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Process intensification is defined as the strategies which are applied to make the
conventional operations of chemical engineering more intensified. By intensified, it means the
reduction in the processing cost, energy required, equipment size or the reduction in the steps
which are carried out for the final production of the products. The physical changes applied to any
existing technology like changing the equipment geometry or replacing any huge equipment with
smaller one which can produce the same result, are considered under process intensification. Any
change carried out by changing the chemistry of the process or changing the operating conditions
like catalyst cannot be considered as the process intensification although it may have very huge
positive effect in the product formation. Process intensification has been proved to be very efficient
for carrying out chemical changes. Process has been intensified by using various energy sources
such as centrifugal field, ultrasound, solar energy, microwaves, electrical field, plasma technology.
Out of all these, cavitation phenomenon found to be very promising technology for intensifying
the process.

When the pressure inside the liquid suddenly changes and become low than the vapor
pressure of the liquid then there is formation of cavities inside liquid. Cavities are formed in the
form of bubbles, which grow and collapse due to this large amount of energy is released. This
phenomenon is known as cavitation. Gogate el al.[2008]
The four principle types of cavitation and their causes can be summarized as follows.

a) Acoustic cavitation: Cavitational phenomenon is caused by sudden variations in pressure,

when these pressure variations are induced by the sound waves this is known as acoustic
cavitation. Sound waves of generally 16 kHz to 100 MHz are used .

Cavitating bubbles are produced by sound waves, which induces chemical changes,
known as sonochemistry.
b) Hydrodynamic cavitation: Sudden pressure variations induced in the system by changing
the geometry of the system in the path of flowing fluid, produces cavitating bubbles which
help in carrying out chemical changes, this phenomena is known as hydrodynamic
c) Optic cavitation: Induced by photons.
d) Particle cavitation: Cavitation which is produced with the help of elementary particles.

Out of these, hydrodynamic and acoustic cavitation found to be useful. In comparison between
hydrodynamic and acoustic cavitation, hydrodynamic cavitation is found be producing more
cavitational yield as compared to acoustic cavitation. Cavitation produced by ultrasonic is found
to be more costly. Amount of cavitation in the case of acoustic cavitation is not controlled.


Cavitation has many applications in the various fields. Some of its applications are present in
the following fields.
a) Biotechnology: Cavitation phenomenon has been utilized in the field of biotechnology.
Collapse of bubbles has been used to rupture the cells to release the selective enzymes.
Rupturing of cells using cavitational process found to be energy efficient compared to
conventional method by 10%. Hydrodynamic cavitation proved to be have greater energy
efficiency comparing to acoustic cavitation.
b) Water treatment: Due to the cavitation, bubbles are collapsed in water to produce free
radicals OH and H which are oxidizing in nature. These free radicals are responsible for
destroying the waste chemicals present in water. Hydrophobic part reacts at gas/ liquid
surface and the hydrophilic part reacts in bulk portion of liquid. Apart from chemical
treatment, cavitation can be carried out for the treatment of microbial disinfection and
microbial sludge.
c) Chemical synthesis Cavitation has found to be have huge role in carrying out the chemical
changes. It is responsible for bringing changes in the rate of reaction. It makes the reaction
rate faster. Yield of chemical reaction have found to be increased by the application of
cavitation. Reactions in which there is requirement of high temperature and pressure via
conventional routs can be eradicated if there is requirement of high temperature and
pressure via conventional routs can be eradicated if these are carried out
by the cavitation. For homogenous reactions, cavitation found to be effective for reactions
which have free radicals as intermediates. Reactions which are ionic in nature
have no effect of cavitation on them. For heterogeneous reactions, both ionic and free
radical reactions can be utilized by the cavitation as the in the heterogeneous reactions
interphase mixing between the two or more different phases is very important parameter
and due to the collapse of bubbles there is intense mixing and turbulence locally which
removes this mixing constraint. With the intense mixing between different phases, rate of
reaction increases.


In the present study enhancement of two chemical reactions by hydrodynamic cavitation
reactor has been proposed. Following are the two chemical reactions:
a) Weissler reaction: This homogenous reaction in which it has solution of KI in water as
the reactant, has been utilized to test the hydrodynamic cavitation reaction reactor. Due to
the cavitation in water, bubbles are collapsed and there is production of OH and H radicals
which enhances the conversion of KI into iodine. The more is the conversion, the more is
the cavitational yield, more efficient is the setup.
b) Transesterification: Simple trans esterification is used to produce biodiesel by the simple
reaction between the vegetable oil and alcohol by the use of catalyst. This is heterogeneous
reaction containing two different phases comprises of vegetable oil and methanol. Due to
collapse of cavitation bubbles intense mixing and turbulence occurs which results in
mixing of two immiscible phases. These collapsing of bubbles occur at millions of location
inside the cavitation reactor due to this, these specific locations experience high pressure
and temperature with other locations at ambient conditions. Thus the chemical reactions
which require very rigorous conditions can be carried out in the cavitation reactor with
surrounding ambient conditions. Free radicals are formed from dissociation of vapor which
is trapped inside the cavitating bubbles. These free radicals are responsible for the
intensification of a chemical reaction. Cavitation results in local turbulence, which
increases the rates of mass transport between the immiscible reactants and hence eliminates
the major constraint in multiphase reaction. This cavitational setup can be utilized to
eliminate the mass transfer or mixing resistance which is always present in the case of
heterogeneous reactions.

Due to increase in population and over dependency on fossil fuel for energy requirement,
the petroleum reserves are getting depleted day by day. So there is need to shift our fuel
dependency from conventional sources to some new sources which gives us energy efficiency and
environmental concerns can also be fulfilled. These new sources of energy should be sustainable
and environment friendly. Those countries which are rich in floura and fauna can easily utilize
fuels from bio-origin such as biogas, vegetable oil, alcohol. These fuels can easily take place of
conventional fuels as they are present in abundant.
India as a country depends heavily on the crude sources to meet its energy demands. As estimated
crude oil reserve will last for nearly 40 to 50 years. Among the conventional sources diesel is most
used fuel. Either in agricultural, industrial, transportation in every field diesel has come out to be
major source of energy. Due to over dependency on diesel, environmental concerns have arises.
For any alternative fuel three factors are really important. First, the sources of fuel should be easily
available and must be present in abundant quantity. Second, fuel should be environment friendly.
Third, it should be able to compete in the market economically. Among the alternative fuels
Triglyceride has emerged as a strong contender for replacement of diesel. It is environment
friendly and renewable source. Triglycerides are found mainly in vegetable oils As vegetable oil
is of bio-origin, it is present in abundant quantity. Depending on the availability and climatic
conditions different types of vegetable oils are used in different parts of world. Vegetable oils are
mainly triglycerides and very less composition of mono and di glycerides. Triglyceride molecule
in Figure 1 is ester molecule of three fatty acids and of glycerol.

Fig 1.1 Triglyceride molecule

If Vegetable oil is directly used as diesel fuel in engines it leads to many problems because
the properties of vegetable oil varies significantly from conventional diesel oil. It is more viscous
than the diesel oil so its injection time and atomization is quite different from conventional diesel
oil, also there is no proper mixing of oil and air, due to which incomplete combustion occurs and
heavy smoke releases. These problems can be overcome if we convert these triglycerides
molecules chemically into mono alkyl esters, which has quite similar properties of conventional
diesel. These mono alkyl esters are known as biodiesel.

Biodiesel is mono alkyl esters derived from the reaction between the vegetable or animal
oil containing triglycerides and alcohol, which is known as trans esterification. Biodiesel has
properties quite similar to conventional diesel and can be blended with it in any proportion. With
the help of this simple transesterification, drawbacks of simple vegetable oil containing
triglyceride can be removed. Its molecular weight reduces to approximately one-third, viscosity
reduces to one-eighth and marginal increase in its volatility. These all transformations in the
properties of vegetable oil makes it a suitable option for the replacement of conventional diesel.

In the first step triglyceride is reacted with alcohol in the presence of catalyst and converted
into di glyceride and ester molecule. Similarly in next step di glyceride is converted into mono
glyceride and in next mono glyceride in converted into glycerol and ester molecule is produced.
This ester molecule is known as Biodiesel.

Fig 1.2 Transesterification reaction


The variables which influence trans esterification reaction are:
a) Temperature of reaction

b) Alcohol to oil ratio
c) Catalyst concentration
d) Mixing
Literature has revealed that maximum yield is obtained at temperatures ranging from 60C to
80C. Temperature of the reaction is limited because of the boiling point of methanol. The boiling
point of methanol is around 65C. As the temperature of reaction goes beyond 70C, methanol
gets converted into vapor phase and vegetable oil remains in the liquid state. So, no reaction is
possible beyond 70C Barnwal et al.[2005] . It has been reported in the literature that trans
esterification requires 3moles of alcohol per mole of triglyceride to yield one mole of glycerol and
3 moles of methyl ester. These series of reactions are reversible reaction, so by Le chatelier
principle the reactant concentration should be increased or products should be removed to carry
reaction in forward direction. When the alcohol is used 100% in excess i.e. the alcohol to oil ratio
of 6:1, the rate of reaction was found to be maximum. Alcohol to oil ratio can be increased beyond
6:1 to obtain more conversion but the separation of products (Glycerol, Methyl ester) would
become difficult. For trans esterification, alkali metals are found more suitable. Sodium hydroxide,
Potassium hydroxide have been used as the catalyst, however Sodium Alkoxide is found to be
favorable as catalyst. Rate of reaction hugely depends upon the mixing of different phases of
reactants, If the reactants form immiscible phases. Vegetable oil and alcohol are immiscible to
each other, so mass transfer resistance between these two phases is major constraint in carrying
out the trans esterification reaction. To overcome these effects, many methods have been adopted.
Behzadi et al.[2009] utilized the continuous gas liquid reactor to eliminate mass transfer resistance.
Halim et al.[2009] used packed bed reactor. Singh et al.[2009] utilized the batch reactor to carry
out trans esterification reaction. In recent times, the biodiesel production is being carried out by
using the cavitation phenomena. Cavitation phenomena found to be useful for eliminating the mass
transfer resistance between the two immiscible phases.
For biodiesel production, out of four types of cavitation discussed earlier only
hydrodynamic and acoustic cavitation found to be useful as they are capable of producing desired
intensity through their bubble collapse which is suitable for carrying out any chemical change.
Both the acoustic and hydrodynamic cavitation have been utilized for carrying out trans
esterification reaction. Both have been found to be very energy efficient and giving high
conversion for the reaction than the conventional stirring method for the same duration. Hingu et

al.[2010] have reported the conversion obtained by ultrasonic cavitation and conventional stirring
method. From acoustic cavitation conversion of 89.5% was obtained and 57.5% of conversion was
obtained from stirring method which is much lower than the cavitational method. As the reactants
form immiscible phase, so the mass transfer between them is the major constraint. To remove this,
cavitational process have found to be more useful, as they provide more interfacial area because
they create micro level turbulence due to the formation of cavitational bubbles. The extent of
mixing is higher for the cavitational process compared to stirring method provided same amount
of energy is imparted to fluid. Extent of mixing can be increased in stirring method to provide the
same conversion level as obtained in cavitational process but the energy input would be much
larger compared to cavitational process.
Hydrodynamic and acoustic cavitation has also been compared. It has been reported that
percentage conversion of the trans esterification reaction using hydrodynamic cavitation is more
than the acoustic cavitation for the same duration of reaction. Gogate et al.[2008] have compared
all three, hydrodynamic cavitation, acoustic cavitation and mechanical stirring method. It has been
shown that the hydrodynamic cavitation is most energy efficient process. The energy efficiency is
40 times greater for hydrodynamic cavitation than acoustic cavitation and 160-400 times greater
than stirring method. Hydrodynamic cavitation is more efficient than the acoustic cavitation, it can
attributed to the fact that the large number of cavitational bubbles are produced and collapsed with
smaller intensity, producing small pressure pulses whereas in acoustic cavitation less number of
bubbles are produced and collapsed with high intensity producing large pressure pulses.


In this section previous work on hydrodynamic cavitation reactor and production of

biodiesel have been reviewed. Most of the work on hydrodynamic cavitating reactor has been done
by utilizing the the oxidation of potassium iodide. It is utilized to measure the cavitational yield of
cavitating reactor. Most of the work on hydrodynamic cavitation has been done by utilizing orifice
plates to produce the cavitating bubbles. Methods of biodiesel production using transesterification
reaction also have been reviewed. It been done by many methods including mechanical stirring,
packed bed reactor, but most of them have utilized the cavitation phenomena. Many of them have
worked on hydrodynamic cavitation and ultrasonic cavitation.

Kumar et al. (2000) studied aq. KI solution decomposition reaction which was
ultrasonically induced using a set up of 501 - hydrodynamic cavitation. Acoustic cavitation has
already been studied previously for this reaction. But they found the effect of using hydrodynamic
cavitation for increasing the rate of reaction by changing the device used for throttling and
operating conditions. They used orifice plate as their throttling device and found that liberation
rate of iodine has been increased three times greater than obtained by using acoustic cavitation for
same rate of power dissipation and also studied possibilities of scaling up of this process as this
process provides efficiency equal to or more than acoustic cavitation. The iodine liberation
increment was nearly linear with increase in time of reaction upto 15 minutes. The liberation of
iodine increased as there was a decrease in cavitation number but increment reached a maximum
and then again dropped.

Sivakumar et al. (2002) compared the degradation of rhodamine B (rhB) solution, a

cationic dye, using hydrodynamic cavitation and cavitation produced by ultrasound and studied
the variations and results of multiple hole plate used for orifice plate. Hydrodynamic cavitation
was found to be highly efficient in terms of energy consumption as compared to cavitation

produced by ultrasound and also degree of dye solution degradation was also found to be high.
And scale up possibilities was also found to be high for hydrodynamic cavitation.

Ambulgekar et al. (2004) compared acoustic and hydrodynamic cavitation for

heterogeneous oxidation reaction of toluene and aqueous solution of KMnO4 . They varied and
optimized various operating reaction conditions of amount of KMnO4 , ratio of toluene to aqueous
phase, time of reaction. Also optimization of cavitation parameters was also performed which
included orifice plate and discharge pressure of pump. The result of comparison was that for the
same energy consumption, the product obtained by hydrodynamic cavitation was six times more
than that of acoustic cavitation.

Ji et al. (2006) compared the power ultrasonic method and hydrodynamic cavitation
method for production of biodiesel by soyabean oil and this methanolysis reaction was catalyzed
by NaOH. Both methods were found to consume less energy and time of reaction was also
relatively shorter than prevailing mechanical stiring method as it was observed after estimating
energy consumption of power ultrasonic method, hydrodynamic cavitaion method and mechanical
stiring method. The scaling up feasibility of hydrodynamic cavitation method was also studied.

Kelkar et al. (2008) studied hydrodynamic cavitation for esterification of fatty acids in the
range of C 8 C 10 and methanol by using conc. sulphuric acid as catalyst. They optimized various
parameters of the reaction which are mole ratio of fatty acid to methanol and amount of catalyst
used for hydrodynamic as well as acoustic cavitation along with setup geometry of orifice plate
optimization. Caprylic acid and capric acid were also tested with methanol for determining effect
of the process in terms of yields and process intensification extent was quantified. The ambient
temperature and pressure were found to be adequate for reaction for giving conversion greater than
90%. Energy consumption was obtained to be relatively more efficient for hydrodynamic
cavitation than acoustic cavitation.

Behzadi and Farid (2009) developed a continuous reactor for biodiesel production from
fats and oils which operated at high reaction rate continuously. Also the separation of product from
reactant was easier than conventional processes. They used a methanol vapor filled reaction
chamber working in a countercurrent mode and heated fat/oil was sprayed into it after being
atomized which supplied product continuously. 50% to 96% conversion of feed was observed in
one cycle and 94 to 96% was observed by using sodium methoxide as 5-7g/L of methanol and at
a condition of methanol and oil flow rate of 17.2 L/h and 10L/h respectively. Also they obtained
the variation trends of reaction parameters like reaction flow rates, reaction temperature and
catalyst type/concentration with conversion of reaction.

Kawashima et al. (2009) produced biodiesel from plant oil and methanol by
transesterification and catalyst used was developed by using calcium oxide which was pretreated
by methanol which accelerated the catalytic acticvity of calcium oxide. On optimization of reaction
parameters the results obtained were as catalyst loading was 0.1g, amount of methanol was 3.9g,
rapeseed oil was 15g and activation time of 1.5h followed by reaction time of 3h and methyl ester
yield obtained was around 90%. The activation was done at room temperature and reaction was
done at 60C. The mechanism followed during activation involved the conversion of CaO into
Ca(OCH3 )2 which initiated the transesterification which further formed a calcium glycerin
complex, glycerin was obtained as a byproduct in transesterification, which acted as main catalyst
and accelerated the whole process of transesterification.

Halim et al. (2009) studied the waste cooking oil transesterification catalyzed by lipase
enzyme using a packed bed reactor and optimized the reaction parameters by using response
surface methodology (RSM). The RSM methodology was based on central composite rotable
design (CCRD). Optimization of two variables was mainly done which are substrate flow rate and
packed bed height for the transesterification process. The optimized results obtained were as
0.57ml/min of flow rate of substrate and packed bed height was 10.53cm and on this condition
yield of fatty acid methyl esters obtained was 80.3% compared to actual flow rate of 79%. They
developed the reaction control models and mass transfer control cases and experimental results
were found compatible with these models. Also they found that in this case reaction was mass
transfer controlled.

Pal et al. (2009) studied the biodiesel production from Citrullus colocyntis or Thumba oil
using hydrodynamic cavitation and compared the properties of pure diesel and blend of diesel with
biodiesel using a four cylinder, water cooled, direct injection diesel engine. The performance of
biodiesel blended diesel was relatively better as it is more eco-friendly and other performance
variation trends were obtained similar. And from industrial application point of view
hydrodynamic cavitation was found to be time saving, easy and efficient.

Supardan et al. (2012) generated a two step process of biodiesel production from waste
cooking oil in a setup of hydrodynamic cavitation. The two steps of the process are esterification
and transesterification. The esterification process step used acid catalyst to decrease the fatty acids
(free) amount from oil. The transesterification process step then used basic catalyst to final
conversion of biodiesel from waste cooking oil. The yield of biodiesel produced was quite high as
89.4% and after GC/MS it was observed to contain fatty acid methyl esters around five.

Ghayal et al. (2013) utilized the hydrodynamic cavitation for carrying out the
transesterification reaction. He utilized used frying oil and methanol to carry out the reaction the.
Potassium hydroxide was used as a catalyst. Upstream pressure and the geometry of the system
has been changed to observe the rate of reaction. Turbulence created by hydrodynamic cavitation
was proved to be efficient method to remove the resistance of mass transfer between the two
different phases of methanol and triglycerides. They have used different geometry of plates to find
the optimum geometry with which maximum conversion can be obtained. Pump discharge
pressure increment from 1 to 3 bar decreased reaction time significantly because of increasing the
velocity of fluid passing through orifice which further lead to increase in cavity collapse intensity.
Difference in the configuration of geometry did not significantly affected rate of the reaction at
higher upstream pressure. Larger the free area of the plate increased the cavitation number for the
same pressure otherwise on increment in the total perimeter of the plate led to increase in
cavitational events. The ratio obtained by dividing the holes total perimeter and total flow area had
significant effect on conversion as it increased from 77% to 94% when ratio got increased from
0.4 to 1.33 for upstream pressure of 1.5 bar and reaction time of 20 min. Also the ratio of hole
diameter present on orifice to diameter of pipe also affected the conversion in such a way that
smaller the value of ratio more will be conversion at same pressure and time as stated above.

Gole et al. (2013) used hydrodynamic cavitation and synthesized methyl esters from non-
edible oil having high acid value. The process used for synthesis is a two step process comprising
of acid esterification and then alkaline transeterification. The acid value of oil was reduces by acid
esterification from 18.7mg of oil/ g of oil to less than 1.5 mg of oil/g of oil. And reduced acid value
of oil made easier the use of alkaline transesterification step by solving the problem of soap
formation. Various reaction parameters of the two steps were optimized and obtained results were
as optimized mole ratio were 1:3 and 1:6 for the two steps respectively and in these conditions
conversion obtained was around 92% in the final step. And hydrodynamic cavitation was also
proved to be very energy efficient.
Maddikeri et al. (2014) have generated biodiesel and triacetin from waste cooking oil by
interesterification reaction using hydrodynamic cavitation reactor. They used orifice plate, circular
and slit venturi as cavitating devices and obtained high yield of biodiesel (90%) from aste cooking
oil by varying operating conditions like inlet pressure, molar ratio of oil to methyl acetate, catalyst
loading and different cavitating devices and among them slit venturi gave better results. The mass
transfer resistance in intensifying interesterification reaction was reduced by micro level
turbulence caused due to the cavitation bubbless dynamic action which formed a fine emulsion
and provided increased area for reaction and turbulence. The cavitation number was found to be
decreasing with pump discharge pressure. And among all cavitating devices, slit venture gave least
cavitation number. On increasing the reaction time also conversion increased. Biodiesel yield
increased from 79% to 89% when inlet pressure increased from 2 to 3 bars Biodiesel yield
increased to 89% from 83% when mole ratio changes to 1:12 from 1:10. Increase in biodiesel yield
was observed from 79% to 89% on increasing concentration of catalyst from 0.75% to 1%.

Badve et al. (2014) developed a mathematical model for hydrodynamic cavitation variables
which are shear rate and pressure of the flow field. The rotor of the cavitation reactor had surface
indentations because of which phenomena of cavitation occurred within indentations. The
experimental verifications and the support of numerical modeling gave the results which showed
that the properties of pressure field and shear rate were slightly different at higher and lower
rotational speed as with variation in pressure the development of structure of isotropic streamlined
fluid flow was relatively fast. They found intended reactor rotation to be as a key variable for
controlling reaction mass transfer and pressure variations. Also rotations were obtained to be lower
than number of vortices generated and process of designing hydrodynamic cavitation reactor by
optimization using numerical modeling along with results validated by experiments was outlined.

Chuah et al. (2015) used waste cooking oil transesterification reaction to produce biodiesel
by using setup of hydrodynamic cavitation and used a basic catalyst. Waste cooking oil was
obtained from palm olein. Reaction parameters like catalyst loading, molar ratio of oil to methanol
were optimized and effects of these parameters were studied and a plate with optimized number
of holes and diameter was obtained. In comparison to mechanical stiring, the yield efficiency was
obtained eight times higher for hydrodynamic cavitation and reaction times was obtained to be six
times lesser.

Author Experimental setup Operating conditions Observations

Kumar A closed loop Operating Cavitation Yield=
2000 reactor pressure 10 to 50 1.11*10-9 gm/J.
Tank of 100 L Generation of chemical
Temperature 360 effects by hydrodynamic
Centrifugal pump
C cavitation was proved
(2900 rpm, 5.5
using a simple model.
The role of turbulent
I.D. of pipe 38mm
shear zone behind the

Plate 1 consists of orifice plate in enhancing

8 holes of 5mm cavitational activity was

dia. with 0= 0.138 established.

Plate 2 consists of HC holds potential for

33 holes of 2mm large scale applications.

dia. with 0=

Potassium iodide

Sivakumar 50litre Solution of Temperature 36- Effect of number of and 2002 Rhodamine 40C perimeter on cavitation
dissolved in number has been shown.
water(5-6g/ml) is
Effect of plate
dimensions on the
Holding tank of 50 degradation of rhodamine
liter has been established.

Closed loop Cavitational yield has

system been calculated for each

Centrifugal pump plate of different
5.5KW , 2900 rpm dimensions.

Orifice plates of Maximum cavitational

different diameter yield has been found to
and holes of be 3.00*10-8 gm/J
various perimeters.

Cooling jacket
around the tank.

Ambulgekar Hydrodynamic Temperature 350 Heterogeneous oxidation cavitation reactor C of toluene using aq.
2004 KMnO4 is considerably
Collecting Tank Pump discharge
accelerated at ambient
of 10 L pressure 1-4
temperature in the
Multistage presence of HC.

Hydro dynamically
pump (1.5 kW)
generated cavitation is

Two pressure much more energy

gauges efficient than sonicated

generated cavitation for
Orifice plate the oxidation reaction.

Six times more product

would be obtained in the
case of HC than in case
of AC at same energy

Ji 2006 Hydrodynamic Temperature 280 C Power Ultrasonic and

cavitation reactor HC were proved to be
efficient methods than

Collecting Tank Power (150W, mechanical stirring for
200W) preparation of biodiesel
by transesterification of
Centrifugal pump
soybean oil.

Two pressure
HC was a potential
method that could be

Orifice plate used for biodiesel

production at industrial
Thermometer scale due to its easy scale
up property.
Soybean Oil

Kelkar Hydrodynamic Temperature 280 C Cavitational Yield for
2008 cavitation reactor HC=1.66*10-4 gm/J)

Collecting Tank of Cavitational yield for

10 L ultrasonic
Centrifugal pump
(1.5 kW) Optimization results in
>95% conversion in
Two pressure
about 90min of
processing time.

Three transducer
Use of heterogeneous
(20kHz, 120W)
clay catalyst significantly

Catalyst H2SO4 slows down the process

and catalyst cannot be
Orifice plate recycled after use.

Fatty acids with Hydrodynamic cavitation

methanol has been found more

efficient compared to
acoustic cavitation.

Pal Hydrodynamic Temperature 450 C Maximum biodiesel

2009 cavitation reactor to 550 C yields up to 80% can be
achieved within 30 min.
Feed Tank of 10 L
Thumba biodiesel is
Centrifugal pump
relatively less pollutant
(2.2 kW)
as compared to pure

Two pressure diesel.

Biodiesel blending of

4 orifice plates thumba oil can be done

with 1,3,5,7 hole for CI engines.

of dia 3 mm each)
Biodiesel production

Thumba Oil through hydrodynamic

cavitation technique
seem to be simple,
efficient, time saving,
eco-friendly, and
industrially viable

Kawashima Batch reactor flask Activation time of Catalyst calcium oxide

et al. 2009 (two necked). calcium oxide = 1 weight was optimized as
50 ml flask. hour. 0.1g.
Activation Methanol amount was
temperature of optimized as 3.9g.

Calcium oxide and calcium oxide = Rapeseed oil amount was
methanol used was 25C. optimized as 15g.
3.9g. Reaction time = 1 Methyl ester yield as
Rapeseed oil used hour. 90%.
was 15g. Reaction
Centrifugation for temperature =
separation. 60C.
HPLC for
quantified analysis.
Behzadi and Injection pump. Temperature of oil Atomization increased
Farid 2009 Height of tank = = 100 to 120 C. area of contact.
2.3m. Temperature of On increasing
Diameter of tank = methanol = 85 to temperature of reaction
0.38m. 95 C. but below 200 C , its
Spray reaction Operating rate got increased.
system. temperature = Use of methanol in quite
Flow direction was 100C. hight amount was
counter current. Saturated steam(1 allowed in this process
bar) was used for because of recycling
heating. which increased rate of
Time of one run = reaction.
30 to 40 minutes.
Flow rate of
methanol was 100
to 300 ml per min.
Flow rate of oil
was 100 to 200 ml
per min.
Amount of catalyst
was 0 to 10 g per

Halim et al. Packed bed reactor. Molar ratio of oil Reactor height was
2009 Oven used having and methanol = 1 : optimized as 10.53 cm.
dimensions 60 cm 4. Flow rate of substrate
60 cm 45 cm. Solvent used was was optimized as 0.57
Temperature Tert-butanol. ml/min.
controller used for Temperature of the Yield obtained for fatty
oven was PID. reaction = 40C. acid methyl esters was
Peristaltic pump. Rection time = 3 79.1%.
Packing used was hours. Transesterification was
an immobilized observed as a process
enzyme. controlled by mass
Palm oil. transfer.
Supardan Hydrodynamic Temperature 600 C The initial acid value of 2012
cavitation reactor WCO of 3.9 mg KOH/g
Pump discharge
can be decreased to 1.81
Collecting Tank pressure is 2 bar
mg KOH/g in 120 min.

Centrifugal pump KOH catalyst

Highest yield =89.4%

Orifice plate obtained in 150 minutes.

Waste cooking oil Experiments shows that

cavitation is an excellent
way to achieve process
intensification of
biodiesel production

Ghayal Hydrodynamic Pump discharge The rate of

cavitation reactor pressure 1 bar transesterification
reaction is found to be
Tank of 10 L Temperature 600 C
dependent on mass

Centrifugal pump KOH used as transfer between oil and

(7.5 kW) catalyst methanol phases.

2 pressure gauges More than 95% of
conversion has been
4 orifice plates
achieved in 10 min of
with diameter
reaction time.
10,2,3,3 and no. of
holes 1,25,16,20 The highest cavitational
respectively. yield obtained was almost
1.28*10-3 gm/J.
Frying oil is used
The energy efficacy of the
HC reactor for
reactions found to be
enhanced by optimizing
the geometry of the
orifice plate.

Gole et al. Hydrodynamic Temperature of the Conversion obtained was

2013 cavitation reactor process was lesser 91.2% for treatment time
Tank of 10 L. than methanol of 20 minutes.
Centrifugal pump boiling point. Hydrodynamic cavitation
(1.5kW). Molar proved to give relatively
Nagchampa oil was ratio(Methanol to higher energy efficiency
used having acid oil) was 1:2 to 1:5. than others.
value initially as Time of High efficiency for
18.7 in terms of mg experiment was 0- intensification of process.
KOH for 1 g oil. 200 minutes.
Catalyst used was Catalyst
KOH. concentration was
used in the range of
0.5 to 3 in

Badve et al. Assembly of a stator Temperature of the Mathematical model for
2014 with rotor as a Wiesler reaction change of pressure and
cavitation device. was 25C. rate of shear developed
Variable frequency KI volume was 4L and established
drive connected to with concentration numerically.
gear for driving initially as 2000 Vortices generation was
rotor. ppm. higher in number when
Equal distance 204 Time of one number of rotations were
indentations on experiment was 15 lower.
cylinder used as minutes. Change in field of
rotor. Range of speed of pressure and rate of shear
Diameter and depth rotor was 2000 to were depending upon
of indentations were 3000 rpm. speed of rotation value
12mm and 20mm Spectophotometer whether it is higher or
respectively. used was UV - lower.
10mm of space VIS.
between rotor and
Maddikeri Hydrodynamic Temperature 500 - Slit venturi gives better 2014
cavitation reactor 600 C biodiesel yield (89.24%)
as compared to orifice
Collecting Tank of Discharge pressure
plate and circular venturi.
15 L of pump is 2-5 bar.
The energy efficient
Multistage Catalyst:
approach based on the use
centrifugal Potassium
of HC as compared to the
pump(1.5kW) methoxide
conventional method has

Two pressure been confirmed.

The approach based on

Cavitating devices HC gives intensified

such as Orifice
plate, circular

venturi & slit processing with higher
venturi. biodiesel yield.

Waste cooking oil Cavitational yield for

HC=0.00122 g/J for
AC=0.0000476 g/J for
approach=0.0000322 g/J.

Chuah et al. Hydrodynamic Molar ratio of oil Conversion of methyl

2015 cavitation reactor. and methanol = esters = 96.5%.
Capacity = 50 1:4 to 1: 7. Time of reaction was
litres. Catalyst amount = relatively less than other
Diaphragm pump. 0.5 to 1.25 conventional processes.
Compressed air; weight%. Biodiesel obtained
power output = Temperature of satisfied diesel
4kW. the reaction = 50- standards.
Geometry plate 65 C.
number of holes = Amount of oil =
21. 5kg.
Diameter of holes Reacting mixture
= 1 mm. amount = 6.2
Inlet pressure = 2 litres.
Waste oil of


Some work has been reported that the cavitating bubbles have been generated in the
hydrodynamic cavitating reactor mostly by the use of orifice plates or venturi. So, in present work
for utilizing the cavitation phenomena use of sudden contraction has been proposed. There is also

a scope of analytical and numerical modeling of reactor. There is also scope of improvement in
the production of biodiesel by employing various oils as the source of triglycerides.

Keeping in mind, the gap present in the literature the following objectives have been decided.

a) To find out the hydrodynamic characteristics of the setup by using water.

b) To find out the cavitational yield of the current setup, utilizing the weissler reaction i.e. the
oxidation of potassium iodide.

c) Utilizing this current setup, for carrying out heterogeneous chemical reaction, such as
transesterifaction for production of biodiesel.


Before using the cavitational setup for the biodiesel production, it is important to test the
cavitational setup for its cavitational properties such as pressure recovery, pressure drop across the
contraction cavitational yield, So that it can be utilized for carrying out chemical changes.


3.1.1 Hydrodynamic cavitation setup

A schematic of the experimental setup has been presented in Figure 3.1. It consists of tank
of 80 liter capacity. The discharge line of tank is connected to the suction of centrifugal pump. The
discharge line of centrifugal pump is divided into two branches; one main and other one is bypass
line. The material from the tank is made to discharge with the help of centrifugal pump and it is
made to return back to the tank via main and bypass line. The flow rate is made to be controlled
with the help of two valves. One is present on the bypass line and other one is present on the main
line just before the rotameter. Series of contracting tubes of different diameters are employed.
Tubes which are made up of stainless steel, where cavitation phenomena is taking place is 1 m.
Tube with larger diameter is followed by smaller one. Larger tube is having I.D of 10mm and
smaller tube is having I.D of 6 mm. A rotameter of range from 0 to 30 LPM with a least count of
2 LPM is used for flow measurement. Two pressure sensors (Range 0 to 6 bar) are employed into
main line of stainless steel where sudden contraction is taking place. Signals from pressure sensors
are transferred to the data acquisition. From data acquisition voltage signals are generated and
recorded in PC.
For biodiesel production, slight changes have been made in the setup. Centrifugal pump
has been replaced by the rotary gear pump. Apart from other two sensors third pressure sensor

has been placed in the cavitational setup just beside the contraction in the downstream side of the
stainless steel pipe.

3.1.2 Batch reactor setup

Apart from hydrodynamic cavitation, biodiesel has also been prepared by using mechanical
stirring method. Schematic of setup has been presented in the figure 3.2. Round bottom flask of
250ml has been utilized for carrying out trans esterification. It has been placed in the silicone oil
bath to make temperature uniform. Condenser has been placed above the round bottom flask to
condense any vapor emerging from it. Thermometer is installed in oil bath to measure the
temperature of reactants.

Fig 3.1 Hydrodynamic cavitation Setup

Fig3.2 Schematic of Batch reactor setup


3.3.1 Hydrodynamic characterstics of cavitation reactor using water

Water has been utilized for testing the passage. 40 liters of water was transferred into the
tank. It is made to run with the help of centrifugal pump. Initially both bypass and mainline valve

were kept open. Initially no flow of water was observed in the main line. Gradually, bypass valve
was made to close. When bypass valve was close partially closed, the rotameter installed in the
main line started to show some flow rate. When the flow rate of 4 LPM was observed, the water
flow rate is kept constant and the experiment is carried out for minimum of 5 minutes. The pressure
at upstream and downstream are noted using two absolute pressure sensors (Honeywell). Data
acquisition system (National Instrument) is used to have a continuous recording of signals in PC.
Pressure taps are located at 0.5 m upstream and downstream of the plane of area change. After that
the flow rate again increased in the main line by closing bypass valve and set to a higher value of
6 LPM. Similarly, the experiments were repeated for 6 LPM, 8 LPM and 10 LPM. Experiment
with each flow rate has been repeated 5 times to get an average signal and an averaged deviation
of a single repetition with respect to the averaged signal. The averaged signal is representative of
the averaged influence of the bubbles on the response. The standard deviation provides an
estimation of the fluctuations on the pressures induced in the system by the collapse of the bubbles.

3.3.2 Weisslier Reaction

The model reaction used for the validation of hydrodynamic cavitation is
decomposition/oxidation of aqueous KI solution. The conversion of potassium iodide into iodine
is utilized for obtaining the cavitational yield of any hydrodynamic cavitation reactor. Solution of
40 liters of water and 1.5 wt % potassium iodide was made and transferred into tank. Solution was
made to run with the help of centrifugal pump. Initially both the valves were opened. Gradually
by pass valve was made to close to increase flow rate in main line. Flow rate of 8
LPM was maintained. Solution passing through the series of contracting pipes, again reaches the
tank and get mixed up with the solution in tank. This continuous process was made to run for half
an hour. Samples of solution from the tank were collected at interval of 5 minutes. These samples
were analyzed in UV spectrometer for absorbance at 353nm to measure the iodine concentration
which was produced from the oxidation of potassium iodide. Similar experiment was performed
for flow rate of 10 LPM. Iodine concentration was measured with the help of pre calibrated chart.
It was prepared by making some known concentration of iodine solution and plotting their
absorbance at 353nm against the known concentration with the help of UV spectrometer.
3.3.3 Oil testing
For the production of biodiesel, choice of oil is very important. Its viscosity and free fatty
acid content are very important factors for production of biodiesel. Oil should have less free fatty
acid content to avoid soap formation. It should be less viscous, so that less amount of energy would
be required to pump or to create turbulence in it. So keeping in mind these above factors various
non-edible oils has been tested for their viscosity using rheometer and acid value (Free fatty acid
content) by carrying out titration against standard KOH solution in presence of ethanol. Oil having
less viscosity and higher acid value is preferred for biodiesel production. Oil of alsi was found
suitable as it has less free fatty acid content and has less viscosity.

3.3.4 Biodiesel production Using Batch reactor

Both mechanical stirring method and hydrodynamic cavitation are employed for
production of biodiesel. In mechanical stirring method, alsi oil and methanol were used with the
KOH as catalyst to produce biodiesel. First, 50ml of methanol was taken and KOH pellets with 1
wt% of oil were made to dissolve in methanol with the help of magnetic stirrer. Methanol
containing catalyst, were mixed with 200ml of alsi oil in round bottom flask used as batch reactor.
A condenser was mounted over round bottom flask to condense any vapour produced during
reaction. The magnetic stirrer was used to completely mix the reactants and it was made to stir
continuously for 6 hours at 65C temperature to carry out trans esterification. After completion of
the reaction, biodiesel and glycerol were formed. Using hydrodynamic cavitation reactor

Pottasium hydroxide which is 1 wt% of oil is dissolved in 8 liters of methanol and
transported into the tank of cavitation setup along with 32 liters of oil. Initially both the valves are
open. Valve in the by-pass line was made to close slowly, so that the flow rate in the main line
could reach 10 LPM. As the by-pass valve was partially closed, flow rate of 10 LPM was achieved.
At this flow rate, setup was made to run for 1.5hrs. Sample was drawn from the tank after 1.5 hrs.
Simultaneously pressure signals have been recorded for 1.5 hours. Without using cavitation reactor

Chemicals were made and transported in the tank as mentioned above. Valve present in the
main line was fully closed and by pass vlave was fully opened. Reactants were made to run through
the by pass line only . There was no passage of reactants through the sudden contraction. This was
done to visualize the contribution of by pass section in creating the turbulence for biodiesel
production. It was again made to run for 1.5 hours. The sample was drawn after 1.5hours from
tank. Glycerol separation, Washing and drying

The product mixture was transferred to the separating funnel where methyl esters and
glycerol mixture was kept for about 2 hours. After 2 hours, both methyl esters and glycerol forming
layer of different phases. Figure 3.3 shows the different layers of biodiesel and glycerol where
biodiesel on top and glycerol in bottom. Glycerol layer is separated from bottom by opening the
knob of separating funnel. Washing of Biodiesel which is formed after trans esterification is done
to remove the soap, which is formed during trans esterification. Distilled water is utilized for
washing. Distilled water which is equal volume to that of biodiesel was taken and heated upto
40C. Heated distilled water was mixed with the biodiesel in separating funnel and readily shaken.
The mixture of biodiesel and water was left for around 1 hour to get the mixture of biodiesel and
water settled and to form separate phases. Separate phases of biodiesel at top and water layer at
the bottom can be seen in the figure 3.4. When distinct layer between the different phases was
visible, the water from the bottom was separated by opening the bottom knob of separating funnel.
This is repeated 3 to 4 times until the water which was removed found to be clear and soap free.
Moisture content in the biodiesel usually increases after water wash and it becomes hazy. To
remove the excess methanol and moisture content from the formed biodiesel, vacuum evaporation
was performed. The biodiesel sample was made to be vacuum evaporated for 45 minutes at 65C.
After that clean, moisture free biodiesel was obtained GC Analysis
The methyl ester content in biodiesel was determined by the gas chromatography technique.
The conversion of triglycerides into fatty acid methyl ester was also determined by the GC.
Following methods were adopted for biodiesel sample analysis:
a) Solution of 10mg methyl heptadeconate in 1ml of hexane is made which is internal solution
used for gas chromatography.
b) 100L sample of biodiesel was measured and mixed with 1ml of internal standard solution.
1L of that solution of biodiesel and internal standard was made and injected into GC.

Fig 3.3 Layer of Biodiesel and glycerol Fig 3.4 Layer of washed water and biodiesel

Following GC conditions were used for biodiesel testing

Table 3.1 GC conditions for biodiesel testing

Gas Chromatograph Netel Ltd (Michro 9100) GC
Inject Temperature 230C
Injection Volume 1 L
Oven Program Initial Temperature 180C
Hold Time 1 0 min
Ramp 1 4C/ min
Oven Program Final Temperature 240C
Hold Time 2 6 min
Column Optima wax (30m * 250m*0.25m) fused
silica capillary column
Carrier Gas Nitrogen
FID Temperature 240C
Detector Flame Ionization Detector
Gas Flow 3.0 mL / minute Biodiesel characterization

Biodiesel produced was used to test for its different properties like cloud point, flash
point, pour point, kinematic viscosity. Following methods are employed to determine the
properties mentioned above.

Table 3.2 Methods for characterization of biodiesel

Parameter Characterization Technique

Kinematic viscosity Redwood Viscometer
Flash and fire points Pensky Marten flash point tester (ASTM D
Cloud and Pour points Cloud and pour point tester (ASTM D 93)



4.1.1 Hydraulic characteristics of set up

In This section the results obtained from the experimental setup are discussed. With the
experiment performed with the water, pressure signals were obtained for upstream and
downstream side of the contraction of for the flow rates of 4, 6,8, 10 LPM . As the experiment has
been repeated 4 times for each flow rate, average pressure has been taken. Figure 4.1 shows the
average pressure signal of each flow rate with time for the upstream side. Similarly figure 4.2
shows the average pressure signal of each flow rate with time for downstream side. From the figure
it is clear that the as the flow rate increases the average pressure on upstream side increases. It can
be attributed to the fact that as the valve is made to open to increase the flow rate it creates less
pressure drop. It also depicts that average values of pressure are constant for entire duration of
time. However for the downstream this is not true. It can be seen from the figure that there exists
some fluctuations in the pressure signals which may be a result of continuous bubble collapse
occurring after pressure recovery at downstream.

Pressure (bar)

10 LPM
-1 0 1 2 3 4 5 6
Time (sec)

Fig 4.1 Pressure signals for upstream with water



Pressure (bar)
1.5 10 LPM
-1 0 1 2 3 4 5 6
Time (sec)

Fig 4.2 Pressure signals for downstream with water

Standard deviation of pressure signals for upstream and downstream side of contraction has been
shown in the figure 4.3 and figure 4.4. It can be seen from the figure, that the standard deviation
for the downstream side is more as compared to upstream side. This can be attributed to the fact
that on the downstream side pressure is getting recovered, due to the pressure recovery, the
cavitation bubbles are collapsed. Due to collapse, more deviations in the pressure signals are
generated with time. So the pressure fluctuations in the downstream side are more than the
upstream side.

standard deviation

0.12 4 LPM
0.1 6 LPM
0.08 8 LPM
0.06 10 LPM
0 1 2 3 4 5 6
Time (sec)

Fig 4.3 Standard deviation for upstream


Standard deviation
0.15 6 LPM
10 LPM
0 1 2 3 4 5 6
Time (sec)

Figure 4.4 Standard deviation for downstream

It can also be seen that as the flow rate in the system is increased the standard deviation of
pressure signals also increases. So there are more pressure fluctuations with higher flow rate. It
can be seen from the figure that the standard deviation of 8LPM is found to have higher value as
compared to 10 LPM, this needs further investigation in the setup. This can be done by placing
straight tube of uniform i.d in the place of contracting tubes and measuring the pressure signals at
8 LPM and 10 LPM respectively. Pressure drop can be defined as the difference between the
average of upstream pressure and the average of downstream pressure obtained with time. Figure
4.5 shows the pressure drop with respect to time. It can be seen from the figure that, as the flow
rate is increases the pressure drop across the contraction increases. As the pressure drop increases
the intensity of bubble collapse also increases. So this setup can be utilized to carry out the
chemical changes. Figure 8 shows the recovery ratio i.e. ratio of pressure at downstream to pressure
at upstream. It can be seen from the figure that, with increase in flowrate the pressure recovery
also increases which enhances the bubble collapse at downstream. This also explains increase
fluctuations in pressure signals for higher flowrate, however recovery ratio for 8 LPM is found to
be greater than 10LPM.



Pressure Drop (bar) 0.5

0.35 8 LPM
10 LPM


-1 0 1 2 3 4 5 6
Time (sec)

Fig 4.5 Pressure drop with time

4.2 Weisllier reaction

The conversion of potassium iodide into iodine is utilized for obtaining the cavitational
yield of any hydrodynamic cavitation reactor. Figure 4.6 shows the iodine liberation with respect
to time for both the flow rates of 10 LPM and 8 LPM. It can be seen that liberation of iodine
increases with time for both the flow rates. Aqueous solution of KI is repeatedly experiencing the
cavitation zone with the passage of time, this explains the increase in concentration of iodine with
time. From the figure it can be noted that the iodine liberation is higher for higher flow rate. At
higher flow rate the aqueous solution experience the higher pressure drop which results in increase
in cluster collapse intensity. Due to the collapse of cavities, locally there is increase in the
magnitude of pressure and temperature which results in higher cavitational effects. It can also be
stated that the aqueous solution flowing with higher flow rate experience the cavitational zone
created by the sudden contraction in the pipe line more number of times for same amount of period
comparing with lower flow rates.



Iodine(milimoles/lit) 0.16


0.12 8 LPM

0.1 10 LPM


0 5 10 15 20 25 30 35
Time (min)

Fig 4.6 Liberation of Iodine with time

Cavitational yield has been calculated for the existing setup. Cavitational yield can be defined as
the effect of cavitation produced per unit consumption of energy. In present case, cavitational
effect can be measured in the terms of iodine liberation per unit energy. Cavitational yield has been
calculated for 8LPM and 10LPM

Cavitational yield= Iodine liberated/ Energy imparted to the fluid

Energy imparted to the fluid for half an hour= 1.5*1000*30*60 J

= 2.7*106 Joule

For 8 LPM, iodine produced= 0.0399732 gm

For 10LPM, iodine produced=0.04325 gm

Cavitational yield for 8LPM = (0.0399732/(2.7*106))

= 1.48*10-8 gm/J

Cavitational yield for 10LPM =(0.04235/(2.7*106))


Cavitational yield is found to be higher for the 10LPM.

4.3 Viscosity and Acid value of oils
Oil containing triglycerides is the major reactant for the production of biodiesel, so it is
necessary to examine the properties of various oils so that suitable oil can be selected for
production. Viscosity and acid value of various oils have been tested.
Table 4.1 Properties of various oils

Oil Viscosity [Pa.s] Acid Value

[mg KOH/ g of oil]
Mahua 0.0695 17.95

Kalongi 0.029 40.93

Neem 0.155 74.052

Alsi 0.0315 3.342

Chameli 0.0262 1.122

Devdar 0.0263 46.022

Keeping in mind the various factors such acid value and viscosity and buying cost of oil, oil of alsi
was selected for carrying out the transesterification reaction.

The following figures show the gas chromatogram of biodiesel produced from the batch
stirring and with hydrodynamic cavitation and without cavitation. Peaks of heptane, methyl
heptadeconate and fatty acid methyl esters have been shown in the chromatogram. The % FAME
conversion has been obtained from the GC analysis.

Fig 4.7 GC graph of biodiesel produced from batch stirrer

Fig 4.8 GC graph of biodiesel produced from hydrodynamic cavitation

Fig 4.9 GC graph of biodiesel produced without using cavitation


The conversion of methanol and oil mixture to form methyl esters is represented as %
FAME conversion. It is calculated with the help of the following formula:

( .) . ()
% FAME = X X

X X 100
.() 100

a) Batch reactor: With batch reactor the % FAME conversion was obtained as
b) Hydrodynamic cavitation reactor: With hydrodynamic cavitation reactor % FAME
conversion was
c) Without cavitation: % FAME conversion was

From figures 4.7 it can be seen that the peaks obtained in the case of biodiesel production using
batch stirring method are high and clear which also resembles with the result of % FAME
conversion for batch stirrer. In figure 4.8, the peaks obtained in the case of hydrodynamic
cavitation setup is very low and not very much clear which can also be related to % FAME
conversion obtained which was very low and it was nearly zero for without cavitation setup. It can
be attributed to the fact that the, due to some setup constraints flow rate obtained with rotary gear
pump in the main line of cavitation setup was near to 5 LPM. At this flow no intense mixing or
effects of cavitation can be extracted. FAME conversion for setup without using cavitation is
nearly zero. There is no formation of biodiesel is observed.