WASTE TO ENERGY CONVERSION

ENERGY PRODUCTION FROM WASTES THROUGH

TRANSESTERIFICATION-2

DR. PRASENJIT MONDAL

CHEMICAL ENGINEERING DEPARTMENT

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 Contents

 What is transesterification ?
 Organic wastes for transesterification
 Production of bio oil from oil seeds and its major composition
 Need of upgradation of bio oil to bio diesel
 Bio diesel properties
 Upgradation flowsheets
 Steps for upgradation
 Biodiesel production from mixed waste pant oil
 Combustion of bio oil/bio diesel in diesel engine

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Steps for upgradation
 The complete process for the production of methyl ester from plant oil and
other feedstocks therefore involves basically five steps:

o Acid esterification Pre treatment

o Transesterification
o Methanol recovery
o Biodiesel refining
o Glycerin refining
.

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Acid Esterification (AE)
 Free fatty acids (FFAs) in biodiesel feedstocks react with alkali catalysts like NaOH
and KOH and form soaps, which reduce the oil properties of the biodiesel.
Triglycerides + FFAs+ Alcohol Base catalyst Na/K salt of FAs+ Triglycerides
o Low levels of FFAs (upto 4%) can be managed by using additional catalyst and
allowing soap formation. NaOH [%FFA](0.144) + 1 %; KOH: [%FFA](0.197)/0.86 +
1 %; Sodium methoxide: [%FFA](0.190) + 0.25 %.
 Feedstock containing > 4 % FFAs (Animal fats and recycled greases) are first
filtered and then pre-processed to remove water and other contaminants such as
unwanted solids. The pretreated oil is then fed to the acid esterification process.
Most plant oils and some food-grade animal fats do not require AE, (FFA< 4 %).
 The sulfuric acid, is dissolved in methanol and then mixed with the pretreated oil.
The mixture is heated and stirred, and the FAs are converted to biodiesel. Once
the reaction is complete, it is dewatered and fed to the transesterification process.
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Alternative method to remove/ manage free fatty acids (FFAs)
• Enzymatic methods – Very costly, not a popular choice.
• Glycerolysis – Glycerol is added to high FFA feedstock with catalyst (ZnCl2) at
200°C, which converts FFAs to monoglycerides and diglycerides.
ZnCl2 catalyst
FFA + glycerol monoglyceride and diglycerides + water

• Water is vented as it is formed. Requires high temperature and slow process.

• Acid catalysis followed by base catalysis- Acid catalysis for conversion of FFAs to
methyl esters, until FFA < 0.5% followed by addition of methanol and base
catalyst to finish the reaction
o Acid such as H2SO4 catalyzes both esterification and transesterification reactions.
Esterification of FFA is fast (1 hour) but transesterification is slow (2 days) at 60°C.
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Conversion of FFA
The conversion of FFAs can be determined from the following Equation
Where S0 is initial acid value and Si is the acid value at some
reaction time

Determination of acid value : Known amount of sample is added to some amount of

neutralized ethanol and is fully dissolved by heating. Phenolphthalein (0.5 mL) is used
as an indicator. The sample is then titrated with standard KOH solution.

The acid value is calculated as

where S is the acid value (mg KOH/g WCO); c is the concentration of the KOH used
for titration (mol/L); V is the volume of KOH employed for titration (mL); m is the mass
of the sample taken to be analyzed (g).
Ding et al., 2012, Energies, 5, 2683-2691
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Transesterification
 The plant oil, which contains less than 4% free fatty acids, is first filtered and
then pre-processed to remove water and other contaminants.
 The pretreated oil is then fed directly to the transesterification process along
with any products of the acid esterification process.
 The catalyst, potassium hydroxide, is dissolved in methanol and then mixed with
the pretreated oil. Heterogeneous catalyst can also be used.
 If an acid esterification process is used, then additional alkaline catalyst must be
added to neutralize any excess acid remaining from that step.
 Once the reaction is complete, the major co-products, biodiesel and glycerin,
are separated into two layers.

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Factors affecting transesterification process performance
 Reaction temperature
 Reaction-time
 Alcohol to oil mole ratio
 Catalyst concentration
 Free fatty acids content
 Mixing
 Water content
 Types of alcohol
 Catalyst types
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Some heterogeneous catalysts for bio diesel production
Operating conditions
Solvent Catalyst Yield
Feed stocks Catalyst Temp Alcohol Reaction
used loading (%)
(oC) oil ratio time (h)
wt%
Sunflower
Methanol SrO 65 12:1 3 0.5 90
oil
K2CO3/TiO2 (Ti:K
Soybean oil Methanol 60 12:1 6 2 25.15
= 0.65:1)
Amberlyst-15:
Babassu
Methanol Sulfonated ion 60 100:1 - 8 80
coconut oil
exchange resin
Waste Sulfonated carbon
Methanol 80 30:1 10 4 92
cooking oil based catalyst
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 Methanol recovery

 The methanol is usually removed immediately after the biodiesel and glycerine
have been separated. This is done to prevent the reaction from reversing itself.
Recovered methanol is cleaned and recycled back to the beginning of the process.

 Biodiesel refining

 Once separated from the glycerin, the biodiesel goes through a series of cleaning-
up or purification steps to remove excess alcohol, residual catalyst and soaps.
 These consist of multistage washings with clean water.
 The product biodiesel is then dried and sent to storage.
 It can be further refined through an additional distillation step to produce a
colorless, odorless, zero-sulfur, and premium quality biodiesel.

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Glycerine refining
• The crude glycerine from the transesterification process may be recovered or
used in a fuel blend for steam production.
• The crude glycerine contains unreacted catalyst and soaps that must be
neutralized with an acid.
• The water and alcohol are also removed to produce 50%-80% crude glycerin.
• The remaining contaminants include unreacted fats and oils.
• In large biodiesel plants, the glycerin can be further purified through a series
of unit operations to produce a product of 99% or higher purity.
• This purified product is suitable for use in the pharmaceutical and cosmetic
industries.

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Biodiesel production from mixed waste pant oil Modified from “Biofuels from Plant Oils”,
ASEAN Foundation, 2010
NaOH Catalyst
Waste cooking oil Pretreatment agent & Methanol
5-10% crude glycerin
Screening tank
Cleaned Heating Esterification
Feed tank
waste oil reactor
Sedimentation of soap
0.3 % activated
ZnSO4 0.5 % white earth
ZnSO4
glycerin
Warm Warm
Glycerin water Settling Crude
water
separator wash tank biodiesel Filters
tank
tank tank
Crude Glycerin
Waste water Sediments Biodiesel
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Pre treatment of waste mixed oils
• Waste plant oils recovered from restaurants and other sources is fed into a vessel
with metal filter to remove undesirable materials.
• The filtered oil accumulates at the bottom of the vessel and is transferred by a
gear pump to the Feed Tank.
• The Feed Tank is then heated to 500-600C.
• A pre-treatment agent and 5-10% crude glycerin are added to prevent
solidification of the oil and hasten the precipitation and sedimentation of soap
particles.
• The mixture is agitated for about 20 minutes and then settled for about one hour.
• The soap sediment is removed from the bottom of the tank and the pre-treated
oil is fed into the esterification reactor.
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Esterification process and biodiesel recovery

• Methanol and caustic soda, as catalyst, are mixed together in the methanol tank.

• Normally, the amount of caustic soda is about 4.7% of that of methanol, which is
sufficient to raise the temperature of the mixture in the methanol tank to 500C,
still below the boiling temperature of methanol of 650C.

• This mixture is pumped to the continuous esterification reactor to mix and react
with the pre-treated feed oil.

• Feed oil is first preheated to 700C by passing it through a tube coil heater before it
enters the esterification reactor.

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• The preheated feed oil and the solution from the methanol tank are mixed
through a line mixer and then reacted inside the continuous tube esterification
reactor where the retention time is around 30 minutes and the temperature is
kept under 600C.
• The reaction products are sent to the glycerin separator where crude glycerin,
which contains residual soap and methanol, is separated.
• The crude biodiesel is sent to the warm water tanks and the warm water wash
tank (heated and equipped with an agitator) for further treatment and refining.
• Zinc sulfate is added to the crude biodiesel in the warm water wash tank to
destroy the emulsion and precipitate residual soap.
• The mixture then goes to the warm water separator where the impurities are
separated from the supernatant crude biodiesel, which looks whitish and muddy
due to residual water contaminants in emulsion.
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• This crude biodiesel is sent to the settling tank to remove the contaminants. The
recovered water from the settling tank is treated under vacuum to remove
contaminants and then recycled back into the warm water wash tank.

• The crude biodiesel is further treated in the crude biodiesel tank by the addition
of 0.5% glycerin as de-watering agent and 0.3% activated white earth as
sedimentation agent (agitated for 15 minutes and settled overnight).
• The sediments are removed from the bottom and the treated supernatant is
further refined through filtration in the filtration tank.
• Further cleaning is attained by a second stage filtration in a paper filter.
• The refined biodiesel product is then placed in regular drums ready for delivery
and use.

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Glycerine recovery
The crude glycerine from the glycerin separator is stored in a neutralization tank,
which is glass-lined and equipped with a closed-type agitator.
It is heated under normal pressure to distil out the methanol, which is recovered
from the condenser located at the top of the neutralization tank.
The remaining crude glycerine is neutralized by the addition of hydrochloric acid and
the residual soap is converted into oil, which is removed from the upper layer.
Crude glycerine is taken from the bottom of the neutralization tank and pumped
first to the crude glycerin tank and then to the crude glycerin concentrator for
further treatment.

The crude oil that is skimmed off from the neutralization tank is burned as fuel for
heating the vacuum distillation unit.
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• The crude glycerin concentrator is equipped with steam-heated jacket and
vacuum ejector to remove water from crude glycerin.
• The crude glycerin is then sent to a two-stage vacuum distillation unit where
dissolved solids such as sodium chloride are removed (first stage) and 99.5%
glycerin with a light yellow color is produced.
• This product is further refined in the activated carbon treatment tank to remove
residual color.
• The amount of activated carbon needed to produce a product of acceptable
quality is 2-3% of the amount of glycerin.
• The activated carbon is mixed with glycerin for 15 minutes at a temperature of
900-1000C.
• The mixture is then passed through the glycerin filter to produce the final product
of clear 99.5% glycerin.
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Biodiesel production from mixed waste pant oil Alternative flowsheet

Heterogeneous acid catalysts for biodiesel production: current status and future challenges, Juan et al,
2009, Green Chemistry,11, 1285-1308 (with permission)
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Combustion of bio oil/bio diesel in diesel engine
• When diesel fuel is injected into the cylinder, it normally produces fine mist
ranging in size from 5 to 20 microns.
• The finer the mist and the more uniform the mist size, the better is the
combustion inside the cylinder.
Compressed air
Fuel 450-700 0C
Cylinder
injector
Finer droplets 5 µm
Diesel
Fuel

Size of fine mist: 5 to 20 µm Modified from Technical paper, Nippon

Ecosolutions, Ltd., japan 2007
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• Plant oils that are generally much more viscous than diesel fuel cannot be
injected into the cylinders as effectively and efficiently as diesel fuel.
• And even if the plant oil can be successfully injected, the injector, which was
carefully engineered to the specifications of the diesel fuel, cannot provide a fuel
mist as fine as when plant oils are used.
• Larger fuel droplets result burning causing difficulty with starting and incomplete
combustion, which leads to build-up of carbon residue.
• More deposits inside the engine, cause poor engine performance resulting from
low compression due to sticking piston rings or coked valves.

• Deposits on the injector nozzle produce poor injection spray pattern resulting in
even more incomplete combustion and possible piston damage due to increased
heat on piston surfaces.
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Modification in engine technology for handling viscous oil like bio oil
Twin Tank or Dual Fuel System
• The engine is started on the conventional diesel fuel and the waste heat
generated by the engine is used to heat the plant oil.
• This avoids running viscous plant oil through a cold engine at start up.
• A temperature gauge in the fuel line determines when the plant oil is hot enough
for the fuel supply to be switched to 100% plant oil. The fuel supply is switched by
a three-way valve.
• Before shutting down for extended periods, the fuel supply is switched back to
conventional diesel fuel and the engine is allowed to run for about 3 to 5 minutes
so that any residual plant oil is flushed from the fuel system.
• The vehicle or engine is then ready to be restarted on diesel fuel.
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Thanks