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Improvemet of Gasoline Production

Technical Report April 2014
DOI: 10.13140/RG.2.1.4475.4805

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SAJJAD KHUDHUR ABBAS
National University of Malaysia
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Improvement of gasoline
production

Prepared By :
SAJJAD KHUDHUR ABBAS
Wael Khalil Ibrahim
Zahra Ali Hameed
Supervised by
Professor Raed Tariq al-Khatib

Historical Overview
Late 1800s, Crude oil primary processed for heating fuel and lighting.
Refineries removed all of the light products and burned the fuel in pits.
Turn of the Century, evolution of the internal combustion engine.
Refineries begin to sell the light products to be utilized in the internal
combustion engine. Early 1900s, demand for gasoline increases beyond
current refining capabilities.
Automobile industry began to perfect the design of the internal
combustion engine which required an increase in quality of the
gasoline.
In the 1950s the demand for higher quality of gasoline increased and
the refiners needed to develop a way to upgrade the low quality gasoline
into new higher quality.
1970s to present, environmental regulations driving change to the
existing processing technologies as well as improved gasoline blending
components by birth of unleaded gasoline, reformulated gasoline, etc.
Refineries forced to upgrade technology as well as blending capabilities.

Summary
Gasoline is one of the products derived from distilling and refining
petroleum. Compounds of organic lead were added to gasoline in the
past to reduce knocking in engines, but due to environmental concerns
this is no longer common. Other chemicals are also added to gasoline to
further stabilize it and improve its color and smell in a process called
"sweetening."

1. 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. One important process for improving the octane value is the
isomerization unit in the refinery.
It takes low-octane, normal-paraffins and chemically reshapes them into
higher-octane, iso-paraffins. The octane increase can be significant. For
example, n-pentane (nC5) has a Research Octane Number (RON) of
61.7; whereas, its isomer form, iso-pentane (iC5), has an RON of 92.3.
A typical feed to an isomerization unit of Light Straight Run (LSR)
gasoline can have an overall RON boost from 70 to 84.

1.1.The Gasoline:
Gasoline is a complex mixture of light hydrocarbons containing (5 to 11)
carbon atoms and having a boiling range of (15 to 190 ).
In the atmospheric distillation, the fraction identified as light naphtha,
medium naphtha and heavy naphtha are the potential components of
gasoline.
The clear research octane number ,RON, of these components varies
from 60 to 70 for light naphtha and 40 to 60 for medium and heavy
naphtha. So they are not used directly as gasoline, since the RON
requirements of gasoline are 90 to 98.
To meet the gasoline octane requirements portion of the recovered
naphtha should be upgraded.
Usually a catalytic reformer used for this purpose, where a higher
octane components such as isoparaffines and aromatic are formed.
Lead compounds, mainly tetra ethyl lead, TEL, are then added to to
enhance the octane number of the gasoline.
As high as 0.84 gm/liter of TEL is added to the gasoline.
About 47% of the atmospheric lead is caused by the gasoline additives
and gasoline combustion accounts for about 95% as the source of lead
emissions.
Most countries have taken serious actions to reduce the lead content of
gasoline or to switch completely to unleaded gasoline. By reducing
gasoline lead content, airborne lead emissions can be reduced.
Evidently, lead is considered as a harmful pollutant. Its concentration in
the populated cities at high traffic locations reached the threshold level
which can cause bad health effects.
The reduction of lead in the gasoline is desirable not only because of its
toxicity but also it hindered the reduction of the other automotive
pollutants, mainly hydrocarbons, carbon monoxide and nitrogen oxides.
All of the automotive pollution control devices currently in use are
intolerant of lead and require lead-free gasoline.
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1.2. Components of the mixture :

Paraffin hydrocarbons (paraffins) branching and straight chains,
naphthenic hydrocarbons pentagonal and hexagonal sub-groups, as well
as aromatic hydrocarbons and unsaturated.

1.3. The Operations and units to produce the final mixture

(gasoline):
1- Atmospheric Distillation.
2- Catalytic Reforming.
3- Catalytic Cracking.
4- Thermal Cracking.
5- Alkylation.
6- Isomiration.
7- Hydrocracking.

1.4. Important properties of gasoline:

1- Chemical composition of the blend gasoline:
The speed of formation of a homogeneous mixture (air fuel) in the
engine at required specifications (speed and quality of evaporation).
2- Fractional composition during the atmospheric distillation.
3- Saturated vapors pressure is a measure in (RVP).
Show the stability of a chemical - not to change in the conditions of
transport and unloading and using.
4- Sulfur and resins:
Non-acids formation and alkalis easy soluble in water, causing erosion
of reservoirs metals and disable the engines due to blockage of valves.
5- The Octane Number.
6- Ratio of lead:
Not configured exhaust and toxic waste to humans and the environment as
a result of the combustion process.
4

1.5. 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.

1.6. Modern gasoline specifications according to the global ranking

Properties
RON

Normal
(85)
85

Regular
(90)
90

Premium
(95)
95

Super
(98)
98

Searching
method
ASTM
D 2699 - 94

Lead Content
(g / L)

0.01

0.01

0.01

0.01

90 - 5164 ISO

0.05

0.05

0.05

0.05

D 3237
ASTM
237 90 EN

)no more than)

Sulfur Content
%
)no more than)

Benzol Content
%
)no more than)

Outward
appearance
(color)

MTBE Content
%
)no more than)

Net and
Net and
Net and
transparent transparent transparent
or without or without or without
Color
Color
Color
Less or
equal to
(8)

12

15

ASTM D
2622 - 94
ASTM D
4249 - 90
ISO 8754 - 92
Net and
ASTM D
transparent
4420 -94
or without ASTM D4053
Color
- 91
238 EN
15
GOST P 5105
-97

1.7. PRODUCTION
Originally, straight-run gasoline was produced by simple distillation
of 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
developed several processes to contribute to the production of gasoline.
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.
7

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,
8

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).

1.8. Additives
Additives and blending agents are added to improve the performance
and stability of gasoline. These compounds include anti-knock agents,
anti-oxidants, metal deactivators, lead scavengers, anti-rust agents, antiicing agents, upper-cylinder lubricants, detergents, and dyes (IARC
1989; Lane 1980).

1.9. Import and Export

Between 1988 and 1989, net U.S. imports of gasoline declined by 14%
to an average of 13.0 million gallons/day. By 1990, imports were up to
an average of 14.3 million gallons/day (DOE 1990).
Typically net U.S. imports of gasoline account for 4-5% of
demand(DOE 1989a).
During the month of January 1989, the primary countries exporting
gasoline to the United States were ( in order of decreasing volume )
Saudi Arabia , Venezuela , Brazil , Canada , France, Spain, and the
United Kingdom ( DOE 1989b).
Between 1988 and 1989, U.S. exports of finished motor gasoline
increased from 924,000 gallons/day to 1.6 million gallons/day. Exports
reached the highest point ever in 1989 at 2.4 million gallons/day ( DOE
1990). During the month of January 1989, the United States exported
primarily to Guatemala, Japan, and Mexico ( DOE 1989b).

1.10. Use
Gasoline is used almost exclusively to fuel internal combustion engines
(IARC 1989). Consumption of gasoline decreased slightly in 1982 and
then again in 1989. In 1989, 306.6 million gallons of gasoline were
consumed in the United States. During 1989, the use of unleaded
gasoline continued to rise, accounting for 88.8% of the total gasoline
demand in that year (DOE 1989a).

1.11. Disposal
Most gasoline is burned in internal combustion engines. Limited data
are available on the disposal of gasoline. A suggested method is to
spray
it
into
an
incinerator
(OHM/TADS
1991).

10

1.12. The Isomerization Unit

The feed to the isomerization unit in a refinery is typically a light
straight run gasoline stream high in C5 and (C6+ normal- paraffins).
This feed enters the deisopentanizer tower that removes any iC5 already
present in the stream. It also removes the iC5 created in the reactors
that are returned to the feed as part of the nC5 recycle.
As the iC5 is being sent out the overhead of the deisopentanizer tower,
the balance of the feed stream is sent to the isomerization reactor.
Hydrogen is also added to the stream to encourage the proper reactions
and to help minimize coke formation on the catalyst.
After passing through the reactor, the stream enters a H2 separation
unit that removes and recycles the H2 back to the feed of the reactor.
The stream then enters a stabilizer tower that removes any light
hydrocarbons made during the reactions. These light compounds exit
the top of the stabilizer tower and will typically be blended into the
refinery fuel gas system. The product stream leaves the bottom of the
stabilizer tower and enters a C5/C6 splitter tower.
At the C5/C6 splitter, the C5s are sent out the top of the tower and are
recycled back to the beginning of the process unit. The nC5 in the C5s
will be reprocessed while the iC5 will leave the top of the
deisopentanizer as finished iC5 product. The C6 and heavier
components leave the bottom of the splitter and either go to gasoline
blending or to the reformer unit to be made into aromatics.

Figure - Flow Diagram of a Typical Isomerization Unit in a Refinery

11

1.13. Gasoline Blending

1- Each individual refinery gasoline product is sent to a large storage tank.
2- None of the individual gasoline products meet the specifications for
customer use.
3- The individual refinery gasoline products are then combined in a
manor that would satisfy the specifications for the finished customer.
4- This product is then stored in another large tank where it is certified
for sale to the final customer.

12

REFERENCES
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Linear Programming, Oil and Gas (European Magazine) 23(2) June
1997.
2- I.S. Al-Mutaz, "Automotive Emission Problem in Saudi Arabia",
Environment.
3-Al-Mutaz,I.S., Al-Fariss,T.F., and Abdullah,A.I, Production of LeadFree Gasoline From Riyadh Refinery", Transaction of Egyptian Society
of Chemical Engineers(TESCE), vol. 14,1988. (Presented at the Third
Chemical Engineering Congress, Egyptian Engineering Society, Cairo,
March 19-21, 1988.)
4- Takashi Hagiwara, Technology Department, Petroleum Energy
Center (PEC)
5- Petromin Report on Strategy for controlling Automotive Emissions,
General Petroleum and Mineral Organization, Petromin Services,
Project Management and Data Processing, Jeddah, August 1986.
6- Shilstone, Beatrice. The First Book of Oil. Franklin Watts, Inc., 1969

7- http://www.madehow.com/Volume-2/Gasoline. J
8- Gary, J.H. and Handwerk, G.E. (1984). Petroleum Refining
Technology and Economics (2nd Edition ed.). Marcel Dekker,
Inc. ISBN 0-8247-7150-8.
9- Leffler, W.L. (1985). Petroleum refining for the nontechnical
person (2nd Edition ed.). PennWell Books. ISBN 0-87814-280-0.
10-James G, Speight (2006). The Chemistry and Technology of
Petroleum (Fourth Edition ed.). CRC Press. 0-8493-9067-2.
11-Briefing on Benzene in Petrol From website of United Kingdom
Petroleum Industry Association (UKPIA).

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