Chemical Engineering & Processing: Process Intensification 135 (2019) 93–107

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Chemical Engineering & Processing: Process Intensification

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

Improvement of the butyl acetate process through heat integration: A T

sustainability-based assessment
⁎
Patrick V. Mangili , Diego M. Prata
Department of Chemical and Petroleum Engineering, Universidade Federal Fluminense, 24210-240, Niterói, RJ, Brazil

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

Keywords: The heat integration of a conventional and a reactive distillation technologies for butyl acetate production is
Butyl acetate studied in this work. Different configurations were evaluated and compared to the original designs in terms of
Eco-efficiency their sustainable performances. The comparison was carried out through the Eco-efficiency Comparison Index
Heat integration method by determining six ecological indicators (raw materials consumption, fuel consumption, energy con-
Process simulation
sumption, CO2 emissions, water consumption and wastewater generation), five economic indicators (specific
Sustainability indicators
raw materials cost, specific energy cost, specific water cost, liquid waste cost fraction and yield factor) and three
safety indicators (safety hazard fire/explosion, chemical exposure index and chronic toxicity factor). The heat
integration proved to be a convenient strategy since it significantly improved the conventional and reactive
distillation processes’ eco-efficiencies. While the reactive distillation technology has a 53% higher environmental
performance than the conventional route, the former’s integrated arrangement increases its eco-efficiency up to
62% when compared to the latter. Finally, we propose new intensified flowsheets for both the conventional and
reactive distillation schemes, being the latter approximately 49% more sustainable than the former.

1. Introduction
Butyl acetate (BuAc) is a chemical product associated with a broad
market mainly due to its use as an organic solvent for manufacturing
lacquers, inks and adhesives, as well as dehydrant in several industrial
applications [1]. It is also used in fragrances and cosmetic products in
the pharmaceutical industry and as a flavoring agent in the food in-
dustry [2]. Butyl acetate may be synthesized either by esterification of
n-butanol (BuOH) with acetic acid (HOAc) or by liquid-phase transes-
terification of methyl acetate (MeAc) with BuOH. Both technological
routes have been studied by numerous authors. For instance, con-
sidering the esterification reaction, Steinigeweg and Gmehling [3]
performed several catalytic distillation experiments in order to
investigate the kinetics and thermodynamics of the system. The authors
then developed a process scheme based on computational simulation
consisting of a pre-reactor and a reactive column. A similar study was
carried out by Singh et al. [4], who evaluated the influence of various
parameters (e.g. feed flow rate and composition, boil-up rate, conver-
sion/selectivity, etc.) through experiments performed in a laboratory-
scale reactive distillation column. Gangadwala and coworkers [5], in
turn, studied different catalytic distillation configurations with regard
to design parameters such as reboiler duty, catalyst loading and feed
tray location, among others. It was reported that the best alternative
corresponded to a design composed of a reactive middle section and
nonreactive stripping/rectifying sections. The assessment of different
design variables and system configurations was also carried out by

Abbreviations: AP, acidification potential; ATP, aquatic toxicity potential; BuAc, butyl acetate; BuOH, butanol; CAPEX, capital expenditures; CDe, carbon dioxide
emissions indicator; CEI, chemical exposure index; CP, conventional process; CTF, chronic toxicity factor indicator; cw, cooling water; Ec, energy consumption
indicator; ECI, eco-efficiency comparison index; EP, eutrophication potential; ERPG-2, emergency response planning guidelines value; Fc, fuel consumption indicator;
FC, fixed costs; FF, fossil fuel use; GWP, global warming potential; hps, high-pressure steam; HIDiC, heat-integrated distillation column; HTPI, human toxicity
potential by ingestion; HTPE, human toxicity potential by inhalation; LCA, lice cycle assessment; lps, low-pressure steam; LWCF, liquid waste cost fraction indicator;
MAN, maleic anhydride; MeAc, methyl acetate; MeOH, methanol; mps, medium-pressure steam; NRTL, non-random two liquid; ODP, ozone depletion potential;
PCOP, photochemical oxidation potential; RD, reactive distillation; RMc, raw materials consumption indicator; SEc, specific energy cost indicator; SHFE, safety
hazard fire/explosion indicator; SRMc, specific raw material cost indicator; SWc, specific water cost indicator; TAC, total annualized cost; TPC, total production costs;
TTP, terrestrial toxicity potential; VC, variable costs; VRC, vapor recompression; WAR, waste reduction; Wc, water consumption indicator; WWg, wastewater
generation indicator; YF, yield factor indicator
⁎
Corresponding author.
E-mail address: patrickmangili@gmail.com (P.V. Mangili).

https://doi.org/10.1016/j.cep.2018.11.020
Received 13 October 2018; Received in revised form 24 November 2018; Accepted 26 November 2018
Available online 28 November 2018
0255-2701/ © 2018 Elsevier B.V. All rights reserved.
P.V. Mangili, D.M. Prata Chemical Engineering & Processing: Process Intensification 135 (2019) 93–107

Nomenculture V̇ Water volumetric flow rate

v̇bfw Volumetric flow rate of boiler feed water
Symbols v̇bfwb Volumetric flow rate of boiler feed water loss due to
blowdown
A Heat transfer area v̇bfwmu Volumetric flow rate of boiler feed water make-up
C1 Column 1 v̇bfwt Volumetric flow rate of boiler feed water loss due to
C2 Column 2 treatment
C3 Column 3 v̇cp Volumetric flow rate of condensate loss in the process
CBuAc Butyl acetate composition v̇cwb Volumetric flow rate of cooling water loss due to blow-
CBuOH Butanol composition down
CMeAc Methyl acetate composition v̇cwe Volumetric flow rate of cooling water loss due to eva-
CMeOH Methanol composition poration
Di Inner diameter v̇cwmu Volumetric flow rate of cooling water make-up
E1 Extra heater or cooler v̇cwp Volumetric flow rate of cooling water loss in the process
H Pump head v̇cws Volumetric flow rate of cooling water supply to process
L Vessel length v̇dw Total volumetric flow rate of treated wastewater discharge
lA Side A of minor triangle v̇hps High-pressure steam volumetric flow rate
lB Side B of minor triangle v̇lps Low-pressure steam volumetric flow rate
P1 Pump 1 v̇mps Medium-pressure steam volumetric flow rate
P2 Pump 2 v̇wmu Total volumetric flow rate of water make-up
P3 Pump 3 xBuAc Butyl acetate molar fraction
Q Boiler energy requirement xBuOH Butanol molar fraction
R1 Continuous stirred tank reactor xMeAc Methyl acetate molar fraction
Sa Area of minor triangle xMeOH Methanol molar fraction
ST Shape area
ST* Area of the largest shape Greek symbols
Tcond Condenser temperature
Tmin Minimum temperature Δ Difference
Treb Reboiler temperature

Arpornwichanop et al. [6], who compared three different reactive dis-
tillation systems with regard to their total annualized costs (TACs). The
authors concluded that although the hybrid pervaporation–reactive
distillation scheme had the lowest energy requirements, the single-re-
active column structure was the most economically attractive. More
recently, Cho and coworkers [7] studied the effects of using an extra-
neous entrainer instead of the conventional internal entrainer for BuAc
production through reactive distillation. They reported not only an
enhanced process efficiency but also a significant reduction of energy
consumption and capital costs.
With regard to the transesterification route, Jiménez and Costa-
López [8] performed process modeling, simulation and control to study
the effects of key variables in the design of reactive and extractive
distillation schemes. The authors examined an alternative for a waste
stream from polyvinyl alcohol manufacturing processes and found that
high-purity BuAc and MeOH could be obtained from such configura-
tion, although no profitability was reported. Design and control stra-
tegies of reactive distillation schemes were also investigated by Wang
et al. [9]. They evaluated the performance of a thermally coupled dis-
tillation and found that lower energy consumption and better con-
trollability can be achieved when compared to the conventional con-
figuration. Harvianto et al. [10] also studied the advantages of
thermally coupled catalytic distillation, but developed a new config-
uration considering a pervaporation unit that, as reported by Steini-
geweg and Gmehling [11], can achieve conversions close to 100%. The
system was designed and optimized on the basis of a conventional re-
active distillation scheme and was reported to have an improved pro-
cess performance in relation to the latter, which was due to the former’s
lower energy consumption and TAC. Behroozsarand and Shafiei [12], in
turn, used thermal coupling design for developing a multi-objective
optimization study to minimize reboiler duty and maximize pro-
ductivity by increasing both BuAc and MeOH flow rates. Although nine
decision parameters were selected, no restriction on the temperature of
the reactive section was assumed, which should be kept lower than
393 K in order to prevent thermal degradation of the catalyst (Amber-
lyst 15), according to Steinigeweg and Gmehling [11]. Švandová and
Markoš [13] performed a steady-state analysis, including said opera-
tional restriction on a hybrid configuration, which includes a perva-
poration unit. The analysis was based on the numerical continuation
and bifurcation methods and showed that, although high conversions
were achieved, three steady-state behaviors were predicted. However,
only one of them met the temperature condition, but was deemed un-
stable. Finally, Luyben et al. [14] designed a conventional and a re-
active distillation process in which no entrainer was used. According to
the authors, the use of a solvent (e.g. o-xylene) would cause the product
to be contaminated with small amounts of the entrainer, which would
then require an extra purification column and consequently increase
the capital costs. Both solvent-free configurations were proven to be
feasible and compared in terms of operability and annual costs, being
the latter more economical due to the lower overall energy require-
ments.
In light of the above, one should note that most studies regarding
BuAc manufacturing technologies are focused on process operability,
controllability and economics. There is a lack of studies related to such
processes regarding both environmental and safety aspects, which
should be included in the overall sustainability assessment of industrial
processes. Many authors usually assert which configuration is the best
one according to single metrics (e.g. TAC, energy, etc.) and, therefore,
fail to provide a broader and more complete multicriteria analysis with
respect to economic, environmental and safety features. In this regard,
this paper aims to compare the sustainable performance of two butyl
acetate manufacturing technologies – and their respective heat-in-
tegrated designs – on the basis of a joint evaluation of process metrics.
The assessment was performed by means of the Eco-Efficiency
Comparison Index (ECI) method by means of six ecological indicators
(raw material consumption, fuel consumption, energy consumption,
CO2 emissions, water consumption and wastewater generation), five
economic indicators (specific raw materials cost, specific energy cost,

94
P.V. Mangili, D.M. Prata
specific water cost, liquid waste cost fraction and yield factor) and three
safety indicators (safety hazard fire/explosion, chemical exposure index
and chronic toxicity factor), totalizing 14 sustainability metrics. It must
also be pointed out that the indicators were calculated in this paper by
taking both the utility plant (cooling water and steam generation sec-
tions) and wastewater treatment into account, which is usually dis-
regarded by most authors.
Sustainability indicators were used in this paper for qualitatively
and quantitatively assessing the environmental performance of the
processes studied due to their relevance in providing a fair and cate-
gorical comparison. Such metrics have been used for assessing the
sustainability of industrial processes in several studies, including those
regarding process intensification techniques. For instance, Pal and Dey
[15] analyzed the intensification of a lactic acid production process by a
membrane-integrated hybrid reactor in terms of space, flexibility, en-
ergy reduction and cost advantage. The authors found that such tech-
nology is not only more environmentally friendly but also more eco-
nomically attractive than the conventional process, since the former
requires less equipment operating at less severe conditions. Santaella
et al. [16], in turn, compared different reactive distillation technologies
for ethyl acetate manufacture by means of eight sustainability metrics.
It was concluded that their reactive dividing wall scheme has the
highest energy savings and lower annual costs, thus offering better
sustainability performance when compared to the conventional, di-
viding wall and reactive distillation configurations. More recently,
Sharma and coworkers [17] investigated the energy consumption, CO2
emissions and economics of the intensification of the formic acid
manufacture process. The authors compared different configurations,
including vapor recompression and dividing wall reactive distillation,
in order to demonstrate the relevance of process intensification for the
improvement of the processes’ sustainability. Mangili et al. [18] and
Junqueira et al. [19] applied the Eco-efficiency Comparison Index (ECI)
approach to evaluate the sustainability of different processes. The
former compared three acetone-methanol separation technologies, in-
cluding a heat-integrated scheme, considering the energy consumption,
Fig. 1. Luyben et al. [14]’s conventional butyl acetate production process.
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Chemical Engineering & Processing: Process Intensification 135 (2019) 93–107
CO2 emissions and water consumption, whereas the latter compared six
cumene production processes with different intensification strategies in
terms of environmental burdens and economics.
It is worth mentioning that this studied was carried out considering
the transesterification route to be more appropriate for evaluation.
From the literature survey, one may infer that the main drawback re-
lated to both technological routes refers to corrosion of process
equipment due to the use of homogeneous acid catalysts [5]. Hence,
recent studies on solid heterogeneous catalysts have been developed for
both processes considering different design configurations. Never-
theless, the conventional esterification route presents significant dis-
advantages when compared to the transesterification technology. For
instance, dilute HOAc feedstock must be previously recovered from its
original aqueous solution, which represents a relevant downside in both
economic and environmental aspects since a pretreatment step is re-
quired [6]. In addition, the reaction between n-butanol and acetic acid
results in the formation of toxic undesired side product dibutyl ether,
thus corresponding to a major safety issue [5]. Moreover, considering
that hybrid technologies (e.g. pervaporation) are prone to operate
under unstable states [13] and thermal-coupling schemes may present
some operational challenges associated with vapor flow [20], Luyben
et al. [14]’s design was selected as a case study since their control
analysis demonstrated that the processes studied here are effectively
controlled against large disturbances.
In the next section, a brief revision regarding the butyl acetate
manufacturing processes via transesterification is presented. In Section
3, we describe the method for calculating the sustainability indicators,
whereas their joint evaluation through the Eco-Efficiency Comparison
Index method is described in Section 4. In Section 5, we discuss the
results regarding the comparison results and, in Section 6, we sum-
marize the main findings and provide some suggestions for future
works.
P.V. Mangili, D.M. Prata
2. Butyl acetate production
The liquid-phase transesterification of MeAc with BuOH for butyl
acetate manufacture is studied in this paper. According to Jiménez and
Costa-López [8], this is achieved by using a sulfonic ion-exchange resin
catalyst and co-produces methanol (MeOH), as described by Eq. (1).
This system has a particular complexity due to its low equilibrium ex-
tent and the formation of MeAc/MeOH and BuOH/BuAc azeotropes,
which can be overcome by the use of reactive distillation and pressure
swing distillation, respectively [14].
MeAc + BuOH ⇔ BuAc + MeOH
The conventional and reactive distillation technologies for BuAc
production studied in this paper were proposed by Luyben et al. [14].
Both processes, as well as their thermally integrated designs and utility
plant, were simulated in UniSim® Design Suite R390.1 in order to ob-
tain the data required to determine the indicators. The same feed
conditions and equipment specifications used by the authors were
considered. The processes were simulated under steady-state conditions
by using the Non-Random Two Liquid (NRTL) thermodynamic model.
2.1. Conventional technology
The process flow diagram for the conventional BuAc production
process (CP) is illustrated in Fig. 1, which shows the results obtained by
simulation. In the schematic, cw, lps and hps stand for cooling water,
low-pressure steam and high-pressure steam, respectively.
Fresh butanol at 34.84 kmol/h is mixed with 94.35 kmol/h of a
butanol recycle stream prior to being fed to a 5 m3 continuous stirred
tank reactor that operates at 90 °C and 7 bar, which is also fed by a
mixture of a MeOH/MeAc stream, at 58.20 kmol/h, and a MeAc recycle
stream, at 71.20 kmol/h. The reaction kinetics is shown in Eq. (2).
r = 7 × 106 exp(−71, 960/ RT ) CMeAc CBuOH − 9.467 × 106 exp( −72, 670
/ RT ) CMeOH CBuAc
−3 −3 -1
Compositions and reaction rate are in kmol m and kmol m s ,
respectively, while R is 8.316 kJ kmol-1. The reactor product is sent to a
distillation column C1, from which a stream containing 41 mol % MeAc
and 59 mol % MeOH is retrieved at the top and sent to the methanol
distillation column C2 at 129.4 kmol/h. C1′s bottom product, con-
taining 61 mol % BuOH and 39 mol % BuAc, is pressurized by pump P1
from 1 bar to 3.5 bar and sent to the BuAc distillation column C3 at
129.19 kmol/h. C2′s top product is recycled to the feed section, whereas
its bottom product, containing approximately 99 mol % MeOH, is re-
trieved at 58.20 kmol/h. C3′s top product is recycled to the feed section,
Fig. 2. BuOH/BuAc vapor-liquid equilibrium at 175 °C.
Chemical Engineering & Processing: Process Intensification 135 (2019) 93–107
while its bottom product, containing approximately 99 mol % BuAc, is
retrieved at 34.84 kmol/h.
2.2. Heat-integrated conventional technology
The steady increase in both the costs of energy resources and en-
vironmental constraints related to energy generation emissions has
compelled industries to develop process integration techniques in order
to lessen the energy requirements of their activities. Thermally in-
tegrating process systems reduces not only the environmental impacts
(1) associated with energy generation but also the plant’s operating costs.
Heat integration may be designed in numerous configurations with
different purposes such as reaction heat recovery and optimization of
the process’ thermodynamic efficiency.
Distillation sequences are proper examples of process systems whose
integration has a particular relevance, since most industrial processes
currently rely on such operations in order to separate and purify their
products. Nevertheless, reducing energy requirements – and, therefore,
the operating costs – through thermal integration may considerably
increase the capital expenses since larger heat transfer areas are
needed. Various studies on different integration strategies have been
published. For instance, Mane and Jana [21] proposed two configura-
tions of heat-integrated distillation columns (HIDiC) that operate at
different pressures for benzene/toluene separation. The authors sug-
gested the intensification by vapor recompression (VRC), investigating
several operating parameters such as reflux ratio, stage pressure drop
and compression ratio, among others. Their new technique proved to
have significant energy savings and cost reduction. HIDiC and VRC
configurations were also studied by Kiss and Olujić [22], who per-
formed a review of the last developments regarding said technologies in
terms of various engineering aspects such as energy savings, thermo-
dynamics, process control and mechanical design, among others. Ac-
cording to their analysis, both technologies were deemed prominent
strategies for reducing energy requirements, being the VRC technique
(2)
occasionally less economically attractive since the use of a heat pump
(e.g. compressor) results in higher capital investments. Diaz and Tost
[23], in turn, compared different integration arrangements for ethanol
and isobutanol dehydration processes. The authors performed simula-
tion studies in order to evaluate the total annualized costs of VRC and
double-effect distillation designs, which were found to be significantly
lower than the conventional technology’s. The TAC of heat-integrated
distillation configurations was also the object of study of Gutiérrez-
Guerra et al. [24], who defined said variable as an objective function
for carrying out a systematic design and optimization analysis. Several
parameters were investigated, being the compression ratio and reflux
96
P.V. Mangili, D.M. Prata
ratio the most influential in energy consumption and equipment
costing.
Distillation columns can be integrated if the condenser’s tempera-
ture (Tcond) is sufficiently higher than the reboiler’s temperature (Treb),
as shown in Eq. (3), where ΔTmin refers to the minimum temperature
difference approach [25].
Tcond ≥ Treb + ΔTmin (3)
According to the heuristics provided by Seider et al. [26], near-
optimum ΔTmin are usually 10 °C for temperatures below ambient, 20 °C
for temperatures from ambient up to 150 °C and 50 °C for temperatures
higher than 150 °C. In this regard, the only reasonable integration de-
sign for the conventional BuAc production process is between C3′s
condenser and C2′s reboiler, as illustrated in Fig. 4 (b). In fact, as as-
serted by Luyben et al. [14], the former’s temperature (160 °C) is high
enough to allow it to be heat-integrated with the latter, since its tem-
perature is sufficiently lower (70 °C).
However, C3′s pressure can still be increased to obtain a higher
condenser temperature and thus allow it to be integrated with C1′s
reboiler instead, as shown in Fig. 4(a). The authors considered an op-
erating pressure of 3.5 bar since higher pressures also result in higher
reboiler temperatures, which would then require more expensive,
higher-pressure steam as a heating source. Nevertheless, in this work,
we also take the environmental burdens into account, which may be
reduced and thus counterbalance the higher costs. In order to achieve a
temperature of at least 175 °C (50 °C higher than C1′s reboiler tem-
perature) by maintaining a butanol composition of approximately
90 mol %, an operating pressure of 5.3 bar should be used, as shown in
the P-x-y diagram of Fig. 2.
By operating at 5.3 bar, the reboiler temperature and heat require-
ment increase to 206 °C and 14.81 GJ/h, respectively, still allowing the
use of high-pressure steam at the conditions assumed in Section 3.1. In
addition, as can be seen from Fig. 3, the composition profiles barely
changed, thus preserving the actual plant design.
The same description of the conventional process of Fig. 1 applies to
the heat-integrated configurations of Fig. 4, with the exception of the
need for an extra 0.50 GJ/h heater and an extra 1.76 GJ/h cooler in the
C1-C3 and C2-C3 integrated designs, respectively. Also, for the C1-C2
design, the pump P1′s work increases to 0.98 GJ/h to pressurize C1′s
bottom product to 5.3 bar, whereas pump P3′s work decreases to
1.21 GJ/h.
2.3. Reactive distillation technology
As previously discussed, Jiménez and Costa-López [8] proposed the
use of an extractive catalytic distillation system for the manufacture of
Fig. 3. C3′s composition profiles at 5.3 bar (heat-integrated CP).
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Chemical Engineering & Processing: Process Intensification 135 (2019) 93–107
butyl acetate via esterification of methyl acetate with butanol. How-
ever, since the authors did not provide sufficient details concerning the
process conditions and equipment specifications, Luyben et al. [14]
designed a reactive distillation technology without using an entrainer.
The process flow diagram for the reactive distillation (RD) BuAc pro-
duction process is illustrated in Fig. 5, which shows the results obtained
by simulation. In the schematic, cw, lps, mps and hps stand for cooling
water, low-pressure steam, medium-pressure steam and high-pressure
steam, respectively.
Fresh MeOH/MeAc stream at 58.38 kmol/h is fed to a distillation
column C1, which is also fed by a methanol recycle stream, at
62.14 kmol/h. C1′s bottom product, containing approximately 99 ml %
MeOH, is retrieved at 58.21 kmol/h, whereas its top product, con-
taining 64 mol % MeAc and 36 mol % MeOH is sent at 62.31 kmol/h to
the catalytic distillation column C2. This column is also fed by a mix-
ture of a fresh butanol stream, at 34.88 kmol/h, and a BuOH recycle
stream, at 24.49 kmol/h. The reaction kinetics are the same as for the
conventional route. C2′s top product, containing 91 mol % MeOH and
9 mol % MeAc is recycled to C1, while the bottom product, containing
39 mol % BuOH and 61 mol % BuAc, is pressurized from 1.1 bar to
3.5 bar prior to being sent to the BuAc column C3 at 59.54 kmol/h. C3′s
top product is recycled to C3, whereas its bottom product, containing
approximately 99 mol % BuAc, is retrieved at 35.05 kmol/h.
2.4. Heat-integrated reactive distillation technology
Here again, in agreement with Seider et al. [26]’s heuristics, the
only adequate integration design for the reactive technology is between
C3′s condenser and C1′s reboiler, since the former’s temperature
(158 °C) is sufficiently higher than the latter’s (71 °C), as also indicated
by Luyben et al. [14]. Similarly to the heat-integrated conventional
process, the thermal integration of the reactive technology is essentially
based on the pressure difference between columns, since the high
pressure in column C3 prompts a sufficiently high condenser tem-
perature to allow energy integration with C1′s reboiler. Nevertheless,
C3′s pressure can be increased to allow its condenser to be integrated
with C2′s reboiler instead. According to Fig. 2, C3′s pressure was
changed to 5.3 bar in order to have a condenser temperature of at least
175 °C (50 °C higher than C2′s reboiler temperature) and keep the
BuOH composition at 90 mol %. In these conditions, the reboiler tem-
perature and heat requirement increase to 203 °C and 7.11 GJ/h, re-
spectively, thus still allowing the use of high-pressure steam. In addi-
tion, the composition profiles remained steady, as illustrated in Fig. 6.
The integration between C3′ condenser and C1′s reboiler is illustrated
in Fig. 7(a), while the integration between C3′ condenser and C2′s re-
boiler is illustrated in Fig. 7(b).
P.V. Mangili, D.M. Prata Chemical Engineering & Processing: Process Intensification 135 (2019) 93–107

Fig. 4. Conventional process integration arrangements: (a) C1-C3; (b) C2-C3.

Fig. 5. Luyben et al. [14]’s reactive distillation butyl acetate production process.

Fig. 6. C3′s composition profiles at 5.3 bar (heat-integrated RD process).

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Fig. 7. Reactive distillation process integration arrangements: (a) C1-C3; (b) C2-C3.

Fig. 8. Utilities plant flowsheet.

Table 1 Table 2
Utilities plant variables. Environmental indicators equations.
Variable Definition Unit Indicator Equation Unit

v̇cws Volumetric flow rate of cooling water supply to process 3

m /h RMc Total molar flow rate of raw materials kmol/kmol
v̇cwp Volumetric flow rate of cooling water loss in the process m3/h Total molar flow rate of products
Fc Total mass flow rate of natural gas kg/kmol
v̇cwe Volumetric flow rate of cooling water loss due to evaporation m3/h Total molar flow rate of products
v̇cwb Volumetric flow rate of cooling water loss due to blowdown m3/h Ec Total energy consumption(electricity and thermal) GJ/kmol
v̇cwmu Volumetric flow rate of cooling water make-up m3/h Total molar flow rate of products
v̇bfw Volumetric flow rate of boiler feed water m3/h CDe Total CO2 emissions t/kmol
v̇bfwb Volumetric flow rate of boiler feed water loss due to blowdown m3/h Total molar flow rate of products
Wc Total water make-up volumetric flow rate m3/kmol
v̇lps Volumetric flow rate of low pressure steam supply to process 3
m /h Total molar flow rate of products
v̇mps Volumetric flow rate of medium pressure steam supply to 3
m /h WWg Total wastewater volumetric flow rate m3/kmol
process Total molar flow rate of products
v̇hps Volumetric flow rate of high pressure steam supply to process m3/h
v̇cp Volumetric flow rate of condensate loss in the process m3/h
v̇bfwt Volumetric flow rate of boiler feed water loss due to treatment m3/h The same description of the RD process of Fig. 5 applies to the in-
v̇bfwmu Volumetric flow rate of boiler feed water make-up m3/h tegrated configurations of Fig. 7, with the exception of the need for an
v̇ wmu Total volumetric flow rate of water make-up m3/h extra 1.45 GJ/h cooler and an extra 4.71 GJ/h heater in the C1-C3 and
v̇dw Total volumetric flow rate of treated wastewater discharge m3/h
C2-C3 integrated designs, respectively. For the C2-C3 design, pump P1′s
work increases to 1.95 GJ/h to pressurize C2′s bottom product to

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Table 3 Table 7
Utilities plant heuristics. Safety indicators equations.c
Variable Value Reference Indicator Equation Unit

v̇cws Simulation result – SHFE Probable energy potential for reaction withO2 GJ/kg
v̇cwp 3% of v̇cws [26] Mass of product
CEI Maximum airborne quantity –
v̇cwe 1% of v̇cws [25] 0.655
ERPG-2
v̇cwb 3% of v̇cws [26]
CTF Volume of air polluted to a workplace threshold value m3/kg
v̇cwmu v̇cws + v̇cwe + v̇cwb – Mass of product
v̇bfw (v̇lps + v̇mps + v̇hps ) + v̇bfwb [26]
c
v̇bfwb 3% of v̇bfw [34] ERPG-2: Emergency response planning guidelines value (mg/m3).
v̇lps Simulation result –
v̇mps Simulation result – Steam is usually considered as a heating source, since it provides a fast
v̇hps Simulation result –
and uniform heating, whereas water is usually utilized for cooling. Such
v̇cp 10% of (v̇lps + v̇mps + v̇hps ) [33]
utility may be provided either by a once-through system or by a closed-
v̇bfwt 1% of v̇bfwmu [25]
loop recirculating system. Since the former has significant ecological
v̇bfwmu v̇bfwb + v̇cp + v̇bfwt –
consequences and fresh water is currently a global scarce resource, the
v̇ wmu v̇cwmu + v̇bfwmu –
v̇dw v̇cwp + v̇cwb + v̇bfwb + v̇cp + v̇bfwt –
latter turns out to be the most appropriate alternative. In this paper, the
utility plant was designed on the basis of Junqueira et al. [19]’s work
and Smith [25]’s book in order to permit a more realistic estimation of
Table 4 the capital costs, water consumption and wastewater generation of each
Equipment cost basis.a process. Its flowsheet is illustrated in Fig. 8, while the variables are
defined in Table 1.
Equipment Cost Equation
Water is supplied to a cooling water system and a steam generation
Pumps exp{9.7171-0.6019[ln(V̇ (H)0.5)]+0.0519[ln(V̇ (H)0.5)]2} system. In the former, it is mixed with a cooling water-returning stream
Heat exchangers exp{11.667-0.8709[ln(A)]+0.09005[ln(A)]2} prior to being treated with chemicals in order to inhibit corrosion and
Vessels 361.8(Di)0.7396(L)0.70684 microbiological growth. The water is then sent to a cooling tower,
Water treatment 43000(V̇ )0.64 where it is cooled down to the supply temperature by flowing down in
Cooling tower 164f(V̇ )0.61 contact with air. Some of the circulating water is lost due to evapora-
Boiler 0.36(Q)0.77
tion and the remaining is blown down to prevent the buildup of con-
a
V̇ : Volumetric flow rate (gal/min). H: Pump head (ft). A: Heat transfer area taminants. The remaining water is pressurized and supplied to the
(ft2). Di: Inner diameter (in). L: Length (in). Q: Energy requirement (Btu/h). process coolers and condensers, which are associated with water losses
due to leaks. The hotter water then returns to be cooled again, closing
Table 5 the cycle.
General production expenses. In the steam generation system, water is first treated to remove
solids and dissolved salts, where some water is lost. Water is then mixed
Basis Parameter Value Reference
with a condensate return stream and sent to a deaerator for gas removal
Fixed costs Maintenance 5% of CAPEX [36] in order to prevent boiler corrosion. Treated water is subsequently
(FC) Overheads 5% of labor pressurized prior to being pumped to a steam boiler, where some of the
Insurance, license fees and 2% of CAPEX water is blown down to avoid buildup of any remaining solids. The
royalties
Variable costs Personal protective equipment, 1% of [36]
water is vaporized to high-pressure steam, which is partially expanded
(VC) cleaning materials, charts and maintenance to medium and low-pressure steams depending on the process’ demand.
accessories, etc. The generated steam is supplied to the process reboilers, which are
Other Sales and marketing 2% of FC + VC [36] associated with condensate losses due to process leaks. The remaining
Human resources, accounting, 35% of labor
condensate returns to be re-evaporated, closing the cycle.
finance, etc.
With exception of the evaporation, all water loss streams are sent to
a wastewater treatment facility prior to being discharged to the en-
Table 6 vironment. For simulation purposes, chemicals and salts were not si-
Economic indicators equations.b mulated due to the software limitation regarding solids modeling.

Indicator Equation Unit

SRMc Total raw material cost per hour $/kg

3. Sustainability assessment
Total mass flow rate of products
SEc Total annual energy cost $/$ As previously discussed, to the best of our knowledge, most studies
TPC
SWc Total annual water cost $/$ regarding butyl acetate production processes have only been carried out
TPC
in terms of process design and economics. Nevertheless, with regard to
LWCF Total annual wastewater treatment cost $/$
TPC environmental sustainability, only two works have come to our atten-
YF 1 m3/kmol tion. Cardona et al. [27] applied the Waste Reduction (WAR) Algorithm
Reaction yield
to compare the conventional and reactive distillation technologies via
b
Reaction yield: Mass of product divided by the theoretical mass of product. esterification of butanol with acetic acid in terms of eight LCA in-
dicators, namely Global Warming Potential (GWP), Ozone Depletion
5.3 bar. Potential (ODP), Acidification Potential (AP), Photochemical Oxidation
Potential (PCOP), Human Toxicity Potential by Ingestion (HTPI),
Human Toxicity Potential by Inhalation (HTPE), Aquatic Toxicity Po-
2.5. Utility plant tential (ATP) and Terrestrial Toxicity Potential (TTP). Bories and
coworkers [28], in turn, compared two different pathways for produ-
Most industrial processes require external heat supply and removal. cing ethyl and butyl acetates, namely by independent reactions and by

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P.V. Mangili, D.M. Prata Chemical Engineering & Processing: Process Intensification 135 (2019) 93–107

Fig. 9. Equipment contributions: (a) Original CP design; (b) Original RD design.

Table 8 Table 9
Utilities plant results. Environmental indicators results.
Variable CP Heat-integrated CP RD Heat-integrated RD Indicator CP Heat-integrated CP RD Heat-integrated RD

C1-C3 C2-C3 C1-C3 C2-C3 C1-C3 C2-C3 C1-C3 C2-C3

v̇cws 613.22 389.30 264.92 273.74 212.39 189.10 RMc 1.000 1.000 1.000 1.000 1.000 1.000
v̇cwp 17.81 11.68 7.51 8.21 6.37 5.67 Fc 8.625 7.815 8.206 5.799 4.716 3.507
v̇cwe 5.94 3.89 2.50 2.74 2.12 1.89 Ec 0.550 0.373 0.404 0.291 0.239 0.224
v̇cwb 17.81 11.68 7.51 8.21 6.37 5.67 CDe 0.030 0.020 0.022 0.016 0.013 0.012
v̇cwmu 41.46 27.25 17.52 19.16 14.86 13.23 Wc 0.475 0.313 0.209 0.217 0.168 0.154
v̇bfw 20.27 14.37 15.08 11.20 9.31 8.60 WWg 0.410 0.376 0.180 0.190 0.150 0.140
v̇bfwb 0.61 0.43 0.45 0.34 0.28 0.26
v̇lps 11.11 5.25 6.08 1.80 – 1.80
v̇mps – – – 5.02 5.02 2.37 variables (ecological impacts, process economics, hazard and safety)
v̇hps 8.55 8.69 8.55 4.01 4.01 4.17 must be taken into account in the design phase of a process, LCA ap-
v̇cp 1.97 1.39 1.46 1.08 0.90 0.83 proaches are not the most appropriate during such a phase. In addition,
v̇bfwt 0.03 0.02 0.02 0.02 0.01 0.01 performing an environmental analysis through LCA metrics may be
v̇bfwmu 2.60 1.84 1.93 1.46 1.19 1.10 exhausting due to the excessive amount of data required [30]. In this
v̇ wmu 44.16 29.09 19.45 20.62 16.05 14.33 regard, we evaluated the butyl acetate processes in terms of six ecolo-
v̇dw 38.23 25.20 16.95 17.86 13.93 12.44
gical indicators, five economic indicators and three safety indicators.
The methodologies for each metric applied in this paper are described
in the following sections.
co-production. They performed said analysis in terms of several LCA
metrics such as climate change, human toxicity, ionizing radiation,
eutrophication and land use, among others. 3.1. Environmental indicators
Although the development of an LCA assessment provides suitable
information on the environmental impacts of a particular process, it The world is currently facing an alarming scenario in terms of en-
does not take into consideration other sustainability aspects (e.g. eco- vironmental burdens such as atmospheric emissions, imprudent ex-
nomic performance, safety characteristics, etc.) [29]. Since all design ploitation of natural resources, water shortage, etc. In this context, the

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Table 10
Resulting equipment costs (M$).
Equipment CP Heat-integrated CP RD Heat-integrated RD

C1-C3 C2-C3 C1-C3 C2-C3

Reactor R1 0.99 0.99 0.99 – – –

Column C1 0.88 0.88 0.88 0.83 0.83 0.83
C1’s condenser 0.12 0.12 0.12 0.08 0.08 0.08
C1’s reboiler 0.12 0.22 0.12 0.10 0.20 0.1
Column C2 0.93 0.93 0.93 1.21 1.21 1.21
C2’s condenser 0.14 0.14 0.14 0.09 0.09 0.09
C2’s reboiler 0.09 0.09 0.24 0.11 0.11 0.26
Column C3 1.19 1.19 1.19 1.05 1.05 1.05
C3’s condenser 0.05 – – 0.02 0.02 –
C3’s reboiler 0.15 0.15 0.15 0.09 0.09 0.09
Extra cooler – – 0.12 – – 0.22
Extra heater – 0.1 – – 0.16 –
Pumps 0.41 0.41 0.41 0.35 0.35 0.35
Utility Plant 1.57 1.55 1.55 1.36 1.34 1.35

Table 11
Economic indicators results.
Indicator CP Heat-integrated CP RD Heat-integrated RD

C1-C3 C2-C3 C1-C3 C2-C3

SRMc 104.355 104.355 104.355 104.107 104.107 104.107

SEc 0.440 0.290 0.310 0.230 0.210 0.195
SWc 0.070 0.034 0.060 0.010 0.010 0.004 Fig. 10. ECI chart considering all alternatives.
LWCF 0.230 0.137 0.150 0.180 0.170 0.165
YF 5.236 0.5236 5.236 1.724 1.724 1.724
managing their businesses with regard to the environment. In this
paper, raw materials consumption (RMc), fuel consumption (Fc), en-
ergy consumption (Ec), carbon dioxide emissions (CDe), water con-
Table 12
Safety indicators results.
sumption (Wc) and wastewater generation (WWg) were chosen as en-
vironmental indicators, which were calculated through the formulae
Indicator CP Heat-integrated CP RD Heat-integrated RD presented in Table 2.
C1-C3 C2-C3 C1-C3 C2-C3
The fuel consumption was calculated by assuming that the utility
plant’s boiler consumes natural gas and operates with 80% thermal
SHFE 0.010 0.010 0.010 0.010 0.010 0.010 efficiency, which corresponds to the worst scenario for mid-efficiency
CEI 70.854 70.854 70.854 70.833 70.833 70.833 heating systems [31]. The natural gas net calorific value was inter-
CTF 7.228 7.228 7.228 7.227 7.227 7.227
preted as 0.048 GJ/kg [32]. The energy consumption, CO2 emissions
and water consumption were determined in accordance with Mangili
Table 13
et al. [18] and Junqueira et al. [19]’s procedure. Pumps and turbines
Normalized indicators. were assumed to operate with electricity and 75% efficiency (software
default), whereas heaters and reboilers were interpreted to operate with
Indicator CP Heat-integrated CP RD Heat-integrated RD
steam generated in the utility plant’s boiler. The same conversion fac-
C1-C3 C2-C3 C1-C3 C2-C3 tors for electricity (0.0227 tCO2/GJ) and natural gas thermal energy
(0.0561 tCO2/GJ) to carbon dioxide emissions were considered since,
d d d d d
RMc 1.0000 1.0000 1.0000 1.0000 1.0000 1.0000d similar to said references, the plants were assumed to be installed in
Fc 1.0000d 0.9061 0.9514 0.6723 0.5468 0.4066
Brazil.
Ec 1.0000d 0.6782 0.7345 0.5291 0.4345 0.4073
CDe 1.0000d 0.6667 0.7333 0.5333 0.4333 0.4000 Cooling water was assumed to be supplied at 30 °C and return at
Wc 1.0000d 0.6589 0.4400 0.4568 0.3537 0.3242 45 °C [21]. Low-pressure steam was considered to be supplied at 135 °C
WWg 1.0000d 0.9171 0.4390 0.4634 0.3659 0.3415 and 3.05 bar and medium-pressure steam was assumed to be supplied at
SRMc 1.0000d 1.0000d 1.0000d 0.9976 0.9976 0.9976 185.5 °C and 11.35 bar, whereas high-pressure steam was considered to
SEc 1.0000d 0.6591 0.7045 0.5227 0.4773 0.4432
be supplied at 254 °C and 42.38 bar [33]. The wastewater generation
SWc 1.0000d 0.4857 0.8571 0.1429 0.1429 0.0571
LWCF 1.0000d 0.5957 0.6522 0.7826 0.7391 0.7174 indicator was determined by considering the heuristics presented in
YF 1.0000d 1.0000d 1.0000d 0.3293 0.3293 0.3293 Table 3.
SHFE 1.0000d 1.0000d 1.0000d 1.0000d 1.0000d 1.0000d
CEI 1.0000d 1.0000d 1.0000d 0.9997 0.9997 0.9997
CTF 1.0000d 1.0000d 1.0000d 0.9999 0.9999 0.9999
3.2. Economic indicators
d
Highest values by indicator category.
The economics of both technologies was determined by estimating
governmental organizations, along with companies and industries, have their capital expenditures (CAPEX) and total production costs (TPC).
been developing practical measures to mitigate the ecological impacts The CAPEX of each process was estimated on the basis of the equipment
resulting from their activities. Most of these measures are based on the cost equations given by Seider et al. [26]’s book and assuming Plant
so-called “environmental indicators”, which are metrics that aid the Cost Index of 600 [19]. The equipment cost equations are presented in
institutions in assessing their environmental performance and better Table 4. Pumps were assumed to be of centrifugal type, whereas the
reactor and columns were costed as vertical pressure vessels [18]. The

102
P.V. Mangili, D.M. Prata
Fig. 11. Intensified CP technology.
reboilers were of kettle type, while all other heat exchangers were in-
terpreted as floating head type. Carbon steel was considered the con-
struction material for columns and heat exchangers. Stainless steel 304
was assumed to be the construction material for pumps and reactor
[26].
Regarding the production costs, electricity and water were assumed
to be worth 16.80 $/GJ and 1.04 $/GJ [33], respectively, while natural
gas was priced at 4.24 $/GJ [35]. The plants were considered to operate
for 8,000 h per year, while labor costs were assumed to be 50,000
$/operator/year, with 3 shifts and 5 operators per shift [33]. BuOH and
MeOH/MeAc feedstocks were not taken into account in the calculations
since all processes have similar raw materials flow rates and only re-
lative values of the economic indicators are required in the ECI analysis.
Other escalation parameters used to estimate the production costs are
shown in Table 5.
Economic indicators are predominantly associated with the profit-
ability of a process. On one hand, they can be used in the evaluation of
the economics of an existing process to simplify mathematical indexes
and enable a better understanding of the company’s financial position.
On the other hand, said metrics can be taken into consideration when a
new process is being designed in order to assist in decision-making
tasks, such as selecting a particular technology or configuration. In this
work, specific raw material cost (SRMc), specific energy cost (SEc),
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Chemical Engineering & Processing: Process Intensification 135 (2019) 93–107
specific water cost (SWc), liquid waste cost fraction (LWCF) and yield
factor (YF) were chosen as economic indicators, which were calculated
through the formulae presented in Table 6. They were determined in
accordance with Ruiz-Mercado et al. [37]’s work, which presents a
more detailed description regarding the calculation procedures.
One should note that we used a yield factor corresponding to the
inverse ratio of the indicator presented by the author. This approach
was used in order to avoid miscalculating the Eco-efficiency
Comparison Index, since it rates the indicators according to a “the lower
- the better” approach. Thus, a high reaction yield results in a lower,
and therefore better, value. Such an approach is particularly convenient
due to the evaluation methodology required by the ECI method, which
groups the indicators in order to determine the smaller area (i.e. the
best index).
3.3. Safety indicators
The use of safety indicators in the analysis of the sustainability of a
process has a particular relevance in today’s context, especially with
regard to industrial activities. Unfortunately, the corporate culture of
numerous companies is still primarily tied to profitability instead of
incident prevention strategies. Safety metrics should be the top priority
in an organization’s doctrine, since they are crucial to establish a
P.V. Mangili, D.M. Prata
Fig. 12. Intensified RD technology.
suitable management system and effectively monitor the performance
of critical elements related to process efficiency. In this regard, we
chose Safety Hazard Fire/Explosion (SHFE), chemical exposure index
(CEI) and chronic toxicity factor (CTF) as safety indicators, which were
calculated through the formulae presented in Table 7. Such formulae
were proposed by Ruiz-Mercado et al. [37], which presents a more
detailed description regarding the calculation procedures.
4. Eco-efficiency comparison index
The term “Eco-efficiency” was first introduced by the World
Business Council for Sustainable Development at the Rio de Janeiro
Earth Summit in 1992 to draw the attention of companies to the im-
portance of developing business-related strategies to balance economic
progress and environmental responsibility [38]. In this context, the
sustainability assessment of industrial activities through the determi-
nation of environmental indicators has gained more and more attention
due to its significance to correlate commercial activities and mitigation
of environmental impacts. However, in order to be consistent, such an
assessment must jointly and concurrently evaluate various indicators
instead of individually doing so.
Accordingly, in this paper, we employed the ECI methodology to
compare the environmental performance of the BuAc processes, on the
basis of the methodology developed by Pereira et al. [39]. The authors
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Chemical Engineering & Processing: Process Intensification 135 (2019) 93–107
evaluated the sustainability of a petrochemical facility in terms of five
eco-indicators and compared, with real industrial data, the process eco-
efficiency in different periods. Hence, they could demonstrate the sig-
nificance of such a methodology for assisting practitioners in decision-
making tasks aimed at identifying potential impacts and developing
mitigating strategies. As previously stated, the ECI approach was fur-
ther applied by Mangili et al. [18] and Junqueira et al. [19] to compare
different acetone-methanol separation technologies and cumene man-
ufacture processes, respectively. However, none of the above-men-
tioned references either considered safety metrics into account or pro-
posed new, more sustainable configurations.
The ECI method is used to normalize the indicators by grouping
their respective categories and dividing them by the highest value in
that category. The values vary from 0 to 1, which represent the best and
the worst-case scenario, respectively. Finally, the normalized indicators
are plotted on a radar chart, forming a shape that depends on the
number (n) of metrics evaluated. The areas (Sa) of the n minor triangles
present are determined through the Law of Sines, shown in Eq. (4), and
are summed up in order to calculate the shape area (ST). Eq. (5) gives
the resulting expression of ST considering n metrics [39].
lA⋅lB 2π
Sa = ⋅sin ⎛ ⎞
2 ⎝n ⎠ (4)
P.V. Mangili, D.M. Prata
Fig. 13. ECI for the proposed schemes.
n−1
1 2π ⎛
ST =
2
⋅sin ⎛ ⎞⋅⎜l1⋅ln + ∑ li⋅li +1⎞⎟
⎝ n ⎠⎝ i=1 ⎠ (5)
lA, lB correspond to the adjacent sides A and B of each minor tri-
angle, respectively, while l refers to the indicator values, being the
subscript corresponding to the respective metric. The ECI is then cal-
culated as described in Eq. (6), in which ST* refers to the area of the
chart’s largest shape, i.e. the least eco-efficient process.
S
ECI = ⎜⎛1 − T ⎟⎞⋅100%
⎝ S T* ⎠ (6)
5. Results and discussion
The eco-efficiency assessment performed in this study is composed
of four steps. First, we simulated the processes in order to obtain the
required calculation parameters. Subsequently, on the basis of the si-
mulation results, we evaluated different heat integration configurations
for both technologies. We then calculated the indicators according to
the methodologies described in Section 3. The same procedure was
applied to all designs since they all have similar raw materials and
product conditions (i.e. flow rates, composition, temperature and
pressure). The values were then normalized so we could compare the
four technologies in terms of their eco-efficiencies.
5.1. Environmental indicators
The RMc, Fc, Ec and CDe indicators were directly calculated on the
basis of the simulation results. The Wc and WWg indicators, in turn,
were determined with the aid of the supplementary simulation of the
utility plant. Fig. 9 shows the contributions of all equipment to both
energy and water consumption regarding the CP and RD original
schemes, while Table 8 discloses the indicator results for all config-
urations.
Attention should be drawn to the decrease in the cooling water
supply to the processes (v̇cws ). The heat integration in the conventional
process resulted in decreases of about 37% and 57% for the C1-C3 and
C2-C3 designs, respectively. In the RD process, decreases of 22% and
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Chemical Engineering & Processing: Process Intensification 135 (2019) 93–107
31% were achieved for the C1-C3 and C2-C3 configurations, respec-
tively. Since the recirculating cooling water flow rate is much higher
than the other utility plant variables, loss variables that depend on it
(e.g. v̇cwp , v̇cwe and v̇cwb ) will also be high, thus resulting in large cooling
water make-up requirement and wastewater discharge.
Table 9 shows the results for the environmental indicators calcu-
lated with the formulae from Table 2. With the exception of the raw
material consumption – which is the same for all processes since they
produce the same amount of product by the same amount of feedstock
–, we verify that the integrated technologies have lower indicator va-
lues than their respective original processes. This mainly relates to the
lower energy requirements due to thermal integration, which reduces
significantly the utility demand. The decrease in the utility demand in
the conventional process is more expressive than on the reactive tech-
nology. In fact, the conventional C1-C3 design consumes 30% and 34%
less energy and water, respectively, than the original process. For the
conventional C2-C3 configuration, such values are 28% and 56%, re-
spectively. With regard to the RD technology, the C1-C3 arrangement
consumes 19% and 22% less energy and water, respectively, while
these values are 24% and 30%, respectively, for the C2-C3 design.
5.2. Economic indicators
The economics of the butyl acetate production technologies were
estimated by taking into consideration the assumptions disclosed in
Section 3.2. Fig. 9 gives the contributions of all equipment to the overall
production costs for the CP and RD original schemes. The conventional
process presents a CAPEX of $6,628,100 and a TPC of $4,925,800. The
heat-integrated CP with C1-C3 configuration has a CAPEX of
$6,767,200 and a TPC of $4,088,800, while for the integrated CP with
C2-C3 configuration such values are $6,835,300 and $4,501,300, re-
spectively. For the RD technology, a CAPEX of $5,295,700 and a TPC of
$3,818,600 were estimated. For the heat-integrated RD with C1-C3
design, such values are $5,533,100 and $3,615,100, respectively,
whereas the integrated RD with C2-C3 design presents a CAPEX of
$5,625,300 and a TPC of $3,573,500. The capital costs calculated in
this paper differ from Luyben et al. [14]’s results since we not only used
a different economic basis but also considered updated values of cur-
rencies and prices. Table 10 summarizes the resulting cost of all
equipment for all configurations, including utility plant data. We note
that, although the integrated schemes have lower utility plant costs
than their respective original designs’ – which is due to their lower
energy and water requirements that render utility equipment smaller –,
their CAPEX is higher since the reboilers were re-designed and extra
heat exchangers were installed.
With regard to production expenses, the thermally integrated con-
figurations present lower costs when compared to their original designs
due mostly to the decrease in the water and energy requirements. Such
interpretation is evidenced by the results for the economic indicators
shown in Table 11.
The SRMc is approximately the same for the four processes since
they all have similar flow rates of both raw materials and products.
Nevertheless, the intensified heat-integrated configurations have lower
SEc, SWc and LWCF due to the decrease in the utility demand, which
can be inferred from the lower production costs associated with them.
As previously stated, the authors did not consider higher operating
pressures for C3 since its reboiler would require more expensive,
higher-pressure steam. Nevertheless, since in this work steam is pro-
vided by a utility plant instead of an external source, the specific energy
and water expenses are lower when high-pressure C3 is integrated to C1
in the conventional process and to C2 in the reactive distillation tech-
nology. The YF indicator, in turn, is noticeably lower for the reactive
distillation designs, which suggests they have higher reaction yields.
Such result is in accordance with Jiménez and Costa-López [8]’s
statement that applying reactive distillation for producing BuAc is quite
advantageous not only due to its lower costs but also in terms of
P.V. Mangili, D.M. Prata
overcoming both the unfavorable equilibrium and azeotropes forma-
tion.
5.3. Safety indicators
The calculation of safety indicators is based on the process operating
conditions and considering possible incidents related to chemical re-
lease to the environment. They are determined by gathering the phy-
sicochemical properties, hazard values and classification codes of po-
tentially hazardous substances [40]. Hence, since all designs studied in
this paper have similar process conditions and comprise essentially the
same substances, the safety indicators should also be similar to one
another, as presented in Table 12.
Ruiz-Mercado et al. [37] stated that the best case for the SHFE in-
dicator corresponds to a value of 0 GJ/kg, while the worst scenario
should consider that all process substances release their entire heat of
combustion (0.05 GJ/kg for the processes evaluated here). The CEI, in
turn, varies from 0, when no significant risk of acutely affecting people
due to chemical release is present, to 1000, when such risk is singularly
substantial, thus requiring further hazard assessment. For the CTF in-
dicator, the best and worst values are 0 and 107 m3/kg, respectively. In
this regard, we can infer that the butyl acetate processes are fairly non-
hazardous.
5.4. Eco-efficiency comparison
Since single metrics are not sufficient to establish a well-founded
comparison, a joint evaluation of the indicators was required. In ac-
cordance with Pereira et al. [39], Mangili et al. [18] and Junqueira
et al. [19]’s works, the indicators were grouped into their respective
categories and subsequently divided by the highest value in that group,
as disclosed in Table 13.
As previously discussed, the ECI method arranges the indicators in a
“the lower - the better” ranking that varies from 0, best case, to 1, worst
case. However, even if most indicator values of a process are 1, it
cannot be necessarily considered as having the lowest environmental
performance. In order to assert which design is more sustainable, the
normalized indicators are plotted in a radar chart, as illustrated in
Fig. 10, and the area of the shapes representing the respective processes
are calculated through Eq. (5). The eco-efficiencies were then de-
termined through Eq. (6). It is worth mentioning that the same weight
was assumed for all categories and that the areas illustrated in the said
figure are given in order to simply provide a convenient, qualitative
analysis of the impact of each indicator on the sustainability assess-
ment.
The conventional technology is clearly the least environmentally
efficient process since all of its normalized indicators are 1. Relatively,
its integrated configurations resulted in higher performances, being the
C1-C3 and C2-C3 designs 30% and 31% more eco-efficient, respec-
tively. Hence, C3′s condenser is recommended to be thermally in-
tegrated with thermally integrating C2′s reboiler in the conventional
process, although integrating the former with C1′s reboiler would not
markedly affect the process performance. Therefore, increasing C3′s
pressure is not advantageous, since another integration arrangement is
feasible.
The reactive distillation technology, in turn, is evidently much more
eco-efficient than the conventional route (53%), which is especially due
to the lower energy and water requirements, as well as to the higher
reaction yield. The RD integrated designs have even higher environ-
mental performances, being the C1-C3 and C2-C3 configurations 58%
and 62%, respectively, more eco-efficient than the conventional pro-
cess. In this case, increasing C3′s pressure may also not be advantageous
since it may require a more complex control structure. A more detailed
study comparing the plantwide control system of the integrated pro-
cesses may be carried out in order to evaluate whether operating C3 at a
higher pressure is feasible.
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Chemical Engineering & Processing: Process Intensification 135 (2019) 93–107
5.5. Proposed flowsheets
From our results, we verified that both conventional and reactive
distillation processes can be heat-integrated in order to improve their
respective sustainable performances. Although different configurations
were obtained for each technology, we note that integrating C2 and C3
correspond to the best strategy in either scenario. Figs. 11 and 12 give
the flowsheets of the proposed intensified CP and RD schemes, in which
the intensification is highlighted in red.
Applying the same ECI procedure considering only the best alter-
natives for the conventional and reactive distillation processes, we note
that the proposed RD configuration is approximately 49% more sus-
tainable than the proposed CP alternative. This evidences the sig-
nificance of process intensification (reactive distillation) for improving
the performance of chemical processes. Fig. 13 shows the radar chart
for the intensified technologies.
6. Conclusions
This study compared four butyl acetate production processes with
regard to their sustainability performance. The analysis was performed
by means of the Eco-efficiency Comparison Index method on the basis
of six ecological indicators, five economic indicators and three safety
indicators. The comparison demonstrated that by thermally integrating
the original technologies we could improve the processes’ sustainability
due principally to the reduction of their water and energy requirements.
The reactive distillation process showed to be 53% more eco-efficient
than the conventional technology, which is mainly due not only to the
above-stated reasons but also to the higher reaction yields. The heat-
integrated RD configurations proved to have even higher environ-
mental performances, being the C1-C3 and C2-C3 configurations 58%
and 62%, respectively, more eco-efficient than the conventional pro-
cess. Nevertheless, since both integrated arrangements have nearly the
same performances, a more detailed study regarding their plantwide
control structure may be performed in order to analyze the feasibility of
operating C3 at a higher pressure.
Moreover, based on our results, the new flowsheets corresponding
to the intensified CP and RD configurations were proposed. It was then
determined that the latter is approximately 49% more sustainable than
the former, which is due to the intensification performed by a reactive
distillation scheme. Further improvements on this evaluation can be
achieved by a multiobjective optimization analysis considering the in-
tensified sections and a controllability assessment. Although process
control is beyond the scope of this study, it is expected that the pro-
posed configurations will prove to have suitable operability since the
operating conditions do not differ significantly from Luyben et al. [14]’s
original design.
It is also worth noting that, as stated earlier, the eco-efficiency
comparison methodology presented in this paper assumes that all me-
trics have the same weight. The ECI approach relies on a relative as-
sessment in which the indicators are linearly related to their normalized
values. Therefore, assigning weights to said metrics would change their
individual values, but would not change the end results. Although such
a limitation does not represent an obstacle to providing an overall as-
sessment of the sustainability of industrial processes, as intended by the
present study, future works should aim at developing new strategies for
allocating weights to the evaluation metrics. In fact, weighting ap-
proaches may affect process optimization techniques since decision
variables could present multiple different relevances depending on the
practitioner’s criteria.
Acknowledgements
This study was financed in part by the Coordenação de
Aperfeiçoamento de Pessoal de Nível Superior - Brasil (CAPES) -
Finance Code 001.
P.V. Mangili, D.M. Prata
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