Bioresource Technology 101 (2010) 826828

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Bioresource Technology
journal homepage: www.elsevier.com/locate/biortech

Short Communication

Properties of Tung oil biodiesel and its blends with 0# diesel

Qiong Shang, Wei Jiang, Houfang Lu *, Bin Liang
College of Chemical Engineering, Sichuan University, Chengdu 610065, PR China

a r t i c l e i n f o a b s t r a c t

Article history: Tung oil was used to produce biodiesel by transesterication with methanol catalyzed by potassium
Received 3 June 2009 hydroxide and the inuence of the transesterication temperatures on the properties of the Tung oil bio-
Received in revised form 10 August 2009 diesel was investigated. FT-IR, UV, and GCMS results indicated that the triconjugated double bonds of
Accepted 11 August 2009
Tung oil were stable during the transesterication procedure between 25 and 60 C. The results of prop-
Available online 6 September 2009
erties showed that Tung oil biodiesel had a low cold lter plugging point (CFPP, 19 C) and a higher
kinetic viscosity (KV, 7.070 mm2/s). Acid value (AV), KV, and CFPP increased with the increase of storing
Keywords:
time. Blending Tung oil biodiesel with 0# diesel could improve its stability. B20 or lower blends could still
Tung oil
Biodiesel
meet the specication of ASTM D7467 after storage for a month. They were more stable than pure Tung
Transesterication oil biodiesel.
Blends 2009 Elsevier Ltd. All rights reserved.
Property

1. Introduction of biodiesel goes down with an increase in its unsaturated degree

Biodiesel is an alternative diesel fuel consisting of alkyl mono-
esters of fatty acids produced from vegetable oils or animal fats
through transesterication with methanol. It has been the focus
of a considerable number of recent studies as it is renewable and
environmental friendly (Moser, 2009). At present, the main raw
materials used for a large-scale production of biodiesel are edible
oils such as rapeseed oil in Europe, soybean oil in American, and
palm oil in Southeast Asia. But it is also widely questioned because
of the shortage and high cost of edible oils.
Non-edible woody plant oils, such as Jatropha curcas L. oil
(Berchmans and Hirata, 2008; Lu et al., 2009; Zhou et al., 2006)
and Tung oil (Park et al., 2008a), are promising biodiesel materials
in China. Tung trees are spread widely in China, especially in the
southern mountain areas. Tung oil, called China wood oil, is ob-
tained by pressing the seeds of the Tung tree. The productivity of
Tung oil varies from 300 to 450 kg/ha (Ma et al., 2007).
The fatty acid (FA) composition of Tung oil varies with its origin.
It usually contains more than 80 wt.% of a-elaeostearic acid, a long-
chain (C18) fatty acid with three conjugated double bonds (at car-
bons 9 cis, 11 trans, 13 trans). The FA composition is a major factor
inuencing the properties of biodiesel. Biodiesel from Tung oil
exhibits excellent low-temperature operability due to its polyun-
saturated structure (Park et al., 2008a,b). However, the stability
* Corresponding author. Tel./fax: +86 28 85460557.
E-mail address: luhouf@163.com (H. Lu).
(Bouaid et al., 2007; Knothe, 2007). Therefore, the main problem of
biodiesel from Tung oil is its oxidative stability and care should be
taken in the handling and storage process.
Oils, like Tung oil, with higher degree of unsaturation are more
susceptible to lipid oxidation and polymerization of glycerides oc-
curs at elevated temperature (Encinar et al., 2005). The transeste-
rication process for the biodiesel production is conducted under
the boiling point of methanol (6070 C). The heating process
potentially induces the reactions of unsaturated bonds of the fatty
acid chains. But no literatures concerning the change of both con-
tent and structure of a-elaeostearic acid in Tung oil during the
transesterication are available.
The conversions of edible oils to biodiesel were intensively re-
searched, but only a few of the work was concerned about the con-
version of Tung oil. Park et al. (2008a) reported a two-step process
for the Tung oil conversion with a pre-esterication at 80 C by an
Amberlyst-15 solid acid catalyst followed by a transesterication
by alkaline catalyst. Xu et al. (2006) also reported the transesteri-
cation of Tung oil with methanol at 43 C using an immobilized
lipase NOV0435 catalyst. However, Tung oil biodiesel is still in
the laboratory testing process. In order to promote the Tung oil
biodiesel into the commercial practice, the chemicophysical prop-
erties of the Tung oil biodiesel must be well investigated.
In this work, different transesterication conditions were tested
in order to investigate the inuence of the production conditions
on the unsaturated structure of Tung oil. To the biodiesel from
Tung oil, we measured the oxidation stability of pure biodiesel
and the blends of the biodiesel with fossil diesel. The basic data

0960-8524/$ - see front matter 2009 Elsevier Ltd. All rights reserved.
doi:10.1016/j.biortech.2009.08.047
 Q. Shang et al. / Bioresource Technology 101 (2010) 826828
will be useful for the storage and commercial usage of the Tung oil
biodiesel.
2. Experimental methods
2.1. Materials
Tung oil was prepared by pressing seeds collected from Pingwu,
Sichuan province, southwest China. Its acid value (AV) was 4.72 mg
KOH/g; moisture content was 0.16 wt.% and its kinetic viscosity
(KV) was 97.58 mm2/s (40 C). All chemicals used were of analyti-
cal grade, which were purchased from Changzheng Chemical Com-
pany, China.
2.2. Experimental procedures
In order to completely convert the oil to ester and investigate
the structural stability of Tung oil under different temperatures,
a two-step transesterication was carried out at 25 and 40 C (pro-
cesses I and II, respectively) and one-step transesterication was
conducted at 60 C (process III). The transesterication process
and handling of the product were similar to those described in ref-
erences (Lu et al., 2009; Yan et al., 2008). In the two-step transeste-
rication process, a given amount of Tung oil was mixed together
with corresponding methanol and KOH at different temperatures
for a xed time; the product mixture was then centrifuged and
separated in two phases; taking the upper methyl ester phase
and adding supplementary methanol and KOH facilitated the
transesterication reaction.
2.3. Analytical methods
The moisture content, AV and glycerol content were determined
following standards of PRC: GB 6283-86, GB/T 5530-1998, and GB/
T 13216.6-91, respectively. The fatty acid structure of Tung oil was
analyzed by ultravioletvisible spectrophotometer (UV) from 200
to 320 nm (Beijing Purkinje General Instrument Company,
TU1810), Fourier transform infrared spectroscopy (FT-IR) (Nicolet,
Nexus 670). The composition of fatty acid was analyzed by gas
chromatography and mass spectrometry (GCMS) (Shimadzu,
GCMS-QP2010) employing a silicon capillary column (Rtx-5SilMS,
30 m in length  0.25 mm in inner diameter, 0.25 lm). The meth-
od of GCMS was similar to that described in reference (Zhang
et al., 2008). The properties of biodiesel, such as density at 20 C,
KV at 40 C, cold lter plugging point (CFPP), ash point and sulfur
content were measured following PRC standards: GB/T 2540, GB/T
265-88, SH/T 0248, GB/T 261, and GB/T 380-77, respectively.
3. Results and discussion
3.1. Effect of reaction temperature
Different transesterication processes were conducted. The oil
conversions of processes I, II and III were 91.60%, 99.68%, and
99.96%; and the methyl ester yields were 86.58%, 86.70%, and
88.88%, respectively. These products were detected by GCMS.
Their a-elaeostearic acid (18:3) contents were 70.43, 69.36, and
68.25 wt.%, respectively.
The biodiesel products were also measured with the UV and FT-
IR spectrum. The characteristic triconjugated double bonds of the
Tung oil were detected. The FT-IR spectrum of the Tung oil methyl
ester obtained in process III showed an absorption of m (C@C bond)
in CH@CHCH@CHCH@CH at 1859 cm 1, 1583 cm 1, and an
absorption of d (CH bond) in CH@CHCH@CHCH@CH at
992 cm 1, also indicating the presence of triconjugated double
827
bonds (Pretsch et al., 2000). The results indicated that the transe-
sterication did not inuence the structures of the fatty acid
chains. The side reactions such as the polymerization were not ob-
served in the conversion process, even at the temperature of 60 C.
Considering conversion and yield, transesterication of Tung oil
under 60 C is more advisable.
3.2. Properties of Tung oil biodiesel
AV, density, KV, CFPP, ash point and sulfur content were com-
pared for the biodiesel products prepared by processes II and III.
The results are listed in Table 1, compared with the ASTM D6751.
The properties of biodiesel made from process II and process III
were very similar. This further veried that temperatures from 25
to 60 C could not obviously change the content and structure of
Tung oil. Densities of Tung oil biodiesel were much smaller than
that of Tung oil (0.9338 g/cm3). And the KVs were a little higher
than the specication listed in ASTM D6751; this could be attrib-
uted to the higher KV of its original oil (97.58 mm2/s) compared
with other vegetable oils. Theoretically speaking, the triconjugated
carboncarbon double bonds in a-elaeostearic acid caused stron-
ger intermolecular interactions among the p electrons of the
poly-double bonds (Rodrigues et al., 2006), resulting in a higher
KV. On the other hand, Tung oil biodiesel had a much lower CFPP
than 0# diesel, a good low-temperature ow property and so could
be used in cold winter. The lower CFPP of Tung oil esters was a re-
sult of their unsaturated structure.
3.3. Stability of Tung oil biodiesel
Stability of biodiesel is an important property for the storage of
the biodiesel (Dunn, 2008). Sample III were stored in a sealed glass
bottle for a month between 10 and 15 C. AV, KV, and CFPP were
measured every seven days. AV, KV, and CFPP of Tung oil biodiesel
increased with the storing time. The AV increased from 0.11 mg
KOH/g to 0.18 mg KOH/g stored for a month, but still could meet
the standards of ASTM D6751 and EN 14214. KV increased about
13% and CFPP changed little in two weeks, and then increased by
4 C after a month.
3.4. Properties of Tung oil biodiesel-0# diesel blends
Biodiesel is used in either purity or blends with petroleum die-
sel. In Europe and the United State, B20 (20 v% biodiesel) or lower
blends have been widely used because they provide a good balance
between material compatibility, cold weather operability, perfor-
mance, emission and costs. In China, the usage standards for the
blends of biodiesel are under discussion.
Some physiochemical properties of Tung oil biodiesel (obtained
by process III) 0# diesel blends were measured. The results are
shown in Figs. 1a and 1b.
The density and KV increased with the increase of the Tung oil
biodiesel volume fraction in the blends. Densities of blends were
linear with the volume fraction of biodiesel. Although the KV of
pure Tung oil biodiesel was higher, the B20 or lower blends could
Table 1
Comparison of the properties of biodiesel from Tung oil in different processes.
Property Units Process II Process III ASTM D6751
AV mg KOH/g 0.12 0.11 Max. 0.5
Density (20 C) g/cm3 0.9007 0.9010
KV (40 C) mm2/s 6.617 7.070 1.96.0
CFPP C 15 19
Flash point C 159 167 Min. 130.
Sulfur content wt.% 0.0078 0.0020 Max. 0.05 (S500)
828 Q. Shang et al. / Bioresource Technology 101 (2010) 826828
Fig. 1a. Density and KV of Tung oil biodiesel blends.
Fig. 1b. CFPP and ash point of Tung oil biodiesel blends.
meet the specication of ASTM D7467 (1.94.1 mm2/s). In addi-
tion, The CFPP kept at 1 C with the volume fraction of biodiesel be-
low 20%; whereas it decreased sharply from 0 C to 19 C as the
biodiesel volume fraction increased from 70% to 100%. As expected,
the ash point of blends was also increased with the increased bio-
diesel; the higher the volume fraction of biodiesel in the blend, the
higher the ash point.
3.5. Stability of tung oil biodiesel-0# diesel blends
KV and CFPP of B0B20 blends were measured after different
storing times. The results showed that the CFPP remained at 1 C
in all the times tested. At the same time, the KV of B20 or lower
blends increased about 2% in a month. This changing ratio was
much lower than that of B100 (13%). It showed that the blends
were more stable than pure Tung oil biodiesel. After storage for a
month, its KV was still well within the maximum limit of 4.1
mm2/s in the ASTM D7467 (1.94.1 mm2/s) specication. In this
sense, the blending of Tung oil biodiesel with diesel could improve
its qualities.
4. Conclusions
The processes of transesterication between Tung oil and meth-
anol catalyzed by KOH at 25, 40, and 60 C were studied. UV, FT-IR,
and GCMS results showed that the reaction temperature had little
effect on the structure and composition of Tung oil during transe-
sterication. Properties of Tung oil biodiesel and its blends with 0#
diesel were measured. After a month, the AV changed from 0.11 to
0.18 mg KOH/g, the KV increased about 13% and the CFPP increased
from 19 C to 15 C. In addition, stability results indicated that
B20 or lower blends were more stable than Tung oil biodiesel.
Acknowledgements
We thank the key grant project of Chinese Ministry of Education
(No. 307023) and National Key Technology R&D Program (No.
2007BAD50D05) for nancial support.
References
Berchmans, H.J., Hirata, S., 2008. Biodiesel production from crude Jatropha curcas L.
seed oil with a high content of free fatty acids. Bioresour. Technol. 99, 1716
1721.
Bouaid, A., Martinez, M., Aracil, J., 2007. Long storage stability of biodiesel from
vegetable and used frying oils. Fuel 86, 25962602.
Dunn, R.O., 2008. Antioxidants for improving storage stability of biodiesel. Biofuels
Bioprod. Bioref. 2, 304318.
Encinar, J.M., Gonzalez, J.F., Rodryguez-Reinares, A., 2005. Biodiesel from used frying
oil. Variables affecting the yields and characteristics of the biodiesel. Ind. Eng.
Chem. Res. 44, 54915499.
Knothe, G., 2007. Some aspects of biodiesel oxidative stability. Fuel Process.
Technol. 88, 669677.
Lu, H., Liu, Y., Zhou, H., Yang, Y., Chen, M., Liang, B., 2009. Production of biodiesel
from Jatropha curcas L. oil. Comput. Chem. Eng. 33, 10911096.
Ma, Z., Zhu, W., Wei, Q., 2007. Advances in the researches of biodiesel from woody
oil-bearing plants. J. Northwest For. Univ. 22, 125130.
Moser, B.R., 2009. Biodiesel production, properties, and feedstocks. In vitro cell. Dev.
Biol. Plant 45, 229266.
Park, J.-Y., Kim, D.-K., Wang, Z.-M., Lu, P.-M., Park, S.-C., Lee, J.-S., 2008a. Production
and characterization of biodiesel from Tung oil. Appl. Biochem. Biotechnol. 148,
109117.
Park, J.-Y., Kim, D.-K., Lee, J.-P., Park, S.-C., Kim, Y.-J., Lee, J.-S., 2008b. Blending
effects of biodiesels on oxidation stability and low temperature ow properties.
Bioresour. Technol. 99, 11961203.
Pretsch, E., Bhlmann, P., Affolter, C., 2000. FT-IR Spectrum. Structure
Determination of Organic Compounds Tables of Spectral Data. Springer-
Verlag, Berlin, Heidelberg, New York. pp. 245312.
Rodrigues, J., Cardoso, F., Lachter, E., Estevo, L., Lima, E., Nascimento, R., 2006.
Correlating chemical structure and physical properties of vegetable oil esters. J.
Am. Oil Chem. Soc. 83, 353357.
Xu, G., Zhang, B., Liu, S., Yue, J., 2006. Study on immobilized lipase catalyzed
transesterication reaction of Tung oil. Agric. Sci. China 5, 859864.
Yan, S., Lu, H., Liang, B., 2008. Supported CaO catalysts used in the
transesterication of rapeseed oil for the purpose of biodiesel production.
Energy Fuels 22, 646651.
Zhang, H., Shang, Q., Lu, H., Liang, B., 2008. Phase composition in the process of
biodiesel preparation from palm oil and the properties of biodiesel. China Oils
Fats 33, 4952.
Zhou, H., Lu, H., Liang, B., 2006. Solubility of multicomponent systems in the
biodiesel production by transesterication of Jatropha curcas L. oil with
methanol. J. Chem. Eng. Data 51, 11301135.