b i o m a s s a n d b i o e n e r g y 3 6 ( 2 0 1 2 ) 4 3 e4 9

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http://www.elsevier.com/locate/biombioe

Bio-oil production from pyrolysis of corncob (Zea mays L.)

_
Ilknur Demiral a,*, Alper Eryazıcı b, Sevgi S‚ensöz a
a
Department of Chemical Engineering, Faculty of Engineering and Architecture, Eskis‚ehir Osmangazi University,
Mes‚elik,26480, Eskis‚ehir, Turkey
b
Öznur Pres, Machine and Metal Industry A.S‚, Eskis‚ehir, Turkey

article info abstract

Article history: Pyrolysis experiments have been conducted on a sample of corncob to determine the
Received 17 March 2010 effects of pyrolysis temperature, heating rate and sweep gas flow rate on the pyrolysis
Received in revised form product yields and their chemical compositions. The temperature of pyrolysis, heating rate
7 August 2011 and sweep gas flow rate were varied in the ranges of 400e550
C, 7e40
C min1 and
Accepted 6 October 2011 50e200 cm3 min1, respectively. The maximum oil yield of 26.44 wt.% was obtained at
Available online 29 November 2011 a pyrolysis temperature of 500
C, heating rate of 40
C min1 and sweeping gas flow rate of
100 cm3 min1. The elemental analysis and calorific value of the oil were determined, and
Keywords: the chemical composition of the oil was investigated using chromatographic and spec-
1
Biomass troscopic techniques (column chromatography, FTIR, H-NMR). Chromatographic and
Bio-oil spectroscopic studies on the bio-oil showed that the bio-oil obtained from corncob could be
Feedstock used as a renewable fuel and chemical feedstock with a calorific value of 26.22 MJ kg1 and
Corncob (Zea mays L.) empirical formula of CH1.34O0.28N0.01.
Pyrolysis ª 2011 Elsevier Ltd. All rights reserved.
Bio-oil characterization

1. Introduction more attractive fuel also in the industrialised countries,

Renewable energy gained a growing interest recently because
of the significant environmental problems such as global
climate changes, pollution and reduction of availability of
fossil energy resources. In this context, biomass has become
a renewable resources with high potential for energy
production [1].
Biomass resources including wood and wood wastes,
industrial or agricultural residues and their waste byproducts,
municipal solid waste, animal wastes or dedicated energy
crops (e.g., fast growing trees, shrubs and grasses) are main
biomass fuels having a growing interest since biomass is the
fourth largest energy source in the world, accounting for
about 15% of the world’s primary energy consumption and
about 38% of the primary energy consumption in developing
countries [2,3]. Biomass is however becoming a more and
because it is a renewable energy source and it is CO2 neutral
[4,5]. Due to the lower contents of sulfur and nitrogen in the
biomass waste, utilization of biomass will also lead to
a cleaner and safer environment via reduction of greenhouse
gases (CO2, N2O) and other toxic gases (NOx, SO2) which are
produced by the use of fossil fuels [6,7].
Conversion of biomass to energy is undertaken using two
main process technologies: thermochemical and biochemical/
biological. Pyrolysis is one of the primary thermochemical
conversion methods to convert biomass into valuable prod-
ucts, namely; solid char, liquid and gas product yields [8e10].
The liquid obtained from a pyrolysis process is considered to
be a very promising biofuel. The liquid fraction usually
contains acids, alcohols, aldehydes, ketones, esters, hetero-
cyclic derivatives and phenolic compounds [11e14]. It is useful
as a fuel, can be easily transported, be burned directly in

* Corresponding author. Tel.: þ90 222 2393750-3290; fax: þ90 222 2393613.
E-mail address: idemiral@ogu.edu.tr (I._ Demiral).
0961-9534/$ e see front matter ª 2011 Elsevier Ltd. All rights reserved.
doi:10.1016/j.biombioe.2011.10.045
44 b i o m a s s a n d b i o e n e r g y 3 6 ( 2 0 1 2 ) 4 3 e4 9

thermal power stations, diesel engines, or gas turbines, be In this study, pyrolysis of corncob was investigated in
utilized as a feedstock in a conventional petroleum refinery a fixed-bed reactor. Particularly, the influence of final pyrol-
and be upgraded to obtain more valuable light hydrocarbon ysis temperature, heating rate and sweep gas velocity on the
fuels [8,15]. Their direct use as conventional fuels may present product yields were studied. In addition, the bio-oil obtained
some difficulties due to their high viscosity, poor heating under the condition of maximum liquid product yield was
value, corrosiveness and instability [16,17]. Consequently, investigated using some spectroscopic and chromatographic
research has developed into upgrading the oils by catalytic techniques such as 1H-NMR, FTIR, elemental analysis, calorific
treatment to produce a derived fuel product similar quality to value, and column chromatography to determine its possi-
a refined petroleum fuel [18]. bility of being a potential source of renewable fuel and
Tsai et al. [19] fast pyrolyzed to produce valuable products chemical feedstock.
from rice straw, sugarcane bagasse and coconut shell in an
externally heated fixed-bed reactor. The effect of process
parameters such as pyrolysis temperature, heating rate and 2. Experimental section
holding time on the yields of pyrolysis products and their
chemical compositions were investigated. Wei et al. [20] 2.1. Materials
studied the effect of the particle size in the pyrolysis process
in a free fall reactor, and they concluded that smaller particles The corncob sample investigated in this study has been taken
lead to an increase in the gas yield and a decrease in char and from the city of Bursa located in Marmara region. Prior to its
tar yields. Fluidized bed flash pyrolysis experiments have been use, the corncob sample was air dried, grounded in a high
conducted by Antony Raja on jatropha oil cake to determine speed rotary cutting mill and sieved. Particle size range was
particularly the effect of particle size, nitrogen gas flow rate between 0.425 mm < dp < 0.600 mm. Table 1 shows the main
and temperature on the pyrolytic yield and obtained characteristics of the corncob used.
maximum liquid yield of 64.25% at temperature of 500
C with
a particle size of 0.7e1.0 mm and at a nitrogen gas flow rate of 2.2. Pyrolysis
1.75 m3 h1 [21]. Wang et al., investigated effect of the low
pyrolysis temperature (400e700
C) and low heating rate The pyrolysis experiments were performed on 15 g of each of
(5e20
C min1) on the pyrolysis characteristics of oil sludge in the biomass samples in a fixed-bed reactor with a length of
a horizontal quartz reactor. They have found that the optimum 104 mm and an internal diameter of 70 mm equipped with
oil fraction conditions obtained at a pyrolysis temperature of a sweep gas (nitrogen) connection. The reactor was heated
500
C, retention time of 20 min at 400
C and a heating rate of externally by an electric furnace, with the temperature being
10
C min1. Three additives used in their work as catalyst did controlled by an NieCr thermocouple inside the bed. The gas
not improve oil product quality markedly although they outlet of the reactor consists of a 180 mm long stainless steel
promoted pyrolysis conversion significantly [22]. pipe with an internal diameter of 45 mm. The traps were also
Bio-oil can be made from a wide variety of forest and connected to this pipe. Steel tubing was used for the connec-
agricultural waste materials. In North America and Europe, tions between the traps. The 600 W furnace with an inner
bio-oil is produced from forestresidues (sawdust, bark, and volume large enough to contain the whole reactor was
shavings). In Central and South America, the Caribbean and employed for heating. The thermocouple was connected to
South Pacific, Australia, Asia, and Africa, it is produced from a proportional controlling unit which was capable of
sugarcane bagasse and other agricultural wastes. Other
abundant potential feedstocks include wheat and other
straws, rice hulls, coconut fiber, etc. [23]. Furthermore, there
are lots of pyrolysis processes in operation with different Table 1 e Main characteristics of the corncob.
capacities (20e8400 kg/h) in several countries such as, Can- Characteristics Corncob
ada, UK, Netherlands, Malaysia, Germany, Finland, USA,
Moisture content (%) 7.36
China, Italy and Spain [24,25].
a
There are a number of biomass sources being considered Proximate analysis (%)
as potential sources of fuels and chemical feedstock in Turkey Volatiles 79.58
Ash 1.49
[15,26e30]. In Turkey, among grain, corn has got the widest
Fixed carbonb 11.57
field for planting after wheat and barley. Corn is an important
plant both as human nourishment, animal fodder and Ultimate analysisa (%)
Carbon 49.32
industrial raw material. Today, corn crop in the country is
Hydrogen 5.35
cultivated in area of 600,000 hectares and 4,200,000 tonnes of
Nitrogen 0.63
corn is produced in a year. In 2005, corn cultivation yield was Oxygenb 44.70
7000 kg ha1 in Turkey [31].
Empirical formula CH1.3O0.68N0.01
It was thought that corncob could be utilized as a renew-
H/C molar ratio 1.3
able energy source. Residual corncob from various applica- O/C molar ratio 0.68
tions is a significant biomass resource. In recent years, Gross heating value (MJ kg1) 16.66
condensed research has been reported on the production of
a Weight percentage on dry basis.
activated carbon and the production of liquid and gas prod-
b By difference.
ucts by pyrolysis from corncob [1,32e40].
 b i o m a s s a n d b i o e n e r g y 3 6 ( 2 0 1 2 ) 4 3 e4 9
maintaining the oven temperature within an accuracy range
of 5
C and installed into a control panel.
The experiments were carried out in two groups. The first
was carried out to determine the effect of the pyrolysis
temperature and the heating rate on pyrolysis yields with the
particles of 0.425e0.600 mm. The temperature was increased
from room temperature to 400, 450, 500 and 550
C while the
heating rates were either 7 or 40
C min1. Experimental
apparatus was held at adjusted temperature either
a minimum of 30 min or until no further significant release of
gas was observed. Following pyrolysis, the volatile products
passed through five traps, which were placed in an ice bath.
Liquid products were condensed in ice cooled traps and
recovered with DCM (dichloro methane) washing. The
aqueous phase was separated from oil phase with a sepa-
rating funnel. The bio-oil and solvent mixture was passed over
dry sodium sulphate to make it water free and then the
solvent was recovered from bio-oil by rotavapour. The
residual solid in the reactor was weighed as char. The gas yield
was calculated by taking the difference.
The second group of experiments was performed to
establish the effect of sweep gas (nitrogen) velocity on the
pyrolysis yields. The experiments were conducted at sweep
gas flow rates of 50, 100, 150 and 200 cm3 min1. For all
experiments, the final pyrolysis temperature and heating rate
were 500
C and 40
C min1, respectively, based on the
optimum results of the first group of experiments. All the
yields were expressed on a dry, ash-free (daf) basis, and the
average yields from at least two experiments were presented
within the experimental error of <0.50 wt%.
2.3. Characterization
The bio-oils selected for the characterization were those ob-
tained at the pyrolysis conditions which gave the maximum
bio-oil yield. For this purpose, spectroscopic and chromato-
graphic methods were used. The elemental composition and
calorific value of the oils were determined. The calorific
values of the corncob and oil were determined using Gal-
lenkamp Auto Adiabatic Bomb Calorimeter according to
ASTM D 240. Elemental analyses of the raw material and
product were performed on an LECO CHNS 932 Elemental
Analyzer.
The chemical class compositions of the oils were
determined by liquid column chromatography technique.
The column was conditioned by washing with n-pentane.
About 1 g of oil was separated into two fractions as pentane
soluble and insoluble compounds (asphaltenes) by using n-
pentane. The n-pentane soluble fractions were further
separated on activated silica gel (70e230 mesh), pretreated
at 105
C for 2 h prior to introduction into column. The
column was eluted successively with n-pentane, toluene
and methanol to produce aliphatic, aromatic and polar
fractions, respectively. The oil and its column chromato-
graphic fractions were analysed by using PerkineElmer 100
Model Fourier transform infrared (FTIR) spectrophotom-
eter. The 1H-NMR spectrum of the oil was obtained at an H
frequency of 400 MHz using a Bruker Avancet DPX-400
instrument. The samples were dissolved in deuterated
chloroform.
45
3. Results and discussion
3.1. Influence of pyrolysis parameters on the product
yields
Figs. 1 and 2 show the product yields from the pyrolysis of
corncob in the Heinze retort with heating rates of 7 and
40
C min1 in relation to final pyrolysis temperatures of 400,
450, 500 and 550
C without any sweep gas. For the lower
heating rate of 7
C min1, the char yield decreased from
32.16% to 27.19% as the pyrolysis temperature increased from
400
C to 550
C. In other words, the pyrolysis conversion yield
increased from 67.84% to 72.81%. The decrease in the char
yield with increasing temperature could be due either to
greater primary decomposition of biomass at higher temper-
ature or to secondary decomposition of the char [9,41]. The
pyrolysis liquid product yield contain an aqueous phase yield
and an oil phase yield. In this study the target pyrolysis
product was the oil. The oil yield was 17.99% at the pyrolysis
temperature of 400
C. It appeared to go through a maximum
of 21.05% at the final temperature of 500
C. Then, at the final
pyrolysis temperature of 550
C, the oil yield decreased to
20.04%. The higher treatment temperature has led to more
bio-oil cracking resulting in higher gas yield and lower bio-oil
yield [33,41e43]. The gas product yield increased with
increasing pyrolysis temperature. The gas yield obtained was
found to be minimum 34.85% at 400
C and maximum 37.27%
at 550
C. The increase in gas products is thought to be
predominantly due to secondary cracking of the pyrolysis
vapours at higher temperatures. The secondary decomposi-
tion of the char at higher temperatures may also give some
noncondensable gaseous products, which also contributes to
the increase in gas yield, which is parallel to the increase in
temperature of pyrolysis [9,42,44,45].
For the heating rate of 40
C min1, the char yield
decreased from 26.89% to 23.29% as the pyrolysis temperature
increased from 400
C to 550
C. For both heating rates, the
char yields decreased with increasing temperature. Char
yields for this rate of heating were also lower than the yields
40
35
30
Yield, (wt%)
25
20
char
15 bio-oil
gas
10
350 400 450 500 550 600
Temperature, (°C)
Fig. 1 e Yields of pyrolysis products at heating rate of
7
C minL1.
46 b i o m a s s a n d b i o e n e r g y 3 6 ( 2 0 1 2 ) 4 3 e4 9

40 40

35 35

30 30
Yield, (wt%)

Yield, (wt%)
25 25

20 20
char
char
15 15 bio-oil
bio-oil
gas
gas
10
10
0 50 100 150 200 250
350 400 450 500 550 600 3 -1
Nitrogen flow rate, (cm min )
Temperature, (°C)
Fig. 3 e Effect of sweep gas flow on the pyrolysis yields.
Fig. 2 e Yields of pyrolysis products at heating rate of
40
C minL1.

maximize the liquid yield [45]. As a result, the maximum oil

achieved at the lower heating rate of 7
C min1. This may be yield of 26.44% was obtained at a final pyrolysis temperature of
related to rapid heating which leads to a fast depolymeriza- 500
C with sweeping gas flow rate of 100 cm3 min1 and heat-
tion of the solid material to primary volatiles while dehydra- ing rate of 40
C min1.
tion to more stable anhydrocellulose is limited and very slow
at the lower heating rate [46]. The oil yield was 23.07% at 3.2. Characterization
a pyrolysis temperature of 400
C and the maximum oil yield
was 25.12% at a final pyrolysis temperature of 500
C. Table 2 presents the analysis results of the oil. The average
Increasing the pyrolysis temperature to 550
C, the oil yield chemical composition of the oil is CH1.34O0.28N0.01. The oil was
goes down to 23.75%. Furthermore, the oil yields at the heating characterized by lower oxygen content than that of the orig-
rate of 40
C min1 were about 19.33% higher than that of inal feedstock. The significant decrease in the oxygen content
7
C min1, particularly at the pyrolysis temperature of 500
C. of the oil compared to the original feedstock is favorable since
The gas product yield increased with pyrolysis temperature. the high oxygen content is not attractive for the production of
The gas yield obtained was found to be minimum 35.04% at transport fuels. The calorific value of the oil was 26.22 MJ kg1.
400
C and maximum 37.96% at 550
C for the heating rate of The calorific value of the oils was lower than that of petroleum
40
C min1. The aqueous phase yields were obtained as fuels (40 MJ/kg) [11]. The H/C ratios of oils were greater than
z14e15% at all pyrolysis temperatures and heating rates. that of the raw material. A comparison of H/C ratios with
To determine the effect of sweep gas flow rate on yields of conventional fuels indicates that the H/C ratios of the oils
pyrolysis products, the experiments were performed at four obtained in this study lie between those of light and heavy
different flow rate of either 50, 100, 150 or 200 cm3 min1. For petroleum products [48].
this group of experiments the pyrolysis temperature and heat- The Fourier transform infrared (FTIR) spectra of the oil and
ing rate were 500
C and 40
C min1, respectively. The product column chromatographic fractions are given in Fig. 4. The
yields of pyrolysis in relation to nitrogen flow rate are given in OeH stretching vibrations between 3200 and 3600 cm1 of the
Fig. 3. It was observed that the pyrolysis conversion has
increased in small amounts and there was no obvious influence
on the yield of char as the rate of nitrogen increased. The gas
product yield increased with sweep gas flow rate. The increased Table 2 e Properties of the pyrolysis products.
sweep gas flow rate from 50 cm3 min1 to 200 cm3 min1
Properties Bio-oila
increased the gas yield from 35.20% to 38.24%. Similar results
were also observed in previous studies [26,27,29,47]. The oil Ultimate analysis (w/w%)
Carbon 66.78
yield, obtained as 25.12% without any sweep gas, increased to
Hydrogen 7.43
26.44% with the sweep gas at a flow rate of 100 cm3 min1. In this
Nitrogen 0.83
work it was observed that sweep gas flow rate had no significant Oxygenb 24.96
effect on the oil yields. This can be occurred due to the experi-
Empirical formula CH1.34O0.28N0.01
mental conditions, especially insufficient quenching. As re-
H/C molar ratio 1.34
ported in the literature, nitrogen flow influences the residence O/C molar ratio 0.28
time of the vapour phase produced by pyrolysis, and hence, Gross heating value, (MJ kg1) 26.22
a rapid flow serves to remove the product quickly from the hot
a Obtained at 500
C with heating rate of 40
C min1.
zone to the cold to minimize the secondary reactions, such as
b By difference.
thermal cracking, repolymerization and recondensation and to
 b i o m a s s a n d b i o e n e r g y 3 6 ( 2 0 1 2 ) 4 3 e4 9
Fig. 4 e The FTIR spectra of (a) oil, (b) n-pentane
subfraction, (c) toluene subfraction, (d) methanol
subfraction.
bio-oil indicate the presence of phenols and alcohols. The
presence of alkanes is indicated by the absorbance peak of
CeH vibrations between 2800 and 3000 cm1 and by 1350 and
1475 cm1 bands due to the CeH bending. The C]O stretching
vibrations with absorbance between 1650 and 1780 cm1
indicate the presence of ketones, aldehydes and carboxylic
acids [49]. The absorbance peaks between 1590 and 1630 cm1
indicate the presence of alkenes and aromatics. The peaks
between 900 and 1300 cm1 are due to the presence of
Fig. 5 e 1H-NMR spectrum of the oil.
47
primary, secondary and tertiary alcohols and also phenols and
they are showing the CeO stretching and OeH bending [50,51].
Furthermore, the absorption peaks between 650e900 and
1420e1610 cm1 indicate mono and polycyclic and substituted
aromatic groups. Obtained bio-oil has a typical FTIR spectrum
compared with the previous studies [26].
Oil was separated into fractions as n-pentane soluble and
insoluble compounds (asphaltenes) by using n-pentane. The n-
pentane soluble material was further separated by adsorption
chromatography. The results of adsorption chromatography of
the oils showed that the oil consists of 51.28% n-pentane
solubles. Oil from corncob pyrolysis contains 22.24% aliphatic,
28.89% aromatic and 48.87% polar subfractions. The content of
polar organic compounds in corncob oil is higher than in
Euphorbia Macroclada [52] and olive bagasse [26] while the
content of aromatic ring is lower. The aliphatic and aromatic
subfractions make up 51.13%, and this seems to be more
appropriate for the production of hydrocarbons and chemicals.
An integrated approach to chemical and fuel production offers
interesting possibilities for shorter term economic imple-
mentation. Chemicals that have been reported as recovered
include polyphenols for resins with formaldehyde, calcium
and/or magnesium acetate for biodegradable deicers, fertil-
isers, levoglucosan, hydroxyacetaldehyde and a range of fla-
vourings and essences for the food industry [53].
Fig. 5 represents the 1H-NMR spectrum of the oil product
from the pyrolysis of corncob. The percentages of the hydrogen
types that were calculated on the basis of the chemical devia-
tion values obtained from the 1H NMR spectra are in Table 3.
Resonances between 6.0 and 9 ppm were assigned to aromatic
structures. Aromatic ring-joining methylene protons, so called
HF, were observed in the bio-oil and their characteristic peaks
are in the range of 3.0 and 4.0 ppm. bCH3, CH2, CHg or further
from an aromatic ring protons (centered at 1.25 ppm) were
indicated in the bio-oil. Moreover CH3, CH2 and CH protons a to
an aromatic ring were present in the highest proportion in the
48 b i o m a s s a n d b i o e n e r g y 3 6 ( 2 0 1 2 ) 4 3 e4 9

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