Bioresource Technology 99 (2008) 89958998

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

Short Communication

Acid-catalyzed esterication of Zanthoxylum bungeanum seed oil with high free

fatty acids for biodiesel production
Junhua Zhang *, Lifeng Jiang
College of Forestry, Northwest A&F University, Taicheng Road 3, Yangling, Shaanxi Province 712100, China

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).

reaction rate (Zhang et al., 2003a). Therefore a process combining

pretreatment with alkaline-catalyzed transesterication for feedstocks having high FFA content was investigated by many authors
(Canakci and Van Gerpen, 2001; Ramadhas et al., 2005; Veljkovic et
al., 2006; Berchmans and Hirata, 2008).
Generally, when the FFA level is less than 2 mg KOH/g corresponding to a free fatty acid content of 1%, the FFA can be ignored.
Alkaline rening, acid-catalyzed esterication, distillation, solvent
extraction and membrane separation can be used for the reduction
of FFA of vegetable oils (He, 2005). Also acid-catalyzed esterication of high FFA content vegetable oils is a typical method of biodiesel production due to high reaction speed and high yield
(Canakci and Van Gerpen, 1999). Some raw feedstocks with high
FFA such as yellow and brown grease (Canakci and Van Gerpen,
2001), rubber seed oil (Ramadhas et al., 2005), mahua oil (Ghadge
and Raheman, 2005, 2006), tobacco seed oil (Veljkovic et al., 2006),
waste cooking oil (Wang et al., 2007) and jatropha oil (Tiwari et al.,
2007) have been used to produce biodiesel with acid-catalyzed
esterication followed by transesterication using alkaline
catalyst.
The present work was undertaken to investigate the pretreatment process for reducing the FFA content of ZSO to less than 1%
for ZSO biodiesel production. This paper focuses on the reaction
parameters that affect the conversion of FFA in crude ZSO by
means of acid-catalyzed esterication with methanol. The main
goal was to develop an approach that would enable us to understand the relationships between the variables and the acid value
after pretreatment, and discuss the potential of ZSO as a raw feedstock for biodiesel production.

0960-8524/$ - see front matter Crown Copyright 2008 Published by Elsevier Ltd. All rights reserved.
doi:10.1016/j.biortech.2008.05.004

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J. Zhang, L. Jiang / Bioresource Technology 99 (2008) 89958998

2. Methods

Table 2
Effect of H2SO4 on reduction the acid value of ZSO

2.1. Materials

The rst step

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.

The second step

Molar ratio

Acid value (mg KOH/g)

Molar ratio

Acid value (mg KOH/g)

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 (%)

Rapeseed oil (%)

Soybean oil (%)

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

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J. Zhang, L. Jiang / Bioresource Technology 99 (2008) 89958998

Table 3
Effect of methanol-to-oil molar ratio, catalyst amount, temperature and reaction time on reduction of acid value of ZSO (speed of stirring 600 rpm)
Methanol-to-oil molar ratio

Catalyst amount (%)

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

the course of acid-catalyzed esterication, the acid value of ZSO

continued to decrease from 40 C to 60 C. With further increases
in temperature there was no reduction in the acid value and the
optimum temperature was xed at 60 C.
FFA in ZSO easily reacted with methanol in the rst 20 min and
the acid value of ZSO decreased from 45.51 to 2.30 mg KOH/g. The
rate of esterication slowed from 20 to 80 min. It was also observed that increasing reaction time beyond 80 min did not have
much effect on reducing the acid value.
3.3. Monitoring esterication and transesterication by 1H NMR
In the 1H NMR spectra of fatty acid and their derivatives, signals
at approximately 3.7 ppm and 2.3 ppm are related to protons of
methyl ester and a-carbonyl methylene, and signals at 4.1
4.4 ppm are assigned to glyceridic protons (Gelbard et al., 1995).
The 1H NMR spectra of pure ZSO, pretreated ZSO and ZSO biodiesel
were obtained (data not shown). There was no methyl ester-related signal (at about 3.7 ppm) observed in the spectrum of pure
ZSO extracted from Z. bungeanum seed by petroleum ether (b.p.
6090 C). In the spectrum of pretreated ZSO, signals at 3.66 ppm
were assigned to the protons of the methyl ester, which supported
that FFA in ZSO could be transformed into methyl ester during the
pretreatment. No visible glyceryl-related signals in the 1H NMR
spectrum of ZSO biodiesel were found at 4.14.4 ppm indicating
its high conversion into methyl esters, as can be noticed in the
spectrum at 3.66 ppm. The conversion of transesterication was
above 98% as calculated from the integration values of the glyceridic and methyl ester protons in 1H NMR by Knothe (2000).

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,

Reaction time (min)

Acid value (mg KOH/g)

was selected as optimum for the acid-catalyzed esterication. The

pretreated ZSO was used for alkali-catalyzed transesterication,
and such process gave an yield of above 98% ZSO biodiesel. This
one-step pretreatment reduced the production cost of the ZSO biodiesel. However, further research on transesterication and fuel
properties of the ZSO is also necessary.
Acknowledgement
This work was supported by school fund of Northwest A&F University (01140403).
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