Accepted Manuscript

A comparison between microalgae virtual biorefinery arrangements for bio-oil

production based on lab-scale results

C.M. Silva, A.F. Ferreira, A.P. Dias, M. Costa

PII: S0959-6526(15)01275-5
DOI: 10.1016/j.jclepro.2015.09.053
Reference: JCLP 6142

To appear in: Journal of Cleaner Production

Received Date: 13 April 2015

Revised Date: 30 June 2015
Accepted Date: 13 September 2015

Please cite this article as: Silva CM, Ferreira AF, Dias AP, Costa M, A comparison between microalgae
virtual biorefinery arrangements for bio-oil production based on lab-scale results, Journal of Cleaner
Production (2015), doi: 10.1016/j.jclepro.2015.09.053.

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 ACCEPTED MANUSCRIPT

Chlorella vulgaris

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Best compromise bio-oil quantity and
energy/carbon footprint?

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Lipid extraction and

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transesterification

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Nannochloropsis oculata
(path #1)
Bio-oil

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OR

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Pyrolysis (path #2)

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Scenedesmus obliquus TE OR
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Path #1 and lipid
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depleted biomass
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pyrolysis (path #3)

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A comparison between microalgae virtual biorefinery arrangements for
bio-oil production based on lab-scale results
C.M. Silva*, A.F. Ferreira, A. P. Dias, and M. Costa
IDMEC, Mechanical Engineering Department, Instituto Superior Técnico, Universidade de
Lisboa, Lisboa, Portugal

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* Corresponding author: Tel.: +35121849546; Fax: +351218417640;
Corresponding Address: IDMEC/LAETA - Instituto Superior Técnico, Dept. of Mechanical
Engineering, Av. Rovisco Pais, Pav. Mecânica I, 2º Andar, 1049-001

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Lisbon, Portugal
E-mail: carla.silva@tecnico.ulisboa.pt

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Abstract
Bio-oils are typically produced by pyrolysis processes. Bio-oils can be used directly in a

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generator to produce electricity or upgraded to produce transportation fuels. Nowadays the
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interest is that they come out in a biorefinery context. This paper compares bio-oil production
within three possible procedures. Targeting the bio-oil product, in virtual biorefinery #1,
microalgae is processed by solvent ultrasound-assisted extraction, and lipids follow
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transesterification; in virtual biorefinery #2, bio-oil comes out from fresh microalgae
pyrolysis, and, finally, in virtual biorefinery #3, lipid extraction leftovers proceed for slow
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pyrolysis. Solvent ultrasound-assisted extraction and slow pyrolysis are tested and measured
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experimentally using three microalgae as feedstock: Chlorella vulgaris, Nannochloropsis

oculata, and Scenedesmus obliquus. These stand-alone processes are analyzed aiming to
provide the best option in a virtual biorefinery context. Although very fast/slow pyrolysis
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produces markedly different products, previous thermogravimetry analysis allowed choosing

an adequate pyrolysis temperature. Nevertheless, the influence of temperature, catalyst and
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nitrogen flow is depicted. The comparison indicators for final remarks relate to final energy
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consumption and greenhouse gas emissions. Conditions that favor bio-oil production may not
be favorable in terms of energy required per mass or energy output. If mass allocation
criterion is used lipid extraction followed by slow pyrolysis of the leftovers is advantageous
over slow pyrolysis of fresh dry microalgae. Still the fossil energy input largely surpasses the
bio-oil energy content.

Keywords: bioenergy; microalgae; solvent extraction; pyrolysis; bio-oil

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1. Introduction
The conversion of microalgae biomass to biofuels and added value products are globally gaining
significant prominence and there has been an increased focus on this research area over the last
few years (Liew et al., 2014). Microalgal contain high levels of oils, carbohydrates and proteins
which make them versatile raw materials for fuels production in parallel with valuable chemicals
and human and animal food in a biorefinery context. Bio-oils are typically produced by

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disruption or pyrolysis processes, where the biomass is heated in the absence of oxygen. The bio-
oils can be used directly in a generator to produce electricity or upgraded to produce

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transportation fuels.
(Lee et al., 2012) provides an overview of microalgal cell disruption processes which are

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potentially suitable for large scale lipid extractions. The energy requirements of these processes
were compared with each other and then compared with estimates of the theoretical minimum
energy required for disruption. Figure 1 shows the typical disruption methods that can be used

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per si or combined with each other. A range of 9.6 to 529 MJ/kgdry microalgae is reported for the
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final energy consumption, covering different microalgae and different methods.
Three different thermochemical conversion routes are found according to the oxygen content in
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the process: combustion (complete oxidation), gasification (partial oxidation) and pyrolysis
(thermal degradation without oxygen). The last one is used for biodiesel production.
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Pyrolysis is a promising bioconversion technique for energy recovery, waste management,

and converting biomass into useful energy products that has attracted considerable attention
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during the past decades due to its bioenergy production capability (Liew et al., 2014).
Within a pyrolysis process the raw material is converted into different reactive intermediate
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products: solid (bio-char), liquid bio-oils (heavy molecular weight compounds that condense
when cooled down) and gaseous products (light molecular weight gases) (Fernández et al.,
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2011).
The pyrolysis method has been used for commercial production of a wide range of fuels,
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solvents, chemicals and other products from biomass feedstock. Conventional pyrolysis
consists of the slow, irreversible, thermal decomposition of the organic components in
biomass. Slow pyrolysis has traditionally been used for the production of char. Short
residence time pyrolysis (fast, flash, rapid) of biomass at moderate temperatures has generally
been used to obtain high yield of liquid products (Yaman, 2004).
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CELL DISRUPTION
METHODS Decompression
Osmotic shock
Bead mill Physical Termolysis (autoclave)
Homogenizer Freeze drying

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High pressure Microwave

High speed
Cavitation
Mechanical Non-Mechanical Antibiotics

Ultrasound Chelating agents

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Hydrodynamic Detergent
Chemical
Microfluidizer Solvent
Alkalis
Supercritical CO 2

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Lytic
Enzymatic Autolysis
phage

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Figure 1. Classification of cell disruption methods (adapted from (Lee et al., 2012)).
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Depending on the pyrolysis temperature, the char fraction contains inorganic materials ashed
to varying degrees, any unconverted organic solid and carbonaceous residues produced from
thermal decomposition of the organic components. Bio-char offers numerous benefits when
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applied to soils and it potentially delivers a net reduction of atmospheric carbon dioxide,
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achieved across the combined cultivation and processing regime overall as a function of time
(Grierson et al., 2011). The oil fraction is a complex mixture of water and organic chemicals.
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The pyrolysis technology can be classified as seen in Table 1.

Table 1. Pyrolysis technology classification (Fernández et al., 2011).

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Residence Heating rate (K / s) Temperature (K) Classification

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time (s)
450-550 0.1-1 550-950 Slow
0.5-10 10-200 850-1250 Fast
<0.5 >1000 1050-1300 Flash

Recent studies were developed using microwave assisted pyrolysis. Conventional heating
pyrolysis (CP) is different than microwave assisted pyrolysis (MP) in the material heating
process. In MP the heating material is at higher temperature than the surrounding area, unlike
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conventional heating where it is necessary that the conventional furnace cavity reach the
operating temperature, to begin heating the material (Shuttleworth et al., 2012).
The energy and emissions data inventory is relevant for comparing processes (Castanheira et al.,
2015), improving a process itself (Pérez-López et al., 2014) or consider it sustainable. For
example Renewable Energy Directive 2009/28/EC (RED) consider that biofuels must achieve
life cycle greenhouse gas savings of at least 35% in comparison to fossil fuels. This savings

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requirement rises to 50% in 2017. In 2018, it rises again to 60% but only for new production
plants.

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(Zhong et al., 2010) reported the life-cycle assessment of flash pyrolysis of wood waste. The
authors showed that the process of flash pyrolysis of wood waste is in fact environmentally

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friendly. (Steele et al., 2012) reported bio-oil feedstock produced using whole southern pine
(Pinus taeda) trees, chipped, and converted into bio-oil by fast pyrolysis (in CP category, with
conditions: Fluidized bed pyrolysis feed, 500 ºC, 2.75 kg air/kg, 59% bio-oil yield). It indicates

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1.39 MJ//MJbio-oil primary energy consumption and 0.04 kg CO2/MJbio-oil for bio-oil production
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stage. (Khoo et al., 2013) reported lipid extraction and bio-oil production by fast pyrolysis (in CP
category, with a fixed-bed reactor, 550 ºC, nitrogen flow rate of 650 mL/min and a yield of 15.4
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wt.% bio-oil) using the microalgae Nannochloropsis sp. It considers lipid extraction with solvent
(85.7 MJ/kgdry microalgae) followed by fast pyrolysis to obtain bio-oil. For the lipid depleted
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biomass feedstock, the energy input for the CP is 0.17 MJ/ MJbio-oil and the CO2 emissions for the
CP is 0.38 kg CO2/MJ bio-oil. (Wang et al., 2015) investigated if a pyrolysis refinery using
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municipal solid waste (MSW) would be environmentally friendly using the life cycle assessment
methodology. Authors conclude that the refinery of each kg MSW requires 4.71 MJ from which
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71.3% are due to fast pyrolysis.

(Xu et al., 2011) reported lipid extraction and bio-oil production by fast pyrolysis (in CP
category, conditions: transesterification and pyrolysis for 70 wt.%. bio-oil yield) using the
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microalgae Chlorella vulgaris. It considers lipid extraction by cell disruption by a stirred ball
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mill and solvent extraction (final energy consumption of 0.24 MJ/kgdry microalgae), followed by fast
pyrolysis to obtain bio-oil (final energy consumption of 0.06 MJ//MJbio-oil).
(Du et al., 2011) reported microwave-assisted pyrolysis of microalgae Chlorella sp. for biofuel
production. No energy or emissions balance information was reported which makes impossible a
comparison among processes.
(Araujo et al., 2013) reported an ultrasound-assisted extraction. The authors verified that
sonication increased the efficiency of the extraction since it was partially responsible for cell
disruption. (Prommuak et al., 2012) examined solvent extraction of lipid from microalgae, H.
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pluvialis and C. vulgaris assisted by microwave. No energy or emissions balance information
was reported which makes impossible a comparison among processes.
Catalyzed pyrolysis of biomass over ZSM-5 catalysts was previously reported by several
researchers (Bulushev and Ross, 2011). (Pan et al., 2010) studied the catalyzed and non-
catalyzed pyrolysis of Nannochloropsis sp. in a tubular fixed bed reactor under N2 flow. They
used different amounts of HZSM-5. The authors reported lower oxygen content for bio-oils

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obtained by catalyzed pyrolysis, 19.5 wt.% instead 30.1 wt.%, and higher heating-value
32.7 MJ/kg instead 24.6 MJ/kg. (Lappas, 2002) compared the catalytic performances of ZSM-5,

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quartz sand and a commercial FCC catalyst during the biomass pyrolysis in a circulating bed
reactor. Basic catalysts, such as alkaline and alkaline earths carbonates, are also referred to be

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active for biomass pyrolysis e.g.: (Zhang et al., 2008) studied the effect of additives (Na2CO3,
NaOH) on the pyrolysis of waste rubber; The effects of basic catalysts (MgO and CaCO3) were
studied on the pyrolysis products of waste rubber (Shah et al., 2008) .The catalyzed pyrolysis of

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biomass generally leads to higher yields of water, coke and gases than that of non-catalyzed
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pyrolysis. However the catalyst application had a significant effect on the bio-oil properties and
noticeable improvements in the bio-oil quality.
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This spectrum of possible bio-oil production processes stress the need for a comparative analysis
that potentially indicates what would be the best approach to use in a biorefinery context. A
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‘biorefinery’ is a conceptual model for future biofuel production where both fuels and high value
co-product materials are produced (Fatih Demirbas, 2009). A proper planning of the intended
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biorefinery scheme must be performed initially. The way the processes are integrated is very
important for the desired objectives (Holm-Nielsen and Ehimen, 2014).
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This paper uses lab-scale experimental results to evaluate possible virtual biorefineries for
bioenergy production in an exploratory approach. The objective is to choose the configuration
that minimizes final energy consumption, fossil primary energy consumption and GHG
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emissions per mass or energy of the obtained bio-oil product. This data is compared with
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reference data for bio-diesel in Europe and with the RED biofuel sustainability criteria. Three
microalgae species are analyzed and pine bark is used as the reference biomass. Lipid extraction,
transesterification and pyrolysis methods are considered. Ultrasound with solvent extraction and
different pyrolysis conditions, including temperature, N2 flow and catalysts were experimentally
studied at lab-scale. Finally preliminary recommendations for implementation in a biorefinery
context are made, despite the exploratory nature of the research.
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2. Methodology
Several engineering options are available for bio-oil production but there is a need to decide
which should be used: only cell disruption with transesterification or only pyrolysis or a
combination of the two. In this paper the indicators chosen to help making a decision are
based on scope 1 and scope 2 energy and carbon footprint from the GHG protocol (World
Resources Institute and Development, 2013). Other indicators are equally relevant when

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comparing and deciding the sustainability of a biorefinery/or a system versus another, e.g. the
social impact and the economic impact. This research only focuses on the energy and

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environmental indicators.

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2.1 Goal, scope and boundaries
The scope of this research encompasses the bio-oil production stage. The energy and mass
flows inventory (LCI) covers the fundamental steps concerning the biomass refinery Gate-to-

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Gate, enters dry microalgae exits bio-oil and other co-products, with the advantage of this
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module may also later be linked in a production chain to form a complete cradle-to-gate
evaluation. Figure 2 shows the scheme of the considered boundaries. The MJ of energy and g
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of CO2 will be expressed as a function of 1 kg of dry biomass, 1 kg of produced bio-oil or 1

MJ of produced bio-oil.
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The microalgae used in this study were grown and obtained by A4F-Algae for Future, Pataias,
Portugal. These microalgae production units were developed in high-emitting industries for
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CO2 mitigation adapted to the specific conditions. Table 2 shows the chemical properties of
the present microalgae. The proximate and ultimate analyses and the determination of the
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heating values of the microalgae used herein were carried out following the procedures
specified in the standards ASTM-E-870, CEN/TS 14918 and CEN/TS 14775 and the
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chemical composition of the ashes of all biomass fuels was determined by use of X-ray
fluorescence spectroscopy.
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To obtain the microalgae bio-oil three processes were considered: solvent ultrasound-assisted
extraction plus transesterification (pathway #1), slow pyrolysis (pathway #2) and ultrasound-
assisted extraction following slow pyrolysis of biomass leftover (pathway #3).
The solvent ultrasound extraction method (pathway #1) was used to extract the lipids from the
microalgae and a transesterification for bio-oil. This extraction was carried out using 5 g of
milled microalgae with n-hexane-isopropanol (2:1 v/v) mixture for 3 h in a P-select
ultrasounds-H. The most popular chemical for solvent extraction is hexane, which is relatively
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inexpensive. However, the solvent system selected contains both polar and non-polar
solvents, which show better extraction efficiency compared to using non-polar solvent alone.
The solvents are assumed to be fully recycled (in reality the amount of solvent recovered is
high but less than 100%, depending on the extent and characterization of the contamination
and on the recovery process employed. In this case the solvent was stripped from the oil and
recycled using distillation (Biddy et al., 2013)). The energy required was obtained by

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multiplying the direct current measurement of the ultrasound equipment, by the voltage, work
time (seconds) and by the energy mix factor. The solution was filtrated. The resulting oil

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extracts were evaporated in a Butchi Rotavapor R-210 for 20 min.
In pathway #2, using the slow pyrolysis process, three products were obtained from the

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microalgae: bio-oil, bio-char and gas. Figure 3 shows a scheme of the pyrolysis apparatus
employed in this study. In fact in general, pyrolysis of organic substances produces gas and
liquid products and leaves a solid residue richer in carbon content, char. Extreme pyrolysis,

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which leaves mostly carbon as the residue, is called carbonization. In our case the solid
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residue is less than 50% then the process is designated as slow pyrolysis throughout the
document.
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Table 2. Chemical properties of the microalgae studied.

Nannochloropsis Chlorella Scenedesmus
Parameter
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oculata vulgaris obliquus

Proximate analysis (wt.%, as received)
Volatiles 73.4 72.7 76.8
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Fixed Carbon 9.4 11.4 11.0

Moisture 3.3 4.9 4.4
Ash 13.9 11.0 7.8
Ultimate analysis (wt.%, dry ash free)
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Carbon 48.10 47.10 50.30

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Hydrogen 7.09 6.78 7.29

Nitrogen 7.83 10.27 8.26
Sulphur 0.87 0.72 0.62
Oxygen 36.11 35.13 33.53
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Figure 2. Scheme for the biomass virtual refinery boundaries with several possibilities for bio-
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oil production.
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N2

Furnace

Biomass
Glass wool

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Inert SiC

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Gas
Condenser

Water/ice
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bath

Figure 3. A schematic diagram of the fixed bed pyrolysis apparatus.

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The pyrolysis experiments were all performed in a quartz fixed bed reactor in nitrogen
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atmosphere. The reactor had an internal diameter of 16 mm and a length of 150 mm. The
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quartz reactor was filled with carborundum. The reactor was externally heated using a
Termolab circular electric furnace equipped with PID controller to ensure complete pyrolysis.
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After the 30 minutes of the pyrolysis process, the reactor was removed of the oven and the
bio-char was removed. After this procedure the bio-oil was recovered by washing (leached)
the reactor with acetone. The gas flow from the reactor outlet was partially condensed in a
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trap, with ice, and then directed to the analysis system (gas chromatography). However, the
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analysis was not included in this study. The biomass pyrolysis temperature was select by a
previous thermogravimetry analysis, under N2 flow, using by Netzsch STA 409 PC. The TGA
samples were heated from 30 ºC to 1050 ºC at a heating rate of 25 ºC/min. Figure 4 shows
typical microalga and pine bark thermogravimetric curves. The main weight loss occurred in
the range 300 ºC and 500 ºC. Thus, the pyrolysis reference condition was chosen to be 375 ºC.
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T(ºC)

0 150 300 450 600 750 900 1050

0

-20
Sc. obliquus
Weight loss (%)

C. vulgaris

-40 Pine bark

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N. oculata

-60

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-80

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-100
25 ºC/min, under N2

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Figure 4. Example of microalga and pine bark thermal analysis.
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The pyrolysis test was started by placing a certain amount of fresh microalgae (about 5 g) into
the quartz reactor. The reactor was placed in the circular furnace pre-heated to 375 ºC.
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Nitrogen was used as the carrier gas and its reference flow (83 mL/min) was monitored using
a mass flow controller. A condenser coupled to the reactor was used immersed in an ice-water
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bath to obtain a liquid product. The uncondensed gas was not collected; however it was
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analyzed by gas chromatography. The pyrolysis was set to 375 ºC and N2 flow to 83 mL/min
for LCA data. This was assumed to be the reference conditions. According to Figure 4, the
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475 ºC temperature was also tested. The N2 flow of 200 and 300 mL/min was also tested. For
the best pair temperature/N2, commercial catalysts of USHY zeolite, ZSM-5 zeolite and HY-
2014 were tested in 0.25 wt.%. The influence of different pyrolysis conditions on the
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comparison results, were then analyzed for the reference and non-catalyzed best condition.
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The amount of pyrolysis liquid was determined by the mass difference of the condensers
before and after each pyrolysis test. The bio-oil was recovered by washing the reactor with
acetone followed by rotating evaporation of acetone under a reduced pressure. The acetone
used in this process could be recycled for further use.
The weighted mass of char and bio-oil allowed calculating the yield of such products. The
yield of gas was calculated from the difference of the char and bio-oil yield.
After the oil extraction by solvent ultrasound extraction, the microalgae were recovered and
dried to obtain value added products from microalgae by pyrolysis process (pathway #3). It is
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possible to convert oil extract depleted dry biomass to produce three co-products – char, bio-
oil and gas. For this purpose, each biomass leftover were used. The pyrolysis process is
similar to pathway #2 procedures.
The solid residues after raw and leftover microalgae pyrolysis were characterized by X-ray
diffraction. The obtained patterns (Figure 1) presented features belonging to low amorphous
materials mixed with several inorganic crystalline phases. The phases identification was

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performed taking into account the elemental composition of the raw microalga (Ferreira et al.,
2015). Bio-char co-product has nutrient elements in crystalline minerals located within the

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complex pore structure which can act as a carbon sink and as a means to improve crop yield.
The bio-char from the raw microalga displayed lines belonging to calcite (CaCO3) and sylvite

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(KCl) whereas the analogous obtained from the alga leftover presented additional diffraction
lines belonging to mixed Ca and K phosphate (Ca2KP3O10 and KCaPO4) and pyrophosphates
(K2CaP2O7) (identified in Figure 5).

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Intensity (a.u.)

Calcite
Sylvite
Pyrophosphite
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raw algae
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algae leftover
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10 15 20 25 30 35 40 45 50 55 60

θ (0)
2θ

Figure 5 Example of bio-char X-ray diffraction method from S. obliquus.

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2.2 Inventory
To get final energy consumption data, the direct electricity consumption of the equipment was
monitored using a multimeter and using the following approximation (power factor assumed
to be 1 and constant voltage of 220 V):
௧

‫ܧ‬௘௤௨௜௣௠௘௡௧ ሺ‫ܬܯ‬ሻ = ܸ. ෍ሺ‫ܣ‬ሚ௜ . ∆‫ݐ‬௜ ሻ

଴

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where à is the alternate electric current (A), V is the electric tension (V) and ∆t is the working
time (s) at a specific current.

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For the mass flows, inputs and outputs were measured by a digital balance.
The following tables (Table 3, Table 4 and Table 5) summarize the inventory values for the

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lab-scale experiments on the three microalgae and the reference biomass pine bark. Due to the
exploratory nature of the research and “virtual” biorefinery analysis, a hypothetical

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transesterification process was added to the lipids conversion to bio-oil (biodiesel). This way
the three possible biorefinery arrangements are comparable and it is possible to see which
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transformation steps need further adjustment and optimization. From the literature (Kiwjaroun
et al., 2009; Lardon et al., 2009), typically, 100 kg of oil or fat are reacted with 10 kg of
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methanol plus the catalyst to produce 100 kg of biodiesel and 10 kg of glycerin and 1.2 MJ
heat energy. Energy requirements and GHG emissions to produce methanol are 38.08 MJ/kg,
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730 g/kg, and to produce Sodium hydroxide (NaOH) are 19.87 MJ/kg, 877 g/kg. The glycerin
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coming out the transesterification process could replace glycerin produced from fossil raw
material. Conventional production of glycerin from the oil refinery requires 126.6 MJ/kg and
emits 5291 gCO2/kg, 9.45 g CH4/kg and 0.196 g N2O/kg (Jungk et al., 2000). By using IPCC
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100 years global warming potential this gives 5556 g GHG/kg emissions.
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Table 3. Inventory for direct lipid extraction (pathway #1, own data).
Chlorella vulgaris Nannochloropsis oculata Scenedesmus obliquus Pine bark
Input

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Dry microalgae 5.014 g 5.015 g 5.070 g 5.033 g
Ultrasound 0.585 MJ 0.585 MJ 0.585 MJ 0.585 MJ

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Filtration 0.020 MJ 0.020 MJ 0.020 MJ 0.020 MJ
Solvent evaporation 0.138 MJ 0.138 MJ 0.138 MJ 0.138 MJ
Outputa)

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Lipid 1.005 g 1.551 g 1.624 g 0.836 g
b)
Dry Lipid depleted biomass 3.940 g 3.430 g 3.420 g 4.160 g

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a) mass loss < 1.35%.

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b) drying energy is accounted when the biomass leftovers are used see Table 5.

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Table 4. Inventory for CP of fresh dry biomass (pathway #2, own data).

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Chlorella vulgaris Nannochloropsis oculata Scenedesmus obliquus Pine bark
Input

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Dry biomass 5.002 g 5.001 g 5.003 g 5.004 g
Heating 1.524 MJ 1.524 MJ 1.524 MJ 1.524 MJ
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Output*
Dry bio-oil 1.850 g (37%) 1.964 g (39%) 2.487 g (50%) 2.362 g (47%)
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Dry bio-char 2.055 g (41%) 2.160 g (43%) 1.940 g (39%) 2.250 g (45%)
Gas w/o water vapour 1.065 g (22%) 0.247 g (5%) 0.516 g (10%) 0.372 g (8%)
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* Bio-oil + bio-char + gas + water = 100%

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Table 5. Inventory for CP of lipid depleted biomass (pathway #3, own data).
Chlorella vulgaris Nannochloropsis oculata Scenedesmus obliquus Pine bark
Input

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Heating for drying 2.298 MJ 2.298 MJ 2.298 MJ 2.298 MJ
Dry Lipid depleted biomass 3.940 g 3.430 g 3.420 g 4.160 g

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Heating for CP 1.524 MJ 1.524 MJ 1.524 MJ 1.524 MJ
Output*

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Dry bio-oil 1.418 g (36%) 1.200 g (35%) 1.573 (46%) 1.082 (26%)
Dry bio-char 1.773 g (45%) 1.441 g (42%) 1.231 (36%) 1.872 (45%)
Gas w/o water vapour 0.749 g (19%) 0.529 g (23%) 0.616 (18%) 1.206 (29%)

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* Bio-oil + bio-char + gas + water = 100%.

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2.3 Indicators
Cumulative energy demand (CED) and global warming potential (GWP) are the chosen
indicators for comparison purposes. CED represents total primary energy requirements of both
renewable and non-renewable sources, including fossil, nuclear, biomass, wind, solar,
geothermal energy and hydropower. The CO2 equivalent or GHG emissions are based on a
100-year time frame. The energy indicator fossil energy ratio (FER, i.e., fraction of fossil

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energy used) is also used being described as:

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EinFossil
FER = (2)
Ein

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where Ein is the total primary energy used. Results of energy and GHG are expressed as a
function of the oil based products (bio-oil for pathway #1 and #2 and lipids plus bio-oil for

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pathway #3). For primary energy data, solvent, N2, catalyst energy requirements were
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accounted along with the Portuguese national average generation mix in 2012. Due to the
recyclability potential of the solvent its requirement was neglected. Ecoinvent database was
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used and, for example, N2 gas has a value of 280 g CO2eq/kg and 2 MJ/kg of final energy
consumption. The national average electricity it is composed of 60% non-renewable energy and
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40% renewable energy (average electricity generation efficiency of 45.25%) with 8% energy
losses in distribution (electricity and distribution companies of Portugal, EDP and REN
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provided the data for 2013). The resulting average energy consumption and GHG emissions per
1 MJ of electricity produced was calculated (by using each powerplant’s efficiency and
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contribution to the generation mix) as being 2.21 MJ (1.91-2.33) and 105.58 g (100.84-110.53),
respectively. The GHG emissions of the electricity generation mix are, on mass basis,
90.5% CO2, 0.33% CH4 and 0.0045% N2O. The uncertainty of the values was considered based
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on the JRC, EUCAR and CONCAWE study (Edwards et al., 2007). Only operational processes
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were accounted for, i.e., equipment production, maintenance, and oil storage and distribution
were not included. For sure it would increase the carbon footprint, but fall outside of the scope
of this study. To gain insight on other electricity generation mix realities, from other
geographical locations, or marginal versus national approaches, a 0% renewables scenario
(FER=1) and a 100% renewables scenario (FER=0) was added to the discussion.
Energy consumption and emission burdens for production processes can be associated 100% to
bio-oil (most penalizing scenario, no allocation) or accordingly to the main product mass
allocation criterion taking into account the respective percentage of bio-oil produced in each

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process. This means that if 20% of bio-oil is produced, 20% of the energy consumed and
produced emissions are attributable to it. Another approach could be the system expansion. The
bio-char production may replace fertilizer on the market and contribute to carbon sequestration
(Spokas et al., 2012), which means that there is an avoided production of fertilizer and thereby
a negative contribution to the environmental impact from the lifecycle of bio-oil. In this case
the system is then expanded to include the system of processes, which are involved in fertilizer

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production. Following the exploratory nature of the work, it may be assumed as a first approach
that 50% of the bio-char obtained is composed by 50% of sylvite and 50% of calcite. By using

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the Ecoinvent data, the avoided primary energy consumption and the avoided GHG emissions
for replacing K-fertilizer would be 12.6 MJ/kg and 0.80 kgGHG/kg, respectively. For the
calcite the chemical equation: CaCO3 +CO2 +H2O = Ca2++2HCO3- suggests that for every mole

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of calcite that is dissolved, one mole of CO2 is consumed, or 0.44 kgCO2/kgcalcite.

2.4 Bio-oil characteristics

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As a potential substitute for crude oil the bio-oil characteristics obtained in each biorefinery
configuration are assessed by means of gravimetric method, DIN standard CEN/TS 15400 for
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heating value (HHV) and elemental analysis method for N, C, H and S.

These parameters could be directly compared with crude oil characteristics and other bio-oils
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obtained through other processes in the literature, which is also useful in terms of implementing
a virtual biorefinery. Also give indication if the pyrolysis process and their conditions must be
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optimized to get similar characteristic to the fossil fuel.

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3. Results and Discussion

A possibility for the bio-oil production is first doing a lipid extraction. The lipid extraction of
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microalgae by solvent combined with ultrasound was performed. For the lipid extraction
method, solvent combined with ultrasound, the values obtained per kg of dry biomass were
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∼147 MJ/kgdry microalgae , Table 6, which falls in the range found in literature data (Lee et al., 2012).
(Khoo et al., 2013) reported a value of 114 MJ per kg of lipid depleted dry biomass for
Nannochloropsis sp. lipid depleted by solvents hexane and methanol in the ratio of 3:1 (by
volume) using the high shear homogenizer for mixing the wet biomass and solvents, which is
22% lower than the energy required in this study (dry biomass basis) but is for a different
microalgae species.

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Table 6. Lipid extraction results (pathway #1).
Final energy Final energy Final energy
Lipid
Biomass (MJ/kgdry (MJ/kgoil (MJ/kgoil product mass
(%)
biomass) product) allocation)
C. vulgaris 20.04 148.25 739.64 150.32
N. oculata 30.93 148.22 479.26 149.23
S. obliquus 32.03 146.61 457.72 147.37

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Pine bark 16.61 147.69 889.15 148.79

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In the present processes the main form of energy used is electricity with a FER of 82%. Therefore
the primary energy relates with the final energy by the factor 2.21 and is almost directly

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proportional to the GHG with slightly differences attributable to solvent, catalyst and N2 inputs.
For the CP of fresh and lipid depleted biomass the results are given in Table 8 and Figure 6. The
yield of bio-oil decreases in the LD pyrolysis which is in agreement with the literature encountered

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for the microalgae (Porphy, Simon Jegan and Farid, 2012). Concerning the pine bark the reduction
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of the bio-oil yield is higher due to the temperature of pyrolysis process, which may not have been
adequate. This was verified because the resulting char indicated that the thermal conversion of
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pine bark extracted biomass was probably not complete. Therefore, for this specific case the
temperature should be increased (> 375 ºC).
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For the case of lipid extraction followed by pyrolysis of the leftovers (pathway #3) or direct fresh
microalgae pyrolysis (pathway #2), a sensitivity analysis was done to temperature, N2 flow and
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catalyst activity in the pyrolysis bio-oil outcome for S. obliquus. The result is as follows in Figure
6. Increasing the N2 flow, for the same temperature, tends to decrease the oil outcome. (Jourabchi
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et al., 2014) shows that the influence of N2 sweeping gas on Jatropha curcas pyrolysis decrease
the oil outcome for the same temperature.
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For the same N2 flow, a temperature increase means bio-oil outcome increase. According to (Li et
al., 2012) and (Chaiwong et al., 2013) this is true for a maximum of 500 ºC-550 ºC and the effect
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is opposite for higher temperatures.

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100 375ºC 475ºC
90
80
70
% bio-oil

60
50
40
30

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20
10

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0
83 200 300
N2 (mL/min)

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Figure 6. Pyrolysis conditions influence for fresh S. obliquus.

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The best condition, maximum bio-oil yield, was obtained for 200 mL/min and 475 ºC. For this
best pair temperature/N2, commercial catalysts HY-2014, HZSM5 and USHY were tested in a
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0.25 wt.% and results are shown in Figure 7. Only the catalyst USHY worked slightly as a
booster for bio-oil yield, but clearly a new composition of catalyst must be found to boost bio-
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oil production.
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28.6 25.6 25.1

26.6 25.9
Gas
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57.4 57.6 27.0 58.1 Bio-char

38.8 42.8
Bio-oil
16.3
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None None None HY-2014 HZSM5 USHY

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83 200 300 200 200 200

475 ºC

Figure 7. Catalyzed pyrolysis vs pyrolysis bio-product yields (wt.%)for fresh S. obliquus. Gas
mass percentage was obtained by difference.

Nevertheless the same species cultured at different weather/temperature/nitrogen stress

conditions can have remarkably different lipid/protein/sugar content; the characteristics of the

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bio-oil obtained in the best non-catalyzed pyrolysis are in Table 8 compared with other bio-oil
from microalgae, pine chips and crude oil.

Table 7. Bio-oil characteristics.

Fresh S. LD S. Bio-oil Bio-oil Crude oil
obliquus (our obliquus (Steele et (Thangalazhy-

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data) (our data) al., 2012)* Gopakumar et
al., 2012)**

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Water and 60 49 17 (water) 0.1 (water)
volatiles (wt.%)

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HHV (MJ/kg) 25.4 29.8 18.6 ± 0.3 43.05 ± 1.40
LHV(MJ/kg) 23.6 28.0 17.2 45.30 ± 1.47
N (wt.%) 7.5 8.1 < 0.1 12.4 ± 1.1 <1
C (wt.%) 54 62
U 45.7 51.4 ± 2.3 83-86
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H/C 0.16 0.14 1.5–2.0
H (wt.%) 8.4 8.7 7 10.4 ± 0.4
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S (wt.%) <2 <2 0.02 <4

* Fluidized bed pyrolysis feed of pine chips, 500 ºC, 2.75 kg air/kg
**catalyzed pyrolysis of C. vulgaris using fixed bed reactor, 500 ºC, N2 flow 30 mL/min
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The moisture of the obtained bio-oils is much higher than crude oil, with higher levels of
nitrogen and about 60% of the calorific value. For use in internal combustion engines, is
advisable to make N content lower (for lower NOx emissions) and decrease moisture to avoid
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ignition problems. This may give indication that the pyrolysis process and their conditions must
be optimized to get similar characteristic to the fossil fuel.
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It is important to understand the least amount of fossil energy needed expressed as a ratio of fossil
energy input per the energy content of the output (using the LHV) (see Figure 8). The electricity
generation mix was considered to have a range of 0 g/kWh (100% renewables, 100%
efficiency) to 900 g/kWh (100% coal, 40% efficiency). These results, despite being on the lab-
scale and exploratory, may give insight on the operating conditions in a hypothetical biorefinery
context.
It is noteworthy the LD biomass tendency to produce less bio-oil, but having a favorable ratio
of energy spent per product outcome. Regarding the trade-off between the fossil fuel input and

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energetic output there is an indication that the energetic output is hardly larger than the required
fossil fuel input for the processing of microalgae. To resolve this situation an optimization of
the pyrolysis must further occur. This result strongly points out to the urge of using more
renewables fulfilling the biorefinery electricity energy needs.
Both functional units (kgbio-oil or MJbio-oil) used to express the results reveals the same
qualitative information: pathway #3 is preferable over pathway #2. Table 8 shows the results

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for the other microalgae for the Portuguese case study (82% FER = 0.82). S. obliquus produces
more bio-oil and has similar energy to mass ratio.

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60
58

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29.5 MJfossil/MJbio-oil (0-36)
56
54
Bio-oil wt%

52

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21.6 MJfossil/MJbio-oil (0-26)
50
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48
46
44 LD 375 ºC, 83 mL/min
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42 475 ºC, 200 mL/min

40
0 100 200 300 400 500
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MJfossil/kgbio-oil

Figure 8. Sensitivity of results to pyrolysis conditions, functional unit (kgbio-oil or MJbio-oil) and
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range due to electricity generation mix (dashed lines) for fresh and LD S. obliquus (mass
allocation criteria).
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If a system expansion criterion is chosen over the mass allocation criterion then different results
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come out as shown in Figure 9, for 1 kg bio-oil FU, S. obliquus. ISO standard 14044 on LCA
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states that system expansion is preferable to mass or economic allocation. However, performing a
system expansion means that the product (or products) under study must be identified and that
alternative products for the other products must be identified and quantified, which is not straight-
forward as seen in this case. Therefore some assumptions must be taken and increase the
uncertainty of the results.

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Investigated system Alternative system Resulting system
Path #1 - crude oil refinery = Path #1

Bio-oil (1 kg) Glycerin (0.1 kg) Glycerin (0.1 kg)

319.6 MJ/kgbio-oil

325.7 MJ Lipid extraction 12.7 MJ 15.2 kg GHG/kgbio-oil

+
6.6 MJ Transesterification 0.56 kg GHG
332.3 MJ

15.6 kg Lipid extraction

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+
0.2 kg Transesterification
15.8 kg GHG

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Investigated system Alternative system Resulting system
Path #2 - crude oil refinery = Path #2

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Bio-oil (1 kg) Bio-char(0.78 kg) K-fertelizer (0.2 kg)
1473.9 MJ/kgbio-oil

2.4 MJ 70.1 kg GHG/kgbio-oil

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1476.3 MJ
0.62 kg GHG
70.8 kg GHG
+0.09 kg GHg
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0.71 kg GHG

Investigated system Alternative system Alternative system Resulting system

Path #3 - crude oil refinery - crude oil refinery = Path #3
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Bio-oil (1 kg) Glycerin Bio-char Glycerin ( 0.045 kg) K-fertelizer (0.11 kg)
0.45 lipid ( 0.045 kg) (0.43 kg) 954 MJ/kgbio-oil
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extraction
+ 0.55 kg 5.7 MJ 1.4 MJ 45.7 kg GHG/kgbio-oil
pyrolisis
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0.3 kg GHG 0.09 kg GHG

+ 0.05 kg GHg
146.6 MJ Lipid extraction 0.14 kg GHG
+
2.97 MJ Transesterification
+
812 MJ Pyrolisis
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961.5 MJ

7.02 kg Lipid extraction

+
0.09 kg Transesterification
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+
38.9 kg Pyrolisis
46.1 kg GHG
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Figure 9 System expanded for 1 kg of Bio-oil obtained from S. obliquus (Primary energy and GHG emissions for
FER=0.82)

It is interesting to note that by using system expansion over mass allocation criteria still pathway
#3 is preferable over pathway #2 but definitely the winner is pathway #1 despite having less
product spectrum. Probably this suggests that the economic value of products should not be
overlooked.

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Regarding biodiesel production in Portugal (Castanheira et al., 2015) the values of GHG referring
to oil extraction, refining and production of Soybean methyl ester (SME) are below
0.1 kg CO2eq/kgSME ( 0.7- 6.7, for overall pathway) well below the obtained data. This stresses out
the needs for process optimization.
Regarding the RED biofuel sustainability criteria, and the reference value for 83 g/MJ (3.7 kg/kg
diesel), the 35% threshold will be only possible to achieve by reducing the GHG emissions by 13-

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67 kg/kg bio-oil (FER=0.82 case study).

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M
D
TE
C EP
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Table 8. Direct and after lipid extraction CP for FER= 0.82 and mass allocation criteria.
Biomass Fresh (direct CP, pathway #2) Lipid depleted (CP after lipid extraction and drying, path #3)
Bio- Primary energy GHG Bio-
Final energy Final energy Primary energy GHG

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oil (MJ/kgbio- (g/kgbio- oil 3
(MJ/kgbio-oil) 3 3
(MJ/kgbio-oil) (MJ/kgbio-oil×10 ) (g/kgbio-oil×103)
(%) oil×10 ) oil×10 ) (%)

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0.67 32 0.77 36
C. vulgaris 37 305 36 289

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(0.58-0.71) (30.7-33.7) (0.64-0.78) (34.0-37.3)
0.67 32 0.71 34
N. oculata 39 305 35 278

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(0.58-0.71) (30.5-33.5) (0.62-0.75) (29.9-32.8)

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0.69 33 0.80 38
S. obliquus 51 305 46 295
(0.60-0.73) (31.5-31.9) (0.69-0.84) (32.9-36.1)

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0.67 32 1.23 59
Pine bark 47 305 26 272

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(0.58-0.71) (30.1-33.5) (1.06-1.30) (31.0-34.0)

TE
C EP
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If microalgae falls in one of the tested species (similar chemical analysis
), than our values could be directly used for comparisons of other pyrolysis/lipid extraction
methods.
For researchers interested in using our data to include in extensive inventories and more
complete life cycle analysis (LCA) studies, and for different microalgae, our results could be
summarized in distributions for a “generic microalgae” and for 1 kg of produced oil the
metadata file could contain expected values for electricity input and GHG output. This could be

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a good subject for a future work but should require more experiments to get better and more
meaningful distributions.

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Briefing up, helpful exploratory results:
• Solvent n-hexane-isopropanol combined with ultrasound requires final energy

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consumption of 146-148 MJ/kgdry microalgae. Maximum oil product is achieved from Scenedesmus
obliquus;

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• Conventional slow pyrolysis of lipid depleted biomass decreases the bio-oil output, as
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compared to the fresh biomass pyrolysis, for the same residence time and temperature;
• Maximum overall oil product yield and favorable energy to mass/ energy to energy
output ratio is obtained for pathway#3 by using Scenedesmus obliquus;
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• A maximum bio-oil yield of 57% was achieved for slow pyrolysis of fresh Scenedesmus
obliquus for the conditions, 475 ºC, N2 flow 200 mL/min
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• Catalyst HY-2014, HZSM5 and USHY in 0.25 wt.% do not show a bio-oil boost effect;
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• A maximum bio-oil yield of 57.6% was achieved for non-catalyzed, 475ºC, N2 flow
200 mL/min, whose properties show a much higher water content, 60% heating value and a
H/C ratio 10 times lower than crude oil;
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• Lipid depleted pyrolysis bio-oil reveals to have a higher heating value and lower
moisture;
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• Pyrolysis of lipid depleted biomass as a favorable energy spent per product energy
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output;
• For use in internal combustion engines, is advisable to make N content lower (for lower
NOx emissions) and decrease moisture to avoid ignition problems in a high it does not harm
atomization;
• The energetic output is hardly larger than the required fossil fuel input for the
production and processing of microalgae. Therefore, the use of renewables fulfilling the
biorefinery electricity energy needs is mandatory as well as optimization of pyrolysis process.

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4. Conclusions
The processes occurring inside a biorefinery may vary significantly and there is a need to
choose ones over the others. In this paper three potential configurations for producing bio-oil
are experimentally studied in lab-scale and its mass and energy flows analyzed in a “virtual”
biorefinery context. It is an exploratory endeavor but the methodology followed can be helpful

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to decide on the best configuration targeting minimum energy and environmental burdens.
Mass allocation, system expansion and different functional units show how large the

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differences in results can be depending on a few methodological choices.
Lipid extraction followed by transesterification as a stand-alone process has the disadvantage of

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producing lower quantities of bio-oil for the same initial microalga biomass and fewer co-products
spectrum. However, shows the best values of primary energy consumption and GHG emissions
per kg of dry bio-oil produced. Pyrolysis has the advantage of including bio-char as a co-product

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that could be used as fertilizer and act as a carbon sink.
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Lipid extraction followed by lipids transesterification and lipid depleted biomass pyrolysis is
advantageous if the goal is to maximize the quantity of oil products, and simultaneously minimize
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the energy per quantity of oil product or per energy content of oil product.
From the three microalgae species analyzed, Scenedesmus obliquus is the most suitable for the
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specific objectives of maximizing bio-oil production with minimum carbon footprint. A

maximum bio-oil yield of 57% was achieved for conventional catalyzed pyrolysis of fresh
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Scenedesmus obliquus for the conditions, 475 ºC, N2 flow 200 mL/min. Lipid depleted
pyrolysis bio-oil reveals to have a higher heating value and lower moisture content than fresh
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microalgae pyrolysis one. The energetic output is hardly larger than the required fossil fuel
input for the production and processing of microalgae, therefore the use of renewables is
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strongly advisable as well as the optimization of the lipid extraction and pyrolysis processes.
Sensitive analyses to both functional unit and allocation criterion must be performed to handle
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result variations and make informed decisions.

Acknowledgements
This work was supported by Fundação para a Ciência e a Tecnologia (FCT), through IDMEC,
under LAETA-UID/EMS/50022/2013. Ana F. Ferreira is pleased to acknowledge the FCT for

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the provision of the scholarship SFRH/BPD/95098/2013 and Carla Silva the FCT 2012
researcher competition (IF/00181/2012).

Glossary
‫ܣ‬ሚ Alternate current
CP Conventional pyrolysis

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CED Cumulative energy Demand
FER Fossil energy ratio

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FU Functional unit
GWP Global warming potential

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GHG Greenhouse gas
H/C Ratio of hydrocarbon to carbon on a mass basis
HHV Higher Heating Value
LCA Life cycle assessment
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LD Lipid depleted biomass
LHV Lower Heating Value
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MP Microwave pyrolysis
t Working time of the equipment
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V Voltage
wt Weight
TE
C EP
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