See discussions, stats, and author profiles for this publication at: https://www.researchgate.

net/publication/291385722

Review and experimental study on pyrolysis and hydrothermal liquefaction

of microalgae for biofuel production

Article  in  Applied Energy · January 2016

DOI: 10.1016/j.apenergy.2015.12.001

CITATIONS READS

41 180

5 authors, including:

David Chiaramonti Matteo Prussi

University of Florence RE-CORD Consortium
129 PUBLICATIONS   1,959 CITATIONS    56 PUBLICATIONS   756 CITATIONS   

SEE PROFILE SEE PROFILE

Marco Buffi Andrea Maria Rizzo

University of Florence University of Florence
32 PUBLICATIONS   110 CITATIONS    47 PUBLICATIONS   220 CITATIONS   

SEE PROFILE SEE PROFILE

Some of the authors of this publication are also working on these related projects:

HEAT-TO-FUEL View project

H2020 BECOOL View project

All content following this page was uploaded by Marco Buffi on 13 February 2018.

The user has requested enhancement of the downloaded file.

 Applied Energy 185 (2017) 963–972

Contents lists available at ScienceDirect

Applied Energy
journal homepage: www.elsevier.com/locate/apenergy

Review and experimental study on pyrolysis and hydrothermal

liquefaction of microalgae for biofuel production
David Chiaramonti a,⇑, Matteo Prussi a, Marco Buffi a, Andrea Maria Rizzo a, Luigi Pari b
a
Renewable Energy COnsortium for R&D, RE-CORD c/o Department of Industrial Engineering, School of Engineering, University of Florence, Viale Morgagni 40, I-50134 Florence, Italy
b
Consiglio per la Ricerca in Agricoltura e l’Analisi dell’Economia Agraria, Unità di Ricerca per l’Ingegneria Agraria, Rome, Italy

h i g h l i g h t s

A review of microalgae thermochemical conversion to bioliquids was carried out.

We focused on pyrolysis and hydrothermal liquefaction for biocrude/biofuels.

Original experimental research on microalgae pyrolysis was also carried out.

Starvation does not impact significant on the energy content of the biocrude.

This result is relevant for designing full scale microalgae production plants.

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

Article history: Advanced Biofuels steadily developed during recent year, with several highly innovative processes and
Received 16 June 2015 technologies explored at various scales: among these, lignocellulosic ethanol and CTO (Crude Tall Oil)-
Received in revised form 29 November 2015 biofuel technologies already achieved early-commercial status, while hydrotreating of vegetable oils is
Accepted 4 December 2015
today fully commercial, with almost 3.5 Mt/y installed capacity worldwide. In this context, microalgae
Available online 19 January 2016
grown in salt-water and arid areas represent a promising sustainable chain for advanced biofuel produc-
tion but, at the same time, they also represent a considerable challenge. Processing microalgae in an eco-
Keywords:
nomic way into a viable and sustainable liquid biofuel (a low-cost mass-product) is not trivial. So far, the
Microalgae
Downstream processes
most studied microalgae-based biofuel chain is composed by microorganism cultivation, lipid accumula-
Hydrothermal liquefaction tion, oil extraction, co-product valorization, and algae oil conversion through conventional esterification
Pyrolysis into Fatty Acids Methyl Esters (FAME), i.e. Biodiesel, or Hydrotreated Esters and Fatty Acids (HEFA), the
Biofuels latter representing a very high quality drop-in biofuel (suitable either for road transport or for aviation).
Bioliquids However, extracting the algae oil at low cost and industrial scale is not yet a mature process, and there is
not yet industrial production of algae-biofuel from these two lipid-based chains. Another option can
however be considered: processing the algae through dedicated thermochemical reactors into advanced
biofuels, thus approaching the downstream processing of algae in a completely different way than sep-
aration. The present work examines the possible routes for thermochemical conversion of microalgae
into liquid biofuels, distinguishing between dry-processes (namely Pyrolysis, PO) and wet-processes
(near critical-water HydroThermal Liquefaction, HTL). A literature review on algae-HTL was carried
out, distinguishing between batch and continuous experiments, and compared to original results from
algae pyrolysis. In particular, pyrolysis was carried out on both starved (lipid-accumulated) and non-
starved microalgae. Typical composition of major products is given for both PO and HTL, comparing
the main characteristic of the products.
Major engineering advantages and challenges in thermochemical conversion of algae into liquid biofu-
els were identified and discussed for both processes, in view of the production of a transport biofuel and
the full exploitation of this renewable feedstock in energy and biorefinery complexes.
Ó 2015 Elsevier Ltd. All rights reserved.

⇑ Corresponding author.
E-mail address: david.chiaramonti@re-cord.org (D. Chiaramonti).

http://dx.doi.org/10.1016/j.apenergy.2015.12.001
0306-2619/Ó 2015 Elsevier Ltd. All rights reserved.
964 D. Chiaramonti et al. / Applied Energy 185 (2017) 963–972
1. Introduction and scope of work
A large number of scientific works demonstrated that the pro-
duction of biofuels from microalgae is technically feasible [1], even
if not yet optimized: however, the achievement of a positive eco-
nomical and energy balance is still under demonstration [2–4].
Today, as well as probably in the short/medium-term, biofuels
from microalgae represent a niche area, with few existing commer-
cial applications in non-energy sectors: nutraceuticals/functional
foods, feed supplements, aquaculture, pigments, and polyunsatu-
rated fatty acids, diagnostic and fine chemicals. Micro-algae mar-
ket volume in 2004 was estimated equal to 5000 tons dry weight
per year, accounting for 1 Bill.€ economic value [5] (i.e. 200 €/kg
dry alga in average). Clearly, the conversion of algae to sustainable
biofuels has not yet reached commercial level, despite the large
potential offered by the algal feedstock. Among the main factors
limiting the development of algae markets, especially biofuels
and food, the most relevant ones are probably the biomass produc-
tion and processing costs, mostly due to the complexity of the cul-
tivation phase and the downstream processes required to extract
the high-value products in a biorefinery concept. Despite these
critical issues, and the actual light conversion (photosynthetic)
efficiency, algae biofuels are particularly attractive thanks to the
following major elements: (i) algae can be produced on marginal
or degraded lands, avoiding competition with traditional food
crops; (ii) algae are able to accumulate significant amounts of
lipids (for biodiesel, HVO, and other processes) or carbohydrates
(for bioethanol); (iii) algae can be grown without pesticides or her-
bicides; (iv) algae can grow in saline waters, thus without deplet-
ing fresh water resources; (v) algae can use carbon from flue gases;
(vi) they can be cultivated on wastewaters, where algae can also
find part of those nutrients needed to grow [6].
The development of an efficient microalgae-biofuel production
pathway is still a major challenge toward commercial deployment,
both from a strictly technical point of view as well as from an eco-
nomic one. Despite the high biomass production of microalgae per
unit of land (t ha1), energy consumption of biofuels from algae –
including harvesting and extraction – is a major limiting factor
for the economics balance and overall sustainability. The algae har-
vesting phase is responsible for a significant share of energy con-
sumption and it can account for a 20–30% of the total production
cost [7]. Downstream processing must separate very small cells
(1–50 lm) from a cultivation medium characterized by a very
low density of microorganisms (from 0.5 to 3 gr l1). Moreover,
there is no optimal solution for algae harvesting and downstream
processing, as each algae strain and product destination can set dif-
ferent technical specifications [8–10]. In fact, physical shape, cell
wall structure, and microorganism composition can show signifi-
cant variations even considering the same strain cultivated follow-
ing just two different procedures. The selection of the harvesting
method for a certain strain should be carried out taking into
account the specific downstream process. As various authors agree,
also the dewatering phase should be evaluated on the base of the
following thermochemical treatment, so to achieve a proper oper-
ation and reducing overall energy consumptions [7,11].
The approach to downstream processing of microalgae toward
biofuels and bio products can be very different. We can identify
two major possible pathways:

Microalgae are pre-processed, extracting the high added value
compounds as lipids and/or carbohydrates, and then biofuels
and biochemical are produced from the different fractions.

The entire microorganisms are processed in the cultivation
medium (wet processing), and bioliquids or intermediates are
produced.
While carbohydrates are interesting for ethanol production, so
far the lipid production for biodiesel has attracted the greatest
interest: the potential oil yield per unit of used land of microalgae
is 5–20 times higher that of palm oil (ton ha1 yr1) [12,13].
In a lipid-based approach toward diesel-like biofuels, as biodie-
sel and HVO (Hydrotreated Vegetable Oils), specific cultivation
techniques – such as Nitrogen and Phosphorous starvation can
improve the oil quantity and quality toward downstream pro-
cesses. In fact, depending on microalgae strain, removing nutrients
(such as Nitrogen) from the growth medium reduces the cell divi-
sion process, generating a ‘‘stress” effect that increase cell size and
accumulate lipids, as observed in Chlorella vulgaris [14] and
Nannochloropsis sp. Bondioli [15] showed that oil from starved
Nannochloropsis sp. F&M-M24 has suitable characteristics for bio-
diesel production: algae accumulated neutral lipids up to 50% of
the dry biomass, with triglycerides representing the most
abundant component. This algal oil – with the exception of a PUFA
– mostly fulfills chemical requirements for a feedstock to be
converted into biodiesel. However, lipids contained in microalgae
are located intracellular: this makes the oil extraction significantly
more complex than the extraction from conventional oil seeds,
such as sunflower or rape. In fact, mechanical pressing is not
applicable to microalgae [16]. After harvesting, the algae paste still
contains more than 80% water (on wet basis): this is a key element
for the selection of the following downstream processing methods.
Wet extraction can thus be adopted in order to avoid biomass dry-
ing and therefore save energy, improving the overall sustainability
[17].
However, dry extraction routes are today the more mature
technologically options: moreover, they separate the protein-rich
cake, a high added value co-products that contribute to improve
the economic performances of the system. Chemical solvent
extraction is the most common methods used to extract lipids from
oily seeds: the efficiency of the solvent extraction process is
strongly dependent on the specific algae strain under consideration
[18].
Wet extraction has the important advantage of avoiding the
drying step. In wet pathways, cell disruption can be based on
mechanical approaches (e.g., microwave, ultrasonication, high
pressure stresses, sudden changes of pressure, etc.), biological
approaches (e.g., use of enzyme for cell disruption, osmotic stres-
ses, etc.) or thermochemical processing (e.g. Hydro Thermal
Liquefaction).
Among the biological extraction methods, enzymatic extraction
degrades the cell wall, with relevant energy saving [19]. In fact,
even if cell membranes of several microalgae (such as Chlorella)
have very resistant layers, these can be degraded by the action of
a proper mixture of enzymes [20]. The advantages offered by the
enzymatic route are the mild reaction conditions and the high
selectivity: compared with mechanical methods, enzymatic meth-
ods thus exhibit very competitive performances [21]. The critical
element of this method is represented by the enzyme cost.
Hydrotreating can be economically competitive only if imple-
mented at large scale. Efforts have been done even to retrofit exist-
ing refineries to HVO, with a first installation entered in operation
in Porto Marghera, Venice.
Once the oil is extracted from the cells, the most diffused route
toward biofuels is the transesterification process, which generates
biodiesel, a mixture of Fatty Acid Methyl Esters (FAME). Biodiesel,
which consists of ‘‘oxygenated” components, can be blended with
fossil fuels only up to a certain percentage, and therefore subject to
the so called ‘‘blend wall” (7% v/v in the EU). Actually, biodiesel exhi-
bit several limitations, such as low oxidation stability, poor charac-
teristic at low temperatures, and it becomes a solvent at higher
blends. A way to overcome these limits, and to produce a very high
 D. Chiaramonti et al. / Applied Energy 185 (2017) 963–972
quality diesel-like biofuel from lipid-feedstock is represented by the
hydrotreatment of triglycerides. Hydroprocessing of vegetable oils/
lipids consist of hydrogenation of the double bonds existing in the oil
chains and the removal of Oxygen (through decarboxylation/decar
bonylation and hydrodeoxygenation, that produces straight chain
paraffins), followed by catalytic selective hydrocracking/isomeriza-
tion and separation of the different hydrocarbon cuts. This process
leads to a product consisting in a mixture of C15–C18 hydrocarbons,
sometimes named as ‘‘green diesel”, ‘‘renewable diesel” or ‘‘bio-
hydrogenated diesel”, fully compatible with fossil diesel [22]. Other
lighter liquid and gaseous fractions from the process consist in
hydrocarbons in the boiling point range of jet fuel or gasoline, and
propane [23,24]. Hydrotreating, as almost all biofuel technologies,
requires large scale production facilities in order to be economically
competitive, such as those developed by Neste Oil (NEXBTL) and
ENI–UOP (Ecofining). Both new dedicated HVO installations (Neste
Oil) and retrofitting of existing refineries (ENI–UOP) have been real-
ized in the last years in the EU and abroad. These systems already
investigated the use of algal oil in the process.
However, considering microalgae, and taking into account the
difficulties in extracting the lipids from the microorganisms, a pos-
sible alternative route is processing the whole algae stream. Ther-
mochemical processes are available both on dry (pyrolysis) as well
as on wet (hydrothermal liquefaction) phase: despite PO and HTL
pathways have been largely investigated for lignocellulosic feed-
stock, processing algae presents different challenges than lignocel-
lulosic biomass.
Rizzo et al. [25] already carried out a preliminary investigation
on the characterization of intermediate microalgae pyrolysis oil
from Chlorella and Nannochloropsis sp. at CREAR/RECORD facilities.
This work highlighted that algae pyrolysis oil exhibited interesting
properties as intermediate energy carrier, especially when com-
pared to oil from fast pyrolysis of lignocellulosic biomass (e.g. pine
chips): lower Oxygen content – thus a higher HHV, H/C ratio closer
to diesel, lower density and a mild basic pH. The same semi-batch
pyrolysis reactor has been used to further investigate the conver-
sion of algae biomass.
Recently, a continuous and increasing amount of studies and
research works were carried out on the subject of thermal treat-
ment of microalgae. This growing interest reflects the number of
funded research projects and industrial initiatives that entered into
operations in the last year, and the biorefining approach that is
currently being promoted and combines high added value products
with bioenergy components.
Raheem et al. [26] recently carried out a literature review on
microalgae processing through the thermochemical route to obtain
biofuels. They remarked how these studies indicate that microal-
gae pyrolysis oils are more stable and less oxygenated than pyrol-
ysis oils from lignocellulosic biomass. They also confirmed that the
liquefaction of microalgae is a very promising pathway to produce
higher quality bio oils, with calorific value close to those of petro-
leum oil. Previously, also Chen et al. [27] reviewed the thermo-
chemical conversion of microalgae. Silva et al. [28] compared
different routes to microalgae biofuels, namely microalgae pro-
cessed by solvent ultrasound-assisted extraction followed by lipids
transesterification, bio-oil from microalgae pyrolysis, and, slow
pyrolysis of lipid extraction leftovers. Carbon footprint of each
chain as well as product quality were discussed, as N content.
López-González et al. [29] made an assessment of pyrolysis and
combustion of microalgae and their oils from the energetic, eco-
nomic and environmental point of view, comparing Scenedesmus
sp. and N. gaditana.
Na et al. [30] studied rapid pyrolysis (in Py-GC/MS) of oleaginous
microalga, Chlorella sp. KR-1 with different triglyceride contents,
confirming the role of triglycerides in the biofuel characteristics,
and concluding that the triglycerides in the microalgae could be
965
extracted in the form of suitable raw materials for biofuels without
solvents by pyrolysis. Wang et al. [31] compared direct and indirect
pyrolysis of microalga Isochrysis. They concluded that defatted
microalgae pyrolysis represents a potential way to convert protein
and carbohydrate to biofuels, even if the increase of N-heterocyclic
compounds and phenols and a decrease for hydrocarbons were
observed. Zhao et al. [32] examined the effect of co-pyrolysis of
Isochrysis and Chlorella. There was no obvious difference in the
maximum biocrude yields for individual pyrolysis and co-
pyrolysis, but carboxylic acids decreased and N-heterocyclic com-
pounds increased in co-pyrolysis.
Studies also addressed the catalytic cand non-catalytic pyrolysis
of algae residues after lipid extraction. Murata et al. [33] investi-
gated the use pyrolysis of Botryococcus (B.) Braunii residue after
Botryococcus Braunii oil (Bot-oil) extraction. Using a Py-GC/MS sys-
tem coupled with H-ZSM-5 catalyst, they obtained 88.6% of hydro-
carbon, a significantly higher amount compared to the 35.2%
without catalyst. However, yields were in the range of 30%. Aysu
and Sanna [34] also analyzed catalytic (ceria-based) pyrolysis of
microalgae Nannochloropsis in a fixed bed reactor. The presence
of the catalyst allowed for higher retention of the initial energy
in the microalgae, as well as higher aliphatic and lower acids and
oxygen content, even if the highest bio-oil yield was slightly above
23% at best. Francavilla et al. [35] carried out fast pyrolysis exper-
iments on lipid-extracted microalga Dulaniella Tertiolecta, observ-
ing that the quality of obtained bio-oil still requires upgrading,
namely deoxygenation and denitrogenation. Char was also
obtained, but the surface area was almost negligible, thus hamper-
ing its potential use as sorbent.
As regards microalgae HTL, recently, Patel et al. [36] and Guo
et al. [37] carried out reviews on hydrothermal pretreatment of
microalgae and bio-oil production, identifying major achievements
and research needs. Yoo et al. [38] investigated the HTL of microal-
gae versus the quality of the produced oil and the energy return on
investment. Their major finding was that high-lipid containing
microorganisms are necessary to target transport fuels, and that
increasing the process conditions toward higher severity (i.e.
higher temperature) will determine higher yields but lower quality
liquids. Faeth et al. [39] previously demonstrated in a lab-scale
batch reactor that biocrudes of similar quality may be produced
in higher yields and in a fraction of the time previously thought
necessary, with the positive effects on plant capital costs thanks
from the reduced reactor volume.
Similarly to Wang et al. [31] for pyrolysis, Garcia Alba et al. [40]
previously suggested that HydroThermal Treatment (HTT) is most
suited as post-treatment technology in an algae biorefinery sys-
tem, after the wet extraction of high value products, such as
protein-rich food/feed ingredients and lipids. Yang et al. [41]
examined the behavior of low-lipid microalgae major components,
namely crude polysaccharides, crude proteins and their binary
mixtures, in HTL. The main outcome of the study was that while
polysaccharides provide only a small (less than 5%) contribution
to bio-oil and more than 60% were distributed in the aqueous
phase as water soluble organics, proteins have a major role on
bio-oil formation (maximum 16.29%). The higher energy recovery
was however observed from the mixture.
Jazrawi et al. [42] and Roussis et al. [43] investigated two stage
HTL, and and Costanzo et al. [44] recently compared this approach
versus single stage HTL in a lab-scale batch reactor, with the aim of
reducing nitrogen content in biocrude, increasing the nutrient con-
tent in the aqueous phase, and producing a biocrude that can be
co-processed in conventional oil refineries thanks to its lower N
and O content. Costanzo et al. [44] concluded that, given the signif-
icant reduction in biocrude yield observed for high protein algae,
the two-stage approach could be interesting for high-lipid content
microalgae.
966 D. Chiaramonti et al. / Applied Energy 185 (2017) 963–972
An important element of hydrothermal liquefaction of microal-
gae is represented by the water-phase, and its possibility of re-use
in the algae cultivation system itself. Xu and Savage [45] investi-
gated the water-soluble and water-insoluble fraction of HTL bio-
crude from microalgae, demonstrating the effect of reaction time
and algae loading. The aqueous phase of biocrude was reduced
increasing reaction time, while the water-insoluble fraction
increased with reaction time. Similar but larger effects were
observed at higher algae loading. Hognon et al. [46] compared
pyrolysis and HTL of Chlamydomonas reinhardtii, focusing on the
recovery of the aqueous medium for microalgae cultivation, a
key issue in industrial application of microalgae HTL. Pyrolysis
and HTL showed opposite trend in bio-oil yield at increasing tem-
perature, with pyrolysis improving from 400 °C to 550 °C and HTL
reducing from 220 °C to 310 °C. Tests on re-use of aqueous phase
for microalgae growth showed promising results, but they con-
cluded that the high organic carbon content may be toxic, and thus
water need to be treated.
The biocrude obtained from microalgae hydrothermal treat-
ment needs upgrading: among other, Wang et al. [47] recently
addressed the upgrade of HTL oil through hydrogen treatment
from microalgae grown in wastewater, showing that it is possible
to improve in this way the quality of the biocrude. They also
observed that some liquid products and sulfur were deposited in
the spent catalysts. Some authors, as Yang et al. [48] also investi-
gated aviation biofuels from microalgae, concentrating on the car-
bon distribution and comparing different process routes. Pyrolysis
and HTL lead to high bio-kerosene products.
It is finally important to remark that most of the past research
works addressed batch systems and autoclave experiments, while
hydrothermal treatment will necessarily be a continuous process
in industrial installations. In this respect, a recent work by Elliott
et al. [49] focused the attention on continuous-flow processing sys-
tems. In their review they elaborated process models and mass/
energy balances. However, they also observed that engineered sys-
tems so far did not yet achieved a demonstration scale: neverthe-
less, there is significant potential for commercialization of the
technology.
The present work focused on past selected works in the field of
thermochemical treatment of microalgae, specifically HTL, and
integrate these with original results from dedicated experimental
works of microalgae pyrolysis, investigating specifically selected
microorganism so to derive innovative conclusions on their energy
conversion.
2. Pyrolysis of algae
Pyrolysis is a thermochemical process which is normally carried
out at atmospheric pressure and temperature ranging from 300 to
700 °C and above, in complete absence of Oxygen. Main products of
pyrolysis are a solid (char), an organic liquid (crude oil) and a low
calorific value gas (pyrogas), in different ratios depending on pro-
cess conditions, reactor type and feedstock characteristics. Fast
and flash pyrolysis, characterized by high heating rate and short
vapor residence time, maximize liquid yield (pyrolysis oil, also
called bio-crude oil) when temperatures are in the range of
approximately 450–550 °C, with mass yield of the organic liquid
typically between 50% and 70% w/w [50]. Fast pyrolysis oil from
lignocellulosic biomass is an acidic and very complex liquid pro-
duct [51], easily subject to separation in different fractions. Feeding
a pyrolysis unit requires extensive drying of biomass at inlet, nec-
essary to achieve high heating rates in the reactor and adequate
temperature control, so to reduce phase separation during storage.
Pyrolysis oil is generally seen as an intermediate energy/chemical
carrier, suitable for further biorefining in downstream plants.
However, pyrolysis of algae feedstock present very different and
peculiar characteristics compared to lignocellulosic biomass: these
unique properties reflect in the pyrolysis product itself.
Fig. 1 shows a possible general scheme coupling microalgae
cultivation and pyrolysis process, while Fig. 2 describes a HTL-
based scheme. Following the cultivation stage, microalgae are
separated and then extensively dried (as required by the pyrolysis
process). Pyrolysis oil and char are the main products recovered
from the pyrolysis step, while the non-condensable gases can be
used to provide heat to the thermochemical process as well as to
dry the algae paste. Exhaust gases, recovered from the combustion
of non-condensable, can be used to supply up to 10% w/w of the
CO2 needed by the microorganism during cultivation (without
considering CO2 distribution efficiencies). This scheme will process
the whole algae stream, i.e. the entire alga composed by carbohy-
drates, proteins, lipids, and other remaining components as ash.
An alternative route could be based on biomass fractionation
just after the microalgae separation step. In this way, high added
value products can be recovered from the algae stream, and then
the remaining biomass/co-product can be fed to the pyrolyzer,
after drying.
Pyrolysis oil can be seen as an intermediate energy carrier, a
crude oil, or a chemical carrier, while the aqueous phase could be
recovered either through anaerobic digestion (AD), or sent to other
agronomic uses. Excess charcoal (the solid coproduct of pyrolysis,
used to provide heat to the process) could also be used as biochar
in the soil [52].
Scientific literature reports a significant number of experimen-
tal research works carried out on algae pyrolysis, confirming the
feasibility of pyrolysis oil production from microalgae [53–57].
Slow pyrolysis was investigated by Grierson et al. [58], that
considered six different microalgae species: oil yields range
between 24% and 43% w/w, with char yields ranging from 34% to
63% w/w. Pan et al. [59] studied the influence of temperature
and catalysts on of Nannochloropsis sp. under slow pyrolysis condi-
tions. In their work the oil yield ranged from 19% w/w with
catalyst to 31% w/w in presence of HZSM-5 catalysts. A further
advantage of using a catalyst was the higher heating value of the
obtained liquid product (32.7 MJ kg1). However, being charcoal
the main product from biomass slow pyrolysis, the interest in
using algae in combination with this process is today very
marginal.
Rizzo et al. [25] processed Chlorella sp. at 450 °C under interme-
diate pyrolysis conditions, obtaining a net yield of 34% w/w for liq-
uid and 29% w/w for char. Pyrolysis oil from Chlorella sp. showed
peculiar characteristics, being less oxygenated than lignocellulosic
PO (35 vs. 54% w/w), higher HHV (28.4 vs. 17.2 MJ kg1), lower
acidity (pH 9.2 vs. 2.3) and lower density (1 vs. 1.1–1.2 kg m3).
Fast pyrolysis has also been investigated with the aim of maxi-
mizing the algae bio crude oil yield. Miao et al. [60,61] studied fast
pyrolysis of several microalgae species, as Chlorella protohecoides
and Microcystis aeruginosa, obtaining oil yields ranging from
17.5% w/w to 23.7% w/w.
3. Algae HTL (hydrothermal liquefaction)
Hydrothermal liquefaction (HTL) can directly convert wet bio-
masses into liquid bio crude (or solid bio coal at less severe pres-
sure–temperature conditions) either with or without the use of a
catalyst [62]: after initial investigations years ago, as reported in
recent review works [63,64], HTL gained again the attention of
the researchers in recent years [65], when processing wet feed-
stock such as micro or macro algae, lignin from lignocellulosic
ethanol production, organic wastes or other highly wet organic
feedstock has become a very up-to-date issue.
 D. Chiaramonti et al. / Applied Energy 185 (2017) 963–972 967

Fig. 1. Scheme of possible microalgae–pyrolysis integrated process.

Fig. 2. Scheme of possible microalgae–HTL integrated process.

The thermochemical reaction take place on wet biomass in
water near critical conditions, i.e. process temperatures and pres-
sures around 280–370 °C and 10–25 MPa (<2 MPa: HTC) [66].
The HTL conversion efficiency of microalgae depends on various
parameters such as reaction temperature, residence time and feed-
stock composition. Differently from the algae-to-biodiesel path-
way, which essentially depends on the microalgae strain and
lipid contents, HTL and pyrolysis can be used to convert not only
the lipid fraction of microalgae, but also the other organic compo-
nents such as proteins and carbohydrates [67], either as a whole or
separated. The chemical properties of biocrude oil are directly
related to feedstock composition [44]. HTL oil contains approxi-
mately 10–20% w/w of Oxygen and Nitrogen, with energy density
in the range of 30–37 MJ kg1 [68]. Hydrothermal liquefaction of
microalgae thus appears to be a very interesting technology for
wet biomass processing and biofuel production, but not industri-
ally yet developed [64], with few and small scale continuous reac-
tor used for testing.
The typical HTL oil yield reported in several studies is equal to
approximately 50–60% w/w [67], depending also on the use of
homogeneous or heterogeneous catalysts. Minowa et al. [69] pub-
lished some results on hydrothermal liquefaction of microalgae (B.
braunii and D. tertiolecta) in a batch reactor fed with high concen-
tration of algae: 50–78.4% w/w. At 300 °C the oil yield was between
37% w/w and 64% w/w depending on the type of algae processed.
More recent research works investigated C. vulgaris and Chlorella
pyrenoidosa, Nannochloropsis occulata, Scenedesmus dimorphus, Por-
phyridium cruentum, Desmodesmus sp. as well as Chlorogloeopsis
fritschii and Spirulina cyanobacteria. These works demonstrated
that a wide range of microalgae can be processed in HTL reactors,
obtaining a mixture of Oxygenated hydrocarbons with a high mass
yield [40,62,70,71]. Zou et al. [72] investigated HTL of microalgae,
combined with wastewater treatment, demonstrating that both
low-lipid high-protein Nannochloropsis sp. (B) and high-lipid low-
protein Chlorella sp. (Y) can be efficiently converted to biocrude
oil. The observed highest yields were 55.0% and 82.9% respectively.
968 D. Chiaramonti et al. / Applied Energy 185 (2017) 963–972
The hydrocarbon content in biocrude was in the range of 6.7–29.8%
for Nannochloropsis sp. and 4.7–17.9% for Chlorella sp. Elliott et al.
[66] achieved high conversions yields even at high algae concen-
trations, up to 35% w/w of dry solids. Elliott et al. effectively
applied catalytic hydrotreating for hydride oxygenation, hydroden-
itrogenation, and hydrodesulfurization of the biocrude. An impor-
tant result of this study was that catalytic hydrothermal
gasification can be effectively applied for HTL bio-product water
clean-up, in order to allow nutrients recycle in algae growth ponds.
From an industrial and economic point of view, continuous
reactors are most likely needed for process scale-up, but several
technological challenges still have to be addressed. Continuous
reactors are fed at low concentration of solid (algae), in order to
avoid various technical problems as component plugging, deposi-
tions, etc. Jazrawi et al. [73] investigated Chlorella and Spirulina
with a loading factor between 1 and 10% w/w biomass, at 250–
350 °C, for 3–5 min residence time and 150–200 bar. The maxi-
mum biocrude yield was 41.7% w/w.
Most significant elements for the development of microalgae
HTL processes are related to the feeding stage, especially in terms
of aggregation state and load concentration, temperature, resi-
dence time, use of catalysts, product separation and water
recirculation.
4. Material and methods
4.1. Pyrolysis unit
A 1.5 kg h1 semi-continuous intermediate pyrolysis pilot unit
was designed and built at CREAR/RE-CORD-University of Florence.
The reactor consists of a cylindrical body made of corrosion resis-
tant stainless steel (AISI 310) externally heated by ceramic-shell
electrical resistors, able to heat and maintain the oxygen-free
nitrogen-blown reactive chamber up to 600 °C. Feedstock mixing
is promoted by paddles connected to a variable speed shaft. The
reactor presents three openings: one for biomass loading, a second
one for continuous extraction of pyrolysis vapors, and the last one
for discontinuous, manually operated, solid residue removal.
Vapors are cooled by a series of condensers. The mixture of non-
condensable gases are vented outside by an ATEX-certified blower.
A PID (proportional–integral–derivative) controller regulates pro-
cess temperature; data acquisition is performed continuously. A
scheme of the pilot unit is reported in Fig. 3.
Fig. 3. Scheme of the semi-continuos pyrolysis reactor [74].
The test procedure starts with reactor heating under a constant
Nitrogen flow of 4 l min1; the Nitrogen is injected by means of a
serpentine pipe coiled along the body of the reactor, so to maintain
the inlet Nitrogen temperature close to the reactor one. A mass of
10 kg of metal spheres of 22 mm diameter are to the reactor and
stirred by paddles, so to increase the biomass heating rate. Then,
as the system achieves steady conditions, the feedstock is fed in
batches of 20–40 g. Before loading the biomass into the reactor,
the material is flushed for 30 s with Nitrogen. The rotational speed
of the shaft driving the paddles in the reactor (fixed at 15 rpm) is
controlled by an inverter. The PID control then regulates the power
supplied to the resistors to keep the process temperature constant
during biomass thermochemical conversion. Once the material is
completely processed, paddle stirring is stopped and solid dis-
charge port opened, to un-load the reactor from solid residue
(char). Solids (char) are collected in a closed vessel purged with
Nitrogen, and then cooled down to room temperature before being
opened for material collection.
4.2. Analytical methods
Analyses on feedstock and bio-oils were carried out at the RE-
CORD chemical laboratory in Scarperia (Italy), and unless differ-
ently specified, all determinations were carried out in triplicates.
The content in Carbon, Hydrogen, Nitrogen and Sulfur (CHN + S)
was determined through a Leco TruSpec for Carbon, Hydrogen and
Nitrogen and a TruSpec Add-On Module for Sulfur according to an
internal lab method. Water content was measured according to
UNI EN ISO 8534, that specifies a method for the determination
of the water content of animal and vegetable fats and oils using
Karl Fischer apparatus and a reagent which is free of pyridine.
Ash content was determined with a Leco TGA 701 according to
UNI EN 14775 by heating up to 550 °C and holding there for at least
2 h 30 min. Ash content of pyrolysis products was measured by
heating the sample up to 750 °C and holding there for at least
1 h 30 min.
Higher heating value (HHV) was measured according to UNI EN
14918 for solid samples, or DIN 51900-2 for liquid samples, by
means of a Leco AC500 isoperibol calorimeter. The lower heating
value (LHV) was calculated according to UNI EN 14918, Sections
4.2 and 12.2. This value was derived from the HHV, providing that
the total hydrogen content of the moisture-free sample can be
determined by experiment (i.e. CHN analysis).
 D. Chiaramonti et al. / Applied Energy 185 (2017) 963–972 969

Density of liquids was measured at 20 °C by means of a cali-

brated glass hydrometer according to UNI EN ISO 3675.
Kinematic viscosity of pyrolysis liquids were measured accord-
ing to UNI EN ISO 3104 with a Lauda viscometer made by an Ubbe-
lohde capillary (k = 0.3) at several temperature between 20 and
60 °C. Each measurement was carried out at the selected tempera-
ture for five times: two times in order to precondition the capillary
tube, then the last three times for analyses: an interval of 90 s was
allowed between each measurement.
Acid value (TAN) was determined according to UNI EN 14104,
where the sample is dissolved into a solvent mixture and titrated
with a dilute solution of potassium hydroxide using phenolph-
thalein as indicator.

4.3. Mass yield, energy and carbon recovery

Bio-oil mass yield, carbon recovery and energy recovery were

calculated and compared for each tested feedstock.
Oil mass yield is calculated according to Eq. (1). Oil mass yield
(mass yield) is defined as the ratio of the recovered bio-oil
(mbio-oil), either as a whole or considering the water- and organic-
rich fractions collected, to the mass of feedstock (mfeed).
mbio-oil Fig. 4. Fine powder algae sample.
mass yield ¼ ð1Þ
mfeed
The energy recovery in the products was calculated according to Table 2
the following Eq. (2). Energy recovery (ER) is the ratio between HHV Algae processed and PO yield (centrifugation@2500 rpm, 20 min).
of the products (HHVbio-oil) multiplied by the products amount, on
Parameter Unit of measurement A B
the HHV of the feedstock (HHVfeed) multiplied by the feedstock
Processed biomass grdb 685 420
amount:
Raw oil yield gr 305 170
Raw oil yield % w/w 44.5 40.5
HHVbio-oil  mbio-oil
ER ¼ ð2Þ Water phase yield gr 54 20
HHVfeed  mfeed Organic phase yield gr 251 150
Organic phase yield % w/w 36.6 35.7

5. Experimental results
5.1. Characterization of microalgae
Two microalgae samples were analyzed and then fed to the
intermediate pyrolysis pilot unit. Both samples were originated
from the same strain of Nannochloropsis sp. F&M-M24, but culti-
vated according to two different protocols, either aimed to maxi-
mize the protein (case A) or the lipid content (case B) through
Nitrogen starvation. Table 1 reports the chemical characteristics
of the two feedstock on a dry base.
As expected, the most relevant difference between the two
samples relates to the Nitrogen content. In fact, sample A had
7.8% w/w Nitrogen (representing a total protein content of about
47%wt) and only 23% w/w of total lipids, while sample B had
3.8%wt Nitrogen content and a total lipid content of the
45% w/w. Fig. 4 shows the algae aggregation state.
The total amount of algal biomass fed to the pyrolysis reactor is
reported in Table 2 with the oil yield, and water/organic phases of
this.
Both oils were composed by two phases: a water rich phase and
an organic one. The amount of the organic phase for both batches,
after 20 min of centrifugation at 2500 RPM, was equal to approxi-
mately 36% w/w of the initial biomass. Oil main characteristics are
presented in Table 3.
These two pyrolysis oils mostly show similar characteristics:
however, they are considerably different from lignocellulosic bio-
mass pyrolysis oils or vegetable oils. While viscosity of algal PO
is comparable to lignocellulosic pyrolysis oils [25], pH (close to
7) represents a major difference from lignocellulosic biomass
Table 3
Characterization of pyrolysis oil from microalgae samples A and B.

Parameter A B Unit of Norm

Table 1 measurement
Elemental analysis of tested microalgae samples. Kinematic 30.9 31.8 mm2/s UNI EN ISO 3104
viscosity@40 °C
Parameter A B Unit of measurement Norm
pH 7.25 8.12 – –
Ashes 10.9 14.3 % w/wdb UNI 14775 Water content 19.4 16.7 % w/w UNI EN ISO 8534
C 52.1 53.9 % w/wdb UNI 15104 Higher heating value 29.3 28.2 MJ/kg DIN 51900-2
H 7.2 7.5 % w/wdb UNI 15104 Lower heating value 26.9 26.1 MJ/kg DIN 51900-2
N 7.8 3.8 % w/wdb UNI 15104 S 0.19 0.3 % w/w Internal method
S 0.7 0.6 % w/wdb UNI EN 15289 C 58.8 52.1 % w/w ASTM D 5291
O 21.3 19.6 % w/wdb Calc. by difference H 10.6 10.2 % w/w ASTM D 5291
Higher heating value 25.8 25.5 MJ/kgdb UNI 14918 N 4.0 5.8 % w/w ASTM D 5291
Lower heating value 24.3 23.9 MJ/kgdb UNI 14918 O 26.4 31.6 % w/w Calc. by
difference
db = dry basis
970 D. Chiaramonti et al. / Applied Energy 185 (2017) 963–972

Table 4 5.2 Pyrolysis and HTL process comparison

Balance of energy conversion.

Parameter Unit of measurement A B
Processed biomass gr 605
Biomass HHV MJ/kg db 25.8
Energy input (in biomass) MJ 15.6
Pyrolysis oil yield gr 251
Pyrolysis oil HHV MJ/kg 28.2
Pyrolysis oil energy output MJ 7.1
% of Energy yield in oil % 45.6
pyrolysis oil (around 2–3), having significant impact on materials
for reactor and plant construction as well as systems for oil use.
Also the water content, even if slightly below lignocellulosic oil,
still requires dewatering during upgrading: also the amount of
Oxygen and Nitrogen is considerable, and need reduction. The pos-
sibility of using catalytic (hydro)treatments to remove Oxygen and
Nitrogen in pyrolysis oil from microalgae C. vulgaris has already
been demonstrated by various authors, including López Barreiro
et al. [64] in a recent work. Interestingly, despite Oxygen, Nitrogen
and water content, the heating value of microalgae pyrolysis oil is
equivalent to approx 2/3 of the diesel oil and similar to other
widely diffused biofuels (as bioethanol).
Mass and energy balances of the process carried out at lab/pilot
scale are reported in Table 4: clearly, given the pilot scale of the
experimental facilities, the process is not optimized and/or
energy-integrated, and thus results could be largely further
improved.
The mass balance for the total oil collected, already given in
Table 2, is almost 36% w/w. The result is even more relevant in
terms of energy yield: in fact, while the primary energy input
(algae) is equal to 15.6 MJ for sample A, the energy yield is
7.1 MJ, corresponding to an energy conversion rate of approxi-
mately 46%. The same data for sample B are slightly lower, around
41%.
Another major results of these results is related to the effect of
the process on two microorganisms (feedstock) that either are
lipid-rich (starved culture) or carbohydrate/protein rich: in terms
of energy yield, no significant differences were observed in
pyrolyzing the two samples. In other terms, the collected data indi-
cate that, at least at this stage, no energy-yield advantages are pre-
sent in increasing the lipid content of the algae, expecially if it
generates a reduction in the algae plant productivity.
When comparing microalgae pyrolysis and HTL, some critical
420 issues for the pyrolysis step can be highlighted. Drying represents
25.5 a major critical point from a system perspective for pyrolysis: this
10.7 is particularly relevant for microalgae due to their extremely low
150 concentration in the cultivation medium (typically ranging from
29.3
4.4
10% to 20% even after harvesting and some pre- concentration
41.1 stage).
Table 5 reports a comparison among major physical and chem-
ical characteristics of algae pyrolysis oil, algae HTL oil, lignocellu-
losic HTL oil, vegetable oil and diesel oil: HTL appears as a very
interesting and promising option.
Based on literature review, experimental analysis and product
characterization, some useful indications toward engineering of
algae PO and HTL processes can be derived.
As regards pyrolysis, the peculiarity of the algal feedstock intro-
duces unique and critical key points for the design of the reactor
itself as well as the entire system. The pyrolysis reactors used for
these preliminary tests and in similar experiments available in liter-
ature (excluding the batch reactors, not relevant for these consider-
ations) are essentially still those used with lignocellulosic biomass:
however, algae clearly have very different characteristics, such as
composition (mainly carbohydrates, proteins and lipids), high inor-
ganic and ashes content, peculiar state of aggregation depending on
the harvesting and pretreatment (fine powder or fluffy material). It
is certainly necessary to develop a reactor specifically designed for
microalgae, so to optimize the feeding system, the heating methods,
the reactor design, and the overall performances. Also innovative
integration of plant components is needed, as low temperature heat
streams from the pilot unit could be effectively used for algae dry-
ing, thus achieving significant energy optimization not yet in place
today.
HTL offers the immediate advantage of processing wet feed-
stock and determining a less oxygenated biocrude, thus more
appropriate for upgrading into biofuels. Continuous HTL unit will
operate at lower algae concentration than batch system, but are
necessary to design industrial scale concepts. However, the high
nitrogen content will require adequate hydrodenitrogenation
stages, while the use of salty water for algae cultivation will
require careful design and evaluation of possible corrosion-
related problem. In addition, deposition of inorganic is expected
near critical conditions: these will have to be removed from the
liquid stream in order to allow its re-use in the system after the

Table 5
Comparison among pyrolysis, HTL and vegetable oils.

Parameter Pyrolysis oil Pyrolysis oil HTL lignocell. HTL algae (biocrude) HTL algae (aqueous) Vegetable oil from Diesel Unit of
algae A algae B [75] [64,76,77] [64,66,77] sunflowera EN590 measurement
Kinematic 31.8 30.9 >300 110–350 1–2 26.0 2–4.5 mm2/s
viscosity@40 °C
pH 8.12 7.25 – – 7.5–7.8 n.a n.a. –
TAN – – 30–60 2–8 – 1.06 n.a. mgKOH/g
Density – – 0.82–1 0.94–0.96 1–1.05 0.91 0.84 kg/dm3
Water content 16.7 19.4 3–13 2–8 95–96 0.085 <0.02 % w/w
HHV 28.2 29.3 30–35 35.4 Negligible 39.48 42–43b MJ/kg
LHV 26.1 26.9 n.a. n.a. Negligible 36.97 44–45b MJ/kg
S 0.3 0.19 n.a. 0.3–0.5 – 0.002 <0.001 % w/w
C 52.1 58.8 67–80 77–80 1.8–3.7 77.8 87b % w/w
H 10.2 10.6 6–8 10 11–12 11.9 13b % w/w
N 5.8 4 0–2 4 0.5–1.1 0.01 – % w/w
O 31.6 26.4 11–23 5–8 84–85 10.3 – % w/w
COD – – – – 60,000–125,000 – – mg/kg
a
Reference norm DIN 51605.
b
Typical.
 D. Chiaramonti et al. / Applied Energy 185 (2017) 963–972
separation of the organic liquid. HTL thus presents significant chal-
lenges in terms of materials and plant components.
6. Conclusions
A literature review of microalgae to liquid biofuel production
through thermochemical processing has been carried out, and inte-
grated with original research results of algae intermediate pyroly-
sis. The scope of our work was to key elements of pyrolysis versus
hydrothermal liquefaction, identify opportunities for optimization
of the energy conversion phase and provide useful insights neces-
sary to design the whole biofuel chain, i.e. from microalgae to bio-
fuel. Microalgae based biofuels are technically feasible, but positive
economic and energy balances still have to be demonstrated. HTL
has been investigated in batch and continuous reactors, the latter
being operated also at very high algae concentrations. The oil is
characterized by low oxygen content, compared to algae pyrolysis,
but a significant amount of nitrogen is observed in the biocrude. As
regards pyrolysis, two batches of algae samples were tested in a
semi-continuos pyrolysis reactor, and results compared the with
literature data. The samples differ significantly in terms of lipids
and proteins ratio, as consequence of different cultivation methods
(nitrogen starved vs. unstarved). Pyrolysis was carried out at
450 °C, without the catalysts: the organic phase yield was approx-
imately equal to 36% w/w for both samples. Viscosities were close
to lignocellulosic biomass fast pyrolysis oils, while pH (close to 7)
represents a major difference with pyrolysis oil obtained from lig-
nocellulosic materials. In contrast, water, Nitrogen and Oxygen
contents are significant and require downstream upgrading/
removal. The experimental mass yield of the pilot reactor oil
achieved approximately 36% w/w, while the energy yield was
equal to 46% w/w for sample A, even if the experiment did not tar-
geted energy optimization and ad-hoc revised design will certainly
lead to better performances. A relevant results of the experimenta-
tion carried out is that no significant differences have been
observed in treating the two samples: in terms of overall energy
yield, no advantages were observed from using lipid-rich algae.
This conclusion is particularly important, as the cultivation method
adopted to increase the algae lipid content can lead to lower algae
plant productivities. This is a significant result in view of practical
industrial application, together with the variation in Nitrogen con-
tent associated with thermochemically processing starved or non-
starved microorganism, or whole or lipid extracted microalgae.
Future microalgae bioerefineries could therefore, for instance, con-
sider microalgae cultivation in non-starved systems (the most used
method to accumulate lipids), extraction of the proteins and
removal of a significant amount of Nitrogen, thermochemical con-
version of the remaining biomass into biocrude and finally bio-
crude upgrading, possibly in existing refineries.
Regarding the technological pathways, the analysis indicated
that algae-HTL is a very promising pathway, probably more than
pyrolysis in terms of product quality and at least comparable with
respect to energy yield. On the other hand, HTL is todays at an
early-stage of development, while pyrolysis is more mature and
already industrialized. The specificity of the feedstock introduces
critical issues and opportunities for both reactor design and pro-
cess optimization.
Acknowledgments
Authors wish to thank dr Ilaria Marsili Libelli for the coordina-
tion and support to the analytical part of the research work, as well
as Prof Ing Francesco Martelli, CREAR Director.
971
References
[1] Davis R, Aden A, Pienkos PT. Techno-economic analysis of autotrophic
microalgae for fuel production. Appl Energy 2011;88:3524–31. http://dx.doi.
org/10.1016/j.apenergy.2011.04.018.
[2] Tredici MR. Photobiology of microalgae mass cultures: understanding the tools
for the next green revolution. Biofuels 2010;1:143–62. http://dx.doi.org/
10.4155/bfs.09.10.
[3] Lardon L, Helias A, Sialve B, Steyer J-P, Bernard O. Life-cycle assessment of
biodiesel production from microalgae. Environ Sci Technol 2009;43:6475–81.
http://dx.doi.org/10.1021/es900705j.
[4] Razon LF, Tan RR. Net energy analysis of the production of biodiesel and biogas
from the microalgae: Haematococcus pluvialis and Nannochloropsis. Appl
Energy 2011;88:3507–14. http://dx.doi.org/10.1016/j.apenergy.2010.12.052.
[5] Milledge J. Microalgae-commercial potential for fuel, food and feed. Food Sci
Technol 2012;26.
[6] Wijffels RH, Barbosa MJ, Eppink MHM. Microalgae for the production of bulk
chemicals and biofuels. Biofuels, Bioprod Biorefining 2010;4:287–95. http://
dx.doi.org/10.1002/bbb.
[7] Barros AI, Gonçalves AL, Simões M, Pires JCM. Harvesting techniques applied to
microalgae: a review. Renew Sustain Energy Rev 2015;41:1489–500. http://dx.
doi.org/10.1016/j.rser.2014.09.037.
[8] Sanders KB. Downstream processing of microalgal biomass for
biofuels. Oregon State University; 2010.
[9] Molina Grima E, Belarbi E-H, Acién Fernández FG, Robles Medina A, Chisti Y.
Recovery of microalgal biomass and metabolites: process options and
economics. Biotechnol Adv 2003;20:491–515.
[10] Pragya N, Pandey KK, Sahoo PK. A review on harvesting, oil extraction and
biofuels production technologies from microalgae. Renew Sustain Energy Rev
2013;24:159–71. http://dx.doi.org/10.1016/j.rser.2013.03.034.
[11] Bennion EP, Ginosar DM, Moses J, Agblevor F, Quinn JC. Lifecycle assessment of
microalgae to biofuel: comparison of thermochemical processing pathways q.
Appl Energy 2015:1–10. http://dx.doi.org/10.1016/j.apenergy.2014.12.009.
[12] Chiaramonti D, Tredici M, Prussi M, Biondi N. Algae Biofuels. In: Yan J, editor.
Handb Clean energy Syst; 2015.
[13] Studt T. Algae promise biofuel solutions. Inform 2010;21:319–24.
[14] Stephenson AL, Kazamia E, Dennis JS, Howe CJ, Scott SA, Smith AG. Life-cycle
assessment of potential algal biodiesel production in the United Kingdom: a
comparison of raceways and air-lift tubular bioreactors. Energy Fuels
2010;24:4062–77. http://dx.doi.org/10.1021/ef100312.
[15] Bondioli P, Della Bella L, Rivolta G, Chini Zittelli G, Bassi N, Rodolfi L, et al. Oil
production by the marine microalgae Nannochloropsis sp. F&M-M24 and
Tetraselmis suecica F&M-M33. Bioresour Technol 2012;114:567–72. http://dx.
doi.org/10.1016/j.biortech.2012.02.123.
[16] Dejoye Tanzi C, Abert Vian M, Chemat F. New procedure for extraction of algal
lipids from wet biomass: a green clean and scalable process. Bioresour Technol
2013;134:271–5. http://dx.doi.org/10.1016/j.biortech.2013.01.16.
[17] Reddy HK, Muppaneni T, Patil PD, Ponnusamy S, Cooke P, Schaub T, et al. Direct
conversion of wet algae to crude biodiesel under supercritical ethanol
conditions. Fuel 2014;115:720–6. http://dx.doi.org/10.1016/
j.fuel.2013.07.090.
[18] Grima EM, González MJI, Giménez AG. Solvent extraction for microalgae lipids.
Algae for biofuels and energy. Netherland: Springer; 2013. p. 187–205.
[19] Taher H, Al-Zuhair S, Al-Marzouqi AH, Haik Y, Farid M. Effective extraction of
microalgae lipids from wet biomass for biodiesel production. Biomass
Bioenergy 2014;66:159–67. http://dx.doi.org/10.1016/j.
biombioe.2014.02.034.
[20] Braun E, Aach HG. Enzymatic degradation of the cell wall of Chlorella. Planta
1975;126:181–5. http://dx.doi.org/10.1007/BF00380622.
[21] Zheng H, Yin J, Gao Z, Huang H, Ji X, Dou C. Disruption of Chlorella vulgaris cells
for the release of biodiesel-producing lipids: a comparison of grinding,
ultrasonication, bead milling, enzymatic lysis, and microwaves. Appl
Biochem Biotechnol 2011;164:1215–24. http://dx.doi.org/10.1007/s12010-
011-9207-1.
[22] Choudhary TV, Phillips CB. Renewable fuels via catalytic hydrodeoxygenation.
Appl Catal A Gen 2011;397:1–12. http://dx.doi.org/10.1016/j.
apcata.2011.02.025.
[23] Sotelo-Boyás R, Trejo-Zárraga F, de Jesús Hernández-Loyo F. Hydroconversion
of triglycerides into green liquid fuels. InTech 2012. http://dx.doi.org/10.5772/
3208.
[24] Neste Oil. NExBTL Diesel n.d. http://www.nesteoil.com [accessed 13.01.14].
[25] Rizzo AM, Prussi M, Bettucci L, Marsili Libelli I, Chiaramonti D.
Characterization of microalga Chlorella as a fuel and its thermogravimetric
behavior. Appl Energy 2013;102:24–31. http://dx.doi.org/10.1016/j.
apenergy.2012.08.039.
[26] Raheem A, Wan Azlina WAKG, Taufiq Yap YH, Danquah MK, Harun R.
Thermochemical conversion of microalgal biomass for biofuel production.
Renew Sustain Energy Rev 2015;49:990–9. http://dx.doi.org/10.1016/j.
rser.2015.04.18.
[27] Chen W-H, Lin B-J, Huang M-Y, Chang J-S. Thermochemical conversion of
microalgal biomass into biofuels: a review. Bioresour Technol
2015;184:314–27. http://dx.doi.org/10.1016/j.biortech.2014.11.050.
[28] Silva CM, Ferreira AF, Dias AP, Costa M. A comparison between microalgae
virtual biorefinery arrangements for bio-oil production based on lab-scale
results. J Clean Prod 2015. http://dx.doi.org/10.1016/j.jclepro.2015.09.053.
972 D. Chiaramonti et al. / Applied Energy 185 (2017) 963–972
[29] López-González D, Puig-Gamero M, Acién FG, García-Cuadra F,
Valverde JL, Sanchez-Silva L. Energetic, economic and environmental
assessment of the pyrolysis and combustion of microalgae and their oils.
Renew Sustain Energy Rev 2015;51:1752–70. http://dx.doi.org/10.1016/j.
rser.2015.07.022.
[30] Na J-G, Park Y-K, Il Kim D, Oh Y-K, Jeon SG, Kook JW, et al. Rapid pyrolysis
behavior of oleaginous microalga, Chlorella sp. KR-1 with different triglyceride
contents. Renew Energy 2015;81:779–84. http://dx.doi.org/10.1016/j.
renene.2015.03.088.
[31] Wang X, Zhao B, Tang X, Yang X. Comparison of direct and indirect pyrolysis of
micro-algae Isochrysis. Bioresour Technol 2015;179:58–62. http://dx.doi.org/
10.1016/j.biortech.2014.11.015.
[32] Zhao B, Wang X, Yang X. Co-pyrolysis characteristics of microalgae Isochrysis
and Chlorella: kinetics, biocrude yield and interaction. Bioresour Technol
2015;198:332–9. http://dx.doi.org/10.1016/j.biortech.2015.09.021.
[33] Murata K, Liu Y, Watanabe MM, Inaba M. Production of bio-oil from a
Botryococcus Braunii residue. J Anal Appl Pyrol 2015;114:187–96. http://dx.doi.
org/10.1016/j.jaap.2015.05.017.
[34] Aysu T, Sanna A. Nannochloropsis algae pyrolysis with ceria-based catalysts
for production of high-quality bio-oils. Bioresour Technol 2015;194:108–16.
http://dx.doi.org/10.1016/j.biortech.2015.07.027.
[35] Francavilla M, Kamaterou P, Intini S, Monteleone M, Zabaniotou A. Cascading
microalgae biorefinery: fast pyrolysis of Dunaliella tertiolecta lipid extracted-
residue. Algal Res 2015;11:184–93. http://dx.doi.org/10.1016/j.
algal.2015.06.017.
[36] Patel B, Guo M, Izadpanah A, Shah N, Hellgardt K. A review on hydrothermal
pre-treatment technologies and environmental profiles of algal biomass
processing. Bioresour Technol 2016;199:288–99. http://dx.doi.org/10.1016/j.
biortech.2015.09.064.
[37] Guo Y, Yeh T, Song W, Xu D, Wang S. A review of bio-oil production from
hydrothermal liquefaction of algae. Renew Sustain Energy Rev
2015;48:776–90. http://dx.doi.org/10.1016/j.rser.2015.04.049.
[38] Yoo G, Park MS, Yang J-W, Choi M. Lipid content in microalgae determines the
quality of biocrude and energy return on investment of hydrothermal
liquefaction. Appl Energy 2015;156:354–61. http://dx.doi.org/10.1016/j.
apenergy.2015.07.020.
[39] Faeth JL, Valdez PJ, Savage PE. Fast hydrothermal liquefaction of
Nannochloropsis sp. to produce biocrude. Energy Fuels 2013;27:1391–8.
http://dx.doi.org/10.1021/ef301925d.
[40] Garcia Alba L, Torri C, Samorì C, Van Der Spek J, Fabbri D, Kersten SRA, et al.
Hydrothermal treatment (HTT) of microalgae: evaluation of the process as
conversion method in an algae biorefinery concept. Energy Fuels
2012;26:642–57. http://dx.doi.org/10.1021/ef201415.
[41] Yang W, Li X, Li Z, Tong C, Feng L. Understanding low-lipid algae hydrothermal
liquefaction characteristics and pathways through hydrothermal liquefaction
of algal major components: crude polysaccharides, crude proteins and their
binary mixtures. Bioresour Technol 2015;196:99–108. http://dx.doi.org/
10.1016/j.biortech.2015.07.020.
[42] Jazrawi C, Biller P, He Y, Montoya A, Ross AB, Maschmeyer T, et al. Two-stage
hydrothermal liquefaction of a high-protein microalga. Algal Res
2015;8:15–22. http://dx.doi.org/10.1016/j.algal.2014.12.010.
[43] Roussis SG, Cranford R, Sytkovetskiy N. Thermal treatment of crude algae oils
prepared under hydrothermal extraction conditions. Energy Fuels
2012;26:5294–9. http://dx.doi.org/10.1021/ef300798b.
[44] Costanzo W, Jena U, Hilten R, Das KC, Kastner JR. Low temperature
hydrothermal pretreatment of algae to reduce nitrogen heteroatoms and
generate nutrient recycle streams. Algal Res 2015;12:377–87. http://dx.doi.
org/10.1016/j.algal.2015.09.019.
[45] Xu D, Savage PE. Effect of reaction time and algae loading on water-soluble and
insoluble biocrude fractions from hydrothermal liquefaction of algae. Algal Res
2015;12:60–7. http://dx.doi.org/10.1016/j.algal.2015.08.005.
[46] Hognon C, Delrue F, Texier J, Grateau M, Thiery S, Miller H, et al. Comparison of
pyrolysis and hydrothermal liquefaction of Chlamydomonas reinhardtii.
Growth studies on the recovered hydrothermal aqueous phase. Biomass
Bioenergy 2015;73:23–31. http://dx.doi.org/10.1016/j.biombioe.2014.11.025.
[47] Wang Z, Adhikari S, Valdez P, Shakya R, Laird C. Upgrading of hydrothermal
liquefaction biocrude from algae grown in municipal wastewater. Fuel Process
Technol 2016;142:147–56. http://dx.doi.org/10.1016/j.fuproc.2015.10.015.
[48] Yang X, Guo F, Xue S, Wang X. Carbon distribution of algae-based alternative
aviation fuel obtained by different pathways. Renew Sustain Energy Rev
2016;54:1129–47. http://dx.doi.org/10.1016/j.rser.2015.10.045.
[49] Elliott DC, Biller P, Ross AB, Schmidt AJ, Jones SB. Hydrothermal liquefaction of
biomass: developments from batch to continuous process. Bioresour Technol
2015;178:147–56. http://dx.doi.org/10.1016/j.biortech.2014.09.132.
[50] Oasmaa A, Källi A, Lindfors C, Elliott DC, Springer D, Peacocke C, et al.
Guidelines for transportation, handling, and use of fast pyrolysis bio-oil. 1.
Flammability and toxicity. Energy Fuels 2012;26:3864–73. http://dx.doi.org/
10.1021/ef300418d.
[51] Bridgwater AV. Fast pyrolysis of biomass for the production of liquids. In:
Rosendahl L, editor. Biomass Combust Sci Technol Eng. Woodhead Publishing;
2013.
View publication stats
[52] Grierson S, Strezov V, Bengtsson J. Life cycle assessment of a microalgae
biomass cultivation, bio-oil extraction and pyrolysis processing regime. Algal
Res 2013;2:299–311. http://dx.doi.org/10.1016/j.algal.2013.04.004.
[53] Yanik J, Stahl R, Troeger N, Sinag A. Pyrolysis of algal biomass. J Anal Appl Pyrol
2013;103:134–41. http://dx.doi.org/10.1016/j.jaap.2012.08.016.
[54] Kim SW, Koo BS, Lee DH. A comparative study of bio-oils from pyrolysis of
microalgae and oil seed waste in a fluidized bed. Bioresour Technol
2014;162:96–102. http://dx.doi.org/10.1016/j.biortech.2014.03.136.
[55] Borges FC, Xie Q, Min M, Muniz LAR, Farenzena M, Trierweiler JO, et al. Fast
microwave-assisted pyrolysis of microalgae using microwave absorbent and
HZSM-5 catalyst. Bioresour Technol 2014;166:518–26. http://dx.doi.org/
10.1016/j.biortech.2014.05.100.
[56] Yuan T, Tahmasebi A, Yu J. Comparative study on pyrolysis of lignocellulosic
and algal biomass using a thermogravimetric and a fixed-bed reactor.
Bioresour Technol 2015;175:333–41. http://dx.doi.org/10.1016/j.
biortech.2014.10.108.
[57] Bae YJ, Ryu C, Jeon J-K, Park J, Suh DJ, Suh Y-W, et al. The characteristics of bio-
oil produced from the pyrolysis of three marine macroalgae. Bioresour Technol
2011;102:3512–20. http://dx.doi.org/10.1016/j.biortech.2010.11.023.
[58] Grierson S, Strezov V, Ellem G, Mcgregor R, Herbertson J. Thermal
characterisation of microalgae under slow pyrolysis conditions. J Anal Appl
Pyrol 2009;85:118–23. http://dx.doi.org/10.1016/j.jaap.2008.10.003.
[59] Pan P, Hu C, Yang W, Li Y, Dong L, Zhu L, et al. The direct pyrolysis and catalytic
pyrolysis of Nannochloropsis sp. residue for renewable bio-oils. Bioresour
Technol 2010;101:4593–9. http://dx.doi.org/10.1016/j.biortech.2010.01.070.
[60] Miao X, Wu Q. High yield bio-oil production from fast pyrolysis by metabolic
controlling of Chlorella protothecoides. J Biotechnol 2004;110:85–93. http://
dx.doi.org/10.1016/j.jbiotec.2004.01.013.
[61] Miao X, Wu Q, Yang C. Fast pyrolysis of microalgae to produce renewable fuels.
J Anal Appl Pyrol 2004;71:855–63. http://dx.doi.org/10.1016/
j.jaap.2003.11.004.
[62] Yu G, Zhang Y, Schideman L, Funk TL, Wang Z. Hydrothermal liquefaction of
low lipid content microalgae into bio-crude oil. Am Soc Agric Biol Eng
2011;54:239–46. http://dx.doi.org/10.13031/2013.36241.
[63] Vardon DR, Sharma BK, Blazina GV, Rajagopalan K, Strathmann TJ.
Thermochemical conversion of raw and defatted algal biomass via
hydrothermal liquefaction and slow pyrolysis. Bioresour Technol
2012;109:178–87. http://dx.doi.org/10.1016/j.biortech.2012.01.008.
[64] López Barreiro D, Prins W, Ronsse F, Brilman W. Hydrothermal liquefaction
(HTL) of microalgae for biofuel production: state of the art review and future
prospects. Biomass Bioenergy 2013;53:113–27. http://dx.doi.org/10.1016/j.
biombioe.2012.12.02.
[65] Duan P, Savage PE. Upgrading of crude algal bio-oil in supercritical water.
Bioresour Technol 2011;102:1899–906. http://dx.doi.org/10.1016/j.
biortech.2010.08.013.
[66] Elliott DC, Hart TR, Schmidt AJ, Neuenschwander GG, Rotness LJ, Olarte MV,
et al. Process development for hydrothermal liquefaction of algae feedstocks in
a continuous-flow reactor. Algal Res 2013;2:445–54. http://dx.doi.org/
10.1016/j.algal.2013.08.005.
[67] Biller P, Ross AB. Potential yields and properties of oil from the hydrothermal
liquefaction of microalgae with different biochemical content. Bioresour
Technol 2011;102:215–25. http://dx.doi.org/10.1016/j.biortech.2010.06.028.
[68] Yang Y, Gilbert A, Xu C Charles. Production of bio-crude from forestry waste by
hydro-liquefaction in sub-/super-critical methanol. AIChE J 2009;55:807–19.
http://dx.doi.org/10.1002/aic.11701.
[69] Minowa T, Murakami M, Dote Y, Ogi T, Yokoyama S. Oil production from
garbage by thermochemical liquefaction. Biomass Bioenergy 1995;8:117–20.
http://dx.doi.org/10.1016/0961-9534(95)00017-. ST – oil production from
garbage by therm.
[70] Ross AB, Biller P, Kubacki ML, Li H, Lea-Langton A, Jones JM. Hydrothermal
processing of microalgae using alkali and organic acids. Fuel
2010;89:2234–43. http://dx.doi.org/10.1016/j.fuel.2010.01.02.
[71] Brown TM, Duan P, Savage PE. Hydrothermal liquefaction and gasification of
Nannochloropsis sp. Energy Fuels 2010;24:3639–46. http://dx.doi.org/
10.1021/ef100203u.
[72] Zou S, Wu Y, Yang M, Li C, Tong J. Bio-oil production from sub- and
supercritical water liquefaction of microalgae Dunaliella tertiolecta and related
properties. Energy Environ Sci 2010;3:1073. http://dx.doi.org/10.1039/
c002550j.
[73] Jazrawi C, Biller P, Ross AB, Montoya A, Maschmeyer T, Haynes BS. Pilot plant
testing of continuous hydrothermal liquefaction of microalgae. Algal Res
2013;2:268–77. http://dx.doi.org/10.1016/j.algal.2013.04.006.
[74] Rizzo AM. Biomass pyrolysis for liquid biofuels: production and use. University
of Florence 2015. http://dx.doi.org/10.13140/RG.2.1.3091.5045.
[75] Hoffmann J. Upgrading of bio-crude from hydrothermal liquefaction.
TCBiomass 2013, Chicago: 213AD; 2013.
[76] Elliott D. Conversion of algal biomass to liquid fuels by hydrothermal
processing in continuous-flow reactors. TC Biomass 2013, Chicago; 2013.
[77] Jena U, Das KC, Kastner JR. Effect of operating conditions of thermochemical
liquefaction on biocrude production from Spirulina platensis. Bioresour
Technol 2011;102:6221–9. http://dx.doi.org/10.1016/j.biortech.2011.02.057.