1. Epoxidation of Castor oil fatty acid methylesters (COFAME) as a
lubricant base stock using heterogeneous Ion-Exchange resin
(IR-120) as a catalyst
Venu Babu B
Research Scholar
Dr Vaibhav V Goud
Asst Professor
Department of Chemical Engineering
Indian Institute of Technology Guwahati

2. PRESENTATION PLAN

Introduction
 Materials & Methods
 Objectives
 Experimental work
 Results & Discussions
 References
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Synthesis of Bio-Lubricant from Castor Oil Methyl Esters via Epoxidation
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3. PRESENTATION PLAN
 Introduction
 Literature review
 Knowledge gap
 Objectives
 Preliminary Studies
 Future Work Plan
Lubricant
 References
December 10,
10-Dec-13
2013
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4. INTRODUCTION
What is Lubricant
?
“Lubricant (Base stock oil + Additives) is
a substance introduced between two
moving surfaces to reduce the friction
between them, improving the efficiency
(lifespan), and reducing wear (stress)”
 Conventional lubricant base-stocks are
originated from Fossil fuels- Contains
hydrocarbons, S, N and other metals
Courtesy: Jumat salimon et.al, Eur.J.Lipid Sci. Technol. 2010, 112, 519-530
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Synthesis of Bio-Lubricant from Castor Oil
Methyl Esters via Epoxidation
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5. Current Status
40
25
MMT
35
20
21.9
30
15
36.2
Lubrication Purpose
Energy Transfer
16.4
10
5
5.3
4.4
3.5
3.2
2.8
2.2
1.9
1.9
0
Higher quality and need for longer
life products
3.3% per year by 2014
10-Dec-13
Courtesy: India’s Lubricant consumption is on the rise, 2011 by Geeta Agashe, Vice President - Energy
http://blogs.klinegroup.com/2011/03/31/india_lubricant_1/
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Synthesis of Bio-Lubricant from Castor Oil Methyl Esters via Epoxidation

6. End up in
Environment
50% world wide
Environmental Effects
Volatility
Toxicity,
Accidental Spills
Troubles
Total loss
Non-recoverable
usage
non-biodegradable,
threat to ecology,
Surface and ground
water, contamination
air pollution,
soil contamination,
agricultural product
and food contamination
Courtesy: Savita Kaul et.al, Renewable and sustainable energy reviews 16, 2012, 764-774
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Synthesis of Bio-Lubricant from Castor Oil Methyl Esters via Epoxidation
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7. Contd…
Food Contamination
Soil ,Water Contamination
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www.thehindu.comSynthesis of Bio-Lubricant from Castor Oil Methyl Esters via Epoxidation
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8. Contd…
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9. Alternative Resources
 Edible
 Non-edible
 Fats
 Used Cooking Oils
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9

10. Historical Development
19th Centaury
Abundance and Low cost of Petroleum
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Courtesy: Biobased Lubricants and Greases by Lou A.T Honary, Erwin Rechter

11. Advantages
Environmental friendly
Easily biodegradable (90-98%)
Renewable raw materials
Low cost and Readily available
High viscosity
Low volatility,
Good anticorrosion,
Higher flash points (3000 C),
Higher freezing points and
Display better tribological properties
Good lubricity
Courtesy: Rafael Garces et.al, Grasa Y Aceites, 62 (1), ENERO-MARZO, 21-28, 2011
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Synthesis of Bio-Lubricant from Castor Oil Methyl Esters via Epoxidation
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12. Applications of Bio-lubricants
 Saw chains and blades,
 Railway points,
 Conveyers,
 Two-stroke engines,
 Between gears,
 Automobile Gears
 Hydraulic and transmission systems
 Plasticizers
 Polymer Stabilizers
 Functional Coatings
Courtesy: Savita Kaul et.al, Renewable and sustainable energy reviews 16, 2012, 764-774: Shangde sun et.al, Industrial Crops and Products 33, 2011, 676-682
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Synthesis of Bio-Lubricant from Castor Oil Methyl Esters via Epoxidation
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13. Hydraulic Lubricants Applications
Hydraulic Break System
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Synthesis of Bio-Lubricant from Castor Oil Methyl Esters via Epoxidation
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14. Materials
Annual production
790,000 Metric tones
in
India
Only 10-15% is utilizing properly
in various applications such as
Adhesives, coatings, paints, lubricant
and dyes
Castor Oil (CO)
Courtesy: Borugadda V B et.al, Rev Sust ene rev. 2012, 16, 4763-4784
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Synthesis of Bio-Lubricant from Castor Oil Methyl Esters via Epoxidation
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15. Composition
All the disadvantages due to the
presence of unsaturation, i.e. by
What it Contains
Esters of glycerol with fatty
the presence of
double bonds in
the fatty acid chain between ‘C=C’
atoms
acids (85 %) with different
degrees of unsaturation
Palmetic Acid
(chain length, C12-C22)
Stearic Acid
Disadvantages
poor oxidative,
Oleic Acid
Poor thermal stability,
poor cold flow behavior
Linoleic Acid
Linolenic Acid
Courtesy: Nazim M K et.al, NCON-PGR, Malaysia 2009
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Synthesis of Bio-Lubricant from Castor Oil Methyl Esters via Epoxidation
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16. How and which Route
By elimination of unsaturated
bonds C=C would improve the
thermal and oxidative
stability of base stock
Structural Modification
Genetic Modification
Blending with additives
Courtesy: Savita Kaul et.al, Renewable and sustainable energy reviews 16, 2012, 764-774
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Synthesis of Bio-Lubricant from Castor Oil Methyl Esters via Epoxidation
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17. OBJECTIVES
Synthesis of methyl esters of CO using KOH
catalyst
Structural modification of COFAME via
epoxidation reaction and product confirmation
Determining the required physico-chemical
properties of epoxidised COFAME and comparison
with conventional servo hydraulic lube oil
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Synthesis of Bio-Lubricant from Castor Oil Methyl Esters via Epoxidation
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18. Synthesis of COFAME
Base Catalysed Transesterification
Reaction Conditions
Run No
1
2
3
4
5
6
Oil to alcohol
Temperature
molar ratio (mol) (oC)
1:6
1:6
1:6
1:9
1:9
1:9
Catalyst Loading
(wt %)
60
55
65
60
55
60
1
1
1
1
0.5
0.5
Thin Layer Chromatograms (TLC) of prepared
methylesters from CO at various reaction conditions.
Oil : Alcohol (Methanol)-1:6 mol
Catalyst Loading (KOH)- 1 wt%
Reaction time – 90 min
Reaction Temperature – 60 oC
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Transesterification Mechanism
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19. Structural Modification Mechanism
Raw Materials
Castor Oil Fatty Acid
Methyl Esters (COFAME)
Acetic Acid (Oxygen
Carrier) 0.5 mol
Hydrogen Peroxide
(Oxygen Donor) 1.5 mol
Ion-exchange resin
heterogeneous acidic
catalyst (IR-120) 15wt%
CH3COOH + H2O2
Epoxidation reaction
Reaction Time: 10 h
Reaction Temperature : 60 oC
CH3COOOH + H2O
o
CH3COOOH + R1-CH= CH-R2
R1-CH- CH-R2 + CH3COOOH
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Synthesis of Bio-Lubricant from Castor Oil Methyl Esters via Epoxidation

20. Product Confirmation by 1H-NMR
Castor Oil
Other Ways
Iodine Value
Oxirane Value
Castor oil fatty acid methyl ester
(COFAME)
Epoxidised castor oil fatty acid methyl ester
(epCOFAME)
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Synthesis of Bio-Lubricant from Castor Oil Methyl Esters via Epoxidation

21. Thermal Stability by TGA
180 oC
260 oC
COFAME TGA, DTG@10C in N2
340 oC
Servo Hydraulic grade Lube oil
TGA, DTG@10C in N2
Ability of a material to withstand
the higher temperature in inert
atmosphere
epCOFAME TGA, DTG@10C in N2
Synthesis of Bio-Lubricant from Castor Oil Methyl Esters via Epoxidation
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22. Oxidative Stability by TGA
155 oC
250 oC
COFAME TGA, DTG@10C in O2
305 oC
Servo Hydraulic Grade Lube oil
TGA, DTG@10C in O2
Ability of a material to withstand
the higher temperature in oxygen
atmosphere
epCOFAME TGA, DTG@10C in O2
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Synthesis of Bio-Lubricant from Castor Oil Methyl Esters via Epoxidation

23. Physico-chemical Characterization
Properties
COFAME
epCOFAME
Method
Acid Value (mg KOH/g)
1.65
1.08
AOCS (Te 1a-64, 1997)
Density (kg/m3)
930
956
ASTM D 4052-91
Iodine Value (gI2/100g of oil)
84.6
1.27
AOCS (Tg 1-64, 1997)
Kinematic Viscosity (CSt) at 40 oC
59.49
263.6
ASTM D-445
Pour Point (oC)
-6
8
Specific Gravity
0.94
0.96
ASTM D854-10
Oxirane Content (Experimental)
-
4.86
AOCS Cd-9, 120
Oxirane Content (Theoretical)
-
5.06
-
Relative percentage
-
96.04
-
ASTM D97
conversion of oxirane (%)
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Synthesis of Bio-Lubricant from Castor Oil Methyl Esters via Epoxidation

24. Conclusions
Studied the structural modification of COFAME (Chemical modification) to use as
a Bio Lubricant from renewable raw material
Epoxidation reaction was performed to convert the un-saturation into oxirane ring
formation (Epoxide)
Significant physico-chemical and thermal – oxidative stability of modified epoxide
and unmodified COFAME properties were studied thoroughly
Finally, it could be concluded that COFAME can be used as a potential high
temperature lubricant base-stock
Further, cold flow properties can be improved by additivation or extending the
chain length by ring opening reaction
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Synthesis of Bio-Lubricant from Castor Oil Methyl Esters via Epoxidation

25. REFERENCES
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lubricant base oil properties, Industrial Crops and Products, 21, pp. 113–119.
[2] Birova, A., Pavlovicova, A., and Cvengros, J. (2002) Lubricating Oils Based on Chemically Modified
Vegetable Oils, Journal of Synthetic.Lubrication, 18, pp. 291-299.
[3] Shashidhara, Y.M. and Jayaram, S.R. (2010) Tribological Studies on AISI 1040 with Raw and Modified
Versions of Pongam and Jatropha Vegetable Oils as Lubricants, Tribology International, 43,pp. 1073–1081.
[4] Yao, L., Earl, G., Hammond., Wang, T., Bhuyan, S. and Sundararajan, S. (2010) Synthesis and physical
properties of potential biolubricants based on recinoleic acid, Journal of American oil Chemists
society, 87, pp. 937-945.
[5] Salih, N., Salimon, J. and Yousif, E. (2011) The physicochemical and tribological properties of oleic acid
based trimester biolubricants, Industrial crops and products, 34, pp. 1089-1096.
[6] Lathi, P.S. and Mattiasson, B. (2007) Green Approach for the Preparation of biodegradable lubricant
base stock from epoxidised vegetable oil, Applied Catalysis B: Environmental, 69, pp. 207-212.
[7] Hwang, H.S. and Erhan, S.Z. (2006) Synthetic lubricant basestocks from epoxidized soybean oil and
Guerbet alcohols, Industrial Crops and Products,23,pp. 311–317.
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26. Contd…
[8] Salimon, J. and Salih, N. (2010) Chemical Modification of Oleic Acid Oil for Biolubricant Industrial
Applications, Australian Journal of Basic and Applied Sciences, 4(7),pp. 1999-2003.
[9] Campanella, A., Fontanini, C. and Baltanas, M.A. (2008) High yield epoxidation of fatty acid methyl
esters with performic acid generated in situ, Chemical engineering journal,144(3),pp. 466-475.
[10] Salimon, J., Salih, N. and Yousif, E. (2012) Biolubricant basestocks from chemically modified ricinoleic
acid, Journal of king saud university,24 (1),pp. 11-17.
[11] Salimon, J., Salih, N. and Yousif, E. (2011) Synthetic biolubricant basestocks from epoxidised ricinoleic
acid:Improved low temperature properties, Chemical Industry,60(3),pp. 127-134.
[12] Jin, F.L. and Park S.J. (2008) Thermomechanical behavior of epoxy resins modified with epoxidised
vegetable oils, Polymer International, 57,pp. 577-583.
[13] Farias, E.A., Leles, M.I.G., Ionashiro, M., Zuppa, T.O. and Filho, N.R.A. (2002) Ecl Quím, 27,pp. 111.
[14] Sricharoenchaikul, V. and Atong, D. (2009) Thermal decomposition study on Jatropha curcas L. waste
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[15] Imahara, H., Minami, E., Hari, S. and Saka, S. (2006) Thermal Stability of Biodiesel Fuel as Prepared by
Supercritical Methanol Process, The 2nd Joint International Conference on “Sustainable Energy and
Environment (SEE 2006)” C-037 (P) 21-23 November 2006, Bangkok, Thailand.
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