Review on Biodiesel Production using Process Intensification Techniques 7

2
Review on Biodiesel Production using Process
Intensification Techniques
Anvita Sharma*, Dr. Pravin Kodgire* & Dr. Surendra Singh Kachhwaha**

* Department of Chemical Engineering, Pandit Deendayal Petroleum University, Gandhinagr,

Gujrat, India
** Dean, Head of Mechanical Engineering Department, Pandit Deendayal Petroleum
University, Gandhinagar, Gujrat, India

Abstract
The article reviews the recently developed process intensification techniques used
for biodiesel production. The effect of novel processes like ultrasonic and microwave
irradiation and hydrodynamic cavitation significantly influenced the final conversion,
yield and the quality of product.

1. Introduction esters and glycerol. A triglyceride has a glycerine

Biodiesel is generally produced from different
sources such as plant oils: soybean canola,
sunflower, linseed, olive, peanut, tobacco,
palm, recycled cooking oils and animal fats.
The major economic factor to consider for
input costs of biodiesel production is the
feedstock. Using agricultural wastes, high acid
oils, soapstock, waste frying oil and algae
oil as raw materials for biodiesel production
are being reported in literature. [1]
Biodiesel is produced by transesterification
using base catalyzed transesterification as it
is the most economical process, requiring only
low temperatures and pressures while
producing a 98% conversion yield. The
transesterification process is the reaction of
a triglyceride (fat/oil) with an alcohol to form
molecule as its base with three long chain fatty
acids attached. The characteristics of the fat
are determined by the nature of the fatty acids
attached to the glycerine. The nature of the
fatty acids can, in turn, affect the characteristics
of the biodiesel.
The figure 1 below shows the chemical process
for methyl ester biodiesel. The reaction
between the fat or oil and the alcohol is a
reversible reaction, so the alcohol must be
added in excess to drive the reaction towards
the right and ensure complete conversion.
A successful transesterification reaction is
signified by the separation of the methyl ester
(biodiesel) and glycerol layers after the
reaction time. [2]
8 Proceedings of International Conference on Chemical Industry

Fig.1. Transesterification Reaction for Biodiesel Production

Researchers have focused on development on mechanical stirring process have been

process intensified biodiesel production methods summarized in Table 1.
and the optimization of the processes. Various
processes such as microwave assisted method
and ultrasound assisted method have recently
developed.

2. Literature Review
Literature review of catalytic processes is done
based on the processes used for production
of biodiesel. These are separated on the bases
of generation.
 Primary Technique Fig. 2: Mechanical Stirring Apparatus [1]
o Mechanical Stirring Drawbacks
 Process Intensification Techniques The conventional process of biodiesel
o Ultrasound Cavitation production is time consuming and energy is
o Microwave Technique lost as the reaction time required is of hours.
As it is a slow reaction process if the system
o Hydrodynamic Cavitation is open system and there is moisture formation
o Hybrid Techniques or there is unsufficient water in the reaction
then there is a fear of soap formation which
2.1 Primary Technique is a major issue, because in this case the
2.1.1 Mechanical Stirring whole batch of biodiesel is wasted. The yield
obtained is comparatively impure. As this is
Mechanical stirring is a method in which stirrer
a catalytic process use of catalyst is also a
is placed in a beaker having oil and alcohol
major issue for production cost. Recovery of
mixture (refer Fig. 2). Details about the
catalyst is also difficult in this process.
Review on Biodiesel Production using Process Intensification Techniques 9

Table 1: Literature review for Mechanical Stirring

Sr. No Author & Year Oil Catalyst & Proportion Operating Condition Outcome

1. R. Alcantara Soyabean, Tallow,  A: O ratio- 6:1  Operating Yield: 75%

et al. [3] Frying Oil  Catalyst: NaOH temperature:
 Wt% of catalyst-1% 60°C
 RPM:600

2. Berchmans & Jatropha  Two step transest-  Step 1:50°C 1hr  90% yield
Hirata [4] erification  Step 2: 65°C
1 hr

3. Pal & Kach- Thumba  Catalyst: KOH  Temperature  Yield 79 – 90%

hwaha [5]  A:O ratio- 6:1 and 4.5:1 50 – 60°C
 3 catalyst %: 0.5%,
0.75% and 1%

4. R B Sharma Thumba  Catalyst: KOH  Temperature:  Reaction Time:

et.al [6] 55-60°C 60 min
 Open system  Yield 94%

Therefore, there is a strong quest to develop
an efficient, time saving and economically
functional, environmental friendly biodiesel
production process.
Based on the drawbacks in Mechanical
Stirring, new technologies have been
developed which help in curbing these
drawbacks.
The aim of this study is to see the eûects of
low frequency ultrasonic irradiation on the
transesteriûcation of different types of oils
under catalysis conditions. The results of the
investigation of the transesteriûcation of oil
with short-chain alcohols (C1–C4) in the
presence of ultrasound to give alkyl esters
of fatty acids are given in the table 2. [5]

2.2 Process Intensification Techniques

2.2.1 Ultrasound Cavitation
Low frequency ultrasonic irradiation is a useful
tool for emulsiûcation of immiscible liquids.
The collapse of the cavitation bubbles disrupts
the phase boundary and causes emulsiûcation,
by ultrasonic jets that impinge one liquid to
another.

Fig. 3: Ultrasonic cavitation technique [8]

10 Proceedings of International Conference on Chemical Industry

Table 2: Literature review for Ultrasonic Cavitation

• • •
•
• •
•
• •
• •

• •

• • •

• • •

• • •

• •
•
•

• •
• • •

• • •
•
• •
•

•
Review on Biodiesel Production using Process Intensification Techniques 11

5. Shishir M. Waste • Catalyst: • Temperature: • Reaction time: 40

Hingu [11] cooking KOH 45C min
oil • A:O ratio- • Frequency: 20 • Yield: 85%
rd
6:1 kHz • 1/3 energy
• Catalyst • Power: 200W consumption
wt%: 1%
6. Pal & Thumba • Catalyst: • Frequency: 28.5 • Reaction Time: 3
Kachhwaha KOH kHz – 30min
[4] • A:O ratio- • power • Yield 81 – 95%
6:1 and 4.5:1, dissipation: 50W • Lower frequency
3 • Temperature: 50 is efficient
• Catalyst %: – 60°C
0.5%, 0.75% • Probe type
and 1% ultrasound
7. Joungdu Shin Rapeseed • Catalyst: • Temperature: • Reaction Time:40
et.al [12] Oil NaOH 40°C min
• A:O ratio- • Frequency: 40 • Yield: 75.6%
6:1 kHz
• Catalyst %:
0.3%, 0.5%
and 1%
8. Gole & Nagcham • Two step • Frequency:20 • Yield: 91.5%
Gogate[13] pa process kHz
• Catalyst- • power
KOH dissipation of
120 W
• Optimum temp:
40°C
• Bath type
ultrasound
9. Gude & Waste • Catalyst:0.5 • Frequency:20 • Yield: 86.5%
Grant [14] Cooking % (wt/wt) kHz • Reaction time: 1–
Oil • A:O ratio- • power 2 min.
9:1 dissipation of • eliminates
120 W external heating
• Optimum temp: • Optimum temp
40°C 45–60C
• Probe type
ultrasound
12 Proceedings of International Conference on Chemical Industry

10. Pal & Waste • Catalyst: • Frequency 28- • Yield: 85 -

Kachhwaha Cooking KOH 33 kHz 95%
[15] Oil, • Catalyst %: • Reaction time
Thumba, 0.5%, 0.75% is shorter
Jathropa and 1% • Relatively
better yield

11. Ganesh L. waste • Methyl • Frequency: 22 • Yield: 90%

Maddikeri cooking Acetate as kHz
et.al [16] oil raw material • power
• Catalyst: dissipation of
KOH 750 W
• oil to methyl • Probe type
acetate ratio- ultrasound
1:4- 1:14
• catalyst
concentration
: 0.5, 1.0 and
1.5%
• amplitude of
ultrasound:40
, 50, 60 and
70%
12. D.C. Boffito tobacco • Catalyst: • Frequency:20 • Catalyst-
et.al [17] and organic kHz chemically
canola oil species on • power and
Amberlyst 46 dissipation of mechanical
120 W ly stable for
• Optimum temp: over 90
40°C cycles and
540 h
13. J. Sáez- Rapeseed • Catalyst:KO • Frequency:20 • Yield: 95.03%
Bastante et.al oil, Soy H kHz
[18] bean, • Probe type
coconut ultrasound

Review on Biodiesel Production using Process Intensification Techniques
The conclusions from literature survey that:
 Majority of oils used in this technique
are edible and vegetable oils like
cottonseed oil, soybean oil and under
non-edible oils; thumba, rapeseed,
tobacco seed oil, nagchampa and waste
cooking oil
 The catalysts used in this process are
homogeneous like KOH, NaOH, and
H2SO4. Use of heterogeneous
catalysts is not reported till date.
 Type of alcohol used is methanol, as
it is the cheapest available alcohol
and the structural chain is shortest. It
is easy to separate methanol from the
final product. Yield compared to
Mechanical stirring is high and the
time required for the completion of
transesterification is low, hence it is
an energy efficient process.
 Probe type sonicator is extensively
used for the production of biodiesel
as it can be easily withstand more
than ambient pressures and
temperatures.
 The process doesn’t need high
temperatures hence it is
environmentally friendly. At the
maximum temperature of 60ºC the
yield is high. The pressure conditions
are also ambient.
Fig.4 Microwave technique for Biodiesel Production [19]
13
 Requirement of a smaller amount of
excess methanol for equivalent levels
of equilibrium conversion saves
considerable energy in the methanol
separation units.
 There is higher ease of separation of
glycerine and catalyst, which reduces
the purification time and energy.
2.2.2 Microwave
Generally, heating coils are used to heat the
raw material in biodiesel production process.
This treatment can be also done by microwave
method [Fig. 3]. An alternative heating system
“microwave irradiation” has been used in
transesterification reactions in recent years.
Microwaves are electromagnetic radiations
which represent a nonionizing radiation that
influences molecular motions such as ion
migration or dipole rotations, but not altering
the molecular structure, microwave irradiation
as a non-conventional energy has been widely
applied in organic synthesis. Spectacular
accelerations, higher yields under milder
reaction conditions, and higher product purities
have all been reported. Such phenomena are
not usually accessible by classical heating,
and the existence of non-thermal effects of
highly polarizing radiation, [19]. A summary
of microwave process is shown in Table 3.
14 Proceedings of International Conference on Chemical Industry

Table 3: Literature review for Microwave Technique

Sr. Author & Oil Catalyst Operating Outcome
No Year & Conditions
Proportion
1. N.Azcan et.al Cotton • Catalyst: KOH • Temperature: • Reaction
[20] seed oil 333 K time:7min
• c:o ratio- • Yield: 92.7%
1.5%
2. Su Zhang Yellow • Heteropolyacid • Temperature: • Yield 96.22%
et.al[21] horn oil catalyst: 60° C • Reaction time:
Cs2.5H0.5PW1 10 min
2O
• A:O ratio- 12:1,
• Catalyst wt%-
1%
3. Ming-Chien Soybean • Heterogeneous • Temperature: • Reaction time:
et.al[22] oil catalysts: Nano- 60°C 10 min
sized oxides

4. N.Tippayawo Jatropha • Catalyst: • Power:800 W • Yield: 96.5%

ng et.al [23] oil Sodium • irradiation
methoxide time between
• O:A ratio- 1:3– 10–40 s
1:9 • continuous
flow
5. Prafulla D. Waste • Catalyst: BaO • Time of • Yield: 96%
Patil et.al[24] cooking and KOH reaction: 6
oil • Two step min
process
6. Savaliya & Karanja • Catalyst: KOH, • Temperature • Yield 97%
Dholakiya NaOH 60 ˚C
[25] • O:A ratio-1:6
7. Bin Ye et.al Soybean • Catalyst: • Yield 96.5 %
[19] Oil alumina/silica
with potassium
sodium tartrate
• One step sol-gel
process

Review on Biodiesel Production using Process Intensification Techniques 15

The conclusions of literature survey are given 2.2.3 Hydrodynamic Cavitation

below:
 As the mechanism of microwave is
just that the waves penetrate into the
reactant materials the reaction takes
place at a faster rate. Hence there is
a noticeable reduction in reaction time.
 Industrial scale-up is difficult as the
microwave generator has to work in
a specific environment so that the rays
stay intact and the material is heated
evenly. If probe type of microwave
generator is used, multiple probes are
required.
Table 4. Literature review for Hydrodynamic Cavitation
Hydrodynamic cavitation is the cheaper
alternative for the above processes. Here,
cavitation is generated by the flow of a liquid
under controlled conditions through simple
geometries such as venturi-tubes and orifice
plates. When the pressure at the throat falls
below the vapour pressure of the liquid, the
liquid flashes, generating a number of cavities
which subsequently collapse when pressure
recovers downstream of the mechanical
constriction.[26]. Some of the literatures have
been listed in table 4.

Sr.N Author & Year Oil Catalyst Operating Outcome

o & Conditions
Proportions
1. Jianbing Ji, et.al Vegetable oil • Catalyst: NaOH • Reaction time: 10–30
[28] • A:O ratio- 6:1 min.
• Scale-up is easy
2. PR. Gogate [29] Vegetable oil • O:A ratio-4:4 • Reaction time: 15 min
• Catalyst :NaOH • Yield:98%
• Wt. Of catalyst: 1% • 40 times Energy
of oil efficient
3. M.A. Kelkar et. Vegetable oil • Catalyst: H2SO4 • Temperature: • Yield 95%
Al [30] • Catalyst wt: 1% 28°C ±1°C • Energy efficient
• A:O ratio- 5:1 or
10:1
4. A Pal et.al [31] Thumba • Temperature • Yield: 80%
45-55°C • Run of 45 min
• Change in yield
depends on change in
number of holes
5. M.D.Supardan Waste cooking • Two step process • Temperature • Yield: 89.4%
et.al [32] oil 60°C • Run of 150 min

6. V. L. Gole et.al Nagchampa • Two step process • Temperature • Yield 92%

[25] • A:O ratio- 3:1 or 60° C
6:1 • Pressure:10-40
psi
• Varying flow
rates
7. D.Ghayal et.al Used frying oil • Catalyst: KOH • Temperature: • Yield 95%
[33] 60°C
• Pressure:1-3 bar

16 Proceedings of International Conference on Chemical Industry

Prominent features from the literature survey
 Industrial scale-up is possible as it is an
energy efficient technique. The
temperature and pressure are also near
to ambient hence its environmental
friendly.
process intensification techniques are designed
in a two ways as per the literature (i) sequential
(ii) merging with each other.
Sequential Process

2.2.4 Hybrid Technique

Hybrid technique is a combination of different
processes which are available for production
techniques. This technique is the new venture Fig.6 Diagrams showing possible hybrid
towards the production of biodiesel. These technique

Table 5: Literature review for Hybrid Technique

Sr. Author & Year Oil Catalyst & Operating Outcome
No Proportion Conditions
1. VL. Gole & P.R. Gogate Nagchampa • Two step • sequential effect
[34] MW-US process • reaction time reduces
from 60 min to 15
min
2. I. Choedkiatsakul et.al palm oil • Catalyst: • preheat • combination of US
[35] MS-US NaOH temperature - and MS Yield: 80%
• Catalyst 45°C • US Yield: 60%
wt% - 0.15% • feed flow • MS Yield: 50%,
rate: 55
mL/min
• Stirrer
speed:160
rpm.

Significant Features of Hybrid Technique  Inspite of the sequential process the
Using they hybrid technique is adds on to the energy required low
benefits of the processes. When two methods  Pre heating of oil is not required as
are combined for the transesterification reaction the first technique which is selected
we get the following benefits: can be selected in such a way that
Higher yield compared to individual process oil gets heated up.
intensification techniques  Sequential process or cyclic process
 Reaction time reduces to almost half is efficient as less energy is required
compared to individual process  These processes are still batch
intensification techniques processes
 Increase in number of transducers of  Very limited data is available for the
an ultrasound can aid in increasing hybrid technique
yield of biodiesel
Review on Biodiesel Production using Process Intensification Techniques
Conclusions
Various technologies employed to date were
reviewed in this paper. Related to the
conventional mechanical stirring technique the
process intensification techniques are more
energy efficient, eco-friendly and industrially
viable. Design and fabrication of sequential
techniques would yield biodiesel of better
quality. Efforts are required to be concentrated
on techniques which are continuous.
References
[1] E. Santacesaria, et.al, Main technologies in
biodiesel production: State of the art and
future challenges, Catalysis Today 195 (2012)
2– 13
[2] Source: www.esru.strath.ac.uk/EandE/
Web_sites/0203/biofuels/what_biodiesel.htm
(10/5/14)
[3] R. Alcantara et.al, Catalytic production of
biodiesel from soy-bean oil, used frying oil
and tallow, Biomass and Bioenergy 18 (2000)
515-527
[4] H.J.Berchmans & S.Hirata, Biodiesel production
from crude Jatropha curcas L. seed oil with a
high content of free fatty acids, Bioresource
Technology 99 (2008) 1716–1721
[5] Amit Pal, *S. S. Kachhwaha, Biodiesel
production of non-edible oils through ultrasound
energy, International Conference On Current
Trends In Technology, 2 ‘NUiCONE – 2011
[6] R B Sharma et.al, Production of Bio-Diesel
from Non-Edible Thumba (CitrullusbColocyntis)
Seed Oil Using Mechanical Stirring
Methodology and Analysis of Fuel Properties,
Int. Journal of Engineering Research and
Applications, Vol. 3, Issue 6, Nov-Dec 2013,
pp.2082-2089
[7] C.Stavarache et.al, Fatty acids methyl esters
from vegetable oil by means of ultrasonic
energy, Ultrasonics Sonochemistry 12 (2005)
367–372.
[8] C. Stavarache, et.al, Aspects of ultrasonically
assisted transesteriûcation of various vegetable
oils with methanol, Ultrasonics Sonochemistry
(2006)
17
[9] Jianbing Ji et.al, Preparation of biodiesel with
the help of ultrasonic and hydrodynamic
cavitation, Ultrasonics 44 (2006) e411–e414
[10] Omotola Babajide, et.al, Low-Cost Feedstock
Conversion to Biodiesel via Ultrasound
Technology, Energies 2009, 3, 1691-1703
[11] Shishir M. Hingu et.al, Synthesis of biodiesel
from waste cooking oil using sonochemical
reactors, Ultrasonics Sonochemistry 17 (2010)
827–832
[12] Joungdu Shin et.al, Effects of ultrasonification
and mechanical stirring methods for the
production of biodiesel from rapeseed oil,
Korean J. Chem. Eng., 29(4), 460-463 (2012)
[13] Vitthal L. Gole and Parag R. Gogate,
Intensification of Synthesis of Biodiesel from
Nonedible Oils Using Sonochemical Reactors,
Ind. Eng. Chem. Res. 2012, 51, 11866"11874
[14] Veera Gnaneswar Gude , Georgene Elizabeth
Grant, Biodiesel from waste cooking oils via
direct sonication, Applied Energy 109 (2013)
135–144
[15] Amit Pala and Surendra Singh Kachhwaha,
Biodiesel Production of Waste Cooking Oil
through Ultrasound Cavitation, International
Journal of Engineering Research and
Technology, Volume 6, Number 3 (2013), pp.
291-306
[16] Ganesh L. Maddikeri et.al, Ultrasound assisted
interesterification of waste cooking oil and
methyl acetate for biodiesel and triacetin
production, Fuel Processing Technology 116
(2013) 241–249
[17] D.C. Boffito et.al, Ultrasonic free fatty acids
esterification in tobacco and canola oil,
Ultrasonics Sonochemistry (2014)
[18] J. Sáez-Bastante et.al, Influence of vegetable
oil fatty acid composition on ultrasound assisted
synthesis of biodiesel, Fuel(2014)
[19] Bin Ye et.al, Transesterification of Soybean
Oil to Biodiesel in a Microwave-Assisted
Heterogeneous Catalytic System, Chem. Eng.
Technol. 2014, 37, No. 2, 283–292
[20] Nezihe Azcan, Aysegul Danisman, Alkali
catalyzed transesterification of cottonseed oil
by microwave irradiation, Fuel 86 (2007) 2639–
2644
18 Proceedings of International Conference on Chemical Industry
[21] Su Zhang et.al, Rapid microwave-assisted
transesterification of yellow horn oil to biodiesel
using a heteropolyacid solid catalyst,
Bioresource Technology 101 (2010) 931–936
[22] Ming-Chien et.al, Microwave-Assisted
Heterogeneous Catalytic Transesterification of
Soybean Oil, 2012 International Symposium
on Computer, Consumer and Control
[23] N. Tippayawong, P. Sittisun, Continuous-flow
transesterification of crude jatropha oil with
microwave irradiation, Scientia Iranica B (2012)
19 (5), 1324–1328
[24] Prafulla D. Patil, Biodiesel Production from
Waste Cooking Oil Using Sulfuric Acid and
Microwave Irradiation Processes, Journal of
Environmental Protection, 2012, 3, 107-113
[25] Mehulkumar L Savaliya, Bharatkumar Z
Dholakiya, Chemical Transformation of
Triglycerides of Fatty Acid of Pongamia pinnata
Seed to Fatty Acid Methyl Esters by Microwave
Irradiation, Chemical Sciences Journal, Vol.
2013: CSJ-104
[26] V.S. Moholkar, et.al, Hydrodynamic cavitation
for sonochemical effects, Ultrasonics
Sonochemistry 6 (1999) 53-65
[27] Vitthal L. Gole et.al, Hydrodynamic cavitation
as an efficient approach for intensification of
synthesis of methyl esters from sustainable
feedstock, Chemical Engineering and Processing
(2012)
[28] Jianbing Ji et.al, Preparation of biodiesel with
the help of ultrasonic and hydrodynamic
cavitation, Ultrasonics 44 (2006) e411–e414
[29] Parag R. Gogate, Cavitational reactors for
process intensification of chemical processing
applications: A critical review, Chemical
Engineering and Processing 47 (2008) 515–
527
[30] Mandar A. Kelkar et.al, Intensification of
esterification of acids for synthesis of biodiesel
using acoustic and hydrodynamic cavitation,
Ultrasonics Sonochemistry 15 (2008) 188–194
[31] Amit Pal et.al, Biodiesel production through
hydrodynamic cavitation and performance
testing, Renewable Energy 35 (2010) 619–624
[32] Muhammad Dani Supardan et.al, Biodiesel
production from waste cooking oil using
hydrodinamic cavitation, makara, teknologi, vol.
16, no. 2, november 2012: 157-162
[33] Dyneshwar Ghayal et.al, Optimization of
biodiesel production in a hydrodynamic
cavitation reactor using used frying oil,
Ultrasonics Sonochemistry 20 (2013) 322–328
[34] Vitthal L. Gole, Parag R. Gogate, Intensification
of synthesis of biodiesel from non-edible oil
using sequential combination of microwave and
ultrasound, Fuel Processing Technology 106
(2013) 62–69
[35] I. Choedkiatsakul et.al, Biodiesel production
from palm oil using combined mechanical
stirred and ultrasonic reactor, Ultrasonics
Sonochemistry 21 (2014) 1585–1591