ME301A: Energy Systems – I

Lecture 2
Instructor: Santanu De
NL – 302, Northern Lab
Ph: 6478, Email: sde@[Link]
Office hour: F 5:30 – 6:30 p.m. or by appointment

Course Website: [Link]

Fossil fuels
 Formation– Dead marine animals and plant matter accumulated over
millions of years, transformed into oil in sedimentary rocks due to heat
and pressure.
 Deposits found beneath the crust, have a water body below and
pressurized natural gas above.

 Thick and dense rock layer seals of the deposit, ensuring no leakage.

Conventional
Petroleum Drilling
 Drilling through the rock layer causes pressure release, pushing oil and Advanced Petroleum
gas to surface. When pressure is attenuated, oil can be pumped up. Drilling
Various Sources of Petroleum and Drilling Arrangement
Liquid Fuels - Composition

 Primarily, oil is a mixture of hydrocarbons, which may

contain N2, O2, S.
 Major portion of hydrocarbons are paraffin like methane,
ethane, propane, butane (gases) and pentane, hexane and
octane (liquids). The proportion of hydrocarbons varies
with deposit location.

 It may also contain cyclo-paraffin, iso-paraffin and

aromatic compounds.
 Irrespective of crude oil source the proportion of basic
elements C (75 to 80%), H (11 to 16 %), O + N (0 to 7% )
and S (0 to 4%) is fairly constant within limits.
 Additionally, it may contain some moisture and sediment.

 Refining - The crude oil is first distilled and separated into a number of fractions.
 The lighter fractions (having lower boiling points) like petrol, kerosene, light diesel oil, lubrication oil
are chief transportation and machine fuels.
 The heavier fractions are used as boiler fuels and in chemical production.
Fossil Fuels - Gases
 Natural gas is formed with petroleum in the subterranean deposits.
 Oil wells drilled to extract the gas as well, but flared off or burned
in some cases due to lack of transport facility.
 In some cases, it can be used as fuel for power generation.
 Mode of transport for natural gas is through pipelines.
 Composition - Mixture of most volatile paraffins– methane to pentane.
 High hydrogen content and produces significant water vapor when burned.
 Properties - Cleanest of the fuels, undergoes complete combustion while mixing well with air with no
smoke.
 Heat of combustion – 33.5 to 40 MJ/m3 .
 Specific Gravity – 0.63 relative to air.
 Storage – Major component is Methane (critical temperature– 83°C), so cryogenic temperature is required
to store the gas as a liquid at moderate pressures.
 Liquefied Natural gas (LNG): Transported by tankers and stored in spherical vessels for emergency use
during peak loads.
 Liquefied Petroleum Gas (LPG): Consists of hydrocarbons like propane, propylene, butane, butylene etc.,
used for domestic purposes.
 Compressed Natural Gas (CNG): Used as alternative in automobiles.
Processing Chart for Fossil Fuels
Petroleum Refining

Separator– Gases are removed, natural gasoline is the final product.

 Vaporization in a still at 600°C and products are feed to bottom of fractionating tower.
 Forced upwards through maze like plate arrangement and vapor passes over liquid fuel maintained at
different temperatures.
 Compounds with higher boiling points condense out at the lower portion of the column.
 Lower boiling point compounds move further up and eventually condense at appropriate
temperature. Top fraction gives straight run gasoline.
 Fraction like kerosene, diesel oil, fuel oils obtained at higher boiling temperatures.
Petroleum Refining Processes
Cracking
 Breaking down large, complex hydrocarbons into simpler ones.
 Thermal cracking – high temperature and pressure cause large molecules to breakdown into smaller
ones with lower boiling points.
 Catalytic cracking – use of catalyst allows breakdown at lower temperatures and pressures.
 Catalytic cracking imparts better antiknock characteristics than thermal cracking.
 Other ways of improving the fuel quality are isomerization, reformation etc.
Isomerization
 Isomerization converts n-butane, n-pentane and n-hexane into their respective isoparaffins of
substantially higher octane number.
 The straight-chain paraffins are converted to their branched-chain counterparts whose component
atoms are the same but are arranged in a different geometric structure.
Reforming
 Reforming is a petroleum refinery process in which low octane distillation products known as
naphthas are chemically converted into high octane reformates.
 Reforming process involves restructuring hydrocarbon molecules in the naphthas in such a way that
they form more complex chemical structures with higher octane ratings.
Types of Alkanes
 Normal alkane: Straight chain alkane, e.g., n-pentane CH3– CH2-CH2-CH2-CH3
 Iso alkane: Branched alkane containing tertiary carbon (carbon attached to three other carbons)
CH3–CH–CH2–CH3
CH3
 Neo alkane: Branched alkane containing quaternary carbon (carbon attached to four other carbons)
CH3
CH3–C–CH2–CH3
CH3
Fuels: Performance Properties
(1) Calorific Value
 Solids and Liquids -Defined as the heat liberated in kJ by complete combustion of 1 kg of fuel.
 For Gases – Expressed in kJ/m3 of gas at S.T.P.
 Further classified as higher calorific value (HCV) and lower calorific value (LCV):
(a) Higher Calorific Value (HCV)
 All fuels containing hydrogen in the available form will react with oxygen during combustion to
generate steam.
 The steam may condense when the products of combustion are cooled to initial temperature.
 This results is maximum heat being extracted. This heat value is called Higher or Gross Calorific
Value (HCV)
(b) Lower Calorific Value (LCV)
 It is the difference in the HCV and the heat absorbed by water during its conversion to vapor,
constituents supplied at air temperature.
 The amount of latent heat depends on the pressure at which the phase change has occurred, which is
difficult to estimate.
 It may be assumed for the evaporation to take place at saturation pressure corresponding to Std.
temperature of 15 °C.
 The latent heat corresponding to this saturation temperature is 2466 kJ/kg. Hence,
L.C.V. = (H.C.V. – x . 2466) kJ/kg
Here , ‘x’ – fraction of water vapor present in the products of combustion for 1 kg of fuel.
Fossil Fuels: Composition and Properties

Specific % composition by weight HCV

Fuel
Gravity C H2 S kJ/kg

Petrol 0.74 85.4 14.6 - 46900

Paraffin 6.79 86.3 13.6 0.1 46500
Diesel Oil 0.87 86.3 12.8 0.9 46000
Heavy fuel oil 0.95 86.1 11.8 2.1 44000

Liquid Fuels

Calorific Value
Percentage Volumetric composition
Fuel kJ/m3
H2 CO CH C2H4 CO2 N2 HCV LCV
Coal Gas 27 7 48 13 3 2 31900 29000

Town Gas 55 14 23 2.5 2 3.5 19500 17500

Coke Oven gas 50 8 29 4 2 7 21300 19300

Producer Gas 6 23 3 0.2 5.8 62 5000 4800

Gaseous Fuels
Fuels: Performance Properties
(2) Flash point
 Lowest temperature at which a volatile substance can vaporize to form a ignitable mixture with air.
 Different from Auto-ignition temperature which does not require an ignition source or Fire
point viz. temperature above which the fuel continues to burn after being ignited.

(3) Pour point

 Lowest temperature at which the liquid becomes semisolid and loses its flow characteristics.

(4) Heat of formation

 The free energy of chemical elements at 1 atm. 25 °C arbitrarily assumed to be zero.

 Standard free energy of formation (Enthalpy of formation) of a compound, gf0 , is the free energy
change when one mole of the compound is formed directly from its constituent elements.
 The constituents are at 298 K & 1 atm. The value will be different at different conditions.

Compound ∆H˚ (J/ kg. mole) ∆G˚ (J/ kg. mole)

CO -110 x 106 -137 x 106
CO2 -394 x 106 -395 x 106
Water -286 x 106 -237 x 106
Fuels: Performance Properties
(5) Octane Number
 Rating of SI engine fuels is based on its antiknock property.
 The property is compared with that of a mixture of iso-octane (C8H18) and normal heptane (C7H16).
Iso-octane – rating 100, heptane- rating 0).
 Octane number is the percentage by volume of, iso-octane in a mixture of iso-octane and normal
heptane, which exactly matched the knocking intensity in a standard engine under standard
conditions.
(6) Cetane Number
 Cetane number is the percentage by volume of normal cetane in mixture of reference fuels that gives
same knocking intensity as of the fuel under standard conditions.
 Reference fuels are normal cetane (rating 100) and alpha methyl naphthalene (rating 0).

(7) Knocking Characteristics

 Difference between time of injection and actual combustion termed as ‘ignition lag’.
 Increase in ignition lag – increase in amount of fuel being accumulated in the cylinder. Hence,
combustion afterwards, leads to abnormal release of energy causing knocking.
 Lag leads to problems in starting, warm up and exhaust smoke. Hence, high Cetane rating fuel
preferred.
Fuels: Performance Properties
(8) Antiknock Quality
 Abnormal burning causes unwanted temperature and pressure surges in the cylinders, affects the
efficiency.
 Antiknock quality resists the tendency for detonation during combustion.
 It depends on self ignition characteristics and composition of the fuel.
 Better SI engine – less knocking – higher compression ratios – better efficiency -more power output.

(9) Volatility
 Depends on fractional composition of the fuel in terms of
hydrocarbon components.
 Standard process of measuring the volatility of the fuel is by
distillation at atmospheric pressure, in presence of its vapor.
 The fraction that boils off at a particular temperature is
measured.
 Characteristic points – 10, 40, 50 & 90 % of fuel evaporation
and the temperature at which boiling ceases. Distillation curves for Petrol
Fuels: Performance Properties
(10) Starting and Warming up
 Certain part of the fuel should vaporize at room temperature for easy starting.
 Hence, the distillation curve temperature values for 0 -10 % boil off should be relatively low.
 As the engine warms up, the temperature will gradually reach operating value.

(11) Crankcase Dilution

 Liquid fuel in cylinders deteriorates oil quality or dilutes the oil causing weak oil films between
rubbing surfaces.
 So, the upper portion of distillation curve should have low boil off temperatures so that all the fuel is
vaporized before combustion.

(12) Vapor Lock Characteristics

 Faster vaporization of fuel can affect the carburetor metering or stop fuel flow due to vapor lock in
passages.
 This requires the presence of high boiling point components throughout the distillation curve, which
contradicts the previous requirements.
 Hence, the about requirements must be optimized for desired temperature.
Fuels: Performance Properties
(13) Sulphur Content
 Free sulphur, H2S and other such compounds may corrode the fuel lines and fuel control devices.
 Sulphur may also combine with oxygen and later with water to form sulfuric acid.
 Low ignition temperature of Sulphur can promote knocking.

(14) Gum Deposits

 Storage of the fuel causes hydrocarbons or impurities to oxidize and form gum like substances.
 These can hinder the normal operation of valves and piston rings.

(15) Corrosion and Wear

 Should not damage the system in operation. Associated with presence of sulphur and impurities.

(16) Handling
 Easily flow under wide range of conditions
 Low Pour point.
 High Flash and Fire point.
Drivers for Alternative Sources and Possible Alternatives
 Energy Security: Issue of concern for oil importing countries
 Availability of crude oil.
 Large fluctuation in price and quality of Crude.
 Sustainability and long term availability of the fuels for large scale application.
 Energy Efficiency
 Fuel economy / CO2 Standards have been introduced in US, Europe and Japan.
 Bureau of Energy Efficiency (BEE) is in the process of notifying the fuel economy standard for the
passenger cars and LCVs.
 Alternative fuels with possibility of use of alternate power pack.
 Emission Regulations
 Several alternative fuels have prospects for lower emissions.
 Well to wheel – life cycle analysis.

Fuel Type Properties Possible Alternative

Diesel Cetane number (40–60), Good cold Biodiesel/Fatty acid, Methyl esters
properties
Gasoline Octane number (87–91), Energy content Bioethanol, Butanol/isobutanol
Biodiesel
Source
 Biodiesel produced from transesterification of vegetable oils like Soya bean, rapeseed, palm, cotton seed, etc.
 In India, non-edible sources like Jatropha, Pongamia (karanjia) etc. preferred.
Application
 5% biodiesel blending in diesel is allowed in India.
 Up to 20% blending of biodiesel is done Globally.
Issues
 Food vs fuel debate in various countries where crops like soya, palm, rapeseed etc. are used for production of biodiesel.
 Oxidation stability and material compatibility.
Engine Performance
 Higher Cetane number improves the combustion process in CI engines.
 Higher/ better lubricity results in increased life of the fuel injection equipment and maintain the performance of engine in terms of power
and emissions.
Environmental Benefits
 Reduction in CO, HC, Particulates but marginal increase in NOx emission.
 Improved combustion with bio-diesel blends also reduces the PAH emissions and also the PM size and numbers.
Bio-butanol
History
 Earlier at the end of World War II in 1945, 2/3rd butanol and 1/10th acetone in USA was produced by fermentation. After World War II,
ABE fermentation industry suffered acute competition from the petrochemical industry.
 Now there is new resurgence of fermentation based bio-butanol production from lignocellulosic biomass.
Benefits
 Butanol has better fuel properties in terms of volatility, miscibility, transportation ease, energy content and less corrosivity.
Process
 Selected bacteria transform sugar through Acetone-butanol-ethanol (ABE) route.
• Clostridium tyrobutyricum
• Clostridium acetobutylicum
• Clostridium butylicum
 Process is scaled up to Pilot plant/demonstration scale.
Issues
 Low yield of butanol
 Less solvent tolerance of fermentative microbes.
Ethanol
Source

 Ethanol is mostly produced from sugarcane molasses in India.

 In Brazil, it is produced from sugarcane juice and molasses.

 In US, it is produced from Corn.

Application

 In India, 5% blending of ethanol in gasoline is proposed.

 In US & Brazil, higher percentages of ethanol is blended in gasoline (10% and 22-24% respectively).

 Govt. of India intends to increase of blending percentage of ethanol from 5% to 10% in gasoline.

Issues

 Availability of ethanol and material compatibility in old/in-use vehicles is an issue of concern.

 Ethanol has lower energy content as compared to gasoline but due to higher octane number better volumetric efficiency is obtained.

Environmental Benefits

 Reduction in CO & HC emissions with marginal increase in NOx emissions.

 Reduction of green house gases through improved efficiency and renewable source/feedstock.