the economic evaluation was performed by considering that pumps and
CC

compressors were of centrifugal type, whereas feed tanks, filter, deaerator and ionic beds were
assumed to be vertical pressure vessels. Cooling water tower and boiler costs were estimated
with basis on the Leeper’s book71 and PEDCo Environmental, Inc.’s report72, respectively. High
A

pressure heater was assumed to be of shell and tube type. All construction materials were
interpreted as stainless steel 304. Regarding the OPEX, some other assumptions were taken into
consideration, as shown in Table 5.

From the TAC results and by estimating the processes’ revenue due to cumene production, as
well as to fuel and hps credits, we could determine the gross annual profits (GAPs) of each
technology. However, comparing the processes’ economics by only considering such variable
 22

would not be the most appropriate strategy since they have different production capacities.
Hence, in order to establish a more categorical comparison, a specific production cost indicator
(SPCi) was used, which could be determined by dividing the TAC of each design and by their
respective total annual production rate.

Table 5. OPEX estimation assumptions.

Basis Variable Value Reference

________
Plant operating time 8,000 h/year
________
Guidelines Internal Rate of Return 15%

T
________
Project lifetime 20 years

IP
Benzene cost 93.43 $/kmol Sharma et al.21
Propylene cost 56.50 $/kmol Sharma et al.21

R
Electricity cost 16.80 $/GJ Turton et al.13
Natural gas cost 3.71 $/GJ Aspen Plus Basis

SC
Process Cooling water cost 1.04 $/GJ Turton et al.13
Chilled water cost 4.43 $/GJ Turton et al.13
Turton et al.13
High pressure steam credit
Fuel gas and DIPB credit
U
12.33 $/GJ
6.00 $/GJ Luyben15
N
Cumene selling priced 198.73 $/kmol Sharma et al.21
Operators per shift 9e Turton et al.13
A
Operator Cost (OC) 44,315 $/year Turton et al.13
M

Supervisors per shift 2 Turton et al.13

Labor Supervisor Cost (SC) 53,178 $/year Turton et al.13
Number of shifts 5 Turton et al.13
ED

Laboratory labor 20% of (OC + SC) Silla69

Maintenance Labor (ML) 2% of CAPEX Silla69
Operating costs 10% of ML Sinnott70
PT

Supply
Maintenance 2%/year of CAPEX Sinnott70
Overhead expenditures 80% of labor costs Silla69
Silla69
E

Taxes and insurance 2%/year of CAPEX

Other
Depreciation 10%/year of CAPEX Turton et al.13
CC

________
Unscheduled equipment 10% of CAPEX
General Sales and R&D 3% of the total costs Sinnott70
d
All cumene product streams are approximately 99.9 mol % pure. Therefore, the same selling
A

price can be assigned for all six technologies.

e
The number of operators per shift in the RD plant was assumed to be 5 since its configuration
is much more compact than the other processes’.

5. Eco-efficiency Comparison Index

The joint evaluation of several different eco-indicators not always results in a simple and easy
way to rule out the least eco-efficient processes, since assuming which indicators are more
 23

important for each scenario is not always possible. This difficulty was overcome by Pereira and
coworkers47, who developed a methodology called “Eco-efficiency Comparison Index (ECI)”.
Such methodology was applied by Mangili et al.45 to compare the eco-efficiencies of three
different acetone-methanol separation processes. The strategy consists in normalizing the
environmental and economic indicators by dividing them by the highest value of their respective
category. The normalized indicators are then arranged in a radar type chart to form polygon-
shaped diagrams corresponding to the processes to be compared. The shape area (ST) is then
determined by summing up the areas (Sa) of the n minor triangles formed, which are calculated

T
through the Law of Sines shown in Eq. (6), where lA and lB correspond to the adjacent sides A
and B of the minor triangle, respectively. θ refers to the angle formed between lA and lB, and

IP
corresponds to 2π divided by the number n of indicators evaluated, since all axis are equidistant

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from one another and set apart in a 360° circle45,47.

SC
l A  lB
Sa   sen (6)
2

U
The ECI is calculated as described in Eq. (7), where ST* refers to the area of the largest shape
formed in the chart.
N
 S 
ECI  1  T*  100%
A
(7)
 ST 
M

The environmental performances of the cumene production processes were quantitative and
qualitatively compared by means of the ECI method. Since all processes were optimized by the
ED

reference authors with basis on economic parameters, a fair and categorical analysis can be
performed. Moreover, such evaluation strategy is singularly convenient since it allows the
determination of the environmental impacts of industrial processes without the undue burden of
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re-designing the technologies to be evaluated. Hence, it is possible to appropriately compare

high-capacity processes (e.g. Flegiel et al.12’s) with lower-capacity designs (e.g. other
E

technologies), since relative metrics are used. The same required procedure and formulae
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described by Mangili and coworkers45 were applied in this work.

6. Results and Discussion

A

The simulation of the cumene production processes provided the required variables for
calculating their respective indicators. The results are shown in Figures 1, 2, 3, 4, 5 and 6 which
show that our results are indeed comparable to the authors’ and, therefore, demonstrate the
plausibility of our study. Some differences regarding energy requirements were found when
compared to the data provided by the reference authors. Such deviations might be due to the
 24

different software used. With exception of Flegiel et al.12, which simulated the two-flash
energy-integrated technology in Aspen HYSYS, all authors used early versions of Aspen Plus.

One should note that, since the cumene product stream of all six processes is approximately
99.9 mol % pure, the indicators were equally determined in accordance with the methodology
described in Section 3. The results for the environmental indicators are given in Table 6.

Table 6. Eco-indicator results.

Maity Flegiel Zhai Pathak Norouzi
Process Luyben15
et al.16 et al.12 et al.17 et al.11 et al.19

T
Production rate, t/h 11.17 11.89 38.36 12.11 11.96 12.24

IP
Tofal feed flow rate, tmp/h 12.02 12.16 40.22 12.92 12.25 12.01
RMCi, t/t 1.0761 1.0227 1.0485 1.0669 1.0242 0.9812

R
Fuel flow rate, tfuel/h 0.69 0.63 0.49 0.35 0.30 0.40
FCi, tfuel/t 0.0618 0.0530 0.0128 0.0289 0.0251 0.0327

SC
Energy demand, GJ/h 33.40 30.62 26.97 16.86 14.31 19.45
EUi, GJ/t 2.9902 2.5753 0.7031 1.3922 1.1965 1.5891
CO2 emissions, tCO2/h
CO2Ei, tCO2/t
1.87
0.1674
1.72
0.1447
U
1.40
0.0365
0.94
0.0776
0.80
0.0669
1.09
0.0891
N
3
Make-up flow rate, m H2O/h 12.05 10.40 14.19 11.56 8.34 12.34
3
WCi, m H2O/t 1.0788 0.8747 0.3699 0.9546 0.6973 1.0082
A
Wastewater flow, m3ww/h 12.19 10.53 15.43 12.57 8.36 12.70
M

WGi, m3ww/t 1.0913 0.8856 0.4022 1.0380 0.6990 1.0376

6.1. Raw Material and Fuel Consumption

ED

The total amount of raw material required to feed each process was simply determined by
summing up fresh benzene and fresh propylene’s flow rates. The eco-indicator was then
PT

calculated by dividing the result by their respective total flow rate of cumene. With regard to
fuel consumption, in turn, the simulation of the conventional and transalkylation technologies
provided the fired heater’s energy demands, while the simulation of the utilities plant provided
E

the boiler’s energy requirements. Hence, the fuel consumption eco-indicator could be
CC

determined for each process through Eq. (4).

Table 6 shows the results for each process, from which it can be observed that all modifications
A

in relation to the conventional technology provided a decrease in both the raw materials
consumption and fuel consumption indicators. In fact, the higher fuel consumption of the
conventional and transalkylation processes is due to the fact that they not only have a boiler to
generate utility steam but also a fired heater to pre-heat the reactor’s inlet stream.
 25

6.2. Energy Use and CO2 Emissions

The total energy requirements of each process were divided by their respective cumene
product’s flow rate in order to calculate their energy use indicators. Their equivalent CO2
emissions were then estimated by following the procedure described by Mangili et al.45. It can
be seen that Flegiel et al.12’s process consumes much less energy and emits less carbon dioxide
per ton of product than the other technologies. Such advantage is due to both the energy
integration between C1’s reboiler and the recompressed C2’s top product and the use of the
electricity generated by the reactor product’s gas expander in C2’s top product compressor.

T
The low energy consumption of Pathak et al.11’s technology, in turn, can be associated with the

IP
RD column, which integrates the process by allowing the utilization of the heat of reaction to
assist in the colum’s separation mechanism and, thus, increases overall conversion. As for Zhai

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and coworkers17’s process, the low energy requirements are due to liquid/vapor interconnection

SC
As previously highlighted, the electricity-CO2 emissions factor of 0.0227 tCO2/GJ was used
since the process plants were assumed to be installed in Brazil, whose energy mix mainly

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consists of hydroelectric plants. In order to show how such factor affects the CO2 emissions
N
depending on the energy generation source, different locations with different energy mixes were
evaluated. The results are shown in Figure 9, in which the bars refer to the left y-axis and the
A
data-labeled curves relate to the right y-axis. We note that Hong Kong has the highest emission
values, followed by South Korea and United States. Hong Kong’s energy mix is mainly based
M

on coal power stations (70%), which results in an electricity-CO2 emissions factor as high as
0.2138 tCO2/GJ. South Korea’s energy mix comprises 40% coal plants and 30% nuclear
ED

stations, thus having a factor of 0.1533 tCO2/GJ, whereas United States’ consists mainly of
natural gas thermal plants (30%), resulting in a factor of 0.1385 tCO2/GJ72.
E PT
CC
A

Figure 9. CO2 indicator for different locations.

 26

Canada, Brazil and France’s energy mixes, in turn, are mostly comprised of either hydroelectric
or nuclear power plants, which justifies the lower CO2 emissions per GJ of energy generated. In
fact, Canada and France’s factors are as low as 0.0456 tCO2/GJ and 0.0163 tCO2/GJ,
respectively72. Although the locations evaluated have significantly different electricity-CO2
conversion factors, the carbon dioxide indicators do not vary greatly. This is due to the low
electricity consumption of the cumene processes studied. As we can see, the energy consumed
by pumps and compressors only accounts for a maximum of 1% of the processes’ total energy
requirements.

T
6.3. Water Consumption and Wastewater Generation

IP
The water consumption eco-indicators were calculated with basis on the procedure described by
Mangili et al.45, that is, only water and steam losses were taken into account. Besides Flegiel et

R
al.12’s HE1 and C2’s condenser, which use chilled water, all condensers and coolers operate

SC
with cooling water, whereas tubular reactors are BFW-cooled. Regarding heaters and reboilers,
LPS, MPS and HPS were assumed to be supplied deending on the equipment’s temperature

U
requirements, in accordance with the data provided by Mangili et al.45. The required make-up
water for the utility plant was given by simulation and used to determine the indicators. From
N
the results given in Table 6 we observe that Flegiel et al.12’s process proved to be the most
A
water consumption-efficient technology, which is, again, due to C1’s reboiler energy
integration.
M

Finally, the wastewater generation indicator from each process was determined by dividing the
the total wastewater flow rate produced – sum of all process losses and equipment blowdown –
ED

by their respective production rate. Again, Flegiel and coworkers12’s two-flash energy-
integrated technology showed to be the best alternative since it produces less wastewater per ton
PT

of product than the other processes. It is important to highlight that the wastewater generation
and water consumption indicators are interconnected, since the lower the water and steam
requirements, the lower the process losses.
E

6.4. Economic Analysis

CC

From the assumptions described in Section 4 it was possible to determine the capital and
operating expenditures for all six cumene manufacturing processes. In addition, by calculating
A

the processes’ TACs and credits we estimated the gross annual profit (GAP) associated with
each technology. The results are shown in Table 7, from which it can be verified that the
intensified processes are not only more environmentaly friendly but also economically
attractive.

The economic results provided in this paper are different from those calculated by the reference
authors due to the differences regarding the methodology applied. None of the authors took into
 27

accounts the utility plant costs to estimate CAPEX and other general expenses such as the
number of shifts and operators, overhead costs, maintenance costs and taxes and insurance,
among others, to estimate OPEX. In addition, the values found in this study were determined
with basis on Aspen PEA’s estimation method and updated currencies/prices.

Table 7. Gross profit results.

Maity Flegiel Zhai et Pathak Norouzi
Process Luyben15
et al.16 et al.12 al.17 et al.11 et al.19
CAPEX (106 $) 7.33 8.13 17.87 8.22 5.90 8.09

T
6
OPEX (10 $/year) 132.71 140.31 469.41 143.24 140.11 138.97
Payback period (years) 3 3 3 3 3 3

IP
TAC (106 $/year) 135.15 143.02 475.37 132.11 131.54 141.67
6 ________
HPS credit (10 $/year) 0.92 1.02 2.69 1.71 0.77

R
6 ________
Fuel/DIPB credit (10 $/year) 0.03 0.03 0.06 0.01 0.02

SC
6
Cumene revenue (10 $/year) 147.70 157.24 507.32 160.47 158.19 158.98
GAP (106 $/year) 13.50 15.27 34.70 15.74 16.11 18.11

U
As previously discussed, although the intensified processes present higher annual profits, such
parameter is not appropriate for comparing the processes’ economics. In fact, according to the
N
results for the specific production cost indicators shown in Table 8, we note that Zhai et al.17’s
A
technology has the lowest costs per production rate, followed by Pathak et al.11’s process. We
verify, however, that although Flegiel and coworkers12’s design has the highest GAP, its
M

production cost indicator is the lowest. This indicates a lower economic performance when
compared to the other alternatives.
ED

Table 8. SPCi results.

Maity Flegiel Zhai Pathak Norouzi
Process Luyben15
et al.16 et al.12 et al.17 et al.11 et al.19
PT

TAC, 106 $/year 135.15 143.02 475.37 132.11 131.54 141.67

3
Production rate, 10 t/year 89.36 95.12 306.88 96.88 95.68 97.92
E

SPCi, 103 $/t 1.5124 1.5036 1.5490 1.3636 1.3748 1.4468

CC

6.1 Eco-efficiency Comparison

Following Mangili and coworkers45 ECI methodology, the cumene production processes were
A

compared in terms of their respective environmental performances. Since each eco-indicator

falls into different categories, they were normalized by dividing them by the highest value
present in the same group, as presented in Table 9. We can verify that the results vary from 0 to
1, that is, from the most eco-efficient to the least eco-efficient in that category.

The normalized eco-indicators were then plotted in a radar-type chart to provide a qualitative
analysis of ther eco-efficiency, as illustrated in Figure 10. The ECI diagram resulted in
 28

heptagon-formed shapes since 7 indicators were evaluated. It should be pointed out, however,
that the same relevance (weight) was assumed for all categories.

Table 9. Normalization of eco-indicators.

Maity et Flegiel et Zhai et Pathak Norouzi et
Eco-indicator Luyben15
al.16 al.12 al.17 et al.11 al.19
RMCi 1.0761* 1.0227 1.0485 1.0669 1.0242 0.9812
FCi 0.0618* 0.0530 0.0128 0.0289 0.0251 0.0327
EUi 2.9902* 2.5753 0.7031 1.3922 1.1965 1.5891
CO2Ei 0.1674* 0.1447 0.0365 0.0776 0.0669 0.0891
WCi 1.0788* 0.8747 0.3699 0.9546 0.6973 1.0082

T
WGi 1.0913* 0.8856 0.4022 1.0380 0.6990 1.0376
SPCi 1.5124 1.5036 1.5490* 1.3636 1.3748 1.4468

IP
Normalized eco-indicators
RMCi 1.0000 0.9444 0.9722 0.9907 0.9537 0.9074

R
FCi 1.0000 0.8333 0.1667 0.5000 0.3333 0.5000
EUi 1.0000 0.8629 0.2341 0.4682 0.4013 0.5318

SC
CO2Ei 1.0000 0.8824 0.2353 0.4706 0.4118 0.5294
WCi 1.0000 0.8148 0.3426 0.8889 0.6481 0.9352
WGi 1.0000 0.8165 0.3670 0.9541 0.6422 0.9541
SPCi 0.9742 0.9677 1.0000 0.8774 0.8839 0.9355
* Highest values by category.
U
N
The normalized eco-indicators were then plotted in a radar-type chart to provide a qualitative
analysis of ther eco-efficiency, as illustrated in Figure 10. The ECI diagram resulted in
A
heptagon-formed shapes since 7 indicators were evaluated. It should be pointed out, however,
M

that the same relevance (weight) was assumed for all categories.
ED
E PT
CC
A

Figure 10. Qualitative ECI for all six cumene production technologies.
 29

Although we can visually infer that some processes are less eco-efficient than others due to the
differences of their polygon areas, some technologies present similar shapes and sizes.
Therefore, it is necessary to develop a quantitative evaluation with basis on the indicators. The
areas of each minor triangle inside the heptagon-shaped polygons were calculated through Eq.
(6) and subsequently summed up in order to determined their respective heptagon areas45,
through Eq. (7). The quantitative ECI for each production plant was then determined, as
presented in Table 10.

We can note that the conventional process is the least eco-efficient due to its bigger ECI

T
heptagon area, followed by the transalkylation technology, which is 22.94% more eco-efficient

IP
than the former. The intensified processes, in turn, proved to be much more environmentaly
efficient, having the two-flash energy integrated technology the highest performance (79.20%

R
more than the conventional process). This substantiates the relevance of energy integration in

SC
improving process economics and reducing ecological impacts, even more than two of the most
promising process intensification technologies (DWC and RD).

Luyben15
Maity et U
Table 10. Quantitative ECI for all six cumene production technologies.
Flegiel Zhai et Pathak et Norouzi
N
Indicator x indicator
al.16 et al.12 al.17 al.11 et al.19
RMCi x FCi 1.00 0.79 0.16 0.50 0.32 0.45
A
RMCi x EUi 1.00 0.81 0.23 0.46 0.38 0.48
RMCi x CO2Ei 1.00 0.83 0.23 0.47 0.39 0.48
M

RMCi x WCi 1.00 0.77 0.33 0.88 0.62 0.85

RMCi x WGi 1.00 0.77 0.36 0.95 0.61 0.87
RMCi x SPCi 0.97 0.91 0.97 0.87 0.84 0.85
ED

FCi x EUi 1.00 0.72 0.04 0.23 0.13 0.27

FCi x CO2Ei 1.00 0.74 0.04 0.24 0.14 0.26
FCi x WCi 1.00 0.68 0.06 0.44 0.22 0.47
FCi x WGi 1.00 0.68 0.06 0.48 0.21 0.48
PT

FCi x SPCi 0.97 0.81 0.17 0.44 0.29 0.47

EUi x CO2Ei 1.00 0.76 0.06 0.22 0.17 0.28
EUi x WCi 1.00 0.70 0.08 0.42 0.26 0.50
E

EUi x WGi 1.00 0.70 0.09 0.45 0.26 0.51

CC

EUi x SPCi 0.97 0.84 0.23 0.41 0.35 0.50

CO2Ei x WCi 1.00 0.72 0.08 0.42 0.27 0.50
CO2Ei x WGi 1.00 0.72 0.09 0.45 0.26 0.51
CO2Ei x SPCi 0.97 0.85 0.24 0.41 0.36 0.49
A

WCi x WGi 1.00 0.67 0.13 0.85 0.42 0.89

WCi x SPCi 0.97 0.79 0.34 0.78 0.57 0.87
WGi x SPCi 0.97 0.79 0.37 0.84 0.57 0.89
Sum 20.85 16.05 4.34 11.19 7.65 11.85
Heptagon area (ST)45,47 8.15 6.28 1.70 4.38 2.99 4.63
ECI (Eq. (7))45,47 ______
22.94 79.20 46.32 63.29 43.14
 30

As previously discussed, the ECI method consists of a joint evaluation of indicators, thus
representing an appropriate strategy to compare the environmental performance of processes,
since the determination of single indicators is not sufficient to assert which technology is the
most eco-efficent. However, when the assessment lacks sufficient data to establish a composite
analysis, the assessor may perform a rough comparison in terms of single, yet adequate
indicators.

Although practical, the raw materials consumption indicator may be deemed unessential either
when the reaction yields of different processes are similar or when no reactions take place,

T
which is the case of Mangili et al.45’s work. The fuel consumption, in turn, cannot be estimated

IP
for applications where no fuel consumers are used, or when the utilities are provided by an
external source instead of a utility plant, which is assumed by most authors (including the

R
references studies here). When the utilities plant is considered, particular care must be taken

SC
when investigating the other indicators, especially in relation to the energy consumption, which
is associated with all other metrics. The energy results obtained from simulation are useful in
determining the amount of fuel consumed in the boiler to generate steam for providing the

U
required heat to reboilers and heaters. Also, such results are used to estimate the CO2 emissions
N
due to electricity and fuel consumption, as well as the amount of water necessary in coolers and
condensers. In this regard, the water consumption indicator is also of particular importance
A
since it is directly related to the wastewater generation, which is calculated from the utility plant
M

heuristics that are mainly based on the recirculating water flow rate. The energy and water
requirements are then utilized in the estimation of the production costs.
ED

Hence, determining the energy use and production cost indicators may be deemed sufficient for
carring out a rough comparison, especially when it comes to process intensification techniques,
since they are aimed at fostering the development of more energy-efficient technologies In fact,
PT

most authors compare process plants in terms of energy consumption and economics, which
then provides a partial, preliminary assessment to assist decision-making procedures.
E

Nevertheless, attention must be drawn to the fact that the energy consumption is sufficient only
CC

when no off-gas stream is combusted (e.g. in a flare, heat recovering unit, etc.), or when vent
streams directly release CO2 to the environment. In Mangili et al.45’s work, for instance, no such
streams are present, whereas in this paper they are assumed to be exported as fuel credits. On
A

one hand, for applications where a flare or a heat recovering system is considered, the carbon
dioxide produced from combustion must be taken into consideration, which is the case of
Guillén-Gozálbez et al.40’s toluene hydrodealkilation processes. The authors stated that the
methane purge streams are combusted in oder to recover the heat. On the other hand, if CO2 is
directly vented to the atmosphere its flow rate must be accounted, as in the case of Jia et al.36’s
 31

ethanol production processes via ethylene and via cellulose. These aspects would affect greatly
the CO2 indicator, which would then be required in the analysis.

7. Conclusion
This study compared six cumene production processes, including their utilities plants, with
regard to their respective economics and ecological performance. The environmental analysis
was carried out with basis on the calculation of six different equally-weighted categories of eco-
indicators, while the economic evaluation was performed with the aid of Aspen PEA and

T
equipment specifications provided by the reference authors in order to determine the

IP
processes’specific production cost indicator. The environmental performances of all
technologies were compared through the Eco-efficiency Comparison Index. The comparison

R
showed that the intensified processes are both more economically and environmentaly attractive

SC
in relation to the conventional and transalkylation processes. The two-flash energy-integrated
technology proved to be the best alternative, even when compared to the DWC and RD designs,
since it is the most eco-efficient (79% more than the conventional process). Such conclusion is

U
mainly based on the energy integration between column C1’s reboiler and the recompressed
N
column C2’s top product.
A
It was, therefore, possible to demonstrate the significance of process intensification in terms of
not only reducing process’ costs but also minimizing environmental impacts from the industry.
M

In light of these results, it is possible to develop future studies based on eco-indicators to

analyze the feasibility of a thermal integration in the conventional and transalkylation
ED

technologies. A future evaluation regarding the use of a dividing wall reactive column could
also be carried out with basis on both Pathak et al.11 and Zhai et al.17’s configurations.
PT

Symbols Used
Symbols
E
CC

C1 Column 1
C2 Column 2
C3 Column 3
A

Cbenzene Benzene composition

Ccumene Cumene composition

Cpropylene Propylene composition

D Vessel diameter
E Required energy
E1 Expander
 32

FEHE Heat exchanger

H1 Fired heater
HE1 Cooler 1
HE2 Cooler 2
HX1 Heater 1
HX2 Heater 2
K1 Compressor
L Vessel length

T
ṁng Natural gas mass flow rate

IP
n Thermal efficiency
ng Natural gas

R
NCVng Natural gas net calorific value

SC
P1 Pump 1
P2 Pump 2
P3
R1
Pump 3
Tubular reactor U
N
R2 Transalkylator
A
V1 Vessel 1
M

V2 Vessel 2
xBz Benzene molar fraction
xC3 Propane molar fraction
ED

xC3= Propylene molar fraction

xCu Cumene molar fraction
PT

xDIPB p-Diisopropyl benzene molar fraction

Subscripts
E

i Equipment (fuel consumer)

CC

Abbreviations
A

ANOVA Analysis of Variance

BFP Boiler Feed Pump
BFW Boiler Feed Water
CAPEX Capital Expenditure
CHW Chilled Water
CW Cooling Water
 33

DIPB p-Diisopropyl benzene

DWC Dividing Wall Column
ECI Eco-efficiency Comparison Index
ESCAP Economic and Social Commission for Asia and the Pacific
GHG Greenshouse Gas
GAP Gross Annual Profit
GWP Global Warming Potential
HPS High Pressure Steam

T
LCA Lice Cycle Assessment

IP
LPS Low Pressure Steam
ML Maintenance Labor

R
MOO Multi Objective Optimization

SC
MPS Medium Pressure Steam
NPV Net Present Value
OPEX
PEA
Operating Expenditure
Process Economic Analyzer U
N
PEPA Process Environmental Performance Assessment
A
RAPID Rapid Advancement in Process Intensification Deployment
M

RD Reactive Distillation
TAC Total Annualized Cost
WMO World Meteorological Organization
ED

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PT

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