1.

1 BACKGROUND OF STUDY

World energy supplies are primarily fulfilled through the use of fossil fuels. It is

wellknown that burning coal and crude based fuel leads to depletion of conventional

resources and are associated with environmental concerns such as air pollution,

greenhouse effect, waste disposal, climate change, etc. (Singh et al., 2019). These

primary challenges need full engagement from all the concerned stakeholders (Joshi

et al., 2017b). The carbon footprint increased, especially by automobile and allied

sectors, plays a vital role in issues of environmental health (Bergthorson and

Thomson, 2015). Hence, attempts have been made to bring a diversity of renewable

fuels used in vehicles. This approach is one of the efficient solutions to counter

environmental problems caused by the combustion of non-renewable fuels (Chang et

al., 2017). Biodiesel plays a significant role in satisfying the demand for sustainable

alternative fuel, which will help in reducing the carbon footprint (Neupane and Rubin,

2017). Biodiesel is a biodegradable and environment-friendly option as compared to

non-renewable fuels.

1.1.1 Biodiesel and Importance

Biodiesel is a renewable resource obtained by the transesterification of triglycerides

present in vegetable plant oils or animal fat (Fadhil et al., 2017). It contains

insignificant sulfur and aromatic compound as well as have more than 10 % inbuilt

oxygen fraction, which supports complete combustion (Parida et al., 2016). Biodiesel

production improves the environment by reducing particulate matter (by 47 %), and

hydrocarbon emissions (by 67 %) (Report to Congress on Black Carbon, 2012). The

fast growth of the biodiesel industry has created exciting opportunities for several

biodiesel enterprises. Biodiesel can be used as it is or blended with gasoline-diesel in

the existing diesel engine (Lertsathapornsuk et al., 2008). The major issues with

biodiesel production using conventional biodiesel processing technology are

feedstock flexibility, yield efficiency, the ecological influence due to the use of

excessive raw materials and cost efficiency (Tan et al., 2019b).

1.1.2 Policy Used for Selection of Materials

The selection of feedstock is a critical step in the production of biodiesel, driven by

several factors, such as cost, purity, yield, and composition of the produced biodiesel.

Thus, availability and source (e.g. non-edible, edible, and waste) are the key

parameters of selecting a feedstock (Demirbas, 2009). The selection of a particular

feedstock depends on the suitability, ease of availability, oil content, physical

properties, chemical composition, and economic aspect (Ambat et al., 2018).

Based on the availability and type feedstock can be categorized in the four generations.

First-generation biodiesel being produced from edible oil feedstock was not a long

term practical solution because of the global food insecurity and its effect on

fluctuations in food prices (Renzaho et al., 2017). For these reasons, secondgeneration

biodiesel came into the limelight, which was produced from non-edible oil feedstock

originated from plants [such as Jatropha carcass (Lee et al., 2011),

Madhuca longifolia (Muthukumaran et al., 2017), Pomgamia pinnata (Sharma and

Singh, 2008) and Ricinus communis (Chaudhary et al., 2015)]. Besides this,

secondgeneration biodiesel is known for higher yields, favorable oxygen stability, and

cold flow properties as per the specifications of ASTM D6751 and EN14214.

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However, high acidity resulting due to the higher fractions of free fatty acid (FFA) is

the major limitation of second-generation oil feedstock (Milano et al., 2018b). The

third generation consists of microalgae oils. The advantages of this generation are

higher growth rate, productivity, a higher volume of oil content, and the reduced

greenhouse effect, struggle towards farming land, and no effect on food supply. The

main drawbacks are the requirement of higher capital investment, continuous sunlight,

larger-scale production, and difficulties in the extraction of oil. Lastly, the fourth

generation consists of modifications in the first, second, and third-generation

feedstocks using biomass processing technology (Singh et al., 2019).

Based on the current estimates, about 75 % of the total manufacturing cost of biodiesel

produced from fresh edible feedstock are 1.5 times more than commercially produced

diesel (Phan and Phan, 2008) and additionally, there is a concern about food security.

Commercially used vegetable oil upon repeated usage undergoes degradation by

hydrolytic and oxidative reactions. This makes chemical and physical property

changes of the oil as compared to fresh oil (Utlu, 2007). Such reused cooking oil is

known as waste cooking oil (WCO). The existence of harmful substances (classified

as (i) compounds originating from the degradation of oil, and (ii) liposoluble

contaminants) can cause health issues due to the off-limit presence of. these

substances as well as toxicological reasons (Firestone et al., 2000). The price of WCO

is cheaper compared to virgin vegetable oil by a factor of around 2-3 times (Zhang et

al., 2003). The utilization of WCO minimizes environmental pollution by recycling

the oil instead of disposing of in landfills (Milano et al., 2018b). Thus, biodiesel

produced from WCO is gaining momentum in the fuel and the lubricant market as a

potential feedstock since it is solving the problems stated above. The latest National

Policy on Biofuels – 2018 promotes supply chain infrastructure for biodiesel

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production from non-edible oilseeds and used cooking oil (terms UCO and WCO are

interchangeable). UCO is a potential feedstock for biodiesel which will prevent

diversion in the food industry (Ministry of Petroleum & Natural Gas, 2018).

The Indian government launched a national biodiesel mission program in the year

2003 with a target to achieve the blending of biodiesel up to 20 % by 2011 – 12.

Subsequently, in the year 2009, to strengthen the biofuel industry National policy on

Biofuels was proposed. This policy encourages the use of renewable fuels. It also

proposes a mandate to blend 20 % biofuel (ethanol and biodiesel) by the end of 2017

(Purohit and Dhar, 2015). The biodiesel blending program has the goal to enable the

availability of biodiesel in the market by increasing its blending percentage. Currently,

biodiesel blending percentage with diesel is less than 0.1 % and the indicative goal is

of 5 % biodiesel blending with petrodiesel has been proposed by the year 2030

(Ministry of Petroleum & Natural Gas, 2018).

This mission could not succeed due to the section of second-generation feedstock,

fluctuating weather conditions, unscientific cultivation, maintenance of nonedible oil

feedstock, and 20-50 % higher production cost compared to the declared purchase

price (Tabatabaei et al., 2019). Thus, to satisfy an increase in the demand for biodiesel,

WCO was selected as the most promising, economical, and sustainable alternative

feedstock with high availability for biodiesel production (Fonseca et al., 2019).

Worldwide there is a huge availability of WCO every year such as in Europe; 4 Mt

(European biomass industry, 2019), USA; 0.75 Mt (U.S. Energy Information

Administration, 2019). India consumes 22.5 Mt of vegetable oil, of which about 40 %

is spent by restaurants/mega kitchens and processed food industry. Another 30 %

discarded as WCO, is mostly bought by street merchants and small restaurants at

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government prescribed rates (WCO statistics in India, 2018). Food safety and

standards authority of India (FSSAI), the estimate suggests that India has the potential

to salvage 2.2 Mt of UCO for the biodiesel production by the year 2022 (“UCO for

biodiesel,” 2018). By utilizing this large resource of WCO, India sees the potential to

achieve a target of 5 % blending by 2030 (Ministry of Petroleum & Natural Gas,

2018).

1.2 TRANSESTERIFICATION PROCESS

Triglyceride reacts with alcohol in the presence of a catalyst to produce esters and

glycerol is called transesterification. High viscosity and low volatility of virgin

feedstock derived from animal fats and vegetable oils limit their direct usage in diesel

engines. The major goals of transesterification reaction are to remove these problems

(Oh et al., 2012). Stoichiometrically a 3:1 molar fraction of alcohol to oil is necessary

to complete the transesterification reaction. However, in actual practice surplus

alcohol is used to shift the reversible reaction equilibrium to the product side and the

product yield is increased. Transesterification reaction scheme is shown in Fig. 1.1 for

biodiesel production (Singh et al., 2019). Triglyceride and alcohol are two main

reactants in this reaction. When methanol is used as a co-reactant, the process is called

as methanolysis. Triglyceride has three long-chain fatty acids attached to the glycerin

molecule as its base. The structure of fatty acids attached to glycerol determines the

characteristics of the oil/fats and in turn affects the characteristics of the biodiesel

(Vicente et al., 2004).

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 O
CH2-O- C-
R CH2-OH

O
O
+ Catalyst 3 CH-OH
CH-O-C -R R-OH 3 R-O-C-R

O CH2-OH
CH2-O-C -
R Triglyceride Glycerol
Alcohol Biodiesel +
Fig. 1.1 Stoichiometric transesterification reaction (Singh et al., 2019)

The reaction products are separated upon completion of the transesterification process,

the biodiesel floats on top and the glycerol sinks due to higher molecular weight. In

the methanolysis process, the mixture of oil (80–90 %) and methanol (10– 20 %) is

heated. Proper mixing is essential since methanol has poor solubility in oil to make

the mixture homogeneous and later form biodiesel (Zhou et al., 2006). The obtained

biodiesel product is called fatty acid methyl ester (FAME) (Verma and Sharma,

2016). From an economic point of view biodiesel produced from the

transesterification process is favorable for commercial production as it has properties

such as calorific value, density, viscosity, etc. comparable with diesel.

1.2.1 Alcohol

Alcohol is the other most important raw material for biodiesel production. Typically,

a primary and secondary monohydric aliphatic alcohols comprise 1–8 carbon atoms

in the structure (Ma and Hanna, 1999). Among the large number of alcohols

investigated for biodiesel production, the most commonly used acyl acceptors are

methanol and ethanol. The other alcohols such as normal alcohols: propanol, butanol,
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and branched alcohols: isopropanol, tert-butanol, and octanol have been utilized for

biodiesel production but are expensive (Yusuf et al., 2011). For the successful

application of alcohol in the production of biodiesel, the water content of < 500 ppm

is typically maintained (Mosali, 2010), because, with the presence of water, soap

formation occurs as the triglycerides are hydrolyzed to free fatty acids which

ultimately leads to poor biodiesel yield. Generally, short-chain alcohols are

hygroscopic due to the existence of a -OH group in its structure, it hence precaution

should be taken to avoid water absorption from the atmosphere (Gerpen et al., 2004).

Amongst the two most commonly used alcohols, methanol, and ethanol, the former is

being preferred in the production of biodiesel over later due to physical and chemical

advantages, even though methanol is a petrochemical product. It is less expensive, has

higher reactivity with triglycerides thus provides better conversions, catalyst dissolves

faster as compared to other alcohols (Sanli and Canakci, 2008), and can be easily

separated from glycerol since methanol is insoluble in it (Zhou et al., 2006). Ethanol

and butanol are also of great interest because these are bio-based, renewable, less

toxic, and environmentally friendly.

1.2.2 Catalyst

During transesterification process catalyst is used to augment the rate of reaction and

improves the produced fuel properties. Nature and catalyst concentration play an

important role during the transesterification process to produce biodiesel (Sanli and

Canakci, 2008). Catalysts are generally classified into homogeneous, heterogeneous,

and biocatalyst and a detailed sub-classification is shown in Fig. 1.2. While selecting

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a catalyst, much emphasis is given to features like catalytic activity, selectivity, wt.

%, and reusability (Chouhan and Sarma, 2011).

It is a well-known fact that in the case of alkaline homogeneous catalyzed

transesterification reaction the rate of reaction is 4000 times faster when compared to

acid-catalyzed reactions. Due to the former favorable effect of glycerol precipitation

(Formo, 1954). Few of the frequently used alkaline homogeneous catalyst for

biodiesel production are sodium hydroxide (NaOH), potassium hydroxide (KOH) and

sodium methoxide (CH3ONa).

Fig. 1.2 Classification of catalysts used in transesterification reaction (Chouhan and

Sarma, 2011)

These catalysts have the advantage of providing a faster reaction rate, room

temperature is enough for the reaction, requires lesser catalyst amount and fuels

produced using them are not corrosive (Ma and Hanna, 1999). Despite having

advantages, an alkaline catalyst is not suitable for feedstock having high FFA content.

FFA decreases biodiesel yield by causing soap and water formation (Ramachandran
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et al., 2013) and subsequent gel formation leads to an increase in viscosity (Canakci

and Gerpen, 1999) as well as, difficulty in separation from biodiesel (Birla et al.,

2012).

Generally, alkali oxides or alkaline earth metals oxides are available in heterogeneous

catalysts which are having benefits over homogenous catalysts like easy separation

from the product and higher chances of reusability and regeneration along with high

biodiesel yield and salt-free glycerol (Ramachandran et al., 2013). Among the

available heterogeneous catalyst, most of the attention is attracted by calcium oxide

(CaO) because of their comparatively high basic strength and generation from cheap

sources like limestone and calcium hydroxide (Lam et al., 2010) but have low

solubility in methanol.

The alkaline-catalyzed transesterification reaction has a four-step mechanism

(Tabatabaei et al., 2019). First is the formation of alkoxide and protonated catalyst due

to the reaction of base catalyst with the alcohol. During the second step, nucleophilic

attack of the alkoxide at the carbonyl group of the triglyceride generates tetrahedral

intermediate. The third stage includes the production of the alkyl ester and the

corresponding anion of diglyceride. In the last step, catalyst deprotonation takes place

that regenerates the active sites, which is available to react with another alcohol

molecule, starting a new catalytic cycle. Diglyceride and monoglyceride follows a

similar mechanism and gets converted to produce a mixture of alkyl esters and

glycerol.

Due to its biological origin, reuse of agro-industrial residues, production of high

purity products, and ease of separation from glycerol biocatalyst have recently been

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considered as a sustainable synthesis technology for catalyst (Teixeira et al., 2014).

These catalysts are insensitive to FFA and water content in feedstock (Matsumoto et

al., 2002). With their ability to use all mono, di, and triglycerides along with FFA and

also low product inhibition, high activity, lower time, temperature, and alcohol

resistance, biocatalyst has been reported to be used for biodiesel production. However,

the major difficulty in the usage of biocatalysts are expensive which becomes a barrier

for industrial applications (Aarthy et al., 2014).

1.3 BIODIESEL PRODUCTION TECHNIQUES

1.3.1 Mechanical Stirring (MS) Technique

The MS technique has been predominantly developed and adopted for biodiesel

production. In this technique, the rate of activation of reactants is very slow owing to

the immiscibility of oil and methanol causing limitation in mass transfer (Dubé et al.,

2007), and heating of reactants happens by the conventional external heating source.

Fig. 1.3 demonstrates the heating mechanism used in MS technique wherein the heat

source is outside and the heat travels using the conventional mode to the reactants

(Surat et al., 2012).

Thus, this technique has certain drawbacks like reaction reversibility and

immiscibility of reactants (Choedkiatsakul et al., 2014), high amount of reagents

required, poor activation energies (Yadav and Sharma, 2019) leading to longer

residence time, increased capital cost with high product separation and purification

interval (Chuah et al., 2017).

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Fig.1.3 Heating mechanism of MS technique (Surat et al., 2012)

This technique has encouraged the application of other types of stirring reactors to

improve yield and shorten the time of the transesterification process with low reaction

reagents levels.

1.3.2 Process Intensification (PI) Techniques

Process intensification techniques focus on reducing the disadvantages of MS

techniques; provide shorter time with higher biodiesel yield; require low molar

fractions, catalyst concentration. Further, PI process has the benefit of lower energy

utilization and operating cost for biodiesel purification as well as better recovery of

glycerol, catalyst, and excess alcohol during production (Qiu et al., 2010; Tan et al.,

2019b). PI technologies also allow feedstock flexibility and rapid reaction permitting

continuous production and separation of the reaction products with a reduction in

environmental impact (Oh et al., 2012). Fig.1.4 exhibits the classification of process

intensification techniques on the basis of equipment and techniques (Oh et al., 2012).

Among the various process intensification techniques, microwave and ultrasound

techniques are selected in this study.

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[Link] Ultrasound cavitation technique

Cavitation is the most essential part of ultrasound process which involves stages like

the formation, enlargement, and implosive breakdown of bubbles (cavities) in a liquid

medium. These bubbles are filled with reactants, their vapors, and dissolved gases,

which grow and recompress (Veljković et al., 2012). A powerful asymmetric

breakdown of cavitation bubbles under low frequencies (20 – 40 kHz) results in

releases of a large amount of energy.

Fig.1.4 Process intensification in terms of equipment and techniques (Oh et

al., 2012)

It significantly enhances mixing intensity because of the generation of micro-jets

formed due to liquid impingement. This impingement damages the phase boundary

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that leads to the emulsification of alcohol into the oil phase. Due to the formation of

such emulsion, the availability of large surface area significantly accelerates the

reaction between the two phases and enhances the mass and heat transfer rates

(Aghbashlo et al., 2017). The collapse of bubbles causes the reactant molecules to

energize, thus enhancing the activation energy (Tan et al., 2019b). The mechanism of

ultrasonication can be seen in Fig. 1.5.

Fig.1.5 Schematic illustration of the mechanism of ultrasonication (Kumar

and Kumar, 2018)

The homogeneous distribution of reactants owing to the ultrasonic cavitation process

shifts the reaction equilibrium in the forward direction by concurrently providing

physical and chemical effects in the reaction medium. Ultrasonication provides

physical mixing and also provides requisite activation energy for the initiation of the

transesterification reaction. Sonication helps to increase the temperature at the phase

boundary enhancing the transesterification reaction. In an immiscible liquid-liquid (oil

and methanol) medium (Gogate et al., 2006), the above-described mechanism remains

the same, whereas in an immiscible solid-liquid (catalyst, oil, and methanol) medium

the cavitation causes liquid jet formation at the surface of solids (Gogate, 2008). This

happens due to the uneven flow of the liquid to the catalyst cavities; this may shrink

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the size of the liquid particle due to splitting and increase the surface area available in

contact with the catalyst. The jet formation causes the disturbance of the liquid

boundary layer which then causes an increase in mass transfer from the liquid bulk

phase to the surface of the catalyst. This further removes impurities occupying the

inactive sites and also activate the catalyst (Veljković et al., 2012).

The commercially large-scale ultrasound reactors that are implemented for extraction

or various other operations are mentioned below:

• Scale-up bath reactor system up to 30 L reactor sizes with total power of 800

W are developed by company named M/s REUS (“REUS,” 2020).

• Continuous large-scale probe type ultrasound produced by M/s

Sonomechanics generating 3000 W power, amplitude 24 microns and capacity

starting from 1 L (“Sonomechanics,” 2020).

• Large-scale probe-type ultrasound are available for batch sizes from 200 mL

to 1000 mL with power ranging from 500 to 16000 W are manufactured by

M/s Hielscher ultrasound technology (“Hielscher ultrasound technology,”

2020).

This indicates scale-up with ultrasound reactors is possible and can be similarly

implemented for biodiesel production.

[Link] Microwave irradiation technique

In microwave irradiation technique energy is directly delivered to the reactant

resulting in effective and efficient heat transfer compared to conventional heating

which in turn further leads to the reduced time of transesterification reaction (Milano

et al., 2018b; Selvaraj et al., 2019). Thus, microwave is one of the best techniques to

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 CHAPTER 1

apply, for having reduced the time and obtaining higher yields. It further makes the

post-production separation process simpler in contract to conventional MS techniques

(Motasemi and Ani, 2012).

Fig. 1.6(a) and (b) illustrate the microwave heating mechanism. Non-ionizing nature

of microwave radiations influences molecular motion via two modes of action: dipole

rotations and ionic conduction without changing the molecular structure (Gude et al.,

2013). Microwave accelerates the molecular level heating of oil, methanol, and

catalyst mixture (Talebian-Kiakalaieh et al., 2013).

In the microwave technique, waves penetrate inside the reaction mixture, and heat is

generated through direct microwave – material interaction (Grewal et al., 2013).

Microwave heating demonstrates a better option as the transfer of energy into a

reaction mixture depends upon thermal conductivity and convection currents of the

mixture (El Sherbiny et al., 2010; Hernando et al., 2007).

Fig.1.6(a) Heating mechanism of microwave technique (Surat et al., 2012)

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 Fig.1.6(b) Two modes of microwave heating: dipolar rotation and ionic conduction
(Gude et al., 2013)

The microwave technique further helps to improve heat transfer effects resulting in

shorter transesterification time. The heat transfer depends on the ability of the mixture

of oil and methanol to convert electromagnetic energy into heat (Milano et al., 2018b).

However, microwave is costly due to the high capital cost (Martinez-Guerra and Gude,

2015).

The microwave irradiation technique has been commercially implemented by various

industries, a few are mentioned below:

• Large-scale microwave are available up to 500 L for microwave for a total

power of 6000 W are manufactured by M/s Tianshui Huayuan Pharmaceutical

equipment technologies Co. Ltd (“Huayuan Technology,” 2020).

• M/s SAIREM produces continuous flow microwaves operating at a power of

75 kW to treat up to 200 kg of biomass per hour (“Sairem,” 2020).

• Other industries producing large scale microwave for different commercial

implementations are M/s Advanced Microwave Technologies Ltd.

(“Advanced microwave,” 2021), M/s AMTek Microwaves (“Amtek,” 2021),

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M/s Ferrite Microwave Technologies LLC(“Ferrite,” 2021), and M/s

Microwave Chemical Co. Ltd. (“Sineo microwave,” 2020).

This indicates scale-up with microwave irradiation reactors is possible and can be

easily implemented for biodiesel production.

[Link] Conjoint microwave + ultrasound technique

As mentioned earlier, microwave energy acts as a non-ionizing radiation energy

source caused due to molecular motions of ions and rotation of the dipoles. It does not

disturb the molecular structure nor able to remove the limitation of mass transfer.

Whereas, ultrasound has a significant formation of microbubbles that affect the rate

of various processes but is not enough to cause an overall escalation in temperature of

the reaction mixture.

Fig.1.7 Conceptual diagram of wave propagation of microwave and ultrasound

(Martinez-Guerra, 2014)

The ultrasound and microwave techniques, independently have definite limitations

like weakening effect in the case of ultrasound and low diffusion depth in the case of

17
microwave (Gole and Gogate, 2013). This necessitates to develop and embrace a

suitable conjoint microwave and ultrasound effect.

Thus, the combination of both irradiations brings about the physical effect which

includes the formation and breakdown of microbubbles that causes the formation of

high pressure and heat release cycles at micro-scale resulting in better mass and heat

transfer. Such that, the high energy level of bubble cavitation under ultrasound can

prompt particle fragmentation and molecule excitation, whereas microwave

polarization can encourage dielectric volumetric heating and selective heating of

molecules (Chemat et al., 2004).

1.4 THE PRESENT INVESTIGATION

a. Globally depleting fossilized fuel reserves and increasing environmental

pollution are the key motivating factors to pursue research for an

alternative fuel derived from biomass which can fulfill the ever-increasing

energy demand for sustainable development.

b. Biodiesel helps in the protection of the environment due to its non-toxic,

renewable, and biodegradable nature and produces less sulfur emissions

and greenhouse gases.

c. Utilization of large available WCO as feedstock increases the biodiesel

and reduces the cost of the biodiesel production process.

d. Research using the application of process intensification techniques was

done as it reduces time and the use of large amounts of reagents in

comparison to MS technique.

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