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FUEL CHEMISTRY

LEARNING OUTCOMES
◦Classify fossil fuels. (CO1)
◦Discuss the different steps in petroleum
processing and petroleum products.
(CO1)
◦Recognize biofuels as an alternative
energy source. (CO1)
FOSSIL FUELS
◦ The product of natural changes in organic materials over
millennia.

◦ It is a general term for buried combustible geologic deposits


of organic materials formed from decayed plants and
animals by exposure to heat and pressure in the earth’s
crust.
FOSSIL FUELS
◦ Ancient marine bodies first turn into kerogen (complex
waxy mixture of hydrocarbon compounds that is the
primary organic component of oil shale) before becoming
a fossil fuel.

◦ Kerogen + pressure and heat  Fossil fuel (coal, oil or gas)


FOSSIL FUELS: Types
▪ Coal is a solid fossil fuel formed
over millions of years by decay of
land vegetation.
▪ When layers are compacted and
heated over time, deposits are
turned into coal.
▪ Coal is quite abundant compared https://www.miningreview.com/new-
coal-fired-power-plant-in-kenya-to-
to the other two fossil fuels. incorporate-clean-coal-technology/
FOSSIL FUELS: Types
▪ Natural gas is a gaseous fossil
fuel that is versatile,
abundant and relatively
clean compared to coal and
oil.
▪ More evenly distributed than
oil supplies.
https://www.anirudhsethireport.com/n
▪ Natural gas mainly consists of atural-gas-crude-crucial-update/
methane (CH4).
FOSSIL FUELS: Types
Natural gas is highly compressed in small volumes
at large depths in the earth.

Other components:
a. Energy components
- ethane, propane, butane,
isobutene, and pentane
b. Non-energy components
- carbon dioxide, nitrogen,
http://www.history.alberta.ca/EnergyHeritag
hydrogen sulfide, and water e/gas/premodern-global-history/physical-
character-of-natural-gas.aspx
FOSSIL FUELS: Types
Wet Natural Gas
- If it contains hydrocarbons in addition
to methane

Dry Natural Gas


- Gases other than methane are
removed
http://www.history.alberta.ca/EnergyHeritag
e/gas/premodern-global-history/physical-
character-of-natural-gas.aspx
FOSSIL FUELS: Types
▪ Oil is a liquid fossil fuel that is
formed from the remains of
marine microorganisms
deposited on the sea floor.

▪ Oil/Crude oil is the most widely https://richtopia.com/smart-


used fossil fuel. investing/crude-oil-prices-history-since-
1900s
FOSSIL FUELS: Types
FOSSIL FUELS: Types

Oil and Gas Reservoir


Carbon Content of Fossil Fuels
Carbon Content Coefficients Used in this Report (Tg Carbon/QBtu)
Industrial Coal 25.74
Aviation Gasoline 18.87
Distillate Fuel Oil 19.95
Jet Fuel 19.33
Kerosene 19.72
Lubricants 20.24
Motor Gasoline 19.34
Crude Oil 20.29
Carbon Content of Fossil Fuels
▪ Energy gained from burning fossil fuels is converted to
electricity and heat in commercial power plants.

▪ When fossil fuels are burned carbon and hydrogen react


with oxygen in air to carbon dioxide (CO2) and water (H2O).
During this reaction heat is released which further amplifies
the reaction. (EXOTHERMIC PROCESS – COMBUSTION)

▪ Electricity is generated by transforming mechanical energy


(heat) to electrical energy in a turbine or generator.
Petroleum
◦ Petra = rock; oleum = oil
◦ a.k.a crude oil

◦ Crude petroleum is made up of


thousands of different chemicals
including gases, liquids and solids,
ranging from methane to asphalt.

◦ useless in its natural state (the


components are useful)
Petroleum

◦ Crude Oil – dark and sticky liquid


◦ Condensate – clear and volatile (evaporates easily)
◦ Bitumen – semi-solid form petroleum
◦ Asphalt – solid form

◦ Most constituents are hydrocarbons but there are


amounts of compounds containing nitrogen (0 to 0.5%),
sulfur (0 to 6%), and oxygen (0 to 3.5%).
Petroleum Constituents
1. Aliphatics (Open chain hydrocarbons)
a. Alkanes (n-Paraffin series) CnH2n+2
b. Iso-alkanes (iso-Paraffin series) CnH2n+2
c. Olefin (Alkene series) CnH2n

2. Ring compounds
a. Cycloalkanes (Naphthene series) CnH2n
b. Aromatic (Benzenoid series) CnH2n-6
Petroleum Constituents
3. Lesser components
Sulfur (0-6%)– useless and undesirable
– has bad odor and can cause corrosion in
pipes
Nitrogen (0-0.5%), Oxygen (0-3.5%), trace metals, salts

4. Natural Gas Liquids


– part of underground reservoir
– major feedstock of petrochemicals
Petroleum Constituents
Alkanes (n-Paraffin series) CnH2n+2
➢ saturated HC and comprise the large fraction of most
crude oil
➢ Has low anti-knock properties and octane rating.
➢ e.g. n-hexane, n-heptane
Knocking

https://www.youtube.com/watch?v=maZyPJIOknE
Octane-Rating

https://www.youtube.com/watch?v=1ToBZ74Yhas
Petroleum Constituents
Iso-alkanes (iso-Paraffin series) CnH2n+2
➢Branched chain
➢Higher anti-knock properties and octane rating than
n-paraffin (better performance of internal combustion
engines
➢e.g. 2-methylpentane
2-methylhexane
Petroleum Constituents
Olefin (Alkene series) CnH2n
➢ not naturally present in petroleum but
produced during cracking

➢ relatively unstable which improve the anti-


knock quality of gasoline

➢ e.g. ethylene, propylene, butylene


Petroleum Constituents
Cycloalkanes (Naphthene series) CnH2n
➢ Same formula as olefins but lacks their
instability and reactivity.

➢ second most abundant in crude oil next to


n-paraffin.

➢ e.g. methylcyclopentane, cyclohexane,


methylcyclohexane
Petroleum Constituents
Aromatic (Benzenoid series) CnH2n-6
➢ only small amounts of this is present in crude oil.

➢ has high anti-knock properties and octane rating.

➢ e.g. benzene, toluene


xylene, ethylbenzene
Petroleum Processing
Petroleum: Refining
➢ The process of transforming crude oil into useful
products such as liquefied petroleum gas (LPG),
gasoline or petrol, kerosene, jet fuel, diesel oil and
fuel oils.

➢ Involves: separation process and conversion


process.
PROCESS
Petroleum: OF
Refining REFINING
Fractional Distillation
➢ Because crude oil is a mixture of hydrocarbons with
different boiling temperatures, it can be separated
by distillation into groups of hydrocarbons that boil
between two specified boiling points.

Large Hydrocarbon Small Hydrocarbon

bottom of fractionating column higher up the column

high boiling points Low boiling point


Fractional Distillation
Fractional Distillation
Petroleum: Common Refinery Fractions
Natural Light Intermediate Heavy
Residues
(casing head) Distillates distillates Distillates
Motor Heavy fuel Heavy Lubricating
Natural gas
gasoline oils mineral oils oils
Solvent Heavy
LPG Diesel oils Fuel oils
naphthas flotation oils
Lubricating
Jet fuel Gas oils Petrolatum
oils
kerosene Waxes Road oils
Light heating
Asphalts
oils
Coke
Conversion Processes
1. Cracking
➢ the breaking down of large hydrocarbon molecules
into smaller molecules by heat (thermal) or catalytic
action.
➢ Zeolites are the common catalyst used.
• breaking down large hydrocarbons into smaller molecules
• by heat or catalytic reaction; zeolite
Conversion Processes
2. Polymerization
➢ a substance of low molecular weight is transformed
into one of the same composition but of higher
molecular weight, maintaining the atomic
arrangement present in the basic molecule.
• linking of similar molecules
➢ Joining together of light olefins
• joining together of light olefins
Temp: 500°C
Conversion Processes
Pressure: 200-400 bars
Catalyst: strong acids (i.e., sulfuric acid [H2SO4] and hydrofluori
acid [HF])
3. Alkylation
Products: mixture
➢ the union of higher
of olefins molecular
with weight
an aromatic oriso-paraffins (i.e.,
alkylate) as a high-octane
paraffinic hydrocarbonnumber blending component for the
gasoline pool
Conversion Processes
4. Hydrogenation
• addition of hydrogen to an olefin
➢ addition of hydrogen to an olefin.
• Feedstock: hydrotreated light straight-run naphtha, light natural
Conversion Processes
gasoline, or condensate
• Reaction conditions:
- Temp: 300°C
5. Isomerization
- Catalyst: AlCl3
• alteration
➢ of the arrangement
Products: high-octane of the
number gasoline atoms
stocks in adoption
after the
aofmolecule without
lead-free gasoline changing
(branched the number of
chain)
atoms
heavy naphtha
• Conversion
Reaction conditions: Processes
- Catalyst: platinum as the active metal supported on alumina, and
some6. Reforming/Aromatization
may contain additional metals such as rhenium and tin in bi- or
tri-metallic catalyst formulations
➢ conversion of naphthas to obtain products of
- Products: high-octane, low-sulfur reformate, which is a major
higher octane number.
blending product for gasoline
Conversion Processes
7. Coking/Pyrolysis
➢ converts the residual oil from the vacuum distillation
column or the atmospheric distillation column into
low molecular weight hydrocarbon gases, naphtha,
light and heavy gas oils, and petroleum coke
➢ Petroleum coke - is a black colored solid composed
primarily of carbon, and may contain limited
amounts of elemental forms of sulfur, metals and
non-volatile inorganic compounds.
Petroleum: Common Refinery Fractions
Natural Light Intermediate Heavy
Residues
(casing head) Distillates distillates Distillates
Motor Heavy fuel Heavy Lubricating
Natural gas
gasoline oils mineral oils oils
Solvent Heavy
LPG Diesel oils Fuel oils
naphthas flotation oils
Lubricating
Jet fuel Gas oils Petrolatum
oils
kerosene Waxes Road oils
Light heating
Asphalts
oils
Coke
Fuel Gas/Natural Gas
➢ Composed of hydrocarbons (such as methane,
ethane, or propane ), hydrogen, carbon
monoxide, oil vapors and other mixtures
Liquefied Petroleum Gas (LPG)
➢ LPG is obtained from the natural gas and from the
fractional distillation of petroleum.

➢ It can be propane or butane, which are


flammable mixtures of hydrocarbon gases used as
fuel in heating appliances, cooking equipment,
and vehicles.
Gasoline or Petrol
➢ It is a mixture of paraffins (alkanes), cycloalkanes
(naphthenes), and olefins (alkenes).

➢ Gasoline is primarily a mixture of two volatile


liquids, n-heptane and iso-octane.

n-heptane iso-octane (2,2,4-Trimethylpentane)


Gasoline or Petrol
➢ it easily ignites; BP: 20oC- 70oC

➢ Used to fuel internal combustion engines for cars,


motorbikes, trucks, boats and other transport
vehicles (light vehicles)

➢ Other chemicals are also added to gasoline to


further stabilize it and improve its color and smell.
Gasoline or Petrol

➢ Gasoline has an octane rating which compares


the gasoline blend with the performance of pure
octane hydrocarbon with eight carbon atoms.

➢ The octane rating is a measure of the resistance


of gasoline and other fuels to detonation
(engine knocking) in spark-ignition internal
combustion engines.
Knocking

➢ the result of the rapid combustion of the end- gas


ahead of the flame front which undergoes
chemical reactions prior to normal combustion.

➢ Knock is the sharp metallic noise cause by high


frequency pressure oscillations inside the cylinder.
Anti-Knock Agent

➢ a chemical that, when added to gasoline, raises the


octane value of the gasoline which, in turn, raises the
temperature and pressure at which gasoline will auto-
ignite.

➢ Example: tetraethyl lead and tetra methyl lead


(TEL/TML), benzole, methyl tertiary butyl ether (MTBE)
Gasoline or Petrol

◦87% iso-octane
◦13% n-heptane
DIES
Diesel Fuel

➢ Composed of about 75% saturated


hydrocarbons (primarily paraffins
including n-, iso-, and
cycloparaffins), and 25% aromatic •

hydrocarbons (including
naphthenes and alkylbenzenes)
➢ fuel used in diesel engines, whose
fuel detonation takes place without
spark.
Diesel Fuel

➢ has a cetane (n-C16H34) number


limit which describes the ignition
quality of the fuel
➢ Cetane number - is a measure of
the fuel's delay of ignition time
Diesel Fuel

◦40% n-hexadecane
◦60% 1-methylnapthalene
Kerosene
➢ a thin, clear liquid formed from hydrocarbons,
with density of 0.78-0.81g/cm3.
➢ obtained from the fractional distillation of
petroleum between 150°C and 275°C,
resulting in a mixture of carbon chains
containing 12 to 15 carbon atoms.
➢ Kerosene is widely used to power jet-engine
aircraft (Jet fuel) and some rockets, and is also
commonly used as a heating fuel.
Residues
➢ constituents that are not volatile enough after
distillation
➢ E.g. Asphalt - road paving material, waterproofing
structures, roofing material
Biofuels

http://www.alternative-energy-news.info/technology/biofuels/
Biofuels
➢ produced from living organisms or from metabolic
by-products (organic or food waste products).
➢ In order to be considered a biofuel, the fuel must
contain over 80 percent renewable materials.

https://lawofalgae.wiki.zoho.com/Chapter
-1----Introduction-to-Algae-Biofuels.html
Biofuels: Types
1. Wood

https://gadgets.ndtv.com/science/news/could-super-wood-replace-steel-in-cars-
airplanes-1810304
Biofuels: Types
2. Liquid biofuel
– e.g. ethyl alcohol
produced from
fermenting starch or
sugar

https://www.sciencedirect.com/science/article/pii/S0961953416300903
Biofuels: Types
3. Liquid biofuel
– e.g. Biodiesel which is made
primarily from oily plants (such
as the soybean or oil palm) and
to a lesser extent from other oily
sources (such as waste cooking
fat from restaurant deep-
frying). http://www.washingtonagnetwork.co
m/2018/05/02/biodiesel-ranks-first-
among-fleets-for-alt-fuel-use/
Biofuels: Types
4. Biogas– includes methane
gas and other gases which
can be derived from the
decomposition of biomass in
the absence of oxygen—and
methanol, butanol, and
dimethyl ether—which are in
development.
https://technologytimes.pk/post.php?title=Bi
ogas+production++from+livestock+manure
Biofuels
promise of biofuels:
▪ in combination with an emerging technology called
carbon capture and storage, the process of producing and
using biofuels may be capable of perpetually removing
carbon dioxide from the atmosphere.

▪ Under this vision, biofuel crops would remove carbon


dioxide from the air as they grow, and energy facilities
would capture the carbon dioxide given off as biofuels are
burned to generate power.
Biofuels
promise of biofuels:
▪ Captured carbon dioxide could be sequestered (stored) in
long-term repositories such as geologic formations beneath
the land, in sediments of the deep ocean, or conceivably
as solids such as carbonates.