Journal of Analytical and Applied Pyrolysis 106 (2014) 6370

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Journal of Analytical and Applied Pyrolysis
j our nal homepage: www. el sevi er . com/ l ocat e/ j aap
Rape straw as a source of bio-oil via vacuum pyrolysis: Optimization
of bio-oil yield using orthogonal design method and characterization
of bio-oil
Yongsheng Fan

, Yixi Cai, Xiaohua Li, Haiyun Yin, Ning Yu,

Rongxian Zhang, Weidong Zhao
School of Automotive and Trafc Engineering, Jiangsu University, Xuefu Road No. 301, Zhenjiang, Jiangsu 212013, PR China
a r t i c l e i n f o
Article history:
Received 11 August 2013
Accepted 24 December 2013
Available online 2 January 2014
Keywords:
Rape straw
Vacuumpyrolysis
Orthogonal design method
Yield optimization
Bio-oil characterization
a b s t r a c t
Rape straw from China rural area was treated by vacuum pyrolysis for bio-oil preparation. The orthogonal
designmethod was employed to minimize the number of experiments. The effects of the factors including
pyrolysis temperature, reactor pressure, heating rate and holding time on bio-oil yield were analyzed. The
optimal conditions were obtained by using SPSS Statistics 20.0 (IBM, USA) and Matlab 7.12.0 (MathWorks,
USA). Furthermore, the physicochemical properties of the bio-oil obtained at optimal conditions were
evaluated. The composition was examined using gas chromatograph/mass spectroscopy (GC/MS). The
thermo-gravimetric analysis (TGA) of the bio-oil was investigated within N
2
and O
2
, respectively. The
results showed that the order of the effects of the factors on bio-oil yield was heating rate > pyrolysis
temperature >reactor pressure > holding time. Heating rate and pyrolysis temperature had a signi-
cant interaction. Optimal conditions were obtained at pyrolysis temperature of 495.5

C, heating rate
of 19.4

C/min, reactor pressure of 5.0 kPa and holding time of 50min. Conrmation runs gave 43.15%
and 43.44% of bio-oil yield compared to 43.62% of predicted value. The water content, carbon residue,
density, pH value, dynamic viscosity and higher heat value of bio-oil were 34.20%, 4.03, 1.14 g/cm
3
, 2.22,
4.28 mm
2
/s and 18.72 MJ/kg, respectively. Polymerization in the condensation process contributed to the
higher average molecular weight distribution than pyrolysis vapors. Light aromatics (mainly including
light phenols) were the dominant component for the bio-oil, which contributed to the relatively low poly-
dispersity with a value of 1.25. The direct liquefaction bio-oil was unstable and corrosive due to the high
reactivity of carbonyl extensively existing in acids, aldehydes and ketones. High oxygen content made
the behavior of decomposition in O
2
be similar to that in N
2
before 450

C. Further study on upgrading of

the bio-oil should be performed to make it become an alternative fuel.
2013 Elsevier B.V. All rights reserved.
1. Introduction
As is well known, at least two compelling forces drive global
interest in renewable energy supplies, in particular energy derived
frombiomass: (1) increasing concernabout environmental impacts
associated with fossil fuels and nuclear energy; and (2) increasing
anxiety regarding the security and longevity of fossil fuel resources
[1]. One effective strategy that addresses both concerns is the sup-
plementing traditional, dominantly fossil, fuels with renewable
biomass fuels, since biomass comes from indigenous sources and
can be essentially CO
2
-neutral if derived fromsustainable cultiva-
tion practices. Also, Biomass is clean for it has negligible content
of sulfur, nitrogen and ash, which gives lower emissions of SO
2
,

Corresponding author. Tel.: +86 158 6298 3726; fax: +86 511 88797620 2009.
E-mail addresses: yongsheng fan@163.com, fan yongheng@126.com(Y. Fan).
NO
x
and soot than conventional fossil fuels [2]. Therefore, biomass
derived oils could be a source of the prospective fuels and chemical
materials of tomorrow. So far the rst generation bio-oils, includ-
ing bio-ethanol and bio-diesel, have been implemented around the
world [3,4]. However, bio-ethanol is produced fromthe fermenta-
tionof sugar or starchand bio-diesel is produced onthe basis of fats
[5,6]. These technologies rely on food grade biomass, which raises
a problem as the requirement for food around the world is a con-
straint and the energy efciency per unit land of the required crops
is relative lowcomparedtoenergycrops [7]. Consequently, the new
research focuses on developing second generation bio-oils, which
can be produced from other biomass such as agricultural waste,
wood. Of the second generation bio-oils paths, a lot of efforts have
been spent on the biomass to liquid route via pyrolysis over the
last two decades [8,9]. It demonstrated that pyrolysis technology
plays a signicant role in the development of biomass conver-
sion technology. Vacuum pyrolysis is one of the most promising
0165-2370/$ see front matter 2013 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.jaap.2013.12.011
64 Y. Fan et al. / Journal of Analytical and Applied Pyrolysis 106 (2014) 6370
thermo-chemical conversion routes to convert biomass into a feed
stock for both fuels and chemical productions, which enables the
production of large quantities of pyrolysis bio-oil. The bio-oil typ-
ically consists of a complex mixture of organic compounds, with
the yield and composition varying with biomass type and applied
pyrolysis process conditions, so in-depth research for vacuum
pyrolysis is important andextensive fundamental works are under-
way [10,11].
The National Energy Administration of China in 2010 projected
that biomass is expected to contribute to approximately one thirds
of the renewable energy requirements by 2020. To reach this goal,
existing agricultural residues such as straw need to be utilized
alongside dedicated energy crops. At present, there are many agri-
cultural residues such as rice husk, corn stalk and wheat straw,
which have been identied as suitable energy crops around the
world [1214]. While there is no detailed study on the strawfrom
rape and it is a potential candidate for the bioenergy sector. As
everyone knows, rape straw is one of the main cereal straws in
agriculture. In China, with the huge planting area, a total approxi-
mately 1.9610
7
tonnes of rape straw were generated annually.
Rape straw, which is a by-product of the edible oil processing
industry, can be readily obtained in huge amount in one loca-
tion. The utilization of this source of biomass through pyrolysis
processes would solve both a disposal problem and also generate
useful energy. This paper presents a study on bio-oil prepara-
tion from vacuum pyrolysis of rape straw in order to exploit
rape strawinto value-added products. The objectives of this study
are:
1. To obtain detailed data of rape straw composition and thermal
decomposition.
2. To rational design experiment by employing orthogonal design
method.
3. To analyze the effects of the operation parameters of vacuum
pyrolysis onbio-oil yieldandoptimize bio-oil yieldby using SPSS
Statistics and Matlab software.
4. To assess characteristics of the bio-oil obtained at opti-
mal conditions, including physicochemical properties, chemical
composition, and thermo-gravimetric characterization.
5. To provide a better understanding of the possible industrial
applications of vacuum pyrolysis as conversion technology for
fuels or chemical products.
2. Materials and methods
2.1. Materials
The rape strawused was collected fromrural area in Zhenjiang,
China. The rape straw was ground and sieved for small parti-
cles in the 100150m range. The sample was dried at 105

C
for 2h to remove external moisture. The ultimate analysis of the
dried sample was carried out in an elemental analyzer (Model:
FLASH1112A, Italy) and results showed that it was composed of
42.22wt.% of carbon, 5.53wt.% of hydrogen, 0.41wt.% of nitro-
gen, 0.07wt.% of sulphur and 51.77wt.% of oxygen (by difference).
The proximate analysis was performed according to ASTMD-2974
using a thermo-gravimetric analyzer (Model: TGA/DSC 1, Swiss)
and it was obtained at moisture content of 6.12wt.%, volatile mat-
ter content of 72.84wt.%, xedcarboncontent of 17.35wt.%andash
content of 3.69wt.%. The caloric value was determined by using a
bomb calorimeter (Model: ZDHW-5G, China) andits higher heating
value was 15.92MJ/kg (air-dry basis).
2.2. Thermo-gravimetric analysis
Fundamental test of the pyrolysis for rape strawwas conducted
using the thermo-gravimetric analyzer. The sample weight loss and
the rate of weight loss were recorded continuously under dynamic
conditions, as functions of temperature, in the range of 40600

C.
The sample was uniformly spread into crucible and automatically
weighed during the test. The nitrogen gas was used for the test at a
ow rate of 50ml/min. The heating rate of 20

C/min was selected

for this test. The temperature was increased to the setting value of
600

C at the pre-selected heating rate and it was kept constant at

this value until steady conditions were obtained.
2.3. Pyrolysis experiment procedure
Vacuum pyrolysis of rape straw was conducted in a xed-bed
reactor as shown in Fig. 1. The reactor consisted of a 1.5m long
quartz tube (diameter 60mm), heated by six well-insulated, com-
puter controlledheatingelements. Theheatedreactor chamber was
connected to a condensation trap and a vacuum pump. The pipes
leading fromthe reactor to the condensation trap were maintained
at 150

C to limit condensation before the trap. The condensation

temperature was set at 20

C (The cooling medium: ethylene gly-

col) for all experiments. A control programwas used to control the
nal pyrolysis temperature, heating rate and pyrolysis time. Once
the reactor was loaded (1500.01g of biomass), heating started
after the reactor was sealed and evacuated to the desired operating
pressure. A typical run would take between 1h and 2h depend-
ing on the conditions employed. At last, protective gas (N
2
) was
introduced into the reactor to prevent products oxidation at high
temperature. The bio-oil collectedwas removedandweighedwhen
the reactor was cooled to roomtemperature.
2.4. Experimental design
There are many factors that have effects on bio-oil yield, such as
pyrolysis temperature, reactor pressure, heating rate, hold time.
Therefore, one of purposes is to investigate the effects of main
factors on the yield of bio-oil. For the full factorial experiments,
we should vary a single factor one time. This is not always feasi-
ble because the total number of experiments will be unacceptable
as the number of factors and the number of levels for each factor
increase. The orthogonal design method that is a fractional facto-
rial design provides us a useful tool for experimental design. An
orthogonal array is denoted by L
N
(S
m
), where S and m is the num-
ber of levels and factors, respectively. It is an Nm matrix, whose
columns are mutually orthogonal. For any pair of columns, all pos-
sible combinations of factor levels appear and they appear an equal
number of times. An L
25
(5
4
) orthogonal array which allows the
study of four factors at ve levels as shown in Supplementary Table
1. The values from Y
1
to Y
25
in the rows of the orthogonal array
are obtained by experiments. The average experimental value of a
factor level, e.g. A
1
is calculated by Eq. (1) as follows [15]:
m
A
1
=
(Y
1
+Y
2
+Y
3
+Y
4
+Y
5
)
5
(1)
Only experiments No. 1, 2, 3, 4, 5 are those whose setting of
factor A is 2. Accordingly, we can calculate the other mean of
experimental values corresponding to each level for a design vari-
able. The effect degree of all factors can be determined by range
analysis. The greater the range value is, the more signicant effect
of the design variable on objective function is. The range of design
variable A is dened as Eq. (2):
R
A
= max(m
Ai
) min(m
Ai
)i = 1, 2, 3, 4, 5 (2)
Y. Fan et al. / Journal of Analytical and Applied Pyrolysis 106 (2014) 6370 65
Fig. 1. Schematic diagramof the vacuumpyrolysis system.
Four main factors that have effects on bio-oil yield were con-
sidered in this study, including pyrolysis temperature, reactor
pressure, heating rate and holding time. As shown in Table 1, each
factor has ve levels in the range of experimental parameters. For
this problem, the minimumorthogonal array is selected as L
25
(5
4
)
inTable 1. All experimental runs were repeatedto ensure reliability
of the data and results reproducibility.
The optimization process of the yield of bio-oil was analyzed
by employing SPSS Statistics 20.0 (IBM, USA) to conduct regression
analysis. The quadratic equation model for predicting the optimal
point was chosen and expressed according to Eq. (3):
y =
0
+
k

i=1

i
x
i
+
k

i=1

ii
x
2
i
+

i=1

j=i+1

ij
x
i
x
j
+ (3)
where
0
,
i
,
j
and
ij
are regression coefcients for the inter-
cept, linear, quadratic andinteractioncoefcients, respectively, and
x
i
and x
j
are the coded independent variables. The variability is
explained by the multiple coefcient of determination, R
2
which
gives the overall predictive capabilities of the model obtained.
2.5. Characterization
2.5.1. Physicochemical characterization
The bio-oil characterized was obtained fromexperimental con-
ditions that gave the maximum bio-oil yield. The water content
was determinedby Karl Fisher titration(ASTMD-1744). The carbon
residue was measured according to ASTM D-189 method. Density
was measured using 10ml picnometer (ASTMD-369). The caloric
value was determined by using a bomb calorimeter. The acidity
was measured by a pH probe with digital meter. The dynamic vis-
cosity was measured with capillary viscometer (ASTMD-455). The
ultimate analysis of the bio-oil was carried out in the elemental
analyzer. Molecular weight distributionwas determinedbygel per-
meation chromatography (GPC) using a Waters 510 pump with
410 refractive index detector. Separation was performed using two
columns in series: Styragel

HR 4
E
and HR 1 with 5m parti-
cle diameter. Both columns were 300mm long with a diameter of
7.8mm. Tetrahydrofuran(THF) was usedas the eluent at a owrate
of 1ml/min. Bio-oil sample was dissolved in THF at a concentration
of 2wt.%.
2.5.2. Chemical composition characterization
The composition of the bio-oil was analyzed using GC/MS (Agi-
lent 7890 series GC with a 5975 MS detector). 1ml of bio-oil
was used and vacuum ltration removing the impurities in the
bio-oil by using 0.45m lter membrane, then adding 0.1mol/L
H
2
SO
4
solution to the bio-oil until the pH value of solution to 2.0.
Adding dichloromethane (CH
2
Cl
2
) solution (dichloromethane to
bio-oil volume ratio=3) for extraction and then separated, repeat
the procedure 3 times. Add 1mol/L NaOHsolution to the separated
aqueous phase until the pHvalue to 12.0. Adding dichloromethane
(CH
2
Cl
2
) solution for extraction as described above and then mix
all of the extraction phases. The obtained extraction phase was
then evaporated and concentrated at 50

C water bath in a rotary

evaporator and nally sampled 1ml. Followed by a total of 1L of
sample was injected into the injection port set at 250

C in a split-
less conguration. The column was operated in a constant ow
mode using helium as the carrier gas. The column temperature
was initially maintained at 40

C for 2min, then programmed to

increase to 100

C at 20

C/min and then to 250

C at 8

C/min, set
the solvent delay time for 3min. The mass spectrometer ion source
was at 250

C with 70eV ionization potential, and the 30500m/z

range was scanned every second. The identication of the peaks in
the chromatogram was based on the comparison to the standard
spectra of compounds in the National Institute of Standards and
Technology (NIST) library.
2.5.3. Thermo-gravimetric analysis
Thermo-gravimetric analysis of the bio-oil was performed using
the TGA/DSC 1 mettler Toledo. Bio-oil samples of 10.00.1mg
were heated from 30

C to a maximum temperature of 600

C at
a gas ow rate of 50ml/min and at a heating rate of 30

C/min.
The samples were characterized by thermal decomposition curves
(under N
2
ow) and combustion curves (under O
2
ow).
Table 1
Experimental variables and levels.
Levels Pyrolysis temperature A/

C Reactor pressure B/kPa Heating rate C/

C/min Holding time D/min

2 400.0 5.0 4.0 15.0
1 450.0 20.0 8.0 30.0
0 500.0 35.0 12.0 45.0
1 550.0 50.0 16.0 60.0
2 600.0 65.0 20.0 75.0
66 Y. Fan et al. / Journal of Analytical and Applied Pyrolysis 106 (2014) 6370
Fig. 2. TG and DTG curves of rape straw.
3. Results and discussion
3.1. Thermal decomposition of rape straw
Fig. 2 shows the thermo-gravimetric (TG) and differential
thermo-gravimetric (DTG) curves for rape straw pyrolysis. It can
be seen from Fig. 2 that pyrolysis process can be divided into
three stages based on TG curve. It was observed that the initial
stage indicated moisture loss of up to 106.13

C followed by the
primary degradation of biomass over 106.13

C up to 403.29

C,
and the remaining residue was 21.68% at 600

C. The most of
the volatile materials released between around 200

C and 400

C,
which mainly attributed to the destructive reaction of cellulose
and hemicellulose [16]. For the DTG curve, the derivative weight
is reported and is representative of the percentage weight loss per
centigrade. The maximum rate of weight loss was found between
300

C and 350

C for rape straw. The thermal decomposition of

cellulose was primarily thought to occur between these temper-
atures. The thermal decomposition temperature of hemicellulose
had been found to take place at lower temperatures in comparison
to cellulose [17]. A shoulder-like feature could be seen at the tem-
perature of 290

C, which was considered to be partly related to

the hemicellulose. Yang et al. [18] found that the lignin thermal
decomposition occurs over a broad temperature range and par-
tially contributes to the hemicellulose and cellulose decomposition
regions. Inorganic content, inparticular alkali metals suchas potas-
sium, sodiumandphosphorus wereknowntoinuencethethermal
decomposition due to their catalytic activity. Wang et al. [19] found
that potassiumandphosphorus content stronglycatalyzes thether-
mal degradation process. The information based on the results of
TGA is extremely useful that the pyrolysis temperature should be
correctly set in pyrolysis experiments.
3.2. Factors affecting bio-oil yield
Fig. 3 shows the mean value of bio-oil yield corresponding to
each level of the four factors. The coded values of A, B, C and D
represent pyrolysis temperature, reactor pressure, heating rate and
holding time, respectively.
3.2.1. Effect of pyrolysis temperature
The effect of temperature on bio-oil yield should be analyzed
through the point view of the component composition of biomass
andthereactionenergy. Themaincomponents of biomass werecel-
lulose, hemicellulose, lignin and organic extractives, which would
be in order from least stable to most stable: the extractives
Fig. 3. Effects of the factors on bio-oil yield ( level 2; level 1; level 0;
level 1; level 2).
(100250

C), hemicelluloses (220350

C), cellulose (315400

C)
and lignin (250500

C) yielding combustible gases and conden-

sable liquidtar, andligninyielding mainly char [18,20]. Meanwhile,
shorter chain length compounds were easily formed at the lower
pyrolysis temperaturesinceless energywas neededtoreleasethese
compounds than would be required to release the more complex
compounds. While at the higher temperature, an amount of con-
densable compounds decomposed into non-condensable gaseous
products leading to the decrease of bio-oil yield.
3.2.2. Effect of reactor pressure
The bio-oil yield decreased as the reactor pressure increased
from 5.0 to 65.0kPa. With the increasing pressure, the pressure
differential between inside and outside of reactor reduced, which
resulted in longer residence time of the pyrolysis vapors inside
the reactor that caused larger possibility of the condensable com-
pounds to decompose again or polymerize to form coke residues.
Simultaneously, the boiling point of the compounds increased with
the increase of reactor pressure, which would slowdown the evap-
oration rate of the condensable compounds, causing much more
secondary decomposition reactions and lowering bio-oil yield.
3.2.3. Effect of heating rate
It is generally assumed that an increase in heating rate will tend
to higher liquid yield [21,22]. However, heating rate of the reactor
was limited with a maximum value of 20

C/min in our case. The

bio-oil yieldincreasedconsistently withthe heating rate increasing
from 4.0 to 20.0

C/min. The reason was that the inside temper-

ature of biomass particles increased rapidly to generate a large
number of free radicals with the increasing heating rate. When the
generation rate of the free radicals could not match with the reac-
tion rate between free radicals and intrinsic hydrogen, the internal
polymerization reactions among the free radicals would generate
long chain condensable molecules, which contributed to the liq-
uid yield. While the heating rate was lower, the residence time of
biomass particles at relative low temperature became longer, the
feeblish oxygen-bridged bonds and branched chains on the ben-
zene rings would become more easily to crack. This caused parallel
and sequence of poly-condensation reactions to more easily gen-
erate stable carbon skeletal structures, which contributed to the
production of coke but decreased bio-oil yield.
3.2.4. Effect of holding time
Holding time had no signicant effect on bio-oil yield. The max-
imumbio-oil yieldwas 34.96%whenthe holding time was 60.0min
Y. Fan et al. / Journal of Analytical and Applied Pyrolysis 106 (2014) 6370 67
Table 2
The analysis of variance for the model.
Source df Sumof square Mean square F value p-value
Model 14 276.863 19.776 36.420 <0.001
Residual 10 5.430 0.543
Sum 24 282.293
(Level 1), nearly the same as the bio-oil yield obtained at the
other levels. Salehi et al. [23] found the process of the pyrolysis
is controlled by the intrinsic kinetics rate when the particle size
of biomass is smaller. While the particle size was larger, it had a
signicant effect on heat transfer, especially at higher heating rate
when the heating rate on the particle surface was far higher than
inside and the pyrolysis process was controlled by both heat and
mass transfer. If holding time was extended, it would contribute to
transfer completely, which would higher yield of bio-oil. The parti-
cle size was relatively small (100150m) in our case, so holding
time had a little effect on bio-oil yield.
3.3. Range analysis of factors
Range analysis of the four factors were conducted based on Eq.
(2) and the value of R
A
, R
B
, R
C
and R
D
were 7.10%, 3.11%, 11.38%
and 0.52%, respectively. It was indicated that the order of the bio-
oil yield range of the factors was C>A>B>D, which meant that
the order of the effects of the factors on bio-oil yield was heating
rate >pyrolysis temperature >reactor pressure >holding time.
3.4. Regression analysis
Inorder tofurther increasethebio-oil yield, aregressionanalysis
was conducted and made by using coded values and expressed by
Eq. (4):
Yield = 38.9300.889A0.888B + 2.819C + 0.065D
+0.038AB + 0.399AC0.036AD + 0.066BC + 0.001BD
0.013CD1.347A
2
+0.091B
2
0.711C
2
0.066D
2
(4)
Quadratic model was suggested with R
2
value of 0.9811 and
indicated that 98.11% of the total variation in the bio-oil yield was
attributed to the experimental variables studied. The analysis of
variance was conducted and results are shown in Table 2. It was
indicated that the regression relation between the factors and bio-
oil yield was signicant with p-value of <0.001. Therefore, Eq. (4)
could be employed to predict the bio-oil yield.
The analysis of signicance to partial regressioncoefcients was
also conducted and the results are shown in Table 3. It can be seen
fromTable 3that the linear items of A, B, C, the interactionof ACand
the quadratic items of A
2
, C
2
are signicant with p-value of <0.05.
Therefore, pyrolysis temperature, reactor pressure andheating rate
had signicant effects on bio-oil yield. Furthermore, pyrolysis tem-
perature and heating rate had a signicant interaction.
When the reactor pressure and holding time were set as level 0
(35.0kPa and 45min), the bio-oil yield can be expressed by Eq. (5):
Yield = 38.9300.889A + 2.819C + 0.399AC
1.347A
2
0.711C
2
(5)
To further illustrate the interactive effects of pyrolysis temper-
ature and heating rate, surface chart were drawn based on Eq. (5).
The interactive effects of pyrolysis temperature and heating rate
on bio-oil yield as shown in Fig. 4. It showed that the moderate
Fig. 4. Surface chart to show the interactive effects of pyrolysis temperature and
heating rate on bio-oil yield.
temperature contributed to the higher yield of bio-oil, and temper-
ature difference between inside and outside of biomass increased
with the rise of heating rate resulting in pyrolysis hysteresis in the
interior of biomass which made the bio-oil yield offset to high-
temperature side at higher heating rate. Simultaneously, the heat
resistance in biomass particle interior increased with the increase
of heating rate which caused the yield of bio-oil growth slowing.
3.5. Optimization and conrmation
Optimization analysis was conducted by using Matlab 7.12.0
(MathWorks, USA) to determine the optimal conditions to obtain
high percentage of bio-oil yield. The results from the software
suggested the optimal conditions can be attained at pyrolysis tem-
perature of 495.5

C, heating rate of 19.4

C/min, reactor pressure

of 5.0kPa, holding time of 50.0min and predicted bio-oil yield was
43.62%. Conrmation runs were conducted with the above condi-
tions and gave 43.15% and 43.44% of bio-oil yield. It was indicated
that the experimental values obtained were in good agreement
with the values predicted from the models, which recorded small
errors betweenthe predicted and the actual values, whichwas only
1.08% and 0.41%. Hence, orthogonal experimental design method is
a useful tool for experimental designand SPSS Statistics and Matlab
software can be employed to conduct optimization analysis.
Table 3
The analysis of signicance to partial regression coefcients.
Parameters Coefcient Standard error t-value p-value
Constant 38.930 0.737 52.831 <0.001
A 0.889 0.150 5.909 <0.001
B 0.888 0.150 5.903 <0.001
C 2.819 0.150 18.740 <0.001
D 0.065 0.150 0.435 0.673
AB 0.038 0.184 0.207 0.840
AC 0.399 0.184 2.168 0.045
AD 0.036 0.184 0.193 0.851
BC 0.066 0.184 0.356 0.729
BD 0.001 0.184 0.003 0.997
CD 0.013 0.184 0.071 0.945
A
2
1.347 0.219 6.142 <0.001
B
2
0.091 0.219 0.414 0.688
C
2
0.711 0.219 3.240 0.009
D
2
0.066 0.219 0.299 0.771
68 Y. Fan et al. / Journal of Analytical and Applied Pyrolysis 106 (2014) 6370
Table 4
The physical properties, elemental and GPC analysis of bio-oil.
Physical property Bio-oil Dry basis
Water/wt.% 34.20 0
Carbon residue/wt.% 4.03 nd
b
Density/g/cm 1.14 nd
Higher heat value/MJ/kg 18.72 28.44
pH 2.22 nd
Dynamic viscosity/mm
2
/s 4.28 nd
Ultimate analysis/wt.%
C 39.33 59.77
H 9.81 9.14
N 0.12 0.18
S <0.01 <0.01
O
a
50.74 30.91
GPC analysis

Mn/g/mol 243.80 nd

Mw/g/mol 304.97 nd

Mz /g/mol 425.42 nd
Polydispersity 1.25 nd
a
By difference.
b
Not determined.
3.6. Characterization of bio-oil
3.6.1. Physicochemical characterization
The properties of bio-oil were analyzed in terms of water
content, density, higher heat value (HHV), pH value, dynamic vis-
cosity, ultimate analysis and GPC analysis and the results are
listed in Table 4. Repeated experiments results revealed that
bio-oil under the optimal conditions had a good reproducibility.
The values of all properties uctuated in the range of 3% by
the average of the repeated experiments. High water and oxy-
gen contents were observed in the bio-oil which was responsible
for the lower HHV than fossil fuels. In generally, taking wood
and agricultural residues as pyrolysis materials, the obtained raw
bio-oil has a higher heat value of about 1520MJ/kg [24]. The
dynamic viscosity of the bio-oil was 4.28mm
2
/s which was much
lower than bio-oils produced fromFraxinus mandshurica and Corn
stalk with a dynamic viscosity of 1070mm
2
/s and 510mm
2
/s,
respectively [24]. The relatively low viscosity was good for the
atomization and combustion when used as a fuel for gas turbine
or engine applications; however, it should be note that the high
water content contributed to the lower viscosity. The density of
bio-oil was higher than water with 1.14g/cm
3
. Simultaneously,
bio-oil might comprise substantial amounts of acids, such as acetic
acid, which led to lower pH value of 2.22. The amount of resid-
ual carbon was 4.03wt.% that was lower than that of gasoline
and kerosene (about 5wt.%) which showed that the bio-oil had
a lower coking tendency when applied it as a fuel to combus-
tion.
An amount of 39.33wt.% of C, 9.81wt.% of H, 50.74wt.% of O
and small contents of S and N were detected in the bio-oil. Many
researchers reported raw bio-oil from various biomass pyrolysis
to have carbon content values of 41.70wt.% [25], 50.60wt.% for
the oil phase [26], 42.52wt.% for upper phase and 57.87wt.% for
lower phase, respectively [27]. The difference might be due to the
pyrolysis conditions. In our case, the bio-oil was a homogeneous
liquid. It was noted that the bio-oil was highly oxygenated, with
50.74wt.% of oxygen distributed in hundreds compounds which
indicated that further upgrading research work should be needed
to decrease the oxygen. Nitrogen and sulphur contents detected
were very low, showing its potential as a clean fuel when used for
combustionpurpose. As a comparison, the properties of dry basis of
bio-oil were also listed in Table 4 obtained by calculation. The HHV
of dry basis was as high as 28.44MJ/kg on the basis of the elemental
Fig. 5. GCMS total ion current spectra of the bio-oil fromvacuumpyrolysis of rape
straw(peak assignment as listed in Supplementary Table 2).
composition in wt.% [28]:
HHV[MJ/kg] = 0.349C + 1.178H + 0.101S 0.103O
0.015N0.021ash (6)
where ash content of the bio-oil was ignored in calculation. It
demonstrated that trying to remove the water in the bio-oil and
then using it as an alternative fuel should be also taken into con-
sideration.
The molecular weight distributionof the bio-oil calculatedusing
GPC, the number average molecular weight (

M
n
) and the weight
average molecular weight (

M
w
) were 243.80 and 304.97g/mol,
respectively. At present, other researchers have studied on the
molecular weight range of biomass pyrolysis oils. Kim et al. [29]
analyzed the bio-oil derived from the fast pyrolysis of palm kernel
shells at the maximum bio-oil yield conditions and found com-
pounds in the bio-oil with the

M
n
and

M
w
were 325g/mol and
463g/mol, respectively. Other work [30] on the molecular weight
distribution of the vapors within the pyrolysis reactor had shown
much lower molecular weights of between 100 and 150g/mol.
Therefore, it was indicatedthat thelargeamount of pyrolysis vapors
generated from biomass pyrolysis were highly reactive and when
condensation took place they quickly polymerized to form higher
molecular weight compounds. Polydispersity (

M
w
/

M
n
) is dened
as the difference in the values of

M
n
and

M
w
which is a measure
of the molecular weight homogeneity of the samples. The bio-oil
had a relatively low polydispersity of 1.25, which indicated a less
complex array of compounds present in the bio-oil from vacuum
pyrolysis of rape straw.
3.6.2. Chemical composition characterization
Fig. 5 shows the total ionchromatogram(TIC) of the bio-oil sam-
ple. The mass spectra would be obtained by scanning the peaks in
Fig. 5 according to the retention time, and then the corresponding
compounds were identied by comparison with the NIST library.
Simultaneously, the relative content of compound was prelimi-
narily calculated by using the peak area normalization method.
It should be note that although the peak areas are not directly
related to specic concentrations, the peak area still reects the
distribution of the organics in the products to some extent.
36 main compounds were detected by GC/MS and the total peak
area of quantitated compounds is 86.06% and represents the most
of typical components that exist in the bio-oil. The most repre-
sentative organic compounds of the raw bio-oil can be classied
in 13 major functional groups: aromatic hydrocarbons, aliphatic
Y. Fan et al. / Journal of Analytical and Applied Pyrolysis 106 (2014) 6370 69
Fig. 6. Classication of organics in the bio-oil fromvacuumpyrolysis of rape straw.
hydrocarbons, phenols, furans, acids, esters, alcohols, ethers,
aldehydes, ketones, polyaromatic hydrocarbons (PAHs), nitro-
gen compounds and heavier compounds. Among them, aromatic
hydrocarbons, aliphatic hydrocarbons and alcohols are considered
as desirable products for biofuels production, while phenols and
furans are also regarded as high added value chemicals. On the
other hand, carboxylic acids are responsible for the corrosiveness
and thus considered undesirable. The same stands for ketones and
aldehydes, which are related with the instability of the bio-oil dur-
ing transport and storage. Ethers, esters and in general oxygenates
are also undesirable as they reduce the heating value of the bio-oil.
At last, PAHs and nitrogen compounds are detrimental for environ-
mental and harmful reasons. The above classication in desirable
andundesirable compounds has beenadaptedhere inorder toeval-
uate our results and the classication results are shown in Fig. 6.
As can be seen in Fig. 6, the peak area of the aromatics in the
bio-oil was as high as 71.55%, and the aromatics were composed
of 72.98% of light phenols, 15.02% of aromatic ketones, 6.60% of
aromatic aldehydes, 3.30% of aromatic alcohols and 2.10% of other
aromatics. Hydrocarbons (non-aromatic hydrocarbons), alcohols
and furans in the bio-oil were as low as 0.50%, 4.04% and 2.22%
respectively. In addition, 1.89% of aldehyde compounds and 15.99%
of ketone compounds were also detected in the bio-oil. It demon-
strated that the bio-oil obtained from vacuum pyrolysis of rape
strawwas better thanexpected, as it had a large amount of the light
phenols (52.22%) based on peak area calculation. Previous stud-
ies had showed that the light aromatics mainly generated through
the cracking of organic macromolecules with the benzene rings,
such as lignin contained a number of benzene ring structures [31].
Besides, some low molecular weight molecules produced from
pyrolysis reaction might subsequently undergo further polymer-
ization and aromatization in the condensation process to form
aromatics, which also contributed to the higher average molecu-
lar weight distribution of the bio-oil than that of vapors. Hence, a
large number of light aromatics explained that the average molec-
ular weight distribution of the bio-oil was relatively homogeneous.
Among the compounds detectedby GC/MS, Phenol,2,6-dimethoxy-
with a peak area of 9.23% was the dominant component for the
bio-oil which could be further extracted for avor additives in
the food industry [32]. The other main phenolic compounds, such
as Phenol,2-methoxy- (7.66%); Phenol,2-methoxy-4-(1-propenyl)-
(6.89%); 2-Methoxy-4-vinylphenol (5.15%), might be extracted and
utilized for preparing the phenolic resins [33]. Besides, a certain
amount of undesirable acids, aldehydes and ketones, including aro-
matic ketones and aromatic aldehydes, also existed in the bio-oil
which might affect its stability to some extent owing to the high
Fig. 7. TG and DSC curves of the bio-oil in N
2
and O
2
.
reactivityof carbonyl. Duetotheelectronegativityof oxygeninC O
bond was very strong, which made the carbonyl carbon having a
partial positive charge, easy toaccept the attack of nucleophile. And
the carbonyl oxygen having the partial negative charge could eas-
ilyreact withelectrophilic reagent, especiallywithcarboxylic acids.
Thus, the chemical stability of direct liquefaction bio-oil was poor.
Moreover, hydroxyl and carboxyl groups widely existed in various
compounds had a stronger hydrophilicity which made it difcult
to remove the water. Fromthis perspective, further research work
should be needed to remove or convert these undesirable com-
pounds. For example, Abu Bakar et al. [34] carried out catalytic
pyrolysis experiments on rice husk to obtain bio-oil using zeolite
catalyst and showed that it increased the production of aromatic
hydrocarbons andlight phenols. Xuet al. [35] upgradedthe vacuum
pyrolysis bio-oil over the Mo-Ni/-Al
2
O
3
catalyst and showed that
it was possible toimprove the properties of bio-oil byhydrotreating
and esterifying carboxyl group compounds in the bio-oil.
3.6.3. Thermo-gravimetric analysis
Thermo-gravimetric experiments were conducted by using the
thermo-gravimetric analyzer and the only difference was that
they were performed under different atmosphere. The thermo-
gravimetric (TG) anddifferential scanningcalorimetry(DSC) curves
of the bio-oil are shown in Fig. 7. It can be seen from Fig. 7 that
the weight loss of bio-oil in N
2
can be divided into two stages,
including the stage of volatilization of lowboiling fraction and var-
ious products generated by reacting with each other before 250

C,
such as esters and water generated by esterication reaction, and
some unstable carboxylic acids decomposed to generate CO
2
. In
this stage, there was a negative endothermic peak on the DSC curve
since the evaporationof lowboiling compounds. TGandDSCcurves
tended to be attened after 250

C. It was the second stage in which

some high boiling components continued to decompose to gener-
ate small amount of gas. At last, 4.75wt.% of residue carbon was
formed at 600

C. The combustion behavior of bio-oil in O

2
was
similar to the thermal decompositionbehavior before 450

Cwhich
attributed to the high oxygen content in the bio-oil. However, a
small weight loss appeared on the TG curve when the tempera-
ture reached 450

C and above, simultaneously, a corresponding

exothermic peakalsoappearedontheDSCcurve. This phenomenon
was caused by combustion of the coke produced from the oxy-
genated organics cracking in the bio-oil and 1.55wt.% of ash was
produced at 600

C. Therefore, the bio-oil from vacuum pyrolysis

of rape straw should be further upgraded to decrease the oxygen
content and then making it possible to be used as an alternative
fuel.
70 Y. Fan et al. / Journal of Analytical and Applied Pyrolysis 106 (2014) 6370
4. Conclusion
Thermo-gravimetric analysis of rape strawwas carried out and
shows that rape straw is a good pyrolysis material for bio-oil
preparation. The effects of pyrolysis temperature, reactor pressure,
heating rate and holding time on the bio-oil yield were investi-
gated, and the order of the effects of the factors on bio-oil yield
is heating rate >pyrolysis temperature >reactor pressure> holding
time. Heating rate and pyrolysis temperature have a signicant
interaction. The optimal conditions were obtainedat pyrolysis tem-
perature of 495.5

C, heating rate of 19.4

C/min, reactor pressure

of 5.0kPa and holding time of 50.0min. Conrmation runs gave
43.15% and 43.44% of bio-oil yield compared to 43.62% of predicted
value. The orthogonal experimental design method is a useful tool
for experimental design.
The physicochemical of bio-oil was evaluated and shows that
some problems, suchas highwater content (34.20wt.%), anamount
of O (50.74wt.%) and low pH value (2.22), have blocked its
industrial utilization. Polymerization in the condensation process
contributes to the higher average molecular weight distribution
(

M
n
= 243.80 g/mol and

M
w
= 304.97 g/mol) than the vapors.
Light aromatics (mainly including light phenols) are the domi-
nant component for bio-oil, which contributes to the relatively low
polydispersity with a value of 1.25. Moreover, many phenolic com-
pounds might be further extracted and utilized as industrial raw
materials. Due to the high reactivity of carbonyl extensively exist-
ing in acids, aldehydes and ketones, the direct liquefaction bio-oil
is unstable and corrosive. High oxygen content makes the behavior
of combustion in O
2
being similar to the behavior of decomposition
in N
2
before 450

C. Based on the results of this study, it is thought

that further study on upgrading of bio-oil fromvacuumpyrolysis of
rape straw should be performed to make it become an alternative
fuel.
Acknowledgments
This work is currently supported by the National Natural Sci-
ence Foundation of China (No. 51276085), the Natural Science
Foundation of Jiangsu Province (No. BK2011488), the Foundation
of Jiangsu Province Key Laboratory (QK13005) and the Priority
Academic ProgramDevelopment of Jiangsu Higher Education Insti-
tutions ([2011]No.6).
Appendix A. Supplementary data
Supplementary data associated with this article can be found, in
the online version, at http://dx.doi.org/10.1016/j.jaap.2013.12.011.
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