Mario R. Eden, John D. Siirola and Gavin P.

Towler (Editors) Proceedings of the 8 th International Conference

on Foundations of Computer-Aided Process Design FOCAPD 2014
July 13-17, 2014, Cle Elum, Washington, USA 2014 Elsevier B.V. All rights reserved.

Design Analysis of Integrated Microalgae

Biorefineries
Melina Psycha,a* Kostantinos Pyrgakis,a Patricia J. Harvey,b Ami Ben-Amotz,c
A. Keith Cowan,d Antonis C. Kokossisa
a

School of Chemical Engineering, National Technical University of Athens, Zografou

Campus, 9, Iroon Polytechniou Str., GR-15780 Athens, Greece
b
School of Science, University of Greenwich Central Avenue, Chatham Maritime, Kent
ME4 4TB, UK
c
Seambiotic Ltd, Azrieli Center, 132 Menachem Begin Blvd., Tel Aviv 67021, Israel
d
Institude for Environmental Biotechnology, Rhodes University, PO Box 94,
Grahamstown 6140, South Africa
melpsycha@mail.ntua.gr

Abstract
The study discusses the development of an integrated process that addresses the coproduction of glycerol, -carotene and proteins from microalgae biomass using a
multitude of solvents and scoping to reduce energy consumption. An evolutionary
approach is adopted in order to establish feasible and sustainable flowsheeting. Process
integration is applied to target efficiency scoping reviewing thermal integration and the
use of alternative separation schemes. The analysis reviews economic benefits as well
as the impact of process integration in securing the viability of the incentive.
Keywords: glycerol; -carotene; microalgae; thermally coupled distillation; biorefinery

1. Introduction
The indispensable need to replace fossil oil based chemicals and fuels directed great
interest to the development of biorefineries. However, bio-chemicals production has
been mainly focused on lignocellulosic feedstocks that refer to agricultural and forestry
supplies. Less attention has been paid to upcoming technologies that include the
development of microalgae systems able to offer alternative chemical production paths
with high economical potential.
A notable case relates to halophytic Dunaliella cultures capable to convert CO 2 into a
multitude of products. One needs to select Dunaliella for its extraordinary tolerance to
salt stress establishing it as one of the few organisms that can survive in extreme
environments. Harvey et al. (2012) have reported the promise of glycerol extracted from
Dunaliella as a new biofuel. Glycerol can be combusted at very high efficiencies and
with very low emissions and will serve as an intermediate to replace various fossil oilbased bulk chemicals in the biorefineries of the future. Additionally, -carotene serves
as an essential nutrient and has high demand in the market as a natural food colouring
agent, as an additive to cosmetics and also as a health food (Raja et al., 2007).
There is high interest to screen designing options for the development of microalgae
biorefineries. However, the lack of data regarding thermodynamic property models for

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new chemistries, the lack of industrial applications to draw knowledge and the diversity
of chemical production techniques compared to treatment of lignocellulosic feedstocks
and conventional industry appear to be designing obstacles. As a result, the
development of a systematic approach analysis is not possible. Instead, an evolutionary
approach has been addressed to establish feasible and sustainable flowsheet options
referring to single and multi-product microalgae biorefineries based on extensive
interaction with practitioners.

2. Process flowsheeting methodology

The general procedure of processing microalgae and extracting the desired products in
the form of a biorefinery is presented in Figure 1 as a block diagram. The four stages
shown can be implemented by using a number of technologies. Cultivation can be
achieved by using open raceway ponds or closed photobioreactors and harvesting by
the use of centrifuges or membranes. Additionally, oil extraction is possible either in a
mechanical way (e.g. press) or by the use of solvents. For the stage of product recovery
there are numerous technologies such as countercurrent chromatography, membrane
processes, distillation columns and supercritical extraction. The challenge is to select
the most suitable and efficient technology to apply depending on the microalgae and the
selected products.

Figure 1. Block diagram for extracting products from microalgae

A base line motif (Agarwal, 1990) is presented in Figure 2 including a single-product

microalgae biorefinery flowsheet. This reference flowsheet follows and gives designing
guidelines that conform to the above mentioned stages. A significant drawback of this
process (Fig.2) is the existence of a single product which is opposed to the concept of
the biorefinery. Thus, a series of flowsheets are presented below for the purpose of
designing an integrated multi-product microalgae biorefinery flowsheet.
There is a crucial incentive to add products to the reference process that are feasible
from the algae value chain and offer significant economic potential to the overall
biorefinery. There are numerous products that Dunaliella has to offer, except glycerol,
such as phytoene, phytofluene, violaxanthin, zeaxanthin, transferrin, -carotene, carotene etc. For the purpose of this study -carotene has been chosen, especially
because of its high profitability. The unique characteristic of Dunaliella is the lack of a
rigid cell wall, which permits rapid cell volume changes in response to extracellular
changes in osmotic pressure (Ben-Amotz and Avron, 1990). Therefore, when Dunaliella
is under osmotic transition, the osmotic shock initiates the synthesis of glycerol. Bcarotene accumulates in the microalgal cell during cultivation and its amount depends
on the amount of light absorbed by the cell. Based on the well understood biology of
Dunaliella, there are established guidelines that delimit the designing potentials for the
development of flowsheets.

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593

Figure 2. Single-product reference flowsheet

Figure 3. a. First multi-product flowsheet, b. Optimized multi-product flowsheet (from left to

right)

Figure 4. Final multi-product microalgae biorefinery flowsheet

Based on the reference flowsheet (Fig.2), further designing perspectives regarding oil
extraction and product recovery are replaced and added (Avron and Ben-Amotz, 1978).
The conceptual block diagrams that are developed are presented in Figures 3a and 3b. In

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the first evolution to a multi-product flowsheet (Fig.3a) a multitude of solvents and a

wide range of devices were used. This may have resulted to an increase in operating
cost; however, the inclusion of -carotene raises the profit. It is worth mentioning that
the inclusion of -carotene as a product did not bring on changes to the processes
regarding cultivation and harvesting of the single-product flowsheet (Fig.2). This states
that the chemical paths of both glycerol and -carotene are complementary and not
competitive.
As expected, the flowsheet in Figure 3a presented certain limitations. Namely, the
conditions in the osmotic tanks do not favour the osmoregulation of Dunaliella
especially because glycerol does not accumulate well in the dark. Microalgae can be
harvested directly by centrifuges obviating the settling tanks. Furthermore, there is a
need for a more detailed design in regard to the operating conditions (T, p) and to the
technologies being used. The second multi-product flowsheet (Fig.3b) also required
further optimization. Specifically, the belt press can destroy the Dunaliella cells and a
centrifuge is used instead. The spray dryer is considered unsuitable for this microalga as
it can lead to significant losses of cells and colouring agents. Moreover, the function of
the screen separator is to remove the excessive amount of salt. However, in this case
most of the salt has already been removed, establishing this process redundant.
Additionally, several of the solvents used (cyclohexane, trichloroethane and alum/ferric
chloride or alum sulfate) are not suitable, since the recovering proteins are to be used as
food supplement (e.g. fishmeal). Therefore, cyclohexane is substituted by n-hexane and
the remaining solvents are not being used.
Since the last two designs do not match maximum efficiency in the use of materials and
energy, the flowsheet of Figure 4 is proposed which avoids the inadequacies of previous
flowsheets and is validated by practioners. In the open pond (0.5 ha) algae feed from
CO2, sunlight, nutrients and NaCl in order to grow. The production reaches up to 3.5
tones biomass per year. Subsequently, Dunaliella is induced in osmotic shock in the
osmotic stress ponds by the rapid increase of salt concentration (from 2M to 4M) and
glycerol is accumulated in the cells. At the harvesting stage two centrifuges are
necessary to remove the waste water and the damaged cells. An extra amount of water is
added to facilitate this process. The next step is to add ethanol to the mixture in order to
extract the accumulated glycerol and -carotene as well as other components. First, carotene (4.474 kg/h) is separated from the mixture by the use of n-hexane. The
remaining mixture of ethanol/water/glycerol is distilled and glycerol is recovered
(24.213 kg/h). The residue could find use as animal feed. It is worth mentioning that
after the distillation, ethanol is recycled for the purpose of operating cost reduction and
is reused.

3. Energy integration
Distillation is a highly energy-intensive unit operation and some processes can consume
a third or more of their energy in distillation alone. As Linnhof et al. (1983) have
reported, there are numerous well-known schemes to achieve better energy efficiency in
distillation, like thermal coupling, multi-effect systems, heat pumping etc. Multi-effect
separations are able to reduce the energy cost of a distillation with more effects being
added to the system resulting to a subsequent impact on investment cost. In this study
there is a scope to assess potentials using thermal coupling and complex distillation
instead of multi-effect systems. In regard to the process presented above, the distillation

Design Analysis of Integrated Microalgae Biorefineries

595

of the ethanol/water/glycerol mixture is the most energy intensive process raising

questions about sustainability. Energy integration is a powerful tool able to secure the
feasible and sustainable margins for energy efficiency improvement. Thermally coupled
distillation columns are assessed in a systematic approach (Shah and Kokossis, 2002) as
promising alternatives offering important energy and capital cost savings compared to
conventional distillation columns (even higher than 30 % in total annual cost).
In this paper two cases are studied, both referring to the final flowsheet (Fig.4). The
challenge of studying two cases is to witness the significance of energy integration not
only when a high-value product is present (-carotene), but also when the need for cost
reduction is of vital importance due to the presence of low-value products (glycerol).
The first case addresses the recovery of glycerol as the single product and the second
one the co-production of glycerol and -carotene. The required ethanol/water fraction
for the extraction of glycerol in the first case is 66 % w/w, as opposed to the second
case where the fraction of ethanol/water for the extraction of glycerol and -carotene is
95 % w/w. In both cases, ethanol is being recycled and the pressure of the distillation
columns is set up to 2.67 kPa in order to avoid the appearance of the ethanol/water
azeotrope, which is encountered in higher pressures. The degrees of freedom for both
cases are the configurations (conventional and thermally coupled distillation columns)
and the distillation design specifications. The configurations are: direct simple, indirect
simple, prefractionator, side rectifier, sloppy split and side stripper. The distillation
design specifications are ethanol recovery and ethanol feed. It should be noted that the
valorization of every configuration refers to the optimized distillation design
specifications.

4. Results and discussion

Tables 1 and 2 show the results of thermal coupling for the two cases studied, 66 % and
95 % w/w of ethanol/water fraction respectively. The calculations derived from shortcut
models using the Fenske-Underwood-Gilliland equations for non-azeotropic mixtures
and from implementing both simple and hybrid distillation models (thermally coupled).
It should be noted that ethanol recovery is over 99.9 % for each configuration.
For both case studies, side rectifier gives the lowest annual utility cost with ethanol feed
cost being kept in the lowest possible number (4,800 $/y for case 1 and 5,900 $/y for
case 2). This is of high importance especially for the case of 66 % ethanol/water fraction
where the high profit of -carotene is missing. More specifically, both cases display a
glycerol profit of 56,000 - 64,000 $/y, but in case 2 the profit from -carotene,
18,700,000 $/y, is more than enough to cover the losses due to energy cost and ethanol
feed cost.
Table 1. Results regarding case 1 (66% w/w ethanol/water)

Configurations
Side Rectifier
Direct Simple
Indirect Simple
Sloppy Split
Prefractionator
Side Stripper

Annual cost
($)
53,890
66,420
73,846
75,596
101,519
122,055

Cost increase
(%)
23
11
2
34
20

HOT Units
(MW)
0.34
0.35
0.32
0.26
0.37
0.87

COLD Units
(MW)
0.23
0.26
0.31
0.33
0.38
0.33

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M. Psycha et al.

Table 2. Results regarding case 2 (95% w/w ethanol/water)

Configurations

Annual cost
Cost increase
HOT Units
COLD Units
($)
(%)
(MW)
(MW)
Side Rectifier
306,144
2.27
1.10
Direct Simple
431,204
41
1,88
1.72
Indirect Simple
449,856
4
1.81
1.75
Sloppy Split
478,994
6
1.45
1.99
Side Stripper
520,091
9
3.66
1.42
Prefractionator
664,124
28
2.34
2.35
It is noteworthy that the main characteristic affecting the economic viability of the
process is the low pressure of the distillation columns (2.67 kPa), thus avoiding the
appearance of the ethanol/water azeotrope. As a result, ethanol is distilled under very
low temperatures leading to high cost refrigeration levels. A pressure increase close to
the atmospheric pressure would cause an increase in cooling temperatures reducing the
operating cost. This deduction is raising questions regarding the existence of the optimal
solution in the current study or in a future work related to the azeotropic mixture.

5. Conclusions
With biorefineries being in the spotlight for the last decade, it is of high significance to
secure their feasibility and sustainability. This study proves that multi-product processes
can achieve both goals. On one hand, the development of a multi-product process is
sufficient to secure the sustainability of the biorefinery, due to the introduction of highprofitable products such as -carotene. The adopted evolutionary approach can prove
useful and practical when resources are limited, especially in the case of microalgae
biorefineries. On the other hand, energy integration is obligatory for a single-product
process to secure its sustainability and process integration is significant to detect the
appropriate margins of energy savings and offer non-conventional design perspectives.

References
A. Ben-Amotz, M. Avron, 1990, The biotechnology of cultivating the halotolerant alga
Dunaliella, Trends in Biotechnology, 8, 121-126
A.C. Kokossis, A. Yang, 2010, On the use of systems technologies and a systematic approach for
the synthesis and the design of future biorefineries, Computers and Chemical Engineering, 34,
9, 1397-1405
B. Linnhoff, H. Dunford, R. Smith, 1983, Heat integration of distillation columns into overall
processes, Chemical Engineering Science, 38, 8, 1175-1188
G. P. Agarwal, 1990, Glycerol, Advances in Biochemical Engineering/Biotechnology, 41, 95-128
J.A. Caballero, I.E. Grossmann, 2004, Design of distillation sequences: from conventional to
fully thermally coupled distillation systems, Computers and Chemical Engineering, 28, 11,
2307-2329
M. Avron, A. Ben-Amotz, 1978, Production of glycerol from algae, U.S. Patent 4,115,949,
September 26
P.B. Shah, A.C. Kokossis, 2002, New synthesis framework for the optimization of complex
distillation systems, AIChE Journal, 48, 3, 527-550
P.J. Harvey, M. Psycha, A. Kokossis, A.L. Abubakar, V. Trivedi, R. Swami, A.K. Cowan, D.
Schroeder, A. Highfield, G. Reinhardt, S. Gartner, J. McNeil, P. Day, M. Brocken, J. Varrie,
A. Ben-Amotz, 2012, Glycerol production by halophytic microalgae: Strategy for producing
industrial quantities in saline water, Conference proceedings, European Biomass Conference,
Milan, Italy, 2012
R. Raja, S. Hemaiswarya, R. Rengasamy, 2007, Exploitation of Dunaliella for -carotene
production, Applied Microbiology and Biotechnology, 74, 517-523