1099114x, 2022, 4, Downloaded from https://onlinelibrary.wiley.com/doi/10.1002/er.7453 by Egyptian National Sti. Network (Enstinet), Wiley Online Library on [09/11/2022].

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Received: 3 July 2021 Revised: 24 October 2021 Accepted: 25 October 2021
DOI: 10.1002/er.7453

REVIEW PAPER

Biolubricant production via esterification and

transesterification processes: Current updates and
perspectives

Godfred Appiah1,2 | Samuel Kofi Tulashie3 | Ephraim Edem Amoah Akpari3 |

Eldon R. Rene4 | Daniel Dodoo5

1
Department of Water Supply, Sanitation
and Environmental Engineering, IHE
Summary
Delft Institute for Water Education, Delft, The growing concern and limitations for existing lubricants have driven the
The Netherlands need for biolubricants, extensively proposed as the most suitable and sustain-
2
Department of Green Chemistry and
able lubricating oils. Biolubricants are generally synthesized from various bio-
Technology, Faculty of Bioscience
Engineering, Ghent University, Ghent, based sources, including vegetable oils, microbially derived oils, waste cooking
Belgium oil, etc. They are promising commodities and advantageous to mineral-based
3
Industrial Chemistry Section, analogues due to their exceptional properties like their lubricity, biodegrad-
Department of Chemistry, School of
Physical Sciences, College of Agriculture
ability, reduced toxicity, and reduced volatility. Yet, their utilization as
and Natural Sciences, University of Cape lubricants is constrained due to their relatively poor cold-flow and thermo-
Coast, Cape Coast, Ghana
oxidative stability uncertainties even after being chemically modified. Hence,
4
Department of Environmental
many chemical modification pathways have been reported to overcome this
Engineering and Water Technology, IHE
Delft Institute for Water Education, Delft, limitation, with the most exploited approaches being esterification and trans-
The Netherlands esterification. This modification pathway enhanced the thermo-oxidative sta-
5
Department of Chemistry, Faculty of bility and the cold-flow properties of these bio-based oils, increased the yield,
Science, Aix-Marseille University,
Marseille, France
and enhanced the quality of the lubricants. With this in mind, this paper
reviews up-to-date works conducted in this area and critically report the
Correspondence
advancement in esterification and transesterification production of bio-
Samuel Kofi Tulashie, Industrial
Chemistry Section, Department of lubricants. The study further reviews the latest published literature, current
Chemistry, School of Physical Sciences, updates, and future perspectives related to the synthesis of biolubricants. Also,
College of Agriculture and Natural
the review highlights the significant factors that govern the entire reaction pro-
Sciences, University of Cape Coast, Cape
Coast -Takoradi Rd, Cape Coast, Central cess, selection criteria of renewable feedstocks, and the tribological perfor-
Region, P.M.B. University Post Office, mance of biolubricants.
Ghana.
Email: [email protected] KEYWORDS
bio-based sources, biodegradability, biolubricant, chemical modification, esterification/
transesterification, lubricity

1 | INTRODUCTION Besides, the growing use of fossil fuels at an increased

rate will cause an escalation of local air pollution and
The current global energy originates from fossil sources, exacerbate issues about the warming of the Earth as a
which would soon be exhausted in a short time due to result of CO2 emissions.1 New and sustainable lubricants
their limited amount for a significant number of people. are also needed to replace conventional lubricants

3860 © 2021 John Wiley & Sons Ltd. wileyonlinelibrary.com/journal/er Int J Energy Res. 2022;46:3860–3890.
 1099114x, 2022, 4, Downloaded from https://onlinelibrary.wiley.com/doi/10.1002/er.7453 by Egyptian National Sti. Network (Enstinet), Wiley Online Library on [09/11/2022]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons License
APPIAH ET AL. 3861

derived from fossil fuels. This could solve many recent components, same as being environmentally friendly.
environmentally-related challenges and will resolve Vegetable oils used for biolubricant are made from plant
issues concerning their sustainability.2,3,4 With additional seeds, either for human consumption or otherwise. Gen-
problems surrounding climate change on the global scale, erally, plant oils have outstanding properties for their
and exhaustion of oil reserves rising, the need for several possible utility as biolubricants.
environmentally friendly and sustainable options com- Biolubricant oils are suitable substitutes to conven-
pared with current practices continues to gain maximum tional and synthetic oils since they are environmentally
focus and attention.5 For instance, in Europe, yearly, friendly due to their biodegradability potential. Both
research has shown that 20% of the 5.2 million tonnes of boundary and hydrodynamic lubrication are obtainable
lubricant used is discharged into the ecosystem, and 1 kg from biolubricants as a result of their saturated/
of said mineral oil has the potency to contaminate large unsaturated extended fatty acid chains and the occur-
and significant volumes of water.6 Therefore, pollution rence of polar groups in the structure of vegetable oil,
caused by lubricants cannot be touted as insignificant. In rendering it amphiphilic.17 It is also noteworthy to know
addition, lubricants sourced from petroleum can destroy that additives play a critical role in lubricant formulation.
the soil directly and pollute the air.7,8 Lubricant producers have started a reformulation exer-
Health-wise, there have been several studies docu- cise as well as a redesigning of additives, such as fatty
menting the harmful effects of lubricants. In circum- amides, fatty alcohols, fatty amines, propyl gallate,
stances where there is a long-term breathing or skin engineered specifically for biolubricants with huge
exposure to crude oil-based lubricants, there is a proba- achievements17,18 instead of the usual mineral-based
bility of causing a high degree of inflammatory effects on additives. These additives act as anti-foams, anti-oxidants
the respiratory system and locality of the contact, aside (AO), anti-wear agents (AWA), detergents, dispersants,
from being carcinogenic.9 An area of importance that extreme pressure additives (EPA), friction modifiers
could act to cut back dependence on fossil fuel and (FM), pour point depressants (PPD), rust/corrosion inhib-
anthropogenic influence on the environment is the usage itors, and viscosity index improvers (VII).19,20,21
of biodegradable-based lubricants in place of the gener- It is worth knowing that several recent reviews have
ally applied petroleum-based lubricants. These products, been carried out on advancing the production of bio-
referred to as “biolubricants,” possess numerous environ- lubricants. Mcnutt et al,8 focused on vegetable oils' differ-
mental, health, and performance benefits over contempo- ent chemical modification pathways and highlighted
rary petroleum-based lubricants.8 A host of these their respective merits and demerits. In the excellent
biolubricants are highly decomposable, eco-friendly, and review of Syahir et al,22 they covered the various applica-
thus have a lower percentage of risk or zero risks to the tions of biolubricants where they looked at the molecular
environment or operators.9,10 Higher flashpoints, better structure and physicochemical characteristics of some
lubrication, lower evaporative losses, greater viscosity common feedstocks. Moreover, Ho et al,13 discussed and
indices, higher shear stability, better detergency, and underlined some commercial biolubricant compounds
greater dispersancy are some of the positive traits of made from vegetable oil. Also, they examined the promis-
biolubricants.11,12,13 ing Kolbe-electrolysis technology for the manufacturing
Irrespective of these merits, biolubricants are still not of renewable hydrocarbons. In the review report of
commercially used due to some challenges in their per- Wickramasinghe et al,23 they investigated the sustainable
formance and production. Unfortunately, low- machine applications of green metalworking fluids (bio-
temperature and low thermal-oxidative stability are the lubricants) and how to improve their unfavourable draw-
major performance setbacks characterized by bio- backs for lubricant use. Furthermore, Almasi et al,24
lubricants.14,15,16 However, both features can be upgraded covered the aspects of biolubricant production solely
to generate biolubricants via suitable chemical transfor- from non-edible oil-bearing biomass resources in Iran.
mation steps, a viable option to petroleum/mineral and Ailanthus, camelina, algae, castor, jatropha, bitter
synthetic lubricants for several applications.8 Over the almond, and waste fish oil feedstock were thoroughly
years, a host of research activities has centred on the con- captured. Additionally, Azim et al,25 looked at the use of
sideration of novel feedstocks and chemical alteration microwave-combined technology (ie, ionic solvent, a vac-
methods, the progress of developing very effective cata- uum, acoustic cavitation, and a supercritical-subcritical
lysts for the improvement of vegetable oils, and the opti- approach) for biolubricant and biodiesel synthesis via the
mization of the chemical modification process. transesterification process. The review showed that the
Biolubricant oil bases can be synthesized from natural combined technologies vastly enhanced the energy effi-
sources like vegetable oil and animal fat, which are ciency and the yield of bio-based products. The most
renewable and safe to humans and other ecosystem recent review work carried out by Salih and Salimon26,27
 1099114x, 2022, 4, Downloaded from https://onlinelibrary.wiley.com/doi/10.1002/er.7453 by Egyptian National Sti. Network (Enstinet), Wiley Online Library on [09/11/2022]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons License
3862 APPIAH ET AL.

highlighted the trends, challenges, and prospects of green found in VOs bring about low melting points as well as
food-grade biolubricants in terms of their biodegradabil- better thermo-oxidative stability and viscosity index, thus
ity, toxicity, toxicity testing methods as well as their such VOs are widely and generally preferred over the
global eco-labelling. However, a comprehensive review of other low oleic and palmitic acid content VOs for bio-
the recent updates and prospects on the potential of bio- lubricant production.6
lubricants production from solely esterification and trans- Another reason VOs are widely used in synthesizing
esterification processes are necessary. The esterification biolubricants is because of their environmentally friendly
and transesterification process as a chemical modification and biodegradability credentials.29 Through photosynthe-
pathway is the most pragmatic and highly studied in the sis, a significant amount of carbon (IV) oxide is absorbed
literature. from the atmosphere by vegetable oil-producing plants
Therefore, the specific objectives of this review can be compared with the amount contributed as a result of
stated as follows: (a) to discuss the feedstock selection burning.30,31 Table 1 shows the percentage composition
criteria used for biolubricant production, (b) to assess the of fatty acid by gas chromatography of some VOs.
advantages and disadvantages of the use of biolubricants VOs are obtained from various crop seeds with oil
as alternatives to mineral-based lubricants, (c) to outline quantities throughout the world.58,59 Palm kernel,60 coco-
the performance requirements of biolubricants, (d) to nut, castor,60 canola,59 soybean,61 sunflower,62 safflower,
evaluate the modifications of oils chemically via the rapeseed,63 cottonseed, jatropha,64 karanja,42,43 les-
esterification and transesterification process for the pro- querella, pennycress, and peanut oils are most commonly
duction of biolubricants, (e) to highlight the recent tribol- used VOs, with a host of many others in a pilot study for
ogy studies of biolubricants, and (f) to identify the their potential use. Although more research work has
challenges, current updates as well as future perspectives gone into both edible and non-edible oils for biolubricant
concerning biolubricant production. production, non-edible oils stand out as they are more
desirable and do not give any competition for culinary
usage. However, edible oils such as coconut and palm
2 | CRITERIA FOR kernel oils have shown great prospects for biolubricant
B I O LU B R I C A N T F E E D S T O C K S synthesis due to their high oleic and palmitic acid con-
tent.64 Major edible VOs such as jojoba oil, Crambe oil,
Feedstock usually used for producing biolubricants is soybean oil, tallow oil, palm oil, and canola oil could be
vegetable oils (VOs), as they are the most convenient raw used industrially for plastics, resins, detergents, lubri-
materials available. Chemically, VOs are natural oils that cants, and solvents.65
comprise triglycerides, esters of glycerol, and three Non-edible oils are oils that are not consumable. For
straight-chained fatty acids.6,23,24 Fatty acids from VOs example, jatropha oil derived from jatropha plant seeds is
are mostly in the category of C12-C24. These three fatty non-edible as it contains several harmful components.
acids are dependent on feedstocks and provide a vital The seeds contain toxalbumin curcin, a poisonous chemi-
function in ascertaining the properties of the oil.8 Double cal, and also contain carcinogenic phorbol. The jatropha
acyl bonds and the glycerol backbone (ie, large amount plant is highly tolerant of drought and pests and yields
of unsaturated fatty acids) present in the VOs give it a ter- seeds comprising 27% to 40% oil averaging 34.4%.66,67 The
tiary β-hydrogen, making it thermo-oxidative unstable, plant can grow in varied pH conditions; it can grow on
hence the need to enhance its physicochemical properties non-fertile lands. The Pistacia atlantica trees, commonly
via chemical modification mechanisms.28 Generally, found in Iran, share a similar fate to jatropha.42 Pistacia
chains with longer lengths result in high melting point atlantica mutica oil (PAM oil), an oil obtained from one
and viscosity, while those with more double bonds relate of the species of the P. atlantica trees, contains a high
to lower melting points and reduced viscosity.6 VOs pos- amount of α-tocopherol, which is a valuable antioxi-
sess high viscosities: a vital physical property of lubri- dant.42 Crops such as rubber plant, karanja, neem,
cants in the range of 30 to 50 cSt. Some special VOs such mahua, castor, rice bran, linseed, milkweed, coriander,
as castor oil show incredibly high viscosity of around and several others can be cultivated on nutrient-lacking
250.24 cSt due to the existence of a hydroxyl group on the land and do not compete with present agricultural
C9-carbon.6 This shows the lubrication potential of VOs resources.68 It is, for this reason, some researchers have
in their natural state and their good metal adherence. targeted and exploited their use in biolubricant produc-
Moreover, the closely packed carbonyl groups aid in for- tion lately.
ming monolayer film during lubrication activities of The prospect of applying waste cooking oil (WCO) for
metal surfaces, therefore reducing friction. However, biolubricant production is on the rise as more researchers
studies have shown that oleic and palmitic acid fractions are investigating its lubricity propensity. The availability
 TABLE 1 Percentage composition of fatty acid by gas chromatography of some bio-based oils

Oil source C6:0 C8:0 C10:0 C12:0 C14:0 C16:0 C16:1 C18:0 C18:1 C18:2 C18:3 C20:0 C21:0 C22:0 Reference
a
APPIAH ET AL.

Sunflower – – – – – 6.1 – 5.3 21.4 66.4 – – – – 32

High oleic sunflower – – – – – 3.5 – 4.4 80.3 10.4 – – – – 32
Safflower – – – – – 6.4 – 2.5 17.9 73.2 – – – – 32
High oleic safflower – – – – – 4.6 – 2.2 77.5 13.2 – – – – 32
High linoleic safflower – – – – – 6.7 – 2.6 14.6 75.2 – – – – 32
Soybeana – – – – – 6.0 – 5.2 20.2 63.7 5.0 – – – 32
High oleic soybean – – – – – 6.2 – 3.0 83.6 3.7 1.7 – – – 32
Corn – – – – – 10.6 – 2.0 26.7 59.8 0.9 – – – 32
Cottonseed – – – – – 18.0 – 2.0 41.0 38.0 1.0 – – – 32
Sunflowerb – – – – – 6.65 0.1 1.92 18.70 68.55 1.9 – – – 33
b
Soybean – – – – – 9.32 1.71 4.72 27.26 48.53 5.62 – – – 33
a
Jatropha – – – – – 14.59 – 10.5 39.59 33.51 0.69 – – – 33
Waste cooking oila – – – – – 19.71 1.9 18.38 22.88 31.82 2.02 – – – 33
c
Soybean – – – – 0.18 11.34 0.05 4.21 25.64 50.22 8.20 0.16 – – 34
b
Jatropha – – – – – 13.19 0.40 6.36 43.32 36.70 – – – – 35
a
Rapeseed – – – – – 3.5 – 0.9 19.4 22.3 8.2 – – – 36
Canola – – – – – 2.5 – 1 64.4 22.2 8.2 – – – 36
Peanut – – – – – 10 – 3 50 30 – – – – 36
Linseed – – – – – 5 – 3 22 17 52 – – – 36
Olive – – – – – 14 – 2 64 16 2 – – – 36
Coconut – – – – – 9 – 2 7 1 – – – – 36
a
Palm oil – – – – – 42 – 5 41 10 – – – – 36
Calabash (Bushel gourd oil) – 0.06 5.94 – 0.29 16.32 0.25 7.86 36.23 1.74 – 2.32 1.21 8.72 37
Calabash (Bottle gourd oil) – – – 0.11 0.16 0.02 – 0.10 25.90 65.80 0.08 0.005 – – 38
Calabash (Lump-in-neck bottle gourd oil) – – 0.0013 0.5100 0.1640 – 0.0240 – 29.5000 62.2000 0.0110 – – – 38
Citrullus linatus – – – 0.0350 0.0045 12.9000 – 7.7800 16.6000 61.6200 0.6100 – – – 38
Citrullus colocynthis – – – – – 10.10 – 9.58 18.40 60.90 0.61 – – – 39
b
Waste cooking oil – – – – 0 28.91 0.93 26.51 27.44 4.60 0.33 – – 39
Moringaa – – – – – 5.50 5.70 73.20 1.00 – 3.90 – 6.8 40
b
Moringa – – – – – 6.65 – 6.09 73.85 0.99 – 3.98 5.85 – 41
Salvia macrosiphon – – – – – 11.71 – 2.85 24.90 54.06 3.52 – – – 42
3863

(Continues)

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 TABLE 1 (Continued)
3864

Oil source C6:0 C8:0 C10:0 C12:0 C14:0 C16:0 C16:1 C18:0 C18:1 C18:2 C18:3 C20:0 C21:0 C22:0 Reference
Nourazak – – – – – 8.22 – 2.33 24.46 40.90 0.48 – – – 42
Yellow Indian mustard – – – – – 3.8 – 2.60 38.80 28.9 15.1 4.7 – 6.1 43
Brown Indian mustard – – – – – 3.7 – 2.40 39.00 28.9 15.3 4.7 – 6.0 43
Rapeseedb – – – – 0.076 4.75 – 1.496 66.955 16.79 7.803 0.495 – 0.37 44
High oleic palm oil – – – – 0.4 3.7 – 3.6 74.9 17.4 – – – – 45
c
Waste cooking oil – – – – 0.16 8.69 0.40 5.51 55.14 25.53 0.34 0.67 2.01 0.86 46
Palm fatty acid distillate (PFAD) – – – – 0.6 43.7 – 4.4 42.8 8.5 – – – – 47
Waste cooking oild – – – – 1.37 6.66 – 3.04 17.87 72.13 – – – – 48
Housefly larvae – – – 1.03 6.79 29.79 17.89 3.76 24.58 11.96 0.95 0.57 – – 49
Black soldier fly larvae – – 3.1 35.6 7.6 14.8 3.8 3.6 23.6 5.8 – – – – 50
e
Waste cooking oil – – – – 1.1 37.5 1.7 6.2 38.7 13.1 0.75 0.55 – – 51
Palm oilb – – – 0.2 0.9 42.4 – 4.3 42.1 9.8 0.3 – – – 52
b
Palm oil – – – 0.319 0.999 39.242 0.195 4.36 42.52 11.347 – – – – 53
d
Palm oil – – – – 0.63 41.85 – 3.58 44.85 9.09 – – – – 54
a
Palm kernel oil – 0.11 5.08 41.85 18.34 6.13 – 1.18 17.45 9.86 – – – – 4
Palm kernel oilb – 2.0 3.1 51.0 16.4 7.9 – 2.0 15.3 2.2 – – – – 55
a
Rubber seed – – – – – 9.3 0.2 8.4 25.4 41.1 15.3 0.3 – – 56
b
Rubber seed – – – – – 7.9 – 9.0 28.9 40.5 13.5 – – – 57

Note: “a to e” represent/show similar/same raw oil samples and their fatty acid compositions researched/investigated by different authors under different conditions.
APPIAH ET AL.

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APPIAH ET AL. 3865

of the WCO is one of the key reasons it is garnering more curvatus.73 The physicochemical characteristics of NPG-
interest in this field. Most importantly, the high cost of HMO obtained esters depicted they could be applied as
using virgin oils is recently also instigating such moves biolubricants and definite properties could be enhanced
since WCOs are relatively very cheap.47,48 Biolubricants after using additives.74 Table 2 shows the fatty acid
that are produced from WCO based biodiesel have pro- arrangement of microbial oils realized from yeast and
nounced enhanced properties (ie, viscosity index, flash fungal strains in batch fermentations applying flour-rich
point, and pour point) compared with the ISO VG10 base left-over derived hydrolysate.
oil standard, making it highly smart and a sustainable
substitute to fossil fuel-based lubricants.69
Furthermore, some oil-bearing crops have also been 3 | GENERAL O VERVIEW OF
genetically modified in recent times to be used as bio- BIOLUB RICANTS
lubricant bases. In that regard, these oils are converted to
high oleic vegetable oils (HOVOs) since oleic acid con- Biolubricants have cropped up as alternatives to substi-
tents in VOs increase the lubrication abilities of that oil. tute long-established mineral oils manufactured from
They give the oil a suitable balance of low-temperature petroleum in recent times despite being on a small scale
properties and high-temperature thermo-oxidative stabil- for now as the scientific world has driven towards that
ity. Seeds from palm, rape tree, and soya bean have cur- field. Some important fundamentals of biolubricants
rently been engineered using genetic methods, hence an include their merits and associated demerits, and physi-
alteration in their oil compositions.40,49 cochemical characterizations are subsequently explained.
Most recently, biolubricants have been produced from
microbial-derived oils via fermentation. This novel
approach of extracting oils is necessary because a homo- 3.1 | Advantages of biolubricants
geneous acidic catalyst generates impurities, and its
recovery is difficult. These effluents require treatment Decreasing wear and heat loss between two surfaces in
and high-water consumption during product purifica- motion is the main use of lubricants. They are used in
tion.50,51 Moreover, the use of basic catalysts during different industries such as agriculture, forestry, mining,
chemical hydrolysis causes oxidation of the final prod- and vehicle, assisting as engine oils, chainsaw oils, trans-
uct.70 Using biocatalysts in the form of enzymes repre- mission oils, and hydraulic oils.74 Lubricants reduce oxi-
sents a more sustainable process nullifying the challenges dation (corrosion) and act as insulators for transformer
of using conventional homogeneous catalysts as they purposes. Like good lubricants, biolubricants from coco-
offer high specificity and selectivity, inhibiting the forma- nut, palm kernel oil, and many others may less likely
tion of unwanted side products.71 Biolubricants produced undergo oxidation since they contain certain natural anti-
from a two-step enzymatic (lipase) process using castor oxidants such as tocopherols, phenolics, sterols, etc.
oil described by Greco-Duarte et al,72 were better in terms
of properties than most biolubricant in literature.
More so, high conversion yield was obtained through 3.2 | Disadvantages of biolubricants
enzymatic ester production of neopentyl glycol (NPG)
and trimethylolpropane (TMP) with hydrolysed microbial As mentioned earlier, biolubricants have a weak oppo-
oil (HMO) of Rhodosporidium toruloides and Cryptococcus sition to thermal and oxidative degradation due to the

T A B L E 2 Fatty acid composition of microbial oils obtained from yeast and fungal strains in batch fermentations applying flour-rich
waste-derived hydrolysate73

Myristic Palmitic Palmitoleic Stearic Oleic Linoleic Linolenic Linolenic Content of

acid acid acid acid acid acid acid acid saturated
Microbial strains (C14:0) (C16:0) (C16:1) (C18:0) (C18:1) (C18:2) (C18:3) (C18:3a) fatty acids
R. toruloides DSM 4444 1.5 28.2 0.5 6.5 53.2 8.8 1.1 – 36.2
R. toruloides NRRL Y-27012 1.4 24.2 0.7 6.7 55.3 9.5 2.1 – 32.3
C. curvatus ATCC 20509 0.5 26.3 0.9 10.8 52.7 7.4 0.7 – 37.6
M. ramanniana MUCL 9235 1.0 20.8 0.7 3.7 49.0 16.2 – 7.1 25.5
C. echinulata 0.4 15.1 1.2 2.9 49.3 17.5 – 11.8 18.4

γ-linolenic acid (GLA).

a
 1099114x, 2022, 4, Downloaded from https://onlinelibrary.wiley.com/doi/10.1002/er.7453 by Egyptian National Sti. Network (Enstinet), Wiley Online Library on [09/11/2022]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons License
3866 APPIAH ET AL.

existence of acyl groups in their molecules.75 The low existing characteristics and imparting neoteric properties
thermo-oxidative property of VOs has been reported to in regards to cutting down on energy and increasing the
be instigated by methylene intermittent poly-unsaturation.76 lifecycle of the machines.114,115,116 Generally, physico-
Furthermore, biolubricants have reduced low-temperature chemical properties of the lubricants such as hydrolytic
properties due to the creation of macrocrystalline assem- and thermo-oxidative stabilities, viscosity, pour point (cold-
blies (at reduced temperatures via even stacking of triglycer- flow ability), and reduction in corrosion/rust can be signifi-
ides' backbones), which restricts the effortless flowability of cantly improved. The adsorption of additives physically or
the fluids because the kinetic energy of the molecules is lost chemically to the surfaces of metal results in tribofilm,
through the self-stacking.77 which consequently averts abrasive wear of the surface and
reduces friction.117 Due to the eco-toxicity effects of some
additives currently used, such as molybdenum dithiocarba-
3.3 | Applications of biolubricants mate (MoDTC) and zinc dialkyldithiophosphate (ZDDP),
there has been a great interest in the use of eco-friendly
Over the years, synthesized and formulated biolubricants additives that may be of the organic or inorganic source.118
have been implemented on a small scale. Lubricants, as Recently, ionic liquids (ILs), polymers, and plant-
well as biolubricants, are utilized in systems that can be sourced compounds made up of heteroatoms and long-
open or closed. In closed systems, the lubricants are shut chain fatty acids have shown great potential as additives
within vessels to avert uncontrolled releases, unlike in of lubricants as well as biolubricants, hence remedying
the case of an open system, there is the discharge of bio- this environmental menace. In a most recent study by
lubricants into the environment. A summary of the uses Kontham et al,114 some novel thioether Schiff base addi-
of some of the biolubricants and their respective charac- tives (ie, containing substituted phenyl rings, sulphur,
teristics and advantages was captured in the excellent and nitrogen), which were produced from 10-undecenoic
review of Cecilia et al.65 Some of them could function as acid and different aromatic aldehydes, enhanced the tri-
hydraulic oils, insulating oils, compressor oils, transmis- bological performance and oxidative stability properties
sion oils as well as engine oils. of the lubricant base oil even at low concentration of
0.8 wt%.114 The Schiff base additives' class has been
shown to produce lubricants with high thermo-oxidative
3.4 | Performance requirements of resistance. The additives decreased the wear scar diame-
biolubricants ter by 21% to 30% at 0.6% and increased the viscosity of
the lubricant as well as the anti-friction tendencies. Also,
There are a few international bodies that regulate and Delgado et al, studied the potential of ethyl cellulose as
standardize the production of lubricants worldwide. additives for biolubricants, and it was evident at low con-
ASTM International, previously the American Society for centration that the viscosity of the biolubricants
Testing and Materials, and some other European bodies increased significantly.119 Moreso, Singh et al,120 synthe-
are responsible for the quality of the lubricants produced. sized cellulose laurate esters and evaluated their potential
The physicochemical traits of biolubricants ought to be as additives for biolubricants. The tribological perfor-
similar to those of mineral oil-based lubricants. There are mance was investigated, and the biolubricants exhibited
so many lubricant testing methods on the website of decreased wear scar diameter and the average coefficient
ASTM International. A number of the major standard of friction as the additives increased in degree of substitu-
ASTM tests comprise D97-12, D445, D2270, D2500, and tion and concentration. Hence, the overall lubricity attri-
D4172, which determine the most important properties butes of the lubricants were increased.120
including pour point, viscosity, viscosity index, cloud Ionic liquid additives are characterized by low melt-
point, and anti-wear characteristics, respectively.58,78 ing point, low eco-toxicity, low volatility, low flammabil-
Some standard commercial lubricants, in addition to ity, low vapour pressure, and relatively high
some raw (unmodified) VOs properties, are shown in thermochemical stability and lubricity properties (ie,
Table 3. antiwear, highly viscous, and friction reduction tenden-
cies).121 The tribological performance of a study con-
ducted by Gusain et al,122 shows the outstanding
3.5 | Additivization in blolubricants enhancement in the antifriction and antiwear features of
the lubricant. Furthermore, a study by Liu et al,123
Additives have a central task in upgrading the operation whereby chemically modified tung-oil-based fatty acid
of lubricant as well as biolubricant by bolstering the esters were used as additives to enhance the lubricity
 TABLE 3 Physicochemical characterization of some standard lubricants, raw bio-based oils, and esterified and transesterified biolubricants
APPIAH ET AL.

Viscosity Viscosity Pour Oxidative Wear scar Total base

Viscosity 100 C index Flashpoint point stability Coefficient diameter Number (Potential)
Lubricant type 40 C (cSt) (cSt) (VI) ( C) ( C) (min) of friction (mm) (mg KOH/g) Applications References

ISO standards

ISO VG 2 >1.98 – >90 70 40 – – – – Used as a low-pressure hydraulic fluid for: 79,80,81,82

• Lubricating high-speed spindle bearings in machine tools with
particularly minor gaps
• Devices that require precision such as laboratory equipment and
optical instrumentation

ISO VG 5 >4.14 – – 65 48 – – – – Used as a low-pressure hydraulic fluid for: 79,80,81,82

• Lubricating high-speed spindle bearings in machine tools with
particularly minor gaps
• Devices that require precision such as laboratory equipment and
optical instrumentation

ISO VG 10 >9 >2.6 >90 177 39 – – – – Used as a low-pressure hydraulic fluid for: 79,80,82,83
• Lubricating high-speed spindle bearings in machine tools with
particularly minor gaps
• Devices that require precision such as laboratory equipment and
optical instrumentation
ISO VG 15 >13.5 >3.3 >84 174 33 – – – – Used as a high operation hydraulic fluid mostly for: 79,80,82,83
• Cold applications (ie, cold stores, off shores and outdoors)
• Steering power and brake systems

ISO VG 22 >19.8 >4.19 >102 200 30 – – – – • Used as a high operation hydraulic fluid mostly used in airlines 79,80,82,83,84
for air tools
• Used in heat transfer parts in a generator

ISO VG 32 >28.8 >4.1 >90 204 6 – – – – • Used as a high operation hydraulic fluid for machine parts and 77,79,83,85
tools
• Used for turning, drilling, and sawing and other demanding
works

ISO VG 46 >41.1 >4.1 >90 220 6 – – – – Used as a high-pressure operation hydraulic fluid for: 77,79,83,85
• Industrial plant workings
• Gear shaping and other metal works

ISO VG 68 >61.4 >4.1 >198 226 6 – – – – Used as a high-pressure operation hydraulic fluid for: 77,79,83,85
• Systems that demand a large load-bearing ability

ISO VG 100 >90.0 >4.1 >216 246 6 1670.26 – – – Used as a high-pressure hydraulic fluid for: 30,57,79,85
• Industrial systems that demand a large load-bearing ability

ISO VG 150 >135 >14.5 >96 236 18 – – – – Used as a high-pressure operation hydraulic fluid for: 79,80,82,83
• Lubrication of heavy machine parts such as vacuum pumps
• Crankcase and mist lubrication
3867

(Continues)

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 3868

TABLE 3 (Continued)

Viscosity Viscosity Pour Oxidative Wear scar Total base

Viscosity 100 C index Flashpoint point stability Coefficient diameter Number (Potential)
Lubricant type 40 C (cSt) (cSt) (VI) ( C) ( C) (min) of friction (mm) (mg KOH/g) Applications References

ISO VG 220 >198 >19.4 >96 238 18 – – – – Used as a high-pressure operation gear oil for: 79,80,82,83
• Extremely high-temperature systems such as industrial
gearboxes, winches, conveyors, hoists etc.
• industrial pressure-feed systems

ISO VG 320 >288 >25.5 >96 245 10 – – – – Used as high-performing gear oil for: 79,80,82,83
• Extremely high-temperature systems such as industrial
gearboxes, winches, conveyors, hoists etc.
• Lubrication of other heavy machine parts/loads

Paraffin VG95 95 10 102 – – – – – – Used as a high-performing gear and/or hydraulic oil for: 86,87
• Lubrication of blades that cut paper
• Aids in mechanical mixing
• Lubrication of sewing machine parts

Paraffin VG460 461 31 97 – – – – – – Used as a high-performing gear and/or hydraulic oil for: 86,87
• Lubrication of blades that cut paper
• Aids in mechanical mixing
• Lubrication of sewing machine parts

Paraffin Gear oil H1 70 9.2 107 120 15 – – 0.54 – Used as high-performing gear oil for: 87,88
• Plain and ball bearings
• Used in the cosmetic, food and pharmaceutical industries as
plasticizers for capsules and tablets etc

SAE 20 W40 105 13.9 132 200 21 – 0.117 0.549 – Used as a high-performing engine oil for: 10,89
• Four-stroke motorcycle diesel engines

SAE 15 W40 99 13.7 136 230 30 – – – – Used as a high-performing engine oil for: 89
• Four-stroke motorcycle diesel engines

SAE 10 W30 71 10.5 135 220 25 – – – – Used as a high-performing engine oil for: 89
• Four-stroke motorcycle diesel engines.

SAE 20 W50 185 20.5 130 230 33 – – – – Used as a high-performing engine oil for: 89
• Four-stroke motorcycle diesel engines

SAE Crankcase 40 170.45 15.60 98 175 62 – – – 3.54 Used as a high-performing engine oil for: 60
• Four-stroke gasoline engines (ie, passenger cars, light trucks,
motorcycles, etc.)
• High-throttling engines in small cars and light trucks

R150 150.04 – – 195 – 931.16 – – – Used as a high-pressure hydraulic oil for: 90

• industrial machine applications such as drilling etc

AG100 216 19.6 103 244 18 – – – – Used as a high-pressure engine oil for: 91
• Two-stroke motorcycle engines
APPIAH ET AL.

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 TABLE 3 (Continued)

Viscosity Viscosity Pour Oxidative Wear scar Total base

APPIAH ET AL.

Viscosity 100 C index Flashpoint point stability Coefficient diameter Number (Potential)
Lubricant type 40 C (cSt) (cSt) (VI) ( C) ( C) (min) of friction (mm) (mg KOH/g) Applications References

SAE 75 W-90 120 15.9 140 205 48 – – – – Used as high-performance gear oil for: 92
• railway gearboxes and other heavy types of machinery such as
trucks and other passenger cars

SAE 75 W-140 175 24.7 174 228 54 – – – – Used as high-performance gear oil for: 93
• railway gearboxes and other heavy machinery such as trucks
and other passenger cars

SAE 80 W-140 310 31.2 139 210 36 – – – – Used as high-performance gear oil for: 92
• railway gearboxes and other heavy machinery such as trucks
and other passenger cars

Raw bio-based oils

Soybean 28.86 7.55 246 325 9 – – – – • Culinary purposes 94
• Bioenergy sources (ie, biodiesel, biolubricants, etc)

Sunflower 40.05 8.65 206 252 12 – – – – • Culinary purposes 94

• Bioenergy sources (ie, biodiesel, biolubricants, etc)

Passion fruit 31.78 – – 228 – 7.5 – – – • Culinary purposes, medicinal purposes 90

• Bioenergy sources (ie, biodiesel, biolubricants, etc)

Moringa 44.88 – – 204 – 28.27 – – – • Medicinal purposes 90

• Bioenergy sources (ie, biodiesel, biolubricants, etc)

Castora 250.24 19.45 88 240 60 – – – 0.17 • Medicinal purposes 60

• Bioenergy sources (ie, biodiesel, biolubricants, etc)

Castorb 218.18 – – – – – – – 2 • Medicinal purposes. 95

• Bioenergy sources (ie, biodiesel, biolubricants, etc)

Rapeseed 45.60 10.07 180 240 12 – – – – • Culinary and medicinal purposes 96

• Bioenergy sources (ie, biodiesel, biolubricants, etc)

Jatropha 35.4 7.9 205 186 6 5 – – – • Medicinal purpose 97

• Bioenergy sources (ie, biodiesel, biolubricants, etc)

Coconut 24.8 5.5 169 325 21 – 0.101 0.601 – • Culinary and medicinal purposes. 10
• Bioenergy sources (ie, biodiesel, biolubricants, etc)

Rice bran 40.6 8.7 169 318 13 – 0.073 0.585 – • Culinary and medicinal purposes 10
• Bioenergy sources (ie, biodiesel, biolubricants, etc)

Palm kernel 29.46 6.30 173 245 52 – – – 0.13 • Culinary and medicinal purposes 60
• Bioenergy sources (ie, biodiesel, biolubricants, etc)

Lesquerella 119.8 14.7 125 – 21 – 0.045 0.857 – • Culinary and medicinal purposes 98
• Bioenergy sources (ie, biodiesel, biolubricants, etc)

Pennycress 40.0 9.3 226 – 21 – 0.054 0.769 – • Culinary and medicinal purposes 99
• Bioenergy sources (ie, biodiesel, biolubricants, etc)
3869

(Continues)

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 TABLE 3 (Continued)
3870

Viscosity Viscosity Pour Oxidative Wear scar Total base

Viscosity 100 C index Flashpoint point stability Coefficient diameter Number (Potential)
Lubricant type 40 C (cSt) (cSt) (VI) ( C) ( C) (min) of friction (mm) (mg KOH/g) Applications References

Palm oil 52.4 10.2 186 – 5 – – – – • Culinary and medicinal purposes 99

• Bioenergy sources (ie, biodiesel, biolubricants, etc)

Karanja 43.42 8.35 1.72 – 9 – – – – • Bioenergy sources (ie, biodiesel, biolubricants, etc) 66

Pistacia atlantica mutica 37.9 8.19 199 175 3 – – – 0.12 • Bioenergy sources (ie, biodiesel, biolubricants, etc) 42
(PAM)

Bio-based derived biolubricants

Ethylene glycol soybean 27.643 4.643 72 305 15 – – – – Hydraulic fluid substitute 100
triester

Ethylene glycol palm 25.315 4.315 56 215 9.01 – – – – Hydraulic fluid substitute 100
kernel triester1

Ethylene glycol palm 32.67 6.10 232 216 6 – – – – Hydraulic fluid substitute 101
kernel triester2

TMP jatropha triester 42.57 9.37 215 183 6 – – 0.33 – Hydraulic fluid substitute 64

2-ethyl-2-hydroxymethyl- 75.5 10.7 128 210 – 296.4 – – – Hydraulic fluid substitute 2

1,3-propanediol rape
seed triester

TMP palm kernel triestera 41.76 8.73 154 320 10 254 – – – Hydraulic fluid substitute 102

TMP sesame triester 35.55 7.66 193 196 21 – – – – Hydraulic fluid substitute 103

TMP rape seed triestera 35.34 7.99 209.2 – 15.5 – – – – Hydraulic fluid substitute 103,104

TMP castor triester 45.3 9.21 191 215 8 – – – – Hydraulic fluid substitute 105

TMP palm kernel 42.53 10.65 139 235 11 – – – – Hydraulic fluid substitute 4
triesterb

Isoamyl alcohol Moringa 68.0 8.8 102 – – – – – – Hydraulic fluid and/or cutting/metal and working fluid substitute 106
oleifera Lam triester

TMP yeast crude oil 47.80 9.65 192 320 30 11 – – – Hydraulic fluid and/or transmission oil substitute 107
triester

TMP yeast oil triester 47.33 9.59 193 321 45 10 – – – Hydraulic fluid and/or transmission oil substitute 107

TMP cotton triester 51.89 8.53 140 296 6 – 0.07484 0.849 – Hydraulic fluid and/or transmission oil substitute 108

TMP Litsea cubeba kernel 28.92 5.99 163 258.3 15 35 – – – Hydraulic and transmission fluid substitute 109
triester

TMP oleic acid triester 224.34 37.20 237 320 34 – – – – Hydraulic and transmission fluid substitute 110
(trioleate
trimethylolpropane)

TMP rapeseed triesterb 12.2 3.7 163.7 244 15 72 – – – Hydraulic and transmission fluid substitute 111
APPIAH ET AL.

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APPIAH ET AL. 3871

properties at low concentrations of the base oil. The over-

Note: “a and b” represent/show similar/same raw oil samples the same/similar bio-based derived biolubricants synthesized from similar/same tertiary alcohol and raw oil samples, researched/investigated by different authors under
References
all lubricity properties were enhanced remarkably.

112

112

113
3.6 | Physicochemical characterization
of biolubricants

Lubricants and biolubricants have certain features that

determine their performance and suitability for certain
applications. Some of these include:
Hydraulic and/or transmission fluid substitute
Hydraulic and transmission fluid substitute

Hydraulic and transmission fluid substitute

3.6.1 | Viscosity

The viscosity is the key physical/rheological property of

lubricant and biolubricant, and it is defined as the mea-
sure of resistance to flow by fluid substances. The two
(mg KOH/g) Applications

types of viscosity of importance to the oil industries

(Potential)

include kinematic viscosity and dynamic viscosity. Kine-

matic viscosity refers to the resistance to the flow of a
fluid under gravity, whereas dynamic viscosity is the
Wear scar Total base

measure of internal resistance. This property is usually

Coefficient diameter Number

measured in two temperatures (100 C and 40 C). Gener-

ally, biolubricant performs the function of reducing fric-
–

tion between metal surfaces, thus the ability of a

of friction (mm)

lubricant to flow easily between metal parts is critical. A

biolubricant with low viscosity will flow too easily
–

between metal parts. As a result, it will not accomplish

its basic function unless used for very light duties such as
automotive transmission or hydraulic oils. Moreover, bio-
–

lubricant of high viscosity (ie, very thick) will flow with

Pour Oxidative
Flashpoint point stability
( C) (min)

much difficulty, hence not able to lubricate most metal

parts.124 A good biolubricant must have an optimum vis-
–

cosity concerning the type of work it is intended for.

29
3

3.6.2 | Viscosity index

( C)

250
–

–
Viscosity Viscosity

The viscosity index (VI) of a biolubricant is an arbitrary

index

number that defines the rate of change of viscosity with

(VI)

199

167

135

temperature. It is usually estimated from viscosity values

measured at 40 C and 100 C. The higher the VI, the
Viscosity 100 C

8.324

4.930

22.29
40 C (cSt) (cSt)

smaller the effect of temperature and the less the oil will
thin at a higher temperature.76 Operating machinery sys-
tems that require higher temperatures will require bio-
Oleic acid jatropha curcas 220.00
38.64

21.22

lubricants with high VI.

(Continued)

TMP soybean fatty acids

NPG soybean fatty acids

distillate (SFAD)

distillate (SFAD)

3.6.3 | Flash point

different conditions.
Lubricant type
TABLE 3

octaester
triester

triester

The flash point is the lowest liquid temperature adjusted

to a pressure of 101.352 kPa at which function of the test
flame causes the vapour of the test specimen of the
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3872 APPIAH ET AL.

sample to ignite and maintain burning for a minimum of paramount to maintain, protect equipment, and prevent
5 seconds.79,80 The flash point determines the flammabil- damage in advance. TAN is determined by applying
ity hazard of biolubricants and lubricants; the tempera- ASTM D664-18.
ture at which the biolubricant forms a combustible
mixture with air when the biolubricant is heated in an
engine. The flashpoint of each biolubricant can be deter- 3.6.8 | Total base number
mined by using various ASTM standard tests and ISO
standard procedures, but it can easily be determined The total base number (TBN) is the number of basic con-
using the ASTM D92-18, by the Cleveland open cup COC stituents in petroleum products and biolubricants.129 The
method.125 basic constituents contained in the biolubricants are due
to the alkaline additives' formulation needed to neutral-
ize the build-up of acids, which may cause corrosion dur-
3.6.4 | Fire point ing combustion. It can be referred to as a measure of
biolubricant degradation in service. TBN is determined
The fire point is a flammability hazard indicator, which by applying ASTM D2896-15.
is the temperature at which the biolubricant combustion
would be prolonged for, at least, 5 minutes once the igni-
tion source has been detached. It determines the volatil- 3.6.9 | Iodine value
ity and fire resistance of the biolubricant. It can also be
determined by applying ASTM D92-18.125 The iodine value (IV) is a degree of the unsaturation of
biolubricants, and it is denoted by the number of centi-
grams of iodine absorbed per gram of sample.130 Bio-
3.6.5 | Pour point lubricants characterized with a higher iodine number
exhibit poor thermo-oxidative stability due to the exis-
Pour point (PP) is the lowest and last temperature at tence of more C═C bonds. Iodine value is characterized
which the biolubricant ceases to flow at specific condi- by seed oils, making them better raw materials for soaps,
tions particularly colder temperatures.126 It is an index of lubricants, pharmaceutical, and cosmetics industries.96 It
the lowermost temperature of its utility for certain appli- is determined by applying ASTM D5554-15.
cation flow matrices. The resistance to movement of the
biolubricant in such cold temperatures is due to the for-
mation of wax, thus increasing the viscosity of the 3.6.10 | Thermo-oxidative stability
biolubricants.
Thermo-oxidative stability is one of the chemical proper-
ties that characterize a biolubricant. It predicts the bio-
3.6.6 | Cloud point lubricants' service life, especially in higher temperature
conditions.124 Most VOs have relatively low oxidative sta-
The cloud point (CP) is the temperature of the bio- bility as a result of the increased unsaturation and acyl
lubricant at which wax crystals have been created ade- groups in their molecules. Oxidation of biolubricants
quately to be seen as a cloud with a resolution of may cause polymerization and increase viscosity.131 Mod-
0.1 C.127 It is typically higher than the PP. Wax crystals ifying VOs chemically through esterification and trans-
of appropriate quantity can plug filters applied in some esterification reactions, epoxidation, estolides formations,
fuel systems, therefore leaving deposits on surfaces of and hydrogenation can increase the oxidative stability of
those fuel systems. these VOs.

3.6.7 | Total acid number 3.6.11 | Hydrolytic stability

The total acid number (TAN) depicts the number of acid Hydrolytic stability is one of the crucial features of a
constituents in lubricants and biolubricants. It is appro- lubricant as well as a biolubricant. In the presence of any
priate for determining acids whose dissociation constants chemical attack where water is either the product or reac-
are smaller than 10 9.128 It measures lubricant degrada- tant, it predicts the relative stability/resistance of the bio-
tion in service. The TAN value indicates the potential of lubricant under such conditions. Biolubricants comprise
corrosion to machine parts. Running a test for TAN is esters of which are disposed to hydrolytic breakdown by
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APPIAH ET AL. 3873

their alcohols and carboxylic acids. The use of short- TABLE 4 Chemical modification pathways of (unsaturated)
chain and branched alcohols during transesterification of fatty acids
VOs into biolubricants has shown tremendous stability Modification pathway Catalyst (s)
for hydrolysis.132 Unstable lubricating fluids produce
Modification of carboxyl groups
acidic and non-soluble toxicants that induce corrosion
and change the lubricant's viscosity. It is determined by Esterification/transesterification Acids, bases
applying ASTM D2619-09 (2014).133 Estolide formation HClO4
Modification of (unsaturated) fatty acid chains
Selective hydrogenation Copper catalysts
4 | CHEMICAL MODIFICATION OF Dimerization/oligomerization Aluminosilicates
O IL S F O R B IO L U B R I C A N T S
Diels-Alder cycloaddition –
SYNTHESIS
Telomerisation H2O vapour

Several methods can chemically modify and transform Co-oligomerization RhCl3.3H2O

vegetable and microbially derived oils to improve their Hydroformylation(oxo-synthesis) Rh (Ph3P)3
physicochemical properties. Previous studies have dis- Friedel-Crafts alkylation Et3Al2CL3
closed that the genetic engineering of the fatty acid pro- Aminoalkylation [Rh (COD)Cl]2
file of oils, straight addition of antioxidants, viscosity
Friedel-Crafts acylation EtAICI2
modifiers, and PP depressant to vegetable oils are not as
Ene-reaction EtAICI2, SnO4
propitious as chemical modification about improving
chemical and wide temperature range stability of the Radical addition Mn (OAC)3, Cu
VOs. Transformation of the fatty acid chain triggers a Acyloxylation Nafion/SiO2
balance between the subsequent criteria: performance Cyclopropanation CH2l2, Zn (Cu)
(tribological properties), stability towards oxidation, low- Metathesis Grubbs' catalyst
temperature behaviour, biodegradability, and cost.134,135 Epoxidation Peracids, chemo-enzymatic
Currently, only a few modification reactions are industri-
Ozonation –
ally applicable due to appropriate highly selective cata-
Oxidative cleavage Pb3O4
lysts and for cost purposes. There is so much potential in
this field. Various chemical modifications of VOs are
summarized in Table 4,135 of which the most common
derivatization/transformations are esterification and reaction of hydrogen with the unsaturated fatty acid
transesterification, estolides formation, epoxidation, and profile, which causes isomerization of those acids into
selective hydrogenation. However, this paper highlights their cis- and trans- forms. Selective hydrogenation
the chemical modification pathway of esterification and may result in solid biolubricants, and the presence of
transesterification in the subsequent section, covering the wax in the biolubricants as the degree of unsaturation
recent updates in this field. is reduced and the thermo-oxidative stability is
Taking estolides into consideration, they have increased. A major setback of this chemical modifica-
branched esters formed when one fatty acid connects to tion method is the requirement of high temperature
the site of unsaturation of another fatty acid and forms during the reaction.
carbocation via nucleophilic addition/attack with the Furthermore, epoxidation of VOs modifies the double
help of Brönsted acid catalyst and an oxidant.136 This bonds (alkenes) present and integrates alkyl side chains,
reaction causes a chemical modification of the triglycer- transforming them into biolubricants with better lubricity
ide molecules in the VO, which makes the produced and enhanced thermo-oxidative and anti-wear proper-
branched esters (estolides) more hydrolytically and ties.137 It takes place in the presence of hydroperoxides
thermo-oxidatively stable, and finally with high viscosity and other carboxylic acids. Some major concerns about
indices hence more suitable for biolubricants applica- this chemical modification method are the relatively
tions. The major demerit of estolides formation is its asso- decreasing viscosity index and also decreased cold-
ciated high cost of production. It is noteworthy to know temperature properties. To curb this situation, the
that estolides and also products with opened rings can epoxidized VO can undergo hydroformylation, trans-
also be transesterified. esterification, cooligomerization, acyloxylation, amino
For selective hydrogenation, the main modification alkylation, alkylation, hydroaminomethylation, or acyla-
of the vegetable-based oil is characterized by the tion, to increase its lubricant potential.
 1099114x, 2022, 4, Downloaded from https://onlinelibrary.wiley.com/doi/10.1002/er.7453 by Egyptian National Sti. Network (Enstinet), Wiley Online Library on [09/11/2022]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons License
3874 APPIAH ET AL.

4.1 | Biolubricants synthesis using conversion efficiency and yield and the yield and cost of
esterification and transesterification production.138 This molar ratio is monitored in the first
process stage of the whole process. To boost the contact between
the molecules of the alcohol and that of the triglycerides
The reaction of a carboxylic acid and an alcohol to create as well as enhance the miscibility of the two reactants, it
an ester as the product of the reaction is an esterification is essential to use higher molar ratios as compared to the
reaction process. Concerning bio-based oils like VOs, the stoichiometric molar ratio of 3:1.141 As a matter of fact,
chemical structures are made of natural esters (triglycer- molar ratios of 4-6:1 or above are needed for an effective
ides) that need to be transesterified to produce better reaction.141 The high amount of methanol has been asso-
lubricity qualities. For biolubricant production, the trans- ciated with the breaking down of the bonds holding
esterification reaction is a two-staged process. The first together the glycerin and the fatty acid.142 Several studies
stage process is the reaction in which the triglyceride have shown that increasing the molar ratio of the pri-
molecule reacts with primary short-chain alcohol such as mary alcohol and the oil could enhance the yield and
methanol/ethanol to form another alcohol and mixtures purity of the produced biodiesel. In an optimization study
of fatty acid methyl/ethyl esters (FAME/FAEE). It is carried out by Eevera et al,143 using the methanol
worth knowing that methanol is the preferred alcohol amount in the range of 120 to 240 mL, it was evident that
due to its inherent physicochemical attributes such as the maximum yield of methyl ester was reported at a
being easily dissolved in a sodium hydroxide (NaOH) methanol content of 180 mL and 210 mL for edible and
solution and its fast triglyceride reaction.138 Methanol is non-edible oils, respectively. In another study by Patil
known as the “wood alcohol” because of its readily et al,144 an acid-catalysed esterification reaction exhibited
availability.139 the maximum ester conversions for jatropha and karanja
The second-stage transesterification process is the oil at 90% to 95% and 80%, respectively, at a methanol
reaction of the vegetable oil-derived methyl esters with and oil molar ratio of 6:1.
polyols, to produce triesters (biolubricants). The primary Also, the second stage of the biolubricant synthesis is
merit of employing a polyol is the absence of α-hydrogens affected by the molar ratio of the polyol and the produced
that augments the thermal stability of the biolubricant at FAME to be used. The esterification and trans-
high temperatures by preventing self-polymerization esterification reaction achieves equilibrium before attain-
from forming free fatty acids. Figure 1 shows the esterifi- ing a complete conversion because it is a reversible
cation and transesterification (ie, two-staged) reaction reaction.
process using tertiary alcohol, TMP. In agreement with Le Chartelier's principle, a higher
molar ratio than that from stoichiometry would guaran-
tee a better yield as the whole reaction will be driven to
4.2 | Factors that affect the esterification completion.
and transesterification process However, there is a controversy in the literature stud-
ies as to whether increasing the alcohol as compared with
Catalyst type and loading, the water content in alcohol, the FAME would increase the biolubricant yield. With
reaction temperature, reaction or contact time, reactants that said, excess FAME is used by some researchers
molar ratio (primary alcohol: oil and FAME: polyol), stir- because of its relatively low cost as against that of the
ring rate, and free fatty acids in the biomass oil affect the alcohol.144 Also, at a higher molar ratio of the FAME to
transesterification process.45,102,140 However, only the alcohol, a significant triester yield was achieved in some
influence of the critical parameters such as the molar cases.145 In the report of Menkiti et al,140 they tabulated
ratio of primary alcohol/oil and polyol/FAME, reaction the percentages of triester yield at different combinations
temperature and time, catalyst type and loading are sub- of Jatropha methyl ester and TMP molar ratio and that of
sequently highlighted. different temperatures. It was evident that at the highest
temperature of 160 C and a molar ratio of 7:1, a remark-
able 84% of triesters (biolubricant) was achieved and this
4.2.1 | Molar ratio of primary alcohol/oil could be seen as the molar ratio of the FAME to alcohol
and polyol/FAME kept increasing. In contrast, Encinar et al,146 reported a
biolubricant (ie, from rapeseed and castor) yield of
The molar ratio of the reactants (primary alcohol and oil) around 93% using 2-ethyl-1-hexanol: FAME molar ratio
is one of the key aspects of the esterification and trans- of 3:1 at 160 C, 250 minutes and a catalyst (titanium
esterification process. It influences biodiesel's (FAME) isopropoxide) concentration of 1% w/w. This result
 1099114x, 2022, 4, Downloaded from https://onlinelibrary.wiley.com/doi/10.1002/er.7453 by Egyptian National Sti. Network (Enstinet), Wiley Online Library on [09/11/2022]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons License
APPIAH ET AL. 3875

FIGURE 1 Esterification and transesterification (two-staged) reaction using a polyol, TMP

justifies Le Chartelier's principle. It is worth knowing 2,2-dimethyl-1,3-propanediol and cardoon-oil-derived-

that the operating costs may increase with a high amount FAME and 1.5% Ti (IV) isopropoxide catalyst. Also, Resul
of alcohol because of the amount of alcohol that needs to et al,64 recorded a similar trend whereby the highest yield
be evaporated after the reaction, which demands a higher of jatropha triester (ie, 47.38%) was recorded at 200 C
heat load.147 with reaction conditions of 1.0% (wt/wt) of sodium
methoxide catalyst and after 3 hours of reaction. At ele-
vated temperatures, the esterification and trans-
4.2.2 | Reaction temperature and esterification reaction rate increases, but the probability
reaction time of reverse reaction occurrence is high when not con-
trolled, leading to a reduction in the triester yield.
The two-stage esterification and transesterification of oils Esterification and transesterification reaction pro-
for the synthesis of biolubricants are highly influenced by cesses like most processes are affected by the reaction
the reaction temperature as well as the reaction time. time. From reaction kinetics, it is evident that the longer
Kinetically, the reaction temperature affects the reaction the two-stage esterification and transesterification reac-
rate and the yield of the produced biolubricant. To avoid tion process, the higher the conversion of the triglycer-
evaporation of the primary alcohol used during the ides into FAME and as well as into polyol esters.
FAME synthesis, the temperature used must be less than However, there are reports of contrasting results espe-
its boiling point.148 In the first stage of the whole process, cially when the esterification and transesterification pro-
an increase in temperature yields a high amount of cesses are enzymatically catalysed. Some studies show
FAME as evidenced in the case of Istiningrum et al.149 high FAME yield at low reaction time and vice-versa.
The waste cooking oil methyl ester content significantly Sbihi et al,152 reported a high FAME yield (>80%) at a
rose (ie, 60%-80%) as the temperature increased from shorter period of 4 hours for Prunus mahaleb biodiesel
45 C to 55 C in the enzymatically catalysed trans- production using lipase/enzyme as a biocatalyst at condi-
esterification. This assessment is in line with a lot of stud- tions of 40 C and methanol: oil molar ratio of 5:1,
ies in the literature.150 The same analogy is translated to whereas Amini et al,153 showed a higher yield of FAME
the second stage of the process. At higher temperatures, (>92%) at a longer period of 68 hours for a lipase-
higher yields and purity of triesters (biolubricants) are catalysed transesterification of Ocimum basilica L. (sweet
synthesized. In the most recent studies made by Delgado basil) seed oil at conditions of 40 C, 12:1 M ratio of meth-
et al,151 over 90% biolubricant yield was obtained as the anol to oil. The former results were in line with the study
temperature increased from 100 C to 140 C. This was of Afifah et al,154 where the palm stearin trans-
reported at reaction conditions of a 1:1 M ratio of esterification was enzymatically catalysed. These
 1099114x, 2022, 4, Downloaded from https://onlinelibrary.wiley.com/doi/10.1002/er.7453 by Egyptian National Sti. Network (Enstinet), Wiley Online Library on [09/11/2022]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons License
3876 APPIAH ET AL.

enzymatical transesterification reactions are character- esters and triglycerides mixture.158 Secondly, these pro-
ized by the specificity of the enzyme as well as the oil duced esters are then transesterified using a base catalyst
make-up and choice of alcohol. Continuous reactor sys- with methanol/ethanol as the alcohol source. However,
tems such as packed bed reactor (PBR) fluidized-bed the slow acid-catalysed transesterification process
reactors (FBRs) have been shown to offset for the long requires a higher temperature, and it is independent of
reaction time for enzymatically catalysed reactions.153 the feedstock category. Recent acid-catalysed esterifica-
Furthermore, most acid and base-catalysed reactions tion and transesterification studies show significant con-
show higher FAME yields at longer reaction times. In a version (ie, >91% and >98%) and yield (ie, >79% and
kinetic study of esterification reaction of 10-undecenoic >80%) for Bahadi et al,156 and Moreira et al,159
and ricinoleic acids and supercritical methanol, Narayan respectively.
et al,147 reported more than 80% conversion at different Moreover, it is worth noting that homogeneous cata-
molar ratios (ie, 1:1;2:1;5:1, and 40:1). For both reactions lysts possess certain demerits. They consume a lot of
(ie, methanol and 10-undecenoic acid and methanol and energy and are corrosive. Also, they are difficult to
ricinoleic acid), the conversion of the reactions increased retrieve from the solution. Applying heterogeneous solid
with time at respective temperatures of 523 K, 573 K, and enzymatic catalysts in the transesterification process
623 K, and 673 K. For the second-stage process, a similar has become widespread lately due to the disadvantages of
relationship is witnessed at a longer period of the process. homogeneous catalysts and their excellent biolubricant
Idrus et al,155 reported the higher conversion of the palm conversion results. Heterogeneous acid catalysts, for
oil methyl ester (POME) using pentaerythritol alcohol example, ion-exchange resins, sulfated inorganic oxides,
(PE) at 2 hours for conditions of 160 C, POME: PE molar inorganic super-acids (WO3/ZrO2) as well as the basic
ratio of 4.5:1, 10 mbar and 1.25% w/w NaOCH3. Higher catalysts such as alkaline earth oxides (CaO, MgO),
PE tetraester (36%) was formed with no trace of PE alco- alkali-supported catalysts (KF/K2CO3 or KNO3 supported
hol at the end of the reaction. Results from a recent opti- Al2O3), zeolites, and guanidine-supported catalyst are
mization biolubricant synthesis (ie, from Elaeis being utilized for several research activities in recent
guineensis kernel oil) study by Bahadi et al,156 showed a times.160 As mentioned above, Encinar et al,146 reported
similar trend when the reaction time increased using di- a 93% biolubricant yield from rapeseed and castor oils
trimethylolpropane (Di-TMP) as the polyol and sulphuric using titanium isopropoxide. Additionally, Oh et al,161
acid as catalyst. The optimum reaction yield (> 79%) synthesized soybean biolubricants using sulfated zirconia
selectivity of tetraester was reached at a time of catalysts [Zr (OCH2CH2CH3)4] at conditions of 140 C,
4.61 hours with a selectivity of tetraester of 91%. It is pru- 4 hours, and catalyst weight of 100 mg. The results
dent to suggest the importance of this reaction showed a > 90% oleic acid conversion and a biolubricant
parameter. yield of 84%.
In the case of enzymatic catalysed esterification and
transesterification reactions, Cavalcanti et al,61 synthe-
4.2.3 | Catalyst type and catalyst loading sized soybean oil biolubricants using three commercial
lipases (ie, Candida rugosa, Rhizomucor miehei, and Can-
Transesterification reactions can be catalysed by either dida antarctica) immobilized onto microporous polypro-
homogeneous (acid/base), heterogeneous, and enzymatic pylene beads with different polyhydric alcohols (ie,
catalysts. Homogeneous bases catalyse the reaction by neopentyl glycol, NPG; trimethylolpropane, TMP; and
eliminating a proton from the alcohol, therefore increas- pentaerythritol, PE). In the end, biolubricants from Can-
ing reactivity. In contrast, acids catalyse the reaction by dida rugosa reported the highest conversions for all three
providing a proton to the carbonyl group, thus increasing polyols (ie, 97% for NPG, 100% for TMP, and 55% for PE)
reactivity.157 For the base catalyst to be used for biodiesel followed by the results of Candida antarctica and
synthesis, the fats and oil source should be fatty-acids- Rhizomucor miehei enzymatically catalysed reactions.
free or the FFA should be negligible.158 The presence of Moreso, Afifah et al,154 showed excellent results in their
FFAs leads to soap formation as a result of the base cata- recent study in enzymatic transesterification of palm oil
lyst being used.158 Low-quality feedstocks comprise non- biolubricant. They employed Candida antarctica lipase
edible VOs, animal fats, waste cooking oils, and grease. and produced a maximum yield of 95% at 60 C, 8 hours,
Acid catalysts such as H2SO4, HCl, H3PO4 function much and lipase concentration of 6.0 wt%. Additionally, Ma
more slowly than their base counterparts. Therefore, to et al,107 used microbial oil (R. glutinis lipid) for enzymatic
synthesize biodiesel from a low-quality feedstock, the ini- transesterification. Candida sp. 99 to 125 enzyme was
tial step to be considered is converting the FFAs into employed in the process and a yield of 89.5% TMP triester
acid-catalysed esters, which results in fatty acid alkyl was reached at conditions of 26 hours; 50 C; FAME:
 1099114x, 2022, 4, Downloaded from https://onlinelibrary.wiley.com/doi/10.1002/er.7453 by Egyptian National Sti. Network (Enstinet), Wiley Online Library on [09/11/2022]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons License
APPIAH ET AL. 3877

TMP ratio of 3.4:1; and enzyme loading of 15 wt% towards environmentally friendly lubricants due to their
(5250 U/g substrates). The tribological characteristics of excellent tribological performance.170 As a result, there
the produced biolubricant were comparable with petro- have been numerous reports and research on using bio-
leum and mineral-based alternatives with the equal vis- lubricants with advanced lubricity and reduced friction
cosity grade (ie, ISO VG46). and wear for special applications. Singh et al,170 altered
Considering the influence of catalyst loading or con- desert date oil with copper nanoparticles to lessen the
centration, several studies have positively influenced the friction and wear behaviour of the biolubricants com-
two-stage esterification and transesterification reac- pared with the traditional lubricants. Moreover, Soltani
tions.106-110 Ghafar et al,162 produced biolubricants from et al,171 compared the biolubricants such as Crambe seed
waste cooking oil (WCO) from the solid heterogeneous oil, linseed oil, and jojoba oil with petroleum based-
catalyst (ie, CaO was obtained from waste cockle shell). lubricant to evaluate their tribological performance. The
They reported a rise in triesters conversion from 94% to biolubricants displayed improved and acceptable wear
97% with increasing catalyst concentration (ie, from 3% and lubricity behaviour than the petroleum based-lubri-
to 5% w/w) in the two-stage esterification and trans- cant, depending on their proposed applications. Other
esterification reaction at a constant molar ratio of FAME recent applications of biolubricants prepared by the ester-
to TMP (3:1). Furthermore, Hussein et al,3 reported ification and transesterification process with enhanced
results that showed an increment in conversion (ie, from tribological behaviours have been reported by Hamdan
62% to 98%) when the CaO catalyst loadings were et al,172 Hassan et al,173 Wan et al,174 Ameen et al,175
increased from 0.8% to 1.5% (w/w) at reaction conditions Pérez-de Brito et al,176 and Gemsprim et al.177 However,
of 130 C; 90 minutes; and 3.5:1 M ratio of FAMEs: ethyl- biolubricants in the preceding years underperformed in
ene glycol. Similar results were reported in the research certain applications at high temperatures and highly oxi-
studies of Afifah et al,154 and many others. It is essential dative environments, affecting their tribological perfor-
to suggest the eminence of catalyst loading in the two- mance. This is because the maximum of the produced
stage esterification and transesterification reaction pro- biolubricants is obtained from vegetable sources, with
cess to produce biolubricants. some portions containing high unsaturated fatty acids
exposing them rapidly to lipid oxidation. Low oxidative
stability means that the oil, when used as a biolubricants,
4.3 | Tribological performance of will oxidize rapidly, mostly at extremely high tempera-
biolubricants tures and in the oxidative environment when the antioxi-
dants begin to degrade.164 In this scenario, a corrosive
The area of tribology has tended to be important in the film can develop on the surface of the lubricated mate-
evaluation of biolubricants for various applications. rials reducing the tribological performance of the bio-
Experts in tribology employ the science and notion of tri- lubricants.123,130,132 Yet, biolubricants from tropical oils
bology studies concerning the interacting surface in rela- sources (coconut oil, palm oil, and palm kernel oil) have
tive motion to investigate friction, wear, and lubricity of been unveiled to have high oxidative stability due to their
lubricants.163 Generally, friction is the resistance when large quantities of saturated fatty acids and natural anti-
two bodies are in motion resulting in wear and tear.118,119 oxidants.134,135,136 Furthermore, few reports revealed VOs
The studies and impact of tribology have expanded across have low or high-temperature limitations, affecting the
diverse disciplines, which cannot be covered in this lubricity, wear, and frictional behaviour of the bio-
review. Specific details of tribology can be found in the lubricants.19,120,123 These challenges have been the bottle-
study reported by Ciulli et al,163 Meng et al,164 Jason neck of biolubricants tribological performance for the
et al,165 Gulzar et al,166 Sazali et al,167 Sun and Du,168 preceding years.19,137
and Philip et al.169 In this review study, we considered Recently, key chemical modifications along with the
the recent evaluation of the tribological performance of esterification and transesterification approach have sub-
biolubricants. It is worth noticing that the majority of the dued these limitations to advance their tribological
biolubricants reported in this section for their improved behaviour in extreme thermo-oxidative conditions. As
tribological performance were synthesized by the esterifi- pre-discussed, introducing ionic liquids additives (ILs)
cation and transesterification process. into biolubricants has been established to stabilize the
As already disclosed in the literature, biolubricants low thermo-oxidative behaviours of specific bio-
specifications and utilization for a given application, lubricants. ILs are liquid salts bearing cation and anion
studies, and production can be identified by examining at room temperature or below 100 C. The widespread
its tribological performance. Lately, the research for industrial application of ILs as additives to boost the tri-
highly thermo-oxidative stable lubricants has driven bological behaviour of biolubricants is their thermal
 1099114x, 2022, 4, Downloaded from https://onlinelibrary.wiley.com/doi/10.1002/er.7453 by Egyptian National Sti. Network (Enstinet), Wiley Online Library on [09/11/2022]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons License
3878 APPIAH ET AL.

stability. Earlier studies on ILs showed that IL additives non-remedial segment of the Codonopsis Pilosula) subdue
in lubricating oils strongly addressed the major tribology the friction, wear, and oxidation of lubricating alloys
concerns of several lubricating.138-146 In their studies, the (steels) at temperatures beyond 150 C.184 Graphene,
addition of relatively non-corrosive, thermally stable, and multi-layer forms, is notably known to have high resis-
oil-miscible ILs in lubricating oils showed a drastic reduc- tance to oxidation, a critical property for high-
tion in wear and friction behaviour in both laboratory temperature applications of biolubricants.154-157 With that
and industrial tribology testing, implying possible indus- said, multi-layered graphene additives have been consid-
trial applications. In addition to this, Naveed et al,178 ered one of the most assuring materials for addressing the
examined the tribological performance of ILs as additives high-temperature limitations of biolubricants.124,153
to biolubricants. The striking outcomes of their results
showed that the phosphorus-based ILs in biolubricants
could reduce friction and wear between the interacting 4.4 | Current updates on the
surfaces in extreme temperature conditions. Most biolubricants synthesis
recently, Reeves et al,179-181 affirmed that blending ILs
with biolubricants boosts their tribological performance This section covers the latest literature reports and find-
caused by the formation of strong boundary films to safe- ings on the esterification and transesterification of oils
guard against wear and corrosion. Thus, the tribological (ie, VOs, WCOs, FAMEs, microbially derived oils, etc). It
performance of the IL-biolubricants was greatly height- captures research works done on biolubricant synthesis
ened with an increase in the hydrophilic nature of the via esterification and transesterification in terms of
anionic constituents. This was attributed to the ILs possi- parameters that influence the process and its products.
bility of forming a monolayer film adsorbed onto the The type of catalysts and catalyst loadings used, the
lubricating metal surface, forming a protective layer that adopted reaction temperature and time, and different
minimizes wearing and maximizes the lubricity of the starting/raw materials (ie, oils) used are all described in
biolubricants. Based on their previous work, Reeves this sub-section. Figure 2 shows a flow chart depicting
et al,182 and his group further investigated the effects of the chemical modification of oils through the esterifica-
varying the cation-anion constituents in ILs and their tion and transesterification (two-staged) reaction process
impact on tribology performance when mixed with bio- using a polyol, TMP.
lubricants. From their findings, the type of cations or Researchers have used a variety of catalysts in the
anions can modify the friction and wear behaviour of bio- synthesis and production of biolubricants as earlier
lubricants, which can be of tremendous interest to indus- highlighted, as it influences the bioproduct yield and
trialists, tribologists, and engineers.182 energy efficiency. In this regard, Shehu et al,20 used a
In other studies, mixing ILs with allotropes of carbon homogeneous acid catalyst (sulphuric acid) to produce a
like graphene has shown great potential in biolubricants 97% yield of dimer acid 2-ethylhexyl esters as bio-
formulation. For example, Hasnul et al,183 utilized lubricant base stock as well as an additive for petroleum
graphene and ionic liquid additives in biolubricants to and mineral base oils. The reaction conditions employed
improve the biolubricants tribological performances. This were 120 C, 72 hours, FAME: ethylhexanol ratio of 1:3
is because graphene oxide can form a stable colloidal sus- and 1% w/w of H2SO4. The biolubricant base showed
pension without using surfactant in pure ionic liquid. remarkable lubrication properties and was comparable
Hence, synergistic improvements occurred by mixing the with commercial lubricant base stock, polyalpha olefin
biolubricants such as neopentyl glycol dioleate and (PAO). The recorded characteristics were a VI of 134, a
trimethylolpropane trioleate with graphene-ionic liquid PP of 47 C, and a density of 0.91 g/mL. As an additive
additive blends. They further tested the tribological to commercial base oils, it increased the VI and PP of
behaviour of the graphene-IL biolubricants and the PAO to a little over 138 C and 59 C. The biolubricant
graphene additive and IL-additive biolubricants with a acted as a PPD and VII.
high-frequency reciprocating rig. The frictional perfor- Furthermore, Parente et al,34 carried out an esterification
mance decreased by 13% and 7% for the ILs and graphene and transesterification biolubricant process using soybean as
biolubricants, while 33% decreased for the graphene-IL an oil source. The esterification reaction produced FAME at
biolubricants. reaction conditions of methanol to oil molar ratio of 6:1; 1 g
Nevertheless, aside IL additives, other strategies of of sodium methylate catalyst, 60 C, and at a reaction time of
biolubricants synthesis and formulation have emerged 1 hour. The second-stage transesterification process occurred
that address the technical limitations of biolubricants. at optimum conditions of FAME: 2-ethylhexanol molar ratio
For instance, the use of a multi-layered graphene additive of 1:3; 10% wt para-toluenesulfonic acid (PTSA); 80 C
mixed with a natural wax (ie, which was obtained from a for 4 hours. Its lubrication properties (ie, a VI of 78 and a PP
 1099114x, 2022, 4, Downloaded from https://onlinelibrary.wiley.com/doi/10.1002/er.7453 by Egyptian National Sti. Network (Enstinet), Wiley Online Library on [09/11/2022]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons License
APPIAH ET AL. 3879

F I G U R E 2 Flow chart
depicting the chemical modification
of oils via the esterification and
transesterification (two-staged)
reaction process using a
polyol, TMP

of 12) were comparable to commercial hydraulic and In another study by Qiao et al,186 where biolubricant
transmission oils. trimethylolpropane trioleate (TMPTO) was catalytically
Moreover, Ferreira et al,185 studied the synthesis of synthesized from TMP and oleic acid (OA) of a VO and
TMP ester from pequi oil using methyl biodiesel as the its properties were evaluated. At the end of the research
starting material. The methyl biodiesel (fatty acid methyl study, it was evident that using a benzenesulfonic acid as
ester) was synthesized using a homogeneous basic cata- the catalyst and reaction conditions of 2% (w/w)
lyst, KOH, which reduced the inconvenience in the sepa- OA/TMP; a temperature of 180 C; vacuum degree of
ration between the biodiesel-glycerine phase, and also 0.095 MPa; a reaction time of 3 hours; and a catalyst/
the biodiesel showed great thermal stability. The pequi TMP 3.2:1 (molar ratio), a high TMP triester conversion
oil-based triester was formulated using a heterogeneous rate of 92.8% yield was produced.
catalyst, sodium methoxide under a vacuum of 400 to In recent times, most esterification and trans-
450 mmHg for 6 hours, and the total acid value of the esterification studies have been carried out using
obtained TMP ester was about eight times reduced, as enzymes, particularly lipases as biocatalysts. As men-
well as a significant reduction in the viscosity, which is tioned above, reasons such as insensitivity to FFA levels,
similar to mineral-based lubricants. The acid value is high product selectivity, short reaction times, recovery of
associated with the corrosion effects and tendencies of catalysts, low-to-no chemical residues, and low reaction
engines; thus, corrosion would be controlled with a temperature (ie, low energy cost) present enzymatic cata-
decreased acid value in the synthesized TMP ester. More lysts as a superior alternative in comparison to chemical
so, a thermogravimetric analysis (TGA) showed great catalysts.71 The excellent review by Bolina et al,187
thermo-oxidative stability of the biolubricant. For base broadly captures the advancement of enzymatic catalysis
catalysed reactions, Tulashie and Kotoka60 chemically as well as the immobilization practices for heterogeneous
modified castor oil, coconut oil, and palm kernel oil were biocatalysts (lipases) for biolubricant production. Physical
into their respective biodiesels at 60 C and 120 rpm stir- adsorption, covalent bonding, entrapment, and CLEAs
ring speed for 2 hours. The heterogeneous potassium are the main lipases immobilization protocols thoroughly
methoxide as well as special additive addition greatly elaborated in their work.
improved the respective biolubricants produced in terms With that said, a recent enzymatically catalysed trans-
of their viscosity indices, PPs, and flashpoints. Further- esterification work by Wafti et al,188 showed the effects of
more, TMP esters were synthesized from palm kernel oil three commercial immobilized lipases (ie, Lipozyme TL
via transesterification process using sodium methoxide IM from Thermomyces lanuginosus, Novozyme 435 from
(NaCH3O) as a catalyst, and the physicochemical param- Candida antarctica lipase B [CALB], and Lipozyme RM
eters improved with regards to their viscosity index and IM from Rhizomucor miehei) on the synthesis of TMP
pour point.160 triester of palm oil. The transesterification reaction
 1099114x, 2022, 4, Downloaded from https://onlinelibrary.wiley.com/doi/10.1002/er.7453 by Egyptian National Sti. Network (Enstinet), Wiley Online Library on [09/11/2022]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons License
3880 APPIAH ET AL.

occurred optimally at reaction conditions of 70 C, transesterification process. Several transesterification

23 hours, FAME: TMP molar ratio of 3.9:1, 5% w/w optimization works carried out by researchers show how
enzyme dosage and a pressure of 0.1 mbar. At the end of temperature affects the entire process in terms of product
the process, Novozyme 435 recorded the highest yield yield and cost. For instance, Menkiti et al,140 investigated
(95.7%), followed by Lipozyme TL IM and Lipozyme RM the effects of temperature on the yield of jatropha methyl
IM. This showed that Novozyme 435 demonstrates strong ester (JME) and TMP molar ratio from 3:1 to 7:1 at a con-
activation during the reaction, which promotes enzyme stant catalyst [Ca(OH)2] loading of 1.0% wt/wt of the
activity as a result of its good hydrophobic support. The reaction mixture. The reaction was monitored for 1 to
biolubricant produced showed significant and compara- 5 hours, and the temperatures under consideration were
ble lubrication properties with a VI of 229; PP of 6 C; CP at 80 C, 100 C, 120 C, 140 C, and 160 C for each of the
of 3 C, and a 32.4 minutes oxidative stability using mole ratios. The results showed that increasing tempera-
rotating pressure vessel oxidation test (RPVOT). Further- ture increased the yield until 3 hours. It was also shown
more, using a circular economy biorefinery approach, that the favourable condition for the transesterification of
Barbosa et al,106 produced waste Moringa oleifera (WMO) TMP ester of jatropha oil was found at 3 hours, 140 C,
isoamyl esters biolubricant base stock via enzymatic and JME: TMP of 4:1 at 1% w/w catalyst loading. The PP
catalysed solvent-free transesterification reaction. The for the produced biolubricant was 12 C, with a viscosity
enzyme, Candida rugosa lipase was immobilized on a sil- of 39.45 and 8.51 cSt at 40 C and 100 C, respectively,
ica (SiO2), and hybrid silica (SiO2-WMO) supports with the VI of 204. The biolubricant properties met the
through interfacial adsorption; however, the SiO2-WMO specifications of ISO VG 32 standard.
recorded an immobilization yield of around 86%. The On the subject of using unconventional raw/starting
optimized conditions for a recorded 94% biolubricant material, many researchers have employed different bio-
yield after eight cycles were at a reaction temperature of based sources. The ability to use a variety of renewable
40 C, for 1 hour, with a lipase catalyst loading of feedstocks (ie, both edible and non-edible) renders bio-
22.6 mg/g and at an equimolar oleic acid/isoamyl alcohol lubricants superior to their petroleum counterparts. The
ratio (1:1). The produced biolubricant was as good as the feedstock ranges from animal fats, microbial oils from
commercial hydraulic fluid of ISO VG68 grade as a result yeasts, waste cooking oils, filamentous fungus, and pre-
of its lubrication properties (ie, VI of 102; density of dominantly VOs.17,65,132,187,189,190 Majority of these spe-
0.892 g/cm3; and TAN of 0.26 mg KOH/g). cific oil sources are captured in Tables 1 and 3. Taking
Additionally, Greco-Duarte et al,72 carried out the unconventional feedstocks into consideration, Cai
synthesis and characterization of biolubricants using a et al,191 produced and evaluated a novel potential bio-
two-step enzymatic process from castor oil, which is rich lubricant source from a high-purity fatty acid value
in ricinoleic acid. The first step was the hydrolysis step, (61.8 mg of KOH/g) larval lipids of Housefly (Musca
which utilized castor seeds as catalyst yielding 93.13 domestica L.) fed by municipal waste using a wipe-film
± 5.9% castor oil free fatty acids in 1 hour, and with the short path distillation. The biolubricants source (ie, fatty
second (transesterification) step, C. rugosa lipase reduced acid n-octyl esters) was synthesized catalytically with
the acidity by over 80% after 96 hours, using NPG, TMP, benzenesulfonic acid under these conditions: n-octanol/
and PE. Also, a 70% acidity decline was witnessed when FFA molar ratio of 3:1; loading of the catalyst, 2 wt%;
it was polyol-free. With the help of a nuclear magnetic time, 2 hours and a temperature of 100 C and the esteri-
resonance (NMR), the chemical characteristics of the syn- fied product could be an alternative for some mineral
thesized product showed that an estolide biolubricant lubricants including SN 500, polyalphaolefin and liquid
with a polymerization degree of 6/7: VI of 162, oxidation paraffin. Additionally, Patience et al,192 conducted a
stability of 51 minutes, and PP of 42 C. Papadaki et al,73 research work where a VO containing OA was tran-
produced microbial oil-derived biolubricant via fermenta- sesterified into a biolubricant with significant cold-flow
tion of confectionery industry wastes employing enzy- properties characterized by PP using 1,3-propanediol
matic hydrolysis (ie, Rhodosporidium toruloides and and Amberlyst15-H catalyst. With the aid of ultrasonic
Cryptococcus curvatus) and transesterification by lipase intensification and these operational conditions: reac-
Lipomod 34-MDP biocatalyst in a solvent-free system tion time of 6 hours, temperature around 120 C, and
with TMP and NPG. The results showed high bio- diol/FFA molar ratio of 4:1 resulted in the production of
lubricant conversion yields, and their specific physico- long-chain diesters (biolubricant) with great lubricity
chemical properties could be improved when special potential.
additives are added. In a recent study, Aziz et al,193 investigated the effect
As elaborated earlier, reaction temperature and time of microwave irradiation on transesterified biolubricants
play a critical role in the esterification and synthesized from TMP and palm oil methyl ester
 TABLE 5 Conversion of several fatty acid methyl and ethyl esters derived from bio-based oils to biolubricants via esterification and transesterification process

Viscosity Viscosity Pour Oxidative/

40 C 100 C Viscosity point thermal
APPIAH ET AL.

Reactants Products Catalyst Reaction conditions (cSt) (cSt) index ( C) stability Yield (%)

Jatropha ME and TMP TMP triesters Sodium methoxide 150 C, 10 mbar, 3 hours 43.9 8.71 180 6 – >80
Jatropha ME and TMP TMP triesters Sodium methoxide 150 C, 55 minutes 42.57 9.37 183 6 325 C Degradation temp –
High oleic palm ME and TMP TMP triesters Sodium methoxide 120-150 C, 0.3 mbar, 45 minutes 45.5-50.7 9.2-10 183-200 ( 37) – –
Palm ME and TMP TMP triesters Sodium methoxide 140 C, 25 mbar, 25 minutes, 47.1 9.0 176 2 35.5 C Degradation temp 94.6
Oscillatory flow reactor at
1.5 Hz with 20 mm amplitude
Palm ME and TMP TMP triesters Calcium methoxide 180 C, 50 mbar, 8 hours – – – – – 92.38

Canola ME and TMP TMP triester Sodium methoxide 110 C, 1 mbar, 5 hours 40.5 7.8 20.4 66 Induction time: 0.7 4 hours 90.9
Castor ME and TMP TMP triester Dibutyltin dilaurate 170 C, QO1 bar 287.2 26.13 119 27 RPVOT: 43 minutes (Butylated 89.7
hydroxytoluene added)
Castor ME and TMP TMP triester Amberlyst 15 ionic 120 C, QO1 bar 20.94 4.467 127 – – –
exchange resin
Castor ME and TMP TMP triester Sodium methoxide 120 C, QO1 bar 11.28 3.100 141 – RPVOT: 150 minutes (Butylated –
hydroxytoluene added)
WCO ME and TMP TMP triester Potassium hydroxide 128 C, 200 Pa, 1.5 hours 38.6 8.44 204 8 FP: 240 C 85.7

Soybean oil and various n-alcohol-esters Sulfated zirconia 140 C, 4 hours 10.3-432.7 3.0-34.4 45-195 – – >80
alcohols
Sunflower oil and octanol FA-n-octyl esters Fe-Zn double-metal cyanide 170 C, 8 hours 7.93 2.74 226 3 23 minutes (RBOT) 98
(DMC) complexes
Oleic acid ME and Pentaerythritol tetraoleate Ion-exchange resin, indion- 110 C, 6 hours toluene solvent 63.08 12.00 190 24 – –
Pentaerythritol ester 130
Valeric acid ME and TMP Valeric acid TMP ester Silica-sulphuric acid 70 C molar ratio of 3:1, toluene 9.5 2.5 80 75 – –
Rubber ME and NPG/TMP/ NPC/TMP/PE triesters P-Toluensulpuric acid 135-140 C, until theoretical 23.1-62.6 5.9-12.6 206-222 ( 15) to ( 3) 10-15 minutes (RBOT) 94.5-65.5
PE reaction complete FB: 266-308 C
Rapeseed ME and NPG/TMP/ NPC/TMP/PE triesters C. antarctica lipase 150-200 C, 50 hours 7.8-38.2 2.7-8.4 205-224 ( 31.3) to ( 18) Δv: 90.1-147.1 98
PE ΔAc: 2.9-7.7
Thumba ME, xylene, and NPC/TMP/PE triesters P-Toluenesulphuric acid 135 C-140 C until complete 20.65-60.26 5.45-11.89 209-220 ( 12) to ( 3) 10-15 minutes (RBOT) 89-95
NPG/TMP/PE FP: 270-318 C
Soybean ME and Ethylene Ethylene glycol diesters – – 27.64 4.64 305 15 – –
glycol
Palm kernel ME and Ethylene glycol diesters – – 25.315 4.315 215 9 – –
Ethylene glycol
Rapeseed ME and 2-ethyl- 2-ethyl-2-hydroxymethyl- Sodium methoxide 1.5 hours, 120 C, 1:1 alcohol: 75.5 10.7 128 – 4.94 hours 99.41
2-hydroxymethyl- 1,3-propanediol triesters FAME ratio, 1.5 wt% catalyst
1,3-propanediol
Palm kernel ME and TMP TMP triesters Sulphuric acid 5.98 hours, 150 C, 3.05:1 FAME: 41.76 8.73 154 10 254 minutes 86.13
alcohol, 1.01 wt% catalyst
3881

(Continues)

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 1099114x, 2022, 4, Downloaded from https://onlinelibrary.wiley.com/doi/10.1002/er.7453 by Egyptian National Sti. Network (Enstinet), Wiley Online Library on [09/11/2022]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons License
3882 APPIAH ET AL.

(POME). The evaluated reaction parameters were catalyst

Yield (%)
loading, the molar ratio of TMP and POME, vacuum

88.17
83.9

92.9

84.8

71.2

52.9
pressure, reaction time, and temperature. At optimum
conditions of sodium methoxide solution at 0.6 wt%,
130 C, 10 mbar, 10 minutes reaction time, and the molar
ratio of TMP to PME at 1:4., the resulting yield of the bio-

35 (min, ROBT 150 C)

lubricant synthesized was around 66.9 wt% with the
needed heat energy decreased significantly while the pro-
Oxidative/

cess reaction occurred very fast.

23 minutes

30 minutes
thermal
stability

On the topic of waste management and circular econ-

196 C

228 C


omy, Unugul et al,194 recently researched the production

–
of biolubricants from coffee wastes where oils were
extracted. By enzymatic hydrolysis (ie, using Lipozyme
TL IM [Thermomyces lanuginosus]) and enzymatic esteri-
Viscosity point
Pour

( C)

15
5

fication (ie, using Novozyme 435 [Candida antarctica]) of

9.0
–

the free fatty acids with TMP, the transesterified bio-

138.74
index

lubricants depicts around 88% FFA conversion at optimal

103

163

199

167

196

conditions of 5% enzyme loading (w/w), non-aqueous

Viscosity

media, FFA/TMP mole ratio (3:1), 24 hours, and a reac-

100 C

8.324

4.930
(cSt)

tion mixing speed of 500 rpm. The only limitation of this

12.6

9.32

5.99

2.8

approach is the costly nature of these enzymes when

Viscosity

used for the biolubricants synthesis. The conversion of

73.39

28.92

38.64

21.22
(cSt)
40 C

75.9

several methyl and ethyl esters derived from bio-based oil

8.6

sources to biolubricant ester base stocks are shown in

Table 5.8,102,109,195
>2 hours, >130 C, 4:1 FAME:
alcohol, 3.08 wt% catalyst.
5.5 hours, 150 C, 1:1 FAME:

alcohol, 1.0 wt% catalyst.

24 hours, 45 C, 3:1 FAME:

24 hours, 45 C, 2:1 FAME:

>1 hour, 70 C, 1:2 FAME:

1 hour, 140 C, 1:1 FAME:

alcohol, 4 wt% catalyst.

alcohol, 4 wt% catalyst.

alcohol, 2 wt% catalyst

alcohol, 0.3 g catalyst
Reaction conditions

4.5 | Challenges and future perspectives



of biolubricants

Generally, biolubricants are scarcely exploited in the

global market and industries due to their limited numer-
ous applications. A major reason is their vulnerability to
Candida rugosa lipase

Candida rugosa lipase

thermo-oxidative conditions requiring a more cost-

potassium solution

Potassium hydroxide
Trimethylolpropane-
Sodium methylate

effective and intensive approach to chemical modifica-

Sulphuric acid

tion of these oils.8,187 Another setback of biolubricants is

Catalyst

the homogeneity of the feedstock, which results in varia-

tion in the final biolubricant. For large-scale
manufacturing operations, the changes in the oil chemis-
High-oleic safflower ME and 2-ethyl-2-(hydroxymethyl)-
1,3-propanediol triesters

2-ethyl-1-hexanol (2E1H)

try would yield unsatisfactory biolubricant properties.

Most reported works in this field usually employed edi-
ble VOs as the base oils. Yet, these oils have been
Abbreviations: EE, ethyl ester; ME, methyl ester.
TMP triesters

TMP triesters

Soya bean Fatty acid distillate TMP triesters

Soya bean Fatty acid distillate NPG diesters

reported to interfere with the food chain and supply sec-

triesters
Products

tors. As a consequence, a price fluctuation could occur,

making their use socially and economically unaccept-
able.65 Non-edible oils have been on the rise as a suitable
(Continued)

2-ethyl-2-(hydroxymethyl)-

Litsea cubeba kernel ME and

Indian mustard seed oils EE

Crude Palm kernel ME and

and sustainable alternative. Furthermore, several manu-

and 2-ethyl-1-hexanol

facturers of machines and operators do not endorse bio-

1,3-propanediol

lubricants making commercial-scale production a

ME and TMP

ME and NPG

fruitless venture.24,187
TABLE 5

Reactants

(2E1H)

The future development on the engineering of bio-

TMP

TMP

lubricants should focus on continuously improving the

cost-effectiveness of production methods. More
 1099114x, 2022, 4, Downloaded from https://onlinelibrary.wiley.com/doi/10.1002/er.7453 by Egyptian National Sti. Network (Enstinet), Wiley Online Library on [09/11/2022]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons License
APPIAH ET AL. 3883

ecologically sustainable formulations of biolubricants are A C KN O WL ED G EME N T S

expected to be industrialized in many areas: hydraulic The authors are thankful to IHE Delft Institute for Water
oils, compressor oils, engine oils, and insulating fluids, Education and the University of Cape Coast for their
among others. Cheaper feedstocks development and infrastructural and staff time support.
identification, superior performance catalysts, and opti-
mized reaction processes must be required in advancing CONFLICT OF INTEREST
the synthesis of biolubricants to make economic break- The authors declare that they have no known competing
throughs and benefits that could attract lubricants and financial interests or personal relationships that could have
the oil industry players.2 Although biolubricants have appeared to influence the work reported in this paper.
shown great propensity as substitutes to mineral and
synthetic-based lubricants over the years, more testing is AUTHOR CONTRIBUTIONS
needed to convince manufacturers and operators of their Godfred Appiah: Conceptualization, Methodology,
capabilities. Writing-Original draft preparation, Writing-Review and
It is also noteworthy that the scientific elites are cur- Editing, Supervision. Samuel Kofi Tulashie: Supervision,
rently heightening steps to intensify efficiency in synthe- Conceptualization, Methodology, Writing-Review and
sizing biolubricants. Mechano-chemical treatments, Editing. Ephraim Edem Amoah Akpari: Methodology,
microwaves, or ultrasounds processes have greatly Writing-Review and Editing. Eldon R. Rene: Methodol-
improved the yields of biolubricants under mild condi- ogy, Writing-Review and Editing. Daniel Dodoo: Writing-
tions.65 Most recently, enzymatic catalysis processes have Review and Editing, Supervision.
been used to produce biolubricants at low reaction tem-
peratures. Nanoparticles, a subject with so much contro- NOMENCLATURE
versy, have also been used to revamp the anti-wear AO anti-oxidants
properties of biolubricants lately.196,197 AWA anti-wear agents
EPA extreme pressure additives
FAME fatty acid methyl ester
5 | C ON C L U S I ON S FFAs free fatty acids
HMO hydrolysed microbial oil
In this study, the current updates and prospects of bio- HOVOs high oleic vegetable oils
lubricants production via exclusively esterification and ILs ionic liquids
transesterification processes were reviewed and pres- JME jatropha methyl ester
ented. The use of esterification and transesterification NPG neopentyl glycol
enhanced the yield, cold-flow, and thermo-oxidative sta- OA oleic acid
bility properties of the biolubricants. The review study PAO polyalpha olefin
highlighted: PPD pour point depressants
ROME rapeseed oil methyl ester
1. The importance of feedstock selection: high FFA- TGA thermogravimetric analysis
containing feedstocks lead to soap formation in TMP trimethylolpropane
the esterification stage; hence, to improve the qual- VI viscosity index
ity of the biolubricants, such feedstocks must be VII viscosity index improvers
avoided. VOs vegetable oils
2. The effects of higher operating temperatures: higher WCO waste cooking oils
temperatures relatively increase the yield and quality
of esterified and transesterified biolubricants at speci- ORCID
fied catalyst loadings. Godfred Appiah https://orcid.org/0000-0002-1028-1657
3. The essence of adding special additives: alpha-tocoph- Samuel Kofi Tulashie https://orcid.org/0000-0002-6744-
erol, butylated hydroxyanisole, tert-butylhydroquinone, 2917
and ILs improve further the thermo-oxidative Eldon R. Rene https://orcid.org/0000-0001-5974-2808
stability and the cold-flow abilities of the esterified/ Daniel Dodoo https://orcid.org/0000-0003-1949-4170
transesterified biolubricants.
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