processes

Article
Mass and Heat Integration in Ethanol Production
Mills for Enhanced Process Efficiency
and Exergy-Based Renewability Performance
Pablo A. Silva Ortiz 1,2, *, Rubens Maciel Filho 1 and John Posada 2
1 School of Chemical Engineering, Laboratory of Optimization, Design and Advanced Process
Control-LOPCA, University of Campinas, Campinas 13083-852, Brazil; [email protected]
2 Department of Biotechnology, Faculty of Applied Sciences, Delft University of Technology,
2629 HZ Delft, The Netherlands; [email protected]
* Correspondence: [email protected] or [email protected]




Received: 30 June 2019; Accepted: 20 September 2019; Published: 27 September 2019


Abstract: This paper presents the process design and assessment of a sugarcane-based ethanol
production system that combines the usage of both mass and heat integration (pinch analysis)
strategies to enhance the process efficiency and renewability performance. Three configurations were
analyzed: (i) Base case: traditional ethanol production (1G); (ii) mass-integrated (1G2G); and (iii) mass and
heat-integrated system (1G2G-HI). The overall assessment of these systems was based on complementary
approaches such as mass and mass–heat integration, energy and exergy analysis, exergy-based
greenhouse gas (GHG) emissions, and renewability exergy criteria. The performances of the three
cases were assessed through five key performance indicators (KIPs) divided into two groups:
one is related to process performance, namely, energy efficiency, exergy efficiency, and average unitary
exergy cost (AUEC), and the other one is associated to environmental performance i.e., exergy-based
CO2 -equation emissions and renewability exergy index. Results showed a higher exergy efficiency
of 50% and the lowest AUEC of all the systems (1.61 kJ/kJ) for 1G2G-HI. Furthermore, the destroyed
exergy in 1G2G-HI was lower by 7% and 9% in comparison to the 1G and 1G2G cases, respectively.
Regarding the exergy-based GHG emissions and renewability performance (λindex ), the 1G2G-HI case
presented the lowest impacts in terms of the CO2 -equivalent emissions (94.10 gCO2 -eq/MJ products),
while λindex was found to be environmentally unfavorable (λ = 0.77). However, λindex became
favorable (λ > 1) when the useful exergy of the byproducts was considered.

Keywords: exergy analysis; lignocellulosic ethanol; integrated first- and second-generation ethanol;
heat integration; renewability exergy index

1. Introduction
Increasing global energy demand combined with global warming effects associated with greenhouse
gas (GHG) emissions have accentuated the need to find more sustainable and environmentally friendly
energy sources to replace fossil fuels [1]. In this context, biofuels could contribute as a player in achieving
environmental goals and energy demand. In particular ethanol is the most important biofuel, with USA
and Brazil as the largest producers worldwide with an annual production (by 2018) of 58 billion liters
(primarily from cornstarch) and 28 billion liters (primarily from sugarcane), respectively [2].
One of the key factors to implement and consolidate a more efficient process in the biofuel sector
is related to technological improvements in conventional biorefinery systems (i.e., mass and energy
integration). In the particular case of ethanol production, the integration of second-generation processes
into traditional ethanol mills (1G2G biorefineries) could increase its supply potential and process

Processes 2019, 7, 670; doi:10.3390/pr7100670 www.mdpi.com/journal/processes

Processes 2019, 7, 670 2 of 31

efficiency due to the use of lignocellulosic materials into the process, which are nonfood crops, abundant,
and cheaper than first-generation feedstocks like sugarcane or corn [3]. However, to understand to what
extended these processes could potentially be improved, mass and heat integration strategies are needed
along with the development of suitable process performance indicators and renewability metrics.
The multi-faceted nature of the assessments has led to the derivation of various indicators such as
technical, economic, social, and environmental [4]. A set of energy-based key performance indicators
(KPIs) have been proposed in literature, often with similarities or discrepancies (material efficiency,
total energy input, energy intensity, energy efficiency). Nevertheless, they are still useful if applied as
complementary measures considering that they depend on the specific context, therefore conclusions
on process performance should not be generalized [3]. These indicators could present some biases and
provide ambiguous results in certain conditions. Hence, decision-support systems on exergy basis and
traditional cost or economic analysis have also been developed in order to carry out multidimensional
analyses. Magnanelli et al. [5] presented exergy-based KPIs for industrial practices. This work
outlined the advantages and limitations of the reviewed indicators aiming their use towards industry.
The selected case studies were an offshore oil and gas processing plant, a gas-fired combined cycle
power plant, and a silicon production process. Meanwhile, Stougie et al. [6] assessed the environmental,
economic, and exergetic sustainability of the five power generation systems (i.e., coal-fired power
plant, coal-fired power plant with carbon capture and storage, biomass-fired power plant, offshore
wind farm, and photovoltaic park) using the total cumulative exergy loss (TCExL) as an indicator.
This method was developed with the aim of taking into account many aspects of sustainability and
all exergy losses caused by a technological system during its life cycle. Posada et al. [7] carried out
a conceptual design of sustainable integrated microalgae-based biorefineries through a parametric
analysis of energy use, GHG emissions, and techno-economic assessment. This study showed possible
processing pathways and important technologies for industrial scale microalgae valorization, as well
as identified microalgae-based biorefinery arrangements, presenting the best configuration regarding
environmental, technical, and economic performance.
Systems design, process performance, and economic analysis had been devoted to integrating
second-generation technology into first-generation plants (1G2G integrated systems). For instance,
Santos et al. [8] presented a techno-economic analysis and an environmental assessment of the whole
production chain (biomass production, sugar extraction, biomass pretreatment, sugars fermentation,
and products recovery and purification) of an integrated 1G2G sugarcane-based biorefinery for biojet
fuel production. Albarelli et al. [9] analyzed a scenario related to the integration of the autonomous
distillery with the second-generation ethanol production using the bagasse pith (P-fraction) as feedstock.
These authors accomplished a heat integration evaluation, analyzing the role of product diversification
in the economic viability of 2G processes. Whereas Palacios et al. [10] investigated the exergetic
performance and exergetic cost of the ethanol production through the enzymatic hydrolysis of sugarcane
bagasse integrated into the conventional process. Three levels of solids content in the hydrolysis
reactor, 5%, 8%, and 10%, were considered using evaporation and membrane systems. They found
that the highest ethanol yield was achieved by means of the membrane system with a solid
content of 5% in the hydrolysis reactor, which resulted in an increase of 22% over conventional
distilleries. Dias et al. [11] performed a process simulation of an integrated production of first-
and second-generation ethanol from sugarcane, including technical, economic, and environmental
aspects. The second-generation ethanol production adopted steam explosion as pretreatment and
enzymatic hydrolysis of sugarcane bagasse. These authors established that 1G2G integrated processes
present advantages over stand-alone 2G ethanol production from sugarcane when both technical and
economic perspectives are considered, while the environmental performance is method and allocation
criteria dependent.
Although some studies have addressed the thermodynamic assessment, there is not a systematic
method reported yet to understand the renewability of mass and heat-integrated systems that take
into account exergy-based GHG emissions, the exergy analysis, and the mass–heat integration.
Processes 2019, 7, 670 3 of 31

Thus, three sugarcane ethanol biorefineries process with different levels of integration were here
analyzed: (i) base-case: traditional ethanol plant (1G) as reference system; (ii) mass-integrated (1G2G):
increased ethanol production and surplus electricity by introducing the pretreatment and hydrolysis
processes; and (iii) mass and heat integration (1G2G-HI) of the first- and second-generation plant.
The overall assessment of these systems was based on complementary approaches, i.e., mass and
mass–heat integration, energy and exergy analysis, exergy-based GHG emissions, and renewability
exergy criteria. Furthermore, the comparison metrics used were: global energy and exergy efficiency,
average unitary exergy cost, specific CO2 -equivalent emissions in exergetic base, and renewability
exergy index, respectively, in order to assess these biochemical biorefineries.

2. Process Description of Ethanol Production

2.1. Battery Limits

The control volumes adopted in this work include a sugarcane distillery (first generation-1G) and
an integrated first and second-generation ethanol process (1G2G biochemical plant). An exergy-based
Processes
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sugarcane ethanol process chain, as shown in Figure 1 and as described below.

Simplifiedblock
Figure1.1.Simplified
Figure blockdiagram
diagramof
ofthe
theethanol
ethanolproduction
productionprocesses.
processes.

2.2. First-Generation (1G) Ethanol Process

Extraction System: In this step, sugarcane bagasse is obtained, which represents a byproduct in
suitable condition for burning in the boilers. Then, two kinds of devices are used to perform this
Processes 2019, 7, 670 4 of 31

2.2. First-Generation (1G) Ethanol Process

Extraction System: In this step, sugarcane bagasse is obtained, which represents a byproduct
in suitable condition for burning in the boilers. Then, two kinds of devices are used to perform this
operation: mills and diffusers. A comparison of milling and diffusion systems from sugarcane is
presented in Palacios-Bereche et al. [12].

• Juice treatment: The sugar juice is heated up from 30 to 70 ◦ C, and subsequently processed with
lime (CaO) to precipitate impurities or sludge that are taken out by filtration. The clear juice is
further heated up to 105 ◦ C and flashed to eliminate water. This clarified and concentrated juice is
adequate for use in the fermentation process [13].
• Fermentation: In this stage, yeast or other microorganisms are used to produce ethanol (and other
organic compounds as byproducts). The ethanol recovery from the fermentation gases is performed
by an absorption column [14].
• Distillation: Initially, the fermentation broth is centrifuged to take out yeast and the other suspended
substances. A clarified broth containing around 7–12 v/v% ethanol is obtained. Subsequently,
distillation is applied to remove water, remaining solids, and lighter organics to produce an aqueous
solution containing 90–95 v/v% ethanol [13].
• Dehydration: Ethanol 95 v/v% is dehydrated to fuel-grade anhydrous ethanol (>99 v/v%) by utilizing
molecular sieves in a pressure swing adsorption (PSA) process. In contrast with azeotropic
distillation, PSA saves roughly 840 kJ of energy per liter of ethanol produced [13].
• Combined heat and power (CHP): In the cogeneration system, bagasse coming from the extraction
step is sent to the utility plant to produce steam, which is used in backpressure steam turbines.
Equipment responsible for matching the electromechanical demands of the mill.

2.3. Second-Generation (2G) Ethanol Process

Sugarcane bagasse and straw (lignocellulose materials) could be used as feedstock for ethanol
production through pretreatment and hydrolysis processes [15], which are the main technologies of the
second-generation ethanol production.
Regarding the biomass pretreatment processes, hot water and steam explosion are commonly
used in the biofuel industry. Hot water dissolves biomass and removes part of lignin and hemicellulose.
Whereas in the steam explosion, high-pressure steam rapidly heats biomass to promote hemicellulose
hydrolysis, followed by rapid pressure release [16]. Reaction time, temperature, particle size,
and moisture content are considered the important variables in the biomass pretreatment technologies.
In the pretreatment process, a fraction of hemicellulose (represented by xylan) is transformed
into xylose and xylose oligomers. A diffuser is used to separate a liquid stream of the pretreated
material, named C5 liquor. Thus, C5 liquor undergoes a neutralization treatment for pH correction
prior to deoligomerization and fermentation of C5 liquor to ethanol. The solid fraction of the pretreated
material is directed to the enzymatic hydrolysis reactor [17]. Enzymatic hydrolysis is an important step
of the biochemical route since it impacts the overall process performance and costs in the production
of fermentable sugars. Subsequently, the C5 and C6 fermented streams (resulting in a clarified broth
from fermentation, known as beer or wine) are mixed and directed to distillation columns as depicted
in Figure 1. Similar to 1G autonomous distillery, ethanol dehydration is conducted using molecular
sieves. More details of the second-generation process descriptions can be found elsewhere [17,18].

3. Methodology
To understand the effects of two levels of process integration (mass and heat), the 1G and 2G ethanol
production process were conceptually designed and simulated. Then, the obtained mass and energy
flows were used to identify opportunities for heat integration by applying the pinch methodology.
Finally, three process performance indicators (i.e., energy efficiency, exergy efficiency, and the average
unitary exergy cost) and two exergy-based GHG emissions and renewability performance indicators
Processes 2019, 7, 670 5 of 31

(i.e., specific CO2 equivalent emissions and renewability exergy index) were calculated and compared
to the two levels of integration and with respect to the autonomous ethanol production process.
The flow diagram of the conceptual process design, simulation, and assessment methodologies
is shown
Processes in Figure
2019, 7, x FOR 2.
PEER REVIEW 6 of 33

2. Flow diagram of the conceptual process design

Figure 2. design and assessment
assessment methodologies.
methodologies.

3.1.
3.1. Process
Process Simulation
Simulation
Technical
Technical datadata forfor aastandard
standardsugarcane
sugarcanebiorefinery
biorefineryprocessing
processing 4 million
4 million tons tons of sugarcane
of sugarcane per
per season, with a recovery rate of 50% of straw (30 w/w% moisture content)
season, with a recovery rate of 50% of straw (30 w/w% moisture content) were considered [19]. The were considered [19].
The feedstock
feedstock composition
composition adopted
adopted in in thisstudy
this studyisispresented
presented in in Appendix
AppendixASection Section(Tables
(Tables A1
A1 and
and A2).
A2).
Simulations were carried out using Aspen Plus software V8.8 [20]. Firstly,
Simulations were carried out using Aspen Plus software V8.8 [20]. Firstly, mass and energy balances mass and energy
balances were determined
were determined for eachThe
for each process. process.
simulationTheprocedure
simulationincludes
procedure flowincludes
sheeting,flow sheeting,
selection of a
selection of a suitable thermodynamic model, and the specification of appropriate
suitable thermodynamic model, and the specification of appropriate operating conditions. Cellulose, operating conditions.
Cellulose, hemicellulose,
hemicellulose, and lignin andarelignin are defined
defined as user-defined
as user-defined substances
substances to allow
to allow the the calculation
calculation of
of thermodynamic physical properties like boiling points, molecular
thermodynamic physical properties like boiling points, molecular weights, etc. The component weights, etc. The component
properties
properties ofof the
the lignocellulosic
lignocellulosic material
material werewere retrieved
retrieved from
from thethe biofuel
biofuel databank
databank developed
developed by by
NREL [21]. For this study, due to the presence of vapor–liquid components
NREL [21]. For this study, due to the presence of vapor–liquid components such as ethanol and such as ethanol and
steam,
steam, the
the non-random
non-random two-liquid
two-liquid (NRTL)
(NRTL) modelmodel waswas used
used to
to predict
predict the
the activity
activity coefficients
coefficients of
of the
the
components in the liquid phase. The thermodynamic properties of the
components in the liquid phase. The thermodynamic properties of the vapor phase were estimated vapor phase were estimated
based
based ononRedlich–Kwong
Redlich–Kwong equation
equation of state for non-ideal
of state conditions
for non-ideal such as such
conditions operation under moderate
as operation under
pressures (around 10 bar) or a high concentration of sugar. The Hayden
moderate pressures (around 10 bar) or a high concentration of sugar. The Hayden O’Connell O’Connell (NRTL-HOC)
(NRTL-
equation was utilized
HOC) equation for vapor-phase
was utilized calculations
for vapor-phase when the
calculations when concentration of acetic
the concentration acid and
of acetic acidother
and
carboxylic
other carboxylic acids was significant, for instance, on fermentation and distillation units. Forturbine
acids was significant, for instance, on fermentation and distillation units. For steam steam
power
turbinegeneration, STEAM-TA
power generation, properties
STEAM-TA were taken
properties wereinto account.
taken into account.

3.1.1. Simulation of the First-Generation (1G) Ethanol Process

Detailed parameters and processing conditions used for the simulation of the 1G ethanol process
are included in Tables A4 and A5. In addition, a simplified flowsheet of the ethanol production
process implemented in Aspen Plus is given in Figure A1 of the Appendix Section, which considers
the following stages:
 Cleaning of sugarcane and extraction of sugars: sugarcane is prepared for extraction through
Processes 2019, 7, 670 6 of 31

3.1.1. Simulation of the First-Generation (1G) Ethanol Process

Detailed parameters and processing conditions used for the simulation of the 1G ethanol process
are included in Tables A4 and A5. In addition, a simplified flowsheet of the ethanol production
process implemented in Aspen Plus is given in Figure A1 of the Appendix A Section, which considers
the following stages:

• Cleaning of sugarcane and extraction of sugars: sugarcane is prepared for extraction through
shredders and then juice is extracted in the mills. For the simulations, a dry-cleaning system using
air was considered.
• Juice treatment: following extraction, sugarcane juice suffers a physical treatment including
cyclones and filters for eliminating solids and insoluble contaminants. Soluble contaminants are
eliminated at the chemical treatment process by adding some reactants such as phosphoric acid,
hydrated lime.
• Juice concentration: treated juice is concentrated to reach an appropriate sugar concentration
(approx. 18 w/w%) for the fermentation process [22]. The concentration of treated juice takes place
in a multiple effect evaporation (MEE) system in order being mixed with the must of sugarcane
juice for the integration of hydrolysis process to traditional plants of ethanol.
• Fermentation: in this step the conversion of sugars into ethanol occurs. The process is simulated
considering the Melle–Boinot configuration based on [9,10,23]. The major parameters and
fermentation reactions are shown in Appendix A Section.
• Distillation and dehydration: The produced ethanol is recovered from the beer in the distillation
area. Hydrated ethanol (93 w/w%) was obtained in the distillation process as a result of stripping
(A–A1–D) and rectification columns, B–B1, as described in Figure A1. Beer is fed in column A1
and the three major output streams are the volatile impurities, which are removed in the top
of column D; vinasse, the bottom product from column A; and phlegm, a stream rich in ethanol,
which follows to the rectification columns. From the bottom of column B1, a closely pure water
stream is removed, named phlegmasse; hydrated ethanol is obtained on top of column B; and a side
stream, containing most of the higher alcohols, is removed from Col. B as well. Adsorption by
means of molecular sieves was used to dehydrate the azeotropic solution from Col. B to obtain
99.6 w/w% anhydrous ethanol [17].
• Combined Heat and Power (CHP): A steam cycle operating with superheated steam at 485 ◦ C and
65 bar with backpressure steam turbines is here considered for this process unit. This configuration
was used to generate only the necessary process steam, allowing a surplus of bagasse, which could
be used in an enzymatic hydrolysis process [24]. The bagasse with 50 w/w% of moisture content
was adopted as fuel for the cogeneration unit. Moreover, the combustion reactions in the boiler
section were here studied as indicated by NREL [21,25]. The process flow diagram of the CHP unit
is described in Figure A3 and the parameters of the cogeneration system, including the chemical
reactions of the boiler section, are given in Table A6.

3.1.2. Simulation of the Second-Generation (2G) Ethanol Process

The second-generation process was based on the steam explosion pretreatment technology
followed by enzymatic hydrolysis. Data was gathered from the optimal conditions reported by
Carrasco et al. [26]. Thus, considered in the pretreatment reactor was the formation of xylose
(C5 H10 O5 ) and acetic acid (C2 H4 O2 ) from hemicelluloses (C5 H8 O4 ), the formation of furfural from
xylose, and the formation of glucose (C6 H12 O6 ) from cellulose (C6 H10 O5 ). The hydrolysis steps are
performed at 50 ◦ C with a residence time of 24 h and a cellulase concentration of 15 FPU/g of biomass
(enzyme activity 65 FPU/g) [26]. The cellulosic hydrolysate (C6 liquor) is concentrated to achieve
appropriate glucose content for the fermentation process. After the concentration, the hydrolysate
is mixed with must of sugarcane juice and added to the fermentation process. Moreover, steam for
pretreatment is supplied from the cogeneration system.
Processes 2019, 7, 670 7 of 31

Glucose hydrolysate is preheated with steam flash recuperated from the pretreatment
decompression before undergoing the evaporation system, which operates with steam at 2.5 bar.
A five-stage evaporation system was adopted to reduce the steam consumption. In the simulation,
each stage of the evaporation system was considered by two unit operations: a heat exchanger and
a flash separator [24]. It was assumed that the condensate of exhaust steam from this evaporation system
returns to the cogeneration unit and a solid content of 10% in the hydrolysis reactor. Detailed processing
conditions, flowsheets (Figure A2) and chemical reactions adopted for the simulation of the 2G ethanol
Processesare
process 2019, 7, x FOR PEER
included REVIEW
in the Appendix A Section. 8 of 35

3.2.Heat
3.2. HeatIntegration
Integrationthrough
throughPinch
PinchAnalysis
Analysis
Processintegration
Process integration is aiskey
a key aspect
aspect of the
of the designdesign of sustainable
of sustainable industries.
industries. According
According to FootoetFoo et al.
al. [27],
pinch analysis is an insight-based framework that uses a two-step strategy comprised of targeting andof
[27], pinch analysis is an insight-based framework that uses a two-step strategy comprised
targeting
system and system
design. Targetingdesign.
may Targeting
be done usingmay abevariety
done using a variety
of graphical orof graphical
algebraic or algebraic
methods methods
to determine
to optimal
the determine the optimal thermodynamically
thermodynamically feasible extent of feasible
energyextent of energy
and material and material
recovery recovery
in a system, in a
the net
system, the net utility requirements from external sources, and the system
utility requirements from external sources, and the system bottleneck. Process integration is associated bottleneck. Process
integration
with the systemis associated
design (heat with the systemand
integration) design (heat point,
the pinch integration)
that is,and the pinch
the point where point, thatforces
driving is, the
point where driving forces (related to heat transfer)
(related to heat transfer) are at the minimum feasible value [27]. are at the minimum feasible value [27].
Thus,after
Thus, afterdefining
definingthe themaximum
maximumheat heatrecovery
recoverypotential
potentialbetween
betweenhot hotandandcold
coldstreams
streamsand and
considering aaminimum
considering minimumtemperature
temperaturedifference
differenceapproach
approach(∆T (ΔT ),
),
min
min the
the optimal
optimal thermal
thermal process
process
integrationis is
integration obtained.
obtained. Detailed
Detailed steps
steps for pinch
for the the pinch
design design methodology
methodology can be can
found beelsewhere
found elsewhere
[28,29].
[28,29].
The pinch The pinch was
method methodherewas here adopted
adopted to determinate
to determinate the minimal
the minimal energyenergy consumption
consumption targetstargets
after
after doing
doing processprocess
designdesign
and simulation. The ∆TThe
and simulation. min ΔT min considered
considered in thisin this
study study
for thefor the
process process streams
streams was
◦
was 10 °C, except for flow streams coming from evaporation systems,
10 C, except for flow streams coming from evaporation systems, where 4 C was selected [24,30]. where ◦
4 °C was selected [24,30].
Oncethese
Once these values
values are are
commoncommon practice
practice in the in the and
sugar sugar and plants,
ethanol ethanolfocusplants,
is onfocus
thermal is integration
on thermal
integration implementation. The thermodynamic parameters (data
implementation. The thermodynamic parameters (data extraction) of the streams selected for extraction) of the streams selected
heat
for heat integration
integration are includedare inincluded
Table A9 in (Appendix
Table A9 (Appendix
A Section).Section).

3.3.
3.3.Exergy
ExergyAnalysis
Analysis
The
The exergy approach, which
exergy approach, whichcombines
combines thethe First
First andand Second
Second Law of Law of Thermodynamics
Thermodynamics is
is applied
applied
to assess to the
assess the performance
performance of the
of the two twoof
levels levels of integration
integration in the ethanol
in the ethanol production
production process.process.
Exergy
Exergy
analysis analysis is an effective
is an effective tool
tool for for evaluating
evaluating the quality
the quality and and quantity
quantity of a of a resource,
resource, as itasrepresents
it represents
the
the maximum
maximum of of
thethe quantity
quantity ofofthe
theresource
resourcethatthatcan
can be
be converted
converted into work,work, given
giventhe theprevailing
prevailing
environmental
environmentalconditions
conditions[31].
[31]. In
In this
thisstudy,
study,thethechemical
chemical(B(BCH ) )and
CH andphysical
physical(B(BPHPH ))exergies
exergiesareare
considered
consideredin inthe
theassessment
assessment due
due to the physico-chemical processesinvolved.
physico-chemical processes involved.The Thephysical
physicalexergyexergyof
ofa astream
streamcan canbe be calculated
calculated based
based on on thermodynamic properties obtained, obtained, such
such as
asenthalpy
enthalpyand and
entropy
entropyobtained
obtainedafter
afterprocess
processsimulation
simulationin inAspen
AspenPlus
Plussoftware
softwareof ofeach
eachstream
streamwithin
withineach each unit.
unit.
TheBB
The PHPHwas
wasdetermined
determinedaccording
accordingto toEquation
Equation(1).(1).

BPH𝐵𝑃𝐻==H𝐻−−H𝐻0−−T 𝑇(0S(𝑆−−S 𝑆)0 ) (1)

(1)
0 0 0
where H, T, S represents enthalpy, temperature, and entropy, respectively. The subscript 0 means the
where H, T,environmental
reference S represents enthalpy, temperature,
state (25 °C, 1 atm). and entropy, respectively. The subscript 0 means
the reference environmental state (25 ◦ C, 1 atm).
On the other hand, chemical exergy is defined as the energy available to do work when the
On the undergoes
substance other hand,achemical exergy
reversible is defined
process from theas the energy available
restricted referencetostate do work
to a when the substance
thermodynamically
undergoes a reversible process from the restricted reference state to a
dead state in which the system is in a complete thermodynamic equilibrium (thermal, pressure, thermodynamically dead state
and
inchemical)
which the[31].
system is in a complete
Conceptually, then,thermodynamic
chemical exergy equilibrium
quantifies(thermal,
the valuepressure, and chemical)
of a chemical [31].
substance, or
Conceptually, then, chemical exergy quantifies the value of a chemical
compound, as measured against a selected reference environment [32]. Equation (2) defines the substance, or compound,
aschemical
measured against a selected reference environment [32]. Equation (2) defines the chemical exergy:
exergy:
 
X 𝑐ℎ
X 
B𝐵 𝐶𝐻=
CH =n𝑛mix
𝑚𝑖𝑥  [∑xi𝑥b𝑖ch
i
𝑏𝑖+ + Ru𝑅T𝑢0𝑇0 ∑xi𝑥ln𝑖 Ὑ i𝑖xi  ] (2)
 
i 𝑖 i 𝑖

where nmix is the total amount of moles of all constituents in a mixture, xi is the mole fraction of
component i in the mixture, and the term 𝑏𝑖𝑐ℎ is the standard chemical exergy. In this work, the
influence of activity coefficient (Ὑ) was evaluated for each compound, allowing us to observe that it
provides values close to one.
The exergies of ethanol–water solutions, such as hydrated and anhydrous ethanol, were
Processes 2019, 7, 670 8 of 31

where nmix is the total amount of moles of all constituents in a mixture, xi is the mole fraction
of component i in the mixture, and the term bch i
is the standard chemical exergy. In this work,
the influence of activity coefficient (῾Υ) was evaluated for each compound, allowing us to observe that
it provides values close to one.
The exergies of ethanol–water solutions, such as hydrated and anhydrous ethanol, were determined
following the procedure reported in Ensinas and Nebra [33]. For the calculation of the chemical exergies
of the resulting clarified broth (beer or wine), vinasse and phlegmasse from distillation columns and
pentose liquor attained by hydrolysis were considered as ideal solutions. Therefore, molar fraction was
used instead of activity since these streams are very diluted solutions and activity data for the main
components in fermentation and pretreatment steps such as aconitic acid-C6 H6 O6 , glycerol-C3 H8 O3 ,
Processes 2019, 7, x FOR PEER REVIEW 9 of 33
furfural-C5 H4 O2 , xylose-C5 H10 O5 , yeast, and enzymes, which are not available in literature. Moreover,
theavailable
exergy of exergy btoch of the
in dissolution is significantly
literature. Moreover, low in
the exergy ofcomparison
dissolution is tosignificantly
the standardlowchemical
in comparison i the
pure components [10]. 𝑐ℎ
standard chemical exergy 𝑏𝑖 of the pure components [10].
The Thestandard
standardchemical
chemical exergies
exergies for
for various compoundsare
various compounds arefound
foundininthetheliterature
literature [31,34];
[31,34];
however, it can also be calculated based on correlation functions. The values of the b ch𝑐ℎcompounds and
however, it can also be calculated based on correlation functions. The values of the i𝑏𝑖 compounds
theand
correlation used in
the correlation thein
used exergy analysis
the exergy werewere
analysis included in Table
included A12.A12.
in Table
It is
It noted
is noted thatthat
the the
specific chemical
specific exergies,
chemical in reference
exergies, conditions
in reference of temperature
conditions and pressure
of temperature and
(T0pressure
and P0 ),(Tare usually close to its lower heating value (LHV) for fuels, as shown
0 and P0), are usually close to its lower heating value (LHV) for fuels, as shown in the in the relation
relationbCH
between and LHV
between given
bCH and LHVin Figure
given in 3. Figure
Hence,3.the chemical
Hence, exergy ofexergy
the chemical a substance can be evaluated
of a substance can be
evaluated
using using correlations
correlations (ϕ) based on (φ)the
based on the composition,
composition, as presented
as presented by Szargut byetSzargut
al. [31]etand
al. [31]
Kotas and[34],
Kotas
such as: [34], such as:

𝑏bCH ==𝜑 ϕ·LHV.

∙ 𝐿𝐻𝑉. (3) (3)
𝐶𝐻

Figure
Figure 3. 3.Standard
Standardchemical
chemicalexergy
exergy and
and lower
lower heating
heating value
valuefor
forselected
selectedresources.
resources.Adapted
Adaptedfrom
from
Frenzel and Pfennig [35].
Frenzel and Pfennig [35].

Thetechnological
The technologicalcomparisons
comparisons carried
carried out
out in
in Section
Section44arearefounded
foundedononthe theexergy efficiency
exergy efficiency
calculations of each system. First, the exergy of the products (B ) and the inputs (B ) are determined.
calculations of each system. First, the exergy of the products (Bp ) and the inputs (Bi ) are determined.
p i

Table
Table A13
A13 (AppendixASection)
(Appendix presents
Section) presentsthethe
bchbch
andand
LHVLHVvalues for several
values fossilsfossils
for several and bio-based raw
and bio-based
materials. This table is used in the benchmark of biorefinery configurations (Section 4.2.1), once it
reports the exergy values for sugarcane (SC), SC bagasse, straw, and sugar.
Afterward, the exergy balance for an integrated ethanol sugar plant was applied to calculate the
irreversibility (I) of the processes, according to Equation (4).

𝐵̇𝑠𝑢𝑔𝑎𝑟𝑐𝑎𝑛𝑒 = 𝐵̇𝑒𝑡ℎ𝑎𝑛𝑜𝑙 + 𝐵̇𝑠𝑢𝑔𝑎𝑟 + 𝐼𝑜𝑣𝑒𝑟𝑎𝑙𝑙

̇ . (4)
Processes 2019, 7, 670 9 of 31

raw materials. This table is used in the benchmark of biorefinery configurations (Section 4.3), once it
reports the exergy values for sugarcane (SC), SC bagasse, straw, and sugar.
Afterward, the exergy balance for an integrated ethanol sugar plant was applied to calculate
the irreversibility (I) of the processes, according to Equation (4).
. . . .
Bsugarcane = Bethanol + Bsugar + Ioverall . (4)

3.4. Key Performance Indicators (KPIs)

A set of complementary performance indicators were selected for assessing biorefinery sustainability
based on thermodynamic performance and environmental impacts (see Table 1). These metrics are
suitable for comparison of biorefinery alternatives and identification of the processing pathways over
fossil-based configurations.

Table 1. Key performance indicators for process efficiency, exergy-based greenhouse gas (GHG) emissions,
and renewability.

Process Efficiency
Indicators Definition Equation
Efficiency ratio between net energy output to energy input
(e.g., total biomass calorific value).
Energy efficiency P . .
(m ∗ LHV )products + wnet (5)
(ηE )
ηE = P .
(m ∗ LHV )resources

The ratio between the exergy of the products

(ethanol and surplus electricity) and the exergy of the resources
(sugarcane and straw).
Exergy efficiency
. (6)
(ηB ) P
Bproducts
ηB = P .
Bresources

The AUEC is a measure of the exergy destruction, which occurs

during the upstream processes to form a given exergy stream.
Average unitary exergy cost
cethanol ∗ Bethanol + celectricity ∗ Belectricity (7)
(AUEC) 1
AUECProcess =
Bethanol + Belectricity

Exergy-based GHG emissions and renewability performance

Ratio between the estimated specific CO2 equivalent emissions
emitted into the atmosphere due to the process and the exergy
Exergy-based of the products.
CO2-eq. emissions (8)
(BCO2 EE ) 2 Global CO2equivalent emissions
BCO2 EE =
Bproducts

λ values indicate if the net exergy of the products could be used

to restore the environment to its conditions prior to the process
and yet have a net output of exergy.
Renewability exergy index (λ) 3 (9)
ΣBproducts/byproducts
λ=
Bfossil + Bdestroyed + Bdeactivation + Bdisposal + ΣBemissions/residues

1 See Section 3.4.1, 2 Section 3.4.2, 3 Section 3.4.3 for more details.

3.4.1. Average Unitary Exergy Cost

Exergetic cost is a conservative value accounting for the external exergy that is necessary to make
an exergy flow available within a specific productive process [36]. Thus, the AUEC is a measure of the
irreversibilities, which occur during the upstream processes in order to form a given exergy stream.
Therefore, higher irreversibilities result in a higher unit exergy cost. It is important to highlight that
Processes 2019, 7, 670 10 of 31

the exergy cost allows a closer view of the contribution of each product to plant efficiency, allowing for
the allocation of losses between products based on a thermodynamic premise.
The unit exergy cost c (kJ/kJ) of the ethanol and the electricity production is calculated as the inverse
of the exergy efficiency of the ethanol process and cogeneration unit, respectively, given in the Appendix A
Section (Figure A4). Furthermore, the exergy assessment (Figure A5) and the exergy efficiency definitions
of the cogeneration unit, the ethanol process, and the overall process are reported in Table A10.

3.4.2. Exergy-Based CO2 Equivalent Emissions

This work focuses on the environmental impact assessment throughout the industrial processing
(sugarcane ethanol process chain) with quantification of the CO2 emission effects in the first generation
process and integrated 1G2G ethanol process (also with mass and heat integration), according to the
system boundaries defined in Figure 1.
Carbon dioxide emissions are based on the CO2 equivalent emissions of global warming potential
(GWP) reported by the Intergovernmental Panel on Climate Change (IPCC) [37]. The values are
calculated as a weighted sum of the mass flow rates of the greenhouse gas components using as weights
the 100-year GWP [20]. Consequently, the balance of each unit operation block displays the CO2
equivalents of the combined feed streams, combined product streams, and net production in the
simulation results. In the case of the comparison of ethanol producing scenarios, boundaries were set
from cradle to gate and the functional unit defined as one liter of ethanol.
Life cycle inventory (LCI) data adopted in this study is reported in Table A11. LCI data for the
sugarcane production were developed by Brazilian Bioethanol Science and Technology Laboratory
(CTBE). Details on the methodological approach of the model and the assumptions considered for the
definition of the inventory can be found elsewhere [38,39]. Since the focus of this study is placed on
the comparison of technological routes (industrial processes stage), main parameters were assumed
as average values representative for sugarcane production in São Paulo state, which is the largest
producer of sugarcane and ethanol in Brazil.

3.4.3. Renewability Exergy Index

The renewability concept has mainly been associated with mass and energy efficiencies
without taking into account the reduction of the energy quality related to conversion processes.
Thus, the renewability exergy index (λ) was proposed, founded on the concept of reversible processes
to develop the renewability analysis in a rational basis by thermodynamic parameters [40].
Equation (9) shows the renewability exergy index; where, Bproduct denotes the net exergy associated
with the products and/or byproducts, Bfossil is the nonrenewable exergy consumed in the production
processes chain, which denotes the exergy associated with the chemical and biochemical compounds
specified in Table A14. Moreover, Bdestroyed is the exergy destroyed inside the system, punishing the
process for its inefficiencies. Bdeactivation accounts for exergy required for passing the streams leaving
the system, considered as wastes, to not harm environmental conditions. Bdisposal is the exergy
related to waste disposal of the process, Bemissions is the exergy of wastes that are not treated or
deactivated. Thus, according to Oliveira Jr. [40], depending on the value of the renewability exergy
index, it indicates that: (i) processes with 0 ≤ λ < 1 are ranked as environmentally unfavorable.
(ii) λ = 1 points to internal and externally reversible processes with nonrenewable inputs. (iii) If λ > 1,
the process is environmentally favorable, and additionally, increasing λ implies that the process is
more environmental friendly. (iv) When λ →∞, it means that the process is reversible with renewable
inputs and no wastes are generated.
Lastly, Table A14 (Appendix A Section) presents the inventory of process-related data that are
needed for the renewability exergy index (λ) calculation for the conventional-1G, mass integrated-1G2G,
and the heat integrated 1G2G-HI sugarcane biorefinery scenarios.
Processes 2019, 7, 670 11 of 31

4. Results and Discussion

In this section, the conventional system is compared to two levels of process integration by
first doing mass integration and then mass–energy integration for ethanol production and power
generation based on the results of the key performance indicators (KPIs). In addition, the distribution
of exergy destruction in the different units of the biorefinery plants and a discussion on the renewability
of processes are given.

4.1. Exergy-Based Performance Analysis

An exergy-based performance analysis was conducted from a cradle-to-gate approach. This analysis
represented a trade-off between mass and heat integration options with respect to a conventional sugarcane
plant using multiple KPIs, which combined exergy analysis, heat integration, and the renewability exergy
approach. The exergy efficiency, destroyed exergy, and the irreversibility per liter of ethanol produced
by subsystem for each scenario are presented in Table 2. It is noted that the 2G unit refers to the
second-generation processes, while (1G2G-HI) represents the 1G2G heat-integrated process.

Table 2. Exergy efficiency and irreversibilities of the systems.

Exergy Efficiency Exergy Destruction Exergy Destruction

Parameter
(%) (%) Breakdown (MW)
1G2G 1G2G 1G2G
Configuration 1G 1G2G 1G 1G2G 1G 1G2G
HI HI HI
Sub-system
Extraction 87.9 87.0 87.2 10.5 9.0 9.2 83.30 67.99 63.68
Juice Treatment 95.0 95.0 95.4 4.9 4.2 4.3 38.70 32.08 30.07
Juice Concentration 96.5 95.8 96.1 1.9 1.5 1.4 14.88 11.48 9.94
Fermentation 80.3 80.8 81.4 15.5 12.1 12.2 123.06 91.67 84.55
Distillation 94.2 94.0 94.1 6.3 6.5 6.1 50.28 48.94 42.47
Dehydration 98.9 98.8 99.0 0.6 0.5 0.5 4.58 4.02 3.15
Cogeneration 53.6 50.1 54.2 59.0 58.6 58.3 469.67 443.40 403.84
Condensate tank 70.1 79.1 80.5 1.4 1.1 1.1 11.24 8.22 7.55
2G Unit N/A1 86.0 88.4 N/A 1 6.4 6.8 N/A 1 48.24 47.03
1 N/A: not apply.

The cogeneration unit, which is common to the three process configurations, accounts
for approximately 58% to 60% of the irreversibilities in all scenarios, mainly due to biomass burning
as fuel and the low energy conversion efficiencies. Fermentation unit also contributes 12% to 14%
of destroyed exergy, mainly due to the biochemical reactions because of the exothermic nature,
taking into account the low temperature.
Regarding the irreversibility per liter of ethanol, the mass and heat integration allowed
reduction respect, with the conventional sugarcane plant moving from 1G = 11.4 kWh/lethanol to
1G2G = 8.3 kWh/lethanol and to 1G2G-HI = 6.8 kWh/lethanol , respectively (Table A18). Thus, the pinch
analysis led to a reduction of 8% in the destroyed exergy of the 1G2G-HI system over the 1G base case.

4.2. Renewability Exergy Index

Figure 4 provides the λ results for the sugarcane plants. It is noted the relation between the exergy
efficiency (ηB ) and the associated exergy destruction (resource degradation) with regard to the renewability
exergy index for several technological configurations. Although there is a direct relation, the terms involved
in λindex allow a better analysis from the thermodynamic perspective of the alternatives to improve
the renewability a given biofuel production (ethanol process), aiming to highlight their potential processing
and consequent valorization.
Processes 2019, 7, 670 12 of 31

Figure 4. Relation between the exergy efficiency and the renewability performance indicator.

First, the λ index was calculated considering the useful exergetic effects of the products Bproduct
(ethanol and electricity) and later taking into account the exergy flow rate of byproducts. In light
of these results, special attention must be given to these exergy values (Appendix A Section) in regards
to the sugarcane-based biorefinery byproducts (i.e., filter cake, lignin cake, vinasse, and pentoses
liquor) valorization.
λ renewability performance is ranked as environmentally unfavorable for the conventional, mass,
and mass–heat integration cases analyzed in this study. The trend of λ index was to increase according
to the levels of integration. In order to contrast the λ renewability performance of bioenergy systems
and verify the relation between λ and the exergy efficiency, a comparison with respect to technological
configurations is given in Figure 4.
For example, Pellegrini and Oliveira Jr. [41] presented a thermo-economic, environmental analysis,
and optimization in sugarcane mills combining the production of sugar, ethanol, and electricity
(as an annexed plant), evaluating different types of cogeneration systems. The results show λ = 0.66
and ηB = 43.5% in the exergy-based analysis of the traditional Brazilian mill (1G plant, base case). It has
also been reported that the performance of the mentioned system could be improved by allowing
commercialization of the surplus electricity. In this way, the λ indicator could be increased from
0.66 to 1.03, becoming the process renewable through the implementation of the biomass integrated
gasification combined cycle (BIGCC) and supercritical cycle (SuSC) technologies. Furthermore,
backpressure steam turbine (BPST) and condensing extraction steam turbine (CEST) systems have
a λ lower than 1, indicating that these cogeneration processes may not be considered renewable from
the second law of thermodynamics point of view [41].
Velásquez et al. [42] reported the exergo-environmental evaluation of liquid biofuel production.
These authors indicated that the ethanol process from the lignocellulosic material contained in the
hanging cluster of the banana plant represented the lowest performance, ηB (12.2%) and λindex (0.13).
Thus, according to their λ values, the ethanol production from the amylaceous material contained
in the banana pulp (λ = 0.41) and in the banana fruit (λ = 0.30) were determined as nonrenewable
processes. Similarly, the traditional mill with λ (0.72) and ηB (45.7%) is also ranked in the same category
(Figure 4). However, the exergy destroyed in the sugarcane 1G plant is slightly higher than the exergy
in products (I/Bp = 1.06). Lastly, biodiesel production from the fresh fruit bunches (FFB) of palm oil
exhibits the highest values of the nonrenewable exergy used in the production plant, mainly due to the

1
Processes 2019, 7, 670 13 of 31

high consumption of methanol (oil transesterification reaction). Thus, the use, in this case, of oils with
a low free fatty acid content allows using less methanol in the reaction and obtained higher yields
in the transesterification reaction, which results in a λ higher than 1.
A comparison related to fossil-based configurations reported by Carranza and Oliveira [43] shows
the λ index calculation of an offshore platform for two case studies. First, an offshore plant without
CO2 capture system (CCS) and next an offshore plant with CCS, getting λ values of 0.064 and 0.065,
respectively. Thus, λ index of less than 1 indicate that these exploration processes of the oil and gas
industry are environmentally unfavorable. According to the authors, these results are explained
because the additional exergy consumption required by the CCS configuration is a nonrenewable
resource, and its negative effect in λ index is more significant than the positive effect produced by
the exergy of byproducts and the irreversibility of the emissions. Lastly, the insights when comparing
1G, 1G2G, and 1G2G-HI against the offshore plants show superior renewability of the processes that use
renewable materials rather than fossil-based resources. Concerning the performance of autonomous
plant (1G case) versus the annexed plants, it is noted the higher renewability of the latter due to the
lower irreversibility of the processes involved in the joint sugar and ethanol production.

4.3. Analysis of KPIs for Ethanol Production Configurations

The overall performance of the ethanol production processes is carried out based on the KPIs
applied to analyze the design and assessment of sugarcane biorefineries that combines usage of first-
and second-generation (1G2G) feedstocks. Hence, the combination of process efficiency, exergy-based
CO2-eq. emissions, and renewability indexes can give a better representation of a specified biorefinery
system. Table 3 shows the main results obtained in the assessment of these technological scenarios
in order to synthesize the performance criteria.

Table 3. Key performance indicator (KPI) results for the ethanol processes configurations.

Mass and Heat

Base Case (1G) Mass Integration (1G2G)
Integration (1G2G-HI)
Process performance
Energy efficiency (%) 50.1 53.4 58.9
Exergy efficiency (%) 42.4 45.3 49.9
AUEC process (kJ/kJ) 2.09 1.69 1.61
Exergy-based GHG emissions and renewability performance
Specific CO2- eq. emissions (gCO2 /MJproducts )
BCO2 EE 1 160.56 108.12 94.10
Renewability exergy indicator (λ)
λ Products 0.66 0.70 0.83
λ Products and By-products 2 0.75 0.93 1.09
Main products
Anhydrous ethanol production (l/t cane) 3 83.8 109.9 121.5
Surplus electricity (kWh/t cane) 168.3 49.8 52.8
1 Considering the exergy of the ethanol and surplus electricity. 2 Considering the exergy of byproducts (filter cake,
lignin cake, vinasse, and pentoses liquor) as indicated in Table A14. 3 Scale of production in terms of crushing
capacity SC (833 t/h) and SC Straw (44.95 t/h).

In general, the results of process performance show higher energy and exergy efficiencies for the
1G2G and 1G2G-HI plants, whereas the AUECprocess presents a reduction as a consequence of the
irreversibility minimization at the different levels of integration. These values were compared with
the exergetic assessment of the cogeneration process and the ethanol unit in Appendix A Section.
Emphasizing that the efficiency of the utility system is lower (24%) for all the scenarios (Figure A5) once
it entails a large amount of irreversibility in the combustion processes.
Processes 2019, 7, 670 14 of 31

On the other hand, the exergy-based GHG emissions and renewability performance focuses on
the cane ethanol process chain, which presented lower specific CO2 emissions for the mass and heat
integration cases, allowing for a reduction in the carbon footprint related to the conventional process
by 12% and 16%, respectively.
Even though the exergy values of the products (anhydrous ethanol and electricity) are considered
in the λ calculation, the resulting renewability values of the sugarcane-based ethanol production
processes are in all cases environmentally unfavorable (λ < 1). However, when the exergy flow of the
byproducts is pondered, the λ increases as well to the point that 1G2G-HI represented a λ value higher
than one (environmentally favorable). Regarding the steam demand of the configurations, base case
(1G) achieved 739 kgsteam /t cane, mass integration (1G2G) attained 1048 kgsteam /t cane and mass–heat
integration (1G2G-HI) reported 926 kgsteam /t cane. It represents a reduction of the steam consumption
of 12% in contrast to the 1G2G case.

Benchmark with Other Sugarcane Biorefinery Studies

Findings of this study were compared with the literature. Table 4 shows the performance
assessment of different technological configurations using the exergy values (Appendix A Section)
and applying the exergy balance (Equation (4), Section 3.3). This table describes these configurations
in order to contrast the findings with similar processes. Thus, global exergy efficiency, irreversibility
rate, and the average unitary exergy cost (AUEC) were calculated for each sugarcane biorefinery,
aiming to complement the analysis.

Table 4. Performance comparison of the different processes.

In This Study Dias et al. [11] Albarelli et al. [9] Palacios et al. [10]
Parameters 1G 1G2G 1G2G-HI 1G A 1G2G B 2G C 1G2G D 1G2G E 1G2G F
Process performance
System Exergy
42.4 45.3 50.0 38.8 40.2 30.1 40.4 45.1 34.7
Efficiency (%)
AUEC process (kJ/kJ) 2.09 1.69 1.61 2.58 2.49 3.32 2.48 2.22 2.88
Irreversibility (MW) 1 796 756 692 436 620 331 619 388 518
Bout (%) 2 26 17 0.3 37 33 57 32 18 38
Bin (%) 3 58 55 50 61 60 70 60 55 53
kWh/lethanol 4 11.4 8.3 6.8 10.8 10.5 17.4 10.4 8.3 11.8
Main products
Anhydrous ethanol
83.9 109.9 121.5 81.0 118.0 38.0 119.0 93.6 87.7
(l/t cane)
Anhydrous ethanol
446 585 647 259 377 122 381 275 280
(MW) 5
Surplus Electricity
168 49 52 35 80 42 77 87 60
(kWh/t cane)
Surplus Electricity
140 42 44 18 40 21 39 44 44
(MW)
B products (MW) 587 626 690 277 417 143 419 318 323
A B
Optimized autonomous distillery with maximization of surplus electricity. Integrated 1G2G (fermentation).
C Stand-alone 2G plant and pentoses fermentation. D Integrated 1G2G and pentoses biodigestion.
E Second-generation ethanol production from bagasse P-fraction. F Ethanol production via steam explosion and

enzymatic hydrolysis. 1 Irreversibility per raw material, SC (833 t/h), and SC Straw (44.95 t/h). 2 Irreversibility per
percentage of total exergy of the products. 3 Irreversibility per percentage of total exergy of the inputs.
4 Irreversibility in terms of the anhydrous ethanol production. 5 Value of the biofuel flow rate in exergy base.

Dias et al. [11] show an ethanol production scale of 120 l/t cane for an integrated process (their Scenarios
C and E), using steam explosion as pretreatment technology, which represents an increase of 46.9%
in ethanol production and around 128% in power generation over their base case (1G plant).
Albarelli et al. [9] reported an integrated 1G and 2G process with thermal and water integration.
With that, better use of energy and water was accomplished, allowing higher surplus electricity
Processes 2019, 7, 670 15 of 31

production. Palacios et al. [10] evaluated the exergy and exergetic cost associated with the ethanol
production process from sugarcane biomass, including the route of bagasse enzymatic hydrolysis.
The results showed that the exergy destruction resulting from the introduction of the enzymatic
hydrolysis correspond to an important portion between 7–10% of the total exergy destruction and
losses of the entire process.

5. Conclusions
Combined 1G2G-HI ethanol production plant resulted in a better thermodynamic performance
in terms of destroyed exergy reduction compared to the base case (1G) and the mass integration (1G2G)
configurations. This higher thermodynamic efficiency was basically due to the heat integration system,
included as part of the conversion process, which allowed the lowest unitary exergy cost of these
biorefineries. Thus, the pinch analysis led to an 8% reduction in the irreversibility, and a decrease
of 12% steam consumption in contrast to the 1G2G case.
Furthermore, a technological comparison of the biorefinery scenarios (i.e., 1G, 1G2G and 2G) was
carried out based on key performances indicators. Results showed the correlation between the exergy
and renewability of the processes, which allowed to identify the use of renewable and nonrenewable
resources associated with a particular system.
The exergy-based performance assessment can support decision-making for process design
of a sugarcane ethanol plant towards a sustainable biorefinery configuration. Hence, the renewability
index points out the effect of useful exergy of the products and byproducts involved in the cane-ethanol
process chain once the byproducts’ valorization could translate in environmentally favorable systems.
Lastly, it was demonstrated that the reduction of the entropy generation (destroyed exergy) in 1G2G-HI
case mainly corresponds to increased efficiency in cogeneration and fermentation processes.

Author Contributions: Conceptualization and methodology design: P.A.S.O. and J.P.; data analysis and validation:
P.A.S.O., R.M.F. and J.P.; Writing—Original draft preparation: P.A.S.O. and J.P.; supervision: R.M.F. and J.P.;
project administration, R.M.F. and J.P.
Funding: This research was funded by the São Paulo Research Foundation (FAPESP), grants number 2017/03091-8
and 2017/16106-3.
Acknowledgments: The authors acknowledge the financial support of FAPESP. In addition, this work was carried
out within the framework of the BIOEN thematic project, FAPESP process 2015/20630-4.
Conflicts of Interest: The authors declare no conflict of interest.

Nomenclature
AUEC Average unitary exergy cost (kJ/KJ).
B Exergy flow rate (kW).
b Specific exergy (kJ/kg).
BCO2EE Specific carbon dioxide CO2 equivalent emissions (gCO2 /MJ products).
Bch, i Standard chemical exergy (MJ/kg, kJ/kmol).
Bdestroyed Destroyed exergy (kW).
Bdeactivation Destroyed exergy rate of additional natural resources during waste de-activation (kW).
Bdisposal Exergy rate or flow rate related to waste disposal of the process (kW).
Bemissions Exergy rate of wastes that are not treated or deactivated (kW).
Bfossil Nonrenewable exergy rate consumed in production processes chain (kW).
Bproduct Exergy rate or flow rate associated to the products and byproducts/useful effect (kW).
Butilities Exergy rate or flow rate required by the utilities of the process (kW).
BQo Supply heat exergy to the heat recovery section of the utility systems
c Unit exergy cost
CO2- eq. Carbon dioxide equivalent.
H, h Enthalpy (kJ/kg)
I Irreversibility rate (kW).
m Mass flow rate (kg/s).
Processes 2019, 7, 670 16 of 31

ηB Exergy Efficiency (%).

ηE Energy Efficiency (%).
R Universal gas constant (J/mol K).
S, s Entropy (KJ/kg-K)
T0 Temperature (K).
xi Mole fraction of component i.
v/v Volume/Volume%.
w/w% Weight Percent.
W Power (kW).
῾Υ Activity coefficient.
λ Renewability exergy index.
ϕ Ratio between the specific chemical exergy and the lower heating value.

Abbreviations
1G First-generation ethanol production process.
2G Second-generation ethanol production process.
1G2G Integrated first- and second-generation ethanol production technology.
BIGCC Biomass integrated gasification combined cycle.
BPST Backpressure steam turbine.
CEST Condensing-extraction steam turbine.
CHP Cogeneration system.
FPU Filter paper cellulase units.
GWP Global warming potential.
GHG Greenhouse gases.
HEN Heat exchanger network.
NRTL Non-random two-liquid.
MEE Multiple effect evaporation
LCA Life cycle analysis and assessment.
LCI Life cycle inventories.
LHV Lower heating value.
KPIs Key performance indicators.
SuSC Supercritical cycles

Appendix A

Appendix A.1 Feedstock Composition and Processing Capacity Adopted in the Simulations
Table A1 presents the feedstock composition (mass percent) adopted in this study for the sugarcane (SC),
whereas Table A2 shows the dry mass composition of SC bagasse and straw used as inputs. Lastly, Table A3 displays
the processing capacity adopted in the simulations.

Table A1. Raw material composition.

Formula Components 1 Molar Weights (g/mol) Sugarcane Composition (w/w%)

C6 H10 O5 Cellulose 162.14 5.95
C5 H8 O4 Hemicellulose 132.12 3.52
C7.3 H13.9 O1.3 Lignin 122.49 3.19
C12 H22 O11 Sucrose 342.29 13.92
C6 H12 O6 Glucose 180.16 0.60
K2 O Minerals 94.2 0.20
KCl Potassium chloride (salts) 74.55 1.17
C6 H6 O6 Aconitic acid (organic acids) 174.1 0.6
H2 O Water 18.015 69.82
SiO2 Silicon dioxide (soil) 60.08 1.03
1 Adapted from Dias [25], Palacios-Bereche [44].
Processes 2019, 7, 670 17 of 31

Table A2. Dry mass composition of sugarcane (SC) bagasse and straw.

Components 1 Bagasse Straw

Carbon 0.50 0.47
Hydrogen 0.07 0.07
Oxygen 0.41 0.38
Ash 0.02 0.08
1 Palacios-Bereche [44].

Table A3. Processing capacity adopted in the simulations.

Process Parameters Value Units References

Sugarcane processed (wet basis) 4 million t cane/year [19]
Harvest period (operation time) 200 days [19]
Straw production (dry basis) 140 kg/t cane [45]
Straw fraction recovered from the field 50 % [45]
Sugar extraction efficiency 96 % [19]
Straw moisture 30 % [19]
Bagasse moisture 50 % [19]

Appendix A.2 Technical Parameters of the First-Generation Ethanol Plant

The technical parameters for a standard sugarcane biorefinery are presented in Table A4. Hence, the assumptions
in the simulation of the first-generation (1G) ethanol process are specified in this table for each subsystem
under consideration.

Table A4. Main technical parameters used in the traditional ethanol production (1G) plant simulation.

Process Parameters Value Units References

JUICE TREATMENT
First juice stage—temperature heating 70 ◦C [23]
Phosphate content of the juice after H3 PO4 addition 250 ppm [25]
Amount of lime added in liming (ethanol/sugar production) 0.6/1.0 kgCaO /t cane [25]
Second juice stage—temperature heating 105 ◦C [19]
Filter cake moisture content 60–70 % [25]
Insoluble solid retention in the filter 65 % [25]
Wash water related to filter cake 15 % [23]
Bagasse fines supplemented in the filter 6 kg/t cane [23]
Removal efficiency of insoluble solids in the clarified juice 65 % [25]
JUICE CONCENTRATION
Effects number in the evaporation process 5 - [25]
Syrup 65 ◦ Brix [25]
FERMENTATION AND CELL TREATMENT
Fraction of the reactor fed with yeast solution 25 w/w% [23]
Fermentation temperature 33 ◦C [23]
Efficiency of solid retention (centrifuges) 99 % [25]
Ethanol content in the wine (distillation feed) 80 g/L [25]
Ethanol content of the yeast concentrated solution (centrifuges) 6.5 w/w% [25]
H2 SO4 addition in yeast treatment (on 100% basis) 5 kg/m3 ethanol [25]
DISTILLATION
Vinasse and phlegmasse ethanol content <200 ppm [19]
Fusel oil per ethanol produced 0.2 v/v% [19]
Hydrated ethanol purity 93 w/w% [19]
MOLECULAR SIEVES
Feed temperature 150 ◦C [23]
Steam pressure 6 bar [23]
Ethanol recovered as final product 81.4 % [25]
Anhydrous ethanol (AE) purity 99.6 w/w% [45]
Molecular sieves steam consumption 0.6 kgsteam /lAE [45]
Processes 2019, 7, 670 18 of 31

In the simulation of the fermentation process (C6 sugars) were taken into account the following
reactions (Table A5).

Table A5. Fermentation Reactions.

FERMENTATION REACTIONS 1 Description Equation

C12 H22 O11 + H2 O → 2C6 H12 O6 Sucrose inversion (A1)
C6 H12 O6 → 2C2 H6 O + 2CO2 Ethanol production (A2)
3.2618 C6 H12 O6 + 2.8469 NH4 OH +2.1352 CO2 →
Cell growth (A3)
1.0359 C2 H4 O2 + 6.9454 H2 O + 19.6342 CH1.8 O0.9 N0.1
0.7630 C6 H12 O6 → 0.7630 C4 H10 O + 1.5260 CO2 + 0.7630 H2 O (A4)
0.6107 C6 H12 O6 + 0.5236 H2 O → 0.5234 CO2 + 1.047 C3 H8 O3 (A5)
By-products Formation
C6 H12 O6 → 3C2 H4 O2 (A6)
0.827 C6 H12 O6 → 0.662 C5 H12 O + 1.654 CO2 + 0.9927 H2 O (A7)
1 Bonomi et al. 2016 [17].

In the model, it was assumed that these reactions occur sequentially. The reactions comprise sucrose
hydrolysis (A1), ethanol production (A2), yeast growth (A3), and formation of byproducts (isoamyl alcohol (A4),
isobutanol (A5), glycerol (A6) and acetic acid (A7)).
In addition, A1 conversion was fixed as 100%, whereas A2 was defined in 90% (average yields of a conventional
fermentation process). Reactions from A3 to A7 had their stoichiometric coefficients estimated in order to balance
the equations as indicated in Bonomi et al. 2016 [17].

Appendix A.3 Process Flow Diagrams

The flowsheet of the ethanol production process implemented in Aspen Plus is given in Figure A1,
where Col. A, Col. A1, Col. B-B1, and Col. D represented the stripping section, rectification section,
phlegm rectification, and the top concentrator in the distillation unit, respectively. Furthermore, the process flow
diagram of the second-generation production is described in Figure A2 and the flowsheet diagram of Figure A3
shows the utility system (cogeneration unit).
Appendix C. Process flow diagrams
The flowsheet of the ethanol production process implemented in Aspen Plus is given in Figure
A1, where Col. A, Col. A1, Col. B-B1, and Col. D represented the stripping section, rectification
section, phlegm rectification, and the top concentrator in the distillation unit, respectively.
Furthermore,
Processes the process flow diagram of the second-generation production is described in Figure
2019, 7, 670 19 of 31
A2 and the flowsheet diagram of Figure A3 shows the utility system (cogeneration unit).

Figure A1. Flow diagram of the ethanol production process.

Processes 2019, 7, x FOR PEER REVIEW 21 of 33
Processes 2019, 7, 670 20 of 31
Processes 2019, 7, x FOR PEER REVIEW 21 of 33

Figure A2. Process flow diagram of the second-generation ethanol production.

Figure
Figure A2. Process
Process flow
flow diagram
diagram of
of the
the second-generation
second-generation ethanol production.

Figure A3. Process flow diagram of the utility system.

Appendix
AppendixA.4
D.Technical
TechnicalParameters of the
parameters ofCogeneration
the flow System
cogeneration
Figure A3. Process diagram ofsystem
the utility system.
The cogeneration system (CHP unit) adopted in the simulation consists of a steam cycle with backpressure
steamThe
Appendix
cogeneration
turbines. The mainsystem
D. Technical process(CHP unit) adopted
parameters
parameters of theand
in the
chemical
cogeneration
simulation consists of a steam cycle with
reactions
systeminvolved in the cogeneration section are
given in Table A6.
backpressure steam turbines. The main process parameters and chemical reactions involved in the
The cogeneration
cogeneration system
section are given (CHP unit)
in Table A6.adopted in the simulation consists of a steam cycle with
backpressure steam turbines. The main process parameters and chemical reactions involved in the
cogeneration section are given in Table A6.
Processes 2019, 7, 670 21 of 31

Table A6. Combined heat and power unit.

Process Parameters Value Units References

COGENERATION SYSTEM
Steam temperature (superheated steam) 485 ◦C [46]
Pressure of the boiler system 65 bar [46]
Boiler thermal efficiency (LHV basis) 87.7 % [46]
Gases outlet temperature 160 ◦C [46]
Turbine isentropic efficiency 85 % [46]
Generator efficiency 98 % [46]
Isentropic efficiency of direct drive steam turbines 50 % [24]
Pump isentropic efficiency 70 % [24]
Electricity consumption 1G 30 kWh/t cane [47]
Condensing pressure 0.11 bar [47]
Condensate losses 5 % [47]
Fraction of bagasse for start-ups of the plant 5 % [47]
CHEMICAL REACTIONS (boiler section) Equation
C6 H10 O5 + 6O2 → 5H2 O + 6CO2 (A8)
C5 H8 O4 + 5O2 → 4H2 O + 5CO2 (A9)
C7.3 H13.9 O1.3 + 10.95O2 → 5.8H2 O + 10CO2 (A10)

In the boiler section, the combustion reactions for each component present in the lignocellulosic material
(mainly cellulose, hemicellulose, and lignin) were inserted in the simulation as solid components (Table A12)
and conversion was set as 100%. Thus, the inefficiencies of the boiler were represented as the loss of a fraction
of the hot gases after combustion. Therefore, the lower heating value (LHV) of sugarcane bagasse (50% moisture)
and straw SC (15% moisture) was calculated based on the enthalpy of combustion for each component as given
in Table A13.

Appendix A.5 Technical Parameters of the Second-Generation Ethanol Process

The 2G process was based on the steam pretreatment technology followed by an advanced enzymatic
hydrolysis process. Table A7 depicts the detailed parameter conditions implemented in the 1G2G ethanol
simulation process.
Stoichiometric model reactors were utilized to denote pretreatment and hydrolysis reactors as well as pH
adjustment and fermentation of C5 liquor. Solid–liquid separation units (diffuser and filter) and centrifuge were
simulated taking into account the separation efficiencies.

Table A7. Main technical parameters adopted in the simulation of the second-generation (2G)
ethanol process.

Process Parameters 1
STEAM EXPLOSION PRETREATMENT Value Units
Temperature 210 ◦C

Residence time 5 min

Pretreatment reactor pressure 12.5 bar
Pretreatment reactor steam consumption 0.55 kgsteam /kgfeedstock
Pressure at unitary pretreatment block 1.01 bar
Cellulose solubilization 5.5 %
DIFFUSER Value Units
Proportion of water added 180 % of cellulignin fibers
Insoluble solid retention 99.5 %
Soluble solids recovered in the liquor 98 %
Cellulignin moisture 50 %
ENZYMATIC HYDROLYSIS Value Units
Temperature 65 ◦C

Residence time 36 h
Enzymatic load—cellulase 53 FPU/g dry biomass
Processes 2019, 7, 670 22 of 31

Table A7. Cont.

Process Parameters 1
Enzymatic load—bglucosidase (enzyme activity) 83 IU/g dry biomass
Solid content 20 %
Cellulose conversion to glucose 80 %
Xylan conversion to xylose 80 %
Electricity consumption for the 2G process 51 kWh/t cane
PRETREATMENT REACTIONS Yield (%) Equation
C5 H8 O4 + H2 O → C5 H10 O5 61.4 (A11)
C5 H8 O4 + H2 O → 2.5C2 H4 O2 9.2 (A12)
C5 H10 O5 → C5 H4 O2 + H2 O 5.1 (A13)
C6 H10 O5 + H2 O → C6 H12 O6 4.1 (A14)
HYDROLYSIS REACTIONS Yield (%) Equation
C5 H8 O4 + H2 O → C5 H10 O5 40.6 (A15)
C6 H10 O5 + H2 O → C6 H12 O6 55.8 (A16)
1 Adapted from Milanez et al. [18] and Palacios–Bereche [44].

Simultaneously to pentose fermentation, deoligomerization reactions (Equations (A17) and (A18)) occur
in the reactor. Additionally, glucose conversion, ethanol production (Equation (A19)) and byproduct formation
(Equations (A20)–(A23)) from xylose were inserted in the simulation, as given in Table A8. Hence, the reaction
conversion of Equations (A17)–(A19) was fixed as 80%, whereas reactions from Equations (A20)–(A23) had their
stoichiometric coefficients estimated in order to balance the equations as indicated in Bonomi et al. 2016 [17].

Table A8. Pentose fermentation reactions.

PENTOSE FERMENTATION 1 Description Equation

C5 H10 O5 Oligomers + n H2 O → n C5 H10 O5 (A17)
Deoligomerization reactions
C6 H12 O6 Oligomers + n H2 O → n C6 H12 O6 (A18)
3C5 H10 O5 → 5C2 H6 O + 5CO2 Ethanol production (A19)
6C5 H10 O5 → 5C4 H10 O + 10CO2 + 5H2 O (A20)
7C5 H10 O5 + 5H2 O → CO2 + 10C3 H8 O3 (A21)
Formation of by-products
2C5 H10 O5 → 5C2 H4 O2 (A22)
3C5 H10 O5 → C5 H12 O + 5CO2 + 3H2 O (A23)
1 Bonomi et al. 2016 [17].

Appendix A.6 Data Extraction

The thermodynamic parameters of hot streams or process heat sources, which present a cooling demand
(heat supply), and cold streams or process heat sinks, which present a heat demand for heat integration through
pinch analysis were described in the Table A9.

Table A9. Streams selected for heat integration.

Tinitial Tfinal Heat Flow Heat Flow 1

Hot Streams
Ti (◦ C) Tf (◦ C) ∆H (MW) (MJ/t)
H1 Sterilization of juice 130.0 32.0 55.3 5501
H2 Fermented wine 39.0 33.0 10.2 1015
H3 Vinasse 109.3 35.0 37.5 3730
H4 Anhydrous ethanol 81.5 35.0 12.4 1231
H5 Vapor Condensates 85.2 35.0 15.0 1487
H6 Condenser column B (Concentration) 81.6 81.6 26.5 2636
H7 Condenser column D (Rectification) 85.1 32.0 32.5 3233
H8 Vapor recovered from steam explosion 100.9 100.0 16.6 1651
Processes 2019, 7,
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x FOR PEER REVIEW 23
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33

Tinitial Tfinal Heat Flow Heat Flow 1

Cold Streams Table A9. Cont.
Ti (°C) Tf (°C) ∆H (MW) (MJ/t)
C1 Juice treatment Tinitial34.2 98.0
Tfinal 42.7
Heat Flow 4247Flow 1
Heat
Cold Streams
C2 Juice preheating (before MEE) Ti (◦ C)98.0 (◦ C)
Tf 120.0 ∆H10.8
(MW) 1074
(MJ/t)
C1 C3 Juice
Juice for sterilization
treatment 34.2 89.0 130.0
98.0 21.4
42.7 2129
4247
C2 Juice preheating (before MEE)
C4 Centrifuged wine 98.0 31.2 120.0
89.0 10.8
39.4 1074
3919
C3 JuiceC5for sterilization
Reboiler column A 89.0 112.1 130.0
112.1 21.4
59.5 2129
5922
C4 Centrifuged wine 31.2 89.0 39.4 3919
C6 Reboiler column B (Rectification) 104.0 104.0 37.2 3699
C5 Reboiler column A 112.1 112.1 59.5 5922
C7 Reboiler recovery column
C6 Reboiler column B (Rectification) 104.0149.6 149.6
104.0 2.6
37.2 259
3699
C8 Hydrolysis
C7 Reboiler recovery column water 149.6 30.0 50.0
149.6 8.6
2.6 855259
C8 Hydrolysis water
C9 Glucose liquor preheating 30.0 50.0 50.0
115.0 8.6
29.6 855
2944
C9 Glucose liquor preheating 50.0 per ton 115.0
1 Energy requirement of ethanol. 29.6 2944
1 Energy requirement per ton of ethanol.
Appendix G. Unit exergy cost and exergy efficiency
Figure
Appendix A.7A4 showed
Unit Exergythe Costunit
and exergy cost c (kJ/kJ) of the anhydrous ethanol and the electricity
Exergy Efficiency
calculated in this study as the exergy efficiency inverse of the ethanol process and cogeneration unit,
Figure A4 showed the unit exergy cost c (kJ/kJ) of the anhydrous ethanol and the electricity calculated in this
respectively.
study In addition,
as the exergy Figure
efficiency A5ofpresented
inverse theprocess
the ethanol exergyandassessment of the
cogeneration cogeneration
unit, respectively.process, the
In addition,
ethanolA5unit,
Figure and the
presented theoverall
exergyconfiguration. Later,
assessment of the the exergyprocess,
cogeneration efficiency definitions
the ethanol unit,for
andeach
the system
overall
configuration. Later, A10.
are given in Table the exergy efficiency definitions for each system are given in Table A10.

Figure A4. Average unitary exergy cost (AUEC) of each

each configuration.
configuration.

Table A10. Unit exergy cost and exergy efficiency definitions.

Definition Equation
1
Unit exergy cost, c c= ηB (A24)
. .
wnet +BQo
Cogeneration unit ηB = P . (A25)
Bresources
. .
Bethanol +Bbagasse
Ethanol process 1 ηB = P . . . . (A26)
Bresources +wconsumption +Bsteam +B f ossil
. .
Bethanol +wnet
Overall process ηB = . . (A27)
Bcane +Bstraw
1 The term Bresources represents the exergy of the raw material, whereas Bfossil denotes the exergy associated with
the chemical and biochemical compounds specified in Table A14.
Processes 2019, 7, 670 24 of 31
Processes 2019, 7, x FOR PEER REVIEW 25 of 33

Figure A5.
Figure Efficiencycomparison
A5. Efficiency comparison for
for each
each configuration.
configuration.

Appendix A.8 Life CycleTable

Inventory
A10. Unit exergy cost and exergy efficiency definitions.
Table A11 shows the life cycle inventory for the conversion processes per ton of processed sugarcane.
Definition Equation
1
Unit exergy cost, c Table A11. Life cycle𝑐inventory
= data 1 . (A24)
𝜂𝐵
Compounds GHG (kgCO2/x ) Units 𝑤̇𝑛𝑒𝑡 + Ḃ𝑄𝑜 Comments
Cogeneration unit 𝜂𝐵 = (A25)
∑ ḂIncluding
𝑟𝑒𝑠𝑜𝑢𝑟𝑐𝑒𝑠 transportation, without trash burning,
Sugarcane (SC) 0.034 kg SC ̇
B𝑒𝑡ℎ𝑎𝑛𝑜𝑙 + Ḃ𝑏𝑎𝑔𝑎𝑠𝑠𝑒
with sugar yield of our process
Ethanol process0.01
SC straw
1 𝜂𝐵 = kg SC straw Using the (A26)
yield of ̇ sugars, of SC straw/SC
∑ B𝑟𝑒𝑠𝑜𝑢𝑟𝑐𝑒𝑠 + 𝑤̇𝑐𝑜𝑛𝑠𝑢𝑚𝑝𝑡𝑖𝑜𝑛 + Ḃ𝑠𝑡𝑒𝑎𝑚
̇ + B𝑓𝑜𝑠𝑠𝑖𝑙
Commercial phosphoric acid used has
H3 PO4 1.423 kg H3 PO4 Ḃ
𝑒𝑡ℎ𝑎𝑛𝑜𝑙 + 𝑤̇𝑛𝑒𝑡
a concentration of 85% by mass
Overall process 𝜂𝐵 = (A27)
CaO 0.15 kg CaO Ḃ𝑐𝑎𝑛𝑒 + Ḃ𝑠𝑡𝑟𝑎𝑤 Lime
H2 SO
The
1 term
4 0.124
Bresources represents kg H2ofSOthe
the exergy 4 raw material, whereasSulfuric acid
Bfossil denotes the exergy
NH4 OH 2.089 kg NH4 OH Ammonia, liquid at regional storehouse/kg/RER 2
associated with the chemical and biochemical compounds specified in Table A14.
Enzyme 4.09 kg Enzyme Enzyme cocktail
Analyzing 1 kg ‘Sodium hydroxide, 50% in H2 O,
NaOH
Appendix H. Life cycle 1.096
inventory kg NaOH
production mix at plant/RER 3 ’
SO2 0.44 kg SO2 Sulphur dioxide, liquid, SO
Table A11 shows the life cycle inventory for the conversion processes per ton of2 processed
C2 H4 O2 1.403 kg C2 H4 O2 Acetic acid via methanol carbonylation
sugarcane.
Electricity 0.486 kwh Electricity, Brazilian mix GLO/kWh
1 Adapted from [8,38,39]. 2 RER: Europe (geographical location). 3 GLO: global (geographical location).
Table A11. Life cycle inventory data 1.

Compounds GHG (kgCO2/x) Units Comments

Appendix A.9 Standard Chemical Exergy Including transportation, without trash burning, with
Sugarcane (SC) 0.034 kg SC
sugar yield
Table A12 shows the standard chemical exergy (bch ) for the conventional of our process
compounds used in the exergy
analysis. Furthermore, Equation (A28) presents a correlation related to the bch calculations of of
SC straw 0.01 kg SC straw Using the yield of sugars, theSC straw/SC
‘nonconventional’
components that were inserted, such as solids in the models carried out in Aspen Plus.
Commercial phosphoric acid used has a concentration
H3PO4 1.423 kg H3PO4
of 85% by mass
CaO 0.15 kg CaO Lime
H2SO4 0.124 kg H2SO4 Sulfuric acid
NH4OH 2.089 kg NH4OH Ammonia, liquid at regional storehouse/kg/RER2
Enzyme 4.09 kg Enzyme Enzyme cocktail
Analyzing 1 kg ‘Sodium hydroxide, 50% in H2O,
NaOH 1.096 kg NaOH
production mix at plant/RER3’
SO2 0.44 kg SO2 Sulphur dioxide, liquid, SO2
C2H4O2 1.403 kg C2H4O2 Acetic acid via methanol carbonylation
Electricity 0.486 kwh Electricity, Brazilian mix GLO/kWh
1 Adapted from [8,38,39]. 2 RER: Europe (geographical location). 3 GLO: global (geographical location).
Processes 2019, 7, 670 25 of 31

Table A12. Standard chemical exergy of the compounds used in the simulations.

Chemical Formula Component Type bCH Specific (kJ/kmol)

C6 H10 O5 Cellulose ** Solid 3,404,400
C5 H8 O4 Hemicellulose ** Solid 2,826,640
C7.3 H13.9 O1.3 Lignin ** Solid 3,449,500
Ca3 (PO4 )2 Calcium phosphate ** Solid 19,400
CH1.8 O0.9 N0.1 Yeast1 ** Solid 513,560
CH1.57 N0.29 O0.31 S0.007 Enzyme 2 ** Solid 541,376
CaO Calcium oxide * Conventional 110,200
Ca(OH)2 Calcium hydroxide * Conventional 53,700
CO Carbon monoxide * Conventional 275,100
CO2 Carbon dioxide * Conventional 19,870
C2 H6 O Anhydrous ethanol * Conventional 1,250,900
C6 H12 O6 Dextrose (Glucose) * Conventional 2,928,800
C2 H4 O2 Acetic acid * Conventional 908,000
C3 H8 O3 Glycerol * Conventional 1,705,600
C5 H10 O5 Xylose ** Conventional 2,361,900
C5 H4 O2 Furfural * Conventional 2,338,700
C5 H12 O Isoamyl alcohol * Conventional 3,311,700
C4 H6 O Succinic acid * Conventional 1,609,400
C6 H6 O6 Organic acids * (Aconitic acid) Conventional 3,128,500
C12 H22 O11 Sucrose * Conventional 6,007,800
K2 O Potassium oxide * Conventional 413,100
KCl Potassium chloride * (Salts) Conventional 19,600
NO Nitric oxide * Conventional 88,900
N2 Nitrogen * Conventional 720
O2 Oxygen * Conventional 3970
H2 Hydrogen * Conventional 236,100
H2 O Water * Conventional 900
H2 SO4 Sulphuric acid * Conventional 163,400
H3 PO4 Phosphoric acid * Conventional 104,000
NH3 Ammonia * Conventional 337,900
NH4 OH Ammonium hydroxide 3 Conventional 328,800
SiO2 Silicon dioxide 4 Solid 3545
SO2 Sulfur dioxide * Conventional 313,400
* Adopted values for bCHspec from Szargut et al. [31]. ** Calculated using the correlations linking the ratio of the
standard chemical exergy and the net calorific value of the substances [34]. 1 For the enzymes, the composition
(CH1.57 N0.29 O0.31 S0.007 ) was assumed, as indicated per NREL [21]. 2 The yeast component was created based
on the chemical formula (CH1.8 O0.9 N0.145 ) specified by Eijsberg [48]. 3 Adopted values from Szargut 2005 [49].
4 A content of amorphous material of 25% was considered in the calculation of the b
CH specific of SiO2 . In addition,
the proportions of cristobalite and quartz were assumed to have 16% and 59% (in mass), according to the parameters
for sugarcane bagasse ash reported in Cordeiro et al. [50].

The following expression was used in terms of mass ratios for dry organic materials contained in solid fossil
fuels consisting of c, h, o, and n with a mass ratio of oxygen to carbon less than 0.667; where c, h, o, and n are
the mass fractions of carbon, hydrogen, oxygen, and nitrogen, respectively. According to Kotas [34], the accuracy
of this expression is estimated to be better than ±1%.
Calculation of standard chemical exergy of the ‘nonconventional’ compounds.
 
1.0438 + 0.1882 hc − 0.2509 1 + 0.7256 hc + 0.0383 nc
ϕdry = . (A28)
1 − 0.3035 oc

Appendix A.10 Standard Chemical Exergy and Lower Heating Value for Selected Resources
It is noted that the specific chemical exergy in reference conditions of temperature and pressure (T0 and P0 )
are usually close, or equal to, its heating value (LHV). Table A13 presents the bch and LHV values for several
fossils and bio-based raw materials.
Processes 2019, 7, 670 26 of 31

Table A13. Values of bch and LHV for diverse compounds.

Standard Chemical Exergy Net Calorific Value

bCH LHV
FORMULA SUBSTANCES References References
(MJ/kg) (MJ/kg)
FOSSIL RAW MATERIALS
H2 Hydrogen (g) 117.12 [31] 120.00 [51]
CH4 Methane, Natural Gas (g) 51.84 [31] 45.00 [51]
Crude Oil 42.38 [52] 42.69 [53]
Coal (s) 23.59 [52] 22.73 [53]
CnH1.87 n Gasoline (l) 47.39 [54] 44.00 [51]
BIOMASS/BIOBASED FEEDSTOCK
C6 H12 O6 Glucose-D-Galactose (Cellulose) 16.26 [31] 15.60 [55]
Sugarcane bagasse 1 9.67 17.55
Sugarcane 1 5.22 4.43
Straw 1 13.84 11.5
Plant Oil 40.00 [35] 35.60 [53]
INTERMEDIATES
C2 H4 Ethene (Ethylene) (g) 48.52 [31] 47.16 [56]
C2 H6 O Anhydrous ethanol (l) 29.47 [31] 26.81 [51]
CH4 O Methanol (l) 22.41 [31] 20.09 [51]
C3 H8 O3 Glycerol 18.52 [57] 14.30 [58]
CO Carbon monoxide 9.82 [31] 10.10 [51]
CO2 Carbon dioxide 0.45 [31] 0 -
PRODUCTS
(C2 H4 )n PE—Polyethylene 46.0 [35] 40.0 [59]
(C3 H6 )n PP—Polypropylene 45.5 [35] 41.0 [59]
(C2 H3 Cl)n PVC—Polyvinyl chloride 45.0 [35] 42.9 [59]
(C8 H8 )n PS—Polystyrene 38.0 [35] 38.6 [59]
(C10 H8 O4 )n PET—Polyethylene terephthalate 24.7 [35] 23.8 [59]
Sugar 17.5 [41] -
(s): Solid, (l): liquid, (g): gas. 1 Calculated based on the correlation for the standard chemical exergy of the
‘nonconventional’ compounds, as described in the previous section.

Appendix A.11 Renewability Exergy Index Calculation

The λindex components used in the assessment of the industrial processing stage are presented in Table A14.
The λindex calculation was addressed according to Equation (9) through the exergy of the ‘fossil’ (chemical and
biochemical inputs), the exergy of products, the exergy of the CO2 emissions, and the irreversibilities. It is worth
mentioning that the exergy flow rates (kW) are given in terms of the processing capacity of each biorefinery plant.

Table A14. Estimated exergy terms involved in renewability exergy calculation.

1G 1G2G 1G2G-HI
B Fossil kW kW kW
Sulfuric acid (H2 SO4 ) 47,031 38,674 38,674
Nutrients (NH4 OH) 1442 4441 4441
Phosphoric acid (H3 PO4 ) 41.34 33.55 33.55
Calcium oxide (CaO) 278.91 293.7 293.7
Enzymes - 51,581 51,581
Yeast 6260 12,521 12,521
P
Bfossil inputs (kW) 55,053 107,544 107,544
B products
Surplus electricity 140,320 41,542 43,567
Anhydrous ethanol 446,328 584,795 646,520
P
Bproducts (kW) 586,648 626,336 690,087
Processes 2019, 7, 670 27 of 31

Table A14. Cont.

1G 1G2G 1G2G-HI
B by-products 1

Filter cake 12,572 7552 7552

Lignin cake 0 70,213 70,680
Vinasse 72,866 91,099 99,004
Pentoses Liquor 0 34,942 37,250
P
Bby-products (kW) 71,285 217,032 221,049
B emissions
CO2 Emissions 1 42,536 30,580 29,326
P
Bemissions (kW) 42,536 30,580 29,326
Irreversibilities
P
Bdestroyed (kW) 2 795,713 756,025 692,274
Bin (%) 3 57.6 54.7 50.1
kWh/lethanol 4 14.6 8.3 8.8
1 The exergy flow rate (kW) of the component i is determined based on the mass flow rate (kg/s) and the standard
. .
chemical exergy bch i
(kJ/kg), Bi = mi ∗ bch
i
. 2 Irreversibility per raw material, SC (833 t/h) and SC Straw (44.95 t/h).
3 Irreversibility per percentage of total exergy of the inputs. 4 Irreversibilities in terms of the ethanol production.

Appendix A.12 Properties of the Key Streams and Irreversibilities per Liter of Ethanol in the Systems
This Appendix A Section shows the parameters of the key streams of the biorefinery configurations.
Thus, Table A15 presents the operating conditions of the flows involved in the 1G case. Furthermore, Tables A16
and A17 indicate the key streams of the mass-integrated (1G2G) and mass and heat-integrated system (1G2G-HI),
respectively. Lastly, Table A18 presents the irreversibilities per liter of ethanol of each system.

Table A15. Key streams parameters of the traditional ethanol production (1G).

MW
Streams m (kg/s) T (◦ C) P (bar) b (kJ/kg) B (MJ/s)
Cane 231.48 25 1.013 5223 1209.03
Bagasse 62.81 25 1.013 9667 607.23
Straw 12.49 25 1.013 13,845 172.87
Sulfuric acid (H2 SO4 ) 28.23 25 1.013 1666 47.03
Nutrients (NH4 OH) 0.15 25 1.013 9382 1.44
Phosphoric acid (H3 PO4 ) 0.04 25 1.013 1061 0.04
Calcium Oxide (CaO) 0.14 25 1.013 1965 0.28
Yeast 0.36 33 1.013 17,350 6.26
Filter cake 5.82 98 1.013 2162 12.57
Vinasse 164.48 75 1.4 443 72.87
Anhydrous ethanol 15.14 78 1.013 29,471 446.33
CO2 Emissions 94.19 25 1.013 451.59 42.54

Table A16. Key streams parameters of the mass-integrated case (1G2G).

MW
Streams m (kg/s) T (◦ C) P (bar) b (kJ/kg) B (MJ/s)
Cane 231.48 25 1.013 5223 1209.03
Bagasse 62.81 25 1.013 9667 607.23
Straw 12.49 25 1.013 13,845 172.87
Sulfuric acid (H2 SO4 ) 23.21 25 1.013 1666 38.67
Nutrients (NH4 OH) 0.47 25 1.013 9382 4.44
Phosphoric acid (H3 PO4 ) 0.03 25 1.013 1061 0.03
Processes 2019, 7, 670 28 of 31

Table A16. Cont.

MW
Calcium Oxide (CaO) 0.15 25 1.013 1965 0.29
Enzymes 2.17 30 1.013 23,730 51.58
Yeast 0.72 33 1.013 17,350 12.52
Filter cake 3.49 98 1.013 2162 7.55
Lignin cake 6.50 50 1.013 10,802 70.21
Vinasse 205.64 75 1.4 443 91.10
Pentoses liquor 20.57 37 1.013 1699 34.94
Anhydrous ethanol 19.84 78 1.013 29,471 584.79
CO2 Emissions 64.94 25 1.013 451.59 29.33

Table A17. Key streams parameters of the mass and heat-integrated system (1G2G-HI).

MW
Streams m (kg/s) T (◦ C) P (bar) b (kJ/kg) B (MJ/s)
Cane 231.48 25 1.013 5223 1209.03
Bagasse 62.81 25 1.013 9667 607.23
Straw 12.49 25 1.013 13,845 172.87
Sulfuric acid (H2 SO4 ) 23.21 25 1.013 1666 38.67
Nutrients (NH4 OH) 0.47 25 1.013 9382 4.44
Phosphoric acid (H3 PO4 ) 0.03 25 1.013 1061 0.03
Calcium Oxide (CaO) 0.15 25 1.013 1965 0.29
Enzymes 2.17 30 1.013 23,730 51.58
Yeast 0.72 33 1.013 17,350 12.52
Filter cake 3.49 98 1.013 2162 7.55
Lignin cake 6.54 50 1.013 10,802 70.68
Vinasse 223.49 75 1.4 443 99.00
Pentoses liquor 21.92 37 1.013 1699 37.25
Anhydrous ethanol 21.94 78 1.013 29,471 646.52
CO2 Emissions 64.94 25 1.013 451.59 29.33

Table A18. Irreversibilities per liter of ethanol in the systems.

kWh/Lethanol
Sub-System 1G 1G2G 1G2G-HI
Preparation and Extraction 1.192 0.742 0.629
Juice Treatment 0.554 0.350 0.297
Juice Concentration 0.213 0.125 0.098
Fermentation 1.760 1.001 0.835
Distillation 0.719 0.534 0.419
Dehydration 0.065 0.044 0.031
Cogeneration 6.719 4.841 3.989
Condensate tank 0.161 0.090 0.075
2G Unit - 0.527 0.465
TOTAL 11.38 8.25 6.84

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