Ministry of Higher Education and

Scientific Research
Al-Muthanna University
Engineering College
Chemical Engineering Department

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Introduction
Due to the health consequences of lead exposure and the wide use of
catalytic converters many countries were forced to reduce the lead
content in the gasoline toward the complete elimination of lead
additives in motor gasoline. Leaded gasoline is a major source of human
lead exposure. By reducing gasoline lead content, airborne lead
emissions and blood lead levels can be reduced. Evidently, lead is
considered as a harmful pollutant. A
growing number of countries have seen a successful transition to
unleaded gasoline. In the United States, lead was completely eliminated
from all US motor gasoline since 1990.Almost all Western European
countries had reduced the lead contents in gasoline to 0.4 gm/liter since
1986. A further reduction to 0.15 gm/liter was planned. In Japan about
96% of the gasoline pool is already lead-free .There are some
operational changes that can be done for immediate reduction of lead
concentration of gasoline. These changes require no capital investment.
For further reduction of lead, installations of new refinery units and/or
modifications of the existing ones are required. Many of the
processes in a modern refinery are devoted to improving the octane
value of chemical compounds that are used in blending gasoline.

Gasoline is a clear petroleum-derived flammable liquid that is used

primarily as a fuel in most spark-ignited internal combustion engines. It
consists mostly of organic compounds obtained by the fractional
distillation of petroleum, enhanced with a variety of additives. On
average, a 160-liter (42-U.S.-gallon) barrel of crude oil can yield up to
about 72 liters (19 U.S. gallons) of gasoline after processing in an oil
refinery, depending on the crude oil assay and on what other refined
products are also extracted.[1] The characteristic of a particular gasoline
blend to resist igniting too early (which causes knocking and reduces
efficiency in reciprocating engines) is measured by its octane rating,
which is produced in several grades. Once widely used to increase octane
rating, tetraethyl lead and other lead compounds are no longer used in
most areas (they are still used in aviation and auto-racing). Other
chemicals are frequently added to gasoline to improve chemical stability
and performance characteristics, control corrosiveness and provide fuel
system cleaning. Gasoline may contain oxygen-containing chemicals
such as ethanol, MTBE or ETBE to improve combustion.
Gasoline can enter the environment uncombusted, both as liquid and as
vapor, from leakage and handling during production, transport and
delivery (e.g., from storage tanks, from spills, etc.). As an example of
efforts to control such leakage, many underground storage tanks are
required to have extensive measures in place to detect and prevent such
leaks.[4] Gasoline contains benzene and other known carcinogens. Most
refiners produce gasoline in three grades (unleaded regular, premium,
and super-premium) and, in addition, supply a leaded regular gasoline to meet the needs
of farm equipment and pre-1972 automobiles. The principal difference between the
regular and premium fuels is the antiknock performance. In 2005, the posted method
octane number (PON) of unleaded regular gasolines (see Section 2.3) was about 87 and
that of premium gasolines ranged from 89 to 93. For all gasolines, octane numbers
average about two numbers lower for the higher elevations of the Rocky Mountain
states. Posted octane numbers (which are required by the EPA to be posted on dispensing
pumps) are arithmetic averages of the motor octane number (MON) and research octane
number (RON) and average four to six numbers below the RON.
Gasolines are complex mixtures of hydrocarbons, having typical boiling ranges
from 100 to 400°F (38 to 205°C), as determined by the American Society for Testing
and Materials (ASTM) method. Components are blended to promote high antiknock
quality, ease of starting, quick warm-up, low tendency to vapor-lock, and low engine
deposits. Gruse and Stevens [3] give a very comprehensive account of properties
of gasolines and the manner in which they are affected by the blending components.
For the purposes of preliminary plant design, however, the components used in
blending motor gasoline can be limited to light straight-run (LSR) gasoline or
isomerate, catalytic reformate, catalytically cracked gasoline, hydrocracked gasoline,
polymer gasoline, alkylate, n-butane, and such additives as ETBE, TAME
(tertiary amyl methyl ether), and ethanol. Other additives, for example, antioxidants,
metal deactivators, and antistall agents, are not considered individually at this time,
but are included with the cost of the antiknock chemicals added. The quantity of
antiknock agents added, and their costs, must be determined by making octane
blending calculations.
Light straight-run gasoline consists of the C
5
-190°F (C
5
-88°C) fraction of the
naphtha cuts from the atmospheric crude still (C
5
-190°F fraction means that pentanes
are included in the cut but that C
4
and lower-boiling compounds are excluded and
the TBP end point is approximately 190°F). Some refiners cut at 180 or 200°F
(83 or 93°C) instead of 190°F, but, in any case, this is the fraction that consists of
pentanes and hexanes and cannot be significantly upgraded in octane by catalytic
reforming without producing too large a quantity of benzene. As a result, it is
processed separately from the heavier straight-run gasoline fractions and requires
only caustic washing, light hydrotreating, or, if higher octanes are needed, isomerization
to produce a gasoline blending stock. For maximum octane with no lead
addition, some refiners have installed isomerization units to process the LSR fraction
and achieve blending octane number (BON) improvements of 13 to 20 octane
numbers over that of the LSR.
Catalytic reformate is the C
5
+
gasoline product of the catalytic reformer. Heavy
straight-run (HSR) and coker naphthas are used as feed to the catalytic reformer, and
when the octane needs require, FCC and hydrocracked gasolines of the same boiling
range may also be processed by this unit to increase octane levels. The processing
conditions of the catalytic reformer are controlled to give the desired product antiknock
properties in the range of 90 to 104 RON (85 to 98 PON) clear (lead free).
The FCC and HC gasolines are generally used directly as gasoline blending
stocks, but in some cases they are separated into light and heavy fractions, with the
• Stability
Quality gasoline should be stable for six months if stored properly, but as
gasoline is a mixture rather than a single compound, it will break down
slowly over time due to the separation of the components. Gasoline stored
for a year will most likely be able to be burned in an internal combustion
engine without too much trouble but the effects of long-term storage will
become more noticeable with each passing month until a time comes
when the gasoline should be diluted with ever-increasing amounts of
freshly made fuel so that the older gasoline may be used up. If left
undiluted, improper operation will occur and this may include engine
damage from misfiring or the lack of proper action of the fuel within
a fuel injection system and from an onboard computer attempting to
compensate (if applicable to the vehicle). Gasoline should ideally be
stored in an airtight container (to prevent oxidation or water vapor mixing
in with the gas) that can withstand the vapor pressure of the gasoline
without venting (to prevent the loss of the more volatile fractions) at a
stable cool temperature (to reduce the excess pressure from liquid
expansion and to reduce the rate of any decomposition reactions). When
gasoline is not stored correctly, gums and solids may result, which can
corrode system components and accumulate on wetted surfaces, resulting
in a condition called "stale fuel". Gasoline containing ethanol is
especially subject to absorbing atmospheric moisture, then forming gums,
solids or two phases (a hydrocarbon phase floating on top of a water-
alcohol phase).
The presence of these degradation products in the fuel tank or fuel lines
plus a carburetor or fuel injection components makes it harder to start the
engine or causes reduced engine performance. On resumption of regular
engine use, the buildup may or may not be eventually cleaned out by the
flow of fresh gasoline. The addition of a fuel stabilizer to gasoline can
extend the life of fuel that is not or cannot be stored properly, though
removal of all fuel from a fuel system is the only real solution to the
problem of long-term storage of an engine or a machine or vehicle.
Typical fuel stabilizers are proprietary mixtures containing mineral
spirits, isopropyl alcohol, 1,2,4-trimethylbenzene or other additives. Fuel
stabilizers are commonly used for small engines, such as lawnmower and
tractor engines, especially when their use is sporadic or seasonal (little to
no use for one or more seasons of the year). Users have been advised to
keep gasoline containers more than half full and properly capped to
reduce air exposure, to avoid storage at high temperatures, to run an
engine for ten minutes to circulate the stabilizer through all components
prior to storage, and to run the engine at intervals to purge stale fuel from
the carburetor.[63]
Gasoline stability requirements are set by the standard ASTM D4814.
This standard describes the various characteristics and requirements of
automotive fuels for use over a wide range of operating conditions in
ground vehicles equipped with spark-ignition engines.

• Energy content
A gasoline-fueled internal combustion engine obtains energy from the
combustion of gasoline's various hydrocarbons with oxygen from the
ambient air, yielding carbon dioxide and water as exhaust. The
combustion of octane, a representative species, performs the chemical
reaction:
2C8H18 +25O2→16Co2+18H2O
By weight, gasoline contains about 46.7 MJ/kg (13.0 kWh/kg;
21.2 MJ/lb) or by volume 33.6 megajoules per litre (9.3 kWh/l;
127 MJ/US gal; 121,000 Btu/US gal), quoting the lower heating
value. Gasoline blends differ, and therefore actual energy content varies
according to the season and producer by up to 1.75% more or less than
the average. On average, about 74 L (19.5 US gal; 16.3 imp gal) of
gasoline are available from a barrel of crude oil (about 46% by volume),
varying with the quality of the crude and the grade of the gasoline. The
remainder are products ranging from tar to naphtha.
A high-octane-rated fuel, such as liquefied petroleum gas (LPG), has an
overall lower power output at the typical 10:1 compression ratio of an
engine design optimized for gasoline fuel. An engine tuned for LPG fuel
via higher compression ratios (typically 12:1) improves the power output.
This is because higher-octane fuels allow for a higher compression ratio
without knocking, resulting in a higher cylinder temperature, which
improves efficiency. Also, increased mechanical efficiency is created by
a higher compression ratio through the concomitant higher expansion
ratio on the power stroke, which is by far the greater effect. The higher
expansion ratio extracts more work from the high-pressure gas created by
the combustion process. An Atkinson cycle engine uses the timing of the
valve events to produce the benefits of a high expansion ratio without the
disadvantages, chiefly detonation, of a high compression ratio. A high
expansion ratio is also one of the two key reasons for the efficiency
of diesel engines, along with the elimination of pumping losses due to
throttling of the intake air flow.
The lower energy content of LPG by liquid volume in comparison to
gasoline is due mainly to its lower density. This lower density is a
property of the lower molecular weight of propane (LPG's chief
component) compared to gasoline's blend of various hydrocarbon
compounds with heavier molecular weights than propane. Conversely,
LPG's energy content by weight is higher than gasoline's due to a
higher hydrogen-to-carbon ratio.
Molecular weights of the representative octane combustion are C8H18 114,
O2 32, CO2 44, H2O 18; therefore 1 kg of fuel reacts with 3.51 kg of
oxygen to produce 3.09 kg of carbon dioxide and 1.42 kg of water.
• Octane rating
Spark-ignition engines are designed to burn gasoline in a controlled
process called deflagration. However, the unburned mixture may
autoignite by pressure and heat alone, rather than igniting from the spark
plug at exactly the right time, causing a rapid pressure rise which can
damage the engine. This is often referred to as engine knocking or end-
gas knock. Knocking can be reduced by increasing the gasoline's
resistance to autoignition, which is expressed by its octane rating.
Octane rating is measured relative to a mixture of 2,2,4-
trimethylpentane (an isomer of octane) and n-heptane. There are different
conventions for expressing octane ratings, so the same physical fuel may
have several different octane ratings based on the measure used. One of
the best known is the research octane number (RON).
The octane rating of typical commercially available gasoline varies by
country. In Finland, Sweden and Norway, 95 RON is the standard for
regular unleaded gasoline and 98 RON is also available as a more
expensive option.
In the United Kingdom, over 95% of gasoline sold has 95 RON, and is
marketed as Unleaded or Premium Unleaded. Super Unleaded, with
97/98 RON and branded high-performance fuels (e.g. Shell V-Power, BP
Ultimate) with 99 RON make up the balance. Gasoline with 102 RON
may rarely be available for racing purposes.[71] [72] [73]
In the United States, octane ratings in unleaded fuels vary between
85[74] and 87 AKI (91–92 RON) for regular, 89–90 AKI (94–95 RON) for
mid-grade (equivalent to European regular), up to 90–94 AKI (95–99
RON) for premium (European premium).
Global ranking of gasoline according to the octane number :
Depending on the octane number of unleaded gasoline is divided to:
1- Normal gasoline (Normal-85): In this type, the octane number must
be at least (85).
2- Regular – 90 : In this type, the octane number must be at least (90).
3- Premium – 95: In this type, the octane number must be at least (95).
4- Super – 98: In this type, the octane number must be at least (98).

As mentioned these types usually specify the amount of lead and in

order to allow it to use as a gasoline for automobile unleaded must be
the percentage of lead not more (0.013 g / L) for the normal gasoline
and regular and not more than (0.01 – 0.005 g / L) for the premium and
super gasoline.

-Modern gasoline specifications according to the global ranking

Originally, “straight-
run” gasoline was
produced by simple
distillation
PRODUCTION
Originally, “straight-run” gasoline was produced by simple
distillationof crude oil without the use of chemical conversion
processes (Lane 1980; Sax and Lewis 1987). Shortly after 1900, motor
vehicles began to appear in growing numbers, and gasoline began to
have a marketable value as a refinery product. Around 1912, distillation
of crude oil alone could not satisfy the rapidly growing demand for
gasoline. At this time, gasoline-range hydrocarbons were recovered
from “wet” natural gas.
However only a limited amount of natural gasoline could be included in
finished gasoline because of its high volatility and its relatively low
anti-knock quality (Lane 1980). Since then, petroleum refineries have
gasoline.eveloped several processes to contribute to the production of d
In general, gasolines are blended from several petroleum refinery
process streams that are derived by the following methods: direct
distillation of crude oil, catalytic and thermal cracking, hydrocracking,
catalytic reforming, alkylation, and polymerization. Modern petroleum
refining begins with the distillation of crude oil into the following
fractions: light naphtha (used as a component of finished gasoline
without additional refining ), heavy naphtha (catalytically reformed to a
higher-octane blending stock ), kerosene and light gas-oil (used in the
production of kerosene, jet fuel, diesel fuel, and furnace oils), heavy
gas-oil (used in heavy diesel fuel, industrial fuel oil, and bunker oil),
and reduced crude.
The heavy gas-oil and other heavy oils recovered from the reduced
crude can be cracked into gasolines (Lane 1980). The use of cracking to
produce gasoline began in 1913. Cracking breaks down higher-boiling
hydrocarbons into lower-boiling ones. The two general types of
cracking used are catalytic and thermal. Catalysts may consist of
naturally occurring clays or synthetic compounds. Catalytic cracking
produces blending components for high-octane gasoline. Therefore, in
addition to serving as a gasoline-production process, catalytic cracking
also serves to improve octane (Hood 1973; Lane 1980). Hydrocracking,
which consists of cracking in the presence of added hydrogen, permits
wide variations in yields of gasoline and furnace oils to meet seasonal
demand changes and can effectively process hard-to-crack stocks.
However, since hydrocracked stocks lack the high-octane olefins
present in catalytically cracked stocks, they must be reformed (Lane
1980). Reforming processes convert low octane gasoline-range
hydrocarbons into higher-octane ones. Thermal reforming has been
almost completely replaced by catalytic reforming. Most reforming
catalysts are bimetallic catalysts consisting of platinum with another
promoting metal, such as rhenium (Hood 1973; Lane 1980). Alkylation
converts refinery gases into gasoline-range liquids of exceptionally high
anti-knock quality. However, the process is costly and is not commonly
used in gasoline production (Domask 1984; Lane 1980). Polymerization
combines two or more low molecular weight olefin gases into higher
molecular weight olefin liquids suitable for gasoline blending or for use
as chemical feed stocks. However, because olefinic liquids have low
anti-knock quality and the reactants, olefin gases, are valuable chemical
feeds, the polymerization process is no longer widely used to produce
gasoline blend streams.
After the various gasoline streams have been blended, foul-smelling,
corrosive, sulfur compounds are removed by hydrogenation (Lane
1980). At the end of the refining process, finished gasoline typically
contains more than 150 separate compounds although as many as 1,000
compounds have been identified in some blends (Domask 1984;
Mehlman 1990). At present, the only commercial source of gasoline is
petroleum, but it has been produced from shale oil, Athabasca tar sands,
and by hydrogenation or gasification of coal (Hood 1973; Sax and
Lewis).
Gasoline is available in the United States in leaded and unleaded grades.
In the past, organic lead compounds were widely used as anti-knock
agents in gasoline; however, methyl-tertiary-butyl ether has almost
completely replaced tetraethyllead as an anti-knock agent and is now
widely used in the production of unleaded gasoline (Sax and Lewis).
Now, EPA regulations do not permit intentional addition of lead or
phosphorous to unleaded gasoline and limits their maximum
concentrations to 0.013 g lead/L and 0.0013 g phosphorus/L . Leaded
gasoline is produced in much smaller quantities for use in engines not
equipped with catalytic converters. According to EPA regulations,
leaded gasoline can contain any lead additive at a concentration higher
than 0.013 g lead/L but no more that 1.1 g lead/L. The two common
grades of both leaded and unleaded gasoline, premium and regular,
differ in their anti-knock quality. Better anti-knock quality is indicated
by a higher octane number (IARC 1989). Gasoline is marketed as
several products and, within each product line, in various grades (IARC
1989).
The U.S. production volume of motor gasoline has steadily increased
between 1983 and 1989 from 277.2 million gallons/day to 306.6 million
gallons/day (DOE 1989a). During the month of January 1989, U.S.
production of unleaded gasoline was nearly six times as high as U.S.
production of leaded gasoline (DOE 1989b). The states leading
production of unleaded gasoline were Texas, California, and New
Jersey and the states leading production of leaded gasoline were Texas,
California, and Illinois (DOE 1989b). In 1989, the 10 U.S. companies
leading gasoline sales were the following ( in descending order of sales
Shell, Amoco, Exxon, Mobil, Chevron, Texaco, Unocal, BP America,
Sun and Phillips(API 1991).

Uses
1-used as fuel for internal-combustion engines
2-used as a solvent for oils and fats.
3-Gasoline is most often used in vehicles like cars, vans, etc.