Chemical Engineering Research and Design 185 (2022) 130–145

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Chemical Engineering Research and Design

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Alternative distillation configurations for

bioethanol purification: Simulation, optimization
]]
]]]]]]
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and techno-economic assessment

Mágda Correia Santos a,b, Daniel Fernandes Costa c,
Allan Almeida Albuquerque b,d, João Inácio Soletti b,
⁎
Simoni Margareti Plentz Meneghetti a,
a
Group of Catalysis and Chemical Reactivity (GCAR), Institute of Chemistry and Biotechnology, Federal University
of Alagoas, Maceió, Alagoas 57072-970, Brazil
b
Laboratory of Separation Systems and Process Optimization (LASSOP), Technology Center, Federal University of
Alagoas, Maceió, Alagoas 57072-970, Brazil
c
Usina Coruripe, Coruripe, Alagoas, Brazil
d
Experimental Biorefinery of Organic Solid Waste (BERSO), Department of Nuclear Energy, Federal University of
Pernambuco (UFPE), Recife, PE, Brazil

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

Article history: Considering the economic and environmental importance of bioethanol fuel, this research
Received 21 April 2022 evaluated the energetic, economic, qualitative and environmental aspects of the con­
Received in revised form 15 June ventional purification system and also of two alternatives aimed at eliminating secondary
2022 flows and reducing costs associated with utilities and operation. Using the Aspen Plus
Accepted 22 June 2022 software with the insertion of a relevant number of components of the industrial process,
Available online 27 June 2022 the purification of hydrated bioethanol was investigated, optimizing the specifications of
the distillation set. The conventional process (C), composed of columns A and B and
Keywords: condensers RR1 and EE1E2, is subdivided into sections AA1D and BB1, respectively. In
Bioethanol turn, the alternative systems (I & II) are similar to process C but without section D of
Distillation column column A; in the first system without the condensers R and the second including R1.
Optimization These processes were satisfactorily developed and in compliance with the quality stan­
Simulation dards of specific Brazilian legislation. From the energy, economic and environmental
Techno-economic assessment point of view, the alternative processes lead to better results than the conventional
system, especially alternative I, which provided reductions of 11.5 %, 6 % and 7.5 % in

Abbreviations: A, section responsible for the depletion of the wine; A1, section promoting wine heating; ANP, Brazilian National
Agency of Petroleum, Natural Gas and Biofuels; B, section responsible for the concentration and purification of bioethanol; B1, section
responsible for the depletion of phlegm; Column A AA1D, first column of the process, composed of sections A, A1 and D; Column B,
second column of the process, composed of sections B and B1; D, purifying section of column A, responsible for the concentration and
removal of contaminating components in the process.; E, primary condenser that uses the wine flow for cooling in column B; E1,
secondary condenser that uses water for cooling in column B; E2, auxiliary condenser that uses water for cooling in column B; EPA,
United States Environment Protection Agency; Flegmass, bottom by-product from column B; Fusel oil, stream composed of congeners
mainly higher alcohols; Heat exchanger K, promotes wine heating and vinasse cooling; HOC, Hayden-O`Connell; Hydrated bioethanol,
top product from column B; J, chiller; k$, thousand dollars; Liquid phlegm, secondary product of column A; MM$, million dollars; NRTL,
Non-Random Two-Liquid; Process A1, alternative process I composed of columns A (sections AA1) and B (sections BB1), plus the
condensers EE1E2, only.; Process A2, alternative process II composed of columns A (sections AA1) and B (sections BB1), plus the con­
densers RR1 and EE1E2, respectively.; Process C, conventional process consisting of columns A (sections AA1D) and B (sections BB1), plus
the condensers RR1 and EE1E2, respectively.; R, column A main condenser; R1, column A auxiliary condenser; Second-grade bioethanol,
top by-product from column A; Vapor phlegm, main product of column A; Vinasse, bottom by-product from column A; VLE, vapor-liquid
equilibrium; Wine, fermented sugarcane liquor
⁎
Corresponding author.
E-mail addresses: [email protected] (M.C. Santos), [email protected] (S.M.P. Meneghetti).
https://doi.org/10.1016/j.cherd.2022.06.036
0263-8762/© 2022 Institution of Chemical Engineers. Published by Elsevier Ltd. All rights reserved.
 Chemical Engineering Research and Design 185 (2022) 130–145 131

terms of steam consumption, operating costs and CO2 emissions, respectively. Although
the application of the conventional process can be used to comply with the biofuel
standard, simplified industrial plants, such as those proposed in the alternative processes,
are sufficient and their use should be encouraged to extend the application to more types
of products.
© 2022 Institution of Chemical Engineers. Published by Elsevier Ltd. All rights reserved.

operational conditions of industrial units, and a better un­

1. Introduction
derstanding of the thermodynamic behavior is required to
improve the production (Albarelli et al., 2014; Batista et al.,
The production of biofuels from renewable sources, such as
2012; Bessa et al., 2012; Ferreira et al., 2013; Tgarguifa et al.,
biomass, minimizes carbon emissions, the effects of global
2017). Of the congeners listed in Table 2, for instance, only
warming and the generation of polluted air, constituting the
methanol and acetic acid have limits for hydrated bioethanol
main alternative to the use of fossil sources, which could
fuel defined by current Brazilian legislation (ANP, 2015).
become scarce in the next five decades (Issa et al., 2019).
However, acetaldehyde requires the most attention, since
Currently, the USA leads the world production and export of
oxidation can produce acetic acid during product storage.
bioethanol, produced mainly from corn. In Brazil, sugarcane
According to Shuqing et al. (1992), Zhang et al. (2018) and Han
became the predominant raw material for the production of
et al. (2019), the oxygen content and temperature are the
biofuels in around 1970, with the aim of partially or fully
main factors associated with the oxidation of acetaldehyde
replacing the use of fossil fuels (Morganti et al., 2018; Puga
in the presence of air, which, together with the bioethanol
and Castro, 2018). Although this country has the second
storage time and conditions, makes the estimation of the
largest production of bioethanol in the world, it is considered
acetic acidity a complex task. Batista and Meirelles (2009)
to be the most evolved in terms of biofuel production tech­
simulated industrial forms to control the acetaldehyde con­
nology and use, and sugarcane has a more favorable energy
tent in hydrated bioethanol, assuming complete conversion
balance than corn (Baeyens et al., 2015; Manochio et al., 2017;
to acetic acid. They noted that pasteurized bioethanol must
OECD/FAO, 2020).
be produced by the conventional process to obtain the wine
Bioethanol produced in Brazil can basically be hydrated or
concentration shown in Table 2.
anhydrous. The former is used directly as biofuel and less
Aiming to represent the industrial operating conditions,
pollutants, such as nitrogen oxides and carbon monoxide,
an ethanolic wine containing 12 components (Table 2), as
are emitted into the environment, allowing CO2 emissions to
previously defined by Batista et al. (2012), was used in this
be reduced by more than 60 % when compared to the use of
study. The cited authors obtained data on the congeners in
gasoline (Balat and Balat, 2009; Manochio et al., 2017; Sydney
samples collected from a Brazilian industrial unit by gas
et al., 2019). Anhydrous bioethanol is added to gasoline (up to
chromatography. The non-random two-liquid (NRTL) model
27 %), increasing the oxygen concentration and consequently
was used due to the presence of strong polar compounds in
improving the oxidation of hydrocarbons and engine effi­
the bioethanol purification process carried out at low pres­
ciency (ANP, 2015; OECD/FAO, 2020).
sures. In addition, the Hayden-O'Connell model was em­
In distilleries, after the fermentation stage, the purifica­
ployed to calculate the fugacity coefficient for the vapor
tion of bioethanol is based on the conventional system, with
phase, since carboxylic acid group association or solvation
the use of distillation columns, which efficiently separate the
effects cannot be neglected in the presence of short fatty
non-ideal ethanol-water mixture, removing undesirable ele­
acids, such as acetic acid (Hayden and O’Connell, 1975).
ments to meet current quality specifications. Hydrated
These models were also considered in simulations carried
bioethanol has an azeotropic limit, in mass concentration,
out by Albarelli et al. (2014), Batista et al. (2012), Bessa et al.
close to 95.6 % ethanol and 4.4 % water (Abdollahipoor et al.,
(2013), Dias et al. (2011), Junqueira et al. (2009), Marquini et al.
2018; Barreto and Coelho, 2015; Tututi-Avila et al., 2017). In
(2007) and Souza et al. (2016).
this context, the quality of bioethanol to be used as a fuel in
A vast academic literature has been published on some
Brazil is controlled by the National Agency of Petroleum,
aspects of industrial processes for the purification of bioe­
Natural Gas and Biofuels (ANP), which provides specifica­
thanol fuel. Marquini et al. (2007) and Valderrama et al.
tions for hydrated and anhydrous bioethanol, as shown in
(2012), for example, performed simulation with different
Table 1 (ANP, 2015). Other types of bioethanol are given as
thermodynamic models and proposed the most appropriate.
Copersucar industrial (H1) and neutral (HN) forms
Batista et al. (2012) determined and used a relevant quantity
(Copersucar, 2022). HN bioethanol is purer than H1, since it is
of components of a fermented liquor (wine) obtained from
used to obtain products destined for human consumption.
sugarcane, identifying their importance regarding the pro­
However, both have low levels of congeners when compared
duction characteristics and quality of the product. Other
to bioethanol used as a fuel.
studies that have contributed to a better understanding and
Although bioethanol distillation has been extensively in­
improvement of this process include Bessa et al. (2012), who
vestigated in the literature, the effects of contaminants
analyzed the energy integration of the columns and obtained
(congeners) in this process are, mainly, reported in studies
a reduction in the consumption of steam, and Matugi et al.
related to alcoholic beverages (Batista et al., 2013; Esteban-
(2018), who evaluated the most important influencing con­
Decloux et al., 2014; Valderrama et al., 2012). However, con­
geners in the production process. However, despite these
geners also play a key role in the process performance in
rigorous studies, simplifications were adopted for the
biofuel production, since they can negatively affect the
132 Chemical Engineering Research and Design 185 (2022) 130–145

Table 1 – Quality specifications of Brazilian bioethanol.

Characteristics Unit Limit Fuel bioethanola Copersucar standard bioethanolb

Hydrated Anhydrous H1 HN

Ethanol grade wt. % Min. 92.5–94.6 99.3 92.8 94.0

Density (at 20ºC) kg/m³ – 805.2 – 811.2 ≤ 791.5 – –
Acetic acid mg/L Max. 30 30 20 10
Conductivity (at 25ºC) µS/m Max. 300 300 500 50
pH – – 6.0 – 8.0 – 6.0 – 8.0 6.0 – 8.0
Chloride mg/kg Max. 1 1 – –
Sulfate mg/kg Max. 4 4 4 0.2
Fe mg/kg Max. 5 5 5 5
Na mg/kg Max. 2 2 2 2
Copper mg/kg Max. 0.07 0.07 – –
Methanol % Max. 0.5 0.5 - -
mg/L Max. - - 40 5
Acetaldehyde mg/L Max. – – 50 5
Ethyl acetate mg/L Max. – – 120 5
Acetone mg/L Max. – – – 1
Isopropanol mg/L Max. – – 20 2
n-Propanol mg/L Max. – – 180 8
n-Butanol mg/L Max. – – 10 0.5
Isobutanol mg/L Max. – – 120 2
Acetal mg/L Max. – – – 5
Isoamyl alcohol mg/L Max. – – 200 3
Higher alcohols mg/L Max. – – 400 15
a
ANP (2015).
b
Copersucar (2022).

Table 2 – Main components found in industrial fermented liquor (wine) obtained from sugarcane.
Component Molecular formulaa Tboiling (1 atm) (ºC)a Pvapor, 100ºC (mmHg)a Industrial wineb

Water H2O 100.0 760 0.935

Ethanol C2H6O 78.4 1694 0.0642
Methanol CH4O 64.7 2610 1.63 × 10-5
Isopropanol C3H8O 82.5 1482 1.00 × 10-6
Propanol C3H8O 97.8 846 5.737 × 10-5
Isobutanol C4H10O 108.0 565 4.748 × 10-5
Isoamyl alcohol C5H12O 130.6 237 0.0001712
Ethyl acetate C4H8O2 77.1 1533 1.877 × 10-5
Acetaldehyde C2H4O 20.2 7047 1.09 × 10-5
Acetone C3H6O 56.5 2806 1.00 × 10-5
n-Butanol C4H10O 117.5 389 1.00 × 10-6
Acetic acid C2H4O2 118.1 427 0.0004351
a
Green and Southard (2018).
b
Batista et al. (2012).

simulation of the hydrated bioethanol purification process and without simplification of the columns are scarce in the
for convergence purposes. literature. Moreover, no simulation studies with energetic,
However, this practice is not recommended in the simu­ economic, environmental and qualitative evaluations could
lation of the process applied for the purification of bioethanol be found in the literature, These evaluations cover the effects
fuel, since the industrial operating conditions (Fig. 1) are not of (i) acetaldehyde oxidation and (ii) alternative processes for
adopted, with the use of a single column to represent the the purification of bioethanol fuel based on common in­
three sections (AA1D) of the distillation column A or the re­ dustrial practices of removing section D and/or condensers
moval of section D and the phlegm vapor stream is fed from from column A.
section A at the top of section A1. In the first situation, it is Therefore, the conventional bioethanol fuel purification
important to note that section D does not have direct contact process was simulated and optimized without simplifica­
with section A1 and steam flows through an adjacent pipe­ tions based on a fractional factorial design (FFD) and a cen­
line and the base current of section D is the net phlegm, tral composite design (CCD) considering ten and three input
which is forwarded to column B. Also, a change in the point variables, respectively. In relation to the optimal design, two
of withdrawal of the main product from column A modifies alternative configurations, processes A1 and A2, were also
the composition and concentration of the components in this simulated based on the removal of section D from column A
stream. without and with the condensers R and R1, respectively. The
In this context, rigorous simulation studies of the bioe­ aims of these processes were to increase the productivity,
thanol fuel purification process considering industrial data based on eliminating the flow of second-grade bioethanol,
 Chemical Engineering Research and Design 185 (2022) 130–145 133

Fig. 1 – Conventional process (Batista et al., 2012; Santos et al., 2020; Zarpelon, 2020).

and to decrease the utility and operating costs, following the liquid and vapor streams sent to the rectification column
common industrial practices. Finally, the three configura­ are removed at the bottom and top of sections D and A, re­
tions were evaluated and compared in terms of energy con­ spectively (Albarelli et al., 2014; Barreto and Coelho, 2015;
sumption, product quality and economic and environmental Batista et al., 2013; Junqueira et al., 2009; Nadaleti et al., 2020).
aspects. In the rectifying column, section B1 is responsible for the
depletion of phlegm. Thus, the vapor phlegm stream (almost
2. Materials and methods free of bioethanol) is removed, with a tolerable ethanolic
concentration similar to that of the vinasse. Section B, in
2.1. Description of processes for bioethanol fuel turn, has the function of purifying bioethanol with the help
purification of condensers, which also maintain the reflux of the column.
The heat exchangers E1 and E2 use water for cooling, which
2.1.1. Conventional process is already in condenser E, and normally the wine flow is used,
The production of hydrated bioethanol by the conventional which is preheated and later, based on the integration of
process, referred to herein as process C, is basically com­ additional heat practiced in the distilleries, using heat ex­
prised of two distillation columns, as shown in Fig. 1. The changer K, the wine is heated to a final temperature of 94 °C
initial stage of the process consists of a column divided into and then the flow of vinasse in section A is cooled, opti­
sections A, A1 and D, plus condensers R and R1. The next mizing the consumption of energy (Albarelli et al., 2014;
phase takes place in the rectification column, divided into Barreto and Coelho, 2015; Bessa et al., 2013; Kumar
sections B1 and B, including condensers E, E1 and E2. At the et al., 2010).
bottom of the columns, the heat necessary for distillation is In section B, a stream of fusel oil is also removed to aid in
provided indirectly (reboiler), and at the top the condensers the purity of the product. This fusel flow is composed of
are responsible for the condensation of the light vapors and congeners, mainly isoamyl alcohol, propanol and isobutanol.
purification of the products (Barreto and Coelho, 2015; Dias Hydrated bioethanol fuel is normally removed between
et al., 2011; Silva et al., 2017). stages 2 and 5 at the top of the rectification column, so that it
Section A is responsible for the depletion of the wine. The meets the quality requirements of the Brazilian National
main product is the vapor phlegm, with an ethanolic con­ Agency of Petroleum, Natural Gas and Biofuels (ANP), es­
centration between 30 % and 60 % (v/v). Vinasse is purchased tablished as an ethanol concentration of 92.5–94.6 wt. %
as a by-product, with an ethanol content of up to 0.03 % (v/v) (ANP, 2015; Batista and Meirelles, 2011; Ferreira et al., 2013;
being industrially tolerated. Section A1 has the function of Matugi et al., 2018).
heating the wine and consequently separating the most vo­
latile components and sending them to Section D for con­ 2.1.2. Alternative process I
densation in condensers R and R1. Here, reflux and product Alternative process I, referred to as process A1, describes a
currents of the so-called second-grade bioethanol are gen­ common practice in Brazilian distilleries, which consists of
erated, with a concentration of around 90 wt. %. Meanwhile, disconnecting section D as well as condensers R and R1 in
134 Chemical Engineering Research and Design 185 (2022) 130–145

Fig. 2 – Alternative I process (Batista and Meirelles, 2009; Santos et al., 2020; Zarpelon, 2020).

column A. As a result, the flows of liquid phlegm and second- such as values for temperature, pressure, flow rate, com­
grade bioethanol plus the purification by degassing in position, efficiency, percentage of loss and reflux ratio.
column A are not considered in this process. This condition Moreover, the industrial operating conditions were fol­
is favored mainly due to the low quality requirements of lowed, such as an average concentration of ethanol in the
hydrated fuel bioethanol. However, an increase in the con­ wine of 8 % (v/v) and a mass flow rate of the wine feed of
taminants in the bioethanol fuel and the potential for che­ 180 t/h. An exception was related to the steam supply of
mical degradation during storage may increase the acetic columns A and B, where reboilers were considered instead
acidity (Batista et al., 2012; Batista and Meirelles, 2011; of a direct injection of steam, as proposed by Batista et al.
Esteban-Decloux et al., 2014). Aware of this industrial oper­ (2012), Bessa et al. (2012) and Esteban-Decloux et al. (2014).
ating condition, and due to the absence of studies on this Although the use of reboilers is less common in the in­
configuration, process A1 was simulated omitting section D dustrial process of hydrated bioethanol purification, less
and the condensers of the first column (Fig. 2), while main­ human interference is involved in Aspen simulations,
taining the other steps found in process C. providing more representative results. The following con­
straints were also considered in the process simulation:
2.1.3. Alternative process II ethanol losses equal to or less than 0.02 wt. % for the by-
The configuration of alternative process II, referred to as products (vinasse and flegmass); maximum theoretical
process A2, is a modified version of that described for process value for the mass percentage of bioethanol in the vapor
A1, including the condensers, where alcoholic vapors from phlegm of 38 %; mass ratio of second-grade bioethanol to
section A1 are directly fed to condenser R, and degassing is hydrated bioethanol less than 5 %; and purity of the hy­
applied for additional purification. As in process A1, second- drated bioethanol of 94.2 wt. %.
grade bioethanol is not produced, in order to avoid possible Although the process simulation of distillation columns
bioethanol losses, as found in process C. As a consequence, for bioethanol purification has been extensively studied, it
vapor recycling in the heat exchanger is proposed in process remains a complex task, and the configurations are com­
A2, constituting the liquid phlegm to be fed to the rectifica­ monly simplified to improve convergence. In contrast, the
tion column B (Fig. 3). The other steps are maintained as in first distillation column is composed of sections A, A1 and D
process C. with liquid and vapor streams moving directly between the
first two sections. However, only the vapor stream moves
2.2. Industrial operating conditions and model validation among sections A1 and D, so that section D must be simu­
lated using a separate RADFRAC block. After this top section,
To ensure more reliable results, a validation of the simu­ condenser R is responsible for the reflux of the liquid in
lations was carried out based on an industrial unit located section D, while condenser R1 aids the degassing and con­
in Coruripe, Alagoas, Brazil. In this case, process data as­ densation of excess alcohol vapors coming from condenser
sociated with the conventional process of bioethanol fuel R. As a consequence, second-grade bioethanol is obtained as
purification were adopted to validate Aspen simulations, a by-product.
 Chemical Engineering Research and Design 185 (2022) 130–145 135

Fig. 3 – Alternative II process (Batista et al., 2012; Marquini et al., 2007; Santos et al., 2020; Zarpelon, 2020).

On the other hand, there is direct contact between the Statistical calculations were performed using the software
liquid and vapor streams from sections B1 and B, and thus STATISTICA® (Version 10.0, by StatSoft Inc., Tulsa, USA).
the rectification column can be represented as a single
RADFRAC block. Moreover, hydrated bioethanol must be re­ 2.4. Process simulation
moved between stages 2 and 5, and at least two condensers
need to be considered in the simulation in order to represent Simulations of the three processes were carried out using the
the industrial operating conditions. Aspen Plus software based on the schemes shown in
Figs. 1–3. For the three processes, the industrial wine stream
2.3. Fractional factorial design and optimization by was fed at the top (stage 7) of section A1 with a flow rate of
central composite rotational design 180,000 kg/h, temperature of 94 ºC and the composition given
in Table 2. The vinasse stream (by-product) was removed at
The simulation of process C was initially performed in the the bottom of section A, where the saturated steam was also
Aspen Plus software using an experimental design, taking injected at a pressure of 1.5 bar. Moreover, the vapor phlegm
into account the effects of the main variables. These vari­ stream was obtained at the top of the section A with a flow
ables and their levels were chosen based on industrial rate of 27,000 kg/h and fed to the bottom of section B. The
knowledge and recommendations in the literature. In this following were also defined: ethanol losses in the vinasse
case, a 210
III
6
fractional factorial design (FFD) was defined in­ and flegmass streams (EL) equal to or less than 0.02 wt. %,
cluding ten important input variables for process C of hy­ mass purity of hydrated bioethanol (BP) of 94.2 wt. %, fusel oil
drated bioethanol purification, as shown in Table 3. The removal in the side stage 41, and fusel oil mass flow rate
mass purity of hydrated bioethanol (BP), bioethanol recovery (FOF) of 300 kg/h. These last four variables were optimized as
(BR), steam consumption (SC) and ethanol loss (EL) in the described for the CCRD study.
vinasse and flegmass streams were the responses in­ For the conventional and alternative II processes, the
vestigated. Unpasteurized bioethanol was removed as a side vapor mass flow rate adopted was 3,000 kg/h from section A1
stream in section B of the rectification column, in order to to section D for process C or to condenser R for process A2.
improve the convergence of the simulations. All other con­ Moreover, the liquid phlegm stream was obtained in section
figurations were kept as previously defined. The fusel oil D and the condensers, respectively, and fed five stages above
removal stage (FOS) was located between the feeds of the the vapor phlegm feed stage in section B. With regard to
liquid and vapor phlegm, which are separated by five stages. section A, the saturated steam was injected at the bottom of
Based on the results, an optimization study was carried section B1 with a pressure of 1.5 bar and the flegmass was
out applying a central composite rotational design (CCRD) 23, also removed. The hydrated bioethanol was produced at
for the three most significant effects identified in the FFD stage 4 of column B (top to bottom) and the fusel oil was
using normal probability plots. Axial points were defined for obtained at an intermediate stage between the feed stages of
the effects involved in the CCRD. The main conditions for the the liquid and vapor phlegm streams.
maximization of BP and BR, as well as minimization of SC For the simulation of process A1 (Fig. 2), the concept
and EL, were then investigated. Lastly, the empirical models commonly adopted in industrial bioethanol plants was con­
were fitted and surface responses were analyzed, and the sidered, which consists of blocking the passage of alcohol
optimal conditions were found based on a multivariate and vapors from sections A1 to D. For this reason, column A was
multi-response methodology using the desirability function. composed only of the sections A and A1, without condensers,
136 Chemical Engineering Research and Design 185 (2022) 130–145

Table 3 – Levels of independent variables for fractional planning 210

III
6
and rotational central composite 23 .
Independent variable Tag Level

-α* -1 0 +1 +α*

Number of stages in section A NSA 16 18 20

Number of stages in section A1 NSA1 4 6 8
Number of stages in section D NSD 4 6 8
Reflux ratio of section D RRD 20 20(25) 30 40(35) 40
Number of stages in section B1 NSB1 8 13 18
Number of stages in section B NSB 38 43 48
Reflux ratio of section B RRB 4 4(5) 6 8(7) 8
Fusel oil mass flow rate (kg/h) FOF 200 250 300
Fusel oil removal stage FOS 2 3 4
Bioethanol mass flow rate (kg/h) BFR 11,600 11,000(11,750) 11,600(11,900) 12,200(12,050) 12,200
*
Axial value α = 1.68 of the central composite rotational design (CCRD). Data in parenthesis represent conditions for the CCRD.

keeping the other conditions the same as those in process C. the CO2 emissions, applying a method proposed by the
As a result, liquid phlegm was not obtained in column A and United States Environmental Protection Agency (EPA). An
only the vapor phlegm stream was fed to column B. operation factor of 8,766 h per year and a carbon tax of $15/
For process A2 (Fig. 3), a configuration similar to that of ton was adopted, in order to assess the most economical and
process A1 was simulated in the Aspen Plus software, eco-friendly conditions (Agência de Proteção Ambiental -
maintaining the major conditions from process C. However, EPA, 2021; Albuquerque et al., 2020).
the supply of alcohol vapors was allowed, moving them from
section A1 to condenser R with total condensation and ob­
taining the liquid phlegm stream to be fed into the rectifi­
3. Results and discussion
cation column. Moreover, the degassing of non-condensable
gases was carried out in condenser R and thus second-grade
3.1. Validation of the simulations
bioethanol was not obtained.
The conventional process, applying the industrial operating
conditions detailed in Section 2.2, was simulated according
2.5. Technical, energy and economic assessment to the scheme shown in Fig. 4, with the insertion of all sec­
tions and flows of the columns that make up the distillation
Three process configurations for hydrated bioethanol fuel set, observing its characteristics.
purification were investigated in order to achieve the tech­ Fig. 5 shows the temperature profiles for (a) columns A
nical standard defined by the National Agency of Petroleum, and (b) B, as well as the liquid and vapor composition profiles
Natural Gas and Biofuels (ANP), as presented in Table 1 (ANP, for columns A (c, e) and B (d, f). According to the results re­
2015). Conventional and alternative configurations were si­ ported in Fig. 5a, c and e for column A, section D is given by
mulated according to the descriptions and conditions found stages 1–6, section A1 by stages 7–14 and section A by stages
in Sections 2.1 and 2.4, respectively. The technical feasibility 15–32, responsible for the wine depletion. In contrast, for the
of the processes was also evaluated based on the develop­ rectification column, section B is given by stages 1–43 and
ment of acetaldehyde oxidation, in order to investigate the section B1 by stages 44–56. The simulated temperature and
effects of acetaldehyde decomposition on the stored biofuel composition profiles showed satisfactory agreement with the
(Batista and Meirelles, 2009; Shuqing et al., 1992). samples collected at the industrial unit for columns A and B,
The three processes were also assessed and compared corroborating the function of each section for the process
based on the energy requirements associated with steam, investigated.
water and electricity. In addition, the steam consumption per In Fig. 5a, sections A and A1 show some stages with dif­
liter of bioethanol produced was analyzed, since it is the ferent temperatures and this may be associated with varia­
most relevant energy indicator for the purification process tions in the in loco measurements (PT-100 temperature sensor
(Barreto and Coelho, 2015; Zarpelon, 2020). Moreover, for the or pyrometer) and, more importantly, operational factors
most favorable energetic system, a simulation of the electric such as production control and maintenance of the column
power generation for a distillery was carried out. An eco­ stages, that require rigorous attention due to the incrusta­
nomic assessment was also carried out activating the Aspen tions caused by the wine. In the case of the temperature
Process Economic Analyzer tool in the simulation flowsheets profile of column B (Fig. 5b), the simulated and experimental
(Dimian, 2003; Luyben, 2013). In this step, the sizes and de­ points are clearly in agreement. It is worth noting that the
sign parameters for each process configuration were kept product withdrawal temperature in stage 4 is higher than at
fixed at the same values, in order to investigate the effects on the top of column B, characterizing pasteurized hydrated
the operation costs. In this case, an industrial plant that is bioethanol.
already constructed was considered, aiming to reduce the The graphs for the liquid composition in Fig. 5c and d
costs and increase the profits involved in hydrated bioe­ show that the results for the sampled points are in agree­
thanol fuel production. ment with simulated values for the components ethanol and
The processes were compared based on the following water. For column A, the wt. % of ethanol in the vinasse
economic indicators: total annualized cost (TAC), total op­ (which is practically free of ethanol) and in the second-grade
erating cost (Coper ) and total utilities cost (Cutil ). Additionally, bioethanol (90 wt. %) and liquid phlegm (41 wt. %) flows were
an environmental assessment was carried out by calculating determined, the latter located at the top and bottom of
 Chemical Engineering Research and Design 185 (2022) 130–145 137

Fig. 4 – Simulated flowsheet of the conventional process (process C) for hydrated bioethanol purification from sugarcane
fermented liquor (wine).

section D, respectively. For column B, the wt. % of ethanol in FOF and BFR. The variable BFR was significant for all four
the flegmass was similar to that in the vinasse. Flows of responses (EL, BP, SC and BR), while the variables RRD, RRB
65 wt. % for fusel oil and 94 wt. % for pasteurized hydrated and FOF affected three responses (EL, BP and BR). In contrast,
bioethanol were also determined, located in stages 41 and 4 the variable NSB only affected one response (SC). Thus, the
of section B, respectively. The simulated profiles of the vapor NSB value was kept fixed at the center point (Table 3), taking
composition of the ethanol and water components are into account the number of stages of the industry. In the
shown in Fig. 5e and f for columns A and B, in that order. preliminary simulations carried out for the CCRD, the flow
rate of fusel oil (FOF) removal was not found to be significant
3.1.1. Purification steps of the conventional process for the fitting of the mathematical models, and thus FOF was
The conventional industrial process for obtaining hydrated kept fixed at 300 kg/h. As a consequence, the CCRD was
bioethanol is commonly comprised of purification steps such carried out aiming to evaluate the effects of the variables
as degassing in condensers and the removal of second-grade RRD, RRB and BFR on the four responses EL, BP, SC and BR.
bioethanol in section D and fusel oil in column B (Barreto and For the CCRD study, the predicted results were in sa­
Coelho, 2015; Jacques et al., 2003). The last two steps were tisfactory agreement with those obtained by simulation, as
applied in process C and the resulting streams are shown in shown in Fig. S2 (see Supplementary information). Moreover,
Table T1 (see supplementary information). Second-grade according to Table 4, high values for the coefficients of de­
bioethanol was produced with a purity of 90 wt. % and a mass termination were obtained and the calculated F-value was
flow rate of 168.82 kg/h, which represented 1.4 % of the hy­ greater than the one tail value in the F-table (95 % con­
drated bioethanol and 1.3 % of the bioethanol found in the fidence). Thus, the regression was significant and confirmed
industrial wine. The mass flow rate of the fusel oil was this agreement. Considering the limits of the conditions in­
maintained at 300 kg/h, since process C was better re­ vestigated for the three independent variables, it can be ob­
presented under this condition, according to the fractional served in the contour graphs of Fig. 6a and b that, for the EL
factorial design. In addition, for mass percentages of 63 % response, from the central point of BFR, independent of the
and 28 % of ethanol and water in the fusel oil, respectively, values of RRB and RRD, low ethanol losses are obtained,
and assuming complete separation in the decanter coupled showing the strong influence of this variable. For low product
to the rectification column (Fig. 1), 91 % of this current is flow, minimum RRB and maximum RRD at the midpoint are
returned to the process. As a consequence, 1.9 kg of fusel oil required. Therefore, the irrelevant losses of the process are
was obtained per m³ of hydrated bioethanol, containing the central optimal points. Thus, all simulations obtained
mainly propanol, isoamyl alcohol and isobutanol. ethanol losses in the vinasse and flegmass below the max­
imum tolerated limit of 0.02 wt. %. For the BP response, va­
3.2. Fractional factorial design and optimization by lues from the central point of BFR and lower reflux rates,
central composite rotational design mainly of RRB, contributed to obtaining a mass purity of
hydrated bioethanol below the mean limit established by the
Process C was simulated to define optimal conditions for the ANP (Fig. 6c and d). In the case of the BR response (Fig. 6g and
alternative processes studied based on the evaluation of ten h), the minimum BFR at the midpoint, independent of the
potential variables, as shown in Table T2 (see Supplementary reflux rates, favored a high recovery of ethanol in the pro­
information). In this case, a 210
III
6
fractional factorial design cess. However, a balance between production and the safety
was adopted, where normal probability plots were evaluated margin of product purity, obtained in this study at the op­
for the responses, as presented in Fig. S1 (see Supplementary timal central point, with BP of 94.2 wt. % and BR of 97.04 %, is
information). It was found that only five independent vari­ recommended. In the case of steam consumption (SC), the
ables significantly affected the responses: RRD, NSB, RRB, satisfactory result of around 2 kg of steam per liter of
138 Chemical Engineering Research and Design 185 (2022) 130–145

Fig. 5 – Temperature, liquid and vapor composition profiles for columns A (a, c, e) and B (b, d, f).

bioethanol produced was obtained from mean values of BFR 3.3. Process simulation
for any RRB and minimum RRD at the central point (Fig. 6e
and f). However, considering the four responses evaluated in Figs. S3a and S3b (see Supplementary information) show the
this study, the optimal point of the process presented a flow temperature and vapor composition profiles for column A for
rate of 11,900 kg/h and reflux rates of 6 and 30 for columns B the three processes studied. The profiles for process A2 be­
and D, respectively. haved similarly to those for the conventional process, be­
A trade-off analysis based on unity values for the desir­ cause both had the partial removal of vapors generated in
ability function suggested optimum values of 4.0 × 10-4 wt. %, section A1. In this case, the absence of section D did not af­
94.34 wt. %, 2.10 kg/L and 97.16 % for EL, BP, SC and BR, re­ fect the production behavior of column A, since reflux did not
spectively, adopting (xRRD ; xRRB ; xBFR ) = (0.0; 0.0; 0.0) equivalent occur in section D. In addition, the absence of the second-
to (RRD; RRB; BFR ) = (30.0; 6.0; 11,900 kg/h), as shown by the grade bioethanol stream did not affect column A of process
red lines in Fig. 7. As a consequence, the contour plot and A2, since this column basically produced the feed stream
desirability function allowed the same optimal conditions to (liquid phlegm) for the rectification column B. In contrast, the
be found, aiming to maximize the mass purity of the bioe­ absence of section D and condensers caused bioethanol ac­
thanol produced (BP) and the recovery of bioethanol (BR), as cumulation in column A, because alcoholic vapors were not
well as to minimize the steam consumption (SC) and ethanol removed in process A1. This was evidenced in the wine de­
losses in the vinasse and flegmass streams (EL). Table 4 pletion region by a decrease in temperature (Fig. S3a - see
shows the optimal values for the ten input variables and four Supplementary information) and increase in the vapor mass
responses, showing excellent agreement between values of fraction of ethanol (Fig. S3b - see Supplementary informa­
the simulated and predicted responses. tion), since an ethanol content of 42.78 wt. % was identified in
 Chemical Engineering Research and Design 185 (2022) 130–145 139

Table 4 – Statistical results and optimal working conditions.

Independent variable Tag Optimal operation point

Number of stages in section A NSA 18

Number of stages in section A1 NSA1 8
Number of stages in section D NSD 6
Reflux ratio of section D RRD 30
Number of stages in section B1 NSB1 13
Number of stages in section B NSB 43
Reflux ratio of section B RRB 6
Fusel oil mass flow rate (kg/h) FOF 300
Fusel oil removal stage FOS 3
Bioethanol flow rate (kg/h) BFR 11,900

Objective functions Optimal response ANOVA

Predicted Simulated R² (%) Fcalculated Ftabulated

Ethanol losses in vinasse/flegmass (wt. %) EL 4.0E-04 6.9E-06 98.04 226.76 4.77

Bioethanol purity (wt. %) BP 94.34 94.2 95.17 92.89
Steam consumption (kg/L) SC 2.10 1.95 88.97 36.09
Bioethanol recovery (%) BR 97.16 97.04 99.43 872.69

the vapor phlegm stream while for the conventional (C) and Fig. S4d (see Supplementary information) shows the li­
A2 processes this value was 38 wt. %. quid mass fraction profile for acetaldehyde, a component not
On evaluating the components identified in column A of specified in the hydrated bioethanol standard. However,
process A1, the concentration of congeners in the vapor acetaldehyde can oxidize to ethanoic acid in the presence of
phase increased, as shown in the profiles of Figs. S3b-f (see oxygen during the product storage. Since the acetic acidity
Supplementary information) for ethanol, methanol, acet­ limit for hydrated bioethanol is 30 mg/L, the aldehyde com­
aldehyde, ethyl acetate and isoamyl alcohol. As a con­ position must be controlled (Batista and Meirelles, 2009;
sequence, a decrease in the methanol concentration of 15 % Jacques et al., 2003; Tgarguifa et al., 2017). Acetaldehyde and
was observed in the vapor phlegm stream compared to the ethyl acetate (Fig. S4e - see Supplementary information) have
conventional (C) and A2 processes (Table T3 - see high relative volatility compared to ethanol. For process C,
Supplementary information). This was caused by an increase for instance, both components are mainly removed in the
in the concentration of ethanol at the top of section A, con­ second-grade bioethanol stream (Figs. S3d and S3e - see
tributing to the liquid phase of this substance and conse­ Supplementary information), and thus there are lower con­
quently accumulating in the vapor phase in the intermediate centrations in column B compared to processes A1 and A2
regions of this section. (Table T3 - see Supplementary information). The effects of
In column B, the temperature and composition profiles of increasing the acetaldehyde composition are detailed in
the ethanol-water mixture were similar for the three systems Section 3.4.1.
investigated, as shown in Figs. S4a and S4b (see Regarding the isoamyl alcohol content (Fig. S4f - see
Supplementary information), respectively. In contrast, there Supplementary information), an increase of 15 % was iden­
was an increase in contaminants found in column B in pro­ tified in the vapor phlegm stream of process A1 compared to
cess A1 due to the vapor phlegm stream containing higher processes C and A2 (Fig. S3f - see Supplementary information
levels of impurities, with the exception of methanol, as and Table T3 - see Supplementary information). Never­
previously explained. For system A2, slightly lower tem­ theless, similar profiles for this contaminant were evidenced
peratures were identified between stages 39 and 45 at the in section B for the three processes, suggesting that the
bottom of section B due to an increase in the flow of the li­ proposed changes in the column configurations did not affect
quid phlegm stream, since there was no removal of second- the hydrated bioethanol production.
grade bioethanol in this process.
According to Fig. S4c (see Supplementary information), 3.4. Technical assessment of the hydrated bioethanol
process A1 presented a decrease in methanol compared to purification processes
the conventional (C) and A2 processes (of approximately 19 %
and 21 %, respectively). A lower methanol concentration in The three simulated processes provided a product that ad­
the vapor phlegm stream of process A1 contributed to its hered to the quality specifications defined for hydrated
decrease. On the other hand, methanol presents lower re­ bioethanol fuel (Table 1), as shown in Table 5, and thus they
lative volatility in mixtures with high concentrations of proved to be feasible techniques for the production of this
ethanol, making it difficult to separate (Batista et al., 2012; biofuel. It was observed that even on omitting section D and
Matugi et al., 2018). In general, methanol remains within the the condensers in process A1, or removing only section D in
quality specifications for bioethanol fuel, requiring an addi­ process A2, purification was achieved and the hydrated
tional column to meet the requirements of high-purity bioethanol fuel was obtained. In contrast, process C was the
bioethanol, such as HN in Table 1 (Batista et al., 2013; only configuration capable of producing H1 hydrated bioe­
Esteban-Decloux et al., 2014; Jacques et al., 2003; Valderrama thanol, since both alternative processes resulted in bioe­
et al., 2012). thanol with mass fractions of acetaldehyde and ethyl acetate
140 Chemical Engineering Research and Design 185 (2022) 130–145

Fig. 6 – Contour plot for responses: (a, b) ethanol losses in vinasse and flegmass streams (EL); (c, d) mass purity of hydrated
bioethanol (BP); (e, f) steam consumption (SC) and (g, h) bioethanol recovery (BR).
 Chemical Engineering Research and Design 185 (2022) 130–145 141

Fig. 7 – Multivariable and multi-response optimization of the conventional process (process C) for hydrated bioethanol
purification using the desirability function technique (RRD = reflux ratio of section D; RRB = reflux ratio of section B;
BFR = bioethanol mass flow rate; EL = ethanol losses in vinasse and flegmass streams; BP = mass purity of hydrated
bioethanol; SC = steam consumption; and BR = bioethanol recovery).

greater than 50 mg/L and 120 mg/L, respectively. Thus, the

removal of the second-grade bioethanol stream in column A
played a key role in controlling the level of impurities, aimed Table 5 – Quality parameters obtained for the simulated
at producing a higher purity hydrated bioethanol, such as H1. processes aimed at the production of hydrated
However, the three processes need improvements and ad­ bioethanol.
ditional purification steps to obtain neutral hydrated bioe­ Characteristics Unit Hydrated bioethanol fuel
thanol (HN), since the mass fractions of acetaldehyde, ethyl
Process C Process A1 Process
acetate, acetone, isopropanol, isobutanol and higher alcohols
A2
were above those presented in Table 1 for HN bioethanol
(Batista et al., 2013; Esteban-Decloux et al., 2014). As a result, Ethanol grade wt. % 94.2 94.2 94.2
Acetic acid mg/L trace trace trace
the complexity of the process is related to the required
Methanol % 0.02 0.02 0.02
quality standard for bioethanol.
Acetaldehyde mg/L 26.5 130.4 130.5
Ethyl acetate mg/L 70.8 225.9 226.6
3.4.1. Effect of acetaldehyde oxidation Acetone mg/L 6.7 12.1 12.1
Based on the quality parameters obtained for the three pro­ Isopropanol mg/L 11.6 11.6 11.4
cesses (Table 5), higher concentrations of some impurities n-Propanol mg/L trace trace trace
were identified for processes A1 and A2 compared to process n-Butanol mg/L trace trace trace
Isobutanol mg/L 110.9 104.9 105.6
C. For example, acetic acid can be produced through the
Isoamyl alcohol mg/L trace trace trace
oxidation of acetaldehyde during the storage of bioethanol
Higher alcohols* mg/L 122.5 116.5 117.0
fuel, leading to a 5-fold increase. Thus, additional simula­
*
tions were performed adopting degassing only in the con­ Alcohols with three, four or five carbons, which are formed by
densers of column B in the three processes, to ensure the decomposition of yeast cells (isopropanol, n-propanol, n-
butanol, isobutanol and isoamyl alcohol) (Copersucar, 2022;
comparable conditions and thus investigate the effect of in­
Jacques et al., 2003).
creasing the acetaldehyde content, as shown in Table 6.
142 Chemical Engineering Research and Design 185 (2022) 130–145

Table 6 – Degassing, acetaldehyde concentration and acetic acid levels in bioethanol fuel.
Unit Process

Conventional Alternative I Alternative II

a
Degassing – No Yes No Yes No Yes
Flow rate kg/h – 1.15 – 10.13 – 10.21
Composition mg/L – 78.59 – 681.09 – 686.67
Losses % – 0.01 – 0.08 – 0.08
Acetaldehydeb
Flow rate kg/h 0.39 0.16 1.94 0.17 1.94 0.17
Composition mg/L 26.55 11.06 130.41 11.28 130.46 11.32
Acetic acidc
Composition mg/L 36.07 15.04 177.35 15.35 177.43 15.39
Reduction % – 58.35 – 91.35 – 91.32
a
Degassing data where Yes and No indicate the use or not of a degassing step for each process.
b
Acetaldehyde data for each process.
c
Acetic acid composition for total conversion of acetaldehyde for each process and the percentage reduction using degassing.

In this study, the complete conversion of acetaldehyde to cess) were 11.5 % and 1.2 % for processes A1 and A2, re­
acetic acid was assumed, as in the work of Batista and spectively. This trend was expected, since process A1 re­
Meirelles (2009). Thus, according to the results in Table 6, the quires less steam due to the high ethanol concentration in
percentage of losses generated by degassing were lower than the vapor phlegm stream and the absence of a liquid phlegm
0.1 % and thus well below the value considered to be ac­ stream. Process A2, on the other hand, presented a slightly
ceptable by the industry (up to 1 %) (Codistil, 1978; lower steam consumption compared to process C because of
Copersucar, 1987; Jacques et al., 2003). Moreover, the alter­ the higher liquid phlegm flow rate fed to column B due to the
native processes presented a higher flow rate of released absence of a second-grade bioethanol stream, and thus the
gases compared to the conventional process, due to the flow rate of the bioethanol stream increased, although more
higher content of impurities. In contrast, all processes steam was required to concentrate the product.
showed a decrease in the acetic acidity of the hydrated
bioethanol fuel, with values being approximately 50 % of the 3.5.2. Energy efficiency
limit established by ANP (Table 1). It is important to note that The energy efficiency results for processes A1 and C were
this percentage could be lower with a tolerated increase in also compared, since 11 % of steam consumption was saved
the degassing flow. However, the values for acetic acidity of in the case of process A1. As a consequence, this value was
~15 mg/L for the three processes, C, A1 and A2, were con­ allocated to generate electricity using a condensing steam
sidered sufficient. Thus, industrial degassing carried out turbine for an existing industry based on process C. Table T4
continuously by the atmospheric distillation set, even when (see Supplementary information) presents the process data
applied only to the condensers of column B, proved to be an and savings in terms of energy and cost. For a daily pro­
effective method to control the level of impurities in hy­ duction of 400 m³ of hydrated bioethanol fuel, a saving of
drated bioethanol fuel. 260 kg of steam per m³ of bioethanol produced was obtained.
For 200 days of harvest, the steam turbine operates with a
3.5. Energy assessment of the hydrated bioethanol ratio of 6 tons of steam for each 1 MW of electricity gener­
purification processes ated, and thus an additional 3,467 MW per harvest was ob­
tained. Based on the price fixed in the contract of the
3.5.1. Steam consumption industrial unit, the cost saving was significant ($150,121),
The steam consumption was also estimated from simula­ representing over 50 % of the cost associated with chemical
tions of the processes C, A1 and A2 adopting three common products used in this distillery.
mass percentages of ethanol in the bioethanol stream:
92.8 wt. %, 93.5 wt. % and 94.2 wt. %. Moreover, percentage 3.6. Economic and environmental assessment of the
reductions in the steam consumption of processes A1 and A2 hydrated bioethanol purification processes
were also calculated, as shown in Fig. 8. Process C presented
a steam consumption of between 1.89 and 1.95 kg of steam The processes were also assessed and compared based on
per liter of bioethanol produced with a mass percentage of economic and environmental aspects. For the economic
ethanol between 92.8 and 94.2 wt. %. These steam con­ evaluation, the same value for the total capital cost (Fig. 9a)
sumption values are in excellent agreement with those was assumed for the three processes, since this study fo­
found in the industrial unit and are within the range of cused on an industrial unit already constructed. In this case,
1.8–2.0 kg/L commonly reported in the literature. Also, it was the total annualized cost (TAC) was calculated adopting a
verified that the energy consumption increased for all pro­ payback period of 3 years to return the investment. Also, the
cesses with an increase in the mass percentage of ethanol in TAC followed the same trend as the utilities (Cutil ) and op­
the bioethanol stream, as expected, since a higher amount of erational (Coper ) costs, since the same value for the total ca­
heat was required to concentrate the product. pital cost (Ccap) was adopted (Dimian, 2003; Luyben, 2013).
The average decreases in the steam consumption of the As seen in Fig. 9a and c, processes A1 and A2 presented
alternative processes (in relation to the conventional pro­ lower values for TAC, Coper and Cutil than process C. Similarly,
 Chemical Engineering Research and Design 185 (2022) 130–145 143

Fig. 8 – Steam consumption and its reduction (%) for the processes with three common bioethanol concentrations.

Fig. 9 – Economic, energy and environmental results for the processes C, A1 and A2.

the alternative processes showed lower values for steam, 4. Conclusions

water and electricity costs, as shown in Fig. 9b, d and f.
Process A1, for instance, reduced the steam, water and Three process configurations were investigated for the pur­
electricity costs by around 7.5 %, 5.0 % and 2.0 %, respec­ ification of hydrated bioethanol fuel and all of them provided
tively, compared to process C. Thus, although the alternative products that adhered to the quality standards of specific
systems operated with a higher internal volume than the C Brazilian legislation. For the alternative processes I and II, as
process, due to the absence of a second-grade bioethanol expected, there was an increase in the concentration of some
flow, there was no increase in the utilities cost, as this was components compared to the conventional system, especially
offset by higher productivity. The proposed alternative pro­ acetaldehyde. However, even considering the total conversion
cesses also contributed to the reduction in CO2 emissions of this contaminant into acetic acid during the product storage,
(Fig. 9e) and represent concise and optimized processes. this study demonstrated that qualitative control was simply
When these economic and environmental indicators are achieved by using degassing in the simulated processes, and
compared, a decrease in the process cost is observed as fol­ for an industrial unit, this purification is carried out con­
lows: process C > process A2 > process A1. tinuously by the atmospheric distillation set.
144 Chemical Engineering Research and Design 185 (2022) 130–145

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Declaration of Competing Interest
Batista, F.R.M., Follegatti-Romero, L.A., Meirelles, A.J.A., 2013. A
new distillation plant for neutral alcohol production. Sep.
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nancial interests or personal relationships that could appear Bessa, L.C.B.A., Batista, F.R.M., Meirelles, A.J.A., 2012. Double-ef­
to have influenced the work reported in this paper. fect integration of multicomponent alcoholic distillation col­
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Appendix A. Supporting information
fusel oil distillation process. Ind. Eng. Chem. Res. 52,
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