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Biodiesel production and

optimization from Calophyllum
inophyllum linn oil (honne oil) – A
three stage method
C Venkataramana Reddy

Bioresource Technology

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An empirical and st at ist ical analysis of biodiesel product ion by t ransest erificat ion process
Alagumalai Avinash

Callophyllum inophyllum linn (honne ) oil, a source for biodiesel product ion
SUPRIYA BOBADE

Honn oil
basant sharma
 Bioresource Technology 100 (2009) 5122–5125

Contents lists available at ScienceDirect

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

Biodiesel production and optimization from Calophyllum inophyllum

linn oil (honne oil) – A three stage method
B.K. Venkanna a,*, C. Venkataramana Reddy b
a
Department of Mechanical Engineering, Sri B.V.V.’s Basaveshwar Engineering College, Bagalkot 587 102, Karnataka, India
b
Al Habeeb College of Engineering and Technology, Damerigidda, R.R. District 501506, Andhra Pradesh, India

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

Article history: The present work examines the production of a biodiesel from a non-edible oil namely honne oil (Calo-
Received 28 March 2009 phyllum inophyllum linn). A three stage process viz., pre-treatment, alkali catalyzed transesterification
Received in revised form 8 May 2009 and post treatment adopted for the production is discussed. The reaction parameters such as methanol
Accepted 17 May 2009
to oil molar ratio, catalyst concentration, temperature and time have been optimized for the production
Available online 7 June 2009
of biodiesel. The yield of biodiesel from the honne oil under the optimized conditions is found to be 89%.
Ó 2009 Elsevier Ltd. All rights reserved.
Keywords:
Honne oil
Biodiesel
Acid
Alkali
Transesterification

1. Introduction ignition (diesel) engine. Transesterification produce ester from

The continuing rise in global prices of crude oil, increasing
threat to environment for exhaust emissions, global warming and
threat of supply instabilities have adversely impacted the develop-
ing countries, more so to the petroleum importing countries like
India. Fossil fuels especially petroleum diesel will continue to dom-
inate the transport sector and mechanized agriculture food pro-
duction system in the future, but their consumption can be
minimized by exploring alternative sources of energy. Vegetable
oils as an alternative fuel for diesel engine offers an advantage be-
cause of its comparable fuel properties with diesel fuel. The various
edible vegetable oils like sunflower oil, cotton seed oil and palm oil
have been tested successfully in the diesel engine. But as India still
imports huge quantities of edible oils, the use of edible oils for die-
sel engine fuel is not feasible. However, non-edible vegetable oil
species such as honge (Pongamia pinnata), jatropha (Jatropha cur-
cas), Mahua (Madhuca indica) and honne (Calophyllum inophyluum
linn) etc., could be used as alternative fuel for diesel engine. Vege-
table oil has a heating value comparable to that of diesel fuel but
its high viscosity and low volatility prohibit it to burn completely.
The alternate way to make use of vegetable oil possible in the
existing diesel engine is to esterify it to produce biodiesel. Biodie-
sel is defined as the mono alkyl esters of long chain fatty acids de-
rived from vegetable oils or animal fats for use in compression
* Corresponding author. Tel.: +91 9902005452.
E-mail address: swativenky@gmail.com (B.K. Venkanna).
vegetable oil. Transesterification is a process of producing a reac-
tion between a triglycerides and alcohol in the presence of a cata-
lyst to produce glycerol and ester (biodiesel). Transesterification
makes the viscosity lowered.
Biodiesel production normally incorporates use of conventional
catalysts like acids and alkali catalysts. Choice of acid and alkali
catalysts depends on the acid value (or free fatty acid (FFA) con-
tent) in the raw vegetable oil. Sharma and Singh (2008) used acid
esterification prior to alkali transesterification with karanja oil as
feedstock having FFA of 2.53% (5.06 mg KOH/g) using H2SO4.
According to Patil and Deng (2009), biodiesel production from high
FFA oil needs a two step transesterification process, i.e., acid ester-
ification followed by alkali transesterification to get high biodiesel
yield. There is a chance of having small quantities of un-reacted oil
and glycerol in biodiesel produced from transesterification process.
This may cause problem when it is used in the diesel engine. Many
researchers have investigated the production of biodiesel from
honge oil (Raheman and Phadatare, 2004; Sinha et al., 2007; Shar-
ma and Singh, 2008), jatropha oil (Ramesh and Sampathrajan,
2008) and mahua oil (Puhan et al., 2005).
Honne is found extensively in the Philippines along its sea-
shores. It is native to Tropical Asia and its geographical distribution
area also includes Melanesia and Polynesia. It grows near the sea
coast throughout India also. Its seeds sprout easily in muddy and
saline soils. The tree is 20–30 m high, and has a thick trunk covered
with a rough, black and cracked bark. It has elliptical, shiny and
tough leaves. Its flowers, arranged in auxiliary cymes, have a sweet,

0960-8524/$ - see front matter Ó 2009 Elsevier Ltd. All rights reserved.
doi:10.1016/j.biortech.2009.05.023
 B.K. Venkanna, C. Venkataramana Reddy / Bioresource Technology 100 (2009) 5122–5125
lime-like fragrance. The numerous fruits, arranged in clusters, are
spherical drupes. Once ripe, their smooth, yellow epidermis dis-
closes a thin layer of pulp, which tastes somewhat like apple.
The grey, ligneous and rather soft nut contains a pale yellow ker-
nel, which is odourless when fresh. Once chewed, it coats the
mouth and emulsifies saliva, and its insipid taste becomes bitter.
Kernels have very high oil content (75%). It is obtained by cold
expression and yields refined, greenish yellow oil, similar to olive
oil, with an aromatic odour and an insipid taste. Once grown, a tree
produces up to 100 kg of fruits and about 18 kg of oil.
Very little information is available about the production and
optimization of biodiesel from honne oil. The method to remove
un-reacted oil and glycerol present in the biodiesel is not reported
in the literature.
In the present work, honne oil has been used as feed stock for
the production of biodiesel by three stage method viz., pre-treat-
ment, alkali catalyzed transesterification and post treatment (to re-
move un-reacted oil and glycerol). The reaction conditions have
been investigated to optimize the yield of biodiesel from honne
oil. Yield is defined as the weight of the final product (wb) (transe-
sterified, washed and purified biodiesel) to the initial weight of oil
(moisture free) (woil).
2. Methods
The quality of oil is expressed in terms of the fuel properties
such as viscosity, density, flash point, FFA, acid value, iodine value
and saponification value. Density, kinematic viscosity and flash
point of honne oil were determined as per the methods approved
by Bureau of Indian Standards. Determination of density (IS:
1448 [P:16]), kinematic viscosity (IS: 1448 [P:25]) and flash point
(IS: 1448 [P:69]) are carried out using hydrometer, Redwood vis-
cometer No. 1 and Cleveland open cup apparatus, respectively.
The acid value, saponification value and iodine value were deter-
mined by titrimetry (Sadasivam and Manickam, 2004). Methanol,
potassium hydroxide and H2SO4 were purchased from local shop
namely, Ravi Scientific Instruments Company, Hubli and honne
oil purchased from Vasavi oils, Bagalkot. All the chemicals used
were of analytical reagent quality.
The apparatus used for transesterification consisted of an oil
bath, a 500 ml three necked round bottom flask equipped with dig-
ital controlled mechanical stirrer, a platinum RTD temperature
sensor with an accuracy of ±1 °C connected to a digital indicator
and a condenser. A separating funnel with a valve at the bottom
was used for collection of the final product. Honne oil was heated
to 110 °C for 30 min to remove moisture and was allowed to cool in
desiccator. Hundred grams of moisture free honne oil was used for
each trial.
The effect of the variables such as catalyst concentration (0.75–
1.5% (weight of KOH (w)/weight of moisture free honne oil (woil))
in steps of 0.25%), methanol to oil molar ratio (4:1, 6:1, 8:1 and
10:1), reaction temperature (45, 55, 60 and 65 °C), reaction time
(30, 60, 90, 120 and 150 min) on the biodiesel yield was studied.
The speed of the stirrer was kept constant at 700 rpm for all test
runs.
2.1. Stage 1: Pre-treatment process (acid esterification)
High FFA honne oil was converted to triglycerides in a pre-treat-
ment process with methanol using anhydrous H2SO4 (acid cata-
lyst). The variables affecting acid esterification such as methanol
to honne oil molar ratio and acid catalyst concentration were stud-
ied to get the maximum conversion efficiency of FFA to triglycer-
ides. The reaction was conducted at 60 ± 1 °C for 120 min. When
the first stage of the acid esterification was complete, the product
5123
was transferred to a separating funnel, where the excess methanol
along with impurities moved to the top layer and was removed.
The bottom layer was used for the alkali transesterification.
2.2. Stage 2: Alkali catalyzed transesterification process
The bottom layer product of acid esterification was heated to
the desired temperature before starting the reaction. The potas-
sium hydroxide–methanol solution was prepared. The alkali meth-
oxide solution was added to preheated product of the acid
esterification while mixing by means of a mechanical stirrer fixed
into the transesterification flask. The product was allowed to settle
under gravity for 8 h in a separating funnel. The products of the al-
kali transesterification process result in the formation of two layers
viz., an upper layer containing a mixture of small quantities of un-
reacted oil, glycerol and transesterified products (esters) and a
lower layer of glycerol. The lower layer of glycerol was removed.
2.3. Stage 3: Post treatment process
The upper layer of alkali transesterification product was mixed
with petroleum ether. The esters and un-reacted oil readily mixed
into the petroleum ether with glycerol as a separate layer. The low-
er layer of glycerol was removed. The upper layer was a mixture of
esters and un-reacted oil. These two were separated by diluting the
mixture with fresh and sufficient quantity of methanol. The esters
went into the methanol and un-reacted oil remained as a separate
layer. The lower layer of un-reacted oil was removed. The upper
layer was heated to 65 °C to remove methanol. The product was
a honne oil methyl ester (HOME) i.e. biodiesel.
The HOME was mixed gently with distilled water (30% (volume
of distilled water to volume of biodiesel)) at 60 °C in order to re-
move impurities like catalysts. The mixture was allowed to settle
under gravity for 8 h. The settled layer of mixture with impurities
was drained out. Water wash was repeated till the pH of drained
water was nearly same as that of distilled water before water
wash. After washing, the final product was again heated to
110 °C for 10 min to remove moisture.
3. Results and discussion
3.1. Oil properties and characteristics
Table 1 gives properties of honne oil in comparison with diesel
fuel and other vegetable oils. The density of honne oil is higher
than that of diesel fuel. The kinematic viscosity of honne oil is
10.4 times more than that of diesel fuel determined at 40 °C. The
flash point of honne oil is better than diesel fuel for the engine
application. The acid value of honne oil was found to be 4.76 mg
KOH/g and therefore its FFA content is 2.38%. Honne oil is rich in
Oleic acid. The compositions of oil are C16:0; 14.8–18.5%, C18:0;
6.1–19.2%, C18:1; 36.2–53.1, C18:2; 15.8–28.5% and C22:1; 3.3%
(Anonymous a).
3.2. Moisture and free fatty acid
The free fatty acid and moisture content are important param-
eters for determining the viability of the vegetable oil transesteri-
fication process (Meher et al., 2006a). In the present study, honne
oil was heated to 110 °C for 30 min in order to remove moisture
and ensured that the honne oil used for transesterification process
was free from moisture. The acid esterification with 0.5 ml anhy-
drous H2SO4 at 60 ± 1 °C for 120 min at 4:1 (methanol to honne
oil) molar ratio gave the maximum conversion efficiency of FFA
to triglycerides. The acid value of honne oil was reduced from
5124 B.K. Venkanna, C. Venkataramana Reddy / Bioresource Technology 100 (2009) 5122–5125

Table 1
Properties of honne oil in comparison with diesel and other vegetable oils.

Properties Diesel fuel Honne oil Rice bran oila Turkish raisin oilb Karanja oilc Jatropha oilc Rubber seed oild Biodiesel standarde
ASTM D 6751 – 08
Method Limit
Density, kg/m3 830.0 910.0 922.0 919.2 909.0 913.6 910.0
K.V. at 400 °C cSt 3.12 32.48 43.52 69.4 at 20 °C 41.8 40.4 76.4 D 445 1.9–6.0
Flash point, °C 56 224 316 232 240 198 D 93 93 min
Saponification value – 191–202 – 195.2 185.5 195 206
Iodine value – 82–98 108 123.4 89 101.7 135.3
Acid value mg KOH/g – 4.76 – 0.4 1.52 3.52 53 D 664 0.50 max
a
Venkataramana (2003).
b
Aksoy et al. (1990).
c
Kalbande and Vikhe (2008).
d
Ramadhas et al. (2005).
e
Anonymous b.

4.76 to 1.64 mg KOH/g during acid esterification reaction. The acid
value of 1.64 mg KOH/g is within the acceptable limit for alkali cat-
alyzed transesterification.
3.3. Effect of methanol to oil molar ratio
The methanol to oil molar ratio is one of the most important
variables affecting the ester yields. In the present work, the meth-
anol to oil molar ratio was varied from 4:1 to 10:1. Fig. 1 shows the
effect of methanol to oil molar ratio on yield of biodiesel at differ-
ent catalytic concentrations. It was observed that the yield of bio-
diesel increased with increase in molar ratio. This result is
comparable to the reported values (Meher et al., 2006b; Patil and
Deng, 2009; Sinha et al., 2007). At higher molar ratio, more triglyc-
eride would have reacted. However, an excess of methanol inter-
feres with separation of glycerine because there is an increase in
solubility. When glycerine remains in solution, it helps drive the
equilibrium back to the reverse direction, lowering the yield of es-
ters (Murugesan et al., 2008). A molar ratio of 13:1 and above re-
sulted in three layers in the separating funnel viz., bottom layer
of glycerine, middle layer of esters and top layer of un-reacted
methanol. The percentage increase in biodiesel yield decreased
with increase in the molar ratio. This is in accordance with the re-
sult of Sinha et al. (2007). The molar ratio of 8:1 gave the maxi-
mum yield of 89%.
3.4. Effect of catalyst concentration
Transesterification of honne oil was carried out with KOH as a
catalyst at a concentration of 0.75–1.5% (w/woil) in steps of 0.25%.
Third wash, water at 600C
0
Reaction time 2 h
90 Reaction temperature 60±1 C
Fig. 2 shows the yield of biodiesel versus KOH concentration at dif-
ferent methanol to oil molar ratios. The lower catalytic concentra-
tion i.e., 0.75–1.00% of KOH was insignificant to catalyze the
reaction to completion. It was found that the biodiesel yield
increased as the amount of catalyst concentration increased from
1.0% to 1.25% for the entire molar ratios under study. With the
increase in the concentration of catalyst i.e., beyond 1.25% KOH,
there was decrease in the yield of biodiesel. This is in accordance
with the result obtained by Meher et al. (2006b). The decrease in
the yield of biodiesel may be due to formation of emulsion,
increasing viscosity and leading to the gelation. The KOH concen-
tration of 1.25% gave the maximum yield of 89%.
3.5. Effect of reaction temperature
Catalytic transesterification of vegetable oil is normally investi-
gated close to the boiling point of the methanol (Antolin et al.,
2002; Kalbande and Vikhe, 2008; Sinha et al., 2007). Experiments
were carried out at different temperatures such as 45, 55, 60 and
65 °C with 1.25% (w/woil) KOH as catalyst and molar ratio of 4:1–
10:1 for a reaction time of 120 min. The yield of biodiesel versus
reaction temperature at different methanol to oil molar ratio is
shown in Fig. 3. It was observed that temperature had positive ef-
fect on transesterification of honne oil for 55, 60 and 65 °C while
for 45 °C no significant effect was seen. Similar results have been
reported by earlier researchers for other vegetable oils (Srivastava
and Prasad, 2000; Sinha et al., 2007). The biodiesel yield follows an
increasing trend with increase in reaction temperature up to
60 ± 1 °C. This may be attributed to the fact that higher reaction
temperature helps in faster settlement of glycerol. The biodiesel
yield decreased beyond a reaction temperature of 60 ± 1 °C. The
reason may be due to saponfication of the triglycerides before
the completion of transesterification (Meher et al., 2006b; Patil
and Deng, 2009; Sinha et al., 2007).

90
Bio-Diesel Yield % (wb /woil)

Reaction temperature 60±10C

KOH 0.75%
Third wash, water at 600C
Bio-Diesel Yield % (w b /woil)

80 KOH 1.0%
Reaction time 2 h
KOH 1.25% 80
KOH 1.5%

70 Molar ratio 4:1

70
Molar Ratio 6:1
Molar Ratio 8:1
Molar Ratio 10:1
60
60
4:01 6:01 8:01 10:01 0.75 1 1.25 1.5
Molar Ratio (Methanolto Oil) KOH Concentatrion % (w/woil)

Fig. 1. Effect of molar ratio (methanol to oil) on biodiesel yield at different KOH Fig. 2. Effect of KOH concentration on biodiesel yield for different molar ratio
concentration keeping other process parameters constant. (methanol to oil) keeping other process parameters constant.
 B.K. Venkanna, C. Venkataramana Reddy / Bioresource Technology 100 (2009) 5122–5125 5125

90 1.64 mg KOH/g during acid esterification reaction. The combina-

tion giving optimum reaction conditions for alkali transesterifica-
Bio-Diesel Yield % (wb/woil)

tion of honne oil was found to be 8:1 M ratio of methanol to oil,

1.25% KOH (w/woil), 60 ± 1 °C reaction temperature and 120 min
Molar Ratio 4:1 reaction time, followed by thrice gentle washing of the biodiesel
Molar Ratio 6:1 with distilled water (30% v/v) of 60 °C. The biodiesel obtained by
80
Molar Ratio 8:1 means of this process (there is no un-reacted oil and glycerol) is
Molar Ratio 10:1 suitable for use in direct injection diesel engines.

1.25% KOH Concentration Acknowledgements

Reaction time 2 h Third wash, water at 600C
70 The equipments used for this work have been procured under
55 60 65 Technical Education Quality Improvement Program (TEQIP) fund
Reaction temperature (0C) of World Bank Assisted Program. TEQIP and the Management of
Sri B.V.V. Sangha, Bagalkot 587 101, Karnataka, India are gratefully
Fig. 3. Effect of reaction temperature on biodiesel yield for different molar ratio
acknowledged. Our special thanks are due to the Principal, Sri.
(methanol to oil) keeping other process parameters constant.
B.V.V.’S. Basaveshwar Engineering College and H.O.D., Mechanical
Engineering for their continuous encouragement and support.
Molar Ratio 8:1 Third wash, water at 600C Our special thanks are also due to Dr. P.B. Gangavati, Professor,
department of Mechanical Engineering for his suggestions and
Reaction temperature time 60± 10C
90 editing the paper.
Bio-Diesel Yield % (wb/w oil)

80
70
60
90
Reaction time (minutes)
Fig. 4. Effect of reaction time on biodiesel yield at different KOH concentration
keeping other process parameters constant.
3.6. Effect of reaction time
Studies were carried out at different reaction time such as 30,
60, 90, 120 and 150 min. The yield of biodiesel versus reaction time
at different KOH catalyst and methanol to oil molar ratio of 8:1 for
a reaction temperature of 60 ± 1 °C is shown in Fig. 4. It was ob-
served that biodiesel yield increased with increase in reaction time
from 90 to 120 min for all the catalyst concentrations of the study.
As the reaction time was increased beyond 120 min, the biodiesel
yield decreased. However, for reaction time of 30 and 60 min, the
biodiesel yield was insignificant, hence not considered. Optimum
reaction time in order to get maximum biodiesel yield was found
to be 120 min.
4. Conclusions
The cultivation of honne plant can be considered as a potential
alternative for renewable energy sources. Honne oil could be
transesterified. A three stage transesterification process has been
studied which comprised of acid esterification, alkali transesterifi-
cation and post treatment. The acid esterification with 0.5 ml
anhydrous H2SO4 at 60 ± 1 °C for 120 min at 4:1 (methanol to oil)
molar ratio gave the maximum conversion efficiency of FFA to tri-
glycerides. The acid value of honne oil was reduced from 4.76 to
KOH 0.75%
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