An article on fossil fuels
Internal Combustion Engines are the generators of the energy mainly
used for transportation. Almost more than 90% of the total IC Engines
run on fossil fuels or different derivatives of petroleum.
IC Engines are a kind of open cycle heat engine where heat is
supplied to the engine by the combustion of working fluids thus
releasing huge amount of energy due to the combustion processes of the
working fluids. Combustible working fluids are called fuels.
The natural petroleum oil is the largest single source of internal
combustion engine fuels. Petrol and Diesel are the most used among them.
The boiling point of petrol is 30°C to 200°C and that of diesel oil is
from 200°C to 375°C.
Fuels of most of the IC Engines are the derivatives of Petroleum
like gasoline, diesel oil, kerosene, jet fuel etc. All of these fuels
are produced during the fractional distillation of Petroleum Oil
obtained from crude from oil wells.
The fuels used in the IC Engines are designed to satisfy the
performance requirements of the engine system in which they are used. As
a result the fuels must have certain
- (i) physical,
- (ii) chemical and
- (iii) combustion properties.
Following are the some characteristics a fuel must have in order to produce the desirable output to the engine performance.
- A fuel must have a large energy density to be capable to release
huge amount of energy during its combustion in side the combustion
chamber.
- A fuel must posses a good combustion quality to produce large amount of energy in smooth way.
- A fuel must have high thermal stability or pre-ignition may occur.
- A fuel must show a low deposit forming tendency else gum
formation and other deposit forming processes will hamper the combustion
process.
- A fuel must be non-toxic, easy to handle and storage.
CRUDE PETROLEUM OIL:
Petroleum or often referred as "Crude Oil" is a naturally occurring
inflammable mixtures of liquid and mud and it contains a complex
mixture of different hydrocarbons of various molecular weights. It is
mainly recovered through a process called "Oil Drilling".
Oil Wells and Gas Wells:
An oil well produces mainly crude oil with some natural gas
dissolved in it. In contrast a gas well produces natural gases although
it may contain heavier hydrocarbons like pentane, hexane or hepthane in
gaseous state due to the extreme pressure and temperature inside the
well, but at surface conditions condensation starts and forms "Natural
Gas Condensate" or simply known as Condensate.
COMPOSITIONS OF CRUDE WELL:
Basically, crude well is the muddy mixtures of different
hydrocarbons of different molecular weights. Alkanes, Cyclo-alkanes or
napthenes, aromatics. It contains nitrogen, oxygen, sulfur and
phosphorous. It may also contains metallic compounds too.
Four different types of hydrocarbon molecules appear in crude oil.
The relative percentages are widely varied from oil to oil. They are:
- i) Paraffins (alkanes,
CnH2n + 2 )
- ii) Olefins (alkenes, CnH2n),
- iii) Napthenes (cyclo-alkanes, CnH2n ),
- iv) Aromatics (having benzene ring, CnH2n - 6).
It is then refined by fractional distillation in oil refinery to
obtain a large number of consumer products, from petrol or gasoline,
diesel to kerosene, heavy oil, fuel oil, asphalt, chemical reagents,
plastics etc.
Most of the derivatives of the petroleum have been used as fuel or
heating purpose. The major products of a petroleum refinery are:
- (i) Gasoline,
- (ii) Kerosene,
- (iii) Diesel Oil,
- (iv) Fuel oil,
- (v) Heavy Oil,
- (vi) Lubricating Oil,
- (vii) Asphalts
INTRODUCTION:
As the demands for gasoline, kerosene/ jet fuel and diesel oil are
maximum, refineries around the world have started to convert heavy fuels
and other higher hydrocarbons into gasoline, kerosene and diesel oil.
To perform this, refineries have adopted several thermo-chemical
processes those can convert high molecular weight hydrocarbons into
lighter ones by breaking them.
GENERAL REFINERY PROCESSES:
Petroleum refining has evolved
continuously in response to changing consumer demand for better and
different products. The original requirement was to produce kerosene as a
cheaper and better source of light than whale oil. The development of
the internal combustion engine led to the production of gasoline and
diesel fuels. The evolution of the airplane created an initial need for
high-octane aviation gasoline and then for jet fuel, a sophisticated
form of the original product, kerosene. Present-day refineries produce a
variety of products including many required as feedstock for the
petrochemical industry.
a) Distillation Processes:
The first refinery, opened in 1861,
produced kerosene by simple atmospheric distillation. Its by-products
included tar and naphtha. It was soon discovered that distilling
petroleum under vacuum could produce high-quality lubricating oils.
However, for the next 30 years kerosene was the product consumer wanted.
Two significant events changed this situation. The invention of the
electric light decreased the demand for kerosene and the invention of
the internal combustion engine created a demand for diesel fuel and
gasoline (naphtha).
b) Thermal Cracking Processes:
With the advent of mass production and
World War I, the number of gasoline-powered vehicles increased
dramatically and the demand for gasoline grew accordingly. However,
distillation processes produced only a certain amount of gasoline from
crude oil. In 1913, the thermal cracking process was developed, which
subjected heavy fuels to both pressure and intense heat, physically
breaking the large molecules into smaller ones to produce additional
gasoline and distillate fuels. Visbreaking, another form of thermal
cracking, was developed in the late 1930's to produce more desirable and
valuable products.
c) Catalytic Processes:
Higher-compression gasoline engines
required higher-octane gasoline with better antiknock characteristics.
The introduction of catalytic cracking and polymerization processes in
the mid- to late 1930's met the demand by providing improved gasoline
yields and higher octane numbers. Alkylation, another catalytic
process developed in the early 1940's, produced more high-octane
aviation gasoline and petrochemical feedstock for explosives and
synthetic rubber. Subsequently, catalytic isomerization was developed to
convert hydrocarbons to produce increased quantities of alkylation
feedstock. Improved catalysts and process methods such as hydrocracking
and reforming were developed throughout the 1960's to increase gasoline
yields and improve antiknock characteristics. These catalytic processes
also produced hydrocarbon molecules with a double bond (alkenes) and
formed the basis of the modern petrochemical industry.
d) Treatment Processes:
Throughout the history of refining,
various treatment methods have been used to remove non-hydrocarbons,
impurities, and other constituents that adversely affect the properties
of finished products or reduce the efficiency of the conversion
processes. Treating can involve chemical reaction and/or physical
separation. Typical examples of treating are chemical sweetening, acid
treating, clay contacting, caustic washing, hydrotreating, drying,
solvent extraction, and solvent dewaxing. Sweetening compounds and acids
desulfurize crude oil before processing and treat products during and
after processing.
Following the Second World War,
various reforming processes improved gasoline quality and yield and
produced higher-quality products. Some of these involved the use of
catalysts and/or hydrogen to change molecules and remove sulfur.
Basics of Hydrocarbon Chemistry:
Crude oil is a mixture of hydrocarbon
molecules, which are organic compounds of carbon and hydrogen atoms that
may include from one to 60 carbon atoms. The properties of hydrocarbons
depend on the number and arrangement of the carbon and hydrogen atoms
in the molecules. The simplest hydrocarbon molecule is one carbon atom
linked with four hydrogen atoms: methane. All other variations of
petroleum hydrocarbons evolve from this molecule.
Hydrocarbons containing up to four
carbon atoms are usually gases, those with 5 to 19 carbon atoms are
usually liquids and those with 20 or more are solids. The refining
process uses chemicals, catalysts, heat, and pressure to separate and
combine the basic types of hydrocarbon molecules naturally found in
crude oil into groups of similar molecules. The refining process also
rearranges their structures and bonding patterns into different
hydrocarbon molecules and compounds. Therefore it is the type of
hydrocarbon (paraffinic, naphthenic, or aromatic) rather than its
specific chemical compounds that is significant in the refining process.
Principal Groups of Hydrocarbon
-
Paraffins - The paraffinic series of hydrocarbon compounds found in crude oil have the general formula CnH2n+2
and can be either straight chains (normal) or branched chains
(isomers) of carbon atoms. The lighter, straight chain paraffin
molecules are found in gases and paraffin waxes. Examples of
straight-chain molecules are methane, ethane, propane, and butane (gases
containing from one to four carbon atoms), and pentane and hexane
(liquids with five to six carbon atoms). The branched-chain (isomer)
paraffins are usually found in heavier fractions of crude oil and
have higher octane numbers than normal paraffins. These compounds
are saturated hydrocarbons, with all carbon bonds satisfied, that is,
the hydrocarbon chain carries the full complement of hydrogen atoms.
-
Aromatics -
Aromatics are unsaturated ring-type (cyclic) compounds which react
readily because they have carbon atoms that are deficient in
hydrogen. All aromatics have at least one benzene ring (a single-ring
compound characterized by three double bonds alternating with three
single bonds between six carbon atoms) as part of their molecular
structure. Naphthalenes are fused double-ring aromatic compounds.
The most complex aromatics, polynuclears (three or more fused aromatic
rings), are found in heavier fractions of crude oil.
-
Naphthenes - Naphthenes are saturated hydrocarbon groupings with the general formula CnH2n,
arranged in the form of closed rings (cyclic) and found in all
fractions of crude oil except the very lightest. Single-ring
naphthenes (monocycloparaffins) with five and six carbon atoms
predominate, with two-ring naphthenes (dicycloparaffins) found in the
heavier ends of naphtha.
Other Hydrocarbons
-
Alkenes - Alkenes are mono-olefins with the general formula CnH2n
and contain only one carbon-carbon double bond in the chain. The
simplest alkene is ethylene, with two carbon atoms joined by a double
bond and four hydrogen atoms. Olefins are usually formed by thermal
and catalytic cracking and rarely occur naturally in unprocessed
crude oil.
-
Dienes and Alkynes
- Dienes, also known as diolefins, have two carbon-carbon double
bonds. The alkynes, another class of unsaturated hydrocarbons, have a
carbon-carbon triple bond within the molecule. Both these series of
hydrocarbons have the general formula CnH2n-2. Diolefins such as
1,2-butadiene and 1,3-butadiene, and alkynes such as acetylene,occur
in C5 and lighter fractions from cracking. The olefins, diolefins,
and alkynes are said to be unsaturated because they contain less
than the amount of hydrogen necessary to saturate all the valences of
the carbon atoms. These compounds are more reactive than paraffins
or naphthenes and readily combine with other elements such as
hydrogen, chlorine, and bromine.
-
Example of simplest Alkyne: Acetylene (C2H2), Typical Diolefins with the same chemical formula (C4H6) but different molecular structures: 1,2-Butadiene and 1,3-Butadiene
Non-hydrocarbons
-
Sulfur Compounds - Sulfur may be present in crude oil as hydrogen sulfide (H2S),
as sulfur compounds such as mercaptans, sulfides, disulfides,
thiophenes, etc. or as elemental sulfur. Each crude oil has
different amounts and types of sulfur compounds, but as a rule the
proportion, stability, and complexity of the compounds are greater
in heavier crude-oil fractions. Hydrogen sulfide is a primary
contributor to corrosion in refinery processing units. Other
corrosive substances are elemental sulfur and mercaptans. Moreover, the
corrosive sulfur compounds have an obnoxious odor. Pyrophoric iron
sulfide results from the corrosive action of sulfur compounds on the
iron and steel used in refinery process equipment, piping, and
tanks. The combustion of petroleum products containing sulfur compounds
produces undesirables such as sulfuric acid and sulfur dioxide.
Catalytic hydrotreating processes such as hydrodesulfurization
remove sulfur compounds from refinery product streams. Sweetening
processes either remove the obnoxious sulfur compounds or convert them
to odorless disulfides, as in the case of mercaptans.
-
Oxygen Compounds - Oxygen compounds such as phenols, ketones, and carboxylic acids occur in crude oils in varying amounts.
-
Nitrogen Compounds -
Nitrogen is found in lighter fractions of crude oil as basic
compounds, and more often in heavier fractions of crude oil as
nonbasic compounds that may also include trace metals such as copper,
vanadium, and/or nickel. Nitrogen oxides can form in process furnaces.
The decomposition of nitrogen compounds in catalytic cracking and
hydrocracking processes forms ammonia and cyanides that can cause
corrosion.
-
Trace Metals -
Metals, including nickel, iron, and vanadium are often found in
crude oils in small quantities and are removed during the refining
process. Burning heavy fuel oils in refinery furnaces and boilers
can leave deposits of vanadium oxide and nickel oxide in furnace boxes,
ducts, and tubes. It is also desirable to remove trace amounts of
arsenic, vanadium, and nickel prior to processing as they can poison
certain catalysts.
-
Salts - Crude
oils often contain inorganic salts such as sodium chloride,
magnesium chloride, and calcium chloride in suspension or dissolved
in entrained water (brine). These salts must be removed or
neutralized before processing to prevent catalyst poisoning, equipment
corrosion, and fouling. Salt corrosion is caused by the hydrolysis
of some metal chlorides to hydrogen chloride (HCl) and the
subsequent formation of hydrochloric acid when crude is heated.
Hydrogen chloride may also combine with ammonia to form ammonium
chloride (NH4Cl), which causes fouling and corrosion.
- Carbon Dioxide - Carbon dioxide
may result from the decomposition of bicarbonates present in or
added to crude, or from steam used in the distillation process.
-
Naphthenic Acids -
Some crude oils contain naphthenic (organic) acids, which may
become corrosive at temperatures above 450° F when the acid value of
the crude is above a certain level.
Major Refinery Products
- Gasoline. The most important refinery product is
motor gasoline, a blend of hydrocarbons with boiling ranges from
ambient temperatures to about 400 °F. The important qualities for
gasoline are octane number (antiknock), volatility (starting and vapor
lock), and vapor pressure (environmental control). Additives are
often used to enhance performance and provide protection against
oxidation and rust formation.
- Kerosene. Kerosene is a refined middle-distillate
petroleum product that finds considerable use as a jet fuel and
around the world in cooking and space heating. When used as a jet
fuel, some of the critical qualities are freeze point, flash point, and
smoke point. Commercial jet fuel has a boiling range of about
375°-525° F, and military jet fuel 130°-550° F. Kerosene, with
less-critical specifications, is used for lighting, heating,
solvents, and blending into diesel fuel.
- Liquified Petroleum Gas (LPG). LPG, which
consists principally of propane and butane, is produced for use as
fuel and is an intermediate material in the manufacture of
petrochemicals. The important specifications for proper performance
include vapor pressure and control of contaminants.
- Distillate Fuels. Diesel fuels and domestic
heating oils have boiling ranges of about 400°-700° F. The desirable
qualities required for distillate fuels include controlled flash
and pour points, clean burning, no deposit formation in storage tanks,
and a proper diesel fuel cetane rating for good starting and
combustion.
- Residual Fuels. Many marine vessels, power
plants, commercial buildings and industrial facilities use residual
fuels or combinations of residual and distillate fuels for heating
and processing. The two most critical specifications of residual fuels
are viscosity and low sulfur content for environmental control.
- Coke and Asphalt. Coke is almost pure carbon with
a variety of uses from electrodes to charcoal briquets. Asphalt,
used for roads and roofing materials, must be inert to most
chemicals and weather conditions.
- Solvents. A variety of products, whose boiling
points and hydrocarbon composition are closely controlled, are
produced for use as solvents. These include benzene, toluene, and
xylene.
- Petrochemicals. Many products derived from crude
oil refining, such as ethylene, propylene, butylene, and
isobutylene, are primarily intended for use as petrochemical
feedstock in the production of plastics, synthetic fibers, synthetic
rubbers, and other products.
- Lubricants. Special refining processes produce
lubricating oil base stocks. Additives such as demulsifiers,
antioxidants, and viscosity improvers are blended into the base
stocks to provide the characteristics required for motor oils,
industrial greases, lubricants, and cutting oils. The most critical
quality for lubricating-oil base stock is a high viscosity index,
which provides for greater consistency under varying temperatures.
Common Refinery Chemicals
- Leaded Gasoline Additives: Tetraethyl lead (TEL)
and tetramethyl lead (TML) are additives formerly used to improve
gasoline octane ratings but are no longer in common use except in
aviation gasoline.
- Oxygenates: Ethyl tertiary butyl ether (ETBE),
methyl tertiary butyl ether (MTBE), tertiary amyl methyl ether
(TAME), and other oxygenates improve gasoline octane ratings and
reduce carbon monoxide emissions.
- Caustics: Caustics are added to desalting water
to neutralize acids and reduce corrosion. They are also added to
desalted crude in order to reduce the amount of corrosive chlorides
in the tower overheads. They are used in some refinery treating
processes to remove contaminants from hydrocarbon streams.
-
Sulfuric Acid and
Hydrofluoric Acid: Sulfuric acid and hydrofluoric acid are used
primarily as catalysts in alkylation processes. Sulfuric acid is also
used in some treatment processes.
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