Evaluation of camellia oleifera as a source for biodiesel

production
Jinming Zheng , Hui Liu * , Lubin Zhou
State Key Laboratory of Biogeology and Environmental Geology, China University of Geosciences
Wuhanˈ430074ˈChina
E-mail˖hliu2009@cug.edu.cn

Abstract: According to the major specifications of biodiesel
standards of China, USA and Germany, a criterion has been
established for the preliminary evaluation of eight different
kinds of camellia oleosa seeds collected from Hubei province
as potential biodiesel raw materials. The criterion included:
Ԙoil content㧪30% in seeds; ԙacid value㧨1mg/gKOH; Ԛ
iodine number㧨120; ԛcetane number㧪49; Ԝ1.9mm2/s㧨
viscosity㧨6.1 mm2/s; ԝCFPP (cold filter plugging point)
㧨ć. Eight kinds of camellia oleosa seeds were collected
from the southeast of Hubei province. Among those, three
kinds of camellia oleosa seeds were found to be appropriate
sources for biodiesel production, including chicken heart
camellia, algae skin tongzi camellia, hybrid camellia.
However, the other kinds of camellia oleosa were not suitable
as raw materials for biodiesel due to the low oil content or
high acid value.
Key words: Camellia oil; biodiesel; raw materials; evaluation
1 Introduction
Due to the limitation of fossil fuel resources and global
warming, biodiesel has attracted considerable attention recently
all over the world. However, one of the key limitations of
biodiesel production was the availability of raw oil material. As a
large population country with large mountain areas, woody oil
plants are a promising feedstock for biodiesel production in
China [1-2].Camellia is a famous kind of woody oil planted in
China, which mainly distributes in Sichuan, Yunnan, Guizhou,
Hunan and Hubei provinces. It centrally located in south of the
Yangtze where can supply warm climate, full rainfall and
slightly acidic soil. The seed oil content ranges from 17 to 50%.
These oil seeds have great potential for being transesterified to
produce biodiesel. Its major fatty acid is oleic (C18:1). Camellia
grows rapidly, taking 2̚3 years of crop cycle to reach maturity
and generate economic yields. And it has a long full fruit period
of 15̚60 years, during this period 1200 kg/hm2 oil yield would
be gotten in a year. Various parts of the plant have medicinal
values. And the seed oil can produce edible oil, soap and lube.
The nutshell can be made into activated carbon. The seedcake
can be used for feed and fertilizer.
Camilla oleosa, as one of the four woody oil plants in the
world, has a long history in Yangxin considered as the main
cultivated fields in hubei province and now the total area has
reached 75000 mu. In this paper, eight different kinds of Camilla
oleosa seeds were collected from yangxin,hubei province. the oil
content, acid value, iodine number, fatty acid compostions were
analyzed and also the cetane number, viscosity and cold filter
plugging point of biodiesels based on raw materials were
predicted through the prediction models between fatty acid
compositions and biodiesel properties. According to the criterion
[3-4], the Camilla oleosas suitable for biodiesel production were
preliminarily screened out. These woody oil plants potentially
provide abundant and sustainable raw materials for biodiesel
industry.
.
2 experimental
2.1 Materials
Eight different kinds of Camilla oleosa seeds were collected
from yangxin,hubei province and the sample information and
pretreatment process were shown in Table 1 and Fig.1,
respectively. Methanol (99.5%), ethanol (95%), KOH (99%), ICl,
KI (99%) are of analytical grade and were purchased from Aopu
Chemical Company, China.

Table 1 Sample information

number sample name sampling location sampling time
1 Thick skin tongzi camellia Xingguo,Yangxin,hubei 2010.10.18
2 Chicken heart camellia Xingguo, Yangxin,hubei 2010.10.18
3 Algae skin tongzi camellia Xingguo, Yangxin,hubei 2010.10.18
4 Guohe camellica Guohe, Yangxin,hubei 2010.10.18
5 Rice camellia Guohe, Yangxin,hubei 2010.10.18
6 Local camellia Tufu, Yangxin,hubei 2010.10.18
7 Hybrid camellia Tufu, Yangxin,hubei 2010.10.18
8 Comprehensive camellia Comprehensive farm, Yangxin,hubei 2010.10.18

Supported by: “New Century Excellent Talent of Ministry of Education of China” project (Grant No. NCET-09-0713), the Natural Science Foundation of Hubei
Province of China for excellent young scientist (Grant No. 2009CDA043), and Science and Technology Project of Wuhan city, China (Grant No. 201060723316).

978-1-4244-8165-1/11/$26.00 ©2011 IEEE

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 Raw material strip the shuck
Fig.1 The pretreatment of the raw materials
2.2 Experimental procedures
2.2.1 Analysis of physical and chemical characteristics of the
raw materials
The crude oils were extracted with soxhlet extraction and
the oil content, acid value, iodine number, water and volatility
content, density were determined according to GB/T 14772-2008,
GB/T 264-1983, GB/T 5532-2008, GB/T 5528-1995,GB/T
265-88.
2.2.2 Analysis of fatty acid compositions of the crude oils
One gram crude oil dissolved in 10ml hexane was esterified
to fatty acid methyl ester with 0.5ml 2mol/LKOH/CH3OH on
concussion for 5.0min and keep static after the reaction. The
upper layer was analyzed on GC, using an Agilent 7890N gas
chromatograph with a flame ionization detector (GC-FID). The
capillary column was a HP-5ms with a length of 30m, a film
thickness of 0.25ȝm, and an internal diameter of 0.32mm. The
detector temperature was maintained at 260ćThe column
temperature program was initiated at 180ć for 5.0min, increased
to 230ć at a rate of 2ć/min, and held for 5min. The flow rate of
the carrier gas N2 was kept constant at 1.2mL/min.The samples
were injected onto GC in split mode (100:1) with an inlet
temperature of 26ć.
2.3 Prediction of biodiesel properties
The centane number, viscosity and cold filter plugging point
of biodiesels based on the raw materials were predicted through
the prediction models between fatty acid compositions and
biodiesel properties, as follows [5-7]:
Equation (1) is Klopfenstein’s equation for estimation of the
cetane index of pure fatty acid ester, centane number for
biodiesels was predicted using equation (2). Where n is the
carbon number, XME is the percentage of fatty acid:
CN=58.1+2.8(n-8)/2-15.9*(number of double bond䯵 (1)
CN = ¦ X ME (wt%).CN ME (2)
Equation (3) is used for the estimation of kinematic
viscosity, where ai is the percentage of fatty acid, μi is the
viscosity of the pure fatty acid methyl ester.
ln μ = ¦ ai ln μi
(3)
Equation (4) is used for the estimation of cold filter
plugging point (CFPP) and equation (5) is used for predicting the
LSCF. Where LSCF is the long chain saturated factor, wt% is the
the percentage of fatty acid:
CFPP = 3.1417 ∗ LSCF − 16.477 (4)
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shatter
LSCF = 0.1∗ C16(wt%) + 0.5 ∗ C18(wt%) +
(5)
1∗ C 20(wt%) + 2 ∗ C 24(wt%)
3 Preliminary screening standards for biodiesel
3.1 Oil content
The oil content refers to the oil content of seeds or other parts.
The oil content is an important decision factors for the raw
materials to produce biodiesel. Only those with high oil content
materials have potential values. In this study, we defined the oil
content should be more than 30%.
3.2 Acid value
The ideal biodiesel raw materials should have low acid value.
High acid value was easy to form saponification preventing the
crude oils for biodiesel production. Because of this , the acid of
the crude oil should be less than 1mgKOH/g.
3.3 Iodine number
Iodine number is a measure of total unsaturation with a
mixture of fatty acid. It is expressed in grams of iodine which
react with 100g of the respective sample when formally adding
iodine to the double bonds. High unsaturated degree will result in
polymerization during the combustion process, which will
produce sediment. For this reason, iodine number was limited to
120gI2/100g.
3.4 Cetane number
As indicator of ignition quality, the CN is a prime indicator
of fuel quality in the realm of diesel engines. Cetane number has
a great impact on the operation of diesel engines. Diesel
locomotives must have the appropriate CN, otherwise it will
cause accelerated wear of diesel engine. In this study, we defined
the oil content should be more than 49 according to the Chinese
BD100 standard.
3.5 CFPP
The major limitation of a biodiesel derived from raw
materials is its tendency to crystallize below a specific low
temperature, which can plug an engine filter. This so-called
“CFPP” is derived from the low-temperature flow properties and
the fatty acid composition. High saturated fatty acid levels yield
higher CFPP values. In this research, CFPP was limited to ć
3.6 Viscosity
Viscosity is an important indicator of internal fluid flow
properties and aerosol performance. Viscosity affects the
atomization of a fuel upon injection into the combustion chamber
and thereby ultimately the formation of engine deposits. The
higher the viscosity, the greater the tendency of the fuel to cause
such problems. In this study, we defined the viscosity between
1.9mm2/s and 6.0mm2/s.
4 Results and discussion
4.1 Physical and chemical characteristics of the crude oil
Table 2 presents the physical and chemical characteristics
of the crude oil. It showed that the oil content of eight kinds of
camellia oils had obvious difference, ranged from 29.7% to
47.1%, and the average oil content was 41.1%. The acid value of
rice tea was 4.71mgKOH/g, which was far higher than that of the
others. The iodine number of the crude oils was between 86 and
94.
4.2 The fatty acid compositions of the crude oils
Table 3 showed the fatty acid compositions of the crude

Table 2 Physical and chemical characteristics of the crude oils

Sample The oil content Acid value Iodine number density water and volatility
% mgKOH/g gI2/100g g/mL content %
1 29.7 1.46 86 0.910 0.0018
2 47.0 0.41 94 0.918 0.0025
3 42.6 0.48 82 0.915 0.0016
4 43.2 1.50 90 0.913 0.0030
5 44.5 4.71 89 0.909 0.0014
6 40.1 4.42 84 0.916 0.0022
7 34.5 0.78 88 0.914 0.0026
8 47.1 3.05 77 0.912 0.0028

oil. It showed that all kinds of camellia oils were composed of production. In addition, the oil content of the others could
five main fatty acids, including palmitic acid, stearic acid, meet the standard.
oleic acid, linoleic acid, gadoleic acid. Oleic acid was the The acid value is an important index for biodiesel
main fatty acid and the mean content was 81.9%. Fig 2 was production. High acid value can be easy to form
the gas chromatogram of the fatty acid compositions of saponification in the production process. From table 1, only
chicken heart camellia oil. the acid value of chicken heart camellia, algae skin tongzi
camellia, hybrid camellia could meet the standard (acid value
Table 3 Fatty acid compositions of the crude oils ”1mgKOH/g). The iodine number of all the camellia oils
Sample C16:0 C18:0 C18:1 C18:2 C20:1 could meet the standard.
a
RT/min 9.854 15.39 14.44 14.62 21.07 Based on the previous results, mono-unsaturated fatty acid
1 8.0 1.1 79.9 9.9 1.0
methyl esters such as methyl oleate was considered to be
2 8.8 1.9 78.7 10.1 0.3
3 7.0 2.1 84.7 5.7 0.4 better than poly-unsaturated ones such as methyl linoleated
4 8.1 1.8 82.4 7.2 0.4 and methyl linolenate for cetane number and iodine value
5 7.6 2.0 83.6 5.6 0.7 with any adverse effect on biodiesel CFPP. The predicted
6 7.6 1.8 81.8 8.2 0.5 biodiesel properties were represented in Table 4. The centane
7 9.1 2.4 80.6 6.8 0.6 number, CFPP, viscosity of the camellia oils could all meet
8 7.7 1.9 83.8 5.5 1.1 the standard, which may be due to the high concentration of
a
RT represents retention time of pure fatty acid methyl ester.
monounsaturated fatty acids (like oleic acid, C18:1) [6].

Table 4 Predicted biodiesel properties of camellia oils

Number Cetane number CFPP Viscosity
ć mm2/s
1 55.7 -12.2 3.32
2 55.9 -10.7 3.31
3 56.4 -11.0 3.48
4 56.3 -11.1 3.40
5 56.3 -10.9 3.47
6 56.0 -11.3 3.40
7 56.4 -9.8 3.41
Fig.2 The gas chromatogram of the fatty acid compositions of
chicken heart camellia oil 8 56.4 -11.1 3.58

4.3 Evaluation of the raw material for biodiesel 5 Conclusion

Table 2 showed that thick skin tongzi camellia was low in Chicken heart camellia, algae skin tongzi camellia, hybrid
oil content (29.7%) which could not meet the criterion. Thick camellia could meet all the preliminary screening standards. So
skin tongzi camellia is unsuitable as raw materials for biodiesel they are ideal raw materials for biodiesel production. We could

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provide abundant and sustainable raw materials by planting them
in a large scale. However, the other kinds of camellia oleosas
were not suitable as raw materials for biodiesel due to the low oil
content or high acid value.
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