A SEMINAR REPORT

on
“bio-lubricant”

Submitted in partial fulfilment of the requirements

for the award of the degree of
MASTER OF TECHNOLOGY
in
CHEMICAL ENGINEERING
Sardar Vallabhbhai National Institute of Technology – Surat

By
Akshit kikani
[P23CH003]
Under the Guidance of
Dr. jigisha kamal parikh
(Supervisor)

DEPARTMENT OF CHEMICAL ENGINEERING,

SVNIT – SURAT, GUJARAT
Spring 2023 – 24
 CERTIFICATE

This is to certify that the Seminar entitled Bio Lubricant presented by Mr.
Akshit Kikani (P23CH003) of Chemical Engineering has been completed
successfully. This is in partial fulfilment of the requirements of the Master of
Technology in Chemical Engineering under Sardar Vallabhbhai National Institute
of Technology – Surat, Gujarat.

____________________ _______________________

Dr. Jigisha K. Parikh Dr. S.K. Sundar

(Professor) (Assistant Professor)

DoChE, SVNIT – Surat DoChE, SVNIT – Surat

(Examiner – 1) (Examiner – 2)

Dr. Parimal A. Parikh Dr. Mousumi Chakraborty

(Supervisor) (Head of Department)

(Professor - HAG) (Professor)

DoChE, SVNIT – Surat DoChE, SVNIT – Surat

Bio lubricant
 _______________________ _______________________

(Examiner – 3) (Examiner –4)

Dr. Z.V.P. Murthy Dr. Sarita Kalla

(Professor - HAG) (Assistant Professor)

DoChE, SVNIT – Surat DoChE, SVNIT – Surat

_________________

(Examiner – 5)

Dr. Vineet Kumar

Rathore

(Assistant Professor)

DoChE, SVNIT –
Surat

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 ACKNOWLEDGEMENT

I express my deepest gratitude and heartiest thanks to my supervisor, Dr. Jigisha Kamal
Parikh, DoChE, Sardar Vallabhbhai National Institute of Technology, Surat, for continuous
guidance, help and support during the seminar.

I express my sincere thanks to Dr. Mousumi Chakraborty, Head of the Department of

Chemical Engineering, Sardar Vallabhbhai National Institute of Technology, Surat, who
helped me to accomplish my dissertation work with preciseness and excellence. I have learnt
writing skills from my advisors with the help of which I can write down my thoughts clearly
and concisely.

I would also like to acknowledge the contribution of all faculty and staff members of the
Department of Chemical Engineering for their continuous support towards the completion of
my dissertation work.

Bio lubricant
 Table of Contents

CERTIFICATE ................................................................................................ III

ACKNOWLEDGEMENT …………………………………………………....V
List of Figures ................................................................................................ VIII
List of Tables .................................................................................................. VIII
CHAPTER 1 Introduction ................................................................................. 1
1.1 Overview .......................................................... Error! Bookmark not defined.

1.2 Lubricant ......................................................... Error! Bookmark not defined.

1.3 Function Of Lubricant .................................. Error! Bookmark not defined.

1.4 Type Of Lubricant BaseStocks ................................................................... 3

CHAPTER 2 Bio Lubricant ............................................................................... 8

2.1 Introduction to Bio lubricant ....................................................................... 8

2.2 Bio lubricant base stocks ............................................................................ 10

2.2.1 Vegetable Oils............................................................................... 10

2.2.2 Fatty Acids .................................................................................... 12
2.2.3 Microalgae .................................................................................... 12
2.3 Physicochemical Properties........................................................................ 14

2.4 Biodegradability .......................................................................................... 16

2.5 Structure of biolubricant ............................................................................ 17

2.5.1 Influence of Structural Features on BiolubricantPerformance……..17

2.6 Characterization of bio‑lubricants………………….…………………...20
2.7 Applications of the Biolubricants .............................................................. 22

2.8 Advantages and Disadvantages.................................................................. 26

CHAPTER 3 Production Techniques .............................................................. 29

3.1 Epoxidation .................................................................................................. 29

3.2 Esterification/transesterification ............................................................... 30

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3.3 Estolide formation ....................................................................................... 33

3.4 Selective hydrogenation .............................................................................. 33

3.5 Microwave Technology ............................................................................... 33

3.6 Microwave and supercritical/ subcritical ................................................. 34

CHAPTER 4 Research Outlook ...................................................................... 36

4.1 prospect ........................................................................................................ 41

CHAPTER 5 Conclusion .................................................................................. 43

REFERENCES .................................................................................................. 44

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 List of Figures

Figure 1.4.1 Lube Oil Refinery Process

Figure 1.4.2 general composition of oil
Figure 1.4.3. Chemical modifications of vegetable oils to obtain lubricants.
Figure 2.1.1 The life cycle of bio lubricant
Figure 2.2.1. Biolubricant classification according to feedstock.
Figure 5.1.1. The polarity of the FAME structure and main oxygen attack areas.
Fig. 6.1.1 Various lubricant characterisation equipment.
Figure 3.2.1. Reaction pathways of the three main chemical modification methods. Red, green
and blue solid arrows represent the pathway of esterification/transesterification, solid
formation, and epoxidation/ring opening, respectively.
Fig. 3.2.1. Experimental procedure flow diagram folubricantnt production from WCO and
EG.

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 List of Tables
Table:1.2.1 global lubricant market
Table 2.8.1 advantages and disadvantages

Table 4.1.1 Lubricant requirements and unmodified vegetable oil properties.

Table 4.1.2 Physical properties and reaction conditions of lubricants derived from fatty acid
methyl esters

Table:4.4.1- characteristics of lubricants The addition of graphite as a modifier has been

proven to remove most of the impurities and dissolved substances in the based oil and
successfully make the based oil cleaner and clearer.

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CHAPTER 1 Introduction

1.1 overview

Energy consumption has increased as a result of modernity, industrialization, and growing

world population. Because of societies' dependence on fossil fuels over the past century, fuel
reserves have been gradually depleted to the point where it is predicted that this non-renewable
energy source will run out in the medium term. As a result, efforts are being made to find
alternative chemicals and energy sources that could take the place of conventional fossil fuels.
Numerous renewable energy sources, including geothermal, wind, sun, hydropower, and
biomass energy, have been suggested as possible energy sources. Of them, biomass is the only
renewable source that can be used to produce energy and chemical products, making it the only
option that can currently replace petroleum[1].

Lubricant acts as anti-friction media, facilitates smooth operation, maintains reliable machine
functions, and decreases the risk of frequent failure. A lubricant may be a liquid, a semi-solid
(grease), or a solid (including coatings and particles). The major objectives of lubrication
include: [2]
(a) reducing wear and preventing heat loss due to the contact of moving surfaces;
(b) protecting the surface from corrosion by reducing the oxidation;
(c) acting as an insulator in transformer applications; and
(d) acting as a sealant against dust, dirt and water.

While it is difficult to eliminate wear and heat using lubricants, they can be minimized and
controlled to acceptable levels. Minami pointed out the three main functions of lubricants as
follows:
(a) controlling friction;
(b) cleaning contact; and
(c) cooling the contact.[2]

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1.2 lubricant

A lubricant is a substance in the form of a liquid oil / semi-solid grease applied between two
metal surfaces in relative mutual motion to prevent their direct contact and thus reduce friction
and wear between them.

Lubrication:-
Lubrication is the act of applying lubricating substances that are capable of reducing friction
between moving mechanical parts.

Global lubricant market:-

YEAR DEMAND(MMTPA) YEAR DEMAND(MMTPA)

2000 36.4 2009 32.2

2001 35.6 2010 34.5
2002 35.7 2011 35.1
2003 35.4 2012 35
2004 36.1 2013 35.3
2005 36.5 2014 35.4
2006 36.9 2015 35.6
2007 36 2016 35.7
2008 36 2017 36.1
Table:1.2.1 global lubricant market

1.3 Function Of Lubricant

 To maintain the moving components of a mechanical device in design condition as long

as possible.
 Removal of contaminants and wear particles from the metal surfaces.
 Dissipation of heat from the mechanical device during operation.
 Prevention of rust and corrosion.
 To provide a seal at moving contacts to prevent leakage.

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1.4 Type Of Lubricant BaseStocks
Bastocks for lubricant formulation
 Petroleum-based mineral oil
 Vegetable oil or animal fat
 Synthetic type

 Mineral oil base stock:-

Mineral oils are highly complex mixtures of C20-C50hydrocarbons in a boiling range of 300-
370ºC containing a range of linear and branched alkanes (paraffin), cycloalkanes(naphthenes),
alkenes (olefins) and aromatics plus a significant amount of non-hydrocarbon sulphur
compounds[16].

Mineral oil base stocks are derived from crude petroleum in a series of refining operations
involving high vacuum distillation, solvent deasphalting, solvent extraction, solvent or
catalytic dewaxing and hydro-finishing processes[16].

Mineral oils accounted for 95% of global lube oil basestock demand in 2014. Synthetics and
biolubesbasestocks respectively accounted for 4% and 1% of global basestock demand during
this period[16].

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 Figure 1.4.1 Lube oil refinery process flow

 Vegetable oil or animal fat

Natural oils and fats are amphiphilic compounds of vegetable or animal origin which consist
predominantly of...

triglycerides (98%) and

minor amounts of mono-and di-glycerides(0.5%),
free fatty acids (0.1%)

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sterols (0.3%) and
tocopherols(0.1%).

Figure 1.4.2 general composition of oil

Most fatty acids in natural oils and fats are long-chain (C18-C24) linear aliphatic acids (R-
COOH).

The small linear chain fatty acids (C6) are hydrophilic due to the presence of the polar water-
soluble carboxyl (‒COOH) group, whereas long chain fatty acids are increasingly higher
hydrophobic (or lipophilic) due to the presence of non-polar water-insoluble long hydrocarbon
chain.

The value and application of oil are determined largely by its fatty acid (FA) composition or
the carbon chain distribution.

The chain length range of C12(e.g. lauric acid) provides important raw materials for detergents
and surfactants. The chain lengths of C18–C22(e.g., oleic and erucic acid) are used mainly in
industrial applications such as lubrication and polymer additives[16].

 Synthetic-type basestock
Synthetic base stocks are chemically engineered by combining low molecular-weight
compounds in a chemical reaction carried under controlled reaction parameters to produce high
molecular-weight compounds of uniform consistency and tailored performance properties[16].

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 Figure 1.4.3. Chemical modifications of vegetable oils to obtain lubricants.

Classification of synthetic base stocks:

Synthetic organic esters (e.g.aliphatic diesters, polyol esters, phosphate esters)

Synthetic Hydrocarbons (e.g.polyalphaolefins, alkylated aromatics, polybutenes)
Others (e.g.polyalkyleneglycols, silicones, etc.)

 Problems with mineral oil-based lubricants:-

 Depleting crude oil reserves
 Fluctuating oil prices
 Lack of biodegradability and
 Adverse effects on health, safety and environment.
 The current supply of crude oil is not going to last indefinitely.
 The researchers may argue over the life of the existing crude oil resource base; whether
it will be for another 100 years or 200 years or so, but there is a consensus that sources
of crude oil will exhaust sooner or later.

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  The theory of resource depletion is strengthened by the fact that the production rate
from the existing fields is declining and new reserves are not being found at the same
rate.
 The total quantity of lubricants lost to the environment every year has been estimated
at 50% or approximately 10–15 MMTPA worldwide nearly the same in properties and
appearance.
 In addition, significant quantities can enter the biosphere through leakage or failures of
seals, pipes or cylinders, quantity remaining in filters and containers, incidental or
purposive spillage, industrial and municipal discharge, hydraulic and cutting fluids and
accidents.
 Mineral oil-based lubricants present environmental hazards of the same severity as that
displayed by general petroleum.
 These lubricants are poorly biodegradable and toxic and pose serious threats to health,
safety and the environment at each stage of their production, use and final disposal.
 Possibilities include air pollution, surface and groundwater contamination, soil
contamination, and crops and food contamination.

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CHAPTER 2 Bio Lubricant

2.1 Introduction to Bio lubricant

The term bio lubricant applies to all lubricants which are both rapidly biodegradable and
nontoxic for humans and aquatic environments
A lubricant can be:
• vegetable oil-based (e.g.soybean oil, rapeseed oil),
• based on synthetic esters manufactured from modified renewal oils.

The term lubricant 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, they are promising candidates as they are renewable and emit net
zero greenhouse gases to the environment. Some of the key terms to be understood include
mineral oil, base stock, and base oil.

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.

Figure 2.1.1 The life cycle of bio lubricant

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It has been described that lubricant has excellent lubricity and causes a reduction in friction
coefficient, frictional forces and wear compared to other lubricants. 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 vegetable oils have
been reported to be poorer than conventional mineral oils and should be improved.

The economic and environmental significance of base oils and sustainable lubricants was
discussed by Shah et al]. As nearly 66% of fuel energy is lost to the surroundings due to
thermal, frictional, transmission and other components, the design of sustainable bio-lubricants
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 material. Biolubricants can also be prepared from waste
cooking oil and cyclic oxygenates through a four-step catalytic process.

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. Eco-
friendly multipurpose lubricating greases from vegetable residual oils have been studied, and
it has been observed that they have superior tribological performance as compared to
commercial grease.

By studying the rheological and wetting behaviour 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 considered while selecting a stern tube lubricant. Researchers produced
environmentally friendly ethylene glycol di-esters (EGDEs) as lubricants 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).

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 [2]

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2.2 Bio lubricant base stocks

Proper Classification for Biolubricants from Feedstock:-

Figure 2.2.1. Biolubricant classification according to feedstock.

2.2.1. Vegetable oils

Conventional lubricants are generally extracted from crude oil. They typically consist of
mineral oils and different kinds of additives which increase their overall performance and
efficiency.

On the other hand, bio-lubricants are based on renewable resources such as vegetable oils,
animal fats and plant-based feedstocks like synthetic esters etc. One of the major drawbacks of
conventional lubricants is their non-biodegradable nature which results in soil and water
contamination if they are not properly disposed of. They also generally cause pollution and are
harmful to the ecosystems.

On the contrary, bio-lubricants are biodegradable and easily break down naturally and are eco-
friendly. In addition, conventional lubricants possess detrimental chemicals and additives that
are harmful to humans. However, bio-lubricants are less toxic and generally safer for human
health.

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Although vegetable-based lubricant oils do not match petroleum-based lubricant standards,
they exhibit higher flash points, lower evaporative losses, higher viscosity index and better
lubrication. On the contrary, vegetable oils indicate unsaturated fatty acids, which make them
unsuitable for lubricating applications by imparting poor oxidation and thermal properties.
However chemical modification procedures (hydrogenation, transesterification, and
epoxidation) can reduce the degree of unsaturation and make vegetable oils comparable to
conventional lubricants with improved tribological characteristics. The common feedstocks for
bio-lubricants are enlisted below:

 Sunflower oil is mainly extracted from Helianthus Annuus seeds. Oil is primarily a
triglyceride which is usually comprised of oleic acid (monounsaturated), linoleic acid
(polyunsaturated), palmitic acid and stearic acid (saturated). Sunflower oil exhibits
higher viscosity in cold temperatures owing to higher levels of unsaturated fats.
 Castor oil is extracted from the Ricinus plant (castor beans). The triglyceride of castor
oil contains 90% of fatty acid chains as ricinolate (ricinoleic acid). Castor oil possesses
low-temperature viscosity and higher-temperature lubricity, making it perfect for
diesel, jet, and racing engines. Rapeseed oil is mainly cultivated for oil-rich seed (54%
Erucic acid).
 Canola oil plant is a subtype of rapeseed plant with high nutritional value and low erucic
acid. Jatropha oil is extracted from the Jatropha Curcas plant, which can grow in all
terrains with a higher seed production rate and is used in synthesizing lubricants owing
to higher fatty acid content.
 Coconut oil possesses a higher degree of saturated fats responsible for slow oxidation.
Coconut oil derivatives (fatty acids), can be utilized as a transformer oil and lubricant.
 As palm oil has a higher percentage of saturated fat (palmitic acid) and
monounsaturated oleic acid as the main component, it lends itself to producing
lubricants with a more extraordinary load-carrying ability. However, palm oil lacks
thermo-oxidative stability. With 51% linoleic acid and 23% monounsaturated oleic
acid, soybean oil is typically used for cooking.
 Soybean oil’s ability to increase flash points and prolong transformer life made it
suitable for dielectric fluid portrays the physicochemical attributes of distinct lubricant
oil sources

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The lubricant oil can be extracted from many sources, and the research is going towards finding
novel sources. Algae is one of the novel sources of lubricant oil with competitive
physicochemical properties with other sources.

2.2.2. Fatty acids

The primary constituent of fats and oils is fatty acids, which are esterified by glycerol. The
chemical treatment of fatty acid carboxyl and unsaturated group residues provides the basis for
oleochemical compounds. The commercially accessible oils and fats are lipid mixes that
primarily contain free fatty acids, monoacylglycerols, and diacylglycerols in varying ratios.
They might also contain hydrocarbons, phospholipids, triterpene alcohols, sterol esters, and
fat-soluble vitamins.

2.2.3. Microalgae
Microalgae possess a high photosynthetic potential and CO2 retention. The primary industrial
use of algal biomass as a bio-lubricant source. The thousands of different species of algae with
lipids, proteins, and carbohydrates in their composition.

The oil concentration varies from 10 to 50% depending on the microalgae condition and growth
pace. The fact that a large agricultural field is not necessary for microalgae growth has worked
in the microalgae’s favour. The microalgae source is cheap as it can be produced by industrial
effluents or in seawater.

Higher surface protection against wear and a lower degree of friction are critical benefits of
microalgal and yeast oils, which can be credited to an optimal combination of unsaturated and
saturated fatty acids. Microalgal and yeast oils have a significantly reduced friction coefficient
and metallic surface wear when compared to conventional mineral-based lubricants like PEG
200.

The number of fatty acids in the feedstock has a major impact on its tribological characteristics,
for example, the double bonds in the fatty acid chain make it extremely vulnerable to auto-
oxidation when in contact with air.

Moreover, some limitations of using microbial oils as bio-lubricants, including oxidative and
hydrolytic stability, can be further improved through chemical modifications in oil static sites,

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such as double bonds and acyl groups or by blending with some oils having different fatty acid
profiles Algal cyanobacterial biomass can be cultivated from industrial effluents and seawater
more early in contrast with plants.

The shorter cultivation time makes them desirable for an uninterrupted supply of raw material,
and the ability to grow in seawater eliminates the requirement for fresh water. The pigments
and carbohydrates are value-added by-products of algal biorefineries. The proportion of
carbohydrates can be detached and utilized for bio-lubricant (C-BLUB) production to minimize
production costs for primary products.

Three factors including macronutrient starvation, salinity rise, and mild ozonation responsible
for maximum microalgae/ cyanobacteria production. In open ponds or raceways (sea water,
saline water, organic/inorganic growth medium, and industrial wastage), algal/cyanobacterial
strains can outcompete bacteria by producing metabolites with an allelopathic impact.
Algal biomass production linked with bioremediation can considerably decrease water and
nutrient needs. However, the production cost can be abridged by the continuous supply of raw
materials. Simple stresses like nutrient starvation and ozonation for a brief passage of time can
enhance the accumulation of carbohydrates in cells - the sonification technique used to extract
lubricant oil from algae. Moreover, the physicochemical attributes of carbohydrates derived
from cyanobacteria/algae exhibit compliance with mandatory attributes for bio-lubricants.

Cultivated microalgae in wastewater to establish a correlation between the selected species for
a specific type of wastewater. Desmodesmus maximus CN06 showed an excellent growth rate
of 0.23/day, exhibited excellent nutrient removal efficiencies and highest Lipid productivity of
3.43 mg/L ・ day.

The extracted fatty acids indicated a good potential to be applied for biodiesel and bio-lubricant
production. Additionally, microalgae have a good potential to utilize CO2 and sunlight to
generate biomass for commercial applications. In such applications, microalgae are considered
a promising Carbon capture and utilization technology.

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2.3 Physicochemical Properties

The physicochemical properties significantly impact lubricant performance, therefore it is

necessary to study these properties in detail. The physicochemical properties of bio lubricant
are briefly explained below:

2.3.1. Viscosity and viscosity index

Bio lubricants mostly possess higher viscosity due to the higher chain length of the alcohol
hydrocarbon chain in ester (carboxylic acid) bio-lubricants. However, the viscosity index (VI)
explains the variation in viscosity due to temperature. As the VI is higher, the minor viscosity
variation occurs over the comprehensive temperature range. The VI decreases by increasing
the branches of carboxylic acid/alcohol while keeping a constant number of carbons.

investigated the impact of vacuum pressure on the viscosity index of lubricant oil during the
transesterification of palm oil methyl esters with trimethylolpropane (TMP). The improvement
in viscosity index from 171 to 214 was observed when vacuum pressure was reduced from 50
to 10 mmHg.

2.3.2. Flash point

Flashpoint (FP) is a minor temperature around which the vaporization of lubricant leads to an
explosive air mixture. The FP exhibits an inversely proportional relation with flammability.
The flashpoint assesses lubricant behaviour under atmospheric temperature and indicates the
lubricant volatility and fire tolerance. Bio-lubricants usually possess higher flashpoints.

2.3.3. Carbon residue

The bio-lubricants possess lower carbon residue than base mineral oil because the bulk of
mineral oils (paraffinic nature) account for higher residues. Carbon residue determines fuel
decay and carbonaceous material formation that resultantly chokes the nozzle and hinders fuel
injection.

2.3.4. Moisture content

Moisture content as certains the amount of water in the lubricant sample and affects the
physical properties of the lubricant, including viscosity, weight, conductivity and density.

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The oil’s moisture content is equivalent to mass lost during heating. Bio-lubricant oils possess
moisture content naturally, which is inevitable. Therefore, to reduce moisture content in
lubricant oil, the composition of base oil should be higher in bio-lubricants.

2.3.5. Pour point

A pour point is a minor temperature beneath which a lubricant fails to sustain flow ability and
maintain liquid properties. The viscosity index and pour moment are related to bio-lubricants.
Trimethylolpropane (TMP), one of the ternary alcohols used in bio-lubricants, exhibits a lower
pour point and less resilience against thermos oxidation.

Larger branched alcohols with lower pour points and improved oxidative stability, such as
neopentyl polyols, have shown promise as a substitute for bio-lubricants.

2.3.6. Total acid number (TAN)

TAN is the amount of base expressed in milligrams of potassium hydroxide needed to
neutralize the amount of acid in one gram of lubricant oil. If its value is too high, then it
indicates higher contamination, oxidation and acidic sludges.

2.3.7. Thermo-Oxidative Stability

As indicated above, unsaturated bonds harm the thermo-oxidative stability of lubricants.
However, it is possible to achieve an appropriate relationship between the behaviour of the
bonds with low temperature and thermo-oxidative stability; some lubricants with excellent
properties and vegetable oil (sunflower, canola, or soybean) content above 80% were reported
to show these properties.

Thermo-oxidative stability can also be improved by chemically modifying the vegetable oil
via saturation of the –C=C– bond, thereby obtaining lubricants that can be used as hydraulic
lubricants, transmission fluids, and engine or compressor lubricants. Thermo-oxidative
stability and the viscosity index can be further improved by saturating –C=C– bonds (via
epoxidation) and then causing them to become branched. Therefore, it is possible to modulate
the viscosity by modifying the length of the alkyl chain.

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2.3.8. Hydrolytic Stability
The resistance of lubricants to chemical attacks, where H2O is involved as a reactant or
product, is another parameter to be considered regarding biolubricant stability. Generally,
lubricants are formed by esters, which are prone to hydrolysis by their respective carboxylic
acid and alcohol. Previous authors reported that saturation improved hydrolytic stability.
Similarly, saturated dicarboxylic esters were shown to be highly stable due to sterice_ects.

The hydrolytic stability of lubricants is enhanced when short-chain alcohols are employed. This
resistance can be further improved by using branched alcohols. The use of glycerol as the
alcohol in a lubricant results in hydrolytic stability, which is comparable to that shown in mono-
esters formed by branched alcohols. Despite the hydrolytic stability causing the
physicochemical lubricant properties to deteriorate, this parameter is key to obtaining
lubricants with high biodegradability and lesser negative environmental.

2.4 Biodegradability

Biodegradability is an important characteristic for the majority of today's chemical industry

products and represents a way of measuring the risk level of decomposition presented by these
products when deployed to the environment. Biodegradation is a natural process caused by the
action of microorganisms, in the presence of oxygen, nitrogen and minerals.

In the process of formulating lubricant oils, biodegradability is strongly dependent on the oil
used. The base stock oil sand finished lubricants are products with a potential risk of being in
direct contact with the environment, which may happen in their production, distribution,
services usage or even disposal after their utilisation.

Therefore, environmental authorities have been increasingly demanding less toxicity in these
products, so they will cause less harm to nature. The impacts on the environment caused by
inappropriate disposal of the waste are huge.

Lubricants, when in intentional or accidental contact with the soil, make it use less for farming
and civil construction, killing the vegetation and the microorganisms. Brazilian Environmental
National Council (CONAMA) determines that the best environmental management for used or

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contaminated oils is re-refining and, for that, there are many companies properly registered in
this Council that can perform this activity.

Some kinds of lubricants are riskier to be in contact with the environment and because of that,
they must be preferably formulated with less environmentally toxic and more biodegradable
products. Some pathways are already being explored such as chainsaw oil, drilling fluids and
lubricants for the train line.

Other applications of highly biodegradable lubricants are in services that may contain leaking
risks, like forest and mining equipment and in very sensible areas like platforms, agricultural
equipment and hydroelectric power plants. However, environmental agencies have been trying
to put more restrictions on all the products with low biodegradation rates, whether they are
used for risky applications or not.

The intention is that when these products get in touch with the environment, accidentally or
not, they may be quickly isolated and treated. Nowadays, there are plenty of evaluation
methods for biodegradability. Most use microorganisms to obtain the data, even though they
are difficult to adjust and long time methods.

The analysis methods of biodegradability without using microorganisms are relatively recent
and were based on the oil components and their degradation reactions. However, it is still not
clear what is the criteria to determine if certain basestock oil is biodegradable or not, that is,
what quantity of sample will biodegrade and how long it will take, yet the evaluation of the
biodegradability is an important tool of comparison between two different lubricants.

2.5 Structure of lubricant

The greatest part of vegetable oils is triglycerides (98%).

A triglyceride is the reaction product of one molecule of glycerol and three molecules of fatty
acids to produce three molecules of water with one molecule of triglyceride.

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2.5.1. Influence of Structural Features on Biolubricant Performance

Among the structural characteristics that determine the physicochemical and tribological
properties of a lubricant, the following stand out: the presence of double bonds or unsaturation;
the length of the chains present; or the molecular weight, polarity, and the presence of branches
in the structures that make it up. reviewed the influence of these parameters on their
performance as bio-lubricants.

 Presence of Double Bonds

The molecular structure of these compounds can contain zero (saturated), one
(monounsaturated), or multiple C=C double bonds (polyunsaturated). Each FA introduces the
double bonds at a specific position in its structure, for example, at the 6, 9, and 12 carbon atom
positions. The presence of double bonds promotes oxygen attack on the carbons adjacent to
these bonds, The areas most affected by this phenomenon are the carbon atoms located between
two double bonds, so that the oxidative stability of the structure decreases as the areas of
oxygen attack increase. This oxidative stability refers to the ability of lubricants to retain their
properties when exposed to environmental oxygen without suffering oxidative degradation. It
has also shown an increase in PP and a tendency to increase viscosity and decrease viscosity
index (VI) by reducing the content of unsaturated FAs.

Figure 5.1.1. The polarity of the FAME structure and main oxygen attack areas.

 Carbon Chain Length

Chain length and molecular weight are parameters that directly influence important
physicochemical properties. Increasing the chain length leads to structures with higher
molecular weights, resulting in a higher FP, which is relevant as the FP is an important factor
in determining the required safe transport and storage temperatures. In addition, kinematic

Bio lubricant Page | 18

viscosity increases with the molecular weight and the VI also increases as denser structures
help to ensure that the viscosity does not fluctuate significantly with increasing temperature.

In terms of tribological properties, it has been found that COF and wear volume decrease with
increasing chain length due to the better anti-wear performance of the film formed by the ester
groups on the contact surfaces. This is achieved due to the stronger film formed by the bio-
lubricant.

 Polarity of the Structures

The structures of vegetable oils are linear, unbranched chains with polar end groups. The
polarity of these esters increases the effectiveness of wear reduction by forming an adsorbed
protective layer on the contacting metal surfaces, which reduces the surface energy and
increases the strength of the formed tribological film due to their high polarity.

These tribological films exhibit a low COF at both low and high temperatures. This is why the
degree of polarity is important when looking at the molecular structure of a lubricant: COOH
> CHO > OH > COOCH3 > CO > COC (decreasing polarity degrees). Parameters such as VI
or PP are also strongly influenced by the high polarity of these structures, resulting in higher
VI values as the polarity increases, or a drop in PP due to polar functionality.

 Branching Degree
The chains that constitute these oils are characterized by the fact that they are formed by linear
chains of 4 to 26 carbon atoms, with a natural lack of branches. For this reason, the shorter the
chain length, the more the structure tends to clump together, while the longer the chain length,
the more linear they are due to the absence of branches. As a result, these chains have higher
PP values than branched structures with the same number of carbon atoms, due to the molecular
structure, which tends to compact.

 Selecting Vegetable Oils for Biolubricant Formulation

Based on the evaluation of the influence of the molecular structures of vegetable oils on their
physicochemical and tribological properties, This scheme follows the one proposed by Farfán-
Cabrera et al, dedicated to the selection of microalgae species for the production of lubricants.

Bio lubricant Page | 19

Critical input variables are considered to be the FFA content or acidity, the degree of
unsaturation, and the chain length of the corresponding FAs, which have more influence on the
properties of interest of lubricants, such as hydrolytic, oxidative stability, lubricity, PP, and
viscosity.

If the balance between these properties does not meet the minimum requirements for a given
application, the diagram shows the chemical conversions typically used as a function of the
input variable to be improved. Other alternatives may be found in the use of additives or the
selection of less demanding applications.

2.6. Characterization of lubricants

applications, accurate characterization is necessary. Characterization of lubricants is also

important to evaluate the effectiveness and performance of lubricants. It involves measuring
physico-chemical, rheological, tribological and thermal properties.

2.6.1. Physico-chemical, rheological, thermal, and tribological characterization

Physico-chemical properties are related to the chemical composition of lubricants such as
acidity, unsaturation, chain length etc. which are measured by acid value, iodine value and
saponification value respectively.

This indicates the shelf life and oxidative stability of lubricants. Rheological properties are
related to the flow behavior of lubricants such as viscosity index, kinematic viscosity, etc.
Kinematic viscosity and dynamic viscosities are often determined using a redwood and a
rheometer respectively.

Contact angle measurements are done by employing a goniometer. Tribological properties are
related to the interaction between two surfaces such as wear, friction, etc. The coefficient of
friction, wear scar diameter, and weld load by extreme pressure tests are determined by using
a four-ball tester.

Thermal properties are related to the performance of lubricants at different temperatures such
as thermal decomposition, flash point and fire point, pour point and cloud point etc.

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Thermal degradation was analyzed by thermo-gravimetric analyzer Flash and fire point, pour
and cloud points were analyzed using flash point apparatus and cold filter plugging point
apparatus respectively. The pour point can be confirmed by Differential scanning colorimetry
the various characterization techniques and the instruments being used for lubricant analysis.

2.6.2. Evaluation of bio-lubricants

Many formulations are wrongly considered bio-lubricants and ecologically acceptable even if
contain some unacceptable additives. Regardless of whether the base oil is biodegradable, the
overall lubricant may not be environmentally acceptable if it contains a toxic additive, even in
traces. It compromises the lubricant’s “environmentally friendliness.

Fig. 6.1.1 Various lubricant characterization equipment.

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2.7 Applications of the Biolubricants

The systems requiring lubrication can be of closed or open types. Lubricants are often split into
the environment during service and may pollute it in many open systems. Petroleum-based
lubricants exhibit this feature more dominantly and they need to be replaced with clean
alternatives, in open systems.

Lubricants in closed systems must be shielded to stop them from leaking into the surrounding
area. Unexpected incidents, mistakes made by people, and unintentional leaks may all harm
the environment. In both open and closed systems, it becomes preferable to utilize
biocompatible lubricants to prevent environmental damage and to lower global warming.

About 90–98% of vegetable oils can be degraded safely without affecting the environment.
Bio-based lubricants have several uses in different types of contexts, such as hydraulic fluids,
greases, engine oils, and gear oils, as well as cutting or compressor oils and metalworking
fluids.

2.7.1. Hydraulic oils

The flow of the hydraulic fluid assists as a contact between force and energy, transmitting the
force. Compressibility is an important key element of hydraulic fluids; the lower the degree,
the greater the power transmission, the quicker the rate of pressure transfer, and the greater the
efficiency[2].
Systems such as tractors, harvesters, excavators, and trucks that necessitate a lot of force for
movement employ hydraulic fluids.

Vegetable oils that degrade easily provide good options for hydraulic systems’ power transfer.
Vegetable oils have benefits for hydraulic systems, including quiet and gentle operation, rapid
direction change, low compressibility, and improved pressure transmission. Related research
in this area demonstrates that rapeseed, moringa oil, soybean oils, and passion fruit, as well as
palm, rubber seeds, and rapeseed oil, have the required qualities to be employed as hydraulic
fluids.

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2.7.2. Cutting/metalworking fluids
One of the most essential types of lubricants being utilized in a variety of industrial
productions, such as the automotive, aerospace, and marine sectors, is cutting/metalworking
fluid. According to reports, the number of metalworking fluids (MWF) consumed in 2018 was
39.4 million Mt, and in 2022, the number rose approximately to 43.9 million Mt. The three
primary purposes of metalworking/cutting fluids are to:
(a) lubricate throughout the cutting process to decrease friction and lengthen the lifetime of
the parts; (b) cool cutting components and work equipment to eliminate heat while reducing
wear, and
(c) improve workpiece quality by removing chips from cutting components and equipment.
Since the metalworking fluid is based on petroleum, both the environment and employees’
health are at risk when it is used.

In addition, the hazardous substances included in MWF result in skin sensitization and the
intake of dispersed metal flux particles, causing cancer in employees and pulmonary system
damage. According to Agrawal et al., cottonseed oil has a higher potential to be employed as a
metalworking fluid than the industry’s standard MFW due to its good tribology features, low
toxicity, and further practical use. According to Syahir et al. using bio-based metalworking
fluid in the cutting sector extends tool life by up to 40%.

Another study was conducted by Wickramasinghe et al. and it was revealed that the application
of vegetable-oil-based machining fluid in the welding industry ensured the health of workers
and the environment because it offered the desired level of performance in the metal cutting
and desirable characteristics for renewability and biodegradability.

Non-edible oils have a significant potential to replace mineral-based cutting lubricants because
of their better efficiency, enhancing tool life, reducing energy consumption, and lowering COF,
according to scientific studies.

2.7.3. Engine oils

The wear and friction in the piston and cylinder sections of the engine are reduced by boundary
lubrication of the working parts. Engine oils are thought to be primarily responsible for this
function, with other duties including cooling, cleansing, and avoiding corrosion and rust.

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Engine oil degrades over time when exposed to acidic impurities in engines operating under
high temperature and pressure settings. Automotive oil quality is very important. For example,
if the engine lubricant is of low quality, it will result in greater worn-out parts, tear and wear,
cost of maintenance, and decreased engine performance.

Due to their excellent physicochemical qualities and environmental-friendly traits (non-

toxicity and biodegradability), the requirement for bio-lubricants has risen in this regard.
Numerous research programs have been done comparing mineral and bio-based lubricants in
terms of engine efficiency and pollution. Masjuki et al. found that using palm oil was more
effective than using mineral lubricants in lowering the emissions of CO and HC pollutants from
two-stroke engines[2].

Another study found that adding coconut and palm oils to mineral oils could decrease CO2 and
NO2 emissions and increase fuel efficiency in four-stroke engines.

2.7.4. Greases
Grease is a thick, semi-solid lubricant that gets its name from the Latin word Crassus, which
means fat. Grease is produced when filler, the substance that thickens lubricating fluids,
disperses. Thickeners act as a kind of lubricating oil sponge, absorbing it and giving it
consistency and adherence; in fact, they control the temperature range at which grease
functions. Base oils (75–95%), additives (0–5%), and thickeners (5–20%) make up a grease
composition[2].

Investigators have been inspired to create bio-greases, which are greases derived from
triglycerides and natural oils. The adverse impacts of traditional greases on the atmosphere and
their negative effects have prompted this effort.

The rheological, thermal, and mechanical qualities of biodegradable oils and natural thickening
agents including glyceryl stearates, cellulose derivatives, and sorbitan monostearate may be
superior to those of lithium greases, according to various research programs.

In some other studies, the tribological and rheological properties of grease reliant on calcium
and lithium were contrasted with those of grease based on castor oil and chitosan thickener. It

Bio lubricant Page | 24

was demonstrated that sustainable grease exhibited superior rheological, mechanical and
thermal resistance; nevertheless, the wear rate of bio grease was superior to that of conventional
grease.

2.7.5. Transmission Oils

Transmission oils must display high viscosity, high thermal stability, and high friction
resistance and must be able to dissipate heat efficiently since these processes involve great
amounts of friction. The temperature at which a transmission engine is regulated is another
very important parameter to consider since decreased stabilization temperatures imply
decreased friction coefficients, improved thermo-oxidative stability, allowing oils to have
longer service lives, and improved process efficiency.

Nowadays, the use of bio-based lubricants as starting materials for transmission oils is limited.
It was reported that the addition of tetraoleate ester was possible, although this bio-based
lubricant exhibited a higher weld load and lower wear scar diameter than commercial
transmission oils. Currently, the few commercialized bio-based gear and transmission oils that
are employed mainly in gear in roller machinery are based on rapeseed oil.

2.7.6. Chainsaw Oils

Chainsaw lubricants must be renewable and biodegradable since they are often thrown to the
ground or into water during their handling. Moreover, these bio-based lubricants must display
high flash point temperatures and low vapour pressures to minimize the inhalation of volatile
compounds. To improve chainsaw oil formulations, Stanovský et al. established that fewer bio-
based lubricants and fuels were consumed than mineral chainsaw lubricants.

The need for chainsaw lubricants with high biodegradability has led to high commercialization
of these products from several companies, mainly soybean oil and rapeseed oil. The main
challenge in this field is related to the incorporation of additives, which elongate tool life and
improve performance, to replace traditional mineral oils[2].

2.7.7. Insulating Oils

Insulating fluids are usually used to prevent electrical discharge, dissipate heat, and lubricate
and insulate surfaces. These fluids must display high electrical resistivity to avoid electrical
arcing. Nowadays, traditional mineral oils are employed as insulating fluids in capacitors,

Bio lubricant Page | 25

bushings, and transformers, although strict environmental regulations have led to continuous
modifications of their
formulations.

In a study carried out with vegetable oils, Beroual et al. reported that all bio-based formulations
displayed greater breakdown voltage than traditional mineral oils since the vegetable oils
adsorbed moisture up to 30 times more than the mineral oils. On the other hand, vegetable oils
usually displayed higher dielectric constant in comparison to mineral oils, thereby allowing
them to be considered as sustainable insulating fluid alternatives in electrical transformers. The
presence of a hydroxyl group in the C-9 position in castor oil further increased the dielectric
constant[2].

Despite the good behaviour observed in the bio-based insulating fluids, they still demonstrated
poorer oxidative degradation due to the presence of copper wires. Nonetheless, the degradation
of these bio-based insulating fluids can be minimized by chemical modification of vegetable
oils via esterification/transesterification reactions or by the addition of stabilizers. Industrially,
several formulations based on canola or sunflower oils have been marketed, which were proven
to improve transformer loading by up to 20%.

2.8 Advantages and Disadvantages

For a holistic view of lubricant performance, its advantages and disadvantages need to be
discussed. It will open new avenues for future research to minimize the disadvantages and
utilization of lubricants at a large scale.

Vegetable oil has excellent lubricity, a higher viscosity index, and biodegradability is less toxic
and renewable. But then, vegetable oil has less oxidative stability, higher pour point, higher
biological deterioration (bacterial) and aqueous decomposition.

Bio lubricants possess 2 to 4 times higher lubricity than petroleum-based lubricants, resulting
in reduced friction and energy saving from 5 to 15%. Bio lubricants have a higher viscosity
index and can be used in high-temperature applications, mostly above 250 ◦C. Bio lubricants
produce lower emissions owing to higher boiling temperature ranges of esters.

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Bio lubricants depict higher safety standards regarding lower volatility, oil mist, emissions,
stable viscosity, and higher flash points. Bio lubricants create lower dermatological issues due
to better compatibility with skin. Bio lubricants possess higher biodegradability and eco-
friendly characteristics, reducing their disposal costs.

Bio lubricants are non-toxic and have minimum corrosion tendency interlinked with energy
savings. On the contrary, bio-lubricants possess a bad smell due to contaminants, are viscous
at a lower temperature, and have lower thermooxidativestability at higher temperatures and
lower pour points.

The limited availability of bio-lubricant base stock and higher production costs are significant
challenges linked with bio-lubricant production. The numerous factors involved in the
determination of biolubricant cost. These factors comprised processing technology, plant
capacity, feedstock quality, net energy balance in the purification process, storage and base
stock prices etc.

The feedstock cost determines 75% of the total bio-lubricant cost. The lower pour point and
lower thermos-oxidative stability are primarily responsible for bio-lubricant performance
setbacks.

advantages disadvantages
High lubricity High cost.
High viscosity index Several vegetable oils are edible. This can
lead to a food vs. fuel debate.
High volatility Vegetable oils have higher melting points.
high boiling point (lower emissions) Vegetable oils have low oxidative stability.

Longer tool life Biolubricants are less developed compared

to fossil-based technologies.
Better skin compatibility Poor oxidation stability of pyrolysis bio-
oils.
Better safety on the shop floor High acidity of pyrolysis bio-oils.

Bio lubricant Page | 27

 Biodegradability is high (as they are A higher extent of upgradation is required
free of aromatics) for
thermochemically derived base stocks.
High volatility High viscosity of HTL crudes.
Customizable chemical structures
A lesser amount of contaminants
The base stocks for lubricants can
be derived from a variety of sources
Table 2.8.1 advantages and disadvantages

Bio lubricant Page | 28

CHAPTER 3 Production techniques

Bio lubricants can be categorized as per their chemical conformation in synthetic and natural
oils. Natural oils usually originate from animal fats and vegetable oils, while synthetic oils are
comprised of natural oil as base oil and further modifications can be made according to
requirements.

The modification can be made through microorganisms, polyglycols, ester synthesis,

perfluoroalkyl ethers, and polyalcohols in natural oil.

The main sources of bio lubricant are seeds, animal fats, and vegetable oils, which go through
a distillation and extraction process for conversion into oils. However, the bio lubricant can be
synthesized through the aforementioned modifications and possesses lubricity, wear resistance,
corrosion resistance, and oxidative stability greater than mineral oils.

However, synthetic oil has some limitations, including increased cost during chemical
modification, higher volatility, higher toxicity, reduced frictional tolerance, and mismatch
between esters and mineral oils in contrast to neat vegetable oils.

Bio lubricants possess a wide range of applications owing to their low cost and higher
biodegradability than mineral oils. The consumption of natural oils to synthesize bio-lubricants
is inconsistent due to food security issues, crop prices, and social imbalance. Synthetic esters
are developed by chemical treatment of plant-based oil and animal fats.

The main focus of today’s research is to optimize the physicochemical attributes of bio-
lubricants through different chemical modifications or catalytic processes. The unsaturated oils
usually modify through a chemical process as their double bonds are susceptible to reaction
with atmospheric oxygen.

3.1. Epoxidation:-
The molecules with a higher degree of unsaturation are more susceptible to hydrolytic
degradation. Moser and Erhan suggested an auto-oxidation process that may occur through the
reaction between oxygen and free radicals to produce peroxy radicals.

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This peroxy radical then reacts with lipid molecules to form hydroperoxide and other free
radicals, and thereby oxidation process may propagate. The modification in the alkene group
and the addition of alkyl side chains improve thermo-oxidative stability and other
physicochemical attributes.

Epoxidation is the key process to modify C–C double bonds through alkyl hydroperoxides,
dioxiranes, peroxy acids, and peracids as foundations to produce bio-lubricants with better
acidity, improved pour points, higher adsorption on the metal surface, higher viscosity index,
better lubricity and higher thermo-oxidative stability.

After epoxidation, it is necessary to modify physicochemical properties especially pour point,

further through acyloxylation, hydroaminomethylation, hydroformylation, interaction,
alkylation, cooligomerization, acylation, esterification and amino alkylation.

Many researchers reported that modification processes significantly improve lubricity, thermo-
oxidative stability, COF, pour point and viscosity index.

Both acetylation and esterification reactions were conducted through homogeneous acid
catalysts (H2SO4) blended with alcohols. The reaction medium’s corrosion potential leads to
solid acid catalysts’ formation through sulfated-SnO2 and cationic exchange resins.

3.2. Esterification/transesterification
Transesterification reactions include the replacement of glycerol molecules of the
triacylglyceride with long/ branched chain alcohol. However, the esterification process
includes a reaction between free fatty acid of natural oil and long-chain alcohol, ultimately
forming respective esters. Both transesterification and esterification reactions can take place in
the presence of acidic or basic catalysts.

The properties of acids and alcohols significantly affect synthetic esters’ physicochemical
properties. Synthetic esters possess better properties in terms of higher flash points, higher pour
points, lower volatility, and higher thermo-oxidative stability than their respective esters or
natural oils.

Bio lubricant Page | 30

The esters are prone to thermal degradation and hydrolysis. But thermal characteristics can be
amended by substituting longer alkyl/branched chains such as trimethylolethane (TME),
trimethylolpropane (TMP), 2-ethyl hexanol, neopentylglycol (NPG), pentaerythritol (PE),
trimethylolethane (TMH). Transesterification mainly occurs under acidic conditions, but this
is a slow process and is intermittently used. The base-catalyzed reaction is approximately four
thousand times faster and entails low temperature and reaction time in comparison with acid-
catalyzed. The mineral acids like H3PO4, HCl and H2SO4 are mainly used as catalysts[4].

Figure 3.2.1. Reaction pathways of the three main chemical modification methods. Red,
green and blue solid arrows represent the pathway of esterification/transesterification, solid
formation, and epoxidation/ring opening, respectively.

Despite better conversion ability, there are several disadvantages related to corrosion,
purification, and separation of obtained lubricants. Considering the weaknesses, the ion
exchange resins or oxides like WO3, Nb2O5, ZrO2, Ta2O5, Al2O3, TiO2 and zeolites show
the potential to replace conventional mineral oils. However, the 98% yield can be achieved
through base catalysts like alkaline earth oxides, carbonates, alkoxides and hydroxides
compared with solid acid catalysts[4].

Bio lubricant from waste cooking oil:

The experimental procedure followed in this work starts from WCO to the produced lubricant.
The WCO was heated to 105 ◦C for 30 min to get rid of any water contaminated in it. The dried
WCO was transformed into biodiesel by a transesterification reaction with methanol using
anhydrous potassium hydroxide (KOH) as a homogeneous catalyst (typical alkali-catalyzed
transesterification). The produced biodiesel (fatty acid methyl esters) was separated from

Bio lubricant Page | 31

glycerol by settling. The properties of the produced biodiesel were then estimated. The next
step was the transesterification reaction of biodiesel with ethylene glycol using calcium oxide
(CaO) as a heterogeneous catalyst. The CaO catalyst was then filtered and removed from the
product mixture. The usage of CaO heterogeneous catalyst in transesterification reactions was
proven to be effective by several researchers. Where, besides its high catalytic efficiency it is
a cheap, available and environmentally benign catalyst. In general, the usage of a
heterogeneous catalyst has many advantages as Sun et al. (2017) stated. Where it is less
corrosive, it can be reused, green catalyst and it is not sensitive to water and free fatty acids[13].

Fig. 3.2.1. Experimental procedure flow diagram folubricantnt production from WCO and
EG.

Bio lubricant Page | 32

3.3. Estolide formation
The branched/oligomeric esters (solids) are synthesized when the unsaturated site of one fatty
acid gets attached to the carboxylic acid of other fatty acids through carbocation (nucleophilic
attack) during the presence of an acid catalyst (H2SO4) and oxidant (HClO4). Estolides have
more resistance against hydrolytic degradation as compared to triglycerides[16].

The physicochemical attributes of bio lubricant depend on the hydrocarbon chain length and
solid number as specified by solids formed from 2-ethyl hexanol, oleic acid, and lauric acid.

The solids possess higher lubricity, viscosity index, thermo-oxidative stability, and lower pour
point. Further, the solids esters have higher biodegradability than commercially available
solids, which can only be used as a blend with vegetable oils with modified physicochemical
properties.

3.4. Selective hydrogenation

The degree of unsaturation exhibits an antagonistic impact on the thermo-oxidative stability of
bio-lubricant. However, the degree of unsaturation can be reduced through hydrogenation
through Ru, Ni, Pt or Pd-based catalysts at higher temperatures (250–300 ◦C) and higher
pressure (25–35 MPa).

The hydrogenation (chemical modification) results from isomerization in cis and trans acid, as
well as the decreased fluid ability of the lubricant. Therefore, hydrogenation is more suitable
for solid lubricants or waxes. Thus, hydrogenation is not considered effective in improving
physicochemical properties.

3.5. Microwave technology

Microwave heating transforms electrical energy to radiation by increasing the internal energy
of reactant molecules, and this technology is mainly used to enhance transesterification.
Significant energy saving can be achieved through microwave technology as it helps reduce
reaction time by 60% in comparison with conventional heating (convection/ conduction).
Microwave heating is most suitable for drying polar compounds. The moisture presence aligns
the OH bond and constantly varies the magnetic field to generate molecular friction and heat.

Bio lubricant Page | 33

Microwave heating is unsuitable for heating non-polar compounds and requires modification,
such as polar species addition into a reactive mixture. The researchers have already studied the
impact of adding the passive heating element and ionic liquid to heat non-polar substances
(hexane, chloroform, toluene).

Dipolar and polar ionization are two mechanisms to generate heat from microwave irradiation.
The polar molecules in the reactive mixture are engaged in dipole-dipole interaction, as free
ions are impacted by ionic polarization as oriented in the electric field. The applied electric
field varies continuously as the ion field tries to re-align itself, which is responsible for heat
energy loss through dielectric loss and molecular friction[16].

Sufficient energy is required for reactant molecules for effective collisions, and this sufficient
energy is usually achieved from optimum temperature. The higher temperature provides higher
reactant solubility and product conversion. Methanol is generally used as a catalyst to drive the
reaction in the forward direction with the generation of more methyl ester in less reaction time.

The molar ratio of methanol to oil is usually kept between 6:1 to 60:1, with a conversion
efficiency of 71.4 to 98.9%. A higher proportion of methanol is used for highly viscous oil to
augment oil solubility in methanol. The temperature measurement is a significant limitation in
microwave ovens by a thermocouple (k-type) due to arc formation when the interaction
between microwave and metallic probe occurs. This arc/spark can also be produced from metal
scrap or chipped paint inside the surface. The hot spot usually occurs for materials whose
dielectric loss increments with overheating or temperature.

3.6. Microwave and supercritical/ subcritical

The microwave-assisted subcritical or supercritical process is a catalytic-free process that does
not need any pretreatment or purification steps, as it is free from wastewater. This process is
easy for trans-esterifying bio-based resources[16].

However, the higher temperature and pressure required for both subcritical and supercritical
reactions consume higher energy. Water is utilized in sub-critical conditions (2 MPa and 488
K) as a solvent to enhance oil extraction of jatropha curcas oil seed through increasing porosity
and weakening sample structure.

Bio lubricant Page | 34

Lipid hydrolysis becomes more feasible as transesterification of fatty acid methyl ester
(FAME) occurs at lower activation energy under 250 ◦C and 13 MPa. used acetic acid and
methanol solvent and found that the transesterification process takes place in 105 min with a
65.1% yield rate.

A molar ratio of 1:42 was used for the transesterification of methyl acetate and rapeseed oil in
another study of the non-catalytic synthesis of FAME under supercritical conditions. The yield
rate was 97% in 45 min at 320 ◦C and 20 MPa.

Bio lubricant Page | 35

CHAPTER 4 Research Outlook

1. Development of lubricants from vegetable oils via chemical modification

In response to the increasing environmental pollution concern and depleting petroleum

reserves, biobased lubricants have received a great deal of interest as a substitute for mineral
oil-based lubricants. Biolubricants have several advantages over mineral lubricants, including
high biodegradability, low toxicity, excellent lubrication performance, and minimal impact on
human health/environment[4].

This paper reviewed the most recent advancements in the synthesis of lubricants from vegetable
oils through chemical modification methods such as esterification/transesterification, solid
formation, and epoxidation of vegetable oils.

The most commonly used feedstock for developing biolubri-cants is vegetable oils.
Molecularly, vegetable oils are triglycerides, esters of glycerol and three straight-chained fatty
acids.

The chain length of the fatty acids is usually in the range of C12–C24. The three fatty acids
vary between feedstocks, and play an important role in determining the properties of the /;poil.
The two main variables among fatty acids are the number of double bonds and the chain length.
In general, a longer chain length results in a higher melting point and viscosity, and more double
bonds correspond to lower melting points, decreased viscosity, and decreased thermo-oxidative
stability.

Bio lubricant Page | 36

 Table 4.1.1 Lubricant requirements and unmodified vegetable oil properties.

Table 4.1.2 Physical properties and reaction conditions of lubricants derived from fatty acid
methyl esters

Bio lubricant Page | 37

2. lubricant production from waste cooking oil

Waste cooking oil (WCO) or frying oil was used for the synthesis of lubricant via
transesterification reaction. Biolubricant (dioleoyl ethylene glycol ester) was prepared from
fatty acid methyl esters (FAMEs) of WCO with ethylene glycol (EG).
The reaction was performed using a calcium oxide (CaO) heterogeneous catalyst. Dioleoyl
ethylene glycol ester is a potential biodegradable lubricant that could be used in industrial
lubricant applications[13].
The effect of changing operating conditions such as temperature, molar ratio of reactants,
reaction time and catalyst loading was studied. The optimal conditions that achieved the highest
conversion were found to be 130 ◦C, 3.5: 1, 1.5 h and 1.2% (w/w) catalyst dosage.
The produced biolubricant structure was tested using the FTIR spectrum technique and its
thermal stability was examined using the TGA technique.
The lubricant properties were compared to two other lubricants and also to the specifications
of four different ISO viscosity grade lubricants.
The produced mixture of lubricant and unreacted biodiesel was separated by distillation to
obtain biodiesel-free lubricant which was characterized. It has proven successful in producing
environmentally friendly lubricants using leftover cooking oil as a starting material. The impact
of operational variables like a catalyst, temperature, on time On the transesterification reaction
conversion, the amount and molar ratio of reactants (FAMEs: EG) were examined[13].

3. bio lubricant from castor oil via chemical softening

In the 21st century, environmental sustainability is considered to be the superficial, coherent

vision in the development of a societal goal.
At the moment, the prices of crude oil have been skyrocketing which results in the depletion
of petroleum reservoirs contributing to environmental pollution cum hazards.
This has inspired researchers globally in the development of non-toxic, renewable, and
sustainable[14].
ecologically sound alternative i.e., Bio-lubricant which will aim to replace conventional
petroleum-based lubricants towards a green and clean society deliberately.
The proposed work introduces the design and development of biodegradable bio-lubricant from
commercially available, non-edible castor oil via chemical softening by two successive
transesterification stages.

Bio lubricant Page | 38

The presented study explores the chemical modification process of vegetable oil to intensify
the yield, grade, and physicochemical vis-a-vis tribological properties of the produced
lubricant.
At the outset, the proposed method of production of bio-lubricant from castor oil via chemical
softening is made to achieve a high yield, exceeding 97.4 % and its testing.
The esterified castor oil had the lowest thermal stability due to the introduction of ester groups,
which are more susceptible to thermal degradation.
In the light of sustainability and the ecological-contemporary world alongside, bio-lubricants
will provide a potential non-toxic, biodegradable alternative lubricant for automobile
applications and many more.
Many petroleum-based lubricants caused environmental harm during or after use, as a
consequence of accidents and rapid industrialization.

4. bio-lubricant from Jatropha curcas oils

Renewable, biodegradable and environmentally friendly bio-lubricant has been produced from
non-edible Jatropha curcas oil which has a high viscosity index, high lubricity, high flash
point, and very low volatility[17].

Table:4.4.1- characteristics of lubricants

The addition of graphite as a modifier has been proven to remove most of the impurities and
dissolved substances in the based oil and successfully make the based oil cleaner and clearer.
Nevertheless, the flash point of the modified Jatropha curcas bio-lubricant was too low and
did not meet the characteristics of the commercial lubricants.

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Therefore, it was recommended to further improve the Jatropha curcas-based bio-lubricant by
adding other additives such as glycols and olefins copolymers to achieve bio-lubricant, which
meets the characteristics of commercial SAE bio-lubricant.
The suggested additives should have high viscosity and high flash points to modify the physical
and chemical properties of the based oil to produce desirable bio-lubricant.

5. BIOLUBRICANT PRODUCTION FROM PAWPAW SEED (Carica papaya) OIL

Biolubricant was produced via a double transesterification process of pawpaw seed oil with
Ethylene Glycol (EG) as a polyol in the presence of a potassium hydroxide catalyst.
Central composite design (CCD) in response surface methodology (RSM) was applied to this
experimental layout and the effects of temperature, reaction time, and catalyst concentration
on the synthesis of pawpaw seed oil lubricant (PBL) were evaluated.
The EG ester of pawpaw seed oil was characterized by its flash point, pour point, viscosity at
40 o C and 100 0 C and viscosity index. Fourier Transform Infra-Red (FT-IR) and Gas
Chromatography-Mass Spectrophotometer (GC-MS) analysis were carried out on the biodiesel
and lubricant to confirm the presence of the ester group and the composition of the synthesized
lubricant, the characterization showed favourable lubricating properties.
The presence of an ester group in the resulting lubricant was confirmed by FT-IR analysis and
the percentage of the composition of lubricant determined by GC-MS analysis revealed a
saturated fatty acid composition is much higher than unsaturated fatty acid composition, this is
promising as high saturation content in the lubricant will lead to higher resistance towards
thermal- oxidative treatment.

6. Ethylene Glycol-Based Bio-lubricant from Palm Kernel Oil (PKO)

Internationally exploited lubricants are derived from coal and petroleum. Due to their high
consumption and the effects of their long-term pollution on the environment, it is imperative
to use renewable and cheap feedstock for the synthesis of bio-based lubricants.
This study presents the synthesis and optimization process of Ethylene Glycol (EG) based bio-
lubricant from palm kernel oil[18].
The effects of molar ratio, reaction time, and temperature on the synthesis of palm kernel bio-
lubricant (PKBL) were evaluated. The PKBL structure was characterized by Fourier Transform

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infrared (FT-IR) and Gas Chromatography-Mass Spectrometry (GC-MS) analysis, showing
favourable lubricating properties.
The PKME yielded 94.53 wt% based on the weight of the oil, while transesterification of the
in situ derived PKME with EG yielded 93.08 wt% of the EG ester (Bio-lubricant).
The maximum bio-lubricant recovery was 81.48 wt% obtained at a molar ratio of 3:1, time of
2.48 h, and temperature of 135 C.
The temperature and mole ratio were established to be the most significant terms. PKBL
characteristics conformed to ISO VG criteria and had a high potential for bio-lubricant
feedstock.
The experimental result of the bio-lubricant produced showed that EG ester exhibited
favourable characteristics.

4.1 Future prospect:-

Modernization and expansion of the manufacturing sector satisfy the rising need for lubricants
worldwide. Due to its relatively low labour costs and political stability, the Asia-Pacific region,
driven by China, will continue to be the critical driver of growth in the lubricant markets.

The main concern in 1950 regarding lubricant was maintaining appropriate viscosity without
any acid components in the base oil. Base oils were demoted to the status of solvents or carriers
for additions in the 1960s.

However, in the 1970s, synthetic fluids with a consistent chemical structure outperformed
mineral-based oils in terms of performance. The quasi-synthetic hydro-cracked lubricants were
launched in Europe at low prices with properties similar to synthetic lubricants in the 1980s.

In the 1990s, the environmental, health and safety standards influenced base oil development
and the need to develop lubricants that could match these standards. Future research explores
new avenues for developing bio-lubricant production techniques to lower production and
operational costs. The production cost could also be reduced by exploring cheaper feedstocks
that do not threaten food security.

The new generation additives can also be developed, which ensure biodegradability and
environmental protection. To ensure appropriate lubricant developments, it is mandatory to
understand the methodological concept of biodegradability.

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This concept does not mean that biodegradability provides complete environmental protection
because intermediate products are also involved in the decomposition cycle.

But technology is advanced to a great extent. It can develop such lubricants and additives,
which would perform far better than mineral oils in terms of zero carbon footprint, thermo-
oxidative stability, viscosity, and volatility.

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CHAPTER 5 Conclusion

Over 50% of all lubricants used globally end up in the environment as a result of spills,
accidents, volatility, and incorrect disposal. This leads to significant contamination of the air,
land, and water, as well as adverse effects on plant and human life.
Natural plant oils and fats are now widely used because of the concerns surrounding
environmental conservation and the growing interest in employing bio-based lubricants, which
are renewable, biodegradable, and environmentally friendly lubricants.
Plant oils have good lubricity, biodegradability, viscosity-temperature properties, and low
volatility, making them interesting candidates for use as the basis fluid in environmentally
friendly lubricants.
The best argument in favour of plant oils' industrial application is their biodegradability. Their
proven biodegradability is between 70 and 100%, hence they are not very environmentally
friendly.

Bio lubricant Page | 43

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