J. Anal. Appl.

Pyrolysis 83 (2008) 205–212

Contents lists available at ScienceDirect

Journal of Analytical and Applied Pyrolysis

journal homepage: www.elsevier.com/locate/jaap

Pyrolysis oil from fast pyrolysis of maize stalk

Zheng Ji-Lua,b,*
a
Department of Chemistry, Zhengzhou University, 75#, DaXue Street, Zhengzhou, Henan Province 450052, China
b
Zheng Zhou YaXing Energy Co., Ltd., FuHua Building, 59#, Dong Street, Zhengzhou, Henan Province 450000, China

A R T I C L E I N F O A B S T R A C T

Article history: Maize stalk was fast pyrolysed at temperatures between 420 8C and 580 8C in a fluidized-bed, and the
Received 12 June 2008 main product of pyrolysis oil was obtained. The experimental results showed that the highest pyrolysis
Accepted 10 August 2008 oil yield of 66 wt.% was obtained at 500 8C for maize stalk. Chemical composition of the pyrolysis oil
Available online 19 August 2008
acquired was analyzed by GC–MS and its heat value, stability, miscibility and corrosion characteristics
were determined. These results showed that the pyrolysis oil could be directly used as a fuel oil for
Keywords:
combustion in a boiler or a furnace without any upgrading. Alternatively, the fuel could be refined to be
Biomass
used by vehicles.
Maize stalk
Pyrolysis
ß 2008 Elsevier B.V. All rights reserved.
Pyrolysis oil

1. Introduction only possible with coupling between gasification of biomass

Nowadays, the demand for energy is increasing rapidly due to
the growth of population, the desire for comfort, material
acquisition, mobility and communication. Before the Middle East
War in 1973, world community dedicated their industries on coal
and petroleum, which were plenty and cheap. But with the oil crisis
after the war, depletion of natural reserves of coal and oil and
greenhouse effect has attracted great interest to sustainable
energy production [1]. Renewable energy sources such as biomass
have a role to play in each one of these energy and environmental
concern.
Biomass (agricultural residues, forestry products and city
wastes) can be used for energy production in several ways from
old direct burning to modern gasification and fast pyrolysis [2]. For
the recovery of maximum energy from a particular biomass, the
technically and economically viable process [3] should be selected.
By the direct combustion, the biomass is completely transformed
into heat, of which only 10–15% is effectively heated the target.
Thus the commercial energy production by this process is not
economically viable at present. The fast pyrolysis and gasification
are the modern techniques for the conversion of biomass into
combustible liquid (pyrolysis oil) and/or gaseous fuels before
burning it. The liquid and gas products can be used in engine and
turbine for power generation. Power generation by gasification is
* Correspondence address: Department of Chemistry, Zhengzhou University,
75#, DaXue Street, Zhengzhou, Henan Province 450052, China.
E-mail address: triace@163.com.
unit and the power generation unit [4]. The other problem of
gasification is the difficulty of storage, transportation and handling
of gaseous fuels [5].
It is reported [6] that the biomass fast pyrolysis to produce
liquid fuels is advantageous over gasification and combustion.
Liquid (pyrolysis oil) products in fast pyrolysis of biomass have
advantages in transport, storage, combustion, retrofitting and
flexibility in production and marketing.
Fast pyrolysis [7] is a process in which organic materials are
rapidly heated at 450–600 8C in absence of air. Under these
conditions vapours, permanent gases and charcoal are produced.
The vapours are condensed to pyrolysis oil. Typically 60 wt.% of the
feedstock is converted into pyrolysis oil. Fast pyrolysis transforms
difficult-to-handle biomass of different nature into a clean and
uniform liquid. Pyrolysis oil can be used for the production of
renewable/sustainable energy and chemicals [8]. Its energy
density is four to five times higher than the original solid material,
which offers important logistic advantages.
A large number of feedstocks, such as wood, rice husk, bagasse,
sludge, tobacco, tires shredder waste, palm-oil residues, straw,
olive stone residues and many more, can be processed in the fast
pyrolysis process.
The geographic and climate conditions of China are suitable for
growing maize thus producing huge amount of maize stalk as
agricultural by-product [9]. The maize stalk is used as a solid fuel
for cooking in the rural area. However, this maize stalk can be used
for pyrolysis oil production using a modern technology such as fast
pyrolysis. The pyrolysis oil can be used in various energy sectors
as liquid fuel, thus reducing foreign petroleum dependence. This

0165-2370/$ – see front matter ß 2008 Elsevier B.V. All rights reserved.
doi:10.1016/j.jaap.2008.08.005
206 J.-L. Zheng / J. Anal. Appl. Pyrolysis 83 (2008) 205–212

concept motivates many researchers to develop an economic some thermocouples and pressure meters. The hopper was used
process, which can efficiently produce pyrolysis oil from their won to contain feedstock such as maize stalk. The two screw feeders
biomass resources. Many pilot plants especially in Europe have had the same configuration and size; the first one was used to
already been demonstrated for pyrolysis oil production, although control the feeding rate and the second one operated at a
they have very limited biomass resources. However, there have relatively high speed to prevent jamming of the feeding system.
been not yet available literature to produce pyrolysis oil from The fluidized-bed reactor had a height of 2 m and a diameter of
chinese maize stalk. In this work, the pyrolysis oil was produced by 70 mm, in which maize stalk was rapidly heated for pyrolysis.
fast pyrolysis of maize stalk. The electric heater could pre-heat the nitrogen to the tempera-
ture range of 300–600 8C before entering into the fluidized-bed
2. Experimental material, device and method reactor. The two cyclones were used to separate solid particles
such as charcoal and ash from the hot gas. The condenser was
2.1. Experimental material equipped with some nozzles and a heat exchanger. The
condenser could quickly cool the cleaned hot gas into a liquid.
The experimental materials included maize stalk, sand and An oil pump was used to pump the condensed liquid from the
nitrogen. To ensure the consistent feeding and optimized pyrolysis bottom of the condenser to the nozzles on the top of the
products, the maize stalk was crushed with a crashing machine to condenser. Pumping the cooled liquid back into the condenser
about 0.1–0.5 mm in size. The physical properties of maize stalk assisted in the scrubbing and condensation process. Thermo-
and sand, such as bulk density and particle size, were listed in couples and pressure meters were used to monitor and control
Table 1. The heating value of the maize stalk was determined using the pyrolysis system.
a LECOAC 350 instrument according to ASTM D 3286-91a.
Proximate analysis was performed on the maize stalk sample to 2.3. Experimental method
determine the weight fractions of volatile, ash and fixed carbon
contents. The ASTM Standard Test Method for Proximate Analysis In the first experiment, some ethanol was put into the
of Wood Fuels (D870-82) was used. Then, the fixed carbon content condenser for scrubbing the hot gas. Therefore, the liquid obtained
was obtained by subtracting the percentages of volatile matter and from the condenser actually consisted of a mixture of ethanol and
ash from 100%. The proximate analysis of maize stalk was listed in pyrolysis oil pyrolysed from maize stalk. As ethanol has a high
Table 2, in which ash is the remains after complete combustion, volatility, its concentration in the mixture would continually
volatile is the volatilized proportion from maize stalk when it is decrease during the experiments until the ethanol was completely
heated without oxygen, fixed carbon is the remains after complete gone. According to our experience, it can be considered that the
volatilization, and calorific value is the thermal energy contained mixture only consisted of the pyrolysis oil pyrolysed from maize
in maize stalk. The elemental analysis of maize stalk was listed in stalk if the experiment lasted for more than 10 h. After the
Table 3. Elemental analysis of the pyrolysis oil was performed experiment lasted for more than 10 h, ethanol was not detected by
using a CARLO ERBA 1106 instrument according to ASTM D 5373. GC–MS in the pyrolysis oil. Besides pyrolysis oil, two by-products,
Elemental composition was performed according to ASTM D 3176. namely charcoal and an un-condensable gas, could also be
Sand was used as the thermal carrier to quickly transfer heat obtained when maize stalk was pyrolysed.
from hot nitrogen to the maize stalk in the fluidized-bed reactor. Maize stalk was fast pyrolysed in a fluidized-bed reactor and
Nitrogen was used as the carrier gas to fluidize the maize stalk and the pyrolysis temperature was between 420 8C and 580 8C.
sand in the fluidized-bed reactor. The yield of pyrolysis oil could be determined from the
condensed liquid. The yield of charcoal could be determined from
2.2. Experimental device the charcoal collected from the two cyclones. The yield of un-
condensable gas could be determined from the fact that the sum of
As shown in Fig. 1, the experimental device mainly consisted three product yields should equal 100%.
of a hopper, two screw feeders, an electric heater, a fluidized-bed Pyrolysis tests at a certain temperature were replicated five
reactor, two cyclones, a condenser, and an oil pump, as well as times. Hence 5 observations of gas yields, 5 observations of
charcoal and 5 observations of pyrolysis oil were obtained at a
Table 1 certain temperature. The 5 observations, for example 5 observa-
Physical property of experimental materials tions of gas yields, were formed to be a vector which had five
Material Bulk density (kg/m3) Particle size (m) components and the vector was called to be x or y.
In order to analyze influence of temperature on the product
Maize stalk 220 0.0003
Sand 2600 0.00045
yields, a two-sample t-test was performed [12].
The null hypothesis (H0) was that the mean of the vector x was
equal to the mean of the vector y. The vector x contains 5
Table 2 observations. Each of the observations was certain product yield
Proximate analysis of maize stalk such as gas yield at a certain temperature. The vector y also
contains 5 observations. Each of the observations was certain
Material Moisture Ash Volatile Fixed carbon Lower heat
(wt.%) (wt.%) (wt.%) (wt.%) value (MJ/kg)
product yield such as gas yield at another temperature.
The alternative hypothesis (H1) was that mean of x was less
Maize stalk 7.67 8.33 71.95 12.05 15.07 than mean of y (left-tail test).
In the test, the p-value was used. The p-value of the test was the
probability, under the null hypothesis, of obtaining a value of the
Table 3
test statistic as extreme or more extreme than the value computed
Elemental analysis of maize stalk
from the sample.
C (wt.%) H (wt.%) O (wt.%) N (wt.%) S (wt.%) In the test, the significance level was 5%. The significance level
of the test was a threshold of probability agreed to before the test
49.1 6.1 43.7 0.7 0.11
was conducted. If the p-value of the test was less than the
 J.-L. Zheng / J. Anal. Appl. Pyrolysis 83 (2008) 205–212
Fig. 1. The experimental device.
significance level, the test rejected the null hypothesis (H0) and
approved the alternative hypothesis (H1).
The yield of pyrolysis oil was heavily impacted by the
cooling in the condenser. The cooling must be quick; otherwise,
some condensable gas would be converted into un-condensable
gas and bitumen. Scrubbing with well-sprayed liquid in the
bottom of condenser was the best way for cooling as a
large quantity of heat could be quickly absorbed by the liquid
mist.
In the experiment, maize stalk was fed at the rate of 6.9 kg/h.
The water in pyrolysis oil was determined by a Karl Fischer
titrator based on theory of Karl Fischer titration. The model
number of the Karl Fischer titrator was KF2-187.
The chemical compositions of the pyrolysis oil from maize stalk
were analyzed by GC–MS (QP5050A, Japan). A capillary column
(30 m  0.25 mm) was employed to separate the pyrolysis oil.
Acetone was used as solvent to dilute the pyrolysis oil to a
concentration appropriate for analysis. The analysis parameters for
the GC–MS (QP5050A, Japan) was listed in Table 4.
The chemical compositions of un-condensable gas from
maize stalk were analyzed by GC–MS (GC-14B). A packed
column (GDX-502), FID detector and carrier gas (N2) were
employed for CH4 and C2H4 measurement. A packed column
(GDX-101), TCD detector and carrier gas (He) were employed for
N2, H2, CO and CO2.
The stability characteristics of pyrolysis oil from maize stalk
were studied in terms of variation of viscosity over time. Viscosity
measurements were done over a period of time under two different
Table 4
The analysis parameters for the GC–MS (QP5050A, Japan)
Injection temperature 230 8C Oven temperature 60–260 8C, 10 8C/min
Interface temperature 230 8C Total flow 30.2 ml/min
Solvent cut time 2.5 min Split ratio 25
Threshold 1000 Aacquisition mode Scan
Interval 0.5 s Column inlet pressure 100 kPa
207
storage conditions, one stored at 20 8C and the other stored at
60 8C, for each of the oil samples. The viscosity was measured
according to the standard procedure (ASTM D-445-88).
In order to analyze the variation of the pyrolysis oil viscosity
over time, a two-sample t-test was performed [12].
The null hypothesis (H0) was that the mean of the vector x was
equal to the mean of the vector y. The vector x contains 5
observations. Each of the observations was the pyrolysis oil
viscosity at a certain time. The vector y also contains 5 obser-
vations. Each of the observations was the pyrolysis oil viscosity at
another time.
The alternative hypothesis (H1) was that mean of x was less
than mean of y (left-tail test).
In the test, the p-value was used. The p-value of the test is the
probability, under the null hypothesis, of obtaining a value of the
test statistic as extreme or more extreme than the value computed
from the sample.
In the test, the significance level was 5%. The significance level
of the test was a threshold of probability agreed to before the test
was conducted. If the p-value of the test was less than the
significance level, the test rejected the null hypothesis (H0) and
approved the alternative hypothesis (H1).
In order to identify how the pyrolysis oil can be used within
petroleum-based infrastructure, the miscibility of the pyrolysis
oil were investigated with diesel and emulsifier. The pyrolysis
oils from rice husk were mixed with diesel and emulsifier in
different ratio and pH and viscosity were measured for each of
the mixtures.
Corrosion test on copper and stainless steel was performed
with the pyrolysis oils. Polished Cu and stainless steel strip
were immersed in a given quantity of oil sample kept at 60 8C
and the weight loss characteristics of the strips were tested
with time. Each of the strips was removed at 12-h interval,
washed and weighed. The corrosiveness was expressed in
terms of the weight loss (wt.%) of copper or stainless steel versus
time (h).
208 J.-L. Zheng / J. Anal. Appl. Pyrolysis 83 (2008) 205–212

Table 5 Table 7
The result of the two-sample t-test and gas yield The result of the two-sample t-test and pyrolysis oil yield

Temperature (8C) Temperature (8C)

420 460 460 500 500 540 540 580 420 460 460 500 540 500 580 540
x y x y x y x y x y x y x y x y

Gas yield (wt.%) 10.0 14.5 14.5 15.6 15.6 21.1 21.1 23.6 Pyrolysis oil 59.7 64.6 64.6 66.1 64.9 66.1 64.3 64.9
9.9 15.3 15.3 15.8 15.8 21.1 21.1 24.0 yield (wt.%) 59.9 63.9 63.9 66.0 65.2 66.0 64.2 65.2
10.0 14.8 14.8 15.7 15.7 20.8 20.8 24.3 60.3 64.4 64.4 66.7 64.9 66.7 63.8 64.9
10.5 15.4 15.4 16.4 16.4 21.2 21.2 24.2 59.4 63.6 63.6 65.1 65.1 65.1 64.0 65.1
9.6 14.6 14.6 15.8 15.8 21.2 21.2 24.0 60.1 64.6 64.6 65.9 64.3 65.9 64.4 64.3

Average (wt.%) 10.0 14.9 14.9 15.9 15.9 21.1 21.1 24.0 Average (wt.%) 59.9 64.2 64.2 66.0 64.9 66.0 64.1 64.9

The p-value 0.0000 0.0017 0.0000 0.0000 The p-value 0.0000 0.0004 0.0041 0.0019

x: the vectors which contains 5 observations. Each of the observations is gas yield at x: the vectors which contains 5 observations. Each of the observations is pyrolysis
a certain temperature. y: the vectors which also contains 5 observations. Each of the oil yield at a certain temperature. y: the vectors which also contains 5 observations.
observations is gas yield at another temperature. Each of the observations is pyrolysis oil yield at another temperature.

3. Results and discussion

3.1. Influence of temperature on product yields

The result of the two-sample t-test and product yields were

listed in Tables 5–7. Relationships between product yields and
temperature were shown in Fig. 2.
The results of the two-sample t-test were listed in Tables 5–7.
Because the p-value of the tests were less than the significance
level, the tests rejected the null hypothesis (H0) and approved the
alternative hypothesis (H1). Namely mean of x was less than mean
of y. Hence it could be found that: (1) pyrolysis oil yields first
increase and then decrease while pyrolysis temperature was
increased from 420 8C to 580 8C and the maximum ones for maize
stalk is 66%; (2) un-condensable gas yields always increase while
pyrolysis temperature was increased while pyrolysis temperature
was increased from 420 8C to 580 8C; (3) charcoal yields always
decrease while pyrolysis temperature was increased from 420 8C
to 580 8C.
For fluidized bed operation similar influence of temperature on Fig. 2. Relationship between pyrolysis temperature and product yields.
product yields were reported under almost the same pyrolysis
conditions [13–15]. From Table 8, it could be found that: (1) the energy density of the
pyrolysis oil is much higher than that of the maize stalk so that it is
3.2. The properties and compositions of the pyrolysis oil convenient for transportation and utilization; (2) the pyrolysis oil
contains small concentrations of S, N and other pollutants; (3) the
The water in pyrolysis oil was determined by a Karl Fischer oxygen content of the pyrolysis oil was high. The oxygen content of
titrator based on theory of Karl Fischer titration. The compositions the pyrolysis oil was very much dependent on the raw material and
of pyrolysis oil and un-condensable gas were analyzed with gas the pyrolysis conditions under which they were produced. The
column–mass spectrometry. The properties of pyrolysis oil were oxygen content of the maize stalk was 43.7 wt.% and the oxygen
presented in Table 8, and the compositions of pyrolysis oil and of content of the pyrolysis oil must be higher than the oxygen content
un-condensable gas are listed in Tables 9 and 10, respectively. of the maize stalk because 20–30 wt.% charcoal which was mainly

Table 6
The result of the two-sample t-test and charcoal yield

Temperature (8C)

580 540 540 500 500 460 460 420

x y x y x y x y

Charcoal yield (wt.%) 12.2 14.0 14.0 18.3 18.3 20.9 20.9 30.4
11.8 13.7 13.7 18.2 18.2 20.8 20.8 30.2
11.9 14.3 14.3 17.5 17.5 20.7 20.7 29.7
11.8 13.7 13.7 18.5 18.5 20.9 20.9 30.1
11.6 14.5 14.5 18.3 18.3 20.8 20.8 30.3

Average (wt.%) 11.9 14.0 14.0 18.2 18.2 20.8 20.8 30.1

The p-value 1.0e 005  0.1357 1.0e 005  0.0057 1.0e 005  0.0143 1.0e 005  0.0000

x: the vectors which contains 5 observations. Each of the observations is charcoal yield at a certain temperature. y: the vectors which also contains 5 observations. Each of the
observations is charcoal yield at another temperature.
 J.-L. Zheng / J. Anal. Appl. Pyrolysis 83 (2008) 205–212 209

Table 8 made from carbon was produced when maize stalk was fast
Main properties and elements of pyrolysis oil from maize stalk
pyrolysed. Moreover maximum yields of pyrolysis oil were
Properties Pyrolysis oil obtained at temperatures in the range 450–550 8C and residence
times of 0.5–5 s depending on the particular process; these being
H2O (wt.%) 22.5
pH 3.2 typical conditions of fast pyrolysis. In this case the pyrolysis oil was
Density (kg/m3) 1220 highly oxygenated. The high oxygen content was indicative of the
Viscosity (mm2/s) 138 presence of many highly polar groups leading to high viscosities
LHV (MJ/kg) 19.6
and boiling points as well as relatively poor chemical stability. As
C (wt.%) 44.3
H (wt.%) 6.3
the table showed a significant fraction of the oxygen was present as
O (wt.%) 47.5 water. On account of their high oxygen content and hydrophilic
N (wt.%) 0.6 character it was not surprising that fast pyrolysis oils were mostly
S (wt.%) 0.3 insoluble in hydrocarbon solvents; (4) the calorific value of the
pyrolysis oil was 19.6 MJ/kg but the calorific value of diesel is
42.6 MJ/kg, the calorific value of coal is 29.3 MJ/kg, and the calorific
Table 9 value of gasoline is 44.0 MJ/kg. It revealed that the calorific value of
Compositions of pyrolysis oil from maize stalk
the pyrolysis oil was much lower than the calorific value of fossil
Composition Contents (wt.%) fuel because the oxygen content of the pyrolysis oil was high.
Extensive reviews on physical properties of pyrolysis oils have
Dihydroxyacetone 3.9
Acetic acid 2.7 recently been published [16]. The lower heating value (LHV) of
Methylacetic acid 1.6 pyrolysis oil was found to be 19.6 MJ/kg which is comparatively
Butyric acid 1.5 higher than those of some pyrolysis oils produced from rice husk
3-Methyl-2-cyclopenten-1-one 1.7
[17] or straw [10]; however, it is about 48% of light-medium
1-Hydroxybutan-2-one 1.9
Dimethyl succinate 2.9
hydrocarbon fuel oils [16].
Phenol 1.4 The viscosity of the pyrolysis oil as produced can be greatly
Guaiacol 2.5 varied depending on the temperature, feedstock, water content of
2-Acetylfuran 2.4 the oil, amount of light ends that have been collected and the
extent to which the pyrolysis oil has aged. The viscosity of
pyrolysis oil produced from maize stalk was found to be 129 mm2/
Table 10 s at 20 8C. This value was much lower than many pyrolysis oils [16]
Compositions of uncondensed gas from maize stalk
and also lower than some hydrocarbon fuels [16]. In the
Composition Content (wt.%) application of liquid as fuel, the lower the viscosity of the oil,
the easier it is to pump and to atomize and achieve finer droplets.
N2 85
H2 0.03 This is the major criterion upon which the oils are aged. Since the
CO 2.37 pyrolysis oil from maize stalk was lower viscous than many other
CO2 5.78 pyrolysis oils and hydrocarbon fuels [16], it was assumed that this
CH4 0.78
pyrolysis oil can be used in the internal combustion engine for
C2H4 0.62
transportation and power generation.

Fig. 3. Gas chromatogram of the pyrolysis oil.

210 J.-L. Zheng / J. Anal. Appl. Pyrolysis 83 (2008) 205–212

Table 11
The result of the two-sample t-test and viscosity of the pyrolysis oil

At temperature of 20 8C

0h 5h 5h 10 h 10 h 20 h 20 h 40 h 40 h 80 h
x y x y x y x y x y

Viscosity (mm2/s) 128 150 150 179 179 204 204 212 212 241
129 149 149 180 180 205 205 208 208 239
129 150 150 182 182 204 204 211 211 239
132 150 150 179 179 205 205 210 210 240
129 149 149 182 182 203 203 210 210 242

Average (mm2/s) 129 148 148 178 178 204 204 211 211 240

The p-value 0.0000 0.0000 0.0000 0.2438  e 4 0.0000

x: the vectors which contains 5 observations. Each of the observations is viscosity of the pyrolysis oil at a certain time. y: the vectors which also contains 5 observations. Each
of the observations is viscosity of the pyrolysis oil at another time.

Table 12
The result of the two-sample t-test and viscosity of the pyrolysis oil

At temperature of 60 8C

0h 5h 5h 10 h 10 h 15 h 15 h 20 h 20 h 30 h
x y x y x y x y x y

Viscosity (mm2/s) 40 75 75 90 90 94 94 98 98 106

42 74 74 89 89 94 94 101 101 105
39 74 74 88 88 96 96 100 100 104
40 73 73 91 91 94 94 99 99 105
42 76 76 90 90 93 93 100 100 106

Average (mm2/s) 42 75 75 91 91 95 95 98 98 105

The p-value 0.0000 0.0001  e 4 0.9352  e 4 0.3046  e 4 0.1044  e 4

x: the vectors which contains 5 observations. Each of the observations is viscosity of the pyrolysis oil at a certain time. y: the vectors which also contains 5 observations. Each
of the observations is viscosity of the pyrolysis oil at another time.

Gas chromatography–mass spectrometry was applied to the increase of viscosity of pyrolysis oil are enhanced by higher
separate and identify the products. Identification of the GC/MS temperature, and the rate of increase of viscosity of pyrolysis oil
peaks was based in most cases on comparison with spectra of the was found to reduce after some time. This result is quite consistent
NIST 98 spectrum library. Fig. 3 showed Gas chromatogram of the with many reported results [18].
pyrolysis oil. From Fig. 3 it could be found that more than 100 peaks Hence though pyrolysis oil has certain instability, the
were displayed in the GC/MS chromatograms. The perfect instability is not too strong to use the pyrolysis oil. If in the
separation of all the peaks was not possible due to the complex presence of inhibitors for example hydroquinone, the rate of
composition of the pyrolysis vapours. Only those separated increase of viscosity of pyrolysis oil can dramatically reduce,
products were quantitatively evaluated which arose in consider- due to the suppression of thermal polymerization reactions by
able amounts. The quantitative analysis of the products was based the inhibitors.
on the peak areas of selected characteristic molecular or fragment
ion chromatograms. There were 10 kinds of compositions which
were quantitatively evaluated. The information in Table 9
indicated that the pyrolysis oil is a complicated organic compound
that mainly consists of water, acids and heterocyclic substances.
The pyrolysis oil contains all kinds of carboxylic acids. Moreover
the pyrolysis oil contains some heterocyclic substances which
make pyrolysis oil viscous and easily be polymerized.
The data in Table 10 showed that the un-condensable gas is a
complicated gaseous mixture with low caloric value, mainly due to
the dilution of carrier gas (nitrogen). This implied that the nitrogen
should be substituted with the un-condensable gas so that the
product gas can be used as fuel gas.

3.3. Stability characteristics of the pyrolysis oil (viscosity variation)

The results of the two-sample t-test and viscosity of the

pyrolysis oil at different storage conditions were listed in Tables 11
and 12. The change of viscosity of pyrolysis oil at different storage
conditions were presented in Fig. 4.
It was found that the pyrolysis oil’s viscosity increases during
storage, due to slow polymerization and condensation reactions, Fig. 4. Stability characteristics of bio oil (viscosity variation).
 J.-L. Zheng / J. Anal. Appl. Pyrolysis 83 (2008) 205–212
Table 13
Properties of emulsions
25% pyrolysis oil + 74%
diesel + 1% emulsifier
Viscosity (mm2/s) 81
pH 3.2
LHV (MJ/kg) 36.3
Fig. 5. Corrosivity of the pyrolysis oil from maize stalk.
3.4. Miscibility study of pyrolysis oil with diesel
Experimental results indicated that the pyrolysis oil is
completely immiscible in diesel and stratification formats when
the pyrolysis oil is directly blended with diesel. But homogeneous
emulsions are obtained when mixing the pyrolysis oil, emulsifier
with diesel in different ratios. The emulsifier contents of the
emulsions is 1 wt.%, and it was reported that the optimal range of
emulsifier to provide acceptable viscosity was between 0.5 wt.%
and 2 wt.% [19]. The physical properties of the emulsions like pH,
heat value and viscosity were reported in Table 13, which shows
emulsions have higher heat value, lower pH and lower viscosity
than the pyrolysis oil.
Therefore it is possible to consider the pyrolysis oil emulsification
as a possible and relatively short-term approach to the direct use of
the pyrolysis oils in diesel engines reducing the investment in
technologies, but the effect of the long-term use of emulsions on the
stainless steel engine and its subassemblies should be estimated.
3.5. Corrosivity of the pyrolysis oil
Fig. 5 showed the weight loss of Cu strip and stainless steel strip
versus time for the pyrolysis oil stored at 60 8C. It was found that
the pyrolysis oil stored at 60 8C results in a weight loss of about
0.6% and 0.85% for Cu strip and stainless steel strip, which is kept in
the pyrolysis oil at 60 8C for 128 h, respectively. Hence the
corrosivity of the pyrolysis oil is very mild towards copper and
stainless steel. But the corrosivity of pyrolysis oil is very severe
towards mild steel [11,20].
3.6. The quality of pyrolysis oil from fast pyrolysis of maize stalk
Comparing the density and energy content in the maize stalk
with rice straw, it has been found that the density of maize stalk
(220 kg/m3) is higher than the density of rice straw (63.85 kg/m3).
211
50% pyrolysis oil + 49% 75% pyrolysis oil + 24%
diesel + 1% emulsifier diesel + 1% emulsifier
135 198
3.0 2.7
30.3 24.8
Furthermore, the energy content in the maize stalk is 15.07 MJ/kg
which is higher than the energy content of rice straw (13.62 MJ/kg)
[10]. This clearly suggests that the bioenergy plant using maize
stalk will be more efficient than some straw available in the world.
Fixed carbon content and the volatile fraction in maize stalk is
higher than many agricultural biomass [11]. And so it can be
realized that pyrolysis oil from fast pyrolysis of maize stalk has
higher quality.
4. Conclusion
In this study, fast pyrolysis of maize stalk was investigated in a
fluidized-bed reactor. Pyrolysis oil from fast pyrolysis of maize
stalk has higher quality. Pyrolysis yields depend mainly on
pyrolysis temperature. The yield of pyrolysis oil first increases
and then decreases when pyrolysis temperatures increased. The
highest oil yield obtained was 66% with pyrolysis temperature of
500 8C. The pyrolysis oil is a complicated organic compound that
consists mainly of water, acids and heterocyclic substances.
Though the pyrolysis oil has certain instability, the instability is
not too strong to use the pyrolysis oil. Pyrolysis oil is completely
immiscible in diesel, but homogeneous emulsions are obtained
when mixing the pyrolysis oil, emulsifier with diesel in different
ratio. The corrosivity of the pyrolysis oil is very mild towards
copper and stainless steel. Hence the pyrolysis oil can be used
directly as a fuel oil for combustion in a boiler or a furnace without
any upgrading or it is possible to consider the pyrolysis oil
emulsification as a possible and relatively short-term approach to
the direct use of the pyrolysis oils in diesel engines reducing the
investment in technologies. Alternatively, it can be refined for use
as vehicle fuel.
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