SYNOPSIS

Name of College: Tatyasaheb Kore Institute of Engineering and Technology,

Warnanagar.

Name of Course: ME- Chemical Engineering.

Name of Student: Mr. PATIL ABHIJEET DILIP

Date of Registration: July 2011

Name of Guide: Dr. S.V. ANEKAR

Principal,

Tatyasaheb Kore Institute of Engineering and Technology,

Warnanagar. Dist: Kolhapur.

Proposed Title:

KINETIC STUDY OF TRANSESTRIFICATION OF THUMBA OIL FOR

BIODIESEL PRODUCTION USING HETROGENEOUS CATALYST.
Introduction:
Presently most of the world’s energy needs are provided through petrochemical
sources, coal and natural gas. All of these sources are finite and at current usage rates they will
become consumed in near future. Due to less availability of these sources & increasing prices of
these sources, lot of efforts have been started to find the different alternatives. One of the
substitutes is derivatives of vegetable oils that approximate the properties and performance of the
fuels like mineral diesel.
Transesterification is one of the successful processes to convert vegetable oils into
diesel like liquid biodiesel; chemically biodiesel is Fatty Acid alkyl Esters. . Biodiesel is mono-
alkyl esters of long chain fatty acids, which falls in the carbon range C12-C23. Biodiesel (fatty
acid alkyl esters) is an alternative fuel similar to diesel. It is obtained from the reaction of
vegetable oils or lipids or animal fats and alcohol with or without presence of a catalyst.
Biodiesel can be produced by means of various conventional methods like alkali catalyzed, acid
catalyzed and lipase catalyzed. The vegetable oil mainly contains triglycerides and free fatty
acids. It has similar flow and combustion properties compared to diesel but with low emission
behavior. It is very easy to handle safely because it is low in volatile compound content.
Triglycerides + 3R-OH 3 fatty acid alkyl ester + Glycerol

Transesterification is reversible process by which different triglycerides in oils react

with alcohol usually methanol or ethanol to produce fatty acids esters and glycerol in presence of
suitable catalysts at particular temperature.
Catalysts used:
Catalysts are important for many transesterification systems to accelerate reactions.
Usually acid catalysts and alkaline catalysts are required. There are different types of catalysts
available which are broadly classified as homogeneous (liquid) catalyst and heterogeneous
(solid) catalysts.
The main advantage of alkaline or basic of catalyst is high conversion under mild
conditions in comparatively short reaction times. Also proceed about 4000 times faster in the
presence of an alkaline catalyst than in the presence of the same amount of an acidic equivalent.
The catalysts like Sodium hydroxide (NaOH), Potassium hydroxide (KOH), Sodium meth oxide
and Potassium meth oxide are used as basic catalysts. Though these catalysts provides faster
reaction rate than heterogeneous catalyst, but it is costly to separate homogeneous catalyst from
reaction mixture.

Acid catalysis offers the advantage of esterifying free fatty acids contained in the fats
and oils and is therefore especially suited for the transesterification of highly acidic fatty
materials However; acid-catalyzed Transesterification are usually far slower than alkali
catalyzed reactions and require higher temperatures and pressures as well as higher amounts of
alcohol. The catalysts like Conc. Sulphuric acid [H2SO4] (Cheap, decomposition products,
corrosion) and Acidic ion exchange resins (High price, continuous reaction possible, low
stability) can be used as acid catalysts.

The catalysts like Alkali metal carbonates (Na 2CO3, NaHCO3K2CO3, and KHCO3),
Alkaline earth metal oxides (CaO, SrO, and BaO), Strong anion exchange resins (Amberlyst A
26, A 27), Transition metal salts of amino acids (Zn- and Cd-arginate) can be used as
heterogeneous catalysts.

In view of this heterogeneous catalyzed reactions are economically and

environmentally important field of research and development as Solid catalyst has many
advantages: they are corrosive, environmentally friendly and few disposal problems. Some of the
solid catalysts promote higher activity & selectivity & prolonged life.

To evaluate the potential use of solid catalyst for transesterification, knowledge of

the reaction mechanism and accurate kinetics is essential.

Relevance:

As mentioned above transesterification reaction is very important from the

industrial and commercial point of view. Fatty acid alkyl esters are important fine chemicals
used in manufacturing of cosmetics, perfumery agents, detergents, surfactants, fuel additives,
pharmaceutical products etc.

The overall transesterification process occurs in three steps. In the first step, from
triglycerides, diglycerides are obtained. In the second step, from diglycerides, mono glycerides
are obtained. In the last step from mono glycerides, glycerol is obtained as a byproduct. In each
of these steps fatty acid methyl ester is produced which is the constituent of biodiesel. The
optimistic alcohol to oil ratio is chosen and excess of alcohol is more preferable. Molar ratio of
4.5:1 or 6:1 is taken. The overall reaction can be summarized as follows

Triglycerides (TG) + CH3 OH = diglycerides + R1COOCH3

Diglycerides + CH3 OH = monoglycerides + R2COOCH3
Monoglycerides + CH3 OH = glycerin + R3COOCH3

R1 COO CH2 R1 COOCH 3 HO CH2

R2 COO CH + 3 CH 3OH R2 COOCH 3 + HO CH

R3 COO CH2 R3 COOCH 3 HO CH2

Triglyceride Methanol Methyl ester Glycerol

With R1, R2, R3 = hydrocarbon chain from 15 to 21 carbon atoms

The rate equation for the above reaction can be written as

-rA = - dCA / dt = k x CAα x CBβ
Where “A” means triglyceride, “B “means methanol and α, β represents the order with respect to
triglyceride and methanol respectively.
The raw material being exploited commercially for transesterification reaction are
edible fatty oils derived from rapeseed, soybean, palm, sunflower, coconut, linseed. Some of the
non edible oils derived from crops like Jatropha, karanja, mahua, cottonseed, polanga, and rice
brain oil can be used.
But still plenty of oil seed remain un utilized, Thumba (Citrullus Colocynthis) is an
unexploited perennial creeper growing wild in ho Indian arid zone. It has very good soil binding
capacity & has potential to yield one million tons of oil rich seeds in arid districts of Rajasthan.
Thumba (Citrullus Colocynthis) is non edible vegetable oil which can be a potential alternative
fuel. In india, it grows in rain fed parts of Gujarat & Rajasthan states. It has annular rough stems
& leaves which are 3 to 7 lobed, 5-10cm middle. The fatty acid composition of thumba oil is
given in the following table.
 Table 1: Fatty acid profile of Thumba oil
S. No. Fatty acids wt %
1. Palmitic (C16H34) 9.38
2. Stearic (C18H38) 27.34
3. Oleic (C18H36) 17.04
4. Linoleic (C18H34) 61.05
5. Behenic (C21H43) 4.05

Thumba oil biodiesel or thumba methyl ester (TME) can be produced through
transesterification using suitable catalyst like Amberlyst -15 or any solid catalyst at particular
temperature by varieties of technologies mentioned below-
1- Conventional mechanical stirring method
2- Ultrasound power (acoustic cavitation)
3- Super critical methanol processes
4- Hydrodynamic cavitation,
Hydrodynamic cavitation is also potential method at industrial scale due to scale up property but
has poor mixing efficiency. Thus using ultrasound problem of mixing could be overcome
because during the collapse of cavitational bubbles of alcohol supersonic jets are created
generating nano sized drops which are mixed & they enhance reaction surface. This method is
also simple, efficient, time saving, viable & gives higher yield. Conventional stirring method
also gives optimum yield but time consuming one.
The produced Thumba oil biodiesel has properties nearly comparable to mineral diesel which is
mentioned below-
Table 2: Physico-chemical properties mineral diesel & TME
Properties Specific Kinematic Cloud Pour Flash Fire Calorific
Gravity(at viscosity(cst) point point point oC point value(MJ/Kg)
150C) o
C o
C o
C
Diesel 0.8329 2.6 -5 -12 65.5 70.5 46.05
TME 0.88 5.2 -1 -8 187.5 195.5 39.79

Literature Review:
 Amit Pal et. al. [1]: studied transesterification of Thumba oil with methanol in molar
ratio of 1:4.5 in presence of NaOH as catalyst (1% by weight of oil) through Hydrodynamic
cavitation. In this experimentation, initially oil was heated up to 110 0C. The mixture of alcohol
and NaOH was mixed with this oil and finally entire mixture was charged to feed tank. During
the reaction the temperature of mixture was kept between 45 and 55 0C.The temperature of
mixture is controlled by circulation of cooling water in the jacket of the reactor. The reaction was
carried 45 minutes and the products were collected in bucket and the byproduct glycerin was
allowed to settle for 2-3hours as it was denser than methyl esters. The collected methyl ester was
further washed with water to remove impurities. He reported yield was 80% within first 30
minutes. Further the yield increases with increase in the number of orifice holes and afterwards it
remains more or less constant for all type of orifice plates.

Ghayal et. al. [2]: studied biodiesel production of used frying oil with methanol in
presence of KOH as catalyst. The set up was made in such manner that 10 liter reservoir was
connected to centrifugal pump in closed loop. In this experimentation, an approximate quantity
of oil with dissolved mixture of methanol and KOH was added to reservoir and was allowed to
circulate through closed loop of cavitating orifice and pressure was varied using valve in by pass
line section. During the reaction, the temperature of mixture was kept constant at 60 0C.The
temperature of mixture is controlled by circulation of cooling water in the jacket of the reactor.
The reaction was carried 60 minutes. Glycerol was allowed to separate by settling followed by
centrifugation and final samples were analyzed by HPLC. The reported conversion was 95%
within first 10 minutes because of large no of pulses of small magnitudes achieved during cavity
oscillation.
S.S.Kachhwaha & Amit Pal [3]: studied transesterification of non edible oil with
methanol in molar ratio of 1:4.5 in presence of KOH as catalyst.(0.5%). The transesterification
reactions were carried out in a horn type ultrasound reactor in which horn is attached with the
transducer which produces ultrasound irradiation in the mixture. Methyl alcohol and potassium
hydroxide are mixed and stirred till potassium hydroxide is dissolved in alcohol. The ultrasound
horn is dipped into the prepared liquid mixture. During the reaction the generation, subsequent
growth and collapse of bubble cavities result in very high irradiation densities. The temperature
of mixture is kept between 50-60 0C. They reported yield of 81 to 95%. Further they reported
that low frequency ultrasound method is efficient, time saving & economically functional.
Muhammad et. al. [4]:studied transesterification of waste cooking oil with methanol in
presence of KOH (1% by weight of oil). The setup consists of a closed loop circuit consisting of
a feed tank, centrifugal pump (2.2 kW), and the orifice plate. The transesterification reaction was
carried out with methanol to oil molar ratio of 3, 6, 9, and 12. KOH concentration of 1.5% (w/w)
of oil was used as an alkaline catalyst. The reaction was carried out at 60 0C and for different
reaction times. They observed rapid increase in the yield in the first 60 minutes and reported
biodiesel yield of around 65-75% within the first 60 min. The results indicated that the reaction
rate was higher at lower reaction times. At longer time, only gradual increase in yield was
observed, attributed to high concentration of methyl ester in the reaction vessel to promote
reverse reaction
Theerayut L., et.al. [5]: This paper reports the Transesterification of palm oil using
sodium hydroxide pallet. The governing set of second order rate equations characterizing the
stepwise reactions for Transesterification was presented. The reaction rate data presented in the
paper was an based on rate of homogeneous reaction. The mixing intensity ( Nre=2000) provides
sufficient mixing to avoid an effect of mass transfer in the transesterifcation reaction. The
reaction rate constants were reported for the reaction carried out at 600C with catalyst
concentration 1wt% of oil and methanol to oil ratio of 6:1.
Casio C.S., et.al. [6]: This paper reports the use of various metal oxides for
transesterifcation reaction of soybean oil. The use of catalyst like Al 2O3, (Al2O3 )4 (ZnO) and
(Al2O3 )4 (SnO) were studied. With Al2O3 catalyst the yield of FAME obtained was 80 % at 600C
after 4 hrs of reaction. Further authors observed that presence of other metal oxides like (ZnO)
and (SnO) with Al2O3 does not increase the yield of FAME significantly. The authors had
reported the yield of FAME by using different alkyl alcohols and (Al 2O3)4 (ZnO) catalyst for
transesterification of soybean oil under same operating conditions. The highest yield of 84.3%
was achieved with methanol.
Dae-Won Lee A, et.al. [7]: This paper classifies the solid base catalysts for
transesterification into the following six categories based on Hattori’s classification: single metal
oxides, mixed metal oxides, zeolites, supported alkali/alkaline earth metals, clay minerals
(hydrotalcites), and non-oxides (organic solid bases). This paper also gives the development in
the various heterogeneous catalysts used for transesterification of oil.

Vyas A.P., et.al. [8]: The author had reported the effect of molar ratio, catalyst
concentration and temperature on transesterification of jatropha oil under ultrasonic irradiation.
The author had also reported the reaction rate constant at different temperatures. The comparison
of ultrasound assisted transesterification reaction using different homogeneous catalyst and oil
were compared. transesterification of fish oil with ethanol using sodium ethoxide catalyst
showed the yield of 98.2%.
Proposed Work

It is proposed to carry out the transesterification reaction between Thumba oil and
methanol in presence of selected heterogeneous ion exchange resin catalyst such as Amberlyst
-15 catalysts in laboratory glass batch reactor fitted with reflux condenser as well as in a horn
type ultrasound cavitation reactor and to study its kinetics. The project is aimed to study the use
of solid heterogeneous ion exchange resin catalyst such as Amberlyst -15bfor transesterification
of thumba oil. The above procedure is followed for determining the optimum values methanol to
oil(molar ratio), temperature and catalyst required.

Objectives:
1] To carry out the transesterification reaction between Thumba oil and methanol in presence of
selected heterogeneous catalysts in laboratory glass batch reactor fitted with reflux condenser
and horn type ultrasound cavitation reactor and to compare result obtained
2] To study the effect of variables such as temperature, molar ratios of methanol to oil, catalyst
loading etc on the conversion of thumba oil
3] To study the kinetics of transesterification reaction in laboratory glass batch reactor
Experimental Setup:

1] Conventional Stirring method: The setup consists of glass batch reactor fitted with reflux
condenser and stirrer. The temperature can be controlled by using hot water bath or heating
mental. The Figure experimental set up is as shown below.. The above mentioned reaction will
be carried out in the reactor. The stirring will be kept constant. Under stirring condition, catalyst
will be dispersed in the oil. Then, the methanol will be added into the mixture and it will be
heated. Samples will be taken from the reaction mixture after 10 minute interval. The sample
will be washed by water to washout unreacted methanol. The sample will be kept for gravity
settling to separate FAME and glycerol. The top layer of FAME will be analyzed.

Agitator

Stand

2] Ultrasound horn type reactor:

The transesterification reactions after
optimizing for methanol,
temperature, & catalyst will be
carried out in a horn type ultrasound reactor in which horn is attached with the transducer which
produces ultrasound irradiation in the mixture. Because of this intense but local cavitation is
generated. The horn operates at a particular frequency of with rated power dissipation and time
limit is ranging between 3 min to 30 min. The transesterification reaction is carried out by
ultrasound irradiation from the acoustic rod horn incorporated with the transducer. Figure shows
the experimental set up below

Ultrasound horn type reactor

After completing the reaction, Samples will be taken from the reaction mixture. The sample will
be washed by water to washout unreacted methanol. The sample will be kept for gravity settling
to separate FAME and glycerol. The top layer of FAME will be analyzed.

Experimental Procedure:
1] Conventional Stirring method: The thumba oil is mixed with methanol and catalyst. The
reaction will be allowed to proceed for 60 minutes at a temperature 50 °C at constant agitation
speed, after which the contents of the flask will be poured into a separating funnel. The mixture is
separated into two layers. The top layer is analyzed for the concentration of FAME. The above
procedure is followed for determining the optimum methanol, temperature and catalyst required.

A sample is withdrawn from the reaction mixture after 10 minute interval and is then washed by
water to washout unreacted methanol. The sample is kept for gravity settling to separate FAME
and glycerol. The top layer of FAME is analyzed.

The experimental data thus obtained by above procedure is used to find the rate of reaction using
reaction mechanism. The graph of concentration of FAME against time will be plotted.

2] Ultrasound horn type reactor :After finding the optimum methanol to oil(molar ratio),
temperature and catalyst requirement by above method, same reaction will carried out by
ultrasound irradiation in ultrasound horn type reactor.

The sample will be washed by water to washout unreacted methanol. The sample will be kept for
gravity settling to separate FAME and glycerol. The top layer of FAME will be analyzed.

Finally the results obtained will be compared with Conventional Stirring method
Place of Work and Facilities Available:

It is proposed to carry out all the experimental work in the laboratories of Chemical
Engg. Department of P.V.P.I.T., Budhgaon, Sangli.. The following laboratory facilities are
available at the place of work such as- Experimental setup with required accessories, heating
device, temperature measuring instruments, flow rate measuring instruments, essential glassware
etc. Some of the experimental work is also proposed to carry in laboratories of Chemical Engg.
Department of T.K.I.E.T , Warananagar. The extended facilities for analysis are available at-

(1) University Science Instrumentation Centre, USIC (CFC), Shivaji University, Kolhapur,

(2) Nikhil Laboratories, Sangli.

(3)Indian Institute of Technology, Pawai, Mumbai.

Approximate Expenditure: Rs. 40000/-

References:

[1] Pal A, Verma A, Kachhaha S.S and Maji S, “Biodiesel production through hydrodynamic
cavitation and performance testing”, Renew Energ,35(3),(2010),pp 619-624.

[2] Dyneshwar Ghayal, Anniruddha.B.Pandit and Virendra K. Rathod, “Optimization of

biodiesel production in a hydrodynamic cavitation reactor using used frying oil”, Ultrasonic’s
Sonochemistry, 20, (2013),pp 322-328.

[3] Amit Pal and S.S.Kachhwaha, “Biodiesel production of non edible oils through ultrasound
energy”, Institute of Technology, Nirma University, Ahmadabad, (2011), 382481

[4] Muhammad Dani Supardan, Satriana,and Mahlinda, “Biodiesel production from waste
cooking oil using hydrodynamic cavitation”, Makara, Technology, vol. 16, no. 2, November
(2012), pp 157-162.

[5]Theerayut Leevijit, Worawut Wisutmethangoon, Gumpon Prateepchaikul, Charktir Tongurai

and Michael Allen., “A Second Order Kinetics of Palm Oil Transesterifcation”, The joint
International Conference on “ Sustainable Energy and Environment”, 2004.
[6] Caio C.S.Macedo, Frederique R. Abreu et. al., “New Heterogeneous Metal-Oxides Based
Catalyst for Vegetable Oil Trans-Esterification”, Journal of Braz. Chem. Soc., Vol17, No.7,
(2006),pp 1291-1296,
[7] Dae-Won Lee Æ Young-Moo Park Æ Kwan-Young Lee, “Heterogeneous Base Catalysts for
Transesterification in Biodiesel Synthesis,” Catalyst Surv Asia, 13: (2009),pp 63–77.
[8]. Amish P Vyas, Jaswant L. Verma, Nandula Subrahmanyam, “ Effects of Molar Ratio,
Alkali Catalyst Concentration and Temperature on Transesterification of Jatropha Oil with
Methanol under ultrasonic Irradiation”, Advances in Chemical Engineering and Science, 1,
(2011), pp 45-50.
[9] Ashish Karnwal, Naveen Kumar, M.M.Hasan, Rajeev Chaudhary, Arshad Noor Siddiquee
and Zahid A Khan, “Production of biodiesel from Thumba oil: optimization process parameters”,
Iranica journal Of Energy and Environment, 1(4), (2010),pp 352-358.
 [10] Shiv Lal, V.K.Gorana and N.L.Panwar, “A comparative study of Thumba seed biodiesel”,
Journal of Environmental Protection, 2, (2011), pp 454-459.

[11] Amit Pal and Surendra Kachhwaha, “Waste cooking oil: a promising feedstock for
biodiesel production through power ultrasound and hydrodynamic cavitation”, Journal of
Scientific and Industrial Research, Vol 72, (June 2013),pp 387-392

[12] Meher L C, Sagar D V and Naik S N, “Technical aspect of biodiesel production by

transesterification –A Review”, Renew Sustain Energy Rev, 10, (2010),pp 248-68.

[13] Eevera, T.K.Ranjendran and S.Saradha , “Biodiesel production process optimization and
characterization to assess the suitability of the product for varied environmental conditions”,
Renewable Ener,34(3),(2009),pp 762-765.

[14] Barnwal BK and Sharma MP, “Prospects of biodiesel production from vegetable oils in
India”, Renew Sustain Ener Rev, 9, (2005),pp 363-378.
[15] Sonntag NOV, “Composition and characteristics of individual fats and oils”. Bailey’s
industrial Oil and Fat Products, Vol.1, 4.(New York: John Wiley and Sons; pp,1979), 343.
[16] Biodiesel Production: “Technologies and European Providers”, Report T39-B6 06 July
2007.
A.D.Patil Prof. N.H. Shinde Dr. S.V. Anekar
Student HOD ,Chemical Dept Guide & Principal
T.K.I.E.T., Warananagar. T.K.I.E.T., Warananagar T.K.I.E.T., Warananagar

Date:
Place: T.K.I.E.T., Warananagar.