Journal of Cleaner Production 208 (2019) 1053e1064

Contents lists available at ScienceDirect

Journal of Cleaner Production

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

Review

Review on cultivation and thermochemical conversion of microalgae

to fuels and chemicals: Process evaluation and knowledge gaps
Thangavel Mathimani a, Arianna Baldinelli b, Karthik Rajendran c, d, Desika Prabakar e,
Manickam Matheswaran f, Richard Pieter van Leeuwen g, Arivalagan Pugazhendhi h, *
a
Department of Energy and Environment, National Institute of Technology, Tiruchirappalli - 620 015, Tamilnadu, India
b
Department of Engineering, University of Perugia, Italy
c
Department of Biological and Ecological Engineering, Oregon State University, Corvallis, United States
d
MaREI Centre, Environmental Research Institute, University College Cork, Cork, Ireland
e
Anna University, ACT Campus, Chennai, Tamilnadu - 600 025, India
f
Department of Chemical Engineering, National Institute of Technology, Tiruchirappalli - 620 015, Tamilnadu, India
g
Research Chair Sustainable Energy Systems, Saxion University of Applied Sciences, Enschede, the Netherlands
h
Innovative Green Product Synthesis and Renewable Environment Development Research Group, Faculty of Environment and Labour Safety, Ton Duc Thang
University, Ho Chi Minh City, Viet Nam

a r t i c l e i n f o a b s t r a c t

Article history: Over the last decades, microalgae have gained a commendable role in the rising field of biofuel pro-
Received 25 November 2017 duction as they do not compete with food supply, reduce greenhouse gases emission, and mitigate CO2.
Received in revised form Specifically, thermochemical processing of microalgae yields products, which can be used both for en-
8 October 2018
ergy and other industrial purposes, depending on the algal strain, processing method and operative
Accepted 9 October 2018
conditions. Algae are converted into various high-value products, including nutraceuticals, colourants,
Available online 10 October 2018
food supplements, char, bio-crude, electricity, heat, transportation fuel, and bio-oil. Therefore, micro-
^ as de
Handling Editor: Cecilia Maria Villas Bo algae are believed to be a strategic resource for the upcoming years and their utilization is meaningful for
Almeida many industrial sectors. In this framework, this review addresses the various thermochemical processing
of microalgae to various biofuels and their industrial significance. The obstacles in various thermo-
Keywords: chemical conversion methods have been critically flagged, in order to enable researchers to choose the
Microalgae optimal method for fuel production. Furthermore, light is shed on cultivation systems to generate rapidly
Thermochemical processing microalgal biomass for thermochemical processing. Eventually, all recent literature advancements con-
Hydrothermal liquefaction
cerning microalgae cultivation and thermochemical processing are critically surveyed, and summarized.
Pyrolysis
© 2018 Elsevier Ltd. All rights reserved.
Gasification
Carbonization

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1054
2. Review methodology . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1055
3. Microalgae . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1055
3.1. Microalgae cultivation and condition . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1055
3.1.1. Outdoor cultivation systems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1055
3.1.2. Indoor cultivation system . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1056
4. Thermochemical conversion methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1057
4.1. Hydrothermal liquefaction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1057
4.2. Pyrolysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1059
4.3. Gasification . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1059

* Corresponding author. Innovative Green Product Synthesis and Renewable

Environment Development Research Group, Faculty of Environment and Labour
Safety, Ton Duc Thang University, Ho Chi Minh City, Viet Nam.
E-mail address: [email protected] (A. Pugazhendhi).

https://doi.org/10.1016/j.jclepro.2018.10.096
0959-6526/© 2018 Elsevier Ltd. All rights reserved.
1054 T. Mathimani et al. / Journal of Cleaner Production 208 (2019) 1053e1064

4.4. Carbonization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1060

4.5. Combustion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1061
5. Biofuel and other bio-products from microalgae . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1061
6. Upgradation of bio-oil . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1061
7. Future perspectives . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1062
8. Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1062
Acknowledgement . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1062
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1062

1. Introduction 1. High lipid content and sustainable lipid productivity over

terrestrial crops
Fossil fuels are used to fulfil the majority of mankind energy 2. No competition with agricultural crops and, as a consequence,
requirement (Medeiros et al., 2015). According to qualified esti- no interference with food production
mations, fossil fuels satisfy about 80% of the world's energy 3. They do not require large arable or fertile land for cultivation,
requirement and e what is worse e they are responsible for a high especially when compared to oilseed crops devoted to biofuels
share of greenhouse gases (GHGs) emissions (Medeiros et al., 2015; production
Piemonte et al., 2016). Notwithstanding that, the industrial devel- 4. High biomass productivity and quick growing rate over other
opment currently exhibits a growing rate that is not feasible at all, biofuel crops.
to cope with such limited primary energy resources and the climate 5. They can grow and utilize the nutrients in polluted municipal
overriding concern. In this moment, the global society is strongly wastewater, paving economical way for wastewater
engaged in building an energy future, which guarantees the secu- bioremediation.
rity of supply and easy access to resources, underlying a step to-
wards environmental issues. Regarding the reduction of GHG However, bioenergy projects need to be re-directed from
emission, natural processes alone are not able to absorb all of the multidisciplinary points of view, to benefit from the intersections
emissions associated with anthropogenic activities. Therefore, among mutual microeconomic and macro-economic sectors
alternative methods are needed to compensate the inefficiencies. (Blengini et al., 2011). Further, it is stated that biodiesel production
This can be achieved by the implementation of high efficiency using microalgae could be economical, but it still requires research
technologies, coupled with a rational utilization of carbon neutral efforts to obtain substantial productivity (Mata et al., 2010). With
resources, especially renewable resources. In these frame, for an reference to economically viable biodiesel, wet biomass-handling
enlighted industrial development, it is not possible to defer techniques - i.e., thermochemical methods e deserve attention, in
anymore the implementation of new energy technologies based on order to avoid expensive process bottlenecks (drying), especially
eco-friendly resources. They are expected to coexist with the pre- for high-water biomass feedstock (Barreiro et al., 2013; Silva et al.,
sent ones and to gradually replace them. 2016). Several recent scientific studies have focused on the ther-
Among the eco-friendly fuel options, biofuels are considered to mochemical conversion of algal biomass to fuel (Benson et al., 2014;
be renewable fuels which contribute actively to the GHG emissions Reyimu and Izsimen, 2017). Thermochemical processes include
balance. Biofuels may be either solid, liquid, or gaseous fuel (Monari hydrothermal liquefaction (HTL), pyrolysis, gasification, carbon-
et al., 2016). Depending upon the feedstocks used, biofuel pro- ization (Barreiro et al., 2013). HTL is a better technique to produce
duction is categorized into three generations. In the first- liquid fuels from wet algal biomass, since it does not require
generation feedstocks (FGF), food crops like sugarcane (bio- completely dried microalgal biomass (Garcia Alba et al., 2011).
ethanol through fermentation of sugar) or oil crops (biodiesel During HTL reactions, bio-oil or bio-crude is produced as the main
through transesterification of lipid) are used (Loong and Idris, product, together with solid, gas and aqueous by-products (Barreiro
2017). However, at the industrial scale, biofuel production using et al., 2013). HTL bio-oil can be used as a substitute for petro-crude
FGF is hindered by several issues such as the food-vs.-fuel contro- in petroleum refinery. Combustion of bio-oil emits low sulfur and
versy and large agricultural land requirement (Mathimani et al., particulate matter (low ash) (Barreiro et al., 2013). The major issues
2016; Mathimani et al., 2015). To overcome these issues, second- hindering a deeper implementation of those methods include: i)
generation feedstocks (SGF) based on non-edible sources, like lack of understanding in reaction chemistry and kinetics, ii) proper
lignocellulosic residues (Guil-Guerrero et al., 2017; Reyimu and catalysts selection to withstand reaction conditions, iii) solid by-
Izsimen, 2017) or Jatropha, Cassava, Miscanthus and other non- products management practices, iv) fouling and plugging, v)
food oleaginous crops, have been considered for biofuel produc- reactor manufacturing and material selection (Peterson et al.,
tion. However, SGF requires surplus land area for their cultivation, 2008). Further, the bio-oil might contain high nitrogen content
sophisticated equipment, high investment for large-scale facilities, derived from microalgae chlorophyll and proteins and, therefore,
and correspondingly they do not replace fossil fuels completely, as bio-oil emit high NOx upon combustion (Costa and De Morais,
the produced volumes cannot fulfill world's large energy demand 2011). Hence, challenges associated with thermochemical
by the transportation sector (Maity et al., 2014; Nigam and Singh, methods need to be addressed to select the appropriate method for
2011). a more efficient and less impactful biomass-to-fuel conversion. This
In this perspective, production of biofuel from aquatic organ- comprehensive review covers cultivation- extraction- production
isms such as microalgae, cyanobacteria, diatom, seaweed and other in which it discusses the various thermochemical methods, and its
microbial communities have been studied as third-generation challenges and scope. In addition to the thermochemical conver-
feedstocks (TGF) (Dragone et al., 2010). TGF possesses several ad- sion of algal biomass to fuels, extensive discussion on the bottle-
vantages (Mata et al., 2010; Mathimani et al., 2017; Rawat et al., necks in microalgal cultivation systems with an emphasis on
2013a), as summarized below: biodiesel makes this review article different from other published
 T. Mathimani et al. / Journal of Cleaner Production 208 (2019) 1053e1064 1055

literature. In the context of various issues mentioned above, this microalgal biofuel economically viable, by reducing the cultivation
review appraises and discusses the established methods used for cost through inexpensive nutrients inputs. However, deep studies
the production of fuel from microalgae. Further, it aims at high- on large-scale cultivation of microalgae need to be undertaken for
lighting the challenges in the production of liquid and gaseous sustainable and contamination-free cultivation for an extended
products through thermochemical processes. In addition, types of period of the run without frequent re-inoculation. As a whole,
cultivation systems and the challenges in microalgal cultivation large-scale microalgal cultivation has substantial obstacles for cost-
systems will be extensively discussed. effective biofuels production, which entails, robust strain selection,
cultural integrity, retaining monoculture, cultivation conditions,
2. Review methodology expensive medium formulation, and gaseous exchange.
Microalgae are distinctive groups of photosynthetic organisms,
Among all alternative renewable energy sources, microalgae are which grows in various types of habitats like freshwater, seawater,
emerging research topic in many regions of the world. Therefore, and wastewater. Certain strains of alkaliphile (high pH), halophile
cultivation strategies and thermochemical conversion technologies (high salinity) were found to thrive in outdoor by restricting the
to convert microalgae into valuable fuels have become overriding cross-contamination of other microalgal strains; further in order to
concerns. Hence, this is the key focus of this review paper. Several overcome the contamination at the long run, seed culture should be
most quoted recent articles published in peer-reviewed interna- propagated constantly as a dominant culture (Day et al., 2012). In
tional journals were collected and analysed by researchers from general, microalgae are cultivated using outdoor (open pond) and
different scientific areas (biology, agricultural science, thermal indoor (tubular photobioreactor) cultivation system (Handler et al.,
engineering). Hence, journal articles of particular relevance to the 2017). Both the cultivation systems are regulated by means of
scope of the review were selected and their results were discussed, light source and its intensity (Mata et al., 2010). In outdoor culti-
with a glance on the future needs to accomplish the so-called en- vation systems, microalgae are provided with the natural light
ergy production. A representation of the methods used for selection source from the sun, while for indoor cultivation systems different
of the review contents has been shown in Fig. 1. Therefore, the artificial sources like light emitting diodes (LED) and optical fibers
review contents are organized into three four subjects, namely i) are used. Further transmission of solar energy to electrical energy is
thermochemical conversion methods, ii) types of microalgae also possible using optical fibre systems, which promote healthy
cultivation, iii) biofuel and other bioproducts from microalgae and growth in indoor conditions. However, in both cultivation systems,
iv) upgradation of bio-oil. photo synthetically active radiation (PAR) above the saturation
point might be a growth limiting factor and, thus minimizing
biomass productivity. Laboratory-based cultivation systems can be
3. Microalgae
monitored and regulated whereas outdoor systems cannot be
manually controllable, being less predictable (Grima et al., 2003).
Algae are categorized into green algae, diatoms, golden brown
and cyanobacteria and more than 25,000 species are available
3.1.1. Outdoor cultivation systems
(Balat, 2011). Microalgae - sunlight-driven cell factories - are either
As the name suggests, outdoor cultivation systems are based on
prokaryote or eukaryotes photosynthetic microorganisms, pro-
the cultivation of microalgae under open systems like ponds, tanks,
ducing several valuable products such as proteins, polyunsaturated
lakes and raceway ponds. This is the first and foremost method
fatty acids, pigments, immune modulators, vitamins (Pulz and
practised for mass cultivation of microalgae (Junying et al., 2013).
Gross, 2004; Spolaore et al., 2006), which are relevant for many
Taking into account the cost factor entailing microalgae cultivation,
industrial branches (i.e. food, aquaculture, poultry, pharmaceutical
the open pond system was developed for microalgae industrial-
and biofuel industries. Worldwide, total microalgal biomass pro-
scale cultivation, so as to attain high biomass productivity.
duction is about 10,000 tons per year (Balat, 2011). The microalgae
Several studies have put forth the challenges involved in cultivating
contain carbon, hydrogen, nitrogen, phosphorus and potassium,
microalgae under open conditions. The open pond system is one of
which play a dominant role in aiding their growth and biochemical
the simplest cultivation technologies, and it can be widely used in
composition. The carbohydrates and protein contents of microalgae
various countries successfully for cultivating microalgae viz., Asian
have been given in Table 1.
countries, Mexico, the USA and certain parts of Europe (Italy, Spain,
and the Netherlands). Spirulina and Chlorella species are mainly
3.1. Microalgae cultivation and condition cultivated in open pond system worldwide (Demirbas and
Demirbas, 2011). A typical raceway pond has a flat bottom and
Microalgae bulk cultivation is practised extensively to generate vertical walls with 0.25e0.30 m depth and surface not exceeding
copious amount of biomass, taking benefit from the fast growth of 0.5 ha. Among the concrete and PVC raceway ponds, concrete made
this feedstock. Moreover, extensive cultivation will make ponds provide high-value biomass production (Chisti, 2013). The
raceway ponds are shallow raceways with 15 cme35 cm water
wherein biomass yield is about 10 magnitudes higher than exten-
sive ponds system. In general, raceway ponds are widely used for
the cultivation of Arthrospira platensis, A. maxima, D. salina,
C. vulgaris and H. pluvialis (Maity et al., 2014).
The various aspects that need to be considered for raceway pond
construction are mixing need, feeding and harvesting facility, car-
bon dioxide input, drainage, overflow and cleaning (Chisti, 2016). In
the outdoor system, agitation or mixing of microalgal suspension
with growth medium is a major factor and it is usually provided by
means of a paddle wheel. For the cultivation of microalgae in open
system, a low-cost medium formulated using either sewage water
or wastewater or seawater with fertilizer- grade nutrients (Phos-
Fig. 1. Step-by-step depiction of the organization of review contents. phorous, Potassium, Nitrogen) is used. Atmospheric CO2 is
1056 T. Mathimani et al. / Journal of Cleaner Production 208 (2019) 1053e1064

Table 1
Protein and carbohydrate content of various microalgae on a dry matter basis (%).

Name of the organism/group Protein (% dwt) Carbohydrate (% dwt)

Anabaena cylindrical/Cyanophyceae 43e56 25e30

Aphanizomenon flos-aquae/Cyanophyceae 62 23
Arthrospira maxima/Cyanophyceae 60e71 13e16
Chlamydomonas rheinhardii/Chlorophyceae 48 17
Chlorella pyrenoidosa/Chlorophyceae 57 26
Chlorella vulgaris/Chlorophyceae 51e58 12e17
Dunaliella bioculata/Chlorophyceae 49 4
Dunaliella salina/Chlorophyceae 57 32
Euglena gracilis/Euglenaceae 39e61 14e18
Porphyridium cruentum/Porphyridiaceae 28e45 40e57
Prymnesium parvum/Prymnesiaceae 28e45 25e33
Scenedesmus obliquus/Chlorophyceae 50e56 10e17
Scenedesmus quadricauda/Chlorophyceae 47 e
Scenedesmus dimorphus/Chlorophyceae 8e18 21e52
Scenedesmus sp./Chlorophyceae 51.14 23.19
Spirogyra sp./Chlorophyceae 6e20 33e64
Spirulina maxima/Cyanophyceae 60e71 13e16
Spirulina platensis 52 8e14/Cyanophyceae 46e63 8e14
Synechoccus sp./Cyanophyceae 63 15
Tetraselmis maculate/Prasinophyceae 52 15

sufficiently available for open pond system. In a raceway pond, approximates the maximum. Once maximal growth is reached,
batch culture and steady-state continuous culturing can be per- the culture is harvested and used for extracting products.
formed with 10% of microalgal inoculum in a nutrient medium. As
In continuous systems, the culture medium is given in a
reported by Ashokkumar and Rengasamy (2012), hydrocarbon continuous inflow and collected through the continuous
producing B. braunii AP103 cultivated in raceway pond showed reception of biomass.
high heptadecane content of 34% followed by hexadecane (12.5%).
In semi-continuous systems, continuous addition of culture
Raceway pond systems require relatively low capital investment medium is performed and simultaneously, just a partial harvest
and represent the first choice for microalgae cultivation, although of biomass is performed in order to maintain constant algal
low productivity. In certain cases, open pond cultivation is coupled growth.
with wastewater treatment, to enable microalgae to treat nitrogen
and phosphorus in the wastewater. Therefore, this type of cultiva- The selection of the proper cultivation method and PBR design
tion process offers a double benefit, such as wastewater remedia- with respect to enhanced light penetration (no shading effect) and
tion and low-cost nutrients for algal growth (Manninen et al., large space provision is essential for an efficient cultivation of
2016). microalgae to generate high-cell density biomass. Albeit numerous
photobioreactors are proposed and designed, only a few of them
are practically implemented. As a matter of fact, the major draw-
back in the extensive production of microalgae in photobioreactor
3.1.2. Indoor cultivation system is mass transfer (Ugwu et al., 2008). The light source for photo-
Indoor cultivation or laboratory system is one of the most bioreactor is provided by means of artificial light sources, like
strictly controlled and monitored systems for microalgal cultiva- fluorescence lamps or LED (Wang et al., 2007). Air and CO2 are
tion. Indoor cultivation systems are also called closed cultivation blown from the bottom of the reactors to ensure uniform contact
systems since they are performed in photobioreactors (PBRs). In between gas and microalgae. In concern with light intensity mea-
those reactors, microalgae are closely monitored for light and surement, automated sensors have also been used to measure the
temperature, contamination due to parasites, predators and intensity of light (Ogbonna et al., 1999). Even though photo-
competitive species of algae (De˛ bowski et al., 2012). The utilization bioreactors facilitate culturing, the cost of the reactor still remains
of CO2 is much more efficient in PBRs compared to open ponds, high (De˛ bowski et al., 2012). In the recent past, integrated culti-
where most of CO2 leaks into the atmosphere. The main drawback vation system entailing microalgal cultivation with wastewater/
of PBRs is the oxygen management, since it requires suitable flue gas are being practiced for CO2 mitigation. Further, thin-layer
degassing stations. PBRs are widely used as microalgae cultivation culture system was found to be successful in cultivating Chlorella
system, regardless climatic conditions (Cuaresma et al., 2011; species for biofuel and starch application (Branyikova et al., 2011; Li
Demirbas and Demirbas, 2011). The different types include sack et al., 2013), and it is noteworthy that 50 g L1 biomass yield can be
system or large bags cultivation, tubular photobioreactor and plate achieved using thin layer cultures system (Rastogi et al., 2018). As
photobioreactor (Amin, 2009; Borowitzka, 1999). Flat and tubular reported by Singh and Gu (2010) the Italian Energy Company ENI, is
PBRs are the most proficient and productive system for higher using 1-ha capacity open ponds and photobioreactors aiming at the
biomass yield compared to raceway ponds, as they are protecting cultivation of microalgae for bio-oil production.
microalgae from predators, cross-contamination, and pathogens In concern with indoor PBRs, growth of algae on the wall, scale-
(Maity et al., 2014). Based on the duration and method, PBRs can be up, low surface-to-volume ratio are still bottlenecks (Rastogi et al.,
divided into three categories, namely batch, continuous and semi- 2018). Yet, PBRs are able to handle a higher biomass production and
continuous culturing systems (Chisti, 2013; De˛ bowski et al., 2012). to allow an accurate control of the process. In these terms, open
pond systems are simpler in construction and cheaper. Neverthe-

In batch cultivation, the culture is inoculated in a single dose into less, they are still not completely standardized with respect to
the medium and cultivated until the population reaches its contamination, low biomass yield and inadequate mixing.
maximum density or when cell density in the culture
 T. Mathimani et al. / Journal of Cleaner Production 208 (2019) 1053e1064 1057

Large-scale microalgae cultivation generally depends on the

aspects of the two approaches, using photobioreactors and/or the
raceway pond system. As debated both the techniques have their
own benefits and drawbacks. Though various cultivation systems
are used, overall cost-effectiveness stands in the other steps of the
supply chain too, hence harvesting, algae farming and slurry pro-
cessing are essential to lucratively produce a microalgae-derived
fuel that can be competitive with fossil fuel in the upcoming
future (Nigam and Singh, 2011).

4. Thermochemical conversion methods

The complex mixture of carbohydrates, proteins and lipids of

algae make them a promising candidate for the production of
carbon-neutral fuel like biodiesel, biomethane, biohydrogen and
bioethanol (Li et al., 2008). The advantages in the utilization of
microalgae for fuel application are many (Rawat et al., 2013a,
2013b)

- microalgae fix atmospheric CO2 thanks to the natural photo-

synthesis process;
- when compared to fossil fuels, microalgae pose marginal envi-
ronmental pollution;
- particularly, they produce less harmful gas emissions such as
sulfur oxide, which beside the environmental impact, is also a
precursor of corrosion in energy conversion devices;
- microalgae produce an eco-compatible renewable biodiesel;
- microalgae-derived fuels such as bio-diesel can be used without
Fig. 2. Conversion of microalgae to fuel using thermochemical process.
modifying existing engines, hence enabling the utilization in
state-of-art technologies.
algal biomass for end-use application (internal/external combus-
The complete conversion of biomass to fuels can be widely tion engines, gas turbines). Hydrothermal liquefaction of algal
classified into thermochemical, biochemical and physicochemical biomass yields mainly bio-oil or bio-crude with a calorific value
processes. Dealing in detail with the further processes category, between 33 and 39 MJ/kg (Ross et al., 2010).
thermochemical methods are in turn grouped into five classes, Here below, a detailed dissertation is provided regarding each
according to the prevailing methodology: hydrothermal liquefac- thermochemical processes, aiming at summarizing the major out-
tion, pyrolysis, gasification, carbonization and combustion (Huang comes found in the literature to the matter of microalgae conver-
et al., 2011). As shown in Fig. 2. Thermochemical conversion of sion to bio-oil. Further, this review highlights the challenges in each
microalgae to bio-oil entails different methods and they are methods to understand and select the ideal method for microalgal
selected with respect to the products formed and final application. biomass conversion. Finally, a complete overview is resumed in
Different thermochemical processes are used to produce bio-oil or Table 2.
bio-crude from microalgal feedstock (Silva et al., 2016). Of the
thermochemical techniques, pyrolysis is widely applied to obtain a
liquid fuel (“bio-oil”), in which the reaction between the microalgal 4.1. Hydrothermal liquefaction
substrate and an inert medium at temperature in the range of
400e600  C and atmospheric pressure was taken place. Under sub- Hydrothermal liquefaction (HTL) is a thermochemical process
critical conditions, in the presence of aqueous medium, hydro- aimed at producing a liquid fuel out of a biomass feedstock. HTL
thermal decomposition of microalgae yield a combination of solid, takes place in an aqueous medium at high pressure (5e20 MPa) and
liquid and gaseous products. In contrast, super-critical gasification at temperatures in the range of 250 and 370  C. These conditions
results in the formation of syngas. Nonetheless, gasification can be are sub-critical in which complex structures of biomass decom-
performed even in the lack of a water medium, supplying other posed to smaller molecules with high energy density through hy-
reactants as oxidizing species (air or oxygen). Process variables, drolysis and re-polymerization reactions. In this regard, it is
feedstock selection and load and catalyst activity (if any) affect the important to maintain the process water pressure at the above-
quality, yield and the energy density of the product. Furthermore, mentioned conditions (Barreiro et al., 2013). Microalgae are fed as
gasification operates at temperatures >700  C under controlled slurry to the HTL reactor. Usually, their mass fraction is about
oxygen atmosphere, resulting in products suitable for different 5e20% out of the total reactor feed, while the other is just reaction
applications including heat, electricity, combined heat and power medium, i.e., water. For the water medium used, the main product
generation (CHP), and transportation fuel. Syngas (gaseous prod- is a liquid blend called bio-oil or biocrude, which is more de-
uct) is the main product that is utilized for the above-mentioned oxygenated and vicious than bio-oil from pyrolysis. The bio-oil is
applications. Carbonization involves the conversion of solid similar to crude oil and therefore when refined it could be used in
biomass at temperature higher than 280  C, to store solid carbon in various applications. The leftover in the liquefaction ends up as tar,
the form of charcoal (solid product). This solid charcoal is used as a a mixture of high-boiling point cyclic and polycyclic hydrocarbons
catalyst in fuel and energy production. Combustion e whether (such as 2-5-rings aromatics). The choice and the physical state of
complete - results in fewer effluents, mainly gaseous products. The the products mainly depend on the operating conditions and the
heat due to the operating conditions used helps the combustion of end-use application. All three physical state of products exists,
1058 T. Mathimani et al. / Journal of Cleaner Production 208 (2019) 1053e1064

Table 2
Thermochemical processing of various algae to fuel and its operating conditions.

Microalgae Process Product Catalyst Reaction Pressure Res. time Yield Bio-Fuel HHV Reference
feedstock temperature [ C] [MPa] [min] [%w] [MJ/kg]

Botryococcus braunii HTL Bio-oil No 300 e e 64% 45.9 (Dote et al., 1994)
Chlorella HTL Bio-oil No 350 e 60 33% 35.1 (Biller and Ross, 2011)
No 300 e 60 46.6% 37.5 (Biller and Ross, 2012)
No 350 e 3 41.7% e (Jazrawi et al., 2013)
SPY Bio-oil No 500 0.1 20 41% (Grierson et al., 2009)
Yes 300e450 0.1 30 35e55% (Babich et al., 2011)
Yes 500 0.1 29e36% (Campanella and Harold, 2012)
FPY Bio-oil No 400e700 0.1 58e72% 27.9 (Belotti et al., 2014)
Bio-oil No 500 0.1 53% 24.57 (Wang et al., 2013)
SCG Syngas Yes 350 18 (Minowa and Sawayama, 1999)
Syngas Yes 400e700 24 (Chakinala et al., 2009)
Syngas Yes 500 36 (Onwudili et al., 2013)
Desmodesmus HTL Bio-oil No 300e350 60 41% 36.0 (Garcia Alba et al., 2011)
Dunaliella tertiolecta HTL Bio-oil Yes 300e340 e 60 29% 35.2 (Minowa, 1995)
Yes 360 e 60 42% 37.0 (Shuping et al., 2010)
SPY Bio-oil No 500 0.1 20 24% e (Grierson et al., 2009)
Nannochloropsis HTL Bio-oil No 250e350 60 38% 38.3 (Brown et al., 2010)
No 350 60 35% 38.5 (Duan and Savage, 2010)
No 350 60 26% 34.5 (Biller and Ross, 2011)
SPY Bio-oil No 300e500  C 0.1 120 21e31% (Pan et al., 2010)
Yes 400  C 0.1 120 21e25% 32.2 (Pan et al., 2010)
GSF Syngas No 850  C 0.1 38.3 (Khoo et al., 2013)
No 850  C 0.1 (Sanchez-Silva et al., 2013)
No 600e850 0.1 (Duman et al., 2014)
SCG Syngas No 400e500 35 (Brown et al., 2010)
No 450e500 24 (Guan et al., 2012)
Yes 450 24 (Guan et al., 2013)
Scenedesmus HTL Bio-oil No 300 30 45% 35.5 (Vardon et al., 2011)
FPY Bio-oil No 440 0.1 22% 29.6 (Kim et al., 2014)
No 480 0.1 55% (Harman-Ware et al., 2013)
Spirulina HTL Bio-oil No 350 60 29% 36.8 (Biller and Ross, 2011)
No 300 60 35.5% 36.1 (Biller and Ross, 2012)
No 300 60 41% 34.2 (Jena and Das, 2011)
350 60 30% 34.7
No 300 30 31% 35.8 (Vardon et al., 2011)
SPY Bio-oil No 350 0.1 60 23% 29.30 (Jena and Das, 2011)
500 60 29% 33.62
GSF Syngas No 800 0.1 (Yang et al., 2013)
No 850e1000 0.1 (Hirano et al., 1997)
SCG Syngas Yes 400 30 (Stucki et al., 2009)

Abbreviations: HTL ¼ hydrothermal liquefaction; GSF ¼ gasification (conventional); SCG ¼ supercritical gasification; SPY ¼ short pyrolysis; FPY ¼ fast pyrolysis.

while the demand of particular products determines what method pretreatments such as drying, that are expensive and high energy-
should be used. In addition to bio-oil, secondary products appear in consuming. Indeed, microalgal water content is rather high, on
gaseous and solid phase. The gaseous phase is made of nitrogen, average about 80e90% on weight basis, and complete drying would
hydrogen, carbon monoxide, light hydrocarbons, carbon dioxide end in a great efficiency penalty. Moreover, the small size of
(Brown et al., 2010), while the latter substantially consists of char microalgae particles makes thermal transfer faster, thereby
and ashes. Biocrude, in turn, undergoes a further upgrading process benefitting the process conditions. Of course, these facts imply an
to obtain distillate fractions in the same range of petroleum- easier implementation and reduced costs.
derived fuels. Dealing with microalgae, average HTL biocrude yield is between
When the temperature is lower than 250  C, the process yields 38%w and 64%w on a dry and ash-free basis, corresponding to en-
hydrochar as the main product, a matter, which is similar to coal. In ergy efficiency in the range 60e78% (Elliott et al., 2013; Jazrawi
this event, the process is referred to as hydrothermal carbonization. et al., 2013). In detail, as reported in the literature, performing
When microalgae are concerned, hydrochar comes mostly from the HTL at 300  C on a Botryococcus braunii substrate (Dote et al., 1994),
carbohydrate and protein fractions, enabling the lipid extraction achieved a maximum biocrude yield of 64% (weight fraction on a
prior the carbonization phase (Heilmann et al., 2010). Conversely, dry basis). Similarly, Dunaliella tertiolecta (Minowa, 1995) yielded
for temperature higher than 380  C, the process is dominated by 42% biocrude on a weight dry basis. Also, the feedstock being uti-
gasificationelike reactions, thereby yielding syngas as the main lized is known to bring about alterations corresponding to the
product. Hence, in these conditions, the process is defined as hy- heating value of the biocrude. Referring to the studies already
drothermal gasification. Hydrothermal gasification presents some mentioned, biocrude from Botryococcus braunii estimated HHV is
advantages over HTL, since the produced synthetic gas does not 45.9 MJ/kg, while for Dunaliella tertiolecta HHV is lower, about
contain nitrogen, with clear advantages in terms of energy density. 35 MJ/kg. A higher bio-oil yield (42%w) from the latter strain was
Hydrothermal processing is a promising method for the complete observed in the conditions tested by Shuping et al. (2010), i.e.,
conversion of algae under wet conditions. Compared to other Na2CO3 catalyst at 360  C. Furthermore, in a work by Biller and Ross
conversion paths, hydrothermal processes do not require feedstock (2011), HTL biocrude was studied for several microalgae strains: in
 T. Mathimani et al. / Journal of Cleaner Production 208 (2019) 1053e1064 1059

particular, at a temperature of 350  C and 1-h residence time, pyrolysis reactor is of the order of magnitude of one hour with low
Chlorella, Spirulina and Nannochloropsis exhibited bio-oil yields heating rate (5e10  C min1), the process is referred to as slow
equal to 33%w, 29%w and 26%w respectively. With regard to energy pyrolysis. However, progress in pyrolysis technology indicates that
density, the best result in terms of HHV was scored in the trial with fast pyrolysis (residence time of a few seconds, with heating rate up
Spirulina (36.8 MJ/kg), yet the other feedstock produced a bio-oil to 600  C min1) is more favorable towards the realization of a
with a slight lower HHV (approximately 35 MJ/kg). In the same continuous process. The main pyrolysis products are bio-oil, solid
operating conditions, Scenedesmus dimorphous gave a bio-oil yield char and noncondensable gases (called pyrogas or generally
of 27%, as reported in Biller and Ross (2012). Microalgae of the same syngas).
strain processed at a lower temperature (300  C) and a shorter The utilization of microalgae has some advantages over lingo-
duration (30 min) gave a better yield according to the work by cellulosic feedstock since bio-oils produced from microalgae were
Vardon et al. (2011). Similarly, a temperature of 300  C produced found to be more stable. Again, the kind of microalgae strain,
higher yields in the case of Chlorella and Spirulina (46.6%w and together with the operating parameters determine the quality of
35.5%w respectively) as demonstrated by Biller and Ross (2012) and the produced bio-oil. Dealing with slow pyrolysis in fixed bed
Spirulina is also showed the similar results as reported by Jena and reactor for Spirulina platensis (Jena and Das, 2011), yielded a bio-oil
Das (2011). The hydrotreatment of bio-crude produced by contin- about 29%w. The best yield observed is related to a reaction tem-
uous flow reactor system is conducted using C and gamma perature of 500  C and a residence time of 1 h. Then Grierson et al.
aluminium oxide supported, Pt, Pd, Ru and NiMo (5% load) cata- (2009), analysed the potential applications of Dunaliella tertiolecta,
lysts. The higher upgraded bio-crude yield over 60% was obtained while performing experiments at 500  C. With a residence time of
through NiMo/Al2O3 catalyst and upgraded bio-crude showed 20 min, the bio-oil yield from Dunaliella tertiolecta resulted in 24%w.
improved HHV (38.36e45.40 MJ/kg) due to the low oxygen content In the same study, upon the same operating conditions, the authors
(Patel et al., 2017). The Cyanidioschyzon merolae biomass was sub- found that Chlorella vulgaris provides a better bio-oil yield that is
jected for HTL at reaction temperatures between 180 and 300  C 41% w. Bio-oil yield from Chlorella could be further enhanced by the
with two base and acid catalysts on bio-crude yield. The high bio- aid of a catalyst in the reactor fixed bed. Babich et al. (2011) proved
crude yield of 16.98% was noticed at 300  C without catalyst and the this, scoring a bio-oil yield up to 55%w using a Na2CO3 catalyst
yield was increased to 22.67% with the addition of KOH catalyst (maximum temperature 450  C, residence time 30 min), However,
(Muppaneni et al., 2017). In another study, a 50 mL autoclave fast pyrolysis results had witnessed a higher yield of bio-oil. For
reactor was used for direct liquefaction of low-lipid cyanobacte- instance Belotti et al. (2014), reported a bio-oil yield in the range of
rium Spirulina using ethanol and water as co-solvent and the 58e72%w, corresponding to a temperature frame between 400  C
standardized operating conditions for higher conversion rate and 700  C. Similarly Wang et al. (2013), obtained a 53%w bio-oil
(94.73%) and bio-oil yield (59.5%) were 300  C temperature, 45 min yield for Chlorella (residues, after lipid extraction), operating a
time, 50% ethanol (Ji et al., 2017). In a very recent research, wet fluidized bed at 500  C. A similar outcome (bio-oil yield 55%w at
Scenedesmus obliquus biomass was converted into bio-crude with/ 480  C) is presented in the work by Harman-Ware et al. (2013),
without catalyst aid carried out at different temperatures; 200, 250, where results concerning fast pyrolysis of Scenedesmus in a fluid-
300  C, pressure; 100, 200, 300 bar and holding time; 30, 60 min. At ized bed. For the same microalgae strain, but at lower temperatures
300  C, and 200 bar pressure, 35.7% bio-crude was obtained in (Kim et al., 2014), found a less encouraging result, which is a bio-oil
60 min time without catalyst and however the yield is increased to yield of just 22%w. In the last results mentioned, no catalyst was
45.1% by addition of CH3COOH as a catalyst to the HTL reactor added to the reaction bed.
compared to other acid and base (Koley et al., 2018). In addition, In order to exploit the potential of pyrolysis in microalgae
impact of CO2 as a reaction medium on HTL efficiency of Arthrospira conversion, the process has to be enhanced towards a higher bio-oil
platensis was studied and results revealed that addition of CO2 yield and a curtailment of process residence time. This may be
reduced nitrogen containing species from 63 to 59% and oxygen addressed through the development of more performing catalysts.
containing species from 31 to 27% in the produced bio-crude (Choi Moreover, another interesting path that pushes through a wider
et al., 2017). In order to improve the HTL process efficiency, influ- implementation of pyrolysis, is the utilization of bio-char, and its
ence of cost-effective catalyst (Fe/HZSM-5) was studied using properties can be turned into an excellent raw material for other
Nannochloropsis biomass and the results showed that higher bio- processes e for instance adsorptive cleaning in fuel processing, or
crude yield of 38.1% was attained at 365  C in the presence of Fe/ renewable support for advanced batteries (Baldinelli et al., 2018).
HZSM-5 catalyst compared to uncatalyzed reaction (Liu et al., To improve the yield and quality of bio-oil, ceria based catalysts
2018b). Also, Fe/HZSM-5 regulates the migration and distribution were used for the pyrolysis of Tetraselmis sp. and Isochrysis sp. in a
of carbon and nitrogen elements during the HTL i.e., increased fixed bed reactor and maximal bio-oil yield was observed with the
content of carbon and nitrogen in biocrude and aqueous phase was addition of NieCe/Al2O3 and NieCe/ZrO2 catalysts and further it had
seen respectively (Liu et al., 2018a). In addition to above, effect of improved HHVs of 34e35 MJ/kg. Further, bio-oil obtained through
palladium-based catalysts on the bio-crude yield Spirulina was ceria catalyst contains lower oxygen content, and higher aliphatic
studied. High bio-oil yield of 37.30% and low coke yield of 8.56%, compounds (Aysu et al., 2016). As reported, the kinetics of pyrolytic
was observed with Pd/HZSM-5@MS catalyst and the experimental process can also be calculated using non-isothermal thermogravi-
results suggested that Pd/HZSM-5 promoted hydrodenitrogenation metric analysis at various heating rates and the several kinetic
and Pd/HZMS-5@MS promoted hydrodeoxygenation of the bio-oil methods were adopted for pyrolysis of Chlorella vulgaris, Nanno-
and eventually, the performance of the recycled catalysts were chloropsis limnetica, Nannochloropsis gaditana, Spirulina platensis,
also studied (Liu et al., 2018a). Isochrysis galbana, Phaeodactylum tricornutum (Soria-Verdugo et al.,
2018). Recently, non-isothermal pyrolysis was carried out for a red
4.2. Pyrolysis algal species Porphyra tenera through thermogravimetric analysis
with two types of analytical pyrolyzer (Kim et al., 2018).
Pyrolysis is the thermal decomposition of biomass at high
temperature (400e600  C), in an atmospheric-pressure inert 4.3. Gasification
environment. Nonetheless, it might still increase up to 800  C in the
event of microwave pyrolysis. When biomass residence time in the Gasification is a well-known method to process a wide variety of
1060 T. Mathimani et al. / Journal of Cleaner Production 208 (2019) 1053e1064

feedstock. Low-moisture feedstocks such as lignocellulosic biomass integrated system to convert algae to hydrogen is established for
are particularly suitable for this process. Despite that, microalgae attaining maximal total energy efficiency and the combined system
are not among the conventional type of biomass used for this mainly contains supercritical water gasification, separation of
purpose, there is evidence of the possibility to implement gasifi- hydrogen, hydrogenation, combined cycle. In this process, at first
cation to convert them into a valuable fuel. Gasification processes algal biomass is converted to hydrogen-rich syngas by supercritical
for microalgae can be branched as conventional gasification and water gasification process and the hydrogen produced via hydrogen
supercritical gasification. The conventional process consists of the separation process is hydrogenated to attain appropriate storage
partial oxidation of biomass, which is performed providing a gasi- and transport. Eventually, remaining gas is combusted using com-
fication medium, i.e. air, oxygen, steam. Usually, the whole process bined cycle for power generation and the whole combined system
realized into a gasifier, is made of some steps occurring in tem- achieve high total energy efficiency >60% (Aziz, 2017).
perature range between 700 and 1000  C (Basu, 2010): (i) drying, to
remove the residual moisture; (ii) pyrolysis, to break the solid 4.4. Carbonization
structure of biomass into less complex molecules; (iii) oxidation, to
burn a portion of the incoming biomass and provide heat to sustain Carbonization refers to the conversion of organics to carbon or
further endothermic processes; and, finally, (iv) gasification, to carbon-rich residue. Carbonization is an exothermic reaction dur-
convert pyrolysis products into smaller molecules with a high en- ing which heat is released out of the system. With the technological
ergy value. Hence, the process delivers the products of the syn- advancements, technical issues including costs for algal cultivation
thetic gas mixture (usually called syngas), residual char and tars, could be sorted out, especially when wastewaters are used.
and waste ashes. On average, syngas is a mixture of hydrogen, Recently, carbon-rich compounds had gained adequate interests in
carbon monoxide, carbon dioxide, methane with a low heating the market and a revision of policies would bring benefit to
value of about 3e10 MJ Nm3. Depending on the gasifier design microalgae carbonization. There are studies which report that
adopted and the kind of feedstock processed, the quality and the gravimetric yields can reach to 60% on a weight basis in less than
distribution of the products is subject to a sensible variation. For 1 h at 200  C and 20 bar, therefore it seems that there is potential
instance, literature reports that performing the steam-gasification considering the carbonization of algae in the future (He et al., 2013;
of Nannochloropsis gaditana at 850  C (Sanchez-Silva et al., 2013), Heilmann et al., 2011). The higher heating value (HHV) of the algal
obtained a syngas mixture featuring 46% H2, 33% CO, 12% CO2 and biochar is around 30 MJ/kg, which is equivalent to coal and other
less than 5% CH4. Processing the residue of Nannochloropsis oculata fossil fuel. For that, algal biochar is a strong alternative to ensure
in a fixed-bed steam gasifier (Duman et al., 2014), found a syngas energy security across the globe. Moreover, the energy demand in
mixture featuring, on average, 46% H2, less than 6% CO, 35% CO2 and carbonization is significantly lower than that of other thermo-
about 10% CH4. Likewise, in a study by Hirano et al. (1997) the chemical conversion technologies available today (Benavente et al.,
average syngas produced from Spirulina platensis exhibited the 2017). Nonetheless, the high nitrogen content and the costs asso-
following average composition: 42% H2, 14% CO, 34% CO2 and about ciated with algal cultivation lowers its applicability as a feedstock
10% CH4. In this work, mixed oxygen/steam gasification was per- for carbonization.
formed in the temperature range of 850e1000  C in a fluidized bed. Biochar absorbs hydrophobic lipids present in the mixture
Of course, the most prominent variations in terms of low heating where most of the triacylglyceride and fatty acids are retained in
value and gas composition occur when changing the oxidizing the hydrochar and recovered using solvent extraction principles.
medium. To this end, the results by Yang et al. (2013) with regard to However, the key disadvantage of this method is that the HHV is
the co-gasification of Spirulina platensis and woody biomass in an reduced when any of the lipid components is extracted from bio-
air-steam fluidized bed gasifier at 800  C revealed an average char (Lu et al., 2014). The chemicals present in biochar could be a
composition of 20% H2, 35% CO, 40% CO2 and less than 4% CH4. On possible mixture of sugars, amino acids in addition to hetero-cyclic
the contrary, supercritical gasification seems more suitable to compounds. During the carbonization, the aqueous phase contains
convert microalgae into a biofuel, for high water content of the carbohydrates and proteins where most of the cell walls are
feedstock that requires extensive drying in the event of conven- degraded to its monomeric forms facilitating easy recovery (Levine
tional gasification. Supercritical gasification occurs in an aqueous et al., 2013).
medium, showing similarities to hydrothermal liquefaction. Hence, Hydrothermal carbonization (HTC) is usually operated between
pressure and temperature are in the range of 24e36 MPa and 150 and 250  C at a pressure lower than 100 bars. With regard to
400e500  C respectively, considering supercritical conditions for different thermochemical techniques, HTC is a mild treatment
water. Therefore, in opposition to hydrothermal liquefaction which method, however, the residence times for this process is usually
is performed at subcritical conditions, supercritical water is able to longer (>1 h). The core objective in HTC is concentrating the carbon
decompose microalgal structure in smaller molecules, breaking the to a high-energy density solid fuel. The biochar obtained from the
CeC bonds that characterize the composition of hydrothermal HTC contains essential nutrients and minerals and therefore it can
liquefaction bio-oils. For that, the main product of supercritical be used as a fertilizer for agriculture. Apart from this, the HTC
gasification is a gas-phase mixture, mostly made of hydrogen, biochar can be used for applications such as water purification and
carbon monoxide, carbon dioxide and slight amounts of light hy- filtration, bioimaging, targeted drug delivery and sensors. In addi-
drocarbons (methane, propane…). Secondary products are tars, tion, HTC biochar can be used as energy storage medium, owing to
char and ashes. The presence of a catalyst might affect the final its energy density. The carbon content of biochar could range be-
composition of the product. Supercritical gasification of Nanno- tween 20% and 60%, which depends on the strain/species, pro-
chloropsis sp. at 450e500  C and 24 MPa, yields a syngas with an cessing methods and operating conditions. Bacteria are capable of
average composition of 32% H2, 30%, CO2 and 30% CH4, as reported producing high-quality char; however, yields are poor, whereas
by (Guan et al., 2012). In this juncture, adding a catalyst to the same blue-green algae have higher yields. Higher carbon concentration
process changes the results for example, with a Ru/C catalyst, the can be reached when operating at slightly harsh conditions; this
ratio between hydrogen and methane changes significantly, as calls for a process optimization and the trade-off between oper-
witnessed in Guan et al. (2012). Moreover, supercritical gasification ating at higher temperatures and higher carbon content needs to be
of Chlorella vulgaris with various catalysts was studied by Chakinala considered (Biller and Ross, 2012) for overall technological issues.
et al. (2009) and Onwudili et al. (2013). In a recent report, With reference to the carbon materials derived from
 T. Mathimani et al. / Journal of Cleaner Production 208 (2019) 1053e1064 1061

thermochemical processes, they can be widely used in different and Chlorococcum sp. have been widely used for biofuels produc-
fields, ranging from environment, industrial chemistry, biology and tion (Maity et al., 2014). Particularly, Haematococcus and Neo-
electrical engineering (Hu et al., 2010). First, thinking of environ- chlorosis strains are ideal for biodiesel while Chlorella, Scenedesmus
mental issues, applications fall into carbon sequestration technol- and Spirulina are pertinent for bio-methanol (Maity et al., 2014).
ogies, water purification and agriculture. A microalgae HTC-based Selection of algal strain is imperative for biofuels applications since
chain represents one of the most efficient way to achieve carbon marine microalgae have also been showcased as a promising source
concentration in a stable medium (the carbon material produced), for biodiesel. For example, marine microalgae C. vulgaris grown
starting from the growth of microalgae which is CO2 consuming. It under ambient condition was found to yield 22% lipid content and
is estimated that the carbon sequestration efficiency is close to one. also the biodiesel yield was 61% (Mathimani et al., 2015). Further,
While this might be true for all kinds of biomass, coming to the fuel properties of biodiesel produced from marine C. vulgaris
microalgae in particular, the quick rotation and growing rate make comply biodiesel standards. On the other hand, freshwater Chlorella
the application of this process really interesting as an active strain was ascertained to accumulate high lipid compared to cya-
method to reduce the atmospheric load of green-house gases and, nobacterial strains (Mathimani et al. 2016) In concern with the
at the same time, to store the CO2 in a stable and easy-to-handle productivity, Chlorella and Nannochloropsis strains were able to
solid residue (Hu et al., 2010). Then, about water purification, show above 100 mg/L/day lipid productivity (Maity et al., 2014).
thanks to their high porosity and composition, such carbon mate- Compounds extracted from microalgae are widely used in the food
rials can be applied as sorbents. In fact, scientists have found out industry as natural food colourants (Becker, 2013). They are used as
that their surface contains functional groups which acts as an ab- food supplements in the form of tablets, capsules and further, they
sorption sites for hazardous pollutants (viz. heavy metal ions, drugs can be used in pastas, snack foods, and beverages (Liang et al., 2004;
residues, pesticides etc.). Yamaguchi, 1996). Moreover, microalgae are nutritionally rich
owing to their diverse chemical composition; for example, Chlorella
4.5. Combustion vulgaris comprises of 51e58%, 12e17%, 14e22% of carbohydrate,
protein and lipid respectively (Spolaore et al., 2006). In the agri-
Combustion burns microalgae in the presence of oxygen at a cultural sector, algae can be used as biofertilizers and soil condi-
temperature around 850  C. Combustion occurs in boiler or furnace tioners owing to their capability to fix ambient nitrogen, thereby
where microalgal biomass could be loaded with a moisture content enhancing soil fertility (Song et al., 2005). It is a well-known that
>50%. Generally, the air pumped in a combustor is nearly 10% in algal biomass is used as nourishment for many animals and zoo-
excess with regard to the feedstock, in order to facilitate the release planktons (aquarium fish, ornamental birds, horses, and breeding
of heat and the completion of reactions. As harvested algal biomass bulls) since they are rich in proteins. Additionally, it is observed that
does not meet the requirements for combustion, it is essential to the immune response of animals was elicited when fed with
dry them to the desired moisture content, ideally no more than 20% Arthrospira, Chlorella, Dunaliella biomass (Pulz and Gross, 2004).
w. The chemical energy obtained using photosynthesis in the Among the various algal species, Arthrospira, Chlorella, Dunaliella,
microalgae is converted to hot gases during the combustion pro- Aphanizomenon, Haematococcus, and Crypthecodinium strains are
cess. The heat produced from the combustion cannot be stored and only commercialized for value-added products (Li et al., 2013). In
it has to be converted to a valuable product, for instance, electricity addition to fuel production, various algae have been reported to
generation in a turbine. Cost of energy production using microalgae yield high-value products, which are widely used as nutraceuticals,
is higher mainly due to the impact of pre-treatment stages (see cosmeceutical, pharmaceuticals, lubricants, detergents, antioxi-
crushing and drying pre-processes). dants, pigments, for ex. agar, agarose, acetylic acids, alginates,
Due to the high moisture content of the algal biomass, com- lutein, b-carotene, PUFA, and vitamin B (Suganya et al., 2016).
bustion processes have been deeply explored. However, techno- Further, bioactive algal compounds of Arthrospira and Chlorella
logical developments on low-energy drying could potentially uplift have been used as water binders and antioxidants (Pulz and Gross,
the adherence of microalgae to combustion process (Medeiros 2004; Stolz, 2005).
et al., 2015). Other alternative are offered by the co-firing of algae
and either coal or natural gas, so as to simply mitigate greenhouse 6. Upgradation of bio-oil
gases emissions of fossil fuel sources. Indeed, carbon dioxide is
absorbed from the process and used for algal cultivation (Chen In thermochemical processes, there are various challenges that
et al., 2015; Raheem et al., 2015). need to be addressed through in-depth research endeavor, such as
high nitrogen content and viscosity of bio-oil and undesirable
5. Biofuel and other bio-products from microalgae emission profile of bio-oil. Especially in HTL, albeit the higher bio-
oil obtained from algae, bio-oil still possesses high nitrogen, oxygen
Biofuels can be produced from sources such as oil crops, animal and sulfur heteroatoms (Peterson et al., 2008), and these hetero-
fats, used kitchen oils and algal biomass by means of biochemical atoms could be converted and emitted as NOx and SOx during
conversion and thermochemical conversion (Kumar et al., 2015). combustion.
Among the various biological resources, using algae as feedstock for Presence of long-chain fatty acid yield high-viscosity bio-oil
biofuels could help to achieve environmental sustainability. (40e100 cP at 50  C), which in turn contributes to poor cold flow
Nevertheless, the overall life-cycle sustainability not only depends property during transportation (Roussis et al., 2012). With this
on the resource, but it highly depends on the processes. Various context, the produced bio-oil need to be enhanced undergoing an
biofuels like biodiesel, bioethanol, hydrogen, methanol are ob- upgrading process (deoxygenation and Hydrotreating) to improve
tained from microalgae (Maity et al., 2014). Biodiesel e a non-toxic its characteristics before being used in refinery (Guo et al., 2015).
and safe fuel, featuring a higher flash point than diesel (usually There are various bio-oil upgrading processes such as hydrofining,
between 50 and 65  C, according to the hydrocarbon blend) - hydro-cracking, hydrogenolysis, catalytic cracking, emulsification/
contains 10% in-built oxygen, which ensures complete burning. It emulsions, steam reforming, solvent addition (Xiu and Shahbazi,
does not emit sulfur oxides and reduces levels of carbon monoxide, 2012). These further processes are meant to improve the bio-oil,
unburned hydrocarbons, and other pollutants (Hemaiswarya et al., which is able to satisfy standard requirements, notwithstanding
2012). Among all algal feedstocks, green algae such as Chlorella sp. the process variability ascribed to the heterogeneous feedstock
1062 T. Mathimani et al. / Journal of Cleaner Production 208 (2019) 1053e1064

used. For example, reforming and cracking decompose big mole- residence time, presence and absence of catalysts. Hence, most
cules to produce lower chain hydrocarbons, which are more likely thermochemical technologies would not yield a liquid product and
to go through a complete and fast conversion in the end use therefore, this might affect the transportation sector as it uses
application (for instance, in combustion engines). mostly liquid fuels. In this regard, in-depth research efforts are
Hydrotreating is the process in which hydrogen donors are used required to ascertain the ideal technique and its process design and
to stabilize the fragmented intermediate products by hampering optimization to attain high product yield. In addition, life cycle
condensation, cyclization, repolymerization, and thus increases the assessment of thermochemical conversion of microalgae need to be
bio-oil yield by decreasing tar and coke yield (Xu and Etcheverry, studied concerning energy efficiency of the process or energy bal-
2008). As reported by Eboibi et al. (2014), the bio-oil yield of Spir- ance of an entire process. There is a scope of bio-oil production
ulina sp. and Tetraselmis sp. was increased from 33e58% to 73% (97% using HTL processes, however, the technology is yet to be proven on
of deoxygenation) via upgradation process by vacuum distillation. a large scale. The future assessments of microalgae for thermo-
Further, increased bio-oil yield with higher hydrogen content and chemical technologies should include the following: 1. Assessment
H/C ratio was seen by addition of hydrogen (Duan and Savage, of emission, 2. Overall energy and economic balances, 3. Optimi-
2010). The high bio-oil yield is might be due to the hydrogenation zation of reaction parameters and 4. Technology and innovation. A
reaction in the surplus Hþ and OH ions, which were obtained from comprehensive assessment of triangular matrix involving tech-
water at 374  C temperature and 22.1 MPa and therefore enhances nology, economics and sustainability is necessary for different
the conversion of organic algal biomass molecules (Jena and Das, thermochemical technologies. Further, understanding of the ther-
2011). In addition, hydrogenation reaction enhances the bio-oil mochemical process and systematic optimization of operating
yield of N. salina from 55.6 to 78.5% (Li et al., 2014). Hydrogena- condition on the yield and quality of bio-crude is imperative.
tion/hydrorefining is a cheaper and commercialized upgrading Adding to the above, commercial possibility of the process need to
process used to remove nitrogen, oxygen and sulfur content of bio- be determined by developing pilot-scale plant.
oil in the form of NH3, H2O and H2S addition (Xiu and Shahbazi,
2012). Bio-oil upgradation is also done by using hydrogen donor 8. Conclusion
solvent like Formic acid and acetic acid, which might be decom-
posed to H2 and CO to react with algal hydrolysates for enhancing Microalgae represent one of the possible players for a sustain-
bio-crude (Guo et al., 2015). Hydrocracking is also one of the able energy production. Being a short-rotation kind of biomass,
nondestructive, upgrading process carried out at 394  C and 70 bar they appear very promising in the realization of a carbon-neutral
pressure, in which, light hydrocarbons like naphtha and diesel were energy conversion path, achieving a biologic storage for sun po-
produced from the decomposition of heavy compounds (Zhu et al., wer. Though microalgal based fuel production is being underway, it
2013). Emulsification is one of the easiest upgrading techniques for is still hindered by economic issues due to expensive processing
bio-oil. It is a physical method and it consists of blending immis- methods. Hence, further research works are required to reduce the
cible bio-oil and diesel into a homogenous stable mixture. Surfac- cost of biomass processing techniques. In this frame, there are
tants may be added in certain quantity to improve the stability of thermochemical routes to produce bio-oil from microalgae
the emulsion (Chong et al., 2017). bypassing energy and cost expensive drying methods. With this
Steam reforming is a wide used industrial process. It is well context, this review highlights thermochemical methods with an
known in the refinery and metallurgic industry, for hydrogen pro- emphasis on biocrude production from microalgae. Thermochem-
duction from hydrocarbons. The process is usually driven by a ical processes produce various products including bio-crude, solid
catalyst and carried out at 700  C. Hence, it requires the addition of residue, gas, and aqueous phase products. The yield of these
high temperature steam, which makes the process highly endo- products obtained from gasification, pyrolysis, carbonization,
thermic. However, through steam addition, the overall yield of liquefaction methods have been comprehensively discussed and
hydrogen out of the original feedstock increases. Usually, it is finally, detailed insights on the different types of algal cultivation
combined with a Water Gas Shift Reactor (WGSR), in order to fully systems have been given.
oxidize carbon monoxide to carbon dioxide and further increase
the yield of hydrogen. Catalytic cracking is a thermal process used Acknowledgement
to break long-chain molecules into smaller ones.
The author Dr. T. Mathimani acknowledges Department of Sci-
7. Future perspectives ence and Technology - Govt. of India for awarding INSPIRE Faculty
(Grant no: DST/INSPIRE/04/2017/001922 & IFA17-LSPA87).
Single technology or a process cannot fulfil the entire needs of
humanity. Though open pond, and closed photobioreactor culti- References
vation systems are used, lucrative design is imperative for cost-
effective cultivation, and also ideal harvesting technique is indis- Amin, S., 2009. Review on biofuel oil and gas production processes from microalgae.
pensable for sustainable microalgal fuel production. Harvesting Energy Convers. Manag. 50, 1834e1840.
Ashokkumar, V., Rengasamy, R., 2012. Mass culture of Botryococcus braunii Kutz.
provides wet algal biomass slurry for further processing and under open raceway pond for biofuel production. Bioresour. Technol. 104,
application. So far in microalgae based fuel production, algal sus- 394e399.
pension needs to be harvested or dewatered and dried, which is a Aysu, T., Rahman, N.A.A., Sanna, A., 2016. Catalytic pyrolysis of Tetraselmis and
Isochrysis microalgae by nickel ceria based catalysts for hydrocarbon produc-
hassle in terms of energy balances and processing outlay, as water tion. Energy 103, 205e214.
needs to be eliminated from biomass. In this perspective, thermo- Aziz, M., 2017. Combined supercritical water gasification of algae and hydrogena-
chemical techniques came to use for the conversion of algal tion for hydrogen production and storage. Energy Procedia 119, 530e535.
Babich, I., Van der Hulst, M., Lefferts, L., Moulijn, J., O'Connor, P., Seshan, K., 2011.
biomass to fuel with its own advantages and disadvantages. The
Catalytic pyrolysis of microalgae to high-quality liquid bio-fuels. Biomass Bio-
key merits of thermochemical processing of microalgae include energy 35, 3199e3207.
direct conversion of biomass to fuel without any drying of biomass, Balat, M., 2011. Potential alternatives to edible oils for biodiesel productioneA re-
cost-effective, closed carbon cycle, and faster conversion than view of current work. Energy Convers. Manag. 52, 1479e1492.
Baldinelli, A., Dou, X., Buchholz, D., Marinaro, M., Passerini, S., Barelli, L., 2018.
biological methods. Thermochemical methods yield wide range of Addressing the energy sustainability of biowaste-derived hard carbon materials
products depending on the processing temperature, pressure, for battery electrodes. Green Chem. 20, 1527e1537.
 T. Mathimani et al. / Journal of Cleaner Production 208 (2019) 1053e1064 1063

Barreiro, D.L., Prins, W., Ronsse, F., Brilman, W., 2013. Hydrothermal liquefaction Biotechnol. Adv. 20, 491e515.
(HTL) of microalgae for biofuel production: state of the art review and future Guan, Q., Savage, P.E., Wei, C., 2012. Gasification of alga Nannochloropsis sp. in
prospects. Biomass Bioenergy 53, 113e127. supercritical water. J. Supercrit. Fluids 61, 139e145.
Basu, P., 2010. Biomass Gasification and Pyrolysis: Practical Design and Theory. Guan, Q., Wei, C., Ning, P., Gu, J., 2013. Catalytic gasification of algae Nanno-
Academic press. chloropsis sp. in sub/supercritical water. Procedia Environ. Sci. 18, 844e848.
Becker, E.W., 2013. Microalgae for Human and Animal Nutrition. Handbook of Guil-Guerrero, J.L., Guil-Laynez, J.L., Guil-Laynez, A., 2017. Bioprospecting for seed
Microalgal Culture: Applied Phycology and Biotechnology, pp. 461e503. oils from wild plants in the Mediterranean Basin for biodiesel production.
Belotti, G., de Caprariis, B., De Filippis, P., Scarsella, M., Verdone, N., 2014. Effect of J. Clean. Prod. 159, 180e193.
Chlorella vulgaris growing conditions on bio-oil production via fast pyrolysis. Guo, Y., Yeh, T., Song, W., Xu, D., Wang, S., 2015. A review of bio-oil production from
Biomass Bioenergy 61, 187e195. hydrothermal liquefaction of algae. Renew. Sustain. Energy Rev. 48, 776e790.
Benavente, V., Fullana, A., Berge, N.D., 2017. Life cycle analysis of hydrothermal Handler, R.M., Shi, R., Shonnard, D.R., 2017. Land use change implications for large-
carbonization of olive mill waste: comparison with current management ap- scale cultivation of algae feedstocks in the United States Gulf Coast. J. Clean.
proaches. J. Clean. Prod. 142, 2637e2648. Prod. 153, 15e25.
Benson, D., Kerry, K., Malin, G., 2014. Algal biofuels: impact significance and im- Harman-Ware, A.E., Morgan, T., Wilson, M., Crocker, M., Zhang, J., Liu, K., Stork, J.,
plications for EU multi-level governance. J. Clean. Prod. 72, 4e13. Debolt, S., 2013. Microalgae as a renewable fuel source: fast pyrolysis of Sce-
Biller, P., Ross, A., 2011. Potential yields and properties of oil from the hydrothermal nedesmus sp. Renew. Energy 60, 625e632.
liquefaction of microalgae with different biochemical content. Bioresour. He, C., Giannis, A., Wang, J.-Y., 2013. Conversion of sewage sludge to clean solid fuel
Technol. 102, 215e225. using hydrothermal carbonization: hydrochar fuel characteristics and com-
Biller, P., Ross, A.B., 2012. Hydrothermal processing of algal biomass for the pro- bustion behavior. Appl. Energy 111, 257e266.
duction of biofuels and chemicals. Biofuels 3, 603e623. Heilmann, S.M., Davis, H.T., Jader, L.R., Lefebvre, P.A., Sadowsky, M.J., Schendel, F.J.,
Blengini, G., Brizio, E., Cibrario, M., Genon, G., 2011. LCA of bioenergy chains in Von Keitz, M.G., Valentas, K.J., 2010. Hydrothermal carbonization of microalgae.
Piedmont (Italy): a case study to support public decision makers towards Biomass Bioenergy 34, 875e882.
sustainability. Resources. Conserv. Recycl. 57, 36e47. Heilmann, S.M., Jader, L.R., Harned, L.A., Sadowsky, M.J., Schendel, F.J., Lefebvre, P.A.,
Borowitzka, M.A., 1999. Commercial Production of Microalgae: Ponds, Tanks, and Von Keitz, M.G., Valentas, K.J., 2011. Hydrothermal carbonization of microalgae
Fermenters, Progress in Industrial Microbiology. Elsevier, pp. 313e321. II. Fatty acid, char, and algal nutrient products. Appl. Energy 88, 3286e3290.
Branyikova , I., Mars
alkov a, B., Doucha, J., Branyik, T., Bisov a, K., Zachleder, V., Hemaiswarya, S., Raja, R., Carvalho, I.S., Ravikumar, R., Zambare, V., Barh, D., 2012.
Vítova , M., 2011. Microalgaednovel highly efficient starch producers. Bio- An Indian scenario on renewable and sustainable energy sources with emphasis
technol. Bioeng. 108, 766e776. on algae. Appl. Microbiol. Biotechnol. 96, 1125e1135.
Brown, T.M., Duan, P., Savage, P.E., 2010. Hydrothermal liquefaction and gasification Hirano, A., Ueda, R., Hirayama, S., Ogushi, Y., 1997. CO2 fixation and ethanol pro-
of Nannochloropsis sp. Energy Fuels 24, 3639e3646. duction with microalgal photosynthesis and intracellular anaerobic fermenta-
Campanella, A., Harold, M.P., 2012. Fast pyrolysis of microalgae in a falling solids tion. Energy 22, 137e142.
reactor: effects of process variables and zeolite catalysts. Biomass Bioenergy 46, Hu, B., Wang, K., Wu, L., Yu, S.H., Antonietti, M., Titirici, M.M., 2010. Engineering
218e232. carbon materials from the hydrothermal carbonization process of biomass. Adv.
Chakinala, A.G., Brilman, D.W., van Swaaij, W.P., Kersten, S.R., 2009. Catalytic and Mater. 22, 813e828.
non-catalytic supercritical water gasification of microalgae and glycerol. Ind. Huang, H., Yuan, X., Zeng, G., Wang, J., Li, H., Zhou, C., Pei, X., You, Q., Chen, L., 2011.
Eng. Chem. Res. 49, 1113e1122. Thermochemical liquefaction characteristics of microalgae in sub-and super-
Chen, W.-H., Lin, B.-J., Huang, M.-Y., Chang, J.-S., 2015. Thermochemical conversion critical ethanol. Fuel Process. Technol. 92, 147e153.
of microalgal biomass into biofuels: a review. Bioresour. Technol. 184, 314e327. Jazrawi, C., Biller, P., Ross, A.B., Montoya, A., Maschmeyer, T., Haynes, B.S., 2013. Pilot
Chisti, Y., 2013. Raceways-based production of algal crude oil. Green 3, 195e216. plant testing of continuous hydrothermal liquefaction of microalgae. Algal Res.
Chisti, Y., 2016. Large-scale Production of Algal Biomass: Raceway Ponds, Algae 2, 268e277.
Biotechnology. Springer, pp. 21e40. Jena, U., Das, K., 2011. Comparative evaluation of thermochemical liquefaction and
Choi, D., Lee, J., Tsang, Y.F., Kim, K.-H., Rinklebe, J., Kwon, E.E., 2017. Modification of pyrolysis for bio-oil production from microalgae. Energy Fuels 25, 5472e5482.
hydrothermal liquefaction products from Arthrospira platensis by using carbon Ji, C., He, Z., Wang, Q., Xu, G., Wang, S., Xu, Z., Ji, H., 2017. Effect of operating con-
dioxide. Algal Res. 24, 148e153. ditions on direct liquefaction of low-lipid microalgae in ethanol-water co-sol-
Chong, Y., Thangalazhy-Gopakumar, S., Ng, H.K., Ganesan, P.B., Gan, S., Lee, L.Y., vent for bio-oil production. Energy Convers. Manag. 141, 155e162.
Manickavel, V., Ong, C., Al Hinai, H., 2017. Emulsification of bio-oil and diesel. Junying, Z., Junfeng, R., Baoning, Z., 2013. Factors in mass cultivation of microalgae
Chem. Eng. Trans. 56, 1801e1806. for biodiesel. Chin. J. Catal. 34, 80e100.
Costa, J.A.V., De Morais, M.G., 2011. The role of biochemical engineering in the Khoo, H., Koh, C., Shaik, M., Sharratt, P., 2013. Bioenergy co-products derived from
production of biofuels from microalgae. Bioresour. Technol. 102, 2e9. microalgae biomass via thermochemical conversionelife cycle energy balances
Cuaresma, M., Janssen, M., Vílchez, C., Wijffels, R.H., 2011. Horizontal or vertical and CO2 emissions. Bioresour. Technol. 143, 298e307.
photobioreactors? How to improve microalgae photosynthetic efficiency. Bio- Kim, S.W., Koo, B.S., Lee, D.H., 2014. A comparative study of bio-oils from pyrolysis
resour. Technol. 102, 5129e5137. of microalgae and oil seed waste in a fluidized bed. Bioresour. Technol. 162,
Day, J.G., Slocombe, S.P., Stanley, M.S., 2012. Overcoming biological constraints to 96e102.
enable the exploitation of microalgae for biofuels. Bioresour. Technol. 109, Kim, Y.-M., Han, T.U., Lee, B., Watanabe, A., Teramae, N., Kim, J.-H., Park, Y.-K.,
245e251. Park, H., Kim, S., 2018. Analytical pyrolysis reaction characteristics of Porphyra
De˛ bowski, M., Zielin  ski, M., Krzemieniewski, M., Dudek, M., Grala, A., 2012. tenera. Algal Res. 32, 60e69.
Microalgaeecultivation methods. Pol. J. Nat. Sci. 27, 151e164. Koley, S., Khadase, M.S., Mathimani, T., Raheman, H., Mallick, N., 2018. Catalytic and
Demirbas, A., Demirbas, M.F., 2011. Importance of algae oil as a source of biodiesel. non-catalytic hydrothermal processing of Scenedesmus obliquus biomass for
Energy Convers. Manag. 52, 163e170. bio-crude productioneA sustainable energy perspective. Energy Convers.
Dote, Y., Sawayama, S., Inoue, S., Minowa, T., Yokoyama, S.-y, 1994. Recovery of Manag. 163, 111e121.
liquid fuel from hydrocarbon-rich microalgae by thermochemical liquefaction. Kumar, K., Mishra, S.K., Shrivastav, A., Park, M.S., Yang, J.-W., 2015. Recent trends in
Fuel 73, 1855e1857. the mass cultivation of algae in raceway ponds. Renew. Sustain. Energy Rev. 51,
Dragone, G., Fernandes, B.D., Vicente, A.A., Teixeira, J.A., 2010. Third generation 875e885.
biofuels from microalgae. Curr. Res. Technol. Educ. Topics Appl. Microbiol. Mi- Levine, R.B., Sierra, C.O.S., Hockstad, R., Obeid, W., Hatcher, P.G., Savage, P.E., 2013.
crobial Biotechnol. 2, 1355e1366. The use of hydrothermal carbonization to recycle nutrients in algal biofuel
Duan, P., Savage, P.E., 2010. Hydrothermal liquefaction of a microalga with het- production. Environ. Prog. Sustain. Energy 32, 962e975.
erogeneous catalysts. Ind. Eng. Chem. Res. 50, 52e61. Li, H., Hu, J., Zhang, Z., Wang, H., Ping, F., Zheng, C., Zhang, H., He, Q., 2014. Insight
Duman, G., Uddin, M.A., Yanik, J., 2014. Hydrogen production from algal biomass via into the effect of hydrogenation on efficiency of hydrothermal liquefaction and
steam gasification. Bioresour. Technol. 166, 24e30. physico-chemical properties of biocrude oil. Bioresour. Technol. 163, 143e151.
Eboibi, B.E.-O., Lewis, D.M., Ashman, P.J., Chinnasamy, S., 2014. Hydrothermal Li, Q., Du, W., Liu, D., 2008. Perspectives of microbial oils for biodiesel production.
liquefaction of microalgae for biocrude production: improving the biocrude Appl. Microbiol. Biotechnol. 80, 749e756.
properties with vacuum distillation. Bioresour. Technol. 174, 212e221. Li, T., Zheng, Y., Yu, L., Chen, S., 2013. High productivity cultivation of a heat-
Elliott, D.C., Hart, T.R., Schmidt, A.J., Neuenschwander, G.G., Rotness, L.J., resistant microalga Chlorella sorokiniana for biofuel production. Bioresour.
Olarte, M.V., Zacher, A.H., Albrecht, K.O., Hallen, R.T., Holladay, J.E., 2013. Process Technol. 131, 60e67.
development for hydrothermal liquefaction of algae feedstocks in a continuous- Liang, S., Liu, X., Chen, F., Chen, Z., 2004. Current Microalgal Health Food R & D
flow reactor. Algal Res. 2, 445e454. Activities in China, Asian Pacific Phycology in the 21st Century: Prospects and
Garcia Alba, L., Torri, C., Samorì, C., van der Spek, J., Fabbri, D., Kersten, S.R., Challenges. Springer, pp. 45e48.
Brilman, D.W., 2011. Hydrothermal treatment (HTT) of microalgae: evaluation Liu, C., Kong, L., Wang, Y., Dai, L., 2018a. Catalytic hydrothermal liquefaction of
of the process as conversion method in an algae biorefinery concept. Energy spirulina to bio-oil in the presence of formic acid over palladium-based cata-
Fuels 26, 642e657. lysts. Algal Res. 33, 156e164.
Grierson, S., Strezov, V., Ellem, G., Mcgregor, R., Herbertson, J., 2009. Thermal Liu, Z., Li, H., Zeng, J., Liu, M., Zhang, Y., Liu, Z., 2018b. Influence of Fe/HZSM-5
characterisation of microalgae under slow pyrolysis conditions. J. Anal. Appl. catalyst on elemental distribution and product properties during hydrother-
Pyrol. 85, 118e123. mal liquefaction of Nannochloropsis sp. Algal Res. 35, 1e9.
Grima, E.M., Belarbi, E.-H., Fern andez, F.A., Medina, A.R., Chisti, Y., 2003. Recovery of Loong, T.C., Idris, A., 2017. One step transesterification of biodiesel production using
microalgal biomass and metabolites: process options and economics. simultaneous cooling and microwave heating. J. Clean. Prod. 146, 57e62.
1064 T. Mathimani et al. / Journal of Cleaner Production 208 (2019) 1053e1064

Lu, Y., Levine, R.B., Savage, P.E., 2014. Fatty acids for nutraceuticals and biofuels from 1765e1775.
hydrothermal carbonization of microalgae. Ind. Eng. Chem. Res. 54, 4066e4071. Rawat, I., Kumar, R.R., Mutanda, T., Bux, F., 2013b. Biodiesel from microalgae: a
Maity, J.P., Bundschuh, J., Chen, C.-Y., Bhattacharya, P., 2014. Microalgae for third critical evaluation from laboratory to large scale production. Appl. Energy 103,
generation biofuel production, mitigation of greenhouse gas emissions and 444e467.
wastewater treatment: present and future perspectiveseA mini review. Energy Reyimu, Z., Izsimen, D., 2017. Batch cultivation of marine microalgae Nanno-
78, 104e113. chloropsis oculata and Tetraselmis suecica in treated municipal wastewater
Manninen, K., Huttunen, S., Sepp€ €, J., Laitinen, J., Spilling, K., 2016. Resource
ala toward bioethanol production. J. Clean. Prod. 150, 40e46.
recycling with algal cultivation: environmental and social perspectives. J. Clean. Ross, A., Biller, P., Kubacki, M., Li, H., Lea-Langton, A., Jones, J., 2010. Hydrothermal
Prod. 134, 495e505. processing of microalgae using alkali and organic acids. Fuel 89, 2234e2243.
Mata, T.M., Martins, A.A., Caetano, N.S., 2010. Microalgae for biodiesel production Roussis, S.G., Cranford, R., Sytkovetskiy, N., 2012. Thermal treatment of crude algae
and other applications: a review. Renew. Sustain. Energy Rev. 14, 217e232. oils prepared under hydrothermal extraction conditions. Energy Fuels 26,
Mathimani, T., Kumar, T.S., Chandrasekar, M., Uma, L., Prabaharan, D., 2017. 5294e5299.
Assessment of fuel properties, engine performance and emission characteristics Sanchez-Silva, L., Lo pez-Gonza lez, D., Garcia-Minguillan, A., Valverde, J., 2013. Py-
of outdoor grown marine Chlorella vulgaris BDUG 91771 biodiesel. Renew. rolysis, combustion and gasification characteristics of Nannochloropsis gaditana
Energy 105, 637e646. microalgae. Bioresour. Technol. 130, 321e331.
Mathimani, T., Beena Nair, B., Ranjith Kumar, R., 2016. Evaluation of microalga for Shuping, Z., Yulong, W., Mingde, Y., Kaleem, I., Chun, L., Tong, J., 2010. Production
biodiesel using lipid and fatty acid as a markereA central composite design and characterization of bio-oil from hydrothermal liquefaction of microalgae
approach. J. Energy Inst. 89, 436e446. Dunaliella tertiolecta cake. Energy 35, 5406e5411.
Mathimani, T., Uma, L., Prabaharan, D., 2015. Homogeneous acid catalysed trans- Silva, C., Ferreira, A., Dias, A.P., Costa, M., 2016. A comparison between microalgae
esterification of marine microalga Chlorella sp. BDUG 91771 lipidean efficient virtual biorefinery arrangements for bio-oil production based on lab-scale re-
biodiesel yield and its characterization. Renew. Energy 81, 523e533. sults. J. Clean. Prod. 130, 58e67.
Medeiros, D.L., Sales, E.A., Kiperstok, A., 2015. Energy production from microalgae Singh, J., Gu, S., 2010. Commercialization potential of microalgae for biofuels pro-
biomass: carbon footprint and energy balance. J. Clean. Prod. 96, 493e500. duction. Renew. Sustain. Energy Rev. 14, 2596e2610.
Minowa, T., Sawayama, S., 1999. A novel microalgal system for energy production Song, T., Mårtensson, L., Eriksson, T., Zheng, W., Rasmussen, U., 2005. Biodiversity
with nitrogen cycling. Fuel 78, 1213e1215. and seasonal variation of the cyanobacterial assemblage in a rice paddy field in
Minowa, T., Yokoyama, S.-y., Kishimoto, M., Okakura, T., 1995. Oil production from Fujian, China. FEMS Microbiol. Ecol. 54, 131e140.
algal cells of Dunaliella tertiolecta by direct thermochemical liquefaction. Fuel Soria-Verdugo, A., Goos, E., García-Hernando, N., Riedel, U., 2018. Analyzing the
74, 1735e1738. pyrolysis kinetics of several microalgae species by various differential and in-
Monari, C., Righi, S., Olsen, S.I., 2016. Greenhouse gas emissions and energy balance tegral isoconversional kinetic methods and the Distributed Activation Energy
of biodiesel production from microalgae cultivated in photobioreactors in Model. Algal Res. 32, 11e29.
Denmark: a life-cycle modeling. J. Clean. Prod. 112, 4084e4092. Spolaore, P., Joannis-Cassan, C., Duran, E., Isambert, A., 2006. Commercial applica-
Muppaneni, T., Reddy, H.K., Selvaratnam, T., Dandamudi, K.P.R., Dungan, B., tions of microalgae. J. Biosci. Bioeng. 101, 87e96.
Nirmalakhandan, N., Schaub, T., Holguin, F.O., Voorhies, W., Lammers, P., 2017. Stolz, P., 2005. Manufacturing microalgae for skin care. Cosmet. Toilet. 120, 99e106.
Hydrothermal liquefaction of Cyanidioschyzon merolae and the influence of Stucki, S., Vogel, F., Ludwig, C., Haiduc, A.G., Brandenberger, M., 2009. Catalytic
catalysts on products. Bioresour. Technol. 223, 91e97. gasification of algae in supercritical water for biofuel production and carbon
Nigam, P.S., Singh, A., 2011. Production of liquid biofuels from renewable resources. capture. Energy Environ. Sci. 2, 535e541.
Prog. Energy Combust. Sci. 37, 52e68. Suganya, T., Varman, M., Masjuki, H., Renganathan, S., 2016. Macroalgae and
Ogbonna, J.C., Soejima, T., Tanaka, H., 1999. An integrated solar and artificial light microalgae as a potential source for commercial applications along with bio-
system for internal illumination of photobioreactors. In: Progress in Industrial fuels production: a biorefinery approach. Renew. Sustain. Energy Rev. 55,
Microbiology. Elsevier, pp. 289e297. 909e941.
Onwudili, J.A., Lea-Langton, A.R., Ross, A.B., Williams, P.T., 2013. Catalytic hydro- Ugwu, C., Aoyagi, H., Uchiyama, H., 2008. Photobioreactors for mass cultivation of
thermal gasification of algae for hydrogen production: composition of reaction algae. Bioresour. Technol. 99, 4021e4028.
products and potential for nutrient recycling. Bioresour. Technol. 127, 72e80. Vardon, D.R., Sharma, B., Scott, J., Yu, G., Wang, Z., Schideman, L., Zhang, Y.,
Pan, P., Hu, C., Yang, W., Li, Y., Dong, L., Zhu, L., Tong, D., Qing, R., Fan, Y., 2010. The Strathmann, T.J., 2011. Chemical properties of biocrude oil from the hydro-
direct pyrolysis and catalytic pyrolysis of Nannochloropsis sp. residue for thermal liquefaction of Spirulina algae, swine manure, and digested anaerobic
renewable bio-oils. Bioresour. Technol. 101, 4593e4599. sludge. Bioresour. Technol. 102, 8295e8303.
Patel, B., Arcelus-Arrillaga, P., Izadpanah, A., Hellgardt, K., 2017. Catalytic hydro- Wang, C.-Y., Fu, C.-C., Liu, Y.-C., 2007. Effects of using light-emitting diodes on the
treatment of algal biocrude from fast hydrothermal liquefaction. Renew. Energy cultivation of Spirulina platensis. Biochem. Eng. J. 37, 21e25.
101, 1094e1101. Wang, K., Brown, R.C., Homsy, S., Martinez, L., Sidhu, S.S., 2013. Fast pyrolysis of
Peterson, A.A., Vogel, F., Lachance, R.P., Fro €ling, M., Antal Jr., M.J., Tester, J.W., 2008. microalgae remnants in a fluidized bed reactor for bio-oil and biochar pro-
Thermochemical biofuel production in hydrothermal media: a review of sub- duction. Bioresour. Technol. 127, 494e499.
and supercritical water technologies. Energy Environ. Sci. 1, 32e65. Xiu, S., Shahbazi, A., 2012. Bio-oil production and upgrading research: a review.
Piemonte, V., Di Paola, L., Iaquaniello, G., Prisciandaro, M., 2016. Biodiesel produc- Renew. Sustain. Energy Rev. 16, 4406e4414.
tion from microalgae: ionic liquid process simulation. J. Clean. Prod. 111, 62e68. Xu, C., Etcheverry, T., 2008. Hydro-liquefaction of woody biomass in sub-and super-
Pulz, O., Gross, W., 2004. Valuable products from biotechnology of microalgae. Appl. critical ethanol with iron-based catalysts. Fuel 87, 335e345.
Microbiol. Biotechnol. 65, 635e648. Yamaguchi, K., 1996. Recent advances in microalgal bioscience in Japan, with special
Raheem, A., Azlina, W.W., Yap, Y.T., Danquah, M.K., Harun, R., 2015. Thermochemical reference to utilization of biomass and metabolites: a review. J. Appl. Phycol. 8,
conversion of microalgal biomass for biofuel production. Renew. Sustain. En- 487e502.
ergy Rev. 49, 990e999. Yang, K.-C., Wu, K.-T., Hsieh, M.-H., Hsu, H.-T., Chen, C.-S., Chen, H.-W., 2013. Co-
Rastogi, R.P., Pandey, A., Larroche, C., Madamwar, D., 2018. Algal Green EnergyeR&D gasification of woody biomass and microalgae in a fluidized bed. J. Taiwan Inst.
and technological perspectives for biodiesel production. Renew. Sustain. Energy Chem. Eng. 44, 1027e1033.
Rev. 82, 2946e2969. Zhu, Y., Albrecht, K.O., Elliott, D.C., Hallen, R.T., Jones, S.B., 2013. Development of
Rawat, I., Bhola, V., Kumar, R.R., Bux, F., 2013a. Improving the feasibility of pro- hydrothermal liquefaction and upgrading technologies for lipid-extracted algae
ducing biofuels from microalgae using wastewater. Environ. Technol. 34, conversion to liquid fuels. Algal Res. 2, 455e464.