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Octane Rating of Gasoline and Octane Booster

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A. Demirbas, M. A. Balubaid, A. M. Basahel, W. Ahmad & M. H. Sheikh

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 Petroleum Science and Technology, 33:11901197, 2015
Copyright 
C Taylor & Francis Group, LLC
ISSN: 1091-6466 print / 1532-2459 online
DOI: 10.1080/10916466.2015.1050506

Octane Rating of Gasoline and Octane Booster Additives

A. Demirbas,1 M. A. Balubaid,1 A. M. Basahel,1 W. Ahmad,1 and M. H. Sheikh1
1
Faculty of Engineering, Department of Industrial Engineering, King Abdulaziz University,
Jeddah, Saudi Arabia
Downloaded by [King Abdulaziz University] at 05:55 09 June 2016

Gasoline is a petroleum-derived liquid that is used primarily as a fuel in internal combustion engines
(ICE), particularly spark ignition Otto Engine. Gasoline is a blend of hydrocarbons with some con-
taminants, including sulfur, nitrogen, oxygen, and certain metals. The four major constituent groups of
gasoline are olefins, aromatics, paraffins, and napthenes. Octane number (ON) is measure of the ignition
quality or flammability of gasoline. The ONs are Research Octane Number (RON) and Motor Octane
Number (MON). RON is measured relative to a mixture of isooctane and n-heptane. Antiknock Index
(AKI) is a measure of a fuels ability to resist engine knock or octane quality. The AKI is an arith-
metic average of RON and MON. The ON decreases with an increase chain length in the hydrocarbon
molecule. The ONs increase with carbon chain branching. Another way of increasing the ON is used
gasoline octane boosters as additives, such as tetraethyl lead (TEL), methyl tertiary-butyl ether (MTBE),
and ferrocene. Aromatic alcohols, ethanol, and methanol also increase the ON of gasoline. The advantage
to adding oxygenates, such as MTBE, methanol, and ethanol, to gasoline is that they cause very little
pollution when they burn and are cleaner fuels.

Keywords: petroleum, gasoline, octane number, octane booster, additives

INTRODUCTION

Petroleum composed of crude oil, natural gas, and heavy oil. It is mainly composed of vari-
ous hydrocarbons together with small amount of organic compounds containing oxygen, nitro-
gen, and sulfur. The average composition of crude petroleum is C = 79.587.1%; H = 11.5
to 14.8%; S = 0.13.5%, N and O = 0.10.5%. The composition of petroleum is known
to vary significantly from its origin or geographical location of the refinery (Demirbas et al.,
2015a).
Petroleum is separated into components in the refinery. A refinery is a factory or processing plant
where crude or elementary materials are processed into more usable forms. A petroleum refinery
typically consists of 24 units. The petroleum refinery is a group of manufacturing plants that are
used to separate petroleum into fractions. The configuration of refineries may vary from refinery
to refinery. Some refineries may be more oriented toward the production of gasoline (Demirbas,
2012).
Separation refers to the process of fractional distillation. Crude oil is heated in a furnace so that
hydrocarbons can be separated via their boiling point. Inside large towers, heated petroleum vapors
are separated into fractions according to weight and boiling point. The lightest fractions, which

Address correspondence to A. Demirbas, Faculty of Engineering, Department of Industrial Engineering, King Abdulaziz
University, Jeddah, Saudi Arabia. E-mail: ayhandemirbas@hotmail.com

1190
 OCTANE RATING OF GASOLINE AND OCTANE BOOSTER ADDITIVES 1191

include gasoline, rise to the top of the tower before they condense back to liquids. The heaviest
fractions will settle at the bottom because they condense early.
Most of the compounds in petroleum are hydrocarbons. The hydrocarbon contents of petroleum
(by weight) are (a) paraffins (alkanes): 1560 (average 30); (b) naphtanes (cycloalkanes): 3060
(average 49); (c) aromatics: 330 (average 15), and (d) remainder: average 6. Geographic religion,
geologic and geophysics properties of oil well, platform and transportation costs, resources efficiency,
and bring economic value, environmental influence and ecological cost affect on petroleum cost (Wei
et al, 2014; Ma and Fan, 2015; Mou, 2015; Yin et al., 2015; Yue et al., 2015). Four petroleum-based
fuels used in vehicles are gasoline, diesel, liqufied petroleum gas (LPG), and compressed natural gas
(CNG). Normally natural gas is a cheaper fuel compared to diesel fuel and diesel fuel is a cheaper
fuel compared to gasoline.
Gasoline efficiency of crude oil can be increased by several conversion processes. Cracking is the
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process of taking heavier, less valuable fractions of crude and converting them into lighter products
(Aburas et al., 2015; Demirbas et al., 2015b). Cracking uses heat and pressure to break heavier
elements into lighter ones. Alkylation is another common process, which is basically the opposite of
cracking. In alkylation, small gaseous byproducts are combined to form larger hydrocarbons (Aysu
et al., 2015; Aburas and Demirbas, 2015).
Treatment is the final process of refining, and includes combining processed products to create
various octane levels, vapor pressure properties, and special properties for products used in extreme
environments (Yue et al., 2015). Treatment is highly technical and is the most time consuming step
of refining.

GASOLINE

Gasoline, known as petrol, is a transparent, petroleum-derived liquid that is used primarily as a fuel
in internal combustion engines (ICE), particularly the spark ignition Otto Engine.
In May 1876, Nikolaus Otto built the first practical four-stroke-cycle internal combustion engine
powered by a liquid fuel. The liquid fuel used by Otto became known as gasoline in the United
States; elsewhere it may be known as gasolina, petrol, essence, or benzin.
Gasoline consists mostly of hydrocarbons obtained by the fractional distillation of petroleum,
enhanced with a variety of additives. Natural gasoline contains the C5 -C12 alkanes and cycloalkenes
(naphthenes). The boiling range of natural gasoline is about 40200 C. The use of natural gasoline
has many drawbacks and natural gasoline is never used without changing the original. For example,
when at gas stations, have you ever wondered about the difference between the types of fuels, 87,
89, 91, 95, and 98+ octane gasoline? What is octane rating or octane number (RON [research octane
number])? The characteristic of a particular gasoline blend to resist igniting too early is measured by
its octane rating or RON (Anderson et al, 2012; Yang et al., 2013). Early igniting causes knocking
and reduces efficiency in reciprocating engines.
Gasoline is the most popular product derived from petroleum and constitutes the largest fraction
of product obtained per barrel of crude oil. Internal combustion engines burn gasoline in a controlled
process called deflagration (Demirbas, 2002).
Gasoline is a blend of hydrocarbons with some contaminants, including sulfur, nitrogen, oxygen,
and certain metals. The four major constituent groups of gasoline are olefins, aromatics, paraffins,
and napthenes. The important characteristics of gasoline are density, vapor pressure, distillation
range, octane rating, and chemical composition. To be attractive, a motor gasoline must have (a)
desirable volatility, (b) antiknock resistance (related to octane rating), (c) good fuel economy, (d)
minimal deposition on engine component surfaces, and (e) complete combustion and low pollutant
emissions (Chigier, 1981).
 1192 A. DEMIRBAS ET AL.

OCTANE RATING

Octane number (ON) is measure of the ignition quality or flammability of gasoline. The Research
Octane Number (RON) is indicative of normal road performance at mild conditions of inlet tem-
perature (65.6 C) and revolutions per minute (600 rpm). Motor Octane Number (MON) is in-
dicative of high-speed performance at severe conditions of inlet temperature (148.9 C) and RPM
(900 rpm).
The autoignition of fuels causes a knocking effect in gasoline engines. This is where it ignites
twice; once due to the high pressure and again when the spark ignites the gasoline. Coming from
the engine, knocking is a sharp, pinging sound, which is caused by the combustion of the air-fuel
mixture in the cylinder. The resulting knocking decreases engine efficiency and increase the risk of
engine damage. The RON is a measure of how quickly the gasoline burns. Ordinary gasoline burns
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too fast in cylinder and it causes in detonation. The RON is a value used to indicate the resistance
of a motor fuel to knock. RON are based on a scale on which isooctane (2,2,4-trimethylpentane)
is 100 (minimal knock) and n-heptane is 0 (bad knock). RON is measured relative to a mixture of
isooctane and n-heptane.
Spark ignition engines are designed to burn gasoline in a controlled process called deflagration.
Of importance in this process is the timing of combustion, which can be adversely impacted by
autoignition of gasoline. This leads to the phenomenon commonly referred to as engine knock
(Rothamer and Jennings, 2012). In fact, the resistance to autoignition is the largest difference
between gasoline and jet fuel, jet fuel being highly resistant to autoignition. A gasolines resistance
to autoignition is expressed in its RON. Octane level or ON (RON) is manipulated by the addition
of a particular hydrocarbon called octane. The higher the RON of the gasoline, the more the
fuel can be compressed (Cerri et al., 2013; Liu et al., 2014). Higher compression means higher
temperature and pressure can be achieved inside the engine, which translates to higher power
output.
The 87, 89, and 91 represent the RON of the gasoline, respectively. Anything rated above 90 is
usually referred to as premium gas. On the other hand, if the octane rating is below 90, then it would
be considered a regular unleaded gas (RUN).
Antiknock Index (AKI) or Pump Octane Number (PON; sometimes Posted Octane Number) is a
measure of a fuels ability to resist engine knock or octane quality. The AKI is an arithmetic average
of RON and MON. The AKI of a motor fuel is the average of the RON and MON as determined by
the formula (R+M)/2 (Balaban et al., 1992; Singh et al., 2002; Mendes et al., 2012; Foong et al.,
2014).
The RON of typical commercially available gasoline varies by country. In Saudi Arabia, Sweden,
Norway, and Finland, 95 RON is the standard for regular unleaded gasoline and 98 RON is also
available as a more expensive option. In the United Kingdom, ordinary regular unleaded gasoline
is 95 RON, premium unleaded gasoline is always 97 RON, and super unleaded is usually 9798
RON. In the United States, RONs in unleaded fuels can vary between 85 and 87 AKI (9192 RON)
for regular, through 8990 AKI (9495 RON) for mid-grade, up to 9094 AKI (9599 RON) for
premium. Shell and British Petrol (BP) produce fuel at 102 RON for cars with high-performance
engines. RON and MON values for hydrocarbon fuels forming gasoline are given in Table 1 (Balaban
et al., 1992; Sing et al., 2002; Mendes et al., 2012).
ON decreases with an increase chain length in the hydrocarbon molecule. The ONs increase with
carbon chain branching. The ONs increase in aromatics with same number of carbons. There are
two ways to increase the ON of a fuel. One is to put special additives into the fuel that discourage
autoignition, and the other is to blend high-octane fuels in with the ordinary gasoline. Straight chain
alkanes such as nonane, octane, and heptane ignite very easily and explode too soon. Branched chain
alkanes such as 2,2,4-trimethylpentane (iso-octane) do not tend to autoignite. Cyclic compounds
have a higher octane number than straight chain compounds.
 OCTANE RATING OF GASOLINE AND OCTANE BOOSTER ADDITIVES 1193

TABLE 1
Research Octane Number (RON) and Motor Octane Number (MON) Values for Hydrocarbon Fuels
Forming Gasoline

Name of fuel RON MON

Ethane 114.9 99.0

n-Propane 111.0 96.6
2-Methyl propane 102.1 97.0
2,2-Dimethyl propane 85.5 80.2
n-Butane 94.0 89.1
2-Methyl butane 93.0 89.7
2,2-Dimethyl butane 91.8 93.4
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2,3-Dimethyl butane 104.3 94.2

2,2,3-Trimethyl butane 112.1 101.3
n-Pentane 61.8 63.2
2-Methyl pentane 73.4 73.5
3-Methyl pentane 74.5 73.3
2,3-Dimethyl pentane 91.1 88.5
2,4-Dimethyl pentane 83.1 83.8
3,3-Dimethyl pentane 80.8 86.6
2,3-Dimethyl pentane 92.8 95.6
2-Methyl-3-ethyl pentane 87.3 88.1
2,2,4-Trimethyl pentane 100.0 100.0
2,2,3-Trimethyl pentane 109.6 99.9
2,3,4-Trimethyl pentane 102.7 95.9
n-Hexane 24.8 26.0
3-Methyl hexane 52.0 55.0
3,4-Dimethyl hexane 76.3 81.7
3,3-Dimethyl hexane 75.5 83.4
2,2-Dimethyl hexane 72.5 77.4
2,2,3,3-Tetramethyl hexane 112.8 92.4
n-Heptane 0 0
2-Methyl heptane 21.7 23.8
3-Ethyl heptane 33.5 52.4
3,3,5-Trimethyl heptane 86.4 88.7
n-Octane 0 0
Cyclopentane 101.6 84.9
1,1-Dimethylcyclopentane 92.3 89.3
1,2,4-Trimethylcyclopentane 89.2 79.5
1,1,2,4-Tetramethylcyclopentane 96.2 88.0
Cyclohexane 84.0 77.6
1,1-Dimethylcyclohexane 87.3 85.9
1,1,2-Trimethylcyclohexane 95.7 87.7
2-Butene 101.6 99.9
3,3-Dimethyl-1-butene 111.7 93.3
2,3,3-Trimethyl-1-butene 105.3 90.5
2-Pentene 87.8 87.8
4-Methyl-2-pentene 98.9 85.1
4,4-Dimethyl-1-pentene 104.4 85.4
2,4,4-Trimethyl-2-pentene 103.5 86.2
3-Hexene 94.0 80.1
2-Methyl-3-hexene 97.9 82.0
2-Heptene 73.4 68.8
3-Heptene 90.0 79.3
(Continued on next page)
 1194 A. DEMIRBAS ET AL.

TABLE 1
Research Octane Number (RON) and Motor Octane Number (MON) Values for Hydrocarbon Fuels
Forming Gasoline(Continued)

Name of fuel RON MON

2-Methyl-3-heptene 94.6 80.6

4,4-Dimethyl-1-heptene 79.8 74.8
4-Octene 94.6 80.6
Benzene 90.0 92.0
Ethylbenzene 107.0 124.0
Propylbenzene 129.0 127.0
1,3,5-Trimethylbenzene 137.0 124.0
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Toluene 112.0 124.0

o-Xylene 103.0 120.0
m-Xylene 124.0 145.0
p-Xylene 127.0 146.0
Super gasoline (unleaded) 85.0 95.0
Normal gasoline (unleaded) 81.0 91.0

GASOLINE OCTANE BOOSTERS AND FUEL PERFORMANCE ADDITIVES

Gasoline additives increase gasolines octane rating or act as corrosion inhibitors or lubricants,
thus allowing the use of higher compression ratios for greater efficiency and power. Types of addi-
tives include octane boosters, fuel system cleaners, injector cleaners, metal deactivators, corrosion
inhibitors, oxygenates, antioxidants, and friction modifiers.
Old engines could run on a variety of fuels such as gasoline, ethanol, and even kerosene. But with
each passing decade, passenger vehicles become more and more sophisticated to meet changing
emissions regulations, improve fuel economy, and meet consumer performance demands (Wei
et al., 2014). The fuel injectors, catalytic converters, and on-board computer diagnostic systems
significantly advanced. For example, deposit control additives are critical to maintain ideal fuel
spray patterns for effective combustion. These additives keep the injector nozzles and surfaces free
of deposits. Without them, injectors can easily clog and result in inefficient fuel delivery. With
significant build-up, deposits can actually absorb fuel and prevent the engine from getting the fuel it
needs to run efficiently. But quality gasoline deposit controls additives remove and prevents deposits
and keep values and injectors operating like new. Also friction modifiers in gasoline can provide
significant improvements to fuel economy as well as reduce engine wear.
Tetraethyl lead (TEL; formula, (CH3 CH2 )4 Pb) was mixed with gasoline beginning in the 1920s as
a patented octane booster. Burning of TEL generates lead oxide, which poisons catalytic converters.
The use of compounds containing lead causes environment pollution. The TEL is still used as an
additive in some grades of aviation gasoline, and in some developing countries such as Afghanistan,
Iraq, Myanmar, North Korea, and Yemen.
Methyl tertiary-butyl ether (MTBE) had been used in U.S. gasoline at low levels since 1979 to
replace lead as an octane enhancer. MTBE is an additive, and is used as an oxygenate to raise the
gasoline ON. Oxygen helps gasoline burn more completely, reducing harmful tailpipe emissions
from motor vehicles. Most refiners have chosen to use MTBE over other oxygenates primarily for
its blending characteristics and for economic reasons. MTBE may be carcinogen for animals and
humans in drinking waters.
Ferrocene [Fe(C5 H5 )2 ] is used as octane booster to rise the ON to rise of gasoline. Ferrocene is
a cheaper alternative to MMT and is also used as an alternative to TEL by fuel refineries The iron
 OCTANE RATING OF GASOLINE AND OCTANE BOOSTER ADDITIVES 1195

containing deposits formed from ferrocene can form a conductive coating on the spark plug surfaces
(Stratiev and Kirilov, 2009; Patil et al., 2014).
Aromatic hydrocarbons increase both RON and MON, alkylbenzenes may affect MON to a
greater extent than RON. The aromatic hydrocarbons burn sooty and are carcinogenic. Aromatic
alcohols are effective in increasing the ON higher than 10% dosages. They are highly carcinogenic
and are easily absorbed by the skin.
Ethanol has a higher ON (109), broader flammability limits, higher flame speeds, and higher heats
of vaporization than gasoline. These properties allow for a higher compression ratio, shorter burn
time and leaner burn engine, which lead to theoretical efficiency advantages over gasoline in an ICE
(Eyidogan et al., 2010). Disadvantages of ethanol include its lower energy density than gasoline, its
corrosiveness, low flame luminosity, lower vapor pressure, miscibility with water, and toxicity to
ecosystems (Foong et al., 2014).
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Methanol is a clean burning, high octane blending component produce from alternative non-
petroleum energy sources such as natural gas, coal and biomass (Yue et al., 2015). Methanol has
a higher RON (129134). It may be directly used as a clean fuel or as an additive to the gasoline.
Blending high-octane methanol also replaces aromatic compounds normally used for adding octane
in gasoline, but which also contribute to toxic emissions from vehicles. The disadvantages of
methanol are similar to the ones found in ethanol production, namely that it requires the sacrifice of
food resources in order to have an effective harvest. Because methanol is less volatile than gasoline,
it would be more difficult to start a car in cold weather. Another advantage to adding oxygenates,
such as MTBE, methanol, and ethanol, to gasoline is that they cause very little pollution when they
burn and are cleaner fuels. The advantages and disadvantages of gasoline octane booster additives
are given in Table 2. increasing the ON of gasoline is now achieved in one of the following four
ways: (a) isomerization, (b) catalytic cracking, (c) reforming (dehydrocyclization), and (d) adding
oxygenates.
Straight chain hydrocarbons converted into branched isomers by isomerization process. Isomer-
ization involves changing straight chain alkanes into their isomers. Alkanes are heated in the presence
of a suitable catalyst and the chains break. The chains are allowed to reconnect but they are more
likely to reform in branched-chains than in straight chains. Gaseous olefins streams reacted with
isobutane to produce liquid high-octane iso-alkanes (alkylation).
Catalytic cracking is the breaking down of long chain hydrocarbon molecules into short chain
molecules for which there is greater demand. In oil refineries the heavier fractions, such as fuel oil,
diesel oil and kerosene, are heated in the presence of a catalyst. The short chain alkanes produced
tend to be highly branched and hence have a high octane number. In the fluidized catalytic cracking
(FCC) process, larger hydrocarbons breaks into a product containing 30% aromatics and 2030
olefins.
Zeolites are once again used in this process, as they act as excellent catalysts. Zeolite Y is used to
crack the fuel, as it particularly effective at producing fuels with a high octane rating. As well as the
shorter chained alkanes, alkenes are also formed. These are more often branched and are important
in the petrochemicals industry.
Increasing the weight fraction of isoparaffins in the gasoline should result in an increased
MON/RON ratio although overall R+M/2 could in fact decrease. This is due to the fact that al-
though isoparaffins have higher MON values than RON, their absolute values are generally less than
their olefin counterparts.
Reforming involves the use of catalysts to form ring compounds. Straight chain alkanes are
converted to cycloalkanes and these are converted to aromatic compounds. Aromatic compounds
have high octane numbers and petrol contains 34% benzene, because benzene is a carcinogen this is
a cause for concern. In the catalytic naphtha reforming process, saturated, low-octane hydrocarbons
were converted into higher octane product containing about 60% aromatics.
 1196 A. DEMIRBAS ET AL.

TABLE 2
Advantages and Disadvantages of Gasoline Octane Booster Additives

Additive Advantages Disadvantages

Tetraethyl lead (TEL) or
Pb(C2 H5 )4
Methylcyclopentadienyl
manganese tricarbonyl
Short chain length hydrocarbon
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The ON of gasoline can be improved by
adding TEL is a knock inhibitor. As
anti-knock agents may be added to
further increase the ON.
MMT raise the ON of gasoline as an
alternative to TEL
The shorter the alkane chain, the higher the
ON.
Burning of TEL generates lead oxide,
which poisons catalytic converters. The
use of compounds containing lead
cause environment pollution.
It may be health risks above a certain
concentration.
The volatility of hydrocarbon increases
with a decrease in the chain length.

Aromatic hydrocarbons
Aromatic alcohols
Ethanol
Methanol
Methyl tertiary-butyl ether
(MTBE)
Ferrocene [Fe(C5 H5 )2 ]
Aromatics increase both RON and MON,
alkylbenzenes may affect MON to a
greater extent than RON.
They are effective in increasing the ON
higher than 10% dosages.
It has a higher RON (109). It allows for a
higher compression ratio, shorter burn
time and leaner burn engine. It reduces
harmful emissions.
It has a higher RON (129-134). It may be
directly used as a clean fuel or as an
additive to the gasoline.
MTBE is used as oxygenate to rise the ON
to rise of gasoline. Oxygen optimizes the
oxidation during combustion.
Ferrocene is used as octane booster to rise
the ON to rise of gasoline.
The aromatic hydrocarbons burn sooty
and are carcinogenic.
They are highly carcinogenic and are
easily absorbed by the skin.
Disadvantages of ethanol include its
lower energy density than gasoline, its
corrosiveness, and low flame
luminosity snd lower vapor pressure.
The disadvantages of methanol are similar
to ethanol. It would be more difficult to
start a car in cold weather.
MTBE may be carcinogen for animals
and humans in drinking waters.
The iron containing deposits formed from
ferrocene can form a conductive
coating on the spark plug surfaces.

CONCLUSIONS

The quality of gasolines on the market today can vary dramatically. All gasoline is not the same.
Gasoline is not a single substance. It is a complex mixture of components, which vary widely in
their physical and chemical properties.
Crude oil contains both straight chain and branched alkanes, but it does not contain
enough branched alkanes to give it a high ON. Gasoline obtained from the fractionating col-
umn is not a very efficient fuel. Straight-run gasoline has an ON of about 70. Scientists
have solved this problem; increasing the ONs by isomerism, reforming, cracking, and adding
oxygenates.
The ONs increase by using of gasoline octane boosters as additives. Antiknocking additives are
substances which reduce the tendency of a fuel to auto-ignite, and so increase the ON. Knock reduce
engine performance and reduces the life. Small amounts of boosters have been used as economical
and effective antiknock additives. In practice ONs do not blend linearly.

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