Journal of the UniversityT.

ofVasileva,
Chemical K.Technology
Stanulov, S.and
Nenkova
Metallurgy, 43, 1, 2008, 65-68

PHENOLIC ANTIOXIDANTS FOR FUELS

T. Vasileva, K. Stanulov, S. Nenkova

University of Chemical Technology and Metallurgy Received 05 May 2007

8 Kl. Ohridski, 1756 Sofia, Bulgaria Accepted 12 December 2007
E-mail: nusha_v@uctm.edu

ABSTRACT

The oxidation stability of gasoline and lubricating materials is one of their most important service properties.
Additives are used for improvement of chemical stability, the phenolic antioxidants being one of the most effective. In this
paper, phenolic products, produced by alkaline destruction of lignin – waste product from wood hydrolysis are used as
such compounds. The phenolic compounds are proven to be a mixture of 2-methoxyphenol; 2.6-dimethoxyphenol; 3-
hydroxy-4-methoxybenzaldehyde (vanillin) and 1-(4-hydroxy-3-methoxyphenyl) ethanone. The anti-oxidation effect of
this mixture is characterized by liquid paraffin oxidation kinetics in a laboratory oxygen absorption manometric installa-
tion. Comparative tests are performed with the widely used in practice inhibitor ionol.
Keywords: lignin, phenolic compounds, antioxidant, fuels.

INTRODUCTION of oxygen and decompose through auto-oxidation [6]. It

Modern chemical industry is based on natural
energy sources - coal, petroleum and natural gas, which
have been formed by decomposition of vegetable mate-
rials in the course of millions of years. As their reserves
are limited and gradually exhausted, one of the main
tasks of the industry is the complete, versatile and most
effective utilization of the raw materials. This imposes
reorientation from fossil fuels to renewable sources of
energy. Such an alternative source is the easily acces-
sible and restorable biomass, particularly lignin – a sec-
ondary product of wood chemical processing.
It is well known that by thermo-mechanical treat-
ment in water-alkaline environment the lignin is de-
structed and low-molecular phenolic compounds are
produced [1-5]. These compounds can eventually be used
as additives to the fuels produced of petroleum.
Petroleum products as well as those from the
petrochemical processing are unstable in the presence
is proved that the liquid phase oxidation of hydrocar-
bons goes through a chain-radical mechanism with chain
development and ramification. The antioxidants used
for improvement of the fuel chemical stability are in-
hibitors of hydrocarbons radical-chain oxidation. Most
widely used in practice are the phenols 2 and 6 substi-
tuted by tertiary alkyl groups (i.e. ionol -2,6-di-tert-
butyl-4-methylphenol). They react very fast with the
peroxide radicals and in this way stop the chain reac-
tion. The phenol anti-oxidation action depends on the
number and nature of the substitutes’ [7, 8].
In a lipid oxidation study it has been found that
the anti-oxidation effect of the phenolic compounds iso-
lated from vegetables decreases in the order: 4-allyl-
2,6-dimethoxyphenole>p,p’-biphenol> eugenol>2-allyl-
6- methylphenol> honokiol> magnolol> caffeine acid>
p-ethylphenol> 2-methoxyphenol [9].
There is a proved anti-oxidation also effect of
the product obtained by distillation of beech wood resin.

65
 Journal of the University of Chemical Technology and Metallurgy, 43, 1, 2008
Its main components are: 2-methoxyphenol, 2-methoxy-
4-methylphenol, 3-methylphenol, 4-methylphenol, 2-
methylphenol [10, 11], similar to those produced from
technical hydrolysis lignin [5].
The lignin is used for production of anti-detona-
tion additives for gasoline [12, 13], but the possibility
for production of anti-oxidation additives has not been
examined yet.
The aim of our investigation is to establish the
effect of low molecular phenolic compounds (LMPC),
produced by alkaline treatment of technical hydrolysis
lignin, on the oxidation stability of hydrocarbons (liq-
uid paraffin).
EXPERIMENTAL
The anti-oxidation effect of the phenols produced
from lignin was studied by the oxygen absorption of
liquid paraffin in the laboratory manometric installa-
tion presented in Fig. 1.
The laboratory apparatus consists of the oxida-
tion reactor 7, (containing the oxidation sample – 20
g), connected to the reflux cooler 6. Through the cooler
Fig.1. Scheme of the liquid phase oxidation manometric
installation
66
the reactor is connected to the oxidizing system that
includes the U-shape manometer 5, and the measuring
burette 4, connected to balance vessel 2, which con-
tains dibutylphthalate. The manometer, burette and
cooler temperatures are maintained at 20oC with water
thermostat 3, and thermometer 12. The reactor is placed
in the metal heater 9, interconnected to a relay 11 and
the thermostat 17. The temperature in the metal heater
is regulated by the contact thermometer 8, and the re-
lay. The oxidation is performed under continuous stir-
ring by a magnetic agitator 10. The flow rate of the
oxygen scavenging and entering the installation is con-
trolled by the rotameter 1. The essence of the experi-
ment is the following: after the required oxidation tem-
perature is reached, the installation is scavenged with
oxygen from an oxygen bottle for 10 minutes, after which
every 10 minutes the volume of the oxygen absorbed by
the sample is registered. The oxidation is carried out at
temperatures 120oC for 180 minutes. The temperature
of oxidation was selected to be 120oC, because our ad-
ditives were compared with ionol, which is a typical a
low-temperature inhibitor.
The anti-oxidation action of the methoxyphenolic
compounds produced from lignin is compared to the
effect of ionol (2,6-di-tert-butyl-4-methylphenol). For
the purpose, a sample of liquid paraffin (20 g) contain-
ing 10 ppm ionol is oxidized under the same condi-
tions.
The oxidation degree is characterized also by the
FT-IR spectrophotometer Bruker Equinox 55.
The type and content of the components of the
mixture produced from lignin and used as additive to
the liquid paraffin are determined by
gaschromatography/mass spectrometry. GC/MS was
performed with a Hewlett-Packard gas chromatogra-
phy unit, model 6890, equipped with a mass selective
detector, model 5973. A 30 m x 0.25 mm I.D capil-
lary column HP 5 with a film thickness of 0.25 ìm
was used. The splitless injector was maintained at
280°C. High-purity helium at a constant flow rate of
0,8 cm3.min-1 was the carrier gas. The initial column
temperature was set at 80°C and hold for 1 minute,
after which the following temperature program was
applied: at heating rate 15°C/min. to 190°C, again
heated at 5°C/ min. to 280°C, hold for 10 minutes and
cooled to 80°C.
 T. Vasileva, K. Stanulov, S. Nenkova
RESULTS AND DISCUSSION
The composition of the phenolic compounds mix-
ture used as anti-oxidation additive is shown in Fig. 2
and Table 1.
The peaks on the gas-chromatogram were iden-
tified by the MS spectra comparison with mass spectra
of compounds available in the database of the mass-
spectrometer.
Fig. 2. Gas-chromatogram of the mixture produced from lignin.
Fig. 3 presents the kinetics of the examined oxy-
gen absorption by the samples.
Fig. 3. Kinetic curves of the liquid paraffin samples oxidation at
120 oC.
The oxidation kinetics shows the strong inhibi-
tion effect of the methoxyphenols which is comparable
to that of ionol.
These data are also verified by the IR spectra of
the oxidized samples shown in Fig. 4.
Fig. 4. IR-specters of the oxidized liquid paraffin samples
1. Unoxidized paraffin
2. Oxidized at 120o C, with no additives
3. Oxidized at 120o C, with 10 ppm ionol
4. Oxidized at 120 o C, with 10 ppm methoxyphenols
5. Oxidized at 120 o C, with 50 ppm methoxyphenols
6. Oxidized at 120 o C, with 500 ppm methoxyphenols
The spectra of the samples with the
methoxyphenol additive are absolutely identical with
the spectrum of the non-oxidized liquid paraffin sample
and no band for a running of oxidation process is ob-
served. The characteristic bands are typical for oils of
aliphatic character and the intensive peak at 722.7 cm-1,
shows the presence of a long paraffin chain with CH2 >5.
In the spectrum of the liquid paraffin sample oxi-
dized at 120î C with no additive, a low intensity band with
a well shaped maximum at 3554.2 cm -1 is observed. Is can
be referred to valence fluctuations of the -OH groups of
weak hydrogen bonds (the groups are far apart). A wide
intensive band is observed at 3383.3 cm -1, which is char-
Table 1. Monomer compounds identified by GC-MS.
Retention Area,
Compound
time, min %
* 3.51 2.01
2-methoxyphenol 3.82 24.62
2,6-dimethoxyphenol 6.08 12.37
3-hydroxy-4-methoxybenzaldehyde (vanilline) 6.55 34.90
1-[4-hydroxy-3-methoxyphenyl] ethanone 7.27 26.10
* Unidentified compounds.
67
 Journal of the University of Chemical Technology and Metallurgy, 43, 1, 2008
acteristic for valence fluctuation of the -OH groups of
stronger hydrogen bonds. At 1712.8 cm-1 there is a band
of average intensity that is characteristic for oxidation prod-
ucts due to valence fluctuations of carbonyl groups.
The acid numbers of the paraffin samples were
determined according to ISO 6618:2005.
The results are presented in Table 2.
Table 2. Acid numbers of the studied samples.
Sample
Acid number,
mg KOH g-1
Unoxidized paraffin 0.31
Oxidized at 120o C, with 10 ppm ionol 0.31
o
Oxidized at 120 C, with 10 ppm methoxyphenols 0.32
Oxidized at 120o C, with 50 ppm methoxyphenols 0.31
Oxidized at 120o C, with 500 ppm methoxyphenols 0.29
o
Oxidized at 120 C, with no additives 1.24
The IR-spectral characteristics of all the samples
as well as the experimental results obtained in the in-
vestigation of the liquid paraffin oxygen absorption verify
the methoxyphenols strong anti-oxidation effect.
CONCLUSIONS
The anti-oxidation effect of the methoxyphenols
produced in the lignin alkaline treatment is tested by
investigation of the oxygen absorption in a laboratory
manometric installation. It is shown that their action is
comparable to that of the most widely used low tem-
perature oxidation inhibitor – ionol. The FT-IR spec-
tral investigations prove the anti-oxidation effectiveness
of the isolated phenolic compounds.
68
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