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biomass and bioenergy 35 (2011) 1863 e 1872

biomass and bioenergy 35 (2011) 1863 e 1872 Available at www.sciencedirect.com http://www.elsevier.com/locate/biombioe

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http://www.elsevier.com/locate/biombioe Utilization possibilities of palm shell as a source of
http://www.elsevier.com/locate/biombioe Utilization possibilities of palm shell as a source of

Utilization possibilities of palm shell as a source of biomass energy in Malaysia by producing bio-oil in pyrolysis process

Faisal Abnisa, W.M.A. Wan Daud, W.N.W. Husin, J.N. Sahu *

Department of Chemical Engineering, Faculty of Engineering, University of Malaya, 50603 Kuala Lumpur, Malaysia

article info



Article history:

Agriculture residues such as palm shell are one of the biomass categories that can be

Received 8 September 2010

utilized for conversion to bio-oil by using pyrolysis process. Palm shells were pyrolyzed in

Received in revised form

a fluidized-bed reactor at 400, 500, 600, 700 and 800 C with N 2 as carrier gas at flow rate 1, 2,

10 January 2011

3, 4 and 5 L/min. The objective of the present work is to determine the effects of

Accepted 10 January 2011

temperature, flow rate of N 2 , particle size and reaction time on the optimization of

Available online 17 February 2011

production of renewable bio-oil from palm shell. According to this study the maximum


yield of bio-oil (47.3 wt%) can be obtained, working at the medium level for the operation



temperature (500 C) and 2 L/min of N 2 flow rate at 60 min reaction time. Temperature is

Biomass energy


the most important factor, having a significant positive effect on yield product of bio-oil.

Palm shell

The oil was characterized by Fourier Transform infra-red (FT-IR) spectroscopy and gas


chromatography/mass spectrometry (GCe MS) techniques.


ª 2011 Elsevier Ltd. All rights reserved.

Batch process





energy content of the palm shell varies depending on the moisture, residual oil contents and its high specific energy content [9]. Currently, the wastes are not fully utilized and some were burned without energy recovery. Bio-oil is known as pyrolysisoil, pyrolysis liquid, bio-crude-oil, bio-fuel-oil, wood liquids, wood oil, liquid smoke, wood distil- lates, pyrolytic oil, pyroligneous tar, pyroligneous acid and liquid wood [10,11]. Generally, it is a dark-brown organic liquid and free flowing with a strong acrid smell [11e 13]. The oil comprises of different size molecules which are derived from depolymeriza- tion and fragmentation reactions of three key biomass building blocks: cellulose, hemicellulose, and lignin. Some of the organic groups present in the bio-oil are acids, esters, alcohols, ketones, aldehydes, phenols, nitrogen compounds, furans, guaiacols, syringols, sugar and miscellaneous oxygenates [14,15]. Pyrolysis, a promising route for biomass utilization has been widely used for converting biomass into liquid, gas and

Biomass is a renewable energy source available which has potency to partially substitute fossil fuels. It is composed mainly of carbohydrate compounds which are determined as the elements of carbon, hydrogen and oxygen [1]. Biomass can be categorized into four groups: agricultural residues, wood residues, dedicated energy crops and municipal solid waste [2]. Numerous researchers have investigated the potency of agricultural residues for energy, and the results are very encouraging [3e6] . One of the largest sources of biomass from agricultural residues in Malaysia is palm shell [7]. The waste is generated from oil palm milling process and with more than 270 palm oil mills operating in the country, nearly more than 2.4 million tones of palm shell wastes are produced annually [8]. The amount is equaled to 45.84 PJ (petajoule) of energy unit. The

* Corresponding author . Tel.: þ 60 3 79675297; fax: þ 60 3 79675319. E-mail addresses: faisal.abnisa@gmail.com (F. Abnisa), ashri@um.edu.my (W.M.A.W. Daud), jnsahu@um.edu.my (J.N. Sahu). 0961-9534/$ e see front matter ª 2011 Elsevier Ltd. All rights reserved. doi: 10.1016/j.biombioe.2011.01.033


biomass and bioenergy 35 (2011) 1863 e1872

char [1e4]. Generally, there are two concepts of thermal converter by using pyrolysis [1,2]. The first, which is identified as conventional or slow pyrolysis, has been mainly used for the production of charcoal at the preferred conditions of high temperature, low heating rate and long gas resistance time (varies from 5 min to 30 min). The second concept, known as fast pyrolysis, is a high-temperature process in which biomass is rapidly heated in the absence of oxygen. This concept of pyrolysis is mainly used for maximizing the yield of liquid product at the processing conditions of very high heating rate and heat-transfer rate using finely ground biomass feed (around 2 mm to minimize the water in the product liquid oil), under carefully controlled temperature (around 500 C), short vapor residence time (less than 2 s) and rapid cooling of the pyrolysis vapors to maximize the bio-oil products [10,16,17]. In practice, up to 75 wt% of the biomass (on dry basis) is con- verted into bio-oil by using this method [18,19]. Numerous researchers have studied on fast pyrolysis, where the liquid product is of main interest, since it offers a flexible and attractive way of converting biomass into a liquid product


In this work, palm shell was used to produce bio-oil based on fast pyrolysis process using a fixed-bed reactor. The influ- ence of several operating parameters, such as heating rate of temperatures, reaction times, N 2 flow rate and particle sizes is investigated in batch mode. The bio-oil produced was char- acterized using Fourier Transform infra-red (FT-IR) spectros- copy and gas chromatography/mass spectrometry (GCeMS) techniques.

2. Experimental technique

2.1. Material and sample preparation

Palm shell waste for this study was obtained from local industries, near area of Kuala Lumpur, Malaysia and the samples were grinded and then screened to give desired fractions. Then the samples were dried for 24 h at 105 C. The ligninocellulosic contents of palm shell were determined by using gravimetric method in order to determine the content of cellulose, hemicellulose and lignin, respectively. The results were obtained as shown in Table 1. Ash, moisture and fixed carbon contains were determined according to ASTM Stan- dards (D-1102-84 for ash, D-2016-74 for moisture and D-3174- 89 for fixed carbon). The ultimate analysis for carbon, hydrogen and nitrogen were determined by using TruSpec CHN, LECO Cooperation; Saint Joseph, Michigan USA. The ultimate and proximate analyses have been listed in Table 2 . Elemental analysis results were used to calculate the heating value. In general, heating values can be reported as higher and

Table 1 e Ligninocellulosic contents of palm shell.

Parameter analysis

Value (%)







Table 2 e Proximate and ultimate analysis of palm shell.


Value (wt%)


Value (wt%)









Fixed carbon




Volatile a


O a





a By difference.


lower heating value, HHV (gross) and LHV (net), respectively. The difference between HHV and LHV is equal to the heat of vaporization of water formed by combustion of the fuel. The high heating values in this study were obtained from calcu- lation by Dulong as shown in Eq. (1) and the low heating values were calculated by the Eq. (2) proposed by Oasmaa [22]:




338: 2 C þ 1442: 8 H O



LHV ðMJ=kg Þ ¼ HHV ð0: 218 HÞ

2.2. Experimental Procedure



The pyrolysis experiments were performed by charging 150 g of

palm shell into a stainless steel tubular reactor with a length of

127 cm and an internal diameter of 2.5 cm. The reactor was

heated externally by an electric vertical furnace, with the temperature being controlled by a K-type thermocouple placed inside the reactor.More detailed description of the pyrolysis set up is shown in Fig. 1. The experiments were carried out in several series. The first series of experiments were carried out to determine the effect of the temperatures on pyrolysis yields with a constant particles size of 1.7 < dp < 2 mm, 2 L/min of N 2

flow rate and 60 min reaction time and the temperatures were maintained at 400, 500, 600, 700 and 800 C. At the end of each experiment, the condensable products (liquid) were collected and weighed in a series of condensermaintained at 0.5 C. After that, the solid char was removed from inside reactor and weighed. The gas product was calculated by the material balance. The yields product is calculated as follows:

Yield Wt % ¼ Desired product ðg Þ

Palm shell feed ðg Þ

100 %


The second series of experiments were performed to investigate the effect of particle size on the pyrolysis yields. For this set of experiments, the final pyrolysis process condi- tions were kept constant of temperature 500 C, 2 L/min of N 2 flow rate and 60 min reaction time. The third series of experiment was carried out to study the effect of reaction time on the pyrolysis yield. The reaction times were variated at 30, 60, 90, 120 and 150 min with constant condition process at

500 C, 2 L/min of N 2 flow rate and 1.7 < dp < 2 mm of particle

size. The last group of experiments were performed to study the effect of sweep gas (nitrogen) velocity on the product yields. The experiments were conducted at sweep gas flow rates of 1, 2, 3, 4 and 5 L/min. For all these experiments, the pyrolysis temperature, the particle size and the reaction time were kept constant 500 C, 1.7 < dp < 2 mm, 60 min, respectively.

biomass and bioenergy 35 (2011) 1863 e 1872


biomass and bioenergy 35 (2011) 1863 e 1872 1865 Fig. 1 e Flow diagram of experimental

Fig. 1 e Flow diagram of experimental set-up for bio-oil production.

2.3. Characterization of bio-oil

The bio-oil obtained under the experimental conditions that gave maximum oil yield (pyrolysis temperature of 500 C, reaction time of 60 min, N 2 flow rate of 2 L/min and particle size of 2 mm) was used for further characterization. In order to evaluate the corrosive property of the oil, the pH of the oil was measured by a Metrohm pH meter 827. The water contents of the bio-oil were obtained by Karl Fischer titration method. The density of the oil was estimated with a 25 ml pycnometer and the viscosity of bio-oil was measured using a rotational viscometer equipped with NVst spindle (Haake model VT 550). The measurement was carried out by measuring the shear stress with varying the shear rate ranging from 16.23 s 1 to

3246 s 1 at 50 C.

The chemical compositions of the bio-oil were determined by gas chromatography/mass spectroscopy (GC/MS) analysis Angilent HP 6890 N gas chromatograph equipped with an Agilent HP 5975 mass-selective detector (mass spectrometer), using a 30 m 0.25 mm DB-5ms capillary column (0.25 m m film thickness). The injection port and detector were both operated at 300 C. The GC oven was heated to 30 C for 2 min then to 290 C at a rate of 3 C/min. The injection method was used for analysis of 1 m l samples. An elemental analysis was carried out using a TruSpec CHN, LECO Cooperation; Saint Joseph, Michigan USA and the functional group were analyzed using Perkin Elmer FT-IR Spectrometer Paragon 1000.

3. Results and discussion

3.1. The effect of operating conditions on the bio-oil


3.1.1. Effect of reaction temperature

Fig. 2 shows the effect of reaction temperature on the yields

and the results indicate that as the temperatures were moved from 400 C to 500 C the bio-oil yield increased from 36.8 wt% to 46.1 wt%. The bio-oil yields were sharp increased about

9.3 wt% with a ratio 100 C. It was the optimum condition for

production of bio-oil with temperature maintained at 500 C. Then, from 600 C to the final pyrolysis temperature at 800 C, the bio-oil yields were decreased from 42.9 wt% to 35.6 wt%. The reason why bio-oil product decreased at pyrolysis temperatures of 600e 800 C was the decreases of the organic and specific products and secondary cracking of volatiles at temperatures above 500 C [23] . The cracking has led to more resulting in higher gas production, which were also observed at other biomass wastes in the literatures [24,25].

3.1.2. Effect of particle size

Fig. 3 shows the effect of particle size on bio-oil yield. The results were indicating that the particle size increased from

0.5 mm to 2 mm, it had given a positive effect to increase the

liquid product yield on this research. The yield of pyrolysis oil


biomass and bioenergy 35 (2011) 1863 e1872

1866 biomass and bioenergy 35 (2011) 1863 e 1872 Fig. 2 e Effect of temperature on

Fig. 2 e Effect of temperature on yield products. Particle size: 1.7 < dp < 2 mm, N 2 flow rate: 2 L/min, reaction time: 60 min.

2 mm, N 2 flow rate: 2 L/min, reaction time: 60 min. Fig. 3 e Yield

Fig. 3 e Yield of pyrolysis products at difference particle size. Temperature: 500 C, N 2 flow rate: 2 L/min, reaction time: 60 min.

C, N 2 flow rate: 2 L/min, reaction time: 60 min. Fig. 4 e Influence of

Fig. 4 e Influence of reaction time on pyrolysis yields. Temperature: 500 C, N 2 flow rate: 2 L/min, particle size:

1.7 < dp < 2 mm.

rate: 2 L/min, particle size: 1.7 < dp < 2 mm. Fig. 5 e Yield of

Fig. 5 e Yield of pyrolysis products at difference N 2 flow rate. Temperature: 500 C, reaction time: 60 min, particle size: 1.7 < dp < 2 mm.

biomass and bioenergy 35 (2011) 1863 e 1872


Table 3 e Physical and chemical properties of bio-oil.




Viscosity at 50 C pH





Density at 24 C Elemental composition (wet basis)


kg/m 3











O a






High Heating Value (HHV)



Low Heating Value (LHV) Water content






By difference.

was obtained maximum at 45.8 wt% for the particles of

1.7 < dp < 2 mm. The smallest (0.5 < dp < 0.71 mm) particle

size only produced an oil yield of 27 wt% with a char yield of 38.1 wt%. Based on these results particle size is having a significant influence with the yield of char [26]. If the particle size was sufficiently small it can be heated uniformly, as is consistent with earlier studies [27e 29]. This result suggested that mass- and heat-transfer restrictions had a profound influence at a larger particle size, resulting in maximum oil yield. Working at a particle size range of 1.7 < dp < 2 mm seems suitable for obtaining a high yield of liquid product in fast pyrolysis of palm shell.

3.1.3. Effect of reaction time

Experiments were conducted at different reaction times of 30, 60, 90, 120 and 150 min, under constant reaction temperature 500 C, 2 L/min of N 2 flow rate and particle size of

The reaction times after 60 min showed the stable value of liquid product. However, the longer the reaction time, the higher the cost of process needed. Decrease the particle size and reduce the feed amount ofmaterial is one solution to reduce the reaction time, because the smaller surface area will accelerate the reaction process and the time required will be shorter. However, producing more yields with a short reaction time was to be achieved in the study of this effect.

3.1.4. Effect of N 2 flow rate

To determine the effect of sweep gas flow rate on yields of pyrolysis products, a set of experiments were performed at four different sweep gas flow rates of 1, 2, 3, 4 and 5 L/min. For this set of experiments the pyrolysis temperature, reaction time and particle size range were kept constant at 500 C, 60 min and 1.7 < dp < 2 mm, respectively. The product yields of pyrolysis in relation to the flow rate of sweep gas were given in Fig. 5 . The oil yield reached its maximum of 45.9 wt% with a sweeping gas velocity of 2 L/min. It was observed that liquid product yield increased by only 5.4 wt% upon increasing the nitrogen flow rate from 1 L/min to 2 L/min. Pyrolysis vapors were removed instantly by higher sweeping gas flow rates, and if it was quenched sufficiently, more liquid yield could be obtained. However under the present study, the maximum oil yieldwas reached at 2 L/min instead of at the highest velocity of 5 L/min because of the experimental conditions insufficient quenching. As reported in the literatures, nitrogen flow influ- ences the residence time of the vapor phase produced by pyrolysis and hence, a rapid flow serves to remove the product quickly from the hot to cold zone to minimize the secondary reactions, such as thermal cracking, repolymerization, and recondensation and to maximize the liquid yields [30,31]. The gas yield rises with increasing nitrogen flow rate; whereas the char yield decreases because uncondensed volatiles are removed from the reaction zone by the nitrogen stream [30,31].


< dp < 2 mm. Reaction times were recorded when the

reactionmass was heated to 500 C. Isothermal conditions were maintained until the end of each run of reaction time. From


Physical and chemical characterization of bio-oil

Fig. 4, it can be observed that conversion of oil increased steadily


Physical characterization of bio-oil

with reaction times from 30 min to 60 min. The maximum of liquid product was obtained at 60 min of reaction time (46 wt%).

The typical properties of bio-oil derived from palm shell were given in Table 3. It can be seen from the Table 3, the density of

Table 4 e Comparison physical properties of bio-oil with difference sources of material.




Density (kg/m 3 )


Water content





Palm shell Motorcycle tire Soybean oil cake Hardwood


1051 (at 24 C) 980 (at 20 C) 1107 (at 15 C)

3.2 (at 50 C) 4.66 (at 30 C) 80.12 (at 50 C)


From this study








1251 (at 25 C)


(at 25 C)





(at 50 C)


(at 50 C)


(at 80 C)


(at 80 C)

Maize stalk


1220 b 1130 (20 C) 1160 b 1110 b 1190 b

168.36 b 3.90 (at 20 C) 145 b 2.34 (at 30 C)







Cotton stalk




Jute stick




Rice husk


152.32 b



a Not reported.

b The condition temperature is not reported.



biomass and bioenergy 35 (2011) 1863 e1872

1868 biomass and bioenergy 35 (2011) 1863 e 1872 Fig. 6 e FT-IR spectra of bio-oil

Fig. 6 e FT-IR spectra of bio-oil derived from palm shell.

the bio-oil at 24 C was 1051 kg/m 3 . It is denser than heavy fuel oil, which was typically about 855 kg/m 3 . However, the density is much related to the liquid mass flow rate, which significantly affects the performance of fluid atomizers. Another property that has also given the affect to atomization quality is viscosity. The bio-oil on this experi- ment showed low viscous which has 3.2 cP at 50 C. The low viscous is influenced by the high value of water content in bio- oil (53%). The presence of water content in bio-oil is mainly consisting from lignin-derived materials. From this study, it shows consist of palm shell mostly has a high percentage of lignin (44%). The pH at room temperature is 2.5, which is also consistent with the findings of previous studies. The low pH is attributed to the presence of acidic compounds in the aqueous portion of the bio-oil. It has been reported that bio-oils with low pH are very corrosive to aluminum, mild steel and nickel-based materials. In addition, several parameters and physical properties of bio-oil from this study show that values are close to the other sources of material, as shown in Table 4 . From data at Table 4 , pH of bio-oil derived from pall shell was more acid and amount of water content were higher than other. The differ- ences of value are due to different composition of biomass feedstock and type of pyrolysis process. Changes of physical properties of bio-oil can also be influenced by handling, temperature for proper storage and duration time of storage.

3.2.2. Chemical characterization of bio-oil

The FT-IR spectra of the bio oil were given in Fig. 6, representing functional group compositional analysis of bio-oil. The

analysis was carried out on KBr pellet. The OeH stretching

vibrations between 3200 cm 1 and 3400 cm 1 of the bio-oils indicate the presence of phenols and alcohols; the CeH stretching vibrations between 2800 cm 1 and 3000 cm 1 and CeH deformation vibrations between 1350 cm 1 and

1450 cm 1 indicate the presence of alkane groups. The C]O

stretching vibrations between 1680 cm 1 and 1750 cm 1 are compatible with the presence of ketones, quinones, aldehyde

groups, etc. The absorbance peaks between 1500 cm 1 and

1645 cm 1 represent C]C stretching vibrations indicative of

alkenes. Furthermore, mono and polycyclic and substituted aromatic groups are indicated by the absorption peaks between 690e900 and 1350e1450 cm 1 . The functional group compositional analysis for the bio-oils was shown on Table 5. GCe MS analysis was carried out of oil obtained at pyrolysis temperature of 500 C, reaction time of 60 min, N 2 flow rate of 2 L/min and particle size of 2 mm in order to identify the type of compounds. The results were shown in Table 6. Bio-oil comprises of a various mixture of organic compounds of carbons (C 3 , C 5 , C 6 , C 7 , C 8 and C 9 ). The most abundant prod- ucts, with peak areas around or greater than 2%, are phenol, 2,6-dimethoxy phenol, trimethylamine and 4-hydroxy ben- zoic acid. There are a great number of compounds but their peak areas are very low and not examined in this study. Every compound has been classified as oxygenated aromatic (ArO) and non-aromatic (NAr). Oxygenated aromatic compounds such as phenols, acids and aldehyde (furfural) are dominated in bio-oil. The presence of these compounds may be explained by the thermal degradation of oxygenated components of the palm shell. Generally, the phenols and aldehyde are respon- sible to thermal instability in bio-oil. Furthermore, the highest of peak area was obtained by trimethylamine (47.14%) a substance mainly responsible for the odor and high of water content in the bio-oil (53 wt%)http://en.wikipedia.org/wiki/ Bad_breath. The results in Table 3 show the oxygenated contents in the bio-oil obtained during pyrolysis process. The oxygen contents were obtained at high value (71.40 wt%). The high oxygen content is not attractive for the production of trans- port fuels because it decreases heating value. In brief, the high oxygen from organic components and water content would need to be removed from the bio-oil by using methods such as hydrotreatingehydrocracking process in order to further raise their heating value and reduce the corrosiveness when they are used as a fuel.

Table 5 e Functional group compositions of bio-oil derived from palm shell.


Absorbance (cm 1 )

Class of compounds

O eH

3200 e 3400 2800 e 3000 1680 e 1750

Phenols, alcohols

C eH


C eO

Ketones, quinones,


aldehyde groups

C eC

1500 e 1645 1350 e 1450 690 e 900


C eH


O eH

Aromatic groups

biomass and bioenergy 35 (2011) 1863 e 1872


Table 6 e Identification and quantification of chemical compounds in bio-oil by GC eMS analysis.


Chemical compounds

Molecular formula

Molecular weight (g/mol)

Type of compound


Peak area (%)


C 6 H 5 OH



Phenol C 6 H 5 OH 94 ArO 13.41


2-methoxy phenol

C 7 H 8 O 2



2-methoxy phenol C 7 H 8 O 2 124 ArO 1.93


2,6-dimethoxy phenol

C 8 H 10 O 3





4-ethyl-2 methoxy-phenol

C 9 H 12 O 2





3,4-dimethoxy phenol

C 8 H 10 O 3



3,4-dimethoxy phenol C 8 H 1 0 O 3 154 ArO 0.60


2-methyl phenol (o-cresol)

C 7 H 8 O



2-methyl phenol (o-cresol) C 7 H 8 O 108 ArO 0.45


4-methyl phenol (p-cresol)

C 7 H 8 O



4-methyl phenol (p-cresol) C 7 H 8 O 108 ArO 0.60



C 5 H 4 O 2



Furfural C 5 H 4 O 2 96 ArO 1.88



C 3 H 9 N



Trimethylamine C 3 H 9 N 59 NAr 47.14


biomass and bioenergy 35 (2011) 1863 e18721870 Table 6 ( continued). Chemical compounds Molecular formula
biomass and bioenergy 35 (2011) 1863 e18721870
Table 6 ( continued).
Chemical compounds
Molecular formula
Molecular weight (g/mol)
Type of compound
Peak area (%)
C 7 H 8 O 3
C 7 H 8 O 2
4-hydroxy benzoic acid
C 7 H 6 O 3
3-hydroxy-4 methoxy benzoic acid
C 8 H 8 O 4
4-hydroxy -3-methoxy benzaldehyde
C 8 H 8 O 3
1,4-dimethoxy benzene
C 8 H 10 O 2
C 8 H 8 O 3

biomass and bioenergy 35 (2011) 1863 e 1872




In this study, pyrolysis experiments on palm shell were per- formed in a fixed-bed reactor under a nitrogen atmosphere. The highest liquid yield (bio-oil) of 46.1 wt% was obtained at

a temperature of 500 C with a particle size of 1.7 < dp < 2 mm,

a reaction time of 60 min and a nitrogen flow rate of 2 L/min. Bio-oil derived from palm shell was a mixture of various

organic compounds of carbons (C 3 , C 5 , C 6 , C 7 , C 8 and C 9 ), with

a lot of oxygenated aromatic (ArO). However, it was noted that

the bio-oil product contains a significant amount (53 wt%) of water, low pH (2.5) and high oxygen content (71.40 wt%). FT-IR analysis also showed that the bio-oil compositions were dominated by oxygenated species. Obviously, the high- oxygenated oils need to be upgraded in order to raise the heating values before it can be for industrial fuels.


The authors acknowledge financial support from the Post- graduate Research Fund (No.PS061/2009A), University of Malaya, Malaysia.



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