Accepted Manuscript

Intensification of esterification of non edible oil as sustainable feedstock using

cavitational reactors

Ashish V. Mohod, Abhijeet S. Subudhi, Parag R. Gogate

PII: S1350-4177(16)30439-4
DOI: http://dx.doi.org/10.1016/j.ultsonch.2016.11.040
Reference: ULTSON 3454

To appear in: Ultrasonics Sonochemistry

Received Date: 7 October 2016

Revised Date: 29 November 2016
Accepted Date: 29 November 2016

Please cite this article as: A.V. Mohod, A.S. Subudhi, P.R. Gogate, Intensification of esterification of non edible
oil as sustainable feedstock using cavitational reactors, Ultrasonics Sonochemistry (2016), doi: http://dx.doi.org/
10.1016/j.ultsonch.2016.11.040

This is a PDF file of an unedited manuscript that has been accepted for publication. As a service to our customers
we are providing this early version of the manuscript. The manuscript will undergo copyediting, typesetting, and
review of the resulting proof before it is published in its final form. Please note that during the production process
errors may be discovered which could affect the content, and all legal disclaimers that apply to the journal pertain.
 1

Intensification of esterification of non edible oil as sustainable feedstock using

cavitational reactors

Ashish V. Mohod 1, Abhijeet S. Subudhi1, Parag R. Gogate1*

1
Chemical Engineering Department,

Institute of Chemical Technology,

Matunga, Mumbai- 400019

INDIA

*Author to whom correspondence may be addressed

E-mail: [email protected]; Contact no: +91 22 33612024

 2

Abstract

Using sustainable feed stock such as non-edible oil for the biodiesel production can be one of

the cost effective approaches considering the ever growing interest towards renewable

energy. However, due to the high free fatty acid content, non-edible oils require considerable

preprocessing before the actual transesterification reaction for biodiesel production. The

present work focuses on intensification of the esterification reaction used as preprocessing

step based on acoustic and hydrodynamic cavitation also presenting the comparison with the

conventional approach. Karanja oil with initial acid value as 14.15 mg of KOH/ g of oil has

been used as a sustainable feedstock. Effect of operating parameters such as molar ratio,

catalyst loading, temperature and type of catalyst (sulfuric acid and Amberlyst-15) on the

acid value reduction has been investigated. The maximum reduction in the acid value (final

acid value as 2.7 mg of KOH/g of oil) was obtained using acoustic cavitation at 1:5 molar

ratio of oil to methanol and 2% sulfuric acid loading at ambient temperature. In the case of

hydrodynamic cavitation, acid value reduced upto 4.2 mg of KOH under optimized

conditions. In the second stage esterification using hydrodynamic cavitation and conventional

approach, the final acid value was 3.6 and 3.8 mg of KOH/g of oil respectively. Energy

requirement analysis for ultrasound and conventional approaches clearly established the

superiority of the ultrasound based approach. The present study clearly demonstrated that

significant intensification benefits can be obtained in terms of the reduction in the molar ratio

and operating temperature for the case of acoustic cavitation with somewhat lower effects for

the hydrodynamic cavitation.

Keywords: Esterification; acoustic cavitation; hydrodynamic cavitation; Conventional

approach; karanja oil; Preprocessing

 3

1. Introduction

Enormous increase in the fuel consumption due to increase in the population and

industrialization has resulted in considerable stress on the fossil fuel production, also having

significant impact on economies of many countries. The use of petroleum based products also

creates substantial air pollution problems all over the world and different alternatives are

being explored currently to develop synthesis routes for alternate fuels such as biodiesel [1].

Presently, biodiesel synthesis is performed using different types of vegetable oils such as

soybean, sunflower, palm oil etc. but these sources offer the limitation of food security. Non

edible oils such as Jatropha, Karanja, Nagchampa etc. and processed vegetable oils such as

the waste cooking oil have the potential to replace edible oils as a good source of sustainable

raw material, availability of which can also be considered as plenty [2]. The non-edible oils

usually contain large amounts of free acids and hence there is a limitation for

transesterification processing due to the possibility of soap formation from the reaction of

free acid with alkali. Free fatty acid is also undesirable as it can result in yield loss and

increase the complexity of the product separation processing. There are different methods

that can be applied for the reduction of free fatty acid such as crystallization, adsorption and

distillation [3] though it adds to the production costs. Another approach for pretreatment is

based on the use of esterification reaction [3] which can be either acid catalyzed approach or

heterogeneously catalyzed based on the use of ion exchange resins but these steps are again

energy intensive and require higher processing time. Thus it is imperative to develop a

sustainable process intensification technology for improving the preprocessing before the

actual transesterification reaction for biodiesel. Process intensification using cavitational

reactors is a promising approach due to the operation at ambient conditions. Use of

cavitational reactors can eliminate the mass transfer resistance and mixing issues associated
 4

with the esterification. Cavitation is a phenomenon of formation, growth and collapse of

microbubbles within a liquid [4] and can be classified into acoustic and hydrodynamic

cavitation. Acoustic cavitation is produced by passing ultrasound (frequency of sound > 16

KHz) through the liquid medium. Ultrasound helps in formation of fine emulsion of two

immiscible liquids generating large superficial area for the reaction resulting into requirement

of shorter time and also giving higher yield. In addition, the turbulence and acoustic

streaming (often described together as the physical effects of cavitation) contribute toward

the intensification of reactions limited by mass transfer such as the esterification reaction

between oil and alcohol. Hydrodynamic cavitation is generated by passage of the liquid

through constriction such as throttling valve, orifice plate, and venturi. In hydrodynamic

cavitation, when the local pressure falls below the vapor pressure of the liquid due to sudden

introduction of the mechanical constriction such as venturi or orifice, cavities are generated,

which subsequently collapse downstream of the constriction due to the recovery of pressure

based on an increase in the flow area. It has been demonstrated that the conditions similar to

acoustic cavitation are generated downstream of the orifice or venturi with reliable control

over the cavitational intensity based on the geometry of the constriction as well as the set of

operating parameters such as operating pressure and temperature [5]. Though similar

intensification benefits can be obtained from both acoustic and hydrodynamic cavitation

reactors, the energy efficacy of both the reactors in giving the desired intensification is

different and hence it is important to compare this aspect for deciding the commercial

applications. The present work focuses on investigating the intensification of esterification

reaction of karanja oil as a starting raw material and comparing the efficacy of acoustic and

hydrodynamic cavitation based approaches with the conventional approach.

Karanja oil is a thick yellow – orange to brown colored oil extracted from the karanja

seeds. Typically the processing can be performed using mechanical expeller and the obtained
 5

weight based yields are around 24%. The obtained oil has bitter test and disagreeable aroma

and hence is considered as non-edible. In India, Karanja oil has been used as a fuel for

cooking and lamps. Also, it is used as lubricant, pesticide and in soap making industries.

Karanja tree is widely available because it can grow in humid as well as subtropical regions

with annual rainfall ranging from 500 to 2500 mm. The karanja oil has major content of oleic

(C18:1) and linoleic (C18:2) as the fatty acids with varying total content from 9 to 46% [6].

Presence of free fatty acids in oil causes significant problems in standard processing for the

biodiesel production, since the free fatty acid is readily saponified by the homogenous alkali

catalyst leading to a loss of catalyst and operational problems due to the leaning as well as

increased purification costs. Due to these issues, esterification of karanja oil is required so as

to reduce the free fatty acid content. Esterification generally requires excess of one of the

reactants so as to drive the reaction in forward direction and also higher temperatures to get

higher equilibrium yields. An application of process intensification approach can give

reduction in molar excess and temperature so that commercial application becomes feasible.

Normally esterification is performed using homogeneous acid catalyst such as sulfuric acid

[7-9] but this approach offers difficulties in separation after the reaction and produces a toxic

wastewater that needs adequate treatment. Considering the problems associated with

homogeneous catalyst, the present work also dealt with use of heterogeneous solid catalysts

as a substitute for sulfuric acid. To highlight the novelty of the current work, it is imperative

to provide an overview of the earlier work on karaja oil esterification. Thiruvendadaravi et al.

[10] studied esterification of karanja oil using sulfated zirconia as the catalyst and reported

that reaction progressed rapidly during first hour with no significant reduction after 1 hour. It

was also reported that about 50% reduction in the acid value was obtained at low methanol

loading whereas it increased to 80% for higher methanol ratios. The maximum reduction in

acid value was obtained at 9:1 molar ratio of methanol to oil and 1% acid catalyst as sulfated
 6

zirconia. Alam and Patel [11] investigated the esterification of karanja oil using conventional

reflux method at a capacity of 2 L and reported reduction in the acid value from 16.8 to 0.42

under optimized conditions. Naik et al. [12] studied the esterification reaction for reducing

the acid value of karanja oil at laboratory scale and reported that acid value decreases from

41.9 to 3.9 mg of KOH/gm of oil in one hour using sulphuric acid catalyst. The analysis of

the literature reveals that none of the earlier studies with karanja oil were based on the use of

ultrasound or cavitation and also most of the studies were reported at a laboratory scale

operation. An overview of the literature related ultrasound assisted esterification also revealed

that the studies were at laboratory scale operation with capacity over the range of 100 mL to

1 L [13-15]. The present work concentrated on understanding the effect of operating

parameters such as molar ratio, catalyst loading and temperature on the acid value reduction

of karanja oil using cavitational reactors at an operating capacity of 4 L. The novelty of

present work is that intensification of esterification reaction of karanja oil using ultrasonic

reactors has been investigated at large scale operation as 4 L which has not been done in any

of the earlier works to the best of our knowledge. The work also presents comparison with

the conventional approach in terms of energy requirements for reduction in the acid value. It

is also important to understand that the exact values of optimum parameters as well as the

degree of intensification strongly depend on the feed stock and the reactor configurations,

thus, it is imperative to investigate the effect of different parameters for specific feed stock.

2. Materials and Methods

2.1 Materials

The raw karanja oil was procured from Svas Enterprise Pvt. Ltd. Mumbai. Initially the

oil was filtered to remove the traces of particles and mud. Sulphuric acid (98% concentrated),

methanol, ethanol, amberlyst-15 (wet), potassium hydroxide pellets (LR grade) as well as
 7

methanol (HPLC grade) were procured from S. D. Fine Chemicals. All chemical were used

as received from the suppliers without any processing unless specified otherwise.

2.2 Reactor Configurations

2.2.1. Longitudinal Horn:

The novel sonochemical reactor, procured from a local manufacturer (Roop Telsonic

Ultrasonix Ltd., Mumbai) is based on the irradiation using a single longitudinally vibrating

transducer kept at the bottom of the reactor. The schematic representation of the reactor has

been depicted in Figure 1. Two mechanical stirrers were also used for proper mixing of the

mixture at constant stirring speed of about 1100 rpm. The inner cross-section of the reactor is

having dimensions of 15 cm x 33 cm x 20 cm with a total holding capacity of 8 l (some part

of the reactor is occupied by the transducer). There is a provision for a drain at 8cm from the

bottom of the reactor as well as an outlet at the top at a height of 32cm from the bottom of the

reactor, which gives facility of continuous operation though in the present work, only batch

mode of operation has been investigated. The operating frequency of irradiation is 36 kHz

and maximum power dissipation into the system is 150 W. For all the experiments performed

using varying capacity, it was ensured that the transducer surface is always entirely

submerged in the liquid. The reactor is provided with a timer for controlling the treatment

time and in the current work, 15 min cycle was used. After 15 min of irradiation, a gap of

another 15 min was allowed for the cooling of the reaction mixture (at this stage no

continuous cooling system can be introduced into the reactor) so that the temperature of the

system was maintained at ambient conditions. The off time of 15 min was decided based on

the preliminary studies so as to minimize the possible errors in temperature control. The off

time also ensured adequate cooling of the transducers so as to achieve a safer operation

without any damage to the equipment.

 8

The conventional approach was also studied in the same reactor by keeping the

ultrasound device off and the energy transfer was obtained based on the use of two

mechanical stirrers. This approach was used as control so as to establish the process

intensification benefits due to the use of cavitational reactors.

2.2.2 Hydrodynamic Cavitation:

The hydrodynamic cavitation reactor used in the present work consists of a reservoir

with 10 l capacity that is connected to a piston pump with power rating of 1.5 kW (Figure 2).

The piston pump is the main device for energy dissipation in hydrodynamic cavitation

reactor. The suction side of the pump is connected to the bottom of tank. The discharge from

the pump is divided into two branches which helps in control of the inlet pressure and the

inlet flow rate through the main line housing the orifice (flange is used to accommodate the

orifice plate) with the help of valves V2 and V3. The pressure gauges P2 and P1 are used to

measure the inlet and fully recovered downstream pressure respectively. The operating

temperature of the reactor was maintained at the desired temperature by circulating water in

the surrounding jacket. The circulation of water is required to counter the heat energy

dissipation due to the cavitating events. The cavitating device as slit venture has been used

and the geometric details have been given in the Table 1.

2.3 Experimental procedure

Esterification reaction was performed at a constant 4L batch in longitudinal horn

equipped with two mechanical stirrers for the case of acoustic cavitation assisted and

conventional approach (ultrasound was kept off) and using the recirculation setup based on

hydrodynamic cavitation at same capacity of 4 L. Initially, oil was mixed with methanol (at

desired molar ratio) and then sulphuric acid was added in appropriate proportion for the first

stage of esterification. At a specific interval of time, 3 ml samples were withdrawn for the
 9

acid value analysis. The withdrawn samples were washed by water and centrifuged and then

acid values were monitored to understand the progress of the reaction. All the experiments

were performed at least two times and the observed errors were within 2% of the reported

average value.

2.4 Method of analysis:

The acid value of the samples was determined using acid-base titration technique. A

standard solution of 0.1N oxalic acid was prepared and using this solution, standardization of

potassium hydroxide solution was done. The obtained samples were dissolved in neutralized

ethanol (typically a sample of 0.23g was dissolved in 5ml of neutralized ethanol) and heated

for 5 min. The sample was then titrated against alcoholic potassium hydroxide using

phenolphthalein as indicator. The Acid Value (AV) was calculated using the following

equation:

 
  ..     
AV = .  
……. (1)

3. Results and Discussions

3.1 Conventional approach

3.1.1 Effect of molar ratio

Experiments were performed to check the effect of molar ratio on reduction in the

acid value of oil using conventional method at different molar ratios of oil to methanol as 1:4,

1:5, 1:6 and 1:7 with fixed catalyst loading as 2% (sulfuric acid) and temperature of 33°C.

The obtained results for the reduction in the acid value using conventional approach have

been presented in the Figure 3. It can be seen from the figure that with an increase in the
 10

molar ratio of oil to methanol from 1:4 to 1:6, acid value reduces till the optimal value and

then further increase in molar ratio of oil to methanol to 1:7 there is not much further

reduction in acid value beyond the optimum of 4.5 mg of KOH/g of oil. The molar ratio of oil

to methanol as 1:6 was considered to be an optimum and used for the further experimental

studies using the conventional approach. It has been also observed from the figure that the

initial reduction in the acid value in 10 min of reaction was much faster than the later part of

the reaction. Use of an excess methanol drives the equilibrium toward the formation of ester

and enhances the rate of forward reaction. Similar results have also been reported by Sharma

and Sing [16] for the pretreatment stage of esterification during the synthesis of biodiesel

using kusum oil as the sustainable feed stock. It was reported that the optimum molar ratio of

oil to methanol was 1:10 for acid esterification. Gorro et al. [17] also reported similar

existence of optimum at 1:9 for the esterification reaction of the free acid present in the

jatropha curcas oil and methanol. Gole et al. [13] also studied the effect of molar ratio of oil

to methanol over the range of 1:2 to 1:6 at a constant H2SO4 loading of 1 wt% of oil for the

case of nagchampa oil as the sustainable feed stock. It was reported that at molar ratio of oil

to methanol as 1:3, required reduction in the acid value for carrying out the transesterification

reaction could be obtained using the conventional approach. Ding et al. [19] also reported

similar results for esterification reaction for the case of waste cooking oil with optimum

volume ratio of the effect of molar ratio of methanol/waste cooking oil as 30% yielding

maximum free fatty acid conversion as 95.65%. It is important to understand that though the

trend of existence of optimum is similar, the exact value of the optimum molar ratio and the

extent of reduction obtained in the acid value is different making it important to understand

the effect of molar ratio for each of the sustainable feed stock and hence the presented results

in the current work are important.

3.1.2 Effect of temperature

 11

Operating temperature is also one of the important parameters in the case of conventional

approach which has important effect on the reduction in the acid value. The range of

temperature studied in the present work was 33 0C to 48 0C at an optimum molar ratio of oil to

methanol as 1:6 and 2% (wt) of sulfuric acid loading. The obtained results for the effect of

temperature on reduction in the acid value using conventional approach have been given in

the Figure 4. It has been observed that the final acid value as 4.5 mg of KOH/g of oil

obtained at temperature of 33°C reduced to 3.8 mg of KOH/g of oil when temperature was

increased from 33 to 38°C. However, with a further increase in temperature, there is no

further reduction in the acid value. Thus, optimal temperature as 38°C can be established for

the case of conventional approach and was considered for further studies. Increasing the

temperature initially is apparently favorable for the acceleration of the forward reaction and

also affects the mass transfer in the reaction mixture giving the desired increase in the

reduction in the acid value [19]. Gole et al. [13] reported similar trends for the effect of

temperature on reduction in the acid value. It was reported that final acid value decreases to

1.4 mg of KOH/g of oil with an increase in temperature from 40 to 600C and any further

increase in temperature does not yield additional benefits.

3.1.3 Effect of catalyst concentration

The effect of catalyst loading was varied over the range of 1 % to 4 % (by weight of oil) at an

optimum molar ratio of oil to methanol as 1:6 and constant temperature of 38.0C. The

obtained results for effect of catalyst loading on the reduction in the acid value using

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

observed that at the optimum catalyst loading of 2% by weight of oil, acid value decreases

from 14.15 to 3.8 mg of KOH/g of oil in 50 min of reaction time. The initial increase in the

extent of acid value reduction for an increase in the catalyst loading from 1 wt% (final acid

value was 4.5 mg of KOH/g of oil) to 2 wt% (final acid value was 3.8 mg of KOH/g of oil) is
 12

attributed to the increase in the total number of available active catalytic sites (acidic

hydroxyl groups) for the reaction. Beyond the optimum loading of 2 wt%, not much

favorable results were obtained due to the use of enhanced catalyst loading. Also, it has been

observed from the figure that at the beginning of the reaction, acid value rapidly reduced

from 14.15 mg of KOH/g of oil to 5.7 mg of KOH/g of oil at the optimum loading which

indicates that the rate of forward reaction rate was dominant initially due to availability of

optimum catalytic active sites. Subsequently the reverse reaction rate increased and also the

presence of water formed in the reactions acts negatively on the catalytic sites and hence

there was a slow reduction in the acid value.

Similar trends for existence of optimum concentration have been reported in the literature.

For the Jatropha oil as the feed stock the optimum catalyst loading was 1% resulting in

reduction in the acid value from 15 mg of KOH/g to 1 mg of KOH/g, however, for the case of

waste restaurant oil, the optimum catalyst loading was 1.5% [20]. Gole et al. [13]

investigated the effect of sulphuric acid catalyst concentration over the range of 0.5 to 1.5

wt% of oil at optimum conditions of molar ratio and reaction temperature. It was reported

that 1% catalyst loading was the optimum giving the reduction in the acid value to 0.5 mg of

KOH/g of oil. Shu et al. [21] also reported similar existence of optimum catalyst loading as

0.2 wt% of oil. Again, it is important to understand that though the trends in terms of

existence of optimum loading are similar, the exact value is different and dependent on the

feed stock and hence the importance of the present work is clearly established.

3.1.4 Effect of type of catalyst

The selection of proper catalyst for an esterification reaction is important in deciding the

efficacy of the reaction as well as the downstream processing steps. Various catalysts such as

sulfuric acid, hydrochloric acid etc. are the reported homogenous acid catalysts while
 13

amberlyst-15, Nefion, zeolites etc. are the heterogeneous catalysts being used for the

esterification reaction. Generally for the esterification of sustainable raw materials containing

higher values of initial free fatty acids, base catalysts are not recommended due to the

problems associated with formation of soap. Thus, in the present study, only acid catalysts

were used to understand the effect of type of catalyst on the progress of the esterification

reaction. The objective of using solid acid catalyst was to check the effectiveness in the

reaction as the heterogeneous nature offers ease of separation from the reaction mixture

which can significantly reduce the number of processing steps and also the filtered catalyst

can be recycled for reuse which reduces the cost of catalyst. In the present work, strong acidic

anion-exchange resins as Amberlyst 15 was used as a solid acid catalyst. Experiments were

performed by varying the catalyst loading from 0.5 wt% to 3.0 wt% of oil at optimum molar

ratio of oil to methanol 1:6 and temperature of the reaction was maintained at constant 38 0C.

The obtained results for the effect of catalyst loading on the reduction in the acid value have

been depicted in the Figure 6. From the figure, it has been observed that with an increase in

the catalyst loading, extent of reduction in the acid value also increases dominantly till a

catalyst loading of 1 wt% of oil. With further increase in the catalyst loading, extent of

reduction in the acid value decreases attributed to the higher catalytic activity on the basis of

concentration of acidic sites available for the esterification of FFA [22]. The final acid value

using solid catalyst as obtained in the present work wa6s 4 mg of KOH/g of oil which is

almost similar as compared to the liquid acid catalyst where final acid value was also 4.2 mg

of KOH/g of oil.

3.2 Ultrasound assisted approach:

3.2.1 Effect of molar ratio

 14

The molar ratio is one of the important parameters to study the esterification reaction as the

excess methanol is useful in dissolving the water formed during esterification reaction which

avoids the hydrolysis of triglyceride. Thus, to study the effect of excess methanol on progress

of reaction in the case of ultrasound assisted approach, esterification of karanja oil was

performed using 1:3, 1:4, 1:5 and 1:6 molar ratios of oil to methanol with 2% of sulfuric acid

at a constant temperature of 34 oC and the obtained results have been depicted in the Figure 7.

From the figure, it has been observed that the maximum reduction in the acid value of oil

with final acid value as 2.7 mg of KOH/g of oil was obtained at 1:5 molar ratio of oil to

methanol with 2% catalyst loading. The obtained trends in the figure are quite similar to the

trend obtained in conventional approach except for the required reaction time and the extent

of reduction in the acid value as well as the optimum molar ratio. With an increase in the

molar ratio of oil to methanol, the final acid value of oil also reduced up to the optimum and

then there was no significant change in the acid value of oil with a further increase in the

molar ratio. It was also observed that the time required for reaching the equilibrium acid

value was also lower which can be attributed to the fact that ultrasound creates conditions of

locally higher temperature and pressures as well as generation of fine emulsion in the reactor

and hence intensification benefits are obtained. Cavitation effects in terms of local hot spots

generated simultaneously throughout the reactor and acoustic streaming helps in elimination

of the mass transfer effects as well as better emulsion characteristics between the oil and

methanol phase resulting in higher interfacial area of contact between the two phases of the

methanol and triglyceride molecule in turn giving higher rate of esterification. Gole et al. [13]

studied the effect of molar ratio of oil to methanol over the range of 1:2 to 1:6 using

ultrasound based approach and reported that the molar ratio of 1:2 was the optimum as it

sufficiently reduced the acid value at 2% H2SO4 in only 15 min of reaction time. Gole et al.

[14] studied the intensification of synthesis of biodiesel from nonedible oil using sequential
 15

combination of microwave and ultrasound. It was reported that during esterification reaction,

optimum molar ratio of oil to methanol as 1:3 and reaction time of 60 min was sufficient to

reduce the acid value to the required one for carrying out the transesterification reaction using

the ultrasound approach. The trends regarding the effect of molar ratio were similar to the

conventional approach though the optimum molar ratio was lower in the case of ultrasound

assisted approach.

3.2.2 Effect of catalyst loading

Effect of catalyst loading on the reduction in acid value has been also investigated for the

ultrasound assisted approach performed using the sonochemical reactor with capacity of 4 L.

The reactions were performed at optimum conditions of molar ratio of oil to methanol as 1:5

and with varying catalyst loading over the range of 1% to 4% by weight of oil. The obtained

results for the effect of catalyst loading on reduction in acid value have been depicted in the

Figure 8. Form the figure, it has been observed that with an increase in the catalyst loading,

the reduction in the acid value was maximum till the catalyst loading of 2% and then

suddenly, a decrease in the final acid value was observed with an increasing amount of

catalyst loading. It has been also observed that using acoustic cavitation, maximum reduction

in the acid value of oil obtained was with final acid value of 2.7 mg of KOH/ g of oil at 2% of

catalyst loading. The observed results are consistent with the reports of Kelkar et al. [15]

where it was reported that for esterification of fatty acid cuts, the required optimum loading

was 2%. Another report dealing with esterification of palm fatty acid distillate established the

optimum as 5% catalyst concentration [23] using the ultrasound assisted approach.

3.3 Hydrodynamic cavitation assisted approach:

 16

3.3.1 Effect of molar ratio

The effect of molar ratio of oil to methanol has also been investigated for the case of

hydrodynamic cavitation assisted approach over the range of 1:3 to 1:6 with constant catalyst

loading of 2% under ambient conditions. The slit venturi was used as a cavitating device and

a constant inlet pressure of 3 bar was used for the hydrodynamic cavitation reactor. The

obtained results have been depicted in the Figure 9. From the figure, it has been observed that

as the molar ratio of oil to methanol increases from 1:3 to 1:5, the final acid value of the oil

obtained reduces from 6.9 mg of KOH/ g of oil to 4.2 mg of KOH/g of oil. However, with a

further increase in molar ratio, there is no significant reduction in acid value of oil consistent

with the observed trends for the ultrasound assisted and the conventional approach. The

maximum reduction in the acid value as 4.2 mg of KOH/g of oil was obtained for the molar

ratio of 1:5 and this optimum molar ratio of oil to methanol was used for further experimental

studies. It is important to maintain the forward path of reaction and to dissolve the water

formed during esterification, which is generally achieved using excess molar ratio giving

sufficient reduction in the acid value. The lower reduction in the acid value with increase in

the molar ratio of oil to methanol beyond the optimum was explained on the basis of the fact

that the dilution of the acid catalyst with the water formed in the reaction reduces its catalytic

activity. Similar results have been reported for the case of hydrodynamic cavitation though

the value of optimum molar ratio is typically different. Gole et al. [3] studied the effect of

molar ratio of Nagchampa oil to methanol over the range of 1:2 to 1:5 with 2% (wt) sulfuric

acid using hydrodynamic cavitation consisting of orifice plate. It was reported that 1:3 molar

ratio and 60 min of reaction time reduced the acid value from 18.4 to 3.6 mg of KOH/g of oil.

Kelkar et al. [15] also reported the similar trends for the effect of molar ratio of oil to

methanol using hydrodynamic cavitation. It was reported that 92% conversion was obtained

at 1:10 molar ratio of FA cut to methanol in 90 min of reaction time. It was also established
 17

that hydrodynamic cavitation is more favorable in terms of scale up aspects due to less

energy intensive operation per mole of product. The application of process intensification

approach can reduce the excess requirement of methanol which in turn can reduce the energy

requirement for downstream processing including separation of methanol, making the overall

process as cost intensive.

3.3.2 Effect of catalyst loading

It is always important to optimize the catalyst loading as any unnecessary amount adds to the

separation loads and also can create corrosion issues in the process. Experiments were

performed to study the effect of catalyst loading on acid value reduction using hydrodynamic

cavitation over the range of 1 to 4% and the obtained results for the effect of catalyst loading

optimal conditions of molar ratio as 1:5 are presented in the Figure 10. It can be seen from

the figure that with an increase in the amount of catalyst loading, the final acid value reduced

from 6.5 mg of KOH/ g of oil for 1% loading to 4.2 mg of KOH/ g of oil for the case of

catalyst loading as 2%. However, with a further increase in the catalyst loading to 4%, the

reduction in acid value of oil was reduced with the final acid value as 4.7 mg of KOH/ g of

oil. Thus, catalyst loading of 2% was found to be optimum loading for the reduction in the

acid value of oil similar to the conventional approach as discussed earlier. Gole et al. [3]

investigated the effect of loading of sulphuric acid over the range 0.5 to 3 wt% of oil and

optimum existence of catalyst loading as 1% with maximum reduction in the acid value to 3.7

mg of KOH/g of oil.

3.3.3 Effect of type of catalyst

To understand the effect of using homogenous and heterogeneous acid catalyst in the case of

hydrodynamic cavitation, experiments were also performed with amberlyst 15 catalyst at

optimum molar ratio of 1:5 and at different loadings over the range of 0.5 % to 3%. The
 18

obtained results have been given in Figure 11 and it has been observed that the solid acid

catalyst was more beneficial than the homogenous acid catalyst for the esterification reaction

of karanja oil using hydrodynamic cavitation under equivalent catalyst loadings. The

maximum reduction in the acid value of oil was obtained with final value being 4 mg of

KOH/ g of oil in 60 min of reaction time at 1% of catalyst loading, which was lower than that

obtained for the sulfuric acid catalyst. The trend in the reduction in the acid value of oil for

the case of solid acid catalyst with an increase in the amount of catalyst loading was similar

with optimum loading as 1%. Lower optimum loading and catalyst requirement for the case

of acid catalyst can be attributed to the surface cavitation effects due to the presence of

heterogeneous catalyst which enhances the cavitational activity and hence the rates of

reaction. From the figure, it has been also observed that the acid value reduction reached

equilibrium in 60 min only, with any further increase in the reaction time not giving any

reduction in the acid value which may be attributed to the inhibition of the amberlyst 15 due

to the water formed in the progress of esterification reaction [24].

3.3.4 Two stage esterification

In the first stage of esterification, it was observed that the acid value reduces to 4.2 mg of

KOH/ g of oil at molar ratio of 1:5, catalyst loading of 2% and 3 bar as the operating inlet

pressure. For transesterification reaction, the minimum acid value should be less than 2 mg of

KOH/g of oil. For better reduction in the acid value, additional processing was considered in

terms of second stage of esterification again in the presence of hydrodynamic cavitation and

experiments were performed using esterified oil from the first stage of esterification as a raw

material for the second stage. The optimum operating conditions such as molar ratio of 1:5

and 2% catalyst loading were used for second stage of esterification reaction. It was observed

that the reduction in the acid value was only marginal with the final value being 3.8 mg of

KOH/g of oil indicating that hydrodynamic cavitation is not able to reduce the final acid
 19

value to the desired levels. While the two step approach have been reported successful in the

literature, the results obtained in the present work may be attributed to the type of sustainable

source used in the work and the initial free fatty acid content. Gole et al. [3] reported that first

stage of esterification reduced the acid value to only 3.7 mg of KOH/g of oil but after second

stage of esterification at 1.1 molar ratio of oil to methanol with catalyst loading of 1%, final

acid value reduced to 1.6 mg of KOH/g of oil in 60 min of reaction time in the second stage.

Zhang et al. [25] showed that the esterification of waste cooking oil using a two step method

was effective giving 97% reduction at a molar ratio of methanol to oil 10:1. Gerpen et al. [26]

also reported that acid value reduced to less than 1% with a two step acid catalyzed

esterification reaction. It was also reported that the acid level of high free fatty acid feedstock

containing 20 and 40% FFAs reduced to only 12% FFAs for yellow grease and only 33% for

brown grease, respectively. Thus it can be established that the initial free fatty acid content

and the type of sustainable feed stock as well as the processing approach plays a key role in

deciding whether the desired reduction in the acid value can be obtained.

4. Kinetic analysis:

The reaction considered in the present work for reduction in the acid value is a typical

esterification reaction of fatty acid and methanol in the presence of an acid catalyst producing

triglyceride and water. Kinetic analysis has been perfumed by considering second order

kinetics for esterification to determine rate constants for the different approaches used in the

work. A typical second order kinetic equation can be written as follows [27]:

[]
− = [!]" (2)


Integrating equation 2, we get

 20

# #
− = (4)
[] []$

Where

[A] = Concentration of free fatty acid, moles lit-1

[A] 0 = Initial concentration of free fatty acid, moles lit-1

k = Second order rate constant, lit mole-1 min-1

The obtained kinetic rate constants for the different approaches used in the work as

ultrasound assisted, hydrodynamic cavitation assisted and conventional approach have been

given in Table 2. It has been observed that kinetic rate constant increased with an increase in

the molar ratio of oil to methanol from 1:3 to 1:5 for the case of hydrodynamic cavitation.

Similar trends were also observed for the ultrasound assisted and conventional approaches.

The kinetic rate constant for optimal molar ratio of oil to methanol of 1:5 was 0.15 × 10-3 lit

mole-1 min-1 using hydrodynamic cavitation assisted approach whereas the value of rate

constant for the ultrasound assisted approach was 0.31 × 10-3 lit mole-1 min-1 for same molar

ratio. The higher reaction rate constants for esterification obtained in the case of ultrasound

assisted approach can be attributed to the more intense cavitational effects observed in the

ultrasonic reactors which increase the levels of turbulence and mixing generated in the

reactor giving better efficacy for the generation of microemulsion between heterogeneous oil

and methanol phases taking part in the reaction [14].

The obtained values for the kinetic rate constant under different catalyst loadings for the

ultrasound assisted, hydrodynamic cavitation assisted and conventional approaches also

confirmed the observed trends of increase till an optimum catalyst loading both for the

homogeneous and the heterogeneous catalysts. In the case of hydrodynamic cavitation, at

 21

optimum amberlyst loading of 1% by weight, the kinetic rate constant was 0.231 × 10-3 lit

mole-1 min-1 whereas the value of kinetic constant for conventional approach was 0.2319 ×

10-3 lit mole-1 min-1 at similar catalyst loading.

5. Comparison of conventional approach with cavitation assisted approaches

Comparison of the obtained results for the esterification reaction using conventional,

ultrasound and hydrodynamic cavitation assisted approaches has been established in terms of

the effect of molar ratio, catalyst concentration, temperature, type of catalyst and kinetic rate

constants.

1. The molar ratio used in the reaction affects the reduction in the acid value

significantly for all the approaches and it was established that with an increase in molar ratio

of oil to methanol, acid value reduction also increased till an optimum value and then further

increase in molar ratio of oil to methanol resulted in no significant change in acid value of oil.

It was established that optimum molar ratio was lower in the case of both ultrasound assisted

as well as hydrodynamic cavitation assisted approaches as compared to the conventional

approach attributed to the beneficial cavitational effects in terms of the acoustic streaming

and formation of fine emulsions. The higher conversion obtained due to the use of ultrasonic

irradiations is attributed to the physical effects of the cavitation phenomena. It is important to

note here that only the physical effects in terms of intense turbulence and microstreaming

generated during the cavitation plays a dominating role in intensification [27]

2. Similar to the effect of molar ratio, effect of catalyst concentration on reduction in the

acid value using conventional, ultrasound and hydrodynamic cavitation has been clearly

established. It was observed that maximum reduction in the acid value as 2.7 mg of KOH/ g

of oil at 2% of catalyst loading was obtained using ultrasound assisted approach, which was
 22

about 50% lower than the value obtained using the conventional approach where the

reduction in the acid value was 4.1 mg of KOH/g of oil with same catalyst loading.

3. Ultrasound assisted approach was thus established to be efficient over hydrodynamic

and conventional approaches attributed to the higher cavitational intensity obtained due to the

use of ultrasound. Appendix I give detailed calculations of energy requirement for both

conventional and ultrasound assisted approach. The energy requirement for conventional and

ultrasound assisted approach for unit reduction in the acid value was found to be 82.4 kJ/mg

and 56.6 kJ/mg, respectively, confirming the superiority of the ultrasound assisted approach.

The required time to obtain reduction in the acid value using conventional approach is 50 min

whereas ultrasound assisted approach requires 40 min only. It was reported in several studies

that energy required per unit product formation or per unit reactant conversion for acoustic

cavitation was lower than the conventional approach. Also, in the conventional approach,

most of the energy is required for preheating of oil, however, for the ultrasound assisted

approach no such preheating is required giving favorable results for energy requirement.

4. Amberlyst-15 was found to be more effective for achieving desired reduction in acid

value using hydrodynamic cavitation as compared to the conventional approaches.

Hydrodynamic cavitation reduced acid value to 4 gm of KOH/g of oil, however, in the case

of conventional, acid value reduced only to 4.5 gm of KOH/g of oil in the case of

heterogeneous catalyst. In the case of longitudinal horn, amberlyst was not used due to the

mixing issues and the catalyst was observed to settle down at the bottom possibly attributed

to the ultrasound induced vibrations. The use of solid catalyst need to be investigated even for

the ultrasonic reactor, perhaps using a different reactor configuration where settling will not

be major contributing factor.

5. Conclusions
 23

Intensification of esterification of karanja oil as sustainable feedstock using cavitational

reactors has been established in the present work based on the comparison with the

conventional approach. Karanja oil with initial acid value as 14.15 mg of KOH/ g of oil was

successfully processed with reduction in the acid value to 2.7 mg of KOH/ g of oil using

ultrasound assisted approach at optimum molar ratio of oil to methanol as 1:5 and 2% sulfuric

acid loading at ambient temperature. The obtained results for the effect of molar ratio and

catalyst loading on reduction in acid value established the existence of optimum value which

was dependent on the type of processing approach as well as the feed stock highlighting the

necessity of the study. Overall, it has been observed that the optimum molar ratio of oil to

methanol as 1:5 for both hydrodynamic cavitation (final acid value of 4.2 mg of KOH/ g of

oil) and acoustic cavitation (final acid value of 2.7 mg of KOH/ g of oil) was lower as

compared to the conventional approach (final acid value as 4.1 mg of KOH/ g of oil), where

the optimum was 1:6. In the case of catalyst loading, all the optimum values were 2% catalyst

loading in the case of sulfuric acid with maximum reduction in the acid value for the

ultrasound assisted approach. It has been also established that solid acid catalyst can be

successfully used as a substitute for sulfuric acid to overcome the difficulties like separation

and production of toxic wastewater. Amberlyst-15 was found to be promising in the case of

hydrodynamic cavitation assisted approach though it was not very effective in the case of

conventional approach. Overall, it can be established that ultrasound assisted approach was

the best synthesis approach with proven efficacy at 4 L operation and lower energy

requirement as compared to the conventional approach.

Acknowledgement:

All the authors would like to acknowledge the support of Department of Science and

Technology, India, and National Council of Scientific and Technological Development

 24

(CNPq), Brazil (grant number 400966/2013-1), under the India–Brazil Inter-Governmental

Program of Cooperation in Science and Technology entitled “Intensification of biodiesel

synthesis from sustainable raw materials using cavitational reactors”. One of the authors AS

would also like to acknowledge the funding for summer research fellowship under the TEQIP

program of World Bank.

Appendix I

i. Energy Requirement for conventional method

Total energy requirement = Energy for stirring + Energy for heating

Energy for stirring = power required for stirring × time in sec

= 120 × 50× 60

= 360 × 103 J

Energy for heating = mcp∆T

= 4 × 4.18 × 10 3 × (48-30)

= 468.1 × 103 J

Total Energy = 828.1 × 10 3 J

Assuming basis as 1 g of oil, the net reduction in the acid value under these

optimum conditions = 10.05 mg

Energy required for unit reduction = total energy required/ net reduction

= 828.1 × 103/ 10.05

= 82.4 kJ/mg

ii. Energy Requirement for ultrasound method

Total energy requirement = Energy for stirring + Energy for equipment

Energy for stirring = power required for stirring × time in sec

= 120 × 40 × 60
 25

= 288× 103 J

Energy for equipment = ultrasonic power × time in sec

= 150 × 40 × 60

= 360 × 10 3 J

Total Energy = 648.0 × 10 3 J

Assuming basis as 1 g of oil, the net reduction in the acid value under these

optimum conditions = 11.45 mg

Energy required for unit reduction = total energy required/ net reduction

= 648.0 × 10 3/ 11.45

= 56.6 kJ/mg

References

[1] M. Mittelbach, Diesel fuel derived from vegetable oils, VI: specifications and quality

control of biodiesel, Biores. Tech., 56 (1996) 7-11

[2] V.L. Gole, P.R. Gogate, A review on intensification of synthesis of biodiesel

from sustainable feed stock using sonochemical reactors- Chem. Eng.

Proces., 53 (2012) 1– 9

[3] V. L. Gole, K. R. Naveen, P R Gogate, Hydrodynamic cavitation as an efficient approach

for intensification of synthesis of methyl esters from sustainable feedstock, Chemi. Engg

Proces., 71(2013)70-76

[4]P.R.Gogate, R.K. Tayal, A.B.Pandit, Cavitation: A technology on the horizon, Current

Science, 91(2006)35-46

[5] V S Moholkar, P Senthilkumar A B Pandit, Hydrodynamic cavitation for sonochemical

effects, Ultras. Sono 6 (1999)53-65

[6]V. R. Mamilla, M. V. mallikarjun, G. L. Narayana Rao, Preparation of biodiesel from

karanja oil, International Jour. of Energy Engg. 2(2011)94-100

 26

[7]M. Chai , Q. Tu , M. Lu, Y. J. Yang, Esterification pretreatment of free fatty

acid in biodiesel production, Fuel Proces. Tech., 125 (2014) 106–113,

[8]S. M. Dubey, V. L. Gole, P.R.Gogate, Cavitation assisted synthesis of fatty

acid methyl esters from sustainable feedstock in presence of heterogeneous catalyst

using two step process, Ultra. Sono., 23(2015)165-173

[9]M. S. Khayoon, M. A. Olutoye, B. H. Hameed, Utilization of crude karanja oil as a

potential feedstock for the synthesis of fatty acid methyl esters. Biore.Tech., 111(2012)175-

179

[10] K. V. Thiruvengadaravi, J. Nandagopal, P. Baskaralingam, V. S. S. Bala, S. Sivanesan,

Acid catalyzed esterification of karanja oil with high free fatty acids for biodiesel production,

Fuel 98(2012)1-4

[11] R. Alam, R K. Patel, Thesis on studies on the properties of karanja oil for probable

industrial application, Department of chemistry, NIT, Rourkela, India. (2002)1-29

[12] M. Naik, L. C. Meher, S. N. Naik, L. M. Das, production of biodiesel from high free

fatty acid karanja oil, Biom. and Bioene., 32(2008)354-357

[13] V. L. Gole, P. R. Gogate, Intensification synthesis of biodiesel from nonedible oils using

sonochemical reactors, Indus. Engg Chem. Res., 51(2012)11866-11874

[14] V. L. Gole, P. R. Gogate, intensification of synthesis of biodiesel from nonedible oil

using sequential combination of microwave and ultrasound, Fuel process. Tech.,

106(2013)62-69

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

synthesis of biodiesel using acoustic and hydrodynamic cavitation. Ultrason. Sonochem.,

15(2008)188-194

[16] Y.C. Sharma, B. Sing, An ideal feedstock, kusum (Schleichera triguga) for preparation

of biodiesel: optimization of parameters, Fuel, 89(2010)1470–1474.

 27

[17] G. Corro, N. Tellez, F. Banuelos, M. E. Mendoza, Biodiesel from Jatropha curcas oil

using Zn for esterification step and solar radiation as energy source, fuel, 97(2012)72-79

[18] V. L. Gole, P. R. Gogate, Intensification synthesis of biodiesel from nonedible oils using

sonochemical reactors, Indus. Engg Chem. Res., 51(2012)11866-11874

[19] J. Ding, Z. Xia, J. Lu, Esterification and deacidification of a waste cooking oil (TAN

68.81 mg KOH/g) for biodiesel production, Energies, 5 (2012) 2683–2691

[20] H. J. Berchmans, S. Hirata, Biodiesel production from crude Jatropha curcas L. seed oil

with a high content of free fatty acids, Bioresour. Technol., 99(2008)1716-1721

[21] Q. Shu, J. Gao, Z. Nawaz, Y. Liao, D. Wang, J. Wang, Synthesis of biodiesel from waste

vegetable oil with large amounts of free fatty acids using a carbon-based solid acid catalyst,

Appl. Energy. 87 (2010) 2589–2596.

[22] J. Park, D. Kim, J. Lee, Bioresource Technology Esterification of free fatty acids using

water-tolerable Amberlyst as a heterogeneous catalyst, Bioresour. Technol., 101 (2010) S62–

S65.

[23] V.G. Deshmane, P.R. Gogate, A.B. Pandit, Ultrasound assisted synthesis of isopropyl

esters from palm fatty acid distillate. Ultrason. Sonochem., 16(2009)345-350

[24] M. Rat, M.H. Zahedi-Noaki, S. Kaloaguine, S., T.O. Do, Sulfonic acid functionalized

periodic mesoporous organosilicas as acetalization catalysts, Micro. and Macro. Mate.,

112(2008)26–31

[25]Y.Zhang, M.A. Dube, M.A. McLean, Biodiesel production from waste cooking oil: 1.

Process design and technological assessment, Bioresour Technol., 86(2003)1–16

[26] M. Canakei, J. V. Gerpen, A pilot plant to produce biodiesel from high free fatty acid

feed stocks, ASAE paper No 01-6049, ASAE, St Joseph, MI, USA (1999)
 28

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

containing sustainable feedstock using microwave irradiation, Fuel Proces. Tech.,

118(2014)110-116

[28]G L Maddikeru, A B Pandit, P R Gogate, Ultrasound assisted interesterification of waste

cooking oil and methyl acetate for biodiesel and triacetin production, fuel processing

technology, 116 (2013)241-249.

 29

List of figures

Figure 1: Schematic representation of ultrasonic bath equipped with longitudinally vibrating

horn (plan view).

Figure 2: Schematic representation of hydrodynamic cavitation reactor and slit venturi

Figure 3: Effect of molar ratio on reduction in acid value using conventional approach

(Catalyst loading of 2 wt% of oil; temperature of 33 0C)

Figure 4: Effect of temperature on reduction in acid value using conventional approach

(Catalyst loading of 2 wt% of oil; molar ratio of oil to methanol as 1:6)

Figure 5: Effect of catalyst (sulfuric acid) loading on reduction in acid value using

conventional approach (Molar ratio of oil to methanol as 1:6; temperature of 38 0C)

Figure 6: Effect of Amberlyst-15 catalyst on reduction in acid value using conventional

approach (molar ratio of oil to methanol as 1:6; temperature of 380C)

Figure 7: Effect of molar ratio on reduction in acid value using acoustic cavitation approach

(Catalyst loading of 2 wt% of oil; 30 KHz)

Figure 8: Effect of catalyst (sulfuric acid) loading on reduction in acid value using acoustic

cavitation approach (Molar ratio of oil to methanol as 1:5; 36 KHz)

Figure 9: Effect of molar ratio on reduction in acid value using hydrodynamic cavitation

approach (Catalyst loading 2 wt % of oil; pressure 3 bars)

Figure 10: Effect of catalyst (sulfuric acid) loading on reduction in acid value using

hydrodynamic cavitation approach (Molar ratio of oil to methanol as 1:5; pressure 3 bars)

Figure 11: Effect of Amberlyst-15 catalyst loading on reduction in acid value using

hydrodynamic cavitation approach (Molar ratio of oil to methanol as 1:5; pressure 3 bars)
 30

Figures

Figure 1: Schematic representation of ultrasonic bath equipped with longitudinally

vibrating horn (plan view).

Figure 2: Schematic representation of hydrodynamic cavitation reactor and slit venturi

 31

16

14
1:04 1:05 1:06 1:07
Acid value, (mg of KOH/g of Oil)

12

10

0
0 10 20 30 40 50 60 70
Reaction TIme, min

Figure 3: Effect of molar ratio on reduction in acid value using conventional approach
(Catalyst loading of 2 wt% of oil; temperature of 33 0C)

16

14 33 C 38 C
Acid Value, (mg of KOH/g of Oil)

12 43 C 48 C

10

0
0 10 20 30 40 50 60 70 80
Reaction Time, min

Figure 4: Effect of temperature on reduction in acid value using conventional approach

(Catalyst loading of 2 wt% of oil; molar ratio of oil to methanol as 1:6)
 32

16

14 1% 2%
Acid Value, (mg of KOH/g of Oil)

12 3% 4%

10

0
0 10 20 30 40 50 60
Reaction Time, min

Figure 5: Effect of catalyst (sulfuric acid) loading on reduction in acid value using

conventional approach (Molar ratio of oil to methanol as 1:6; temperature of 380C)

 33

16

Acid Value, ()mg of KOH/g of Oil

14 0.5 1.0

12 2.0 3.0

10

0
0 10 20 30 40 50 60 70
Reaction Time, min

Figure 6: Effect of Amberlyst-15 catalyst on reduction in acid value using conventional

approach (molar ratio of oil to methanol as 1:6; temperature of 380C)

 34

16

Acid Value, (mg of KOH/g of Oil) 14 1:03 1:04

12 1:05 1:06

10

0
0 20 40 60 80 100
Reaction Time, min

Figure 7: Effect of molar ratio on reduction in acid value using acoustic cavitation

approach (Catalyst loading of 2 wt% of oil; 30 KHz)

 35

16

14 1% 2%
Acid Value, (mg of KOH/ g of Oil)

12 3% 4%

10

0
0 10 20 30 40 50 60 70 80
Reaction Time, min

Figure 8: Effect of catalyst (sulfuric acid) loading on reduction in acid value using

acoustic cavitation approach (Molar ratio of oil to methanol as 1:5; 36 KHz)

 36

16

Acid Value, (mg of KOH/g of Oil) 14 1:03 1:04

12 1:05 1:06

10

0
0 20 40 60 80 100
Reaction Time, min

Figure 9: Effect of molar ratio on reduction in acid value using hydrodynamic

cavitation approach (Catalyst loading 2 wt % of oil; pressure 3 bars)

 37

16

14 1% 2%
Acid Value, (mg of KOH/g of Oil)

12 3% 4%

10

0
0 20 40 60 80 100
Reaction Time, min

Figure 10: Effect of catalyst (sulfuric acid) loading on reduction in acid value using

hydrodynamic cavitation approach (Molar ratio of oil to methanol as 1:5; pressure 3

bars)
 38

16

14 0.5 1.0
Acid Value, (mg of KOH/ g of Oil)
12 2.0 3.0

10

0
0 10 20 30 40 50 60 70 80
Reaction Time, min

Figure 11: Effect of Amberlyst-15 catalyst loading on reduction in acid value using

hydrodynamic cavitation approach (Molar ratio of oil to methanol as 1:5; pressure 3

bars)
 39

List of Tables:

Table 1: Dimensions of cavitating device as slit venturi

Table 2: Kinetic rate constants for different approaches based on hydrodynamic

cavitation, ultrasound assisted and conventional approach

 40

Tables:

Table 1: Dimensions of cavitating device as slit venturi

Dimension Slit Venturi

Dimension of throat W = 3.7 mm

H = 0.92 mm

L = 0.92 mm

Venturi Length 86 mm

Length of convergent section 18 mm

Length of divergent section 65 mm

Half angle of convergent 22.6 o

section

Half angle of divergent section 6.5 o

α(perimeter/area) 2.71 mm-1

 41

Table 2: Kinetic rate constants for different approaches based on hydrodynamic

cavitation, ultrasound assisted and conventional approach

Sr. Parameter Range Rate Constant

No. × 10-3(lit/mole. min)
Hydrodynamic Cavitation
1 Effect of molar ratio 1:3 0.074
1:4 0.081
1:5 0.1525
1:6 0.1392
2 Effect of catalyst 1 0.0701
loading (Sulfuric acid) 2 0.2193
3 0.1962
4 0.072
3 Effect of catalyst 0.5 0.1718
loading (Amberlyst 15) 1 0.2310
2 0.2350
3 0.1701
Longitudinal Horn (Acoustic Cavitation)
1 Effect of Molar Ratio 1:3 0.2036
1:4 0.2746
1:5 0.3118
1:6 0.2284
2 Effect of catalyst 1 0.2535
loading (Sulfuric acid) 2 0.2751
3 0.4008
4 0.2782
 42

Conventional Approach
1 Effect of molar ratio 1:4 0.2051
1:5 0.2202
1:6 0.3441
1:7 0.2978
2 Effect of catalyst 1 0.307
loading (Sulfuric acid) 2 0.2623
3 0.2183
4 0.2615
3 Effect of Temperature 33 0.2551
38 0.3027
43 0.2639
48 0.2409
4 Effect of catalyst 0.5 0.1031
loading (Amberlyst 15) 1 0.2319
2 0.1962
3 0.1105
 43

Research Highlights:

• First study to report karanja oil as the sustainable feedstock for cavitationally assisted
esterification

• Comparison of Intensification of esterification using ultrasound and hydrodynamic

cavitation

• Detailed investigation into effect of operating parameters

• Ultrasonic reactor gives higher degree of acid value reduction as compared to all other
approaches

• Demonstrated effectiveness for the heterogeneous catalysts