Bioresource Technology 100 (2009) 2867–2873

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Bioresource Technology
journal homepage: www.elsevier.com/locate/biortech

Pretreatment of empty palm fruit bunch for production of chemicals via

catalytic pyrolysis
Mailin Misson, Roslindawati Haron, Mohd Fadhzir Ahmad Kamaroddin, Nor Aishah Saidina Amin *
Chemical Reaction Engineering Group, Faculty of Chemical and Natural Resources Engineering, Universiti Teknologi Malaysia, 81310 UTM Skudai, Johor, Malaysia

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

Article history: The effect of chemical pretreatments using NaOH, H2O2, and Ca(OH)2 on Empty Palm Fruit Bunches
Received 8 October 2008 (EPFB) to degrade EPFB lignin before pyrolyis was investigated. Spectrophotometer analysis proved con-
Received in revised form 16 December 2008 secutive addition of NaOH and H2O2 decomposed almost 100% of EPFB lignin compared to 44% for the
Accepted 16 December 2008
Ca(OH)2, H2O2 system while NaOH and Ca(OH)2 used exclusively could not alter lignin much. Next, the
Available online 15 February 2009
pretreated EPFB was catalytically pyrolyzed. Experimental results indicated the phenolic yields over
Al-MCM-41 and HZSM-5 catalysts were 90 wt% and 80 wt%, respectively compared to 67 wt% yield for
Keywords:
the untreated sample under the same set of conditions. Meanwhile, the experiments with HY zeolite
Lignin degradation
Catalytic pyrolysis
yielded 70 wt% phenols.
Empty palm fruit bunch Ó 2009 Elsevier Ltd. All rights reserved.
Chemical pretreatment

1. Introduction
Biomass utilization as a source of clean energy and chemicals
has attracted many research attentions in recent years amid to fos-
sil fuel energy crisis and clean energy drive (Aho et al., 2008; Ji-Lu
et al., 2008). Conversion of non-edible biomass such as agriculture
residues, wood chips, and fruit bunches, stalks, industrial and mu-
nicipal wastes into fuels and useful chemicals would solve waste
disposal and energy issues (Baratieri et al., 2008).
Generally cellulose, hemicellulose, and lignin are the three ma-
jor biomass components. Due to the crosslinking, lignocellulosic
materials are insoluble in all solvents and are hard to degrade at
typical biomass pyrolysis temperature (300–500 °C) (Aguado
et al., 2006; Boateng et al., 2006). Hence, pretreatment of EPFB to
dissolve lignin structure and cleave the chains seem to be a prom-
ising option before the pyrolysis process in order to avail important
chemicals from biomass.
Pretreatments of lignocellulosic biomass have been investigated
in many recent studies, for example in production of pulp kraft,
lactic acid and bioethanol (Karin et al., 2007; Rebecca et al.,
2007; Xu et al., 2006). Pretreatments are sometimes needed to
make material handling easier through subsequent processing
steps.
Chemical pretreatments have been widely reported as a poten-
tial technique for lignin degradation using acid and alkaline pre-
treatment, liquid hot water, pH controlled hot water and flow-
* Corresponding author. Tel.: +607 5535588; fax: +607 5581463.
E-mail address: noraishah@fkkksa.utm.my (N.A.S. Amin).
through liquid hot water (Mosier et al., 2005). Effect of sodium
hydroxide (NaOH) and hydrogen peroxide (H2O2) in decomposing
cotton stalks lignin has been reported (Rebecca et al., 2007).
Ca(OH)2 has also been reported (Chang et al., 2001) for chemical
pretreatment owing to its low cost and recovery from water as
insoluble calcium carbonate by reacting with CO2.
Pyrolysis is a thermal degradation of biomass under moderate
temperature over short residence time in the absence of oxygen.
Pyrolysis products consist of bio-oil (condensable gas), synthetic
gas (non-condensable gas), and char (Boateng et al., 2006). Zeolite
catalysts employed to pyrolysis of biomass have excellent perfor-
mance as solid acid cracking catalysts due to their higher selectiv-
ity (Tamunaidu and Bhatia, 2007). Among the most industrially
favored zeolite catalyst is HZSM-5. As a matter of fact, HZSM-5
has been used commercially in synthetic fuels, petrochemicals
and petroleum refining (Xu et al., 2005). Besides, HY and Al-
MCM-41 zeolites are also widely used in the production of bio-
oil (Habib et al., 2008). Compared with microporous zeolites, mes-
oporous Al-MCM-41 provides a larger surface area and more acces-
sible reaction sites.
The objective of this study is to investigate the performance of
different chemical pretreatment methods in degrading EPFB ligno-
cellulose structure. It is envisaged that degrading the rigid and
complex structures of lignin before pyrolyzing the EPFB would im-
prove the quality of the bio-oil. In addition, this study also intends
to investigate the effects of pretreatment process on the chemical
compositions produced through catalytic pyrolysis. Product distri-
butions from HZSM-5, HY and Al-MCM-41 catalyzed pyrolysis
were also investigated for qualitative measurement.

0960-8524/$ - see front matter Ó 2009 Elsevier Ltd. All rights reserved.
doi:10.1016/j.biortech.2008.12.060
2868 M. Misson et al. / Bioresource Technology 100 (2009) 2867–2873
2. Methods
2.1. Materials
Seasoned EPFB sample aged approximately 6–12 months was
obtained from the Faculty of Mechanical Engineering, Universiti
Teknologi Malaysia and was crushed in a high-speed rotary cutting
mill to give particle size in the range of 0.1–0.5 cm. The sample was
dried at 105 °C for 24 h prior to the experiments. The EPFB con-
tained 18.1 wt%, 59.7 wt%, 22.1 wt% of lignin, cellulose and hemi-
cellulose, respectively. Its high heating value (HHV) was reported
to be 16.74 MJ/kg. Elemental analysis has verified the EPFB con-
tains 47.89% carbon, 45.41% oxygen and 6.05% hydrogen.
The catalysts used in the EPFB pyrolysis were HZSM-5, HY and
Al-MCM-41. Both HZSM-5 and HY catalysts were obtained from
Zeolyst International, while Al-MCM-41 was synthesized at the
Faculty of Science, Universiti Teknologi Malaysia. The characteris-
tics of the catalysts are displayed in Table 1. The structural charac-
teristics of the zeolites (pore area, pore volume, and pore diameter)
were measured using nitrogen isothermal adsorption at 77 K in
AUTOSORB-6 Quantachrome equipment.
2.2. Pretreatment condition
Three chemical pretreatment methods were employed in this
study. NaOH and Ca(OH)2 at a concentration of 100 mM were used
to pretreat 5 g of the EPFB samples in each method. The samples
were treated in a 250-mL Erlenmeyer flask under constant stirring
at 200 rpm and temperature being 27 °C.
The first method was exclusively conducted over one type of
chemical, either using NaOH or Ca(OH)2. In the second and third
methods, H2O2 was added simultaneously and consecutively,
respectively. All experiments were conducted within 48 h of the
pretreatment period. At the end of the reaction, the pretreated
samples were washed and dried overnight at 100 °C. A total of se-
ven experiments were performed to investigate the effects of
chemical pretreatment method on lignin degradation. Controls
were carried out at the same operating conditions but in the ab-
sence of any chemicals.
2.3. Pyrolysis experimental procedure
The pyrolysis experiments were conducted in a semi-batch
stainless steel reactor using the pretreated EPFB (30 g) mixed with
5 wt% HZSM-5 catalyst. The experimental system was initially
purged with inert nitrogen for approximately 30 min. The reactor
was externally heated by an electrical furnace at a fixed tempera-
ture of 300 °C, which was monitored by a K-type thermocouple.
Table 1
Characteristics of zeolite catalysts used in catalytic cracking.
Characteristics HZSM-5 HY
SiO2/Al2O3 (w/w) 30 30
Particle size (nm) 14.3 14.5
Micro pore area (m2/g)a 444.8 1375
Micro pore volume (cc/g)a 0.16 0.49
Total pore volume (cc/g) 0.17b 0.34c
Micro pore width (Å)a 8.2 0.22
Average pore diameter (Å) 1.55 15.39
Total weight loss at 50–150 °C (%) 9.45 19.07
a
DR Method.
b
With diameter less than 15.4 Å at P/Po = 0.09442.
c
With diameter less than 14.3 Å at P/Po = 0.07472.
d
With diameter less than 3192.7 Å at P/Po = 0.99395.
Vapors produced from the reaction chamber were collected as li-
quid products in a round bottom flask while non-condensable gas-
eous components were collected into a gas sampling port. The
effect of HZSM-5, HY and Al-MCM-41 catalysts on the production
of important chemicals at the same pyrolysis operating conditions
was also notified.
2.4. Lignin content determination
An amount of 0.1 g EPFB was added into a mixture of 20 mL of
0.02 mol/L potassium permanganate (KMnO4) with 5 mL of
2.0 mol/L sulfuric acid (H2SO4) and mixed well for three minutes.
Solid sample was separated from the solution through filtration,
while the filtrate was measured using UV-Spectrophotometer (Shi-
madzu, USA) at 546 nm of wavelength. The one-point calibration
method was carried out to determine the value of Kappa number
(Chai and Zhu, 1999), as shown in Eq. (1).
 
a Ao  Ae
K¼ ð1Þ
w Ao
where, K is Kappa Number, a is the volume of KMnO4 used in the
solution, w is weight of moisture-free sample used, Ao is spectral
intensities at time t = 0 (before sample is being added) and Ae is
spectral intensities at the end of the reaction.
Accordingly, lignin content in the sample was calculated
from the values of Kappa Number, K using Eq. (2), where the
percent of lignin degradation is illustrated in Eq. (3) (Ohra-aho
et al., 2005).
Lignin Content ðwt%Þ ¼ 0:15 K ð2Þ
Ligninwt% ðuntreatedÞ  Ligninwt% ðtreatedÞ
Lignin degradation ¼
Ligninwt% ðuntreatedÞ
ð3Þ
2.5. Characterization of bio-oil
The functional groups of bio-oils were analyzed by using Fourier
Transform Infrared (FTIR) spectrophotometer. The absorption fre-
quency spectra were recorded and plotted. The standard IR-spectra
of organic compounds were used to identify the functional groups
of the bio-oil.
The chemical compositions of the bio-oil were analyzed using
Gas Chromatography (GC), and the compounds were determined
using Mass Selectivity (MS) detector equipped with a
30.0 m  250 lm  0.25 lm nominal column HP-5MS. Helium
gas was employed as a carrier gas at a constant flow rate of 1 ml/
min. The heating of the column started at 80oC, and programmed
to 250 °C by a rate of 10 °C/min and held for 5 min. Finally, the
temperature was ramped to 300 °C at the same rate and kept iso-
thermal for 15 min. The compounds obtained were grouped as
aldehydes, acids, alcohols, ketones, phenols and polyaromatic
Al-MCM-41 hydrocarbons.
N/A The test of basic fuel properties includes pH, density, kinematic
19.5 viscosity and higher heating value (HHV). The pH value was mea-
1859 sured by a pH probe with digital meter (Lab 850 Schott). The den-
0.66 sity of bio-oil was determined using ASTM 4052 method in
0.97d
0.51
Picnometer. The kinematic viscosity at 40 °C of bio-oil was ana-
43.43 lyzed using ASTM D445-94 in kinematic viscosity bath and viscom-
36.76 eter capillary, while the HHV was determined via bomb
calorimeter.
The yield of EPFB conversion and product yield of gaseous and
liquid oils obtained in the pyrolysis reaction were calculated on
weight basis according to Eqs. (4)–(6):
 M. Misson et al. / Bioresource Technology 100 (2009) 2867–2873 2869

EPFB feedðgÞ  solid residueðgÞ Compared to Ca(OH)2, there was approximately 50% difference in
EPFB conversionð%Þ ¼  100%
EPFB feedðgÞ lignin degradation capacity between NaOH and Ca(OH)2 in all
ð4Þ methods executed. For instance, in the first method, NaOH man-
aged to give 65% of lignin break down which is 7.2 times higher
Desired liquid productðgÞ
Liquid oil yieldðwt%Þ ¼  100% ð5Þ than Ca(OH)2 (9%).
EPFB feedðgÞ
The mechanism of NaOH pretreatment is postulated to be by
Desired gases productðgÞ saponification of intermolecular ester bonds crosslinking xylan
Gaseous yieldðwt%Þ ¼  100% ð6Þ
EPFB feedðgÞ hemicellulose and other polymeric materials, such as lignin or
other hemicellulose. Saponification of the uronic ester linkages in
4-O-methyl-D-glucuronic acids pendant along the xylan chain
3. Results and discussion
readily occurred in presence of alkali (Sun and Cheng, 2002).
The removal of lignocellulose crosslinks apparently increased
3.1. Pretreatment of EPFB
its porosity. It led to decrease in crystallinity and degree of poly-
merization, but the internal surface area of the lignocellulose in-
Pretreatment with NaOH permitted the swelling of the particles
creased. Separation of cellulose hydrogen bonds had caused
that resulted in easy lignin degradation. Lignin is the most difficult
cellulose depolymerization (Damisa et al., 2008).In addition, re-
component of biomass to be degraded due to its complex structure,
moval of crosslinks contributed to the separation of structural link-
high molecular weight and high insolubility. Lignin is linked by
ages between lignin and other lignocellulose components. As a
carbon–carbon and ether bonds to form tri-dimensional network
consequence, pretreatment using NaOH facilitated the lignin
associated with the hemicelluloses polysaccharides inside the cell
breakdown of EPFB in order to increase the surface area prior to
wall (Ibrahim et al, 2005). The delignification reactions involved
pyrolysis.
the cleavage of non-phenolic b-O-4 linkage, phenolic a-O-4 linkage
Increasing NaOH concentration significantly improved lignin
and released the lignin from being associated with the
degradation ability when temperature and residence time are con-
polysaccharide.
stant. Lime has been used to pre-treat wheat straw at 85 °C for 3 h
Direct spectroscopic Kappa number was employed in this study
and poplar wood at 150 °C for 6 h with 14-atm oxygen (Chang
to determine the lignin content in the EPFB samples. Kappa num-
et al., 2001).
ber is generally proportional to the lignin content (Chai and Zhu,
Lignin reduction was remarkably enhanced by the addition of
1999). Lower sample kappa number represents lower contents of
H2O2 as a co-chemical agent both for NaOH and Ca(OH)2. The activ-
aliphatic hydroxyl groups and b-O-4 structures and contains high-
ities of H2O2 enhanced enzymatic conversion through oxidative
er phenolic hydroxyl groups and carboxylic acid groups. Experi-
delignification and reduction of cellulose crystallinity (Martel and
ment without pretreatment was employed as a control of the
Gould, 1990). The purpose of H2O2 addition is to detach and loosen
study for the basis of EPFB lignin content. From the study, the un-
the lignocellulosic matrix. The addition of H2O2 as an oxidative
treated sample was found to have 7.24% of lignin content.
agent was aimed in removing the hemicellulose and lignin to in-
The pretreatment process affirmed reduction in lignin content
crease the accessibility of the cellulose. Several reactions may take
compared to the original untreated substrate. All three methods
place such as electrophilic substitution, displacement of side
demonstrated different capacity in lignin degradation. The perfor-
chains, cleavage of alkyl aryl ether linkages or the oxidative cleav-
mance may be best described by the percentage of lignin degrada-
age of aromatic nuclei (Hendriks and Zeeman, 2009).
tion as illustrated in the histograms in Fig. 1. The degradation
As revealed in Fig. 1, method 3 displayed the greatest ability to
percentage was calculated by dividing the difference between lig-
remove lignin regardless of the chemicals used. Interestingly, com-
nin content of untreated and treated EPFB samples to the lignin
plete lignin removal was successfully achieved under consecutive
content in the original untreated EPFB (Eq. (3)).
treatment of NaOH and H2O2. Meanwhile, consecutive pretreat-
According to the results, similar trends in lignin degradation
ment of Ca(OH)2 and H2O2 could degrade only 44% lignin. These
were observed which implied the use of NaOH chemical gave
two chemicals may not be strong enough to break down the rigid
encouraging performance in all the three methods conducted.
structure of lignocellulosic materials in EPFB. The result was in
accordance with previous art by Azzam (1989) where H2O2 pre-
treatment decomposed 50% of lignin on sugar cane bagasse.
100 Consecutive addition of NaOH and H2O2 appeared as the most
effective way to decompose lignin. The method was able to entirely
Lignin degradation (%)

breakdown the lignin content. Their synergistic activities com-

80
bined with the function of NaOH in primarily hydrolyzing chloro-
lignin and H2O2 in further oxidizing the lignin structure (Martel
60 and Gould, 1990). NaOH was the nucleophiles pulping chemical
that involved in reaction with lignin, leading to the fragmentation
40 and dissolution of lignin. The modification of lignin structure oc-
curred in two ways to enhance its dissolution. The first is by cleav-
ing interunit linkages to degrade lignin to become smaller units.
20
Secondly, hydrophilic groups were introduced into polymer and
the cleaved fragments, making the lignin more soluble.
0 The simultaneous addition of NaOH and H2O2 however was
Ca(OH)2 NaOH Ca(OH)2 NaOH + Ca(OH)2, NaOH, only competent to give approximately 75%. Such method may
+ H2O2 H2O2 H2O2 H2O2 cause incomplete chlorolignin hydrolysis as well as posed resis-
tance to H2O2 oxidizing the lignin component.
Method 1 Method 2 Method 3
Pretreatment method applied in this study proved superior to
(simultaneous) (consecutive)
other pretreatment methods as discussed in Table 2. Rebecca
Fig. 1. The effects of chemical pretreatment on lignin degradation in three different et al. (2007) observed barely 66% of lignin degradation when cot-
methods pretreated by chemicals. ton stalk was pretreated with NaOH at 121 °C while in present
2870 M. Misson et al. / Bioresource Technology 100 (2009) 2867–2873

Table 2
Reported studies on lignin degradation of chemically pretreated biomass.

Author Chemical Biomass Process conditions Lignin degradation (%) Chemical production
This study NaOH, H2O2 EPFB 27 °C, 48 h 99 Biofuel
Ca(OH)2, H2O2 EPFB 27 °C, 48 h 44 Biofuel
Chang et al. (2001) Ca(OH)2 Wood chips 150 °C, 6 h 78 Glucose
Rebecca et al. (2007) H2SO4 Cotton stalk 121 °C, 90 min, 2% (concentration) 24 Ethanol
NaOH 66
H2O2 25
Xu et al. (2006) Ammonia liquor Soybean straw Room temperature, 24 h, 10%, 30 Lactic acid

study almost complete lignin degradation of EPFB was reported
using the same chemical operating at 27 °C. On the other hand,
H2O2 and ammonia indicated respective 25% and 30% lignin break-
down on cotton stalk and soybean straw. The pretreatment using
Ca(OH)2 on wood chips however implied better performance to
give 78% degradation (Chang et al., 2001). Nevertheless, most of
the reported pretreatment were executed at a temperature over
100 °C, and thus were more energy intensive.
3.2. Performance testing
After the pretreatment step, both treated and untreated sam-
ples were pyrolyzed in order to evaluate the effects of pretreat-
ment method on bio-oil production. The reaction has converted
EPFB to vapors that further condensed to form liquid oil and
non-condensable gaseous, while char as solid by-product remained
in the reactor. High conversion is favored to produce high oil yield.
The condensate oil formed two layers of liquid phase that con-
sisted of heavy and lighter fractions. The bottom layer (heavier
components) was light yellow while the upper layer (lighter com-
ponents) was dark brown.
Fig. 2 illustrates the effect of the untreated and treated samples
on the char, liquid and gas product yields in pyrolysis reaction. The
liquid yields were 28 wt% and 30 wt%, respectively, for the treated
and untreated sample. In the gas production however, the treated
sample yielded a total of 30 wt% gas compared to 25 wt% for the
untreated sample.
Theoretically, lower lignin content may contribute to easier
EPFB degradation to give higher conversion during pyrolysis. How-
ever, the treated samples that have lower lignin content demon-
strated lower conversion and thus leaving higher char yield. It
might be due to the disappearance of some important lignocellu-
loses component during pretreatment process. Furthermore, the
80
Yield of product (wt%)
study by Uzun et al. (2007) has verified that the degradation of lig-
nin mainly caused the formation of char.
The treated sample managed to give 48 wt% char compared to
42 wt% by untreated. Nevertheless, char could be further purified
for the application of carbon black or activated carbon (Alam
et al., 2007). The conversions for the treated and untreated EPFB
were 52 wt% and 58 wt%, respectively due to similar operating con-
ditions. Abdullah and Gerhauser (2008) reported higher EPFB con-
version using fluidized bed reactor yielding 70 wt% of liquid, and
thus reducing the production of char to 10 wt%.
Compound distributions of pyrolysis oils were analyzed using
GC–MS based on chemical functional groups, and are summarized
in Fig. 3. The distribution of compounds was semi-quantitatively
determined via the percentage area of the chromatography peaks.
Phenols were the dominant species as untreated EPFB yielded 66%
phenols and its derivatives and the treated sample further pro-
pelled phenols to 81% of liquid oil fraction. Enhanced phenol yield
in treated sample could be attributed to degradation of lignin
structure in EPFB by NaOH and H2O2 chemicals.
Besides phenol, several minor compounds such as alcohols,
acids, aldehydes, ketones, alkanes, alkenes and esters were also de-
tected in the liquid oil. Treated EPFB sample produced almost 10%
more hydrocarbons such as alkanes and alkenes compared to un-
treated sample which highlighted the importance of pretreatments
for biofuel production. The same trend was also reported in previ-
ous work (Dermibas, 2007; Tamunaidu and Bhatia, 2007; Wang
et al., 2007).
FTIR analysis on bio-oil sample may able to verify the analysis
of chemical compounds detected via GC–MS. The infrared spectra
representing functional group compositional analysis for pyrolysis
oil for both samples are tabulated in Table 3. The strong and broad
band at 3427 and 3422 (cm1) on both samples were the charac-
teristic of O–H stretching vibrations. The results agreed well with
the finding on the presence of phenols and alcohols as described
in Fig. 3. Obvious shoulder at between 1750–1650 (cm1) was
characterized by C@O stretching vibration. The bands are compat-
ible with the presence of ketone, aldehyde, carboxylic group and

60 Ester
Treated sample
Alkanes & alkenes Untreated sample
Untreated sample
Ketones & aldehyde Treated sample
40
Acids

Alcohols
20
Phenol

0 20 40 60 80 100
0
Char Liquid Gas Yield of compound (wt%)

Fig. 2. The yield of char, liquid and gas product on bio-oil of treated and untreated Fig. 3. Classification of product compound based on chemical functional group in
sample (reactor temperature = 300 °C, catalyst loading = 0.5 g HZSM-5, 30 g EPFB). pyrolysis oil of treated and untreated sample with HZSM-5 catalyst.
 M. Misson et al. / Bioresource Technology 100 (2009) 2867–2873 2871

Table 3
IR functional group composition of EPFB pyrolytic oils.

Type of functional group Wave number (cm1) Untreated EPFB sample Treated EPFB sample Class of compound
O–H stretching 3600–3300 3427 3422 Phenols, alcohols
C–H stretching 3000–2800 – – Alkanes
C@O stretching 1750–1650 1716 1716 Ketones, aldehydes, carboxylic acids, esters
C@C stretching 1675–1575 1648 1647 Alkenes
C–H stretching 1460–1350 1394 1389 Alkanes
C-O stretching 1300–950 1017, 1049, 1084, 1277 1017, 1272 Primary, secondary and tertiary alcohols, phenols, esters
C–H bending 900–650 758, 884 756 Aromatic compounds

esters. The C@C stretching of alkenes compounds were detected at
1648 and 1647 cm1 band for untreated and treated samples,
respectively.
A bending vibration between 1460 and 1350 cm1, which was
assigned to C–H stretching of alkane group, were detected in both
oils even though it was not found via GC–MS analysis. Perhaps, the
compound yield was very small to be detected during the analysis.
C–H stretching is extremely valuable for the detection of methyl
group (Wang et al., 2007). Meanwhile, the peak between 1300
and 950 (cm1) showed the C–O stretching and O–H bending due
to the presence of primary, secondary and tertiary alcohols. Other
weak absorbance observed at nearly 650–900 (cm1) indicated the
existence of some substituted aromatic groups.
Combining the evidence gathered by IR and GC–MS, it may be
concluded that the chemical pretreatment has effectively degraded
the lignin structures. Catalytic pyrolysis has resulted to high phe-
nol yields, as indicated by the strong O–H stretching band. Besides
phenol, GC–MS analysis and the C@C stretching spectra revealed
the presence of alkenes in the bio-oil.
The analysis and characterization of bio-oils provided impor-
tant data on the physical and chemical properties of these liquids.
The data revealed information about quality, toxicity and stability
of the product and linkages with the pyrolysis process parameters.
As shown in Table 4, it was observed that the properties of the bio-
oil were strongly dependent on the feedstock and production cir-
cumstances (Tsai et al., 2007). Apparently, acidic compounds were
the major compounds obtained in most of the biomass feedstock.
The EPFB feedstock however, demonstrated large production of
phenolic compounds. A total of 23.5 wt% of the phenolic com-
pounds was observed in this study, 1.2 times higher than the study
testified by Ani (2001). The result may possibly revealed the signif-
icance of the pretreatment process where lignin is degraded and
may have cleaved the phenolic chains in the lignin structure.
Chemical products developed in the current study are highly
valuable as raw materials or building blocks for the polymer and
chemical industries, pharmaceutical and also for cosmetic pur-
poses (Effendi et al., 2007). Phenolic compounds have the potential
as potent antioxidants as found in olive fruits (Rodriguez et al.,
2008). More interestingly, other undesired chemicals were cur-
tailed when the EPFB was pre-treated chemically. The pre-treat-
ment method combined with pyrolysis could be one of the most
promising technologies to produce fuels and important chemicals
from biomass since it is renewable, easily available, sustainable,
and has positive environmental effect.
The lignin content in biomass is of particular interest due to its
phenolic nature from which a wide variety of phenols and phenol
derivatives and aromatic chemicals can be derived. The renewable
phenol from pyrolysis of biomass is highly attractive due to ease of
assimilation into phenol formaldehyde formulations (Effendi et al.,
2007). This interest is enhanced by the fact that high lignin content
biomass is widely available, often at low cost and in large quanti-
ties, while phenol is a relatively expensive bulk chemical derived
from crude oil. Phenolic compounds are ubiquitous in aqueous
streams of industrial processes including petroleum refining, cok-
ing and coal conversion, chemical plants, foundries and pulp-
and-paper plants (Ryan et al., 2007).
3.3. Product distribution of different catalysts
Production of phenolic compounds such as guaicol, syringol and
their alkyl-derivatives by thermochemical conversion depends on
the use of appropriate conditions such as small wood particle size,
low reactor residence time, reduced pressure and moderate pyro-
lysis temperature (Amen-Chen et al., 2001). The main chemical
reaction in the transformation of biomass to phenols starts with
the dehydration of HO-groups in the alkyl chain of the lignin phe-
nylpropane basic unit followed by the cleavage of interaromatic
bonds.
The production of phenol and its derivatives was found to be
more encouraging using the pretreated feed. Further study was en-
gaged to enhance its performance by evaluating the potential of
HZSM-5, HY and Al-MCM-41 catalysts in the pyrolysis reaction.
The studies were conducted in a batch reactor under the same
operating conditions.
Catalytic activity is related to structural and active sites charac-
teristics (Aguado et al., 2006). Results in Fig. 4 elucidated the runs
over HY catalyst and without catalyst yielded 70 wt% of phenolic
compounds implying HY zeolite did not contribute much to im-
prove the quality of the bio-oil. Conversely, Al-MCM-41 and
HZSM-5 catalysts produced 90 wt% and 80 wt% of phenols, respec-
tively. The porosity of Al-MCM-41 probably contributed to its
encouraging performance in producing phenols. Al-MCM-41 is a

Table 4
Reported studies of chemical compounds yield (wt%) obtained in pyrolysis oil of biomass.

Author This study Ani (2001) Aho et al. (2008) Ji-Lu et al. (2008) Dermibas (2007)
Feedstock Empty palm fruit bunch (EPFB) Pine Cotton stalk Beech wood
Phenolic 23.52* 19.96* 5.4 – 4.8
Alcohols 3.07 3.47 2 1.88 5.34
Acids 2.32 10.86 4 10.61* 16.04*
Ketones 0.8 1.38 10.2* 2.95 11.2
Aldehydes 0.4 1.6 4 1.23 –
Hydrocarbons 1.31 – 3.2 3.2 –
Esters – 1.25 – 1.75 2
*
The highest compound yields for each feedstock appear in bold.
2872 M. Misson et al. / Bioresource Technology 100 (2009) 2867–2873

bon compounds were found in the bio-oil. With Al-MCM-41

Ester
catalyst, the highly phenol concentrated bio-oil is almost free of
Without catalyst acids, thus making the bio-oil be conveniently processed for fur-
Alkanes & alkenes
Al-MCM-41 ther use.
Ketones & aldehyde HY
HZSM-5 Acknowledgements
Acids
The authors would like to extend their sincere gratitude to the
Alcohols
Ministry of Science, Technology and Innovation, Malaysia (MOSTI)
and the Ministry of Higher Education, Malaysia (MOHE) for the
Phenolic Compound
financial supports received for this work through the project num-
0 20 40 60 80 100 ber 02-01-06 SF 0074 (Vot 79049) under e-Science Fund and Vot
78232 under Fundamental Research Grant Scheme.
Yield of compound (wt%)

Fig. 4. Product distribution in pyrolysis oil of pretreated EPFB using HZSM-5, HY,
Al-MCM-41 zeolite and without catalyst.
Table 5
Properties of biomass pyrolysis oil.
Properties EPFB (Present Typical bio-oil Diesel oil (Mahfud
work) (Mahfud et al., 2007) et al., 2007)
pH 3.4 3.0 7 Aho, A., Kumar, N.K., Eranen, K., Salmi, T., Hupa, M., Murzin, D.Y., 2008. Catalytic
Kinematics Viscosity 2 17 1.2–4.1
(cSt), 40 °C
Density, 30 °C 832 1170 850
(kg/m3)
mesoporous aluminosilicate zeolite (Triantafyllidis et al., 2007). It
has larger particle size namely 19.5 nm compared to 14.3 nm and
14.5 nm for HZSM-5 and HY-5, respectively as tabulated in Table
1. According to Aguado et al. (2006), catalyst pore size enhances
molecules accessibility to its reactive sites.
Low yields of alkanes and alkenes (5 wt%) were detected over
HY and HZSM-5 microporous zeolite catalysts. These catalysts have
strong acidity, high activities and shape selectivity which con-
verted oxygenated oil to hydrocarbon mixture due to its two-
dimensional channel like pore (Adjaye et al., 1999).
Based on the present study, Al-MCM-41 catalyst improved sig-
nificantly the quality of the bio-oil besides increasing the phenol
yield. Over the Al-MCM-41 catalyst, acid content was successfully
eliminated as revealed in Fig. 4. The acid presence in pyrolysis oil is
a major drawback for the oil from being used for transportation
fuel.
The amount of alcohols on the other hand was reduced to 5 wt%,
and obviously 2 times lower as compared with other catalysts.
According to Aguado et al. (2006), catalyst pore size affected
growth of end products inside the pores. The catalyst has large
pore diameter and micro pore volume, namely 43.43 (Å) and
0.66 (cc/g), respectively (Table 1).
The properties of oil are characterized and tabulated in Table 5
where the quality of bio-oil from EPFB seems comparable or even
better in the production of important chemicals. Typical bio-oil is
generally slightly acidic with pH 3.0 compared to pH 3.4 for EPFB
pyrolysis oil. Interestingly, the kinematics viscosity of the oil being
2 cSt was lower compared to 17 cSt for typical bio-oil while the
density also seems equivalent with the diesel oil density.
4. Conclusions
The chemical pretreatment using NaOH and H2O2 was found to
be an effective method to degrade lignin in EPFB. Throughout the
study, NaOH was proved to be superior than Ca(OH)2. Consecutive
addition of NaOH and H2O2 decomposed almost 100% of EPFB lig-
nin. By degrading the lignin content, more phenolic and hydrocar-
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