Bioresource Technology: Junhua Zhang, Lifeng Jiang
Bioresource Technology: Junhua Zhang, Lifeng Jiang
Bioresource Technology: Junhua Zhang, Lifeng Jiang
Bioresource Technology
journal homepage: www.elsevier.com/locate/biortech
Short Communication
a r t i c l e
i n f o
Article history:
Received 26 February 2008
Received in revised form 1 May 2008
Accepted 2 May 2008
Available online 17 June 2008
Keywords:
Biodiesel
Zanthoxylum bungeanum seed oil
Free fatty acids
Acid esterication
a b s t r a c t
A technique to produce biodiesel from crude Zanthoxylum bungeanum seed oil (ZSO) with high free fatty
acids (FFA) was developed. The acid value of ZSO was reduced to 1.16 mg KOH/g from 45.51 mg KOH/g by
only one-step acid-catalyzed esterication with methanol-to-oil molar ratio 24:1, H2SO4 2%, temperature
60 C and reaction time 80 min, which was selected as optimum for the acid-catalyzed esterication.
During the acid-catalyzed esterication, FFA was converted into fatty acid methyl esters, which was
conrmed by 1H NMR spectrum. Compared with the other two-step pretreatment procedure, this onestep pretreatment can reduce the production cost of ZSO biodiesel. Alkaline-catalyzed transesterication
converted the pretreated ZSO into ZSO biodiesel. The yield of ZSO biodiesel was above 98% determined by
1
H NMR spectrum. This study supports the use of crude ZSO as a viable and valuable raw feedstock for
biodiesel production.
Crown Copyright 2008 Published by Elsevier Ltd. All rights reserved.
1. Introduction
At present, the high cost of biodiesel is the major obstacle to its
commercialization. Exploring ways to reduce the high cost of biodiesel is of much interest in recent biodiesel research. Approximately 7095% of biodiesel cost is attributed to raw feedstock
cost (Zhang et al., 2003b). So the use of cheap and non-edible vegetable oils, animal fats and waste oils as raw feedstocks for biodiesel production is an effective way to reduce the cost of biodiesel.
Zanthoxylum bungeanum seed oil (ZSO) is a potential cheap
feedstock for biodiesel production compared with rened and edible-grade vegetable oils, such as soybean oil, rapeseed oil and
sunower oil.
Z. bungeanum is widely used for its medicinal and avor characteristics. It is especially used as a spice in indigenous kitchens in
China. Z. bungeanum seed has an estimated annual production potential of one million metric tons in China and it contains 27%31%
oil. Unfortunately, ZSO contains about 25% free fatty acids (FFA)
therefore it is unsuitable for human consumption.
During alkaline-catalyzed transesterication, high content FFA
will react with alkali catalysts to produce soaps which will inhibit
the transesterication for biodiesel production. Furthermore, the
large amount of soap can gel and also prevent the separation of
the glycerol from the ester (Demirbas, 2003). Acid-catalyzed
transesterication, despite its insensitivity to FFA in the feedstock,
has been largely ignored mainly because of its relatively slower
* Corresponding author. Tel.: +86 01 3892883052; fax: +86 29 87082892.
E-mail address: zjhjerry@nwsuaf.edu.cn (J. Zhang).
0960-8524/$ - see front matter Crown Copyright 2008 Published by Elsevier Ltd. All rights reserved.
doi:10.1016/j.biortech.2008.05.004
8996
2. Methods
Table 2
Effect of H2SO4 on reduction the acid value of ZSO
2.1. Materials
ZSO was provided by a local company located in Hancheng, Shaanxi Province, China. This is a high yield area for Z. bungeanum
Maxin. Methanol, sulphuric acid, potassium hydroxide, anhydrous
sodium sulphate and other chemicals were of analytical reagent
grade.
The unrened ZSO used in this experiment was brown in color
with an initial acid value of 45.51 mg KOH/g. The fatty acid composition of ZSO in comparison with other oils is given in Table 1. ZSO
consists of 12.04% saturation comprising of palmitic and stearic
acids and 86.99% unsaturation comprising mainly of palmitoleic,
oleic, linoleic and linolenic acids. Saturation fatty acid methyl esters increase the cloud point, cetane number and improve stability
whereas more polyunsaturates reduce the cloud point, cetane
number and stability (Ramadhas et al., 2005). The effect of unsaturation levels on ZSO biodiesel properties especially needs to be
evaluated in the future.
2.2. Acid-catalyzed esterication of ZSO
The 80 g ZSO was poured into a round-bottomed ask equipped
with a reux condenser and heated to the reaction temperature.
The solution of H2SO4 (based on the oil weight of ZSO) in methanol
was also preheated and added to the ask. The mixture was stirred
at the same speed of 600 rpm for all test runs. After the reaction,
the mixture was allowed to settle in a separating funnel overnight
and the top methanolwater layer was removed. The methanol in
the lower layer was recovered under vacuum at 50 C with a rotational evaporator. Then, the lower layer was washed four times
using hot water (80 C) and dried with anhydrous sodium sulphate.
The variables affecting the acid-catalyzed esterication such as
methanol-to-oil molar ratio (4:140:1), catalyst amount (0.5
3.0 wt.% of oil), reaction time (20120 min) and temperature
(4065 C) were studied.
2.3. Alkali-catalyzed transesterication of ZSO
The 80 g pretreated ZSO was poured into a round-bottomed
ask equipped with a reux condenser and heated to 60 C.
0.9 wt.% of potassium hydroxide in methanol was heated to 60 C
and added to the reaction ask. The methanol-to-oil molar ratio
was 6.5:1. An additional amount of potassium hydroxide was
added to neutralize the residual FFA in the oil mixture. The mixture
reacted for 90 min at 60 C with a stirring speed of 600 rpm. After
the completion of the reaction, the product was allowed to settle
overnight in a separating funnel for separation of biodiesel. The
lower glycerol layer was drawn off. The excess of methanol in
the upper biodiesel layer was recovered under vacuum at 50 C
with a rotational evaporator. After that, the biodiesel layer was
washed and dried as described previously.
Molar ratio
Molar ratio
9:1
12:1
25:1
5.81
4.19
1.35
40:1
1.88
1.84
2.4. Analysis
The acid value was determined according to the national standard of China. 1H NMR analyses were performed on a Varian INOVA-400 MHz spectrometer using CDCl3 as the solvent.
3. Results and discussion
3.1. Effect of H2SO4 on reduction acid value of ZSO
The acid value of the ZSO after the rst and second pretreatment steps is shown in Table 2. The acid value of 5.81 mg KOH/g
was obtained with a methanol-to-oil molar ratio of 9:1, and the
acid value was reduced to 1.88 mg KOH/g after the second step
pretreatment with a 40:1 molar ratio of methanol based on the
FFA level. In the second step, the molecular weight of FFA was assumed to be 282.
When the molar ratio increased to 25:1 in the rst step, the acid
value was reduced to less than 2 mg KOH/g, which satises transesterication using an alkaline catalyst. These data meant that it
was possible to reduce the acid value of ZSO to the required level
by means of a one-step acid-catalyzed esterication. In order to develop an economical method to pretreat ZSO, the parameters
affecting the reduction of acid value of ZSO during one-step acidcatalyzed esterication were investigated.
3.2. Effect of parameters on reduction of acid value of ZSO
Effect of methanol-to-oil molar ratio, catalyst amount, temperature and reaction time on reduction of acid value of ZSO is shown
in Table 3. The acid values of ZSO after acid-catalyzed esterication
at six different molar ratios were investigated. With a 4:1 methanol-to-oil molar ratio, acid value could not go below 10 mg
KOH/g after 60 min of reaction time at 60 C. When the molar ratio
of methanol-to-oil was 24:1, acid value achieved to 1.16 mg KOH/
g. With further increase in the methanol-to-oil molar ratio there
was little improvement in the reduction of acid value of ZSO.
The effect of catalyst amount varied in the range of 0.53% for
six different values was investigated. The acid value of ZSO was reduced to less than 2 mg KOH/g at 13% of H2SO4, and the minimum
acid value was achieved to 1.16 mg KOH/g at 2% of H2SO4.
Temperature is one of the important variables for acid-catalyzed esterication because the rate of reaction if strongly inuenced by the reaction temperature. Table 3 showed that during
Table 1
Fatty acid composition of ZSO in comparison with the other oils (Li et al., 1994; Ma and Hanna, 1999)
Fatty acid
Formula
Structure
ZSO (%)
Palmitic acid
Palmitoleic acid
Stearic acid
Oleic acid
Linoleic acid
Linolenic acid
C16H32O2
C16H30O2
C18H36O2
C18H34O2
C18H32O2
C18H30O2
16:0
16:1
18:0
18:1
18:2
18:3
10.61
5.19
1.43
32.10
25.60
24.10
3.49
0.85
64.40
22.30
8.32
11.75
3.15
23.26
55.53
6.31
Others
0.64
0.97
8997
Temperature (C)
4
8
16
24
32
40
2.0
60
60
13.36
5.97
1.92
1.16
1.28
0.95
24
0.5
1.0
1.5
2.0
2.5
3.0
60
60
3.48
1.65
1.26
1.16
1.23
1.32
24
2.0
40
45
50
55
60
65
60
2.30
1.79
1.61
1.51
1.16
1.97
24
2.0
60
20
40
60
80
100
120
2.08
1.32
1.16
1.01
1.10
1.02
4. Conclusions
The acid value of ZSO with high FFA can be reduced to less than
2 mg KOH/g in only one-step pretreatment of esterication using
H2SO4 as catalyst. The combination of methanol-to-oil molar ratio
24:1, sulfuric acid 2%, temperature 60 C and reaction time 80 min,
which reduced the acid value from 45.51 to less than 2 mg KOH/g,
8998
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