Arabian Journal of Chemistry (2022) 15, 103591

King Saud University

Arabian Journal of Chemistry

www.ksu.edu.sa
www.sciencedirect.com

REVIEW ARTICLE

Biofuels from microalgae biomass: A review of

conversion processes and procedures
Samuel Ogbeide Ebhodaghe a,*, Ojeaga Evans Imanah b,*, Henry Ndibe b

a
Department of Chemical Engineering, University of Benin, 1154 Benin City, Nigeria
b
Department of Chemistry, University of Benin, 1154 Benin City, Nigeria

Received 26 September 2021; accepted 23 November 2021

Available online 29 November 2021

KEYWORDS Abstract Achieving the EU 2030 vision of a 15% minimum amount of biofuels utilized in the road
Biofuel; transportation require more research on biofuel production from biomass feedstock. To this end,
Microalgae; this review study examines the use of green, deep eutectic solvents and direct transesterification
Lipid; approaches for biomass conversion to biofuels. Next, biogas production from anaerobic co-
Syngas; digestion of microalgae biomass is presented. Lastly, the effect of operating conditions, as well
Anaerobic co-digestion; as advantages and limitations of several biomass conversion techniques are outlined. Of note, this
Pyrolysis; study presents promising microalgae conversion processes which could be progressed are the use of
Transesterification bio-based solvents and supercritical fluids for biodiesel production, hydrothermal liquefaction for
biogas production, microwave-induced pyrolysis for syngas production, and ultrasound/microwave
enhanced extraction for bio-oil production. These are based on the possibility of high yield and pro-
cess economics. We have also enumerated knowledge gaps needed to propel future studies.
Ó 2021 Published by Elsevier B.V. on behalf of King Saud University. This is an open access article under
the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/).

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
1.1. Lipid extraction processes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
1.1.1. Solvent extraction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
1.1.2. The use of deep eutectic solvents . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7

* Corresponding authors.
E-mail addresses: [email protected] (S.O. Ebhodaghe), [email protected] (O.E. Imanah), [email protected]
(H. Ndibe).
Peer review under responsibility of King Saud University.

Production and hosting by Elsevier

https://doi.org/10.1016/j.arabjc.2021.103591
1878-5352 Ó 2021 Published by Elsevier B.V. on behalf of King Saud University.
This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/).
2 S.O. Ebhodaghe et al.

2. Microalgae conversion processes to biofuels. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7

2.1. Biodiesel . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7
2.1.1. Transesterification . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7
2.2. Bio-methane . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9
2.2.1. Anaerobic digestion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9
2.3. Syngas . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11
2.3.1. Gasification . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11
2.3.2. Pyrolysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13
2.4. Bio-oil and Bio-char . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13
2.4.1. Pyrolysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13
2.4.2. Ultrasound/Microwave- enhanced conversion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 14
2.4.3. Hydrothermal pretreatment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 15
3. Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 15
Declaration of Competing Interest . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 16
Acknowledgement . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 16
Funding Statement . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 16
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 16

1. Introduction productivity. These respective productivities were 2.95 to 3.52-fold and

3.63 to 4.77-fold higher than that of C. pyrenoidosa grown in BG-11
Fossil fuels are cheap energy sources which have continued to meet media. Two, the potential suitability of C. pyrenoidosa as a biodiesel
world’s growing energy needs. With an exhaustible reserve, fossil fuel feedstock was demonstrated by the presence of C16:0, C18:0, C18:1,
prices will undoubtedly rise when demands gradually begins to exceed and C18:2 in its’ lipid profile. This observation was made on its’
supply (Georgianna and Mayfield, 2012). This now suggests the need growth profile in the multi-objective optimized pre-treated FCWW.
for more development of sustainable energy sources. This is important Three, cost benefit analysis of the investigated FCWW-based algae
because of the obviously increasing scarcity of conventional fuels asso- indicates the potential of achieving commercial reality of the algal
ciated with the expanding and unimpeded population growth as well as oil cost which is competitive to crude oil. This shows the possibility
industrialization (Ambat, 2018; Ambat et al., 2019). of resolving environmental problems associated with FCWW disposal,
Considering the benefit of not using much arable land space, biofu- because of the mixotrophic cultivation of C. pyrenoidosa NCIM 2738
els can be produced from organisms such as algae since they demon- on the pretreated FCWW. This is also because of the conversion of the
strate a higher yield estimate when compared to most crops. For organics into lipid. Taken together, the study estimates the sum of
example, cultivating algae on a 30-million-hectare plot can yield a con- $9.59million/year as the total profit generated by the integrated two-
servative biofuel estimate of 40,000 L per hectares per year. Research step process model, and $79.03 per barrel as estimated algal oil produc-
has shown that this can potentially substitute the 1,200 billion liters of tion cost. Taking a different approach in developing a sustainable and
petroleum used by the United States, for example (Georgianna and economically viable biofuel production from algal, Garg and Jain
Mayfield, 2012). Comparing this algae biofuel estimate with the United (2020) developed the models of low temperature transesterification of
States soya (29-million-hectare) and corn ethanol production (64- algal oil for biodiesel yield depending on process variables with the
billion-liters from 14-million-hectares), the use of algae is preferable use of response surface methodology (RSM) and artificial neural net-
(Doe, 2010; Akhihiero et al., 2019; Akhihiero and Ebhodaghe, 2020). works (ANN). That is, the effect of process variables such as: methanol
Especially, the merits of bioenergy production, nutrients recovery, to oil percentage (v/v), catalyst concentration, and reaction time on
carbon sequestration, high photosynthetic efficiency, ability to accom- biodiesel production through algal oil transesterification at low tem-
modate high lipids/carbohydrates content, as well as being cultivation perature. Error percentage was lower for the ANN than for RSM,
tolerant (Goswami et al., 2019) indicate the environmental and energy which shows that the ANN provides reliability of the regression model
benefits of microalgae (Independence, 2007; DOE, 2016; Pradhan in predicting possible conversion to any of the conditions provided in
et al., 2017; Ahmed, 2017; Roostaei et al., 2018). These are reasons the study. Also, the Box-Behnken experimental design reveals a 20–
for the current rapid advances in the field. Thus, several notable studies 60% methanol to oil percentage (v/v), 0–2 wt% catalyst concentration
have presented their findings on a number of conversion processes and and 60–180 min reaction time at 50 °C constant temperature. More-
procedures. over, a quadratic regression model with R2 value of 0.99 and 0.96 were
To illustrate, research on biofuel production from microalgae is obtained for the ANN and RSM, respectively. Thus, examining a com-
investigating the cost benefit analysis of several novel production pro- parative view of RSM and ANN models show the good predictability
cesses. For instance, Pandey et al. (2020) proposed a two-step novel of the latter for process optimization of biodiesel production. Building
integrated process to develop a sustainable and economically viable on the work of Pandey et al, a similar research by Phukan et al. (2020)
biofuel production from algal. This was combined with high-strength has investigated the combination of remote sensing data and experi-
FCWW treatment simultaneously. Table 1 shows a list of abbrevia- mental appraisal for cost effective and sustainable microalgae biofuel
tions and their meanings. This integration was based on an earlier production. This work was focused on leveraging microalga feedstock
report that removing total nutrient load by only biological treatment for biofuel production and wasteland reclamation.
of high-strength FCWW was less effective and time consuming Nevertheless, previous review studies have advanced the field of
(Rivas et al., 2010). So, this study showed that integrating the two- biofuels production from microalgae biomass, through several
step novel processes of coagulation and microalgae cultivation is more extended and evaluative studies. For example, Kröger and Müller-
effective for developing biofuels from algae, and it’s also a simultane- Langer (2012) reviewed the important properties of algal, biofuel pro-
ous treatment of the FCWW. This is because of several reasons. duction processes (transesterification and hydro-processing) and its’
One, comparing the microalgae grown in pre-treated FCWW with associated economic and environmental challenges. Alternatively,
Chlorella pyrenoidosa grown in BG-11 media, the former showed Mubarak et al. (2015) reviewed the different methods of extracting
230–270 mg/L/day biomass productivity and 58.84–77.41/mg/day lipid lipids from microalgae biomass for biodiesel production. The work
Biofuels from microalgae biomass 3

advances on catalytic upgrading of alga-derived oil (Zhou and Hu,

Table 1 List of Abbreviations. 2020), and a comprehensive overview of biofuel derivation from race-
FCWW Fresh Cheese Whey Wastewater way pond and photo-bioreactors (Susaimanickam et al., 2020). In
addition, Peng et al. (2020) has reviewed the processes of algae cultiva-
NCIM National Collection of Industrial Microogranism
tion, harvesting, drying and extraction in biofuel production. None of
ANN Artificial Neutral Network
these current reviews have critically addressed a broader range of
RSM Response Surface Methodology
microalgae conversion processes to specific biofuel products. This is
FFA Free Fatty Acid
presently not found in the literature. This is important because it
FAME Fatty Acid Methyl Ester
would enhance more research on biofuel production from improved
MCHA N-methylcyclohexylamine
scope of production possibilities.
WLEP Wet Lipid Extraction Procedure
By extension, Kumar et al. (2015) presented the potential applica-
GCMS Gas Chromatography Mass Spectrophotometer
tion of algal biomass for biofuel and bio-based products production.
LCA Life Cycle Assessment
While this paper describes a variety of processes and pathways of
SCW Subcritical Water
bio-valorizing algal biomass as well as brief discussion of lipid extrac-
WGSR Water-Gas Shift Reaction
tion techniques from algal biomass, an in-depth understanding on why
DES Deep Eutectic Solvents
these techniques are applied and suitable conditions of application in
SCM Supercritical Methanol
biofuel production weren’t presented.
MW Microwave
To this end, different processes for converting microalgae oil to
SCT Supercritical Transesterification
biodiesel, syngas, bio-methane, bio-hydrogen, and bio-oil have been
SCMT Supercritical Methanol Transesterification
analytically presented in this review. The aim of this review is to pre-
FAEE Fatty Acid Ethyl Ester
sent a critical and systematic understanding of recent developments
GA Generic Algorithm
in biofuel production from microalgae biomass, and offer future direc-
OLR Organic Loading Rate
tions for more research. With the presented recommendations for more
FOS-D/TAC Fossil Diesel/ Total Annual Cost
research, the field is expected to evolve more in the coming future. This
CCD Central Composite Design
review presents the challenges associated with the use of most microal-
COD Chemical Oxygen Demand
gae conversion processes and their subsequent adoption into research
HRAP High Rate Algal Ponds
practice. Moreover, technical and methodical limitations associated
UASB Anaerobic sludge blanket
with these processes will be highlighted. Additionally, the use of sol-
TWAS Thickened Waste Activated Sludge
vent extraction as the most reported lipid extraction process is first
WAS Waste Activated Sludge
highlighted. Then, a systematic review on its’ of the extraction process,
GAMS General Algebraic Modelling System
as well as areas of research dispute have been equally presented. A list
SR Stoichiometric Ratio
of abbreviations is presented in Table 1.
SFR Steam Flowrate
HHV Higher Heating Values
WGSR Waste Gas Stream Reactioin 1.1. Lipid extraction processes
HTG Hydrothermal Gasification
CLC Chemical Looping Combustion The use of microalgae for biofuel production is promising due to their
PAH Polyaromatic Hydrodcarbons high lipid content (Jung et al., 2018). This is because, several factors
VOC Volatile Organic Hydrocarbon such as specie type, initial lipid content and amount of biomass treated
NOX Oxides of Nitrogen per unit time do influence the choice of an extraction method (Ranjan
HTL Hydrothermal Liquefaction et al., 2010). Some of the lipid extraction techniques frequently pre-
UHTL Ultrasonic-assisted Hydrothermal Liquefaction sented in the literature include: Bligh and Dryer, microwave oven,
HIP Hexane and Isopropanol supercritical fluid extraction, pressurized fluid extraction, ultrasound,
EMCR Extracted Marine Chlorella sp. Residue sonication and soxhlet extraction. Table 2 shows the advantages and
CS Camellia shell limitations of lipid extraction methods.

1.1.1. Solvent extraction

Phukan et al. (2011) investigated the use of thirteen different solvents
presented that the use of ultrasonication, microwave-assisted tech- for extracting lipids from chlorella sp. This was because this specie pro-
niques in solvent extraction increases microalgae lipid yield. This duces more amount of oil than most other algal species. Excess amount
detailed review specifically considered the use of microalgae for biodie- of lipids were extracted (>10%) with the use of chloroform, ethanol
sel production. Next, Qari et al. (2017) reiterated the importance of and hexane solvents in an optimum time of 3 h. This may be due to
microalgae as a renewable energy source and the associated challenges. the possible formation of volatile degradation products. Also, the bin-
Futhermore, Osman et al. (2021) reviews advances in biomass conver- ary mixture of 1:1 chloroform: ethanol showed better efficiency with a
sion to biofuels and their environmental impact by life cycle assess- lipid production quantity of 11.76%, while the best single solvent –
ment. Also, Zanuso et al. (2021) discusses the advantages and chloroform, produced 10.78%. The high efficiency of the binary mix-
limitations of hydrolytic lignocellulolsic biomass enzymes immobiliza- ture can be attributed to the fact that the use of solvents greater than
tion, and the hydrolysis of different lignocellulosic biomasses, while binary combination will be impractical for upscaling and even increase
Srivastava et al. (2021) considers bio-wastes and the use of microbial the biodiesel production costs. For the chloroform, it produced > 75%
systems for their breakdown. A further review on recent studies involv- fatty acid methyl esters (FAME), which was 58% and 25% greater
ing biodiesel production from microalgae biomass is presented in than those of hexane and ethanol, respectively. This is due to chloro-
Table 4, while Table 5 lists several methods of biodiesel production form’s polarity and solubility properties (Veeranan et al., 2017). Taken
from microalgae with their advantages and limitations together, these findings indicate that of the different examined sol-
Moving forward, Raheem et al. (2018) recently reviewed the use of vents, ethanol, chloroform, and hexane are generally more efficient
different conversion processes – pyrolysis, gasification, hydrothermal in lipid extraction. Moreover, there is need for more research to exam-
liquefaction, fermentation and transesterification, in syngas and bio- ine the cost and economic analyses of the solvent extraction processes.
diesel production. Yet, this review was limited to few microalgae con- This is important because the efficiency of the extraction process is bet-
version processes. Nevertheless, current reviews have focused on recent ter presented when production yields and its’ economics are assessed.
 4
Table 2 Advantages and limitations of lipid extraction methods.
Methods Advantages Limitations References
Conventional  Ease of extraction  Toxic and non-ecofriendly (Sati et al., 2019; Tanzi et al., 2013; Wahlen et al., 2011)
 No set-up cost
Simultaneous extraction and  Economical  Requires dry biomass, though wet biomass can some- (Im et al., 2014; Shomal et al., 2019; Cicci et al., 2018)
transesterification  Saves energy times be used
 Reduces time and solvents
 Significantly reduces energy
consumption
Use of switchable solvents  Easy recyclability  Low technical viability (Samori et al., 2013; Du et al., 2013; Martinez-Guerra
 Greener approach  Non-feasibility of solvent synthesis et al., 2014)
 Energy efficient
Microwave irradiation  Environmentally friendly  Use of volatile or non-polar solvent isn’t efficient (Teo and Idris, 2014; de Moura et al., 2018; Adam et al.,
 Reduces extraction time  Non-standard scale-up 2012)
 Low solvents usage  Prohibitive capital and operational cost
 Enhances lipid yield
Ultrasound  Environmentally friendly  Difficulty in scale-up (Araujo et al., 2013; Meullemiestre et al., 2016; Lee and
 Low extraction time  Very high operational costs. Han, 2015)
 Low solvent usage
 Deeper penetration
Hydrodynamic cavitation  Low extraction time  High energy demands (Setyawan et al., 2018; Wu et al., 2019; Mahmood et al.,
 Fit for wet algae feedstock  High cost of set-up 2017)
 High extraction efficiency
 Easy scale-up
Bio-based solvents  Derived from bio-based  Limited feedstock supply (Breil et al., 2016; Silve et al., 2018; Salana et al., 2014)
feedstock  Not yet feasible on a large scale
 Eco-friendly and efficient
 Cost effective
Supercritical fluids  High FFA recovery  High equipment and operational cost (Santana et al., 2012; Cheng et al., 2011; Seo et al., 2015)
 Low toxicity
 Absence of separation step
Oxidation  High extraction efficiency  High catalyst cost and energy requirements (Hua et al., 2016; Lai et al., 2017; Seo et al., 2016)
Surfactants  Energy efficient  Poor surfactants selection and recovery (Montalbo-Lomboy et al., 2014; Zuorro et al., 2016; Sierra
 Non-toxic et al., 2017)
 Enables wet biomass extraction
Enzymatic catalysis  Low energy consumption  State of microalga determine process efficiency (Zheng et al., 2012; Hu et al., 2017; Ramaluckan et al.,
 High lipid recovery  Difficulty in enzyme selection 2014)
 Enables wet biomass extraction

S.O. Ebhodaghe et al.

Biofuels from microalgae biomass 5

Table 3 Effect of Processing Factors on Lipid Extraction Methods.

Lipid extraction Biomass pre-treatment Solvent used Amount of solvent References
methods
Conventional method
(a) Bligh and Dyer Treatment with HCl and heating for 1hr at Chloroform/water/Methanol 1.50 mL methanol, (Jensen
method 80 °C for 1hr 1 mL chloroform, (2008))
1 mL water
(b) Froch method Biomass were soaked with 10% NaOH at a Chloroform: methanol 2:1 (Cheirsilp
ratio of solid to liquid of 10% and boiled at and Kitcha,
100 ◦C for 15 min 2015)
Simultaneous – Methanol/H2SO4 0.1–0.8 g of (Im et al.,
extraction and methanol/0.1– 2013)
transterficiation 0.4 mL H2SO4
Switchable – N,N-dimethylcyclohexylamine 2–50 mg/L (Samorı̀
solvents (DMCHA) et al., 2013)
Oxidation [a] N-lauroyl sarcosine Methanol: chloroform 1:1 (Yellapu
surfactants et al., 2016)
[b] four different surfactants Ethyl acetate 50 mL (Feng et al.,
2021)
Microwave – Methanol : Chloroform and 2:1 (Krishnan
Irradiation Hexane: water 1:1 et al., 2019)
Ultrasound Defragmentation of lignocellulosics, organic – – (Onumaegbu
matter solubliisation and enhanced et al., 2018)
hydrolysis.
Hydrodynamic Lyophilized N. Salina biomass Hexane: methanol and 7:3 (Ilgyu and
cavitation Chloroform: methanol 2:1 Jong-In,
2015)
Bio-based Solvents Lyophilisation, mortar and pestle. Ethyl acetate, ethyl lactate, 1:1:1:1 (Wan, 2013)
cyclopentyl methyl ether, 2-
methyltetra hydrofuran

Table 4 Recent studies on biodiesel production from microalgae biomass.

Technique Strain Operating conditions Lipid yield References
Enzymatic Micractinium sp 38 °C, 1:3.1 methanol to oil molar ratio, water content of 18.7 ± 1.2% (Huang et al.,
transesterification 2.5%, relative to the oil weight 2015)
Catalytic Chlorella 30 °C reaction temperature, 160u/g enzyme content, 3:1 >90% (Shirazi et al.,
transesterification vulgaris alcohol to oil molar ratio, 0.2 quality ratio of water to oil, 2017)
>5times reuse of lipase GH2 catalyst.
In-situ or direct Spirulina 260 °C temperature of detector and injector, 130gr/L internal 16 wt% (Chauhan et al.,
supercritical methanol platensis standard concentration of 10 ml methyl heptadecanoate 2019)
transesterification solution
In-situ or direct Chlorella sp. Supercritical methanol conditions of: 255 °C, 1200-1400psi 52 wt% (Wahidin et al.,
supercritical methanol FC2 IITG for 25mins 2018)
transesterification
Microwave-assisted Nannochloropsis 1:4 wet algae to methanol ratio (wt/vol), and methanol: ionic 40.9% (Han et al.,
transesterification sp liquid ratio of 1:0.5 at 14mins microwave exposure biochar yield 2020)

Although Ramaluckan et al has initially suggested that the use of sol- Building on the work of Ramaluckan et al, a more recent study
vents greater than binary combination could increase the biodiesel pro- (Patil et al., 2018) has investigated the appropriation of the residual
duction costs, Naghdi et al. (2016) examined the use of chloroform, biomass for bioethanol production. The study evaluated the efficiency
methanol and hexane solvents mixture in extracting Ulva fasciata algal of scalable pretreatments in enhancing lipid recovery from algal slurry.
oil. The study demonstrated that a mixture of chloroform: methanol: This evaluated method of lipid recovery from wet C. muelleri algal bio-
hexane with 1:1:2 vol ratio produced a maximum oil yield of 9.85%. mass when pretreated with ultraviolet light and hexane: ethanol sol-
Also, the acid and saponification values of the algal oil were vent mixture circumvents the need for drying of algal biomass.
13.73 mg KOH/g and 194.7mgKOH/g respectively, while the saturated Pretreatments can compensate for lipid reduction by making the intra-
fatty acid content was 75.43% in the produced algal oil. The presence cellular lipids more readily available to be recovered, which was actu-
of 12- hydroxyl-9-octadecenoic acid essential for biodiesel production ally realized through the utilization of the co-solvent mixture at room
was indicated. Despite the obvious suitability of U. fasciata for biodie- temperature. This process may contribute towards the development of
sel production, this process is not cost effective. a more economical microalgae oil production route. This is because the
6 S.O. Ebhodaghe et al.

Table 5 Methods of biodiesel production from microalgae: Advantages and Limitations.

Method Advantages Limitations References
Supercritical methanol  Enhances similarities of biodiesel prop-  Low quality of biodiesel due to (Wahidin et al., 2018;
transesterification erties to standards presence of 0-C-C bonds Cercado et al., 2018)
 Economically feasible, with elimination
of excess alcohol usage
Microwave-assisted  Uses ‘green’ solvents, which are envi-  Low biodiesel yield (Han et al., 2020; Singh
transesterification ronmentally friendly et al., 2017)
 Cheaper than use of lipids extraction
and biodiesel synthesis
 Increases FAME yield
 Reduces reaction time
Ultrasound-assisted  Higher biodiesel yield than conventional  Occurrence of side-reactions, (Saengsawang et al., 2020;
transesterification transesterification process which reduces yield Ahmad et al., 2020)
 Reduces biodiesel production costs
 Time-saving

residual biomass was analyzed and found to contain carbohydrates for that similarly doesn’t require drying, but additionally removes chloro-
the fermentation process of bioethanol production. In the same way, phyll two contamination prior to lipids collection. The developed wet
using hexane and ethanol on UV-C and thermally pretreated algae lipid extraction procedure (WLEP) provides an approach to algal bio-
slurries led to more than doubling of the total extractable lipids and mass processing with material and energy cost reduction associated
transesterifiable lipids. with biofuel production. This is illustrated through the extraction of
The possible non-economic nature of this process has motivated 79% transesterifiable lipids contained in the wet biomass of 84% mois-
more recent studies. In particular, Yang et al. (2017) analyzed super- ture using acid and base hydrolysis. Also, the procedure removed
critical carbon-dioxide extraction of lipids from algal biomass using chlorophyll two contaminants/organic solvent demand of the algal
azeotropic co-solvents of hexane and ethanol. This study indicates that lipid extract through precipitation. Similarly, the procedure generated
the use of supercritical carbon-dioxide extraction assisted with azeotro- side streams which can be feedstock for microbial conversion to addi-
pic co-solvents is an effective technique for extracting total lipids/bio- tional bio-products. Ponnusamy et al. (2014) takes a different
oils from algae. This is because of several reasons. First, 20–32 % of approach from Sathish et al. They demonstrated the use of photo-
the valuable eicosapentanoic acid was extracted from the algae. Sec- catalysis as a route for bio-oil extraction from wet Nannochloropsis
ond, the utilized method provides the advantages of: increased total oculata algal biomass. The use of solar energy and nanoparticle cata-
lipid yield and selectivity, improved lipid purity, and reduced extrac- lysts reduced cost and energy requirements by omitting the dewatering
tion time with preserved thermo-labile compounds. Third, the heating and drying stages of the algal oil production. The use of GCMS anal-
value for neutral algal lipid of 40.36 MJ/kg obtained was close to that ysis indicated the presence of FAME, an indicator of its’ biodiesel
of petroleum-derived crude. In the same way, a maximum total algal potential. In addition, the titanium oxide properties of photo-
lipid yield of 31.37% was obtained at reaction conditions of 340 bar activity, low cost and toxicity, good chemical and thermal stability,
pressure, 12: 1 co-solvent (hexane + ethanol- 1:1) to algae/solid ratio, suggest that titanium dioxide nanoparticles are efficient photo-
80 °C and 60 min reaction temperature and time respectively, under catalysts for rupturing the rigid micro-algal cell membrane in an aque-
CO2 flowrate controlled condition. The choice to use a high co- ous environment using sunlight.
solvent amount was influenced by its’ ability to increase the total lipid The use of solvents in lipids extraction is obviously an energy-
yield. So, these reaction conditions significantly affect lipid yield, intensive process due to the frequent need for solvent recovery.
recovery of long chain fatty acids and the economics of the extraction Because of this, research is now exploring other similar lesser-
process. Future work should consider explaining how the process can demanding alternatives. For instance, Jian et al. (2015) has analyzed
be improved to enhance the heating value of the lipid. Effect of pro- the life cycle energy requirements and greenhouse gas emission of algal
cessing factors on several lipid extraction methods are shown in biodiesel. They found that biodiesel production using subcritical water
Table 3. (SCW) extraction poses a potential alternative to traditional solvent
In contrast, Sathish and Sims (2012) argues that N- extraction. This is because the SCW extraction process is an energy
methylcyclohexylamine (MCHA) and 1-butyl-3-methylimidazolium efficient one that uses wet algae feedstock, while decreasing energy
hexafluorophosphate (C4-min)(PF6) are feasible extracting and sepa- demand about 5 times lower than the traditional solvent extraction.
rating solvents respectively, which are suitable for algal oil extraction. This is because no considerable energy is spent on drying since dry
This was presented when the study recovered extracted algal oil algae feedstock is not required. Besides, there is reduction in energy
through a simple phase separation method using the solvents. This required for solvent recovery as water is the utilized process solvent.
simple phase separation method doesn’t require drying algal slurries Consequently, the water available after harvesting algae can be poten-
before extraction. This is because, the adopted low-energy consump- tially used as a solvent to extract neutral lipids at selective subcritical
tion method extracted wet algal slurries directly while solvent was recy- conditions of water. Illustratively, this study reveals that about 53 wt
cled. Using (C4-min)(PF6) to separate algal oil from the crude % of extracted dry algae (32 wt%) are neutral lipids. Also found
extraction liquid recovered 77% of the algal lipid, while the use of was that 0.6 kg of CO2 is sequestrated for every 1 kg of biodiesel
MCHA recovered 85% at 200 rpm. This may be because amphiphilic produced.
amine solvents are water miscible, as (C4-min)(PF6) is effective for dis- Furthermore, Hu et al. (2020) later improved on the life cycle
solving polar substances such as amines, due to its’ characteristic prop- assessment (LCA) of Ponnusamy et al by assessing the effects of nitro-
erty as an ionic liquid. While Yang et al investigates the elimination of gen deficiency on algae cultivation and oil extraction on life cycle fossil
the drying process through the use of (C4-min)(PF6) and MCHA energy ratio of biodiesel. The algal oil conversion rate and energy con-
agents, Shwetharani and Balakrishna (2016) had earlier taken a differ- tent of algae have the greatest effects on the LCA results of the biodie-
ent approach. They developed a different method of lipid extraction sel production, followed by utilization ratio of algal residue, energy
Biofuels from microalgae biomass 7

demand for algae drying, capacity of water mixing, and algae produc- content. That is, the aqueous DES pretreatment significantly enhanced
tivity. Changing esterification efficiency and heat value of algae have the lipid recovery (P < 0.05), which actually was a function of DES.
the greatest effects on the life cycle fossil energy ratio of algal biodiesel. Also, treatment of the algae with the DES- a Ch-O, a Ch-EG, and
This is because when esterification efficiency and heat value of algal aU-A reduced the total carbohydrate content recovery in algal biomass
decreased by 40%, the life cycle fossil energy ratio of algal biodiesel at 24.21%, 20.14% and 27.89% respectively. This is because of a
changed by 40% and 36.17%, respectively. Other parameters (such resulting cytoplasm reduction from the microalgae cells (Pan et al.,
as utilization ratio of algal residue, algal cultivation water recycling 2017). Thus, lipid recovery was improved after aqueous DES pretreat-
rate, energy demand for algal drying, capacity of mixing and algal pro- ment, which is due to the fact that aqueous DES can improve the effi-
ductivity) were of negligible effects because 40% reduction of these ciency of lipid extraction from chlorella sp. biomass using a mixture of
properties only resulted in algal biodiesel life cycle fossil energy ratio ethyl acetate and ethanol. This is because of their ability to disrupt cell
changes between 10% and 15%. wall.
Presently, research is investigating the conversion of algal lipid In the same way, Piligaev et al. (2018) investigated the improve-
extraction residue to bio-crude oil. To illustrate, Zhang et al. (2019) ment of extraction yield through cell disruption using acid DES. The
recently gasified algal lipid extraction residues-derived crude oil in effects of solvent amount, DES and biomass mass ratio, extraction
supercritical water (SCW). It is believed that the residue from lipid time and temperature on FAME were studied, while comparing one-
extraction of algal can be used as feedstock to produce high-yield step and two-step processes of biodiesel production from microalgae
and value-added biofuels via liquefaction. This is because of several biomass. It was found that the use of one-step with DES extracts
reasons. One, the study reports that the bio-crude oil yield (65.4 wt FAME feasible for microalgae-based biodiesel production. This is
%-78.5 wt%) was higher than that obtained from rubber wood saw- because of several reasons. Firstly, the total FAME content extracted
dust (48.8 wt%-59.9 wt%) and bamboo sawdust (47.9 wt%-63.7 wt using one-step method with DES treatment was improved by 30%
%), when compared. This is because of enhanced biomass degradation when compared with the two-step method, and also 70% increase
at higher temperatures (Akhihiero et al., 2020). This is confirmed by was observed in comparison to when DES pretreatment was absent.
other studies (Shakya et al., 2015). Two, the main bio-crude oil com- Similarly, the two-step method also improved the FAME content
ponents obtained from algal lipid extraction by-products were hydro- when compared with absence of DES pretreatment. Next, the other-
carbons, aromatics, ketones, and alcohols. In addition, nitrogenated wise increase of DES resulted to a corresponding increase in destruc-
compounds were obtained. These major bio-crude oil components tion of cells and FAME, with the use of one-step method. Since
have been previously confirmed by earlier studies (Guo et al., 2015; microalgae cell destruction is a function of the DES strength, FAME
Sinag et al., 2004). when compared with NaOH (2.13 wt%) and Ru/ recovery can be enhanced with same. So, this explains why 1:3 mol/mol
C catalysts, the use of K2CO3 showed maximum total combustible of chlorine-acetic acid was more effective in the study than other DES
gas yield (8.15 wt%) when used with algal lipid extraction residue- ratios in recovering FAME from both chlorella sp. and chclorococcum
derived bio-crude oil feedstock via SCW gasification at 500 °C for sp. biomass.
60mins and 10 wt% biomass concentration. The suitability of
K2CO3 may be because the reaction between CO2 and KOH produced 2. Microalgae conversion processes to biofuels
a higher CO2 than NaOH yield, in the water–gas shift reaction
(WGSR). This is traceable to the promoted breakage of C-C bonds
and WGSR. By extension, the use of K2CO3 catalyst produced the
2.1. Biodiesel
highest methane yield (0.69 mmol/g). To enhance economics of the
process, current research is also examining the use of some novel meth- 2.1.1. Transesterification
ods for a sustainable biomass production. Building on the work of Hu Currently, research is investigating the use of bio wastes-
et al, Lu et al. (2016) investigated the effect of wet cell disruption based derived catalysts for a more sustained biodiesel production.
on mild pressure and heat shock treatment. Also, the study optimized
As a result, Karpagam et al. (2020) recently provided more
cell growth and lipid productivity at enhanced CO2 concentrations and
at varying photoperiod conditions. The study shows that the novel
understanding on the activity of waste egg shell-derived
method of mild pressure with heat shock extraction process is cost Nano-CaO catalyst on the transesterification and its’ optimiza-
effective for microalgae lipid extraction. This is because of several rea- tion by varied Nano-CaO catalyst dosage, time, and tempera-
sons. One, the method was used to disrupt the cell walls of C.vulgaris ture with five-level central composite design based full factorial
which significantly maximized lipid recovery, while minimizing energy response surface model. 93.44% maximum fatty acid methyl
consumption, as 27.7% elevated energy output was recorded. Two, ester (FAME) yield was obtained at optimal conditions of
oleic acid (C18:1) with 51.62% is the main component in both pro- 2.06% (wt/wt) catalyst at 180mins and 60 °C temperature
cesses of conventional and suggested lipid extraction with respective and 200 rpm constant string speed. Moreover, catalyst
energy outputs of 417.7 and 533.6MJton-1. The latter demonstrated reusability and stability was up to 6 cycles, which confirms
a 26.7% increase in biodiesel yield. Three, respective biomass and lipid
to an average of 85.22% biodiesel yield. This is important
productivities of 94% and 54.8% were induced by 8% elevated CO2.
This was as the novel method (of mild pressure with heat shock extrac-
because catalyst recycling prevents the challenges of solvent
tion) facilitated a 21% lipid recovery, while 12.5% additional total usage, energy consumption and operational restraints. This is
lipid recovery was obtained using mild pressure with heat shock. Also, why the use of a heterogeneous catalysts is preferred to homo-
1.96% and 0.58% of poly- and mono-unsaturated fatty acids were geneous catalysts. Taken together, these findings show that the
respectively recovered using the extraction procedure. Nano-CaO catalyst derived from waste egg shell is sustainable
and cost-effective for biodiesel production. Correspondingly, a
1.1.2. The use of deep eutectic solvents recent study (Nguyen et al., 2020) synthesized and character-
ized bio-nanoparticles from waste seashells as catalysts for
Cheng et al. (2015) investigated the influence of aqueous deep eutectic
the direct transesterification of Coelastrella sp. M 60 for
solvents (DES) on lipid extraction from Chlorella sp. using a mixture
FAME conversion. The investigated bio-nano CaCO3 and
of ethyl acetate and ethanol solvents to enhance the lipid recovery.
Effect of the three aqueous DES (i.e. aqueous choline – chloride (a bio-nano CaO yielded maximum FAME proportions of
Ch-O) - ethylene glycol (a Ch-EG), and aqueous urea-acetamide aU- 20.6 ± 1.7 and 20.3 ± 1.1%, respectively. Comparing these
A)) on the pretreatment of chlorella sp. biomass were evaluated by yields with the conventional acid catalysis indicate that the for-
measuring lipid content, lipid recovery efficiency and carbohydrate mer (bio-nanoparticle mediated transesterification) produced
8 S.O. Ebhodaghe et al.

an average of 1.29 and 1.02 respective fold FAME increase of produced biodiesel with ASTM D-6751 and EN14214 stan-
than the latter (18.8 ± 1.1%). This is because, basic sites pre- dards show identical properties of viscosity (4.554 mm2/s),
sent in the bio-nanoparticle catalysts (due to the corner-shared cetane number (60.236), and flash point (159.236 °C). This
oxygen vacancies) are the active sites responsible for FAME similarity indicate that the produced biodiesel could be a
conversion, which were both easily accessible and highly pop- potential alternative to conventional fuel. So, the use of SCMT
ulated. This is why the bio-nanoparticle mediated transesterifi- can produce biodiesel of good quality. Reporting the alterna-
cation is preferable to conventional acid catalysis. In summary, tive use of ethanol and ethyl esters, Reddy et al. (2014) pro-
bio-waste derived catalysts provides a greener and frugal duced fatty acid ethyl esters (FAEE) from Schizochitrium
means of biodiesel production. Other current findings such limacinum microalga with the use of supercritical ethanol
as those of Das et al. (2020), Wadood et al. (2020) and and ethyl acetate. The rate constants (1.7 * 10-4 to 10.2 * 10-
4
Cheirsilp and Louhasakul (2013) confirm the suitability of for ethanol, and 0.405 * 10-4 to 3.18 * 10-4 for ethyl ethyl acet-
the use of bio-wastes for improved biodiesel production. ate) and activation energies (67.1 and 78.5KJ/mol for ethanol
and ethyl acetate systems, respectively) examined by respective
2.1.1.1. Single-step methods. Patil et al. (2012) studied the role pseudo first order kinetics and Arrhenius equation reveal that
of direct transesterification of microbial lipid into biodiesel. the reaction is faster with ethanol, while the use of ethyl acetate
This was to reduce both the raw material and processing costs decreases the glycerol oversupply. Furthermore, Knothe
of biodiesel production. This transesterification process gave a (2005) studied the effects of process parameters in dry algae
biodiesel yield (FAME > 70% in one hour) comparable to the single-step conversion to ethanol (in wt/vol) ratio of 1:6–
conventional 3-step method, though the former eliminated cell 1:15, reaction temperature of 245–270 °C, and 2-30mins reac-
drying and lipid extraction steps. This is why direct transester- tion time on the FAEE yield at supercritical ethanol condi-
ification process could contribute immensely to industrializing tions. The study indicates that this ‘‘green” conversion
oil production from microbes and industrial wastes. For this process has the potential to provide an energy-efficient and
reason, Rathnam et al. (2020) investigated the direct conver- economical route for the production of renewable biodiesel.
sion of algal biomass into biodiesel using supercritical metha- This is because, the calorific value of FAEE’s was 43 ± 1.8
nol (SCM) and microwave-assisted (MW) transesterification MJ/kg, which is comparable to that of regular diesel fuel. This
methods. The MW approach improved extraction of algal- calorific value is higher than that of FAME produced from the
with a 60% higher conversion efficiency, reduced extractive- same biomass. Moreover, significant energy savings were pos-
transesterification time (4-5mins) and increased 80.13% yield sible by eliminating the algae drying step through the simulta-
based on total lipid content. The non-catalytic SCM produced neous extraction and conversion of wet algae to crude
pure solvents and catalyst residues, and reduced energy con- biodiesel. Additionally, the thermogravimetric analysis of the
sumption in separation and purification stages. This reduction FAEE samples in oxygen and nitrogen atmosphere revealed
in energy consumption is due to the simplified purification the high oxidative stability of FAEE. Similarly, Nan et al.
step. This is because, the study indicated that the GCMS- (2014) examined process optimization in biodiesel production
revealed FAME percent purity could have influenced the effi- from Chlorella protothecoides by non-catalytic transesterifica-
cient separation and purification of the product in supercritical tion. The investigated interaction parameters – temperature
reaction. Also, the sample weight loss occurring through ther- and molar ratio, molar ratio and water content, residence time
mal degradation (from 10%, 50%, and 90% to the initial and water content – have the same effect on the transesterifica-
weight) were observed at temperature values of 195 °C, tion of triglycerides with methanol and ethanol. This is
362 °C, and 430 °C respective to the increasing degradation because, water favors FAME yield by causing hydrolysis and
of the weight losses. Overall, these findings demonstrate the esterification reactions. This is partly because the addition of
reason why the single-step methods are regarded means of water reduces the molar ratio of alcohol to oil needed to
reducing chemical and energy consumption in biodiesel pro- achieve a high yield. Thus, adding water to the process realizes
duction process. However, the study indicated that SCM pro- a high biodiesel yield at reduced alcohol-to-oil molar ratio.
cessed methyl ester has higher thermal stability compared to This is important because it reduces the cost of anhydrous
the MW transesterified product. alcohol and water removal from feedstock. Also, the behaviors
2.1.1.1.1. Supercritical transesterification (SCT). The use of of the FAEE yield under the effects of these interaction param-
catalysts in microalgae conversion to biodiesel is an old con- eters are similar to those of FAME yield.
ventional method that can result to soap formation when free More recently, the conversion of microalgae oil to FAME
fatty acid content is > 0.5%, and reduced biodiesel yield when using SCM transesterification by sequential hybrid optimiza-
water is present in the feedstock. This is why SCT involving tion using RSM, ANN and genetic algorithm (GA) has been
catalysts absence is presently considered. Besides the fact that maximized (Srivastava et al., 2018). The purpose of the study
the absence of catalysts may result in slow reaction processes, was to optimize the non-catalytic transesterification of
its’ usage may incur added costs to the process (Wahidin et al., microalgae oil to biodiesel under supercritical methanol con-
2018). Consequently, Chauhan et al evaluated the feedstock ductions. An optimization condition generated by GA for
quality for direct conversion of Chlorella sp. FC2 IITG micro- the SCM transesterification with temperature of 285.2 °C,
alga into biodiesel using supercritical methanol transesterifica- 26.5mins and MeOH: oil molar ratio all gave 99.16% conver-
tion (SCMT). 96.9% maximum FAME yield was obtained at sion efficiency. Since the SCM transesterification yield was
optimum values of 52% (wt/wt) lipid content, 5.75 mL/g water about 99–100% conversion efficient, the process is considered
content and 115 mL/g methanol loading. This reduced alcohol a zero waste generation process for biodiesel production. Any-
loading as well as high water content per gram of biomass way, research on modifying the supercritical transesterification
demonstrates the economic feasibility associated with the use reaction has been reported by Aghilinategh et al. (2020). They
of SCMT. Also, comparing the physicochemical properties conducted a one-pot production of biodiesel from Chlorella
Biofuels from microalgae biomass 9

vulgaris in SCM in the presence of TiO2 and SrTiO3 nano- was stable at a low organic loading rate (OLR) of 1 g VSL-
l -1
catalysts with the presence of co-solvents. The modification d (volatile solids). This was indicated by a low FOS/TAC
process indicates that preparation of catalysts using photo- ratio of < 0.27, as the ratio being below 0.3 indicate stable
chemical method prevents the catalysts from leaching even at process operation (Drosg, 2013). Second, co-digestion with
harsh reaction conditions. This is because the use of n- carbon-rich co-substrates (such as beet silage, barley straw,
hexane co-solvent produced highest yields of biodiesel and and brown seaweed) increased process stability. This is
other products, due to the material property of very low dielec- because, there is a more balanced nutrient supply, and reduced
tric constant. This is due to its’ ability to improve the rate of formation of inhibitory ammonia when the carbon-rich co-
mass transfer occurring from better biomass dissolution. substrates degrade. This is due to a lower portion of
2.1.1.1.2. Microwave-assisted transesterification. The use of nitrogen-rich biomass in the feedstock mix. For example, add-
MW technology significantly reduces reaction time, increases ing barley straw to A. platensis to balance the C: N ratio
biodiesel yield and makes catalyst recovery processes easy. ensured increased performance of the continuous anaerobic
Accordingly, Bhuana et al. (2020) studied biodiesel production digestion process in process stability. However, co-digestion
through in situ transesterification of Chlorella sp. This was by with L. digitata resulted in the largest increase in process sta-
examining the effects of acid catalyst concentration, micro- bility. This was up to an organic loading of 4.0 g VSL-1d-1.
wave power and retention time. This study showed that a high Table 6 shows recent studies on biogas production from anaer-
biodiesel yield of sufficient quality is possible through the opti- obic digestion of microalgae biomass.
mization process by Box-Behnken Design. This is because, Recently, Sanchez-Bayo et al. (2020) evaluated the WLEP
63.6% biodiesel yield was obtained at 370 W microwave of lipids from Isochrysis galbana to study solvents with differ-
power, 0.2 M catalyst concentration and 82.7mins transesteri- ent polarities. The research suggested that anaerobic digestion
fication time. can enhance the economic feasibility of microalgae bio-
Moving forward, Lawan et al. (2020) recently illustrated the refineries. This is because, biogas production was evenly eval-
role of microwave reactor system in efficient and sustainable uated through the anaerobic digestion process of the residual
waste lard biodiesel production. Building on the work of biomass. Presently, research is considering the use of mono-
Bhuana et al, Teo and Idris (2014) described the use of MW substrates for continuous bio-methane production. For exam-
for enhanced extractive-tansesterification of algal lipids from ple, Klassen et al. (2020) recently confirmed the application of
dry chlorella sp. The extractive-transesterification of dry algal low-N cultivation/fermentation strategy on a robust natural
biomass using MW irradiation can substitute for the simulta- microalgae isolate. Research has shown that this low-N bio-
neous extraction and transesterification two-step reaction. This mass of Chlamydomonas sp. can be applied as a mono-
is because, the MW contributes to higher algal lipid and fatty substrate for a continuous highly efficient methane generation.
acid ethyl ester (FAEE) yields. This is demonstrated from the This is because, the natural wastewater-derived microalga iso-
FAEE conversion of the algal lipids, which were 96.2%, 94.3% late tolerates high temperature and light conditions while cop-
and 78.1% for MW, MW with hexane and the conventional ing with microbial contaminants. This is a demonstration of
Bligh and Dyer (BD) methods respectively. These FAEE con- its’ potential in future biotechnological applications. Also,
versions were obtained from the respective maximum lipid the use of this microalga resulted in 87% energy conversion
yields of 20.1%, 20.1%, and 13.9%. Also, hexane solvent efficiency from biomass to bio-methane. Additionally, biogas
reduced the reaction condition severities, though comparable and bio-methane productivity of 765 ± 20 and 478 ± 15mLN-
lipid and FAEE yields were produced. This is because, hexane g-1VSd-1 respectively, characterized the continuous long-term
and ethanol co-solvent can enhance the extractive ability for anaerobic digestion. This is same as its’ volumetric methane
FFA and eventually improve the transesterification reaction productivity of 1912 mLNL-1.
yields. Similarly, Rathnam et al. (2020) investigated the effect
of microwave irradiation on the simultaneous extraction and 2.2.1.1. Co-digestion. Sittijunda and Reungsang (2018) opti-
transesterification of dry algal biomass to diesel. This study mize concentrations of algal biomass crude glycerol and inocu-
was aimed at optimizing the microwave transesterification lum from co-digestion of the algal biomass with crude glycerol
using RSM. The in-situ transesterification process proved to using RSM and CCD design. From the study, 2.31 mL-CH4/g-
be fast and easy in biodiesel production from the dry biomass. VS added maximum methane yield was obtained at conditions
Methanol assists the reaction to complete faster because it is a of 20.02 g-VS/L crude glycerol, 9.76 g-VS/L inoculum concen-
strong microwave absorption material whose OH– group rad- tration and 5.50 g-VS/L algal biomass concentration. This
ical dominates the microwave spectrum and results in localized maximum methane yield was 57.75 times higher than the
superheating. 0.04 mL–CH4/g-VS added obtained under reduced conditions.
Under optimum conditions, maximum methane and energy
production of 58.88 mL-CH4/L and 92.47 J/g-VS were respec-
2.2. Bio-methane tively obtained, while 14.59% difference between observed and
predicted methane production are reported. Additionally, the
2.2.1. Anaerobic digestion study identifies Methanosarcina sp., Methanoregula sp.,
Herrmann et al. (2016) investigated the co-fermentation of Methanospirillum sp., and Methanoculleus sp. as the main
Arthrospira platensis using carbon-rich co-substrates at a car- methane producers present in the fermentation broth. Sum-
bon to nitrogen ratio of 25 to enhance biomass conversion. marily, the RSM optimized process improved bio-methane
Co-digestion of microalgae and seaweed can be effectively production. Improving upon the work of Sittijunda et al,
applied to integrated costal bio-methane. Actually, the use of Vassalle et al. (2020) evaluates a up flow anaerobic sludge
microalgae assists in indirect biogas upgrading. This is because blanket (UASB) reactor and the use of high rate algal ponds
of several reasons. First, the mono-digestion of A. platensis (HRAP) for sewage treatment efficiency and biogas produc-
10 S.O. Ebhodaghe et al.

Table 6 Recent studies on biogas production from anaerobic digestion of microalgae biomass.
Technique Strain Operating conditions Biogas yield References
Microwave co- Enteromorpha 20:1 slurry liquid: solid ratio, 6mins 53.60 mL/Gts (Zaidi et al.,
treatment pretreatment time, and microwave 2019)
pretreatment power of 600 W
Hydrothermal Tetraselmis 37 °C, 200 rpm of digester stirring 327.2 mL/gVSin for Tet., and 263.4 mL/Gvs FOR (Fernandez
liquefaction chlorella Chlr. et al., 2017)
Ultrasound Microcystis Ultrasound treatment for 30mins, 20 g 30.39, 37.11, 38.06, 42.52, 49.27, 48.93 and 60.84 (Li et al.,
co- sp zero-valent iron/g of algal total solid CH4/Kg accumulative biomethane production in 2020)
pretreatment reactors 1–7, respectively.

tion, at demonstration scale. While 50% COD was removed in 2010). In the same way, Garoma and Nguyen (2016) investi-
the UASB co-dig, the entire process removed a total 65% COD gated the feasibility of producing bio-methane from the anaer-
after the HRAP and 61 % N-NH4. This observation has been obic co-digestion of Scenedesmus quadricauda and thickened
previously reported (Villa-Navarro et al., 2018). However, waste activated sludge (TWAS). The microalgae produced
57% average COD was removed for the UASB cont. The almost same amount of methane as the wastewater sludge,
observed lower average COD reduction in the UASB co-dig TWAS. This is because, the methane produced ranged from
may be due to microalgae biomass recirculation in the co- 234 318 mL/g of chemical oxygen demand digested and
digested reactor, leading to a transport of stabilized organic 329 – 530 mL/g of volatile solids digested at 35 °C. Though
matter from the solid to the liquid phase. On biogas produc- the net methane produced was varied for different S. quadri-
tion, an average 304.42NL/Kg VS (that is, 149.81 NL/Kg cauda/TWAS proportions, results indicate that there were no
COD) for UASB cont, and 331.12 NL/Kg VS (that is, 165.63 significant differences in methane prediction rate amidst the
NL/Kg COD) for UASB co-dig were reported. These values various proportions. This is because, 89% of paired t-tests per-
indicate a 10% UASB co-dig increase after co-digesting sewage formed on the rate of produced methane resulted in p-
with microalgae biomass. For organic content, a 9% increase values > 0.05. These findings show that anaerobic co-
is associated with the use of UASB co-dig than the UASB cont. digestion could be able to enhance renewable energy genera-
Furthermore, Lu et al. (2019) optimized bio-methane pro- tion, even with minimal capital costs.
duction from anaerobic co-digestion of microalgae and septic Current research is examining the effects of low tempera-
tank sludge. The study analyzed the effects of the total organic ture thermal pretreatments in solubility and co-digestion of
concentration and microalgae proportion in optimized bio- waste activated sludge and microalgae mixtures. Specifically,
methane production. The total volatile solids concentration Avila et al. (2020) assessed the effectiveness of 37 °C and
of 16–20 g/L and 26–47% proportion of microalgae biomass 60 °C low temperature thermal pretreatments of 50:1, 25:1
indicates the possibility of observed peak methane production and 10:1 (v/v) waste activated sludge (WAS) and microalgae
and > 300 mL/gVSfed as observed from the surface response ratios in solubility of biomasses and in methane yield of the
plot. Similarly, the methane production depends on several co-digested mixtures. The use of anaerobic microorganisms
factors as the experimental design showed 1.04F-test, 0.96 cor- in the low temperature thermal pretreatment during degrada-
relation coefficient and 5.14% coefficients of variance. These tion produced a high methane yield for the WAS and floccu-
findings indicate that the organic concentrations and microal- lated microalgae mixture of diallyl dimethyl ammonium
gae proportions affect methane production. By extension, chloride flocculant. This is because of several reasons. First,
Zamalloa et al. (2012) valorised by anaerobic digestion, the pretreating the non-flocculated co-digestate mixture at 60 °C
Scenedesmus obliquus and Phaeodactylum tricornutum microal- revealed the effect of time intensiveness on the mixture’s solu-
gae under mesophilic and thermophilic conditions. The bility during the first 24 h, with lower later variations. Then,
microalgae biomass was up-concentrated to the 1.9–2.8gVSL- solubility of the WAS and microalgae mixture increases with
1 -1
d range at a low hydraulic retention time. An overall conver- temperature. This is because, higher solubility of the co-
sion efficiency of 50% was achieved when P. tricornutum was digestates was observed at 60 °C pretreatment when compared
digested at a volumetric organic loading rate of 1.9gVSL-1d-1 with 37 °C. Effect of the diallyl dimethyl ammonium chloride
at a hydraulic retention time of 2.2 days at either thermophilic flocculant addition was revealed in the co-digestate mixture
or mesophilic conditions. Moreover, the 1.5 times higher bio- solubility which was higher in comparison to mixture without
mass potential of P. tricornutum than S. obliquus indicates that the flocculant. Besides temperature effect on the solubility of
the suitability of the former for anaerobic digestion depends the co-digestates, ratio of the co-digestates also influences their
on its’ species. This has been confirmed by an earlier report solubility. This is because, microalgae volume in the mixture
(Mussgnug et al., 2010). These findings suggest that hydrolysis was reported to increase with solubility. More research is
of the microalgae cells limits the anaerobic processing of inten- needed to identify other parameters to determine the effect
sively grown S. obliquus and P. tricornutum biomass. However, of the pretreatment in the co-digestion. This is because, non-
hydrolysis of certain microalgae (such as D. salina) might be enhancement of the co-digestate anaerobic digestibility after
slower in mesophilic fermentation (at 33 °C) than at ther- the pretreatment indicate that solubility of the mixture unlike
mophilic fermentation (at 54 °C). This is because, the biomass temperature pretreatment cannot promote further methane
strain can grow up to temperatures of 35 °C (Hodaifa et al., production.
Biofuels from microalgae biomass 11

2.3. Syngas value and 2.8Nm3/kg dry biomass production rate. The syngas
HHV indicates best performance of microalgae gasification at
2.3.1. Gasification an air–fuel equivalence ratio of 0.23. So, the syngas composi-
The effect of process parameters (such as pressure, tempera- tion is 11.9% H2, 19.5% CO, 8.5 %CXHY and 9.8% CO2.
ture, microalgae concentration and co-reactant addition) on
the supercritical water gasification of microalgae biomass for 2.3.1.1. Direct gasification. Raheem et al. (2015) characterized
hydrogen syngas production has been intensely reported of the process behavior, and optimized syngas production using
recent. To illustrate, Freitas and Guirardello (2013) evaluated microalga gasification. This was conducted using a horizontal
the effects of these parameters for hydrogen and syngas pro- tubular reactor under different conditions of process tempera-
duction using thermodynamic analysis. Investigating the effect ture, heating rate and microalga biomass loading. Beside tem-
of initial temperature under hydrogen formation demonstrated perature, microalgae biomass loading was most influential in
an increase of produced syngas with initial temperature. The enhancing hydrogen yield. That is, optimum hydrogen output
use of Gibb’s energy minimization and entropy maximization was achieved at a loading of 1.44 g. However, an allowable
methods is considered reliable for thermodynamic predictions range of 0.6–2.5 g would still increase hydrogen yield as
in the supercritical water gasification reactive systems of the reported in the study. This increased range may be due to
microalgae biomass. This is because, the use of GAMSÒ increase in mass of reactive species per unit volume required
23.2.1 software resolved initially proposed problems since the to shift the equilibrium of the WGSR to the right (CO + H2-
computational time was inferior to 1 s for all analyzed cases. O M H2 + CO2). Overall these findings indicate that direct
Moving forward, Azadi et al. (2014) simulated the production gasification of microalgae biomass in air can enhance
of algae-derived hydrogen and syngas using a dual fluidized commercial-scale production of syngas. Building on the work
bed gasifier. The lower heating value of the produced syngas of Raheem et al, Adnan and Hossain (2018) gasified microal-
increased from 17 to 24 MJ/Kg dry feed when the oil content gae biomass while integrating converted tar molecules pro-
increased from 0 to 40 wt%. The ratio of H2 : CO in the duced during the gasification stage. The controlled use of
algae-derived syngas increased when the water–gas-shift reac- oxygen as a gasifying agent in the combustion zone aids com-
tion was favored by the operating conditions in the forward plete conversion of tar to syngas. This occurred when a mini-
direction. In brief, algae oil content can possibly influence mum effect of pressure was observed after maximum
the lower heating value of syngas. Table 7 identifies recent gasification system efficiency. This is because, higher pressure
studies on syngas production from microalga, while Table 8, demands higher oxygen energy ratios for the maximum cold
presents methods of syngas production from microalgae with gas efficiency to be reached, which is similar to complete car-
their advantages and limitations. bon conversion. Moreover, the gasification system efficiency
More recently, Li (2018) studied the effect of reaction tem- (GSE) improved through the injection of oxygen in the com-
perature, stoichiometric ratio (SR) and steam flowrate (SFR) bustion zone. This is because, gasifying N. oculata at condi-
on H2/CO ratio in produced syngas. The work evaluated the tions of 1 bar, O2 ER ratio of 0.13 with no steam results in
efficiency of three different Chinese algae for gasification pro- the highest GSE of 0.60 with 0.44 hydrogen concentration. It
cess while utilizing air and steam gasification agents. From the is clear from these findings that the use of oxygen in the com-
study, 44.8 g/kg maximum hydrogen yield was obtained at bustion zone improves the gasification performance and sys-
950 °C and 2.4 kg/h SFR. Moreover, low H2/CO content tem efficiency.
was achieved at higher temperature, while a higher H2/CO
content was gotten at higher SFR. The former occurred 2.3.1.2. Co-gasification. Arun et al. (2020) produce hydrogen-
because gasification temperature increases with CO produc- rich gas from sewage sludge and wastewater-derived microal-
tion, while increase in hydrogen concentration was recorded gae using a battery waste-derived catalyst. The study indicates
at a much reduced rate (Pala et al., 2017). These findings show that the process of HTG is feasible for optimum hydrogen gas
that lower heating value of the syngas increased with SFR and production. This is because, the experiment show that 38.27 wt
gasification temperature. Also, these parameters determine H2/ % maximum hydrogen yield was obtained at 4 wt% catalyst
CO content in syngas. Currently, there is a more targeted inter- loading and temperature of 440 °C for 2:1 waste ratio. Also,
est at pilot-scaling of system gasifiers. For example, Soares the RSM optimization result indicate that 40 wt% hydrogen
et al. (2020) evaluates the effects of air–fuel equivalence ratio gas yield was obtained at the optimum process conditions of
on syngas composition, higher heating value and production 2.3 wt% catalyst load, 426.36 °C, temperature and time of
rates. That is, an experimental investigation of wastewater 70.22mins. However, the use of catalyst can lead to its’ poison-
microalgae in a pilot scale downdraft biomass gasifier. This ing, sintering and even deactivation during the HTG process.
was through the gasification of wastewater microalgae with For this reason, Sztancs et al. (2020) investigated the improve-
the use of air as the gasifying agent. The H2/CO ratio observed ment of biogas production through the process of co-
in the syngas was 0.61, which is quite close to the 0.60 recom- Hydrothermal gasification (co-HTG) of wet Chlorella vulgaris
mended for synthetic fuel production (that is, Fischer-Tropsch biomass and hydro-char (HC). The co-gasification process
gasoline and diesel) (Ciferno and Marano, 2002). This is promotes hydrogen and methane formation as well as selectiv-
important because the H2/CO ratio of 0.61can reduce the pro- ity in HTG. This is because, high yields of hydrogen
cess complexity, as the characteristics of the syngas are already (19.49 mol/kg), methane (2.98 mol/kg) and 82.31% carbon
synonymous with ideal H2/CO ratio (Ferreira et al., 2019). conversion ratio, all demonstrate that the use of wet and waste
This is important as cost which could have been associated biomass feedstock are essential for effective hydrothermal
with installation of additional equipment is averted. Moreover, upgrading. So, the use of HC is preferable to catalysts. This
the cold gas efficiency is 87% with 6.2 MJ/Nm3 higher heating is because, the study reports a 41.6% raise up to 29.97 mol/
kg in the total gas yield when concentration of the co-
12 S.O. Ebhodaghe et al.

Table 7 Recent studies on syngas production from microalga

Technique Strain Operating conditions Gas yields References
Chemical-looping Chlorella  Drying at 105 °C for 24hrs.Micro- 1.16 Nm3/Kg (Hu et al.,
gasification vulgaris wave pretreatments at: 2017)
 Watts power of 0, 750, 1500, 2250,
3000 and 3750
 Time (seconds) of 0, 30, 60, 90 and
120
Microwave- Porphyra  700 °C pyrolysis temperature 73.3 vol% (Hong et al.,
induced pyrolysis  Dried at 105 °C for 24hrs 2017)
Hydrothermal Leachate  600 °C, 28 MPa, 200 g/h flowrate H2, CH4 and CO2 yields of 69.36 ± 4.5, (Damergi
gasification 10.6 ± 2.8, 17.5 ± 4.7 respectively. et al., 2019)
Catalytic Chlorella  851 °C, 16.4 wt% catalyst loading, 48.95 mol% (Raheem
gasification vulgaris and 28.80mins reaction time et al., 2018)
Microwave- Chlorella  400–600 °C 15-25 wt%, 65-85gH2 per kg feedstock (Parvez et al.,
induced pyrolysis vulgaris 2020)
Microwave- Scenedesmus  800 °C 94 vol% (Beneroso
induced pyrolysis almeriensis et al., 2013)

Table 8 Methods of Syngas production from microalgae: Advantages and Limitations

Method Advantages Limitations References
Chemical-looping  High energy efficiency  Difficulty in equipment siz- (Nurdiawati et al., 2019; Liu et al.,
gasification  Efficient syngas production ing and design 2018)
 Challenge in system profits
determination
Microwave-induced  Enhances syngas yields even at low  Non-feasibility of large (Hong et al., 2017; Beneroso et al.,
pyrolysis temperature scale production 2013)
 Minimizes CO2 production
 Produces low PAHs amounts
Hydrothermal  Maintains high chemical energy as in  Inadequate recovery rate (Brown et al., 2010; Onwudili et al.,
gasification microalgae feedstock 2013)
 This is a waste-reducing process
Catalytic  Catalysts are often stable for some time,  Scaling-up of process (Samiee-Zafarghandi et al., 2019;
gasification even after several usage Raheem et al., 2019)

gasifying agent was increased from 0.2 to 2 wt%. Taken Furthermore, Fe2O3 reduced into more Fe3O4 and FeO with
together, these findings indicate that co-HTG of Chlorella vul- temperature increase from 700 °C to 800 °C. This is because,
garis and HC blends enhance the total gas yield, carbon con- the small particles present in the crystal disappeared and were
version efficiency and boosts methane and hydrogen replaced by the larger crystal particles. This is evident from the
selectivity. elemental composition analysis of oxygen carrier under differ-
ent temperature. In brief, these findings show that a high con-
2.3.1.3. Chemical looping combustion (CLC). Recently, the version efficiency of biomass and bio-products yield can be
need to enhance microalgae biomass conversion efficiency achieved at 800 °C.
has motivated more research on other gasification techniques Improving on this work, Adnan and Hossain (2019) applied
besides the direct method. Therefore, Hu et al. (2018) studied the integrated processes of drying and gasification (using CO2
the effect of oxygen carrier content and temperature on chem- absorber and chemical-looping combustion, respectively) on
ical looping gasification of Chlorella vulgaris in a fixed bed wet Spirulina biomass to produce hydrogen-rich syngas. This
reactor. Oxidizing the oxygen carrier at 800 °C produced process considered in-situ energy supply using a thermody-
100% Fe3+. This is probably because with temperature namic approach. Gasifying high moisture content of the
increase from 600 °C to 1000 °C, at 100 °C intervals, the high- microalgae using the integrated process produced syngas with
est gas product yields occurred at the range of 700 °C to high concentration of hydrogen. Also, gasifying the microalgae
800 °C, representing a 11.64% increase from the initial value. with 45 wt% moisture content under process conditions of
However, further temperature increase resulted in a decrease 2.00 S/C ratio and 0.00 02 ER ratio as well as char to CLC
because the promotion of high temperature is stronger than of 1.0, provides the highest hydrogen concentration of 0.72.
the prevention of inactivation occurring because of sintering. Similarly, adjusting char flow to the CLC can provide positive
That is, higher temperature would weaken the oxygen carrier effect on the syngas composition. This is specifically notable
reduction. Also, this continuous temperature increase caused for high moisture gasification containing Spirulina biomass.
a gradual Fe3+ increase which was less, when below 800 °C. Furthermore, the highest cold gas efficiency of 1.15 and 0.62
Biofuels from microalgae biomass 13

GSE were obtained when Spirulina-containing 45 wt% mois- during thermal degradation of biomass (Cho et al., 2015). This
ture content was gasified at process conditions earlier is because the specified gas phase reaction between VOCs and
described. CO2 would probably affect the composition of pyrolytic oils
(Liang et al., 2015). Therefore, the use of CO2 reaction med-
2.3.2. Pyrolysis ium in improving syngas generation is demonstrated.
Rahman (2018) converted the water hyacinth biomass to bio-
oil, bio-char and syngas through the thermochemical conver- 2.4. Bio-oil and Bio-char
sion process of pyrolysis. The effect of temperature, heating
rate, carrier gas flowrate and particle size on product distribu- Taking a closer examination of the previously reported work
tion were investigated for the conversion process. Research has of Rahman (2018), the water hyacinth-produced bio-char pyr-
earlier indicated that the formation of high amounts of syngas olytic product is suitable for renewable solid fuel production.
is due to the presence of an enormous amount of volatile mat- The water hyacinth possessed high carbon content and calori-
ter (of 65.60 wt%), not moisture content (Choudhury et al., fic value. That is, the contents of carbon (33.33 wt%), nitrogen
2014; Harman-Ware et al., 2013). Though a high CO2 evolu- (0.7 wt%), and sulfur (0.4%) indicate the tendency of the
tion was initially observed at 300 °C, a general decrease from pyrolysis process to yield less NOX and SOX amounts while
110 to 29 mL per minute was noted with temperature increase enhancing bio-char production. Also, the 20 MJ/Kg calorific
from 300 to 600 °C. A thorough explanation of CO2 conver- value of the water hyacinth is similar to the reports for potato
sion to CO which led to reduction of the former has been pre- peels (20.3 MJ/Kg) (Abnisa et al., 2013), empty fruit bunches
viously reported (Santos and Capareda, 2016). Also observed (21.34 MJ/Kg) (Bilgen and Kaygusu, 2008), and even coals
was the increase of the decomposition reaction kinetics with (Torri et al., 2011). So, the high carbon content and the physic-
reactor temperature. This led to the shifting of peak flowrate ochemical property of 13.59 MJ/Kg heating value indicate the
value towards shorter time. Taken together, components of suitability of producing bio-char pyrolytic product. Though
the syngas (CO, CH4, and H2) increased with temperature, this study has demonstrated the relation between biomass car-
except for CO2. bon content and bio-char production with reduced NOX and
SOX amounts, it is possible to produce carbon-negative biofu-
2.3.2.1. Microwave-enhanced pyrolysis. The general use of els and chemicals. For this reason, Grierson et al. (2009) inves-
microalgae ubiquitously for syngas production may not yield tigated the potential conversion of Chlamydomonas reinhardti
desirable outcome seeing they differ. Therefore, the need to biomass into nitrogen-rich bio-char, bio-oil and biodiesel. This
determine microalgae suitability using the microwave- was a preliminary investigation conducted after bio-hydrogen
enhanced pyrolysis method has prompted several research production. At a temperature of 350 °C, the biomass was con-
directions. For example, Cho et al. (2016) conducted the verted into bio-oil with elemental composition of 54% carbon,
microwave-enhanced pyrolysis of porphyra, chlorella, and spir- 33% oxygen, 6.7% hydrogen, 0.53% sulfur and 5.4% nitro-
ulina, using pyrolysis of model algae to represent main algae gen. Though research has previously reported a higher bio-
constituents. These constituents include powdered oil, a- oil yield from lignocellulosic biomass (Torri et al., 2010), the
cellulose and ovalbumin, which were useful in the model algae use of C. reinhardtii algae reveals a higher nitrogen content
preparation. Comprising 73.3 vol% of syngas, porphyra was than most lignocellulosic biomass (such as corn stover 0.7%,
most reactive of the three algae having 87.1 wt% gaseous frac- poplar 0.5%, sweet sorghum 1%, switchgrass 0.3%) (xxxx).
tion. Similarly, the presence of high carbohydrate content Having a higher nitrogen content in bio-char is desirable
favored the formation of syngas with 23.4–61.8% increase in because of the abatement of greenhouse gases, which enhances
comparison to spirulina, and 22.8–59.6% increase in compar- the possibility of converting carbon–neutral energy into
ison to chlorella. These occurred because the high carbohy- carbon-negative bio-energy (Kruse and Hankamer, 2010;
drate content in porphyra resulted in PAHs and small gas Amin et al., 2019). Anyway, pyrolysis can reduce this high
molecule formation at high temperatures. These findings nitrogen content in bio-oil when protein is extracted from bio-
demonstrate that the suitability of macro-algae porphyra sea- mass residue such as that of marine chlorella sp. (Sarkar et al.,
weed for syngas production of 85.6–87.1 wt% capacity. How- 2014).
ever, this research can be improved to large-scale commercial
gasification process with further steam reforming of C1-C3 2.4.1. Pyrolysis
hydrocarbons. Confirming the earlier study of Rahman Earlier research has already provided basis for further research
(2018), syngas increased gradually from 400 to 550 °C. How- on work of Ma et al. (2019) on biorefinery integration with
ever, the CO constituent surged when the pyrolytic tempera- biofuels production. Miao et al. (2004) explored the potential
ture increased to 700 °C. of harvested and lipid extracted microalgae pyrolytic feed-
Building on the research findings of Hong et al, Cho et al stock. Pyrolytic algae oil is a renewable feedstock for sustain-
(Cho et al., 2015) investigated the role of CO2 as a reaction able biorefinery development. Since process conditions and
medium in thermochemical production of syngas from red sea- nature of feedstock determines biogas and bio-oil composition,
weed. Having identified red seaweed as suitable for syngas pro- higher temperature and long decomposition time enhanced
duction, this study enhanced the generation of syngas using the biogas yield with lipid bound algae. On the other hand, bio-
reaction medium. A pyrolytic oil reduction of about 70% at gas production increased with hydrogen yield while decreasing
620 °C was observed when the ratio of CO to H2 was improved CO2. This was observed at reduced decomposition time and
by 400% at same 620 °C in the presence of CO2. Besides this temperature. Also, previous findings have shown that the feed-
improvement (2.0 at 750 °C), CO2 can also enhance syngas stock possesses good fuel properties of straight-chain alkanes
production in the thermal cracking of volatile organic carbons in microalgae bio-oils which are similar to those in diesel fuel
14 S.O. Ebhodaghe et al.

(Aboulkas et al., 2017). The bio-oil obtained from the fast to and lower than 20 wt% for the microalgae pyrolysis. The
pyrolysis of microalgae also has low oxygen content with quite study shows that catalyst amount and pyrolysis temperature
high heating value of 29 MJ/kg, 1.16 kg/m3 density and 0.10 influences bio-oil content. This is because, catalyst-enhanced
Pas viscosity. These properties make bio-oils suitable to con- bio-oil containing 20 wt% Na2CO3 yielded 19.4% HHV,
ventional fuel oil. However, Norouzi et al. (2016) disagrees 47.1% lower oxygen content, 83.2% lower acids content, and
with this. They developed processes for bio-oil and biochar 51.2% higher nitrogenated compounds content. This mean
production from algae waste and found that the bio-oil pro- that the presence of low Na2CO3 catalyst content enhance aro-
duced from algae waste cannot be used as bio-fuel, but the matics and nitrogenated compound contents, though car-
bio-char which exhibits good solid fuel properties. This is boxylic acid content significantly reduced. Comparing the
because, the high water and oxygen contents, as well as pres- use of the 20 wt% catalyst amount and lesser, the aromatic
ence of unsaturated and phenolic compounds renders the pyr- hydrocarbons content does not indicate any significant differ-
olized bio-oil unsuitable as fuel. Nevertheless, this presents the ence for the varying catalyst amount. This imply that the use
need for upgrading or pretreatment of bio-oil to enhance their of < 20 wt% low catalyst content didn’t quite satisfy neces-
suitability as bio-fuel (Sarkar et al., 2014). Additionally, the sary conditions for the microalgae pyrolysis.
carbon content and HHV of bio-char ensues its’ suitability
as a renewable solid fuel. Alternatively, it can be used as a car- 2.4.2. Ultrasound/Microwave- enhanced conversion
bon source for carbon materials production, while its’ high Recently, Ido et al. (2018) investigated the effect of ultrasonic
nutrient contents of Ca, K, Mg, N and P, makes it fit as a soil pretreatment on bio-oil yield from microalgae, and its’ heating
additive. value in the low-temperature hydrothermal liquefaction (HTL)
process. This is because, the use of ultrasonic pretreatment is
2.4.1.1. Catalytic and Non-Catalytic pyrolysis. The presence of hypothesized to address HTL pressure and temperature
bio-char introduces catalytic activity in bio-oil production decreases associated with bio-oil yield which is quite challeng-
from microalgae. To illustrate this, Andersson et al. (2020) ing for large commercialization. Based on the study,
determined the potential of Cladophora glomerata for bio-oil ultrasonic-assisted HTL (UHTL) should possibly increase
and hydrogen-rich gas production when converted to gaseous, bio-oil yield at a constant total energy value even at low son-
liquid and solid products. The Caspian Sea green algal is quite ication times (up to 90 s). The latter implies that UHTL-
suitable for the production process as the non-catalytic tests increased bio-oil thermal energy is greater than the electrical
indicate that the highest portion of bio-oil was retrieved at energy consumed in the sonication process. To confirm this,
500 °C. While addition of bio-char increased the phenolic con- the use of UHTL for the bio-oil production reduced its’ oxy-
tent from 8.5 to 20.76 area %, the hydrogen concentration and gen content and increased the heating value, when compared
selectivity were improved as well (1.37 and 1.59, respectively). with the conventional HTL. Moreover, the highest bio-oil
This indicates the catalytic ability of bio-char, which is due to yield of 28.9% was obtained at 250 °C and 90secs sonication
its’ alkali and alkaline earth metals constituents. The catalytic time. Since the use of this new method (UHTL) didn’t change
action of these constituents is due to the effect of water mole- the average nitrogen content, Grierson et al. (2009) had earlier
cule increase and volatile hydrocarbons. Additionally, the investigated the potential conversion of Chlamydomonas rein-
increased phenolic contents are useful in several pharmaceuti- hardti biomass into nitrogen-rich bio-char, bio-oil and biodie-
cal and cosmetic industries. Since Andersson et al reports the sel. In addition, Onwudili et al. (2018) extracted lipids from
use of macroalgae as preferable to microalgae for biofuel pro- scenedesmus obliquus microalgae through the use of
duction, Rahman et al. (2018) has reported the effect of zeolite ultrasonic-assisted solvent extraction (UASE) using hexane
catalysts on macroalgae bio-oil pyrolytic yield. From the and isopropanol (HIP) solvent mixtures. The extracted lipids
study, 41.3 wt% maximum oil yield was obtained at a catalyst containing fatty acids and esters had a HHV of about
to biomass ratio of 1:10, which in comparison to non-catalytic 35.35 MJ/Kg. 26.63 wt% lipid yield was extracted at UASE
process only yields 38.5 wt%. Also, lower number of organic process conditions of 50.06 mm resonance amplitude, HIP ratio
compounds were obtained during the catalytic pyrolytic pro- of 3.99v/v and < 1.5hrs reaction time. Other process condi-
cess, than for the non-catalytic process. Arrangement of the tions of minute nitrogen, sulfur, and ash contents (1.03%,
pyrolytic liquid yield was advanced by the communication of 0.16%, and 0.55% respectively) as well as 79.38% saturated
the radicals as well as cracking of the compounds. Further- fatty acids concentration are noted for biofuel processing.
more, a comparison of the catalysts indicate that Y-zeolite is More recently, Sarkar et al. (2014) studied the characteriza-
most suitable for the U.prolifera bio-oil production. This is tion of Chlorella sp. biomass; extracted marine Chlorella sp.
because of several reasons. First, the catalytically produced residue (EMCR) and EMCR-derived biochar. Then, EMCR
bio-oil using Y. zeolite possess reduced oxygen content, and was applied as microwave absorbent (MA) for the microwave
increased hydrogen and nitrogen contents. This is because pyrolysis bio-oil production. The obtained bio-oil was maxi-
bio-oil yield increased with the use of the catalyst, while its’ mized through the RSM-CCD optimization of temperature,
use with the three zeolites-based catalysts of ZSM-5, Y- time and MA loading. The study found that EMCR is feasible
zeolite and Mordenite was decreased. Second, research has for bio-char and bio-oil production because of several reasons.
shown that the suitability of Y-zeolite may be due to its’ sur- Firstly, 46% bio-oil was produced at the optimum conditions
face area, higher acidity and enhancement of catalytic cracking of 350 °C, 15% MA loading and at 40mins. Next, higher heat-
(Tirapanampai et al., 2019; Xu et al., 2018). ing values (HHV) of 22.43, 15.49 and 10.79 MJ/kg were
Rather, Saber et al. (2017) alternatively evaluated the pos- obtained for the biomass, EMCR and bio-char respectively.
sibility of enhancing bio-oil production from Chlorella vulgaris This shows that the HHV of marine Chlorella sp. is greater
with the use of low catalyst ratios of Na2CO3 applied at equal than those of several other algal species, while that of EMCR
Biofuels from microalgae biomass 15

and bio-char can be compared while being similar to literature system efficiency. Furthermore, 24.5 resp 92ktCO2eq/year of
reports. Finally, adding bio-char for the bio-oil production energy can be saved, assuming a 100 MW algae constant feed-
reduced the time needed to arrive at the final pyrolysis temper- stock supply rate, which is able to generate 184.5, 177.1, and
ature with greater bio-oil yield, which was achieved at 850 W, 229.6GWhbiochar/year. These findings for the macroalgae-
350 °C, 15% MA loading at 40mins optimum conditions. based hydrothermal liquefaction reveals its’ role in ensuring
These may be because of the high EMCR-derived bio-char sur- a high CO2 reduction potential. In addition, comparing the
face area of 266 m2/g. This high surface area is as a result of respective 15.7MWelectricity and 40.5MWelectricity as electricity
the combined effects of ultrasonication extraction with demands for macroalgae and microalgae cultivation/harvest-
pyrolysis. ing, the less energy-intensive requirement of the former is evi-
dent. This implies that the high energy consumption rate of
2.4.3. Hydrothermal pretreatment microalgae cultivation/harvesting depends on the carbon
Ferdous et al. (2002) determined the influence of biomass pre- intensiveness of electricity. As a result, the macroalgae based
treatment on upgraded bio-oil by comparing dry and route demonstrates a larger CO2 reduction potential. Future
hydrothermal torrefaction using batch, quart tube and auger. research can consider the possibilities of storage and continu-
Also investigated were the physical and chemical properties ous harvesting to ensure a constant biofuel process operating
of torrefied bio-char. The study showed that torrefied bio- all-year round.
char is useful for biomass gasification for high quality gafs
products. This is because, the hydrothermal pretreatment pro- 3. Conclusion
cess reduced the bio-oil acetic acid content from 34.5% to
13.2%. Moreover, reducing hemicellulose content in the This review contributes to our understanding of how biofuel produc-
Camellia shell (CS) torrefied bio-char improved the bio-oil tion from microalgae has developed. The contribution of this study
has been to provide more understanding on present state and future
phenols content from 27.23% to 60.05%. This shows that
development of biofuel production from the biomass.
the process of torrefaction influences hemicellulose content in
CS. This may be because, hemicellulose has a random amor-  The research been discussed would influence economic considera-
phous structure of reduced strength and easy hydrolysis using tions through the overview of merits and limitations of several con-
dilute acid or base (Zhu et al., 2018), which could have led to a version processes.
significant decomposition of most hemicellulose. This degener-  Key areas for improvement in microalgae conversion include the
ation process was the main source of the acids. Building on nature of catalysts been utilized. Bio-based catalysts should be pre-
these findings, Holmgren et al. (2018) prepared bio-char ferred due to high cost of synthetic catalysts. Also, since energy
through the processes of torrefaction pretreatment and co- usage and requirements do influence operational costs, recycling
pyrolysis on walnut shell and bio-oil distillation residue. Com- could aid reuse of waste energy. Methodical limitations such as
bining both processes can increase bio-char yield derived from high equipment cost for process scale-up can prevent research from
advancing as it could.
walnut and distillation residue. This is because, the yield of
 Promising microalgae conversion processes which could be pro-
bio-char was increased by a maximum of 13.69% when 50% gressed are the use of bio-based solvents and supercritical fluids
of the distillation residue was added to the blends. This means for biodiesel production, hydrothermal liquefaction for biogas pro-
that the pretreatment assisted in ensuring a positive synergistic duction, microwave-induced pyrolysis for syngas production, and
effect between walnut shell and the distillation residue on the ultrasound/microwave enhanced extraction for bio-oil production.
yield of torrefied blends. However, this was obtained under These are based on the possibility of high yield and process eco-
severe torrefaction conditions. While the bio-char yield nomics. Anyway, further research which take these into considera-
increased, the bio-oil yield however reduced with torrefaction tions will be needed.
temperature. Additionally, the process of co-pyrolysis was pre-  For future developments, the use of the promising conversion tech-
ferred to individual pyrolysis since research has shown that the niques would probably gain the interest of more researchers than at
present, considering the merits of same. In other words, more
bio-oil yield of the former is higher than the latter, and
research is expected to evolve in coming years.
improves the bio-char properties more.
Other studies have examined the effect of HTL on different Knowledge Gap and future research questions
varieties of microalgae such as C.vulgaris, B. braunii, S. platen-
sis, and S. quadricauda on bio-oil quality (Akhihiero et al., 1. How can heat sinks be used to reduce the heat generated from elec-
2020; Kumar et al., 2015). Presently, research is considering tricity production system for mitigating greenhouse gas emissions?
energy and carbon issues in integrating algae-based biofuel (Walker et al., 2018)
production with an oil refinery. This is important in providing 2. What catalytic technologies can convert microalgae biomass into
directions for future research. To this end, Ma et al. (2019) fungible fuels for commercial utilization? (He, 2020)
evaluated the use of macroalgae and microalgae for biofuel 3. How can oxygen carrier catalysts such as metal ferrites be devel-
production with a comparison with transesterified microalgae oped to enhance carbon conversion efficiency from combined
lipid. This study reports the use of macroalgae as preferable anaerobic digestion which chemical looping gasification, and mem-
brane separation technology? (Mu et al., 2018)
to microalgae for biofuel production. This is based on the fact
4. What mechanisms could be used to improve acceleration by substi-
that a very high system efficiency of 38.6% was obtained with tution in biomass conversion of cellulose? (Da Costa et al., 2020)
the use of macroalgae-based hydrothermal liquefaction pro- 5. What measures can be adopted to mitigate the effects of cogenera-
cess, while producing 22.5 MJ per 100MJalgae low liquid fuel tion of electricity? (Sharma et al., 2020)
yield, and 28.0 MJ per 100MJalgae solid biochar produced. 6. What other alternatives to toxic solvents can be used for the scaling
On the other hand, the microalgae-based hydrothermal lique- up of yeast lipid fermentational conversion to high value products?
faction process produced 54.1 MJ per 100MJalgae at a 30.6% (Akhihiero et al., 2019)
16 S.O. Ebhodaghe et al.

7. What are the effects of 10–40 petrol diesel to biodiesel blend ratios Rivas, J., Prazeres, A.R., Carvalho, F., Beltran, F., 2010. Treatment
on the properties of biomass biodiesel? (Osman et al., 2021). of cheese whey wastewater: combined coagulation-flocculation and
aerobic biodegradation. J. Agric. Food Chem. 58 (13), 7871–7877.
https://doi.org/10.1021/j.f100602j.
Garg, A., Jain, S., 2020. Process parameter optimization of biodiesel
Declaration of Competing Interest
production from algal oil by response surface methodology and
artificial neural networks. Fuel. https://doi.org/10.1016/
The authors declare that they have no known competing j.fuel.2020.118254.
financial interests or personal relationships that could have Phukan, M.M., Hazarika, N., Bora, P., Borah, T., Konwar, B.K.,
appeared to influence the work reported in this paper. 2020. Leveraging microalga feedstock for biofuel production and
wasteland reclamation using remote sensing and ex situ experi-
Acknowledgement mentation. Renew Energy 159, 973–981. https://doi.org/10.1016/j.
renene.2020.06.047.
Kröger, M., Müller-Langer, F., 2012. Review on possible algal-
The authors wish to acknowledge the efforts of the researchers biofuel production processes. Biofuels 3 (3), 333.
whose works were cited. Mubarak, M., Shaija, A., Suchithra, T.V., 2015. A review on the
extraction of lipid from microalgae for biodiesel production. Algal
Funding Statement Res. 7, 117–123. https://doi.org/10.1016/j.algal.2014.10.008.
Qari, H., Rehan, M., Nizami, A.-S., 2017. Key Issues in Microalgae
Biofuels: A Short Review. Energy Procedia 142, 898–903.
No funding was received for this research.
Raheem, A., Prinsen, P., Vuppaladadiyam, A.K., Zhao, M., Luque,
R., 2018. A review on sustainable microalgae based biofuel and
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