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Effects of a New Blending Agent on Ethanol−Gasoline Fuels
Filiz Karaosmanolu, Asl Igr, and H. Aye Aksoy
Energy Fuels, 1996, 10 (3), 816-820• DOI: 10.1021/ef950131z • Publication Date (Web): 21 May 1996
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Energy & Fuels is published by the American Chemical Society. 1155 Sixteenth Street
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816 Energy & Fuels 1996, 10, 816-820

Effects of a New Blending Agent on Ethanol-Gasoline

Fuels
Filiz Karaosmanoǧlu,* Aslı Işıǧıgür, and H. Ayşe Aksoy
Department of Chemical Engineering, Istanbul Technical University,
Maslak, Istanbul 80626, Turkey

Received July 7, 1995. Revised Manuscript Received February 23, 1996X

Successful use of ethanol-gasoline blends as engine fuel alternatives depends on producing a

stable homogeneous liquid fuel. It is crucial to avoid the phase separation phenomenon which
occurs due to the hydrophilic character of alcohols and the solubility behavior of gasoline-alcohol-
water three-component system. In this study an industrial byproduct is introduced as a new
blending agent to ethanol-gasoline fuels, and its effects on the phase separation problem were
investigated on samples prepared by blending unleaded gasoline with 5, 10, 15, and 20% (v/v)
azeotropic ethanol, respectively.

Introduction system. The degree of phase separation varies accord-

Transportation fuels worldwide are almost exclusively
derived from petroleum, and 75% of the world’s petro-
leum reserves belong to the countries of the Middle
East. Oil-importing countries around the world are
extremely vulnerable both strategically and economi-
cally to fuel supply disruptions. In addition, there is a
growing global concern about the environmental im-
pacts of using petroleum and other fossil fuels. There-
fore, much research has been directed toward biomass
energy resources and biofuels. Biofuels such as ethanol,
methanol, and biodiesel offer great flexibility in their
usage as engine fuels because they can be used in almost
any type of current and future vehicle technology.
Alcohols (methanol and ethanol) in the form of alcohol-
gasoline blends are considered as one of the current and
near-term transportation fuel options.1 One of the major
difficulties encountered with the use of alcohol-gasoline
blends is their tendency to phase separation due to the
hydrophilic character of alcohols. Phase separation can
cause serious operational problems and damage in an
engine.
Ethanol has been used as an octane booster for
gasoline and in the form of 10% anhydrous ethanol-
gasoline blended fuel (gasohol) since the 1980s. How-
ever, using anhydrous ethanol in blended fuels is not
economically feasible as producing anhydrous ethanol
is a difficult and costly task within the overall alcohol
production process.2-4 Industrial ethanol production
yields an azeotrope that is 95% ethanol and 5% water
by volume. Ethanol in its usual 95% form cannot
readily be used in blended fuels due to phase separation,
which occurs as the natural result of the solubility
behavior of alcohol-water-gasoline three-component
X Abstract published in Advance ACS Abstracts, April 1, 1996.
(1) Biofuels: A Win-Win Strategy; U.S. Department of Energy
Biofuels Systems Division: Washington, DC, 1994; pp 6-8.
(2) Austin, G. T. Shreve’s Chemical Process Industries; McGraw-
Hill: New York, 1984; pp 581-590.
(3) Paul, J. K. Large and Small Scale Ethyl Alcohol Manufacturing
Process from Agricultural Raw Materials; Noyes Data Corp.: Parkridge,
NJ, 1980; pp 44-111.
(4) McKetta, J. J.; Cunningham, W. A. Encyclopedia of Chemical
Processing and Design; Dekker: New York, 1984; Vol. 20, pp 40-51.
ing to the amounts of alcohol and water in the blend,
the chemical composition of the gasoline, and the
ambient temperature. In lower temperatures, even
small quantities of water present in an ethanol-
gasoline fuel can lead to direct hydrogen bonding
between ethanol and water, and phase separation
occurs. The upper phase contains paraffinic hydrocar-
bons and is rich in gasoline; the lower phase is composed
of water, ethanol, and the aromatic components of
gasoline soluble in ethanol. The usual solution to such
a problem is the addition of a blending agent. The water
tolerance of an alcohol-gasoline blend or the amount
of water that a blend can dissolve before breaking into
two phases is dependent upon temperature, the con-
centration and type of the alcohol (methanol or ethanol),
and the characteristics of the gasoline, its aromatic
content in particular.4,5 Various blending agents have
been proposed to lower the phase separation tempera-
ture of the blends below the actual temperatures
experienced during winter.6-11 These blending agents
can be grouped as aromatic compounds, higher aliphatic
alcohols, and aromatic alcohols. In this study molasses
fusel oil was introduced as a new blending agent for
ethanol-gasoline fuels and its effects on phase separa-
tion temperatures were investigated.
Molasses fusel oil is a byproduct of the fermentation
process for industrial ethanol production. It is an
alcohol mixture having a boiling range of 80-132 °C.
The amount and composition of fusel oil produced in the
fermentation process depend on the raw materials used.
A typical fusel oil production ratio during the fermenta-
tion process is 0.2-0.7% (wt) on the basis of pure
(5) Karaosmanoǧlu, F.; Işiǧiǧür, A.; Aksoy, H. A. SAE Tech Pap.
Ser. 1993, No. 932771.
(6) Osten, D. W.; Sell, N. J. Fuel 1983, 62, 268-276.
(7) Mislavskaya, V. S.; Leonow, V. E.; Mislavskii, N. O.; Ryzhak, I.
A. Sov. Chem. Ind. 1982, 14 (3), 270-273.
(8) Englin, B. A.; Kyuregyan, S. K.; Levinson, G. I.; Demidenko, K.
A.; Golosava, V. F. Zh. Khim. 1978, 20, 106-110.
(9) Müeller, H.; Majunke, H. J. Eur. Pat. Appl. EP 171440 A1 (FRG),
1986.
(10) Karaosmanoǧlu, F.; Aksoy, H. A.; Civelekoǧlu, H. J. Inst. Energy
1988, 61, 125-128.
(11) Karaosmanoǧlu, F.; Işiǧiǧür, A.; Aksoy, H. A. J. Inst. Energy
1993, 66, 9-12.

0887-0624/96/2510-0816$12.00/0 © 1996 American Chemical Society

Ethanol-Gasoline Fuels Energy & Fuels, Vol. 10, No. 3, 1996 817

Table 1. Fuel Properties of Unleaded Gasoline Samples

gasoline
property ASTM test method G1 G2 G3 G4
color yellow yellow yellow yellow
density @ 15 °C (kg/m3) D 1298 734.6 742.1 762.5 795.2
composition (wt %) D 1319
saturated hydrocarbons 72.20 60.01 49.70 38.96
aromatic hydrocarbons 27.20 39.02 48.80 59.94
olefinic hydrocarbons 0.60 0.97 1.50 1.10
water (% v/v) D 1744 0.1227 0.3700 0.2504 0.1508
sulfur (kg/m3) D 381 28 × 10-3 8 × 10-3 4 × 10-3 6 × 10-3
distillation test (°C) D 86
10% distillate 57 50 52 78
50% distillate 99 89 121 132
90% distillate 155 143 159 162
residue (%) 1.0 0.5 0.5 0.5
loss (%) 1.0 0.5 1.0 1.0
Reid vapor pressure (kPa) D 323 56.7 63.8 77.0 48.6
octane number
research method D 2699 82.0 85.0 96.6 97.5
motor method D 2700 76.0 74.5 86.5 86.6
corrosion, copper, 50 °C, 3 h D 130 No. 1a No. 1a No. 1a No. 1a

ethanol.12 Although 50 different compounds were identi-

fied using the gas-liquid chromatography method, the
major components of fusel oil are fermentation amyl
alcohols such as 2-methyl-1-butanol and 3-methyl-1-
butanol.13

Experimental Section
Materials. The ethanol-gasoline blends used in the ex-
periments were prepared by adding 5, 10, 15, and 20% (v/v)
azeotropic ethanol to unleaded gasoline. Ethanol was distilled
under normal pressure prior to blending due to its hygroscopic
character. The freshly distilled ethanol used in the blends is
the ethyl alcohol-water azeotrope (EtOH) having a boiling
point of 78.15 °C and containing 4.4 wt % water. Twenty
percent ethanol in gasoline is considered to be the maximum
amount that today’s engines can tolerate without any modi- Figure 1. ASTM distillation curve of FOF.
fications, so this figure was the upper limit in the fuels
tested.14,15 Unleaded gasolines were obtained from Turkish increase the water content of the blend even further.
Petroleum Refineries Inc. and were refinery assured. Table Increasing water content will increase the phase sepa-
1 shows the chemical compositions and physical properties of
ration temperature of the blend.14-18 Therefore, fusel
the four unleaded gasoline samples (G1, G2, G3, and G4)
determined according to ASTM methods. The fuel blends
oil was distilled in a Normschliff Gerätebau fractional
formed using these gasoline samples will be referred to as B1, distillation unit, and the higher boiling fraction (above
B2, B3, and B4, respectively, throughout the text. 120 °C and 75% v/v of FO) of fusel oil (FOF) containing
Methods. Experimental work was performed in four 0.1% (v/v) water was used as the blending agent in the
steps: 1, fractionation and characterization of the molasses experiments. Figure 1 shows the ASTM distillation
fusel oil; 2, investigation of the fusel oil fraction as a blending curve of the FOF which was formed according to the
agent; 3, determination of the relationship between the phase results of the ASTM D 86 method. Chemical composi-
separation temperatures and the chemical compositions of tions of FO and FOF were determined using the gas-
gasolines used in fuel blends; and 4, water tolerances of the liquid chromatography technique. The instrument used
fuel blends. was United Technologies Packard Model 437 A gas
chromatograph fitted with a flame ionization detector
Results and Discussion operating at 200 °C and a stainless steel column (2 m
× 5 mm) packed with 80-100 mesh Propak Q. The
Fractionation and Characterization of the Mo-
injection block temperature was 200 °C, and the flow
lasses Fusel Oil. Fusel oil (FO) used in the experi-
rate of the carrier gas, nitrogen, was 40 mL/min.
ments was obtained from Turkish Sugar Factories Inc.
Results of the gas chromatographic analysis of FO and
It had a high (8.6% v/v) water content, and its density
FOF are given in Table 2.
at 20 °C is 853.6 kg/m3. Using straight fusel oil as a
Use of Molasses Fusel Oil Fraction as a Blending
blending agent for the ethanol-gasoline blends will
Agent. Solubility diagrams of gasoline-ethanol-water-
(12) Ullmanns Encykl. Tech. Chem., 4 1974.
FOF blends at various temperatures were investigated
(13) Thorpe, J. F.; Whiteley, M. A. Thorpe’s Dictionary of Applied
Chemistry; Longmans: London, 1962; Vol. 5, pp 403-408. (16) Keller, J. I.; Hydrocarbon Process. 1979, 2, 127-138.
(14) Use of Alcohol in Motor GasolinesA Review; API Publication (17) Terzoni, G.; Pea, R.; Ancillotti, F. Proceedings of the IV
4082; American Petroleum Institute: Washington, DC, 1971. International Symposium on Alcohol Fuels Technology; ISAF: Brazil,
(15) Alcohols, A Technical Assessment of Their Application as Fuels; 1980; Vol. 1, pp 331-335.
API Publication 4261; American Petroleum Institute: Washington, DC, (18) McKetta, J. J.; Cunningham, W. A. Encyclopedia of Chemical
1976. Processing and Design; Dekker: New York, 1984; Vol. 20, pp 1-40.
818 Energy & Fuels, Vol. 10, No. 3, 1996 Karaosmanoǧlu et al.

Figure 4. PST of ethanol-gasoline blends (B1) containing

various amounts of FOF.

large, whereas introduction of FOF narrows this zone

significantly. Blends containing 20% or more ethanol
form a single homogeneous phase at 25 °C. At lower
temperatures a blend containing 10% EtOH required
the addition of 0.1% FOF to form a single homogeneous
Figure 2. Solubility diagram of ethanol/water-gasoline-FOF phase. Blends containing more than 30% ethanol were
(B1) at various temperatures. always in a single homogeneous phase at 0 °C without
using the blending agent. Blends containing 40% or
more ethanol were homogeneous at -20 °C. At this
temperature the 9.6% ethanol blend required the most
blending agent, which was 3.5% FOF. Using the FOF
in amounts ranging from 0.1 to 3.5% resulted in
homogeneous blends at temperatures of -20, 0, and 25
°C, and the effect of FOF in the prevention of phase
separation was significant.
Phase separation temperatures (PST) of ethanol-
gasoline blends using FOF as the blending agent were
determined by adding FOF to the blends in various
ratios and investigating its behavior in accordance with
the DIN 51583 method. The water content of each blend
was determined according to the Karl-Fischer method
(ASTM D 1744). A mixture of acetone and dry ice was
used to create low-temperature conditions, and the
lowest temperature achievable in this way was -77 °C.
Temperature measurements were taken with an alcohol
thermometer with a scale ranging from -120 to +40
Figure 3. Solubility of ethanol in gasoline at 25 °C in the °C. Blends with PSTs above room temperature were
presence of water. first heated to 39 °C and cooled gradually until separa-
tion occurred. Temperatures higher than that were
Table 2. Chemical Compositions (Weight Percent) of FO avoided because of gasoline’s low vapor pressure.6
and FOF Readings throughout the experiments were taken be-
alcohol FO FOF tween -77 and +39 °C. Ethanol-gasoline blends (B1
ethanol 1.45 0.06 and B4) were prepared using gasolines G1 (rich in
2-propanol 0.15 saturated hydrocarbons and having the lowest octane
1-propanol 1.76 0.41 number) and G4 (rich in aromatic hydrocarbons and
1-butanol 21.94 13.03
fermentation amyl alcohols 74.70 86.50
having the highest octane number). Figures 4 and 5
show the PSTs for blends B1 and B4. Adding 9% FOF
to determine the boundaries of the zone in which the to B1 and 6% FOF to B4 dropped the PSTs below -77
four-component system formed a consistent single ho- °C. A drop in the PSTs was observed when the amount
mogeneous phase. For reasons of simplicity ethanol and of EtOH increased in blends containing a constant
water were considered as one component, and solubility amount of FOF. PSTs also dropped when the amount
diagrams of G1-(ethanol/water)-FOF three-component of EtOH was held constant and the FOF content was
systems at -20, 0, and 25 °C were formed. The amount increased. Results suggested that there was a close
of FOF required to obtain a homogeneous phase was connection between the chemical composition of gaso-
determined by using a micropipet. Figure 2 shows the lines used in the blends and the PSTs.
solubility diagram of an ethanol/water-gasoline-FOF Relationship between the Phase Separation
(B1) system at -20, 0, and 25 °C. Figure 3 is the Temperatures and the Chemical Compositions of
solubility diagram of the ethanol-water-gasoline sys- Gasolines Used in Fuel Blends. In this part of the
tem at 25 °C without the FOF.11,15 In the ethanol- study, the variations in the PSTs of the ethanol-
gasoline-water system the heterogeneous zone is quite gasoline fuel samples (B1, B2, B3, and B4) prepared by
Ethanol-Gasoline Fuels Energy & Fuels, Vol. 10, No. 3, 1996 819

Figure 5. PST of ethanol-gasoline blends (B4) containing

various amounts of FOF.

Table 3. PSTs for Ethanol-Gasoline Blends Prepared

with Gasolines of Different Compositions

FOF EtOH H2O PST (°C)

Figure 6. WTs for B1 fuel blends.
(%) (%) (%) B1 B2 B3 B4
0 5 0.3 >39.0 >39.0 >39.0 >39.0
10 0.5 19.0 17.5 16.5 15.0
15 0.7 11.5 6.5 1.5 -1.2
20 0.9 9.0 2.5 -8.0 -12.5
1 5 0.3 16.5 12.5 10.5 8.5
10 0.5 5.5 4.5 3.0 2.5
15 0.7 -1.0 -3.0 -5.5 -12.5
20 0.9 -3.0 -8.0 -13.5 -18.2
3 5 0.3 -12.5 -16.0 -19.5 -22.0
10 0.5 -17.5 -23.5 -27.0 -35.7
15 0.7 -22.0 -28.5 -33.5 -37.5
20 0.8 -26.5 -34.5 -37.5 -40.5

using gasolines with different chemical compositions

were investigated. Table 3 shows the PSTs of the blends
in the presence of 0, 1, and 3% FOF. In blends that did
not contain the FOF the PSTs dropped as the EtOH and
water content of the blend increased. This was due to
the similar solubility behavior of EtOH in both aromatic
and nonaromatic hydrocarbons. Solubility also in-
creases with temperature level.15,19 For a constant Figure 7. WTs for B4 fuel blends.
amount of FOF and EtOH in a blend, increasing Table 4. WTs for Ethanol-Gasoline Blends Prepared
aromatic character of the gasoline corresponded to a with Gasolines of Different Compositions
decrease in the PSTs.
WT (%)
Water Tolerances of the Fuel Blends. Water
tolerance (WT) of an alcohol-gasoline blend is defined FOF EtOH
(%) (%) B1 B2 B3 B4
as the amount of water that can be added to a blend at
20 °C until a haze is formed.20,21 Water tolerances of 0 5 0.30 0.30 0.30 0.30
10 0.50 0.50 0.50 0.50
blends B1 and B4, which were determined at 20 °C, are 15 0.76 0.77 0.79 0.80
shown in Figures 6 and 7, respectively. At a constant 20 1.08 1.12 1.18 1.23
amount of FOF, increasing the EtOH content of the 1 5 0.31 0.31 0.31 0.32
blend, and at constant EtOH, increasing the FOF of the 10 0.54 0.54 0.55 0.56
15 0.90 0.92 0.96 1.00
blend, increased the WT of the blend. When the WT
20 1.30 1.34 1.38 1.40
values of B1and B4 were compared with each other, 3 5 0.34 0.35 0.37 0.38
B4, which was prepared using G4 (gasoline rich in 10 0.70 0.72 0.74 0.75
aromatic hydrocarbons), had higher WT values than B1. 15 1.20 1.23 1.28 1.31
Results showed that the chemical composition of the 20 1.64 1.71 1.78 1.81
gasoline was an important parameter for WTs of the increase in the PST could be expected. This effect was
blends and the effect of this parameter is shown in further investigated by increasing the water content of
Table 4. From Tables 3 and 4 it can be concluded that the blend B1 and recording the variation in PSTs. The
a high WT value indicates a low PST. However, if a FOF content of the blend also affected the WT; Table 5
blend contains more water than its WT value, an shows the results of the PST readings taken with B1
containing 1 and 6% FOF, respectively. The parameters
(19) Goodger, E. M. Alternative Fuels, Chemical Engineering Re-
sources; MacMillan: London, 1980; pp 141-142.
investigated up to this point are also summarized in
(20) Annual Book of ASTM Standards; Information on Document Table 5. An increase in the water content of the
on Gasohol (Motor Fuel Containing 10% Volume of Denatured Ethanol ethanol-gasoline blends resulted in higher PSTs,
in Gasoline); American Society for Testing and Materials: Philadel-
phia, PA, 1981; Vol. 25, pp 920-937. whereas increasing the FOF content of the blends
(21) MIL G-53006 Appendix Test Method (USA). increased the WT and decreased the PSTs. The pres-
820 Energy & Fuels, Vol. 10, No. 3, 1996 Karaosmanoǧlu et al.

Figure 8. Variation of WTs with temperature for B1 fuel Figure 9. Variation of WTs with temperature for B1 fuel
blends containing 1% FOF. blends containing 3% FOF.

Table 5. Change in the PSTs According to the Water

Content of B1 Blends Containing 1 and 6% FOF separation temperatures and increasing the water toler-
ances of the azeotropic ethanol-unleaded gasoline
FOF (%) EtOH (%) WT (%) H2O (%) PST (°C)
blends. The essential results concerning the change in
1 5 0.31 0.3 16.5 the PSTs in FOF-added ethanol-gasoline blends are as
0.5 29.0 follows:
0.7 >39.0
1.0 >39.0 1. Increasing the amount of the fusel oil fraction in
10 0.54 0.5 10.5 the ethanol-gasoline blends of known alcohol and water
0.7 21.0 content increases the WT values and decreases the PSTs
1.0
of the blends.
>39.0
1.3 >39.0
15 0.90 0.7 18.0 2. The chemical composition of the gasoline used is
1.0 31.0 an important factor for the ethanol-gasoline blends.
1.3 >39.0
Higher aromatic content of gasoline results in lower
1.6
PSTs.
>39.0
20 1.30 0.9 -3.0
1.3 21.0 3. Environmental temperature is vitally important
1.6 >39.0 for the stability of the ethanol-water-gasoline-fusel
2.0
oil fraction four-component system. An increase in
>39.0
6 5 0.57 0.3 -49.5
0.5 -1.0 temperature results in an increase in the WT of the
0.7 23.0 blend, whereas the amount of blending agent required
1.0 >39.0 for a stable blend decreases.
10 1.06 0.5 -55.0
0.7 -27.5 4. Climatic conditions and seasonal temperature
1.0 1.5 variations differ among regions in Turkey. Although
1.3 28.0 -21 °C is the lowest average temperature observed in
15 1.60 0.7 -58.0 winter over the past 5 years, temperatures below -10
1.0
°C are not very common. Therefore, 20% ethanol-
-33.5
1.3 -12.2
1.6 19.5 gasoline blends prepared with gasoline rich in aromatics
20 2.20 0.9 -59.0 and containing 0.1% FOF can be used safely throughout
1.3 -40.2 the year without any phase separation problem, whereas
1.6
the 20% ethanol-parafinic gasoline blends containing
-14.5
2.0 7.2
the same amount of FOF may be used anytime except
ence of water in amounts exceeding the WT values of winter. Fuel ethanol production can yield sufficient
the blends resulted in very high PSTs. WT is highly fusel oil to supply the suggested 0.1% FOF as the
dependent on temperature; therefore, WT values for B1 blending agent.
containing 1 and 3% FOF were determined within a The results obtained in this study suggest that a
temperature range of -20 to +40 °C. Increasing the byproduct of the ethanol production process may be used
temperature as well as increasing the EtOH and FOF effectively in solving the phase separation problem of
content of the blend resulted in an increase in the WTs. the ethanol-gasoline fuels otherwise solved by using
Figures 8 and 9 show the change in WTs versus various pure cosolvents.
increasing temperature.
Acknowledgment. We thank Turkish Petroleum
Conclusions Refineries Inc. and Istanbul Regional BranchsTurkish
Sugar Factories Inc. for their valuable cooperation.
The fusel oil fraction is a new blending agent that was
found to be highly effective in reducing the phase EF950131Z