Energy Integration of Bioethanol Production Process From Algae Biomass: Comparison of SSF, SSCF and Acid Hydrolysis

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A publication of

CHEMICAL ENGINEERING TRANSACTIONS


The Italian Association
of Chemical Engineering
www.aidic.it/cet
Guest Editors: Petar Varbanov, Ji Kleme, Panos Seferlis, Athanasios I. Papadopoulos, Spyros Voutetakis
Copyright 2013, AIDIC Servizi S.r.l.,
ISBN 978-88-95608-26-6; ISSN 1974-9791

VOL. 35, 2013

Energy integration of bioethanol production process from


algae biomass: comparison of SSF, SSCF and Acid
Hydrolysis
ngel D. Gonzlez-Delgado*a,Yeimmy Peralta-Ruza,Yennifer Pardoa, Viatcheslav
Kafarova
a

Industrial University of Santander, Chemical Engineering Department. Carrera 27 con Calle 9, Bucaramanga, Colombia.
Tel +57 7 6344000 ext. 2603
[email protected]

Exists an increasing interest in use of ethanol as substitute of fossil fuels which can be obtained from
renewable resources, microalgae are a promising source for third generation bioethanol due to the high
percentage of carbohydrates/polysaccharides presents in some species and thin cellulose walls. Ethanol can
be produced from either microalgae biomass before lipid extraction or from microalgae cake after cell
disruption and oil extraction. Second option gives the interesting possibility of producing both biodiesel and
ethanol from the same biomass.
Energy analysis can be used for evaluation of the performance and efficiency of a process based on the first
law of thermodynamics. In this work, third generation bioethanol production process was evaluated using the
methodology of energy integration with the software Aspen HX-Net 2006.5, the microalgae genera used was
Chlorella sp. and technologies evaluated were Simultaneous Saccharification and Co-fermentation SSCF,
Simultaneous Saccharification and Fermentation SSF, and Separate Saccharification and Fermentation using
acid hydrolysis (SHF).
Results shows that technology of Simultaneous Saccharification and Co-fermentation SSCF (route 1)
presents the highest bioethanol yield 24.1% of the routes evaluated and also the lowest energy requirements
after energy integration, Separated hydrolysis and fermentation SHF (route 3) presents the lowest efficiency,
DTmin was defined in 9C for SSCF, 4C for SSF, and 8.5C for SHF, the use of molecular sieves technology
for bioethanol dehydration represents lower energy requirements respect to extractive distillation.

1. Introduction
Exists an increasing interest in use of ethanol as substitute of fossil fuels which can be obtained from
renewable resources, CO2 from combustion reaction is fixed by biomass in growing stage. Mature
technologies for bioethanol production from biomass are based on sugars fermentation which are obtained
from industrial processing of feedstocks with high percentage of sugars or cellulose, most of them are
important for human and animal diet, for this reason new possibilities of bioethanol production are been
evaluated in order to avoid problems related with competition of feedstocks with food and feed and use of
land.
1.1 Microalgae biomass
Microalgae is an energy source that potentially can offer considerable amounts of fuel from small crop areas
and and high photosyntetic efficiency, which further helps in the mitigation of global warming; its culturing
tolerates high concentrations of CO2 and decreases the amount of nitrogen oxides released into the
atmosphere. Microalgae biomass is been evaluated mostly for biodiesel production, however, biodiesel-frommicroalgae production chain is still away of sustainability by several factors, in energy terms, comparison of
energy demands for microalgal biodiesel production shows that energy required in all stages of production
process is more than energy produced by third generation biodiesel. In this sense, results of studies related to
bioprospecting, exploration and production of microalgae biomass made by research centers as the NREL In

United States, the CISOT and CIEMAT in Spain, the CIDES and ICP in Colombia such as several researchers
worldwide, concludes that production of biodiesel from microalgae can be economically viable if total biomass
components are used for obtaining biofuels and high value products and the concept of biorefinery is
incorporated. As in an oil refinery, a biorefinery uses all biomass components for obtaining several biofuels
and high value products (Khan et al., 2009).
1.2 Bioethanol from microalgae
Microalgae has a wide variety of components wich can be extracted and/or converted in biofuels and high
value products (Gonzlez-Delgado and Kafarov, 2012), most of microalgae species contains some common
components such cellulose, proteins, lignin, pectins as polyuronic acids, arabinans and glactans,
hemicelluloses as xylans and arabinoglactans and other carbohydrates, most of the polymers located in the
microalgal cell wall can be converted in monomers through an acid, alkaline or enzymatic reactions (Chong Fu
et al., 2010). Ethanol can be produced from microalgae biomass with high percentage of cellulosic material,
fermentable sugars can be produced from microalgae through hydrolysis of harvested biomass (Gonzalez and
Kafarov, 2010). Bioethanol from microalgae biomass can be produced before lipid extraction or from
microalgae cake after cell disruption and oil extraction. Second option gives the interesting possibility of
producing both biodiesel and ethanol from the same biomass (Gonzlez-Delgado and Kafarov, 2011).
1.3 Energy Integration
Energy analysis can be used for evaluation of the performance and efficiency of a process based on the first
law of thermodynamics. Energy integration is a technique for process design which looks for minimize the
energy consumption and maximize the heat recovery. Analysis starts with the mass and energy balance for
the process, simulation tools can be used for achieving this stage. After that, targets for energy
Integration are identified and network is designed. Utility levels that are supplied to the process that is
evaluated or designed, can be part of a centralised utility system. Energy integration provides a wellstructurates methodology for energy saving in cooling and heating, from the basic mass and energy balance
to the total utility system.
In this work, third generation bioethanol production process was evaluated using the methodology of energy
integration with the software Aspen HX-Net 2006.5, the microalgae genera used was Chlorella sp. and
technologies evaluated were Simultaneous Saccharification and Co-fermentation SSCF (route 1),
Simultaneous Saccharification and Fermentation SSF (route 2), and Separate Saccharification and
Fermentation using acid hydrolysis SHF (route 3).

2. Description of technologycal systems


2.1 Simultaneous Saccharification and Co-fermentation SSCF (route 1)
In Simultaneous Saccharification and Co-fermentation pathway, a hydrolysis step reduces cellulose and
hemicelluloses to hexoses and pentoses, which simultaneously are fermented using Zimomonas mobilis and
Saccharomyces cerevisiae. Is reported that production rated does not have a high impact on enzymatic
hydrolysis because its concentrations are low, but presence of alcohol inhibits specific growth rate and
accelerates cell degradation (Spatari et al., 2010).
2.2. Simultaneous Saccharification and Fermentation SSF (route 2)
Simultaneous saccharification and fermentation (SSF) pathway has been experimentally studied for
bioethanol production from lignocellulosic material. One advantage of this pathway is that performs the stage
of hydrolysis with fermentation, this variation allows to decrease the final product inhibition fermentable
sugars, however, as disadvantage presents the finding of operating conditions for efficient performing of
enzymes and fermentation. This technique is one of the most promising because only one reactor is used for
hydrolysis and fermentation, improving the conversion of sugars to ethanol, the key of SSF process is the fast
ethanol production from glucose (Ojeda et al., 2011).
2.3. Separated hydrolysis and fermentation SHF (route 3)
Acid hydrolysis was used as identified experimentally as convenient alternative for reducing sugars production
(Gonzlez-Delgado and Kafarov, 2012), althought literature also reports hih reducing sugars yields from
microalgae using another alternatives for hydrolysis, sugars obtained are mainly glucose, xylose and
cellubiose, when this route is performed, hydrolysis and fermentation steps occurs in different reactors
optimizing operating conditions for each reaction, best operating conditions found by authors in unpublished
research works and literature were used for simulation of pathway, for evaluation of this route, acid hydrolysis
was chosen first stage of bioethanol production chain.

3. Simulation of pathways
For microalgal bioethanol production a commercial industrial processes simulation software (ASPEN Plus TM
2006.5) was used, properties of components was estimated using the NRTL (Non-Random Two Liquid)
thermodynamic model, Table 1 shows the flows of algal biomass and bioethanol specifications of output
streams for main steps in each route obtained from process simulation.

Figure 1: Simulation of routes evaluated for microalgal bioethanol production SSCF (upper), SSF (medium)
and SHF (lower).

Table 1: Compositions of output streams for routes evaluated.


Route

Stages

SSCF

Fermentation

Separation

Total mass flow (kg/s)

56.66

2.26

Bioethanol flow (kg/s)

2.74

2.23

Fermentation
(Pentoses)

Fermentation
(Hexoses)

Separation

Total mass flow (kg/s)

73.85

7.78

2.0

Bioethanol flow (kg/s)

0.758

0.327

1.9

Hydrolysis

Fermentation

Separation

Total mass flow (kg/s)

92.69

94.25

1.69

Bioethanol flow (kg/s)

1.32

1.67

SSF

SHF

4. Results
According to simulation, SSCF technology (route 1) shows the highest efficiency of microalgal ethanol
production for the routes evaluated (24.1%), in addition, acid hydrolysis shows lower efficiencies in terms of
reducing sugars production in comparison to obtained data from enzymatic hydrolysis, this can be explained
by the selectivity of enzymes in comparison to acid hydrolysis reaction which presents low efficiencies in
cellulose hydrolysis.
Table 2: Comparison of microalgal bioethanol production routes using energy integration.
SSCF

SSF

SHF

Base
Case

Energy
Integration

Base
Case

Energy
Integration

Base
Case

Energy
Integration

Heat Exchangers

12

22

19

38

14

26

Total Area (m2)

34,700

26,285

49,059

9,950

35,505

9,078

Heating Service
(GJ/h)

14.6

2.3

548

503

923

700

Cooling Service
(GJ/h)

630

617.1

576

531

832

609

4.1. Energy integration


Table 2 shows energy integration results for routes evaluated, SSF route requires 14,000 kW more in heating
services than SSCF technology, this difference is caused by the higher amount of separation units in SSF
route and the need of additional stages of fermentation products purification. Taking into account energy
requirements and bioethanol yield, SSCF technology is more convenient in a large-scale microalgal
bioethanol production.
As the route with highest bioethanol yield and lower energy requirements, SSCF route was assessed in
energy integration section using as molecular sieves as extractive distillation for bioethanol purification.
Composite curves obtained for each route are show in Figure 2, using these curves the DTmin was defined in
9C for SSCF, 4C for SSF, and 8.5C for SHF.

Figure 2: Composite curves of microalgal bioethanol production routes: A: SSCF using extractive distillation,
B: SSCF using molecular sieves, C: SSF route, D: SHF route.
4.2. Comparison of bioethanol dehydration alternatives for SSCF route)
Extractive distillation was compared to molecular sieves as alternatives for microalgal bioethanol purification
from the energetic point of view (Table 3), difference between energy requirements were calculated in 12.4
GJ/h y 215.3 GJ/h for heating and cooling services respectively, being more convenient the use of molecular
sieves for large scale microalgal bioethanol purification.
Table 3: Compositions of output streams for routes evaluated
Extractive distillation

Molecular sieves

Total Area (m2)

34,700

18,285

Heating Service (GJ/h)

14.7

2.2

Cooling Service(GJ/h)

629.7

414.4

5. Conclusions
Three alternatives for microalgal bioethanol production from residual biomass were evaluated from the
energetic point of view and energy integration methodology was applied to each alternative in order to
optimize the routes proposed, technology of Simultaneous Saccharification and Co-fermentation SSCF (route
1) shows the highest bioethanol yield 24.1% and lowest energy requirements after energy integration,
Separated hydrolysis and fermentation SHF (route 3) presents the lowest efficiency, DTmin was defined in
9C for SSCF, 4C for SSF, and 8.5C for SHF. Finally, it could be established that the use of molecular sieves
technology for bioethanol dehydration in the last part of the process represents lower energy requirements
respect to extractive distillation with glycerol.
Acknowledments
The authors thank to the Colombian Department of Science, Technology and Innovation COLCIENCIAS,
project creacin y fortalecimiento de una red de transferencia de conocimiento y tecnologa entre Estados
Unidos y Colombia mediante el desarrollo de procesos de biorefinera para la obtencin de biocombustibles y
productos de alto valor agregado a partir de biomasa de microalgas, and to Francisco Jose de Caldas
Scolarships for supporting Ph.D. Studies (Angel Daro Gonzalez-Delgado).
References
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A. Gonzlez-Delgado, V. Kafarov, 2012, Microalgae Based Biorefinery: Evaluation of Several Routes for Joint
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S. Khan, Rashmi, M. Hussain, S. Prasad, C. Banerjee, 2009, Prospects of biodiesel production from
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