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Fuels: Classification of fuels, Calorific value, Cetane and Octane number, fuel

quality, Comparison of solid liquid and gaseous fuel, properties of fuel,


alternative fuels: biofuels, Power alcohol, synthetic petrol.
Fuel Any substance used to produce heat or power by combustion.
Combustion Any chemical process accompanied with evolution of heat and light

Fuel + Oxygen Combustion products + Heat

Fossil fuels coal, oil, Natural gas

Classification of Fuels

Solid fuel : Characterized by its mass, composition, specific heat, combustion


residue & other thermal properties
Liquid fuel - Characterized by its composition, specific heat, density, viscosity &
other thermal properties
Gaseous fuel - Liquid fuel - Characterized by its composition, volume, pressure and
thermal properties
Comparison of fuels
Property Solid Liquid Gas
Calorific value Low High Higher
Thermal Efficiency Low High Higher

Internal can not can be can be


Combustion be used used used
engines
Comparison of fuels Merits
Comparison of fuels Merits
Comparison of fuels Merits
Comparison of Fuels Demerits
Solid fuel
Require excess of air for combustion & process cannot be controlled
easily.
During combustion they block air circulation & corrode the furnace
Flue gases released during combustion contain dust & soot particles
Comparison of fuels Demerits
Liquid
fuel
Require
High cost of special
production burners for
Combustion

Cannot be stored Offensive odor


easily
Comparison of Fuels Demerits

Gaseous
fuel
Highly
High cost of inflammable
production

High risk of fire


Cannot be stored hazard
easily
Occurrence based classification

Primary or natural fuels exist naturally


Solid wood, peat, lignite, coal
Liquid Crude petroleum, Natural gasoline
Gas Natural gas
Secondary or prepared fuels- Synthesized from naturally occurring
primary fuels
Solid Charcoal, coal, coke
Liquid- Tar
Petroleum distillates : Gasoline, Kerosene, Gas oils
Petroleum residues, Fuel oils, Alcohol
Gaseous Producer gas, water gas, CNG
Characteristics of a good fuel
Easy ignition, moderate ignition temperature
Should give lot of heat high specific heat
Low smoke & combustible matter (ash)
Free from harmful combustible products
Inexpensive & readily available
Easy to store & transport
Ignition temperature temperature of the fuel at which ignition starts &
continues to burn without further addition of heat.
Low ignition temperature creates fire hazard
High ignition temperature is not good for starting of fire
Ash reduces calorific value, causes hindrance to the flow of air & heat,
reduces specific heat & leads to unwanted disposable problems
Calorific value
Amount of heat obtained from fuel
UNITS
British thermal unit (BTU) : 1/180 of the amount of heat necessary
to raise 1lb of water from 32 F to 212 F
Calorie : 1/100 of the amount of heat necessary to raise 1g of water
from 0 C to 100 C
1 BTU = 252 cal
1 Kg-cal = 1000 cal
Heating value of solid & liquid fuel is given in heat units per unit of
weight
BTU/lb or cal/g
1cal/g = 1.8 BTU/lb
Heating value of gaseous fuels BTU/ft3 at 60 F & 30 inches Hg
Calorific value
Gross calorific value (HCV) total amount of heat liberated when 1
unit of fuel is burnt completely & combustion products are cooled to
room temp.
Net calorific value (LCV) amount of heat liberated when 1unit of fuel
is burnt completely & combustion products are allowed to escape.
Net calorific value = GCV latent heat of vapor formed
NCV = GCV (wt. of Hydrogen X 9 X latent heat of steam)

1
GCV = 8080 C + 34,500 H-O/8 +2240 S K cal/kg
100

Net Calorific value = HCV - 9/100 H X 587 K cal/kg


Knocking in spark ignition engines
In internal combustion spark engine, petrol & air are mixed &
compressed to 1/10th of its volume then spark is produced to
burn the fuel.
Energy produced by burning gives smooth thrust to piston
which moves the wheel

Compression ratio Ratio of cylinder volume at the end of


down stroke to the volume at the end of upstroke of the piston

Higher CR Higher engine efficiency


Knocking
Internal combustion engines

Spark ignition Compression


Engine ignition engine

Petrol Diesel
Knocking
Rapid compression of fuel air mixture heats the engine & detonates
without spark being passed resulting in violent jerk to the piston
giving a metallic rattling sound

KNOCKING

Reduces efficiency of engine

Knocking tendency
Aromatics < Cycloalkanes < Olefins <Branched
Straight chain alkanes >chain alkanes
Leaded Petrol
Knocking can be prevented by adding Tetra ethyl lead (TEL),
Pb(C2H5)4 saving money & energy

1-1.5 ml 1 L Petrol
TEL
Leaded Petrol
TEL get transformed in to lead oxide particles & reacts with H2O2
molecules & prevent their oxidation hence improper
combustion
Antiknock fluid
TEL 60%

Ethylene bromide
26% Antiknock
Fluid
Ethylene chloride
9%

Red dye-2%
Leaded Petrol - Disadvantages
Harmful to environment

Lead oxide deposits on the engine affect its


functioning in longer period

Presence of sulphur compounds decreases its efficiency

Ethylene bromide can be added which converts lead in to lead


bromide which expelled with exhaust gases preventing
deposition of lead oxide
Knocking in compression ignition engines
Diesel engine
Air is compressed to 1/20th of its volume
This raises temp to 300 C & diesel ignites without spark
Diesel should ignites below compression temperature
short induction lag desirable
Diesel consists of straight longer chain hydrocarbons with
minimum content of branched & aromatic HCs.
Octane number

The percentage by volume of isooctane in the isooctane heptane


mixture that matches the knocking characteristics of the fuel being
tested
Octane number

n-heptane Isooctane

Zero Hundred
Cetane number
Diesel consists of straight longer chain hydrocarbons with minimum
content of branched & aromatic HCs.
Diesel should have low spontaneous ignition temperature
Separate scale is required for grading
can not be rated on octane scale
Cetane number - used for rating diesel oil
It represents spontaneous ignition temperature of diesel fuel
Cetane n-Hexadecane ignites more rapidly than any other diesel
fuel assigned cetane no. 100
CH3(CH2)14CH3
n-Hexadecane
methyl naphthalene ignites slowly than any other fuel assigned
cetane no. - 0
Cetane number
Cetane number mixture of n-Hexadecane & methyl naphthalene
forms a standard scale for spontaneous iginition temperature of
diesel fuel

Cetane number is defined as the percentage of cetane present


in a mixture of cetane & methyl naphthalene which matches the fuel
under test in ignition property

A diesel fuel said to have a cetane number 80 - matches in


ignition property to 80% cetane & 20% methyl naphthalene
Alternative fuel-Background
Petrol and diesel, one of the most precious thing of todays life.
These are the non-renewable resources provided to us by nature in
limited amounts.
To find a solution, we must come up with other alternatives and
biodiesel is one of them.
These alkyl esters hold promise as alternative diesel engine fuels.

Alternative Fuels
Biofuels- solid, liquid & gaseous fuels derived from living
organisms and their waste products
+ CO2 Biomass
Solar
Energy

Harvesting

CO2 Pre-processing

Cellulose
Biofuel
Enzymes

Microbial Fermentation
Ethanol Sugars
Biofuels
Biomass - Accumulation of organic waste matter produced by living
things
Biomass Sources Wood , agricultural residue, saw mill waste, sugar
refinery waste, municipal refuse etc.

Utilization of biomass - Two Ways

Direct Combustion Burn biomass directly to obtain energy


For DC moisture should be < 15%
Drying required before combustion
Combustion produces steam used in industries & for the generation of
electricity
Biofuels
Utilization of biomass - Two Ways

Anaerobic fermentation
Bio mass Ethanol

Advantages
Environment friendly
Low initial investment
Disadvantages-
Cost of energy is higher in urban areas
Collection & transportation of biomass is expensive
Biodiesel
Biodiesel - long chain of fatty acid alkyl esters
It is derived from renewable vegetable oils , animal fats , algae and
various low-value materials such as used cooking oils, greases and
soap stocks
Pacific biodiesel became one of the first biodiesel plant in U.S. in
1996.
Attractive features of biodiesel
Renewable resource of energy
Do not increase level of greenhouse gases, a blend of 20% biodiesel fuel
reduces net CO2 emission by 15.66% .
Can produced domestically, hence reduces petroleum imports.
Biodegradable
Waste products like used oils, soap stocks, greases can be utilized
Low toxicity
Negligible sulphur content and lower exhaust emission
Biofuels Transesterification reaction

catalyst
Oils or fats + Alcohol Ester + Glycerol

catalyst
Steps in whole cell catalyzed transesterification

Hydrolysis
Transesterification
Esterification
Hydrolysis
Fats or oil water free fatty acids + glycerol
catalyst
Esterification
free fatty acid + alcohol catalyst ester + water

Overall Transesterification
Fats or oil + alcohol catalyst fatty acid alkyl + glycerol
Enzymatic transesterification
Enzymatic transesterification is better than chemical
transesterification as the recovery of glycerol is easy.
It involves the use of enzyme as a catalyst to carry out
transesterification.
Lipase - an enzyme is effective for transesterification, is
obtained from fungus.
Fungus species Aspergillus, Rhizopus are used to carry out
transesterification and produce biodiesel.
Whole cell biocatalysis
Use of whole cell biocatalyst instead of purified lipase cuts the
cost of isolation, purification and immobilization of pure lipase.
Aspergillus sp., Rhizopus sp. have been used.
Different oils (Cottonseed, Jatropha, Karanj ) are used as
carbon source for growth as well as whole cell catalyzed
transesterification.
TLC of oil , ester and transesterified
sample

ester
Oil

Free fatty acids


Biofuels

Biogas produced by degradation of biological matter by


bacterial action in absence of free oxygen

Natural gas biogas results after long period of decay of


animal & vegetable matter by bacteria under high pressure
& optimum temp.

Gobar gas biogas produced by anaerobic fermentation of


cattle dung
Biofuels
Advantages of gobar gas over heating dried cattle dung
directly

produces more useful energy

provides high device efficiency

free from dust & smoke & environment friendly

used as domestic fuel as well as illuminant


Power alcohol

Petrol blended with 5-10 % of ethanol is called power alcohol

Addition of ethanol increases octane number

E-diesel Diesel blended with ethanol

Used as fuel for small aircrafts in place of leaded gasoline


Ethanol manufacture
1. By fermentation-
Slow decomposition of complex organic compounds in
to simpler ones by enzymatic action

C6H12O6 Yeast 2 C2H5OH + 2 CO2


Ethanol manufacture
2. Using Molasses: Dark brown mother liquor left after crystallization of cane sugar from
sugar cane juice. It contains 50% fermentable sugar

C12H22O11 + H2O Invertase (Yeast) C6H12O6 + C6H12O6


Glucose Fructose

C6H12O6 Zymase (Yeast) 2C2H5OH + 2CO2

Diluted solution of molasses containing 8-10% sugar taken in steel container, small
quantity of ammonium sulphate, ammonium phosphate, some other nutrients are
added. Sulphuric acid is added to attain pH 5.
Yeast is added and mixture is allowed to stand for 2-3 days
Temperature is maintained 25 30o.
Enzumes Invertase and Zymase present in yeast decompose sugar into alcohol with
evolution of CO2.
Ethanol manufacture

Ethanol can also be obtained from starchy materials e.g.


Potatoes, barley, maize or saw dust

Hydrolysis
Starchy materials Sugar
Enzymatic
Fermentation

Ethanol
Power alcohol - advantages
Ethanol Good antiknocking agent

Octane number (PA) 90; Petrol - 65

Moisture gets absorbed by alcohol

Polluting emissions of CO, HC & particulates are reduced

Cheaper than petrol


Power alcohol - Disadvantages
Calorific value of Ethanol 7000 cal/g and PA 11500 cal/g.
Problem is solved by Specially designed engine with higher
compression ratio
Output of power generated is reduced up to 35%
PA- High surface tension, difficult atomization at low temp - causing
starting trouble
It may undergo oxidation to form corrosive acetic acid
Modified carburettor & engine required as less air is required for
combustion
Synthetic petrol
Mixture of alkanes with composition resembling to petrol
Obtained artificially from coal
Methods of preparation Bergius process, Fischer-Topsch process
Bergius (Germany) process
Coal (Raw Material) a mixture of high MW HC with less H paste with coal tar.
Catalyst Sn salt of org compound added
Paste and catalyst put in converter heated to 400-450o under 200 atm pressure with H2
Hydrogenation takes place higher satd comp (HC) which undergo cracking and hydrogenation satd lower
alkanes which leave the reactor as vapours of synthetic petroleum.
Distilled fractionally to give Petrol, Middle oil and heavy oil.
Middle oil is hydrogenated again to give more gasoline (4 times)
Heavy oil is used again to make paste with coal dust.

catalyst (4500C, 200 atm)


Coal dust + H2 Mixture of hydrocarbons
H2 / Cracking

Crude oil
Batteries
Conversion of chemical energy into electrical energy.
Battery is combination of cells either in series or parralel or
both in order to get required amount of electrical energy.
Types of batteries:
Primary cells
Secondary cells
Primary cells
The chemical energy is converted into electrical energy
as long as chemical component is active.
Can not be recharged or regenerated

Secondary cells:
The redox reaction that convert chemical energy into
electrical energy can be reversed by passage of current.
Can be recharged and regenerated
Discharging and Charging of Battery
A cell is a battery packed with active material at anode and cathode.
As anode and cathode are connected to load - redox reaction occur.
Electrons liberated at anode flow to cathode through external wire and
part in reduction reaction.
This process is called Discharging
Active material is converted to inactive material.
Cell become inactive once active material is consumed.
Cell Reaction is reversed if external current is passed in reverse direction.
Process of conversion of inactive material to active material is called
Charging.
Modern Batteries
Metal Air Batteries: are the batteries which breathe air i.e. they
use oxygen directly from the air to bring electrochemical reaction.

Alkaline batteries in which cathodic active material is not stored in


the cell in which NH4Cl is replaced by KOH as the electrolyte.
Zinc-Air Battery
Anode is composed of Granulated Zn powder mixed with aq. 30%
KOH and gelling agent to immobilize the material.
Cathode is composed of mixture of C and catalyst (oxide of
Manganese).
Gelling agent held on Ni-coated steel matrix.
Several hydrophobic, gas permeable, thin layer of Teflon are
provided to steady air entry.
Electrolyte contain 30% KOH.
Vents for entry of O2 into cell
Container is made up of glass and has a separator made of nylon.
Cell represented as Zn 30% KOH/Air,C
Reaction involved in cell are:
at anode: Zn Zn2+ + 2e-
Zn2+ + 2OH----> ZnO + H2O

Zn + 2OH- ---> ZnO + H2O +2e-


At Cathode:
H2O + O2 + 2e- ---> 2OH-
Overall Cell reaction:
Zn + O2 ---> ZnO
Features of Zn-Air Battery
These are light and have high energy density
These are relatively eco-friendly and have unlimited capacity.
Have low energy cost
Applications in hearing aids, medical devices, and military radio
receivers.
Lithium Batteries
Li is light metal with low electrode potential and good
conductivity.
Group of batteries where Li is used as anode are known as Lithium
Batteries.
Li-MnO2 batteries
1. Anode is composed of Li.
2. Cathode is composed of heat treated MnO2
3. Electrolyte contain mixture of LiCl, LiBr, LiAlO4, LiClO4
dissolved on Organic solvents
Cell reaction
At anode: Li Li+ +e-
At cathode: MnO2 + Li+ +e- LiMnO2
Overall cell reaction:
Li + MnO2 LiMnO2
The offers EMF of 3.0 V
Charaterstics:
1. These are light in weight and Compact
2. Known for low maintainance and have high energy density
Applications:
Memory backups, automatic Cameras, Calculators etc.

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