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Simulation of biofuel production via fast pyrolysis of palm oil residues

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DOI: 10.1016/j.fuel.2015.07.043

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 Fuel 159 (2015) 819–827

Contents lists available at ScienceDirect

Fuel
journal homepage: www.elsevier.com/locate/fuel

Simulation of biofuel production via fast pyrolysis of palm oil residues

Jemaa Mabrouki a, Mohamed Ammar Abbassi a, Kamel Guedri b, Ahmed Omri a, Mejdi Jeguirim c,⇑
a
Unite de Recherche Materiaux, Energie et Energies Renouvelables (MEER), Faculte des Sciences de Gafsa, B.P.19, Zarroug, Gafsa, 2112, Tunisia
b
Mechanical Engineering Department, College of Engineering and Islamic Architecture, Umm Al-Qura University, Saudi Arabia
c
Institut de Science des Matériaux de Mulhouse, IS2M, UMR 7361 CNRS, 15, rue Jean Starcky, Mulhouse, France

h i g h l i g h t s

 SuperPro Designer model was developed for the simulation of biomass pyrolysis.
 Biofuels production via fast pyrolysis of palm oil residues was modeled.
 Temperature and residence time effects on product yields were investigated.
 The optimized parameters were 550 °C pyrolysis temperature and 0.5 s residence time.
 Empty fruit bunch is the post promising residues for bio-oil production.

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

Article history: The main purpose of this present work is to optimize the biofuel production from the fast pyrolysis of
Received 8 April 2015 three palm oil residues, namely palm shell (PS), empty fruit bunch (EFB) and mesocarp fiber (MF).
Received in revised form 11 June 2015 Hence, a biofuel process is simulated using SuperPro Designer (SPD) software. The simulation includes
Accepted 14 July 2015
pretreatment, fast pyrolysis, product collection, and upgrading sections. The developed SPD model was
Available online 23 July 2015
validated firstly with published data of the fast pyrolysis of wood oak in fluidized bed reactor.
Secondly, the influence of the operating conditions such as pyrolysis reactor temperature and residence
Keywords:
time on the fast pyrolysis of the different residues was examined. The obtained results indicate that tem-
Biofuels
Fast pyrolysis
perature at 550 °C is suitable for obtaining a maximum liquid yield. Moreover, it was found that 0.5 s is
Palm oil residues the optimized residence time to maximize this liquid yield. Above the optimum residence time, an
Optimization increase in the gas fraction and a decrease of the bio-oil and char fractions are observed. Comparison
SuperPro Designer of the different residues indicates that the higher yield of liquid fraction was obtained from the EFB
and MF while pyrolysis of the PS produced a higher yield of char. These product yields were strongly cor-
related to the biomass polymer components. The obtained correlation was in agreement with the prod-
ucts yields found in literature for various biomass sources. The developed model provides very useful
information about different conditions of pyrolysis for oil palm residues and product yields. Moreover,
the model can be generalized and help to assist in the optimization of the fast pyrolysis process of differ-
ent biomass without performing heavy experimental investigations. Such model will contribute strongly
to the intensification and the improvement of the biomass fast pyrolysis.
Ó 2015 Elsevier Ltd. All rights reserved.

1. Introduction production, which is clean, sustainable and competitive with fossil

Nowadays, the energy consumption control is a major challenge
in the sustainable development context. Growing energy con-
sumption, limited fuel sources, increasing fossil fuel costs and
greenhouse gas emissions intensified research on renewable
energy sources. Recently, a particular attention has been focused
on the utilization of lignocellulosic biomass for biofuels
⇑ Corresponding author. Tel.: +33 3 89608661.
E-mail address: mejdi.jeguirim@uha.fr (M. Jeguirim).
energy [1–3]. Currently, biomass provides approximately 14% of
the primary energy production in the world [4,5]. Energy con-
sumption of biomass is projected to grow at an average annual rate
of 4% from 2007 to 2030 [6]. Various thermo-chemical conversion
methods are used to convert biomass into power, heat, and fuels
including combustion, gasification and pyrolysis. Among these
conversion methods biomass pyrolysis is a powerful method for
the production of bio-fuels/chemicals, electricity, and other useful
products from a wide variety of biomass [7]. During, the last dec-
ade, a great attention was dedicated to the development of

http://dx.doi.org/10.1016/j.fuel.2015.07.043
0016-2361/Ó 2015 Elsevier Ltd. All rights reserved.
820 J. Mabrouki et al. / Fuel 159 (2015) 819–827

advanced fast pyrolysis processes for biofuel production. Fast
pyrolysis, is a rapid thermal degradation of biomass in the absence
of oxygen. It provides generally solid, liquid and gas fractions [3–
8]. The bio-oil yield can be optimized by controlling the pyrolysis
operating conditions. This bio-oil could be used as fuel or as some
chemical source such as phenol. Among the available biomass
resources, palm shell, empty fruit bunch and mesocarp fibers are
the main by-products of the oil palm production sector. These
by-products are an abundant source of lignocellulosic biomass in
the world. In fact, millions of tons of oil palm biomass are gener-
ated every year [9–11]. Various conversion methods into energy
and value added products have been already investigated. Among
these methods, several investigations have examined the conver-
sion of agricultural residues into bio-fuels (bio-oil, bio-char and
gas) through fast pyrolysis [11]. It was shown that the yields and
properties of the product formed are strongly affected by various
operations parameters such as pyrolysis reactor design, pyrolysis
operating conditions (process temperature, residence time. . .)
and biomass characteristics [12,13]. Hence, the main challenge is
the identification of the optimal operating conditions during the
fast pyrolysis of various biomasses. This task is very complicated
since it involves a complex experimental work. Moreover, the
experimental bench should be adapted for different heterogeneous
biomasses. Therefore, simulation tools could help the realization of
such tasks by determining in advance the products yield. Several
models have been developed and applied to simulate biomass
pyrolysis process. Various feedstocks have been studied in order
to determine the optimal conditions to produce higher homoge-
nous pyrolysis liquids [14–22]. The main results selected from lit-
erature are summarized in Table 1. Although, several studies have
examined the effect of the operating conditions on the liquid pro-
duct yield, there is no available study that integrates process sim-
ulation of a small-scale biomass pyrolysis system with localized
fast pyrolysis oil utilization. Generally, the major investigations
focused on the experimental results and few papers provided the
optimization and simulation results which are very important for
process development. Modeling and simulation could be the best
possible option for understanding the thermo-chemical reaction
mechanism, optimize the operating conditions and also optimizing
efficient pyrolysis process design instead of having costly and time
consuming experimental study. Ward et al. [23] developed a com-
putational model using Aspen plus software to analyze the perfor-
mance of the fast pyrolysis process using municipal waste as fuels.
The simulation was performed for four types of biomass, namely
shredded green waste, pine chips, wood and birch. The results
showed that the shredded green waste is the suitable feedstock
for bio-oil production due to its high cellulose and low moisture
contents. Luo et al. [24] have developed a model of wood pyrolysis
in a fluidized bed reactor in which the effect of main operation
parameters on wood pyrolysis product distribution was examined.
The model showed that the reaction temperature played a major
role in wood pyrolysis. The modeling results showed that the reac-
tion temperature played the most important role in wood pyrolysis
behavior. A moderate dense bed temperature of 500 °C, and lower
suspension bed temperature were more suitable for optimizing
bio-oil production, at which the wood particle could undergo a
complete decomposition and bio-oil secondary cracking be well
restrained. Papadikisa et al. [25] simulated the fast pyrolysis of bio-
mass in bubbling fluidized bed reactor. It was found that the model
can predict the residence time of vapors and biomass particle. The
effect of shrinkage on the pyrolysis of thermally thin particles does
not have a significant impact neither on the product yields nor the
pyrolysis time. The progress of the reaction is only dependent on
the heat transfer inside the particle and the effect of the chemical
reaction rate is not significant. The model can be a useful guide for
reactor design where char entrainment is of major importance.
These previous investigations showed that the process design
and simulation can be applied to control the overall process condi-
tions of the biomass fast pyrolysis. In this context, this investiga-
tion proposes the modeling of bio-fuel production from biomass
pyrolysis process using the SuperPro Designer (SPD) simulator.
This latter was used to determine the optimum values for the dif-
ferent factors affecting the fast pyrolysis of oil palm residues for
producing biofuels and other compounds. The optimization inves-
tigation is performed through the evaluation of the effects of pyrol-
ysis reactor temperature and residence time on the product yields.
2. Fast pyrolysis process simulation
2.1. Description of the developed model
2.1.1. Computing tool
Biofuels production is a promising process that can be facili-
tated by the use of simulation tools. Among, the various simulation
tools, SuperPro Designer (SPD) software is a very useful simulator
due to its large database of specific chemical compounds and unit
operations. This database is valuable to facilitate the calculation of
physical, chemical and biological processes [26]. The SPD has been
a modeling tool already used for different integrated processes
evaluation and optimization in a wide range of industries
(Pharmaceutical, Biotechnology, Specialty Chemical, Biofuels,
Food, Consumer Goods, etc.) [26,27]. The SPD was originally devel-
oped for optimization, project economic assessment, waste/pollu-
tion reduction and control as well as utility and work force
management [26]. An economic evaluation of biological conversion
of wheat straw to butanol using this software is presented by
Qureshi et al. [27]. Recently, the SPD was used by Teghammar
et al. to evaluate a process of biogas production [28]. In a similar
investigation, Kwiatkowski et al. simulated the fermentation pro-
cess for the ethanol production from corn dry-grind [29]. The

Table 1
Summary of optimum conditions & yields reported in recent literature for production of Biofuels.

Biomass types Optimum conditions Yield (%) Reactor type Refs

Temperature (°C) Residence times (s) Char Gas Oil
EFB 500 2 27.19 42.83 29.98 [14]
Hazelnut cupula 600 – 25 22 51.45 Fixed-bed reactor [22]
Wheat straw 525 2 25.9 19.4 56.2 Pyrolysis centrifuge reactor, [23]
Wheat straw 550 1.5 24.5 17.8 52.8 – [24]
Wood particles 800 – 5 83 12 Drop Tube Reactor [25]
Pine wood 475–550 – 14 22 64 – [26]
Poplar aspen 500 – 11 14 58.9 Fluidized bed. [27]
Wheat straw 500 – 22 19 37 A continuous fluidized bed [28]
Corn stover 500 – 42.2 13.7 27.3 Fluidized bed [29]
EFB 500 1.1 24.52 22.31 34.71 Fluidized bed. [30]
Washed FB 500 1.1 10.76 14.70 61.34 Fluidized bed. [30]
 J. Mabrouki et al. / Fuel 159 (2015) 819–827
present work is probably the first study proposed to focus on the
energy recovery from palm oil residues through the fast pyrolysis
process using the SPD software.
2.1.2. Process overview
The basic diagram developed for the simulation of the biomass
fast pyrolysis process is based on the available data in the litera-
ture [30]. This diagram is shown in Fig. 1. The involved process
can be represented by the schematic diagram shown in Fig. 2.
This diagram represents a pilot plant of the simplified biomass fast
pyrolysis process. The methodology employed for modeling and
process details in SuperPro Designer along with the definitions of
the investigated parameters is described below.
The flowchart diagram of biomass pyrolysis process in SuperPro
Designer is a generic plant design containing various unit proce-
dures and operations required to convert biomass into fuel.
Biomass fast pyrolysis consists of mainly four sections. The first
section corresponds to biomass pretreatment including shredding,
drying, heating and screw conveying. Each operation is initialized
with the appropriate engineering data such as charge quantities,
reaction stoichiometry and scheduling relations. The pretreatment
section is followed by a second section corresponding to the bio-
mass pyrolysis section. This latter is composed of a stirred reactor,
plug flow reactor and associated auxiliary equipments, such as
component splitter, a mixer, and heat exchanger. Then, the third
section corresponds to the products separation and collection sec-
tion, in which char is separating and vapors are condensed (bio-oil
recovery step) using gas cyclone and condenser, respectively.
Finally, the last section corresponds to the upgrading section in
which the primary products are converted into more useful prod-
ucts using stirred reactor, decanter centrifuge, flash drum and
vertical-on legs tank. The terminology and function of each compo-
nent in the flowchart are specified in Table 2. Hence, each reactor
should apply a kinetic reaction calculation with different kinetic
parameters. The chemical reactions based on kinetic parameters
were provided from academic literature [31,32].
2.1.3. Process description in the SuperPro Designer
2.1.3.1. Biomass pretreatment section. In this section, the biomass
stream is introduced into a shredding unit procedure
(P-9/SR-101) (Fig. 2) that simulates shredding (size reduction)
the feed to give sufficiently small particle to ensure rapid reaction.
Second, the sample needs to be dried using a drum drying unit pro-
cedure (P-14/DDR-101) that simulates drum drying under vacuum
(Fig. 2). After the drying procedure, the water content in the bio-
mass is less than unity. Next, the drying material is transported
to the pyrolysis reactor using screw conveyor. This unit procedure
(P-10/SC-101) simulates transport of biomass into pyrolysis
section.
Biomass
Separator
Drying
Pyrolysis
Shredding
reactor
Fig. 1. The concept process of biomass pyrolysis for bio-fuels production.
821
2.1.3.2. Pyrolysis section. In the pyrolysis section, the biomass heat-
ing occurs by heat exchanging the feed with a hot gas stream. For
each pass through the heat exchangers, temperature increases in
the next section of the reactor, and the hot gas stream looses an
equivalent amount of energy. The stream S-104 (Fig. 2) is fed to
Plug flow reactor (PFR)- which is the first reactor of pyrolysis sec-
tion. During the fast pyrolysis process biomass pyrolysis proceeds
through a series of complex reactions consist of primary activation
and fragmentation reactions which take place in a Stirred Reactor
and which are described by stoichiometry and kinetics. Finally, a
secondary vapor phase cracking reactions take place in a Plug
Flow Reactor (PFR) which models the reformation of unreacted
compound, gas, and tar fractions to char, gas and Bio-oil and
Collect compounds in process products before they are mixed into
one stream S114. [33]. The pyrolysis process reactions are given in
Tables 3 and 4.
2.1.3.3. Products collection section. Char separating and vapors con-
densation for bio-oil recovery are the unit operations grouped in
this section using gas cyclone and condenser. A cyclone separates
the solid char product and the liquid product must be rapidly con-
densed. The produced gases are transported to the incineration
procedure. One may note that no significant waste is generated
since the residual char is recycled back into the process. After the
products collection section, the produced liquid goes through an
up grading step, in order to produce more useful products. Each
product streams from the process consist of organic condensate
(bio-oil), solid residue (biochar) and non-condensable gases (pyro-
lytic gases).
2.1.3.4. Bio-oil refining section. This section is composed of a mixing
vessel (V-102), a reactor (R-104), a decanter centrifugal separator
(DC-101) and a biodiesel storage tank (V-101). The bio-oil is
directly fed to the reactor (R-104). Methanol and the catalyst are
mixed and 90% of the mixture is fed to the first reactor (R-104).
Methanol reacts with bio-oil and yields biodiesel and glycerol.
The material is then fed to a continuous centrifugal separator
(DC-101) to separate the biodiesel from the aqueous phase, which
is fed to the biodiesel crude storage (V-101). [34].
2.2. Modeling methodology
The fast pyrolysis process is modeled in a parallel sequence
combining three standard reactors (in standard continuous reac-
tors (Plug flow reactors or Continuously Stirred Tank Reactors) pro-
cessing cellulose, hemicelluloses, and lignin separately. On the
other hand, cellulose, hemicellulose and lignin are supposed to
be pyrolyzed independently in wood without interactions. Hence
each reactor should apply a kinetic reaction calculation with
kinetic parameters. The chemical reaction based on kinetic param-
eters from academic literatures [31,32].
Condensation Gas
Oil refining
reactor
Oil
822 J. Mabrouki et al. / Fuel 159 (2015) 819–827

P-8 / HX-105
S-123 S-111 S-127 S-125
Heating S-128
S-132
S-126
P-16 / MX-102
Mixing
P-18 / V-102 S-124
Flash P-17 / DC-101
Refining section
S-122
P-12 / V-101 P-15 / R-104
S-129Centrifugation
Storage Stoich. Reaction
S-101 S-110
S-120
S-109
. S-121 P-1 / M-101 P-7 / HX-103
S-131 P-5 / INC-101 Gas Flow Condensation
P-4 / CY-101 S-116
Incineration
Products collection section Main char outlet Cyclone
S-103

P-13 / HX-104
Cellu_reform / PFR-106Heat Exchanging
S-105 Cellu_reform
Cellu_comp PF Stoich Rxn
Pyrolysis section S-114
S-118 S-102 S-119
Cellulose / R-102 Hemi_reform
S-108 S-106 Kinetic Reaction
P-2 / HX-101 P-6 / CSP-101
Feed fragments / PFR-101
Heating Splitting Hemi_reform / PFR-102 P-3 / MX-101
PF Stoich Rxn S-107
S-117 Lignin_reform
S-104 PF Stoich Rxn Mixing
Hemi_comp

S-113 S-112
P-14 / DDR-101
Drum Drying Hemicellulose / R-101
P-10 / SC-101 S-115
nin_reform / PFR-107
Screw Conveying P-11 / HX-102
P-9 / SR-101 PF Stoich Rxn
Pretreatment section Heat Exchanging
Shredding Lignin_comp
Exhaust gas_to sterling

Main Biomass Feed

Lignin / R-103
Kinetic Reaction

Fig. 2. flowchart diagram of biomass pyrolysis process in SuperPro Designer.

3. Results and discussion
3.1. Model validation
In order to check the accuracy of the designed process, the
developed model was validated with the published data of the
experimental investigation of oak fast pyrolysis [33]. During their
investigation, Park et al., have studied experimentally the influence
of the reaction temperature, the size flow rate and the fluidizing
medium on the product yields of the oak wood in a fluidized bed
reactor. The chemical composition and the proximate analysis of
oak wood are presented in Tables 4 and 5, respectively [33].
During their investigation, the authors showed that the bio-oil
yield reaches a maximum in the temperature range 400–450 °C.
Figs. 3–5 show a good agreement between experimental and
simulated values obtained for the char, bio-oil and gas yields,
respectively. However, a slight discrepancy is observed and the
mean error for the all tested values is 8.4%. The estimated yields
were obtained from the results of the pyrolysis of the individual
components (hemicellulose, cellulose, lignin) with the assumption
that no interaction exists between these components. The
simulated values confirm that the bio-oil fraction is maximized
at the temperatures range of 450–500 °C. However, above 450 °C,
the bio-oil fraction decreases with increasing pyrolysis tempera-
ture. In addition, it is confirmed that the gas yields increased and
the char yields decreased with increasing pyrolysis temperature.
This decrease is explained by the rate of the secondary reactions
during pyrolysis phenomena. The char yield decreased with an
increasing temperature. This may be a result of the competition
between charring and devolatilization reactions become succes-
sively more favored. The agreement between predictions and
experiments is good for the different product yields. However, a
slight discrepancy is observed between the experimental and sim-
ulated product yields. Such discrepancy may be due to the interac-
tion of the different biomass components. In fact, as mentioned
previously, the SPD simulation does not take into account such
interaction and the fast pyrolysis process is modeled in a parallel
sequence combining three standard reactors processing cellulose,
hemicelluloses, and lignin separately. The analysis of the discrep-
ancy between each product yield confirms such hypothesis. In fact,
previous results from literature indicated that the interaction
between cellulose and hemicellulose affects weakly liquid and
 J. Mabrouki et al. / Fuel 159 (2015) 819–827 823

Table 2 3.2. The fast pyrolysis of palm oil residues

Reactor block description in the simulation.

SuperPro Description After the model validation, the fast pyrolysis of palm shell,
Designer name empty fruit bunches, and mesocarp fiber is simulated using
Feedstock dryer P-14/DDR-101-simulates the drying process SuperPro Designer tool. The selected palm oil residues contain
Feedstock fine P-9/SR-101-this unit procedure simulates shredding (size mainly cellulose, hemicelluloses and lignin, with minor amounts
shredder reduction) of biomass of extractives and ash. The main components of these biomasses
Screw conveyor P-10/SC-101-this unit procedure simulates transport of
biomass using a screw conveyor
and the proximate analysis obtained from published data are
Cyclone P-4/CY-101-separates the char component from gaseous shown in Tables 6 and 7, respectively [40]. The operating condi-
streams tions used in the simulation are shown in Table 8. The selected
Condenser/ Simulates recovery (separation) of volatile compounds flow rate of the feedstock stream is 62 kg/h of palm oil waste
quencher from a gaseous stream stoichiometric reactor
which represents 2000 MT/day of dry biomasses. Among the vari-
Incinerator The primary objective of the model is to calculate the
composition of the flue gas stream and estimate the ous operating conditions, it is well known that temperature and
flowrate of auxiliary fuel if needed residence time are important parameters affecting the product
Various heat- P-2/HX-101, P-11/HX-102, P-13/HX-104-heating yields [14–22]. Therefore, the effects of temperature and residence
exchanges time on the product yields (bio-char, liquid and gas) during the fast
Sttird tank Cellulose/R-102, Hemicel/R-103, Lignin/R-103-this
pyrolysis of the biomass samples of palm shell, EFB and mesocarp
reactor CSTR procedure is used to represent a sequence of continuous
reactions that take place in a Stirred Reactor (CSTR)and fiber are examined (see Table 9).
which are described by stoichiometry and kinetics The temperature effect on the different yields was firstly exam-
Plug flow reactor Feeds fragments PFR-101-stoichiometric reactor ined between 450 and 600 °C at a residence time equal to 1 s.
PFR decompose the fed stream
Figs. 6–9 show the effect of the temperature on the flow rate of
Decanter P-17/DC-101-simulates a decanter centrifuge for solid–
centrifuge liquid or liquid–liquid separation bio-oil, gas, char and water, respectively. It is seen that different
Flash drum P-18/V-102 flash simulates separation of volatile yields are obtained for the three samples. Such result is expected
compounds in a flash drum. Several thermodynamic to the difference in the sample characteristics as shown in Tables
model options are available for handling the VLE 6 and 7. Tröger et al. reported that different feedstock produced
calculations
different char, condensate and gas fractions due to their ash con-
Storage P-12/V-101 storage-simulates storage of continuous
flows in a vertical-on-legs tank tent and polymer constituents variation [41]. Fig. 6 indicates that
the bio-oil yield for the Empty Fruit Brunch (EFB), palm shell and
mesocarp fiber increased between 450 and 550 °C and then
decreased with temperature. Therefore, the optimum temperature
gas yields that are higher than the one expected, while char yield is for maximizing the bio-oil fraction is 550 °C. Similar results were
lower. Such behavior may explain the higher gas yield and the obtained by Demirbas [42] during the pyrolysis of different bio-
lower char yield obtained in the experimental study comparing mass samples. Author found that the liquid product yields
to the simulation one (Figs. 3 and 4). During the decomposition obtained during the pyrolysis of hazelnut shell, olive husk, beech
of the biomass, the difference in the gas yield in the interval and spruce wood samples raised from 36.3% to 47.5%, from 38.0%
400–450 °C was greater than those encountered in other tempera- to 48.9%, from 34.8% to 45.4%, and from 32.2% to 43.1% when the
ture intervals. As the temperature increased (>550 °C), the primary temperature was increased from 625 to 800 K and then declined
pyrolysis products were transformed into secondary products. from 47.5% to 40.0%, from 48.9% to 42.6%, from 45.4% to 37.3%
According to Hosoya et al. [37] significant interactions were and from 43.1% to 34.9%, when the temperature increases to
observed during the pyrolysis of lignocellulosic biomass, which 875 K, respectively.
are different depending on the product types (bio-oil, gas and Comparison of the different samples indicates that at 550 °C the
char). Furthermore, lignin inhibited the thermal polymerization highest bio-oil yield is obtained for Empty Fruit Brunch (EFB). In
of levoglucosan formed from cellulose and enhanced the formation fact, the EFB has delivered a maximum bio-oil flow rate of
of lower molecular weight products from cellulose with reduced 28.99 kg/h (46.75 wt% from the total yield), while mesocarp fiber
yield of char fraction. In the other hand cellulose reduced the sec- and palm shell produced only 27.93 kg/h (45.05 wt%) and
ondary char formation from lignin and enhanced the formation of 22.72 kg/h (36.65 wt%), respectively. The obtained values for the
some lignin-derived products. Also several reports have used the different samples in this present study are in the same range as
mass transfer effects for explaining of the degradation behaviors
of wood samples [38,39]. Such behavior may also explain the dis-
crepancy observed between the experimental studies compared to Table 4
A Primary pyrolysis reactions and Arrhenius parameters for simulation process.
the simulation one.
1 1
Pyrolysis reactions A (s ) E (kJ mol ) Ref
19
Cellulose ? active cellulose 2.8
10 240 [31]
Cellulose ? 0.60Char + 0.4H2O 6.7
105 110
Table 3
Active cellulose ? gas 3.6
1011 200
Summary of pyrolysis reactions.
Active cellulose ? vapors 6.8
109 140
Pyrolysis reactions Reactor Active cellulose ? 0.6Char + 0.4H2O 1.3
1010 150
Vapors ? gas 3.6
1011 200
Biomass ? cellulose + hemicellulose + lignin + ash Feed fragments/Plug
Vapors ? tar 1.8
103 61
flow reactor- PFR-101
Unreacted fraction + carbon + ash ? char Continuous Kinetic in Hemicellulose ? active cellulose 2.1
1016 186.7 [32]
CSTR:cellulose/R-102 Active Hemicelulosel ? vapors 8.75
1015 202.4
Tar + vapors (condensable) ? bio-oil Continuous Kinetic Active hemicellulose ? x.Char + (1 x)gas 2.6
1011 145.7
reaction in CSTR:lignin Vapors ? gas 4.28
106 108
Gas(unreacted) ? Process gas Cellulose reform PFR- Lignin ? active lignin 9.6
108 107.6 [32]
106, Hemicellulose Active lignin ? vapors 1.5
109 143.8
reform PFR-102, Lignin Active lignin ? x.Char+(1 x) gas 7.7
106 111.4
reform PFR-107 Vapors ? gas 4.28
106 108
824
Table 5
Chemical composition of oak wood [33].
Chemical composition (wt%)
Cellulose 50
Hemicellulose 14.3
Lignin 22.8
those found by Demirbas [42]. Numerous investigations have
shown that liquid yield depends on biomass polymers constituent,
ash contents, temperature and vapor residence time [6,8,30–36].
Therefore, the decrease of bio-oil yield at high temperature may
be attributed due to the secondary reaction, which becomes dom-
inant when the pyrolysis temperature exceeds 550 °C. During, this
secondary reaction, the tar generated by the primary reaction is
decomposed into the char and non-condensable gas [42]. In addi-
tion, the higher bio-oil yield obtained for EFB is attributed to its
higher cellulose content (51.2%) comparing to palm shell (27.7%)
and mesocarp fiber (23.7%). Several investigations have evaluated
the pyrolysis of cellulose extracted from different biomasses.
Hosoya et al. have shown that cellulose leads to the highest tar
yield (72%) during the investigation of wood and its cell wall con-
stituents pyrolysis [37]. Such result was confirmed by Wang et al.
during the investigation on the interaction of components on the
pyrolysis behavior of biomass. Authors showed that during cellu-
lose pyrolysis, the bio-oil yield was 81.41 wt% while the gas and
char yields represent only 12.15 and 6.44 wt%, respectively [43].
The effect of temperature on the char yields was also examined.
Fig. 7 shows that, as expected the char flow rate decreased with
increasing temperature and tend to reach a plateau at higher tem-
perature for the three palm oil residues. In particular, the char flow
rate from the palm shell, EFB and mesocarp fiber pyrolysis
decreased from 41.03 kg/h to 17.62 kg/h, from 35.93 kg/h to
16.77 kg/h and from 33.27 kg/h to 15.75 kg/h, respectively when
temperature increased from 450 °C to 600 °C. The highest char
yield was obtained for palm shell (41.03 kg/h at 450 °C) which is
attributed to its lignin content. The latter is known to increase char
yield since it is the most thermally resistant component compared
to cellulose and hemicelluloses. In fact, lignin has a more complex
chemical composition and its decomposition happened slowly
under the whole temperature range from ambient to 600 °C. The
effect of lignin on the char yield is well mentioned in the literature.
In fact, Shurong et al. [43] indicated that lignin give the highest
amount of char (40.33 wt%) comparing to hemicellulose
(19.05 wt%) and cellulose (6.44 wt%) during these components
pyrolysis. Similar values were also obtained by Hosoya et al. [37]
during the pyrolysis of wood cell wall constituents at 800 °C for
30 s. Authors found that milled wood lignin produced large
50
Experimental results
40 Present work
Char yield (%)
30
20
10
0 the same order as lignin contents (palm shell (44 wt%) > mesocarp
350 400 450 500 550
Temperature (°C)
Fig. 3. Validation of the effect of temperature on char yield with experimental
results of Park et al. [33].
J. Mabrouki et al. / Fuel 159 (2015) 819–827
50
Present work
40
Experimental results
Gas yield (%)
30
20
10
0
350 400 450 500 550 600
Temperature (°C)
Fig. 4. Validation of the effect of temperature on the gas yield with experimental
results of Park et al. [33].
Table 6
Proximate analysis of oak wood [33].
Proximate analysis (wt%)
Water 10.4
Combustibles 87.6
Ash 2.0
amount (40.6 wt%) of char with comparatively lower amount for
glucomannan (30.1 wt%), xylan (20.1 wt%) and cellulose (10 wt%).
In addition to the lignin content, the high char yield obtained for
palm shell could be also attributed to its higher ash content and
composition. Fahmi et al. showed that the increase of ash content
(alkali metals) decreases the yield of organic liquids and tend to
increase char and gas yields. Such results were proven by the
washing of the feedstocks before the pyrolysis experiments [44].
The analysis of the gas yields in Fig. 8 confirms their increase at
high temperature. With the rise of temperature from 450 °C to
600 °C, the gas flow rate during the pyrolysis of palm shell, EFB,
and mesocarp fiber increased from 2.24 kg/h to 19.93 kg/h, from
2.24 kg/h to 8.93 kg/h and from 4.68 kg/h to 14.23 kg/h, respec-
tively. Comparison between the different palm oil residues shows
that mesocarp fiber produces the highest gas yield at temperature
below to 525 °C while palm shell produces the highest gas yields
above 525 °C. This behavior seems to be correlated to the amount
of hemicellulose and lignin. In fact, the investigation on the pyrol-
ysis of the three biomass components found in literature shows
that hemicellulose and lignin generate equivalent gas yield. As an
example, Shurong et al. [43] obtained gas yields of 36.7 wt% and
37.9 wt% for hemicellulose and lignin pyrolysis at 550 °C for 0.1 s
residence time. Hence, the gases produced during the biomass
pyrolysis are mainly provided from the degradation of hemicellu-
lose at low temperature and from lignin at high temperature.
This behavior is in agreement with the obtained values for the
gas yields of the three samples pyrolysis. In fact, at 450 °C the
gas yields (mesocarp fiber (7.64 wt%) > EFB (3.74 wt%) > palm shell
(3.66 wt%)) follow the same order as hemicellulose contents
(mesocarp fiber (30.5 wt%) > EFB (22.5 wt%) > palm shell
(21.6 wt%)). When the temperature increase the gas yield produced
from palm shell pyrolysis increases sharply and became higher
than the gas yield produced from EFB. Such behavior is attributed
to the higher lignin content of palm shell comparing to EFB as
shown in Table 6. In fact, at 600 °C the gas yields (palm shell
(32.6 wt%) > mesocarp fiber (23.3 wt%) > EFB (14.6 wt%)>) follow
600
fiber (27.3 wt%) > EFB (21.63 wt%)).
Residence time is another important factor that influences
strongly the fast pyrolysis products. Hence, after selecting the opti-
mized temperature, the influence of the residence time on the
 J. Mabrouki et al. / Fuel 159 (2015) 819–827 825

60 50

50
40

Char flow rate (Kg/h)

Oil yield (%)

40

30 30
Experimental results
20
Present work
20
10

0 Palm shell EFB Mesocarp fiber

10
350 400 450 500 550 600
Temperature (°C)
0
Fig. 5. Validation of the effect of temperature on the bio-oil yield with experimen- 400 500 600
tal results of Park et al. [33]. Temperature (°C)

Fig. 7. Effect of temperature on char flow rate.

Table 7
The lignocellulosic contents of the palm oil residues [40].

Biomass type Cellulose (%) Lignin (%) Hemicellulose (%) 25

Palm shell 27.7 44 21.6
EFB 51.2 21.3 22.5
20 Palm shell EFB Mesocarp fiber
Mesocarp fiber 23.7 27.3 30.5

Gas flow rate (Kg/h)

15
Table 8
Proximate analysis of the palm oil residues [40].
10
Biomass type Moisture Volatile Fixed carbon Ash
Palm shell 4.7 73.5 19.2 8.6
5
EFB 6.9 79.4 10.8 2.9
Mesocarp fiber 8.6 78 7.6 5.8
0
400 500 600

Table 9 Temperature (°C)

Process parameters provided as input to the model.
Fig. 8. Effect of temperature on gas flow rate.
Parameter Value/range
Main biomass feed rate 62 kg/h
Air temperature 25 °C
Pyrolyser temperature 450–600 °C
Residence time 0.1–20 s 30
Dryer temperature 152 °C
Bio-oil flow rate (Kg/h)

Pressure 1.013 bar

20

30
10
Bio-oil flow rate (Kg/h)

Palm shell EFB Mesocarp fiber

20 0
0 5 10 15 20
Residence time (s)
10
Fig. 9. Effect of residence time on bio-oil flow rate.
EFB Mesocarp fiber Palm shell

0
400 500
Temperature (°C)
Fig. 6. Effect of temperature on bio-oil flow rate.
products yield was examined between 0.1 and 20 s. The products
yield of fast pyrolysis of palm shell, EFB and mesocarp fiber at
550 °C for different residence times are shown in Figs. 9–11. It
can be seen that the residence time have important effects on
the products yield of palm oil residues pyrolysis. Therefore, Fig. 9
shows that the bio-oil yield increases with increasing residence
600 from 0.1 s and reaches the maximum yield at 0.5 s for the three
palm oil residues. Above 0.5 s, the bio-oil yield decreased sharply
with increasing the residence time and reaches a plateau above
10 s. According to Mettler et al. [45], a longer volatiles residence
time maximizes secondary reactions such as cracking and
re-polymerization reactions, which increases the production of
gases and char and decreases the liquid yields [45]. In this present
study, results show also that, at 550 °C when the residence time
increased the flow rate of gas increased. The gas flow rate increases
gradually for all samples from 1.86 kg/h to 29.44 kg/h, from
826
40
Char flow rate (Kg/h)
30
Palm shell EFB
20
10
0 and gas yields depend strongly on the biomass components per-
0 5 10
Residence time (s)
Fig. 10. Effect of residence time on char flow rate.
30
Gas flow rate (K/h)
20
Palm shell EFB
10
0 minimising energy system greenhouse gas emissions. Energy 2014;69:506–15.
0 5 10
Residence time (s)
Fig. 11. Effect of residence time on gas flow rate.
2.06 kg/h to 29.29 kg/h, from 1.64 kg/h to 24.45 kg/h for palm shell,
mesocarp fiber and EFB, respectively, when residence time
increases from 0.1 s to 20 s. The effect of residence time on prod-
ucts yields during pyrolysis has been demonstrated to be signifi-
cant in previous investigations [17,46]. Generally, it is accepted
that short residence times are suitable for production of liquids
from pyrolysis. At pyrolysis conditions, vapors are susceptible to
secondary cracking or repolymerization. [47]. In order to minimize
decomposition of tars, low temperatures and residence times are
preferable [47]. Vapor residence times of few seconds to few min-
utes are often recommended to obtain optimum yields of bio oil
through pyrolysis. However, at very short residence times, it is
doubtful to conceive complete biomass thermochemical conver-
sion due to heat transfer difficulties at particle surface. Residence
times for decomposition of biomass particles must be longer than
the vapor residence times to obtain higher yields and biomass con-
version [14]. As described in Bridgwater et al. [48], researches on
pyrolysis of biomass mainly focused on achieving high liquid oil
yields and little on oil quality. These issues reflect that merely
shorting of residence times may not be a proper solution to obtain
high liquid yields. Optimization of residence times considering
broad range of variables may help to obtain better quality liquid
oils. Lengthy residence time favors the production of gas; with sta-
bilize of bio-oil production.
4. Conclusion
The fast pyrolysis process of palm oil residues was optimized
using SuperPro Designer simulation. The biomass thermochemical
J. Mabrouki et al. / Fuel 159 (2015) 819–827
conversion was modeled by a parallel sequence combining three
standard reactors processing cellulose, hemicelluloses, and lignin
separately. The simulation includes pretreatment, fast pyrolysis,
product collection and upgrading sections. The developed model
Mesocarp fiber
was successfully validated with published experimental results of
wood fast pyrolysis. Then, an optimization investigation on the fast
pyrolysis of palm oil residues was performed. In particular, the
effect of reaction temperature and residence time on pyrolysis
products for different biomass feedstocks was examined. The
obtained results indicated the highest bio-oil yield was obtained
at 550 °C for a residence time equal to 0.5 s. Moreover, comparison
between the different palm oil residues showed that bio-oil, char
15 20
centage. The obtained yields are coherent with results found in lit-
erature for various biomass sources. Hence, the developed model
can be useful for the fast pyrolysis optimization for different bio-
mass without performing heavy experimental investigations.
Such model will contribute strongly to the intensification and the
improvement of the biomass fast pyrolysis.
Acknowledgments
The authors gratefully acknowledge Dr. Tobias Thomsen
(Technical University of Denmark) for the valuable help during
the SPD model development.
Mesocarp fiber
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