Venu Babu BResearch Scholar

Dr Vaibhav V GoudAsst Professor

Epoxidation of Castor oil fatty acid methylesters (COFAME) as a lubricant base stock using heterogeneous Ion-Exchange resin

(IR-120) as a catalyst

Department of Chemical EngineeringIndian Institute of Technology Guwahati

10-Dec-2013

PRESENTATION PLAN

2

Introduction

Materials & Methods

Objectives

Experimental work

Results & Discussions

References

Synthesis of Bio-Lubricant from Castor Oil Methyl Esters via Epoxidation

Apr 10, 2023 3

PRESENTATION PLAN

April 10, 2023 3

Introduction

Literature review

Knowledge gap

Objectives

Preliminary Studies

Future Work Plan

ReferencesLubricant

Lubricant

INTRODUCTION

“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)”

What is Lubricant ?

4Apr 10, 2023

Courtesy: Jumat salimon et.al, Eur.J.Lipid Sci. Technol. 2010, 112, 519-530

Synthesis of Bio-Lubricant from Castor Oil Methyl Esters via Epoxidation

Conventional lubricant base-stocks are originated from Fossil fuels- Contains hydrocarbons, S, N and other metals

USAChi

naIn

dia

Japa

n

Russia

Brazil

German

y

Canad

aUK

Sout

h

Others

0

5

10

15

20

25

30

35

40

21.9

16.4

5.3 4.4 3.5 3.2 2.8 2.2 1.9 1.9

36.2

Apr 10, 2023 5

Current Status

Higher quality and need for longer life products

3.3% per year by 2014

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/

Lubrication PurposeEnergy Transfer

Synthesis of Bio-Lubricant from Castor Oil Methyl Esters via Epoxidation

MM

T

Apr 10, 2023 6

Environmental Effects

Toxicity,

non-biodegradable,

threat to ecology,

Surface and ground

water, contamination

air pollution,

soil contamination,

agricultural product

and food contamination

End up in Environment

50% world wide

Volatility

Accidental Spills

Total loss

Non-recoverable usage

Courtesy: Savita Kaul et.al, Renewable and sustainable energy reviews 16, 2012, 764-774

Troubles

Synthesis of Bio-Lubricant from Castor Oil Methyl Esters via Epoxidation

Apr 10, 2023 7

Food Contamination

Soil ,Water Contamination

Contd…

Synthesis of Bio-Lubricant from Castor Oil Methyl Esters via Epoxidation

www.thehindu.com

Apr 10, 2023 8

Contd…

Apr 10, 2023 9

Alternative Resources

Edible Non-edible Fats Used Cooking Oils

Apr 10, 2023 10

Historical Development

19th Centaury Abundance and Low cost of Petroleum

Courtesy: Biobased Lubricants and Greases by Lou A.T Honary, Erwin Rechter

Synthesis of Bio-Lubricant from Castor Oil Methyl Esters via Epoxidation

Advantages

Renewable raw materials

Apr 10, 2023

Easily biodegradable (90-98%)

Low cost and Readily available

Display better tribological properties

Low volatility,

Good anticorrosion,

Higher flash points (3000

C),

Higher freezing points

and

Good lubricity

Environmental friendly

High viscosity

11

Courtesy: Rafael Garces et.al, Grasa Y Aceites, 62 (1), ENERO-MARZO, 21-28, 2011

Synthesis of Bio-Lubricant from Castor Oil Methyl Esters via Epoxidation

Saw chains and blades,

Railway points,

Conveyers,

Two-stroke engines,

Between gears,

Automobile Gears

Hydraulic and transmission systems

Plasticizers

Polymer Stabilizers

Functional Coatings

Applications of Bio-lubricants

Apr 10, 2023 12

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

Synthesis of Bio-Lubricant from Castor Oil Methyl Esters via Epoxidation

Apr 10, 2023 13

Hydraulic Lubricants Applications

Hydraulic Break System

Synthesis of Bio-Lubricant from Castor Oil Methyl Esters via Epoxidation

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Materials

Annual production in India

790,000 Metric tones

Only 10-15% is utilizing properly in various applications such as Adhesives, coatings, paints, lubricant and dyes

Castor Oil (CO)

Synthesis of Bio-Lubricant from Castor Oil Methyl Esters via Epoxidation

Courtesy: Borugadda V B et.al, Rev Sust ene rev. 2012, 16, 4763-4784

Apr 10, 2023

Disadvantages

poor oxidative,

Poor thermal stability,

poor cold flow behavior

What it Contains

Esters of glycerol with

fatty acids (85 %) with

different degrees of

unsaturation (chain

length, C12-C22)

15

Stearic Acid

Palmetic Acid

Oleic Acid

Linoleic Acid

Linolenic Acid

All the disadvantages due to

the presence of unsaturation,

i.e. by the presence of

double bonds in the fatty acid

chain between ‘C=C’ atoms

Courtesy: Nazim M K et.al, NCON-PGR, Malaysia 2009

Composition

15

Synthesis of Bio-Lubricant from Castor Oil Methyl Esters via Epoxidation

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How and which RouteBy elimination of

unsaturated bonds C=C

would improve the

thermal and oxidative

stability of base stock

Structural

Modification

Genetic Modification

Blending with

additivesCourtesy: Savita Kaul et.al, Renewable and sustainable energy reviews 16, 2012, 764-774

Synthesis of Bio-Lubricant from Castor Oil Methyl Esters via Epoxidation

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

17Synthesis of Bio-Lubricant from Castor Oil Methyl Esters via

Epoxidation

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Apr 10, 2023 18

Synthesis of COFAMEBase Catalysed Transesterification

Reaction Conditions

Oil : Alcohol (Methanol)-1:6 mol

Catalyst Loading (KOH)- 1 wt%

Reaction time – 90 min

Reaction Temperature – 60 oCTransesterification Mechanism

Run No Oil to alcohol

molar ratio (mol)

Temperature (oC) Catalyst Loading

(wt %)1 1:6 60 12 1:6 55 13 1:6 65 14 1:9 60 15 1:9 55 0.56 1:9 60 0.5

Thin Layer Chromatograms (TLC) of prepared methylesters from CO at various reaction conditions.

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Structural Modification Mechanism

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%

Raw Materials

Synthesis of Bio-Lubricant from Castor Oil Methyl Esters via Epoxidation

CH3COOH + H2O2 CH3COOOH + H2O

CH3COOOH + R1-CH= CH-R2 R1-CH- CH-R2 + CH3COOOH

o

Epoxidation reaction

Reaction Time: 10 hReaction Temperature : 60 oC

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Product Confirmation by 1H-NMR

Synthesis of Bio-Lubricant from Castor Oil Methyl Esters via Epoxidation

Castor Oil

Castor oil fatty acid methyl ester (COFAME)

Epoxidised castor oil fatty acid methyl ester (epCOFAME)

Iodine Value Oxirane ValueOther Ways

21

COFAME TGA, DTG@10C in N2

epCOFAME TGA, DTG@10C in N2

Servo Hydraulic grade Lube oil TGA, DTG@10C in N2

Synthesis of Bio-Lubricant from Castor Oil Methyl Esters via Epoxidation

Thermal Stability by TGA

Ability of a material to withstand the higher temperature in inert atmosphere

180 oC

340 oC

260 oC

22

COFAME TGA, DTG@10C in O2

epCOFAME TGA, DTG@10C in O2

Servo Hydraulic Grade Lube oil TGA, DTG@10C in O2

Oxidative Stability by TGA

Ability of a material to withstand the higher temperature in oxygen atmosphere

Synthesis of Bio-Lubricant from Castor Oil Methyl Esters via Epoxidation

305 oC

155 oC 250 oC

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Physico-chemical Characterization

Synthesis of Bio-Lubricant from Castor Oil Methyl Esters via Epoxidation

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 ASTM D97

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

conversion of oxirane (%)

- 96.04 -

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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

Conclusions

Synthesis of Bio-Lubricant from Castor Oil Methyl Esters via Epoxidation

REFERENCES

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[1] Adhvaryu, A., Liu, Z. and Erhan, S.Z. (2005) Synthesis of novel alkoxylated triacylglycerols and their 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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Contd…

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[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 using TGA and fixed bed reactor, Journal of Analytical and Applied Pyrolysis,85,pp. 155–162.

[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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