Journal of Environmental Management 368 (2024) 122141

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Journal of Environmental Management

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

Research article

Unlocking pilot-scale green diesel production from microalgae

Iago G. Costa a , José V. C. Vargas a, b , Wellington Balmant b , Luiz P. Ramos c , André B. Mariano d ,
Anne C. D. Oliveira a, b , Thiago A. da Silva c , Ihana A. Severo a, e, * , Juan C. Ordonez e ,
Diego L. Sousa b , Vinicius F. dos Santos b
a
Department of Mechanical Engineering, Graduate Program in Materials Science Engineering (PIPE), Sustainable Energy Research & Development Center (NPDEAS),
Federal University of Paraná (UFPR), 81531-980, Curitiba, PR, Brazil
b
Department of Mechanical Engineering, Graduate Program in Mechanical Engineering (PGMEC), Sustainable Energy Research & Development Center (NPDEAS),
Federal University of Paraná (UFPR), 81531-980, Curitiba, PR, Brazil
c
Department of Chemical Engineering, Graduate Program in Chemical Engineering (PGEQ), Federal University of Paraná (UFPR), 81531-980, Curitiba, PR, Brazil
d
Department of Electrical Engineering, Graduate Program in Materials Science Engineering (PIPE), Sustainable Energy Research & Development Center (NPDEAS),
Federal University of Paraná (UFPR), 81531-980, Curitiba, PR, Brazil
e
Department of Mechanical Engineering, FAMU-FSU College of Engineering, Energy and Sustainability Center, Center for Advanced Power Systems (CAPS), Florida A&M
University, Florida State University, 32310-6046, Tallahassee, FL, United States

A R T I C L E I N F O A B S T R A C T

Handling editor: Jason Michael Evans Microalgae have emerged as a promising source of biomass to produce renewable biofuels due to their ability to
synthesize high-energy density compounds of commercial interest. This study proposes an approach for pilot-
Keywords: scale oil extraction, purification by fractional distillation, hydrocarbon characterization by gas chromatog-
Industrial photobioreactor raphy coupled to mass spectrometry (GC-MS), evaluation of physicochemical parameters of the produced hy-
Oil extraction
drocarbons, preliminary cost analysis, and challenges and future opportunities for green diesel on a commercial
Fractional distillation
scale. Here, the microalgae Tetradesmus obliquus was cultivated in 12 m3 photobioreactors using biodigested
Paraffinic hydrocarbons
Renewable diesel swine waste as a culture medium. The resulting biomass was subjected to drying and harvesting, followed by oil
Bioeconomy extraction using a hot solvent extraction method, followed by distillation to purify the compounds. Three
different extraction and distillation experiments were conducted, each using different solvent combinations. The
results obtained revealed that extraction with a solvent blend, composed of hexane and ethanol, provided more
significant yields compared to extraction with pure hexane. GC-MS analysis showed the presence of alkanes and
alkenes in the oil samples, and the proportion of solvent used in the extraction directly influenced the production
of alkanes. Additionally, specific hydrocarbons such as 4-methyl-1-decene, 8-heptadecene, 1-pentadecene, 9-
heneicosene, and 2-dodecene were identified. The evaluation of the physicochemical parameters demonstrated
that the calorific value of the distilled oil samples is within the range of typical values for petroleum diesel.
However, it was observed that the distilled oil samples had higher sulfur content compared to conventional
diesel. Regarding the cost analysis, it was found that it varies depending on the experimental conditions. In
particular, the process using a solvent mixture of 70% hexane and 30% ethanol proved to be more economical
than the others, since it extracted a greater quantity of oil with a lower initial biomass requirement. In summary,
this microalgae-derived hydrocarbon production process is promising and offers insights for compound purifi-
cation and future biofuel applications.

1. Introduction prompted a thorough reassessment of the worldwide energy panorama.

Numerous alternative energy solutions are currently being explored,
For decades, fossil fuels have been ubiquitous in our daily lives. such as biofuels derived from biomass (Da Rosa and Ordóñez, 2021). As
However, the over-exploitation of these non-renewable resources has articulated by the U.S. Department of Energy, an important long-term
contributed to the problem of climate change. Thus, the need for sus- goal involves the decarbonization of the transportation sector through
tainable energy sources and environmentally responsible practices has the adoption of green diesel, sustainable aviation fuel (SAF), and

* Corresponding author.
E-mail addresses: [email protected], [email protected] (I.A. Severo).

https://doi.org/10.1016/j.jenvman.2024.122141
Received 16 July 2024; Accepted 6 August 2024
Available online 11 August 2024
0301-4797/© 2024 Elsevier Ltd. All rights are reserved, including those for text and data mining, AI training, and similar technologies.
I.G. Costa et al. Journal of Environmental Management 368 (2024) 122141

biodiesel, for example. This strategic shift aims to gradually replace from oilseed crops due to its low boiling point, low cost, and high
conventional fossil fuels with renewable options. In this transformative extraction efficiency (Prasad et al., 2022; Ennaceri et al., 2023).
pursuit, biofuels are emerging as potential catalysts, positioned to Nevertheless, when used for microalgal oil extraction, non-polar sol-
contribute significantly to achieving competitive cost parity with vents face a challenge in penetrating cells efficiently. This limitation
well-established fuel technologies (DOE, 2023). arises from the robust hydrogen bonds formed between the membrane,
In this context, microalgae have gained considerable attention as a associated with lipids and proteins in the algal cell. A viable solution to
promising feedstock for biofuel production due to their high oil content this hurdle involves utilizing a mixture of polar and non-polar solvents, a
and rapid growth rate. Furthermore, microalgae can thrive in different method that enhances the extraction process, achieving higher lipid
environments with the input of wastewater and CO2, for example, and yields. In this way, the polar compound is used to break hydrogen bonds
generate biomass rich in compounds that can be destined for the most in the cell, while the non-polar compound is used to extract lipids.
varied industrial segments (Vidyashankar et al., 2015; Severo et al., Various pure solvents (e.g. hexane, methanol, ethanol, chloroform,
2019, 2024; Miyawaki et al., 2021; Dias et al., 2023; Rampi et al., 2023). isopropanol, etc.) and different proportions have been studied (Foerster
Green diesel from microalgae is a new energy source, also known as et al., 2023; Russell et al., 2022; Sati et al., 2019; Dong et al., 2016).
"renewable diesel" (or “drop-in biofuels”) and is within the category of Therefore, the optimization of solvent mixtures is a key area of research
liquid fuels. It is a mixture of hydrocarbons, such as alkanes and alkenes, to improve the overall sustainability of green diesel production.
composed of short-chain fractions (similar to gasoline), with 6–12 car- Thereafter, the lipid fraction is separated by distillation which, un-
bon atoms per molecule, and long-chain fractions (similar to diesel), like chemical extraction, is a physical separation process that exploits
typically with chains of 13–20 carbon atoms (Asikin-Mijan et al., 2023). the varying volatility of chemicals over different temperature ranges.
In general, a long carbon chain implies an increase in the boiling point, This technique has been widely used to refine crude oil from microalgae
freezing point, and energy density of the fuel (energy per unit volume), into green diesel. Several distillation methods have been studied to
which is desirable for biofuel production (Schirmer et al., 2010). Hy- separate and enhance the oil produced, including fractional, direct,
drocarbons have chemical structures and physical properties similar to steam, and molecular distillation. Among these, fractional distillation
diesel produced in petroleum refineries and can therefore be used stands out due to its substantial compacted surface area within a
directly in their pure form or as a blend in any desired proportion distillation column, which allows for more efficient separation of
without the need for modifications to the diesel engine, making them an chemical products through repeated cycles of evaporation and conden-
ideal replacement for conventional fossil fuels (IEA Bioenergy, 2019). sation (Nam et al., 2016). Moreover, it yields crude oil with a higher
Like biodiesel, the advantage of green diesel is that it is of biological calorific value, which could be increased by about 25%, while also
origin, has a low environmental impact due to reduced accumulation of improving properties, such as the H/C ratio and viscosity. As an
CO2 emissions, and unlike fossil diesel, does not release aromatic com- upgrading process, fractional distillation is a potential method for
pounds or naphthenes, making combustion cleaner. It is also more sta- practical applications (Liu et al., 2022).
ble, non-corrosive, and has a calorific value compared to petroleum Some studies have explored hydrocarbon production from micro-
diesel, which translates into better performance in internal combustion algae as an alternative to diesel oil. Matsunaga et al. (2009) explored
engines. However, it is important to note that green diesel has a different Scenedesmus rubescens under different cultivation conditions, extracting
chemical structure than biodiesel, which is fatty acid methyl esters lipids using hexane solvent. The main compounds identified were hex-
(FAMEs) (Douvartzides et al., 2019). adecane (C16H34) and 1-docosene (C22H44). Dodson and Leblond (2015)
While the broad potential of microalgae biofuels is widely recog- investigated the production of hydrocarbons in Phaeodactylum tri-
nized, a pivotal step towards their commercialization depends on the cornutum, revealing the production of octane (C8), undecane (C11),
successful translation from laboratory-scale processes to the more nonadecane (C19), and heneicosane (C21) at 20 ◦ C, and heptadecane
challenging domain of pilot and industrial operations (Guieysse and (C17), octadecane (C18), nonadecane (C19), and eicosane (C20) at 30 ◦ C.
Plouviez, 2024). Recent advances in pilot-scale microalgae cultivation Additionally, alkenes, such as heptadecene (C17:1), octadecene (C18:1),
have demonstrated the feasibility of integrating this kind of process with and nonadecene (C19:1) were detected. Vidyashankar et al. (2015)
industrial wastewater treatment. On-site pilot-scale demonstrations studied biomass productivity, fatty acids, and hydrocarbons in 32
have successfully utilized industrial wastewater streams for bio- microalgal strains. Lipids were extracted with a chloroform:methanol
fuel/bioenergy production, showing the potential for circular bio- solvent mixture, purified with n-hexane, and analyzed by gas chroma-
economy applications (Miyawaki et al., 2021; Dzuman et al., 2022; tography. Six strains accumulated over 20% lipids during the stationary
Costa et al., 2022; Abraham et al., 2023). This approach not only ad- phase, and 14 strains had over 10% hydrocarbons (dry biomass). The
dresses wastewater management issues but also provides a sustainable main hydrocarbons were n-paraffins C15-C20, with Scenedesmus sp.
source of nutrients for microalgae growth, potentially reducing pro- exhibiting 49% branched isoprenoids. Kirchneriella cornuta showed a
duction costs. high content of n-tetradecane (40%). Overall, these strains showed
This transition is particularly relevant in the context of utilizing profiles resembling petroleum diesel. O’Neil et al. (2015) proposed a
closed photobioreactors (PBRs), which provide an optimal environment process to isolate alkenones from the Isochrysis sp., which were con-
for microalgae cultivation. PBRs are more precise and scalable ap- verted into smaller hydrocarbon fragments for use as biofuels. The
proaches for biomass production, requiring less land space and being products were a mixture of three alkenones: 8-decen-2-one (C10), 2,
more productive with shorter harvest cycles (Barboza-Rodríguez et al., 9-undecadiene (C12), and 2-heptadecene (C17). Santillan-Jimenez et al.
2024). However, once the microalgae have been cultivated and har- (2016) extracted and purified lipids from Scenedesmus acutus cultivated
vested, the conversion of the oil contained in the biomass is a critical in different PBRs with exhaust gases. The purified lipids were improved
step in the production of green diesel since it involves steps such as via catalytic deoxygenation at high temperatures, which resulted in a
extraction and distillation. liquid product with a high content (75–99%) of diesel-like hydrocar-
Various techniques have been explored for oil extraction, including bons. However, this process requires additional and more complex steps
mechanical, chemical, and enzymatic. Among these strategies, oil to obtain the biofuel (González Fernández et al., 2023). In the study by
pressing, ultrasound-assisted extraction, microwave, supercritical fluid Costa et al. (2022), the microalgae Tetradesmus obliquus was studied to
extraction, and solvent extraction are the most explored (Zhou et al., produce green diesel. The microalga, known for its high lipid content
2022). Each technique has its strengths and weaknesses when consid- and robustness, was cultivated in a compact tubular PBR, producing
ering factors such as extraction efficiency, solvent use, necessary oper- biomass for oil extraction with different solvent mixtures and fractional
ating conditions, toxicity, and cost. However, the use of solvent distillation, and generating hydrocarbons, mainly alkanes with a high
extraction has been the most suitable universal extraction technique cetane number, desirable for internal combustion engines.

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I.G. Costa et al. Journal of Environmental Management 368 (2024) 122141

Based on the previous studies presented above, the review of the to the division Chlorophyta and the family Scenedesmaceae and is
state-of-the-art reveals a wide diversity of studies on hydrocarbon pro- known for its adaptation to local environmental conditions (Escorsim
duction from microalgae with potential application as biofuels. Different et al., 2018). The microalga was cultivated in a 12 m3 compact industrial
cultivation conditions, species, and oil processing techniques are dis- PBR, made of transparent circular PVC pipes with a length of 3.5 km and
cussed. However, the lack of large-scale process data hampers wide- a diameter of 50 mm, horizontally arranged in a stainless-steel structure
spread implementation. In this sense, the purpose of this study is within an area of only 10 m2 each, measuring 5 m × 2 m × 8 m, as shown
precisely to fill this knowledge gap, whose objectives are to evaluate the in Fig. 1.
i) pilot-scale extraction of crude oil derived from microalgae using The microalgae inoculum used had an approximate concentration of
different solvent mixtures from biomass produced in PBRs on an in- 700 × 104 cells/mL, while the cultivation medium consisted of waste
dustrial scale, ii) fractional distillation for the purification of com- from biodigested swine manure. The effluent was diluted in water to be
pounds, iii) characterization of hydrocarbons, iv) analysis of used as a culture medium with an approximate concentration of 5% v/v,
physicochemical parameters, and v) cost analysis. Finally, vi) a critical rich in nitrogen, phosphorus, and carbon to obtain adequate nutrients.
analysis is provided by addressing the challenges and future opportu- The selected dilution was based on previous tests that allowed an in-
nities for green diesel on a commercial scale. crease in biomass production (Miyawaki et al., 2021). The biodigested
Therefore, the novelty of the present research lies in the scale of the swine effluent composition was the following: nitrogen: 197 mg/L;
extraction process, since the work was carried out in a pilot plant, using biochemical oxygen demand: 8100 mg/L, and phosphorus: 7623 mg/L.
13.5 kg of microalgae biomass produced in an industrial PBR under Aeration and circulation were carried out using atmospheric air
different experimental conditions. It is worth mentioning that studies through compressors (Schulz of America, Inc., USA) with a volumetric
reported in the literature typically use 20 to 1000 g of biomass. These air flow rate of 1 L/min ±5%, and a 1 hp submerged pump, respectively
results come from bench-scale operations (laboratory scale), whose (Disconzi et al., 2019; Silva et al., 2015). The experiments were per-
yields are generally not directly comparable to those obtained at the formed during a residence time of 15 days, and after each cycle, the
pilot scale, mainly due to factors such as mass transfer efficiency and biomass was harvested and processed.
practical considerations. Given this scenario, full-scale experiments are
critical to unlock processes for future commercial competitiveness and 2.2. Biomass harvesting
provide a comprehensive understanding of the challenges and perspec-
tives of microalgal biofuels. The harvesting procedure was performed in batches of 3 m3, where
the culture volume from the PBRs was transferred and stored in three
2. Materials and methods tanks, each with a capacity of 1 m3, and the pH was adjusted to 7 (the
flocculant operating range) by adding industrial CO2. A natural tannin-
2.1. Microalgae species and cultivation conditions based flocculant/coagulant (Tanfloc, manufactured by Tanac company,
Brazil) with a solution concentration of 0.22 g/L was added to pre-
The microalga used in this study was Tetradesmus obliquus, previ- separate the microalgal biomass from the cultivation medium. In the
ously identified (LGMM0001) (Corrêa et al., 2017). This strain belongs flocculation tank, stirring was carried out with a mechanical stirrer

Fig. 1. Compact tubular PBR located at NPDEAS.

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I.G. Costa et al. Journal of Environmental Management 368 (2024) 122141

every 1 m3 at a rotational speed of 3355 rpm for 20 min at the beginning 2.5. Fractional distillation
to ensure the homogeneity of the solution, followed by a slower speed of
1730 rpm for 100 min to ensure the contact between the particles and The fractional distillation procedure was carried out according to the
the consequent agglomeration and sedimentation (without shaking) method previously published by Costa et al. (2022). The procedure
(Selesu et al., 2016; Scherer et al., 2018). consisted in separating the compounds that make up the extracted crude
The clarified liquid was then removed and stored, while the sedi- oil, which is in the liquid phase, through the difference in volatility using
mented biomass was centrifuged (US Centrifuge System, model M512) heat as a separating agent. The experimental apparatus used was a
at 3000 rpm, centrifugation speed of 4 L/min, concentrating 1 m3 of fractionation column (Vigreux) with a coupled volumetric flask con-
culture in 5 h with a continuous loading system. The solid fraction of the taining the crude oil, which was heated to separate the compounds
centrifugation resulted in a paste with 80% relative humidity. Then, the through a 500 W heating mantle (Fisatom, class 300) with manual
microalgal paste was uniformly spread on a tray, as illustrated in Fig. 2. control temperature, and a condenser was coupled to the system to cool
it and a volumetric flask to receive the distilled liquid. Three tempera-
tures (100 ◦ C, 150 ◦ C, and 200 ◦ C) were tested at the top of the column to
2.3. Biomass drying
obtain a distillate with light, medium, and heavy compounds, respec-
tively. The distilled oil and its conversion were calculated according to
Biomass drying was performed in a prototype convection oven
Eqs. (1)–(3):
(Disconzi et al., 2019). The walls were thermally insulated to minimize
( )
heat loss to the environment, and a tray was positioned at the bottom of mcrude oil extracted
Mass fraction yield (%) = × 100 (1)
the chamber to accommodate the biomass. The drying air was heated to mdry biomass
70 ◦ C by a 950 W electrical resistance, while an axial fan provided an
( )
airflow (500 m3/h) (NMB-MAT, model 4715MS-23T-B50). Both com- mdistilled oil
Distilled oil (%) = × 100 (2)
ponents were operated at 60 Hz and 2900 rpm. Samples of 5g were mcrude oil extracted
collected to determine the moisture content of the biomass, ensuring ( )
that they did not significantly affect the total mass to be dried. The mdistilled oil
Final conversion (%) = × 100 (3)
drying time was 24 h. Each sample was weighed on an analytical balance malgae
(GEHAKA, model AG200) and then dried in an infrared moisture
Eq. (1) refers to the yield (%) of microalgae oil extraction based on
analyzer (GEHAKA, model IV2000), which provided the final moisture
the relationship between the mass of crude oil extracted and the mass (g)
value of the sample. Finally, the dried biomass was crushed to improve
of dry biomass used, as shown in Table 1 below. Eq. (2) refers to the
lipid mass transfer during extraction (Halim et al., 2011).
percentage (%) of distilled oil converted from the extracted oil, which is
based on the relationship between the amount of distilled oil and the
2.4. Crude oil extraction amount of crude oil extracted (g), according to Table 2 below. Eq. (3)
represents the final conversion (%) of distilled oil taking into account the
The hot solvent chemical extraction technique, which has shown initial biomass: i.e. the amount of distilled oil and the amount of dry
high selectivity and solubility in lipid extraction, was used according to biomass used (g) in the process (Table 2).
the methodology described by Ranjan et al. (2010). The entire process
was carried out using an extractor (Marconi®, model MA 502/25/1), 2.6. Experimental set-up and design
with 2200 W. The equipment was coupled with an ultra-thermostatic
bath (Marconi®, model MA–184), with 20 L capacity, and a For oil extraction, three experiments were performed in triplicate
three-phase induction motor (EBERLE, model B71a4), with 60 Hz fre- using a combination of solvents or a single organic solvent as follows:
quency, and 1700 rpm. The extractor set is divided into three compo- condition 1: 5.25 L of hexane and 2.25 L of ethanol (70% hexane and
nents: the rotation control, the ultra-thermostatic bath, and the extractor 30% ethanol); condition 2: 3.75 L of hexane and 3.75 L of ethanol (50%
itself, as shown in Fig. 3. hexane and 50% ethanol); and condition 3: 7.5 L of pure hexane (100%).
The dried biomass was then placed in the apparatus along with a Each experimental condition required 1.5 kg of dried and ground
solvent mixture and/or a single solvent. The rotation control was set at microalgal biomass, and 7.5 L of organic solvent. The estimated duration
500 rpm, and the ultra-thermostatic bath was maintained at 50 ◦ C. The of the process was 3 h. After extraction, the remaining components
extractor has a condenser that prevents solvent evaporation, thereby (solvent, cellular debris, and unextracted lipids) are directed to a solid-
increasing the final yield. After this step, solvent recovery was carried liquid separation system for the removal of cellular residues.
out through a rotary evaporation process, using an evaporator (Fisatom, In terms of fractional distillation, 16 samples were fractionated for
model 802), connected to a centrifugal pump (Marconi®, model condition 1, where the oil was extracted with a solvent ratio of 70%
MA2057), with a power of 100 W for the vacuum procedure. This pro- hexane and 30% ethanol. Similarly, for condition 2, where the ratio was
cedure allows the removal of various substances present in the sample. 50% hexane and 50% ethanol, another 16 samples were fractionated.

Fig. 2. Biomass harvesting procedure in the PBR. A: Centrifuge; B and C: harvested wet paste.

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I.G. Costa et al. Journal of Environmental Management 368 (2024) 122141

Fig. 3. Microalgae oil extraction by organic solvent.

2.7. GC-MS analysis

Table 1
Extraction of microalgae oil for the three experimental conditions.
The analysis was performed by GC-MS (Shimadzu GC-2010 Plus)
Parameter Conditions equipped with a VF-5MS capillary column (30 m × 0.25 mm) and a mass
70% hexane/30% 50% hexane/50% 100% spectrometry detector (GCMS QP-2010 SE model) (Costa et al., 2022),
ethanol ethanol hexane operating in the ion scanning mode from 35 to 500 Da. The injector
Crude oil extracted 90.96 ± 3.95 97.60 ± 1.70 24.94 ± temperature was set to 250 ◦ C, and the injection was performed in split
(g) 1.22 mode with a split ratio of 1:20. Helium was used as the carrier gas at a
Mass fraction yielda 6.06 ± 0.26 6.50 ± 0.10 1.66 ± flow rate of 0.8 mL/min. The analysis started at 100 ◦ C and was held for
(%) 0.08
1 min, followed by a heating ramp at a rate of 10 ◦ C/min up to 200 ◦ C,
a
kg oil per kg dry biomass. which was then held for 2 min. This was followed by a ramp at a rate of
3.5 ◦ C/min up to 260 ◦ C, which was held for 20 min. The total program
time was 50.14 min. Quantification was performed by normalizing peak
Table 2 areas based on the total ion chromatogram, and peak identification was
Distillation of microalgae oil for the three experimental conditions.
based on the NIST 11 library.
Parameter Conditions

70% hexane/30% 50% hexane/50% 100%

ethanol ethanol hexane 2.8. Physicochemical analysis of distilled oil
Distilled oil (g) 46.59 ± 4.04 39.89 ± 1.68 8.51 ±
0.09 In this study, the following analytical methods were used: i) specific
Conversion to distilled 51.22 ± 1.42 40.87 ± 1.58 34.12 ± gravity, ii) higher heating value (HHV), iii) lower heating value (LHV),
oil (%) 1.42 and iv) total sulfur. These analyses were based on the yields obtained
Final conversiona (%) 3.11 ± 0.27 2.66 ± 0.11 0.57 ± after fractional distillation of the microalgae oil and were therefore only
0.01
performed in experimental conditions 1 and 2, each in triplicate.
a
In relation to initial biomass (1.5 kg). The specific gravity was determined using a density meter (model
DMA 4200 M, Anton Paar) to determine the specific density of the
Finally, condition 3, using 100% hexane as the solvent, yielded an samples, according to the standard test method of ASTM D4052-18a
additional 8 fractions of distilled oil. The initial fractionation time was (ASTM D4052-18a, 2011).
different for each experimental condition. However, after the first drop The HHV was determined according to the standard method of ASTM
was distilled, the interval for collecting the aliquots remained constant, D5468-07 (ASTM D5468-02, 2007). The analyses were performed in a
with collection occurring every 4 min for all conditions. The flasks calorimetric bomb (model 1341, Parr Instrument), a plain jacket bomb
containing the fractionated samples were all weighed, and in the end, calorimeter. Each test was conducted for 25 min, according to pre-
the fractions from each condition were combined into a single flask, defined criteria. A digital thermometer (model 6775, Parr Instrument)
resulting in three samples for analysis, as described above. The entire was used to monitor temperature changes during the experiment. The
procedure was performed in triplicate. Fig. 4 outlines the experimental temperature values and specific correction factors were used to calculate
setup and design carried out in the oil extraction and fractional distil- the HHV of the biofuel, which represents the energy released per unit
lation of microalgal biomass. mass. The LHV was determined using values obtained by calculating the
Dulong equation, which considers the values obtained from the HHV test

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I.G. Costa et al. Journal of Environmental Management 368 (2024) 122141

Fig. 4. Schematic view of the components of oil extraction and fractional distillation of microalgae biomass.

and the hydrogen composition of the sample, estimated at 15.01% by ethanol, contributed to higher extraction yields. This is also related to
mass (ASTM, 2007). the solvent/biomass ratio, which plays a critical role in extraction effi-
The total sulfur content was measured using a monochromatic X-ray ciency. In general, using a larger volume of solvent per unit of biomass
fluorescence sulfur analyzer (model 7039G2, Sindie), according to the can improve the extraction yield. However, this varies between different
ASTM D7039-20 method (ASTM D7039, 2015). The sample was microalgal species and their cultivation conditions. It must also be
collected and prepared, and the volume required for analysis was set at balanced with the costs and environmental impact of using larger
10 ml. The analyzer was then calibrated with known sulfur reference amounts of solvent (Escorsim et al., 2018).
standards. In addition, non-polar solvents, such as hexane, establish van der
Waals interactions with the long hydrophobic chains of fatty acids and
neutral lipids, facilitating the solubilization of these lipid classes. On the
2.9. Uncertainty analysis other hand, polar solvents, such as ethanol, in addition to solubilizing
non-polar molecules, can also solubilize polar lipids present in the cell
The uncertainties of the crude microalgae oil, the distilled oil masses, wall by breaking electrostatic interactions and hydrogen bonds between
and the obtained hydrocarbon mass fractions were estimated according them (Quitério et al., 2022).
to the ASME standards (Smith Jr and Wehofer, 1985). Each set of runs The intermediate polarities of the solvents had a significant influence
produced an average value, which characterized the two proposed on the extraction yields, as observed for the ethanol and hexane mix-
experimental conditions. The precision limit was established as two tures. Simultaneous extraction of polar and non-polar lipids resulted in
times the standard deviation of the mentioned measurements, ensuring improved process performance. Furthermore, the viscosity of the solvent
a confidence level of 95%. mixtures also contributed to increased yields. Ethanol has a lower vis-
cosity than hexane, which facilitates its penetration into the cell wall
3. Results and discussion and leads to higher lipid extraction yields (Tres et al., 2014).
Comparatively, Escorsim et al. (2018) used the Soxhlet extraction
3.1. Crude oil extraction method and ultrasound-assisted extraction using different solvents for
the biomass of Acutodesmus obliquus. The results showed that the yield of
The results of microalgae oil extraction for the three proposed Soxhlet extraction was 4.12 ± 0.06 (wt%). On the other hand, the use of
experimental conditions are shown in Table 1. a mixture of hexane and ethanol (1:1 v/v) yielded 11.76 ± 0.10 (wt%),
It was observed that the extraction condition with pure hexane while a mixture of hexane and ethanol (2:1 v/v) obtained yields of 12.05
presented a lower percentage yield compared to the extraction with a ± 0.30 (wt%). For the ultrasound-assisted extraction, the same number
mixture of solvents, whose values were in the order of 1.66% (100% of solvents was used, but with temperature variations (30 ◦ C and 60 ◦ C).
hexane), 6.06% (70% hexane + 30% ethanol) and 6.50% (50% hexane It was found that the extraction yields were higher at higher tempera-
+ 50% ethanol); the mass yields were 24.94 g, 90.96 g, and 97.60 g, tures, ranging from 1.46 ± 0.06 to 3.22 ± 0.03 (wt%) with hexane, from
respectively. The solvent mixtures demonstrated higher extraction 4.06 ± 0.03 to 6.02 ± 0.01 (wt%) for the mixture of hexane and ethanol
yields due to variations in the polarity and viscosity of the solvents used. (1:1 v/v), and from 4.29 ± 0.04 to 7.54 ± 0.04 (wt%) for the mixture of
The combination of a highly non-polar, high-viscosity solvent, such hexane and ethanol (2:1 v/v).
as hexane, followed by a highly polar, low-viscosity solvent, such as

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I.G. Costa et al. Journal of Environmental Management 368 (2024) 122141

Regarding the ideal temperature for microalgae oil extraction, it can

vary depending on various factors, including the microalgae species, the
desired oil composition, and the solvents used. However, in general, the
recommended temperature range for organic solvent extraction of
microalgae oil, such as hexane and ethanol, is from 50 ◦ C to 70 ◦ C
(Converti et al., 2009). Thus, the temperature used for oil extraction in
this study, which was 50 ◦ C, seems to be within the recommended range
to achieve a good yield when using a solvent mixture. This temperature
can reduce the viscosity of the solvent, which facilitates its penetration
through the microalgae cell wall and increases the extraction efficiency.
In the study by Kim et al. (2019), the species Tetradesmus obliquus
was used, and the modified Bligh and Dyer method was applied for lipid
extraction. Different solvent combinations were used, including chlo-
roform: methanol (2:1 v/v), hexane: isopropanol (3:2 v/v), and
dichloromethane: methanol (1:1 v/v). The results obtained ranged from
10.7% to 21.6% on a dry weight basis (w/w), at different temperatures
(15 ◦ C, 20 ◦ C, and 25 ◦ C). These results once again highlight the
importance of temperature control and appropriate solvent selection to
achieve more efficient extraction yields. Careful selection of these pa-
rameters is crucial to optimize the effectiveness of the lipid extraction
process.
Costa et al. (2019) also used the microalgae species Tetradesmus
obliquus and employed solvents (hexane and ethanol) for crude oil
extraction. The yields obtained were 10.98 ± 1.50 (wt%) for a solvent
mixture (70% hexane and 30% ethanol) and 1.68 ± 0.02 (wt%) for pure
hexane. In summary, the results of these studies corroborate the results
of the present study. Thus, these data highlight the influence of solvent
composition on the efficiency of microalgal oil extraction and provide
valuable insights for the development of more efficient extraction
methods.

3.2. Fractional distillation of microalgae oil

Table 2 presents the results of fractional distillation of crude

microalgae oil after the extraction process. The distillation yield was
evaluated under different conditions.
In condition 3, where only hexane was used as a solvent in the
extraction, the distillation yield was low, with an average of 8.51 ± 0.09
Fig. 5. Fractionated samples of microalgae oil obtained for each experimental
g. The final conversion, compared to the initial biomass used (1.5 kg),
condition. a) Condition 1: 70-30%; b) Condition 2: 50-50%; c) Condition
was only 0.57 ± 0.01%. On the other hand, in conditions 1 and 2 where
3: 100%.
a solvent mixture was used, the results were more satisfactory. The
distillation yield was 51.22 ± 1.42% for the 70-30% ratio and 40.87 ±
evaporate and are subsequently collected as they have lower volatility
1.58% for the 50-50% ratio. These results are in agreement with the
compared to the initially collected components (Solen and Harb, 2011;
study of Costa et al. (2022) who found a yield of 56.96 ± 2.81% for the
Stichlmair et al., 2021).
70-30% ratio.
The profiles of the fractional distillation of microalgae oil for the
Regarding the final conversion of the distilled oil, which refers to the
different experimental conditions analyzed are shown in Fig. 6. In
yield relative to the amount of initial biomass used for extraction, the
condition 1 (Fig. 6a) it can be seen that the first fraction was collected at
value obtained was 3.11 ± 0.27% in condition 70-30% and 2.66 ±
840 s (14 min) in all experiments. The maximum mass fractions for
0.11% in condition 50-50%. These values were lower than expected
conditions 1, 2, and 3 were in the order of 11.29 g, 7.87 g, and 8.17 g,
when compared to the cited study, which reported a yield of 6.26 ±
respectively. Notably, these quantities were consistently obtained at
0.46% for the 70-30% ratio using a lower amount of biomass (1.0 kg).
2280 s (42 min) in all three experiments. The process was completed at
Several factors may contribute to these differences in results. Variations
4440 s (1 h and 14 min) when the yield began to decrease. For condition
in solvent quality can affect the extraction efficiency and therefore the
2 (Fig. 6b), the first fraction was collected at 660 s (11 min) in all ex-
yield obtained, even when using the same solvent. Additionally, minor
periments. The largest mass fractions for conditions 1, 2, and 3 were
differences in biomass preparation, such as drying time, can influence
7.08 g, 6.79 g, and 6.86 g, respectively. The mass yield for conditions 1
the results (Zarrinmehr et al., 2022).
and 3 occurred at 2100 s (39 min), while for condition 2 it occurred at
The distilled fractions showed similar physical appearances in all
2340 s (43 min). The final time of the fractional distillation process in
experimental conditions, as illustrated in Fig. 5. During the fractional
this condition was 4260 s (1 h and 11 min). Finally, in condition 3
distillation process, the sample is gradually heated, causing the more
(Fig. 6c) the distillation process began at 480 s (8 min). The largest
volatile components to evaporate first. These lower boiling components
fraction in each experiment had yields of 3.78 g, 2.24 g, and 3.28 g,
are collected at the top of the column. As the process continues, the
respectively. Notably, as only hexane was used as a solvent, the yields
concentration of these volatile components decreases as they are
were significantly lower compared to previous conditions. The highest
removed from the sample. At a certain point, a minimum is observed in
yields for each fraction were obtained at the beginning, precisely at 720
the distillation curve, indicating the minimum concentration of
s (12 min) in all experiments.
remaining volatiles that have been largely removed. As the temperature
Fig. 7 shows the temperature versus time for the three experimental
continues to rise, components with higher boiling points begin to

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I.G. Costa et al. Journal of Environmental Management 368 (2024) 122141

Fig. 6. Variation of distilled mass over time for each experiment. a) Condition
1: 70-30%; b) Condition 2: 50-50%; c) Condition 3: 100%. Fig. 7. Variation of temperature over time for each experiment. a) Condition 1:
70-30%; b) Condition 2: 50-50%; c) Condition 3: 100%.

conditions described above. The experiments were conducted in a

distillation column, and the temperature was monitored over time at the increase, as hexane has a higher boiling range compared to ethanol,
top of the column with a precision thermometer ranging from − 20 ◦ C to resulting in higher maximum temperatures during distillation.
500 ◦ C. Regarding condition 2 (Fig. 7b), it was observed that the temperatures
In condition 1 (Fig. 7a), it was found that in the three experiments, were slightly lower compared to the three experiments. The temperature
the temperature consistently peaked above 250 ◦ C, reaching maximum peaks occurred within a time range of 3300 to 3540 s. The maximum
values at intervals ranging from 4200 s (1 h and 10 min) to 4440 s, near temperatures were T1: 226.1 ◦ C, T2: 228.8 ◦ C and T3: 227.9 ◦ C. Ethanol
the end of the distillation process. The maximum temperatures recorded may have contributed to this temperature reduction due to its lower
were T1: 260.25 ◦ C, T2: 253.5 ◦ C and T3: 251.65 ◦ C. The higher pro- boiling range compared to hexane. The temperatures in condition 3
portion of hexane in the mixture likely contributed to the temperature (Fig. 7c) were significantly lower than in the previous conditions, with

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I.G. Costa et al. Journal of Environmental Management 368 (2024) 122141

temperature peaks varying between T1: 148.3 ◦ C, T2: 139.9 ◦ C, and T3: Alkanes are non-polar compounds and the amount obtained varies
133.8 ◦ C. This significant reduction in maximum temperatures can be under different growing conditions. They have been described as the
attributed to the fact that pure hexane has a lower boiling range most prominent compound in photoautotrophic cultures and are derived
compared to the hexane/ethanol mixture. Using a single solvent with a from a variety of fatty acids. For example, straight and branched chain
lower boiling point resulted in lower temperatures during distillation. In alkanes are components of fossil-derived diesel, like gasoline. Alkanes
addition, the distillation process was the fastest, lasting only 2400 s (40 and alkenes have often been used as replacement fuels for the complex
min), due to the lower extraction efficiency using hexane alone as the hydrocarbon mixtures that make up fossil diesel, and the effects of alkyl
solvent. chain length and saturation on diesel combustion properties are rela-
These results highlight that the composition of the solvent mixture tively well understood (Hellier et al., 2015; Sorigué et al., 2016; Severo
plays a fundamental role in determining the temperatures obtained et al., 2018).
during the fractional distillation of microalgae oil. The proportion of Alkenes, although identified in smaller amounts compared to al-
hexane and ethanol directly influences the temperature ranges reached, kanes, showed greater variability (larger standard deviations) in con-
allowing more precise control over the separation of components pre- dition 1 (70-30%). This may be a consequence of several factors, such as
sent in the oil (Eden et al., 2018; Wang et al., 2024). sample heterogeneity and variations in extraction procedures. Kim et al.
(2019) and Lopez-Rosales et al. (2019) reported specific alkenes and
their concentrations were influenced by extraction temperatures.
3.3. Hydrocarbon characterization
Notably, alkenes were consistently overshadowed by alkanes in terms of
abundance. This difference may be related to the physicochemical
It is interesting to understand how distillation separates the chemical
properties of the compounds, such as partial polarity, which may in-
compounds in oil into different fractions. The compounds identified and
fluence their solubility and reactivity.
quantified in this study for the extractions and subsequent distillation
The analysis also highlighted the presence of alcohols, with 1-dodec-
conditions, as well as the averages and standard deviations for each of
anol being the only compound consistently identified in all conditions,
them, are presented in Table 3.
but in smaller quantities compared to hydrocarbons. Alcohols are polar
A total of 25 compounds of different chemical classes were detected
compounds due to the presence of the hydroxyl group (-OH) and are
in each distillate, including hydrocarbons, such as alkanes (12) and al-
formed by the oxidation of alkanes. It is generally found in low con-
kenes (5), alcohols (1), esters (2), and carboxylic acids (5). The most
centrations due to its polarity, which affects its solubility and in-
prevalent compounds identified in terms of abundance were hydrocar-
teractions with the sample matrix (Abozenadah et al., 2017).
bons. Within this chemical group, straight-chain alkanes represent the
Ester compounds, including hexadecanoic acid methyl ester and
majority of compounds found, such as pentadecanes and heptadecanes,
diiso-octyl phthalate, have been identified in smaller amounts. Esters are
in the following orders: 62.18% (condition 2), 45.18% (condition 1),
compounds formed by the reaction of a carboxylic acid with an alcohol.
and 38.69% (condition 3) of the total produced. These results indicate
They generally have lower polarity compared to carboxylic acids and
that the proportion of solvents used in the extraction process affects the
have a pleasant odor. According to Kim et al. (2019), the only ester
production of alkanes. In addition, condition 2 (50-50%) had the largest
found was methyl Z-11-tetradecenoate (concentration of 21.6% at
standard deviations for alkanes, indicating greater variability in the
25 ◦ C), while Lopez-Rosales et al. (2019) identified esters such as
results.

Table 3
Compounds identified by GC-MS.
Compound (IUPAC) Molecular formula Polarity Condition 1 (70-30%) Condition 2 (50-50%) Condition 3 (100%)

Hydrocarbons (Alkanes)
1-Dodecane C12H26 NP 1.82 ± 1.29 0.93 ± 1.31 0.71 ± 1.00
Dodecane C12H26 NP 2.37 ± 0.66 2.81 ± 0.59 0.90 ± 0.74
2,6-dimethyl-undecane C13H28 NP 0.87 ± 0.92 2.45 ± 2.57 0.14 ± 0.20
6-methyl-octadecane C19H40 NP 0.73 ± 1.04 0.79 ± 1.12 0.63 ± 0.89
3-Tetradecane C14H30 NP 3.51 ± 0.82 1.60 ± 2.27 0.89 ± 1.26
2,6,10-trimethyl-dodecane C15H32 NP 0.97 ± 1.37 1.02 ± 1.45 ND
Tetradecane C14H30 NP 4.28 ± 052 7.07 ± 1.25 1.94 ± 0.48
2-methyl-tetracosane C26H54 NP 1.86 ± 0.47 1.81 ± 0.75 ND
Pentadecane C15H32 NP 15.65 ± 0.99 24.86 ± 8.37 24.33 ± 5.34
Hexadecane C16H34 NP 3.48 ± 0.27 3.17 ± 0.65 1.55 ± 0.17
Heptadecane C17H36 NP 7.66 ± 0.66 14.52 ± 6.55 7.58 ± 0.86
Nonadecane C19H40 NP 1.93 ± 0.30 1.68 ± 0.43 ND
Hydrocarbons (Alkenes)
4-methyl-1-decene C11H22 PP 0.58 ± 0.82 ND ND
8-heptadecene C17H32 PP 2.25 ± 1.03 1.55 ± 1.65 1.48 ± 1.84
1-pentadecene C15H28 PP 1.31 ± 1.86 1.61 ± 2.27 ND
9-heneicosene C21H40 PP 0.75 ± 1.06 0.89 ± 1.25 1.07 ± 1.52
2-dodecene C12H24 NP 1.52 ± 1.49 2.29 ± 2.02 1.24 ± 0.95
Alcohols
1-Dodecanol C12H26O P 1.39 ± 0.74 0.32 ± 0.45 0.90 ± 0.86
Ester
Methyl ester of hexadecanoic acid C17H32O2 P 4.49 ± 4.13 3.53 ± 3.50 2.36 ± 3.33
Di-iso-octyl phthalate C24H38O4 NP 2.81 ± 3.97 2.21 ± 3.13 0.66 ± 0.94
Carboxylic Acids
Heptanoic acid C7H14O2 P 0.62 ± 0.88 0.67 ± 0.94 0.31 ± 0.44
Octanoic acid C8H16O2 P 0.88 ± 1.03 0.71 ± 1.00 0.65 ± 0.91
Nonanoic acid C9H18O2 P 0.06 ± 0.09 ND ND
Decanoic acid C10H20O2 P 0.78 ± 0.88 2.62 ± 2.65 1.52 ± 1.29
Hexadecanoic acid C16H32O2 P 2.47 ± 3.49 ND ND
Total (% area) 65.12 78.67 48.90

ND: not detected; NP: non-polar; PP: partially polar; P: polar.

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I.G. Costa et al. Journal of Environmental Management 368 (2024) 122141

2-palmitoylglycerol (9.94%) and hexadecanoic acid with bis diesel (13.32%–15.26%) (Zubel et al., 2016; Janecek et al., 2016) is
(2-ethylhexyl) in high concentrations in two strains (45.19% and similar to the estimated hydrogen composition in the distilled oil sam-
39.03%, respectively). Differences in the types and concentrations of ples (15.01% by mass). This suggests that both microalgae oil and pe-
esters between studies highlighted the impact of experimental condi- troleum diesel samples have a similar proportion of hydrogen relative to
tions on results. their total mass. This hydrogen composition can influence the physico-
Carboxylic acids, on the other hand, are polar compounds that are chemical properties and energy potential of these fuels, along with other
present in smaller amounts compared to hydrocarbons. Condition 1 (70- factors such as the H/C ratio, oxygen, and the presence of other com-
30%) had the highest standard deviation in relative area values of car- pounds (Nam et al., 2016; Liu et al., 2022). However, it is important to
boxylic acids with an average of 4.83 ± 3.51. Carboxylic acids played a perform a more comprehensive analysis and consider other specific
significant role in the samples analyzed. This highlights the importance properties and characteristics for a complete comparison between these
of these compounds in these analyses, both in terms of their presence fuels.
compared to alkanes and alkenes, and their distribution under different
conditions and samples.
Finally, it is important to note that distilled Tetradesmus obliquus oil 3.5. Cost analysis
contains thermally unstable components that were not detected during
the analysis, resulting in a total area of less than 100%. In addition, Table 5 provides the costs associated with the process of obtaining
microalgal oil, being a complex matrix, may contain interferents that diesel oil from microalgae. Each stage was analyzed considering the
lead to the underestimation of certain peak areas. In our study, some average price of electrical energy consumed monthly, according to data
compounds were also detected at very low concentrations, contributing from the U.S. Energy Information Administration (EIA, 2023a,b).
to the difference in total area. The process was divided into three steps: 1) extraction, 2) rotary
evaporation, and 3) fractional distillation, lasting 3h, 4h, and 2h,
respectively, totaling 9h of energy consumption. In the extraction step,
3.4. Physical-chemical parameters of the distilled oil the energy-consuming equipment included an extractor, a three-phase
induction motor, a thermostatic bath, and a pump. During rotary
Table 4 shows the analysis of the physicochemical properties of the evaporation, the evaporator system, vacuum and submersible pumps,
distilled microalgae oil considering conditions 1 and 2. Condition 3, and heating bath were considered. For fractional distillation, the
with pure hexane, was not analyzed due to the low yield of distilled oil. equipment considered was a submersible pump, a heating pad, and a
The following parameters were analyzed for the distilled oil: density, temperature controller, the latter being the most energy-consuming.
total sulfur content, higher and lower heating values. Based on the three experimental conditions evaluated in this study
The distilled microalgal oil samples showed density values in the regarding the efficiency of microalgae oil production, there are notice-
range of 845.7 ± 0.64 kg/m3 and 818.17 ± 0.17 kg/m3 for conditions 1 able variations in the initial biomass requirements and the corre-
and 2, respectively. In terms of heating values, the data ranged from sponding costs vary. To produce 1 kg of oil in condition 1 with 50%
41.85 ± 0.79 MJ/kg (HHV) to 38.58 ± 0.86 MJ/kg (LHV) and 43.50 ± hexane and 50% ethanol, approximately 37.91 kg of biomass is needed,
0.59 MJ/kg (HHV) to 39.99 ± 0.69 MJ/kg (LHV) for conditions 1 and 2, incurring a cost of USD 39.31. In condition 2 with 70% hexane and 30%
respectively. Comparatively, the density range of petroleum-derived ethanol, 32.19 kg of biomass are required, resulting in a cost of USD
diesel is 796.8–841 kg/m3 (Bugarski et al., 2016; Karavalakis et al., 33.38. Condition 3 with 100% hexane requires 176.05 kg of biomass and
2016), while the heating value varies from 42 to 45.77 MJ/kg (Gómez costs USD 182.51 per kg of diesel oil produced. As the oil extraction
et al., 2016; Aatola et al., 2009). These results suggest that microalgae efficiency increases, the initial biomass requirement decreases, thus
oil has properties, both energy potential and density, similar to the fossil manifesting a concomitant reduction in oil production costs. Notably,
fuel diesel and meets the requirements of the diesel standard. Optimum
fuel density is important for its ability to improve both engine perfor- Table 5
mance and exhaust emissions in vehicles (Asikin-Mijan et al., 2023). Microalgae diesel oil production costs.
The sulfur content of the distilled oil samples was found to be higher
Step Parameter
compared to diesel fuel, which adheres to stringent regulations limiting
sulfur content to levels below regulatory thresholds (Niemi et al., 2016). Power Energy Applied
consumptiona rate
In our study, the distilled oil samples exhibited significantly elevated
sulfur levels under different conditions, indicating the need for further 1. Extraction 3h
Extractor 0.22 kW 0.66 kWh 0.05821
refinement in the production process. These findings highlight the
Three-Phase Induction 0.368 1.104 kWh 0.09737
importance of optimizing cultivation (e.g., culture medium), extraction, Motor kW
and processing methods to ensure compliance with industry standards. Thermostatic bath 1.5 kW 4.5 kWh 0.39690
It is also observed that the hydrogen composition range of petroleum Pump 0.027 0.081 kWh 0.00714
kW
TOTAL 0.55962
Table 4 2. Rotary evaporation 4h
Physicochemical properties of distilled oil. Submersible pump 0.027 0.108 kWh 0.00953
Analysis Condition 1 Condition 2 Unit Method kW
(70-30%) (50-50%) Vacuum pump 0.127 0.508 kWh 0.04481
kW
Density at 845.7 ± 0.64 818.17 ± 0.17 kg/ ASTM D4052 - 18a Rotation system 0.07 kW 0.28 kWh 0.02470
20 ◦ C m3 Heating bath 1.2 kW 4.8 kWh 0.42336
Total sulfur 1256.66 ± 2.05 1029.67 ± mg/ ASTM D7039 - 20 TOTAL 0.50240
79.82 kg 3. Distillation 2h
HHV 41.85 ± 079 43.50 ± 0.59 MJ/ ASTM D5468 - 07 Submersible pump 0.027 0.054 kWh 0.00476
kg kW
LHV 38.58 ± 0.86 39.99 ± 0.69 MJ/ Proprietary Temperature controller 2.3 kW 4.6 kWh 0.40572
kg methodologya Heating pad 0.47 kW 0.94 kWh 0.08291
a TOTAL 0.49339
Values obtained through the calculation using the Dulong equation, which
a
considers the values from the HHV test and the hydrogen composition in the Data based on the average industrial electricity price in August 2023. This
sample, estimated at 15.01% by mass. price was set at 8.82 cents/kWh (EIA, Electric Power Monthly, 2023).

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I.G. Costa et al. Journal of Environmental Management 368 (2024) 122141

the process using a 70-30% solvent mixture is more economically viable (Koyande and Show, 2022).
compared to the others because it extracts a greater amount of oil with a On the other hand, drying biomass to reduce moisture content before
proportionally lower initial biomass requirement, thus reducing costs oil extraction is energy-intensive and often accounts for a significant
for the same total process time. portion of total production costs, approximately 90% (for drying and
Assessing the economic viability of microalgae oil production re- lipid extraction) (Lardon et al., 2009). The use of low-cost drying
quires a comparative analysis with traditional petroleum-derived fuels. methods (e.g., solar drying) can reduce costs but may compromise ef-
According to the EIA (2023a,b), gasoline and diesel average prices in the ficiency. In addition, the drying process is essential for maximizing oil
U.S. in September 2023 were USD 3.84/gallon and USD 4.56/gallon, extraction efficiency. Achieving low moisture content improves extrac-
respectively. Considering the conversion factor of 1 gallon ≈3.8L and tion yields but requires careful balance to minimize energy consump-
applying tax rates on crude oil and refining (gasoline: 55% and 19%, tion. Thus, it is imperative to develop cost-effective technologies for
diesel: 46% and 26%), the estimated values are approximately USD 0.97 efficient biomass drying and oil obtation.
per kg for gasoline and USD 1.00 per kg for diesel. Despite the enhanced With respect to solvent extraction methods, particularly those using
efficiency of the 70% hexane and 30% ethanol process, the costs for 1 kg hexane-ethanol mixtures, higher yields are achieved, but there are costs
of fuel remain significantly higher – roughly 34 times more than gasoline associated with energy consumption for solvent recovery and recycling.
and 33 times more than diesel. The use of non-toxic, less expensive solvents is a potential area for cost
reduction. In terms of extraction efficiency, it depends on the solvent
3.6. Challenges and future opportunities for green diesel on a commercial system and the extraction conditions (e.g., temperature, duration),
scale which must be strongly specific and selective regarding microalgae
lipids (Kamaroddin et al., 2020). Therefore, optimization of these pa-
Realizing the full potential of using microalgae to produce biofuels rameters is essential to maximize yield and minimize solvent usage.
depends on several factors. The entire process of producing hydrocar- The distillation to purify extracted oils and obtain diesel-range hy-
bons, that is, green diesel from microalgae, from harvest to final prod- drocarbons involves significant capital investment in distillation col-
uct, includes stages such as cultivation, harvesting, drying, oil umns and operational costs for heating and cooling. The use of fractional
extraction, purification by distillation, and final conversion into diesel. distillation, although effective, increases overall energy and mainte-
Each stage involves its own set of economic and efficiency challenges nance costs. Achieving high-purity hydrocarbons requires precise con-
that are critical to scaling up to commercial production, as summarized trol of distillation parameters, which affects both energy consumption
in Fig. 8. and operating efficiency. Process efficiency could be improved through
Microalgae cultivation requires significant capital investment in heat integration and energy recovery techniques (Song et al., 2016). It is
PBRs and operating costs to maintain optimal conditions (e.g., light, important to note in this study that the initial product extracted from
CO2, nutrients). The use of waste streams, such as the biodigested swine Tetradesmus obliquus contains a complex mixture of compounds,
manure used in this study, as a nutrient source can reduce costs. How- including some oxygenated ones (e.g., alcohols, acids, esters). For a
ever, large-scale operations demand extensive infrastructure and energy more accurate economic comparison with diesel fuel, an upgrading
inputs for aeration and recirculation. In terms of efficiency, high pro- process would be required to convert these compounds into pure hy-
ductivity can be achieved in PBRs, with careful control of environmental drocarbons. The upgrading process would be a critical step in ensuring
conditions, but scalability is challenging. that the final product has a competitive economic value and is efficient
In terms of existing downstream processing, they represent 40–50% for commercial-scale green diesel applications. However, the procedure
of the total process cost due to the dilute culture of microalgae (~3 g/L) would not only be more complex, but it would also be more costly due to
and the complex nature of its cell wall, which must be disrupted to the addition of another operation to the process (Asikin-Mijan et al.,
extract the compounds of interest (Davis et al., 2016; Ray et al., 2021). 2023; González Fernández et al., 2023).
For example, efficient harvesting methods, such as flocculation and Finally, as pointed out above, significant challenges remain in terms
centrifugation, are essential to concentrate biomass but are of economics and efficiency at the commercial scale. Overcoming these
energy-intensive. Typically, around 20–30% of total production ex- obstacles will require continued research and development to optimize
penses for biomass production are associated with its harvesting each step of the process, reduce costs, and improve the overall energy

Fig. 8. Steps and challenges involved in microalgae green diesel production. (For interpretation of the references to colour in this figure legend, the reader is referred
to the Web version of this article.)

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I.G. Costa et al. Journal of Environmental Management 368 (2024) 122141

efficiency of hydrocarbon production. The integration of renewable Table 6

energy sources and innovative technologies will be key to overcoming Major challenges presented in this study and future opportunities.
these barriers and achieving large-scale implementation. Table 6 pro- Challenges Opportunities
vides a clear and structured overview of the major challenges in the
High capital and operational costs: Investment in research and development
production of microalgae green diesel at a commercial scale. The initial investment for PBRs, can lead to more cost-effective
downstream processing, including technologies and processes.
4. Conclusions harvesting equipment, distillation
units, and any other upgrading system
is substantial. Ongoing costs for
The present study investigated the extraction of microalgae oil using energy, maintenance, and labor are
different solvent compositions and subsequent fractional distillation also significant barriers to commercial
from biomass produced from a compact industrial photobioreactor with viability of microalgae green diesel.
the overall purpose of evaluating its viability as a source of renewable Energy consumption: The energy Integration of renewable energy sources,
demand for drying, solvent extraction, such as solar or wind, can reduce energy
biofuel.
and distillation is high, making the costs and environmental impact.
The results showed that solvent mixtures (70-30% and 50-50%) process less sustainable. Energy-efficient technologies and
increased extraction efficiency over pure hexane due to variations in innovations can reduce consumption
solvent polarity and viscosity. The combination of a high viscosity non- and operational expenses.
polar solvent (hexane) followed by a low viscosity polar solvent Solvent use and recovery: The cost and The development of green solvents and
environmental impact of solvents used solvent-free extraction methods can
(ethanol) provided higher extraction yields. The study compared its in extraction are major concerns. reduce the environmental footprint.
findings with previous research, emphasizing the impact of solvent Advances in solvent recovery
composition, temperature, and extraction methods on microalgae oil technologies can improve efficiency and
yield. The optimal temperature for extraction ranged from 50 ◦ C to reduce costs.
Process integration: Integrating the Advanced process integration and
70 ◦ C, aligning with the use of 50 ◦ C in the study, improving solvent
various stages of the process to optimization techniques can improve
penetration and extraction efficiency. minimize waste and maximize energy overall efficiency. Waste valorization (e.
Fractional distillation results showed that solvent mixtures resulted and resource efficiency is challenging. g., using by-products for co-products)
in higher distillation yields compared to pure hexane. The distillation can create additional revenue streams,
process was influenced by temperature variations, with different sol- essential for economic viability.
Scale-up: While pilot-scale processes Lessons learned from pilot-scale
vents impacting temperature ranges during distillation. Characteriza- have shown promise, scaling up to operations can inform successful scale-
tion of the hydrocarbons identified 25 compounds with a predominance commercial levels introduces up strategies.
of alkanes such as pentadecanes and heptadecanes. The abundance of complexities related to mass transfer,
alkanes was influenced by the composition of the solvent, highlighting heat management, and process control.
Market competition: Biofuels from Growing demand for sustainable and
the importance of experimental conditions. Alcohols, esters, and car-
microalgae must compete with other renewable energy sources can drive
boxylic acids were also identified, showing the complexity of the renewable energy sources and market acceptance. Policy support and
microalgae oil composition. In evaluating the physical-chemical pa- conventional fossil fuels. carbon pricing can make microalgae
rameters of distilled microalgal oil, similarities with fossil-derived diesel biofuels more competitive with fossil
in terms of density and heating values were identified. However, the fuels.

sulfur content underscored the need for refining processes to meet

existing regulatory standards. Finally, the process cost analysis consid- interests or personal relationships that could have appeared to influence
ered energy consumption during extraction, rotary evaporation, and the work reported in this paper.
fractional distillation. The 70-30% solvent mixture proved to be more
economical, with cost reduction associated with greater oil extraction Data availability
efficiency.
Despite these findings, the production cost of microalgae-derived No data was used for the research described in the article.
biofuel has remained significantly higher than traditional fuels, high-
lighting the latent need for further cost reductions and efficiency im-
Acknowledgments
provements. The present research demonstrated the potential of using
microalgae oil obtained from biomass from a large-scale photo-
To the Brazilian National Council for Scientific and Technological
bioreactor as a sustainable alternative for renewable green diesel pro-
Development, CNPq (projects408073/2021-7, 405864/2022-1, and
duction. However, it also highlighted the current economic and
402313/2022-4), Coordination for the Improvement of Higher Educa-
efficiency bottlenecks that will require technological advances in order
tion Personnel, CAPES, Ministry of Education, Brazil (projects 062/14
to achieve commercial viability.
and CAPES-PRINT-UFPR-88881.311981/2018-01), and Araucaria
Foundation of Paraná, Brazil (project 115/2018, no. 50.579 – PRONEX).
CRediT authorship contribution statement

Iago G. Costa: Conceptualization, Investigation, Methodology, References

Validation, Writing – original draft. José V. C. Vargas: Funding Aatola, H., Larmi, M., Sarjovaara, T., Mikkonen, S., 2009. Hydrotreated vegetable oil
acquisition, Supervision. Wellington Balmant: Validation, Visualiza- (HVO) as a renewable diesel fuel: trade-off between NOₓ, particulate emission, and
tion. Luiz P. Ramos: Conceptualization. André B. Mariano: Project fuel consumption of a heavy-duty engine. SAE International Journal of Engines 1 (1),
1251–1262. https://doi.org/10.4271/2008-01-2500.
administration, Resources. Anne C. D. Oliveira: Conceptualization,
Abozenadah, H., Bishop, A., Bittner, S., Lopez, O., Wiley, C., Flatt, P.M., 2017. Consumer
Methodology. Thiago A. da Silva: Methodology. Ihana A. Severo: chemistry. How Organic Chemistry Impacts Our Lives. CC BY-NC-SA. Available at:
Conceptualization, Visualization, Writing – review & editing. Juan C. https://wou.edu/chemistry/courses/online-chemistry-textbooks/ch105-cons
Ordonez: Writing – review & editing. Diego L. Sousa: Investigation. umer-chemistry/.
Abraham, J., Abimbola, T., Braida, W.J., Terracciano, A., Su, T.-L., Christodoulatos, C.,
Vinicius F. dos Santos: Investigation. Koutsospyros, A., RoyChowdhury, A., Smolinski, B., Lawal, A., 2023. On-site pilot-
scale microalgae cultivation using industrial wastewater for bioenergy production: a
Declaration of competing interest case study towards circular bioeconomy. Bioengineering 10 (12), 1339. https://doi.
org/10.3390/bioengineering10121339.
Asikin-Mijan, N., Juan, J.C., Taufiq-Yap, Y.H., Ong, H.C., Lin, Y.-C., AbdulKareem-
The authors declare that they have no known competing financial Alsultan, G., Lee, H.V., 2023. Towards sustainable green diesel fuel production:

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