REPEATED USE OF METHANOL AND SULFURIC ACID TO PRETREAT

JATROPHA OIL FOR BIODIESEL PRODUCTION

Zhongming Wang1,2, Chuangzhi Wu1, Zhenhong Yuan1 Jinsuk Lee 2, Soonchul Park2
1 GuangZhou Institute of Energy Conversion, CAS, Wushan, 2 Korea Institute of Energy Research,
Tianhe, Guangzhou, 510640, China 71-2, Jang-Dong, Yusong-gu, Daejeon, 305-343, Korea
wangzm@ms.giec.ac.cn bmjslee@kier.re.kr

ABSTRACT reliable feedstock for biodiesel production [1,2]. Jatropha

oil is high in acid; it has the tendency to degrade quickly,
Large-scale plantation of jatropha will provide low-cost and
particularly if not handled properly through the supply
reliable feedstock for biodiesel production, but jatropha oil
chain. The FFA level of jatropha oil can reach 5%
has the tendency to degrade so that it often contains
frequently; sometimes it can be as high as 14% [3]. Most of
excessive free fatty acid (FFA). In this study, an efficient
the commercial biodiesel producers use the
method was developed by repeated use of the mixture of
transesterification process catalyzed by alkaline [4]. In this
methanol and sulfuric acid for the pretreatment of jatropha
case, anhydrous conditions and low FFA level of feedstock
oil with an acid value of 10.4 mg KOH/g. A quadratic
are required in this process [5]. Pretreatment of jatropha oil
polynomial model was established by investigating the
with high acid value is necessary for commercial alkaline
effect of water content on the conversion of FFA, while the
catalyzed biodiesel production.
molar ratio of methanol to FFA was 270:1 and the weight
ratio of sulfuric acid to jatropha oil was 1.6%. This model
Sulfuric acid is a common and effective catalyst for the
was proved to be valid when the mixture of methanol and
pretreatment of feedstock having high FFA contents [6].
sulfuric acid had been used for twenty times. Total sulfuric
Tiwari et al [3] optimized the pretreatment of jatropha oil
acid and methanol used for these twenty experiments was
through a central composite rotatable design. The FFA in
0.21% and 21% respectively, based on the weight of
jatropha oil was reduced from 14% to less than 1% after
pretreated jatropha oil. Average reaction time of them was
88min reaction at 60ć, while methanol was 0.28 v/v and
26min; acid values of the pretreated jatropha oil were about
sulfuric acid was 1.43%v/v.
0.6 mg KOH/g, water contents of it were no more than
0.07%. Biodiesel with an ester content of 98.6% was
Most of the previous studies have focused on a single
produced through the following alkaline catalyzed biodiesel
pretreatment of feedstock with high FFA levels [3,7]. Our
production process.
study investigated the feasibility of repeated use of
methanol and sulfuric acid for the pretreatment of jatropha
oil with a FFA level about 5%. Through a series of
1. INTRODUCTION
experiments and theoretical calculations, a novel
pretreatment process had been developed.
Large-scale plantation of jatropha will provide low-cost and
2414 Proceedings of ISES Solar World Congress 2007: Solar Energy and Human Settlement
2. EXPERIMENTAL
2.1 Material
Jatropha oil was obtained from India, which acid value and
water content were 10.4mg KOH/g and 0.06% respectively.
1, 2, 4-Butanetriol and 1, 2, 3-tricaproylglycerol standards
for the analysis of mono-, di- and triglycerides were
purchased from Supel-Co (USA).
N-methyl-N-trimethylsilyltrifluoroacetamide & methyl
heptadecanoate were obtained from Sigma-Aldrich Co
(Switzerland). HPLC grade methanol, n-hexane and
2-propanol were obtained from J.T. Baker Co (USA). Other
chemicals were bought from Korean companies.
2.2 Pretreatment of Jatropha Oil
2.2.1 Effect of Sulfuric Acid
Effect of the amount of sulfuric acid on the conversion of
FFA in jatropha oil was studied by keeping the sulfuric acid
to be 0.2%, 0.4%, 0.6% and 0.8% based on the weight of
jatropha oil, while the molar ratio of methanol to FFA and
the temperature were maintained at 27:1 and 60 ć
respectively.
2.2.2 Effect of Water Content
To provide qualified pretreated jatropha oil within a short
reaction time for alkaline catalyzed transesterification
process, more sulfuric acid and excess methanol were
needed. Methanol with 1% sulfuric acid and 1%, 2%, 3%,
4% and 5% water content was prepared for these
experiments. Effect of water content on the conversion of
FFA was investigated by reacting methanol having different
water content with 20 g jatropha oil in a two-neck flask. The
molar ratio of methanol to FFA was 270:1 and sulfuric acid
was 1.6%(w/w), which was equal to 32g methanol with 1%
sulfuric acid. Samples were withdrawn at 10min intervals.
2.2.3 Statistical Analysis
The results of these experiments using excess methanol
with various water content were analyzed using SPSS
software (version12). Among the quadratic polynomial
equation obtained, acid value of jatropha oil was dependent
variable; water content and reaction time were independent
variables.
2.2.4 Repeated Use of the Sulfuric Acid and Methanol
10g jatropha oil was heated by hot plate to 60ć in a
100ml two –neck flask, then 16g methanol with 1% sulfuric
acid was introduced. After reaction, all the reactants were
transferred into a 50ml plastic bottle for centrifuging. The
centrifugation was performed for 7 min, at 6000×g and 25
ć.The mixture of methanol and sulfuric acid in the up
layer was separated for repeated use. Additional methanol
was added in the methanol phase to keep the weight at 16g,
therefore the molar ratio of methanol to FFA was 270.
To calculate the reaction time needed according the
quadratic polynomial equation obtained (E1), acid value of
pretreated jatropha oil was fixed at 0.6 mg KOH/g. Because
the water favor methanol phase, all the water produced
from jatropha oil (10g) will transfer into methanol phase
(16g). Therefore the increment of water content of
methanol phase for each repeated use is calculated as
following:
(10.4-0.6)/56.1/1000h10h18/16Ĭ0.20%
Then reaction time for each experiment was calculated
based on the water content (Table1) and specified acid
value (0.6mgKOH/g) according the quadratic polynomial
equation (E1). Two solutions were obtained and the small
one was a reasonable answer (Table 1).
Based on the preliminary experiments, 1.4g methanol with
1% sulfuric acid was adapted to compensate the loss of
both methanol and sulfuric acid before each repeated use of
the mixture.
2.3 Biodiesel Production from Pretreated Biodiesel
Pretreated jatropha oil was heated to 50ć by hot plate in a
100ml two-neck reactor, then the mixture of methanol and
KOH were added in the reactor. The molar ratio of
methanol to TG in jatropha oil was 6; KOH was 1.0%(w/w);
reaction time was 1h.
 7 BIOMASS 2415

TABLE 1: REACTION TIME FOR REPEATED USE OF sulfuric acid was significant when it was increased from
METHANOL AND SULFURIC ACID 0.2% to 0.4%, but the effect became negligible when it
Calculated Real reaction increased from 0.4% to 0.8%. Hence, the catalyst in the
Water reactants can be maintained at some level and much
reaction time
Content (%)
time (min) (min) more methanol was needed to improve the reaction
1 0.06 10.98 11 effectively.
2 0.26 12.58 13
3 0.46 14.174 14 11
4 0.66 15.75 16
10
5 0.86 17.33 17 cat.0.2%
9
6 1.06 18.89 19 cat.0.4%
8

acid value (mgKOH/g)

7 1.26 20.44 20
7 cat.0.6%
8 1.46 21.99 22
6
9 1.66 23.52 24 cat.0.8%
5
10 1.86 25.04 25
11 2.06 26.55 27 4

12 2.26 28.05 28 3

13 2.46 29.53 30 2
14 2.66 31.00 31 1
15 2.86 32.46 32 0
16 3.06 33.91 34 0 30 60 90 120
17 3.26 35.34 35 reaction time (min)
18 3.46 36.75 37
19 3.66 38.15 38 Fig. 1: Effect of amount of sulfuric acid on the acid values
20 3.86 39.53 40 when the molar ratio of methanol to FFA was 27.

2.4 Analysis Methods 3.1.2 Effect of Water Content

Acid value was determined according to KSTM-1051 using
KOH as titrant. Water content was measured by Karl Fisher
titrator.
The composition of the methyl esters was analyzed by HP
6890 gas chromatograph system equipped with
auto-injector. Free and total glycerol and mono-, di-,
triglycerides were determined by 6890N gas chromato-
graph equipped with on-column injector and FID.
The effect of water content in the mixture of excess
methanol and sulfuric acid on the conversion of FFA was
shown in Fig. 2. Even when water content of the mixture
was 5%, the acid value can be reduced to 1 mg KOH/g
within 50min. This result indicated that the mixture of
methanol and sulfuric acid could be used for pretreatment
of crude jatropha oil until the water content of it was
5.00%. The data cited in Fig.2 were analyzed by SPSS
package and a quadratic polynomial equation was
obtained as following:

3. RESULTS AND DISCUSSION z=1.319-0.079x+0.592y+0.001x2-0.12xy+0.26y2 (E1)

3.1 Pretreatment of Jatropha Oil Where z represents acid value (mg KOH/g); x represents
reaction time (min); y represents water content (%). R2
3.1.1 Effect of Sulfuric Acid =0.959, adjust R2 =0.951, F=112.586, P value=0.000. All
these values suggest a good fit of this model to the
experiments data.
As the results shown in Fig. 1, effect of the amount of
2416 Proceedings of ISES Solar World Congress 2007: Solar Energy and Human Settlement

4.00
0.70 0.08%
3.50
0.60 0.07%
3.00
acid value (mgKOH/g)

0.06%

acid value mgKOH/g

0.50

water content(w/w)
2.50 0.05%
0.40
2.00 0.04%
0.30
1.50 0.03%
0.20
1.00 0.02%
0.10 0.01%
0.50
0.00 0.00%
0.00

1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
10 20 30 40 50 60
reaction time (min) acid value water content

1.00% 2.00% 3.00% Fig. 3: Resulting acid values and water contents of
4.00% 5.00%
pretreated jatropha oil during 20 experiments.
Fig. 2: Effect of water content on the conversion of FFA.
The molar ratio of methanol to FFA is 270; reaction Hence the quadratic polynomial model was acceptable for
temperature is 60 ć. calculating the reaction time according the water content
under such reaction conditions. Total sulfuric acid and
3.1.3 Repeated Use of the Sulfuric Acid and Methanol methanol added during these twenty experiments were
calculated to be 0.21% and 21% respectively, based on the
total weight of treated jatropha oil. It was described as
Following reaction was recommended by previous study
following:
[8]:

CH 3OSO 3H+H 2O (16h1%+19h1.4h1%)/200=0.21%

CH 3OH+H 2SO 4
Theoretically, additional sulfuric acid should be added to
maintain the concentration of sulfuric acid at 1% before the
reuse of the mixture of methanol and sulfuric acid. The
concentrations of sulfuric acid after each reuse of the
mixture of methanol and sulfuric acid were analyzed by
titration and the results indicated that they had decreased
from 1.00% to 0.91%, and 0.014g sulfuric acid should be
added. It was calculated as following:
(16+19h1.4)h99%/200=21%
The average reaction time of these 20 pretreatments was
only 26min; particularly, the pretreated jatropha oil with
about 0.6mg KOH/g acid value and no more than 0.07%
water content was a qualified feedstock for subsequent
alkaline catalyzed transesterification process.
3.2 Alkaline Catalyzed Transesterification

16(1.00%-0. 91%)=0.014(g). Alkaline catalyzed biodiesel production from the pretreated

jatropha oil with such low acid value and water content was
very efficient. More than 99% triglyceride in the jatropha
Therefore 1.4g methanol with 1% sulfuric acid was added
oil was converted into FAME with 1h at 50ć, while the
to compensate the loss of both methanol and sulfuric acid
KOH was 1%(w/w) and molar ratio of methanol to TG was
before each repeated use. The acid values (Fig. 3) of
6. After washing and water removal, ester content of the
pretreated jatropha oil in 20 experiments conducted
jatropha biodiesel was 98.4%. Particularly, the sulfur
according Table 1 were around 0.6gKOH/g, coincident with
content of the jatropha biodiesel was measured to be 2 ppm,
the specified value for the calculation of reaction time
less than the limitation required by Korea biodiesel
according to the quadratic polynomial equation (E1).
 7 BIOMASS
specification (5 ppm). That indicates that the repeated use
of sulfuric acid as catalyst will not cause the increase of
sulfur content in the jatropha biodiesel.
4. CONCLUSIONS
The quadratic polynomial model established was proved to
be valid through a series of experiments and reaction time
for pretreatment can be calculated by this regression
quadratic equation.
The total sulfuric acid and methanol used for these 20
experiments was 0.21% and 21% respectively, based on the
weight of pretreated jatropha oil. Average reaction time of
these reactions was 26min, and the resulting acid values
and water contents of the pretreated jatropha oil were good
enough for alkaline catalyzed biodiesel production.
The results of these 20 batch experiments indicate that a
promising process can be developed by repeated use of the
mixture of methanol and sulfuric acid.
5. ACKNOWLEDGEMENT
The authors appreciate the financial support from Korea
New and Renewable Energy Center (KNREC) and Korean
Ministry of Commerce Industry and Energy (KMOCIE) for
this cooperative project between KIER and GIEC.
2417
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