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Second Generation Feedstock: Biodiesel from Jatropha

Apoorvaa Singh and R. P. Singh*
ABSTRACT: Depleting finite oil reserves and the ever increasing demand for the fuel is driving forces to search alternatives fuels
from renewable resources with smaller environmental impact. One of the most promising alternatives to the petroleum based fuels is
the Biodiesel, which is of the plant origin. Biodiesel is defined by the American Society for Testing and Materials (ASTM) as the
mono- alkyl ester of long chain fatty acids derived from a renewable lipid feedstock. The major oil seed crops used for the production
of biodiesel include sunflower, soybean, rapeseeds, linseed, cottonseed, canola etc. Majority of which are edible in nature. Use of
edible oils for biodiesel production is unaffordable and illogical due to the high cost of the edible feedstock, an increasing demand for
food worldwide and concerns about using virgin forests and arable land for large scale biodiesel production have thrown considerable
attention on non- edible oils such as, JATROPHA, as attractive alternative feedstock. Crude Jatropha oil has FFA content up to 15%,
which is beyond the acceptable limit for the processing using a conventional base- catalyzed process. Using a conventional
homogeneous- catalyzed process to produce biodiesel from the crude Jatropha is technically, economically, and environmentally more
challenging than using the same process to make biodiesel from edible oils. It requires multi-step processing, oil pre-treatment,
neutralization of the waste homogenous catalyst, water washing of the crude biodiesel and glycerol, and treatment of the waste
generated. All these processes are complex and are too inefficient to be considered for industrial scale production of biodiesel. The
Problems associated with using a homogeneous catalyzed process to make biodiesel from feedstock with high FFA content have been
addressed by using the heterogeneous catalyzed process for the production of biodiesel from the oil containing FFA. This review
paper will cover the 2and Generation heterogeneous catalyzed process technology, which is a single step integrated process with a high
quality of biodiesel from the crude JATROPHA oil.
KEY WORDS: Jatropha, FFA, feedstock, heterogeneous catalyzed process, trans-esterification, and lipids.
Introduction
The ever increasing energy demand of industrial world for
industry, transport, agriculture etc., the extra dependency on
fossil fuels and consequent pollution problem, day to day
depleting oil reserves are major driving force to search for
alternative fuel from renewable sources with smaller
environmental impact [1]. Biofuels are considered in part, a
solution to such issues as sustainable development, energy
security and a reduction of greenhouse gas emissions
biodiesel, an environmental friendly. Diesel fuel similar to
petro-diesel in combustion properties, has received
considerable attention in the recent past worldwide [2].
Biodiesel is a biodegradable and non-toxic renewable
alternative to diesel fuel that is composed of mono-alkyl esters
of long-chain fatty acids derived from vegetable oils or animal
fats. Biodiesel is increasing in importance because of its
benign impact on the environment.
Corresponding Author- Apoorvaa Singh
Harcourt Butler Technological Institute, Kanpur
208002 India
E-mail: asworthit@gmail.com
*Professor Dr. R. P. Singh
Oil Technology Oil & Paint Technology Department
Harcourt Butler Technological Institute, Kanpur 208002
India
*E-mail: rpshbti@rediffmail.com

Biodiesel is produced mainly through the trans-esterification

of vegetable oils using short-chain alcohols, typically
methanol or ethanol, because these are cheap and readily
available from syngas, in which methanol is usually preferred.
Globally the availability of feedstocks for biodiesel
production varies considerably according to the location and
climate.
The important factors to be considered in the selection of
biodiesel feedstocks are chemical composition of fats and oils,
its cost and availability, transport and pre-treatment. Out of the
three chemical compositions is important to determine the
amount of free fatty acids (FFAs) in oil. In the first generation
feedstock various edible oil seeds such as soybean, rapeseed
oil, sunflower oil, palm oil, and canola oil have been used for
the production of biodiesel. But in todays generation the high
cost of edible feedstocks, an increasing demand for food
worldwide and concern about using virgin forest and arable
land for large scale biodiesel production have thrown
considerable attention on non-edible oils. The use of nonedible oils such as grease, waste oil, JATROPHA oil[3],
animal fats, used cooking oil comprises the second generation
feedstocks. Among the non-edible oils Jatropha is considered
as one of the most advantageous feedstock in terms of
economical, sociological and environmental implications.
Jatropha is considered as the main source of biodiesel in the
future. Apart from its high content of oil up to 40% it has
other numerous advantage as well, such as fast growth, easy
propagation, non-competitive to other crops, ability to grow in
arid and semi-arid region also its high yield per hector per
year. More over jatropha oil has properties similar to that of
petroleum diesel. Traditionally transesterification process is
used to convert the vegetable oil into biodiesel.

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The transesterification of jatropha oil with methanol, also
known as methanolysis, is typically carried out in presence of
homogeneous acid or base catalyst. Homogeneous basic
catalyst including sodium hydroxide, potassium hydroxide,
and sodium and potassium alkoxide have more catalytic
activity compared to the acid catalyst. Since acid catalysts are
more corrosive than basic catalyst, base catalysts are usually
preferred for commercial purposes. Crude jatropha oil can
have an FFA contain of up to 15%, which is beyond the
acceptable limit for the processing using a conventional base
catalysed process [4]. This limitation can be overcome by
using the two steps processes involving an acid-catalysed
esterification followed by a base catalysed transesterification.
How-ever this two-step process increases the system
complexity and raises the cost of producing the biodiesel from
Jatropha oil. Using a conventional homogeneous catalysed
process to produce biodiesel from crude jatropha oil is
technically, economically, and environmentally more
challenging than using the same process to make biodiesel
from edible oils.
It requires multistep processing, oil-pre-treatment,
neutralization of the waste homogenous catalyst, water
washing of crude biodiesel and glycerol, and treatment of
waste generated- all of which make the purification of the
biodiesel to meet the biodiesel quality standards more
difficult. The problem associated with using a homogeneous
catalysed process to make biodiesel from feedstock with high
FFA content have been addressed by using a heterogeneous
catalysed process for the production of biodiesel from jatropha
oil. Recently heterogeneous catalysts used to catalyse the
transesterification reaction to prepare fatty acid methyl esters
(FAME) have attracted the considerable attention. There are
various heterogeneous catalyst that are being used in the
transesterification process which can be divided in to broad
categories namely solid acid catalyst and solid base catalyst.
Solid acid catalysts are replacement of the liquid acids and
also eliminating the corrosion problem and environmental
hazard. Studies have shown that no correlations yet have been
established between the acid strength and the catalytic activity.
Few of the examples of the solid acid catalyst are tungsten
oxide, sulphonated zirconia and artificial acidic zeolite. Solid
basic catalysts have been used a lot as the heterogeneous
catalyst with a great success. Various basic catalysts are under
study and their catalytic effect on the jatropha oil biodiesel
production via transesterification. Various solid basic catalyst
studied in this review work are basic zeolite, Nano-sized
hydrotalcite particles MgO (magnesium oxide), calcium oxide,
and various catalyst supported over alumina. Their initial stage
of the use and the modification made to enhance the yield and
conversions have also been taken into account. The review
suggests that the interest in the heterogeneous catalyst for
biodiesel production have been growing since last few years.
Though the use of heterogeneous catalyst have open up a new
path way for the biodiesel production, but to sustain the ongoing momentum and advancement at the commercial level
more research are need.

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1. Second generation feedstock-jatropha oil
First generation feedstock contain various edible oil seeds
such as soybean, rapeseed oil, sunflower oil etc. using such
crops for the biodiesel production could lead to various
problems. The high cost of edible feedstocks, an increasing
demand of food worldwide and the concern about using the
virgin forest and arable land for the large scale biodiesel
production have thrown considerable attention on the nonedible oils. Using non-edible oils for the commercialised
production of biodiesel have eliminated all the conditions for
the fuel verses food as these non-edible oils can nowhere be
used for the human or animal consumption. The non-edible
oils such as grease, jatropha oil, waste vegetable oil etc.
comprises the second generation feedstock, which dont
require special attention for their production. Among various
available options as the second generation feedstock we
choose Jatropha oil as the key centre of our studies. The
highlighting factors of our choice are mainly based on its yield
per hector per year (its around 5-10 ton per hector per year),
its productivity for forty long years and also importantly its
high oil content that is around 40-60% of the total oil seed
content. Moreover the chemical composition of the jatropha
oil [4] is more or less similar to that of other edible oils, which
is one of the important factor to be considered which selecting
an oil species for the commercialized biodiesel production.
Apart from these major advantages the Jatropha plant can
virtually grow anywhere. It does not particularly require fertile
land. They are inexpensive as well as abundant in nature.
Adding to these it is an easily grown and propagating with
medicinal importance.
Transesterification reaction
The vegetable oil cant be directly used in CI engines because
it requires engine modification and is not feasible due to its
higher viscosity and low volatility. So the Jatropha oil has to
be converted into Jatrodiesel before it could be used for other
commercial purposes. Reducing the viscosity of jatropha oil to
use it in CI engines there are four common methods: blending
them with petro-diesel, pyrolysis, transesterification and
emulsification. With pyrolysis and emulsification the engine
requires a modification as these process produces heavy
carbon deposits and undesirable side products such as alkane,
alkene etc. moreover it leads to incomplete combustion. To
produce biodiesel, the easiest way is transesterification of the
triglycerides using alcohol in the presence of acid/base
catalyst. In transesterification reaction the ester group from the
triglyceride is detached to form three alkyl esters. This process
comprises of three sequential reversible reactions, wherein
triglyceride reacts to form diglycerides, monoglycerides and
glycerol.
Triglycerides + ROH diglycerides+

FAME

Diglycerides + ROH monoglycerides+ FAME

Monoglycerides+ ROH glycerol+ FAME

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The Biodiesel production consist of esterification (or its
variation such as glycerolysis, enzymatic or temporary solid
catalyst) and transesterification. Traditional esterification
method uses methanol with a homogenous acid catalyst such
as sulphuric acid to convert FFA into esters. And
transesterification uses homogenous base catalyst such as
sodium methylate or potassium methylate along methanol to
convert to the triglycerides into biodiesel and glycerine. With
high % of FFA homogenous catalyst start offering various
problems.
Catalyst
Catalyst is a chemical that help speed up the chemical process
without actually participating in the reaction. There are two
type of catalyst typical to any bio diesel production
Homogenous and heterogeneous Homogenous catalysts
function in the same phase (liquid, gaseous, etc.) as the
reactants. Typically homogenous catalysts are dissolved in a
solvent with the substrate. Heterogeneous catalysts occur in
the different phase than that of the reactants. Most of the
heterogeneous are mainly solid that act on a substrate in a
liquid or gaseous reaction mixture. The diverse mechanisms
for the reaction on the surface are known and it depends on
how the adsorption takes place. Total surface area of the solid
has an important effect on the reaction rate for the
heterogeneous catalyst Homogenous catalysts for biodiesel
production have been used for quite a sometime but the uses
for the heterogeneous catalysts have been fairly new
development.
The process
Biodiesel processing involving high FFA content of the oil is
comprised of two steps, esterification and transesterification.
During the esterification, a predetermined quantity of the
sulphuric acid based on the FFA content of the oil being
processed, is added to the oil along with methanol. The
reaction temperature is around 65-70 degree Celsius under
atmospheric pressure. The important by-product of the
esterification process is water which dilutes the conventional
homogeneous catalyst thereby hindering the esterification
process. Higher yield can be obtained if the water is removed.
The addition of the material such as XYLOL to form
azeotropic mixture with water or application of the mild
vacuum to the reaction vessel is useful aid in removing the
water of the reaction. Transesterification reaction also occurs
at the time of the esterification only after esterification has
reached its equilibrium. After reducing the FFA of the oil
through esterification process to less than 1% the oil goes to
the transesterification phase. Direct transesterification more
usages of the catalyst. Higher process cost due to the acid no.
issue that has to be fixed so that fuel produced can meet the
ASTM D6751 specification. During the transesterification of
the oil with high free fatty acids, when the triglycerides are
converted to the di-/mono- glycerides, the FFA is converted
into soaps. Higher FFA, higher soap production, which goes
into the glycerine phase in the settling process or centrifuging.
There is also some residual homogenous catalyst left over

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from bio-diesel process that has to be removed. This increases
the cost of biodiesel. Thus using homogeneous catalysed
process to produce biodiesel from crude jatropha oil is
technically, economically and environmentally more
challenging.
Heterogeneous catalyst
Knowing that catalyst is an important part of a chemical
reaction (transesterification here) and having learnt the
disadvantages of the conventional homogeneous catalyst, the
need for a search for second generation catalyst leads us to
heterogeneous catalyst. Comparing heterogeneous catalyst to
homogeneous catalyst, heterogeneous catalyst [5] offers a
moderate rate of conversion in a continuous process. These are
neither water sensitive nor to FFA. They offer a possibility of
reuse and are cheaper. Heterogeneous catalyst can be broadly
categorized into two categories: solid acid catalyst and solid
base catalyst [6]. Solid acid catalyst is substitute of corrosive
hazardous conventional liquid acid catalyst. But these
catalysts did not an industrial application due to the following
major reasons as these catalyst offer slow reaction
rate/activity, and adverse side reactions. Adding to its solid
acid catalyst must have pores that should be interconnected
and available on entire surface. The surface should be
hydrophobic to poromote preferential adsorption of oily
hydrophobic species on the catalyst surface. The catalyst is
deactivated by the strong adsorption of the polar by products
[7,8]. The thermal stability of the solid acid catalyst becomes
issue at higher temperature (in order to achieve the higher
reaction rate). Moreover the correlation between the acidic
character and the activity has not been studied yet. The various
acid catalysts are: tungsten oxide, sulphonated zirconia,
sulphonated saccharides, acid zeolites (artificial) etc.
Solid base catalyst
They are comparatively more active even at lower
temperature. The various examples of solid base catalyst
includes basic zeolites, Nano sized hydrotalcite particle, CaO,
MgO.
(1) Basic zeolites
The activity of such catalyst depend upon basic site
in cation
Basic strength of alkali ion exchanged zeolite
increases on increasing positive nature of exchanged
cations.
Exchange can affect the water tolerant behaviour.
Li containing zeolites have been used for
transesterification.
(2) Oxides as catalyst
MgO, CaO are extensively used owing to their easy
availability, low cost and non-corrosive nature.MgO initially
gave low conversion(rate of 18%) due to low surface area but
presently 92% conversion was obtained using 12:1 molar
ratio, 5% catalyst.Its activity can be further enhanced by
loading it on mesoporoussilicas which can be done better in

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suite or via impregnation. Magnesium concentration found to
be more dominant over physical properties [9]. KOH loaded
over MgO gave high conversion (99.36%). KOH/MgO after
calcination was resistant to water and at as heterogeneous
catalyst thus displayed better results. K2CO3 and Ca
combination have also been used and a high yield was
obtained (98%) but it was found to be water sensitive. The
catalyst can be reused ^ times, but only after calcination.
Various nano-sized catalyst have been prepared from gammaAl2O3 spheres and Mg(NO3)2.6H2O by urea hydrolysis
method. Mg and Al doubled layered hydroxide are formed
which on heating gave magnesia rich magnesium aluminate
spinel frame work (MgO.MgAl2O4) which was an aggregate
of nano sized particle. Comparing the yield of calcined and
uncalcined double oxide the yield of MgO.MgAl2O4 was
found to be better. The possible reason for this could be high
basic strength, high surface area, large pore size and volume
and better diffusion of reactant and products over its surface.
Like MgO, CaO can also be effectively used for the biodiesel
production after treating it with ammonium carbonate solution
followed by calcination at 900 degree celcius. For Jatropha oil
it gave a high yield of 93% at optimum temperature and
pressure conditions [10]. This catalyst can be used three times
with 92% conversion [11]. Various compounds like lithium
nitrate, potassium nitrate, sodium nitrate were doped on MgO
and CaO and a correlation between the basic strength and the
activity have been established [12]. Leaching of catalyst is a
major drawback in the case of calcium oxide.
(3) Mixed oxides as catalyst
The mixed oxide of Zn and Al offer a high conversion rate of
98.2% but high temperature and pressure condition are
required [9]. ZnO loaded on Sr(NO3)2 and Ba(NO3)2 gave
unsatisfactory results while the other way round gave up to
99% conversion. The yield can be increased using the THF as
a co-solvent. Ca-Zn mixed oxide formed by the coprecipitation has been used as catalyst for the
transesterification. It contains Cao and ZnO nano clusters.
They are smaller in size, high surface area. The amount of
Zinc in the mixture reduces the size. The catalyst could be
used three times.

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i.e. calcination at high temperature also makes the process
energy intensive. Calcination leads to transformation of the
origination compound to a new compound that possesses
catalytic-active species. Calcination also enhances the
basicity, pore size, and pore volume of the catalyst. This is
evidenced from MgO as catalyst which initially did not
showed catalytic activity, but after its modification
(calcination, etc.), a high yield and conversion was obtained.
Alumina loaded with various compound have been tried as
Catalyst and have shown varying results. Alumina loaded with
KNO3 and Eu2O3 have shown conversion less than 90%,
whereas alumina loaded KF and KOH has shown high yield of
9091%. On contrary KI/Al2O3 has shown a high conversion
of 96% and is near to the specification of EN 96.5%). Zeolites
have shown conversion ranging from 85% to 95% and have
taken longer reaction time for completion of reaction and thus
will need further modification for a higher yield and
conversion to meet the international specifications. The energy
efficiency and cost aspect of biodiesel is a very important
aspect and has to be dealt exhaustively for a catalyst. This has
been dealt to some extent in the review paper by examining
the calcination temperature and time, reaction conditions
(molar ratio, time, temperature, and the type and amount to
catalyst used). This is a general assumption and does not
necessarily be used for comparison of catalyst to be suitable in
industrial point of view. A technique that utilizes supercritical
conditions has gained attention for the synthesis of biodiesel
where the catalyst is generally not added. A high temperature,
pressure, and alcohol volume is needed which makes the
process costly. However, the process is tolerant to high FFA
and water contents in the feedstock and the reaction gets
completed in comparatively shorter time duration.
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CONCLUSION
The review indicates a growing interest in the development of
heterogeneous catalyst. The emphasis laid on the application
of heterogeneous catalyst is mainly to overcome the limitation
incurred by homogeneous one. These limitations were mainly:
separation of catalyst from reaction mixture, large amount of
water generated during washing stage. However, most of the
catalysts listed in the review require comparatively longer
time duration while some of them need higher temperature
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