Inuence of vacuum pressure on the vacuum pyrolysis of plant oil asphalt

to pyrolytic biodiesel
Qiang Tang
a
, Yanyan Zheng
a
, Tong Liu
a
, Xiaohua Ma
a,b
, Yuhui Liao
a
, Jinfu Wang
a,
a
Department of Chemical Engineering, Tsinghua University, Beijing 100084, PR China
b
Department of Chemistry, Shangqiu Normal University, Henan 476000, PR China
h i g h l i g h t s
" Plant oil asphalt (POA) components were analyzed qualitatively.
" Inuence of vacuum pressure on reaction selectivity, product composition and properties by the POA vacuum pyrolysis.
" An overall pyrolysis pathway of POA was proposed.
a r t i c l e i n f o
Article history:
Available online xxxx
Keywords:
Plant oil asphalt
Pyrolytic biodiesel
Vacuum pyrolysis
Reaction pathway
a b s t r a c t
Plant oil asphalt (POA) is a waste by-product in the biodiesel and fatty acid industry, especially in China. A
novel vacuum pyrolysis method was developed obtaining diesel-like pyrolytic biodiesel from POA. This
study was aimed at qualitatively analyzing components of POA and probing the inuence of vacuum
pressure on reaction selectivity, product composition and properties in POA vacuum pyrolysis. The
POA was characterized by FT-IR, TGA, positive ion ESI FT-ICR MS, while the pyrolytic oil and pyrolytic bio-
diesel were analyzed by GC/MS. Pyrolytic biodiesel was tested for its properties such as density, viscosity,
ash point, acid value, and cetane number according to the ASTM standard methods. At 400 C, the pyro-
lytic biodiesel obtained at vacuum pressure range of 2060 kPa achieved the ASTM standards of diesel
fuel. An overall pathway of POA pyrolysis was proposed combining general pyrolysis changes and exper-
imental data. The proposed POA components and their pyrolysis pathway reported are useful for the fur-
ther study of POA utilization.
2012 Elsevier B.V. All rights reserved.
1. Introduction
Biodiesel is a green alternative fuel for diesel engines [1,2]. The
US EPAs Renewable Fuel Standards Program Regulatory Impact
Analysis released in February 2010 predicted that biodiesel from
soy oil can result in 57% reduction in greenhouse gases as com-
pared to fossil diesel, and biodiesel produced from waste grease
can result in 86% reduction. Biodiesel is a vegetable oil-based or
animal fat-based diesel fuel consisting of long-chain alkyl (methyl,
propyl or ethyl) esters [3].
Biodiesel is made by chemically reacting lipids (e.g., vegetable
oil [4] and animal fat [5]) with an alcohol to produce fatty acid es-
ters. In Europe, the production of biodiesel from virgin plant oils
now exceeds 3 million tons per year, and is still increasing [6].
However, the large scale production of biodiesel from plant oils
is also of great concern because this use of plant oils competes with
its food use [7], a serious problem in developing countries. In
China, plant oils produced are insufcient to satisfy food demands
due to large population and limited farmland for oil crops, let alone
used as biodiesel feedstock. Therefore, only waste oils/fats such as
waste kitchen oils and soapstocks are available as raw materials for
the biodiesel industry. Besides, the waste oils/fats must be partially
cut for the fatty acid industry. So it is of vital importance to make
full use of the scarce feed stocks. Unfortunately, 1020 wt.% of the
feed stocks are converted to plant oil asphalt (POA) as the biodiesel
or fatty acid rectication residue. At present, in Chinese biodiesel
and fatty acid industries, waste kitchen oil exceeds 5,000,000 tons
per year [8], which produce over 300,000 tons of POA, and soap-
stocks exceed 1,500,000 tons per year [9], which produce over
300,000 tons of POA. Thus over 600,000 tons of POA are produced
each year. Its ultrahigh viscosity, density and highly complex
components make POA difcult for further treatment, and it is
usually burned or abandoned. This has motivated biomass energy
researchers to study if POA can be used as a biomass feed for bio-
fuel [10].
1385-8947/$ - see front matter 2012 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.cej.2012.06.052

Corresponding author. Tel.: +86 10 62796109.

E-mail addresses: tang-q10@mails.tsinghua.edu.cn (Q. Tang), wangjfu@tsin-
ghua.edu.cn (J. Wang).
Chemical Engineering Journal xxx (2012) xxxxxx
Contents lists available at SciVerse ScienceDirect
Chemical Engineering Journal
j our nal homepage: www. el sevi er . com/ l ocat e/ cej
Please cite this article in press as: Q. Tang et al., Inuence of vacuum pressure on the vacuum pyrolysis of plant oil asphalt to pyrolytic biodiesel, Chem. Eng.
J. (2012), http://dx.doi.org/10.1016/j.cej.2012.06.052
Pyrolysis is one of the most popular chemical methods for pro-
ducing biodiesel [11]. Pyrolysis is the thermal decomposition of
materials in the absence of oxygen or with signicantly less oxygen
than is required for complete combustion [12]. The pyrolysis of dif-
ferent plant oils was rst used to supply fuel during the First and
Second World Wars. For example, a tung oil pyrolysis batch system
was used in China as a hydrocarbon supply during World War II
[13]. These hydrocarbons were used as raw materials for gasoline
and diesel fuel production in a cracking system similar to that used
in modern petroleum processing. Several studies on vegetable oil
pyrolysis to obtain chemicals and fuels have been reported in liter-
ature. In the 1980s, Alencar et al. [14] researched the pyrolysis of
babassu (Orbignya martiana), piqui (Caryocar coriaceum), and
palm oils (Elaeis guineensis), respectively. Schwab et al. [15] stud-
ied the conversion of soybean oil to diesel fuel by thermal decom-
position. Ito et al. [16] utilized waste animal fats to produce
biodiesel by pyrolysis. These studies have shown that high yields
of primary liquids and gases, including valuable chemicals, chem-
ical intermediates, petrochemicals, and fuels, can be obtained from
triglyceride feed stocks. In contrast to the transesterication, pyro-
lysis converts part triglycerides to solid char and gases including
CO, CO
2
, which is a waste of raw biomass materials. Owing to high
density and viscosity of POA, pyrolysis is the best method to con-
vert waste POA to valuable components. Recently, Tang et al.
[10] developed a novel vacuum pyrolysis method converting POA
to diesel-like fuel, but failed to study the inuence of operating
conditions such as vacuum pressure on pyrolysis reaction, and just
did primary work on POA components analysis and pyrolysis path-
way proposal.
This study was aimed at analyzing POA components and prob-
ing the inuence of vacuum pressure on reaction selectivity, prod-
uct composition and properties in POA vacuum pyrolysis. The POA
was characterized by FT-IR, TGA, positive ion ESI FT-ICR MS to
qualitatively identify its components. Vacuum pressure in this
study varied from 3 to 80 kPa. The product properties such as den-
sity, viscosity, ash point, acid value, and cetane number were
tested according to the ASTM standard methods. An overall path-
way of POA pyrolysis was proposed combining general pyrolysis
changes and experimental data. The proposed POA components
and their pyrolysis pathway reported are useful for the further
study such as lumping kinetic of POA pyrolysis.
2. Material and methods
2.1. Material
POA samples were collected as the waste by-product of Shan-
dong Bio-Energy Products & Technology Co., Ltd., which produces
50,000 tons of biodiesel per year from soapstocks, and generates
near 10,000 tons of POA per year. The POA was a black, heavy
and thick liquid. Methanol (analytic reagent grade, AR) was used
as the esterifying agent with H
2
SO
4
(AR) as the catalyst to esterify
fatty acids in pyrolytic oil. The methanol and H
2
SO
4
reagents were
purchased from Sinopharm Chemical Reagent Co. Ltd.
2.2. Experimental
Three hundred gram POA sample was pumped into a vacuum
pyrolysis reactor at 400 C, which was heated by a molten salt hea-
ter. Vacuum pressure was the factor studied for its effect on the
pyrolysis reaction. Vacuum pressure was kept at 3, 20, 40, 60,
80 kPa, respectively, which was maintained by a vacuum pump.
The heavy components were continuously pyrolyzed to light com-
ponents, left the tower and condensed as overhead distillate. The
overhead distillate was collected as pyrolytic oil. Meanwhile,
semi-coke was deposited at the bottom and non-condensable
gases (NCG) left via the vacuum system.
The collected pyrolytic oil was converted to pyrolytic biodiesel
via esterication of fatty acids. Fatty acids are prone to ageing
forming colloids, which cause the color of oil becomes dark brown.
If the aged oil was combusted in fossil engine, the engine would
also become smoky, hard to start and corroded. Acid value is one
important factor affecting the color stability and fuel quality of bio-
diesel. Pyrolytic oil became dark brown after 24 h at room temper-
ature and some properties were substandard due to exorbitant acid
value. By contrast, the pyrolytic biodiesel can keep color stable in
the long term and meet ASTM diesel fuel standard. An equal mass
of methanol and 0.3 wt.% H
2
SO
4
relative to the pyrolytic oil were
used as esterifying agent and catalyst, respectively. In this process,
the continuous two-stage esterication was carried out for 2.5 h at
135 C with 200 r/min rotational speed. Finally, a vacuum rectify-
ing tower was set for the purication of the pyrolytic biodiesel.
The vacuum rectifying tower was heated by a molten salt heater
at 300 C with a vacuum pressure of 60 kPa.
2.3. Characterization
The POA was analyzed by Fourier transform infrared spectros-
copy (FT-IR), thermogravimetric analysis (TGA) and electrospray
ionization Fourier transform ion cyclotron resonance mass spec-
trometry (ESI FT-ICR MS). The pyrolytic oil and pyrolytic biodiesel
were characterized by GC/MS. Properties of pyrolytic biodiesel
were tested according to ASTM standard methods including den-
sity (ASTM D86), viscosity (ASTM D445), ash point (ASTM D92),
acid value (ASTM D974), and cetane number (ASTM D613).
The FT-IR analysis was performed to analyse main functional
groups in biodiesel and POA. The samples were tested on a Nicolet
FT-IR spectrometer. The TGA of biodiesel and POA were performed
to compare their boiling point distribution and cracking character-
istic temperature. The tests were carried out on a Perkin-Elmer
Pyris 1 TGA under N
2
atmosphere. The samples were heated from
30 to 600 C at a rate of 10 C/min.
ESI FT-ICR MS can qualitatively analyze the heteroatom compo-
sition of the POA. The sample was analyzed using a Bruker Apex-
Ultra FT-ICR MS equipped with a 9.4 T superconducting magnet.
The operating conditions for positive ion formation were 3.0 kV
emitter voltage, 3.5 kV capillary entrance voltage, and 320 V capil-
lary column end voltage. Ions were accumulated for 0.001 s and
0.001 s in a hexapole with 2.4 V DC voltage and 200 Vp-p RF. The
extraction period for ions from the hexapole to the ICR cell was
set to 1.2 ms. The RF excitation was attenuated to 13 dB and used
to excite ions over the range of m/e 200900.
GC/MS was used to quantitatively analyze the compositions in
the pyrolytic oil and pyrolytic biodiesel products. The sample
(0.5 ml) was diluted with 5 ml of ethanol. 1 ll of the solution
was injected into an Agilent 6890 series G1540A GC with an Agi-
lent 190915-433 80 m 0.250 mm column and a thermal conduc-
tivity detector (TCD). The column temperature program comprised
two stages: initially the temperature was held at 35 C for 5 min,
which was then ramped to 280 C at a rate of 1 C/min and held
for 10 min. Ar was the carrier gas. An Agilent G2579A MS was used
to analyze the compositional formula of the components with dif-
ferent residence times in the GC column.
3. Results and discussion
3.1. Qualitative component analysis of POA
POA as a complex mixture is difcult to be analyzed for specic
components. On the one hand, it is produced from soapstocks, the
2 Q. Tang et al. / Chemical Engineering Journal xxx (2012) xxxxxx
Please cite this article in press as: Q. Tang et al., Inuence of vacuum pressure on the vacuum pyrolysis of plant oil asphalt to pyrolytic biodiesel, Chem. Eng.
J. (2012), http://dx.doi.org/10.1016/j.cej.2012.06.052
mixture of nonglycerides such as free fatty acids, hydrocarbons,
waxes, sterols, vitamins, phospholipids, saccharides and proteins
[17]. Some large molecules such as long chain hydrocarbons,
waxes may fail to be decomposed and remain as POA components.
On the other hand, some reactions are proposed to occur forming
large and less volatile POA molecules during the esterication
and rectication. Even it seems to be impossible carrying out com-
plete components analysis of POA, we tried to do qualitative com-
ponent analysis by deducing from oils/fats and pyrolytic oil
components and data of FT-IR, TGA, FT-ICR MS.
FT-IR can help analysis the main functional groups in POA. As
shown in Fig. 1 the FT-IR spectra of biodiesel and POA, the peaks
of them are all at the same wave numbers, but with different trans-
mittance. The peak at 3008 cm
1
is the stretching vibration of
unsaturated = CAH bond. The peaks at 2926 cm
1
and 2854 cm
1
are the antisymmetric and symmetric stretching vibration of satu-
rated CH
2
bond, respectively. The peak at 1743 cm
1
is the charac-
teristic peak of C@O bond. The peaks at 1465 cm
1
and 723 cm
1
are the bending vibration of CH
2
and (CH
2
)
n
, respectively. The
peaks between 1050 cm
1
and 1250 cm
1
are the stretching vibra-
tion of ester bond. The peak 968 cm
1
is the bending vibration of
C@bond. The peaks at 1437 cm
1
and 1377 cm
1
are the bending
vibration of CH
3
. GC/MS data showed that the biodiesel sample
mainly consists of fatty acid methyl ether (FAME) such as methyl
palmitate, methyl stearate, methyl 9-oleate and methyl 9,12-ole-
ate. Relative to biodiesel sample, FT-IR spectra of POA shows
less = CAH and less CH
3
. It can be proposed that POA molecular
were also assembled by functional groups including CH
2
, ester
bond, C@C and CH
3
. Ester-linked acid dimers are prone to be syn-
thesized via esterication [18,19]. POA may be partly formed due
to polymerization of FAME on double bonds, accounting for the rel-
atively less unsaturated C@C bond transmittance than FAME.
The TG and DTG curves for the biodiesel and POA are plotted in
Fig. 2. The thermal behavior of biodiesel and POA differed substan-
tially. While the peak of the DTG curve for the biodiesel is at tem-
perature about 280 C and presents a mass loss of 99% till 295 C,
the peak for POA is located at a temperature close to 350 C and
shows a mass loss of 97% till 460 C. These differences in evaporat-
ing behavior are good indications of major differences in the com-
position of biodiesel and POA [20]. The peak of biodiesel is sharp
indicating simple components (FAME). The wide and irregular peak
of POA indicates that POA molecular is larger and more complex
than FAME. This data is corresponding to the former FT-IR analysis.
Polymerization of FAME could well explain the higher vaporization
temperature range of POA as compared to FAME thought assem-
bled by the same functional groups.
FT-ICR MS is an advanced method for analyzing the hetero-
atom composition of complex mixtures [21,22]. It offers the high-
est available broadband mass resolution, mass resolving power,
and mass accuracy. Fig. 3 shows a broadband positive ion ESI
FT-ICR mass spectrum of the POA. The data indicated that the
molecular weight distribution of the POA ranged from 250 to
700 Da. The insert in Fig. 3 shows an expanded mass scale spec-
trum at m/z 339 in which several main heteroatom class species
such as O
x
, N
1
O
1
and O
3
S
1
were identied. The O
x
class species
were much more abundant than N
1
O
1
and O
3
S
1
. The relative
abundance of the heteroatom O
x
class species in the mass spectra
from the POA sample is shown in Fig. 4. The O
4
class species was
the most abundant with 37.11%. The relative abundances of the
O
2
, O
3
and O
5
class species were 18.16%, 19.03% and 18.51%,
respectively. The O
1
class species was the least with 7.19%. The
data in Fig. 3 do not quantitatively reect the abundance of the
species in the sample.
Detailed molecular composition analysis of the O
x
class species
were carried out by plotting the relative abundance maps of double
bond equivalents (DBE) as a function of carbon number, as shown
in Fig. 5. The size of the point shows the relative abundance of the
molecules. The O
1
species was mainly in the area with carbon
number 18 (DBE = 4) and carbon number 28 (DBE = 7). The carbon
number of the most abundant O
2
species was 19 with DBE values
from 2 to 3. The O
3
species was mainly at 19 withe the DBE values
varied from 2 to 4. The O
4
species was the most dispersed, and was
composed mostly of carbon number 2224 with DBE values of 26
and carbon number 3536 with DBE values of 25. The most abun-
dant O
5
species had the DBE value of 0, indicating a saturated
structure, and carbon number 33.
Combining the FT-IR, TGA, FT-ICR MS, origin oils/fats compo-
nents with the pyrolysis oil components analyzed by GC/MS dis-
cussed in Section 3.2.2, some proposed POA components and
their formation mechanism are enumerated in Fig. 6. Some natural
components of oils/fats such as hydrocarbons and waxes may re-
main in POA. Hydrocarbons may be squalene or saturated alkanes
with carbon number 2931 [23]. Waxes like fatty acid higher alco-
hol ester, fatty acid sterol ester or fatty acid triterpene alcohol ester
are most possible. The synthetic components may be fatty acid es-
ters and dimer acid esters. Fatty acid esters were supposed to be
formed via Fischer Eesterication [24] in which fatty acids may
be obtained from acidolysis of soap or hydrolysis of waxes, pig-
ments or phospholipid [17] while hydroxyl may be provided by
natural components such as sterol, tieterpene alcohols, lutein, zea-
xanthin, vitamin A, vitamin D, vitamin E and saccharides or hydro-
lysis of waxes, pigments, phospholipid and glycosyldigleceride
[17]. At the same time, dimer acid esters may be formed because
4000 3500 3000 2500 2000 1500 1000 500
4000 3500 3000 2500 2000 1500 1000 500
%

T
r
a
n
s
m
i
t
t
a
n
c
e
Wavenumber (cm
-1
)
Wavenumber (cm
-1
)
3008
2926
2854
1743
1465
1377
1171
968
723
(a) POA
%

T
r
a
n
s
m
i
t
t
a
n
c
e
1377
1743
2854
2926
3008
1465
1437
1246
1196
1171
723
968
(b) Biodiesel
Fig. 1. FT-IR spectra of POA and biodiesel.
Q. Tang et al. / Chemical Engineering Journal xxx (2012) xxxxxx 3
Please cite this article in press as: Q. Tang et al., Inuence of vacuum pressure on the vacuum pyrolysis of plant oil asphalt to pyrolytic biodiesel, Chem. Eng.
J. (2012), http://dx.doi.org/10.1016/j.cej.2012.06.052
of double bond activity, which can be acyclic, monocycle or dicyclic
[19]. The reaction forming monocycle dimer acid ester is famous
DielsAlder reaction [25]. In this way, the main proposed compo-
nents of POA are long chain hydrocarbons, large molecular fatty
acid esters and dimer acid esters. This proposal can properly ex-
plain the pyrolytic products components shown below. Qualitative
components analysis of POA can help researching the pathway and
lumping kinetics of the pyrolysis reaction.
3.2. Effect of vacuum pressure
The POA was converted to char, pyrolytic oil and NCG by the
vacuum pyrolysis. The inuence of vacuum pressure on the reac-
tion selectivity and the distribution of components in the pyrolytic
oil is important to probe, and can help propose the pathway of POA
pyrolysis reaction.
0 100 200 300 400 500 600
0
20
40
60
80
100
120
-1.0
-0.8
-0.6
-0.4
-0.2
0.0
0.2
-2.5
-2.0
-1.5
-1.0
-0.5
0.0
0.5
T
G

(
m
a
s
s

%
)
Temperature (
o
C)
D
T
G

(
1
/
o
C
)
D
T
G
(
1
/
o
C
)
Biodiesel
POA
Biodiesel
POA
Fig. 2. TG and DTG curves of POA and biodiesel.
Fig. 3. Positive ion ESI FT-ICR mass spectrum of the POA. The inset shows the expanded mass scale spectrum at m/z 339.
18.51%
37.11%
19.03%
18.16%
7.19%
O
1
O
2
O
3
O
4
O
5
Fig. 4. Heteroatom O
x
class distribution for POA as derived from the positive ion ESI
FT-ICR mass spectrum.
4 Q. Tang et al. / Chemical Engineering Journal xxx (2012) xxxxxx
Please cite this article in press as: Q. Tang et al., Inuence of vacuum pressure on the vacuum pyrolysis of plant oil asphalt to pyrolytic biodiesel, Chem. Eng.
J. (2012), http://dx.doi.org/10.1016/j.cej.2012.06.052
10 15 20 25 30 35 40 45 50
0
2
4
6
8
10
12
D
B
E
Carbon Number
O
1
10 15 20 25 30 35 40 45 50
0
2
4
6
8
10
12
10 15 20 25 30 35 40 45 50
0
2
4
6
8
10
12
O
3
D
B
E
Carbon Number
O
2
Carbon Number
D
B
E
10 15 20 25 30 35 40 45 50
0
2
4
6
8
10
12
O
4
Carbon Number
D
B
E
10 15 20 25 30 35 40 45 50
0
2
4
6
8
10
12
O
5
Carbon Number
D
B
E
Fig. 5. DBE as a function of carbon number for O
x
class species as derived from the positive ion ESI FT-ICR mass spectrum of the POA.
Hydrocarbons
Nature
Components
C
n
H
2n+2
Wax
CH
3
(CH
2
)
m
COOC(CH
2
)
n
CH
3
(m=20,22; n=22~32)
(n=29~31)
COO
R
1
R
2
( Fatty acid sterol ester or
triterpene alcohol ester)
Synthetic
Components
Dimer acid esters
Diels-Alder reaction
(CH
2
)
m
CH
3
(CH
2
)
n
COOR
7
+
(CH
2
)
P
CH
3
(CH
2
)
q
COOR
8
(CH
2
)
m
CH
3
(CH
2
)
n
COOR
7
(CH
2
)
q
COOR
8
(CH
2
)
P
CH
3
(Fischer Esterification) R
3
O
C OH
R
4
OH
+
H
2
O C
R
3
OR
4
O
Fatty acid esters
(CH
2
)
m
CH
3
(CH
2
)
n
COOR
5
+
(CH
2
)
p
CH
3
(CH
2
)
q
COOR
6
CH
3
(CH
2
)
m
COOR
5
(CH
2
)
n
(CH
2
)
p
CH
3
(CH
2
)
q
COOR
6
(CH
2
)
m
CH
3
(CH
2
)
n
COOR
9
(CH
2
)
p
CH
3
(CH
2
)
q
COOR
10
+
(CH
2
)
p
CH
3
CH
3
(CH
2
)
m
(CH
2
)
n-1
COOR
9
(CH
2
)
q-1
COOR
10
Fig. 6. Proposed POA components and their formation mechanism.
Q. Tang et al. / Chemical Engineering Journal xxx (2012) xxxxxx 5
Please cite this article in press as: Q. Tang et al., Inuence of vacuum pressure on the vacuum pyrolysis of plant oil asphalt to pyrolytic biodiesel, Chem. Eng.
J. (2012), http://dx.doi.org/10.1016/j.cej.2012.06.052
3.2.1. Pyrolysis reaction selectivity
In addition to pyrolytic oil, the products in POA pyrolysis in-
clude NCG and char. The reaction selectivity is a key element for
judging the reaction performance. The vacuum pressure inuenced
the reaction selectivity, as shown in Fig. 7. When the vacuum pres-
sure was low at 3 kPa, at which a very low concentration of oxygen
(from residual air) was present in the system, the POA was con-
verted to 78.4 wt.% pyrolytic oil, 13.8 wt.% char and 7.8 wt.%
NCG. With increasing pressure, the relative amount of pyrolytic
oil decreased while the relative amounts of char and NCG both in-
creased. The products were distributed with 66.5 wt.% pyrolytic oil,
24.1 wt.% char and 9.4 wt.% NCG when the vacuum pressure was
80 kPa. The vacuum pressure inuence on reaction selectivity
may be explained by two factors. First, the oxygen content in the
system determined the amounts of CO
2
and CO in the gas. Second,
the vacuum pressure inuenced the temperature of reaction and
extent of secondary pyrolysis.
3.2.2. Composition of pyrolytic oil
From the pyrolysis behavior, it can be inferred that POA were
converted to a liquid phase mainly consisting of fatty acids, al-
kanes, alkenes. The analysis of pyrolytic oil by GC/MS showed that
POA were cracked to C
9
C
20
alkanes, C
10
C
18
alkenes, C
11
C
14
aro-
matics and various fatty acids including C
6
C
18
saturated fatty
acids, C
7
C
20
unsaturated fatty acids and C
8
C
11
saturated dicar-
boxylic acids. The most abundant fatty acids were palmitic acid,
oleic acid and stearic acid, which matched well with the FT-ICR
MS analysis of POA. Table 1 presents the effect of vacuum pressure
on the composition of the pyrolytic oil analyzed by GC/MS.
The broad picture was that the amount of fatty acids decreased
while alkanes, alkenes and aromatics increased as the vacuum
pressure was increased. The reason accounting for this is that
lower vacuum pressure makes intermediate fatty acids leave the
reaction system more quickly, thus occurring less secondary reac-
tions such as decarboxylation and thermal cracking. Decarboxyl-
ation cracks the ester bond in fatty acid and removes the
carboxyl group to form long chain alkanes and olens. At high tem-
perature, long chain alkanes and olens are further thermally
cracked to shorter chain alkanes and olens.
The changes in the relative amounts of saturated fatty acids,
unsaturated fatty acids and saturated dicarboxylic acids are inter-
esting. In pyrolytic oil produced at 3 kPa, fatty acids comprised
38.74 wt.% saturated fatty acids, 41.24 wt.% unsaturated fatty acids
and 10.36 wt.% dicarboxylic acids. When the vacuum pressure was
increased to 20 kPa, unsatureated fatty acids and dicarboxylic acids
were sharply decreased to 25.21 wt.% and 4.91 wt.%, respectively.
However, saturated fatty acids showed a slight increase to
39.56 wt.%. This is because of the increase of pressure causing a
longer residence time for pyrolysis. Then, reactive unsaturated
fatty acids were pyrolyzed to short chain saturated fatty acids
and alkenes, and dicarboxylic acids underwent decarboxylation
reaction forming saturated fatty acids and alkanes. Although some
saturated fatty acids were consumed to produce alkanes and al-
kenes, there was a net growth. Deeper pyrolysis turned saturated
fatty acids more reactive and appeared amount decrease. When
the vacuum pressure reached 80 kPa, saturated fatty acids and
unsaturated fatty acids were deceased to 37.07 wt.% and
13.87 wt.%, respectively.
3.2.3. Fuel properties of the pyrolytic biodiesel
The pyrolytic biodiesel was obtained after esterication with
methanol during which fatty acid was converted to FAME. So
the amount of FAME in the pyrolytic biodiesel can reect the
amount of fatty acids in the pyrolytic oil. Fig. 8 shows the rela-
tive amounts of alkanes, alkenes, aromatics and FAME in the
0 20 40 60 80
10
20
60
70
80
90
S
e
l
e
c
t
i
v
i
t
y

(
w
t
%
)
Vacuum pressure (kPa)
char
NCG
pyrolytic oil
Fig. 7. Inuence of vacuum pressure on POA pyrolysis reaction selectivity.
Table 1
Composition of pyrolytic oil obtained by POA pyrolysis at various vacuum pressures.
Vacuum pressure (kPa) Alkanes (wt.%) Alkenes (wt.%) Aromatics (wt.%) Fatty acids
Saturated fatty acids (wt.%) Unsaturated fatty acids (wt.%) Dicarboxylic acids (wt.%)
3 4.54 4.99 0.13 38.74 41.24 10.36
20 15.09 14.32 0.91 39.56 25.21 4.91
40 18.46 16.05 1.79 38.87 20.68 4.15
60 19.04 18.01 1.72 38.45 18.21 4.57
80 23.11 20.53 1.22 37.07 13.87 4.20
0 20 40 60 80
0
10
20
60
80
100
w
t
%
Vacuum pressure (kPa)
alkanes
alkenes
aromatics
FAME
Fig. 8. Inuence of vacuum pressure on the pyrolytic biodiesel composition
distribution.
6 Q. Tang et al. / Chemical Engineering Journal xxx (2012) xxxxxx
Please cite this article in press as: Q. Tang et al., Inuence of vacuum pressure on the vacuum pyrolysis of plant oil asphalt to pyrolytic biodiesel, Chem. Eng.
J. (2012), http://dx.doi.org/10.1016/j.cej.2012.06.052
series of pyrolytic biodiesel analyzed by GC/MS. The fuel proper-
ties reect the component distribution in pyrolytic biodiesel at
the macroscopic level. The comparison of the fuel properties in
the series of pyrolytic biodiesel product obtained with diesel
standard ASTM D 975 and biodiesel standard ASTM D6751 can
guide the nding of the proper reaction conditions, as shown in
Table 2.
The fuel properties, including density, kinematic viscosity, ce-
tane number, and ash point, all showed decreases as the vacuum
pressure was increased from 3 kPa to 80 kPa. FAME has higher den-
sities, viscosities, cetane numbers and ash points than fossil diesel
components such as alkanes, alkenes and aromatics. The decrease
of the FAME relative amount resulted in the decrease of the above
physical properties. In addition, the acid number could be about
0.47 mgNaOH/g.
Referring to ASTM D975 and ASTM D6751, pyrolytic biodiesels
obtained at vacuum pressure 3 kPa and 80 kPa were below stan-
dard due to too high kinematic viscosity and too low ash point,
respectively. Pyrolytic biodiesel products produced with vacuum
pressure at 2060 kPa met the standards, but it is also necessary
to take the factors of pyrolysis selectivity, local environment, and
combustion performance into consideration before deciding the -
nal reaction condition.
3.3. Pyrolysis reaction pathway
Pyrolysis is a high temperature process in which biomass is rap-
idly heated in the absence of oxygen. Common changes in pyrolysis
reaction can be enumerated as followed [12,2628]. Thermal diffu-
sion increased the temperature inside the feed; the initiation of
primary pryolysis reactions releases volatiles and forms char; the
hot volatiles and cooler unpyrolyzed feed occurred heat transfer;
condensation of volatiles in the cooler parts of feed , followed by
secondary reactions; autocatalytic secondary pyrolysis reactions
proceed while primary pyrolytic reactions simultaneously occur
in competition. POA was nally converted to NCG, char and pyro-
lytic oil (alkanes, alkenes, aromatics and fatty acids), as discussed
in Section 3.2.2.
Combining these common pyrolysis changes with experimental
data allows to formulate the overall reaction pathway for POA
pyrolysis, as shown in Fig. 9 with some typical components as
examples. Waxes, fatty acid esters, dimer acid esters and long
chain hydrocarbons were rstly thermal cracked at ester bond
and C@C bond forming various fatty acids, long chain alkanes,
shorter chain alkenes and large molecular naphthenic hydrocar-
bons [16]. Fatty acids were then pyrolyzed to alkanes, alkenes
and CO
2
due to decarboxylation [16,29], accompanied by
Table 2
Fuel properties of the pyrolytic biodiesel obtained from POA pyrolysis at various vacuum pressures.
Property (units) Pyrolytic biodiesel Diesel (ASTM D 975) Biodiesel (ASTM D 6751)
3 (kPa) 20 (kPa) 40 (kPa) 60 (kPa) 80 (kPa)
Density (g/cm
3
) 0.881 0.873 0.869 0.863 0.861 0.800.86 0.870.90
Kinematic viscosity (mm
2
/s)
a
7.8 5.6 5.29 4.9 4.6 1.34.1 2.56.0
Cetane number 100 75 65 60 50 4065 Min. 47
Acid value (mgNaOH/g) 0.47 0.46 0.48 0.48 0.46 <0.50
Flash point (C) 110 86 74 65 57 6080 Min. 130
a
Value at 40 C.
R
1
R
2
COO
(CH
2
)
p
CH
3
CH
3
(CH
2
)
m
(CH
2
)
n-1
COOH
(CH
2
)
q-1
COOH
C
n
H
2n
C
m
H
2m
C
n-m
H
2(n-m)
CH
3
(CH
2
)
m
COOC(CH
2
)
n
CH
3
CH
3
(CH
2
)
m
COOH
CH(CH
2
)
n-2
CH
3
C R
2
COOH
R
1
C
p
H
2p+2
C
p
H
2p+2
R
3 R
4
(CH
2
)
p
CH
3
CH
3
(CH
2
)
m
(CH
2
)
n-1
COOR
3
(CH
2
)
q-1
COOR
4
C
q
H
2q
C
b
H
2b+2
R
1
H
R
2
H
CO
2
CH
3
(CH
2
)
m
H
=(CH
2
)
q-1
CH
3
CO
2
Dehydrogenation
Condensation
Ring-opening Reaction
Branched-chain Cracking
Char
Decarboxylation
Branched-chain Cracking
Decarboxylation
Dehydrogenation
Condensation
Char
Ester-bond cracking
C=C bond cracking
C=C bond cracking Ester-bond cracking
C=C bond cracking
Fig. 9. Proposed pyrolysis reaction pathway of POA to pyrolytic oil.
Q. Tang et al. / Chemical Engineering Journal xxx (2012) xxxxxx 7
Please cite this article in press as: Q. Tang et al., Inuence of vacuum pressure on the vacuum pyrolysis of plant oil asphalt to pyrolytic biodiesel, Chem. Eng.
J. (2012), http://dx.doi.org/10.1016/j.cej.2012.06.052
branched-chain cracking of long chain alkanes and alkenes to
shorter chain. Meanwhile, polycyclic napthenic or aromatic hydro-
carbons are formed. When temperature become higher, polycyclic
napthenic or aromatic hydrocarbons may become char after
repeating dehydrogenation condensation [30], while alkanes may
occur main-chain cracking forming short chain alkanes and al-
kenes which may even partial be gas. Above all, the pyrolysis depth
is a function of vaccum pressure for a certain reaction system with
constant volume and temperature. Adjusting pyrolysis products
selectivity and components distribution can be easily realized by
vacuum pressure control.
4. Conclusions
The components of POA were analyzed by deducing from oils/
fats, pyrolytic oil components and means of FT-IR, TGA, FT-ICR
MS. The inuence of vacuum pressure on reaction selectivity, prod-
uct composition and properties in POA vacuum pyrolysis were
studied. Based on the fuel properties including density, kinetic vis-
cosity, ash point, cetane number, the pyrolytic biodiesel obtained
at 400 C and at vacuum pressure in the range from 20 kPa to
60 kPa achieved the ASTM standards for diesel fuel. An overall
pathway of POA pyrolysis was formulated combining general pyro-
lysis changes and experimental data. The proposed POA compo-
nents, pyrolysis pathway and experimental data reported lay a
solid foundation for further study of POA.
Acknowledgement
The authors appreciate Shandong Bio-Energy Products & Tech-
nology Co., Ltd. to provide the experimental feed stock of POA.
References
[1] M.G. Kulkarni, A.K. Dalai, Waste cooking oils-an economical source for
biodiesel: a review, Ind. Eng. Chem. Res. 45 (2006) 29012913.
[2] O.S. Stamenkovic , A.V. Velickovic , V.B. Veljkovic , The production of biodiesel
from vegetable oils by ethanolysis: current state and perspectives, Fuel 90
(2011) 31413155.
[3] F.H. Kasim, A.P. Harvey, Inuence of various parameters on reactive extraction
of Jatropha curcas L for biodiesel production, Chem. Eng. J. 171 (2011) 1373
1378.
[4] S.A. Quintella, R.M.A. Saboya, D.C. Salmin, Transestericarion of soybean oil
using ethanol and mesoporous silica catalyst, Renew Energy 38 (2012) 136
140.
[5] K.H. Chung, J. Kim, K.Y. Lee, Biodiesel production by transesterication of duck
tallow with methanol on alkali catalysts, Biomass Bioenergy 33 (2009) 155
158.
[6] K. Bozbas, Biodiesel as an alternative motor fuel: production and policies in the
European Union, Renew. Sust. Energy Rev. 12 (2008) 542552.
[7] A.A. Refaat, Different techniques for the production of biodiesel from waste
vegetable oil, Int. J. Environ. Sci. Technol. 7 (2010) 183213.
[8] Y.P. Jiao, Distinguishing and detection of waste oils, Mod. Food Sci. Technol. 4
(2008) 378380.
[9] C.G. Ma, Y.B. Si, H.F. Hou, Preparation of biodiesel with soapstock, China Oils
Fats 4 (2006) 5961.
[10] Q. Tang, X.H. Ma, Y.Y. Zheng, J.F. Wang, Synthesis of pyrolytic biodiesel from
unheeded biomass plant oil asphalt, China biodiesel 4 (2012) 1221.
[11] S. Czernik, A.V. Bridgwater, Overview of application of biomiass fast pyrolysis
oil, Energy Fuels 18 (2004) 590598.
[12] D. Mohan, C.U. Pittman, P.H. Steele, Pyrolysis of wood/biomass for bio-oil: a
critical review, Energy Fuels 20 (2006) 848889.
[13] C.C. Chang, S.W. Wan, Chinas motor fuels from tung oil, Ind. Eng. Chem. 39
(1942) 15431548.
[14] J.W. Alencar, P.B. Alves, A.A. Craveiro, Pyrolysis of tropical vegetable oils, J. Agr.
Food Chem. 31 (1983) 1268.
[15] A.W. Schwab, G.J. Dykstra, E. Selke, S.C. Sorenson, E.H. Pryde, Diesel fuel from
thermal decomposition of soybean oil, J. Am. Oil Chem. Soc. 65 (1988) 1781.
[16] T. Ito, Y. Sakurai, Y. Kakuta, Biodiesel production from waste animal fats using
pyrolysis method, Fuel Process. Technol. 94 (2012) 4752.
[17] M.K. Dowd, Gas chromatographic characterization of soapstocks from
vegetable oil rening, J. Chromatogr. A 816 (1998) 185193.
[18] L. Nahar, A.B. Turner, Synthesis of ester-linked lithocholic acid dimers, Steroids
68 (2003) 11571161.
[19] X.L. Zhang, Properties and applications of dimer acids, Chem. Ind. Times 4
(1993) 1119.
[20] M.B. Dantas, A.R. Albuquerque, et al., Evaluation of the oxidative stability of
corn biodiesel, Fuel 90 (2011) 773778.
[21] P. Liu, Q. Shi, K.H. Chung, Y.H. Zhang, N. Pan, S.Q. Zhao, C.M. Xu, Molecular
characterization of sulfur compounds in venezuela crude oil and its SARA
fractions by electrospray ionization fourier transform ion cyclotron resonance
mass spectrometry, Energy Fuels 24 (2010) 50895096.
[22] Q. Shi, C.M. Xu, K.H. Chung, Y.H. Zhang, Characterization of basic nitrogen
species in coker gas oils by positive-ion electrospray ionization fourier
transform ion cyclotron resonance mass spectrometry, Energy Fuels 24
(2010) 563569.
[23] L. Vazquez, C.F. Torres, T. Fornari, F.J. Senorans, G. Reglero, Recovery of
squalene from vegetable oil sources using countercurrent supercritical carbon
dioxide extraction, J. Supercrit. Fluid 40 (2007) 5966.
[24] D.C. Forbes, K.J. Weaver, Brnsted acidic ionic liquids: the dependence on
water of the Fischer esterication of acetic acid and ethanol, J. Mol. Catal A:
Chem. 214 (2004) 129132.
[25] A. Saito, H. Yanai, T. Taguchi, Bis-aluminated triic amide promoted Diels-
Alder reactions of a, b-unsaturated lactones, Tetrahedron Lett. 45 (2004)
94399442.
[26] C.K. Barreto, C.C. Oliveira, G.G. Souza, Evaluation of the stability during the
storage of a diesel-like fuel obtained by the pyrolysis of soybean oil, Biomass
Bioenergy 37 (2012) 4248.
[27] X.W. Peng, H.Z. Chen, Pyrolysis of fermented mass containing microbial oil in a
xed-bed reactor for production of biodiesel, J. Anal. Appl. Pyrol. 88 (2010) 1
6.
[28] Q. Lu, X.C. Yang, C.Q. Dong, Z.F. Zhang, X.M. Zhang, X.F. Zhu, Inuence of
pyrolysis temperature and time on the cellulose fast pyrolysis products:
analytical Py-GC/MS study, J. Anal. Appl. Pyrol. 92 (2011) 430438.
[29] J.G. Na, J.K. Han, Y.K. Oh, et al., Decarboxylation of microalgal oil without
hydrogen into hydrocarbon for the production of transportation fuel, Catal.
Today 185 (2012) 313317.
[30] C.L. Koon, F. Akbar, R. Hughes, et al., Development of an experimental protocol
to evaluate FCC stripper performance in terms of coke yield and composition,
Trans. IChemE 78 (2000) 738744.
8 Q. Tang et al. / Chemical Engineering Journal xxx (2012) xxxxxx
Please cite this article in press as: Q. Tang et al., Inuence of vacuum pressure on the vacuum pyrolysis of plant oil asphalt to pyrolytic biodiesel, Chem. Eng.
J. (2012), http://dx.doi.org/10.1016/j.cej.2012.06.052