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: [email protected]

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

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

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 Journal of the University of Chemical Technology and Metallurgy, 43, 1, 2008

Its main components are: 2-methoxyphenol, 2-methoxy- the reactor is connected to the oxidizing system that
4-methylphenol, 3-methylphenol, 4-methylphenol, 2- includes the U-shape manometer 5, and the measuring
methylphenol [10, 11], similar to those produced from burette 4, connected to balance vessel 2, which con-
technical hydrolysis lignin [5]. tains dibutylphthalate. The manometer, burette and
The lignin is used for production of anti-detona- cooler temperatures are maintained at 20oC with water
tion additives for gasoline [12, 13], but the possibility thermostat 3, and thermometer 12. The reactor is placed
for production of anti-oxidation additives has not been in the metal heater 9, interconnected to a relay 11 and
examined yet. the thermostat 17. The temperature in the metal heater
The aim of our investigation is to establish the is regulated by the contact thermometer 8, and the re-
effect of low molecular phenolic compounds (LMPC), lay. The oxidation is performed under continuous stir-
produced by alkaline treatment of technical hydrolysis ring by a magnetic agitator 10. The flow rate of the
lignin, on the oxidation stability of hydrocarbons (liq- oxygen scavenging and entering the installation is con-
uid paraffin). trolled by the rotameter 1. The essence of the experi-
ment is the following: after the required oxidation tem-
EXPERIMENTAL perature is reached, the installation is scavenged with
oxygen from an oxygen bottle for 10 minutes, after which
The anti-oxidation effect of the phenols produced every 10 minutes the volume of the oxygen absorbed by
from lignin was studied by the oxygen absorption of the sample is registered. The oxidation is carried out at
liquid paraffin in the laboratory manometric installa- temperatures 120oC for 180 minutes. The temperature
tion presented in Fig. 1. of oxidation was selected to be 120oC, because our ad-
The laboratory apparatus consists of the oxida- ditives were compared with ionol, which is a typical a
tion reactor 7, (containing the oxidation sample – 20 low-temperature inhibitor.
g), connected to the reflux cooler 6. Through the cooler 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
Fig.1. Scheme of the liquid phase oxidation manometric cooled to 80°C.
installation

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 T. Vasileva, K. Stanulov, S. Nenkova

RESULTS AND DISCUSSION The oxidation kinetics shows the strong inhibi-
tion effect of the methoxyphenols which is comparable
The composition of the phenolic compounds mix- to that of ionol.
ture used as anti-oxidation additive is shown in Fig. 2 These data are also verified by the IR spectra of
and Table 1. the oxidized samples shown in Fig. 4.
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. 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
Fig. 2. Gas-chromatogram of the mixture produced from lignin. the spectrum of the non-oxidized liquid paraffin sample
and no band for a running of oxidation process is ob-
Fig. 3 presents the kinetics of the examined oxy- served. The characteristic bands are typical for oils of
gen absorption by the samples. 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
Fig. 3. Kinetic curves of the liquid paraffin samples oxidation at
120 oC. * Unidentified compounds.

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 Journal of the University of Chemical Technology and Metallurgy, 43, 1, 2008

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