lubricants

Review

Current Status and Future Prospects of Biolubricants: Properties

and Applications
Rakesh Narayana Sarma 1,2 and Ravikrishnan Vinu 1,2,*

1
Department of Chemical Engineering, Indian Institute of Technology Madras, Chennai 600036, India;
[email protected]
2
National Center for Combustion Research and Development, Indian Institute of Technology Madras,
Chennai 600036, India
* Correspondence: [email protected]; Tel.: +91-44-2257-4187

Abstract: Biolubricants generated from biomass and other wastes can reduce the carbon footprint of
manufacturing processes and power generation. In this paper, the properties and uses of biolubricants
have been compared thoroughly with conventional mineral-based lubricants. The biolubricants,
which are currently based on vegetable oils, are discussed in terms of their physicochemical and ther-
mophysical properties, stability, and biodegradability. This mini-review points out the main features
of the existing biolubricants, and puts forward the case of using sustainable biolubricants, which can
be generated from agro-residues via thermochemical processes. The properties, applications, and
limitations of non-edible oils and waste-derived oils, such as bio-oil from pyrolysis and bio-crude
from hydrothermal liquefaction, are discussed in the context of biolubricants. While the existing
studies on biolubricants have mostly focused on the use of vegetable oils and some non-edible
oils, there is a need to shift to waste-derived oils, which is highlighted in this paper. This
perspective compares the key properties of conventional oils with different oils derived from
renewable resources and wastes. In the authors’ opinion, the use of waste-derived oils is a
potential future option to address the problem of the waste management and supply of
biolubricant for various applications including machining, milling applications, biological
check ror
updates applications, engine oils, and compressor oils. In order to achieve this, significant research needs
Citation: Narayana Sarma, R.; Vinu, to be conducted to evaluate salient properties such as viscosity, flash point, biodegradability,
R. Current Status and Future thermo-oxidative and storage stability of the oils, technoeconomics, and sustainability, which are
Prospects of Biolubricants: Properties highlighted in this review.
and Applications. Lubricants 2022, 10,
70. https://doi.org/10.3390/ Keywords: biolubricant; base stock; biodegradability; vegetable oil; pyrolysis bio-oil;
lubricants10040070 hydrothermal liquefaction bio-crude
Received: 12 February 2022
Accepted: 6 April 2022
Published: 16 April 2022
1. Introduction
Publisher’s Note: MDPI stays neutral
Lubrication is defined as the process or technique by which the wear of one or both
with regard to jurisdictional claims in
moving surfaces in close proximity is reduced by using a substance called lubricant in
published maps and institutional affil-
iations.
between the surfaces. Lubricant carries or helps to carry the pressure generated (or load)
between the opposing surfaces [1]. Lubricant acts as anti-friction media, facilitates smooth
operation, maintains reliable machine functions, and decreases the risk of frequent fail-
ure [2]. A lubricant may be a liquid, a semi-solid (grease), or a solid (including coatings and
particles) [3]. The major objectives of lubrication include: (a) reducing wear and preventing
Copyright: © 2022 by the authors.
heat loss due to the contact of moving surfaces; (b) protecting the surface from corrosion by
Licensee MDPI, Basel, Switzerland.
This article is an open access article
reducing the oxidation; (c) acting as an insulator in transformer applications; and (d) acting
distributed under the terms and
as a sealant against dust, dirt and water. While it is difficult to eliminate wear and heat
conditions of the Creative Commons totally by using lubricants, they can be minimized and controlled to acceptable levels [ 1].
Attribution (CC BY) license (https:// Minami [3] pointed out the three main functions of lubricants as follows: (a) controlling
creativecommons.org/licenses/by/ friction; (b) cleaning contact; and (c) cooling the contact.
4.0/).

Lubricants 2022, 10, 70. https://doi.org/10.3390/lubricants10040070 https://www.mdpi.com/journal/lubricants

Lubricants 2022, 10, 70 2 of 21

The world depends on fossil-fuel based products, such as petroleum products and
petrochemicals, to a great extent in the industrial and transportation sectors. These prod-
ucts can cause serious environmental hazards and pollution. Biomass and solid wastes
can be potential candidates for generating fuels for power generation, such as [4–6] liquid
fuels, methanol [7], bio-oil [8,9], and platform chemicals [10]. In the field of lubrication,
which is an important application of petroleum products, mineral-based lubricants can be
substituted by biolubricants that can potentially address some of the related environmental
effects. Biolubricants exhibit superior lubrication properties over conventional lubricants,
in addition to being renewable and biodegradable [11]. Biolubricants usually have their
origin from vegetable oils, plant polymeric carbohydrates, and wax esters [12]. Biolubricant
preparation involves a transesterification reaction wherein an ester is reacted with an alco-
hol to produce another ester through interchange of the alkyl group. The transesterification
of vegetable oils generates fatty acid alkyl esters of different alcohol chain lengths. The
reaction is usually catalyzed by mineral acids and bases, and the final product, i.e., fatty
acid alkyl esters, can be utilized as fuel, biodiesel, and lubricating agents [1].
The basic constituents of a lubricant include base oil and additives, which enhance
the properties of the oil. The typical ratio of base oil and additives in the lubricant is 90:10.
Synthetic liquids such as hydrogenated polyolefins, esters, silicones, and fluorocarbons are
used as base oils in conventional lubricants, while vegetable oils are used in biolubricants.
Because of renewability and environmental considerations, vegetable oils have also received
attention as base oils [13]. The major constituents of vegetable oils include triacylglycerols
(98%), diglycerols (0.5%), free fatty acids (0.1%), sterols (0.3%), and tocopherols (0.1%) [14].
The triglyceride structure is composed of three hydroxyl groups esterified with the carboxyl
groups of fatty acids. Owing to the high molecular weight, the triglycerides possess high
viscosity and viscosity index.
The term biolubricant is used to represent all lubricants that are easily biodegradable
and non-toxic to human beings and the environment. While its use is still very limited as
compared to mineral oil-based lubricants [15], they are promising candidates as they are
renewable and emit net zero greenhouse gases to the environment [2]. Some of the key
terms to be understood include mineral oil, base stock, and base oil [16]. Mineral oil is the
liquid hydrocarbon by-product obtained from crude oil distillation. Base stock is usually
produced by a single manufacturer to the same specification independent of the feedstock
or manufacturer’s location (API 1509 2005). Base oil refers to a single type of base stock or
a blend of multiple base stocks used to prepare a lubricant.
It has been described that biolubricant has excellent lubricity and causes a
reduction in friction coefficient, frictional forces and wear compared to other lubricants
[17]. As vegetable oils inherently have excellent tribological properties, they are
considered to be very effective lubricants. However, the hydrolytic stability and thermal
stability of the veg- etable oils have been reported to be poorer than conventional
mineral oils, and should be improved [13]. The economic and environmental
significance of base oils and sustainable lubricants was discussed by Shah et al. [18]. As
nearly 66% of fuel energy is lost to the surroundings due to thermal, frictional,
transmission and other components, the design of sustainable biolubricants and
tribological advancements are imperative to enhance fuel efficiency. Estimates suggest
that more than 1% savings in GDP can be achieved annually by implementing better
lubricants in manufacturing, transportation, power generation, and residential sectors.
Another interesting topic of research is the chemical modification of vegetable oils to
produce an alternative to petroleum-based materials [19]. Biolubricants can also be
prepared from waste cooking oil and cyclic oxygenates through a four-step catalytic
process [20]. It has been pointed out by some researchers that viscosity is the most
important property of lubricants, as it determines the amount of friction between two
surfaces. To reduce wear, lubricants with higher viscosity result in a higher viscosity
ratio and lower wear rates [21]. Eco-friendly multipurpose lubricating greases from
vegetable residual oils have been studied, and it has been observed that they have
superior tribo- logical performance as compared to commercial grease [22]. By studying
the rheological
Lubricants 2022, 10, 70 3 of 21

and wetting behavior of Environmentally Acceptable Lubricants (EALs) for use in stern
tube seals, it has been shown that the operational shear rate of the ship should be consid-
ered while selecting a stern tube lubricant [23]. Researchers produced environmentally
friendly ethylene glycol di-esters (EGDEs) as biolubricants from various vegetable oils by
applying CaO as a heterogeneous base catalyst through the transesterification of fatty acid
methyl esters (FAMEs) and ethylene glycol (EG) [24]. Biolubricants can also be produced
by the transesterification of rapeseed and castor oil methyl esters with various alcohols
(2-ethyl-1-hexanol, 1-heptanol and 4-methyl-2-pentanol) using titanium isopropoxide as a
catalyst [25].
The authors have noticed the need for an article which comprehensively describes
various aspects of biolubricants (including source, preparation, properties, biodegradability,
and application), and the need to develop alternate lubricants from non-edible and
waste agroresidues. Even though biomass has been considered as a source of fuels and
chemicals, the lubrication properties of biomass-based oils have not been consolidated
in line with conventional lubricants. The present article thus aims to bridge the gap in the
literature per- taining to biolubricants. The objectives of this mini review are four-fold:
firstly, to describe the sources, preparation and greenness of biolubricants vis-à-vis
conventional lubricants; secondly, to discuss the major properties of biolubricants
including viscosity, thermo- oxidative stability, pour point, eco-toxicity, hydrolytic
stability, and most importantly, biodegradability; thirdly, to present the development of
biolubricants from non-vegetable oil, non-edible sources such as lignocellulosic
agriresidues and wastes via thermochemical transformation, with the aim of determining
the fit of pyrolysis bio-oil and hydrothermal liquefaction bio-crude as biolubricant base
stocks; finally, to present the applications of biolubricants in different fields along with
future prospects and research directions.

2. Sources and Preparation of Lubricating Oils

Conventional lubricants contain high molecular weight hydrocarbons derived from
the vacuum residue in the refinery as base stocks. Biolubricants, which are so far vegetable
oil-based, are constituted by unsaturated fatty acids as base stocks. Owing to oxidizable
functional groups, they possess poor thermal stability and poor oxidation stability, which
make them unsuitable for use in applications such as lubricating oils. Using chemical
modification processes such as transesterification, epoxidation and hydrogenation, un-
saturated fatty acid content can be reduced to make the vegetable oils suitable for use
in engines, thereby making them comparable to traditional lubricants [26]. The life cy-
cle of conventional mineral oil-based lubricant and biolubricant can be explained using
Figures 1 and 2, respectively. Based on the literature review, the types of base stocks used
for lubricating oils are summarized in Table 1. The American Petroleum Institute (API) has
categorized the base oils into five groups (I–V) based on whether they are mineral oil-based
or synthetic [27,28]. The classification also depends on the hydrocarbon composition of the
oils and the sulfur content in them. Table 2 presents the major fatty acids that constitute the
vegetable oil-based biolubricants.
Additives are added to base stocks to improve the physicochemical and thermophysi-
cal properties as well as the chemical and thermal stability of the final lubricant formulation.
Lubricant additives are classified based on their role in lubrication systems, which include
anti-wear or anti-oxidation agents and friction modifiers. They are also classified as per
their working function and their working site. The first category includes tribo-improvers,
rheo-improvers, and maintainers. Tribo-improvers improve the tribological performances
of lubricants. Rheo-improvers are concerned with the fluidity of the base oil. Maintainers
reduce the degradation of the substances participating in the lubrication system and keep
the lubricants and the machine components in good condition. Based on the working
mechanism, the additives can be classified as chemical additives if they undergo chemical
reactions, or physical additives, if they work without any chemical changes [3].
Lubricants 2022, 10, 70 4 of 21

Figure 1. Life cycle of conventional lubricants.

Figure 2. Life cycle of biolubricants.

Lubricants 2022, 10, 70 5 of 21

Table 1. Base stocks for lubricant oils.

Sl. No. Base Stock Source Reference

They are obtained from crude oil
processing after solvent refining,
Mineral oil catalytic dewaxing, hydrotreatment,
1 base stocks and hydrocracking. They can be [26–28]
naphthenic, aromatic, or paraffinic in
nature. They mainly include API
Group I, II, and III oils.
These are obtained from refined
petroleum products after the
Re-refined oil
2 removal of volatile and insoluble
base stocks [26]
components and contaminants via
acid/clay treatment. They mainly
include API Group I, II, and III oils.
They are obtained from petroleum
crude oil after chemical modification
via hydrotreating and
Synthetic oil hydroprocessing. They mainly include
3
base stocks poly-α-olefins, silicones, polyolesters, [26]
phosphate ester-based and
polyalkylene glycol-based oils. They
mainly include API Group IV and
V oils.
They include plants and animal-based
oils including vegetable oils, lipids,
4 Biomass base stocks and oils derived from agro-residues [15,26,29]
and wastes via thermochemical and
catalytic processing.

Table 2. Important fatty acids in plant-based oils [30,31].

Common Name Molecular Formula Fatty Acid Type

Palmitic acid C16H32O2 Saturated
Stearic acid C18H36O2 Saturated
Oleic acid C18H34O2 Monounsaturated
Linoleic acid C18H32O2 Diunsaturated
Linolenic acid C18H30O2 Triunsaturated
Ricinoleic acid C18H34O3 Unsaturated fatty acid

Biodegradable Grease
One effective way of providing lubrication to machine components is by using
grease. Even though liquid lubricant flows easily, a reservoir is needed to store it. Solid
lubricants need direct contact at the point of lubrication for effective lubrication. Grease
is a common lubricant in rolling bearings, and comprises base oil, thickener, and small
amounts of additives. Commercial greases are mostly produced from petrochemical
base oils and thickeners [32]. A semi-solid grease can provide the benefits of liquid
lubricants without needing a reservoir, and also the advantages of solid lubricants by
maintaining body structure. In applications such as the wheel bearing of an automobile,
in which excessive heat is produced, liquid lubricants tend to thin down and could leak
out of the bearing seals. Lubricating grease is a colloidal dispersion of a thickening
agent dispersed in a matrix of lubricant base fluid, and owes its consistency to a gel-
forming network. As cooling and cleaning functions need fluidity, solid lubricants and
greases may be applied to machine elements where contamination and localized heat
generation due to friction
Lubricants 2022, 10, 70 6 of 21

are not serious factors. Researchers have discussed biodegradable greases from palm
oil industry wastes [33] and castor oil [34]. It has been pointed out that
environmentally safe and biodegradable organic compounds can be used to produce
biodegradable grease [35]. Sánchez et al. [36] presented formulations based on various
types of acylated chitosan to produce stable gel-like dispersions in castor oil that are
suitable for application as biodegradable grease.
Lubricating greases are a group of lubricants that exhibit gel-like characteristics.
The gel-like behavior is imparted by the thickening agent, which is usually metallic soap,
phyllosilicate, or polyurea compounds [37]. These are two-phase colloidal suspensions
comprising mineral oil and a thickener forming a three-dimensional gelling network. Fatty
acid soaps of calcium, lithium, aluminum, sodium and barium are usually utilized as
thick- eners [38]. Borrero-López et al. [39] pointed out that the residual lignin-containing
fractions resulting from hydrolysis and kraft pulping biomass conversion processes may
be utilized as thickening agents. The bio-based oleogels with suitable lubricating
properties can be prepared by chemical functionalization, while their chemical
structure and composition can modulate the functional properties of them.
Some researchers have focused on the use of castor oil for formulating biodegradable
grease. Sánchez et al. [40] described the tribological characterization of green lubricating
greases formulated with castor oil and various biogenic thickening agents. They noted
that castor oil-based biodegradable greases provide similar or lower values of the friction
coefficient than traditional lithium greases, which was found to depend on the nature of the
thickening agent and the tribological contact. Gallego et al. [41] subjected many lignocellu-
losic pulps from different sources to cross-linking with hexamethylene diisocyanate, and
dispersed the formulation in castor oil to obtain gel-like semisolid lubricants. Acar et al. [42]
discussed that biodegradable lubricating greases can be prepared using high-oleic sun-
flower oil and castor oil, biodegradable thickening agents such as natural cellulose fibers
of different chain lengths, and glyceryl and sorbitan stearates. Cortés-Triviñ o et al. [43]
pointed out that epoxy-modified cellulose pulp-based biodegradable greases can provide
excellent thermal stability. Modifying the pulp with an epoxide compound strongly altered
the friction coefficient and wear relative to the use of castor oil alone as a biolubricant in
specific low-speed regimes.

3. Properties of Biolubricants
The major functions of biolubricants, i.e., reducing friction and wear, the dispersion of
deposits, the inhibition of rust/corrosion, the dissipation of heat, and the sealing of critical
contact joints, are reflected in the properties of the base oil. The base oil is expected to
possess optimum viscosity and viscosity index, low volatility, low deposit formation,
low temperature solidification, good hydrolytic and thermo-oxidative stability and
biodegrad- ability [13]. A good biolubricant should have its boiling point distribution
towards high temperatures, high viscosity index, corrosion prevention capability, high
thermal stability, low freezing point, and high anti-oxidation potential [2]. While these
are the preferred characteristics of any biolubricant, specific applications do demand
unique properties. For example: (a) engine oil application demands low emissions of
volatile organic compounds and polyaromatic hydrocarbons; (b) metal working fluids
require good emulsifiability;
(c) hydraulic oils require low compressibility and a quick release rate of air; (d)
transmission oils and gear oils require high weld load; and (e) greases should possess
good anti-wear and anti-scoring properties. The salient properties are explained in the
following sections.

3.1. Viscosity
Viscosity is a key parameter that determines the time to replace the lubricant in
a device. The viscosity depends on factors such as the concentration of paraffins and
the additives that affect the internal friction among the molecules, and it increases with
the increase in the chain length of the hydrocarbon portion of the fatty acid or alcohol
in ester-based biolubricants. Owing to increased hydrogen bonding interactions, the
Lubricants 2022, 10, 70 7 of 21

presence of hydroxyl groups in the lubricant formulation or the addition of polyols modifies
the viscosity index [15,44,45]. The viscosity index (VI), a metric used by lubricant users
and refiners, describes the effect of temperature changes on the viscosity of the oil [ 46].
VI measures the temperature dependency of viscosity [47]. A higher value of VI
indicates that the temperature will not affect the viscosity to any large degree and vice
versa [46]. The reference values of VI are determined according to the standard methods
described by the American Society for Testing and Materials (ASTM) D2270-10 [48] and of
the Brazilian Association of Technical Standards (ABNT NBR) 14,358 [49].
In order to understand the temperature effects on the kinematic viscosity of base
stocks and lubricants, VI was first proposed by Dean and Davis of Standard Oil in 1929 [ 50].
Vis- cosity and VI can be measured using ASTM D445-97 and D2270-93. ASTM D445
includes the Standard Test Method for the Kinematic Viscosity of Transparent and Opaque
Liquids. The measurement method includes tracking the flow time of transparent or opaque
liquids through a calibrated glass capillary. Typically, API Group I and Group II base oils
exhibit VI in the range of 80–120, while Group III base oils exhibit VI greater than 120. It is
impor- tant to note that Group I base oils contain <90 wt.% saturated hydrocarbons and
>0.03 wt.% sulfur, while Group II and III oils contain >90 wt.% saturated hydrocarbons with
<0.03 wt.%
sulfur in them. Poly-α-olefins (Group IV base oils) contain >99 wt.% saturated
hydrocar- bons, and they also exhibit a very high VI > 120 [27,28]. From Table 3, it is
evident that
the kinematic viscosity values of the hydrocarbon-based mineral oils are high (40–150 cSt),
while those derived from the degradation of polyethylene or polypropylene are even higher
(200–700 cSt). High molecular weight polymers when degraded at low temperatures, or for
insufficient periods of time, tend to form waxy compounds with carbon chain lengths > 30,
which tends to increase the viscosity. However, after catalytic upgradation, the viscosity
can be brought down to the range of typical oils extracted from edible and non-edible seeds.
The formation of aromatic hydrocarbons such as benzene, toluene, ethylbenzene, xylene
(BTEX) and other alkyl benzenes during the catalytic treatment using acidic catalysts such
as zeolites also tends to decrease the viscosity of the oil. Pyrolysis bio-oil derived from
biomass also possesses low viscosity, but due to its oxygen-rich composition, it cannot
be used as a biolubricant. The co-pyrolysis of polymers/plastics with biomass followed
by catalytic treatment is also shown to lead to the low viscosity of oil, which is typically
in the range of vegetable oil biolubricants.

3.2. Thermo-Oxidative Stability

Auto-oxidation of the lubricant is promoted due to localized high temperatures caused
by frictional heat generated by the rubbing of solid surfaces against each other. This
tends to alter the viscosity of the lubricant due to reactions that promote the cleavage of
long chain hydrocarbon molecules. Therefore, due to exothermic oxidation and
endothermic pyrolysis reactions, the thermo-oxidative stability of the lubricant decreases
with usage [51]. Thermo-oxidative stability can be tested using the RPVOT test (ASTM
D2272). This involves the evaluation of the oxidation stability of the biolubricants in the
presence of a copper catalyst and water at 423 K and 620 kPa of oxygen.
Jedrzejczyk et al. [52] showed that lignin-based additives can be used for improving the
thermo-oxidative stability of biolubricants. They tested four different lignins—commercial
Protobind P1000 soda lignin from straw, solvolytically fractionated Protobind P1000 lignin,
and two lignin fractions from a reductively catalyzed fractionation (RCF) of native birch
wood—in biolubricant formulations with castor oil as the base oil. They reported that
the lignin fractions exhibited excellent performance in comparison to the butylated hy-
droxytoluene (BHT), a petroleum-based antioxidant, utilised commonly as an antioxidant.
The formulations of modified lignin in castor oil held better thermo-oxidative stability,
as illustrated by their increased oxidation induction time. In addition, rheological and
tribological tests demonstrated similar, or in some cases, improved lubricating properties
in comparison to castor oil.
Lubricants 2022, 10, 70 8 of 21

Thermal and thermo-oxidative stability can also be assessed by analyzing the change
in apparent activation energy of the oil with conversion using thermogravimetric analysis.
Tripathi and Vinu [53] evaluated the thermal stability of synthetic and semi-synthetic oils
that were aged at 120, 149 and 200 ◦C. Fourier transform infrared spectroscopy coupled
with chemometric models can be used to determine the Total Acid Number (TAN), Total
Base Number (TBN), oxidation index, nitration index, and sulfation index of the biolubricant
at different thermo-oxidative simulated ageing conditions.

3.3. Pour Point

Pour point is the temperature below which the lubricant loses its flowability. In
biolubricants, it is related directly to the viscosity index. The presence of ternary alcohols,
such as trimethylolpropane (TMP), reduces the pour point of the biolubricant, even though
it tends to reduce the thermo-oxidative stability of the lubricant [15]. It can be measured
using ASTM D5949, which involves the determination of pour point by applying a burst
of nitrogen gas into the lubricant sample, while simultaneously cooling it. It is usually
performed in an automated instrument, which also detects movement of the surface of the
test sample using an optical device.

3.4. Ecotoxicity
Ecotoxicity is a metric used to characterize the environmental toxicity of a
lubricant formulation. It is a major property that determines whether a lubricant
formulation can irreversibly affect living things. As aqueous ecosystems are prone to
damage by the organic and hydrocarbon components of lubricants, it is vital to determine
lubricant water toxicity. This is defined as the potential of a lubricant to poison target
organisms such as bacteria, algae, small fish, or laboratory rats. ASTM D6081-20 is the
standard protocol to test the aquatic toxicity of the lubricant.

3.5. Hydrolytic Stability

The resistance of biolubricants to chemical attack, especially when water
molecules are involved either as a reactant or a product, is characterized by hydrolytic
stability. The ASTM D2619-21 standard test method is used to determine the hydrolytic
stability of petroleum or synthetic-based hydraulic fluids. Biolubricants for use as
insulation fluids require high water solubility and a high dielectric constant. Therefore,
the assessment of hydrolytic stability becomes imperative.

3.6. Biodegradability
If a lubricant can be structurally decomposed by enzymes or microorganisms through
an aerobic or anaerobic process, it can be considered biodegradable [54]. A lubricant
can be considered biodegradable if the percent degradation in a standard test exceeds
a certain value. Vegetable oils are more biodegradable than mineral-based oils [2]. The
environmental concern around the depletion of mineral reserves has sparked interest
in biolubricants derived from natural triglycerides, as well as the fatty acids derived
from them [55]. Biodegradability of the base fluid (or any other component) of an
environmen- tally acceptable lubricant (EAL) depends on both its molecular properties
and the test method utilised [56]. Importantly, the chemical composition of base oils can
change during the application of lubricants, i.e., when they are subjected to varying
temperature, air, humidity, metals, and pressure.
Standard methods for the determination of biodegradability have been discussed by
Luna et al. [57]. CEC L-33-T-82 was one of the first methods used to evaluate biodegradabil-
ity. In this approach, a standard fluid of known biodegradability is used. Both the standard
and the sample are inoculated with microorganisms, and the reaction progress is monitored
over a 28-day period. The quantification of carbon dioxide released from decomposition
can be used to quantify biodegradation reactions, as is adopted in the ASTM D5864-11
method (Standard Test Method for Determining Aerobic Biodegradation of Lubricants and
Lubricants 2022, 10, 70 9 of 21

Their Components). In this test, a natural aqueous environment is simulated, and the
CO2 generation is quantified.
The method presented by the Organization for Economic Cooperation and Develop-
ment (OECD) is also based on CO2 generation during the biodegradation of a sample. CO2
is captured in a sodium or barium hydroxide solution, which is then titrated to quantify the
CO2 emission. A biodegradable sample is expected to exhibit more than 60% degradation
over a 28-day period. For measuring the ultimate stage of the aerobic biodegradation, the
OECD 301 B method is used in aqueous or soil medium as an ultimate biodegradation
test [58]. In the Bartha Respirometer Method, the CO 2 generated is captured by a KOH so-
lution [59,60]. The one global regulation defining environmentally acceptable biolubricants
is the Vessel General Permit (VGP), which prescribes the discharge limit of oils into water
bodies of vessels of different sizes. While better base stocks and additives are required
for performance improvement, low aquatic toxicity and low bioaccumulation are the key
properties of a good biolubricant. The ASTM D5864 method is based on the exposure
of the lubricant to an inoculum under controlled laboratory conditions to determine the
degree of aerobic aquatic biodegradation. ASTM D6731-18 involves the determination of
the aerobic and aquatic biodegradability of lubricants using a closed respirometer. The
biodegradability of greases essentially reflects the biodegradability of their base stocks [ 22].
Researchers have also pointed out that the high biodegradability of vegetable oils can make
the vegetable oil-based greases as suitable alternatives to conventional greases [61].

Table 3. Physicochemical properties of some oils.

Density at Kinematic Viscosity Oxidation Cloud Flash

Sl. No. Oil 3
298 K (kg/m ) Ref.
at 313 K (cSt) Stability, 383 K, Point (K) Point
* h (K)
Non-edible oils
1 Karanja 918 4.80 6.0 282 423
2 Castor 898 15.25 1.2 259.5 533
3 Neem 885 5.20 7.2 287.5 317
4 Jatropha 878 4.82 2.3 275.75 409
5 Tobacco 887 4.25 0.8 NR 439
6 Mahua 850 3.40 NR NR 483
7 Rubber seed oil 870.9 (at 313 K) 31.4 NR NR NR
Edible oils
8 Coconut 805 2.75 35.4 273 598 [2,15,55,62–71]

9 Sunflower 878 4.45 0.9 276.42 525

10 Linseed 890 3.74 0.2 269.2 451
11 Soybean 885 4.05 2.1 274 598
12 Peanut 882 4.92 2.1 278 450
13 Olive 892 4.52 3.4 NR 591
14 Rice bran 886 4.95 0.5 273.3 591
15 Rape seed 880 4.45 7.5 269.7 525
16 Palm 875 5.72 4.0 286 438
Other oils
17 HTL biocrude 940–960 110–350 NR 278 366 [72,73]
18 Waste cooking oil 908–955 35.3 NR 272 NR [74,75]
Pyrolysis-derived oils
19 Biomass 1100–1300 13–80 (at 323 K) NR NR 323–373 [76,77]
20 PS 1100 1.4 NR NR 375 [78]
21 PP 980 212 NR NR 357 [78]
 Lubricants 2022, 10, 70 10 of 21

Table 3. Cont.

Density at 298 Kinematic Viscosity Oxidation Cloud Flash

Sl. No. Oil 3
K (kg/m ) * at 313 K (cSt) Stability, 383 K, h Point (K) Point (K) Ref.

Catalytically
22 979 1.63 NR NR 356 [78]
upgraded oil from PS
Catalytically
23 853 5.98 NR NR 350 [78]
upgraded oil from PP
24 LDPE 856 476.6 NR NR NR [79]
25 PI 841 6.4 NR NR NR [79]
26 PS–biomass mixtures 1096–1192 2.0–2.75 NR NR NR [79]
27 PP–biomass mixtures 615–942 681–729 NR NR NR [79]
LDPE–biomass
28 832–867 139–187.5 NR NR NR [79]
mixtures
29 PI–biomass mixtures 880–892 4.1–7.5 NR NR NR [79]
30 Waste tire 900 1.9 NR NR 300 [80]
31 Rice straw 777–847 34.7–39.6 NR NR 387–390 [81]
32 Bagasse 813–893 28.8–31.2 NR NR 382–385 [81]
Synthetic and mineral oil
33 SAE20W40 NR 105 NR NR 473 [15,82]
34 Neat mineral oil 880 62.9 NR NR 497 [83]
35 ISO VG32 NR >28.8 NR NR 477 [15]
36 ISO VG46 NR >41.4 NR NR 493 [15]
37 ISO VG68 NR >61.4 NR NR 499 [15]
38 ISO VG 100 NR >90 NR NR 519 [15]
39 R150 NR 150 15.52 NR 468 [15]

*—Density measured according to ASTM D4052; NR—Not Reported; HTL—Hydrothermal liquefaction; PS

—Polystyrene; PP—Polypropylene; LDPE—Low-density polyethylene; PI—Polyisoprene.

Biodegradability is a major requirement for current chemical industry products, and

it is also vital from a circular economy viewpoint. The biodegradability metric is used to
quantify the risk caused by the decomposition of products when they are deployed in the
natural environment. Biodegradation, a natural process, occurs due to the action of mi-
croorganisms in the presence of oxygen, nitrogen, and minerals. Biodegradability depends
on the quality and composition of the base oil used. Base-stock oils and finished lubricants
are potentially exposed to the environment during their generation, distribution, service,
and even during the disposal after the usage [57]. The biodegradability of biolubricants
is presented in Figure 3. It is evident that vegetable oil-based hydraulic fluid, vegetable
oil-based grease, and low erucic acid rapeseed have high values of ultimate biodegradation
compared to the mineral oil-based hydraulic fluids and synthetic compounds. Biodegrad-
ability of some base stocks is also represented as percent loss at 21 days [ 29]. Typically,
functional groups can be arranged in the following order based on the maximum percent
loss at 21 days: alkyl benzenes (upto 20%) < polyethylene glycols (upto 75%) < aromatic
esters (upto 90%) < polyols, diesters (upto 95%).
Lubricants 2022, 10, 70 11 of 21

Low erucic acid rapeseed

Moderately biodegradable synthetic PAO
High biodegradable synthetic ester
High biodegradable synthetic PAO
Mineral oil hydraulic fluid
High biodegradable synthetic hydraulic fluid
Vegetable oil-aluminum complex
grease Low biodegradable synthetic
PAO Vegetable oil-based grease
Vegetable oil hydraulic fluid

0 10 20 30 40 50 60 70 80 90
Biodegradability

Figure 3. Biodegradability of different lubricant base stocks as per ASTM D5864.

4. Development of Biolubricants from Biomass via Thermochemical Techniques

Thermochemical conversion processes can be used to generate gaseous fuels [84]
and liquid fuels from biomass [7,8]. Renewable fuels generated through thermochemical
technologies such as pyrolysis, hydrothermal liquefaction (HTL) and the hydrodeoxygena-
tion of bio-oils can potentially be cost competitive in comparison to other alternative fuel
processes [85]. Lignocellulosic biomass is composed of three natural polymers—cellulose
(30–60 wt%), hemicellulose (15–40 wt%), and lignin (15–30 wt%)—while algae species
have proteins, lipids and carbohydrates, along with pigments such as chlorophyll, present
in their matrix [86]. Liquid fuels can be generated from both lignocellulosic biomass
agroresidues and lipid-rich microalgae by making use of pyrolysis and HTL process [87].
Pyrolysis refers to the thermal decomposition/cracking of organic matter in the ab-
sence of air. Based on the heating rate employed, thermal decomposition can occur on a
scale of seconds to minutes. It is the primary chemical reaction, which is the precursor
for both combustion and gasification processes. The thermal decomposition of biomass
through pyrolysis results in the formation of liquid bio-oil, solid bio-char, and gaseous frac-
tions rich in carbon dioxide, methane, hydrogen and carbon-monoxide [88–90]. Bio-oils are
multi-component mixtures of different size molecules obtained from the fragmentation and
depolymerization of lignin, cellulose, and hemicellulose. Typically, algal bio-oil is less dense
than lignocellulosic bio-oil, while its viscosity falls in the typical range of wood-derived
bio-oil. The presence of nitrogen-containing compounds such as indole, pyridine,
amides, nitriles, and ammonia render the algal bio-oil pH alkaline (9.7), which is very
different from that for lignocellulosic bio-oil (typically 2–3). Lignocellulosic biomass-
derived bio-oil is a complex mixture of oxygenated organics including phenolics,
alcohols, acids, dehydrated sugars, furan derivatives, carbonyl compounds, and
aromatic hydrocarbons [91,92]. The acidic nature of lignocellulosic bio-oil is due to the
presence of carboxylic acids and phenols. The major compounds in bio-oil from microalgae
can be classified as aliphatic hydrocarbons, aromatic hydrocarbons (BTEX), nitrogenated
compounds (including nitriles, amides and N-heterocyclic compounds), phenols,
polycyclic aromatic hydrocarbons (PAHs), and others (such as alcohols, fatty acids, and
esters) [93]. The elemental composition of bio-oil and petroleum crude oil are very
different [77]. Owing to the decomposition of bio-chemical components in biomass, bio-
oil is rich in oxygen, which imparts poor calorific value. More-
Lubricants 2022, 10, 70 12 of 21

over, the oxygenated functional groups in bio-oil impart acidity and poor storage stability
to the bio-oil.
The HTL process involves the high-pressure cooking of biomass or wastes in a hot,
pressurized water environment for the necessary time to break down the biopolymeric
struc- ture into liquid bio-crude. The usual hydrothermal processing conditions are 523–
647 K of temperature and an operating pressure ranging from 4 to 22 MPa. HTL is the only
thermochemical process that is agnostic to the type of feedstock used and initial moisture
content. As it is conducted in presence of water with low solid loading (10–20 wt.%), the use
of wastewater or water with co-solvents offers opportunities to alter the product yields and
their quality. The liquid oil from HTL is usually called bio-crude, and the other products
include bio-char, aqueous phase, and gaseous fraction, rich in carbon dioxide. The high
energy efficiency and low operating temperature in HTL makes the liquefaction process
interesting and better than pyrolysis, which is more energy intensive [94].
Generally, HTL bio-crudes possess lower oxygen content and higher carbon content
than pyrolysis bio-oils. This results in better calorific value of HTL bio-crude. The typical
oxygen content in pyrolysis bio-oil from different feedstocks falls in the range of 30–50 wt.
%, while that in HTL bio-crude is 10–30 wt.%. The elemental compositions of HTL bio-
crudes from different feedstocks are well documented by Nallasivam et al. [95], and that
of pyrolysis bio-oils are available in Gautam and Vinu [86]. The moisture content is also
lower in HTL bio-crude than pyrolysis bio-oil. There are huge opportunities to tailor-make
these fuels to produce water containing lubricants and cutting fluids. From Table 3, it is
clear that HTL and pyrolysis-derived liquids can have comparable properties to that of
conventional lubricants in terms of density, viscosity, and flash point, which makes them
suitable for biolubricants, while at the same time solving the waste management issues
and reducing the carbon footprint. The possibility of generating oils from wastes such
as biomass, plastics, paper, refuse-derived fuels, and algae make these two technologies
excellent candidates for producing eco-friendly lubricants for engineering applications.
Additionally, the issues associated with the use of edible seeds for lubricant production
are avoided.

5. Comparison of Biolubricants with Other Lubricants and the Need for

Alternate Biolubricants
Conventionally, mineral oils have been used for the purpose of lubrication.
However, as they are fossil-fuel based, their availability is an issue in the long run.
Additionally, the disposal of mineral oils can cause pollution in aquatic as well as
terrestrial ecosys- tems [2,96]. The burning of mineral oils as a lubricant can emit traces
of metals, such as phosphorous, zinc, calcium, magnesium, and iron nanoparticles
[2,97]. In this context, the use of environmentally friendly and benign biolubricants
becomes imperative.
While vegetable oils can be used as lubricants, there are advantages and disadvan-
tages [2]. It can be noted that vegetable oils have excellent lubricity in comparison to
mineral oils. However, vegetable oils possess high VI, sometimes as high as 220, while a
VI of 90–100 is normal for most mineral-based oils. Viscosity must be optimal, as higher
viscosity affects the flowability of the lubricant. Another major property of vegetable oils
is their high flash point, which relates to easy storability. Typically, the flash point of
vegetable oils is ~600 K, while it is at least 25 K lower for mineral oils. While vegetable oils
are renewable, biodegradable, usually less toxic, and reduce the dependency on petroleum
oils, vegetable oils lack necessary oxidative stability in their natural form for lubricant
application. Vegetable oils oxidize easily and become thick with a plastic-like consistency
due to the polymerization of hydrocarbons at high temperatures. Moreover, vegetable oils
possess an unpleasant smell, flushing propensity because of low viscosity, poor compati-
bility with paints and sealants, and a tendency to clog filters. Table 4 presents the salient
advantages and disadvantages of biolubricants.
Waste cooking oil (WCO) can be a potential base stock for biolubricant preparation.
In a study [98], WCO was chemically modified via epoxidation using H2O2 followed by
Lubricants 2022, 10, 70 13 of 21

transesterification with methanol and branched alcohols (isooctanol, isotridecanol and

isooctadecanol) to generate biolubricants with improved oxidative stability and low
tem- perature properties. Furthermore, tribological performance of these biolubricants
was investigated using four-ball friction and wear tests. The experimental results
showed that modified WCO exhibited favorable physicochemical properties and
tribological perfor- mance, which makes them suitable candidates to formulate eco-
friendly lubricants [98]. It is worthwhile to note that the compositional consistency of WCO
is a concern, as it depends on the quality of oil used. Moreover, its upgradation by
hydrogenation may be required to reduce unsaturation, convert oxygenated functional
groups such as aldehydes, ketones and carboxylic acids, and thus improve its storage and
thermal stability. Jahromi et al. [20] modified fatty acids and WCO through a series of
chemical steps involving hydrolysis, dehydration/ketonization, Friedel–Crafts
acylation/alkylation and mild hydrotreatment to produce biolubricants containing saturated
linear hydrocarbon chains with cyclic rings and polar moieties in the structure.
Importantly, they used model compounds such as anisole, 2-methyl furan,
cyclopentanol, and cyclopentanone, which are typical pyrolysates from biomass, in the
condensation step to produce the desired molecules. The biolubricants had a pour point of
–12 ◦C, a viscosity of 47.5 cP (at 40 ◦C), a viscosity index of 186, and a total acid number
lesser than 1 mgKOH/g [20].
The need of vegetable oil for cooking and the resultant costs make this oil less suitable
for lubrication applications. In this context, it becomes imperative to explore the use of
alternate waste-derived lubricants such as pyrolysis oil and HTL oil for lubrication applica-
tions. The viscosity (at 50 ◦C) of pyrolysis bio-oil derived from wood and heavy fuel oil
have been presented by researchers to be 40–100 cP and 180 cP, respectively. The
specific
gravity values were 1.2 and 0.94 [76,77]. Similarly, for two samples of HTL oil, the density
at 295 K was 1.14 ± 0.02 kg m−3, and the viscosity at 313 K (mPa s) were 67,000 (±5000),
2200 (±200). Viscosity at 353 K (mPa s) were 520 (±40) and 210 (±10), respectively [99].
Pyrolysis bio-oil and HTL bio-crude also require mild upgradation via hydrodeoxygenation
in order to reduce the oxygen content to acceptable levels. While the presence of oxygen
in the biolubricant base stock may be necessary for facile bio-degradation, it eventually
reduces the calorific value of the lubricant and, based on the nature of oxygenated func-
tionality, can also adversely affect the storage stability of the oils. The presence of
multiple oxygenated functionalities in a molecule can lead to high acidity, measured by
total acid number, and an increase in molecular weight due to autoxidation and
polymerization reactions. While HTL bio-crudes can be used in applications that
demand high viscosity, the excessively high viscosity of HTL bio-crude can affect the
flowability of the biolubricant, which is a concern. Incorporating additives such as alcohols
in small quantities is shown to improve the storage stability of the biomass-derived
pyrolysis oils. Therefore, the additions of antioxidants and thinners are essential for
employing HTL bio-crudes as base stocks for biolubricants.
The required properties of cutting fluids are as follows: (a) excellent lubricating
properties; (b) suitable viscosity; (c) cheap cost; (d) good cooling capability; (e) non-
corrosive; (f) high flash point; (g) chemically stable; (h) low evaporation rate; and (i) non-
allergic [100]. Based on the lubricant properties required, waste-derived oils, waste animal
fats, greases and tallow can be sustainable, eco-friendly and cheap, meeting the needs
of biolubricants.

Table 4. Advantages and disadvantages of biolubricants [15,101].

Sl. No. Advantages Disadvantages

1 High lubricity High cost.
Several vegetable oils are edible. This can
2 High viscosity index
lead to food vs. fuel debate.
3 High volatility Vegetable oils have higher melting points.
Lubricants 2022, 10, 70 14 of 21

Table 4. Cont.

Sl. No. Advantages Disadvantages

4 High boiling point (lower emissions) Vegetable oils have low oxidative stability.
Biolubricants are less developed compared
5 Longer tool life
to fossil-based technologies.
6 Better skin compatibility Poor oxidation stability of pyrolysis bio-oils.
7 Better safety on the shop floor High acidity of pyrolysis bio-oils.
Biodegradability is high (as they are
Higher extent of upgradation required for
8 free of aromatics)
thermochemically derived base stocks.
9 High volatility High viscosity of HTL biocrudes.
10 Customizable chemical structures
11 Lesser amount of contaminants
The base stocks for biolubricants can
12
be derived from a variety of sources

6. Applications
Table 5 presents some oils derived from renewable feedstocks and their major applica-
tions. Engine oils tend to minimize the transport of contaminants and other particulates,
and keep them away from the moving parts [102]. As engine oils undergo oxidative
degradation and wear during service, it is vital to characterize the ageing of engine oils at
simulated conditions to understand and evaluate the performance of existing oils and also
design new formulations [52]. Researchers have employed pongamia oil as a compression
ignition (CI) engine lubricant [83], showing that it improves efficiency and, unlike a mineral
oil lubricant, can potentially eliminate the emission of trace metals, as it is devoid of any
metal constituents.
Cutting fluids control the temperature rise by giving adequate lubrication and cooling
between the workpiece and the tool [103]. Even though mineral oils are comparatively
cheaper for this application, they exhibit poor performance due to low-temperature solidifi-
cation, oxidative instability, and loss of viscosity at elevated temperatures. They are also
susceptible to explosion in the presence of an oxidizing agent. Importantly, the additives
used to enhance the performance of the lubricant may be dangerous to humans and the
environment. Non-edible vegetable oils are biodegradable, and are ultimately decom-
posed and mineralized into carbon dioxide and hydrogen by microbes. Biodegradability
ensures the safe integration of biomaterial back into the carbon cycle of nature. Non-edible
vegetable oils degrade faster than mineral oils in the natural environment [103,104].
Kania et al. [105] presented a review of biolubricants in drilling fluids. A good drilling
fluid exhibits these properties: relatively high viscosity, low corrosivity, high lubricating
film strength, low flammability, high solubility, low pour point, high thermal and oxidative
stability, and non-toxic. Lubricants are majorly applied to water-based mud (WBM) in
drilling applications as the lubricity is inadequate. A biolubricant must possess
favorable lubricity, solvency, viscosity, VI, thermal-oxidative and hydrolytic stability in
order to exhibit excellent lubricating performance under wellbore conditions. These
properties are influenced by the presence of an ester functional group. Most esters used
as lubricants in drilling fluids are derived from polyhydric alcohols. Only some esters
are derived from monohydric alcohols, including aliphatic esters and diesters [105].
The minimum quantity lubrication (MQL) is an environmental protection technology
that employs a nozzle to spray a small amount of lubricating fluid and compressed gas
into the cutting zone for the purpose of cooling and lubrication [106,107]. Dong et al. [107]
discussed the temperature of the MQL milling of the 45 steel using cottonseed, palm, castor,
soybean, and peanut oils as base stocks. The effects of the carbon chain length, thermal
conductivity, fatty acid composition and viscosity on the milling temperature were studied.
By simulating the temperature distribution of the milling of the 45 steel with five different
Lubricants 2022, 10, 70 15 of 21

vegetable oils, it was shown that the cottonseed and the palm oils exhibited a good cooling
effect. This is due to the presence of short carbon chain length palmitic acid in cottonseed
and palm oils, which is conducive to the MQL milling.
Gear oils are necessary for industrial and automotive lubrication, wherein they are
generally used in differentials, transmissions, power take-offs and non-drive applications.
Besides the usual functions of lubricants, these oils are required to reduce noise, inhibit
corrosion, transfer heat, and improve overall efficiency [108,109]. In order to obtain good
protection in both the hydrodynamic and elastohydrodynamic regimes, strict viscosity reg-
ulation of the base oil is needed. While vegetable oils do not possess the required viscosity
for these applications, this limitation can be overcome by thermal polymerisation of the oil
by heating the oil in inert ambience to generate high molecular weight products [109]. For
high viscosity applications, lubricants of the required quality can be generated from wastes,
and biocrudes derived through hydrothermal liquefaction can be suitably tailor-made to
meet the requirements. This is also evident from the viscosity values of these fuels shown
in Table 3.

Table 5. Oils, their properties, and their major applications.

Sl. No. Oil Major Properties * Major Applications Reference

Less corrosive, low coefficient Greases, metal working
1 Palm oil of friction, high viscosity [2,15]
fluids (MWFs)
High antiwear, better lubricity,
2 Coconut oil low coefficient of friction Engine oils [2,15]
Greases, surfactants, cosmetics,
3 Crambe oil n.a. [15]
chemicals
4 Sunflower oil Diesel fuels, greases [2,15]
Hydraulic oils, biodiesel fuel, engine
5 Soybean oil oils, transmission fluids, printing
[2,15]
inks, paints, detergents, coatings,
High VI, high flash point than some pesticides, shampoos
conventional oils, high
6 Safflower oil lubricity, low evaporative loss, Resins, diesel fuels, enamels [2,15]
7 Linseed oil low co-efficient of friction, better Stains, coatings, vanishes, paints [2,15]
lubricity, non-toxic
8 Olive oil Engine oils [2,15]
MWFs, transmission fluids,
9 Canola oil food-grade lubes, hydraulic fluids, [2,15]
penetrating oils, transmission fluids
High VI, low volatility, high
10 Castor oil antioxidants, low deposit Greases, gear lubricants [2,15]
formation
Low frictional losses, low

emissions, minimum
11 Pongamia oil Power transformer applications,
break-specific fuel consumption [2,110,111]
anticorrosive coating
and high break thermal
efficiency at medium
loads
Soaps, cosmetics, plastics,
12 Tallow oil n.a. [15]
hydraulic oils
13 Cuphea oil n.a. Motor oils, cosmetics [15]
14 Jojoba oil n.a. Greases, cosmetics, lubricants [15]
High VI, low wear loss, low
15 Jatropha oil cumulative weight loss, low Biodiesel [2,112,113]
coefficient of friction
Lubricants 2022, 10, 70 16 of 21

Table 5. Cont.

Sl. No. Oil Major Properties * Major Applications Reference

Better oxidation stability, better Power transformer applications,

16 Rapeseed oil cold flow property and low hydraulic fluids, greases, [2,15,110]
coefficient of friction chainsaw oils
Biocrude for various engineering
17 HTL liquid High viscosity, high acidity applications, heating, in marine, rail
[95,114]
engines, can be upgraded to
transportation fuels and jet fuels
High viscosity if the feedstock
Biofuel for energy applications,
is
18 Pyrolysis oil polymers, while viscosity is heating, steel, cement industries,
[81,86,88]
low if derived from biomass; generating valuable hydrocarbons
poor oxidation stability, high and petrochemicals
acidity
n.a.—Not available; * the reference fuels used for the comparison of the oil properties include mineral oil,
SAE20W40, SAE 40, and SAE20W50, as elucidated in the references.

Technoeconomic analyses and life cycle assessment of biolubricants involving cradle-

to-grave and cradle-to-wheel approaches must be conducted to understand the commercial
viability of biolubricants vis-à-vis conventional mineral oil-based lubricants. Importantly,
such studies are scarce in the literature. Athaley et al. [115] performed a technoeconomic
analysis of butadiene, jet fuel, surfactant, and lubricant production from furfural, which is a
biomass-derived platform molecule. A sequential catalytic process involving the acylation
of anhydride and furan, the hydrogenation of 2-pentanoyl furan, the hydroalkylation of
pentyl furan, and the hydrodeoxygenation of condensed furan was analyzed. It was found
that the raw material cost was nearly 87% of the total operating cost of the process, and
the minimum selling price of the lubricant was USD 4037 per metric ton [115]. This is
due to the high price of raw materials such as valeric acid, lauraldehyde, and lauric acid.
This necessitates the integration of biolubricant production processes within biorefineries.
Moreover, a thorough study of different scenarios of biolubricant production in typical
bioethanol, biodiesel, oleochemical, and waste biorefineries is required.

7. Conclusions
In this review, the major advantages, disadvantages and applications of edible, non-
edible and mineral oil-based lubricants have been discussed. While vegetable oil-based
lubricants are popular owing to the good lubricative properties they offer, along with
low toxicity, eco-friendliness and biodegradability, their requirement for cooking food
can escalate cost, and affect their availability at large scales. Non-edible oils also present
an interesting option from the viewpoint of waste management and value generation
from wastes. In this context, the use of bio-oils generated from lignocellulosic agro-
residues, microalgae, and plastic-rich fractions such as refuse-derived fuels through
thermochemical technologies such as pyrolysis and HTL need clearer focus.
From the literature, it can be noted that biolubricants can provide better
lubrication properties than the conventionally used synthetic and mineral oils, and more
importantly, the essential properties required for diverse engineering applications can
be obtained. Additionally, as they are non-toxic and clean, biolubricants may potentially
be utilised in highly sensitive applications such as marine and forestry ecosystems,
where strict laws, rules and regulations apply. In this context, the demand for
biolubricants is expected to only increase in the near future in applications such as
hydraulic oils, engine oils, gear oils, cutting fluids, and in electrical appliances and
turbomachinery.
The key challenges involved and the scope for further investigation in the area of
biolubricants from wastes can be summarized as follows. The properties and composition
of thermochemically derived bio-oil or bio-crude are heavily dependent on the type of
feedstock, and so, it is imperative to produce biolubricant base stocks from a specific variety
of biomass residue or plastic. Any variation of feedstock quality can lead to adverse changes
Lubricants 2022, 10, 70 17 of 21

in properties. In fact, utilizing agro-residues, plastics and their mixtures for biolubricant
preparation is a sustainable option, and is a high-value proposition for waste as compared to
its regular utilization as transportation-grade or stationary engine fuel. Systematic studies
on novel biolubricant formulations using bio-oil/bio-crude along with additives need to be
performed to expand our current understanding of the physicochemical,
thermophysical, tribological properties and stability of the biolubricants. Suitable waste
feedstocks used for the preparation of such biolubricants include biomass, and olefinic
plastic mixtures, waste cooking oil, and catalytically upgraded pyrolysis oils derived from
polymers. Usually, pyrolysis oils derived from polymers without catalytic treatment
exhibit a waxy nature and present high viscosity values. Therefore, catalytic treatment
or secondary pyrolysis treatment to improve the flowability of the base oil is a
necessity.
Mild to moderate upgradation of oils from agroresidues may be necessary to reduce the
oxygen content in the fuel. This is usually performed using catalysts in hydrogen ambience.
While this is a well-known process, controlled hydrogenation and hydrodeoxygenation
are necessary to tailor the properties of biolubricants. Studies on the stability of both
existing vegetable oil-based biolubricants and waste-derived biolubricants are scarce. A
basic investigation of storage stability, oxidative stability, hydrolytic stability and
thermal stability is required in accordance with pre-existing standards. A thorough
assessment of biodegradability and ecotoxicity of the biolubricant formulations needs to
be performed, and the existing literature must be expanded. Detailed comparative
studies to investigate the advantages and disadvantages of various biolubricants for
diverse applications need better focus. The limited studies available indicate that the
high price of raw materials can make the biolubricant production process unsustainable
from a monetary viewpoint. This requires a thorough technoeconomic assessment of
using vegetable oil-based and waste- derived biolubricants in a closed-loop biorefinery
for a successful large-scale transition to biolubricants. In addition, impact metrics such
as life cycle CO2 emissions that directly affect climate change, water depletion, fossil
depletion, and land-use change need to be evaluated based on thorough life cycle
analysis. Key policy decisions are determined by the energy and economic benefits offered
by the biolubricants over conventional petroleum- derived lubricants. Sometimes, even
the blending of biolubricants with conventional lubricants may be a sustainable option
from the viewpoint of biodegradability, although this is yet to be fully explored. The
authors are confident that biolubricants are a promising and potential option to utilize
waste and generate value while achieving a sustainable and circular bioeconomy.

Author Contributions: Conceptualization, methodology, validation, formal analysis, data cura-

tion, writing—original draft preparation, R.N.S.; conceptualization, methodology, formal analysis,
writing—original draft preparation, resources, supervision, project administration, funding acquisi-
tion, R.V. All authors have read and agreed to the published version of the manuscript.
Funding: The authors thank Department of Science and Technology (DST), India, for funding the
study through Waste Management Technologies Grant # DST/TDT/WMT/AgWaste/2021/15.
Institutional Review Board Statement: Not applicable.
Informed Consent Statement: Not applicable.
Data Availability Statement: Not applicable.
Acknowledgments: R.N.S. thanks the DST, India for funding the research associateship. The National
Center for Combustion Research and Development is sponsored by Department of Science and
Technology, India.
Conflicts of Interest: The authors declare no conflict of interest. The funders had no role in the
design of the study; in the collection, analyses, or interpretation of data; in the writing of the
manuscript, or in the decision to publish the results.
Lubricants 2022, 10, 70 18 of 21

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