Fuel 228 (2018) 226–233

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Fuel
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Full Length Article

Production process of di-amyl ether and its use as an additive in the T

formulation of aviation fuels
⁎
Renato Cataluñaa, , Zeban Shaha, Vanessa Venturia, Nattan R. Caetanob, Bibiana Porto da Silvab,
Carla M.N. Azevedoc, Rosângela da Silvad, Paulo A.Z. Suarezd, Lincoln P. Oliveirad
a
Federal University of Rio Grande do Sul, Av. Bento Gonçalves 9500, 91501-970 Porto Alegre, RS, Brazil
b
Federal University of Santa Maria, 97105-900 Santa Maria, RS, Brazil
c
Pontifical Catholic University of Rio Grande do Sul, Av Ipiranga 6681, 90619-900 Porto Alegre, RS, Brazil
d
Universidade de Brasilia, Campus Universitário Darcy Ribeiro, 70910-900 Brasilia, DF, Brazil

A R T I C LE I N FO A B S T R A C T

Keywords: This work deals with the production of a high added value ether used as additive in aviation fuel. The ether was
Di-amyl-ether synthesized from the iso-amylenes present in the C5, the five-carbon isomer cuts in petroleum distillates and the
Aviation kerosene iso-amyl alcohol found in the fusel oil of the alcohol industry. Qualitative analyses like mass spectrometry and
Biofuel production nuclear proton magnetic resonance spectroscopy confirmed the formation and structure of the proposed semi-
Characterization
renewable ether, the high molecular weight di-amyl ether (DAE). Optimization of the reaction parameters re-
sulted in a conversion of the 48%, molar fraction, iso-amylenes when using an adiabatic profile reactor. By using
this ether production and purification process, the final product showed 98% w/w of purity. The synthesized di-
amyl ether presented physicochemical properties similar to the commercial aviation kerosene. The physico-
chemical properties evaluation performed in the mixtures of di-amyl ether in aviation kerosene showed relevant
improvements, such as reduction of the freezing point and increase of the oxidation reaction rate. The results
showed this novel fuel has great potential to be used in gas propulsion turbines in commercial flights and is also
strategic for military aircraft.

1. Introduction mixture of a large number of different hydrocarbons. The range of their

In recent decades, there has been a considerable increase in the
concentration of pollutants in the atmosphere, especially greenhouse
gases. The share in anthropogenic carbon dioxide (CO2) emissions from
the aviation sector will rise above the current 2–3%, as a consequence
of the expectation of the aviation industry growth up to 2035 [1–3].
Although the airline industry is 70% more efficient today than 40 years
ago, the development of this sector should exceed the estimation of
increase in fuel efficiency in the same period [4]. In addition, the de-
cline of fossil fuel reserves has also fomented advances in the devel-
opment of alternative fuels for aviation [5–8].
The most commonly used aviation fuels are kerosene-type obtained
from petroleum. Many different types of kerosene are currently being
produced. Jet fuel, aviation turbine fuel (ATF), or avtur, is a type of
aviation fuel designed for use in aircraft powered by gas-turbine en-
gines. It is colorless to straw-colored in appearance. The only other jet
fuel commonly used in civilian turbine-engine powered aviation is Jet
B, which is used for its enhanced cold-weather performance. Jet fuel is a
sizes (molecular weights or carbon numbers) is defined by the re-
quirements for the product, such as the freezing or smoke point.
Kerosene-type jet fuel (including Jet A and Jet A-1) has a carbon
number distribution between about 8 and 16 (carbon atoms per mole-
cule); wide-cut or naphtha-type jet fuel (including Jet B), between
about 5 and 15. [9] Among these, the most employed kerosene is the
commercial fuel Jet A-1 [10,11]. Civil aviation kerosene, also named as
QAV-1, is compatible with the Jet A-1 specifications laid down by the
AFQRJOS (Aviation Fuel Quality Requirements for Jointly Operated
Systems) and complies with the National Petroleum, Natural Gas and
Biofuel Agency specifications [12–16]. Taking into account the en-
vironmental factors along with economic issues a growing interest in
developing alternative fuels for aviation using sustainable feedstock has
been promoted [4,7,17,18]. The investigation in the jet fuel formula-
tion focusing in the alternative fuels with similar properties to Jet A-1.
Before a blend can be approved for use in aviation fuel, it must undergo
extensive testing to show both that it is effective and that it does no
harm to any other fuel properties.

⁎
Corresponding author.
E-mail address: rcv@ufrgs.br (R. Cataluña).

https://doi.org/10.1016/j.fuel.2018.04.167
Received 9 March 2018; Received in revised form 26 April 2018; Accepted 28 April 2018
Available online 03 May 2018
0016-2361/ © 2018 Published by Elsevier Ltd.
R. Cataluña et al.
Several approaches have been developed to produce jet fuels
[6,11,19], including the hydrodeoxygenation of vegetable oils [20,21],
Fischer Tropsch synthesis [22,23], catalytic conversion of sugars
[24,25], synthesis from algae [26,27] and other procedures.
Knowledge of the good antiknock properties of some oxygenated
compounds dates back to the 1930’s, when improvements in aircraft
performance resulted in a demand for fuels of increasingly higher an-
tiknock performance [28]. In the beginning of the 80’s methyl tertiary
butyl ether (MTBE) started replacing tetra-ethyl lead as a gasoline ad-
ditive worldwide. However, its use has been restricted because of its
high solubility in water, toxic effect and the subsequent environmental
and human health problems [29,30]. Due to their high octane numbers
and low volatilities, tert-amyl-ethyl-ether (TAEE), tert-amyl-methyl-
ether (TAME) and ethyl tert-butyl ether (ETBE) are considered as at-
tractive alternatives to MTBE as gasoline blending oxygenates [31–35].
However, these ethers do not have volatility characteristics required to
be used in aviation kerosene formulations. Several requirements must
be met for the fuel to be classified as aviation fuel, among these re-
quirements are: high energy density, aiming to maximize the reach and
reduce the carried fuel load; rapid evaporation and atomization; low
risk of explosion; appropriate viscosity; physical and chemical stability
and low freezing point [4,36].
In the present study, a new process of production and purification,
in semi-pilot scale, of the di-amyl ether (DAE), partially obtained from
renewable source (semi-bio-ether) is reported. The DAE synthesis was
performed for the first time in our laboratory [37–39]. Iso-amyl alcohol
(present in the fusel oil from the distillation of ethanol from sugarcane)
and a C5 hydrocarbons cut (2-methyl-1-butene and 2-methyl-2-butene
olefins provider) were used as reagents, in addition to resin Amberlyst
36 as a catalyst. The DAE was characterized and used as an additive in
formulations with aviation kerosene (QAV-1), supplied by Petrobras.
The physicochemical properties of fuel blends obtained by mixtures of
DAE/QAV-1 (10%, 20% and 30% mass) were evaluated with respect to
volatility, freezing point, viscosity and density [40,41]. These key fuel
properties were compared with commercial aviation kerosene.
The main motivation of this work is to present the process of pro-
duction of a new semi-renewable bio-ether and its performance as
aviation fuel additive. The main characteristics of this ether are the low
freezing point due to its branched structure and the high oxidation
ration rate due to the presence of oxygen in its molecular structure.
2. Material and methods
2.1. Synthesis of di-amyl ether (DAE)
In the synthesis process of the di-amyl ether, iso-amyl alcohol
(present in the fusel oil, an industrial residue obtained from the dis-
tillation of sugarcane ethanol) and C5 hydrocarbons cut from thermal
cracking of naphtha unit were used. The average molar composition of
C5 extracted hydrocarbons used in the DAE synthesis is shown in
Table 1. The single reactive olefins in the DAE synthesis present in the
reaction mixture are the olefins which have a tertiary carbon, i.e. 2-
methyl-1-butene and 2-methyl-2-butene.
The resin Amberlyst™ 36 (A-36), Rohm and Haas France SAS, were
used as a catalyst in the DAE synthesis reaction, in the humidified form.
The reaction system conditions itself, allowing the passage of iso-amyl
alcohol to 80 °C. For this study, an adiabatic reaction system was used,
followed by distillation purification steps. A liquid flow controller was
employed in order to ensure the reactants charge flow in the reaction
system.
The adiabatic reactor used has 1150 mL of internal volume, com-
pletely filled with the catalyst, which operates under 800 kPa. This
reactor was fed by a cylinder containing a predetermined reagents
mixture of the iso-amyl alcohol and C5 hydrocarbon, under a pressure of
1.2 MPa. Fig. 1 shows a schematic diagram of the reaction system and
the global flow of the reactor effluent purification system.
227
Fuel 228 (2018) 226–233
Table 1
The average molar composition of C5 extracted hydro-
carbons, obtained by gas chromatographic analysis using
a flame ionization detector. Where C4′s, C5′s and C6′s
represent the hydrocarbons with 4, 5 and 6 carbon atoms,
respectively.
Chemical Components (% mol)
C4′s 1.38
C5′s 15.72
Isopentane 12.30
2-methyl-1-butene 4.60
n-pentane 16.25
2-methyl-2-butene 17.50
Cyclopentene 15.65
Cyclopentane 14.30
C6′s 2.30
Since the synthesis reaction of the DAE is exothermic, the tem-
perature control of the catalytic bed for an adiabatic reactor was carried
out by adjusting the temperature of the reactor load. A backpressure
valve ensured the pressure inside the reactor and an ice and salt cooling
system was responsible for proper sampling of the reactor effluent. The
synthesis reaction of DAE is an exothermic reaction that tends to
equilibrium. Thus, the lower the temperature of the reaction system,
the greater the conversion of the reagents into products. However,
using low temperatures, the reaction rate decreases considerably,
causing low space velocities to be used to achieve close-to-equilibrium
conversions. Taking into account these requirements and based on a
space velocities of 1.0 h−1, the temperature range between 40 and 45 °C
was defined as an optimal operating condition for the adiabatic reactor
and unit molar ratio, maintaining the reactor pressure at 800 kPa [39].
The DAE obtained was subjected to a fine purification system with
several atmospheric distillation stages, in order to obtain a product
purer than 98%. Distillation process, using packed columns (Fig. 1),
were fed with controlled flow through liquid flow controllers. This
system also promoted the recovery of the reagents for a second pass in
the reaction system, which increases the final conversion rate.
In the first column of the purification system, the light weight
compounds at the top (hydrocarbons inert in the reaction together with
a small fraction of iso-amyl alcohol) were eliminated and at the bottom
of the column, essentially, DAE and residual iso-amyl alcohol were
obtained. The stream at the top should be reprocessed, representing the
second reaction pass of the C5 cut extracted, in order to exhaust it to the
maximum, increasing the production yield. The stream at the bottom
was processed in two other distillation stages, separating iso-amyl al-
cohol and DAE. The iso-amyl alcohol in the purification process of the
DAE does not present adequate purity to pass through the reaction
system. Thus, another distillation system was required to perform the
rectification. In this way, the recovered alcohol was available to be
reprocessed again in the system.
Quantitative analyses were performed applying gas chromato-
graphy coupled to a flame ionization detector (GC-FID, model Varian®
39 XL) with automatic injection, equipped with a CP-Sil PONA capillary
column CB (dimethylpolysiloxane, 100 m × 0.25 mm × 0.25 μm) in
order to monitor the DAE production and purification processes. The
injected sample volume was 0.5 μL for a split ratio of 1:60. Helium was
used as a carrier gas, with purity above 99%, provided by White
Martins®. A heating system keeps the furnace on an isothermal condi-
tion over 10 min in 50 °C, followed by a heating rate 5 °C min−1 until
the temperature reaches to 75 °C, initiating a new heating rate of
8 °C min−1 until 250 °C, remaining until the end of the analysis for
40 min.
The by-products of reaction were identified in a gas chromatograph
with a four-pole mass detector (GC–MS, model Agilent® 6890 plus with
MS 5973 N). HP-1 (dimethylpolysiloxane, 100 m × 0.25 mm × 0.5 μm)
fused silica capillary column was used, initially at 35 °C for 15 min,
R. Cataluña et al. Fuel 228 (2018) 226–233

Fig. 1. The reaction system and the global flow of the reactor effluent purification system. (FIC) flow indicator controllers; (TI) temperature indicators; (TIC)
temperature indicator controllers; (PI) pressure indicators.

followed by heating rate of 1.5 °C min−1 to 70 °C, remaining for 20 min
in this temperature and a new heating rate of 10 °C min−1 to 250 °C,
where it remains for 23.5 min. The amount of sample injected into the
chromatograph was 0.5 μL for a split ratio of 1:60. Helium from White
Martins® (purity above 99%) was used as carrier gas.
After purification, DAE was also analyzed by 1H NMR (nuclear
magnetic resonance spectrometry proton) spectrum was recorded in
CDCl3 solution (99.8% atom D, Acros Organics) on a Varian VNMRS
300 MHz spectrometer. Chemical shifts (δ) are given in part per million
from the peak of tetramethylsilane (δ = 0.00 ppm) as internal standard.
Multiplicities are given as s (singlet), d (doublet), t (triplet), m (mul-
tiplet) and coupling constants (J) are given in Hz.
2.2. Physicochemical characterization of DAE and formulations from the
addition of DAE to aviation kerosene
The civil aviation kerosene (QAV-1), provided by Petrobras, was
used as base fuel for formulations in blends with synthesized DAE. The

228
R. Cataluña et al.
formulations were evaluated with DAE content of 10, 20 and 30% w/w,
denominated 10DAE, 20DAE and 30DAE, respectively.
There are many important physicochemical properties for fuels
characterization. In this work we discuss the main parameters to
quantitatively identify aviation fuels. It is the case of the freezing point,
which allows flights at high altitudes when it’s lower, and the flash
point, which must be high to avoid leak accidents. In addition, the
calorific power must be large in order to avoid mass loading and to
generate adequate thrust during take-off. Other properties are im-
portant, but they are complementary.
This part of the work consists in a specific study, which was de-
signed to examine the effects of DAE on the physicochemical properties
of civil aviation kerosene QAV-1 used as base fuel. The methodology
adapted to the thermal characterization of the fuels is described in this
section. The most suitable standards were used to obtain accurate re-
sults. Important information about the fuel physicochemical properties,
like the melting, freezing, flash, flammability points and the oxidation
reaction rate were done in this work. Thus, the techniques applied to
achieve this information are described below.
2.2.1. Freezing and melting points
For liquid aviation fuels, the American Society for Testing and
Materials (ASTM) defines that the melting point is different from
freezing point, which is given by the sample temperature at the first
crystal appears. In simplified form, the fuel melting point is the tem-
perature that the whole sample solidifies. There are two standards to
get the freezing point, ASTM D5901-9903 [42] and the Standard Test
Method for Freezing Point of Aviation Fuels: D 2386-03 [43] an
American National Standard Standard Test Method for Freezing Point
of Aviation Fuels, which was used in this work.
The temperature of the fuel in the aircraft tank normally falls during
flight depending on aircraft speed, altitude, and flight duration. The
freezing point of the fuel must always be lower than the minimum
operational tank temperature. ASTM D910-17 [44] and D1655-13 [14]
require the freezing point. This method covers the determination of the
temperature below which solid hydrocarbon crystals may form in
aviation turbine fuels. The freezing point, in aviation fuels, the fuel
temperature at which solid hydrocarbon crystals, formed on cooling,
disappear when the temperature of the fuel was allowed to rise under
specified conditions of the test. The freezing point of an aviation fuel is
equal to lowest temperature value at which the fuel remains free of
solid hydrocarbon crystals that can restrict the flow of fuel through
filters if present in the fuel system of the aircraft.
The procedure to measure the fuel was firstly transferring it to the
clean, dry, jacketed sample tube. Close the tube tightly with the cork
holding the stirrer, thermometer, and moisture proof collar and adjust
the thermometer position so that its bulb did not touch the walls of the
tube flask and was approximately in the center. The bulb of the ther-
mometer should be 10 to 15 mm from the bottom of the sample tube.
Clamp the jacketed sample tube so that it extends as far as possible into
the vacuum flask containing the cooling medium. The surface of the
sample should be approximately 15–20 mm below the level of the
coolant. Unless the medium was cooled by mechanical refrigeration,
add solid carbon dioxide as necessary throughout the test to maintain
the coolant level in the vacuum flask.
The recommended volume for the sample is 25 mL of fuel. It was
required stirring the fuel continuously, moving the stirrer up and down
at the rate of 1–1.5 cycles s−1, except when making observations, taking
care that the stirrer loops approach the bottom of the flask on the down-
stroke and remain below the fuel surface on the upstroke. Disregard any
cloud that appears at approximately −10 °C and does not increase in
intensity as the temperature is lowered, because this is due to water.
Record the temperature at which hydrocarbon crystals appear. Remove
the jacketed sample tube from the coolant and allow the sample to
warm, stirring it continuously at 1–1.5 cycles s−1. Record the tem-
perature at which the hydrocarbon crystals completely disappear.
229
Fuel 228 (2018) 226–233
The observed freezing point determined shall be corrected by ap-
plying the relevant thermometer correction resulting from the checks.
Where the observed freezing point falls between two calibration tem-
peratures, the correction at the observed temperature shall be obtained
by linear interpolation. Report the corrected temperature of crystal
disappearance to the nearest 0.5 °C as the freezing point, ASTM D 2386-
03 [43].
2.2.2. Flash, flammability points and reaction rate
Basically, the properties related to the heating of liquid fuels have
definitions regarding flash and flammability points. The flash point
represents the temperature that the fuel must reach so that a flame,
passed on its surface, ignites only the formed vapors. The formed flame
extinguishes immediately, less than five seconds, since the temperature
of the fuel was still insufficient to increase the diffusion coefficient
enough to produce vapors in amounts sufficient to sustain the com-
bustion. The considered methods for measuring the flash point was
ASTM D 92-16 [45]. This property was related to the safe transport,
handling and storage of fuels and lubricating oils, which is a priority for
aviation fuels.
Similarly, the flammability or combustion, a point was defined as
the temperature at which a fuel, if subjected to a heat source capable to
ignite the vapors, initiates a continuous combustion process on the
surface, keeping a stable flame. However, the flammability point
measures the tendency to form a flammable mixture with air while the
point of combustion indicates the tendency for prolonged burning.
The distinction between flammable and combustible products for
the purposes of insurance, transport safety and occupational safety is
based on the flash point. A product was considered flammable if has a
flash point below 65.6 °C (open vessel test) or below 60.5 °C (closed
vessel test). Above this value the liquid was considered combustible and
non-flammable.
The container with the fuel was raised to the surface by a certain
distance. In this way, it allows to heat the sample through the bottom of
the vessel. The temperature of the mixture was constantly monitored by
a K-type thermocouple. As the flash point temperatures may be rela-
tively low (below room temperature) the first task to be performed in
these tests was cooling the fuels sample with steam nitrogen to tem-
peratures close to 0 °C. Thereafter, the samples are gradually heated
through a heating flame while a pilot flame attempts to initiate a
combustion process. The fuel was then heated until the spark causes a
stable combustion, when the temperature obtained as the flammability
point is defined.
The flash point should not be confused with the auto-ignition tem-
perature, which does not require a source of ignition, or the point of
combustion, the temperature at which the vapor continues to burn after
it has been ignited. Neither the flash point nor the point of combustion
was dependent on the auto-ignition temperature, which is much higher.
The method applied for combustion point measuring was similar to
that of flash point identification, just heating continually until the
sample produces sufficient fumes to sustain the combustion. The
method used to measure the combustion point was ASTM D 92-16 [45].
The oxidation reaction rate was measured burning a 30 mL sample
of fuel in a pool-fire configuration. A cylindrical aluminum container,
with 7 mm high and 65 mm in diameter, was used to stabilize a free
flame under conditions of ambient temperature and pressure, 20 °C and
1.0 atm, in which the mass variation of the sample in relation to the
time was monitored using an analytical balance, brand KERN, resolu-
tion of 0.001 g. This rate of fuel consumption presents a linear behavior
of mass variation in time, when the combustion reaches the permanent
regime [46–48]. Thus, the linear fit gives the slope of the line
(R2 > 0.999), which shows the constant value of the oxidation reac-
tion rate, given in mg s−1.
2.2.3. Distillation curves
The distillation curve is expressed by the temperature average value
R. Cataluña et al.
as a function of the distillate volume, which provides important in-
formation regarding the fuel composition associated to volatility and
the engine operation. A distillation curve provides: IB: The initial
boiling point, T10: Temperature at which 10% of the sample was dis-
tilled. This is linked to the slight fuel fractions, important for the engine
starting, T50: Temperature at which 50% of the sample was distilled.
This relates to the average fuel fractions, considering the heating and
optimal engine operating range, T90: temperature at which 90% of the
sample was distilled. This is linked to heavier fuel fractions, related to
engine economy and performance and FB: Final boiling point. For the
determination of the DAE distillation curves, QAV-1 and further for-
mulations, was used a Herzog automatic distiller, Atmospheric
Distillation, HDA 627.
2.2.4. Kinematic viscosity
Viscosity is limited to a maximum value in order to obtain a
minimum pressure loss in the lower temperature flow, as well as, to
allow adequate spraying of the fuel in the injector nozzles, enabling
better combustion conditions. Viscosity can significantly affect the lu-
bricity property of the fuel, and consequently the fuel pump life.
Kinematic viscosity tests at −10 and 40 °C were performed using a
Visco Bath-HVB438 viscometer.
2.2.5. Density and enthalpy of combustion (calorific power)
Calorific power and density guarantee that the fuel used produces
the necessary energy for a given autonomy. Density is an important
feature because is directly linked to the total energy content contained
in a given mass of fuel. It is particularly useful for empirically de-
termining the calorific value when used with other parameters such as
the distillation curves and the aniline point for calculating the energy
content of the fuel. Limiting a fuel density range is important for both
the design and the proper functioning of the engine. Density tests at
20 °C were carried out using a denser Meter, DMA 35 N, Anton Paar and
for the enthalpy of combustion, a semi-automatic calorimeter pump,
brand IKA WORKS, model C-1.
3. Results and discussion
3.1. Synthesis of di-amyl ether (DAE)
The DAE synthesis reaction, Fig. 2, follows the line of the well al-
ready known mechanism of reaction between alcohols and olefins, first
occurring the protonation of the olefins (2M1B and 2M2B) with for-
mation of the same tertiary carbocation. This carbocation is attacked by
the basic site of the isoamyl alcohol and then, the ether is formed [28].
The maximum conversion obtained in the proposed system was
48%. According to the purification steps of the DAE schematically,
Fig. 1, the fraction of C5 hydrocarbons recovered in the first pass has
approximately 10% of remaining reactive olefins. In order to deplete
the reacted olefins to the maximum, this current was reprocessed in a
second pass in the reactor. Thus, the first fractionation distillation
column separates most of the C5 extracted from other compounds from
the reactor outlet, DAE and iso-amyl alcohol. A second distillation
column was responsible for separating the iso-amyl alcohol and DAE,
CH3
CH3
H3C CH3
CH3
+ HO
H3C CH2
Fig. 2. DAE synthesis reaction from C5 (2M1B and 2M2B) reactive olefins and iso-amyl alcohol in acid catalysis.
Fuel 228 (2018) 226–233
the latter being withdrawn to the bottom and fractionated in a third
distillation column to eliminate by-products from the reaction by the
bottom stream thereof. Also shown in Fig. 2, the mass percentages of
DAE and the remaining synthesis components obtained in the iso-amyl
alcohol purification system. In the iso-amyl alcohol recovery phase, a
stream with 83% w/w iso-amyl alcohol and 16% DAE is obtained, the
stream is reprocessed with the recovered C5 in a new reactor pass.
The proposed system of reaction and purification yields, at the end
of the process, a 98% degree of mass purity DAE.
As can be seen in Figs. 3 and 4, proton magnetic resonance and gas
chromatography coupled to selective mass detector spectra showed the
structure of the product isolated from the reaction between the C5 out
of olefins and the iso-amyl alcohol.
The proton signals found in the NMR spectrum in Fig. 3 are con-
sistent with the structure of DAE and the following assignments can be
observed: 0.87 (t, J = 7.5 Hz, 3H (G)); 0.91 (d, J = 6.5 Hz, 6H (AA′));
1.11 (s, 6H (EE′); 1.42 (q, J = 7.5 Hz, 2H (F)); 1.40–1.52 (m, 2H (C));
1.63–1.74 (m, 1H (B)); 3.28 (t, J = 8.1 Hz, 2H (D)).
In addition, Fig. 4, the fragments with m/z 41, 55 and 73 are also
present with appreciable intensity and correspond to two possibilities of
cleavage induced by the radical site (m/z = 101) which loses ethene to
form the fragment of m/z = 73. Already the cleavage of the bond ad-
jacent to the ion charge m/z 101 generates 2-methyl-2-butene (alkene)
which fragments at m/z 41 and 55 ions.
3.2. Characterization of DAE, QAV1 and DAE/QAV-1 formulations
Table 2 presents physicochemical analyses results of DAE and QAV-
1 fuels. Table 3 summarizes the results obtained for the analyses of the
initial point of distillation, density, freezing point, kinematic viscosity
and oxidation reaction rate for the formulations 10DAE, 20DAE and
30DAE.
The parameters in Table 2 shows that DAE presents similar physi-
cochemical properties to the base fuel, QAV-1. DAE showed a lower
value of the freezing point, which has particular importance in aviation
applications, allowing the use of this fuel at high altitudes, which fa-
cilitating the continuous flow into the tubes and combustion chamber.
In addition, it improves the viscosity of the fuel at low temperatures
favoring adequate dispersion in the combustion chamber. At high al-
titudes, the outside temperature normally reaches to −50 °C.
The low freezing point in an aviation fuel has substantial im-
portance to its use in extremely low temperatures during flight altitude
(10–13 km). In these tests, DAE presented lower flash and flammability
points than commercial aviation kerosene at approximately 5 and 6 °C
respectively. That’s the temperatures determined for these points are
high enough to justify their use in safe aviation conditions. The effect of
this property is evidenced as the addition of DAE in the formulation is
increased with QAV-1, as shown in Table 3.
In addition to the information shown in the Table 2, the reaction
rate of the samples, performed in free flame at ambient pressure and
temperature, was also measured, which showed increase in value in-
dicates that DAE is more reactive according to the data indicated in
Table 3.
The enthalpy combustion and density (Table 2) showed very close
CH3
H3C O
CH3
CH3
CH3
H3C
230
R. Cataluña et al. Fuel 228 (2018) 226–233

CH3 E
E
E’
H3C O

D C
F A/G
CH3 B A
CH3
G
H3C
A’

D
C/ F
B

Fig. 3. Proton nuclear magnetic resonance spectrum for purified DAE. The letters A – E indicate the hydrogens of the molecule analyzed and their respective signals
in the spectrogram.

CH3
C B
H3C O
C

CH3
A CH3

H3C
D

M+1

Fig. 4. Molecular fragmentation spectrum with DAE mass selective detector. The major fragments are indicated in the molecule from the letters A-D. M+1 is the
molecular ion and the letter M represents the total mass of the molecule.

Table 2 Table 3
Results of the physicochemical analyses of the fuels QAV-1 and DAE. Results of PI assays, density, freezing point, viscosity and reaction rate per-
formed with the formulations 10DAE, 20DAE and 30DAE from the QAV-1 used
Parameter DAE QAV-1 Unit
as base fuel.
Melting point −120 −115 °C Parameter 10DAE 20DAE 30DAE Unit
Initial boiling point 142.3 163.1 °C
Inflammability 52 58 °C Initial boiling point 133.8 135.1 140.7 °C
Flash point 48 53 °C Density 20 °C 0.823 0.819 0.811 g cm−3
Oxidation reaction rate 62 ± 2 43 ± 2 mg s−1 Freezing point −57 −62 −68 °C
Density 20 °C 0.789 0.788 g cm−3 Kinematic viscosity 40 °C 1.59 1.58 1.57 mm2 s−1
Freezing point −92 −47 °C Oxidation reaction rate 45 ± 2 48 ± 2 56 ± 2 mg s−1
Kinematic viscosity 40 °C 1.50 1.11 mm2 s−1
Kinematic viscosity −10 °C 3.05 3.20 mm2 s−1
Enthalpy of combustion −41.4 −42.8 MJ kg−1

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240
220
200
Temperature (°C)
180
160
10DAE
20DAE
30DAE
140
QAV
DAE
120
0 20 40 60 80 100
Volume (mL)
Fig. 5. Distillation curves of QAV-1, DAE and formulations 10DAE, 20DAE and
30DAE.
values for DAE and QAV-1, which can guarantee that DAE has an
amount of energy required for a flight autonomy similar to QAV-1.
Also, in relation to the values of the density it was observed, in Table 3,
that a small increase occurs with the addition of DAE. This is due to the
intermolecular interactions of the oxygenated compounds with the
hydrocarbons constituting the base fuel.
Fig. 5 shows the distillation curves of QAV-1 and DAE also with
formulations: 10DAE, 20DAE and 30DAE.
A good similarity between the distillation curves profiles for for-
mulations when compared to the QAV-1 was observed, in which a
maximum discrepancy was 5%. The difference considering the initial
point of distillation is due to the presence of light compounds in DAE.
Since DAE was added to the QAV-1 a proportional reduction of the
initial boiling point was caused. The small increase in the final boiling
point (BP) was attributed to the thermal decomposition of DAE during
the distillation at elevated temperatures, which favors the oligomer-
ization of the C5 olefins. However, the BP of the formulations keep
within the specifications for this parameter [49].
4. Conclusions
Qualitative analyses in mass spectrometry and nuclear proton
magnetic resonance spectroscopy confirmed the formation and struc-
ture of the proposed ether. This branched molecular structure con-
tributes to the reduction of the freezing point causing the viscosity to
remain at acceptable levels at low temperatures. In addition, the pre-
sence of oxygen in the molecular structure of DAE increases the oxi-
dation rate during the combustion process. Using the reaction and
purification operating conditions described in this work, a maximum
conversion of the 48 mol% iso-amylenes was obtained. The relatively
low conversion obtained (48%) is due to the fact that the synthesis
reaction tends to equilibrium. In order to increase the conversion level,
it is necessary to remove the products from the reactional medium and
to use reaction systems in series with intermediate purifications. At the
end of the synthesis and purification processes, the product presents a
DAE composition with 98% purity and also presents similar physico-
chemical properties to the base fuel, QAV-1. Additionally, the DAE/
QAV-1 formulations (10DAE, 20DAE e 30DAE) showed relevant
changes in physicochemical properties, such as a decrease in freezing
point and an increase in oxidation reaction rate. These changes in
physicochemical properties indicate a high potential for use DAE as
aviation fuel or in formulations with kerosene of fossil origin, QAV-1.
Acknowledgment
The authors are thankful to CNPq for the financial support.
232
Fuel 228 (2018) 226–233
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