JFUE 9193 No.

of Pages 6, Model 5G
24 April 2015

Fuel xxx (2015) xxxxxx

1

Contents lists available at ScienceDirect

Fuel
journal homepage: www.elsevier.com/locate/fuel

5
6

3 Experimental determination of some physical properties of gasoline,

4 ethanol and ETBE ternary blends
7 Luis Miguel Rodrguez-Antn , Fernando Guterrez-Martn, Carmen Martinez-Arevalo
8 Department of Mechanical, Chemical and Industrial Design Engineering, ETSIDI, Universidad Politcnica de Madrid, Ronda de Valencia, 3, 28012 Madrid, Spain

9
10

1 2
h i g h l i g h t s
13
14  We measured: density, RVP and distillation curves for ethanolETBEgasoline blends.
15  We calculated the most relevant blends parameters for EN 228 and ASTM D4814.
16  The addition of ETBE and/or EtOH to gasoline affects fuel-standard compliance.
17  The addition of ETBE to gasoline affects fuel-standard compliance less than EtOH.
18  The addition of ETBE to EtOHgasoline blends can redirect some standard parameters.

19
a r t i c l e i n f o a b s t r a c t
2 5
3 1
22 Article history: The addition of oxygenated renewable fuels, such as ethanol or ethyl tert-butyl ether (ETBE) to standard 36
23 Received 19 February 2015 gasoline may be necessary to comply with some environmental directives but could also prevent compli- 37
24 Received in revised form 13 April 2015 ance with some fuel regulations and could also seriously change engine performance. From this point of 38
25 Accepted 16 April 2015
view, the Reid Vapour Pressure (RVP), the distillation curve, the oxygen content and the density belong to 39
26 Available online xxxx
the group of the most relevant parameters. This study evaluates the inuence of the simultaneous 40
addition of ethanol and ETBE on some physical properties of engine gasoline. The main conclusion is that 41
27 Keywords:
the simultaneous addition of ETBE and ethanol changes the RVP, the distillation curve and the density in a 42
28 Gasoline
29 Ethanol
way that can affect engine operation and the mandatory EN 228 and ASTM D4814 standards. Some 43
30 ETBE opposite properties of both oxygenates could help to increase the renewable energy content without 44
31 Distillation curve preventing compliance with these regulations. 45
32 Reid Vapor Pressure (RVP) 2015 Published by Elsevier Ltd. 46
33 Density 47
34
48
49
50 1. Introduction into the atmosphere and, second, their foreign energy dependence. 63
In this way, the Directive 2009/28/EC [2] requires 10% of renewable 64
51 From the year 2011 to 2030, global energy consumption is pro- content for transport fuels before 2020 and higher percentages are 65
52 jected to grow by 36% to 16.6 billion toe and the energy consump- foreseeable in the coming years. In parallel with these Directives, 66
53 tion in transport by 27% to 2.7 billion toe [1]. To meet this demand, fuel regulations are being developed to allow the addition of some 67
54 a diverse energy mix is needed. This is the point where biofuels renewable components [3]. 68
55 could help; in the next two decades, biofuels are expected to pro- Alcohols have been used as fuels for engines since the 19th cen- 69
56 vide some 13% (by energy content) of the growth in fuels for road tury. Among the various alcohols, ethanol (100% renewable) is 70
57 transport [1]. Additionally, due to the fast-growing concern about known as the most suitable renewable, bio-based and eco-friendly 71
58 global warming, which can be attributed primarily to the elevated fuel for spark-ignition engines [4]. Nevertheless, isobutanol also 72
59 CO2 levels in the atmosphere, the use of renewable energy is has good future perspectives [5,6]. On the other hand, ETBE (47% 73
60 mandatory. renewable) is one of the most common ethers used as a fuel addi- 74
61 That is the reason why many countries have developed fuel reg- tive [7]. Nowadays, most advanced countries add either ethanol 75
62 ulations in order to reduce, rst, their carbon dioxide emissions and/or ETBE to their gasoline pools [716]. 76
When ethanol and/or ETBE are added to gasoline, some fuel 77

Corresponding author. Tel.: +34 656343982. properties change and the gaseous emissions, the mechanical per- 78

E-mail addresses: lm.rodriguez@upm.es (L.M. Rodrguez-Antn), formance and the reliability of the engine could be affected either 79
fernando.gutierrez@upm.es (F. Guterrez-Martn), carmen.martineza@upm.es positively or negatively. To guarantee compliance with new 80
(C. Martinez-Arevalo).

http://dx.doi.org/10.1016/j.fuel.2015.04.040
0016-2361/ 2015 Published by Elsevier Ltd.

Please cite this article in press as: Rodrguez-Antn LM et al. Experimental determination of some physical properties of gasoline, ethanol and ETBE ternary
blends. Fuel (2015), http://dx.doi.org/10.1016/j.fuel.2015.04.040
 JFUE 9193 No. of Pages 6, Model 5G
24 April 2015

2 L.M. Rodrguez-Antn et al. / Fuel xxx (2015) xxxxxx

81 mandatory renewable fuel contents, but also to maintain good the engine performance when these ternary blends are used and 147
82 engine performance, changes in fuel specications must be made to determine their optimum composition. Throughout this paper, 148
83 step-by-step. the inuence of each parameter over engine performance will be 149
84 It is well known that the RVP, the distillation curve and the presented. 150
85 oxygen content, as well as the octane number, belong to the group
86 of fuel properties that affect engine operation and gaseous emis- 2. Materials and methods 151
87 sions more signicantly. Any changes to these properties could
88 affect engine behaviour negatively, if no precautions are taken. To carry out this research some fuels and experimental facilities 152
89 That is the reason why many researchers have looked into changes that comply with European standards were used. 153
90 in these properties when ethanol and/or ETBE are added to
91 gasoline, by empirical or theoretical determination.
2.1. Materials 154
92 Muzkov [8] has studied the inuence of ethanol up to 10% v/v,
93 ETBE up to 10% v/v, as well as hydrocarbon composition on the
The base gasoline (Table 1), Ethanol and ETBE have already been 155
94 volatility and distillation characteristics of the gasoline blends.
used in a previous work where their specications were stated 156
95 Karonis [9] has examined the impact of simultaneous addition of
[26]. 157
96 ETBE up to 6% v/v and ethanol up to 6% v/v on the main properties
To prepare the gasolineethanolETBE blends, some A class 158
97 of motor gasoline (RVP, E70, E100, E150, RON, MON, and sensitiv-
pipettes, beakers and volumetric asks with the maximum preci- 159
98 ity). Andersen [10,11] has determined the RVP and the distillation
sion (DIN 12600) were used. The abbreviated blend names were 160
99 curves for various alcoholsgasoline binary blends containing up to
built with two letters (E and T) and two numbers between 0 161
100 85% v/v of ethanol. This author has reported a simple method to
and 100. The letter E precedes the volume percentage of added 162
101 prepare two-alcoholsgasoline blends with a RVP that is indistin-
ethanol and the letter T precedes the volume percentage of added 163
102 guishable from that of the base gasoline and has also demonstrated
ETBE (ETBE*). For example: E20T15 means 20% v/v of ethanol, 15% 164
103 that those blends have distillation curves closer to that of the base
v/v of ETBE* and 65% v/v of base gasoline. In this study, base gaso- 165
104 gasoline than single-alcohol blends. Christensen [12] has studied
line contained 0.1% v/v of ethanol, which is negligible, and 6% v/v of 166
105 the chemical and physical properties (RVP, vapour lock protection,
ETBE. It would have been better to use a base gasoline without 167
106 distillation, density, octane rating, viscosity and potential for
ETBE and ethanol but it is not currently possible to nd it on the 168
107 extraction into water) for various alcoholgasoline blends of up
market. 169
108 to 3.7% w/w of oxygen and has compared them with the require-
The tested blends for densities, RVP and distillation curves were 170
109 ments of the ASTM D4814 specication to determine their utility
all possible combinations of base gasoline, ethanol (0, 2, 4, 6, 8, 10, 171
110 as gasoline extenders. Petre [13,14] has used two classical gasoli-
15, 20, 30, 45, 60 and 85% v/v) and ETBE (5, 10, 15, 20, 25 and 30% 172
111 nes with different composition and properties, with proportions
v/v). Note that some combinations as for example T30E85 or 173
112 ranging from 2% to 10% v/v of ethanol and other alcohols, plus
T25E85 are not possible. In the case of distillation curves, the etha- 174
113 addition of ETBE in proportions ranging from 4% to 15% v/v and
nolETBE binary blends were not tested. 175
114 other ethers; she has presented experimental results regarding
115 the effect of the blend with alcohol or ether on the RVP and the dis-
2.2. Methods: experimental facilities and test management 176
116 tillation curve. Pumphrey [17] has reported a simple method to
117 successfully predict vapour pressures of gasoline-alcohol mixtures
The tests were carried out in the Fuels and Petrochemical 177
118 and validate them with blends of gasoline with different
Laboratory of the Gmez Pardo Foundation. This ofcial Spanish 178
119 oxygenates (0100% v/v). French [16] has shown the effect of the
laboratory is accredited by ENAC (National Entity of 179
120 addition of ethanol to gasoline on the RVP, the distillation curves
Accreditation) by the UNE-EN ISO/IEC 17025 standard. The density, 180
121 (010% v/v), the Vapour/Liquid ratio (V/L), the Vapour Lock Index
RVP and distillation curves were measured following the UNE-EN 181
122 (VLI), the Driveability Index (DI), the phase separation and the
ISO 12185, UNE-EN 13016-1 and UNE-EN ISO 3405 standards, 182
123 material compatibility. Menezes [7] has analysed the effect of the
respectively. All the tests were carried out according to corre- 183
124 addition of an azeotropic ETBE/ethanol mixture in two gasolines
sponding equipment instructions. Their main technical specica- 184
125 (017% v/v) on the RVP, the distillation curve, the density and
tions were described in the aforementioned work [26]. 185
126 the octane number. Zemroch [18] has determined what happens
127 to the volatility of the ethanol/gasoline blend up to 25% v/v, specif-
128 ically its E70, E100 and RVP, when ethanol is splash blended into a 3. Results and discussion 186
129 wide range of base gasolines.
130 Many other researchers have studied the inuence of the addi- In this section the main results obtained from the tests (RVP, 187
131 tion of oxygenates to gasoline on engine performance, mainly distillation curve, density and composition) are presented and 188
132 focusing on the gaseous emissions [15,1923], torque, power, fuel discussed. 189
133 economy [1921,24], material compatibility [25], driveability or
134 engine operability and reliability. 3.1. Density 190
135 For all the above reasons, the interest in this matter nowadays
136 seems evident. The high octane number of ethanol or ETBE means Solutions created by mixing ethanol and ETBE with gasoline are 191
137 they are suitable as replacements for alkyl-lead compounds as not ideal because the intermolecular forces and molecular packing 192
138 gasoline octane improvers, owing to environmental and public of the same substance (ethanolethanol, gasolinegasoline or 193
139 health reasons [16]. The main objective of this paper is to offer reli- ETBEETBE) are different from those of different substances (gaso- 194
140 able experimental data of the distillation curves, the RVP and the lineethanolETBE). Thus, the volume of the mixture is different 195
141 density of ternary blends of gasoline, ethanol and ETBE. These from the sum of its components volumes and this difference is 196
142 properties, as well as the chemical composition of the base gaso- called excess volume. It seems to be clear that when ethanol is 197
143 line allow the authors to determine most of the regulated param- blended with gasoline, the intermolecular forces are reduced 198
144 eters in the Directive 2009/30/CE [3] and check their compliance because ethanol is a polar substance and gasoline is not, though 199
145 with the mandatory specications (EN 228, ASTM D4814). nothing can be guaranteed concerning the molecular packing. 200
146 The knowledge of these data could help researchers to foresee The case of ETBE, less polar than ethanol, is similar. If the excess 201

Please cite this article in press as: Rodrguez-Antn LM et al. Experimental determination of some physical properties of gasoline, ethanol and ETBE ternary
blends. Fuel (2015), http://dx.doi.org/10.1016/j.fuel.2015.04.040
 JFUE 9193 No. of Pages 6, Model 5G
24 April 2015

L.M. Rodrguez-Antn et al. / Fuel xxx (2015) xxxxxx 3

Table 1
Heating values, properties, requirements and test methods for base gasoline with maximum oxygen content 2.7% (EN 228).

Property Units Experimental value Minimum limit Maximum limit Test method
3
Density at 15 C kg/m 737.6 720 775 EN ISO 3675
Vapour Pressure (Summer Class A -) kPa 60.5 45 60 (a) EN ISO 13016-1
Distillation
Evaporated at 70 C (E70) % v/v 30.5 20 48 EN ISO 3405
Evaporated at 100 C (E100) % v/v 60.0 46 71
Evaporated at 150 C (E150) % v/v 90.7 75
Final Boiling Point (FBP) C 195.2 210
Distillation Residue (DR) % v/v 0.6 2
Hydrocarbon type content
Olens % v/v 13.09 18 EN14517 EN15553
Aromatics % v/v 27.05 35
Benzene % v/v 0.86 1 UNE EN238
Oxygen and Oxygenates content
Oxygen content % w/w 0.98 2.7 UNE EN 13132
Ethanol % v/v 0.1 5 EN 13132
Ethers (5 or more C atoms) 6
Sulphur and Copper content
Sulphur content mg/kg 7.0 10 EN ISO 20846
Copper strip corrosion (3 h at 50 C) Rating Class 1 Class 1 EN ISO 2160
Heating values
Higher kJ/kg 43238
Lower kJ/kg 41048
a
Extra vapour pressure is permitted depending on EtOH content.

202 volume is positive, the solution density would be less than ideal, and also due to the formation of azeotropic mixtures between 239
203 and vice versa. To evaluate if the excess volume is relevant when ethanol and lighter fractions of gasoline (n-butane, n-pentane, 240
204 gasoline, ethanol and ETBE are mixed, the densities of all the tern- etc.) that reduce the boiling point temperature and increase the 241
205 ary mixtures were measured. The difference between the experi- vapour pressure of the mixture [18]. These facts have been con- 242
206 mental and the ideal density (weighted mean by volumetric rmed by analysing the vapour of different ethanolETBEgasoline 243
207 composition of gasoline, ethanol and ETBE densities) was slightly mixtures by gas chromatography [26]. 244
208 different but always less than 0.5%. Thus, it could be assumed that When the two oxygenates were added simultaneously, the 245
209 the density of a mixture is the weighted mean by volumetric com- behaviour of ternary blends was not ideal. The deviation from 246
210 position of the components densities (737.6 kg/m3 for the base the ideal mixture was positive for the reasons mentioned above. 247
211 gasoline, 794.0 kg/m3 for ethanol and 744.2 kg/m3 for ETBE). This Fig. 1 shows a map of RVP as a function of ethanol and ETBE* con- 248
212 approximation provided a coefcient of determination of 99.93%. tent. The maximum RVP took place between 5% and 10% v/v of 249
213 It is important to remark that the higher density of both oxy- ethanol, while any addition of ETBE reduced the value of RVP. 250
214 genated additives, as compared with base gasoline (0.89% for The increase of RVP due to the addition of 510% v/v of ethanol 251
215 ETBE and 7.65% for ethanol), slightly compensates for their lower (68 kPa [27]) can be compensated by adding about 15% v/v of 252
216 heat value (13.0% for ETBE and 35.4% for ethanol), due to their oxy- ETBE* (E8T15). Higher quantities of added ethanol required lower 253
217 gen content. The higher density of both oxygenates, especially quantities of ETBE*. This corrector effect of ETBE could help to com- 254
218 ethanol, caused ethanol concentrations which were greater than ply with the EN 228 or ASTM D4814 standards. In any case, Fig. 1 255
219 65% v/v to surpass the density upper limit xed by the EN 228 shows that higher amounts of ethanol and ETBE could surpass the 256
220 standard. limits marked by the standards for the total oxygen content. 257
Finally, the measured data have been adjusted to a quadratic 258
surface giving a coefcient of determination of 98.98% and a max- 259
221 3.2. Reid Vapour Pressure (RVP)
imum deviation of 3 kPa. 260

222 RVP has a great inuence on evaporative hydrocarbon emis-

223 sions from the fuel tank of vehicles. This is the reason why all reg- 3.3. Distillation curve 261
224 ulations around the world limit this parameter depending on
225 climatic conditions. The distillation curve prole affects engine behaviour signi- 262
226 The RVP of ETBEgasoline mixtures was almost ideal, that is, it cantly. Prakash [28] describes it in a detailed way. The evaporative 263
227 was the weighted mean by molar fraction composition of ETBE and losses from the tank, the hot or cool engine starting and the vapour 264
228 gasoline RVP. It should be observed that molar and volume lock depend on lighter fractions (0% to 40% of distilled volume). 265
229 fractions have approximately the same values in the case of The ice formation in intake air system, the engine warm-up, the 266
230 ETBEgasoline blends [26]. vehicle acceleration and the short-trip fuel economy depend on 267
231 The behaviour of ethanolgasoline mixtures is signicantly dif- medium fractions (40% to 80% of distilled volume). Finally, 268
232 ferent. Despite the fact that the RVP of ethanol is much lower than the long-trip economy, the oil dilution, the volatile organic com- 269
233 that of gasoline (because of the stronger intermolecular hydrogen- pounds (VOC) and the formation of combustion deposits depend 270
234 bonding interactions between ethanol molecules), some mixtures on heavy fractions (80100% of distilled volume). 271
235 of these fuels increase the RVP of the blend. This positive deviation The strong inuence that the distillation curves have on the 272
236 from the ideal mixture behaviour (Raoults Law) occurs because engine performance means that fuel regulations must have many 273
237 the intermolecular interactions between ethanol and hydrocarbon parameters to control these curves. European regulations (EN 274
238 molecules are weaker than they are in the two pure liquids [27] 228) control the volume evaporated at 70, 100 and 150 C (E70/ 275

Please cite this article in press as: Rodrguez-Antn LM et al. Experimental determination of some physical properties of gasoline, ethanol and ETBE ternary
blends. Fuel (2015), http://dx.doi.org/10.1016/j.fuel.2015.04.040
 JFUE 9193 No. of Pages 6, Model 5G
24 April 2015

4 L.M. Rodrguez-Antn et al. / Fuel xxx (2015) xxxxxx

Fig. 1. RVP, DI and VLI vs. composition of ethanol, ETBE* and gasoline ternary
Fig. 2. Volatility parameters of EN 228 (E70, E100, E150) for ethanol, ETBE* and
blends.
gasoline ternary blends.

276 E100/E150, abbreviations which should not be confused with those

Table 2
277 referring to the mixtures of ethanol with gasoline, mentioned RVP and requirements (EN 228 and ASTM D4814) for the gasoline distillation curve
278 above), the Vapour Lock Index (VLI 10  RVP 7  E70), the (volatility class A).
279 Distillation End Point (DEP) and the Distillation Residue (DR).
Standard Parameter Units Min Max
280 American regulations (ASTM D4814) control the temperatures at
EN 228 (Distillation class A and RVP kPa 45 60
281 which 10%, 50% and 90% of fuel volume are evaporated (T10/T50/
Oxygen content 3%, 7% w/w)
282 T90, which should not be confused with those referring to the mix- E70 % v/v 22 50
283 tures of ETBE and gasoline), the Driveability Index (DI 1:5 E100 % v/v 46 72
284 T10 3:0  T50 1:0  T90 1:33  %Ethanol v =v ), the DEP and E150 % v/v 75
285 the DR. End Point C 210
Residue % v/v 2
286 The study of volatility curves for all the blends prepared in this
VLI Index
287 work was a hard task due to the high number of measurements. To
ASTM 4814 (Distillation class A) RVP kPa 62
288 better understand this hard task, it is advisable to see the volatility
T10 C 70
289 curves of the same base gasoline blended only with ETBE (Fig. 2 T50 C 66 121
290 [26]) or ethanol (Figure 4 [26]). It was more practical to analyse T90 C 190
291 the changes in the parameters controlled by the standards (E70, End Point C 225
Residue % v/v 2
292 E100, E150, VLI, FP and DR for EN 228 or T10, T50, T90, DI, FP
DI C 597
293 and DR for ASTM D4814). The actual limits for the geographical
294 zone and season when the base gasoline was purchased are sum-
295 marized in Table 2. In the following paragraphs, the inuence of not usually a problem because these engines operate with fuel 305
296 the addition of ethanol and ETBE on the above parameters is pumps immersed in the tank and with pressurized fuel lines. The 306
297 discussed. VLI presented a maximum value when ethanol concentration was 307
298 The xed limits for DR and DEP are aimed at controlling the for- around 15% v/v, as shows Fig. 1. The addition of ETBE slightly 308
299 mation of engine deposits, the VOCs emissions and the fuel dilu- reduced the VLI. The maximum value (997.3), reached for E15T0, 309
300 tion in the oil. The addition of both oxygenates reduced both was much lower than the upper limit of the EN 228 standard (there 310
301 parameters and thus, the obtained values are lower than the values is no limit for the summer gasoline tested, Class A, and the limit is 311
302 of the base gasoline and the upper limits. 1068 for the winter gasoline, Class C). 312
303 The VLI tries to control the problems associated with vapour Although each range of a distillation prole is important, the 313
304 formation in the fuel lines. In modern engines, this parameter is gasoline represented by an entire prole is what the engine must 314

Please cite this article in press as: Rodrguez-Antn LM et al. Experimental determination of some physical properties of gasoline, ethanol and ETBE ternary
blends. Fuel (2015), http://dx.doi.org/10.1016/j.fuel.2015.04.040
 JFUE 9193 No. of Pages 6, Model 5G
24 April 2015

L.M. Rodrguez-Antn et al. / Fuel xxx (2015) xxxxxx 5

315 distribute, vaporize, and burn. To predict a fuels cold-start and

316 warm-up driveability, a driveability index (DI) has been developed
317 (ASTM D4814) using T10, T50, T90 and ethanol content [29]. Lower
318 values of DI generally result in better cold-start and warm-up per-
319 formance. The addition of ethanol and ETBE slightly reduced the DI
320 value with respect to the base gasoline, except for ethanol concen-
321 trations higher than 65% v/v. In any case, this value was always
322 lower than the upper limit (597) xed by the ASTM D4814, there-
323 fore no engine problems were expected with this parameter
324 (Fig. 1).
325 To control the gasoline composition (light, medium and heavy
326 fractions respectively) the parameters used are E70, E100 and
327 E150 in EN 228 standard and T10, T50 and T90 in ASTM D4814
328 standard. The addition of ethanol and ETBE substantially modied
329 these parameters, especially those referring to light and medium
330 fractions.
331 The addition of ETBE to gasoline involves lower volatility for
332 lighter fractions and higher volatility for medium and heavy
333 fractions.
334 The case of ethanol is very different as it forms azeotropic mix-
335 tures with many hydrocarbon compounds of gasoline, especially
336 the lightest, having a lower boiling point than ethanol and the
337 corresponding hydrocarbons [30,31]. The addition of ethanol to
338 gasoline involves higher or lower volatility for lighter fractions
339 depending on ethanol concentration. Medium and heavy fractions
340 of the blends are always more volatile than those of base gasoline.
341 The parameter E70 was practically unaffected by the addition of
342 ETBE in the range from 0% to 10% of ethanol. For higher concentra-
343 tions of ethanol, the addition of ETBE slightly increased the value of
344 E70. The addition of ethanol to the gasoline affected E70 in an
345 important way, surpassing the EN 228 standard upper limit (50%)
346 for blends around E10-E20, and giving lower values than the lower
347 limit (22%) for blends with more than approximately 60% v/v of
348 ethanol (Fig. 2).
349 The E100 parameter increased similarly for both oxygenates. Fig. 3. Volatility parameters of ASTM D4814 (T10, T50, T90) for ethanol, ETBE* and
350 The permitted upper limit (72%) was reached with relatively low gasoline ternary blends.
351 concentrations of oxygenates (E18T0, E10T17, E0T26) and higher
352 concentrations substantially surpassed this upper limit (Fig. 2).
compliance with the EN 228 standard regarding the limits of 379
353 The E150 parameter increased similarly with the addition of
sulphur, oxygen and benzene content (Table 1). Because of the 380
354 both oxygenates too, but it does not pose any problem with the
absence of sulphur and benzene in ethanol or ETBE samples, all 381
355 standard, being far away from the lower limit (75%) xed in EN
blends of these oxygenates with gasoline complied with the EN 382
356 228 (Fig. 2).
228 and ASTM D4814 standards regarding the limits for these 383
357 The T10 parameter increased also with the addition of both
substances. 384
358 oxygenated compounds, although the addition of ethanol at low
The oxygen content in ETBE and ethanol is 15.66% and 34.73% 385
359 concentrations showed a minimum around E10. The upper limit
w/w respectively. Consequently, the addition of ETBE and ethanol 386
360 (70 C) is reached with high oxygenate content (E80T0, E75T10)
increases the oxygen content of the blend and could surpass the 387
361 and thus the use of medium or low concentrations does not repre-
EN 228 and ASTM D4814 oxygen content limit. This parameter 388
362 sent a problem (Fig. 3).
has a special relevance because it strongly affects the combustion 389
363 The T50 is the parameter affected in the most signicant way.
stoichiometry, impeding the correct functioning and greatly 390
364 Ethanol addition up to 10% v/v drastically reduced this value,
changing the gaseous emissions and fuel economy of some 391
365 higher concentrations, however, slightly increased it. On the other
engines. 392
366 hand ETBE addition slightly reduced this parameter. The combined
Figs. 13 show the 2.7% and 3.7% w/w oxygen content lines. It is 393
367 action of both oxygenates does not in any case surpass the lower
necessary to keep in mind that the base gasoline had 6% v/v of 394
368 limit (66 C) xed in the ASTM D4814 standard (Fig. 3).
ETBE, which is equivalent to around 2.7% v/v of ethanol. From these 395
369 The T90 parameter is reduced similarly by the action of both
gures it is possible to calculate that 8% of total ethanol or 17% of 396
370 additives, and thus, this is not a problem with the standard, being
total ETBE surpasses the real EN 228 limit (2.7% w/w). The recent 397
371 far away from the xed upper limit (190 C) (Fig. 3). In every one of
increase of this limit to 3.7% w/w extends the use of biofuels up 398
372 the former parameters, the limits were reached with blends having
to 10% v/v of total ethanol or 23% v/v of total ETBE. 399
373 oxygen contents higher than the upper values xed by both stan-
374 dards, depending on the gasoline type (see the 2.7% and 3.7% w/
375 w oxygen lines in the gures). 4. Conclusions 400

376 3.4. Composition-related parameters The main conclusion of this work is that physical properties of 401
ethanol, ETBE and gasoline ternary blends change some important 402
377 The chemical analysis of the base gasoline provided the elemen- parameters controlled by the regulations as they affect engine per- 403
378 tary following formula: C7:18 H12:72 O0:06 and conrmed the formance and gaseous emissions. 404

Please cite this article in press as: Rodrguez-Antn LM et al. Experimental determination of some physical properties of gasoline, ethanol and ETBE ternary
blends. Fuel (2015), http://dx.doi.org/10.1016/j.fuel.2015.04.040
 JFUE 9193 No. of Pages 6, Model 5G
24 April 2015

6 L.M. Rodrguez-Antn et al. / Fuel xxx (2015) xxxxxx

405 The volume excess of these ternary blends was so small (less Council. Brookings (United States): South Dakota State University, NABC; 459
2007. p. 13747. 460
406 than 0.5%) that it could be considered insignicant. Therefore, 461
[7] de Menezes EW, Catalua R, Samios D, da Silva R. Addition of an azeotropic
407 the blend density could be calculated as the weighted mean of ETBE/ethanol mixture in eurosuper-type gasolines. Fuel 2006;85:256777. 462
408 the volumetric blend composition. The high ethanol density [8] Muzkov Z, Pospil M, ebor G. Volatility and phase stability of petrol blends 463
with ethanol. Fuel 2009;88:13516. 464
409 implied that high concentrations of this additive (>65% v/v) sur- 465
[9] Karonis D, Anastopoulos G, Lois E, Stournas S. Impact of simultaneous ETBE
410 passed the upper limits of the EN 228 standard. and ethanol addition on motor gasoline properties. SAE Int J Fuels Lubricants 466
411 The addition of ETBE to gasoline reduced the RVP in a way that 2009;1(1):158494. 467
[10] Andersen VF, Anderson JE, Wallington TJ, Mueller SA, Nielsen OJ. Vapor 468
412 is directly proportional to the ETBE content, but the addition of
pressures of alcoholgasoline blends. Energ Fuel 2010;4(6):364754. 469
413 ethanol increased the RVP of the blend only up to 35% v/v. Thus, [11] Andersen VF, Anderson JE, Wallington TJ, Mueller SA, Nielsen OJ. Distillation 470
414 the addition of ETBE helps to compensate for the RVP increase pro- curves for alcoholgasoline blends. Energ Fuel 2010;24:268391. 471
415 duced by the ethanol at low concentrations, although the com- [12] Christensen E, Yanowitz J, Ratcliff M, McCormick RL. Renewable oxygenate 472
blending effects on gasoline properties. Energ Fuel 2011;25(10):472333. 473
416 bined addition of both oxygenates could surpass the upper [13] Petre M, Rosca P, Dragomir RE, Mihai O. Bioalcohols-compounds for 474
417 oxygen content limit. Additionally, any oxygenates content higher reformulated gasolines. The effect of alcohols on volatility properties of 475
418 than E70T0E45T30 surpass the lower limit for the EN 228 stan- gasolines. Rev Chim-Bucharest 2010;61:70611. 476
[14] Petre M, Rosca P, Dragomir RE. The effect of bio-ethers on the volatility 477
419 dard (45 kPa). properties of oxygenated gasoline. Rev Chim-Bucharest 2011;62:56774. 478
420 Regarding the distillation curves, the parameters most affected [15] Magnusson R, Nilsson C. The inuence of oxygenated fuels on emissions of 479
421 by the addition of oxygenates were those characterizing the light aldehydes and ketones from a two-stroke spark ignition engine. Fuel 480
2011;90:114554. 481
422 (E70) and medium (E100) fractions in the EN 228 standard. The 482
[16] French R, Malone P. Phase equilibria of ethanol fuel blends. Fluid Phase
423 lighter fractions did not full the standards for ethanol content Equilibr 2005;228-229:2740. 483
424 around 1020% v/v or higher than 6075% v/v. The medium frac- [17] Pumphrey JA, Brand JI, Scheller WA. Vapour pressure measurements and 484
predictions for alcoholgasoline blends. Fuel 2000;79:140511. 485
425 tions (E100) surpassed the upper limit at relatively low oxygenate 486
[18] Zemroch PJ et al. Statistical design and analysis of a test programme to assess
426 content (E18T0, E10T17, E0T26). The heavy fractions fullled both the volatility characteristics of ethanol/gasoline blends. doi:10.1109/ 487
427 standards for any oxygenate content. ICSSBE.2012.6396542. 488
[19] Aakko-Saksa P, Rantanen-Kolehmainen L, Koponen P, Engman A, Kihlman J. 489
428 The total oxygen content (2.7% or 3.7% w/w) was the most
Biogasoline options-possibilities for achieving high bio-share and 490
429 restrictive parameter in the EN 228 and ASTM D4814 standards, compatibility with conventional cars. SAE Int J Fuels Lubricants 491
430 followed by RVP, E100 and E70. 2011;4(2):298317. 492
[20] Ycesu HS, Topgl T, inar C, Okur M. Effect of ethanolgasoline blends on 493
engine performance and exhaust emissions in different compression ratios. 494
431 Acknowledgments Appl Therm Eng 2006;26:22728. 495
[21] Ozsezen AN, Canakci M. Performance and combustion characteristics of 496
432 This work was sponsored by the Fuels and Petrochemical alcohol-gasoline blends at wide-open throttle. Energy 2011;36:274752. 497
[22] Chen R, Chiang LB, Chen CN, Lin TH. Cold-start emissions of an SI engine using 498
433 Laboratory of the Gmez Pardo Foundation. The authors grate- ethanolgasoline blended fuel. Appl Therm Eng 2011;31:14637. 499
434 fully thank the undergraduate students Julia Gmez and scar [23] Gravalos I, Moshou D, Gialamas Th, Xyradakis P, Kateris D, Tsiropoulos Z. 500
435 del Saz of the Universidad Politcnica of Madrid for carrying out Emissions characteristics of spark ignition engine operating on lower-higher 501
molecular mass alcohol blended gasoline fuels. Renew Energ 2013;59:2732. 502
436 the laboratory tests. The authors also wish to thank REPSOL and 503
[24] Catalua R, da Silva R, de Menezes EW, Boeira R. Specic consumption of liquid
437 Acciona Energy for providing the fuel additives tested. biofuels in gasoline fuelled engines. Fuel 2008;87:33628. 504
[25] Yoo YH, Park IJ, Kim JG, Kwak DH, Ji WS. Corrosion characteristics of aluminum 505
alloy in bio-ethanol blended gasoline fuel: Part 1. The corrosion properties of 506
438 References 507
aluminum alloy in high temperature fuels. Fuel 2011;90:120814.
[26] Rodrguez-Antn LM, Hernndez-Campos M, Sanz-Prez F. Experimental 508
439 [1] BP Energy outlook 2030, 2013 <http://www.bp.com/en/global/corporate/ 509
determination of some physical properties of gasoline, ethanol and ETBE
440 about-bp/energy-economics/energy-outlook/energy-outlook-downloads. 510
blends. Fuel 2013;112:17884.
441 html>. 511
[27] Rose KD, Thompson ND. Technical Coordinators. Guidelines for blending and
442 [2] Directive 2009/28/EC of the European Parliament and of The Council of 23 512
handling motor gasoline containing up to 10% v/v ethanol [Internet]. Brussels:
443 April 2009 on the promotion of the use of energy from renewable sources and 513
CONCAWE; 2008. <https://www.concawe.eu/DocShareNoFrame/Common/
444 amending and subsequently repealing Directives 2001/77/EC and 2003/30/EC. 514
GetFile.asp?PortalSource=1856&DocID=13847&mfd=off&pdoc=1>.
445 Ofcial Journal of the European Union 2009; 140:1662. 515
[28] Prakash C. Use of higher than 10 volume percent ethanol/gasoline blends in
446 [3] Directive 2009/30/EC of the European Parliament and of The Council of 23 516
gasoline powered vehicles. Transportation Systems Branch Air Pollution
447 April 2009 amending Directive 98/70/EC as regards the specication of petrol, 517
Prevention Directorate Environment Canada 1998.
448 diesel and gasoil and introducing a mechanism to monitor and reduce 518
[29] Gibbs L et al. Motor gasolines technical review. USA: Chevron Corporation;
449 greenhouse gas emissions and amending Council Directive 1999/32/EC as 519
2009.
450 regards the specication of fuel used by inland waterway vessels and repealing 520
[30] da Silva R, Catalua R, de Menezes EW, Samios D, Piatnicki CMS. Effect of
451 Directive 93/12/EEC. Ofcial Journal of the European Union 2009;140:88113. 521
additives on the antiknock properties and Reid vapor pressure of gasoline. Fuel
452 [4] Ko M, Sekmen Y, Topgl T, Ycesu HS. The effects of ethanol-unleaded 522
2005;84:9519.
453 gasoline blends on engine performance and exhaust emissions in a spark- 523
[31] Balabin RM, Syunyaev RZ, Karpov SA. Quantitative measurement of ethanol
454 ignition engine. Renew Energ 2009;34:21016. 524
distribution over fractions of ethanolgasoline fuel. Energ Fuel
455 [5] Kolodziej R, Scheib J. Bio-isobutanol: the next-generation biofuel. Hydrocarb 525
2007;21(4):24605.
456 Process 2012:7985.
457 [6] Ramey DE. Butanol: the other alternative fuel. In: Proceedings of the 19th 526
458 annual conference of the National Agricultural Biotechnology

Please cite this article in press as: Rodrguez-Antn LM et al. Experimental determination of some physical properties of gasoline, ethanol and ETBE ternary
blends. Fuel (2015), http://dx.doi.org/10.1016/j.fuel.2015.04.040