Biodiesel

Introduction
With the advert of the Industrial Revolution, the use of energy in the
form of fossil fuels began, this occurred in stages, from the
exploration of coal deposits to the exploitation of oil and natural gas

But, how long can we depend on this declining fossil fuels to run our
car engine, to light our kitchen stove ?? .. Not long that's for sure !!
What is the Alternative ?
 Why Biofuels ?? Are They Green???

Use of Biofuels makes the environment clean:

• by regulating carbon dioxide rates in the environment
• by maintaining carbon cycle
• by making a way to reduce global warming

For example, a crop of plants

used to produce a barrel of
biofuel will absorb exactly the
same amount of carbon dioxide
as emitted from burning the
barrel produced.
What are Biofuels ?
•Biofuels are fossil fuel substitutes that can be made from a range of
agricultural crops and other sources of biomass.
•Any hydrocarbon fuel that is produced from organic matter (living or
once living material) in a short period of time – days, weeks, or even
months, is considered as biofuel.
•They are considered as an alternative source of energy
Importance:
1. Energy security - increasing oil prices, need for alternative source of
energy
2. To decrease greenhouse gas emission
3. To promote rural development
 Classification of Biofuels

 Also called conventional biofuels. It includes sugar, starch, or

vegetable oil

known as advanced biofuels and can be manufactured from

different types of biomass. The biomass contains lignocellulosic
material like wood, straw and waste plastic

Extract from algae mostly marine algae

BioDiesel – A better fuel vs. Diesel
Features Benefits

 Higher cetane  More mileage

 Greater lubricity  Greater horsepower
 Superior detergency  Less smoke
 Higher flash point  Smoother running engines
 Quicker starts
 Longer engine life
 Reduced maintenance
• The quality of biodiesel can be described in two groups:

1) the general physicochemical properties, for example, density, viscosity,

flash point, % sulfur, Conradson carbon residue, % sulfate, ketonic number,
and acid number, and

(2) the composition and purity of fatty esters such as methanol, free glycerol,
total glycerol, water, and esters contents, among others. The evaluation of
biodiesel quality is achieved through the determination of the chemical
composition and physical properties of fuel
 Property Bio Diesel Petroleum diesel

Cetane number 51 - 62 44 – 49

Lubricity Much greater than diesel. Comparable to oil lubricants Low-sulphur fuel has low lubricity factor

Biodegradability Biodegrades readily Poor biodegradability

Toxicity Essentially non-toxic Highly toxic

Oxygen Up to 11% free oxygen Very low

Aromatics No aromatic compounds 18-22%

Sulphur None 0.05%

Flash point 300-400 degrees. F 125 degrees. F

Spill hazard None High

Material compatibility Degrades natural, butyl rubber No effect on natural, butyl rubber

Shipping Shipped as non-hazardous and non-flammable material Hazardous

Renewable supply Renewable fuel Non-renewable

Energy security Domestic raw materials Mix of domestic and imports

Alternative fuel Yes

No

Production process Chemical Reaction

• Biodiesel reduces carbon dioxide exhaust emissions by up to 80%.

• Biodiesel produces 100% less SOx than petroleum.

• Biodiesel reduces exhaust smoke (particulates) emissions by up to 75% so the usual

black cloud associated with a diesel engine can be eliminated.

• The smell of the biodiesel exhaust is far more pleasant.

• Biodiesel is much easier to handle and does not cause cracking or redness.

• Biodiesel is much less dangerous to put in vehicle fuel tank as its flash point is ± 150°C
(300°F) as opposed to petroleum diesel ± 70°C (150°F).

• Biodiesel provides significant lubricity improvement over petroleum diesel fuel so engines
last longer, with the right additives engine performance can also be enhanced.
 Biodiesel

Transesterification
Trans esterification

Biodiesel production by alkali process

Enzymatic Biodiesel Production

 Transesterification Reaction

Transesterification Reaction , also called as Alcoholysis is the displacement of alcohol from an ester by
another alcohol in a process similar to hydrolysis except that an Alcohol is used instead of water.

This process is used to prepare Bio-diesel

It is the process of using an alcohol – Methanol / Ethanol / Butanol, in the presence of a catalyst – NaOH /
KOH, to break the molecule of the oil chemically in to methyl or ethyl esters, with Glycerol as a byproduct.
 FEEDSTOCK: Low-FFA Waste Vegetable Oil
Triglycerides

Biodiesel
Free Fatty Acids (FFA)
Water

Production
Catfish & French Fries

(Batch type)
Catfish &
French Fries
Screen
Triglycerides
FFA
Water
Methanol
Heat & Time Holding/Settling Tank Water

Triglycerides
FFA
NaOH or KOH

Transesterification Reactor Reversible Reaction

Equilibrium @ ~60%?
Boost using:
Heat & Agitation Methyl Esters  Excess Methanol
(biodiesel)  Heat (<148ºF)
Glycerin Soaps  Pressure
Excess Methanol Diglycerides  Remove some
Monoglycerides glycerin & biodiesel
Settling & Separation Excess Methanol

Methanol Recovery Wash Waste Water

Distillation Glycerin Methyl Esters Soaps

(biodiesel) Diglycerides
Monoglycerides
Compost Excess Methanol
(KOH only) Filter
Pump & Drive

Copyright 2007 Brevard Biodiesel

 Conventional feed stocks
 Rapeseed, the major source (>80%)
 Sunflower oil (10%, Italy and Southern France)
 Soybean oil (USA)
 Palm oil (Malaysia)
 Linseed, olive oils (Spain)
 Cottonseed oil (Greece)
 Beef tallow (Ireland),
 lard,
 Jatropha (Nicaragua),)

NRRaje Feb 06
JATROPHA TREE
 Jatropha can be cultivated anywhere along
canals,roads,railway tracks, on border of farm and
even an alkaline soils.
 Grown in high as well as low rainfall.
 In high rainfall yield is more.
 Occurs mainly at lower altitude(0-500Cm) with
average annual temperature above 200C,
and rainfall of 300-1000mm.
 JATROPHA PROVIDES:

 Prevention of soil erosion.

 Soil improvement.
 Poverty reduction.
 Renewable energy.
 Promotion to labours.
BIO-DIESEL PLANT
 BIODIESEL : FIRST TRIAL RUN ON TRAIN

 First successful trial run of a superfast passenger train was

conducted on Dec 31, 2009
 Delhi - Amritsar Shatabdi Express used 5% of biodiesel fuel.
 Railway annual fuel bill = Rs 3400 crores (for Diesel)
 10% mixture with Diesel = reduced
(Rs.300-400 crores / annum)
 5% substitution is accepted.
 Some more practicalities
• The former President of India,
Dr. Abdul Kalam, is one of the
strong advocaters of Jatropha
cultivation for production of
bio-diesel.

• The State Bank of India

provided a boost to the
cultivation of Jatropha in India Older diesel Mercedes are popular for running on biodiesel
by signing a MoU with D1
Mohan, a joint venture of D1
Oils plc, to give loans to the
tune of 1.3 billion rupees to
local farmers in India.

5/5/2019 24
Microorganisms available for biodiesel
production
 Microalgae Lipids from all cannot be
 Bacteria converted into biodiesel mainly
due to less yield
 Fungi
 Yeast

 Biodiesel production using microbial lipids, which is

named as single cell oils (SCO), has attracted great
attention in the whole world.
 Oleaginous microorganisms are able to accumulate
lipids above the 20% of their biomass, on dry basis.
 Stages of Lipid
accumulation
Prepare medium: high Carbon, low Nitrogen

Microorganisms grow and multiply until a certain time

Exhaustion of N, cells stop divide

Cells convert C → storage lipid (intracellular)

Lipid accumulation → cells expand

Cells reach limit of obesity → stop accumulating.

...
 MICROALGAE
• Can grow rapidly
• Live in harsh conditions due to their unicellular or simple
multicellular structure.

 Of the 33,000 known species of algae at least forty are

considered oleaginous
 Good candidates for biodiesel
production,
 higher photosynthetic efficiency
 higher biomass production and
 faster growth compared to other energy crops
• Can be induced to accumulate substantial quantities of lipids thus contributing
to a high oil yield.

• Some of the common algae

chlorella, crypthecodinium, cylindrotheca, dunaliella, isochrysis,

nannochloris, nannochloropsis, neochloris, nitzschia, phaeodactylum,
porphyridium, schizochytrium, tetraselmis, etc,….

average lipid content- (1-70%)

maximum- 90%
How to obtain biodiesel from
algae?

 Picking up the best algae

 Growing the algae
 Extraction
 Trans esterification
 Biodiesel
 Where To Grow It

 Extensions onto our water treatment

plants
 Clean up our waste and generate fuel
 Agriculture runoff
 Water ponds
 Algae could well grow on salty water as well
as soft water
 How Is Algae Grown?
Open system
Closed systems(photo bioreactor)

Flat plate PBR

Tubular PBR
Extraction
Solvent extraction
Mechanical extraction
Super critical fluid
extraction
Mechanical Extraction
Solvent extraction
Supercritical fluid
extraction
ADVANTAGES OF MICROALGAE AS A SOURCE
OF BIODIESEL
• High Yield
-low cost of production
• Algae can grow
–In places away from farm land
(No destruction to food chain)
–Sewages
–Near to power plants
(takes CO2from smokestacks and yields oil)
• Oil Productivity
–Greater than best producing oil crops
• Higher grade protein→Animal Feed
Characteristics of algae biodiesel that differ from petro diesel:

• Algae biodiesel has virtually no sulfur content.

• Biodiesel has superior lubricating properties, reducing fuel system wear, and increases the life of fuel injection
equipment.

• Biodiesel has about 5-8 percent less energy density than petrodiesel, but with its higher combustion efficiency
and better lubricity to partially compensate, its overall fuel efficiency decrease is only about 2 percent.

• The cloud point, or temperature at which pure (B100) biodiesel starts to gel, is about 32 0F. A blend of B20
(20% biodiesel, 80% petrodiesel) generally does not gel in cold weather. Various additives will lower the gel
point of B100.

• Biodiesel's flash point (lowest temperature at which it can vaporize to form an ignitable mixture in air) is 2660F,
significantly higher than petrodiesel's 1470F, or gasoline's 520F.

• Biodiesel reduces particulate matter by about 47 percent as compared to petroleum diesel. Biodiesel has less
dangerous particulate matter because it reduces the solid carbon fraction on the particulate matter while
increasing the amount of oxygen.
 Biodiesel from
Fungus
Oleaginous fungi has also been considered as
potential oil sources for biodiesel production because
they accumulate large amounts of lipids
Among these microorganisms, particular attention has been
dedicated to various oleaginous zygomycetes species, such
as
Mortierella isabelina and
Cunninghamella echinulata,
which may accumulate up to 86% and 57% of lipids in the
dry biomass, respectively
 Biodiesel from
Fungus
Materials
Fungal Bio Mass Mucor circinelloides

Three Different Solvent Systems:

Chloroform:Methanol (C:M),
Chloroform:Methanol:Water (C:M:W)
n-hexane

Acid Catalyst ( BF3, H2SO4 and HCl )

Biodiesel from Fungal Bio
Mass
Extraction of
lipids Solvent +Dried
biomass Mixture

Ultrasonication

Centrifugation

Rotary
Evaporation

Lipids
Biodiesel from Fungal Bio
Mass
Biodiesel from
yeasts
•
•
•
Rhodosporidium sp.,
Rhodotorula sp. and
Lipomyces
• species can accumulate intracellular lipids as high as 70% of their
biomass dry weight.

• Cryptococcus curvatus
• oleaginous yeast accumulate storage lipid up to >60% on a dry
weight basis)
Biodiesel from
yeasts
Media

Freeze
drying

Lipid
extraction

Tran
esterification

Biodiesel
Pre-culture
Media
YM medium was used as pre-culture to cultivate oleaginous yeast
cells
o glucose as a carbon source
o Peptone
o yeast extract

Sterilization - 120 ºC temperature for 20 minutes

Main culture
Semi-synthetic medium was used as main culture to grow oleaginous
yeasts
o Glucose, xylose or a mixture of both were used as carbon sources
o nitrogen sources (NH4Cl)
o phosphate buffer (KH2PO4)
o Mineral-element solution (CaCl2×2H2O ,FeSO4×7H2O ,citric acid×H2O)

Medium pH - 5.8
Freeze drying
o Collected samples were centrifuged at 10 min and washed with
sterile water once, then centrifuged again
o The pellets were transferred into pre-weighed vials and kept
at -50 °C until freeze drying
Lipid extraction
Chloroform- Methanol Method
Freeze dried pellets + HCL and incubated at 55° C

Adding Chloroform: Methanol mixture

Centrifugation

Solvent Evaporation

Extracted lipids
 Trans esterification
biodiesel
catalyst
Extracted lipids methanol

glycerin
 Biodiesel from
Bacteria
Bacteria can accumulate oil of about 20-40% of
dry biomass
Arthrobacter sp. - 40%
Acinetobacter calcoaceticus - 38%

Have a superiority in the production of biodiesel due to

 Highest growth rate (reach huge biomass only need 12–24 h)
 Easy culture method.

Actinomycete group high amount of fatty acids (up to 70% of the

cellular dry weight) using glucose under growth-restricted condition
Downside

• Very few are oil producer

• Only a few bacteria accumulate complicated lipoid.

• It is difficult to extract because these lipoid are generated in the

outer membrane

• So there is no industrial significance in the actual production of

biodiesel by using oleaginous bacteria as raw material
• Poorly made Biofuel can cause engine problems – cause nitrogen oxide
emission.
• Transportation and storage requires special managements – cause increase in
total cost.
• Biodiesel is less suitable for use in low-temperatures than petro-diesel
• Slightly more expensive to produce (production cost high on large scale)

Main concerns:

• Some countries have limited water sources (cultivation)

• A suitable climate is needed to grow most crops.
• Crops grown for biodiesel use land for food crops.