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Fuel Processing Technology 109 (2013) 8489

Contents lists available at SciVerse ScienceDirect

Fuel Processing Technology


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

Evaluation of process congurations for second generation integrated with rst


generation bioethanol production from sugarcane
Marina O.S. Dias a, b,, Tassia L. Junqueira a, b, Carlos Eduardo V. Rossell a, b,
Rubens Maciel Filho a, b, Antonio Bonomi a
a
b

Laboratrio Nacional de Cincia e Tecnologia do Bioetanol CTBE/CNPEM, Caixa Postal 6170, 13083-970, Campinas, So Paulo, Brazil
Faculdade de Engenharia Qumica, Universidade Estadual de Campinas (UNICAMP), Av. Albert Einstein, n 500, 13083-852, Campinas, So Paulo, Brazil

a r t i c l e

i n f o

Article history:
Received 4 November 2011
Received in revised form 15 May 2012
Accepted 24 September 2012
Available online 13 October 2012
Keywords:
Ethanol
Sugarcane
Simulation
Second generation
Pretreatment
Hydrolysis

a b s t r a c t
Since sugarcane bagasse and trash are used as fuels in conventional bioethanol production, the amount of surplus
lignocellulosic material used as feedstock for bioethanol production depends on the energy consumption of the
production processes. Residues from the second generation process (e.g., unreacted lignocellulosic material) may
be used as fuels and increase the amount of surplus bagasse, along with improved technologies. Pentose fermentation to ethanol instead of biodigestion to produce biogas will lead to higher ethanol production, increasing energy
consumption of the process and consequently, decreasing the amount of surplus lignocellulosic material available.
In this study different congurations of the second generation ethanol production process (e.g. pretreatment with
steam explosion coupled or not with delignication, pentose biodigestion or fermentation to ethanol, solids loading
on hydrolysis), are evaluated in the integrated rst and second generation ethanol production from sugarcane
through simulation using Aspen Plus. The results show which process alternatives, potentially, may lead to higher
ethanol production, pointing towards where research should be directed in order to provide important gains on
ethanol production in the integrated process.
2012 Elsevier B.V. All rights reserved.

1. Introduction
Bioethanol has been considered in the world as the alternative renewable fuel with the largest potential to replace fossil derived fuels,
responsible for a signicant fraction of greenhouse gas emissions. In
face of increasing energy demand, forecasted depletion of oil resources and high costs for exploration, and concern regarding land
use the world has turned its attention to lignocellulosic or second
generation ethanol, which is produced from abundant and relatively
cheap feedstock that do not compromise food security [1,2]. Nevertheless, second generation bioethanol production technologies are
still under development: the intense structure connecting the three
main components of the lignocellulosic biomass (cellulose, hemicellulose and lignin) hinders its transformation into fermentable sugars
[1,3,4].
Brazil has been producing bioethanol on a large scale basis for fuel
for more than 30 years [5], through fermentation of the sugar cane
juice (rst generation bioethanol). During sugarcane processing,
large amounts of lignocellulosic material sugarcane bagasse and
trash (composed of sugarcane leaves and tops), are produced; bagasse
is currently used as fuel in boilers to supply energy to the process or

Corresponding author at: Caixa Postal 6170, 13083-970, Campinas, SP, Brazil. Tel.: +55
19 35183144; fax: +55 19 35183164.
E-mail addresses: marina.dias@bioetanol.org.br, diasmos@gmail.com (M.O.S. Dias).
0378-3820/$ see front matter 2012 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.fuproc.2012.09.041

even to sell the excess to the grid, while most of the trash is burnt or
left in the eld [6].
The integration of the second generation ethanol production process
from lignocellulose with rst generation ethanol production from sugarcane may improve its feasibility. In comparison with a stand-alone
second generation unit, the integrated process will require a lower investment, since operations like sugar concentration, fermentation and
distillation, utilities and storage sectors may be shared between both
plants [7,8]. In addition, fermentation inhibitors generated during
pretreatment will have minor effects on yields since the hydrolyzed liquor will be fermented diluted in the sugarcane juice.
In the Brazilian scenario, where the potential feedstock for second
generation ethanol production is also used as fuel to supply the energy demand of the process, it is essential to maximize the amount of
surplus lignocellulosic material through reduction on process steam
consumption. Various improvements may be included in the conventional rst generation ethanol production process, leading to production of larger amounts of surplus bagasse and trash; several authors
have studied forms of increasing energy efciency during sugarcane
processing [914]. Nevertheless, the introduction of second generation ethanol production from sugarcane bagasse and trash will also
require the improvement of the energy consumption on second generation operations, such as pretreatment and hydrolysis; most of the
published literature about the experimental development of second
generation ethanol production focuses on maximizing yields and minimizing catalyst consumption, like the works developed by Brienzo et

M.O.S. Dias et al. / Fuel Processing Technology 109 (2013) 8489

85

al. [15] and Xu and Cheng [16], among others. However, it is important
to look at the process as a whole, taking into account the ethanol production as well as the net energy available. Since high ethanol concentration in the fermentation media is desirable, to attain lower energy
consumption in the purication step, the concentration of sugars in
the hydrolyzed liquor plays an important role in the process performance [17].
Bearing all this in mind, in this work different congurations of the
second generation ethanol production process (e.g. pretreatment with
steam explosion coupled or not with delignication, pentose biodigestion
or fermentation to ethanol, solids loading for hydrolysis), are evaluated in
an integrated rst and second generation ethanol production process
through simulation using Aspen Plus. The results show which process alternatives may lead to higher ethanol production, pointing towards
where research should be directed in order to provide important gains
on ethanol production in the integrated process.
2. Materials and methods
Simulation of the processes was carried out using the software
Aspen Plus. The thermodynamic model employed in most of the simulation was the NRTL; in the simulation of the cogeneration system,
however, due to the existence of several water and high temperature
streams, Steam Tables and RKS-BM (RedlichKwongSoave equation
of state with BostonMathias alpha function) were employed to more
accurately represent the process. The components that were not available at the simulator database, like the ones required to represent lignocellulosic materials, were introduced in the simulation, and their
properties were obtained from the work of Wooley and Putsche [18].
Lignin structure, however, was modied to represent sugarcane lignin, with molecular formula C9O2.9H8.6(OCH3) [19]. Simulation was
carried out to represent the steady state operation of the bioethanol
production process by taking into consideration the different operational conditions, as described in the following sections. More information about the simulation procedure may be found in a previous
work [8]. The same process simulator has been used to compare various congurations of bioreneries by different authors [2023].
2.1. First generation ethanol production process
The rst generation ethanol production process is based on an optimized autonomous distillery, with process improvements that lead to
reduced steam consumption and large electricity production. This conguration is composed of an efcient cogeneration system (65 bar
boilers), which represent the current trend for new sugarcane facilities
in Brazil [22]. In addition, direct drivers are employed in the mills, leading to higher efciency than the usual steam drivers found nowadays in
the industry. The mill has a processing capacity of 500 t of sugarcane
(TC) per hour, that corresponds to 2 million TC per year, representing
the average capacity in Brazilian mills nowadays. Fig. 1 shows the
basic diagram for the optimized rst generation plant.
The main parameters of the optimized rst generation plant are
based on data provided by the industry, information given by specialists
or available in the literature; they are displayed in Table 1.
Sugarcane trash composition is assumed to be equal to that of bagasse, except for the moisture content, which is dened as 15 and 50%
[22], respectively. The lignocellulosic material composition is based
on analyses carried out on 50 different bagasse samples by Rocha et
al. [24]; average values are given in Table 2.
The double effect distillation system was considered and simulated
like described by Dias et al. [7]; a simple-effect lithium bromide absorption system was employed to supply the chilled water required
in the condenser of the distillation column, and its simulation was carried out based on data provided by Somers et al. [25]. Steam is used as
utility, and the calculated coefcient of performance (COP) of the system is equal to 0.75.

Fig. 1. Block ow diagram of the optimized rst generation ethanol production process
from sugarcane.

2.2. Second generation ethanol production process


Different process congurations were evaluated for the second generation ethanol production process, which consists of pretreatment of
the lignocellulosic material (surplus bagasse and trash) with steam explosion, followed or not by alkaline delignication, and enzymatic hydrolysis. While steam explosion provides signicant hemicellulose
hydrolysis (average 82.7%), lignin removal in this step is not expressive
(7.9%) Rocha et al. [26] carried out experiments comprising steam explosion and alkaline delignication of several sugarcane bagasse samples. The authors show that only after alkaline delignication of the
steam exploded bagasse its lignin content is signicantly reduced
(an average 92.7% of the lignin is removed from the solid pulp). Even
though the authors do not provide results for enzymatic hydrolysis of
the pulp produced, it is known that lignin has an important inhibitory
effect on the cellulolytic enzymes employed in enzymatic hydrolysis
of biomass [26,27].
Pentoses released after pretreatment of the lignocellulosic material
are either biodigested [26], producing biogas which is used as a fuel, or

Table 1
Parameters adopted in the simulation of the optimized autonomous distillery.
Parameter

Value

Sugarcane processed a
Sugarcane total reducing sugars content
Sugarcane ber content
Sugarcane trash produced in the eld b
Fraction of sugarcane trash transported to the industry
Efciency of juice extraction in the mills
Fermentation efciency
Ethanol content of the wine fed in the distillation columns
Hydrated ethanol (HE) purity
Anhydrous ethanol (AE) purity
65 bar boiler efciency (LHV basis)
65 bar steam temperature
Fraction of bagasse for start-ups of the plant
Turbines isentropic efciency high pressure
Turbines isentropic efciency intermediate pressure
Generator efciency
Electric energy demand
Steam pressure process
Steam pressure molecular sieves
Steam demand molecular sieves

500 TC/h
15.3%
13%
140 kg/TC
50%
96%
90%
8.5GL
93 wt.%
99.6 wt.%
87%
485 C
5%
72%
81%
98%
30 kWh/TC
2.5 bar
6 bar
0.6 kg/L AE

a
b

TC: tons of sugarcane.


Dry basis.

86

M.O.S. Dias et al. / Fuel Processing Technology 109 (2013) 8489

considered. After each step of the process (pretreatment, delignication,


and hydrolysis), lters are used to separate the solid phase from the
liquor.

Table 2
Composition of the sugarcane bagasse adopted in the simulation.
Adapted from Rocha et al. [24].
Component

Fraction (wt.%)

Cellulose
Hemicellulose
Lignin
Ash
Extractives

43.38
25.63
23.24
2.94
4.82

2.3. Integrated rst and second generation ethanol production process

fermented to ethanol. Since microorganisms that simultaneously ferment hexoses and pentoses to ethanol with high efciency are not
currently available, pentose biodigestion allows the use of this stream
for energy production, which in turn increases the amount of lignocellulosic material to be used as feedstock for second generation ethanol.
Rabelo et al. [28] performed experiments on mesophilic biodigestion
of the pretreatment liquor obtained from different processes (lime
or hydrogen peroxide pretreatment) and operating conditions, using
as inoculum sludge from an anaerobic digester at a sugar factory.
The authors veried that the amount of biogas produced and its quality (methane content) greatly depends on the process parameters. In
this work, the parameters adopted for the simulation of the pentose
biodigestion unit were based on the data from a stillage biodigestion
process provided by Dedini, one of the largest equipment manufacturers for the ethanol industry in Brazil. In order to avoid inhibition,
COD concentration in the digestor feed should be around 50 g/L;
depending on the process conditions, the stream should be diluted
to achieve that gure [29]. The main parameters of the second generation ethanol production process studied in this work are presented in
Table 3.
Different conditions of the hydrolysis process (solids loading and
yields conversion of cellulose into glucose and of hemicellulose to
pentose) were analyzed; for high solids concentration on the reactor,
relatively low yields were assumed, and vice versa, as shown in
Table 3. Since removal of lignin improves cellulose accessibility to enzymes [28], when the alkaline delignication step was inserted an increase of 10% on the enzymatic hydrolysis yields was assumed, as
indicated in Table 3; thus, when the pretreatment was composed of
steam explosion and alkaline delignication, hydrolysis yields for 20%
solids loading were equal to 55%.
Vapor released during steam explosion was used to pre-heat the
pretreated bagasse prior to alkaline delignication, when this step was

Table 3
Parameters adopted in the simulation of the second generation ethanol production
process.
Parameter

Value

Pretreatment hemicellulose conversion


Pretreatment cellulose conversion
Pretreatment temperature
Pretreatment reaction time
Alkaline delignication temperature
Alkaline delignication reaction time
Alkaline delignication solids loading
Alkaline delignication NaOH content
Alkaline delignication lignin solubilization
Alkaline delignication increase on hydrolysis yields
Hydrolysis yield for 5% solids loading
Hydrolysis yield for 10% solids loading
Hydrolysis yield for 15% solids loading
Hydrolysis yield for 20% solids loading
Hydrolysis temperature
Hydrolysis reaction time
Filters solids removal
Filters soluble solids loss

70%
2%
190 C
15 min
100 C
1h
10%
1% (m/V)
90%
10%
80%
70%
60%
50%
50 C
48 h
99.5%
10%

In the integrated process, sugarcane bagasse and trash are used as


fuels in the cogeneration system, and the amount that exceeds the
one required to supply the thermal energy demand of the plant is
used as feedstock in the second generation ethanol production process. A simplied diagram of the integrated process is shown in Fig. 2.
As shown in Fig. 2, residues of the second generation process are
also used as fuels in the cogeneration system. When only steam explosion is employed, the unreacted solids composed of cellulose and
lignin are fed to the boilers; when alkaline delignication is used,
the lignin is removed prior to hydrolysis, and the unreacted solids
obtained after removal of the glucose liquor produced in the enzymatic hydrolysis reactor contain mainly cellulose. Both lignin and cellulose are fed to the boilers. Pentoses released during pretreatment
are either biodigested, producing biogas which is also burnt to produce energy, or fermented into ethanol.
3. Results and discussions
Several congurations combining steam explosion pretreatment,
alkaline delignication, pentose biodigestion and fermentation, different hydrolysis conditions (displayed in Table 3) were simulated
using Aspen Plus. The owsheet developed allowed evaluation of
the amount of lignocellulosic material available for hydrolysis, since
the amount of hydrolyzed liquor also affects the energy consumption.
In addition, ethanol and electricity production were assessed.
An example of the owsheet developed in Aspen Plus for a scenario where the pentoses released during biomass pretreatment are
biodigested is shown in Fig. 3.
All the unit operations necessary to represent the process were
inserted on the correspondent hierarchy block (MILLS for sugarcane
cleaning and extraction of sugars; TREATFER for juice treatment and
fermentation; DISTILL for distillation; DEHYD for dehydration,
COGEN for cogeneration, BRLI for lithium bromide absorption
chillers and 2G for second generation pretreatment and hydrolysis, as shown in Fig. 3). Several operations (mills, lters, settlers and
adsorption column, among others) were represented as component
splitters, due to the lack of more adequate description of such unit
operations in the simulator database.
Due to the various recycle streams present in the simulation, convergence of the process is not easily achieved. This is a consequence
of the fact that the exact amount of lignocellulosic material surplus
(stream LM) directed for 2G process depends on the amount of residues (LIGNIN, CELLULOS and PENTOSE) produced on second generation (represented by the block 2G) and on the entire steam
consumption of the process, which in turn depends on the amount
of hydrolyzed liquor (HYDROL) sent to fermentation with the sugarcane juice. In addition, the cogeneration unit also provides steam to
the lithium bromide absorption unit, which depends on the amount
of chilled water required in the distillation columns (utility streams
are not shown in the gure).
Ethanol and electricity production in the evaluated congurations
are shown in Fig. 4.
Results presented in Fig. 4 depict that even though high hydrolysis
yields (80%) are assumed for low solids loading on hydrolysis (5%),
this conguration always presents the lowest overall ethanol production (integrated rst and second generation). Nevertheless, the highest
solids loading analyzed (20%) does not present the highest ethanol production, as a consequence of the low hydrolysis yield assumed (50%). In
fact the largest ethanol production is obtained for intermediate conditions (15% solids and 60% yield). In addition, even though alkaline

M.O.S. Dias et al. / Fuel Processing Technology 109 (2013) 8489

87

Fig. 2. Block ow diagram of the integrated rst and second generation ethanol production process from sugarcane dashed lines represent alternatives for pentose use.

delignication promotes an increase on hydrolysis yields (assumed to


be of 10%), overall ethanol production does not increase in the scenarios
where alkaline delignication takes place; in fact, it even presents lower
ethanol production in the cases where pentose fermentation takes
place. This is a consequence of the high energy demand of the alkaline
delignication step, which takes place at 100 C, as well as on the relatively low solids loading (10%). An overall increase on ethanol production in
comparison with the rst generation (1G) ethanol production process
varies from 20% (for low solids loading on hydrolysis 5%, scenario
with steam explosion, pentose biodigestion) to 52% (high solids loading
20 or 15%, steam explosion and pentose fermentation to ethanol).
Electricity production on each scenario is also shown in Fig. 4. It
may be observed that it increases along with the decrease on solids
loading in hydrolysis, due to the fact that low solids loading leads to
high steam consumption and, consequently, high electricity production on turbo generators.
Most of the experimental works in the literature concerning second
generation (2G) ethanol production present as results the optimization

of the pretreatment or hydrolysis stages maximizing either the amount


of ethanol (or sugars) released per amount of lignocellulosic material
(LM) hydrolyzed or the conversion of cellulose into glucose [4,3032].
However, in the Brazilian scenario, or in any other situation where the
lignocellulosic material is also used as fuel for the production of energy
to supply the thermal demand of the process, it is of crucial importance
to analyze the energy demand of the whole process, since the amount of
ethanol produced is directly proportional to the amount of surplus lignocellulosic material (LM).
For this reason, the steam demand of the process, given on kilogram
of steam per ton of sugarcane processed this is the common unit used
to evaluate energy consumption in sugarcane processing in Brazil, was
evaluated for each process conguration analyzed. Results are illustrated
in Fig. 5, along with the amount of hydrolyzed lignocellulosic material
(given as a percentage of the total lignocellulosic material available at
the plant, composed of sugarcane bagasse and trash), the amount of second generation (2G) ethanol produced calculated per ton of dry lignocellulosic material (LM) and ethanol produced per ton of sugarcane (L/TC).

Fig. 3. Flowsheet of the simulation of the integrated rst and second generation ethanol production process in Aspen Plus.

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M.O.S. Dias et al. / Fuel Processing Technology 109 (2013) 8489

Fig. 4. Anhydrous ethanol and surplus electricity production per ton of sugarcane (TC) on each process conguration (s stands for solids loading on hydrolysis (%) and y for yields on
enzymatic hydrolysis (%)).

Results displayed in Fig. 5 show that the fraction of hydrolyzed lignocellulosic material is inversely proportional to the energy consumption of the process, as expected. For instance, the process with
steam explosion and pentose biodigestion with solids loading in hydrolysis of 20% presents a steam consumption of around 600 kg/TC,
and 100% of the lignocellulosic material available is used as feedstock
in hydrolysis. On the other hand, the process with 5% solids loading
has a much higher steam consumption (around 750 kg/TC), what signicantly decreases the fraction of lignocellulosic material hydrolyzed
(45%). In addition, the specic second generation ethanol production
from the lignocellulosic material (around 200 L/t dry LM) is the
highest for low (5%) solids loading and high yields, contrasting with
the amount of lignocellulosic material available for hydrolysis. This is
the reason why overall ethanol production (that can be produced
using the whole sugarcane plant) decreases for low solids loading
(around 100 L/TC for the process with 5% solids, as opposed to nearly
110 L/TC for high solids loading), even though the specic second generation ethanol production increases. This is also the explanation for
the fact that alkaline delignication provides no signicant gains on
ethanol production: the congurations with alkaline delignication
usually demand more energy than those with steam explosion only.
When the different congurations studied in this work are compared, it can be veried that pentose fermentation to ethanol leads to
higher ethanol production, but the amount of lignocellulosic material
hydrolyzed is lower than those on the congurations where pentoses
are biodigested. This is a consequence of both, the elimination of biogas

production, which is used to supply energy and, as a result, increases


the amount of lignocellulosic material available for hydrolysis, and the
increase on the energy demand of the concentration and distillation
steps, due to increase on ethanol production.

4. Conclusions
Simulations of the integrated rst and second generation ethanol
production process from sugarcane showed that high hydrolysis
yields, that may be achieved using low solids loading on the hydrolysis reactor, do not lead to the best results in terms of overall ethanol
production; because the lignocellulosic material (sugarcane bagasse
and trash) used as feedstock in second generation is also used as
fuel, low solids loading requires more steam on the concentration
step. Thus, even though that situation leads to the highest second
generation ethanol production per lignocellulosic material processed
(around 200 and 400 L/t dry LM for the processes with pentose
biodigestion and fermentation, respectively), lower yields and higher
solids loading lead to larger amounts of ethanol produced per ton of
sugarcane (up to 122 L/TC for 20% solids, as opposed to 116 L/TC for
the process with pentose fermentation and 5% solids loading in
hydrolysis).
This study conrmed the importance of evaluating the whole process in order to better understand it and to guide further experiments
aiming the viability of second generation bioethanol production.

Fig. 5. Fraction of lignocellulosic material (LM) hydrolyzed, overall ethanol production (L/TC), second generation (2G) ethanol production per ton of dry lignocellulosic material (L/t
dry LM) and steam consumption per ton of sugarcane (TC) on each process conguration (s stands for solids loading on hydrolysis (%) and y for yields on enzymatic hydrolysis (%)).

M.O.S. Dias et al. / Fuel Processing Technology 109 (2013) 8489

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