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POLYGLYCEROL ESTERS OF OLEIC ACID – ESTOLIDE AS RENEWABLE

LUBRICATING OIL BASE STOCK

Presentation · December 2006

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 X DISCUSS SCIENCE
RSCE SINGAPORE 2006

X EXCHANGE OF IDEAS

X NETWORKING Regional Symposium on

Chemical Engineering
ADVANCES IN CHEMICAL AND BIOMOLECULAR ENGINEERING
3 – 5 DECEMBER 2006
NANYANG TECHNOLOGICAL UNIVERSITY
RSCE
Conference Program
• Nanotechnology
• Energy & Environmental Technology
• Petrochemicals
• Food, Polymer, Fine Chemicals and Pharmaceuticals
• Biochemical Engineering
• Novel Materials Chemical Analysis Techniques
• Molecular Modeling and Simulation
• Chemical Engineering Fundamentals
• Chemical and Biomolecular Engineering Education

Organized by

School of Chemical & Biomedical Engineering

Sponsored By
Supported By

Pfizer Asia Pacific Pte Ltd Merck Sharp & Dohme (Singapore) Ltd. Quantachrome Instruments

Teltec Semiconductor Pacific (S) Techcomp (Singapore) Pte Ltd Bruker Singapore
Pte Ltd
 13th RSCE
3 to 5 December 2006, Singapore
Technical Programme

3 December 2006 (Sunday)

Venue: Seminar Room 2
Session: Energy and Environmental Technology-3

15:15 A study on variables affecting the yield of fatty esters from acid-catalysed transesterifcation of crude rice bran
oil
Orchidea Rachmaniah, Yi-Hsu Ju, Shaik Ramjan Vali, M. Rachimoellah, Institute of Technology, Sepuluh
Nopember/ID
15:35 Characterisation of Co/SiO2-B catalyst and catalytic properties during CO hydrogenation
Pimchanok Tupabut, Bunjerd Jongsomji t, Chulalongkorn University/TH
15:55 The effect of various support materials on the catalytic activity of nickel in the low temperature steam reforming
of methane
Teddy G. Monroy, Leonila C. Abella, Susan M. Gallardo, Hirofumi Hinode, De La Salle University/PH
16:15 Cutting-Oil Removal by Continuous Froth Flotation under Low Interfacial Tension and Relation
Sunisa Watcharasing, Sumaeth Chavadej, John F. Scamehor, Chulalongkorn University/TH
16:30 Coffee Break
16:45 Polyglycerol Esters of oleic acid – estolide as renewable lubricating oil base stock
Dicky Dermawan, Institute Teknologi Nasional/ID
17:05 Characteristics of biodiesel oil atomised by a two-fluid nozzle using PDA
J. Kamrak, T. Charinpanitkul, G. Grehan, Chulalongkorn University/TH
17:25 The effect of preparation method on the properties of Cu/ZnO catalyst in steam reforming of methanol for
hydrogen production
Siravit Chotisubyadchana, Piyasan Praserthdam, Somchai Akaratiwa, Chulalongkorn University/TH
17:45 Improving efficiency of dye-synthesized solar cell by modification of TiO2 electrode layer
Akawat Sirisuk, Kulapong Boonyawes, Chulalongkorn University/TH
18:05 Predicting the effect of random factors to the combustion of oily solid waste using Fluent
Anhkien Le, Quocbinh Nguyen, Xuanhai Le, Vietnam Institute for Tropical Technology and Environmental
Protection/VN
18:30 Welcome Reception @ Function Room

3 December 2006 (Sunday)

Venue: Seminar Room 3
Session: Novel Materials and Analytical Techniques-2

15:15 Determination of isotope ratio of monoterpene and sesquiterpene hydrocarbons in Vietnamese lime essential
oils
Nguyen Thi Thao, Masayoshi Sawamura, Kochi University/JP
15:35 The generation of micropore and/or mesopore on 3D – interconnected macroporous carbon monolith by
physical activation
P. Maneeprom, A. Siyasukh, U. Kijsirichareanchai, S. Larpkiattaworn, N. Tonanon, Chulalongkorn University/TH
15:55 Adsorption of benzene and toulene on pre-treated activated carbon (PAC) and Metal oxide supported on pre-
treated activated carbon (MO/PAC) using temperature programmed desorption (TPD) method
Garllardo Susan M., Hallig Herbert Klaus Martin C., Jason Theresa P., De La Salle University/PH
16:15 Coffee Break
 POLYGLYCEROL ESTERS OF OLEIC ACID –
ESTOLIDE AS RENEWABLE LUBRICATING OIL
BASE STOCK
Dicky Dermawan
Chemical Engineering Department
Faculty of Industrial Technology ITENAS Bandung Indonesia
Email: 2d@itenas.ac.id

EXTENDED ABSTRACT
INTRODUCTION
Nonrenewable hydrocarbon oils and petroleum-derived fluids are commonly used in lubrication.
However, their natural sources are steadily decreasing. There is also tendency toward the use of
environmental-friendly product. This work attempt to make alternative lubricating oil base stock
derived from palm oil as renewable source of raw material. Comparison of lubrication properties of
synthetic lubricants (Booser, 1994) concluded that in overall, polyol esters is the best. Vegetable oil
chemistry revealed that major component of palm oil is triacylglycerol, which in general can be
classified as a poliol ester.
Unfortunately, due to distribution and composition of its fatty acids, simple modification such as
telomerization (Landis, 1993), conversion to polyhydroxy triglyceride via epoxidation (Dahlke, 1995),
alcoholysis, and interesterification (Mittelbach & Koncar, 1998) cannot achieve the satisfactory
product. It is proposed that the triacylglycerol first completely be hydrolyzed to glycerol and fatty acids
and to use only unsaturated part of fatty acid. This part of fatty acid constitutes about 50% of palm oil
fatty acids, mostly oleic acid. In this work, polyglycerol esters of oleic acid – estolide with partly
unconverted hydroxyl group are proposed as ‘tailor made’ synthetic lubricating oil base stock.

PROCESS DESCRIPTION
The reaction pathway (Fig. 1) involved glycerol polymerization (Flinder, 1995), conversion of
oleic acid to estolide (Isbell, 1997), and esterification of the former products. All processes were carried
out batch wise in atmospheric condition. Glycerol polymerization were carried out at 250oC using 1%
caustic soda as catalyst, while estolide were produced diabatically using 2½%v/v - 10%v/v sulfuric acid
as catalyst. For the case under consideration, feed stocks were fed at molar ratio of 1 mole glycerol : 1.5
mole oleic acid.

Figure 1 The Proposed Process

RESULT & DISCUSSION

Table 1 and 2 summarized the results of viscosity measurements (ASTM D-445) at 40oC and
o
100 C, respectively, of esters produced as a function of time of glycerol polymerization (hours) and
percentage of monoestolide in oleic acid – estolide mixture used in the esterification. It is clearly shown
that increasing glycerol polymerization time and estolide content results in esters of higher average
molecular weight thus increasing the viscosity. Table 2 also classifies the viscosity of ester according to
engine oil viscosity classification (SAE J300, 1989).
Table 1 Viscosity of Esters at 40oC
Glycerol Polymerization, hours
1 1.5 2 2.5 3 4
% Estolide 7.5 89.1 97.6 101 101.7 105.4 111.2
10 115.3 113.6 104.1 118.9 132.9 117.3
12.5 131.5 119.8 124.5 142.9 130.2 186.2
15 138.3 139.9 136.3 170 164.1 191.8

Table 2 Viscosity of Esters at 100oC and Corresponding SAE Viscosity Class

Glycerol Polymerization, hours
1 1.5 2 2.5 3 4
11.75 12.45 14.78 14.29 15.02 16.07
7.5
SAE 30 SAE 30 SAE 40 SAE 40 SAE 40 SAE 50
14.41 14.34 13.86 15.62 16 16.53
% Estolide

10
SAE 40 SAE 40 SAE 40 SAE 40 SAE 40 SAE 50
14.86 15.09 16 19.84 17.16 25.57
12.5
SAE 40 SAE 40 SAE 40 SAE 50 SAE 50 SAE 60
15.72 16.3 18.37 18.6 20.07 25.26
15
SAE 40 SAE 50 SAE 50 SAE 50 SAE 50 SAE 60

The physical and chemical properties of oil produced were generally satisfactory and
comparable with those of commercial engine oils. Table 3 shows that the viscosity index of the ester is
already comparable to those of commercial (formulated) lubricant, while its flash point and pour point
are comparable to those of conventional base stock. HT/HS viscosity measurement showed promising
result, while wear test showed that wear characteristic of the ester lies between conventional base stock
and formulated lubricant.
Table 3 Comparison of Several Properties
This Research Typical Conventional Typical Commercial
Base Stock Automotive Lubricant
Viscosity Index
121 to 171 96 to 98 128 to 170
(ASTM D-2270)
Flash Point
259 to 274 265 to 275 220 to 248
(ASTM D-92)
Pour Point
(-6) to (-12) -10 (-21) to less than (-35)
(ASTM D-97)
HTHS (ASTM D-4683) 5.85 cP 3.79 - 5.73 cP
Wear Test Seizure load : 126 kg 80 kg 200 kg
(ASTM D-2783) Welding point : 200 kg 126 kg 315 kg
Load Wear Index : 42.07 21.19 50.79

CONCLUDING REMARKS
Polyglycerol esters of oleic acid - estolide showed some promise as future lubricating oil in term
of raw material availability and environmental concern. Several properties have already comparable
meet current base stock and commercial lubricating oil. Hovewer, further development need to be
elaborated, especially regarding wear characteristic and thermal/oxidation stability improvement.
ACKNOWLEDGEMENT
This research was funded by Indonesian Directorate General of Higher Education via Hibah
Bersaing XI. Publication in RSCE 2006 is made possible by Technological and Professional Skill
Development Project (ADB Loan No. 1792 – INO).
REFERENCES
Booser (1994), CRC Handbook of Lubrication & Technology III, New York
Dahlke (1995), Polyhydroxy Fatty Acids and Their Derivatives from Plant Oils; J. Am. Oil Chem. Soc.,
Vol.72, no.3, pp. 349 - 353
Flinder & Calgene Chemical Inc. (1995), Polyglycerol esters as functional fluids and functional fluid
modifiers (US Patent 5380469)
Isbell (1997), Optimization of The Sulfuric Acid Catalyzed Estolide Synthesis from Oleic Acid, J. Am.
Oil. Chem. Soc. 74, pp. 473-476
Landis & International Lubricants Inc. (1993), Telomerized Triglyceride Vegetable Oil for Lubricant
Additives (US Patent 5229023)
Mittelbach & Koncar (1998), Method for the Preparation of Fatty Acid Alkyl Esters (US Pat.5849939)
 12/3/2006

POLYGLYCEROL ESTERS OF OLEIC ACID – ESTOLIDE

AS RENEWABLE LUBRICATING OIL BASESTOCK

Dicky Dermawan
2d@itenas.ac.id

Chemical Engineering Department

Institut Teknologi Nasional
Bandung - Indonesia

Background

‰ Decreasing Mineral Oil as Conventional Resource for

Lubricating Oil Production

‰ Increasing Environmental Awareness

‰ Availability Renewable Resource, i.e. Vegetable Oil

as Alternative Raw Material

1
 12/3/2006

Review on
Vegetable Oil Chemistry

+ H2O

Glycerol Fatty Acids

Fatty Acid Range Average
12:0 Miristic 0,0 – 0,2 0,1
14:0 Lauric 0,8 – 1,3 1,0
16:0 Palmitic 43,1 – 46,3 44,3
16:1 Palmitoleic 0,0 – 0,3 0,15
18:0 Stearic 4,0 – 5,5 4,6
18:1 Oleic 36,7 – 40,8 38,7
Fatty Acid
18:2 Linoleic 9,4 – 11,9 10,5
Composition of 18:3 Linolenic 0,1 – 0,4 0,3
Palm Oil 20:0 Arachidic 0,1 – 0,4 0,3

Literature Survey:
Comparison among Synthetic Oil

Lubrication Dicarboxylic Polyol PAO Glycol Phosphate Polyphenyl

P
Properties
ti A id E
Acid Ester
t Et
Ester Diester
Di t Et
Ester Eth
Ether
Thermal Stability 5 6 6 4 5 10
Oxidation Stability 7 8 6 4 5 6
Low Temp. Fluidity 10 10 8 6 0 0
Volatilitity 7 7 7 6 6 8
Viscosity Index 8 6 6 10 2 0
Hydrolytic Stability 6 6 10 6 4 10
Liquid Phase Range 7 8 7 6 4 2
O
Overall
ll 50 52 50 42 26 36

Overall for conventional mineral oil = 44

Vegetable oil has a good chance since it is a member of

polyol ester family

2
 12/3/2006

Problem Statement

‰ Is there any simple process to convert vegetable oil to

lubricating oil?
‰What is the molecular structure of vegetable-oil-
derived lubricant to be developed?
‰What is the lubrication properties of the product?
‰ Viscosity and Other Physical – Chemical Properties
‰ Friction/Wear Characteristic
‰ Thermal/oxidation Stability

Literature Survey:
Previous Art

‰ Sulphurization
‰ Chlorination
‰ Chlorosulphurization
‰ Telomerization
‰ Epoxidation followed by polyhydroxilation
‰ Alcoholysis & interesterification
Use unsaturated portion of fatty acid
U
Use the
h processes which
hi h are not followed
f ll d by
b
the increase in melting point

‰ Polyglycerol ester
‰ Estolide of oleic acid

3
 12/3/2006

Polyglycerol Ester of Oleic Acid Estolide

Typical Structure

Hydroxyl group
improve
thermal/oxidation
stability

Preparation of PGE

4
 12/3/2006

Viscosity of PGE
Viscosity @ 40oC
%
1 15
1.5 2 25
2.5 3 4
E
7.5 89.1 97.6 101.0 101.7 105.4 111.2 s
t
115.3 113.6 104.1 118.9 132.9 117.3 o
10.0
l
12.5 131.5 119.8 124.5 142.9 130.2 186.2
i
Viscosity @138.3
100 C o
139.9 136.3 170.0 164.1 191.8 d
15.0 %
a
1 Glycerol
1.5 Polymerization
2 2.5 Time, hour
3 4
E
At7.5 11.75 12.45 14.78 14.29 15.02 16.07 s SAE 30
t
100oC 14.41 14.34 13.86 15.62 16.00 16.53 SAE 40
10.0 o
l
14.86 15.09 16.00 19.84 17.16 25.57 SAE 50
12.5 i
15.72 16.30 18.37 18.60 20.07 25.26 d SAE 60
15.0
a
Glycerol Polymerization Time, hour
Engine Oil Viscosity Classification (SAE J300)

Viscosity of PGE

Viscosity grade can be adjusted as required

5
 12/3/2006

Physical & Chemical Properties

Comparison with Base stock &
Commercial Engine Oil
Conventional Base Commercial
This Research This Research
Properties ASTM Stock Engine Oil
A B C R S T HVI-160S HVI-650 MO SS
SAE Class SAE 50 SAE 40 SAE 50 SAE 50 SAE 50 SAE 50 20W/50 20W/50
API Service SG/CD SG/CD
Specific Gravity D-1296 0,9604 0,9583 0,9621 0,9634 0,9556 0,9635 0,8864 0,9159 0,8900 0,8782
ν 40oC, cSt D-445 143,3 108,7 123,0 172,7 136,5 144,6 110,56 571,7 171 118,0
ν 100oC, cSt D-445 16,83 14,24 16,31 19,5 17,52 17,84 11,33 33,52 19,3 17,19
Viscosity Index D-2270 127 133 142 130 141 137 98 96 128 170
Pour Point, oC D-97 -6 -6 -12 -12 -12 -10 -10 -10 -21 < -35
Flash Point, oC D-92 259 264 272 272 274 262 275 265 248 220
TAN, mg KOH/g D-664 4,199 9,904 7,063 4,170 2,112 2,617 1,37 1,38 - 4,37
TBN,, mg
g KOH/g
g D-2896 5,173
, 4,089
, 4,172
, 4,783
, 8,419
, 4,977
, 0,052
, 0,047
, 10,26
, 11,96
,
Sulphated Ash% D-874 0,729 0,551 0,575 0,687 1,147 0,003 0,003 1,47
Foaming, mL D-892
Sequence I 295/Nil 465/20 380/15 20/Nil 5/Nil 5/Nil 5
Sequence II 20/Nil 100/Nil 30/Nil 10/Nil 10/Nil 5/Nil 20
Sequence III 30/Nil 280/Nil 250/Nil 20/Nil 10/Nil Nil/Nil 5
Corr. Copper D-130 1a 1a 1a

Volatility (TGA)
100%

90%
Thermographymetric
analysis shows
80%
that the volatility
70%
of PGE is lower
than conventional
T G A : %massa

60%

50% fully formulated

40%
engine oil
30%

20% MXP
EPG

10%

0%
0 100 200 300 400 500
Suhu, oC

6
 12/3/2006

High Temp. High Shear-Rate Viscosity

(ASTM D-4683)

Lubricant HT/HS, cP
This Research 5.85
Motul 300 V 5.73
Esso Ultra 4.94
Mesran Prima 4.7
Polo XLD 4.46
Motul 2100 4.4
Meditran S 4.12
Agip Sint 2000 4.05
Fuji Oil 4T 3 79
3.79
Minimum for SAE 50 3,7

PGE has intrinsically high viscosity index thus it does not exhibit
“loss in viscosity” at high operating temperature as engine
oil formulated with viscosity index improver polymer

Four Ball Wear Test

(ASTM D-2783)

This HVI-160S
HVI 160S
Characteristic MXP
Research Base Oil
Seizure load, kg 126 80 200
Welding point, kg 200 126 315
Load Wear Index 42,07 21,19 50,79

Load-carrying capacity of PGE is higher than conventional

base oil, but still lower than commercial engine oil
(needs improvement)

7
 12/3/2006

Oxidation Test (Catalytic)

Sample size : ca 325 gram Oxidation rating:

Catalyst : Fe & Cu Time required for 150%
Test temp. : 150 C
o Kinematic Viscosity Increase
measured at 40oC

PGE base stock : 34 hours

PGE (formulated, best achievement) : 70 hours
Expectation value : 100 hours ++

PGE needs oxidation stability improvement

Problem on
Thermal/Oxidation Stability

In comparison to conventional base oil:

• PGE is more susceptible to oxidation

• Oxidation in PGE is more complex

R-CH=CH-R’ + O2 R-CH-CH-R’
*
O-O*

8
 12/3/2006

Concluding Remarks

‰ Polyglycerol ester of oleic acid – estolide has potential

use as future automotive engine oil base stock

‰ In general, PGE have excellent viscosity index,

flash point, volatility, HT/HS viscosity, and
protection against
p g corrosion

‰ Further improvement is required towards better wear

performance and improved oil useful life

Acknowledgements

‰ Contributors:
M.Danain,
MD i L.Andriani,
L A d i i R.D.Nasution,
RDN ti R.Ningsih,
R Ni ih R.Pascalia,
RP li
M.Maria, Yuliani, Y.Gunawan, B.Nugraha, S.Basman, M.Edi,
F.Pranata, A.Widodo, A.O.H.Prasetia, I.Kurniawan, A.Kusnadi,
R.Reagen, D.A.Ardipraja, R.H.Yusli, Ridwan, Y.S.Kuwer,
M.T.Maulana, R.Andito, I.N.H.W.Tasti

‰ Sponsors:
‰ Tecnological & Professional Skill Development Sector Project
‰ Proyek Peningkatan Penelitian Pendidikan Tinggi cq. Hibah
Bersaing XI Direktorat Jendral Pendidikan Tinggi
Departemen Pendidikan Nasional
‰ Lembaga Penelitian & Pemberdayaan Masyarakat Itenas

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