Fuel 86 (2007) 965–971

www.fuelfirst.com

Nitration of biodiesel of waste oil: Nitrated biodiesel

as a cetane number enhancer
a,*
Laureano Canoira , Ramón Alcántara a, Susana Torcal a, Nikolaos Tsiouvaras a,b
,
Evripidis Lois b, Dimitrios M. Korres b
a
Department of Chemical Engineering and Fuels, School of Mines, Technical University of Madrid, Rı́os Rosas 21, 28003 Madrid, Spain
b
School of Chemical Engineering, National Technical University of Athens, Iroon Polytechniou 9, Athens 15780, Greece

Received 13 July 2006; received in revised form 26 October 2006; accepted 31 October 2006
Available online 27 November 2006

Abstract

Biodiesel has been produced by transesterification of waste frying oil with methanol catalysed by sodium methoxide. The unsaturated
fatty acid methyl esters of the biodiesel produced have been nitrated by two alternative nitration methods, showing an incorporation of
nitrogen between 3.43 and 5.10 wt.%, in the chemical form of nitro, nitrate and acetoxy functional groups. A detailed gas chromatog-
raphy–mass spectrometry analysis has been carried out on the nitrated biodiesel samples in order to identify the nitration products of this
complex mixture. The nitrated biodiesel has been added to a base diesel fuel in a 1000 mg L1 concentration resulting in an increase of
the cetane number of the fuel by more than five points, from 54.7 to 60.5.
 2006 Elsevier Ltd. All rights reserved.

Keywords: Biodiesel; Nitration; Cetane number

1. Introduction In this paper, we report the nitration of biodiesel from

Biodiesel is defined as ‘‘a fuel comprised of mono alkyl
esters of long chain fatty acids derived from vegetable oils
or animal fats’’ [1]. Transesterification (also called alcohol-
ysis) of triglycerides for biodiesel manufacture has been
extensively studied in the past few years [2,3]. The Euro-
pean Union has issued Directive 2003/30/EC, which man-
dates the use of biofuels in a percentage ranging from 2% in
2005 to 5.75% in 2010 (calculated on the basis of energy
content), for all transportation fuels marketed within the
member states, and it is expected that a significant portion
of this amount will be biodiesel. On the other hand, octyl
nitrate (prepared by esterification of 2-ethyl-1-hexanol with
nitric acid) is an additive currently added (from 10 to
1000 mg L1) to conventional diesel fuel to enhance its
cetane number and its combustion properties.
*
Corresponding author. Tel.: +34 1 336 6949; fax: +34 1 336 6948.
E-mail addresses: laucan@qyc.upm.es, laureano.canoira.lopez@
upm.es (L. Canoira).
waste frying oil to produce additives that could substitute
the octyl nitrate of petrochemical origin. Biodiesel was
obtained by transesterification of waste frying oil with
methanol (molar ratio methanol:oil = 7.5:1), at 60 C in a
stirred tank reactor (600 rpm), catalyzed by sodium meth-
oxide (1 wt.% of the oil) [4,5]. The conversion of the oil
was quantitative after 60 min, and the biodiesel showed a
good cetane number without any additional purification
steps, and could be nitrated directly. Nitration of biodiesel
affects the double bonds of the unsaturated fatty acid
methyl esters FAME (oleate, linoleate, linolenate) and
was carried out by two alternative methods: (a) reaction
of the biodiesel with 70% nitric acid and acetic anhydride
(acetyl nitrate) [6] and (b) reaction of biodiesel with fuming
nitric acid, glacial acetic acid and sodium nitrite [7], in
order to compare the results of both methods. The nitrated
biodiesel was blended with base diesel fuel of fossil origin
in a 1000 mg L1 amount and these fuels have been tested
for their cetane number, showing an improvement of this
property with respect to the base fuel.

0016-2361/$ - see front matter  2006 Elsevier Ltd. All rights reserved.
doi:10.1016/j.fuel.2006.10.022
966 L. Canoira et al. / Fuel 86 (2007) 965–971

2. Experimental heating jacket. The temperature was measured by a type

Methanol, sodium, 37 wt.% hydrochloric acid and anhy-
drous sodium sulphate are of commercial purity and were
used without any additional purification step. The waste
frying oil was originally a ca. 50% vol. mixture of olive
and sunflower oils, supplied by the catering service of the
School of Mines.
2.1. Analysis of the raw oils
The waste oils were analysed in order to ascertain their
acidity index, density and fatty acids composition, neces-
sary data to carry out the transesterification reaction. The
acidity index of the raw oils was analysed following a well
established experimental titration procedure [4], and it is
summarised in Table 1; each titration was repeated four
times and the standard deviation is 0.04. The density of
the raw oils at 15 C was determined following the ASTM
standard D1298, and it is also summarised in Table 1.
The fatty acids composition of the waste oils was deter-
mined by a well established gas chromatography (GC) pro-
cedure which has been previously described [8], and it is
summarised in Table 2. The mean molecular weight (Mw)
of the waste oils was calculated averaging the individual
molecular weights (Mwi) of each constituent triglyceride,
according to the fatty acids analysis.
2.2. Transesterification of the waste oils with methanol
2.2.1. Reactor
The reactor used in the transesterification experiments
was a 1 L cylindrical glass reactor with a bottom outlet,
equipped with a glass anchor-shaped stirrer powered by a
Heidolph RZR 2050 motor drive, and surrounded by a
Table 1
Acidity index and density of waste oils
Sample Acidity index (%) Density (g cm3)
Waste oil 1 0.25 0.912
Waste oil 2 0.60 0.890
Waste oil 3 0.57 0.916
K thermocouple connected to a Proportional Integral
Derivative (PID) temperature controller device TC-10 from
the Instituto de Catálisis y Petroleoquı́mica (Madrid) that
regulated the electrical power of the heating jacket. The
reactor was connected to a double jacket water condenser
to avoid the evaporation of methanol.
2.2.2. General procedure
In the reactor described above, 873 mL (702 g, 0.80 mol)
of waste frying oil and 244 mL (190 g, 6 mol) of methanol
were placed. The temperature was raised to 60 C and the
mixture was stirred at 600 rpm. When this temperature
was reached, sodium methoxide (7 g, 0.13 mol, 1 wt.% of
oil, prepared recently from 3 g of sodium metal and
40 mL of anhydrous methanol) was added; the temperature
increased by two to three degrees, decreasing later to 60 C
by the action of the PID controller. Samples of 10 mL (8 g)
were taken from the reaction mixture at regular intervals,
typically 30 min, neutralised, and analysed by gas chroma-
tography (GC, see below). When the conversion of the oil
was quantitative, as determined by the GC, the heating was
switched off. The mixture was then allowed to cool in the
reactor, appearing as two distinct phases after switching
off the stirrer. These two phases were decanted using the
bottom outlet of the reactor. The excess methanol in both
phases was evaporated at vacuum, and 580 g of biodiesel,
17 g of glycerine–water phase (G-phase) and 200 mL of
methanol were recovered. The biodiesel phase was neutra-
lised in a decanting funnel with two washings of aqueous
solution of hydrochloric acid 37%, diluted with water in
a ratio of 1:1, and afterwards it was washed with a satu-
rated aqueous solution of sodium chloride and several
times with water. The biodiesel was then chemically dried
with anhydrous sodium sulfate and filtered. The G-phase
was also neutralised with diluted hydrochloric acid, and
it was composed of glycerine, water and sodium chloride.
Biodiesel, used without further purification, was a clear,
light yellow liquid. If the sodium methoxide catalyst is
going to be reused [4], the neutralization of the G-phase
is omitted, the separation procedure otherwise being the
same as described above.

2.3. Analysis of biodiesel and conversion

Table 2
Fatty acids composition (wt.%) of waste oil The biodiesel obtained was analysed by GC using a
previously described procedure [8], and the FAME compo-
Fatty acid Waste oil
sition of biodiesel matches perfectly the fatty acids compo-
Sample 1 Sample 2 Sample 3
sition of the parent waste oils as summarised in Table 1.
Palmitic (C16:0) 10.40 12.10 12.8 The FAME content of the samples obtained after the Gen-
Stearic (C18:0) ND ND ND
eral Procedure described above was always higher than
Oleic (C18:1) 72.00 33.70 53.0
Linoleic (C18:2) 16.00 54.20 33.0 97 wt.%, and the conversion was calculated after the fol-
Linolenic (C18:3) 1.70 ND 1.0 lowing equation:
Arachidic (C20:0) ND ND ND mbiodiesel
Mw 877.4 871.2 871 M wbiodiesel
Biodieselcontent ð%Þ
Conversionð%Þ ¼ ð1Þ
ND indicates that composition was not determined. 3 Mmwoil
oil
 L. Canoira et al. / Fuel 86 (2007) 965–971 967

Table 3 Table 4
Elemental composition of biodiesel and nitrated biodiesel Properties of the biodiesel of waste oil
Waste oils Biodiesel Nitration products of biodiesel Analysis Biodiesel Max Min Units Standard
70% HNO3 Fuming HNO3 Free glycerol 0.03 0.02 – % mass EN 14105
Monoglycerides 1.29 0.80 – % mass EN 14105
%C %H %C %H %N %C %H %N
Diglycerides 0.17 0.20 – % mass EN 14105
Waste oil 1 78.63 12.18 60.82 9.39 5.10 69.76 11.18 3.82 Triglycerides <0.05 0.20 – % mass EN 14105
(batch 1) Total glycerol 0.36 0.25 – % mass EN 14105
Waste oil 1 78.63 12.18 62.28 9.71 4.89 68.92 10.90 3.43 Water and <0.05 0.05 – % vol ASTM D 1796
(batch 2) sediments
Waste oil 2 78.06 12.10 60.31 9.18 4.48 ND ND ND Density at 15 C 880 900 860 kg m3 ASTM D 4052
Methyl oleate 76.98 12.27 62.54 9.77 4.88 67.66 11.00 3.69 Sulfated ash <0.005 0.02 – % mass ASTM D 482
ND indicates that composition was not determined. content
Copper strip 1a Class 1 Class ASTM D 130
corrosion
Total 24.0 – – mg kg1 EN 12662
where m is the mass and Mw the mean molecular weight. The contamination
conversion was always very high, ranging from 93% to 98%. Flash point 141.9 – 120 C ASTM D 92
Cloud point 5 – – C ASTM D 2500
The elemental composition of biodiesel samples was
Cold filter 5.0 – – C EN 116
determined in a LECO CHN-600 elemental analyser, and plugging point
it is summarized in Table 3. Kinematic viscosity 5.44 5.00 3.50 mm2 s1 ASTM D 445
at 40 C
2.4. Determination of the physicochemical properties of the Higher calorific 40.79 – – kJ g1 ASTM D240
value
biodiesel
Cetane number 57.9 – 51 – ASTM D 613

Some physicochemical properties of the biodiesel pre-

pared according to this recipe were determined following
the Biodiesel European Standard Specification EN14214.
The ASTM, EN or ISO testing methods used as well as
the values obtained for the samples and the reference values
for biodiesel after EN 14214 are summarized in Table 4.
2.5. Nitration of biodiesel
washed with water several times, until neutral pH in the
washing waters, dried over anhydrous sodium sulfate and
concentrated under vacuum. The resulting nitration product
of biodiesel was quantitatively recovered as a clear,
orange yellow liquid that could be used without further
purification.

2.5.1. Reactor
The experiments of nitration of biodiesel were carried
out in a 1 L three-necked cylindrical glass tank reactor,
equipped with glass jacket with a bottom inlet and an
upper outlet for circulation of the refrigerated water. The
reactor has a stirrer powered by a Heidolph RZR 2050
motor drive, a type K thermocouple, a double jacket water
condenser and a 500 mL liquids addition funnel. The solid
sodium nitrite in the nitration (b) procedure was added by
means of a solids microdosifier device model GMD-60/2
from Gericke.
2.5.2. General procedure with acetyl nitrate [6]
The preparation of acetyl nitrate was carried out as fol-
lows: in the 1 L three-necked cylindrical glass tank reactor,
cooled at 15 C with the refrigeration water, 70 wt.% nitric
acid (149.5 g, 2.37 mol, 105.6 mL) was added dropwise to
acetic anhydride (378 g, 3.70 mol, 350 mL) with stirring.
The reaction temperature was controlled between 20 and
25 C by the slow addition of the nitric acid. Biodiesel of
used frying oil (70.0 g, 0.258 mol, 79.5 mL) was added to
the acetyl nitrate solution previously prepared, and the reac-
tion mixture was stirred at 25 C for 1 h. Afterwards, the
reaction mixture was poured over ice-water (1.5 L), and
extracted with diethyl ether. The ethereal extract was
2.5.3. General procedure with fuming nitric acid [7]
In the 1 L three-necked cylindrical glass tank reactor,
fuming nitric acid (19.0 g, 0.303 mol, 12.5 ml) was added
drop wise very carefully over glacial acetic acid (451.2 g,
7.5 mol, 430 mL) at room temperature. Later biodiesel of
waste frying oil (70 g, 0.258 mol, 79.5 mL) and solid
sodium nitrite (35.6 g, 0.515 mol) were added simulta-
neously at room temperature. When the addition has fin-
ished (3–4 h), the reaction mixture was poured over cool
water and extracted with diethyl ether. The ethereal phase
was washed with 10 wt.% sodium bicarbonate several times
and later with water (until neutral pH in the washing
waters), dried over anhydrous sodium sulfate and concen-
trated under vacuum. The resulting nitration product of
biodiesel was quantitatively recovered as a clear, orange
yellow liquid that darkened with the time, although a single
pass through a chromatographic column charged with a
small amount of silicagel restored its original appearance.
2.6. Analysis of the nitration products of biodiesel
2.6.1. Elemental analysis
The elemental composition of the nitration products of
biodiesel samples was determined in a LECO CHN-600
elemental analyser, and it is summarized in Table 3.
968 L. Canoira et al. / Fuel 86 (2007) 965–971

2.6.2. Infrared analysis Table 7

The infrared absorption spectra of the nitration prod- GC–MS analysis of biodiesel of waste frying oil nitrated with acetyl nitrate
ucts of biodiesel were registered in a dispersive infrared RT Area M+ Base Compound
spectrophotometer Foxboro, model Miran 980, with a sin- (min) (%) (Dalton) peak
gle beam. The spectra were registered as thin films between 12.94 0.6 341 74 Methyl-8-nitro oleate 1,
sodium chloride disks, scanning in 3 min from 4000 to methyl-11-nitrooleate 2
14.87 1.1 214 74 Methyl laurate
690 cm1. The characteristic frequencies and transmit- 18.82 4.4 242 74 Methyl miristate
tances (%) for the samples nitrated by both experimental 18.86 Traces 404 74 Methyl-10-nitrate-9-
methods are summarized in Tables 5 and 6. nitrostearate 3, Methyl-9-nitrate
10-nitrostearate 4
22.41 8.8 270 74 Methyl palmitate
23.58 0.8 284 74 Methyl 14-methylpalmitate
2.6.3. Gas chromatography–mass spectrometry analysis
25.66 2.8 298 74 Methyl stearate
(GC–MS) 29.03 5.3 327 55 8-Nitrooleic acid 5,
The GC–MS analysis of the nitration products of bio- 11-nitrooleic acid 6
diesel were carried out in a Hewlett-Packard GC 6890, 30.24–30.80 14.0 341 55 Isomeric nitrates of linoleic acid
equipped with a capillary column HP-5 (25 m · 25 lm · 31.37 5.2 387 55 10-Acetoxy-9-nitrostearic acid
7, 9-acetoxy-10-nitrostearic acid
0.20 lm), coupled with a mass selective detector Hewlett-
8
Packard MSD 5973 with a ionization chamber set at 33.04–33.38 11.3 370 55 Nitroso nitrate linoleic acid
70 eV. Samples were dissolved in dichloromethane and (isomers mixture)
2 lL were automatically injected in splitless mode. The 33.53 7.0 368 55 Nitroso nitro linolenic acid
GC oven temperature was initially set at 60 C (1 min), (isomers mixture)

Table 5
Transmittance (%) of the biodiesel samples nitrated with acetyl nitrate Table 8
(70 wt.% HNO3 + acetic anhydride) in the characteristic frequencies GC–MS analysis of biodiesel of waste frying oil nitrated with fuming nitric
Biodiesel Frequency (cm1) acid

3400 1735–50 1625–60 1545–56 1355–90 RT Area M+ Base peak Compound

(OH) (C@O) (ONO2) (NO2)c (NO2)d (min) (%) (Dalton) (Dalton)

Waste oil 71 20.4 49.4 29.6 37.2 12.98 1.1 341 74 Methyl-9-nitrooleate 9; Methyl-
1a 10-nitrooleate 10
Waste oil 73 26.0 47.8 31.7 44.5 22.55 11.8 270 74 Methyl palmitate
1b 25.67 50.9 296 74 Methyl oleate
Waste oil 70 24.7 45.3 32.0 42.4 25.85 6.1 298 74 Methyl stearate
2 28.70 0.9 326 74 Methyl arachnate
Methyl 70 39.1 66.9 47.4 56.7 29.03 0.7 327 55 9-Nitrooleic acid 11, 10-nitrooleic
oleate acid 12
31.51 8.9 387 55 10-Acetoxy-9-nitrostearic acid 7,
a
Batch 1. 9-acetoxy-10-nitrostearic acid 8
b
Batch 2.
c
Assymetric NO2 stretching.
d
Symmetric NO2 stretching.
and increased at a rate of 6 C/min to 300 C where it
was kept for 10 min. Helium was used as the carrier gas
Table 6 at a constant column head pressure of 4.0 psi. Sample of
Transmittance (%) of the biodiesel samples nitrated with fuming nitric acid biodiesel nitrated after each one of the two experimental
in the characteristic frequencies procedures described above were analysed by GC–MS,
Biodiesel Frequency (cm1) and the results are summarized in Tables 7 and 8.
3400 1735–50 1625–60 1545–56 1355–90
(OH) (C@O) (ONO2) (NO2)c (NO2)d 2.7. Cetane number and total acid number (TAN)
Waste oil 79.0 23.9 68.9 41.2 45.0
1a The cetane number was calculated from the time in ms
Waste oil 76.0 25.1 69.0 37.6 48.0
needed for the rise of the pressure by 2 mbar in the fuel
1b
Methyl 74.0 23.2 69.0 35.6 40.9 ignition chamber after the ASTM D 613 standard. The
oleate equipment used was from Fuel Tech. Co. and for the cool-
a
Batch 1. ing circulation was used the Circulating System 253 from
b
Batch 2. the Precision Co. The fossil diesel was mixed with the
c
Assymetric NO2 stretching. nitrated biodiesel homogenising the solutions with strong
stirring, preparing blends containing 1000 mg L1 of
d
Symmetric NO2 stretching.

Table 9
Cetane and total acid numbers TAN of the samples of biodiesel
Sample Cetane number
ASTM D 613
Fossil diesel 54.7
a
Fossil diesel + biodiesel 60.5
nitrated with fuming HNO3
a
Fossil diesel + biodiesel 60.1
nitrated with 70 wt.% HNO3
a
The nitrated biodiesel was added in a concentration of 1000 mg L1.
nitrated biodiesel. This percentage of biodiesel in the final
blend was chosen in order to prepare samples that are sim-
ilar to the mixtures of fossil diesel and octyl nitrate. The
measured cetane numbers of these mixtures, and of fossil
diesel as reference, are summarized in Table 9. The total
acid number (TAN) of these same fuel samples was deter-
mined in the equipment Metrohm 809 Titrando after the
ASTM D 664 standard, and the values are summarized
in Table 9.
3. Results and discussion
Fig. 1 shows the conversion of the transesterification
reaction of two different samples of waste frying oil versus
time. For these waste oils, the conversion is quantitative
after one hour approximately. The main physico-chemical
properties of the biodiesel of waste oil are summarized in
Table 4, along with the biodiesel specifications required
by the EN 14214 standard [1]. From this Table 4, it can
be seen that this biodiesel meet most of these specifications.
The elemental composition of biodiesel and its nitration
products, showing the incorporation of nitrogen, is sum-
marized in Table 3: as it can be seen, the nitration with ace-
tyl nitrate (method 2.5.2) produces a higher incorporation
of nitrogen (4.48–5.10 wt.%) in less aggressive reaction con-
ditions than the nitration with fuming nitric acid (method
2.5.3) (3.43–3.82 wt.%). Methyl oleate was nitrated by both
methods in order to compare the results of the nitration of
the waste oils with that of a pure compound, showing very
similar values of nitrogen incorporation.
waste oil 1
100
conversion (%)
80
60
40
20
0 0
0 50
time (min)
used oil 1-1
Fig. 1. Conversion versus time in the transesterification reaction of waste oils.
L. Canoira et al. / Fuel 86 (2007) 965–971 969
The nitrogen functional groups incorporated to the
unsaturated fatty methyl esters of the biodiesel have been
TAN ASTM D analyzed by infrared spectroscopy and the results are
664 mg KOH g1 shown in Tables 5 and 6, that summarize the main frequen-
0.600 cies (cm1) and the transmittances (%). Apart from the
0.113 characteristic ester frequency at 1735–1750 cm1 that obvi-
0.133
ously appear in all spectra, the asymmetric NO2 stretching
at 1545–1556 cm1 and the symmetric NO2 stretching at
1355–1390 cm1 are also common to all spectra showing
the incorporation of the nitro NO2 group in all the
samples. The characteristic stretching frequencies of the
nitrate group at 1625–1660 cm1 are also common to all
spectra, showing also the presence of these functional
groups. Also, broad bands of carboxylic acid groups
appear around 3400 cm1 in all infrared spectra due to par-
tial hydrolysis of FAME in the strongly acidic reaction
mediums. However, the infrared spectroscopy cannot iden-
tify the main individual compounds present in the samples,
so a detailed GC–MS analysis was carried out with this
aim.
The GC–MS analysis showed a complex mixture of
compounds for both nitrated samples of biodiesel, from
which only some major components have been identified.
In the biodiesel sample nitrated with acetyl nitrate
(Fig. 2), besides the saturated methyl esters that did not
suffer nitration (methyl laurate 1.1%, methyl miristate
4.4%, methyl palmitate 8.8%, methyl 14-methyl palmitate
0.8% and methyl stearate 2.8%), unreacted methyl oleate
was not found, meaning that it was completely transformed
in these mild nitration conditions. A small amount of two
isomers of methyl nitrooleate (methyl 8-nitrooleate 1 and
methyl 11-nitrooleate 2, RT = 12.94 min, 0.6%) was found
along with traces of nitro nitrate stearate (methyl 10-
nitrate-9-nitrostearate 3 and methyl 9-nitrate-10-nitrostea-
rate 4, RT = 18.86 min). The remaining nitrated products
have suffered hydrolysis in this acidic reaction medium,
and they appear in bigger amounts as nitrated fatty acids:
8-nitrooleic acid 5 and 11-nitrooleic acid 6 (RT =
29.03 min, 5.3%) and 10-acetoxy-9-nitrostearic acid 7 and
9-acetoxy-10-nitrostearic acid 8 (RT = 31.37 min, 5.2%).
A group of peaks with retention times between 30.24 and
waste oil 3
100
conversion (%)
80
60
40
20
100 150 200 0 50 100 150 200
time (min)
used oil 1-2 used oil 3-1 used oil 3-2
970 L. Canoira et al. / Fuel 86 (2007) 965–971

Abundance TIC: OLEAT.D

22.41
2.4e+07
2.2e+07
2e+07
1.8e+07
1.6e+07
1.4e+07 33.53
18.82
1.2e+07 29.03
1e+07 33.23
25.66
8000000
6000000
4000000
2000000
0
Time--> 10.00 15.00 20.00 25.00 30.00 35.00 40.00 45.00

Fig. 2. Nitration of biodiesel with acetyl nitrate. GC–MS analysis.

30.80 min correspond to isomeric nitrates of linoleic acid
(M+ 341) in a very significant amount (14.0%), and another
group of signals between 33.04 and 33.38 min have been
identified as isomers of nitrate nitroso linoleic acid (M+
370) in a great amount (11.3%). Finally, an important peak
(7.0%) appearing at 33.53 min has been identified as a mix-
ture of nitroso nitrate derivatives of linolenic acid (M+
368). This hydrolysis process is very clear in the mass spec-
tra since the methyl esters suffer a retro Diels–Alder reac-
tion giving m/z 74 ðC3 H6 Oþ2 Þ as their base peak or a very
intense peak, whereas the base peak of the nitrated fatty
acids is always m/z 55 (C4 Hþ7 , olefinic fragment).
In the biodiesel sample nitrated with fuming nitric acid
(Fig. 3), besides the saturated methyl esters that results
unaffected by the nitration (methyl palmitate 11.8%,
methyl stearate 6.1% and methyl arachnate 0.9%) and the
unreacted methyl oleate 50.9%, only two nitrated methyl
esters have been identified, two isomers of nitro oleate
(methyl 9-nitrooleate 9 and methyl 10-nitrooleate 10,
RT = 12.98 min, in minor amounts 1.1%). The remaining
nitrated products have suffered hydrolysis in the strong
acidic reaction medium, and they appear as nitrated fatty
acids: 9-nitrooleic acid 11 and 10-nitrooleic acid 12
(RT = 29.03 min, 0.7%) and 9-acetoxy-10-nitrostearic 8
acid and 10-acetoxy-9-nitro stearic acid 7 (RT = 31.51 min,
8.9%). As it has been pointed out above, all nitrated methyl
esters have base peak m/z 74 whereas nitrated fatty acids
have base peak at m/z 55.
From these detailed GC–MS analyses, two different
nitration schemes of the FAME composing the biodiesel
could be drawn, illustrated for methyl oleate (Fig. 4). It
should be highlighted at this point that fuming nitric acid
nitrates into the double bond [7], but acetyl nitrate nitrates
into the allylic positions of the double bond [6].

TIC:BIO-1.D
Abundance
25.67
1.3e+08
1.2e+08
1.1e+08
1e+08
9e+07
8e+07
22.55
7e+07 25.85
6e+07 31.51
5e+07
4e+07
3e+07
2e+07 12.98 28.70
1e+07
0
Time--> 10.00 15.00 20.00 25.00 30.00 35.00 40.00 45.00

Fig. 3. Nitration of biodiesel with fuming nitric acid. GC–MS analysis.

 L. Canoira et al. / Fuel 86 (2007) 965–971
Fig. 4. Nitration products of methyl oleate with acetyl nitrate (70 wt.% nitric acid + acetic anhydride) (top) and with fuming nitric acid (bottom).
The hydrolysis of the FAME to free fatty acids as a con-
sequence of the strong acid medium that implies the nitra-
tion is worrying since the total acid number (TAN) of the
fuels with the nitrated biodiesel added could increase, leav-
ing them out of specifications. For this reason, the TAN of
the blends of base diesel and nitrated biodiesel (Table 9)
have been measured, and it does not affect the quality of
the blends that show lower TAN values than the base
diesel.
The cetane number of the samples of fossil diesel treated
with these new additives was increased by more than five
points (from 54.7 to 60.1), which is a very good preliminary
result on the performance of this nitrated biodiesel. In this
case, there was no appreciable difference between the bio-
diesel nitrated by the two methods exposed in this paper.
In conclusion, this paper proposes a new and feasible
method to incorporate small amounts of renewable addi-
tives as improvers of the cetane number of fossil diesel to
comply, at least in part, with the European directive on
biofuels.
Acknowledgements
We are greatly indebted to the Laboratory of Petroleum
Products of the Gomez-Pardo Foundation for the physico-
chemical analyses of biodiesel, and also to the Laboratory
971
of Molecular Stratigraphy of the School of Mines for the
GC–MS analyses.
Supplementary data
Supplementary data associated with this article can be
found, in the online version, at doi:10.1016/j.fuel.2006.10.
022.
References
[1] European Committee for Standarisation (DIN). Automotive fuels.
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