FOSSIL FUEL:

 Carbon-based materials
 Chemically, fossil fuels are energy-rich combustible geologic deposits consisting largely of
hydrocarbons, which are compounds composed of hydrogen and carbon, as well as smaller amounts of
other compounds such as nitrogen and sulphur.
 Practically speaking, they are non-renewable resources of energy as the rate of their consumption far
exceeds the rate of their formation.
 “Two Conflicting Theories” that explains the “Formation of Fossil Fuels”
 1.) Biogenic (Organic) Theory of Fossil Fuels Formation= states that fossils fuels were formed of
organic materials, from decayed plants and animals, which have been converted to natural gas,
petroleum (oil), or coal ,by exposure to heat and pressure in the Earth`s crust over hundreds of
millions of years.
 2.) Abiogenic (Inorganic) Theory of Fossil Fuels Formation= states that some fossils fuels,
particularly light hydrocarbons, were formed from deep carbon deposits by abiogenic processes,
without any living material involved in their formation, perhaps dating to the formation of the Earth

CLASSIFICATION OF FOSSIL FUELS: (BASED ON THE PHASE)

 COAL- solid state

 PETROLEUM (OIL) – liquid state
 NATURAL GAS- gaseous state

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PETROLEUM:

 Translate from Greek as “Rock Oil”

 Petroleum is a liquid fossil fuel that consists of a complex mixture of hydrocarbon compounds, mostly
alkanes (also referred to as paraffins), cycloalkanes (also referred to as naphthenes), aromatic and
asphaltics.
 Usually contains other organic compounds containing nitrogen, oxygen, or sulphur as well as small
amounts of various non-organic components such as trace metals.
 Commonly referred to by its colloquial term “Oil”
TYPICAL COMPOSITION OF OIL:

PETROLEUM (OIL) STATE OF MATTER:

 The majority of oil exists in liquid phase within natural underground reservoirs. It remains liquid at
atmospheric pressure after passing through surface separating facilities. However oil can also exist in
gaseous form within natural gas reservoirs, but transforms into liquid at controlled atmospheric pressure
or temperature. Furthermore, oil also is found in semi-solid state mixed with sand and water.

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PETROLEUM REFINING PROCESS:

PETROLEUM REFINING PROCESSES:

A.) STAIGHT-RUN PROCESS:

The first step in the refining process is heating the crude oil, thereby converting it into vapor.
These vapors are then condensed into liquid form, but the refining equipment is so constructed
that these vapors are condensed in various levels at the fractioning tower. This is a tall,
cylindrical tower varying in size, but approximating 4-6 ft. (1.2-1.8 m) in diameter and 80-100 ft.
(24.4-30.5 m) in height. Inside the tower are bubble trays, which consist of baffles that permit the
vapors to pass through and upward, retaining the condensed liquids which, in turn, flow out of
the tower into storage tanks. The lightest material condenses at the top, heaviest at the bottom.
STRAIGHT-RUN METHOD of CRUDE OIL
DISTILLATION:

 Starting from the top of the tower, these fractions, or different oils, are obtain from the crude oil
o Gasoline
o Naphtha
o Kerosene
o No.2 Distillate
o No. 5 or 6 fuel oil or residual, also called reduced crude
 These oils are not the only ones that can be obtained, since the refiner can regulate the equipment to
change the types of products produced. Since these products come directly or straight from the crude oil,
they are called straight-run oils This straight-run refining is only a physical reaction, since the crude oil
is composed of oils with various boiling temperatures ranging from approximately 70 to 1000°F (21 to
538°C), and by this refining method, the oils are separated from the crude oil owing to their different
boiling temperatures. These boiling points vary, but as a general rule, they may fall into the following
boiling ranges:
o Gasoline 90-400°F (32-204°C)
o Naphtha 150-300°F (66-149°C)
o Kerosene 300-480°F (149-249°C)
o No.2 Distillate 325-750°F (163-399°C)
o No. 5 or 6 fuel oil 600-1000°F (316-538°C)

 This simple crude-oil distillation is the fundamental separation process on which the subsequent refinery
processes, or steps, are based. In many cases, fractions or oils produced by this method are marketed
without any additional processing. These same oils are also used in a number of other refining processes,
especially as starting material for the various cracking process. The straight-run method is sometimes
also called topping or skimming.
B.) CRACKING PROCESS:

 After the initial straight-run distillation process, further refining can be accomplished using either of
four of the most important methods: thermal cracking, catalytic cracking, vacuum distillation or
visbreaking. The process chosen is influenced by many factors, some of which include source of crude
oil, refining techniques available, demand for the different resultant products, industrial activity, coal
and gas prices, and current price of petroleum products.
 One process or any combination of the four processes can be used in the production of fuel oils, with
specifications varying according to the refining procedures used.

1.) THERMAL CRACKING PROCESS:

 Material for thermal cracking is the straight-run residual. In the cracking of these straight-run
oils, usually the heavy reduced crude oil, the method is almost the same as in the initial process,
the only difference being that a higher temperature and higher pressure are used. It is from using
this high temperature that the process is called thermal cracking.
 The thermal cracking process can be divided into two types- liquid phase and vapor phase. In the
liquid phase process, the cracking takes place while the oil is in a liquid state. In the vapor phase,
the cracking takes place while the oil is completely vaporized. The temperatures are a little
higher in the vapor phase process than in the liquid phase, but the pressures are lower.
 The starting material is first heated in the charge heater, and from there it goes to the reaction
chamber where, with the use of increased temperatures and pressures, the oil is broken or
cracked into lighter and heavier materials. Chemically speaking, the molecule of straight-run oil
is split and broken apart, creating smaller or lighter molecules and larger or heavier ones. The
light ones are formed because a small piece of a large molecule is broken off, while the
remaining portion unites with another one of larger size, forming a heavier molecule than the
original.
  The cracked products then go to the flash chamber where the materials are flashed into vapor.
These vapors then pass on to the fractionating tower where they are condensed, and flow to the
storage tanks. As in the straight-run method, different boiling oils are taken from the
fractionating tower at various levels, producing oils having different characteristics and
specifications than those from the straight-run process. The resulting petroleum products are
called cracked oils.
 The products usually obtained from the thermal cracking process are gasoline, No.2 fuel oil, and
No.5 or No.6 residual oil.

2.) CATALYTIC CRACKING PROCESS:

 In the catalytic cracking process, the same reaction occurs as in thermal cracking, but it is
obtained by a different method. Starting method for catalytic cracking is often straight-run
residual, but thermally cracked products, especially the No.2 distillate, are also used at various
times.
 As in the preceding processes, the charge is first heated and either vaporized or kept in a liquid
state as it is introduced into the reactors. These reactors contain the catalyst that produces the
necessary cracking of the oil and vapor. This catalyst may be in a finely divided form, which
mixes with the oil or it may be in the form of pellets, or balls, over or through which the vapor
pass. After cracking has been completed, the products are run through the fractionating tower, as
in the other processes, and then into the storage tanks.
 The products obtained by this method are gasoline, No.2 fuel and slurry oil.
Slurry oil = a high-pour point, low-viscosity product that can be used as fuel oil, but because of
its high-pour point [75-100°F (24-38°C)]; it is generally blended into the No. 6 fuel oil.
MEANING AND TYPES OF CATALYST:

 A catalyst is a substance, usually a chemical compound, which can either increase or retard the
rate of a chemical reaction, without itself entering into the reaction products or undergoing a
chemical change. By its presence within the refining structure, the catalyst aids in accomplishing
the necessary cracking that the high temperatures and pressures in the thermal process have
produced.
 Catalytic reactions are encountered in both organic and inorganic chemistry. They are used in
many phases of petroleum refining besides cracking, such as polymerization, alkylation, and
desulfurization.
 There are many catalysts used in petroleum refining today, a few of these are sulfuric acid;
hydrofluoric acid, anhydrous aluminum chloride; and various oxides, such as those vanadium,
nickel, aluminum and iron.

VACUUM DISTILLATION & VIZBREAKING PROCESSES:

3.) VACUUM DISTILLATION PROCESS:

 The charge to this refining method is generally reduced crude oil or residue from the straight-run
process. The reaction occurs under the vacuum and not under high pressure. The high
temperatures literally distill or squeeze out the heavy distillate from the charge. The remaining
residue is called vacuum bottoms. The distillate produced is frequently used as charge stock for
the catalytic charging process.
 When reduced crude oil is used as the charge, the vacuum bottoms will be lower in gravity and
much higher in viscosity than the original feedstock. The viscosity easily approaches 2000-3000
 seconds, at 122°F (50°C) Saybolt Furol. These vacuum bottoms can be used to make asphalt or,
blended with a cutting oil or distillate, to make No.6 fuel oil. The bottoms can be used as charge
stock for the visbreaking process when it is necessary to decrease the high viscosity. This
reduces the percentage of expensive cutting stocks needed for obtaining a lower viscosity to
make a suitable No. 6 fuel oil.

4.) VISBREAKING PROCESS:;

 The feedstock for this process is the vacuum bottoms. The reaction is basically the same as in the
thermal cracking process, but, because of the slightly lower temperatures and pressures here, the
cracking is less severe. If too-extensive cracking occurred, a large amount of low-grade gasoline
would be produced, whereas this process is, generally, only used to obtain large volume of
distillate as charge stock for the catalytic process.
 When vacuum bottoms are used as charge, the residual produced is higher in gravity and lower
in viscosity than the original feed. The viscosity, while still high, needs considerably less cutting
oils to make No.6 fuel oil.
 The average consumer will not encounter many of the individual products just as they are
produced, since the oils are frequently altered by blending to meet specifications of the various
grades of fuel oils.

REFINING YIELDS:

 A combination of the five refining processes illustrated has greatly changed the volume of the various
oils produced. The average distillate yield – gasoline, kerosene, fuel oil distillate, and jet fuel – has
increased to 79%. Primarily, this has been at the expense of the residual. The average yield of residual
has dropped to 9%.

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