Chemical Engineering & Processing: Process Intensification 147 (2020) 107784

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Chemical Engineering & Processing: Process Intensification

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Eco-efficiency analysis and intensification of the acetic acid purification T

process
Igor Nardi Caxiano*, Pedro Gabriel Junqueira, Patrick Vaz Mangili, Diego Martinez Prata
Department of Chemical and Petroleum Engineering, Universidade Federal Fluminense, Niterói, RJ 156, 24210-420, Brazil

A R T I C LE I N FO A B S T R A C T

Keywords: This work presents three intensification strategies for an acetic acid purification process. The proposed con-
Acetic acid figurations employing double-effect distillation and vapor recompression were designed by computer simulation
Double-effect distillation in UniSim Design Suite. The simulation of a utility plant was also carried for more accurate estimations of water
Vapor recompression and energy consumption, capital expenditures and production costs. The intensified technologies are compared
Process intensification
to the original process and to a thermally coupled technology using the Eco-efficiency Comparison Index method
Eco-efficiency
based on five environmental indicators (namely carbon dioxide emissions, water consumption, terrestrial toxi-
city potential, aquatic toxicity potential and acidification potential), one safety indicator (namely human toxicity
potential by exposure) and four economic indicators (namely capital expenditures, specific energy costs, specific
water costs and liquid waste cost fraction). The results showed that the intensification strategies were from
28.9–67 % more eco-efficient than the original process. The vapor recompression design resulted in the best
sustainability performance, mainly due to an 80.5 % lower energy consumption, which provided a 67 % increase
in its eco-efficiency compared to the original technology and approximately 44 % compared to one of the
double-effect distillation strategies and the thermally coupled design, which comprised the second and third best
alternatives, respectively.

1. Introduction product. In the terephthalic acid production technology, for instance, a

Acetic acid is a carboxylic acid usually employed as a solvent for
manufacturing pharmaceutical products and cellulose acetate, and as
raw material for producing vinyl acetate monomer, terephthalic acid,
and acetic anhydride. Since these compounds are used in a wide range
of industries (e.g. food ingredients, textiles, automobile, and construc-
tion), acetic acid is deemed to be one of the most important organic
products in the chemical industry [1,2]. In 2014, the worldwide de-
mand for acetic acid was 12.1 million tons, with projections to reach
16.8 million tons by 2022 mainly due to the rising demand for vinyl
acetate monomer from the adhesive and sealant industry [2].
Acetic acid is commonly produced through carbonylation of me-
thanol, oxidation of hydrocarbons, ethylene oxidation and alcohol
fermentation, with methanol carbonylation being the most widely ac-
cepted route [3,4]. In each of these processes, acetic acid is obtained in
aqueous solutions [3]; therefore, purification processes must be em-
ployed to obtain dehydrated acetic acid. The purification of these
aqueous solutions is also important for the manufacturing processes of
other chemical products, in which dilute acetic acid is produced as a by-
dehydration unit using azeotropic distillation or hybrid extraction-dis-
tillation is employed to recover acetic acid used as the solvent. This
recovery unit has great economic significance on the overall process
since the purity of the acetic acid directly influences the quality of the
produced terephthalic acid [5].
The purification of acetic acid is one of the most studied processes in
the chemical industry. Due to hydrogen bonding and intermolecular
association in acetic acid and water mixtures, simple distillation tech-
nologies are usually not efficient, requiring a large number of equili-
brium stages and high reflux ratios, as well as leading to problems in
column design [6,7]. Instead, the recovery of acetic acid is usually
performed through azeotropic distillation, extractive distillation or li-
quid-liquid extraction [8]. For dilute solutions with less than 35−45 wt
% acetic acid in water, hybrid extraction/distillation processes are
usually employed due to their effectiveness regarding energy con-
sumption [1,6]. In this technology, acetic acid is initially removed from
the aqueous solution using extraction agents such as ethyl acetate,
isopropyl acetate and diethyl ether [6]. The extraction agent forms an
azeotrope with water, thus allowing the recovery of nearly 100 wt%

⁎
Corresponding author.
E-mail addresses: igor.caxiano@gmail.com (I.N. Caxiano), pedrojunqueira@id.uff.br (P.G. Junqueira), pmangili@id.uff.br (P.V. Mangili),
pratadiego@gmail.com (D.M. Prata).

https://doi.org/10.1016/j.cep.2019.107784
Received 10 October 2019; Received in revised form 27 November 2019; Accepted 10 December 2019
Available online 16 December 2019
0255-2701/ © 2019 Elsevier B.V. All rights reserved.
I.N. Caxiano, et al.
acetic acid at the bottom of an azeotropic distillation column. The ex-
traction agent is then recovered in a water-stripping tower [3,9].
The aforementioned processes are heavily reliant on distillation
towers, which comprise one of the most energy-intensive unit opera-
tions, mainly due to their low thermodynamic efficiency [10,11]. This
knowledge, combined with the previously presented importance of
acetic acid in many sectors of the chemical industry, makes the acetic
acid purification a particularly interesting target for process in-
tensification. According to Stankiewicz and Moulijn [12], process in-
tensification can be described as the development of apparatuses and
techniques that result in cheaper, sustainable technologies by de-
creasing equipment sizes, energy consumption or waste production.
Regarding industrial processes that involve distillation operations,
double-effect distillation and vapor recompression are among the
technologies that can be employed to reduce energy use. The former is a
particular example of multi-effect distillation and consists of heat in-
tegrating two distillation columns by using the overhead vapor of a
high-pressure column to supply heat to the reboiler of a low-pressure
column [13]. The latter, also called “mechanical heat pumping”, con-
sists in compressing the overhead vapor of a distillation column to
supply heat to the bottom liquid in its own reboiler, increasing the
overall thermal efficiency of the distillation [14].
Previous studies have demonstrated that intensification strategies
focused on heat integration are able to reduce energy consumption and
increase economic performance. In Li et al. [15]’s work, a simplified
heat-integrated distillation column configuration was designed for se-
parating propylene and propane, providing higher energy savings and
lower total annual costs than the conventional design and other in-
tensified technologies. Similarly, a novel middle vapor recompression
design proposed in Cong et al. [16]’s work for the separation of several
organic mixtures presented greater total annual costs but provided
larger operational flexibility and the second-largest energy saving
performance, compared to other intensified designs.
It should be noted, however, that process intensification strategies
are not limited to distillation columns design and may combine dif-
ferent unit processes into a single one for reduced energy consumption,
environmental impacts, and equipment size. This is exemplified in Gao
et al. [17]’s work, in which a heat-integrated reactive distillation
technology was designed to combine the reaction and distillation sec-
tions of a conventional tert-amyl methyl ether process, reducing in
34.17 % and 6.56 % the operating costs and total annual costs, re-
spectively. As highlighted in Feyzi and Beheshti [18]’s work, although
reactive distillation columns are not suitable for many reaction systems,
the simultaneous reaction and separation tasks can lead to advantages
such as improved conversion and selectivity, as well as reduced catalyst
requirement and by-product formation.
Therefore, as demonstrated in previous studies, the aforementioned
double-effect distillation and vapor recompression technologies have
the potential of reducing energy consumption in the acetic acid pur-
ification process; however, any modification of existing technologies or
development of new ones need to be thoroughly evaluated before its
implementation so as to assess the effects not only on environmental
impacts but also on economic performance. This is directly related to
the concept of eco-efficiency, which is an approach used for the de-
velopment and modification of industrial processes that aims to max-
imize the production efficiency (and/or enhance product quality) and
safety procedures while mitigating the negative impacts on the en-
vironment. Eco-efficiency can be quantitatively measured using eco-
indicators, which are usually defined by the ratio between an en-
vironmental variable (e.g. water consumption of emission of green-
house gases) and an economic variable such as production rate [19].
The importance of indicators for measuring the sustainability of
process systems has been demonstrated in several studies in the scien-
tific literature. In the context of process intensification, Junqueira et al.
[20] compared six different cumene production processes using seven
environmental indicators, showing that the intensified processes had
2
Chemical Engineering & Processing: Process Intensification 147 (2020) 107784
better environmental and economic performance, reaching up to a
79.20 % increase in their overall eco-efficiency relative to the worst-
performing design. In Mangili and Prata [21]’s study, four heat in-
tegration alternatives were proposed to the conventional and reactive
distillation technologies for butyl acetate production, with the best
plant configurations being assessed with a joint evaluation of a total of
fourteen eco-indicators encompassing environmental impacts, eco-
nomic performance and safety hazards. Their results showed that the
heat integration of the reactive distillation process provided an eco-
efficiency increase of 62 % compared to the conventional technology.
With regard to the acetic acid purification, there are several studies
available in scientific literature, and many strategies have been pro-
posed for improving its efficiency, with some works investigating en-
trainer selection [1,5,6,8,22] and some focusing on optimization [23]
and intensification [24] of the available purification technologies.
While most of these works have employed either economic factors or
energy saving as selection parameters for more efficient configurations,
as far as we know, there is a lack of studies that propose and compare
different intensification strategies regarding their effects on environ-
mental impacts and economic performance.
In this work, we investigate a conventional acetic acid purification
process and a thermally coupled design presented in Lee and Kim [25]’s
work, while also designing and proposing three additional intensifica-
tion strategies with double-effect distillation and vapor recompression
technologies. The sustainable performance of the original processes and
the proposed intensifications are assessed using the Eco-efficiency
Comparison Index (ECI) method considering five environmental in-
dicators (namely carbon dioxide emissions, water consumption, ter-
restrial toxicity potential, aquatic toxicity potential and acidification
potential), one safety indicator (namely human toxicity potential by
exposure) and four economic indicators (namely capital expenditures,
specific energy costs, specific water costs and liquid waste cost frac-
tion). Data required for eco-indicator analysis was obtained using
computer simulation in UniSim Design Suite. Additionally, a utility
plant was designed and simulated to more accurately assess the water
and energy consumption of each process. Such consideration is not
usually performed by most authors.
2. Process description and simulation
This section provides an overview of the conventional/original
acetic acid purification process, its modified design using a side stripper
and thermal coupling, as presented in Lee and Kim [25]’s work, and
three proposed intensification strategies: two using double-effect dis-
tillation and one using vapor recompression. Details are also provided
regarding the parameters and specifications used for simulating all
processes in UniSim Design Suite.
The conventional acetic acid purification process is originally pre-
sented in Sasaki et al. [3]’s work. The process designed by the authors
was further studied in Lee and Kim [25]’s work, in which an in-
tensification strategy via thermal coupling was proposed to reduce
energy consumption and investment, while also increasing thermo-
dynamic efficiency. Process flow rates, stream compositions, and op-
erating conditions presented in Lee and Kim [25]’s work for both the
original process and the modified one were used in the computer si-
mulations and as a basis for the intensification strategies proposed in
this work.
The UNIQUAC model was used for describing equilibrium relations
and thermodynamic properties in all simulations to correctly compare
the results with the ones from the reference work since the same
thermodynamic model was used in the authors’ simulations. As an ac-
tivity coefficient-based model, the UNIQUAC thermodynamic package
has been widely used for predicting phase equilibria, since it takes into
consideration not only the size and nature of molecules but also inter-
molecular forces in solute-solvent interactions [26]. Additionally, pre-
vious studies have demonstrated, by comparison with reliable
I.N. Caxiano, et al.
Fig. 1. Lee and Kim [25]’s original acetic acid purification process (OP).
experimental data, that the UNIQUAC model provides favorable results
for estimating thermodynamic properties of mixtures involving water
and acetic acid [27].
2.1. Original process (OP)
The original acetic acid purification process as described in Lee and
Kim [25]’s work based on Sasaki et al. [3]’s design is illustrated in
Fig. 1. In this design, dilute acetic acid is dehydrated in a hybrid ex-
traction/distillation process.
The absorption column C101 extracts acetic acid from a fresh feed
of 419.1 kmol/h containing 13.9 mol % water and 86.1 mol % acetic
acid using an extractant mixture of i-propyl acetate (i-PAc) and i-pro-
panol (i-POH). The extract is cooled to 92.43 °C and sent to the azeo-
tropic column C102, where a stream of 57.1 kmol/h with 99.9 mol %
acetic acid is retrieved at the bottom. The organic phase separated in
the decanter is mostly composed of i-propyl acetate and has a fraction
of 119.1 kmol/h sent to the extractor as a solvent mixture, while the
remainder is recycled in the azeotropic column. The aqueous phase is
sent to the dehydration column C103, where 90.9 kmol/h of pure water
is retrieved at the bottom. The raffinate from the absorption column is
sent to the dehydration column C104, where 271.6 kmol/h of water
with 99.4 mol % purity is retrieved at the bottom. The top products of
the dehydration columns C103 and C104 are mixed into a stream of
13.9 kmol/h with 48.7 mol % water that is recycled to the absorption
column.
2.2. Thermally coupled process (TC)
In Lee and Kim [25]’s work, the authors highlight that the two
dehydration columns separate water from mixtures of similar compo-
sitions (98.4 mol % water for C103 and 97.4 mol % water for C104),
which allows the columns to be combined as a single side stripper
connected to the azeotropic column. The modified design proposed by
the authors is illustrated in Fig. 2.
The introduction of the side stripper establishes a thermal coupling
between it and the azeotropic column. Like double-effect distillation
and vapor recompression, thermal coupling is also an intensification
strategy that can be implemented in distillation processes. In the case of
the authors’ design, the heat transfer and reflux provided by the
3
Chemical Engineering & Processing: Process Intensification 147 (2020) 107784
condensers of the original dehydration columns are replaced in the top
of the side stripper by a material flow from the azeotropic column.
According to Agrawal [13], the two-way communication between the
two columns established by thermal coupling often reduces energy
consumption by up to 30–40 %. In this design, raffinate from the ab-
sorption column C201 and aqueous phase separated in the azeotropic
column C202′s decanter are fed into the side stripper C203, where
361.8 kmol/h of water with 99.7 mol % purity is retrieved at the
bottom. Due to the thermal coupling, the overhead product of the side
stripper, comprised of 27.1 kmol/h, is fed to the 14th stage of the
column C202, and there is no longer a recycled stream sent to the ab-
sorption column.
2.3. Double-effect distillation processes (DE1 and DE2)
In the thermally coupled design, the reboiler HX203 of the azeo-
tropic column C202 comprises 76 % of total energy consumption from
heat utilities. In light of the potential of improving the process’ sus-
tainability via additional intensification strategies, we have proposed
two modifications of the TC design using double-effect distillation for
reducing the reboiler HX203’s energy consumption.
The first double-effect process (DE1), illustrated in Fig. 3, was de-
signed following the guidelines from Agrawal [13]’s work for im-
plementing multi-effect distillation in thermally coupled configura-
tions.
In this configuration, the side stripper was redesigned into the
thermally equivalent column C303 to employ a forward heat integra-
tion with the azeotropic column C302. The UniSim shortcut distillation
tool was used to obtain the tray number, feed stages, and operating
conditions of column C303 for the same product recovery of side
stripper C203 from the TC design. The thermal coupling employed in
the side stripper’s top section is replaced by condenser HX305, as
suggested in Agrawal [13]’s guidelines for the proposed intensification
strategy.
The azeotropic column C302 was also redesigned using the shortcut
distillation tool. The operating pressure was increased from 101.3 kPa
to 340 kPa to increase the temperature of the overhead product, which
in turn is used to transfer heat to the bottom product of C303. This
operating condition was used due to it being the smallest pressure value
that provided the minimum temperature approach of 10 °C required for
I.N. Caxiano, et al.
Fig. 2. Lee and Kim [25]’s thermally coupled process (TC).
heat integration, according to Kemp [28]’s heuristics. Such a heuristic is
considered to avoid large heat transfer areas, which could lead to high
capital costs with the heat exchangers. The obtained tray number and
feed stage were similar to the ones from C102 from the original process
and, similar to the dehydration columns of the same design, the over-
head product of C303 is recycled to the absorption column C301.
The second double-effect process (DE2) is illustrated in Fig. 4. In
this design, the azeotropic column of the TC process is replaced by the
columns C402A and C402B, which operate at 80 kPa and 800 kPa, re-
spectively.
Each column is fed a fraction of the absorber C401’s extract after
cooling in HX401, with 53.5 % and 46.5 % being sent to C402A and
C402B, respectively. Although both are thermally coupled with the side
stripper C403, results from UniSim simulation determined that only
C402B provides material flow to the top of the side stripper. The op-
erating conditions were obtained by initially simulating C402A and
C402B with the shortcut distillation tool and altering their operating
pressures in an iterative process to provide the highest possible tem-
perature difference between C402A’s bottom and C402B’s top, while
still ensuring that both columns separated acetic acid with 100 mol %
purity. Subsequently, UniSim’s Case Studies tool was used to obtain the
split ratio of C401’s extract that provides equal heat duties for C402A’s
reboiler C402B’s condenser, which ensures that the heat integration can
be employed without the addition of hot or cold utilities. The results
from the shortcut distillation tool for tray number, feed stages, and
operating conditions were then used in the rigorous simulation of both
columns. The operating pressure of the side stripper C403 was specified
to the same value of 800 kPa from column C402B, and the same tray
number and feed stages from the TC design were used to achieve the
required product recovery.
2.4. Vapor recompression process (VR)
Although the proposed double-effect distillation alternatives have
the potential to considerably reduce energy consumption in the overall
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Chemical Engineering & Processing: Process Intensification 147 (2020) 107784
process, the pressure increase in the columns C302 and C402B has an
undesired side effect of increasing the heat duties of the reboiler HX303
on the DE1 design and of the reboilers HX403B and HX404 on the DE2
design. In light of this, a third intensification strategy is proposed for
the TC process via vapor recompression, which is illustrated in Fig. 5.
The overhead product of azeotropic column C502 is raised from
110 kPa to 700 kPa in compressor K501 to increase its temperature
from 82.90 °C to 149.40 °C, allowing this stream to be used as heat
supply in reboiler HX503. Its pressure is then decreased back to 110 kPa
in a throttling valve and the stream is further cooled to 40.90 °C in
exchangers HX505 and HX502 before being sent to the decanter.
The azeotropic column C502 and the side stripper C503 are de-
signed with the same tray number, feed stages and operating conditions
from the TC process. The outlet pressure in compressor K501 was de-
termined by simulation due to it being the smallest value that provides
the minimum temperature approach of 10 °C suggested in Kemp [28]’s
heuristics, as previously mentioned for the DE1 design. Since columns
C502 and C503 operate at the same pressure from the TC process, there
is no substantial heat duty increase in reboilers HX503 and HX504. The
major drawback of the vapor recompression technology is the increase
in capital costs due to the compressor [29], which will be considered in
the economic analysis and the eco-efficiency comparison.
It should be noted that process intensification strategies, especially
the ones involving full or partial heat integration and/or vapor re-
compression (such as the techniques studied in this work), can present
particularly complex control philosophies due to the design of extra
equipment sequences and the reduction in the degrees of freedom. This
issue, along with suggested methods for start-up procedures in in-
tensified technologies, has been discussed in previous studies [30,31].
Therefore, in order to understand how the operability of such systems
may vary in relation to the conventional distillation scheme, it is ne-
cessary to first sympathize with the dynamic behavior of the latter,
especially with regard to start-up procedures.
The start-up operation of distillation sequences can be generally
divided into three phases, namely the discontinuous phase, the semi-
I.N. Caxiano, et al.
Fig. 3. Double-effect distillation strategy 1 (DE1).
continuous phase and the continuous phase. During the first one, the
column is pressured up prior to the introduction of the feed, after which
the heating step takes place and total reflux operation is implemented.
In the second stage, highly non-linear disturbances occur as the column
is switched from total reflux to the design withdraw ratio. Finally,
during the third phase, the process reaches the desired steady-state
conditions [32].
Although theoretically similar to conventional sequences, the pre-
start operation of multi-effect distillation systems may require an aux-
iliary heating source (e.g. electric heater, back-up boiler, etc.) [31].
This is due to the fact that, during start-up, the top vapor stream from
one column, which serves as a heating medium to the reboiler of an-
other column, is not available. The same applies to heat pump-assisted
configurations, in which the heating source derives from the com-
pressor discharge line. However, the presence of a compressor renders
the start-up of such distillation schemes more complicated as they are
subject to further controllability pitfalls. After the column is pressurized
and the feed is introduced, the top vapor will fill the compressor suction
line. A purging sequence is initiated prior to loading and pressuring up,
after which the vapor stream is discharged and heats up the reboiler. As
the system experiences severe disturbances during start-up, especially
in the semi-continuous phase, the suction pressure will oscillate and
may potentialize the risk of surging. An anti-surge control structure
must then be installed so as to allow the recirculation of part of the
discharge gas back to the compressor suction by means of a gas recycle
line.
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Chemical Engineering & Processing: Process Intensification 147 (2020) 107784
It is clear that a more detailed discussion regarding the start-up
procedure of each proposed alternative is necessary in order to in-
vestigate the major issues and drawbacks related to their operation.
Several aspects such as column bypass, liquid circulation, plugging
prevention, liquid/condensate drainage, suction throttling and surge
prevention/control, among others, could be meticulously addressed.
Nonetheless, it should also be noted that the processes in this work are
simulated and evaluated in steady-state conditions; therefore, the
controllability of the original and the intensified configurations are
beyond the scope of our study. For the same reason, no indicators re-
garding process operation and control have been considered in the eco-
efficiency assessment.
2.5. Process simulation
Computer simulation of the acetic acid purification processes was
carried out in UniSim Design Suite using the UNIQUAC thermodynamic
model. As previously mentioned, the original process and the modified
design were simulated using flow rates, stream compositions, and op-
erating conditions presented in Lee and Kim [25]’s work. These simu-
lations, with the results as presented in Figs. 1 and 2, were used as the
basis for designing the three intensification alternatives presented in
this work.
The design strategies previously described for the DE1, DE2 and VR
processes were implemented to obtain new results for tray numbers and
feed stages in the distillation columns, as well as energy transfer in heat
I.N. Caxiano, et al. Chemical Engineering & Processing: Process Intensification 147 (2020) 107784

Fig. 4. Double-effect distillation strategy 2 (DE2).

exchangers. The remaining results regarding operating conditions and
stream compositions, as previously presented in Figs. 3,4, and 5, were
obtained by simulation to achieve the desired product recovery (i.e.
flow rates and compositions of the acetic acid and water streams) from
the OP and TC designs.
The distillation columns were simulated using UniSim’s Inside-Out
solving method. Such an algorithm uses equilibrium and enthalpy
models to solve component and heat balances in an inner loop, whereas
an outer loop uses rigorous model calculations to update the thermo-
dynamic models [33]. An error tolerance of 1.10−5 was specified for
equilibrium and heat balances in the columns, and the design variables
specified in each one according to their degrees of freedom are
presented in Table 1. For the OP and TC designs, the variables were
chosen based on stream results provided in Lee and Kim [25]’s work,
whereas the variables for the intensified columns were based on si-
mulation results from their original designs to obtain results as close as
possible to the desired product recovery.
The absorption columns are sufficiently specified by their inlet
streams and operating pressure, requiring no additional design vari-
ables. Similarly, distillation columns from the intensification strategies
not presented in Table 1 were simulated as absorption columns with
manually inserted heat exchangers, as well as boil-up and reflux
streams, therefore not requiring additional design variables.

Fig. 5. Intensified process with vapor recompression (VR).

6
I.N. Caxiano, et al. Chemical Engineering & Processing: Process Intensification 147 (2020) 107784

Table 1 Table 2
Design variables for simulation of the distillation columns. Utility plant volumetric flow rate variables.
Process Column Design variables Value Variable Definition

OP C102 Bottom product rate 3440.00 kg/h Fbb Boiler blowdown

C103 Overhead product rate 2.90 kmol/h Fbfw Boiler feedwater
Reflux rate 64.00 kmol/h Fcl Losses from cooling processes
TC C202 Overhead product rate 337.70 kmol/h Fctb Cooling tower blowdown
Bottom product rate 3440.00 kg/h Fcw Cooling water supply
C203 Bottom product rate 6560.00 kg/h Fcwmu Cooling water system make-up
DE1 C302 Bottom product rate 3440.00 kg/h Fe Evaporation and drift losses
C303 Bottom product rate 529.00 kmol/h Fhl Losses from heating processes
DE2 C402A Bottom acetic acid composition 1.00 (mole fraction) Fmu Total make-up water
C402B Overhead product rate 157.00 kmol/h Fs Steam supply to heating processes
Bottom acetic acid composition 1.00 (mole fraction) Fsgmu Steam generation system make-up
C403 Overhead product rate 32.50 kmol/h Ftl Water treatment losses
VR C502 Side draw rate 9.85 kmol/h
C503 Overhead product rate 27.20 kmol/h
[38]. After supplying heat to process streams, the condensate is sent to
a deaerator to remove gas and is recycled as boiler feedwater. Similar to
2.6. Utility plant the cooling water system, a make-up stream replenishes losses asso-
ciated with the water treatment for removal of solids, blowdown to
The utility plant is a central facility from which ancillary services prevent impurities buildup, and leaks in the heating processes.
(e.g. electricity, heat exchange fluids, process water, and compressed Both systems of the utility plant were also simulated in UniSim
air) are supplied to the main process [34]. The acetic acid purification using the results for energy consumption of the acetic acid purification
process requires steam for heat supply in heaters and reboilers, as well process and the intensification strategies. The water treatment chemi-
as cooling water for heat removal in coolers and condensers. To obtain cals were not simulated due to the software’s limitations regarding
more realistic estimations regarding water and energy consumption, as solids modeling. Cooling water was considered to be supplied at
well as capital costs, a utility plant with cooling water and steam 101.3 kPa and 30 °C, leaving the cooling processes at 45 °C [37]. The
generation systems was designed based on Junqueira et al. [20]’s work following operating conditions were assumed for the steam generation
and Smith [35]’s book. The utility plant flowsheet is illustrated in system: low-pressure steam at 308 kPa and 134.5 °C, medium-pressure
Fig. 6, while the volumetric flow rate variables are defined in Table 2. steam at 1136 kPa and 185.5 °C, and high-pressure steam at 4238 kPa
Cooling water is supplied to the cooling processes via an open re- and 253.8 °C [37]. The heuristics considered in this work for estimating
circulating system, whose main advantage is the greater potential to water losses in the utility plant are presented in Table 3. Like the main
save water compared to once-through and closed-circuit systems [36]. processes, the UNIQUAC model was used in the steady-state simulation
After removing heat from process streams, hot water is treated with of the utility plant.
chemicals to inhibit fouling in heat exchanger surfaces [37] and is sent
to the cooling tower so it can return to its original temperature. Make-
up water is supplied to replenish losses due to evaporation and drift in 3. Eco-efficiency analysis
the induced draft system of the cooling tower, blowdown to prevent the
buildup of non-volatile impurities, and leaks in the cooling processes. The main goal of the intensification strategies proposed for the
In the steam generation system, boiler feedwater is pressurized then acetic acid purification process is to reduce its overall energy con-
sent to the steam boiler for vaporization. Steam is produced in the sumption and, therefore, increase its environmental and economic
highest required pressure for the heating processes, then partially ex- performance.
panded to lower pressures depending on the main process’ demands Regarding the sustainability evaluation of chemical process designs
and technologies, several Life Cycle Assessment (LCA) methodologies

Fig. 6. Utility plant flowsheet.

7
I.N. Caxiano, et al.
Table 3
Heuristics for water loss in the utility plant.
Variable Value Reference
Fbb 2 % of Fbfw [35]
Fcl 1 % of Fcw [38]
Fctb 3 % of Fcw [37]
Fe 1 % of Fcw [35]
Fhl 20 % of Fs [39]
Ftl 1 % of Fsgmu [35]
have been developed, such as CML 2001, IMPACT 2002, and Eco-in-
dicator 99. Such methods are indeed useful for providing insightful data
on numerous environmental impacts categories of industrial processes.
However, these methodologies usually do not take into consideration
economic and social issues, if not integrated with their economic and
social counterparts (namely Life Cycle Costing and Societal Life Cycle
Assessment, respectively). As stated in Mangili et al. [40]’s work, this is
a major drawback of the LCA metrics. In addition, as stated by ecoin-
vent [41], LCA studies can be practically impossible to perform without
having access to a complete and reliable inventory database. The Eco-
efficiency Comparison Index methodology proposed by Pereira et al.
[42], on the other hand, is conveniently useful since it may assess not
only environmental impacts but also other eco-efficiency aspects such
as safety metrics and economic performance. The indicators employed
in the ECI method can also be determined using computer simulation
results without depending on data that may not be readily available,
thus presenting an advantage over LCA metrics.
As previously mentioned, eco-efficiency can be measured using eco-
indicators, which can be used as decision-making tools for designing
new processes or modifying already-existing ones. However, the de-
termination of a single eco-indicator is not enough to assert the po-
tential of improving environmental performance, since there are several
categories of environmental impacts associated with complex industrial
processes [43]. Therefore, in this work, the eco-efficiency of the ori-
ginal processes and the proposed intensification strategies are com-
pared through a set of five environmental indicators, one safety in-
dicator, and four economic metrics. These indicators are jointly
evaluated using the ECI methodology to determine which of the con-
figurations of the acetic acid purification process is the most eco-effi-
cient one.
3.1. Environmental and safety indicators
The following eco-indicators were considered for evaluating the
environmental and safety impacts of the acetic acid purification pro-
cess: carbon dioxide emission (CDE), water consumption (WC), aquatic
toxicity potential (ATP), terrestrial toxicity potential (TTP), acidifica-
tion potential (AP) and human toxicity potential by exposure (HTPE).
The carbon dioxide emission (in tCO2/h) and water consumption (in
m3/h) eco-indicators are defined by Eqs. (1) and (2), respectively,
where the total production rate – which for all processes corresponds to
the purified acetic acid stream - is in t/h. The emissions from fuel were
calculated assuming that the utility plant’s steam boiler consumes
natural gas and operates with 80 % thermal efficiency [44], using the
natural gas’ emission factor of 0.0561 tCO2/GJ [45]. Indirect emissions
from electricity consumption were calculated assuming that pumps and
compressors operate at 75 % efficiency (which is the software’s default
value), using an emission factor of 0.0206 tCO2/GJ [46]. Water con-
sumption was determined by the volumetric flow rate of the utility
plant’s make-up stream, obtained from simulation results.
CDE = Total CO2 emissions Total production rate[tCO2 t] (1)
WC = Total water consumption Total production rate[m3 t] (2)
The HTPE, ATP, TTP and AC eco-indicators were calculated via the
8
Chemical Engineering & Processing: Process Intensification 147 (2020) 107784
Waste Reduction (WAR) Algorithm, using the open-access graphical
user interface provided by the U.S. Environmental Protection Agency.
The algorithm was developed aiming to evaluate the environmental
impacts of chemical processes and the possibility of reducing the gen-
eration of waste materials by design modifications [47], which directly
relates to the main goals of eco-efficiency and process intensification.
Environmental impacts are evaluated for a gate-to-gate analysis -
meaning that they are subject to the same control volume comprised of
the chemical plant - and are estimated by the algorithm after providing
the flow rates and composition of inlet and outlet streams, along with
the total energy consumption of the process. The aforementioned eco-
indicators are evaluated in terms of potential environmental impacts
(PEI) leaving the system per mass of product, therefore being expressed
in units of PEI/t.
It should be noted that two additional environmental indicators,
namely energy consumption and wastewater generation, are defined in
Pereira et al. [42]’s work and would be relevant for assessing eco-effi-
ciency in the acetic acid purification process. However, since there are
no purge streams to account for fugitive emissions and, in most pro-
cesses, the steam boiler is the main energy consumer, the energy con-
sumption and the carbon dioxide emissions indicators would only differ
from each other due to the natural gas to CO2 multiplying factor. Si-
milarly, the wastewater generation comprises all water losses in the
utility plant minus drift and evaporation in the cooling tower, making
the results for this indicator too similar to the ones for the water con-
sumption indicator. Nevertheless, the effects of energy consumption
and wastewater generation in the overall sustainability will be taken
into consideration via the specific energy costs and liquid waste cost
fraction indicators from the economic analysis.
3.2. Economic indicators
The economic performance of each process design was evaluated by
estimating its capital expenditures (CAPEX) and total production costs
(TPC). Fixed capital investments (FCI) were determined based on the
equipment cost equations from Seider et al. [38]’s book, as shown in
Table 4.
Pumps and compressors were assumed to be of centrifugal type.
Absorption columns were assumed to be of rotating-disk contactor type,
whereas it was assumed that sieve trays were used in the distillation
columns, with horizontal pressure vessels being considered for their
reflux drums [38]. Reboilers were assumed as kettle-type vaporizers,
while the absorption columns’ overhead stream coolers were inter-
preted as double-pipe exchangers, due to their small heat transfer area
Table 4
Equipment cost basis equationsa.
Equipment Cost equation
Pumps exp {12.1656 − 1.1448 ln [F (HP )0.5] + 0.0862 ln [F (HP )0.5]2 }
Compressors exp [9.1553 + 0.63 ln (PC )]
Heat exchangers Floating head: exp [12.0310 − 0.8709 ln (A) + 0.09005 ln (A)2]
Kettle: exp [12.3310 − 0.8709 ln (A) + 0.09005 ln (A)2]
Double-pipe: exp [7.2718 + 0.16 ln (A)]
Absorption 363[H (D)1.5]0.84
columns
Distillation exp [10.5449 − 0.4672 ln (W ) + 0.05482 ln (W )2]
columns
Vessels exp [5.6336 − 0.4599 ln (W ) + 0.00582 ln (W )2]
Cooling tower 164000(2.0)b (F 1000)0.65
Steam boiler 0.416Q 0.77
Wastewater 48760F 0.64
treatment
a
F: volumetric flow rate in (gal/min). HP: pump head (ft). PC: compressor power
(hp). A: Heat transfer area (ft2). H: column height (ft). D: internal diameter (ft).
W: shell weight (lb). Q: energy requirement (BTU/h).
b
Temperature difference factor for a temperature drop of 15 °C.
I.N. Caxiano, et al. Chemical Engineering & Processing: Process Intensification 147 (2020) 107784

Table 5
General site expenses.
Category Parameter Value Reference

Inside Battery Limits (ISBL) Process equipment costs and bulk items (piping, instruments etc.) 30 % of FCI [50]
Outside Battery Limits (OSBL) Warehouse, lighting, waste handling etc. 40 % of ISBL [34]
Other Land development costs 1 % of FCI [51]
Site development Roads, buildings, ditches etc. 5 % of FCI [51]
Miscellaneous Agent fees, import duties etc. 5 % of FCI [51]
Design and engineering Administration, inspection etc. 7 % of FCI [50]
General Contingency 7 % of FCI [50]
Working capital 5 % of FCI [34]

Table 6
General production expenses [35,37].
Category Parameter Value
Fixed costs (FC) Maintenance 5 % of
Overheads 5 % of
Insurance, license fees and royalties 2 % of
Variable costs Personal protective equipment, 1 % of
(VC) cleaning materials, charts and
accessories etc.
Other Sales and marketing 2 % of FC + VC
Human resources, accounting, finance 35 % of labor
etc.
[38]. All other heat exchangers were interpreted to be of floating head
type. Wastewater treatment in the utility plant was assumed to be of the
secondary type, which comprises screening for removal of large solids,
sedimentation, and biological degradation in recirculating activated
sludge [38]. Stainless steel was adopted as construction material, due to
the presence of water and acetic acid in most process streams. Equip-
ment costs estimated by the equations from Seider et al. [38]’s book for
a Chemical Engineering Plant Cost Index (CEPCI) of 567 were adjusted
for 2018’s average CEPCI value of 603.1 [48]. Other site expenses
considered for estimating capital expenditures are disclosed in
Table 5.Production expenses were estimated assuming prices of 18.72
$/GJ for electricity, 0.0157 $/m3 for water and 0.043 $/m3 for was-
tewater treatment [37], while natural gas was considered to be priced
at 2.99 $/GJ [49]. Raw material costs were not included in the pro-
duction expenses since all process designs correspond to separation
technologies that have the same feedstock flow rates. We assumed that
all process plants operate for 8,000 h per year, and labor costs were
estimated assuming 3 shifts and 5 operators per shift, with annual
salaries of $ 50,000 each [37]. Additional heuristics considered for
general production expenses are presented in Table 6.
Three economic indicators originally presented by Ruiz-Mercado
et al. [52] were considered for the eco-efficiency analysis, namely
specific energy cost (SEC), specific water cost (SWC) and liquid waste
cost fraction (LWCF). Their expressions are given in Eqs. (3),(4) and (5),
respectively. Additionally, the CAPEX of each process design was used
as an indicator itself, for a total of four economic indicators.
SEC = Total annual energy cost TPC[$ $]
SWC = Total annual water cost TPC[$ $]
LWCF = Annual wastewater treatment cost TPC[$ $]
3.3. Eco-efficiency Comparison Index
The ECI methodology was originally proposed by Pereira et al. [42]
as a tool for eco-efficiency analysis and monitoring of industrial pro-
cesses. As previously mentioned, there are several environmental im-
pacts associated with industrial activities; additionally, when com-
paring different technologies or intensification alternatives, several
metrics must be considered to correctly assess the effects on economic
viability and attractiveness. In light of this, the ECI methodology was
developed to quantitatively compare the eco-efficiency of industrial
processes by a joint evaluation of a series of eco-indicators into a single
index, thus taking into account the different impacts of each alternative
CAPEX on the economic and environmental performance.
labor
The said methodology is based on the normalized values of each
CAPEX
maintenance
eco-indicator, which are calculated by dividing them by the highest
value of their respective categories. These normalized values are then
plotted on a radar chat that allows a visual representation of which
processes have the best and worst relative performance on each cate-
gory. It is worth noting that, since all the aforementioned eco-indicators
use an economic variable in their denominators, the normalized results
comprise a “the lower – the better” ranking. The area S of each process’
radar chat is then calculated using the Law of Sines as shown in Eq. (6),
where EI is the normalized value of each eco-indicator and n is the total
number of indicators used in the eco-efficiency analysis.
n−1
(
S = 0.5⋅sin (2π n)⋅ EI1⋅EIn + ∑i =1 )
EIi⋅EIi + 1
(6)
Finally, the ECI for each process is calculated as shown in Eq. (7),
where SMAX refers to the area of the largest radar chart. Since a lower
area corresponds to better overall performance, the ECI value re-
presents the increase in eco-efficiency relative to the process with the
worst economic and environmental performance.
ECI = (1 − S SMAX )⋅100% (7)
As previously mentioned, several works have demonstrated the ef-
fectiveness of the ECI method for comparing different technologies and
intensification strategies in the chemical industry, such as, for instance,
cumene production [20], distillation technologies for acetone-methanol
separation [53], heat integration alternatives for the butyl acetate
production processes [21] and design of two different technological
routes for the production of maleic anhydride [43].
4. Results
In this section, we present the results related to the environmental
and economic analysis of the acetic acid purification process, which
were obtained from information provided by simulated data (i.e. mass
and energy streams). Results for stream temperatures and heat transfer
(3) in heat exchangers were used in the simulation of the utility plant il-
lustrated in Fig. 6 for a more accurate estimation of water and energy
(4) consumption. Additionally, the simulation results were used in the
WAR algorithm to assess each process’ potential environmental impacts
(5)
and in the equipment cost equations presented in Table 4 to estimate
capital and operational expenditures.
4.1. Environmental and safety indicators
The CDE and WC indicators were calculated based on simulation
results for the mass flow rate of process streams and energy consump-
tion of heat exchangers, pumps, compressors and fans of the main
processes and their respective utility plants. Results for energy con-
sumption and water losses for each process are presented in Table 7,

9
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Table 7 extract streams from the absorbers are cooled before azeotropic dis-
Energy and water consumption results. tillation. Their similar results for circulating water demand are ex-
Process OP TC DE1 DE2 VR pected since the intensification strategies do not involve the extract
stream; therefore, these heat exchangers present similar heat duties
Heat exchangers (GJ/h) 27.34 18.61 16.90 11.92 2.89 between each process alternative.
Sensible heat (GJ/h) 2.70 1.84 3.72 4.41 0.29
The use of steam in heaters and reboilers comprises less than 4 % of
Electricity (GJ/h) 0.26 0.18 0.17 0.16 2.48
Energy consumption (GJ/h) 30.30 20.63 20.79 16.49 5.65
circulating water demands in every configuration, which demonstrates
Cooling water losses (m3/h) 3.706 2.575 2.336 1.413 0.983 that the reduced energy consumption from the intensification strate-
Condensate losses (m3/h) 2.030 1.382 1.358 1.062 0.214 gies, as presented in Table 7 and Fig. 7, does not directly translate to
Cooling tower blowdown (m3/h) 11.117 7.725 7.008 4.240 2.948 considerable reductions in water demand. Nonetheless, since these
Boiler blowdown (m3/h) 0.207 0.141 0.139 0.108 0.022
techniques are implemented through heat integration with condenser
Evaporation and drift losses (m3/h) 3.706 2.575 2.336 1.413 0.983
Treatment losses (m3/h) 0.023 0.015 0.015 0.012 0.002 streams, which are the highest consumers of cold utilities, the overall
Water consumption (m3/h) 20.789 14.414 13.192 8.249 5.152 circulating water demands are reduced in the less energy-intensive
process configurations.
The results for the CDE and WC indicators are presented in Table 8
where the sensible heat refers to the necessary energy for heating boiler along with the values for the HTPE, TTP, ATP and AP indicators ob-
feedwater to its saturation temperature before generating steam. A tained from the WAR algorithm. Carbon dioxide emissions and water
breakdown of energy consumption on each process by equipment type consumption showed similar trends in variation between each process
is shown in Fig. 7. since they are directly related to overall energy consumption and heat
In particular, it should be noted that, while the DE1 design is able to demands via cooling water and steam from the utility plant. The other
remove energy consumption from the side stripper and the recycle four indicators, however, did not provide a similar pattern. In fact, al-
heater HX205, its overall consumption is slightly higher than the TC though the VR alternative shows better performance in terms of the
design from which it is based on. This can be explained by the necessary CDE, WC and AP metrics, its results regarding toxicity-related burdens
pressure increase in the azeotropic column for implementing the are not the best ones among all configurations. Since all processes have
double-effect distillation technology, which has the undesired effect of the same feedstock flow rates and the WAR algorithm is based on data
increasing heat demand in the reboiler. Additionally, due to the higher from inlet and outlet streams, this shows that even slight variations in
temperature in the column’s bottom stream, medium-pressure steam the composition of the outlet streams have considerable effects in po-
must be used instead of low-pressure steam, thus increasing the energy tential environmental impacts. These results also demonstrate the im-
use in the utility plant’s boiler. portance of using several indicators for a thorough eco-efficiency as-
On the other hand, the DE2 design presented lower energy con- sessment, since a process design will not always provide the best or
sumption than both its based-on TC configuration and the DE1 design, worst scenario when different categories of environmental impacts are
which employs the same kind of process intensification strategy. taken into consideration.
Although the pressure increase in column C402B to 800 kPa is higher
than the increase in column C302 to 340 kPa on the DE1 design, the 4.2. Economic indicators
energy consumption in the azeotropic column’s reboiler is considerably
reduced due to the lower molar flows involved. This demonstrates that, The capital expenditures for all process designs were calculated
for reducing energy consumption on the acetic acid purification pro- based on the equipment cost equations disclosed in Table 4. The fixed
cess, the double-effect distillation strategy in which the azeotropic capital expenditures by equipment type are presented in Fig. 9. Al-
column is divided for self-heating integration is more efficient than the though heat transfer and component separation equipment comprise
heat integration with its side stripper. the majority of the total costs for all processes, equipment costs origi-
Lastly, results showed that the VR process has the overall lowest nated from the utility plant (i.e. cooling towers, steam boilers, and
energy and water consumption, despite its higher electricity demand wastewater treatment) are also considerably influent on capital ex-
due to the implementation of the compressor K501. Since the azeo- penditures. This corroborates our decision in this work of designing and
tropic columns provide the biggest share of energy consumption in all simulating the utility plant, not only to correctly assess water and en-
other process designs, the heat integration between the bottom and ergy consumption but also to take into consideration its effects on the
overhead streams of column C502 reduces the energy consumption in process’ economic performance.
this configuration to 19.5 % of the original process’ demands. The results presented in Fig. 9 also showcase an additional benefit of
The circulating water demands due to the use of cooling water and reducing water consumption beyond increasing environmental perfor-
steam are detailed in Fig. 8. Cooler demands are related to heat ex- mance: since cooling tower and wastewater treatment costs are directly
changers HX101, HX201, HX301, HX401, and HX501, in which the related to volumetric flow rate, intensification techniques that reduce

Fig. 7. Energy consumption sources of each process.

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I.N. Caxiano, et al. Chemical Engineering & Processing: Process Intensification 147 (2020) 107784

Fig. 8. Circulating water demand on each process.

Table 8 performance and capital expenditures.

Environmental indicator results. Furthermore, although the VR process has the lowest overall energy
Indicator OP TC DE1 DE2 VR
consumption, this design has the second highest TPC due to the savings
in natural gas being compensated by the compressor’s consumption of
CDE (tCO2/t) 0.492 0.335 0.337 0.279 0.070 electricity, which has a cost per gigajoule approximately 6.25 times
WC (m3/t) 6.043 4.190 3.835 2.505 1.571 higher than the former energy source. Nevertheless, the VR design
HTPE (PEI/t) 0.262 0.167 0.179 0.600 0.471
provided the best results for the SEC, LWC and LWCF indicators,
TTP (PEI/t) 2.920 1.860 2.000 6.710 5.270
ATP (PEI/t) 0.273 0.180 0.187 0.379 0.250 whereas the DE2 design comprised the best scenario regarding capital
AP (PEI/t) 8.660 5.900 5.950 4.920 0.959 expenditures.

4.3. Eco-efficiency Comparison Index

consumption of hot and cold utilities also have the potential of greatly
reducing equipment costs originated from the utility plant. This is
Per the ECI methodology proposed by Pereira et al. [42], the en-
particularly beneficial to the VR design, since this effect compensates
vironmental and economic indicators were divided by the highest va-
for most of the additional costs from the compressor, making it only the
lues in their respective categories. These normalized results are dis-
second most expensive technology after the OP design, which has the
closed in Table 11.
highest capital expenditures from utility plant equipment.
As previously mentioned, the normalized eco-indicators comprise a
The following CAPEX were obtained when adding the heuristics for
“the lower – the better” ranking, in which values closer to 0 provide
general production expenses listed in Table 5: $ 6,673,884 for the OP
better scenarios and values closer to 1 provide worse scenarios re-
design, $ 5,190,494 for the TC design, $ 4,997,223 for the DE1 design,
garding sustainability and eco-efficiency. Therefore, the results pre-
$ 4,845,988 for the DE2 design and $ 5,854,223 for the VR design. The
sented in Table 11 indicate that the original process (OP) had the worst
TPC of each process, in turn, were obtained using the heuristics from
performance for all eco-indicators except for ATP, TTP and HTPE, in
Table 6 and the considerations disclosed in Section 3.2, and are pre-
which the DE2 design comprised the worst scenario. This is more
sented in Table 9, whereas the results for the economic indicators are
clearly visualized in the radar charts plotted with the normalized in-
given in Table 10.
dicators, as illustrated in Fig. 10.
Except for general expenses, natural gas comprises the highest
As required by the ECI method, the area of the radar charts must be
production cost for most process designs; therefore, the reduced energy
calculated through Eq. (6) to determine the most eco-efficient process
consumption provided by the intensified technologies not only lessens
design. However, as demonstrated in Mangili et al. [40]’s work, these
the amount of total carbon dioxide emissions but also increases eco-
areas are dependent on the order in which the indicators are arranged
nomic performance due to the reduced operational expenditures.
in the radar plot, which also makes the final ECI results subject to the
Although process water and wastewater treatment do not have con-
order of eco-indicators. Nevertheless, the authors carried out an eva-
siderable effects on production costs, as previously discussed, reducing
luation considering from 3 to 10 indicators of a case study and per-
water consumption provides better results for environmental
formed all possible permutations. Their results showed that, despite

Fig. 9. Equipment costs of each process.

11
I.N. Caxiano, et al. Chemical Engineering & Processing: Process Intensification 147 (2020) 107784

Table 9
Total production costs.
Expenses OP TC DE1 DE2 VR

Electricity $ 38,454 $ 26,678 $ 25,754 $ 24,187 $ 371,094

Water $ 2611 $ 1810 $ 1657 $ 1036 $ 647
Natural gas $ 718,698 $ 489,227 $ 493,249 $ 390,597 $ 75,834
Wastewater treatment $ 5920 $ 4102 $ 3781 $ 2411 $ 1,436
General $ 551,831 $ 495,881 $ 488,826 $ 486,422 $ 578,928
TPC $ 1,317,514 $ 1,017,698 $ 1,013,266 $ 904,653 $ 1,027,940

Table 10 Table 12
Economic indicator results. ECI results.
Indicator OP TC DE1 DE2 VR Process OP TC DE1 DE2 VR

CAPEX (M$) 6.674 5.190 4.997 4.846 5.851 Mean chart area 2.153 1.241 1.189 1.531 0.710
SEC ($/$) 0.575 0.507 0.512 0.459 0.435 Upper ECI – 46.2 % 47.8 % 31.9 % 76.0 %
SWC ($/$) 1.98.10−3 1.78.10−3 1.64.10−3 1.15.10−3 6.29.10−4 Mean ECI – 42.3 % 44.8 % 28.9 % 67.0 %
LWCF ($/$) 4.49.10−3 4.03.10−3 3.73.10−3 2.67.10−3 1.40.10−3 Lower ECI – 39.5 % 42.8 % 27.4 % 59.5 %

Table 11 are presented in Table 12, along with the lower and upper limits of the
Normalized eco-indicators. ECI values considering the maximum and minimum chart areas, re-
Indicator OP TC DE1 DE2 VR
spectively.
As expected, the original acetic acid purification process is the least
AP 1.000 0.681 0.687 0.568 0.111 eco-efficient alternative, since it employs no intensification strategies.
CDE 1.000 0.681 0.686 0.568 0.142 The DE2 process provided better results than the TC and the DE1 de-
WC 1.000 0.693 0.635 0.414 0.260
ATP 0.720 0.475 0.493 1.000 0.660
signs for economic performance and overall water and energy con-
TTP 0.435 0.277 0.298 1.000 0.785 sumption. However, due to worse results for the ATP, TTP and HTPE
HTPE 0.437 0.278 0.298 1.000 0.785 indicators, its final ECI value of 28.9 % is lower than the values of 42.3
LWCF 1.000 0.897 0.830 0.593 0.311 % and 44.8 % for the TC and DE1 processes, respectively, making it the
SWC 1.000 0.898 0.825 0.578 0.318
least efficient alternative among the intensified strategies. This further
SEC 1.000 0.882 0.891 0.798 0.757
CAPEX 1.000 0.778 0.749 0.726 0.877 corroborates the importance of using multiple indicators in eco-effi-
ciency assessment.
The TC and DE1 designs provided similar improvements in eco-ef-
ficiency compared to the original process. Since the final ECI results
presented in Table 12 were obtained from the mean chart areas, it
would be reasonable to assume that there might be eco-indicator ar-
rangements for the radar plot in which the TC alternative has greater
eco-efficiency than the DE1 design. However, we calculated the dif-
ference between the chart areas of both technologies for every eco-in-
dicator permutation and, as demonstrated in Fig. 11, the TC design
provided higher areas than the DE1 alternative in all arrangements,
thus making the former a less efficient technology over the latter in
every scenario.
The VR design has a final ECI value of 67 %, therefore being the
most eco-efficient alternative. Although its results for CAPEX and ATP,
TTP and HTPE indicators were worse than almost all other designs, the
heat integration established in the azeotropic column was able to
considerably reduce energy and water consumption and increase its
overall economic performance, making this technology the best sce-
nario for 6 of the 10 eco-indicators, namely AP, CDE, WC, LCWF, SWC
and SEC.
Applying the ECI method considering only Lee and Kim [25]’s TC
process and the proposed VR design, the latter provides a 43 % increase
in eco-efficiency compared to the authors’ improvement over the ori-
Fig. 10. ECI radar chart for all processes.
ginal process. In a similar way, applying the ECI method only to the
DE1 and VR designs, the latter results in a 43.9 % increase in eco-ef-
variations in the ECI values, permuting the indicators around the radar ficiency over the second-best alternative presented in this work. These
plot did not change the final decision, and the standard deviation of the results demonstrate the potential of the vapor recompression tech-
ECI result tends to decrease the more indicators are used in the eco- nology for improving the sustainability of chemical processes. The
efficiency analysis. radar charts for the two aforementioned ECI scenarios are illustrated in
In light of these observations, we performed all circular permuta- Fig. 12.
tions of the normalized eco-indicators from Table 11 in order to obtain
the mean areas of the radar charts and, consequently, the mean value of 5. Conclusions
the ECI for each process. The circular permutations comprised a total of
362,880 scenarios per process, and the final results for the ECI method This study proposed three intensification strategies for an acetic

12
I.N. Caxiano, et al.
Fig. 11. Chart area difference between TC and DE1 in all permutations.
acid purification process to increase sustainability performance com-
pared to the original process and the thermally coupled alternative
presented in Lee and Kim [25]’s work. The intensification strategies
employing double-effect distillation and vapor recompression were
designed via computer simulation based on process data provided in the
reference work, along with the simulation of a utility plant for more
accurate estimations of water and energy consumption.
An eco-efficiency analysis of the two reference processes and the
intensification strategies was performed using the Eco-efficiency
Comparison Index method based on five environmental indicators, one
safety indicator, and four economic metrics. Results showed that all
intensified designs provided from 30 to 80 % lower water and energy
consumption compared to the original process. However, the double-
effect distillation technique employed between the azeotropic column
and the side stripper on the DE1 design did not decrease overall energy
use of the thermally coupled technology, mainly due to the higher
pressure in the azeotropic column, which increased the energy con-
sumption on its reboiler while also requiring medium-pressure steam
instead of low-pressure steam. This change in the hot utility class cor-
relates to higher energy consumption in the steam boiler and validates
the consideration of the utility plant for the eco-efficiency analysis since
such effect would not be observed via direct comparison of energy
demands.
The double-effect distillation on the two azeotropic columns of the
DE2 design, on the other hand, was able to considerably reduce energy
consumption compared to the TC process. However, due to its worse
results for the ATP, TTP and HTPE indicators from the Waste Reduction
algorithm, this design is only 28.9 % more efficient than the original
process, whereas the TC and DE1 configurations were respectively 42.3
% and 44.8 % more eco-efficient when all indicators were jointly
evaluated. Considering that the evaluation of process intensification
strategies in techno-scientific literature is usually limited to metrics
such as energy savings, utility consumption and total annual costs, the
Fig. 12. Additional ECI scenarios: (a) TC and VR designs; (b) DE1 and VR designs.
13
Chemical Engineering & Processing: Process Intensification 147 (2020) 107784
results for the DE2 design demonstrate the importance of considering
multiple categories of potential environmental impacts for a more
thorough eco-efficiency assessment.
The vapor recompression design provided the best overall results,
being 67 % more sustainable than the original process. This demon-
strates that, although the vapor recompression technology has a major
drawback in its increased capital costs, the heat integration that it
provides between process streams of distillation columns is able to
considerably reduce overall energy consumption, whereas this same
effect in double-effect distillation designs is accompanied by increased
energy use in other heat exchange equipment.
We believe that the results obtained in this work demonstrate the
potential of process intensification strategies in reducing environmental
impacts and improving economic performance. Moreover, the metho-
dology used for the eco-efficiency assessment is described in detail and
requires data that can be conveniently obtained based on computer
simulation runs, enabling its use for evaluating other chemical pro-
cesses and modifications.
It should be reminded that the dynamics and control of the acetic
acid purification strategies were not discussed in detail since the si-
mulations and the eco-efficiency assessment were carried under steady-
state conditions. Therefore, further studies could focus on developing a
systematic start-up and/or shutdown procedure and identifying the
main issues related to the controllability and operability of the in-
tensified strategies. Future works should also consider multi-objective
optimization studies to further increase the eco-efficiency performance.
Declaration of Competing Interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influ-
ence the work reported in this paper.
I.N. Caxiano, et al.
CRediT authorship contribution statement
Igor Nardi Caxiano: Conceptualization, Methodology, Software,
Resources, Writing - original draft. Pedro Gabriel Junqueira: Formal
analysis, Investigation, Resources. Patrick Vaz Mangili: Software,
Validation, Resources. Diego Martinez Prata: Writing - review &
editing, Supervision, Project administration.
Acknowledgements
This study was financed in part by the Coordenação de
Aperfeiçoamento de Pessoal de Nível Superior - Brasil (CAPES) -
Finance Code 001.
The authors would like to thank Honeywell for providing the
UniSim Design Suite simulation software used in this work.
References
[1] C. Chilev, F.D. Lamari, M. Dicko, E. Simeonov, Investigation of acetic acid dehy-
dration by various methods, Journal of Chemical Technology and Metallurgy 51-1
(2016) 73–84.
[2] Creedence Research, Global Acetic Acid Market Is Projected To Reach USD 14, 782
Million By 2022, (2016) Available at: < https://www.credenceresearch.com/
press/global-acetic-acid-market > . Accessed 31 August 2019.
[3] T. Sasaki, M. Fujimoto, T. Miyanari, H. Nishino, Process for purifying acetic acid, US
n. 5662780A, 2 September (1997).
[4] P. Pal, J. Nayak, Acetic acid production and purification: critical review towards
process intensification, Sep. Purif. Rev. 46 (2017) 44–61.
[5] G.R. Harvianto, K.J. Kang, M. Lee, Process design and optimization of an acetic acid
recovery system in terephthalic acid production via hybrid extraction-distillation
using a novel mixed solvent, Ind. Eng. Chem. Res. 56 (2017) 2168–2176.
[6] S. Kürüm, Z. Fonyo, Ö.M. Kut, Design strategy for acetic acid recovery, Chem. Eng.
Commun. 136-1 (1995) 161–176.
[7] L. Pu, Y. Sun, Z. Zhang, Hydrogen bonding in the side-on rings of the hydrates with
one acetic acid molecule, J. Mol. Liq. 154 (2010) 124–130.
[8] H. Demiral, M.E. Yildirim, Recovery of acetic acid from waste streams by extractive
distillation, Water Sci. Technol. 47-10 (2003) 183–188.
[9] De Dietrich Process Systems, Recovery of Acetic Acid by Means of liquid-liquid
Extraction, Available at: < https://www.dedietrich.com/en/recovery-acetic-acid-
means-liquid-liquid-extraction > . Accessed 31 August 2019 (2019).
[10] B. Linnhoff, H. Dunford, R. Smith, Heat integration of distillation columns into
overall processes, Chem. Eng. Sci. 38-8 (1983) 1175–1188.
[11] B. Kiran, A.K. Jana, Introducing vapor recompression mechanism in heat-integrated
distillation column: impact on internal energy driven intermediate and bottom re-
boiler, AIChE J. 65-1 (2015) 118–131.
[12] A.I. Stankiewicz, J.A. Moulijn, Process intensification: transforming chemical en-
gineering, Chem. Eng. Prog. 96-1 (2000) 22–33.
[13] R. Agrawal, Multieffect distillation for thermally coupled configurations, AIChE J.
46-11 (2000) 2211–2224.
[14] A.K. Jana, A. Mane, Heat pump assisted reactive distillation: wide boiling mixture,
AIChE J. 57-11 (2011) 3233–3237.
[15] H. Li, H. Cong, X. Li, X. Li, X. Gao, Systematic design of the integrating heat pump
into heat integrated distillation column for recovering energy, Appl. Therm. Eng.
105 (2016) 93–104.
[16] H. Cong, J.P. Murphy, X. Li, H. Li, X. Gao, Feasibility evaluation of a novel middle
vapor recompression distillation column, Industrial & Chemical Engineering
Research 57-18 (2018) 6317–6329.
[17] X. Gao, F. Wang, H. Li, X. Li, Heat-integrated reactive distillation process for TAME
synthesis, Sep. Purif. Technol. 132 (2014) 468–478.
[18] V. Feyzi, M. Beheshti, Exergy analysis and optimization of reactive distillation
column in acetic acid production process, Chem. Eng. Process. Process. Intensif. 120
(2017) 161–172.
[19] UNCTAD – United Nations Conference on Trade and Development, A Manual for
Preparers and Users of Eco-efficiency Indicators, United Nations, 2004 Available
at: < https://unctad.org/en/Docs/iteipc20037_en.pdf > . Accessed 2 September
2019.
[20] P.G. Junqueira, P.V. Mangili, R.O. Santos, L.S. Santos, D.M. Prata, Economic and
environmental analysis of the cumene production process using computational si-
mulation, Chem. Eng. Process. Process. Intensif. 130 (2018) 309–325.
[21] P.V. Mangili, D.M. Prata, Improvement of the butyl acetate process through heat
integration: a sustainability-based assessment, Chem. Eng. Process. Process.
Intensif. 135 (2019) 93–107.
[22] F. Galli, D. Previtali, S. Casagrande, C. Pirola, F. Manenti, D.C. Boffito, Simulation
of the water-acetic acid separation via distillation using different entrainers: an
economic comparison, Chem. Eng. Trans. 57 (2017) 1159–1164.
[23] B. Saha, S.P. Chopade, S.M. Mahajani, Recovery of dilute acetic acid through es-
terification in a reactive distillation column, Catal. Today 60 (2000) 147–157.
[24] K.-L. Li, I.-L. Chien, C.-L. Chen, Design and optimization of acetic acid dehydration
processes, Proceedings of International Conference on Advanced Control of
Industrial Processes (ADCONIP 2014), 1126-131, Hiroshima, Japan, 2014 May
14
Chemical Engineering & Processing: Process Intensification 147 (2020) 107784
28-30.
[25] E.J. Lee, Y.H. Kim, Energy saving in acetic acid process using an azeotropic dis-
tillation column with a side stripper, Chem. Eng. Commun. 205-10 (2018)
1311–1322.
[26] L. Nasri, Z. Bensetiti, S. Bensaad, Correlation of the solubility of some organic
aromatic pollutants in supercritical carbon dioxide based on the UNIQUAC equa-
tion, Energy Procedia 18 (2012) 1261–1270.
[27] Ç. Demirel, S. Çehreli, Phase equilibrium of (water+formic or acetic acid+ethyl
heptanoate) ternary liquid systems at different temperatures, Fluid Phase Equilib.
356 (2013) 71–77.
[28] I.C. Kemp, Pinch Analysis and Process Integration: A User Guide on Process
Integration for the Efficient Use of Energy, second ed., Elsevier, Oxford, UK, 2007.
[29] A.A. Kiss, Z. Olujic, A review on process intensification in internally heat-integrated
distillation columns, Chem. Eng. Process. Process. Intensif. 86 (2014) 125–144.
[30] S.S. Jogwar, P. Daoutidis, Dynamics and control of vapor recompression distillation,
J. Process Control 19 (2009) 1737–1750.
[31] X. Li, C. Cui, H. Li, X. Gao, Process synthesis and simulation-based optimization of
ethylbenzene/styrene separation using double-effect heat integration and self-heat
recuperation technology: a techno-economic analysis, Sep. Purif. Technol. 228
(2019) 115760.
[32] M.R. Eden, A. Koggersbøl, L. Hallager, S.B. Jørgensen, Dynamics and control during
startup of heat integrated distillation column, Comput. Chem. Eng. 24 (2-7) (2000)
1091–1097.
[33] Honeywell, UniSim Design Operations Guide, Honeywell, Canada, 2010.
[34] G. Towler, R. Sinnott, Chemical Engineering Design: Principles, Practice and
Economics of Plant and Process Design, second ed., Elsevier, Oxford, UK, 2013.
[35] R. Smith, Chemical Process Design and Integration, second ed., John Wiley & Sons,
Inc., Chichester, UK, 2016.
[36] M. Seneviratne, A Practical Approach to Water Conservation for Commercial and
Industrial Facilities, first ed., Elsevier, Oxford, UK, 2007.
[37] R. Turton, J.A. Shaeiwitz, D. Bhattacharyya, W.B. Whiting, Analysis, Synthesis, and
Design of Chemical Processes, fifth ed., Prentice Hall, Upper Saddle River, 2018.
[38] W.D. Seider, D.R. Lewin, J.D. Seader, S. Widagdo, R. Gani, K.M. Ng, Product and
Process Design Principles: Synthesis, Analysis and Evaluation, fourth ed., John
Wiley & Sons, Inc., New York, 2016.
[39] B. Boyd, Guidelines for Estimating Unmetered Industrial Water Use. U.S.
Department of Energy, (2011) Available at: < https://www.energy.gov/sites/prod/
files/2013/10/f3/est_unmetered_industrial_wtr.pdf > . Accessed 2 September
2019.
[40] P.V. Mangili, L.S. Santos, D.M. Prata, A systematic methodology for comparing the
sustainability of process systems based on weighted performance indicators,
Comput. Chem. Eng. 30 (2019) 106558.
[41] ecoinvent, Why Do I Need the Ecoinvent Database When Doing a Life Cycle
Assessment? ecoinvent, Switzerland, 2019 Available at: < https://www.ecoinvent.
org/support/faqs/first-time-users/why-do-i-need-the-ecoinvent-database-when-
doing-a-life-cycle-assessment.html > . Accessed 25 November 2019.
[42] C.P. Pereira, D.M. Prata, L.S. Santos, L.P.C. Monteiro, Development of eco-efficiency
comparison index through eco-indicators for industrial applications, Braz. J. Chem.
Eng. 35-1 (2018) 63–84.
[43] P.V. Mangili, P.G. Junqueira, L.S. Santos, D.M. Prata, Eco-efficiency and techno-
economic analysis for maleic anhydride manufacturing processes, Clean
Technologies and Environmental Policy, v. 21 (2019) 1073–1090.
[44] U.S. Department of Energy, Furnaces and Boilers, (2019) Available at: < https://
www.energy.gov/energysaver/home-heating-systems/furnaces-and-boilers > .
Accessed 25 September 2019.
[45] IPCC – Intergovernmental Panel on Climate Change, IPCC Guidelines for National
Greenhouse Inventories, first ed., IGES, Hayama, 2006 2006. Available at: <
https://www.ipcc-nggip.iges.or.jp/public/2006gl/index.html > . Accessed 25
September 2019.
[46] MCTIC – Ministério da Ciência, Tecnologia, Inovações e Comunicações, Fator médio
– Inventários corporativos, 2019 Available at: < https://www.mctic.gov.br/mctic/
opencms/ciencia/SEPED/clima/textogeral/emissao_corporativos.html > .
Accessed 25 September 2019.
[47] EPA – United States Environmental Protection Agency, Waste Reduction Algorithm:
Chemical Process Simulation for Waste Reduction, (2019) Available at: < https://
www.epa.gov/chemical-research/waste-reduction-algorithm-chemical-process-
simulation-waste-reduction > . Accessed 25 September 2019.
[48] S. Jenkins, Chemical Engineering Plant Cost Index, (2019) annual value. Chemical
Engineering, 2019. Available at: < https://www.chemengonline.com/2019-cepci-
updates-january-prelim-and-december-2018-final/ > . Accessed 25 September
2019.
[49] EIA – U.S. Energy Information Administration, Henry Hub Natural Gas Spot Price,
(2019) Available at: < https://www.eia.gov/dnav/ng/hist/rngwhhdA.htm > .
Accessed 25 September 2019.
[50] M.S. Peters, K.D. Timmerhaus, R.E. West, Plant Design and Economics for Chemical
Engineers, fifth ed., The McGraw-Hill Companies, Inc, New York, 2003.
[51] R.K. Sinnott, Chemical Engineering Design, fourth ed., Butterworth-Heinemann,
Oxford, UK, 2005.
[52] G.J. Ruiz-Mercado, M.A. Gonzalez, R.L. Smith, Sustainability indicators for che-
mical processes: III. Biodiesel case study, Ind. Eng. Chem. Res. 52 (2013)
6747–6760.
[53] P.V. Mangili, Y.P.D.M. Souza, D.Q.F. de Menezes, L.S. Santos, D.M. Prata, Eco-ef-
ficiency evaluation of acetone-methanol separation processes using computational
simulation, Chem. Eng. Process. Process. Intensif. 123 (2018) 100–110.