ESTERIFICATION OF USED MADUCA OIL USING

THEHETEROGENEOUS
MgO / ZrO2 CATALYST FOR PRODUCTION OF BIODIESEL

Presentedby,
S.THULASIRAM

OUT LINE OF THE PRESENTATION

WHY BIOFUEL ? WHY NOW ?

WHAT ARE BIOFUELS ?
21ST CENTURY: THE BEGINNING OF A NEW ERA
CURRENT ROUTE
NEW STRATERGY
GOALS OF THE STUDY
OBJECTIVE
SCHEMATIC DIAGRAM OF A SMALL BIODIESEL REACTOR
LITERATURE REVIEW
INTRODUCTION
MECHANISM OF TRANSESTERIFICATION REACTION
HOW IS IT PRODUCED

Continued.

OUT LINE OF THE PRESENTATION

REASON FOR BIOFUELS PROMOTION

PHOTOGRAPH OF MAHUA TREE & FLOWER
FLOW CHART FOR BIODIESEL
EXPERIMENTAL FLOW CHART FOR BIODIESEL PRODUCTION
HETEROGENEOUS CATALYTIC APPROACH
HETEROGENEOUS CATALYTIC APPROACH
FACTORS INFLUENCING PRODUCTION OF BIODIESEL
TRANSESTERIFICATION
CONCLUSION
SCOPE FOR FUTURE WORK
REFERENCES

WHY BIOFUEL ? WHY NOW ?

WHAT ARE BIOFUELS ?

Biofuels are fossil fuel substitutes that can be made from a range of
agricultural crops and other sources of biomass. The two most common
current Biofuels are ethanol and biodiesel.

Biofuel: Liquid and gaseous fuels produced

from biomass organic matter derived from
plants or animals. (IEA)

Easy availability from biomass sources

Biodegradability
Sustainability
Foreign exchange savings
Energy security
Open up a new income generating path
in rural areas etc.

21ST CENTURY: THE BEGINNING OF A NEW ERA

%

Challenge: TO DIVERSIFY ENERGY SOURCES

Up to 2030, the world demand for energy should increase 58%.
Sources: Nakcenovic, Grbler and MaConald, 1998 and US Energy Information Administration

1.One of the main bottlenecks in manufacturing of liquid

biofuels are their synthesis routes, which relies on the use of
many hazardous and corrosive chemicals such as NaOH,
KOH, H2SO4 as catalysts.
2.This not only causes environmental hazards but also adds
to the carbon footprint and effects the overall economy of
the process.
3.Use of renewables as catalysts or catalysts synthesized
from renewabale precursors such as boimass and waste may
address these issues.

CURRENT ROUTE
Feedstocks
(Renewabal
e Suorces)

Major
Liquid
Biofuels
(Biodiesel,
Bioalcohol
s etc.)

Catalysts/
Reagents
used for
synthesis(Non
-renewabale
Sources

NEW STRATERGY
Feedstocks
(Renewabal
e Suorces)

Major
Liquid
Biofuels
(Biodiesel,
Bioalcohol
s etc.)

Catalysts
synthesized
from
renewabale
Sources

GOALS OF THE STUDY

Our goal is to obtain a renewable multipurpose heterogeneous catalyst that

is faster, active, versatile, and stable under the process conditions capable
of competeing with commercialy employed catalysts in the production of
major biofuels such as biodiesel and bioalchols with greater emphasis on
transesterification.

It will be capable of substituting corrosive chemicals such as H 2SO4,

NaOH, KOH etc in various other reactions, there by eliminating the
problems associated with their use and consequent environmental hazards.

Our proposed catalysts will make biofuel production environmentally

benign and greener as it will be reusable and derived from renewable/waste
materials.

OBJECTIVES
Production of neat Crude Mahua Oil via base
catalyzed transesterification process.
Characterization of fuel properties for neat Mahua oil
and comparison with diesel.
To optimize the reaction conditions for enzymatic
method
To study ethanol production using waste glycerol.

SCHEMATIC DIAGRAM OF A SMALL

BIODIESEL REACTOR

LITERATURE REVIEW
Sl.No.

Author Name
Young-Moo
Park, JoonYeob
Lee

Boyse, R.A., Ko,

E.I.,

Canakci, M.,
Van Gerpen, J

Canakci, M.,
Van Gerpen, J

Year
Published

Title

Vol.No. & Journal No.

Publications

2010

Esterification of used
madhuca oils using the
heterogeneous
WO3/ZrO2 catalystfor
production of biodiesel

101, S59S61

Journal of
Catalysis

1997

Crystallization
behavior of tungstate
on zirconia and its
relationship to acidic
properties

171, 191207

Journal of
Catalysis

2003

A pilot plant to
produce biodiesel from
high free fatty acid
feed stocks

46, 945954

Transactions of
the American
Society of
Agricultural
Engineers

2001

Biodiesel production
from oils and fats with
high free fatty acids

1.

Engineers44, 1429
1436.

Transactions of
the American
Society of
Agricultural
Engineers

Dorado, M.P.,
Ballesteros, E

Ghadge, S.V.,
Raheman, H

Iglesia, E.,
Soled, S.L.,
Kramer, G.M

Kim, H.J., Kang,

B.S., Kim, M.J

2002

. An alkali-catalyzed
transesterification
process for high free
fatty acid waste oils

45,525529

Transactions of
the American
Society of
Agricultural
Engineers

2005

Biodiesel production
from mahua (Madhuca
indica)oil having high
free fatty acids

28, 601605.

Biomass & Bioenergy

1993

Isomerization of
alkanes on sulfated
zirconia: promotion by
Pt and by adamantyl
hydride transfer
species

144, 238253

Journal of
Catalysis

2004

Transesterification of
madhuca oil to
biodiesel using
heterogeneous base
catalyst

9395, 315320

Catalysis Today

Park, Y.-M., Lee,

D.W., Kim, D.K

10

Srivastava, A.,
Prasad, R

2008

The heterogeneous
catalyst system for the
continuous conversion
of free fatty acids in
used madhuca oils for
the production of
biodiesel

2000

Triglycerides-based
diesel fuels

131, 238243

Catalysis Today

4, 111133

Renewable and
Sustainable
Energy Reviews

INTRODUCTION

Biodiesel consists of Fatty acid alkyl esters

It can be produced by transesterification of Triglycerides and
alcohol in the presence of catalyst.

Mechanism of
Transesterification Reaction
CH2-OOC-R1
CH -OOC-R2

Catalyst
3ROH

CH2-OOC-R3

Triglyceride

R2-COO- R
At Temp 60
to 70C

Alcohol

CH2-OH

R1-COO-R

R3-COO- R

CH2-OH
CH2-OH

Esters

glycerol
O

O
O
R2

CH2 O
O

R1

R3

CH
CH2 O

CH3OH

C
+
O

R1

H3CO

C
+
O

R2

H3CO

R3

CH2 OH

Catalyst
+

H3CO
HO

CH

CH2 OH

O
Refined vegetable oil
(Triglycerides)

Methanol

Glycerin

FAME (biodiesel)

Scheme 1 (Reaction scheme for transesterification of lipids)

HOW IS IT PRODUCED
The process used to manufacture Biodiesel from pure madhuca oil is
called ester interchange. In the process, the madhuca oil is combined with
a much smaller amount of Methanol. Methanol can be manufactured by
the fermentation of starch or sugar and it can also be produced from
natural gas. The madhuca oil and methanol are placed in a small quantity
of an MgO /ZrO2 catalyst and it is in this process that the chemical
makeup of the madhuca oil is altered. The result is a clean burning fuel
with a viscosity (flow properties) approximating that of standard diesel
fuel. During this process, approximately 90% of what is manufactured is
Biodiesel fuel, while the remaining 10% is in the form of the glycerine
that was broken down from the madhuca oil. This glycerine can also be
used in soap manufacturing applications in the chemical industry, making
the manufacture of Biodiesel practically waste-free. commercially 1,200
kg madhuca seed oil gives 1,100 kg of crude biodiesel

PHOTOGRAPH OF MAHUA TREE & FLOWER

Mahua oil

o Next to sugarcane, Mahua

flowers or fruit pulp are the
most important source of raw
materials for fermentation
and production of alcohol and
vinegar.
o Mahua oil seed cake can be
used as manure and as
substrate for Lipase
production
o Seeds containing 20 to 50%
fatty oil

EXPERIMENTAL
FLOW CHART FOR BIODIESEL PRODUCTION

EXPERIMENTAL FLOW CHART FOR BIODIESEL

PRODUCTION
After
Glycerin
removal,
cleaned/purified before use:

Transfer To Allow Biodiesel

biodiesel

now

needs

to

be

HOMOGENEOUS CATALYTIC APPROACH

HETEROGENEOUS CATALYTIC APPROACH

Drawbacks of conventional heterogeneous catalysts (Alumina,

Zeolites, sulfated zirconia etc.)
- Expensive
- Leaching
- Poor activity for the price
Solution: Prepare cost effective heterogeneous catalysts

FACTORS INFLUENCING PRODUCTION

OF BIODIESEL
Temperature
Speed
Molar ratio
Catalyst
Time

ACID-CATALYZED
TRANSESTERIFICATION
Acid catalyzed transesterification is very slow
compared to base-catalyzed transesterification.
Suitable for oil that has higher FFAs.
This process uses strong acid to catalyze
esterification of the FFAs and transesterification of
triglycerides.
The process does not produce soap with high FFAs
because no metal is present.
Esterification of FFAs is generally faster but
produces water.
Source: Gerpen et al., 2004. Biodiesel Production Technology

EFFECT OF WATER CONTENT

AND FFA

Source: Ayhan Demirbas, 2008. Biodiesel: a realistic fuel alternative for diesel engines

HIGH FFAs FEEDSTOCKS

Put excess catalyst to form soap and soaps are stripped
using centrifuges (caustic stripping).
Acid-catalysis followed by base-catalysis process.
Acid catalyzed transesterification.

PROCEDURE FOR HIGH FFA

FEEDSTOCKS
Measure FFA level.
Add 2.25 g methanol and 0.05 g sulfuric acid for each
gram of free fatty acid in the oil or fat.
Agitate for one hour at 60-65C.
Let the mixture settle. Methanol-water mixture will
rise to the top. Decant the methanol, water, and sulfuric
acid layer.
Take bottom fraction and measure new FFA level.

Source: Gerpen et al., 2004. Biodiesel Production Technology

YIELD %
Glycerol equivalent converted = Total glycerol present in oil
(Total glycerol present in saponified biodiesel sample
Glycerol present in biodiesel sample (before saponified)
Theoretical biodiesel yield (T) = 3 x Moles of glycerol present in
oil
Actual biodiesel (A) = 3 x Moles of Glycerol equivalent
converted moles of FFA present in the diluted sample.
%Yield = (A / T) x 100

EFFECT OF TEMPERATURE

EFFECT OF pH OF BUFFER

OPTIMIZED VALUE
Temperature (oC)
`
pH of Buffer
Oil:MeOH (mol:mol)
Buffer amount (w/w)
Enzyme amount (w/w)
Mixing Rate (RPM)
Stepwise addition (mol/h)

60
7.0
1:1.5
15%
0.25%
100
0.5

optimum values were tested and yield% were calculated and it was
found that 89.32 2.4% yield was obtained after 7 hrs of reaction time

PROCESS PARAMETERS
SELECTED
FOR
TRANSESTERIFICATION

BIODIESEL PREPARATION &

GLYCEROL SEPARATION

Initial heating of oil in Acid Treatment

Stirring action in Acid Treatment

Settlement of glycerin after Acid Treatment

Settlement of glycerin after Base Treatment

Soap obtained in water

washing process

Clear water in water

washing

Final biodiesel

PROPERTIES
Properties of Diesel & Biodiesel(Crude Mahua Oil)
Fuel property
Unit

Diesel

Bio-Diesel
(Crude Mahua Oil)

Kinematic viscosity at 40C

cSt.

2.56

37.18

Density at 25C

Kg/m

860

881.2

Flash point

47

167

Fire point

78

186

Pour point

< -5

15

Calorific value

KJ/kg-K

42850

42293

CONCLUSION AND SUMMARY

Three different approaches were successfully applied to transform biogenic

wastes into heterogeneous catalysts (both acidic and basic)

All the base catalysts were successfully employed in transesterification of

vegetable oils to FAME (** given that the FFA content in oil was less than 1wt
%).

Highest FAME yields upto 96% was achieved under optimized reaction
conditions over the MgO / ZrO2 catalyst.

MgO / ZrO2 exhibited superior reusability under the investigated reaction

conditions when compared to NaOH.

Continued.

CONCLUSION AND SUMMARY

Catalytic Transformation of

Madhuca oil into fuel and chemicals using

Heterogeneous catalysts/solid acid catalyst-transesterification and hydrotreating,

Green Diesel Production.
The industrial homogeneous catalysts will have to be substituted in the near
future by heterogeneous catalysts due to environmental reasons.
Good strong-base heterogeneous catalysts are still in development. MgO /
ZrO2, are also becoming catalysts of choice in transesterification reactions in
biodiesel production despite their cost.
This is because they offer some advantages as far as pretreatment of process
streams are concerned. Efforts are being made by scientists to develop novel
catalysts that will offer best environmental practices as well as relatively good
cost.

FUTURE SCOPE

Biodiesel production from locally available oil seeds

Development of heterogeneous renewable catalysts for biodiesel production and valorization of

wastes.

Biodiesel being more viscous than diesel may require frequent cleaning of engine components.
Use of preheated biodiesel blends in engines may be studied.

Biodiesel if used for longer time in engines causes corrosive effects. Studies on engine wear and
corrosion due to the use of biodiesel must be carried out.

Biodiesel combustion causes higher combustion and exhaust temperatures. Studies must be
carried out for suitable engine modifications resulting in low temperature biodiesel combustion.

Higher NOx emission due to biodiesel combustion is a great matter of environmental concern.
Investigation must be undertaken for reduction of the same using newer methods like exhaust gas
recirculation.

The madhuca oil biodiesel ester will be test on VCR engine and the results will be analysed in
phase II.

ECONOMIC BENEFITS
Biodiesel is produced locally. A locally produced fuel will be more
cost efficient. There is no need to pay tariffs or similar taxes to the
countries from which oil and petroleum diesel are sourced.
Every country has the ability to produce biodiesel. In fact, biodiesel
costs around 70 cents per gallon, which, as you know, is a far cry from the
price of a gallon of traditional gas.
The biodiesel industry has contributed significantly to the domestic
economy. The 51,893 jobs that are currently supported by the US biodiesel
industry reflect the beginning of the industrys potential to create jobs and
economic growth in the US economy.
Biodiesel has added $4.287 billion to the Gross Domestic Product
(GDP). Biodiesel has the potential to support more than 78,000 jobs by
2012. Diesel Engines (compression ignition engines) can nearly all be run
on biodiesel without modification.

ENVIRONMENTAL BENEFITS
The environmental benefit of biofuels relates to the fact that
during their production, they are Carbon Dioxide (CO2) sinks,
that is, they absorb carbon dioxide.
Over one complete cycle, that is, from vegetable plant
cultivation when they absorb CO2 to combustion when they
emit CO2 the net production of CO2 is lower for biofuels
compared to petroleum fuels which just release CO2 during
their life cycle.
Hence, as shown in the image below in replacing petroleum
fuels with biofuels helps in reducing the release of CO 2 into
the atmosphere and therefore reduces the effect on climate
change.

NOW IN INDIA
In India, the price of bio-diesel was regulated by the
petroleum ministry, which used the retail price of diesel
for its calculation. It was sold at about Rs.30 a litre.
India met just 23% of petro demand through domestic
production while the rest was met from imported crude.
Indias oil import dependency is projected to rise to 93
% by 2030. The Government of India approved a
National Policy on Biofuels in September 2008, setting
an indicative target to raise blending of biodiesel with
diesel to 20 % by 2017 and scrapping taxes and duties
on biodiesel.

REFERENCES

Van Gerpen, J. (2005) Biodiesel processing and production, Fuel Processing Technology, 86,
pp. 10971107.
Barnwal, B.K. and Sharma, M.P. (2005) Prospects of biodiesel production from vegetables oils
in India, Renewable and Sustainable Energy Reviews, 9, pp. 363378.
Ramadhas, A.S., Jayaraj, S. and Muraleedharan, C. (2004) Use of vegetable oils as I.C. engine
fuelsa review, Renewable Energy, 29, pp. 727742.
MaF and Hanna, M.A. (1999) Biodiesel production: a review, Bio resource Technology, 70, pp.
115.
Forson, F.K., Oduro, E.K. and Donkoh, E.H. (2004) Performance of Jatropha oil in a diesel
engine, Renewable Energy, 29, pp. 1135-1145.
Canakci, M., Erdil, A. and Arcaklioglu, E. (2006) Performance and exhaust emissions of a
biodiesel engine. Applied Energy, 83, pp. 594605.
Meher, L.C., VidyaSagar, D. and Naik, S.N. (2006) Technical aspects of biodiesel production
by transesterificationa review, Renewable and Sustainable Energy Reviews, 10, pp. 248268.
Kandpal, J.B. and Madan, M. (1995) Jatropha curcasa renewable source of energy for
meeting future energy needs, Renewable Energy, 6, pp. 159160.
Pramanik, K. (2003). Properties and use of Jatropha curcas oil and diesel fuel blends in
compression ignition engine, Renewable Energy, 29, pp. 239-248.
Ramdhas, A.S., Jayaraj, S. and Muraleedharan, C. ( 2005) Characterization and effect of using
rubber seed oil as fuel in the compression ignition engines, Renewable Energy, 30, pp. 795803.

THANK YOU