Fuel 85 (2006) 25672577

www.fuelrst.com

Addition of an azeotropic ETBE/ethanol mixture in

eurosuper-type gasolines
Eliana Weber de Menezes *, Renato Cataluna, Dimitrios Samios, Rosangela da Silva
Department of Physical Chemistry, Institute of Chemistry, Federal University of Rio Grande do Sul, Avenida Bento Goncalves,
9500, CEP-91501-970 Porto Alegre, RS, Brazil
Received 4 October 2005; received in revised form 6 April 2006; accepted 11 April 2006
Available online 24 May 2006

Abstract
This study proposes an azeotropic ETBE/ethanol mixture as a possible oxygenated additive for the formulation of eurosuper-type
gasolines. Two eurosuper gasolines with dierent chemical compositions and well dened characteristics of density, volatility and octane
numbers are used. Gasoline formulations containing azeotropic mixtures display an intermediary behavior between that of ETBE (ethyl
tert-butyl ether) and ethanol in gasoline blends. Formulations containing this additive oer advantages over ethanol (low volatility and
low solubility in water) and ETBE (higher octane number and lower production cost). Gasolines with azeotropic additives show lower
Reid vapor pressures (RVPs) than gasolines formulated with ethanol, and therefore low levels of volatile organic compounds, similarly to
highly pure ETBE. The use of the azeotropic mixture containing ethanol (renewable, deriving from biomass) and ETBE (produced from
ethanol and isobutene) in its formulation is environmentally attractive in industrialized countries due to the need to reduce carbon dioxide emissions.
2006 Elsevier Ltd. All rights reserved.
Keywords: Oxigenated compounds; Azeotropic (ETBE/EtOH) mixture; Eurosuper gasoline formulation

1. Introduction
Since the removal of alkyl-lead compounds for environmental and public health reasons, oxygenated compounds
have become increasingly important components in the
formulation of automotive gasolines, not only improving
octane ratings [1] but also reducing the emission of carbon
monoxide (CO) and unburned hydrocarbons, minimizing
the emission of volatile organic compounds [26]. The
introduction of a minimal percentage of oxygen in the formulation of gasolines has become a legal requirement in
most countries whose air quality is low.
The oxygenated compounds used worldwide are classied into two categories: alcohols and ethers, both of which
possess desirable octane rating characteristics and reduce

Corresponding author. Tel.: +55 51 3316 6306; fax: +55 51 3316 7304.
E-mail address: eliana@iq.ufrgs.br (E.W. de Menezes).

0016-2361/$ - see front matter 2006 Elsevier Ltd. All rights reserved.
doi:10.1016/j.fuel.2006.04.014

CO emissions [7]. In some countries, ethers are preferred

over alcohols (basically anhydrous ethyl alcohol) due to
its mixture characteristics of low volatility and compatibility with the hydrocarbons that constitute gasoline [8]. Alcohols are considerably more polar than the ethers and
hydrocarbons of gasoline and can cause phase separation
in the presence of small concentrations of water in the gasoline supply system [9]. Moreover, despite the low vapor
pressure of individual compounds, alcohols lead to high
vapor pressure when mixed with gasolines, contributing
to the emission of volatile organic compounds [10].
In Brazil, anhydrous ethyl alcohol fuel is used as an oxygenated compound in the formulation of automotive gasolines. In 2005, the volumetric percentage of ethanol in
Brazilian gasolines is 25 1% v/v. Ethanol shows a higher
octane number mixture than do ramied ethers, but it is
highly volatile, a property usually indicated by distillation
curves, vapor pressure and vaporization enthalpy [11]. Ethanol forms minimum temperature azeotropes with the

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E.W. de Menezes et al. / Fuel 85 (2006) 25672577

hydrocarbons of gasoline, which vaporize easily, and this

eect increases the vaporization of the gasoline/ethanol
mixture, increasing its vapor pressure as well as the emission of volatile organic compounds [8,10,11].
Tertiary ethers such as methyl tert-butyl ether (MTBE),
ethyl tert-butyl ether (ETBE) and tert-amyl methyl ether
(TAME) present advantages in relation to ethanol: low
Reid vapor pressure (RVP), low latent heat of vaporization
and low water solubility [7,12]. In the international market,
the most commonly used ethers are MTBE and ETBE.
With regard to these ethers, it should be noted that ETBE
is considered a semi-renewable compound, since the raw
material used for its production ethanol derives from
biomass, while MTBE is produced from methanol, derived
from synthesized gas [7]. Thus, the production of ETBE
reduces the dependence on methanol (from natural gas)
and also contributes to reduce the greenhouse eect. Comparing these two ethers, ETBE is more important in terms
of octane number as well as more attractive in terms of volatility and solubility, since it presents a lower mixture (gasoline/oxygenate) RVP and lower water solubility than
MTBE and ethanol [8]. Furthermore, the technology to
produce MTBE can be extended to the synthesis of ETBE
[1316].
Since the use of MTBE became restricted due to its toxicity and contamination of groundwater [1725], the manufacturing units producing this ether have been converted
to produce ETBE and isooctane. ETBE is a promising
compound in ethanol producing countries where this alcohol is commercially available at a competitive price, as in
the case of Brazil, where it is produced from sugarcane.
Thanks to its adaptation to the climate and its production
cost, sugarcane yields higher returns for the producer,
when compared with other raw materials such as beetroot
and cereals. In the USA and Europe, ethanol is produced
principally from cereals (such as corn) and beetroot.
In the ETBE production process, nonreacted ethanol
forms an azeotropic mixture with ETBE, which cannot
be separated by distillation. The purication process to
produce ETBE with a high degree of purity requires breaking down this azeotrope, which increases the ethers production costs.
The literature does not contain data about the use of the
azeotropic (ETBE/ethanol) mixture used as additives in
automotive gasolines. Therefore, this work proposes ETBE
as an additive in the azeotropic form and evaluates its eect
on the physicochemical properties (density, volatility and
octane number) in gasolines with dierent chemical
compositions.
2. Experimental
2.1. Materials
Ethyl tert-butyl ether (ETBE) in puried and azeotropic
form (ETBE/ethanol) was produced in the laboratory on a
semi-pilot scale, using a ow reactor under continuous

operation. The reagents utilized were isobutene (the C4

cut of the butadiene unit of Petroqumica do Sul, COPESUL, RS, Brazil, with a mean composition of 36% mole
in the ller) and absolute ethyl alcohol (P.A. Nuclear,
99.5% v/v). Amberlyst 15 resin was used as catalyst, with
a grain size ranging from 0.6 to 0.8 mm.
2.2. Base gasolines (G1 and G2)
The eect of adding the azeotropic (ETBE/EtOH) mixture to gasolines was investigated based on the physicochemical properties of the mixtures and was compared
with the addition of ETBE (obtained experimentally in
puried form) and ethanol. Two base gasolines (dubbed
G1 and G2) with dierent chemical compositions were used
to evaluate the eect of the addition of these compounds,
aiming to meet the quality requisites of European gasolines
(eurosuper). Table 1 lists the physicochemical characteristics of these gasolines.
2.2.1. Composition of the base gasolines
The base gasoline compositions were analyzed by GCFID, Varian 39XL gas chromatographer equipped with a
100 m long, 0.25 mm internal diameter fused silica capillary
column (CP-Sil PONA CB) with 100% dimethylpolysiloxane active phase.
The fractions of the base gasolines were characterized
based on their retention indices, using a Supelco (48264-U) naphtha standard and DHA (Detailed Hydrocarbon Analysis) software, which identies the individual
components of the gasoline, comparing their Kovats indices against the indices in a library of components, whose
elution behavior was characterized under identical conditions and adjusted according to the naphtha standard.
The condence of the results indicated by the DHA software was determined experimentally from a mixture with
a molar composition of 0.5% benzene, 1% n-hexane and
1% n-heptane in pentane. The standard deviation of the
Kovats index of benzene in three analyses carried out on
dierent days was lower than 0.5, indicating little variation

Table 1
Physicochemical characteristics of the base gasolines (G1 and G2)
Characteristics

G1
a

G2

Relative density at 20/4 C

Vapor pressure at 37.8 C (kPa)
Research octane number (RON)
Motor octane number (MON)

0.7446
56.4
98.5
87.3

0.7217
60.6
96.1
87.2

Distillation
Initial boiling point (C)

34.5

33.2

Percentage (v/v) of evaporated liquid

Evaporated at 70 C, % (v/v)
22
Evaporated at 100 C, % (v/v)
52
Evaporated at 150 C, % (v/v)
97

27
58
100

Final boiling point (C)

143

174

Relative density at 20 C in relation to water, at 4 C.

Techniques
ASTM
ASTM
ASTM
ASTM

D
D
D
D

4052
5191
2699
2700

ASTM D 86

E.W. de Menezes et al. / Fuel 85 (2006) 25672577

Addition with the oxygenated compounds was done

based on the oxygen percentages (% w/w), using as reference the maximum limit of 2.7% (w/w), as established by
the European EN 1601 code [26] for eurosuper gasolines.
The values of the mass percentages of oxygen for the
ETBE, ethanol and azeotrope (ETBE/EtOH) compounds
and the maximum percentages of these additives in blends
with the base gasolines to meet the specications for European gasolines (2.7% w/w of oxygen) are listed in Table 4.
The maximum volumetric content for each additive in
the blends, calculated from the densities of the base gasoTable 2
Composition of base gasoline G1 per hydrocarbon group and by carbon
number % volume
Identication

Until C5

C6

C7

C8

C9

C10

C11+

Total

n-Parans
Isoparans
Aromatics
Naphthenes
Olens
Others

6.7
10.8

0.4
6.7
0.3

1.3
5.6
0.3
1.6
1.6
0.1

0.4
1.8
36.7
1.1
0.5
0.05

2.5
17.0
0.3
1.2
0.1

1.3
0.3

0.2

0.6

0.06
0.2
0.3

0.3

10.1
36.7
38.5
4.3
9.1
0.8

The dash represents the hydrocarbons that are below of the detection
limit.

Table 3
Composition of base gasoline G2 per hydrocarbon group and by carbon
number % volume
Identication
n-Parans
Isoparans
Aromatics
Naphthenes
Olens
Others

Until C5
9.3
13.6

0.6
4.9
0.2

C6
1.3
5.0
0.2
1.4
1.2
0.1

C7
0.5
2.3
26.1
1.1
0.5
0.4

C8
2.6
23.7
0.2
1.8
0.1

C9

1.1
0.2

0.5

C10

0.3
0.1

0.06

C11+
0.03
0.1
0.1

0.2

Total
13.7
46.1
26.9
4.9
7.2
1.0

The dash represents the hydrocarbons that are below of the detection
limit.

Additive

ETBE

Ethanol

Azeotrope
(ETBE/ethanol)

General formula

C6H14O

C2H6O

M (g/mol)
% O (w/w)
% (m/m) max. of
additive in the blends
with base gasolines

102
15.7
17.2

46
34.8
7.8

63% molar ETBE and

37% molar EtOH
81.3
19.7
13.7

M = average molecular weight.

According to the ISO 3405 standard, there is no minimum limit for the
oxygen content in gasolines.

lines and oxygenated compounds, was practically identical

to their mass content. Therefore, the two base gasolines
(G1 and G2) received ethanol additive in the volumetric
proportions of 2, 4, 5 and 7% (v/v), ETBE in the proportions of 2, 5, 10, 15 and 17% (v/v), and the azeotrope
(ETBE/EtOH) in the proportions of 2, 5, 8, 10 and 13%
(v/v), respectively.

0.76

(a)
Relative density at 20/4 C

2.3. Addition of the base gasolines with the oxygenated

compounds (ethanol, ETBE and ETBE/EtOH azeotrope)

Table 4
Mass percentages of oxygen of the ETBE, ethanol and azeotrope (ETBE/
EtOH) additives

0.75

G1

0.74

0.73
G2
0.72
0

10

15

20

Additive fraction (%v/v)

0.8

Relative density at 20/4 C

in the shift towards the hydrocarbons of the standard

naphtha identied according to the DHA library.
The analytical conditions were: isotherm at 35 C for
15 min, a heating ramp-up at a rate of 1 C/min up to
60 C, followed by another 20 C/min ramp-up to 180 C.
The total analysis time was 2 h. The injector and detector
temperatures were 250 and 300 C, respectively. The initial
split ratio was 1:200, passing on to 1:20 after 5 min of analysis. The volume of injected sample was 0.5 lL. Tables 2
and 3 list the base gasoline compositions, shown as number
of carbon atoms per molecule (C4 to C12) and total hydrocarbons per group (PIANO parans, isoparans, aromatic compounds, naphthenes and olens).
As Tables 2 and 3 indicate, the G1 base gasoline shows a
higher fraction of aromatic hydrocarbons, while G2 possesses a higher proportion of isoparanic hydrocarbons.

2569

(b)

Ethanol

0.78
Azeotrope

0.76
G1
0.74

ETBE
G2

0.72
0

20

40

60

80

100

Additive fraction (% v/v)

ETBE

Ethanol

Azeotrope

Fig. 1. Relative densities at 20/4 C of the G1 and G2 base gasolines with

additives of ethanol (2, 4, 5 and 7% (v/v)), ETBE (2, 5, 10, 15 and 17% (v/
v)) and azeotrope (ETBE/EtOH) (2, 5, 8, 10 and 13% (v/v)). The dashed
lines indicate the ideal behavior of the mixtures for the intervals of 020%
(a) and 0100% (b) v/v of each oxygenate in the blends.

2570

E.W. de Menezes et al. / Fuel 85 (2006) 25672577

2.4. Evaluation of the physicochemical characteristics of the

base gasolines containing oxygen compound additives
(ethanol, ETBE and ETBE/ethanol azeotrope)

MON (motor octane number) methods, as per the ASTM

D 2699 [30] and ASTM D 2700 [31] standards.
3. Results and discussion

The gasolines containing the aforementioned oxygenated compound additives were evaluated in terms of their
characteristics of density, volatility (distillation curves
and Reid vapor pressure) and octane number (RON and
MON), using ASTM (American society for Testing and
Materials) approved equipment.
The relative densities (measured at 20/4 C) of the fuel
samples and oxygenated compounds were determined using
an Anton Paar DMA 4500 automatic densitometer, following the ASTM D 4052 standard [27]. The volatility of the
base gasolines and blends containing oxygenated compounds was checked by means of distillation assays, using
a Herzog MP 627 automatic atmospheric distillatory,
according to the ASTM D 86 [28] standard, while the Reid
vapor pressure (RVP) was measured with a Grabner Instruments Vapor Pressure Tester MINI VAP VPS device, following the ASTM D 5191 standard [29]. The octane ratings
were measured by the RON (research octane number) and

3.1. Relative density at 20/4 C

The graphs in Fig. 1 depict the densities of the G1 and
G2 base gasolines mixed with the oxygenated compounds
(ETBE, EtOH and azeotrope) in dierent volumetric concentrations. In these graphs, the dashed lines indicate the
ideal behavior of the mixtures for the intervals of zero to
20% (Fig. 1(a)) and zero to 100% (Fig. 1(b)) v/v of each
oxygenate in the blends. The relative densities at 20/4 C
of ETBE, ethanol and azeotrope were 0.7416, 0.7913 and
0.7554, respectively.
The densities were found to display an almost ideal
behavior. Basically, the dierences in the density proles
of the blends containing oxygenated additives should result
from the intermolecular interactions between the base gasolines and the oxygenates. Since G1 and G2 have dierent
chemical compositions, the hydrocarbon/oxygenate inter-

G1 with Ethanol

Temperature (C)

170

(a)

140
110
80
50
20
0

10

20

30

40
50
60
Evaporate %

4% Ethanol

7% Ethanol

70

80

90

100

G1

G2 with Ethanol

Temperature (C)

170

(b)

140
110
80
50
20
0

10

20

30

40

50

60

70

80

90

100

Evaporate %
4% Ethanol

7% Ethanol

G2

Fig. 2. Distillation curves of G1 (a) and G2 (b) and their blends with ethanol in the volumetric proportions of 4 and 7% v/v.

E.W. de Menezes et al. / Fuel 85 (2006) 25672577

actions must also be dissimilar, so the mixtures may display

deviations from the ideal.
The toluene molecules, which are the majority in G1,
show van der Waals forces of attraction. When associated
with ethanol molecules, in addition to this type of interaction, dipolar associations also probably occur. These interactions increase the attraction between molecules, leading
to higher blend densities. The isoparans (isopentane
and isooctane), which G2 contains in a higher proportion,
show lower van der Waals forces than do linear chain compounds. Their association with ethanol causes greater
repulsion of the molecules, which explains the blends
lower density. ETBE and azeotrope molecules mixed with
the isoparanic gasoline (G2) behave like neutral molecules, causing little disturbance and weak intermolecular
interactions (hydrocarbons/oxigenates, hydrocarbons/
hydrocarbons, and oxygenates/oxygenates). In terms of
density, these blends show an almost ideal behavior.
3.2. Distillation curves
According to the ISO 3405 standard [32], the specications for the distillation curves of eurosuper gasolines are

2571

as follows: evaporated at 70 C: 2040% (v/v); evaporated

at 100 C: 4671% (v/v); evaporated at 150 C: min. 75%
(v/v), and maximum nal ebullition point: 210 C. Our
results indicated that the base gasolines (G1 and G2) meet
the quality requisites of eurosuper-type gasolines. Figs. 24
illustrate the eect of adding the oxygenated compounds
(ethanol, ETBE and azeotrope) to the gasolines on the distillation curves. The results correspond to the average of
the tests carried out in duplicate. The repetitiveness of
the successive tests followed the recommendations of the
standard. Considering their physicochemical characteristics, the mixed gasolines fall within group 2 of the aforementioned standard.
3.2.1. Eect of the addition of ethanol
Fig. 2(a) and (b) present the distillation curves of the
base gasolines (G1 and G2) and their blends with ethanol
in the volumetric proportions of 4 and 7% v/v, respectively.
As can be seen in Fig. 2, the addition of ethanol leads to
a distortion of the base gasolines distillation curves, which
becomes more marked the higher the ethanol content. In
both gasolines, the increase in ethanol concentration
reduces the temperature of the evaporate by up to approx-

G1 with ETBE

Temperature (C)

170

(a)

140
110
80
50
20
0

10

20

30

40

50

60

70

80

90

100

Evaporate %
5% ETBE

17% ETBE

G1

G2 with ETBE

Temperature (C)

170

(b)

140
110
80
50
20
0

10

20

30

40

50

60

70

80

90

100

Evaporate %
5% ETBE

17% ETBE

G2

Fig. 3. Distillation curves of G1 (a) and G2 (b) and their blends with ETBE in the volumetric proportions of 5 and 17% v/v.

2572

E.W. de Menezes et al. / Fuel 85 (2006) 25672577

imately 25 C between 30 and 40% v/v of the evaporated

content. These distortions were caused by the formation
of minimum temperature azeotropes between the ethanol
and the components in the fractions that make up the base
gasolines [8]. Starting from 55% evaporate, the addition of
ethanol to both G1 and G2 did not inuence the distillation
curve proles, since most of the ethanol in the mixture had
already evaporated at the temperature corresponding to
this point. Based on the specication for the distillation
curve of European gasolines, it was found that, at a temperature corresponding to 70 C, the fraction of evaporated liquid was slightly higher than the limit specied by
the ISO 3405 standard (see specication in Section 3.2).
The distortions in the distillation curves explain the
increase in the fuels volatility, which can lead to the
appearance of vapor bubbles in the engines feed circuits.
These bubbles can lead to partial temporary or sometimes
even total interruptions in the circuit, causing engine malfunctioning, a phenomenon known as vapor lock. However, vapor lock aects only older, carbureted vehicles.
Another consequence of adding ethanol to gasolines is
the diculty in starting the engine, which is more dicult

the lower the ambient temperature and the higher the percentage of alcohol in the gasoline. This can be justied as a
function of the vaporization enthalpy of ethanol. Among
the physicochemical properties directly related to the fuels
volatility are the vapor pressure, vaporization enthalpy and
distillation curve. Fuels with low vapor pressures and high
vaporization enthalpies do not easily vaporize completely
in the intake manifold, which makes the combustion process dicult and reduces the engines performance [8,11].
The greater the vaporization enthalpy the lower the resulting temperature in the intake manifold, increasing the volumetric yield of the piston. Therefore, the vaporization
enthalpy strongly aects the engines power, for the higher
its value the greater the amount of heat removed from the
intake manifold and, hence, the lower the temperature of
the incoming mixture. This reduction in temperature in
the combustion chamber increases the density of the mixture and therefore the fuel mass to be oxidated, favoring
the increase in engine power. The behavior of the vehicle
with respect to the volatility of gasolines at low temperatures may cause incomplete vaporization of the fuel and
loss of control of the air/fuel ratio [8,11].

G1 with Azeotrope

Temperature (C)

170

(a)

140
110
80
50
20
0

10

20

30

40
50
60
Evaporate %

5% Azeotrope

70

13% Azeotrope

80

90

100

G1

G2 with Azeotrope

Temperature (C)

170

(b)

140
110
80
50
20
0

10

20

30

40

50

60

70

80

90

100

Evaporate %
5% Azeotrope

13% Azeotrope

G2

Fig. 4. Distillation curves of G1 (a) and G2 (b) and their blends with the ETBE/ethanol azeotrope in the volumetric proportions of 5 and 13% v/v.

E.W. de Menezes et al. / Fuel 85 (2006) 25672577

2573

imately 30% of the volume of evaporated liquid. This

indicates that ETBE, when blended with gasolines, reduces
the volatility of the lighter fractions, as demonstrated by
their lower RVPs, as we will see later in Section 3.3. In
the range of 3080% evaporate, the temperature of the
evaporate diminishes as the concentration of ETBE in
the blends increases; however, all the points of the distillation curve follow the standard of the specication for European gasolines. According to the results of the distillation
curve, ETBE facilitates the vaporization of heavy fractions,
contributing to a complete vaporization of the hydrocarbons in the intake manifold. A similar fact is observed
for the mixtures with ethanol, but the ETBE reduces the
mixtures vapor pressure signicantly, reducing the emission of volatile organic compounds.

In Brazil, the addition of anhydrous ethanol is not determined by a maximum limit of oxygen, as specied for
European gasolines, but by a foxed volumetric content,
which is currently 20 1% v/v, as specied by current legislation. The volumetric percentage of alcohol in Brazilian
gasolines varies according to the seasonality of the ethanol
crop in the domestic market. Values exceeding 30% v/v
require engine tuning. Vehicles equipped with a lambda
probe sensor and retro-feed control allow for the use of
gasolines with zero to 100% v/v of alcohol. However, to
meet the tuning requirements of all the vehicles in the Brazilian eet, the limits imposed for the addition of ethanol in
gasolines vary from 15 to 30% v/v.
3.2.2. Eect of the addition of ETBE
Fig. 3(a) and (b) shows the distillation curves of the base
gasolines and their mixtures with ETBE in the volumetric
proportions of 5 and 17% v/v.
Fig. 3 indicates that the increasing addition of ETBE to
both gasolines causes a slight increase in the initial ebullition point and in the evaporate temperature, up to approx-

3.2.3. Eect of the addition of the ETBE/ethanol azeotrope

Fig. 4(a) and (b) presents the distillation curves of the
base gasolines and their mixtures with the azeotrope
(ETBE/EtOH) in the volumetric proportions of 5 and
13% v/v, respectively.

Blends with G1
(a)

55
45

(a')

65
RVP (kPa)

Reid vapor pressure (kPa)

65

35

ETBE
55

Azeotrope

25

45
0

8
12
Additive fraction (% v/v)

16

Ethanol

20

15

10

20

30

40

50

60

70

80

90

100

Additive fraction (% v/v)

Blends with G2
(b)

55
45
65
RVP (kPa)

Reid vapor pressure (kPa)

65

35

ETBE
55

Azeotrope

(b')

25

45
0

15
0

10

8
12
Additive fraction (% v/v)

20

30

16

40

Ethanol

20

50

60

70

80

90

100

Additive fraction (% v/v)

ETBE

Ethanol

Azeotrope

Fig. 5. Reid vapor pressures of the base gasolines G1 (a) and G2 (b) with ETBE (2, 5, 10, 15 and 17% (v/v)), ethanol (2, 4, 5 and 7% (v/v)) and azeotrope
(ETBE/EtOH) (2, 5, 8, 10 and 13% (v/v)). The dashed lines in graphs (a) and (b) indicate the tendency toward the ideal behavior with zero to 100% of
additives in the blends. The dashed lines in graphs (a 0 ) and (b 0 ) indicate the ideal behavior with up to 20% (v/v) of additives.

2574

E.W. de Menezes et al. / Fuel 85 (2006) 25672577

As indicated in the above gure, the distillation curves

of the blends containing the azeotrope (ETBE/EtOH)
showed practically the same distillation proles as the base
gasolines. The fact that the gasolines formulated with the
azeotropic mixture presented the same behavior as the base
gasolines during distillation is relevant, since the fuels
heavy and light fractions remained unaltered. The distillation curves for the azeotropic (ETBE/EtOH) mixture show
that increasing the concentration of azeotrope in the formulation gradually reduces the temperature of the evaporate while subtly increasing the fuels vaporization.
Thus, we found that, in the concentrations studied here,
both the azeotrope and the ETBE only slightly modied
the characteristics of the base gasolines distillation curves,
which nonetheless remained in conformance to the quality
requisites for gasolines. The use of ethanol alters the properties of volatility of base gasolines and, depending on the
gasolines characteristics, the maximum addition of 2.7%
w/w, as established by the ISO 3405 standard, is not
possible.

3.3. Reid vapor pressures (RVPs)

The pressure exerted by gasoline vapors in a conned
space, which is measured at 100 F or 37.8 C, is called
Reid vapor pressure. This test provides a good indication
of the volatility of the gasolines lighter portion and serves
to evaluate the tendency of a gasoline to evaporate, so that
the higher the vapor pressure, the more easily the gasoline
evaporates. A very high vapor pressure may lead to plugging of the fuel ow caused by the gasoline vapors blocking
the line and preventing the fuel from being pumped to the
injection valves. Moreover, fuels with high vapor pressures
present high volatile organic compounds emission rates.
Fig. 5(a) and (b) present the RVPs of the base gasolines
(with zero % v/v of additives in the formulations), of the
oxygenated compounds ETBE, ethanol and azeotrope
(with 100% v/v of additives in the formulations), and
blends of the base gasolines containing dierent volumetric
proportions of these compounds. In the gures insets,
graphs (a 0 ) and (b 0 ) give a magnied view of the formula-

Blends with G1
102
(a)

101

RON

100
99
98
97
96
0

10

12

14

16

18

20

Additive fraction (% v/v)

ETBE

Ethanol

Azeotrope

Blends with G2
102
(b)

101

RON

100
99
98
97
96
0

4
ETBE

8
10
12
14
Additive fraction (% v/v)
Ethanol

16

18

20

Azeotrope

Fig. 6. RON of the base gasolines G1 (a) and G2 (b) mixed with ETBE (2, 5, 10, 15 and 17% (v/v)), ethanol (2, 4, 5 and 7% (v/v)) and azeotrope (ETBE/
EtOH) in the volumetric proportions of 2, 5, 8, 10 and 13% (v/v).

E.W. de Menezes et al. / Fuel 85 (2006) 25672577

tions containing up to 20% v/v of additives. As indicated

by the results in graphs (a) and (b), ethanol as a pure substance (100% v/v in the formulations) is the oxygenated
additive presenting the lowest RVP (15.6 kPa) of all the
oxygenated compounds studied here (ETBE = 30.6 kPa
and azeotrope = 32.6 kPa). However, when one analyzes
its behavior in the blend, in the volumetric proportions studied, one sees the opposite eect, since the RVP
in both gasolines containing ethanol was higher than the
RVP in the base gasolines containing ETBE and the
azeotrope.
The vapor pressure proles of the ethanol-blended gasolines in Fig. 5 indicate a signicant increase in the mixtures RVP for the initial fractions of added alcohol.
Ethanol is the additive that produces the greatest alteration
of the vapor pressure prole in relation to the mixtures
ideal behavior (represented by the dashed lines). At ethanol
concentrations exceeding 7% v/v, the RVP of the blends
tended to decrease. Comparing the RVP proles with the
distillation curves, one notes that the mixtures presenting
high vapor pressures presented the lowest ebullition points,

2575

and vice versa. This increase in vapor pressure in the initial

percentages of ethanol is congruent with the reduction of
the evaporate temperature, as indicated by the distillation
curves in Fig. 2. Moreover, the formation of ethanol/
hydrocarbon azeotropes reduces the ebullition temperature of the blends, increasing their respective vapor
pressures.
The increasing addition of ETBE leads to a proportional
decrease in RVP in both gasolines; in addition, the behavior of the formulations with ETBE is very close to the ideal.
As indicated by the properties of density and distillation
curves, the azeotropic blend shows an intermediary behavior between that of the blends containing ETBE and ethanol. The introduction of ethanol increased the blends
RVP; hence, the formulations with this oxygenate show a
tendency for higher volatile organic compound (VOC)
emission levels. The opposite eect is produced by the addition of ETBE, which reduces the RVP in both gasolines.
The addition of azeotrope to base gasolines leads to a
behavior intermediary to that of gasolines containing ethanol and ETBE.

Blends with G1
90.5
(a)

MON

89.5
88.5
87.5
86.5
85.5
0

10

12

14

16

18

20

Additive fraction (% v/v)

ETBE

Ethanol

Azeotrope

Blends with G2
90.5
(b)

MON

89.5
88.5
87.5
86.5
85.5
0

6
8
10
12
14
Additive fraction (% v/v)
ETBE

Ethanol

16

18

20

Azeotrope

Fig. 7. MON of the base gasolines G1 (a) and G2 (b) mixed with ETBE (2, 5, 10, 15 and 17% (v/v)), ethanol (2, 4, 5 and 7% (v/v)) and azeotrope (ETBE/
EtOH) (2, 5, 8, 10 and 13% (v/v)).

2576

E.W. de Menezes et al. / Fuel 85 (2006) 25672577

3.4. Octane rating (RON and MON)

A gasolines octane rating number is evaluated because
of the need to ensure that the product meets the engines
requirements with regard to the compression rate used
without self-igniting. The research octane number (RON)
(ASTM D 2699) evaluates the gasolines resistance to
self-ignition under mild working conditions with low rotations of the engine (600 rpm), simulating highway drivability conditions. The motor octane number (MON) (ASTM
D 2700) indicates the gasolines antiknock ability under
more severe working conditions and at high rotations
(900 rpm), simulating city drivability conditions. The antiknock index (AKI) number corresponds to the arithmetic
mean of the RON and MON octane numbers.
3.4.1. Eect of the additives on the RON, MON and AKI
octane numbers
Fig. 6 depicts the RON proles of gasolines mixed with
the oxygenated compounds and their respective volumetric
proportions. These graphs show, in general, the growing
tendency for increasing RON with the increase in oxygenated compound (ethanol, ETBE and azeotrope) concentrations in the blends. The trend lines indicate that ethanol is
the oxygenate with the strongest propensity to favor higher
RON in the mixtures in comparison with the other compounds. ETBE and azeotrope mixed with the two gasolines
displayed a very similar behavior, although the formulations containing the azeotropic blend contributed to a
greater increase in RON than did ETBE.
Fig. 7 shows the MON proles of the gasolines blended
with the oxygenated compounds in their respective volumetric proportions. As these graphs indicate, the MON
results of the various blends with oxygenated compounds
displayed no signicant dierences. Due to the test conditions, particularly admission temperature and engine
speed, the oxygenated compounds promoted a growing
increase in the MON practically independently of the base
gasolines compositions.
Table 5 lists the octane ratings according to the RON,
MON and AKI methods of the oxygenated additives with
100% v/v blends in G1 and G2, obtained by extrapolation.
Due to the predominance of aromatic hydrocarbons,
base gasoline G1 (RON = 98.5) displayed a higher RON
than did G2 (RON = 96.1). However, according to the val-

ues in Table 5, the gain in octane rating with the addition

of the oxygenated compounds was greater in G2. In this
case, the octane ratings are closely associated with the base
gasolines compositions. The addition of oxygenated compounds raises the octane number of isoparanic gasolines
(G2) more eectively. Moreover, note that the oxygenated
additives blended with isoparanic gasoline showed a
higher AKI number than did the additives blended with
the aromatic gasoline (G1). This eect is congruent with
the results reported by Silva et al. [8]. The azeotropic blend
showed octane ratings similar to those of the ETBE blend.
4. Conclusions
The azeotropic (ETBE/EtOH) mixture showed an intermediary behavior between those of ETBE and ethanol
when blended with gasolines. The formulations containing
the azeotropic mixture oer advantages over ethanol (e.g.,
low volatility, indicated by the distillation and vapor pressure curves) and over ETBE (higher octane rating and
lower production cost). In addition, its behavior when
blended with gasoline is close to the ideal, with slight variations from the ideal, similar to the blends containing
ETBE. Compared with ethanol, the azeotrope displays
low RVP in blends, hence, low emission levels of volatile
organic compounds (VOCs), similarly to the high purity
ETBE. The results we obtained for the azeotropic ETBE/
EtOH mixture indicate it is perfectly suitable as an additive
for automotive gasolines, improving the engines performance and minimizing VOC emissions. The azeotropic
mixture is potentially applicable in eurosuper gasoline formulations, as well as in formulations of special gasolines
destined for the international market and for Formula 1
racing. It is a known fact that, as of 2006, the European
and Formula 1 gasolines will be required to use environmentally friendly fuels (biofuels), with part of these compounds deriving from biomass. The azeotropic mixture
contains ethanol, representing advantages for the use of
this alcohol in formulations with gasoline, because its volatility is lower (apparently not forming azeotropes with the
constituents of gasoline, as in the case of ethanol). Hence, it
produces lower emissions of VOCs. The azeotrope production system is highly relevant because it minimizes production costs by not requiring purication units, as is the case
of the production process of high purity ETBE.
Acknowledgements

Table 5
RON, MON and AKI numbers of the oxygenated additives with high
degree of purity (100% v/v) blended with G1 and G2, obtained by
extrapolation
G1

IAD
RON MON IAD RON MON IAD (average)
ETBE
Ethanol
Azeotrope
(ETBE/EtOH)

115
121
117

G2

101
102
100

108
112
109

119
134
122

103
102
103

111
118
113

110
115
111

The authors are indebted to the Companhia Petroqumica do Rio Grande do Sul (COPESUL), Brazil, for supplying the raw material (C4 cut) for the production of the
ETBE and the ETBE/EtOH azeotrope used in this work.
We also thank Renaria Alberto Pasqualini, located in
southern Brazil, for providing the base gasolines used in
the formulations with oxygenated additives. Thanks to FINEP/QUALICOM-RS and ANP (Agencia Nacional do
Petroleo)/Brazil.

E.W. de Menezes et al. / Fuel 85 (2006) 25672577

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