Accepted Manuscript

Intensified Synthesis of Medium Chain Triglycerides using Novel Approaches

based on ultrasonic and microwave Irradiations

Ashish V. Mohod, Parag R Gogate

PII: S1385-8947(17)30267-X
DOI: http://dx.doi.org/10.1016/j.cej.2017.02.102
Reference: CEJ 16541

To appear in: Chemical Engineering Journal

Received Date: 18 September 2016

Revised Date: 15 February 2017
Accepted Date: 17 February 2017

Please cite this article as: A.V. Mohod, P.R. Gogate, Intensified Synthesis of Medium Chain Triglycerides using
Novel Approaches based on ultrasonic and microwave Irradiations, Chemical Engineering Journal (2017), doi:
http://dx.doi.org/10.1016/j.cej.2017.02.102

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 1

Intensified Synthesis of Medium Chain Triglycerides using Novel Approaches based

on ultrasonic and microwave Irradiations

Ashish V. Mohod, Parag R Gogate*

Chemical Engineering Department, Institute of Chemical Technology, Matunga,

Mumbai- 400 019.

*Authors to whom correspondence may be addressed

Email: pr.gogate@ictmumbai.edu.in; Tel: +91 22 33612024; Fax:+91 2233611020

 2

Abstract

Glycerides of C8–C10 fatty acids, commonly known as medium chain triglycerides (MCTs),

have wide applications in neutraceutical, food and pharmaceutical industries. In the present

study, intensification of synthesis of MCTs has been investigated based on the use of ultrasound

and microwave irradiations. Effect of different operating parameters such as molar ratio, reaction

temperature and catalyst loading on the conversion has been investigated. It was observed that

the conversion increases as the molar ratio of lauric acid to glycerol increases till an optimum

value beyond which only marginal changes are observed. Similar trends have also been observed

for the effect of temperature and catalyst loading. The sequential approach of microwave

followed by ultrasound gave the best results with maximum conversion as 99.7% in 20 min

whereas sequential approach of ultrasound followed by microwave resulted in slightly lower

conversion of 99.1% but in 40 min of reaction time. In the case of individual approaches,

maximum conversion as 97.8% was obtained in only 20 min using microwave irradiation while

using ultrasonic irradiation, the obtained conversion was 97.3% in 120 min. The extent of

conversion obtained using the conventional approach was only around 40% in 180 min as the

reaction time. Overall it has been conclusively established that the use of microwave and

ultrasonic irradiations result in significant process intensification benefits with the sequential

approach of microwave followed by ultrasound being the best approach.

Keywords: Esterification; cavitation; microwave irradiation; sequential approach; process

intensification
 3

1. Introduction:

Medium-chain triglycerides (MCTs) are the esters derived from fatty acids having carbon

chain length in the range 8 to 10 based on the reaction with glycerol. MCTs are composed of a

glycerol backbone with three fatty acids attached on the backbone. MCTs are generally

considered as an excellent biologically inert source of energy that can be easily metabolized by

the human body. MCTs have potentially beneficial attributes in protein metabolism but may be

contraindicated in some situations due to their tendency to induce ketogenesis and metabolic

acidosis. Due to the ability to be absorbed rapidly by the body, medium-chain triglycerides have

found use in the treatment of a variety of mal-absorption ailments. MCTs provide high level of

energy for animals and humans as well as can be used to control obesity and also for lowering

the serum cholesterol deposition in body tissues. MCTs promote the development of infants and

young children [1,2]. It has also various applications in the food and flavor industry as it gives a

unique cream like flavor to the food and also adjusts the taste and texture of the food. MCTs are

useful in number of pharmaceutical applications such as for treating a number of medicinal

disorders such as obstructive jaundice, pancreatitis, etc. and also as food supplements for patients

with poor digestion issues or low absorption of energy.

MCTs are found in coconut oil, olive oil, butter, palm kernel oil but in smaller fractions.

MCTs are generally prepared by the simple esterification reaction between fatty acid and

glycerol [3]. Mostafa et al. [3] studied the production of MCTs using waste fatty acids and

glycerol with zinc chloride as a catalyst. The obtained purity was about 99% in about 100 min of

reaction time. Cerdan et al. [4] studied the synthesis of Polyunsaturated Fatty Acid (PUFA)-

enriched triglycerides using lipase-catalyzed esterification and reported enriched triglycerides

 4

yield of 84.7% in 24 hr of reaction time. It was reported that the optimal reaction conditions were

9 mL of hexane, operating temperature of 60ºC, glycerol/fatty acid molar ratio of 1:3 and 100 mg

of Novozym 435 (Novo Nordisk A/S) lipase. Deshmane et al. [5] studied the synthesis of

medium chain glycerides using fatty acid and glycerol in the presence of sulphuric acid as a

catalyst in the presence of ultrasound. The obtained extent of conversion was about 98.5% on the

basis of fatty acid consumption in about 6 h as the reaction time. Overall it can be said that

though MCTs offer significant potential in commercial applications, not much of intensification

studies have been reported even though the conventional processing or the reported enzymatic

processing requires significant reaction times for achieving conversions of greater than 90%. The

present work deals with intensification of synthesis of MCTs using ultrasound as well as

microwave irradiation operated individually and in combination with comparison with the

conventional approach based on stirring to clearly establish the process intensification benefits.

Passage of ultrasound through liquid creates cavitation based on the pressure fluctuations

generated by ultrasound waves in the liquid medium. As ultrasound passes through a liquid, the

expansion cycles exert negative pressure on the liquid, pulling the molecules away from one

another. If the ultrasound intensity is sufficient, the expansion cycle can create cavities or micro-

bubbles in the liquid when the negative pressure exceeds the local tensile strength of the liquid,

which varies with the type and purity of the liquid. Once formed, these cavitation bubbles absorb

energy from the sound waves and grow during the expansion cycles and recompress during the

compression cycle. After reaching a maximum size, the cavities typically undergo rapid collapse

phase which results in shock wave that passes through the solvent also creating intense

turbulence enhancing the mass transfer rates. Cavitation is also known to produce intense liquid

circulation at microscale and shear effects which can lead to a formation of a fine emulsion.
 5

Ultrasound can be effectively used to increase the yield and rates of processing in several

applications [5-7] based on the physical and chemical effects generated during the cavitational

events.

Microwave irradiation has also been widely used in the synthesis of chemicals providing

significant advantages over conventional routes. Microwave-assisted synthesis provides faster,

cleaner and controllable route for synthesis of all types of organic compounds and numerous

technologically important inorganic materials [8-9]. Microwave provides significant

intensification due to the rapid heating effects attributed to the polarity of reacting molecules and

their electrical characteristics. Microwave assisted organic synthesis is characterized by

instantaneous heating at molecular level which cannot be achieved using the classical heating.

Microwave irradiation generates efficient heating at molecular level by direct coupling of

microwave energy with molecules of solvent, reagent or catalyst in the reaction mixture. The

irradiation passes through the walls of the vessel directly into the bulk of reaction mixture which

is not possible in the case of conventional approach of heating. The acceleration of chemical

reactions due to microwave exposure results from the interactions between the material and

electromagnetic field leading to the thermal and non-thermal effects. For microwave induced

heating, the substance should possess a dipole moment. A dipole is sensitive to external electric

field and tries to align itself with the field based on intense rotation. When subjected to an

alternating current, electric field is inversed at each alterance and dipoles tend to move together

following an inverse electric field. Such a movement induces rotation and friction of the

molecules, which dissipates as internal homogeneous heating [10]. A critical analysis of

literature revealed that there is no work on the synthesis of MCTs based on the use of lauric acid

using ultrasonic irradiation and microwave irradiation and hence forms the novelty of the present
 6

work dealing with synthesis of MCTs. The earlier work related to the intensification of synthesis

of MCTs using ultrasonic irradiations [5] did not deal with possible combination with microwave

irradiations and also the feed stock was different with limited study on the effect of operating

parameters as molar ratio and temperature. The present work focuses on a detailed study of

process intensification of synthesis of medium chain glycerides using various approaches based

on irradiations with comparison with the conventional approach of synthesis from lauric acid as

the feed stock.

2 Materials and Methods:

2.1 Materials:

Lauric acid (C12H24O2), glycerol, potassium hydroxide (KOH) and sulphuric acid

(H2SO4) were procured from Merck (India) Ltd Mumbai. Molecular weight of lauric acid was

200.31 g/mole whereas the density was 1007 kg/m3. All the chemicals were used as received

from the supplier.

2.2 Chemical reaction scheme:

For the present study, reaction considered is esterification reaction between lauric acid

(C12H24O2) and glycerol with H2SO4 as a catalyst. The reaction steps involved in the overall

synthesis are as follows:

Step 1- Formation of intermediate compound as monolauryl glycerol

CH2OH CH2OOC-C11H23

C11H23COOH + CHOH 98%H2SO4 CHOH + H2O

CH2OH CH2OH

Lauric acid Glycerol Monolauryl Glycerol

 7

Step 2- Formation of intermediate compound as dilauryl glycerol

CH2OOC-C11H23 CH2OOC-C11H23

C11H23COOH + CHOH %H2SO4 CHOOC-C11H23 + H2O

CH2OH CH2OH

Lauric acid Monolauryl Glycerol Dilauryl Glycerol

Step 3- Formation of the main product as trilauryl glycerol or Glycerol trilaurate

CH2COOC-C11H23 CH2COOC-C11H23

C11H23COOH + CHOOC-C11H23 98%H2SO4 CHOOC-C11H23 + H2O

CH2OH CH2OOC-C11H23

Lauric acid dilauryl Glycerol Trilauryl Glycerol

All the above reactions are reversible and endothermic in nature requiring continuous supply of

energy.

2.3 Experimental setup:

2.3.1 Conventional approach:

In the conventional approach, borosilicate glass reactor with 250 ml capacity was used

and the actual volume of the reaction mixture was 150 ml. The reaction temperature was

maintained by using constant temperature water bath. The schematic representation of the

experimental setup has been shown in Figure 1. The glass reactor was provided with openings

for a stirrer (pitched blade turbine with material of construction as stainless steel and height of 25

cm) to ensure the uniform mixing of the reaction mixture.

 8

2.3.2 Ultrasound assisted approach based on Ultrasonic Horn:

Ultrasonic horn, used as a source of ultrasonic irradiations in the present work, operates

at a frequency of 20 KHz. The reactions were carried out in a beaker of 250 ml capacity where

the reaction volume was kept constant for all the reactions at 100 ml. The beaker was immersed

in a water bath to maintain the reaction mixture at constant temperature. A magnetic stirrer was

also provided to stir the reaction mixture. Ultrasonic horn had a rated power of 240W and

calorimetric efficiency (ratio of actual energy dissipated for generation of cavitation events to the

supplied electrical energy) as 7% giving the actual power dissipation into the system as 16.8 W.

The experimental setup used for the synthesis using ultrasound assisted approach has been

represented schematically in Figure 2.

2.3.3 Microwave irradiation based synthesis:

Microwave irradiations were introduced using a domestic oven with rated power of 100–

800 W procured from Chroma Pvt. Ltd. Pune. A hole was drilled in the oven to accommodate the

reflux condenser, sampling port and stirrer. The stirrer used in the work was a pitched blade

turbine made up of teflon. A schematic representation of the experimental setup for the

microwave assisted approach has been shown in Figure 3. Microwave irradiation was used

throughout the reaction time for obtaining the desired intensification.

2.4 Experimental Methodology:

A known quantity of lauric acid was taken in the beaker of capacity 250 mL and

corresponding quantity of glycerol was added based on the selected molar ratio. This reaction

mixture was heated to the desired temperature, which was then maintained constant for total

duration of reaction. Initially, sample was taken out to calculate the initial acid value.
 9

Subsequently desired loading of catalyst as H2SO4 (by weight with respect to lauric acid) was

added with stirring. The reaction mixture is heterogeneous with two immiscible liquid phases of

glycerol and lauric acid and hence use of stirring to achieve uniform mixing is essential. Samples

from the lauric acid phase i.e. from the upper phase were withdrawn at regular time intervals as

15 min for both conventional and ultrasound irradiation assisted approach and at time interval of

2 min for the microwave irradiation assisted approach. The effect of different operating

parameters such as reaction temperature over the range of 60-900C, catalyst loading over the

range of 3.4-13.4% (by weight of lauric acid) and molar ratio of lauric acid to glycerol over the

range of 1:2 – 1:10 on the conversion has been investigated.

2.5 Method of analysis:

In the present study, esterification progresses with a reduction in the free fatty acid

content in the reaction mixture, which can be analyzed in terms of acid value of upper layer of

reaction mixture. The acid base titration method was used to determine the acid value. A

standard solution of 0.1 N KOH was prepared by dissolving KOH in water. A withdrawn sample

of 0.25 g of upper layer of mixture was dissolved in ethanol. The known amount of sample was

titrated against KOH using phenolphthalein as an indicator. The conversion was calculated using

following equation

C0 − C
Extent of conversion = × 100 ……. (1)
C0

Where C0 = Initial acid value

C = Acid value of the withdrawn sample at given time ‘t’

 10

3. Results and Discussion:

3.1 Effect of reaction temperature:

3.1.1 Conventional Approach

The effect of temperature was studied over the range of 60°C to 90°C in the case of

conventional approach at a constant molar ratio of lauric acid to glycerol as 1:10 and catalyst

loading as 3.4% by weight of lauric acid. The obtained results for the effect of temperature on

extent of conversion using conventional approach have been depicted in Figure 4. It has been

observed that the initial acid value was 403.9 mg KOH/ g of mixture which reduced with an

increase in reaction time and reached to 98.7 mg KOH/g of mixture after 150 min of reaction

time at temperature of 900C. It has been observed from the figure that the extent of conversion of

lauric acid increases with an increase in reaction temperature. At lower temperature range of 60-

700C, conversion was in the range of 27.7 to 38.8 % in a reaction time of 180 min, which

increased to 75.6% with an increase in reaction temperature to 900 C in 150 min of reaction time.

It has been observed that at lower temperature of 60 and 700C, the required reaction time to reach

the equilibrium conversion was 180 min which reduced to 150 min at higher temperatures of 80

and 900C. Thus, it can be said that conversion of lauric acid at 900C was found to be maximum

indicating that higher temperature favors the glycerolysis reaction which can be attributed to

intensified kinetics and better miscibility of the reaction phases [8]. It should also be noted here

that the effect of operating temperature in the presence of conventional conditions needs to be

further investigated at still higher operating temperatures as there was no reduction in the acid

value to 100% conversion. Due to the limitations of the present experimental setup the operating

temperature was limited to 90°C. Mostafa et al. [3] have also reported similar effect of operating
 11

temperature on the extent of conversion for the production of mono-, di-, and triglycerides from

waste fatty acids through esterification with glycerol. Similar trends were also reported by

Gerpen et al. [11] who observed a reduction in acid value of oil based on animal fat as the

starting feed stock from 12 to 1 mg of KOH/ g of oil at 2000 C. Felizardo et al. [12] studied the

glycerolysis reaction of high free fatty acid as a feedstock and reported that optimal temperature

of 230 °C was found to be sufficient for reducing the acid value from 80 to 6.4 mg of KOH/g of

oil. The comparison of the current results with the literature reveals that the optimum

temperature for the maximum benefits is different clearly highlighting the importance of the

present work.

3.1.2 Ultrasound assisted approach

The effect of temperature in the case of ultrasound assisted approach was also studied

over the range of 60°C to 90°C at a constant molar ratio of lauric acid to glycerol as 1:10 and

catalyst loading as 3.4% by weight of lauric acid. The obtained results for the effect of

temperature on the progress of glycerolysis reaction using ultrasound assisted approach have

been shown in figure 4. From the figure, it can be seen that the extent of conversion increases

with an increase in reaction temperature. Similar to conventional approach, it has been observed

from the figure that at lower temperature range from 60-700C, conversion was in the range 31.6

to 42.2 % in a reaction time of 180 min, and an increase in reaction temperature to 900C,

resulted in a maximum conversion of 87.2% within 150 min of reaction time. From the results

depicted in figure 4, it has been observed that the acid value decreased from 403 mg KOH/ g of

mixture to 51.6 mg KOH/ g of mixture at optimized reaction temperature of 900C within 150

min. Higher extent of conversion using ultrasound is attributed to the fact that cavitating

conditions results in conditions of intense turbulence and micro-scale liquid circulation currents
 12

that helps in uniform mixing at micro-level and hence in the elimination of the mass transfer

resistances [13] Deshmane et al. [5] studied the effect of same range of temperature from 50-

900C for the ultrasonic assisted approach and reported that the equilibrium conversion of 98.5%

was observed at higher temperature of 900C and 1:3 molar ratio of fatty acid to glycerol. Diaz et

al. [13] have also reported similar effect of operating temperature on the extent of conversion for

the synthesis of medium chain triglycerides. Again it is important to understand that though the

trend for the effect of temperature is similar, the exact value of the optimum temperature and the

extent of increase in the conversion or the extent of decrease in the conversion beyond the

optimum are different making the detailed study into effect of temperature very important.

3.2 Effect of catalyst loading

3.2.1 Conventional Approach

Catalyst loading is also one of the important operating parameters in deciding the

progress of the reaction. The loading of H2SO4 as catalyst was increased from 3.4 % – 13.4 %

(by weight of lauric acid) at a constant temperature of 900C and molar ratio of 1:10. The obtained

results for the effect of catalyst loading on the extent of conversion of lauric acid using

conventional approach has been depicted in the Figure 5. From the figure, it has been observed

that as the loading of sulphuric acid increases, the extent of conversion of lauric acid also

increases. It was observed that there is a steady increase in the extent of conversion with an

increase in the amount of the catalyst upto a catalyst concentration of 11.4%. Increase in catalyst

concentration above this value to 13.4% resulted in a marginal decrease in the extent of

conversion of lauric acid. Based on the observed trends, it can be said that optimum catalyst

loading needs to be selected to get higher efficacy in terms of faster reaction and lesser problems

of separation. The initial increase in the extent of conversion can be attributed to the fact that as
 13

the amount of catalyst increases, more active sites are available for the completion of reaction

driving the reaction progress. The results obtained in the present work confirmed existence of an

optimum catalyst concentration as 11.4% (by weight of lauric acid) of sulphuric acid giving the

maximum conversion of lauric acid as 97.2%. The obtained results are also consistent with the

earlier reports of Kelkar et al. [14] for the esterification reaction where it was observed that the

product yield increases with an increase in the amount of the catalyst till a optimal loading of 3%

by weight of the reactant whereas beyond this catalyst loading, there is not much increase in the

product yield. The comparison has also established that the optimum catalyst loading is

dependent on the feedstock under consideration.

Another important finding of the present work is that the required time (180 min) to achieve

equilibrium conversion at lower catalyst loading of 3.4% and 7.4 % (by weight) was higher as

compared to the catalyst loading of 9.4 % and 13.4% (by weight) where the equilibrium

conversion was reached in 135 min only. Also, an increase in catalyst loading from 3.4 % to

7.4% resulted in an increase in the extent of conversion of lauric acid from 84% to 92 % in

reaction time of 180 min and further increase in catalyst loading to 11.4% reduced the reaction

time to 135 min for obtaining similar levels of equilibrium conversion. Overall, in the case of

conventional approach, it was observed that the acid value changes from 403 mg KOH/ g of

mixture to 11.2 mg KOH/ g of mixture at optimized catalyst loading of 11.4% (by weight) and

reaction temperature of 900C within 135 min. Similar results have been reported by Mostafa et

al. [3] for the esterification reaction using ZnCl2 catalyst, though with different optimum catalyst

loading.

3.2.2 Ultrasound assisted Approach:

 14

In the case of ultrasound assisted approach, effect of catalyst loading has been studied

under the optimized conditions of temperature and molar ratio and the obtained results have been

depicted in the Figure 5. The results are similar to the conventional approach except that the

reaction time required to achieve maximum conversion of lauric acid is lower. It has been

observed that the final acid value decreases from 78.3 mg of KOH/ g of mixture to 8.97 mg of

KOH/ g of mixture with an increase in the catalyst loading from 3.4% to 11.4% for 120 min of

reaction time. With a further increase in catalyst loading, acid value marginally increases from

8.97 mg of KOH/ g of oil to 14.5 mg of KOH/ g of oil confirming lower conversion. Thus, based

on experiments with varying catalyst loadings, it can be said that the optimum catalyst loading of

11.4 % is the same for both the approaches. It has been also observed that the maximum extent

of conversion was 97.8% in 120 min of reaction time when catalyst loading was 11.4% for the

case of ultrasound assisted approach. In the conventional approach, maximum extent of

conversion of 97.2% was obtained at same catalyst loading but required higher reaction time i.e.

in 135 min. Gole et al. [8] also reported similar results for the glycerolysis reaction in presence

of zinc acetate catalyst, where the acid value decreased with an increase in the catalyst

concentration from 0.05 to 0.1 weight% though beyond this optimum catalyst concentration, the

reduction in final acid value was only marginal. It is also important to understand that though the

trends in terms of existence of optimum are similar, the actual value of the optimum catalyst

loading is different depending on the reaction and type of approach and needs to be established

using the approach presented in the current work.

3.2.3 Microwave assisted approach

Experiments were also performed out to study the effect of catalyst loading on the progress of

glycerolysis reaction by changing the catalyst loading over the range of 3.4% to 13.4% by weight
 15

of lauric acid at optimum temperature and constant molar ratio (1:10). The obtained results for

variation in the extent of conversion of lauric acid with reaction time at different catalyst

loadings using microwave assisted approach have been given in Figure 5. It has been observed

that the conversion of lauric acid increased from 77.2% to 98.3% for an increase in the catalyst

loading from 3.4% to 11.4%. The acid value of lauric acid reduced to 6.7 mg of KOH/g of

mixture at 11.4% loading in only 20 min which is much lower as compared to ultrasound

assisted and conventional approach. The final acid value was higher at lower catalyst loading as

compared to 11.4% whereas an increase in the catalyst loading beyond 11.4 % did not result in

any significant effects similar to the conventional and ultrasound approach. Thus, based on

experiments with varying catalyst loadings, it can be said that the optimum catalyst loading is

again 11.4%. A reported study in literature for the microwave assisted esterification of waste

cooking oil also confirmed the existence of optimum loading as 0.5% with a reaction time of 6

min [15]. It is important to note here that selection of optimum catalyst loading not only reduces

the processing cost but also the load on separation steps is reduced making it very important that

a correct catalyst loading is selected.

3.3 Effect of Molar Ratio

3.3.1 Conventional Approach

Another important variable that affects the progress of reaction during synthesis of MCTs

is the molar ratio of lauric acid to glycerol. The effect of molar ratio (lauric acid: glycerol) on the

extent of conversion has been investigated at different molar ratio as 1:2, 1:4 and 1:10 under

conditions of optimized catalyst loading as 11.4% by weight and optimized reaction temperature

of 90°C. Glycerolysis is a reversible reaction and hence usually glycerol is taken in excess with

an objective of driving the reaction in the forward direction. The obtained results for the effect of
 16

molar ratio on the conversion of lauric acid using conventional approach have been shown in the

Figure 6. From the figure, it can be seen that as the molar ratio of lauric acid to glycerol

increases, the extent of conversion of lauric acid also increases. The obtained results can also be

attributed to the fact that as the glycerol amount increases in the reaction mixture, ability to take

up water which is formed during the reaction due to glycerolysis also increases driving the

reaction in forward direction. From the data, it has been observed that the acid value reduced

from 403 mg KOH/ g of mixture to 11.2 mg KOH/ g of mixture at 1:10 molar ratio of lauric acid

to glycerol, which has been considered as optimum for the further set of experiments.

Gole et al. [8] also reported that the final acid value of oil decreases (confirming an increase in

extent of conversion) with an increase in molar ratio for the glycerolysis reaction. Since the

reaction is reversible, excess amount of glycerol drives the reaction in the forward direction.

Thus, it is expected that the final acid value would be lower where a higher excess of glycerol is

available in the reaction mixture. Similar results were also reported by Cerdan et al. [4] for the

synthesis of polyunsaturated fatty acid-enriched triglycerides using lipase-catalyzed

esterification.

3.2.2 Ultrasound assisted approach:

Similar to the conventional approach, experiments were also performed for the ultrasound

assisted approach to understand the effect of molar ratio of lauric acid to glycerol on the extent

of acid value reduction. The different molar ratios used in the study were 1:2, 1:4 and 1:10 at

constant catalyst loading of 11.4 wt% and reaction temperature of 90°C. The obtained results for

the conversion of lauric acid to MCTs using ultrasound assisted approach have been shown in

Figure 6. It has been observed that the conversion of lauric acid increases with an increase in the

molar ratio from 1:1 to 1:4. Further increase in the molar ratio results in only marginal
 17

enhancement in the conversion of lauric acid. It is important to note that lower molar excess is

sufficient to give optimum reduction in the acid value for the case of ultrasound assisted

approach as compared to the conventional approach. It has been observed that a molar ratio of

1:10 in the case of ultrasound assisted approach and reaction time of 135 min was sufficient to

give final acid value as 8.9 mg of KOH/g of acid whereas for 1:2 molar ratio the final acid value

was 29.1 mg KOH/g of acid under optimized parameters. Similar to conventional processing,

excess glycerol enhances the rate of glycerolysis and hence lowers the final acid value reached

during the reaction. Kelkar et al. [14] have also reported similar results for intensification of

esterification of acids using acoustic and hydrodynamic cavitation.

3.2.3 Microwave assisted approach:

With the same catalyst loading (11.4%) as used in study of conventional and ultrasound

assisted approach, effect of molar ratio over the range of 1:2 to 1:10 on the synthesis of MCTs

has been investigated for microwave assisted approach and the obtained results are represented

in Figure 6. From the figure, it has been observed that for a molar ratio of lauric acid to glycerol

as 1:2, the reduction in the acid value was observed from 403.9 mg KOH/ g of mixture to 35.9

mg KOH/ g of mixture and extent of conversion was 91.1%. However, with further increase in

amount of glycerol (molar ratio of 1:4), there was a gradual increase in reduction of acid value

and final value was 10.7 mg KOH/ g of mixture. After this, with further increase in the molar

ratio of lauric acid to glycerol to 1:10, there was no effect in reduction of acid value. The

maximum conversion of lauric acid as 98.3% was obtained for 1:10 molar ratio at catalyst

loading of 11.4% (by weight). It has been also found that using microwave approach, the lowest

final acid value of 6.7 mg KOH/ g of mixture was obtained in all the operating strategies. In

comparison with other two approaches i.e. conventional and ultrasound approaches, microwave
 18

also required minimum time of 20 min only to reach the equilibrium conversion. Similar results

were reported by Perin et al. [16] while studying esterification of esterification of corn oil with

optimum molar ratio of 1:3 sufficient for giving 95% conversion in a reaction time of 3 h and 30

min for conventional and microwave approach respectively. Another study related to microwave

assisted acid esterification of waste cooking oil reported that molar ratio of 1:6 and reaction time

of 6 min was sufficient for giving 92% yield [15].

4. Sequential Approach of combination of Ultrasound and Microwave

To intensify the synthesis of MCTs, experiments were performed using sequential approach of

ultrasound followed by microwave as well as microwave followed by ultrasound. For this

sequential approach as well the effect of catalyst loading on the reduction in the acid value has

been investigated. The range of catalyst loading as 3.4 to 13.4% by weight of lauric acid was

used at constant molar ratio of lauric acid to glycerol as 1:10 using sequential approach of

ultrasound followed by microwave and microwave followed by ultrasound and the obtained

results have been depicted in the Figure 7. From the figure, it has been observed that the effect

of catalyst loading of sulfuric acid on reduction in the acid value was showing similar trends as

the individual approaches. It has been observed that with an increase in catalyst loading from

3.4% to 9.4%, extent of conversion also increases for sequential approach of ultrasound followed

by microwave as well as sequential approach of microwave followed by ultrasound. With further

increase in the catalyst loading to 11.4% and 13.5%, there is only a marginal increase in the

conversion. The major differences observed in the trends were required time for reaching the

equilibrium value which was much lower in the case of combination approach as compared to

the individual approach of ultrasound assisted synthesis. Among the two combination approaches
 19

the time required to reach equilibrium was higher in the case of ultrasound followed by

microwave (40 min) as compared to the approach of microwave followed by ultrasound (20

min). It has been also observed that there was slight increase in the extent of reduction in the acid

value with almost complete conversion as 99.7 % being obtained using sequential approach of

microwave followed by ultrasound whereas the conversion was 99.1 % obtained using approach

of ultrasound followed by microwave at 11.4% of catalyst loading.

The effect of molar ratio on the extent of conversion has also been studied using

sequential approach at optimal catalyst loading of 11.4% by weight of lauric acid. The range of

molar ratio of lauric acid to glycerol was considered as 1:2,1:4 and 1:10 for sequential approach

of ultrasound followed by microwave as well as sequential approach of microwave followed by

ultrasound. The obtained results have been given in the Figure 8 where it can be observed that

with an increase in the molar ratio, conversion also increases similar to the individual approaches

though the extent of conversion as 99.5% and 98.6 % for the case of microwave followed by

ultrasound and ultrasound followed by microwave respectively were higher than the individual

approaches at optimum molar ratio of 1:4 with lower required time to reach the equilibrium

conversion.

Use of microwave provides intense heating at molecular level based on the polarity of

reacting molecules and their electrical characteristics, which removes the barrier for heat transfer

[17]. In the case of ultrasound, micro-emulsion effect for the immiscible liquid phases of

glycerol and lauric acid results in generation of enhanced surface areas leading to increased mass

transfer rate. The combined operation makes use of both these effects and results in higher

degree of intensification when sequential approach was used as microwave followed by

ultrasound. The sequential effect of microwave followed by ultrasound increases the temperature
 20

of the reaction mixture at micro level to avoid the attenuation effect of ultrasound giving

beneficial effects. Gole et al [18] while studying the esterification of Nagchampa oil using

ultrasound and microwave irradiation reported that reaction time of 60 min; 25 min and 15 min

were required to reduce the acid value at desired level using ultrasound, microwave, and

sequential approach of microwave followed by ultrasound respectively. Also using sequential

approach of ultrasound by microwave required 25 min for a reduction in the acid value to 7.1 mg

of KOH/g. The results are also consistent with Prajapat and Gogate [17] who studied

depolymerization of guar gum solution using sequential approaches based on ultrasound and

microwave and Gole et al. [19] who investigated degradation of brilliant green using sequential

approaches. The present work is the first to report the intensification using the sequential

approach for the synthesis of MCTs.

5. Comparison of US, microwave and conventional approaches at optimized conditions

It is important to present the comparison of different approaches as ultrasound, microwave,

conventional or sequential approach in terms of the obtained extent of intensification. It has been

observed that temperature, molar ratio and catalyst concentration are the most influencing

parameters for the glycerolysis reaction irrespective of the synthesis approach. An optimum

value exists for all the approaches and depending on the level of intensification; the value of the

optimum can be lower leading to lower processing costs. In the case of individual operations,

microwave irradiation was found to be the best approach leading to higher degree of equilibrium

conversion in reduced reaction times. It was also established that the sequential approach is more

effective than the individual approach as per the detailed data presented in Table 1. It has also

been observed that the reaction time required for microwave based approach is significantly
 21

lower as compared to the conventional and ultrasound assisted approach. This can be attributed

to the fact that the microwave irradiation enhanced rapid dipolar rotation of polar component and

their interaction with electric field which results in molecular friction and collisions giving rise to

intense localized heating and thereby accelerating the chemical reaction in a short time [5,8,14].

Similar result has been reported for castor oil based process [14] where the time required for

reducing the initial acid value of oil from 55 to 15 mg of KOH/g of mixture (at constant molar

ratio of 1:1) was 7 h and 2 h for the conventional and microwave based approaches, respectively.

Another work on esterification of corn oil reported that molar ratio of 1:3 was sufficient to yield

95% conversion in a reaction time of 3 h and 30 min for conventional and microwave assisted

approach respectively [14]. The study related to microwave assisted acid esterification of waste

cooking oil reported that molar ratio of 1:6 and reaction time of 6 min was sufficient to give 92%

yield [18].

Microwave irradiation directly heats the molecule which in turns increases the molecular

intensity of collision which enhances the reaction in forward direction. Microwave irradiation

also produces efficient internal heating by direct coupling of microwave energy with molecules

of solvent, reagent or catalyst and the irradiation passes through the walls of the vessel directly

into the bulk of reaction mixture which is more effective as compared to the conventional

heating approach.

Based on the optimized parameters presented in Table 1, it can be concluded that microwave

irradiation is the more effective route for the intensification of the process than ultrasound based

approach; off course both the approaches give better results as compared to the conventional

processing. In the case of conventional method, considerable amount of hear energy is required

for heating the reaction vessel using constant temperature water bath and hence leads to energy
 22

intensive operation. However, microwave provides intense heating at molecular level and hence

results into considerable amount energy being dissipated at the location of transformation and

sufficient enough for giving the desired intensification of the reaction. In the present work, due

to microwave irradiation a significant reduction in reaction time from 150 min to 26 min was

clearly observed. Thus, it can be concluded that, microwave irradiation is most effective route

for the intensification of the process.

2.6 Kinetic study

Arrhenius plot can be used to estimate the frequency factor and energy of activation for the

conventional approach and ultrasound approach since the effect of temperature has been

investigated in the present work. The variation in the rate constant with temperature is governed

by the Arrhenius law relationship as given below [20]

E 
k = A exp A 
 RT  ………… (2)

Where R is universal gas constant (J/mol.K) and A is the frequency factor, k is specific reaction

rate constant and EA is energy of activation. A plot of ln k versus 1/T gives the estimation of the

activation energy. The experimental data obtained at different temperatures as 333 K to 363K

were used to plot conversion (X) data as X/ (1-X) versus time for the conventional and

ultrasound approach as shown in Figure 9 and Figure 10. The values of kinetic rate constants at

different temperatures were calculated using such plots and it has been observed that the rate

constant for glycerolysis reaction using conventional approach increases from 0.0304 to 0.2525

l/(mol min) with an increase in temperature from 60 to 90 0C whereas for the case of ultrasound,

rate constant increased from 0.0391 to 0.4630 l/(mol min) for a similar increase in the
 23

temperature. Higher rate constants for the ultrasound assisted approaches also confirm the

intensification benefits due to the use of ultrasound as explained in the earlier sections also.

The activation energy was also obtained using rate constant data for the controlled

temperature experiments over the range of 60 to 90 0C. The obtained values of ln k were plotted

against 1/T for conventional and ultrasound approach as shown in Figure 11 and Figure 12. From

the results, the activation energy calculated was equal to 82.13 kJ/mol for the conventional

approach whereas for the ultrasound based approach, it was 69.48 kJ/mol. The details of the

kinetic data have been shown in the Table 2.

5. Conclusions:

The present work on the synthesis of medium chain triglycerides compared the efficacy of

conventional, ultrasonic irradiation, microwave irradiation and sequential approach in terms of

the desired process intensification benefits. The effect of different operating parameters such as

temperature, catalyst loading and molar ratio on the conversion has been established. From the

study, it has been established that the conventional method gives extent of conversion as 97.2%

in 150 min of reaction time, whereas the ultrasonic irradiation based approach gives the extent of

conversion as 97.8% in reaction time of 120 min under the optimized conditions (optimum

temperature as 90°C, optimum molar ratio of lauric acid to glycerol as 1:10 and optimum

catalyst loading as 11.4% by weight of lauric acid). The maximum extent of conversion as 99.7%

was obtained using sequential approach of microwave followed by ultrasound irradiation within

only 20 min for the same optimized conditions. Overall, microwave irradiation is found to be

very useful and effective in intensifying synthesis of MCTs as compared to the conventional and

ultrasonic irradiation method.

 24

References

[1] V. K. Babayan, Medium Chain Triglycerides- their Composition, Preparation and

Application, The Journal of American Oil Chemists Society, 45 (1968) 23-25

[2] A. C. Bach, V. K. Babayan, Medium chain triglycerides: an update, American Journal of

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[3] N. A. Mostafa, A. Maher, W. A. Delmoez, Production of mono-, di-, and triglycerides from

waste fatty acids through esterification with glycerol, Advances in Bioscience and

Biotechnology, 4 (2013) 900-907

[4] L. E. Cerdán, A. R. Medina, A. G. Giménez, M. J. I. González, E. M. Grima, Synthesis of

Polyunsaturated Fatty Acid-Enriched Triglycerides by Lipase-Catalyzed Esterification, The

Journal of American Oil Chemists Society, 75(1998) 1329-1337

[5] V. G. Deshmane, P. R. Gogate, A. B. Pandit, Process intensification of synthesis process

for medium chain glycerides using cavitation, Chemical Engineering Journal 145 (2008) 351–

354

[6] S.R. Shirsath, S.H. Sonawane, P.R. Gogate, Intensification of extraction of natural products

using ultrasonic irradiations—A review of current status, Chemical Engineering and Processing

53 (2012) 10– 23.

[7] S. Hemwimol, P. Pavasant, A. Shotipruk, Ultrasound-assisted extraction of anthraquinones

from roots of Morindacitrifolia, Ultrasonics Sonochemistry 13 (2006) 543–548

 25

[8] V. L. Gole, P. R. Gogate, Intensification of glycerolysis reaction of higher free fatty acid

containing sustainable feedstock using microwave irradiation, Fuel Processing Technology 118

(2014) 110–116,

[9] U. Riaz, S. M. Ashraf, A. Madan, Effect of microwave irradiation time and temperature on

the spectroscopic and morphological properties of nano structured poly(carbazole) synthesized

within bentoniteclay galleries, New Journal of Chemistry, 38 (2014) 4219.

[10] M. A. Surati, S. Jauhari, K. R. Desai, A brief review: Microwave assisted organic

reaction”, Archives of Applied Science Research, 4 (2012) 645-661.

[11] J. V. Gerpen, B. Shanks, R. Pruszko, D. Clements, G. Knothe, Biodiesel Production

Technology, National Renewable Energy Laboratory, Colorado, August 2002–January 2004. 52–

55.

[12] P. Felizardo, J. Machado, D. Vergueiro, M. J. N. Correia, J. P. Gomes, J. M. Bordado,

Study on the glycerolysis reaction of high free fatty acid oils for use as biodiesel feedstock, Fuel

Processing Technology 92 (2011) 1225–1229

[13] I. Diaz, C. Marquez-Alvarez, F. Mohino, J. Pariente, E. Sastre, Combined alkyl and sulfonic

acid functionalization of MCM-41 Type silica. Part 2. Esterification of glycerol with fatty acids,

Journal of Catalysis 193 (2000)295-302

[14] M. A. Kelkar, P. R. Gogate, A. B. Pandit, Intensification of esterification of acids for

synthesis of biodiesel using acoustic and hydrodynamic cavitation, Ultrasonics Sonochemistry

15 (2008) 188–194.
 26

[15] P. D. Patil, V. G. Gude, H. K. Reddy, T. Muppaneni, S. Deng, Biodiesel production from

waste cooking oil using sulfuric acid and microwave irradiation processes, Journal of

Environmental Protection 3 (2012) 107–113

[16] G. Perin, G. Alvaro, E. Westphal, L. H. Viana, R. G. Jacob, E. J. Lenardao, M. G. M.

D'Oca, Transesterification of castor oil assisted by microwave irradiation, Fuel 87 (2008) 2838–

2841

[17] A. L. Prajapat, P. R. Gogate, Depolymerization of guar gum solution using different

approaches based on ultrasound and microwave, Chemical Engineering and processing: process

intensification, 88 (2015) 1-9

[17] M. A. P. Langone, M. E. De Abreu, M. J. C. Rezende, G. L. Santanna, Enzymatic Synthesis

of Medium Chain Monoglycerides in a Solvent-Free System, Applied Biochemistry and

Biotechnology, 98–100 (2002) 987-996.

[18] V. L. Gole, P. R. Gogate, Intensification of synthesis of biodiesel from non-edible oil using

sequential combination of microwave and ultrasound, Fuel Processing Technology, 106 (2013)

62-69

[19] V. L. Gole, P. R. Gogate, Degradation of brilliant green dye using combined

treatment strategies based on different irradiations, Separation Purification Technology 133

(2014) 212–220

[20] D. D. Pukale, G. L. Maddikeri, P. R. Gogate, A. B. Pandit, A. P. Pratap, Ultrasound assisted

transesterification of waste cooking oil using heterogeneous solid catalyst, Ultrasonics

Sonochemistry 22 (2015) 278-286

 27

List of figures:

Figure 1: Schematic representation of experimental setup for the conventional approach

Figure 2: Schematic representation of experimental set up for synthesis using Ultrasound

assisted approach

Figure 3: Schematic representation of experimental setup for synthesis using Microwave

Irradiation

Figure 4: Effect of temperature on extent of conversion for conventional, ultrasound and

microwave irradiation based approaches (molar ratio of lauric acid to glycerol as 1:10,

catalyst loading as 3.4%, 600 rpm)

Figure 5: Effect of catalyst loading on extent of conversion for conventional, ultrasound

and microwave irradiation based approaches (molar ratio of lauric acid to glycerol as 1:10

and optimized temperature as 90°C, 600 rpm)

Figure 6: Effect of molar ratio of lauric acid to glycerol on extent of conversion for

conventional, ultrasound and microwave irradiation based approaches (Optimized

temperature as 90°C and Optimized Catalyst concentration as 13.4% by weight of lauric

acid, 600 rpm)

Figure 7: Effect of catalyst concentration on extent of conversion using sequential approach

of Ultrasound (U) followed by Microwave (M) irradiation and microwave followed by

ultrasound method (Optimized molar ratio of lauric acid to glycerol as 1:10, 600 rpm)

Figure 8: Effect of molar ratio of lauric acid to glycerol on extent of conversion using

sequential approach of Ultrasound (U) followed by Microwave (M) irradiation and

 28

microwave followed by ultrasound method (Optimized catalyst concentration using

sequential approach as 11.4%, 600 rpm)

Figure 9: Kinetic study for establishing rate constants for glycerolysis reaction using

conventional approach

Figure 10: Kinetic study for establishing rate constants for glycerolysis reaction using

ultrasound assisted approach

Figure 11: Arrhenius plot for estimation of activation energy for glycerolysis reaction using

conventional approach

Figure 12: Arrhenius plot for estimation of activation energy for glycerolysis reaction using

ultrasound assisted approach

List of Tables

Table 1: Results for the detailed studies of effect of operating parameters on glycerolysis

reaction using conventional approach, ultrasound approach, and microwave based

approach and sequential approach

Table 2: Kinetic studies of glycerolysis reaction using conventional and ultrasound

approach.
 29

Figures

Figure 1: Schematic representation of experimental setup for the conventional approach

Figure 2: Schematic representation of experimental set up for synthesis using Ultrasound

assisted approach
 30

Figure 3: Schematic representation of experimental setup for synthesis using Microwave

Irradiation
 31

100.0

90.0 Conventional

80.0 Ultrasound

70.0
Extent of Conversion, %

60.0

50.0

40.0

30.0

20.0

10.0

0.0
50 60 70 80 90 100
Temperature, 0C

Figure 4: Effect of temperature on extent of conversion for conventional, ultrasound and

microwave irradiation based approaches (molar ratio of lauric acid to glycerol as 1:10,

catalyst loading as 3.4%, 600 rpm)

 32

100

80
Extent of Conversion, %

60 Conventional
Ultrasound
Microwave
40

20

0
0 3 6 9 12 15
Catalyst Concentration, %

Figure 5: Effect of catalyst loading on extent of conversion for conventional, ultrasound

and microwave irradiation based approaches (molar ratio of lauric acid to glycerol as 1:10

and optimized temperature as 90°C, 600 rpm)

 33

120.0

100.0

80.0

1:02
60.0
1:04
1:10
40.0

20.0

0.0
Conventional Ultrasound Microwave

Figure 6: Effect of molar ratio of lauric acid to glycerol on extent of conversion for

conventional, ultrasound and microwave irradiation based approaches (Optimized

temperature as 90°C and Optimized Catalyst concentration as 13.4% by weight of lauric

acid, 600 rpm)

 34

100

80
Extent of Conversion, %

60

M/U
40
U/M

20

0
3.4 7.4 9.4 11.4 13.5
Catalyst Loading, %

Figure 7: Effect of catalyst concentration on extent of conversion using sequential approach

of Ultrasound (U) followed by Microwave (M) irradiation and microwave followed by

ultrasound method (Optimized molar ratio of lauric acid to glycerol as 1:10, 600 rpm)
 35

100

Extent of Conversion, % 80

60

M/U
40 U/M

20

0
01:02 01:04 01:10
Molar Ratio

Figure 8: Effect of molar ratio of lauric acid to glycerol on extent of conversion using

sequential approach of Ultrasound (U) followed by Microwave (M) irradiation and

microwave followed by ultrasound method (Optimized catalyst concentration using

sequential approach as 11.4%, 600 rpm)

 36

3.50 60
70 y = 0.0174x
80 R² = 0.8717
3.00 90
Linear (60)
2.50 Linear (70)

2.00
X/(1-X)

1.50 y = 0.0057x
R² = 0.8836

1.00 y = 0.0031x
R² = 0.9314

0.50
y = 0.0021x
R² = 0.9803
0.00
0 50 100 150 200
-0.50
Reaction TIme, min

Figure 9: Kinetic study for establishing rate constants for glycerolysis reaction using

conventional approach
 37

8.00
60
70 y = 0.0319x
7.00 80 R² = 0.7417
90
6.00 Linear (60)
Linear (70)
5.00

4.00
X/(1-X)

y = 0.0084x
3.00 R² = 0.8858
y = 0.0037x
2.00 R² = 0.9161

1.00
y = 0.0027x
R² = 0.9892
0.00
0 20 40 60 80 100 120 140 160 180 200
-1.00
Reaction Time, min

Figure 10: Kinetic study for establishing rate constants for glycerolysis reaction using

ultrasound assisted approach

 38

ln(k)
0
0.0027 0.00275 0.0028 0.00285 0.0029 0.00295 0.003 0.00305
-0.5

-1

-1.5
1/T

-2
y = -9879.3x + 21.415
R² = 0.9348
-2.5

-3

-3.5

-4

Figure 11: Arrhenius plot for estimation of activation energy for glycerolysis reaction using

conventional approach
 39

ln(k)
0
0.0027 0.00275 0.0028 0.00285 0.0029 0.00295 0.003 0.00305

-0.5

-1

-1.5

y = -8357.6x + 26.146
1/T

-2 R² = 0.915

-2.5

-3

-3.5

-4

Figure 12: Arrhenius plot for estimation of activation energy for glycerolysis reaction using

ultrasound assisted approach

 40

Table 1: Results for the detailed studies of effect of operating parameters on glycerolysis

reaction using conventional approach, ultrasound approach, and microwave based

approach and sequential approach

S Parameters Range Extent of Conversion (%)

N Conventional Ultrasound Microwave M/U U/M

1 Effect of 60 27.8 31.3 - - -

Temperature 70 38.9 42.3 - - -

(0C) 80 51.9 60.3 - - -

90 75.6 87.4 - - -

2 Effect of 1:2 83.3 92.77 91.11 96.8 94.8

molar ratio 1:4 95.6 97.22 97.33 98.6 98.1

1:10 97.2 97.8 98.33 99.5 98.6

3 Effect of 3.4 75.55 78.33 77.22 88.3 86.9

catalyst 5.4 84.44 85.55 85 - -

concentration 7.4 92.77 93.88 93.33 95.4 94.8

(%) 9.4 94.44 95.55 95 97.8 96.2

11.4 97.2 97.8 98.33 99.5 99.1

13.5 95 97.5 97.5 98.5 97.9

 41

Table 2: Detailed kinetic studies of glycerolysis reaction using conventional and

ultrasound approach.

SN Approach Temperature (0C) Rate Constant Activation

(l/mol min) Energy

(KJ/mol)

1 Conventional 60 0.0304 82.13

70 0.0449

80 0.0827

90 0.2525

2 Ultrasound 60 0.0391 69.48

70 0.0537

80 0.1219

90 0.4630
 42

Research Highlights:

• Intensified synthesis of MCTs from lauric acid as feed stock for the first time

• Use of sequential approach involving ultrasound and microwave

• Combined approaches much better than the individual approach of ultrasound or

microwave

• Lower molar ratio, temperature and the reaction time are key intensification benefits