Egyptian Journal of Petroleum xxx (xxxx) xxx

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Egyptian Journal of Petroleum

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Review

Chemical modification of vegetable oils for the production of

biolubricants using trimethylolpropane: A review
F.J. Owuna a,⇑, M.U. Dabai a, M.A. Sokoto a, S.M. Dangoggo a, B.U. Bagudo a, U.A. Birnin-Yauri a, L.G. Hassan a,
I. Sada b, A.L. Abubakar c, M.S. Jibrin d
a
Department of Pure and Applied Chemistry, Faculty of Science, Usmanu Danfodiyo University, Sokoto, Nigeria
b
Department of Pure and Industrial Chemistry, Faculty of Natural and Applied Science, Umaru Musa Yaráduwa University, Katsina, Nigeria
c
Department of Biochemistry, Faculty of Science, Usmanu Danfodiyo University, Sokoto, Nigeria
d
Department of Pure and Industrial Chemistry, Faculty of Physical Sciences, Bayero University, Kano, Nigeria

a r t i c l e i n f o a b s t r a c t

Article history: Lubricating oil producers are shifting attention toward the use of renewable and biodegradable energy
Received 21 January 2019 sources for the production of lubricating oils. This is necessitated by the depleting mineral based energy
Revised 17 October 2019 sources and the negative impact of continuous usage of engine oils from fossil sources. Biomass sources
Accepted 21 November 2019
are cheap, environmentally friendly, and offer a good alternative to the conventional mineral oil sources.
Available online xxxx
Biolubricants provide lubricity for two moving-surfaces in contact. They are essential for heat transfers,
power transmissions, lubrication, and corrosion inhibition in machinery. However, the use of biolubricat-
Keywords:
ing oils are associated with challenges such as poorer low temperature properties and poor oxidative sta-
Chemical modification
Biolubricant
bility during usage. Chemical modification of vegetable oils with polyols has been explored as a potential
Lubricating oils source for biolubricant synthesis and production. This paper provides a concise review of the use of
Vegetable oils trimethylolpropane (TMP) as the polyol used for chemically-modified biolubricants using vegetable oils
Trimethylolpropane as base stocks. TMP improves the physicochemical properties of biolubricants and enhances the thermo-
oxidative stability of the biolubricants.
Ó 2019 Egyptian Petroleum Research Institute. Production and hosting by Elsevier B.V. This is an open
access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/).

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
2. Lubricating oil compositions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
2.1. Mineral oil base stocks . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
2.2. Re-refined oil base stocks . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
2.3. Synthetic oil base stocks . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
2.4. Biomass base stocks . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
2.5. Lubricating oil additives . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
3. Merits of using biolubricants. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
4. Demerits of using biolubricants . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
5. Physicochemical properties of biolubricants . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
5.1. Viscosity. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00

Abbreviations: AV, Acid Value; A-W, Anti-Wear; CP, Cloud Point; D, Density; DBP, Dibutyl 3,5-di-t-butyl 4-hydroxy Benzyl Phosphate; EP, Extreme Pressure; FM, Friction
Modifiers; FP, Flash Point; ISO, International Organization for Standardization; IV, Iodine Value; KV, Kinematic Viscosity; OS, Oxidative Stability; PAG, Polyalkylene Glycols;
PAMA, Poly Alkylmethacrylate; PAOs, Poly Alpha Olefins; PKO, Palm Kernel Oil; PKTMP, Palm Kernel Trimethylolpropane; PP, Pour Point; PPD, Pour Point Depressants; SAE,
Society of Automotive Engineers; SOA, Sulfurized Octadecanoic Acid; SV, Saponification Value; TAG, Triacylglyceride; TE, Triesters; TETA, Triethylenetetramine; TMP,
Trimethylolpropane; VG, Viscosity Grade; VI, Viscosity Index; WCO, Waste Cooking Oil; ZDDP, Zinc Dialkyldithiophosphate.
Peer review under responsibility of Egyptian Petroleum Research Institute.
⇑ Corresponding author.
E-mail address: Jzr4do@gmail.com (F.J. Owuna).

https://doi.org/10.1016/j.ejpe.2019.11.004
1110-0621/Ó 2019 Egyptian Petroleum Research Institute. Production and hosting by Elsevier B.V.
This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/).

Please cite this article as: F. J. Owuna, M. U. Dabai, M. A. Sokoto et al., Chemical modification of vegetable oils for the production of biolubricants using
trimethylolpropane: A review, Egyptian Journal of Petroleum, https://doi.org/10.1016/j.ejpe.2019.11.004
2 F.J. Owuna et al. / Egyptian Journal of Petroleum xxx (xxxx) xxx

5.2. Viscosity index . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00

5.3. Cloud point . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
5.4. Pour point . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
5.5. Flash point and fire point . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
5.6. Acid value . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
5.7. Base value . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
5.8. Oxidative stability . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
5.9. Iodine value . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
6. Methods of improving vegetable oils for the production of biolubricants . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
7. Chemical modification of vegetable oils using TMP. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
8. Properties of TMP based biolubricants . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
9. Applications of biolubricants . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
10. Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
Compliance with ethics requirements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
Declaration of Competing Interest . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
Acknowledgement . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00

1. Introduction 2. Lubricating oil compositions

Biolubricants act as antifriction agents which reduce the risks
associated with machine failures and maintains optimum opera-
tions. They are essential for heat transfer, power transmission,
lubrication, and corrosion inhibition in machinery [1].The main
purposes of biolubrication are to protect the surfaces from corro-
sion, reduce oxidation, reduce wear due to contact, prevent heat
loss from the surfaces in contact, act as insulator in transformer
applications, as sealing agents (against dust, dirt and water),
biodegradable, and improve efficiency of machines [1–4].
The major property of any biolubricant is viscosity, which is
responsible for preventing friction between two surfaces in contact
[1]. Other important qualities of biolubricants include temperature
stability, prices, availability, environmental friendliness, toxicity,
chemical stability, corrosiveness, flammability, and compatibility
[4,5].The common chemical-pretreatment (Fig. 1) for the conver-
sion of vegetable oils to biolubricants is esterification of the free
fatty acids with methanol in the presence of acidic catalysts, and
subsequent transesterification of the produced methyl esters to
biolubricants using TMP [6–9]. Jeevan and Jayaram [10] observed
that chemical modification of vegetable oils produced better lubri-
cating effects and improved the lubricating oils’ affinity between
metal surfaces in contact.
Vegetable oils have been found useful in biolubricating pro-
cesses to produce tailor-made products [11–14]. Muhammad
et al. [15] reported that vegetable oil producing plants take more
carbon dioxide from the atmosphere through the process of photo-
synthesis than the amount of carbon dioxide that is added to the
atmosphere during burning. Vegetable based bioluricating oils
are over 95.00% biodegradable and 20.00 – 30.00% degrade faster
compared to mineral based lubricating oils [5].
Biolubricants have been synthesised from crude plant oils by
chemical modification of their porperties in order to achieve better
performances than mineral oil lubricants [3,16–18]. Chemical
modification of fatty acids (Table 1) in vegetable oils enhances
their thermal as well as oxidative stability, and enablesthe biolu-
bricants to withstand wide range of operating conditions [3,10,17].
Trimethylolpropane is a colourless triol with molecular formu-
lar CH3CH2C(CH2OH)3, and it is a good substitute for triacylglyc-
eride (TAG) in the production of triesters (TE) as biolubricants
[3,19–23].
The use of TMP for the formulation of biolubricants from veg-
etable oils has generated interests among researchers. This paper
is aimed at reviewing the chemical modification of vegetable oils
for the formulation/production of biolubricants using TMP as the
polyol.
Pre-defined properties of base stocks, such as, low volatility,
ideal cleanliness, high biodegradibility, high solvency for lubricant
additives, negligible effects on seals and elastomers, are majorly
responsible for determining oxidative stability, low temperature
properties, hydrolytic stability, deposit forming tendencies and vis-
cometric parameters of lubricants [3,17,32–34]. Lubricating oils
are composed of basestocks and additives formulated to enhance
their performance.
2.1. Mineral oil base stocks
Mineral oil base stocks are obtained from petroleum mineral oil
[18,35]. They are available and cheap because they are obtained as
lube fractions (distillates from the vacuum distillation) during
refining of crude oil [36,37]. Their utilisation do not constitute food
crises, however, they are non-renewable and toxic to the environ-
ment [38,39].
2.2. Re-refined oil base stocks
Re-refined oils are used oils derived from petroleum that have
been refined and purified for the removal of contaminants (and
impurities). They are processed via treatment to remove volatile
and insoluble components and additives through acid/clay treat-
ment, solvent extraction, flash/vacuum distillation, and demetal-
lization and hydroprocessing catalysts [40,41]. Hence, products
with equal characteristics with mineral base oils are obtained.
Reactivation of used oils protects the environment from negative
effects of improper disposition, reduces heavy metals and green-
house gas emission compared to burning the exhausted oils as fuel
[41].
2.3. Synthetic oil base stocks
Synthetic base oils are obtained by chemical modification of
petroleum oil or petrochemical feedstocks. They are generally
more stable to heat and oxidation than mineral basestocks. They
are also available with superior viscosity index, and are more
biodegradable in comparison to mineral oils. Synthetic base stocks
are ecofriendly and are end products of reactions that are tailored
for specific operations. Examples of these base oils are synthetic
esters, poly alpha olefins (PAOs), polyalkylene glycols (PAG) [41],
and silicons.

Please cite this article as: F. J. Owuna, M. U. Dabai, M. A. Sokoto et al., Chemical modification of vegetable oils for the production of biolubricants using
trimethylolpropane: A review, Egyptian Journal of Petroleum, https://doi.org/10.1016/j.ejpe.2019.11.004
 F.J. Owuna et al. / Egyptian Journal of Petroleum xxx (xxxx) xxx 3

Fig. 1. Synthesis of polyol ester from vegetable oils using trimethylolpropane. Where R1, R2 and R3 are different alky groups.

Table 1
Percentage Fatty Acids Composition of some Vegetable Oils.

Vegetable oils Palmitic acid (16:0) Stearic Acid (18:0) Oleic Acid (18:1) Linoleic Acid (18:2) Linolenic (18:3) Reference
Calabash oil 12.11 8.49 17.86 60.15 0.12 [24]
Calabash oil 2.11 2.54 20.20 58.20 1.70 [25]
Calabash oil 16.32 7.86 36.23 1.74 – [26]
Palm oil 39.32 4.36 42.52 11.35 – [23]
Palm oil 41.50 2.70 40.60 11.90 0.30 [27]
WCO 28.91 0.93 26.51 27.44 4.60 [8]
Moringa oil 5.50 5.70 73.20 1.00 – [28]

2.4. Biomass base stocks
Biomass base stocks are obtained from plants and animal
sources and are used for the production and or synthesis of biolu-
bricants. Biomass sources include protein, free leaves, vegetable
oils, coffee pulp, seaweeds, paper mill sludge, lignocellulose, and
various agro-residues [42–47].
2.5. Lubricating oil additives
Additives are formulated with lubricating oils to enhance their
physichochemical properties during operations. Lubricating oil
additives that are produced from mineral based resources intro-
duce harmful materials, such as heavy metals and sulphur com-
pounds, into the environment [48]. Some common additives used
for lubricating oil formulations include dibutyl 3,5-di-t-butyl 4-
hydroxy benzyl phosphate (DBP), triphenyl phosphorothionate,
sulfurized octadecanoic acid (SOA), sulfurized docosanoic acid
(SDA), triethylenetetramine (TETA), zinc dialkyldithiophosphate
(ZDDP), and poly alkylmethacrylate (PAMA) [48–50].
In recent times, producers of lubricating oil additives have
started reformulating and redesigning additives, such as fatty
amides, fatty amines, fatty alcohols, propyl gallate, tailored for
biolubricants with great successes [17,48]. These additives func-

Please cite this article as: F. J. Owuna, M. U. Dabai, M. A. Sokoto et al., Chemical modification of vegetable oils for the production of biolubricants using
trimethylolpropane: A review, Egyptian Journal of Petroleum, https://doi.org/10.1016/j.ejpe.2019.11.004
4 F.J. Owuna et al. / Egyptian Journal of Petroleum xxx (xxxx) xxx

Table 2
Physicochemical Properties of some Vegetable Oils.

Oils KV @100 °C KV @40 °C VI D @15 °C FP (oC) PP AV IV

(cSt) (cSt) (g cm 3) (oC) (mg KOH g 1
) (mg I2 g 1
)
Jatropha[18] 14.24 66.74 220 0.92 – 5 29.06 –
Calabash Seed oil [25] – – – – – – 5.92 4.02
Calabash Seed oil[29] – – – – – – 2.02 0.75
Palm oil[23] – 52.13 – 0.91 – – 6.35 –
Palm oilester[23] 10.96 50.33 214 – 253 5 – –
WCO lub. [30] 8.500 36.70 220 – – 2 1.56 –
Palm kernel[31] 7.800 34.90 210 0.92 322 15 0.05 0.89

Keys: KV (Kinematic Viscosity); VI (Viscosity Index); D (Density); FP (Flash Point); PP (Pour Point); AV (Acid Value); IV (Iodine Value).

tion are viscosity index improvers (VII), pour point depressants
(PPD), detergents, dispersants, anti-wear (AW) agents, extreme
pressure (EP) additives, anti-oxidants, friction modifiers (FM),
anti-foams, metal deactivators, and rust and corrosion inhibitors
[17]. Additives and or impurities dependent characteristics of
lubricants include demulsibility, water rejection, colour, foaming,
ash content, acidity, load carrying capacity, corrosion inhibition,
antiwear protection and lubricity [17,32,48].
3. Merits of using biolubricants
Biolubricants have excellent lubricity, higher viscocity index,
have been reported to produce fewer emission due to higher boil-
ing temperature ranges of esters, lower volatility, higher flash/fire
points, less dermatological problems both to humans and animals,
and are biodegradable [3,13,17,18,51].
4. Demerits of using biolubricants
Previous researches revealed that the major concerns with the
use of biolubricants are their poor resistance to thermal and oxida-
tive degradation owing to the presence of acyl group in their mole-
cules (glycol backbone in oil give rise to a tertiary b-hydrogen that
is thermally unstable) [3,10,12,17,51–53]. It was also reported that
low thermal and oxidative property of vegetable oils is caused by
methylene interrupted poly unsaturation [4,10,32]. Biolubricant
also have poor low temperature properties due to the formation
of macro crystalline structures (at low temperatures through uni-
form stacking of triglycerides’ back bones) which limit the easy
flow of the fluids due to loss of kinetic energy of the molecules dur-
ing the self-stacking [30]. The presence of ester group was also
found to be responsible for low-temperature fluidity and reduced
volatility at high temperatures in biolubricants [13].
Further reviews confirmed that for suitability as biolubricant, a
fluid should contain properties such as biodegradability, cleanli-
ness (particle count), less water content, poor acidity, high viscos-
ity, high viscosity index, homogeneity, low volatility, low pour
point, high oxidative stability, low iodine value, and elastomer
compatibility [3,54].
5. Physicochemical properties of biolubricants
Biolubricating oils have some properties that enhance their per-
formances and suitability for various applications. Some of these
properties, which are described in this section, are also presented
in Table 2 and Table 4.
5.1. Viscosity
Viscosity is a measure of biolubricant’s thickness, or resistance
to flow. Quantitative measure of fatty acids’ and vegetable oils’
resistance to flow is called viscosity [4,13]. The higher the biolubri-
cant’s viscosity, the thicker it will be and more energy will be
needed to move an object through it [4,13].Viscosity is a major fac-
tor which determines biolubricant’s application. Low viscosity
stocks can be used for automotive transmission oils, while higher
viscosity stocks are used in diesel engine oils. In metal forming
application, the effectiveness of a firm in separating the work-
piece from the tool (in order to control friction and wear) is deter-
mined by the viscosity of the biolubricant [13]. The kinematic vis-
cosity of biolubricants are measured at 40 and 100 °C, and the
viscosity compared with an empirical reference scale.
5.2. Viscosity index
Viscosity index (VI) of a biolubricant is the measure of the
change of the biolubricant’s viscosity with change in its tempera-
ture. Viscosity of a biolubricant is inversely proportional to its tem-
perature; therefore a machine that operates over a wide
temperature range will require a lubricant with higher viscosity
index. The higher the viscosity index, the lower the effect of tem-
perature on the viscosity of lubricating product [4].
5.3. Cloud point
Cloud point (CP) is the temperature at which the first sign of
wax formation for biolubricant can be detected [13]. It is the tem-
perature at which first sign of haziness is observed. The wax crys-
tals formed can clog filters and openings, thereby leaving deposits
on surfaces such as a heat exchanger, and increase the viscosity of
the biolubricating oil.
5.4. Pour point
At low temperature, the viscosity of the biolubricant will be
very high, causing it to resist flow. The lowest point at which biol-
ubricant sample can flow by gravity alone is known as the pour
point of the oil. It is also the last temperature before movement
ceases, and not the temperature at which solidification occurs
[13]. Pour point (PP) is an important characteristic for an equip-
ment that operates in a cold environment or handles cold fluids.
Highly viscous oils may cease to flow at low temperatures because
their viscosity become too high due to wax formation. In such case,
the pour point will be higher than the cloud point.
5.5. Flash point and fire point
Flash point (FP) of a biolubricant is the lowest temperature at
which the vapourised oil can be ignited by an external source,
while fire point is the temperature at which biolubricant combus-
tion would be sustained for, at least, five minutes after the ignition
source has been removed [16,55]. The flash point and fire point are
used in determining biolubricant’s volatility and fire resistance.

Please cite this article as: F. J. Owuna, M. U. Dabai, M. A. Sokoto et al., Chemical modification of vegetable oils for the production of biolubricants using
trimethylolpropane: A review, Egyptian Journal of Petroleum, https://doi.org/10.1016/j.ejpe.2019.11.004
 F.J. Owuna et al. / Egyptian Journal of Petroleum xxx (xxxx) xxx
Transportation and storage requirements of biolubricant are deter-
mined by the biolubricant’s flash point. Products with a flash point
less than 38 °C (100°F) will normally require cautions for safe han-
dling. Thus, flammability hazard of lubricating oils are determined
by the flash point and fire point [13,74]. Mahmud et al. [76]
reported that the number of carbon atoms in the tryglycerides
determine the flash point of a biolubricant.
5.6. Acid value
When the concentration of acidic compounds in a biolubricant
is high, it can lead to corrosion of machine parts and clogged oil fil-
ters due to the formation of varnish and sludge. Total acid value is a
measure of acid concentration present in a biolubricant. The acid
concentration of any biolubricant depends on the presence of addi-
tive package, acidic contamination, and oxidation by-products
[49,56].
5.7. Base value
Lubricants are formulated with alkaline additives in order to
combat the build-up of acids as they break down. Total base value
is a measure of alkaline concentration present in a biolubricant.
Gasoline oils are typically formulated with total base value of
about 5–10 mg KOH g 1 whereas diesel engine oils, due to more
severe operating conditions, are higher (15–30 mg KOH g 1). The
base value is depleted as the oil remains in service. Depletion of
base value beyond certain limit puts the engine at risk of corrosion,
sludge, and varnish formations. At such point, it is necessary to
change the lubricant or top-off [56].
5.8. Oxidative stability
Reaction of biolubricants resulting in corrosion, acidity, volatil-
ity and viscosity are determined by their oxidative properties.
Oxidative stability is frequently used to predict lubricants’ service
life in conditions of higher temperatures and other extreme appli-
cations [13,23]. Saturated fatty acids have relatively high oxidation
stability, which decrease with increasing unsaturation in the mole-
cules [5]. Vegetable oils have poor oxidative and thermal stability
owing to the presence of acyl group in their molecules. Glycol
backbone in an oil give rise to a tertiary b-hydrogen, which is ther-
mally unstable [13]. Chemical modification of vegetable oils via
reactions such as esterification, acetylation across double bonds
and epoxidation, are promising methods for obtaining valuable
commercial products from biodegradable raw materials. The
unsaturated structures of vegetable oils make them less stable to
oxidation than mineral oils. Antioxidants of 0.10–0.20% are effec-
tive in mineral oil formulation, but vegetable oils may require a lar-
ger amount of such antioxidants (1.00 – 5.00%). A low oxidative
stability indicates that oil oxidizes rapidly during its use, becoming
thick and polymerizing to a plastic-like structure [41].
5.9. Iodine value
Iodine value is a measure of the amount of double bonds pre-
sent in the molecules of a given sample of biolubricant. It reflects
the biolubricant’s susceptibility to oxidation reactions. Unsatu-
rated biolubricants take up iodine while saturated ones do not
and therefore, the later have zero iodine values [57]. Iodine value
is a unique property of seed oils [58] making them good starting
materials for soaps, foods, lubricants, pharmaceutical, and cosmet-
ics industries [58,59].
Please cite this article as: F. J. Owuna, M. U. Dabai, M. A. Sokoto et al., Chemical modification of vegetable oils for the production of biolubricants using
trimethylolpropane: A review, Egyptian Journal of Petroleum, https://doi.org/10.1016/j.ejpe.2019.11.004
5
6. Methods of improving vegetable oils for the production of
biolubricants
Several methods used to improve the lubricating properties of
vegetable oils have been identified. These methods include partial
selective hydrogenation, genetic modification, biotechnology [50],
additive treatment [37], and blending [4,28,60–64]. Other methods
include chemical modifciations via epoxidation, strcutural modifi-
cation, and transesterification [30,65,66].
Chemical modifications and blending have been tested to
improve the flash point, pour point, viscosity and oxidative stability
of vegetable oil based biolubricants [2,4,5,11,63,64,66]. Weimin and
Xiaobo [30] studied the chemical modification of waste cooking oil
(WCO) via expoxidation using H2O2 and followed by transesterifica-
tion with methanol and branched alcohols (isooctanol, isotride-
canol and isooctadecanol) to produce biolubricant with improved
oxidative stability and low temperature properties. It was con-
firmed that the synthesised biolubricants showed improved tem-
perature flow performances due to the introduction of branched
chains in the molecular structures and the oxidative stability of
the WCO showed more than 10 times improvement due to the
elimination of –C@C– bonds in its molecule. The tribological perfor-
mances of the produced biolubricants were investigated using four-
ball friction and wear tester and favourable physicochemical prop-
erties and tribological performances were observed, making these
oils good candidates in formulating ecofriendly lubricants.
Kailas et al. [61] studied the lubrication properties of different
vegetable oils, namely, soybeans oil, olive oil, almond oil, amla
oil, castor oil, groundnut oil, cotton seed oil, coconut oil, mustard
oil, at different temperatures. It was found that the lubricating
properties of oil, such as, cloud point, pour point, flash point, fire
point and % carbon residues, change with changing vegetable oil
blends.
In another research, Yashvir [62] studied the friction and wear
characteristics of pongamia oil blended lubricant at different load
and sliding distance using pin-on-disc tribometer at 3.8 m/s sliding
velocity and applied load of 50, 100, 150 N. A blend of the biolubri-
cant at a ratio of 15, 30, and 50% by volume with the base lubricant
SAE 20 W-40 were carried out and it was found that the lubrication
occurred regime was boundary lubrication while the main wear
mechanisms were abrasive and adhensive wear. It was concluded
that pongamia oil in the base lubricant acted as a very good lubri-
cant additive that reduced the friction and wear scar diameter dur-
ing the test. Also, Ozioko [28] studied the properties of blended
Moringa oleifera oil with conventional SAE 40 lubricant from 10
to 40% by volume using magnetic stirrer. Aluminium pin was used
against carbon steel dics to analyse the viscosity, density and rate
properties of the oil and it was found that at 40 °C and 100 °C, vis-
cosity of MOL 10 (Moringa oleifa lubricant) satisfied SAE 30 and
SAE 40 grades requirements; MOL 20 satisfied SAE 30 but did not
meet SAE 40 grades requirements; the densities of all the blended
samples were found comparable to those of the conventional base
oil; and the wear rate of all the blended samples increased with
applied load. It was concluded that MOL 10 blend could be com-
mercially viable for industrial application since it showed compa-
rable properties with the base lubricant, SAE 40, in terms of
density, viscosity and wear rate.
Furthermore, Obasi et al. [37] investigated the effectiveness of
additives on the performance of engine oil. The performance func-
tion selected include viscosity, density, flash point, colour as well
as foaming ability/stability. The additives were B023233 (compris-
ing of anti-oxidant, detergent, dispersant, pour point depressant,
anti-corrosion and anti-rust additives) and B23333 (comprising
of viscosity modifier additive). All the laboratory tests were carried
out in accordance with the specification of the American Society
6 F.J. Owuna et al. / Egyptian Journal of Petroleum xxx (xxxx) xxx

for Testing and Materials (ASTM). The results of the tests obtained
from the blend show that the properties such as viscosity, density
and flash point, increase with increasing in additive concentration,
while that of the foaming ability decreases with increasing in
additive concentrations
7. Chemical modification of vegetable oils using TMP
TMP is one of the polyols that is used for the modification of
vegetable oils for biolubricant production [66]. Chemical modifica-
tions of seed oils via transesterification of the oils with trimethylol-
propane were employed by various authors for the production of
biolubricants using various conditions of temperatures and cata-
lyst concentrations. Such seed oils include jatropha curcas
[18,23,67,68], rubber seed [69], fluted pumpkin seed [70], and cas-
tor seed [71].
Robiah et al. [27] studied synthesis of palm oil and palm kernel
polyol esters via transesterification of the oils with TMP using tem-
perature column (SGE HT5) operated at 6 °C min 1 starting from 80
to 340 °C. In another investigation, Robiah et al. [19] developed
optimum synthesis method for the transesterification of palm oil
methyl esters and trimethylolpropane to environmentally accept-
able palm oil TMP ester biolubricant. Robiah et al. [31] prepared
and characterized trimethylolpropane esters synthesized from
palm kernel through transesterification of palm kernel oil with
TMP using sodium methoxide as catalyst and the following basic
properties of the non-additive palm kernel trimethylolpropane
ester (PKTMP) were obtained: viscosity at 40 °C in range of
39.70–49.70 cSt, pour point of 1 to 1 °C, and viscosity index of
167–187. Furthermore, Siti et al. [72] examined batch production
of trimethylolpropane ester from palm oil as lubricant base stock
through transesterification reation in a mini pilot reactor.
Zulkifli et al. [73] examined tribological properties of parafin oil
and biolubricant with TiO2 nanoparticles as additives. The biolubri-
cant is a TMP ester of palm oil. The friction and wear experiments
were performed using four-ball machine tribotester for ten min-
utes under 40.00, 80.00, 120.00, and 160.00 kg load at 1200 rpm
at room tempereture. The experimental result showed that
nanoparticles, TiO2, added to TMP ester exhibit good friction-
reduction.
Other scholarly works on syntheses of biolubricants via chemi-
cal modifications of vegetable oils with trimethylolpropane are
presented in Table 3 below:

Table 3
Chemical modifications of vegetable oils with TMP.

Oil sources Oil:TMP ratio Catalyst Reaction conditions Yield (%) Properties References
Jatrophaseed 3.9:1 1% NaOCH3 150 °C;10mba;3h 47.00 PP(-3 °C);VI(178–183 [68]
Palm oil 3.9:1 0.7% NaOCH3 130 °C;50mba;1h 90.00 – [27]
Fluted Pumpkin 6:1 Ca(OH)2 160 °C;6h 81.42 V@40 °C(60.78 cSt);V@100 °C(11.030 cSt);VI(1 7 6); [70]
PP(-14 °C); FP(220 °C)
Rubber seed 3.9:1 2% H2SO4 150 °C;5h 79.00 FP(310 °C);VI(2 8 3);PP(-40 °C) [69]
Jatropha seed 4:1 2% HClO4 150 °C;3h 70.00 PP(–23 °C);FP(>30 °C);VI(1 5 0) [67]
Palm oil 3.9:1 0.9% NaOCH3 130 °C;4h:10 mmHg 97.80 PP(5 °C);FP(2 5 3);VI(2 1 4) [23]
Jatropha seed 3.9:1 0.9% NaOCH3 130 °C;4h 98.20 VI(1 4 0);PP(-3 °C);FP(273 °C) [23]
Palm kernel 3.9:1 0.9% NaOCH3 130 °C;vaccum 98.00 V@40 °C(39.70 cSt);V@100 °C(7.700 cSt);FP(310 °C); [19]
PP(2 °C);IV(18.2;SV(223.10
Castor seed 4:1 0.8% o-phosphoric acid 120 °C;1h(in situ) 96.56 V@40 °C(45.30);V@100 °C(9.200);VI(1 9 1); [71]
PP(-8 °C);FP(215 °C)

Keys: PP (Pour Point); VI (Viscosity Index); V (Viscosity); FP (Flash Point); IV (Iodine Value); SV (Saponification Value)

Table 4
Properties of Crude Oils and TMP Based Biolubricants.

Oils KV @100 °C KV @40 °C VI FP (oC) PP OS Reference

(cSt) (cSt) (oC)
ISO VG32 >4.100 >28.80 >90.00 204 6 – [66]
ISO VG46 >4.100 >41.40 >90.00 220 6 – [66]
ISO VG68 >4.100 >61.40 >198 226 6 – [66]
ISO VG100 >4.100 >90.00 >216 246 6 1670.26 [66]
75 W-90 15.90 120.0 140 205 48 – [66]
80 W-140 31.20 310.0 132 210 36 – [66]
SAE20W40 13.90 105.0 132 200 21 – [66]
Crude Jatropha 7.900 35.40 205 – 6 – [66]
Jatropha TMP 8.710 43.90 180 – 6 325 [66]
Crude Palm 10.20 52.40 180 – 5 – [66]
Palm Oil TMP 9.000 47.10 176 – 2 355 [66]
Crude Castor 19.72 220.6 220 250 27 [66]
Castor Oil TMP 26.13 287.2 119 – 27 [66]
Crude Palm – 52.13 – – – – [23]
Palm Oil TMP (50 mmHg) 7.580 38.25 171 240 5 – [23]
Palm Oil TMP (10 mmHg) 10.87 50.33 214 ‘253 5 – [23]
Crude Jatropha – 36.97 – 273 3 – [23]
Jatropha Oil TMP 8.530 51.89 140 296 3 – [23]
Crude PKO 5.934 26.03 185 200 20 – [75]
PKO TMP 20.54 48.06 110 210 8 [75]
Oleate TMP 15.32 80.80 200 289 59 189 [76]
Crude Jatropha 4.830 17.15 233 92 7 – [77]
Jatropha TMP 8.510 39.51 204 178 12 – [77]

Keys: KV (Kinematic Viscosity); VI (Viscosity Index); FP (Flash Point); PP (Pour Point); OS (Oxidative Stability)

Please cite this article as: F. J. Owuna, M. U. Dabai, M. A. Sokoto et al., Chemical modification of vegetable oils for the production of biolubricants using
trimethylolpropane: A review, Egyptian Journal of Petroleum, https://doi.org/10.1016/j.ejpe.2019.11.004
 F.J. Owuna et al. / Egyptian Journal of Petroleum xxx (xxxx) xxx
8. Properties of TMP based biolubricants
Chemically modified vegetable oils exhibit improved viscosity
indices, flash/fire points, lubricities, and superior anti corrosion
characteristics [13] than their crude basestocks. Furthermore,
TMP modified vegetable oils have enhanced properties than their
original source oils, and are comparable to standards and commer-
cially available lubricants (Table 4).
9. Applications of biolubricants
Biolubricants have been utilized for various maintenance and
industrial applications [78–80]. Biolubricants have found great
uses in machines that loose oil directly into the environment dur-
ing operations (Total Loss Lubricants) and in machinery used in
environmentally sensitive areas such as water treatment and food
processing [48].
Generally, biolubricants are being used as hydraulic fluids
[48,50,79] in power equipment, two-stroke engines [48,50,79], air-
craft jet engine [13], metalworking fluids [79], boat engines [50],
chain saw oils [48,79], drilling fluids [48] used for geological explo-
rations, marines [48], greases [79], and railroad flanges [48]. Other
applications include concrete mould release agent, dust suppres-
sants, metalforming fluids, cutting fluids, and gear oils [79].
Ester based stocks have potentials to be used for the production
of lubricants and additives [13,79], while ecofriendy TMP esters
offer high performance advantages that are being exploited for
their applications as engine oils, gear oils, hydraulic oils, and addi-
tives [80].
10. Conclusion
The renewed effort of producers and consumers of lubricating
oils, coupled with various environmental regulations, that have
resulted in researchers finding alternative sources of energy (from
biomass), is yielding result. TMP has won the interest of research-
ers in biolubricating oil formulation due to its enhancement of the
performance qualities and thermo-oxidative properties of biolubri-
cants. Biolubricants that are produced through chemical modifica-
tion of vegetable oils with TMP are eco-friendly, renewable, and
useful for any operations where mineral based lubricating oils
are applicable.
Compliance with ethics requirements
This paper does not contain studies with human/animal
subjects
Declaration of Competing Interest
The authors declare that they have no known competing finan-
cial interests or personal relationships that could have appeared
to influence the work reported in this paper.
Acknowledgement
Authors acknowledge TheRoyalFamily for financial support.
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