CHINESE JOURNAL OF MECHANICAL ENGINEERING

·792· Vol. 25, No. 4, 2012

DOI: 10.3901/CJME.2012.04.792, available online at www.springerlink.com; www.cjmenet.com; www.cjmenet.com.cn

Effect of Oxygenates Blending with Gasoline to Improve Fuel Properties

BABAZADEH SHAYAN Soheil 1, *, SEYEDPOUR Seyed Morteza2, and OMMI Fathollah1

1 Department of Mechanical Engineering, Tarbiat Modares University, Tehran, Iran
2 Department of Mechanical Engineering, Iran University of Science and Technology, Tehran, Iran

Received May 27, 2011; revised December 23, 2011; accepted February 7, 2012

Abstract: The purpose of this paper is to study the effect of oxygenate additives into gasoline for the improvement of physicochemical
properties of blends. Methyl Tertiary Butyl Ether (MTBE), Methanol, Tertiary butyl alcohol (TBA), and Tertiary amyl alcohol (TAA)
blend into unleaded gasoline with various blended rates of 2.5%, 5%, 7.5%, 10%, 15%, and 20%. Physicochemical properties of blends
are analyzed by the standard American Society of Testing and Materials (ASTM) methods. Methanol, TBA, and TAA increase density
of the mixtures, but MTBE decreases density. The addition of oxygenates lead to a distortion of the base gasoline’s distillation curves.
The Reid vapor pressure (RVP) of gasoline is found to increase with the addition of the oxygenated compounds. All oxygenates improve
both motor and research octane numbers. Among these four additives, TBA shows the best fuel properties.

Key words: gasoline oxygenates, distillation curve, reid vapor pressure, octane number

alcohols and ethers are used as gasoline additives to reduce

1 Introduction ∗ pollutants from vehicle exhaust gases. Proponents of these
oxygenates claim several advantages: they are octane
The Gasoline is a complex mixture of hydrocarbons
enhancers[6], they have significant anti-knock properties
obtained from crude oil distillation and processing, as well
important for unleaded fuels, they can be produced from
as the other organic chemicals derived from other energy
renewable agricultural raw materials instead of fossil
sources. Modern gasoline is a heavily processed product
sources, they reduce carbon monoxide emission from
that can also contain various synthetic components, added
vehicle exhaust. But also reducing the emission of carbon
to improve its performance and meet the demands of
monoxide (CO) and unburned hydrocarbons, minimizing
today’s advanced engine technology. Until recently, one
the emission of volatile organic compounds[7–11]. Methyl
such component was lead, which was added to gasoline to
tert-butyl ether (MTBE) is the oxygenate most commonly
boost octane ratings and reduce engine wear. However,
employed to increase the octane number of gasoline [12].
leaded gasoline cannot be used on cars equipped with the
Use of MTBE has become restricted due to its toxicity and
modern catalytic converters designed to reduce harmful
contamination of groundwater[13–15]. In addition to MTBE,
exhaust emissions, as lead very rapidly and permanently
alcohols such as Methanol, Tertiary butyl alcohol (TBA),
annihilates the performance of the catalyst. With the
and Tertiary Amyl alcohol (TAA) have led to growing
reduction or removal of lead, the octane number, the ability
interest as oxygenated additives[16–17]. Even without the
of petrol to avoid engine knock, must be raised by other
exact composition of the adulterant and the gasoline it is
means, such as increasing the concentration of aromatics,
shown that each solvent has an effect on the
optimizing the use of components such as alkylates and
physicochemical properties of gasoline of specific
isomerates or lending high octane oxygenates. The
magnitude and behavior, depending on the concentration
additives used in the adulteration of commercial gasoline
and chemical nature of the solvent. In this study, an
can be classified as oxygenated, aromatic, and light and
investigation was carried out into density, volatility
heavy aliphatic hydrocarbons, the majority of these
(distillation curves and Reid vapor pressure), and octane
compounds being natural constituents of gasoline[1]. The
number of unleaded gasoline after the addition of different
addition of solvents changes the original composition of the
oxygenates in various proportions.
fuel, affecting in physicochemical properties in different
ways[2]. Distillation curves, vapor pressure and octane
2 Experimental Procedure
rating are properties closely related to the fuel composition
and the characteristics of its components[3–5]. Simple
2.1 Material
Base gasoline composition was used to evaluate the
* Corresponding author. E-mail: soheil.babazadehshayan@gmail.com effect of the gasoline formulations containing oxygenates
© Chinese Mechanical Engineering Society and Springer-Verlag Berlin Heidelberg 2012
 CHINESE JOURNAL OF MECHANICAL ENGINEERING ·793·

(MTBE, Methanol, TBA, TAA). This gasoline
compositions, was obtained from the Tehran Oil Refinery
Company (TORC) located in the province of Tehran, Iran.
Table 1 lists the physicochemical characteristics of this
gasoline.
Analyzer, following the ASTM D 323 standard[24]. The
octane ratings were measured by Zeltex ZX-440 XL liquid
fuel analyzer, according to the ASTM D 2699 (RON)[25]
and ASTM D 2700 (MON)[26] standards.

Table 1. Characteristics of the base gasoline 3 Result and Discussion

Characteristic Quantity Method ASTM
Density /(g·cm–3)(at 16 ˚C) 0.768 2 D 4052 3.1 Relative density
Low heat value /(kJ·kg–1) 4331 3 D 4809 The graphs in Fig. 1 gives the densities of the base
Reid vapor pressure/ gasoline mixed with the oxygenated compounds (MTBE,
59.2 D 323
kPa (at 37.8 ˚C , ) Methanol, TBA, and TAA) in different volumetric
Sulphur/wt % 0.067 D 4294 concentrations. As can be seen in this figure, densities of
Motor octane number 81.6 D 2700 the alcohol oxygenates-gasoline blends increases because
Research octane number 85.3 D 2699 of their high densities, while the densities of the MTBE
Antiknock index 83.45 — oxygenates-gasoline blends decreases because of its low
Oxygen in fuel/(g·cm–3) 0 — density. Changes in the density affect the quantity of fuel
Distillation temperature/℃ D 86 that is injected into the combustion chamber during each
Initial boiling point/℃ 44.4
cycle, altering the ideal air-fuel burning ratio. In the case of
10% Evaporated/℃ 68.4
a gasoline adulterated with a more dense additive, the
50% Evaporated/℃ 124.6
burning will be incomplete, resulting in the emission of
90% Evaporated/℃ 169.5
pollutants to the atmosphere.
Final boiling point/℃ 206.6

The properties for MTBE and the other Oxygenates used

[18–21]
in this study are shown in Table 2 .

Table 2. Properties of the Oxygenates

Property MTBE MeOH TBA TAA
Chemical formula C5H12O CH3OH C4H10O C5H12O
Purity/% 99 99.9 99 99
Oxygen/wt% 18.2 49.9 21.6 22.4
Molecular weight/
88.15 32.04 74.12 88.15
(g·mol–1)
Density/(g·cm–3)
0.744 0.792 0.788 0.805
(at 16 ˚C)
Flash point/℃ –25.6 11 14 20.5
Boiling temperature/℃ 55 65 82 102 Fig. 1. Relative densities of the base gasoline with
Ignition temperature/℃ 460 455 490 425 oxygenates (2.5, 5, 7.5, 10, 15, 20 % (v/v))
Reid vapour pressure /
53.8 31.7 5.5 1.6
kPa (at 37.8 ℃)
Motor octane number 101 92 100 100 3.2 Volatility
Research octane number 116 107 130 130 The Crude oil and the various petroleum fractions and
products derived from it such as gasoline consist of a
2.2 Methods complex mixture of various components, mostly
The gasolines containing the aforementioned oxygenated hydrocarbons. Some of these components are quite volatile,
and some are not so volatile. It is fairly recognized that the
compound additives were evaluated in terms of their
different petroleum fractions and products have inherent
characteristics of density, volatility (distillation curves and
volatility characteristics. Volatility is defined as the
Reid vapor pressure), and octane number (RON and MON)
tendency or ability of a material to change from a liquid
using ASTM (American society for Testing and Materials)
state to gaseous state. When dealing with petroleum
approved equipment. The relative densities (measured at
products, the principal volatility characteristics that are
16 ℃) of the fuel samples and oxygenated compounds
significant are distillation, vapor pressure, and
were determined using an Portable Density/Specific
flammability.
Gravity Meter KYOTO DA-130N, following the ASTM D
4052 standard[22]. The distillation characteristics were 3.2.1 Distillation curves
measured by Tanaka AD-6 automatic distillation analyzer, Gasoline is a mixture of hundreds of hydrocarbon
according to the ASTM D 86[23] standard, Reid vapor compounds, each with its distinctive boiling point.
pressures are measured by Tanaka AVP 30D automatic RVP Therefore, gasoline boils over a range of temperatures and
 ·794· BABAZADEH SHAYAN Soheil, et al: Effect of Oxygenates Blending with Gasoline to Improve Fuel PropertiesY

its tendency to vaporize is characterized by determining a

series of temperatures at which various percentages of the
fuel have evaporated, as described in ASTM D86, “Test
Method for Distillation of Petroleum Products at
Atmospheric Pressure”. A plot of the results is commonly
called the distillation curve. These temperatures
characterize the volatility of the fuel’s light, medium and
heavy fractions. These fractions, in turn, affect the engine’s
different operating regimes.
Figs. 2(a), (b), (c) and (d) present the distillation curves
of the base gasoline and its blends with oxygenates (MTBE,
Methanol, TBA, TAA) in the volumetric proportions of 2.5,
7.5, 10 and 20%, respectively. As can be seen in Fig. 2, the
addition of oxygenates lead to a distortion of the base
gasoline’s distillation curves, which becomes more marked
the higher the oxygenates content. All oxygenates decrease
the distillation temperatures significantly. Fig. 2 indicates
that, among the oxygenated compounds used as additives
for base gasoline, methanol was the one that caused the
most marked change in the distillation curve. Figs. 2(c) and
(d) show the effect of adding more than 10% by volume of
methanol into the base gasoline. Clearly, this results in the
front end to the first region of the curve being heavily
distorted in terms of significantly increasing the volatility
of the fuel in these regions. Adding more than 10% volume
of methanol into gasoline continues to increase the
volatility of the blend as evidenced by further reductions of
both the T50 and T90 distillation temperatures. The
reductions seen in T50 and T90 between 10% and 20%
methanol are greater than the reductions from base gasoline
to the 10% methanol blend, demonstrating a non-linear
trend. The front end of the distillation curve is important
for cold starting with a more volatile curve lower
temperatures providing easier starting. However, if it is too
volatile, hot-starting and hot-fuel-handling driveability can
be a problem. The midrange is important for cold starting
and warm-up driveability. This in turn helps with short-trip
fuel economy. In older vehicles with carburetors, too much
midrange volatility can contribute toward carburetor icing.
A high tail end of the distillation curve contributes to better
fuel economy, but if too high it can contribute to
combustion chamber and other engine deposits. A high tail
end also can contribute to cold-start fuel dilution of the
engine oil[29].
 CHINESE JOURNAL OF MECHANICAL ENGINEERING
Fig. 2. Distillation curve of base gasoline and its blend with
Methanol, TBA, TAA, and MTBE
3.2.2 Reid vapor pressure
The pressure exerted by gasoline vapors in a confined
space, which is measured at 37.8 ℃, is called Reid vapor
pressure. RVP is the most important indicator both
volatility and emissions because of the relation of the
existing volatile organic compounds in fuels. In addition to
these, maximum increase of RVP occurs with 5%-10%
addition of all oxygenates. Also, RVP is very important the
driveability of the fuels in year around. Fig. 3 shows the
effects of the all oxygenates on the RVP. Adding
oxygenates into gasoline cause an increase in vapor
pressure and depress the boiling temperature. Also, higher
RVP values can be cause of the vapor lock and higher
evaporative harmful emissions. That’s why, RVP was
limited more countries with federal legislations. As it seen
in Fig. 3, methanol-gasoline blends has higher RVP. This
means, methanol-gasoline blends more volatile than the
other oxygenates. The vapor pressure profiles of the
methanol-blended gasolines in Fig. 3 indicate a significant
increase in the mixtures’ RVP for the initial fractions of
added alcohol. For this reason, methanol is suitable for
country that are in cold region.
Fig. 3. Reid vapor pressure of base gasoline containing
·795·
addition of 2.5, 5, 7.5, 10, 15, 20 % v/v
of Methanol, TBA, TAA, MTBE
3.3 Octane Number
The critical fuel property of gasoline for internal
combustion engine is resistance to engine knock, expressed
as the octane number of the gasoline. During a normal (no
knock) combustion cycle, a flame front travels smoothly
from the point of ignition at the spark plug outward toward
the cylinder walls. The octane (and auto-ignition
temperature) of various hydrocarbons is related to their
ability to withstand pre flame conditions without
decomposing into species that could auto-ignite before the
flame-front arrives.
The RON and MON methods use two primary reference
fuels, n-heptane and 2, 2, 4 trimethyl pentane, assigned
octane numbers of 0 and 100, respectively. The knocking
intensity of the test fuel is compared to that of reference
fuel blends. The anti-knock index (AKI) is the average of
the research octane number (RON, D 2699) and motor
octane number (MON, D 2700), sometimes expressed as
(RON+MON)/2 or (R+M)/2. Automotive octane ratings are
determined in a standardized single-cylinder engine with a
variable compression ratio (CR 4:1 to 18:1), operated under
standard conditions Cooperative Fuels Research (CFR)
engine. Fig. 4 and Fig. 5 depict the MON and RON profiles
of gasoline mixed with the oxygenated compounds and
their respective volumetric proportions respectively.
Research and motor octane numbers of all blends clearly
increase with both alcohol and ether oxygenates. As it seen
in these figures, maximum increases have been found TBA
and TAA blends. For research octane numbers, best octane
booster is TAA and for motor octane numbers, best octane
booster is TBA. In addition to these results, alcohol
oxygenates have better results versus the ether oxygenates
for both research and motor octane numbers.
Fig. 4. Motor octane number (MON) graphs for base gasoline
containing addition of 2.5, 5, 7.5, 10, 15, 20 % v/v
of Methanol, TBA, TAA, MTBE
 ·796· BABAZADEH SHAYAN Soheil, et al: Effect of Oxygenates Blending with Gasoline to Improve Fuel PropertiesY
Fig. 5. Octane number (RON) graphs for base gasoline
containing addition of 2.5, 5, 7.5, 10, 15, 20 % v/v
of Methanol, TBA, TAA, MTBE
4 Conclusions
(1) A study is carried out on the influence of the addition
of the oxygenates MTBE, Methanol, TBA and TAA on the
parameters density, distillation curves, Reid vapor pressure,
and octane rating.
(2) The addition of alcohols leads to mixtures’ increased
density because of their higher density while addition of
MTBE decreases the density because of their lower density.
(3) The addition of all oxygenates leads to mixtures’
increased RVP, and the highest and lowest effect on the
RVP are obtained by the addition of methanol and TBA
respectively.
(4) Addition of oxygenates improves both RON and
MON, and the highest RON and MON improvement are
found by the addition of TAA and TBA respectively,
while the lowest RON and MON improvement are found
by addition of MTBE.
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 CHINESE JOURNAL OF MECHANICAL ENGINEERING
Biographical notes
BABAZADEH SHAYAN Soheil, born in 1984, is currently an
engineer at Motor and Propulsion Laboratory of Tarbiat Modares
University, Iran. He received his master degree on aerospace at
Tarbiat Modares University, Iran, in 2011.
Tel: +98-912-7135235;
E-mail: Soheil.BabazadehShayan@Gmail.com
SEYEDPOUR Seyed Morteza, born in 1984, is currently an
engineer at Tara Sabalan Co., Iran. He received his master degree
on biomechanical engineering at Iran University of Science and
Technology, Iran, in 2011.
Tel: +98-912-4199905;
E-mail: Morteza.Seyedpour@Gmail.com
·797·
OMMI Fathollah, born in 1952, is currently an associate professor
at Tarbiat Modares University, Iran. He received his PhD degree
from Moscow University of Technology, Iran, in 1997. His
research interests include increase in the output of internal
combustion engines through changes in the type and amount of
fuel consumption, decrease in the pollutants of internal
combustion engines of different vehicles, conversion of carburetor
engines into injectors, designing different types of one-base and
two-base injectors, design of different nozzles, study the subject
of fluid fusion in aerosol space in one phase and two-phase state,
the entire research grounds related to the engine and drives,
Tarbiat Modares University, Iran.
Tel: +98-912-1324767;
E-mail: fommi@modares.ac.ir