Biodiesel

1
 It is vegetable oil or animal fat-based clean diesel fuel consisting of long-
chain alkyl (methyl, ethyl, or propyl) esters.

 Can be used with little or no engine modifications.

 Feedstocks available

1. Edible vegetable oil

2. Non-edible vegetable oil

3. Waste recycled oil

4. Animal fats
 Biodegradable, renewable, non-
toxic substitute to petroleum oil.
 Reduces the air pollution by lower
emission of CO and NO.
 Has the potential to diminish the
global warming problem caused
by CO2 and other particulate
matters.
 Has properties and performance
characteristics similar to
conventional fuels.
 Low sulphur and aromatic content
and high flash point.
 Various Feedstocks for Biodiesel Synthesis
Edible oils Non-edible oils Animal fats Other sources
Sunflower Tobacco seed Poultry fat Switchgrass
Soybean Rubber seed Pork lard Spent coffee grounds
Sesame Neem Fish oil Poplar
Safflower Nagchampa Chicken fat Olive stones
Rice bran Mahua Beef tallow Miscanthus
Rapeseed Krating oil Microalgae
Peanut Karanja Fungi
Palm Jojoba Cyanobacteria
Mustard Jatropha curcas Callophyllum inophyllum
Groundnut Croton meganlocarpus
Corn Cotton seed
Coconut Castor
Canola Camelina sativa
Barley
09-Nov-21 Dr. G. N. Halder- NIT Durgapur 4
Traditional conversion approaches

Other novel Two-step

Alkali Enzyme
Acid catalysis heterogeneous catalyzed
catalysis catalysis
catalysts process
 The acid catalyzed conversion is termed as ‘esterification’ and involves the conversion of free fatty
acids present in the oil to esters and water using polar alcohols such as methanol or ethanol.
 Along with esterification, transesterification of glycerides also takes place albeit to a smaller degree.
 Usually mineral acids (such as HNO3, H2SO4 or HCl) are used as they provide greater reactivity
compared to other weaker acids.
 The esterification process involves adding H+ to the O atom in a carboxyl group, which is followed
by the alcohol performing a nucleophilic attack on the fatty acid aided by the protonated acid
catalyst, which results in breakage of a H2O molecule and a proton (adds back to the acid catalyst),
resulting in ester formation.
 Esterification is the chemical process that combines alcohol (ROH) and an organic acid (RCOOH)
to form an ester (RCOOR) and water. This chemical reaction results in forming at least one product
of ester through an esterification reaction between a carboxylic acid and an alcohol.
 The use of bases in a transesterification are probably the most common practice at conversion of compatible
feedstock (low in free fatty acid and moisture) into esters.
 The conversion involves formation of an alkoxide ion from the base and the alcohol, which then targets the
triglyceride (for example), attacking the carbonyl carbon and forming a tetrahedral shaped intermediate.
 This compounds then undergoes reaction with an alcohol molecule, undergoing a structural rearrangement
during the process to give off an ester molecule and leading to the formation of a diglyceride. This process
will now repeat itself twice to finally yield glycerol as a by-product.
 The process cannot tolerate even traces of free fatty acid and moisture except for KOH, which is why it is
favoured over other bases. along with 2 moles of alkyl ester.
 The process can also include homogeneous and heterogeneous catalysts, with doped basic groups being
more stable compared to acidic groups.
 Many edible and non-edible oils (including waste oils) have been converted into biodiesel through this
process.
 The wastewater generated from washing of fuels generated using acid or base catalysts is not
pH neutral and thus can hamper water bodies connected to the discharge stream if the
generated effluent is left untreated before drainage.
 Enzymes can also be beneficial in conversion of high-free fatty acids feedstock since
saponification cannot take place as both glycerides and free fatty acids are converted to
esters.
 They also offer certain other advantages such as:
i. A low alcohol to oil ratio is needed, with de-emulsification conferring reusability of
enzymes
ii. Low product inhibition and reacting temperature, with easy separation in case of
heterogeneous immobilized enzymes
iii. Single step conversion with appreciable yields and are insensitive to moisture exposure.
 Disadvantages:
i. They do require far longer durations to complete conversion, and since enzymes are very
temperature sensitive, the reaction must be closely monitored.
ii. Another problem associated with them is their high costs as well as limited reusability due
to structural denaturation and moderate conversion efficiencies compared to acid or base
catalyzed systems.
 Lipase is the most common enzyme used, and is obtained from animals, plants or
microbes and must not be stereo-specific for maximum conversion efficiency.

 Bacterial and fungal lipases (example being Novozym 435 obtained from Candida
antarctica or other enzymes extracted from sources such as Penicillium sp., Rhizopus
spp. and Aspergillus niger) used can show maximum yield up to 90%, when operated
between 30°-50°C for anywhere between 8h to 90h depending on feedstock .
 There exist quite a number of reports by researchers on successful conversion of oil into
biodiesel using catalysts that do not fall under the general spectrum of acids, bases or
enzymes. Mostly heterogeneous in nature, they are usually insensitive to the presence of free
fatty acids and can convert them as well into esters.

 The preparation strategies for each catalyst therefore varies greatly as they can be the source
material itself (albeit modified to a certain extent) a chemical compound that exists naturally
as a salt, or other inert supports (carbonaceous or siliceous) that have been doped with
transition metals, which are able to catalyse the transition much more efficiently.

 The form of doping in the last category is usually by the use of analytical grade salts
containing the metal ion which gets impregnated, leaving the anion to be washed off.

 Natural waste materials containing such elements can also be processed and used as a cost-
efficient alternative (such as cow bones for calcium doping).
 Many researchers opt for this method, in which acid esterification is used for pre-treating the
oil in order to make it suitable for base catalyzed conversion before performing alkali
catalyzed transesterification which can completely convert the glycerides into esters, since
bases are sensitive to high free fatty acids (owing to saponification) as well as moisture
(owing to hydrolysis).
 The process can comprise of either esterification-transesterification steps or hydrolysis and
esterification steps .
 Hydrolysis combined with esterification is comparatively more wasteful as generation of
free fatty acids is an energy intensive process since high temperatures (exceeding 300°C)
and pressure (exceeding 10MPa) are required.
 In the two-step catalyzed process involving esterification and transesterification, acid
catalysts remove almost all of the free fatty acids through conversion to esters and water,
which can be then purified and dried prior to using base catalysts which convert the
glycerides into esters and glycerol.
 The glycerol and excess alcohol can be removed through washing or by ultracentrifugation
before being tested for suitability as fuel.
 Non-polar alcohols result in better biodiesel yield compared to polar alcohols and thus, they
hold great potential for use in biodiesel production.
 Transesterification (also called alcoholysis) is the reaction of a fat or oil with an
alcohol to form esters and glycerol

CH2OOR1 Catalyst CH2OH

| |
CHOOR2 + 3CH3OH 3CH3OORx + CHOH
| |
CH2OOR3 CH2OH
Triglyceride Methanol Biodiesel Glycerol

 R1, R2, and R3 are fatty acid alkyl groups (could be different, or the same), and
depend on the type of oil. The fatty acids involved determine the final properties
of the biodiesel
 TRANSESTERIFICATION PROCESS
The process of transesterification (also termed as ‘alcoholysis’)
involves exchanging the alkyl group in an ester by the alkyl group of
the reacting alcohol with the formation of fatty acid alkyl esters and
glycerol.
The wide use of this process is for the reduction of the high viscosity
of triglycerides.
 The process undertaken for feedstock selection, analysis for its
suitability to be transesterified and the final production collection.
Triglyceride transesterification leads to the production of alkyl esters
of fatty acids (FAAE) with the simultaneous production of glycerol.
Since the glycerol layer is heavy, it forms a layer at the bottom when
kept standing for separation in a separating funnel.
 The reaction has 3 steps, with the first step producing diglycerides as
intermediates, after which these diglycerides are utilized to produce
FAAE with monoglycerides as the intermediates in this process.
09-Nov-21 Prof. G. N. Halder- NIT Durgapur 14
 ESTERIFICATION TRANESTERIFICATION

 Esterification is the process in which an  Tansesterification is the exchanging of the

ester is formed alkyl group attached to the oxygen atom of
the ester with the alkyl group of an alcohol

 Ester is the end product  Ester is a reactant

 Byproduct is water molecule  Byproduct is an alcohol molecule

 Requires an acid catalyst  Requires acid or base catalyst or enzyme

 Requires heat energy  Does not require heat energy

 The esterification process depends on various parameters such as the FFA
content, the amount of catalyst, the molar ratio of methanol to oil, reaction
temperature and time.

 Among these parameters, reduction of the FFA content is most challenging

and dominant. High FFA in the oil (>2% w/w) is undesirable during base
transesterification because it affects the biodiesel yield negatively owing to
saponification with the alkali catalyst, which further complicates the process
of separating the biofuel from the glycerine fraction and causes difficulty in

ester purification
 The rate of conversion of FFA or the acid value of oil signifies completion of
the esterification reaction. The FFA value should be finally reduced to less
than 2% before proceeding towards base transesterification.
FFA Determination Methodology:
 A solution of 50 ml of 0.1 N aqueous KOH was prepared for use as a
standard. A 1 g sample of the oil was weighed in a beaker and 50 ml
isopropanol was added and warmed on a hotplate.
 This solution was cooled and two drops of phenolphthalein indicator
were added.
 The solution was then titrated against alcoholic KOH added dropwise
and shaken occasionally until a faint but permanent pink color was
obtained.
 This color should persist for at least 30 minutes. The volume
of standard solution required to turn the solution pink was
noted.

 The titration was performed in triplicate to ensure the

accuracy of the results finally obtained.
 FFA is calculated by the following equation
t x 0.1 x 28.1
FFA (%) = -------------------
W
 Where, t is the titrated value,
 W is the weight of oil sample taken;
 28.1 is the weight of oleic acid present in the sample and
 0.1 N is the strength of the aqueous solution.
 Instrumental analysis

 Catalyst support development

 Optimisation of process parameters

 Reusability study of the spent catalyst

 Process kinetics

 Thermodynamics of transesterification

 Cost estimation of catalyst and the biodiesel synthesis

process for scale-up
 CHEM-CATALYTIC
HETEROGENEOUS
TRANSESTERIFICATION

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 Experimental Study
K-DOPED Ac CATALYST SUPPORT
FOR
BIODIESEL production
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 Development of the catalyst support from waste biomass.

 Optimization of the catalyst synthesis process by response surface

methodology.

 Doping of potassium onto the catalyst support.

 Application of developed heterogeneous catalyst in

transesterification process.

 Characterization of the produced biodiesel.

 Estimation of life span of the catalyst by reusability study.

 Precursor Selection:
O Flamboyant pods (Delonix Regia) collected from
Wardha, Maharashtra
O Abundantly available in tropical regions.
O It is a waste and reported high surface area by
KOH activation.

Biomass Analysis:
1. Proximate analysis
Apparatus- Hot Air Oven, Weighing
Machine, muffle furnace, crucible, Petri Dish
2. Thermo Gravimetric Analysis (TGA)
Analytical Instrument: Thermo-gravimetric
Analyser
Feedstock for biodiesel production: Rubber seed oil
 It is abundantly available in tropical region.

 Rubber tree are cultivated for use of its latex as source of natural rubber.

 Rubber seeds yields 40-50 % of oil.

 India is one among the top most countries producing rubber seed in the world
and Kerala is leading rubber plantation state of India.

 It is estimated that 5000 tonnes per annum oil can be produced from rubber
seeds.

 It is good source of non-edible oil for production of biodiesel in developing

countries like India.
Information to obtain:
Thermal stability of catalyst and
mass loss w.r.t. temperature.

Phase-1: Mass loss due to

moisture removal at 100C
Phase-2: Mass loss due to
volatile matter removal at 450-
800C
Phase-3: Continuous mass loss
occurs after 800C
 KOH
Optimization
Flamboyant impregnation
of the process
pods on activated
by RSM
carbon

Steam
Cleaned activation of Characterizati
and Dried char at 350 C on of the
at 105 °C at 1.5 h catalyst

Proximate Used as a
Carbonization catalyst in
analysis and
at 500 °C Transesterificat
TGA
ion
Parameters chosen for optimization:
1. Activation temperature (300 to 400 °C)
2. Activation time (1 to 2 hr)

Range of chosen parameters:

 For Surface Area

For Total Pore Volume

Information to obtain:
Maximum surface area in
the activation process was
found to be approximately in
range of 800–850 m2/g at an
activation temperature of
350 degree C and activation
time of 1.5 h. With further
increase in activation time
and temperature
leads to significant decrease
in surface area
Information to obtain:
Maximum total pore volume
was found to be 0.3253
cm3/g for activation time of
1.5 h and activation temp
of 350 degree C. If both the
parameters was increased
further then there was
considerable fall in total
pore volume implies the
high significance of these
parameters on total pore
volume.
Surface Texture of Raw Carbon Surface Texture of Steam
Activated Carbon
KOH Impregnated Steam Activated Carbon
Information to obtain:
Percentage composition of
constituent elements of the
material.
Information to obtain:
Presence of functional groups
C-H: Alkane group
O-H: Alcoholic group
C=O: Aldehyde group
C=N: Ketone group
C=C: Ester group
Information to obtain:
Crystallinity of the material
Strong and sharp peaks at 2θ
of 12.28, 23.74, 28.26, 30.72,
40.38, 43.32
Crystalline phase:
Orthorhombic and this is
important for catalytic
activity.
Raw Material: Hevea Brasiliensis oil
Catalyst: KOH impregnated carbon based catalyst
Solvent: Methanol
Apparatus: Hot plate magnetic stirrer, 3 necked reaction vessel with glass condenser,
Thermometer, separating funnel

Process Parameters:

1. Reaction Temperature: 60°C

2. Reaction Time: 1 hour

3. Revolution per Minute: 750

4. Oil to methanol ratio: 1:5 to 1:20

5. Catalyst loading: 0.5 to 5.0 gm of KOH/gm of AC

Information to obtain:
Increase in C.L Decrease in yield

Due to saponification by leaching of

weakly absorbed KOH into reaction
mixture. Again due to increase in
viscosity causing addition of extra
film resistance.
Information to obtain:
Increase in Methanol/Oil ratio:
Increase in yield
Optimum ratio: 15.1, 89.3% yield
Due to unavailability of sufficient
methanol molecules, reaction will be
driven to forward direction for
reversible transformation.
The weight of the final RSME was measured and used to calculate
the biodiesel yield by the following expression:

Weight of biodiesel produced

Yield % = --------------------------------------------- x 100
Weight of rubber seed oil used in reaction
 Optimum condition for physical activation time: 1.5 h and activation
temperature: 350 °C. Maximum response at this condition was obtained:
surface area 812.2 m2/g and total pore volume 0.3253 cm3/g.

 The potassium doped carbon catalyst showed high performance and giving
yield of 89.3% at catalyst loading of 3.5 wt%, methanol to oil ratio of 15:1,
temperature 60°C in 60 minutes.

 Biodiesel produced from Hevea Brasiliensis oil having estimated properties

within limits suggested by ASTM.

 Reusability experiments showed 7-10 % decay in catalyst activity after 7 cycles.

Thank you for your
patience & giving me
an opportunity