NED UNIVERSITY OF ENGINEERING AND TECHONOLGY

CHEMICAL ENGINEERING PROJECT

TOPICS :
Introduction to Biodiesel
Comparison of Biodiesel with Petrodiesel

Need of Alternative fuels in Pakistan

Issues with Conventional Production Methods for Biodiesel
Production of Biodiesel By Reactive Distillation

Reactive Distillation
PFD
Key Advantages
Constraints And How to tackle

Biodiesel ( fatty acid methyl esters )

one of the sustainable fuels which can replace diesel as a transport fuel
usually produced by reacting plant-derived oils, waste cooking oils and
animal fats with an alcohol to form a mixture of fatty acid esters in a reaction
known as transesterification

So far, biodiesel has been produced from edible oil feed stocks all over the
world. Biodieselproduced from non-edible oil extracted from plants grown on
marginal land, such as Jatropha,jojoba, mahua, tobacco seed and castor bean
has shown some encouraging results.
Triglycerides are the main component of fats and oils and consist of three
long-chain fatty acids linked to a glycerol backbone. When the triglyceride
reacts with an alcohol, the three fatty acids are released and combined with
the alcohol to form alkyl ester

The transesterification reaction requires catalysis and apart from alkali

catalysts others have been used including acids, enzymes and solid
catalysts

Why BioDiesel?
Pakistan consumes 8 million tons of diesel in annually
out of which 4 million tons are imported.
Diesel is consumed by the industrial, transportation
and agriculture sectors which make you of 75% of the
countrys annual energy use at 26.280 MOTE.
10% of the countrys annual diesel consumption
replaced with biodiesel will result in estimated savings
in excess of US$ 1 billion per annum.

Why BioDiesel?
To replace diesel without modifying the engine, any substitute will have to be similar
to diesel in the following properties:
A calorific value of 3840 MJ/kg is a measure of the energy available in the
fuel.
A cetane number of around 50 is a measure of the ignition quality of the
fuel.
The viscosity of the fuel is important as it affects the flow of the fuel
through pipelines and injector nozzles where a high viscosity can cause poor
atomization in the engine cylinder.

The flash point is a measure of the volatile content of the fuel and gives a
measure of the safety of the fuel. The flash point for diesel is 6480C.
It must be obtained from renewable resources such as biomass, oil
crops and waste.

Why BioDiesel?
Sustainability/Cleaner Burning
Renewable energy with little impact to the environment.
Significant CO2 Reduction (nearly green house gas neutral).
Reduces harmful diesel emissions such as particulate, carbon

monoxide, and others.

Economic Development
Supports value added channels for Pakistan agriculture.
Creates jobs particularly in high unemployment agriculturally

dependent communities.
Keeps money inside the United States growing our economy.

Energy Independence

Pakistan Made, Pakistan Grown, Pakistan Consumed.

Reduces foreign oil dependence.
Spurs further investments in other renewable energy technologies.
Less money paid to oil producing nations who oppose our interests.

Relative Greenhouse Gas Emissions

B100

B100 = 100% Biodiesel

B20 = 20% BD + 80% PD

Electric

Diesel Hybrid
B20
Ethanol 85%
Diesel
LPG
CNG

Gasoline
0

20

40

60

80

100

120

140

160

Data from A Fresh Look at CNG: A Comparison of Alternative

Fuels, Alternative Fuel Vehicle Program, 8/13/2001

Production Process Factors

there are common international standard for biodiesel (i.e. EN 14214,
ASTM D 6751).
The standards of the fuel production should be:

(1)complete reaction
(2)removal of glycerin
(3) removal of catalyst
(4) removal alcohol
(5) absence of free fatty acid
(6) low sulfur content.
When specifications are met, the biodiesel can be used in most modern
engines without modifications while maintaining the engines durability
and reliability.

REACTIVE DISTILLATION
Since both esterification and transesterification
reactions are almost neutral with regard to heat of reac-tion, biodiesel manufacturing
does not involve importantenergy costs due to the chemical reaction steps.
The energy costs are mainly due to physical separation proc-esses. Therefore,
reducing the number of separationsteps (which are mainly water washing and
distillation),results in substantial savings.

REACTIVE DISTILLATION
Reactive distillation is a suitable technique for biodiesel manufacturing.

A reactive distillation column

has three zones:
a reaction zone where the chemical
reactions producing biodiesel take place,
and
two separation zones, one separation zone
at the top, for waterremoval and alcohol
recycling, and one separation zone
at the bottom for alcohol separation from
fatty ester product.

REACTIVE DISTILLATION

PFD

ADVANTAGES
a. Simplification: From design view point the combinations of reaction system and
separation system can lead to significant capital saving.
b. Improved conversion of reactant approaches 100%. This increase in conversion gives a
benefit in reduced recycle costs.

c. Improved selectivity: where, removing one of the products from the reaction mixture or
maintaining a low concentration of one of the reagents can lead to reduction of the rates
of side reactions and hence improved selectivity for the desired products.
d. Significantly reduced catalyst requirement for the same degree of conversion.

ADVANTAGES
e. Avoidance of azeotropes: RD is particularly advantageous when the reactor
product is a mixture of species that can form several azeotropes with each other.
RD conditions can allow the azeotropes to be reacted away in a single vessel.
f. There is a reduced by-product formation.

g. Heat integration benefits: If the reaction is exothermic, the heat of reaction

can be used to provide the heat of vaporization and reduce the reboiler duty.
h. Removal of the product from a system at equilibrium will cause more products
to form. Therefore reactive distillation is capable to increase the conversion
of equilibrium limited reaction.

REACTIVE DISTILLATION
All esterification reactions produce stoichiometric amounts of water. This
water must be removed from the reaction vessel, to shift the chemical
equilibrium to products side and ensure high FFA conversion.

One way to solve this problem is by using Reactive Distillation (RD), also known as
Catalytic Distillation. Above 100C, the water formed by the reaction migrates from the liquid reactive phase to the vapour phase,from which it can be
continuously removed by condensation and liquid-liquid separation
the key advantage to the use of a reactive distillation process is the possibility of
generating a much larger ratio alcohol/triglyceride than is needed by stoichiometry,
which is necessary to ensure homogeneous liquid reaction phase,
higher driving force and control of temperature profile