BTV3333

Bio-based Fuels and Alternative

Energy Applications

Associate Prof. Lakhveer Singh

[email protected]
 Week 3 & 4

Biodiesel Production
 Introduction: What is Biodiesel?

• Biodiesel is a clean burning fuel

produced from domestic
renewable resource.

• Biodiesel can be used in any

diesel motor in any percentages
from 0-100% with little or no
modifications to the engine.
 Biodiesel: What is it not?

Mixtures of
vegetable oil or
alcohol with
diesel fuel

Ethanol or E85
Unprocessed
Vegetable Oil
 History of Vegetable Oil Based Fuels

 1900 - Rudolph Diesel debuted the first

diesel engine running on peanut oil at the
World’s Exhibition in Paris
 He likely used peanut oil at the request of
the French Government, who were
interested in its use in their African colonies.

 After Diesel’s mysterious death in 1913,

development focused on the use of
petroleum-based fuels
The use of vegetable oils as engine fuels may seem
insignificant today but the such oils may become, in
the course of time, as important as petroleum and
the coal tar products of the present time.
-Rudolph Diesel, 1912
 Advantages of Biodiesel
• Produced domestically with natural resources, its use decreases our
dependence on imported fuel and contributes to our own economy.
• Biodegradable and Non-toxic
• Renewable

• Carbon Neutrality: the fuel is derived from biomass, it does not contribute to atmospheric
CO2 emissions?!

• Complete Combustion of Biodiesel giving a cleaner burn

• Safer Emissions: Biodiesel emissions are, on the whole, lower than petroleum diesel.
The results is substantial reductions of soot, Sulphur, unburned hydrocarbon , and
polycyclic aromatic hydrocarbon (PAH) emissions. 

• The infrastructure: needed for biodiesel already exists. Biodiesel can be used in existing
diesel engines blended with petroleum diesel, or can be run unblended in engines with
minor modifications.
 Advantages of Biodiesel cont...
Biodiesel
• The lubrication property of the biodiesel can
actually improve engine life Because biodiesel
has twice the viscosity of petroleum diesel.

• Can used blended in any proportion with

petroleum diesel fuel.

• *High Cetane Number (CN) and excellent

lubricity. *ASSIGNMENT

• Very high Flashpoint (>300°F)

• Can supply from waste restaurant oils

(waste), non-edible oilseeds and animal
fats.
 Climate Change

• Biodiesel yields a 78% carbon

dioxide (CO2) reduction compared
to petroleum diesel under life-cycle
analysis.
 Environmental Considerations of Biodiesel
Emissions

Biodiesel vs. Biodiesel blend

Emission B100 B20
Carbon Monoxide -47% -12%
Hydrocarbons -67% -20%
Particulate Matter -48% -12%
Sulfates -100% -20%
Carbon Dioxide -78% -20%

Ozone formation -50% -10%

PAH -80% -13%

 Environmental Issues
• Burning fossil fuels increases atmospheric levels of
carbon dioxide
• Fossil fuels are a finite resource.

30% Increase

Graph taken from USF Oceanography

webpage
Carbon emission through
soil
 Sources of biodiesel Raw materials

Plant and algal-derived oil make up the majority of potential

sources for biodiesel production primarily for their direct
utilization of most powerful energy source, the sun.

Animal, yeast and fungal sources* are also important, but

derive their energy primarily from other carbon sources and
would provide to a lesser extent to biodiesel feedstock's.
For example: Fungi exhibit the capacity to accumulate intracellular lipids in
excess of 70% of their biomass during metabolic stress periods.

* Genetic modification ASSIGNMENT

 Classification of Potential
Biomass for Biodiesel Production

1. Plant 3. Animal
• Animal fat, like Tallow, Poultry
• Edible and non edible
fat
Oilseed, like Jatropha,
Sunflower, Canola,
Peanut etc.
4. Waste
• cooking oil waste
2. Microorganism • animal fat waste
• Algae • yellow or brown grease
• Yeast • sludge oil
• Fungi • soapstock from the refining
• Bacteria process of vegetable oil.
 Soybeans
Top 5 producers: US, Brazil, Argentina, China and India

• Primary source for biodiesel production in U.S.

• Market value at $6.60 per bushel (60 lbs) in 2006, forecast for $7.25-
8.25
• 85% of soybeans sold as a meal for animal

• Good oil yield per acre (63 gal)

• Large, diverse market demand reduces

availability for biodiesel
•Meal valuable for livestock
 Canola/Rapeseed

• Rapeseed is a member of the mustard family

• Canola is a variety of rapeseed bred to have
low levels of erucic acid and glucosinolates
(both of which are undesirable for human
consumption)
• Both spring and winter varieties grown
• Depends on geographical location
• Winter crop in NC (North Carolina)

• Good oil yield per acre (76 gal)

• 70% of feedstock for EU

biodiesel production
 Sunflowers
• Wide geographical range for production
• Market value is high for edible oil and seeds, birdseeds
• $.08-.12 per lb. market value
• Second largest biodiesel feedstock in the EU
• Yield: 46 gal/acre
 Peanuts

• Nearly 15% of peanuts are crushed for oil use in U.S.

• Value range of $0.23-.30 per lb. of peanut depending on state, variety,
production system (higher for organic)
• $.50 per gallon of oil obtained (on average)
• Market value for premium quality edible oil currently constrains use in
commercial biodiesel production
• Production limited to southern regions of U.S.
• Research on “industrial” peanuts -not suitable for human consumption-
being conducted at the University of Georgia
• Will potentially make peanuts more economically feasible as
biodiesel source

• Very high yield value, 175 gal/acre

 Camelina
• Camelina sativa is a member of mustard family

• Summer annual crop suited to grow in semi-arid

climates and northern U.S.

• Yield: 59 gal/acre

• Research on variety development and

economic feasibility are being conducted at
Montana State, North Dakota State, and Purdue
University
• The cost of Camelina-based biodiesel would
likely be $2 per gallon compared to 3$ per
gallon for soy-based.
 Other oil crops

• Oil Palm
• Up to 500 gal/acre yield
• The most widely produced oil outside of the USA.
• Fruit grows in bunches, each weighing 22-110 lbs.
• Poor cold weather performance
 Used Cooking Oil, Vegetable Oil
Algae

• Cooking oils contain many types of vegetable-based oils as

well as rendered animal oils. There are enough used cooking oil
and fat generated in the US annually, including 18 billion
pounds of soybean oil and 11 billion pounds of animal fat, to
produce an estimated 5 billion gallons of biodiesel

• Algae; (1978-1996) investigated using algae as a biofuel

feedstock
Theoretical yields of 10,000 gallons/acre
Green Fuel Technologies-promising

• Straight vegetable oil (SVO) & WVO (Waste vegetable oil) for
use as fuel in diesel another potentially viable use for vegetable
based hydrocarbons.
 Production Process
• Main Problem with vegetable oil:
• High viscosity
• Low volatility
• Reactivity of unsaturated hydrocarbon chains
• High contain of free fatty acids
• SVO causes poor combustion in diesel engines due to buildup of carbon deposits
inside the engine, as well as negative impacts of SVO on the engine
lubricant.

• Multiple chemical steps to solve problem:

• Dilution
• Catalytic cracking
• Micro emulsification
• Transesterification
• Pyrolysis
 Oilseed Processing
• The Oilseed Processing Industry:
Separates the “whole seed” into 2 or more products
• Processing Technology (Two General Methods):
• Solvent Extraction
• Standard technology for facilities with daily capacities of
greater than 300 tons per day
• Commonly used in conjunction with some form of mechanical
extraction
• Mechanical Extraction
• Typically used for facilities with daily capacities of less than 150
tons per day
 Solvent Extraction
• The basic process:
• Seed Preparation
• Removal of foreign objects
• Removal of seed hulls or shells for some seeds
• Pre-Pressing
• Seed is crushed through a mechanical press
• Pre-Pressing removes some oil from high oil content seeds
• Solvent Application
• Solvent is applied to the pre-pressed material
• The solvent bonds to the oil in the material
• Solvent & oil mixture is removed from the meal
• The oil is then separated from the solvent which is
reused in the process
 Solvent Extraction

• Benefits:
• Solvent Extraction is capable of recovering of 99%
of the oil contained in the seed
• Lowest cost per ton for commercial processing
• Challenges:
• Large capital investment
• Not feasible for small-scale processing
• Environmental concerns (?)
 Mechanical Extraction

• The basic process:

• Seed Preparation
• Removal of foreign objects
• Removal of seed hulls or shells for some seeds
• Extraction
• Seed is processed by a mechanical press
• Removing 65-80% of oil contained in the seed
Biodiesel Production Process
Biodiesel Production Process
(cont.)
Chemistry and Thermodynamic Aspects of
Biodiesel Production
 Fats & Oils - Definitions
General Formula of
• Fats & oils are esters (acids bonded to alcohols) an Ester
• The acids are know as Fatty Acids and are
made up of hydrocarbon chains.
• The fats and oils used to make biodiesel are
known as triglycerides.

• A triglyceride (TG) or triacylglycerol (TAG) means that three (tri) acids are
bonded to an alcohol, in this case three fatty acids bonded to a glycerin (glycerol).

Triglyceride Formula Acyl Group

 Understanding Fatty Acid
Composition
• Fats and Oils are generally composed of hydrocarbon (carbon and
hydrogen atom) chains.
• The length and degree of saturation of the hydrocarbon chain affects
the physical properties (viscosity, melting point, etc...) of the fat or oil.
• Fatty acids are generally designated in shorthand by: C:X in which the C
corresponds to the number of carbon atoms in the chain and the X
corresponds to the number of double bonds (thereby indicating the
level of saturation).
 Transestrification Process

• All fats and oils consist of triglycerides;

• Glycerol/glycerine= alcohol
• 3 fatty acid chains (FA)
• Transesterification describes the reaction where glycerol
is replaced with a lighter and less viscous alcohol e.g.
Methanol or ethanol
• (The process of Triglyceride breakdown with alcohol and turn it into
an ester)
1. A catalyst (KOH or NaOH) is needed to break the glycerol-FA
bonds.
2. Supercritical
 Transesterification
(for Biodiesel Production)
Methanol
(or Ethanol)
Biodiesel

Triglyceride
Glycerol

One triglyceride molecule is

converted into three mono
Fatty Acid
Alkyl Ester (biodiesel)
Chain
molecules.
Esterification and Transesterification Reactions
 Base or Alkali Catalysis
Base or alkali-catalyzed reactions typically using NaOH or KOH are
most common when the oil are neutral or less free fatty acids. The
specific base catalyzed transesterification occurs in four intermediate
reversible steps that include:
1.producing an active species from alcohol group in reaction with the base
catalyst.
2.nucleophilic attack of the active species to the carbonyl group on the
TAG to form tetrahedral intermediate which is then broken down
3. liberating the fatty acid ester compound and the active species is
regenerated in the final step, and
4.allowing the process to continue for the remaining two attached fatty
acid units

Benefits: High and rapid yield production (2 hr), Low

temperature, Low excess alcohol
 Mechanism of base catalyzed transesterification of
vegetable oils

(alcohol) + (base)
 Homogeneous and Heterogeneous Base Catalyst

Homogeneous: Liquid base catalyst

 Advantages: low cost and high reaction rates at relatively low temperatures.
 Major drawbacks: difficulty in recovering the catalyst, highly corrosive nature that
decrease the useful life of equipment and foam formation in presence of high FFA.
 Example: NaOH, KOH, and sodium methoxide (NaMeO).
•Foam formation: the presence of high free fatty acid (FFA) content (> 0.5% w/w) prevents the
use of homogeneous base catalyst for transesterification reaction. This is because FFA will react
with base catalyst to form soap (foam) leading to lower biodiesel yield and increase the
difficulty to separate biodiesel from glycerol (co-product).

Heterogeneous: Solid base catalyst

 Advantages: ease of separation, potential facilitation of continuous processing,
minimizing product contamination and number of water washing cycle.
 Example: ETS-10 (Na, K), calcium oxide, quaternary ammonium silica gel, and other
anionic exchange resins.
 Acid Catalysis
Acid Catalysis using HCl or H2SO4 typically result in substantially reduced
transesterification rates by as much as 4000 times than homogeneous
base catalysis and require higher reaction temperature of nearly 100 oC.
However, acid catalysis can be very effective in driving the
transesterification process when oils contain large amount of free fatty
acids.
1.The protonation of the carbonyl group of the ester leads to the
carbocation,
2.protonation of the alcohol group
3.proton migration, and
4.breakdown of the intermediates freeing the alkyl ester from the
intermediate TAG.
Benefits: High yield production in High FFA
Drawbacks: Low rate, High temperature (100 °C), Equipment Corrosion
Acid Catalysis mechanism of transesterification

(1)

(2)

(3)

(4)
 Alcohol Effect

• Alcohol solubility played a more important role for the

acid-catalyzed reactions since longer chain alcohols are
considerably more soluble in the initial oil than methanol.

• The longer chain alcohols showed the highest reaction

rates for acid-catalyzed reactions; however for base
catalyzed reactions, an opposite effect was observed.
 Enzyme Catalysis
Nowadays, the biological production of biodiesel with lipases
(enzyme) has received great consideration and it is undergoing
a rapid development.
Main advantages of lipases as biocatalyst:
 mild reaction conditions (Room Temperature),
 easy recovery of glycerol without purification or chemical waste production,
 high purity of product
 no soap formation:
free fatty acids content in the oil can be completely converted to methyl esters, thus
increasing the biodiesel yield and reducing the costs for fuel purification.

This characteristic of the enzymes allows the usage of

materials with high free fatty acids (FFA) or high water
content such as non-edible oils, waste cooking oils and
industrial waste oil.
 Lipase-Catalyzed Interesterification

Interesterification is a process which is used in the oils and fats industry to

modify the properties of triglyceride mixture. In Interesterification reactions
via enzyme catalysis are biologically significant mechanisms for
production of fatty acid esters and may be accomplished efficiently with
enzyme catalysis using lipases secreted from various organisms such as
Candida antarctica.
For example, Novozyme-435 is an immobilized C. antarctica.
 Supercritical process

An alternative, catalyst-free method for transesterification uses

Supercritical methanol at high temperatures and pressures in
a continuous process.

In the supercritical state, the oil and methanol are in a single

phase, and reaction occurs spontaneously and rapidly. The
process can tolerate water in the feedstock, free fatty acids are
converted to methyl esters instead of soap, so a wide variety of
feedstocks can be used.
Also the catalyst removal step is eliminated. High temperatures
and pressures are required, but energy costs of production are
similar or less than catalytic production routes.
Supercritical process
 Thermodynamics of Biodiesel

 Thermodynamic properties of biodiesel fuels and reactants play an

important role in determining the reaction rate and phase separation kinetics.

 In general, the thermodynamics properties in terms of temperature (e.g.,

boiling point, flash point, pour point, cloud point*) are typically higher for
biodiesel than petroleum diesel, gasoline, and alcohols.

 Higher flash point results in a safer fuel for handling. The heating value* for
biodiesel is comparable to petroleum fuels, which are nearly twice that of
alcohols. Density and viscosity of biodiesel is typically higher than the
petroleum.

*ASSIGNMENT
Thermodynamics of Biodiesel (cont.)

ASSIGNMENT
Viscosity, Density, Boiling Point, Flash Point, Cloud
Point, Heating Value, Auto-ignition Temperature,
Cetane No., Octane NO., Lubricity

For

Petroleum Diesel, Biodiesel, Ethanol, Gasoline

 Reaction Kinetics
Reaction kinetics determine the rate at which a given reaction will occur
for the formation of biodiesel esters.

The kinetics for biodiesel depend on the physical state (solid, liquid, gas),
concentration of reactants, temperature, and the types of catalysts
used to lower the activation energy required for the reaction occur.

Reaction kinetics vary with system temperature and pressure.

According to Freedman the transesterification follow pseudo first-order

kinetics and the reverse reaction occurs as described by second-order
kinetics.
 Reaction Kinetics cont.

For conditions near the critical point of methanol, kinetics were

considered first-order represented by the following equation:
In xt / x0 = kt
Where xt= the concentration of unreacted methyl ester at time t
x0= the initial methyl ester concentration
k= the first order reaction rate constant
Once the reaction constants were determined, the Arrhenius equation was applied to
determined the activation energy as given in the following equation:
In k= In A – E a / RT
Where Ea= activation energy, kJ/gmol
R= Universal gas constant
T= temperature, K
The activation energy is defined as the minimum amount of energy required for a reaction to
occur.
 Thermogravimetric Analyzer
• Thermogravimetric Analyzer (TGA) measures the amount
and rate of weight change in a material, either as a function
of increasing temperature, or isothermally as a function of
time, in a controlled atmosphere (nitrogen, oxygen, argon, air
etc.).
• It can be used to characterize any material that exhibits a
weight change and to detect phase changes due to
decomposition, oxidation, or dehydration.
• This information helps us identifying the percent weight
change and correlate chemical structure, processing, and
end-use performance.
Thermogravimetric Kinetics
 Thermogravimetric Curve

Overlay of thermogravimetric curves for waste cooking oil, biodiesel

and mixture (50% -50%) of waste cooking oil and biodiesel.  
Thanks