international j ournal o f h y drogen e nergy xxx (2017) 1 e11

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Catalytic pyrolysis of Mediterranean sea plant for

bio-oil production

Susanna Maisano, Francesco Urbani, Natale Mondello, Vitaliano Chiodo*

Institute CNR-ITAE, Via Salita S. Lucia Sopra Contesse 5, 98126, Messina, Italy

articleinfo abst rac t

Article history: The main objective of the work was to investigate about the feasibility to produce high-
Received 29 March 2017 quality bio-oil from Mediterranean sea plant by catalytic pyrolysis process. Therefore,
Received in revised form experiments using Posidonia Oceanica at 500 C in a fixed bed reactor were explored taking
19 June 2017 into consideration the biomass conversion and bio-products yields. The effect of different
Accepted 17 July 2017 home-made Ni, Ce, HZSM-5 based catalysts in pyrolysis process was analyzed mainly in
Available online xxx terms of conversion yield, bio-oil yield and bio-oil oxygen and organic compounds content.
The highest liquid yields were obtained at 500 C. Particularly, CeO2 (51.15 wt%), NiCe/
Keywords: HZSM-5 (50.66 wt%) and Ni/CeO 2 (49.74 wt%) were the most effective catalysts and these
Catalytic pyrolysis have increased the bio-oil yield compared to non-catalytic ones (47.74 wt%). The highest
Posidonia Oceanica conversions were obtained with Ni/HZSM-5 (80.81%) and CeO2 (79.07%) which were the
Bio-oil most efficient catalysts. Oxygen level was decreased in bio-oils from 25.66 wt% in the
Biofuels starting biomass to 6e8 wt% with CeO2, Ni/CeO2 and NiCe/HZSM-5 catalysts. This is due to
Sea plants the potential of these catalysts to promote deoxygenation reactions, such as dehydration,
decarboxylation and decarbonylation, that enhance the bio-oil quality. In terms of com-
positions zeolite and ceria based catalysts were the best. In absolute the highest content of
hydrocarbons was obtained with HZSM-5 and Ni/HZSM-5, 39.56 and 34.91% respectively.
Therefore, lower content of acids and oxygen in the bio-oil, higher hydrocarbons, com-
bined with higher heating value show promise for production of high-quality bio-oil from
Posidonia Oceanica via catalytic pyrolysis.
2017 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.

conversion process. Among alternatives proposed, pyrolysis

Introduction
Biomass is considered one of the most preferred alternative
energy sources and its employment represents a sustainable
way for solving environmental problems such as greenhouse
effect and depletion of fossil fuels. Biomass can be classified in
i) lignocellulosic, ii) herbaceous and iii) aquatic flora and ma-
nures materials [1]. Further, it can be converted into various
forms of gaseous, liquid, and solid fuels according to the
of biomass has been indicated to obtain bio-oil which can be
employed directly as fuel [2]. However, the traditional use of
lignocellulosic materials promotes a large number of com-
pounds (phenols, acidic species etc) which show several
technical difficulties [3,4]. On the other hand, algal bio-oils
result stable than the corresponding to woody biomass,
essentially due to proteins, lipids and carbohydrates present
in the algae chemical composition [5]. Moreover, bio-oil can be
up-graded in terms of oxygen content, heating value and

* Corresponding author.
E-mail address: vitaliano.chiodo@itae.cnr.it (V. Chiodo).
http://dx.doi.org/10.1016/j.ijhydene.2017.07.124
0360-3199/ 2017 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.

Please cite this article in press as: Maisano S, et al., Catalytic pyrolysis of Mediterranean sea plant for bio-oil production, International
Journal of Hydrogen Energy (2017), http://dx.doi.org/10.1016/j.ijhydene.2017.07.124
2 i n t e r n a t i o n a l j o u r n a l of h y d r o g en e n e r g y xx x ( 2 0 1 7 ) 1 e11
acidity by in situ catalytic cracking during bio-oil production
[6]. Most of investigations were focused on the deoxygenation
effect promoted by the HZSM-5 zeolite. In particular, Pan et al.
[7], observed that the oxygen content (30.09%) of the bio-oil
produced from pyrolysis of Nannochloropsis sp. residue de-
creases efficiently to 19.53% in the bio-oil with HZSM-5
(catalyst/biomass ratio of 1:1). In addition HZSM-5 showed a
selectivity toward the aromatic hydrocarbons formation
[7e10]. Although negative aspects by using of zeolite were
highlighted; such as: i) high nitrogen and oxygen content in
the algal oil and ii) rapid deactivation of the catalyst [9e11].
Hence, investigations on catalysts including metals and ox-
ides were also carried out to adjust the acidity of HZSM-5
zeolite and to increase the yield of the oil in terms of quality
[6,12,13].
Low cost and availability are the main reasons that often
lead to choose Ni based catalysts instead other metal phases
[14]. Ni catalysts result to be active toward creaking and
reforming reactions of biomass matter and tars released
during pyrolysis at low temperature [15]. Bereketidou and
Goula observed that Ni/Al2O3eCeO2 catalyst has a better sta-
bility compared to Ni/Al2O3 catalyst due to redox properties of
ceria. This behavior is due to CeO2 properties that promote the
water gas shift (WGS) reaction and the redox reversibility of
active phase [16]. Among various carriers (ZrO2, CeO2,
MgAl2O4, CeeZrO2), the Ni/CeO2eZrO2 system showed the
highest activity as well as high stability [16]. Nevertheless,
Aysu et al. [14,17], investigated on influence of ceria on based
alumina and zirconia supported catalysts on pyrolysis prod-
uct yields and bio-oil proprieties of algae with high and low
lipid contents. Results highlighted NieCe/Al2O3 catalyst as the
most able system to reduce consistently acid and oxygen
content in the bio-oil. In addition, the oils resulted enriched in
higher aliphatic compounds and depleted in N-compounds.
Zeng et al. [18], showed that catalytic pyrolysis performed
with silica-supported nickel phosphide convert the natural
algae to high quality bio-oil containing long-chained alkanes
(59.4%) where the oxygen content was reduced from 41.7 wt%
in the algae to 8.0 wt% in the bio-oil.
Posidonia Oceanica, a seagrass widely distributed along
coastlines of the Mediterranean sea, leaves residues that
reaching the coasts represents a significant economical, and
hygienic problem in all coastal zones [19,20]. Therefore, the
conversion of this residues into value-added products could
be a good opening for business of the waste recycle industry.
Experimental data on pyrolysis of Posidonia Oceanica, alone
and mixed with waste vegetable oils, at different tempera-
tures (400e600 C) confirmed the feasibility to convert Pos-
idonia Oceanica both in bio-oil and in bio-char [20,21]. In
particular, it was observed that bio-oil yields increasing with
the increase of the operative temperature and the highest rate
was obtained at 500 C (>50%) [21]. Although, many papers are
present in literature on catalytic biomass pyrolysis for bio-oil
production, to the best of our knowledge, there are no works
available in the literature on the behavior of Posidonia Oce-
anica using catalytic pyrolysis with Ni, ceria and HZSM-5
based catalysts. Accordingly, the aim of this work was to
investigate about the feasibility to produce high quality of bio-
oil as biofuels from Mediterranean sea plant by catalytic py-
rolysis process. Hence, efforts were addressed in order to
Please cite this article in press as: Maisano S, et al., Catalytic pyrolysis of Mediterranean sea plant for bio-oil production, International
Journal of Hydrogen Energy (2017), http://dx.doi.org/10.1016/j.ijhydene.2017.07.124
obtain a bio-oil with a higher quality than that produced from
woody biomass or microalgae [2,22,23], mainly in terms of
oxygen content (<8 wt%), carbon content (>79 wt%) and high
heating value (>38 MJ/kg).
Therefore, experiments using Posidonia Oceanica at 500 C
were explored with respect to biomass conversion and bio-
products (bio-char, bio-oil and syngas) yields. Bio-oil was
studied also in terms of oxygen and organic compounds
content. Moreover, the effect of different home-made Ni, Ce,
HZSM-5 catalysts on pyrolysis process in terms of conversion
yield, products selectivity and bio-oils deoxygenation was
investigated.
Experimental section e materials and analytical
methods
Biomass preparation
Posidonia Oceanica samples were collected from the costs of
Sicily region (Italy). First, the samples washed with distilled
water, successively, Posidonia Oceanica was air-dried (at
110 C for 12 h), shredded and sieved into a size range of 16e25
mesh. Samples were conserved in an oven at 100 C.
Catalyst preparation and characterization
Catalysts were prepared by impregnation (incipient wetness)
using g-Al2O3 AKZO-NOBEL 001-3P (SA (BET) 260 m2 g1), ZSM-
5 ALFA AESAR (SA (BET) 400 m2 g1) (30:1 M ratio) and CeO2
Sigma Aldrich (SA (BET): 27 m2 g1) as supports. Ni(5%)/CeO2,
Ni(21%)/Al2O3, Ni(5%)/HZSM-5 were prepared using an
aqueous solution of Ni(NO3)2$6H2O (Sigma Aldrich) as pre-
cursor. Ni(5%)Ce(5%)/HZSM-5 was prepared using an aqueous
solution of Ni(NO3)2$6H2O (Sigma Aldrich) and Ce(NO3)3$6H2O
(Alfa Aesar) as precursors. Dolomite (MgCa(CO3)2) a mineral
catalyst was purchased from Minerali Industriali S.r.l. All
catalysts were dried at 110 C for 3 h and then calcined at
600 C for 3 h before use. Catalysts were pressed at 400 bar,
crushed and sieved and the 16e25 mesh fraction was used for
the catalytic tests. The surface area, pore volume and average
pore size of the prepared catalysts were analyzed by N 2
adsorption method at 195.8 C using Micromeritics ASAP
2020 instrument. The surface area and pore size distribution
of the samples were calculated by using the standard Bru-
nauereEmmetteTeller (BET) equation and the Barret-Joyner-
Halenda (BJH) method, respectively.
Proximate and ultimate analysis
Each sample of biomass was characterized by proximate, ul-
timate analyses and HHV values. Proximate analysis included
measurement of moisture content, volatile matter, fixed car-
bon and ash. The moisture content measurement were per-
formed on biomass samples, dried in a convection oven at
110 C until constant weight was recorded. The volatile matter
content was determined by measuring weight loss after
heating biomass samples to 575 C in an alumina crucible
under N2 atmosphere. The ash content was measured by
heating samples at 575 25 C for 24 h to constant weight in a
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y x x x ( 2 0 1 7 ) 1 e11
muffle furnace and the fixed carbon fraction was calculated by
subtracting the percentages of volatile matter, moisture con-
tent and ash from 100%. Elemental analysis was performed on
biomass samples, bio-oil and bio-char using CHNS-O
Elemental Analyzer (Thermo Fisher Scientific, Flash EA
1112). High Heating Values and protein fraction of biomass
and products were calculated as in a previous work [21,24e26].
Feedstock and products analysis
Thermogravimetric analysis (TGA)
Thermo-decomposition of Posidonia Oceanica under pyroly-
sis was investigated by thermogravimetric analysis (TGA) and
derivative thermo-gravimetric (DTG) measurements. TG-
pyrolysis using N2 as carrier gas was used to determine the
moisture content, volatile matter and fixed carbon and to
compare/confirm with the results obtained by ASTM stan-
dards. Experiments were carried out with a thermogravi-
metric analyzer Netzsch Thermische Analyse TASC 414/2. The
samples, weighing approximately 10 mg, were heated from 25
to 800 C (10 C/min) under N2. In order to determine the ash
and fixed carbon amounts the temperature was decreased to
600 C under air conditions/atmosphere. The moisture con-
tent in the samples was estimated by the loss of weight be-
tween 25 and 105 C. Instead, the volatile components of the
feedstock were calculated from the weight loss between 105
and 800 C (primary volatiles 105e600 C and secondary vol-
atiles 600e800 C). Ash and fixed carbon amounts were
determined in different ways, the first by the solid residue
remaining at the end of combustion stage and the second by
subtracting the ash content from the solid obtained at the end
of the TGA test.
X-ray diffraction (XRD) analysis
The crystalline phases of catalysts, Posidonia Oceanica feed-
stock and bio-chars samples were identified by powder X-ray
diffraction using Philips X'Pert X-ray diffractometer, operating
with Cu/Ka radiation (wavelength 1.5406 A, 40 kV, 30 mA).
Data were collected over the angular range 5e80 in 2q under
atmospheric pressure. The peak profiles of the (2 2 0) reflection
in the face-centered cubic (fcc) structure were obtained using
the Marquardt algorithm. Instrumental broadening was
determined using a standard platinum sample.
pH measurements
pH measurements were carried out with an Orion pH meter
(Thermos Scientific). Bio-char to deionized water ratio
(1:10 wt:wt) was used to form a homogeneous suspension, and
the pH was determined after 1 h of equilibration [21,27].
Gas chromatography-mass spectrometry (GC-MS) analysis
Bio-oil samples were extracted with dichloromethane (1:1, v/v)
and, extracts were semi-quantitative analyzed by gas chro-
matography coupled with mass selective detector (GC-MSD),
performed on an Agilent 7890A-5975C instrument using a DB-
WAXETR Agilent Technologies (30 m 0.25 mm 0.25 mm) [23].
GC and the injector temperatures were the same during anal-
ysis. Helium was used as the carrier gas at a flow rate of
3.0 ml/min 1 mL sample was injected with a split ratio of 1:20.
The GC oven temperature program was as follows: start at
Please cite this article in press as: Maisano S, et al., Catalytic pyrolysis of Mediterranean sea plant for bio-oil production, International
Journal of Hydrogen Energy (2017), http://dx.doi.org/10.1016/j.ijhydene.2017.07.124
3
40 C; hold for 10 min, raise from 40 C to 200 C at a heating rate
of 5 C/min; hold for 15 min, raise to 240 C at a heating rate of
10 C/min; hold for 15 min, raise to 260 C at a heating rate of
10 C/min; hold at the final temperature for 10 min. The end of
column was directly introduced into the ion source of a mass
selective detector of Agilent 5975C series with operating con-
ditions of transfer line at 270 C, ion source at 250 C and
electron energy of 70 eV. Mass spectral library databases
provided by NIST05a.L was used to identify the chemical con-
stituents [14].
Coke analysis
The amount of coke deposited on each catalyst was deter-
mined by the weight change during combustion using a
thermogravimetric analyzer (Netzsch Thermische Analyse
TASC 414/2). 20 mg of sample in the alumina crucible was
heated from 25 C to the final temperature of 900 C (10 C/
min) under a 70 ml/min air atmosphere.
Experimental plant
As shown in Fig. 1 (a), the schematic diagram of the experi-
mental plant consists of a carrier gas system, reactor unit, bio-
oil collectors and GC analyzer as major setups. Regulation and
measurement of gas flow is performed by Mass Flow Con-
trollers ASM-AFC 25.50 model. Fixed-bed reactor details were
presented in Fig. 1 (b), the reactor is made of a preheat zone
(80 mm in length) and a pyrolysis zone (100 mm in length);
particularly, it is a high temperature resistant stainless steel
pipe (length: 300 mm; internal diameter: 16 mm) with a
shrinking point at the bottom. The reactor is placed into an
electric furnace of 1.0 kW, whose temperature is leaded by a
controller driven by one thermocouple (K type) located in an
internal wall within the same. Additional thermocouple (K
type) is placed at the center of the biomass bed to measure
temperature inside the reactor. The heating apparatus was
calibrated so that all temperature measuring points had the
same constant temperature. Bio-oils are collected in three
cold traps maintained at 78 C (liquid nitrogen and ethyl
acetate mixture) and placed immediately next to the reactor
outlet stream. The liquid product is analyzed with gas chro-
matography coupled with mass selective detector (GC-MSD).
Gases are analyzed with a GC 7890A (Agilent Technologies)
with three columns (molecular sieves SA, Porapack Q, Hay-
esep) connected to two detectors; one to thermal conductivity
(TCD) and the other to flame ionization (FID).
Catalytic pyrolysis experiments
Experiments were performed in a stainless steel fixed-bed
reactor under nitrogen flow (50 ml/min) as a carrier gas that
flowed from the top of reactor to the bottom. Measurements
were carried out at atmospheric pressure and 500 C of tem-
perature but before each pyrolysis test, the reaction system
was purged by N2 for 30 min to eliminate inside air. In a typical
run, 3 g of dried Posidonia Oceanica (70%)/catalyst (30%)
mixture was put inside the reactor. An external electric
furnace with temperature controlled was used to heat the
reactor at 60 C/min. The reactor was kept at desired tem-
perature for 60 min. Outlet gas stream was condensed in three
4 i n t e r n a t i o n a l j o u r n a l of h y d r o g en e n e r g y xx x ( 2 0 1 7 ) 1 e11

Fig. 1 e A) Scheme of lab-scale pyrolysis plant; B) details of the fixed-bed reactor.

cold traps (78 C) and the liquid product (bio-oil) was
extracted with dichloromethane (CH2Cl2), then the solvent
was evaporated at 40 C using a rotary evaporator and the bio-
oils weighted. The solid residue (bio-char) remained in the
reactor was successively recovered and weighted. The
amount of gaseous products was calculated by subtracting the
solid and liquid yields from the amount of initial raw algae
(3 g). Conversion and product distribution yields of pyrolysis
tests were calculated as in a previous work [21]. All tests were
performed in triplicate to evaluate the standard deviations
(STD).
Results and discussions
Raw materials characterization: EA, TGA, XRD
stabilization and decomposition of the carbonaceous matter
(600e800 C). In particular, five main stages can be observed;
the first, at T < 150 C, is related to superficial moisture and
carbohydrates decompositions; the second and third, between
200 and 600 C, correspond at protein (270e300 C), cellulose
(325 C) and lipids (450 C) devolatilization [14,30,31]; in the
fourth, among 600e800 C occurs the formation and stabili-
zation of carbonaceous matter. Fixed carbon and ash content
in the starting biomass were calculated in the last stage (air
atmosphere) by oxidation of the solid residue remaining at
800 C (about 26%). Moreover, the TGA/DTG curve shows that
the initial decomposition temperature and the maximum
weight loss rate of Posidonia Oceanica are lower than the
lignocellulosic biomasses. This is due to the different chemi-
cal composition of Posidonia Oceanica and in particular at his

Before performing the pyrolysis experiments, ultimate and

Table 1 e Physico-chemical properties of the Posidonia
proximate analysis of Posidonia Oceanica were performed to
Oceanica feedstock.
determinate the composition and evaluate the potential for
Posidonia Oceanica
production of bio-oil. The ultimate and proximate analysis
results were reported in Table 1. Proximate analysis (wt%) Ash 14.02
Low amount of proteins (7.03 wt%) and lipids (7 wt%) was Moisture 12.67
V.M. 525 C 60.95
recorded meaning this biomass not ideal for biodiesel pro-
F.C. 12.36
duction, but suitable for pyrolysis process. Furthermore, Pos-
Ultimate analysis (wt%)a C 40.29
idonia Oceanica has relatively high carbon content (40.3 wt%) H 5.96
and this makes it suitable for biofuel production. However the N 1.12
high ash rate (14.02 wt%) detected could promote char for- S 0.29
mation since inorganic elements in the ash are known to Ob 25.65
catalyze the formation of char during pyrolysis [26,28,29]. H/C atom ratio 1.40
O/C atom ratio 0.64
Before performing the actual experimental study, thermog-
HHV (MJ/kg) 16.20
ravimetric (TGA) and DTG analysis were used to estimate the Protein (wt%) 7.03
thermal behavior of Posidonia Oceanica, Fig. 2. a
As received.
The pyrolysis diagram can be divided in three steps: i) b
By difference.
dehydration T < 110, ii) devolatilization (200e600 C), iii)

Please cite this article in press as: Maisano S, et al., Catalytic pyrolysis of Mediterranean sea plant for bio-oil production, International
Journal of Hydrogen Energy (2017), http://dx.doi.org/10.1016/j.ijhydene.2017.07.124
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y x x x ( 2 0 1 7 ) 1 e11 5

Fig. 2 e TGA and DTG curves of Posidonia Oceanica.

very low lignin content respect to woody biomasses [14]. XRD char Section (Bio-char) in order to comment both fresh and
diffraction patterns of the fresh biomass is showed in Fig. S1. used catalysts.
The XRD pattern highlights the intermediate behavior of
Posidonia Oceanica sea plant. Indeed, are present the main Pyrolysis experiments
peaks (16 and 22) of cellulose crystalline phase, typical of the
lignocellulosic biomass, and calcite crystalline phase with a Effect of temperature on products distribution
greatest intensity peak at 29.3 that is instead characteristic of The conversion (bio-oil gas yields) and distribution of
the algal biomass [21,32]. products obtained by pyrolysis of Posidonia Oceanica without
and with 30% catalyst are given in Table 3. STD of pyrolysis
Catalysts characterization products yields was reported in Table 3, the values were be-
tween 0.02 and 0.23. Non catalytic tests were performed in the
Table 2 presents the physical properties of the prepared cat- different temperature range (400e600 C) in order to evaluate
alysts and supports that were evaluated using N 2 adsorption the highest bio-oil yield (500 C). Therefore, the catalytic tests
isotherms at 195.8 C. The total pore volume, specific surface were carried out at 500 C. The overall conversion and gas
area (SBET) and average pore diameter of Al 2O3, CeO2, HZSM-5 yields increased sharply according to the temperature in-
supports were evaluated. Addition of metal oxide influenced crease, while bio-char yields decreased at runs with and
the catalyst properties, surface area and pore volume were without catalysts. When temperature was increased from 400
decreased while average pore size was increased slightly. This to 600 C, the conversion was increased from 60.15% to 70.21%
properties is clearly visible for the following catalyst couples, in the non-catalytic tests and from 66.01% (dolomite) to
Al2O3eNi/Al2O3 and CeO2eNi/CeO2, indeed, surface area of the 80.81% (Ni/HZSM-5) in the catalytic tests. At 600 C, gas for-
doped catalyst decreased from 260.02 to 59.57 m2/g and 27 to mation is favored by secondary decomposition reactions and
8.50 m2/g respectively. bio-oil yield decreased. The highest liquid yields were ob-
Also for the zeolite catalysts the impregnation with Ni tained at 500 C, particularly the highest liquid yield (51.15 wt
and/or Ce transition metals reduced the surface area and pore %) was produced with CeO2 catalyst. The lowest bio-char yield
volume respect to HZSM-5 alone. This could be due to pore (19.19%) was obtained with Ni/HZSM-5, this is due to greater
blocking by metal species dispersed in the channels or by the activity of the catalyst on gasification of char by secondary
presence of metal oxide aggregates. The X-ray diffraction reactions.
discussions on prepared catalysts will be reported in the bio-
Effect of catalyst on products distribution
The use of catalysts in the pyrolysis reactor can be useful to
convert the feedstock into bio-fuels [33]. In fact, working with
Table 2 e The physical properties of the catalysts. catalytic materials could encourage the formation of desired
Catalyst Surface Pore size (A) Pore volume products (hydrocarbons, furans, phenols, etc) through the
area (m2/g) (cm3/g) promotion of different reactions such as dehydration, decar-
boxylation, decarbonylation, dehydrogenation and cracking.
Al2O3 260.02 37.44 0.129
Ni/Al2O3 59.57 37.56 0.120
Data reported in Table 3 show that effect of catalysts on
CeO2 27.00 38.01 0.154 product yields are different. All catalysts have increased the
Ni/CeO 2 8.50 39.20 0.132 conversions of Posidonia Oceanica compared to non-catalytic
HZSM-5 498.93 42.21 0.253 runs but the highest conversion is occurred with Ni/HZSM-5
Ni/HZSM-5 385.88 44.34 0.217 (80.81%) and CeO2 (79.07%) catalysts. While dolomite and
NiCe/HZSM-5 263.86 45.86 0.208
alumina based catalysts resulted the worst, further it would
Dolomite 32.09 146.2 0.116
seem promote the formation of charcoal species probably

Please cite this article in press as: Maisano S, et al., Catalytic pyrolysis of Mediterranean sea plant for bio-oil production, International
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6 i n t e r n a t i o n a l j o u r n a l of h y d r o g en e n e r g y xx x ( 2 0 1 7 ) 1 e11

Table 3 e Conversion and products distribution obtained by pyrolysis of Posidonia Oceanica with and without catalyst.
T C Pyrolysis test Conversion % Bio-char yield % Bio-oil yield % Gas yield %
(Total volatiles)
400 No catalyst 60.15 39.85 45.03 15.12
STD 0.10 0.04 0.07
500 63.37 36.63 47.74 15.62
STD 0.11 0.12 0.23
600 70.21 29.79 40.54 29.67
STD 0.05 0.03 0.08
500 CeO2 79.07 20.93 51.15 27.91
STD 0.04 0.10 0.07
500 Ni/CeO 2 78.53 21.47 49.74 28.79
STD 0.15 0.08 0.23
500 HZSM-5 76.37 23.63 48.74 27.62
STD 0.09 0.04 0.13
500 Ni/HZSM-5 80.81 19.19 48.72 32.10
STD 0.03 0.03 0.01
500 NiCe/HZSM-5 78.44 21.56 50.66 27.77
STD 0.02 0.02 0.04
500 Ni/Al2O3 66.37 33.63 48.72 17.66
STD 0.03 0.02 0.04
500 Dolomite 66.01 33.99 41.38 24.62
STD 0.03 0.01 0.05

promoted by different factors as the acidic characteristics of
the catalyst [34,35].
From the bio-oil yields point of view, CeO2 (51.15 wt%),
NiCe/HZSM-5 (50.66 wt%) and Ni/CeO2 (49.74 wt%) were the
most effective catalysts and increased the bio-oil yields than
non-catalytic ones (47.74 wt%). This behavior can be attrib-
uted to the cracking activity of Ni and combined effect of Nie
Ce catalysts, where CeO2 increases the stability, dispersion of
Ni and carbon suppression [34].
In order to evaluate the amount of coke formation on
used catalysts, TGA analysis in pure air were carried out and
results were resumed in Table 4, where three steps of mass
loss are reported.
In the range temperature 25e100 C samples released the
moisture, while from 100 C to 600 C the weight loss was
attributed to the char decomposition. Finally, in the range
600e900 C the mass loss has due to the coke combustion
rates. The last ones are in according to the catalytic activities
showed in Table 3, mainly in terms of total volatiles.
Data reported in Table 4, suggest that the redox properties
of ceria and the ability of ceria system to promote the gas
species formation such as CO2 and CO, employing a lattice
oxygen lead to low coke deposition [36,37]. In the same way,
the addition of Ni improves the catalyst activity through
steam reforming reactions that retard the rate of carbon
deposition [14]. In fact, working with the catalysts: Ni/CeO2
and Ni/HZSM5 leaves to the reduction of carbon formation
rate compared to the use of only supports CeO2 and HZSM5
(from 1.15 wt% and 2.01 wt% to 1.33 wt% and 2.82 wt %
respectively). Also the NiCe/HZSM-5 system showed the
lowest amount of coke deposition (0.14 wt %) probably due to
the combined effect both ceria and Ni.
On the other hand, the Ni presence appeared to have a poor
effect on carbon formation in the Ni/Al2O3 performance, this
could be attributed to the alumina that would seem to be no
active for the purposes of the pyrolysis process.
Characterization of pyrolysis products by EA, TGA, XRD,
XRF and GC-MS analysis
Bio-char
All bio-char was characterized in terms of elemental analysis
and HHV values, the results were reported in Table 5. The bio-
chars had higher carbon content (62e66 wt%) and also high
HHV (22e24 MJ/kg) values if compared with the original raw
material (40 wt%, 16.20 MJ/kg respectively). Moreover, the
good nitrogen content and alkaline pH values calculated make
these materials suitable as soil amendment after separation

Table 4 e Coke amount on the pyrolysis catalysts.

Catalytic bio-chars Absorbed water (wt%) Char decomposition (wt%) Coke combustion (wt%)

25e100 C 100e600 C 600e900 C
CeO2 0.68 35.29 1.33
Ni/CeO 2 0.81 26.31 1.15
HZSM-5 1.71 37.52 2.82
Ni/HZSM-5 1.81 25.75 2.01
NiCe/HZSM-5 1.36 26.98 0.14
Ni/Al2O3 1.77 34.60 4.05
Dolomite 1.1 36.46 5.57

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Table 5 e Results of elemental analysis of the bio-chars obtained from Posidonia Oceanica.
Elemental analysisa (Bio-Char)
T C C H N S Ob H/C molar ratio O/C molar ratio HHV (MJ/kg) pH
No catalyst 400 57.00 3.40 0.80 0.85 37.95 0.76 0.54 21.37 9.94
500 62.15 2.85 0.53 0.81 33.66 0.55 0.41 22.69 10.75
600 68.50 2.08 0.70 0.80 27.92 0.36 0.41 24.13 10.89
CeO2 500 66.22 2.26 1.75 0.58 29.18 0.59 0.33 23.28 12.19
Ni/CeO 2 500 62.68 2.56 1.30 0.62 32.84 0.36 0.39 22.70 10.05
HZSM-5 500 64.03 2.59 1.97 0.62 30.79 0.53 0.36 23.28 10.40
Ni/HZSM-5 500 62.68 2.56 1.30 0.62 32.84 0.36 0.39 22.70 10.05
NiCe/HZSM-5 500 64.03 2.59 1.97 0.62 30.79 0.53 0.36 23.28 10.40
Ni/Al2O3 500 64.48 3.24 1.93 0.48 29.87 0.55 0.35 24.15 11.19
Dolomite 500 63.65 2.49 1.67 0.25 31.94 0.55 0.38 23.04 11.72
a
On dry ash free basis.
b
By difference.

from the catalyst [29]. This resulted to be useful for the 400 to 600 C) both atomic ratios for bio-chars of Posidonia
neutralization of acidic soils improving the soil quality and Oceanica decreased indicating that structural trans-
increasing the productivity of crops [27]. formations induce a carbonization process [38]. Furthermore,
Table 5 reports also the H/C and O/C ratios, the decreasing Spokas and Schimmelpfenning et al. proposed a restricted
of these ratios respect the original biomass indicates an windows of H/C and O/C ratios as tool to assess the bio-char
aromaticity development in the bio-chars structure due to stability [39,40]. The bio-chars obtained by all catalytic
removing of H and O from inside the material. Particularly, the experimental tests fall into this window that has the following
biochar aromaticity is studied by Van Krevelan plot that is values of H/C < 0.6 and O/C < 0.4.
reported in Fig. 3. Increasing the pyrolysis temperature (from The X-ray diffraction patterns of the fresh and used Ceria
and alumina based catalysts are shown in Fig. S2 (a and b).
In the Ceria and Ni/Ceria catalyst was not observed a crys-
1.6 Fresh Biomass tallinity loss of the structure between fresh and used cata-
Char Non catalytic tests (400-500-600C) lysts. Moreover, Ni/CeO2 catalyst exhibit peaks at 2q
1.4
Char catalytic tests (500C)
Fresh scale 28.5, 33.10, 47.60, 56.39, 59.13, 69.51, and 79.10
Atomic H/C ratio

1.2 attributed to the cubic cerium (IV) oxide crystal phase,

instead the peaks of the cubic nickel (II) oxide at 2q
1.0
scale 37.20, 43.18, 62.90, 75.22, 79.40. Differently for
0.8 Char catalytic tests 500C 400C No catalyst alumina based catalysts was observed a remarkable crys-
tallinity loss. This is visible by the formation of amorphous
0.6 500C No catalyst phase to due at coke formation over spent catalyst surface.
0.4 The X-ray diffraction patterns of zeolite and dolomite cata-
600C No catalyst
a) lysts are shown in Fig. S3 (a and b). The similarity of the XRD
0.2 patterns between fresh HZSM-5 and other zeolite catalysts
0.2 0.4 0.6 0.8 indicates that the framework of HZSM-5 was still kept after
Atomic O/C ratio loading Ni and Ce or after reaction, because the presences of
0.7
typical peaks of HZSM-5 (23e24) are still maintained [41].
CeO 2 However, the intensities of diffraction peaks of used cata-
0.6 HZSM-5
lysts are changed compared to fresh catalysts, and this is
Atomic H/C ratio

N i/Al2 O3
Dolomite
due to the distortion of the zeolite lattice caused by the
0.5 NiCe /HZSM -5 deposition of carbonaceous materials within zeolite pores
[42]. The Ni and Ce peaks are not visible in the patterns, this
0.4 is due to the low metal loading but also to the high crys-
tallinity of the zeolite. These results were consistent with
Ni/H ZSM-5
0.3 Ni/CeO 2
those previously reported in literature [14,43,44]. The dolo-
mite catalyst is composed by magnesium and calcium car-
b) bonates and for this reason exhibits main peaks of both
0.2
0.300 0.325 0.350 0.375 0.400 compounds (see Fig. S3) and in the specific case those of
magnesium oxide at 2q scale 37.00, 43.00, 62.30, and
Atomic O/C ratio
78.50 and those of calcium carbonate at 2q scale 26, 29,
Fig. 3 e a) Van Krevelen plot for biomass precursor and bio- 41.18, 50.98. Furthermore, a small decrease in crystallinity
chars; b) Enlargement of the plot corresponding to catalytic is depicted in the initial part of the XRD graph due at the
bio-chars. coke formation over catalyst surface.

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Table 6 e Physico-chemical properties and elemental analysis of the bio-oils obtained at 500 C.
Elemental analysisa (Bio-oil)
No catalyst CeO2 Ni/CeO2 HZSM-5 Ni/HZSM5 NiCe/HZSM5 Ni/Al2O3 Dolomite
Carbon 60.10 83.67 81.31 75.46 77.03 80.96 65.95 62.07
Hydrogen 5.30 6.95 6.12 6.90 6.74 6.81 6.97 6.64
Nitrogen 3.60 2.07 3.40 1.62 2.91 2.52 2.25 1.59
Sulfur 1.10 0.43 0.74 0.50 0.77 0.93 0.44 0.74
Oxygen b 29.90 6.87 8.43 15.52 12.54 8.77 24.39 28.95
H/C molar ratio 1.05 0.59 0.61 0.72 0.67 0.62 0.89 0.99
O/C molar ratio 0.37 0.06 0.08 0.15 0.12 0.08 0.28 0.35
HHV (MJ/kg) 24.44 40.60 37.48 34.79 35.74 38.46 29.03 26.39
a
On dry ash free basis.
b
By difference.

Bio-oils e oxygen content and GC-MS family distribution
Posidonia Oceanica bio-oils produced at 500 C were charac-
terized in terms of elemental analysis, oxygen content and
GC-MS composition. The HHVs and elemental analysis of bio-
oils are reported in Table 6. As bio-chars also bio-oil samples
had higher carbon content (60e83 wt%) and high HHV
(24e40 wt%) values if compared with the original raw mate-
rial. Moreover, some found HHV values can be compared
those with the fossil fuels [45].
The nitrogen content in all bio-oils is low respect to
another type of algal biomass [14]. Indeed, from a fuel quality
point of view, nitrogen originated from chlorophyll and pro-
teins present in the starting biomass is detrimental in biofuels
due to the formation of NOx during its combustion. This
clearly indicates that the starting composition of the biomass
significantly affects on the quality of the bio-oil. Overall, bio-
oils were affected by deoxygenation. The oxygen content is
reported in Fig. 4, the decrease of this value respect to non-
catalytic bio-oil can be attributed to the oxygen remove (as
CO, CO2 and H2O) by deoxygenation reactions.
The most effective catalysts to enhanced the bio-oil quality
were CeO2, Ni/CeO2 and NiCe/HZSM-5 both for the decrease in
oxygen content (6e8 wt%) respect the starting biomass
(25.66 wt%) and for HHV values. These results were consistent
with the elemental analysis and GC-MS. Indeed, GC-MS
Fig. 4 e Oxygen content of bio-oils obtained by non-
catalytic and catalytic tests.
analysis was carried out in order to determine the main
products and verify the improving of the Posidonia Oceanica
bio-oils quality. The list of the compounds identified by GC-MS
analysis are given in Table S1. As expected, degradation of
lignocellulosic components (hemicellulose, cellulose and
lignin) by pyrolysis produced many types of organic com-
pounds with different molecular structures and molecular
weights. In particular, hemicellulose decompose before the
other components (200e280 C) forming the acidic com-
pounds such as acetic acid. On the other hand, decomposition
of cellulose (240e350 C) produces levoglucosan as the pri-
mary breakdown product during thermal treatment, but also
other anhydroglucose, furan and furan derivatives are pro-
duced. Phenols and derivatives such as 2,6-dimethoxy phenol
and 2-methoxyphenol are instead the primary products of
degradation of lignin (280e500 C) during pyrolysis process
[46]. For these reasons, bio-oils are composed to complex
mixtures of organic compounds which included hydrocar-
bons, alcohols, phenols, furans, aldehydes, ketones, carbox-
ylic acid and nitrogen compounds. These functional groups
can be divided into two main subgroups, namely in to desired
and undesired compounds. Desired compounds include hy-
drocarbons, alcohols, phenols and furans, which can be used
as alternatives for fuel or high valued chemicals. On the other
hand, the presence of undesired compounds such as alde-
hydes, ketones, carboxylic acid and nitrogen compounds,
leads to low HHV values and instability of bio-oils. The dis-
tribution of desired and undesired compounds for families
groups are shown in Figs. 5 and 6.
In terms of GC-MS compositions Zeolite and Ceria based
catalysts were the best. Compared to non-catalytic treatment,
all these catalysts have induced a significant increase of hy-
drocarbons in bio-oil. In the zeolite based catalysts the in-
crease of hydrocarbons is due to the rise of aromatic
hydrocarbons as a result of the aromatization reaction on
zeolites [47,48]. HZSM-5 and Ni/HZSM-5 have led to the higher
yield of hydrocarbons, 39.56% and 34.91% respectively.
Instead, bio-oils obtained with CeO2 and Ni/CeO2 had a lower
amount of hydrocarbons if compared to zeolites catalysts but
a highest content of alcohols and phenols (53.26%, 49.4%), and
furans (16.61%, 17.66%). This is due to a different conversion
pathway in presence of metal oxides, which do not enhance
the aromatics formation if compared to the tests carried out
with other catalysts. NiCe/HZSM-5 showed an intermediate

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Fig. 5 e Composition of desired compounds in non-catalytic and catalytic bio-oils.

Fig. 6 e Composition of undesired compounds in non-catalytic and catalytic bio-oils.

behavior between ceria and zeolite catalysts and this has been
due to simultaneous presence of Ni and Ce over HZSM-5.
Dolomite and Ni/Al2O3 were the worst catalysts, indeed have
not led to any improvement of bio-oils quality. Furthermore,
the high content into carboxylic acids, aldehydes and ketones
of these bio-oils compared to non-catalytic treatment makes
them these bio-oils unstable and no suitable as biofuels for
energy purposes. All catalysts induced a decrease of nitrogen
compounds derived from protein degradation of algal
biomass.
Conclusions
Specifically, catalytic pyrolysis is considered to be a promising
method to convert solid biomass into a liquid product in high
yields and then to produce potential fuels.
1. Posidonia Oceanica was evaluated as feedstock for the
catalytic production of pyrolysis oils. Its high carbon con-
tent (40.30 wt%) and low decomposition temperatures
compared to lignocellulosic biomass make it a suitable
feedstock for biofuel production.
2. The highest liquid yields were obtained at 500 C. Particu-
larly, CeO2 (51.15 wt%), NiCe/HZSM-5 (50.66 wt%) and Ni/
CeO2 (49.74 wt%) were the most effective catalysts and
have increased the bio-oil yields of Posidonia Oceanica
compared to non-catalytic ones (47.74 wt%).
3 All catalysts have increased the conversions of Posidonia
Oceanica compared to non-catalytic tests. The highest
conversions were obtained with Ni/HZSM-5 (80.81%) and
CeO2 (79.07%) which were the most efficient catalysts.
4. Alumina based catalyst and dolomite have resulted to the
worse conversions (66.38 and 66.00% respectively) and the
highest coke formation (4.07 and 5.57% respectively) and
this is due to the catalyst acidity and the propensity for
dehydration reaction with formation of charred species.
5. All obtained bio-chars have higher carbon content
(62e66 wt%) and high Higher Heating Values (22e24 MJ/kg)
when compared with that of the raw material (40 wt%,
16.20 MJ/kg). Furthermore, the high ash and nitrogen con-
tents, and pH values them suitable for utilization as soil
amendment.
6. Overall, oxygen level was decreased in all bio-oils from
25.66 wt% in the starting biomass to 6e8 wt% with CeO2,
Ni/CeO2 and NiCe/HZSM-5 catalysts. These results indicate
the high deoxygenation power of ceria and NieCe/Zeolite
catalysts.
7. In terms of GC-MS compositions Zeolite and ceria based
catalysts were the best. In absolute term the highest

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