Biodiesel

What is Biodiesel?

• An alternative fuel
• Biodiesel = monoalkyl esters of long chain
fatty acids derived from a renewable lipid
feedstock
- American Society for Testing and Materials
• “bio” represents the renewable and biological
source in contrast to petroleum-based diesel
fuel
• “diesel” refers to its use in diesel engines
Biodiesel Advantages

• Environmentally friendly

• Reduce vehicle emissions

• Can directly replace diesel fuel or blend with diesel

• Good lubrication properties to reduce wear and
tear in engine and fuel system
• By-product is glycerol
• Reduce dependency on foreign oil markets
The vegetable oils particularly favours more,
Because
• It is renewable, environment friendly and can produce
easily in rural area.

• Its calorific value is almost 90-95 per cent of diesel.

• It has comparable cetane number and can be substituted

between 20 to 100 per cent depending upon processing.

• It produce greater thermal efficiency compared to diesel

fuel.

• An unmodified engine can perform satisfactorily on it..

(Pramanik, 2003, Rao et al, 1991, Bhatt et al 2001, Goering et al, 1982)
Problems with using vegetable oil in diesel
engine

• Long term problems include

– coking of injector nozzles.
– carbon deposits on the piston and cylinder head.
– dilution of the crankcase lubricating oil.
– excess wear on the rings, pistons and cylinders.

• Viscous oils, when injected to the cylinder, they

do not atomize properly and leads to incomplete
combustion of fuel.

(Pratt, 1980; Yarbrough et al. 1981; Ryan et al. 1984; Goering et al. 1981; Zejewski et
al. 1986; Singh, 2004)
How to use Vegetable Oil in diesel engine

• Blending with low viscous oil

• Coking and Carbon deposits
• Plugging and gumming of filters
• Engine wear
• Thermal cracking
• Removal of oxygen
• Expensive equipment
• High energy input
• Transesterification
• Effectively lowers the viscosity
• Less energy need
• Required cheaper chemicals
(Masjuki et al. 2001; Ziejewski et al., 1983; Agarwal et al., 2001; Srivastava and Prasad,
1999; Ali, 1995)
Transesterification

Definition

In organic chemistry, transesterification is

the process of exchanging the alkoxy group of
an ester compound by another alcohol. These
reactions are often enhanced by using acid or
base catalyst.
Transesterification

Biodiesel
Stepwise Reactions
Basic Flow Diagram for conversion of vegetable into
biodiesel
Variables involve in esterification process

• Molar ratio of vegetable oil and alcohol

• Moisture content of vegetable oil
• Amount of free fatty acid presents in
vegetable oil
• Type of Alcohol
• Amount of catalyst
• Type of catalyst
• Settling time
• Rate of agitation
• Reaction temperature
• Reaction time
Effect of variables involve in transesterification
process

• FFA content and water content

– If the FFA value is greater than 0.5%, then
more NaOH is required to neutralize the FFA.

– Water may also caused soap formation, which

consumed catalyst and hence reduced its
efficiency.

(Feuge and Grose, 1949; Wright et al 1944)

• Molar ratio
– The most important variables affecting the yield of
ester is the molar ratio of alcohol to triglyceride.

– The stoichiometric ratio for transesterification

requires three moles of alcohol and one mole of
glyceride to yield three moles of fatty acid ester and
one mole of glycerol.

– Edible grade oil like soybean, sunflower and palm oil

give higher conversion at 6:1 molar ratio.

(Feuge and Grose, 1949; Krisnangkura and Simamaharnnop, 1992; Freedman et al., 1984)
 • Effect of catalyst
– Catalysts are classified as alkali, acid, or enzyme.

– Alkali-catalyzed transesterification is much faster

than acid-catalyzed.

– If a glyceride has a higher free fatty acid content and

more water, acid-catalyzed transesterification is
suitable.

– Sodium methoxide is more effective than sodium

hydroxide.
– Enzyme based reaction has less ester conversion
efficiency.

(Sprules and Price, 1950; Freedman et al., 1984; Sprules and Price, 1950; Freedman et al., 1984;
Hartman, 1956).
• Effect of reaction time
– The ester conversion rate increases with reaction
time. peanut, cottonseed, sunflower and soybean oils
(Freedman et al, 1984)

– An approximate 80% yield of ester is obtained after

five min of reaction and after 1 h, the conversions is
near about 93 to 98%.

– (Ma et al, 1998) studied the effect of reaction time on

transesterification of beef tallow with methanol. The
reaction was very slow during the first minute due to
the mixing and dispersion of methanol. From one to
five min, the reaction proceeded very fast.
• Effect of reaction temperature

– For the transesterification of refined soybean

oil with methanol (6:1) using 1% NaOH, three
different temperatures were used (Freedman
et al., 1984). After 0.1 h, ester yields were 94,
87 and 64% for 60, 45 and 32°C, respectively.
After 1 h, ester formation was identical for the
60 and 45°C runs and only slightly lower for
the 32°C run.
Logical process flow chart for biodiesel production and evaluation

No

Yes
Process Flow Diagram
 Mass Balance
- Veg oil - Water
- Alcohol
- Alcohol - Acid
- Catalysts
- Sulfuric acid

Pre-treatment Main Reaction Post treatment

- Glycerol - Biodiesel
- Alcohol - Glycerol
- Water
- Alcohol
- Trace
Soap/salt
 Biodiesel Production
technique
• Base catalyzed transesterification
• Acid catalyzed transesterification
• Heterogenously catalyzed transesterification
• Biox process of transesterification
• Supercritical process of transesterification
• Non-ionic base catalyzed transesterification
• Enzyme catalysed transesterification
• Ultrasonic irradiation for transesterification
• Use of algae as feedstock
 FEEDSTOCK OPTIONS
• Probable biodiesel yielding trees/plants are:
– Jatropha curcas or Ratanjot.
– Pongamia pinnata or Karanj
– Soyaean oil
– Canola oil
– Sunflower oil
– Plam oil
– Animal fat
– Used cooking oil etc……….
 Feedstocks Quality Issue
Biodiesel production process,
– Free Fatty consuming more catalyst,creating soap,
should be less than 1%

Acids Degrade storage vessel, consuming more

catalyst

– Total acidity Soap production and measurably affect the

completeness of the transesterification
reaction, consuming more catalyst

– Water content Recycle vegetable oil, solid particle

– Solids In the form of phospholipids or gums,

hindering in completion of reaction,

– Phosphorus Indicator of the level of saturation of oil,

mainly effect the quality of biodiesel.
Saturated fats produce biodiesel with
– Iodine Value superior oxidative stability, higher cetane
number, but poor low temperature
properties.
 Feedstocks Quality Issues
– Free Fatty Acids < 1.0%

– Total acidity 5 to 10 mgKOH/g

– Water content < 1.0 %

– Solids Filter with 100µm

– Phosphorus < 100 ppm

– Iodine Value As low as possible

Available Standards for Feedstock Quality
Testing
– Moisture content :
• Air-oven method
• Hot plate method
• Distillation method
• Karl-Fischer moisture meter
– Solids (insoluble impurities)
• Dissolving in organic medium and filter it
– Acid value and FFA
• Titration methods
Available Standards for Feedstock Quality
Testing
– Iodine value
• By using Wijs solution

– Saponification value
• Titration method

– Fatty acid profile

• Using Gas Chromatography method

continue…..
 Biodiesel Quality Issues

• General Quality Parameters of

biodiesel

• Vegetable oil specific

parameters for quality of
biodiesel
 Biodiesel Quality Issues
General Quality Parameters of biodiesel
Parameters Units Explanation

Density and at 15°C, Weight of a given volume of oil to

specific gravity kg/m3 the weight of the same volume of
water at fixed temperature
Kinematic at 40°C, cSt Resistance to flow of liquid due the
viscosity or mm2/s internal friction between the liquid
and surface
Flash point °C Lowest temperature at which
vapour to form an inflammable
mixture
Cetane number - Indicating of its ignition
characteristics
continue…..
 Biodiesel Quality Issues
General Quality Parameters of biodiesel
Parameters Units Explanation

Carbon Residue, percent by Quantity of solid deposits obtained

10% mass when oils are subjected to
evaporation and pyrolysis
Total acidity mg KOH/kg A measure of combine organic and
inorganic acidity
Sulphur content mg/kg Causing corrosion in some part of
engine; bad odors in gas
Ash content percent by Soluble metallic soap, un-removed
(Sulphated) mass catalyst and other solids
Water content mg/kg Consuming more catalyst , soap
formation
continue…..
 Biodiesel Quality Issues
Vegetable oil specific parameters for quality of
biodiesel
Parameters Units Effect on engine

Methanol % mass
Decreasing flash point, corroded rubber
Decreasing flash point, corroded engine
Ethanol % mass
parts

Mono-glycerids % mass Chocking filter, injector, high soot

emission,
Di-glycerids % mass Chocking filter, injector, high soot
emission,
Tri-glycerids % mass Chocking filter, injector, high soot
emission,
Free glycerol % mass Chocking filter, injector, high soot
emission,
continue…..
 Biodiesel Quality Issues
Vegetable oil specific parameters for quality of
biodiesel
Parameters Units Effect on engine

Total glycerol % mass Chocking filter, injector, high soot

emission,

Total mg/kg Corrosion of engine parts, wear

contamination and tear
Phosphorous mg/kg Corrosion of engine parts, wear
and tear
Na & K mg/kg Corrosion of engine parts, wear
and tear
Ca & Mg mg/kg Corrosion of engine parts, wear
and tear
Oxidative stability at 110°C, h Poor stability of fuel, get thicken
 Related Equipments/Instruments
for Biodiesel Quality Assessment
• Density, specific gravity, API gravity
– Pyknometer, Volumetric flask
• Kinematic viscosity
– Redwood viscometer, kinematic viscosity bath
– Volume of liquid flows under gravity through
calibrated capillary
• Flash and Fire point
– Pensky Martin Flash Point (closed) apparatus
– A sample is heated in a close vessel and ignited.
When the sample burns, the temperature is
recorded.
• Ash content
– Muffle furnace
– Sample ignited and burned
– Indication of concentration of metal additives (Ba,
• Cetane number
– Highly instrumented engine lab
– Comparison of combustion characteristics with
reference fuels
• Cetane Index and distillation temperature
– Distillation method
– Bears relation with viscosity, vapor pressure,
heating value, average molecular weight, etc
• Carbon residue
– Carbon residue apparatus
– Evaporation and pyrolysis at elevated temperatures
– Tests the tendency of the sample to form deposits
under degradation
• Cloud and pour point
– Cloud and pour point apparatus
– Sample cooled and examined visually until first
cloud appears.
– Indicates the lowest temperature at which fuel is
• Total acidity
– By titration method
• Water content
– Karl-Fischer moisture meter
• Sulfur content
– Titration methods
– S oxidized to SO2 at high temperatures
– UV phluorescence of emitted gases SO2
• Copper strip corrosion
– Copper strip corrosion apparatus
– A copper strip is immersed into a fixed volume
of sample and heated for a certain period. The
color of the strip is compared to standards.
• Phosphorous content
– By Inductively Coupled Plasma (ICP) Atomic
Emission Spectrometry
– ICP – Determines 8 elements (Ba, B, Ca,Cu,
Mg, P, S, Zn)
• Free and Total Glycerin
– Gas Chromatography with FID detection
– Guard column with analytical column
– Curve calibration with standard solution: mixture
of glycerol, monoolein, diolein, triolein, 1,2,4-
butanetriol, and tricaprin at known concentrations
– Each component in the standard solution is for
determining a class of compounds in sample:
• Glycerol  Glycerol
• Monoolein  Monoglycerides
• Diolein  Diglycerides
• Triolein  Triglycerides
• 1,2,4-butanetriol  Internal Standard
• Tricaprin  Internal Standard
Thank You