Energy Fuels 2010, 24, 1374–1379 : DOI:10.

1021/ef901082k
Published on Web 12/01/2009

Lubricity of Ethanol-Biodiesel-Diesel Fuel Blends

Magı́n Lapuerta,*,† Reyes Garcı́a-Contreras,† and John R. Agudelo‡
†
University of Castilla La-Mancha, Escuela T
ecnica Superior de Ingenieros Industriales, Avda, Camilo Jos
e Cela s/n,
13071 Ciudad Real, Spain and ‡University of Antioquia, Group of Efficient Management of Energy-GIMEL, Engineering
Faculty, Colombia

Received September 23, 2009. Revised Manuscript Received November 6, 2009

Blending bioethanol with diesel fuels is an alternative to incorporate a renewable fraction in vehicle fuels
which is receiving growing attention for its economic and environmental advantages. The generalized
practice in Europe of including some biodiesel content in the commercial diesel fuel has even enhanced the
interest of the ethanol blends as a consequence of the wider range of stability when biodiesel is added.
However, one of the main concerns is related to the loss of lubricity caused by the presence of ethanol. First,
this work reviews the previous experiences studying the effect of renewable components on the diesel fuel
lubricity. Second, an experimental work, carried out in a high frequency reciprocating rig at different
temperatures, is presented trying to distinguish the nonlinear contributions of ethanol, biodiesel, and
petroleum diesel fuel to the lubricity of three series of blends (one composed of binary ethanol-diesel blends
and two more composed by different ternary blends). The incorporation of ethanol did not result in
significant losses of lubricity until the ethanol concentration was close to 100%. Additionally, in this range,
increasing temperatures led to improved lubricities as a consequence of the ethanol evaporation from the
lubricating layer.

1. Introduction The addition of specific fatty acids or fatty acid esters has
proven to enhance diesel fuel lubricity.7 Moreover, the addi-
The continuous advances in diesel engine technology
tion of biodiesel improves the lubricity of low sulfur diesel fuel
and the more stringent emissions standards have led to
even more than pure fatty esters,8 meaning that different fatty
higher injection pressure and to modifications in some fuel
acid esters show synergistic effects when they are mixed.
properties. Among the latter ones, diesel fuels need to
Anastopoulos et al.7 found that the addition of biodiesel,
increase their lubricity to protect the fuel injection system
independently of the raw material, improves the lubricity
and other engine components. A higher boiling point and
more than other fatty acid derivatives (lauric diethylamide
aromatic, nitrogen, and sulfur contents appear to improve
and palmitic dibutylamide) when they were added to two
diesel fuel lubricity.1 Several studies have reported that the
different low sulfur diesel fuels. Additionally, they did not find
key agents are the highly polar compounds (especially
major differences between different biodiesel fuels in the
those containing oxygen and nitrogen) present in diesel
corrected wear scar. Other studies have found that there are
fuels which derive in forming a protective layer on the
no appreciable differences between fatty acids as lubricity
metal surface.2 However, many of these surface-active
enhancers, except with the hydroxylated ones whose OH
polar compounds are eliminated during the desulfuriza-
group makes them more effective as a wear protector.9-15
tion processes causing loss of lubricity.3,4 To meet the wear
Goodrum and Geller11 found that the effect of the oil feed-
scar limits established in diesel fuel standards (460 and 520
stock was minor when biodiesel fuels were added in concen-
μm in European and U.S. regulations, respectively (EN
trations around 5%. However, the addition of biodiesel
590:2009,5 ASTM D 9756)), a variety of lubricity additives
produced from hydroxilated oils, such as lesquerella and
can be used, which have a high affinity to metallic surfaces
castor oils, reduced the wear scar much more sharply (with
forming a thin protective metal-metal contact layer. This
lubricant film is formed by the adsorption of the polar
molecules of the additives on the metal surface, which is (7) Anastopoulos, G.; Lois, E.; Serdari, A.; Zanikos, F.; Stournas, S.;
negatively charged.4 Kalligeros, S. Energy Fuels 2001, 15, 106–112.
(8) Knothe, G. SAE technical paper 2005-01-3672, SAE International
(www.sae.org), 2005.
*To whom correspondence should be addressed. E-mail: Magin. (9) Kajdas, C.; Majzner, M. SAE technical paper 2001-01-1929, SAE
[email protected]. Telephone: þ(34) 926295431. Fax: þ(34) International (www.sae.org), 2001.
926295361. (10) Geller, D. P.; Goodrum, J. W. Fuel 2004, 83, 2351–2356.
(1) Wei, P.; Spikes, H. A. Wear 1986, 111, 217–235. (11) Goodrum, J.; Geller, D. Bioresour. Technol. 2005, 96 (7), 851–
(2) Safran, S. Statistical thermodynamics of surfaces, interfaces, and 855.
membranes; Westview press: Boulder, CO, 2003. (12) Knothe, G.; Steidley, K. R. Energy Fuels 2005, 19, 1192–1200.
(3) Nikanjam, M.; Henderson, P. T. SAE technical paper 932740, SAE (13) Ribeiro, N; Pinto, A.; Quintella, C.; da Rocha, G.; Teixeira, L.;
International (www.sae.org), 1993. Guarieiro, L.; do Carmo, M.; Veloso, M.; Rezende, M.; Serpa da Cruz,
(4) Barbour, R. H.; Rickeard, D. J.; Elliott, N. G. SAE technical paper R.; de Oliveira, A.; Torres, E.; Andrade, J. Energy Fuels 2007, 21, 2433–
2000-01-1918, SAE International (www.sae.org), 2000. 2445.
(5) EN-590:2009. Automotive fuels-Diesel-Requirements and test (14) Moser, B. R.; Cermak, S. C.; Isbell, T. A. Energy Fuels 2008, 22,
methods. 1349–1352.
(6) ASTM D 975 Standard specification for diesel fuel oils. (15) Knothe, G. Energy Fuels 2008, 22, 1358–1364.

r 2009 American Chemical Society 1374 pubs.acs.org/EF

Energy Fuels 2010, 24, 1374–1379 : DOI:10.1021/ef901082k Lapuerta et al.

less than 1% concentrations) than in the case of nonhydroxy- decrease of wear scar when a low dosage of a low acidic
lated oils (rapeseed and soybean). lubricity improver is used. Diesel No. 2 (340 ppm of sulfur)
Almost all studies agree that adding 1% to 2% (% v/v) blended with 10% ethanol and low acidic improver produced
of biodiesel improves fuel lubricity.7,11,16-20 Several studies a wear scar diameter of 377 μm according to ASTM D 607930
have found that there is no longer improvement in lubricity (60 °C) standard; this was a significant reduction with respect
when a certain concentration of biodiesel is added into the to 431 μm reported to the same blend without the additive.
blend with diesel fuel, this optimal concentration ranging Although this result is below the EN 590 standard require-
from 2%16,21,22 up to 15%.23 The same was reported when ment of 460 μm,5 this blend produced a failure in the injection
Fischer-Tropsch (FT) fuel was used as a base fuel. In this pump during the Bosch pump test.
case, the corrected wear scar diminished from 672 μm (pure In a recent work, Barab as et al.31 reported the corrected
FT) to 195 μm when 2% of biodiesels obtained from different wear scar diameters (EN ISO 12156-132 at 60 °C) for some
feedstock was added.21 Contrary to most of the literature, ternary diesel þ ethanol þ biodiesel blends in which the etha-
Bhatnagar et al.24 reported an almost linear decrease in wear nol was added in 5% and 10% (v/v) and biodiesel was added
scar as biodiesel concentration was increased in the blend from 5% to 25% (v/v) every 5%. They found that the lubricity
(tests were made with four Indian indigenous nonedible vege- of the ternary blends lower when the ethanol content is
table biodiesels in a concentration up to 100%). increased, while it is improved when biodiesel concentration
The impurities of biodiesel, such as monoglycerides and free is increased, although with unclear tendency. Nevertheless,
fatty acids, are among the main variables affecting biodiesel the corrected wear scar (WSD 1.4) of all the tested blends
lubricity.8,19,25 On the contrary, triglycerides almost have no remained below that of diesel fuel reference.
effect on lubricity due to its poor solubility with diesel fuel.25 The aim of this work is to evaluate the effect of adding
Ethyl esters have better lubricity than methyl esters, as ethanol over the lubricity of diesel fuel and biodiesel-diesel
reported by Kulkarni et al.26 Renewable diesel fuel obtained blends as base fuels, as well as to investigate the effect of
by pyrolysis of soybean oil (pyrodiesel) has proven to be a temperature on the lubricity of these blended fuels. This work
lubricity enhancer, especially when it is blended in low con- is complementary to other previous studies about blending
centrations (2-5%) with low or high sulfur diesel fuel. For stability of e-diesel33 and e-b-diesel blends34 and about engine
concentrations higher than 5%, biodiesel showed better performance and emissions with ethanol blends under labora-
performance than pyrodiesel.22 tory conditions34-36 and work conditions37 and must be conti-
A small number of lubricity tests have been published on nued with further long-term engine studies, such as those
ethanol-diesel fuel blends (e-diesel) or ethanol-biodiesel-diesel performed by Hansen et al.,38,39 to limit the range of usable
blends (e-b-diesel). However, it is necessary to establish a limit blends and to confirm their capability to partially substitute
of wear scar for these blends in order to ensure that fuel diesel fuels with minor failure risk.
injection system durability is not compromised. In general, the
addition of ethanol to diesel fuel lowers fuel viscosity and 2. Fuels and Experimental Schedule
lubricity,27-29 but as reported in this work, the lubricity of
The following fuels were used for preparing the blends to be
e-diesel and e-b-diesel is governed by the tribological proper-
tested:
ties of the fuel and the ethanol evaporation, showing that no
• Anhydrous ethanol (99.7%) provided by Abengoa
linear relationship between those properties can be found.
Bioenergy and made by fermentation of wheat, barley,
According to Corkwell et al.,29 the addition of 10% (v/v)
and corn, fulfilling the European norm EN 15376:
ethanol (7700 ppm of water content) in diesel fuel does not
2007.40
have a clear effect on lubricity, even if 2000 ppm of water was
• The diesel fuel is a typical low sulfur diesel fuel similar to
added to the final blend. They also reported a dramatic
those available in Spanish petrol stations and supplied
by Repsol. This fuel is supplied with lubricity enhancers
(16) Karonis, D.; Anastopoulos, G.; Lois, S.; Stournas, S.; Zannikos, so as to keep the wear scar far below the limit required
F.; Serdari, A. SAE technical paper 1999-01-1471, SAE International by norm EN 590:20095 (460 mm) for commercial
(www.sae.org), 1999. reasons.
(17) Van Herpen, J. H.; Soylu, S.; Tat, M. E.ASAE paper 996134, The
American Society of Agricultural Engineers, 1999.
(18) Kinast, J. A. Production of biodiesels from multiple feedstocks and
properties of biodiesels and biodiesel/diesel blends; NREL/SR-510-31460; (30) ASTM D 6079. Standard test method for evaluating lubricity of
National Renewable Energy Laboratory: Golden, CO, 2003. diesel fuels by the High-Frequency Reciprocating Rig (HFRR).
(19) Knothe, G. Fuel Process. Technol. 2005, 86, 1059–1070. (31) Barabas, I.; Todorut, A. SAE technical paper 2009-01-1810, SAE
(20) Schumacher, L.; Adams, B. T. Appl. Eng. Agric. 2008, 24 (5), 539– International (www.sae.org), 2009.
544. (32) EN ISO 12156-1:2006. Diesel fuel-Assessment of lubricity using
(21) Wadumesthrige, K.; Ara, M.; Salley, S. O.; Simon, K. Y. Energy the high-frequency reciprocating rig (HFRR)-Part 1: Test method.
Fuels 2009, 23, 2229–2234. (33) Lapuerta, M.; Armas, O.; Garcı́a-Contreras, R. Fuel 2007, 86,
(22) Suarez, P. A.; Moser, B. R.; Sharma, B. K.; Erhan, S. Z. Fuel 1351–1357.
2009, 88, 1143–1147. (34) Lapuerta, M.; Armas, O.; Garcı́a-Contreras, R. Energy Fuels
(23) Sulek, M. W.; Kulczycki, A.; Malysa, A. Wear 2010, 268, 104- 2009, 23, 4343–4354.
108. (35) Lapuerta, M.; Armas, O.; Herreros, J. M. Fuel 2008, 87, 25–31.
(24) Bhatangar, A. K.; Kaul, S.; Chhibber, V. K.; Gupta, A. K. (36) Armas, O.; Cardenas, M. D.; Mata, C. SAE technical paper 2007-
Energy Fuels 2006, 20, 1341–1344. 24-0131, SAE International (www.sae.org), 2007.
(25) Hu, J.; Du, Z.; Li, C.; Min, E. Fuel 2005, 84, 1601–1606. (37) Armas, O.; Lapuerta, M.; Mata, C.; Perez, D. Energy Fuels 2009,
(26) Kulkarni, M. G.; Dalai, A. K.; Bakhshi, N. N. Bioresource 23, 2989–2996.
technology 2007, 98, 2027–2033. (38) Hansen, A. C.; Zhang, Q.; Hornbaker, R. H. Engine fuel system
(27) Hansen, A. C.; Zhang, Q.; Lyne, P. W. L. Bioresour. Technol. durability with ethanol-diesel blends. Proc. of the 10th Biennial Bio-
2005, 96, 277–285. energy Conference, Boise, ID, 2002; pp 10.
(28) Li, D.g.; Zhen, H.; Xingcai, L.; Wu-gao, Z.; Jian-guang, Y. (39) Hansen, A. C.; Zhang, Q. ASAE paper 0306033, The American
Renewable energy 2005, 30, 967–976. Society of Agricultural Engineers, 2003.
(29) Corkwell, K.; Jackson, M. SAE technical paper 2002-01-2849, (40) EN 15376:2007. Automotive fuels-Ethanol as a blending com-
SAE International (www.sae.org), 2002. ponent for petrol-Requirements and test methods.
1375
Energy Fuels 2010, 24, 1374–1379 : DOI:10.1021/ef901082k Lapuerta et al.

Table 1. Fuel Properties Table 2. Methyl Ester Profile of Biodiesel, Made of Soybean and
Palm Oils
diesel soybean/palm
properties fuel oils biodiesel bioethanol methyl ester (% w/w)
density at 15 °C (kg/m )
3
834.9 878 792 myristic C14:0 0.275
viscosity at 40 °C (cSt) 2.72 4.33 1.13 palmitic C16:0 27.453
gross heating 45.54 39.83 28.05 palmitoleic C16:1 0.084
value (MJ/kg) stearic C18:0 5.469
lower heating 42.58 37.22 25.22 oleic C18:1 29.649
value (MJ/kg) linoleic C18:2 32.384
CFPP (°C) -19 7 linolenic C18:3 3.355
lubricity 315 257 842 araquic C20:0 0.507
(μm corrected gadoleic C20:1 0.231
wear scar at 60 °C) behenic C22:0 0.392
ester content (% w/w) 0 98.4 0 erucic C22:1 0.010
acid number 0.48 lignoceric C24:0 0.155
sulfur (ppm w/w) 33.9 0 nervonic C24:1 0.037
water (ppm w/w) 57 448.23 2024
C (% w/w) 86.13 76.74 52.14
H (% w/w) 13.87 12.16 13.13
O (% w/w) 0 11.09 34.73
molecular C15.18H29.13 C18.43H34.82O2 C2H6O
formula
iodine number 90.74
molecular 211.7 288.5 46.06
weight (g/mol)

• The biodiesel used in this study was produced from a

blend of soybean oil with palm oil (61.3% w and 38.7%
w, respectively), accomplishes the EN 14214:2008 stan-
dard,41 and was provided by Biotel. Soybean and palm
oils are nowadays two of the most widely used feed-
stocks for biodiesel production. Their blending propor-
tions are often varied throughout the year to fulfill the
optimal compromise between minimum prize and ac-
ceptable cold-flow and oxidation stability properties. Its
rheological behavior can be used as reference for other
biodiesel fuels.
The main characteristics of these pure fuels are shown in
Table 1, and the methyl ester profile of the biodiesel fuel is
presented in Table 2. Lubricity tests were made on three series
of samples, as shown in the ternary diagram of Figure 1. In the Figure 1. Ternary diagram indicating the tested blends.
first and second series, the base fuels were diesel fuel and B30
(previous blends with 30% v/v biodiesel and 70% v/v diesel 3. Experimental Equipment and Procedure
fuel), respectively, and the ethanol proportions in both The lubricity tests were carried out in a high frequency
e-diesel and e-b-diesel blends were 1%, 2.5%, 7.7%, 17%, reciprocating rig (HFRR) of PCS Instruments. These tests
50%, 75%, and 90% in volume. In the third series, the ethanol provide the wear scar in micrometers of a fuel, following either
content was fixed in 7.7% v/v and the biodiesel concentrations the European EN ISO 12156-1:2006 standard32 or the ASTM D
6079 standard.29 Although the European standard establishes 60
in the previous biodiesel-diesel blend were 1%, 2%, 10%,
°C as the fuel temperature (this specification is just required for
20%, and 30%. The corresponding compositions in volume diesel fuels), the ASTM standard also accepts testing at 25 °C,
and mass are listed in Table 3 for the three series. The selection indicating that this temperature is preferred when there may be
of B30 as a base fuel for the second series (and as a top concerns about loss of fuel because of its volatility or degradation.
concentration for the third) is justified because this biodiesel In this case, the high volatility of ethanol motivates one to
proportion has often been used in transportation fleets and compare tests at both temperatures. While the temperature of
sold in petrol stations in Europe. In fact, some European the engine metallic surfaces will certainly be closer to 60 °C, the
countries have approved standards for this kind of blend. The comparison between both temperature tests permits one to
selection of 7.7% ethanol is justified because this proportion separate the effect of the loss of ethanol by evaporation.
guarantees blending stability, even in the case of the use of Prior to each test, all the components of the HFRR having
contacted the tested fuels were subjected to a cleaning procedure
biodiesel-free diesel fuel as a base fuel, without surfactant or
composed of three 10 min immersions in an ultrasonic bath with
cosolvent additives in a range of reasonably expected extreme toluene (the first and the second) and with acetone (the third). All
ambient temperature and water contamination conditions tests were replicated twice, and if differences in the wear scar were
(-5 °C or 0.5% water m/m).33 higher than 20 μm, then they were repeated once more. During
Among all the tested blends, only the e-diesel blend with the tests, which lasted 75 min, the samples were shaken at a
50% ethanol v/v remained unstable at room temperature,34 frequency of 50 Hz. They remained open to the atmosphere,
thus requiring agitation by ultrasound before testing. which favored the ethanol losses by evaporation from both the
e-diesel and e-b-diesel samples. Afterward, the size of the wear
(41) EN 14214:2008. Automotive fuels-Fatty acid methyl esters scar was measured in an electronic microscope Leica DM IRM
(FAME) for diesel engines-Requirements and test methods. equipped with a 100 magnification lens. The mean diameter
1376
Energy Fuels 2010, 24, 1374–1379 : DOI:10.1021/ef901082k Lapuerta et al.

Table 3. Composition in Volume and Mass of the Tree Series of Tested Blends
1st series: e-diesel blends 2nd series: e-b-diesel blends (with B30) 3rd series: e-b-diesel blends (with E7.7)

ethanol/diesel ethanol/diesel ethanol/biodiesel/ ethanol/biodiesel/ ethanol/biodiesel/ ethanol/biodiesel/

(% v/v) (% m/m) diesel (% v/v) diesel (% m/m) diesel (% v/v) diesel (% m/m)
0/100 0/100 0/30/70 0/31.07/68.93 7.7/0/92.3 7.33/0/92.67
1/99 0.95/99.05 1/29.7/69.3 0.93/30.78/68.29 7.7/0.92/91.38 7.33/0.97/91.70
2.5/97.5 2.37/97.63 2.5/29.25/68.25 2.34/30.34/67.32 7.7/1.85/90.45 7.33/1.95/90.73
7.7/92.3 7.33/92.67 7.7/27.69/64.61 7.23/28.82/63.94 7.7/9.23/83.07 7.30/9.70/83.00
17/83 16.27/83.73 17/24.9/58.1 16.06/26.08/57.86 7.7/18.46/73.84 7.26/19.31/73.43
50/50 48.68/51.32 50/15/35 48.30/16.06/35.64 7.7/27.69/64.61 7.23/28.82/63.94
75/25 74.00/26.00 75/7.5/17.5 73.70/8.17/18.13
90/10 89.52/10.48 90/3/7 89.37/3.30/7.33
100/0 100/0 100/0/0 100/0/0

Table 4. Wear Scar and Corrected Wear Scar for E-Diesel Blends
(Series 1)
tests at 60 °C tests at 25 °C
(EN 12156-1) (ASTM D 6907)
% ethanol MWSD WS 1.4 MWSD
blend v/v (μm) (μm) (μm)
diesel 0 285 315 188.5
e-diesel 1 297 328 276
e-diesel 2.5 364.5 351 274
e-diesel 7.7 335 327 268
(E7.7)
e-diesel 17 277 304 316
Figure 2. Corrected wear scar for e-diesel blends at 25 and 60 °C. e-diesel 50 304.5 307 405.5
e-diesel 75 363 355 465.5
e-diesel 90 372.35 417 529.65
ethanol 100 854 842 632

Table 5. Wear Scar and Corrected Wear Scar for E-B-Diesel Blends
(Series 2)
tests at 60 °C tests at 25 °C
(EN 12156-1) (ASTM D 6907)

% ethanol MWSD WS 1.4 MWSD

blend v/v (μm) (μm) (μm)
b-diesel (B30) 0 257 257 226
e-b-diesel 1 255 258 293
e-b-diesel 2.5 278 253 295
Figure 3. Corrected wear scar for e-b-diesel blends (made by adding e-b-diesel 7.7 313 298 305
ethanol into B30 blends) at 25 and 60 °C. e-b-diesel 17 238 229 288
e-b-diesel 50 255 224 317
of the scar observed in the HFRR ball (MWSD) was obtained e-b-diesel 75 261 288 362
from the maximum and minimum ones as prescribed in the e-b-diesel 90 330 324 403
ethanol 100 854 842 632
norms. When the tests were made at 60 °C, as required by the
EN ISO 12156-1 norm, the resulting scar size was corrected to
be observed in the case of the biodiesel blend, although
normalize the vapor pressure to 1.4 kPa (WS 1.4).
in this case, the effect of temperature is lower (Figure 3).
As a consequence of the previous additivation of the
4. Results and Discussion
diesel fuel, the addition of 30% biodiesel did not provide
The first general observation is that the addition of ethanol a large benefit in lubricity, contrary to other studies.7
into both diesel fuel and B30 fuels decreases lubricity • Small concentrations of ethanol in both the e-diesel and
(increases the wear scar) in almost all cases, as a consequence the e-b-diesel blends provide significant increases in the
of the lower lubricity of ethanol. However, the increase in the wear scar (decreases in lubricity) with respect to the
size of the wear scar is not linear, as the concentration of ethanol-free fuels at low temperature (25 °C), although
ethanol is increased (see Figures 2 and 3 and Tables 4 and 5). such increases are minor at high temperature (60 °C).
This is probably a consequence of the combined effect of the This can be observed more in detail in Figure 4. In the
following properties of the blends: tribological properties, case of e-b-diesel blends, a certain mass loss of ethanol
volatility, blending stability, and of the different sensitivity by evaporation at high temperature leads to even smaller
of these properties to the fuel temperature. wear scar than at lower temperature, as a consequence of
A more detailed description of the lubricity of the tested the better tribological properties of the remaining bio-
samples at different temperatures can be explained as follows: diesel-rich fuel.
• At null ethanol concentration, the diesel fuel decreases its • After the initial peak of wear scar has been reached, as
lubricity as the temperature is increased, since the fuel the ethanol concentration in the blends continues in-
becomes less viscous, thus reducing the metallic contact creasing, the wear scar remains within a small variation
resistance (Figure 2). A similar decrease in lubricity can range or even slightly decreases. This effect can be
1377
Energy Fuels 2010, 24, 1374–1379 : DOI:10.1021/ef901082k Lapuerta et al.

Figure 4. Corrected wear scar for e-diesel (left) and e-b-diesel (right) blends at 25 and 60 °C for small ethanol concentrations.

explained because the expected loss of lubricity (due to

the presence of ethanol) is compensated by the increase
of the evaporation losses of ethanol from the lubricating
layer. In the case of e-diesel blends, this planar range is
extended from 3% to 50% ethanol at 60 °C and from
1% to 7% at 25 °C, while in the case of e-b-diesel blends,
this compensation range becomes even wider: from 0%
to 50% at 60 °C and from 1% to 17% at 25 °C (Figures 2
and 3). At high temperature, the mentioned compensa-
tion leads to a certain synergistic effect, since the lubri-
city of some of the tested blends become even better than
those of their components. This can be explained by the Figure 5. Corrected wear scar of e-b-diesel blends with 7.7% v/v
improved tribological properties of biodiesel with res- ethanol and 92.3% of a base fuel composed of different concentra-
pect to those of diesel fuel, together with the better misci- tions of biodiesel.
bility of ethanol and biodiesel with respect to that of
ethanol and diesel fuel. Both advantages of e-b-diesel Table 6. Wear Scar and Corrected Wear Scar for E-B-Diesel Blends
blends contribute to extend the range in which the poor (Series 3)
lubricity of ethanol is hidden. tests at 60 °C tests at 25 °C
• From this point on, further increases in ethanol content (EN 12156-1) (ASTM D 6907)
lead again to a certain loss of lubricity, this range being
% biodiesel v/v MWSD MWSD
extended up to values close to 100% ethanol. During this blend in the base fuel (μm) WS 1.4 (μm) (μm)
whole range (and during most of the previously men-
e-diesel 0 335 327 268
tioned plateau), the lubricity is improved for high tem- (E7.7)
perature, contrary to what occurs in the case of the pure e-b-diesel 1 288 290 243
components (0% and 100% ethanol), because the evapo- e-b-diesel 2 257 258 205
ration from the lubricating layer removes the component e-b-diesel 10 268 275 265
e-b-diesel 20 281 289 287
with poorest lubricity. The comparison between e-diesel e-b-diesel 30 313 298 305
and e-b-diesel blends shows that the latter ones maintain
better lubricities and lower increases of wear scar with Schedule) is not the optimal in terms of lubricity improve-
increasing ethanol content than the former ones, ment. In fact, lower biodiesel contents would have led to even
throughout the whole concentration range. better lubricities, as shown in Figure 5 and Table 6, where
• Finally, when the ethanol concentration becomes very corrected wear scar results for different biodiesel concentra-
close to 100%, the fuel turns back to behave as a pure tions with a fixed 7.7% v/v ethanol content are plotted. As
substance, therefore with decreasing lubricity for in- observed in this figure, the addition of small biodiesel con-
creasing temperature. In this extreme range, small con- centrations (with the optimal concentration being around
centrations of diesel or biodiesel fuels lead to sharp 2%) improve lubricity much more than adding 30% v/v. This
improvements in lubricity with respect to pure ethanol, result is in agreement with others shown in the literature.22,23
especially when the added fuel contains biodiesel. The However, there are more important reasons than lubricity
evaporation losses, although probably not negligible, do (which, as shown in this work, does not constitute any
not reach to affect lubricity in this case. problem, at least in the range where the blends could guaran-
tee stability and be compatible with current diesel engines) to
In conclusion, e-b-diesel blends lead to smaller wear scars
select the blending proportions, such as the need to keep
and to flatter lubricity curves (less sensitive to ethanol con-
increasing the renewable share of automotive fuels, in line
centration) than e-diesel blends. In both cases, a wide range of
with the current European policy promoting reductions of
intermedium ethanol content (although even wider in the case
greenhouse emissions from vehicles.
of e-b-diesel blends) can be found where the presence of
ethanol reverts the usual trend of lubricity with temperature,
5. Conclusion
leading to improved lubricities when the engine operates
under hot conditions. The addition of ethanol in the currently used diesel fuels
It must be remarked that the concentration selected for (nowadays carrying different contents of biodiesel in Europe)
biodiesel (B30, as justified in Fuels and Experimental is an effective way to incorporate an additional renewable
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Energy Fuels 2010, 24, 1374–1379 : DOI:10.1021/ef901082k Lapuerta et al.

fraction in the vehicle-engine fuels. In the tested blending ethanol. In comparison with e-diesel blends, e-b-diesel blends
ranges, based on the addition of different ethanol contents led to smaller wear scars and to flatter lubricity curves (less
into both a commercial diesel fuel and a B30 biodiesel-diesel sensitive to the ethanol concentration). The results presented
blend and on the addition of 7.7% ethanol v/v into different prove that blending ethanol in biodiesel-diesel blends nowa-
biodiesel-diesel blends, the progressive incorporation of etha- days, within the previously studied range of stability, could
nol did not result in significant losses of lubricity (increases in guarantee the engine preservation to friction wear even better
wear scar) until the ethanol concentration was close to 100%. than in the past, when the presence of biodiesel in the
At 60 °C a certain synergistic effect was observed, since the commercial diesel fuel was unusual.
lubricity of some of the tested blends with intermedium
ethanol content became even better than those of their
Acknowledgment. The authors gratefully acknowledge the
components. Additionally, in this range of ethanol concentra- financial support provided by the Spanish CDTI (research
tion, the effect of temperature was opposite to the usual, this project CENIT 2007-1031, IþDEA). The companies Abengoa
meaning improved lubricities under hot conditions. Both Greencell, Repsol, and Biotel Combustibles Ecol
ogicos S.L. are
effects can be explained because the ethanol evapora- also acknowledged for the supply of the ethanol, diesel, and
tion losses compensate the poorer tribological properties of biodiesel fuels, respectively.

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