Chemistry and Technology of Fuels and Oils, Vol. 45, No.

4, 2009

THE MECHANISM OF THERMAL OXIDATION OF A HYDROTREATED

NAPHTHENIC LUBE BASE OIL AT HIGH TEMPERATURE

Sheng Han, Xinguo Cheng, Shujie Ma, and Tianhui Ren

Using KN4010 as a base stock, we monitored changes in peroxide value and oxygen-containing
compounds were monitored against time at high temperature, using iodometry and infrared spectroscopy
(IR), in order to investigate the mechanism of oxidation of a hydrotreated lube base oil. The results of
the tests indicate that the thermal oxidative mechanism conforms to the radical reaction theory, which
is in the medium oxidative stage. The indirect analytical method of infrared spectroscopy is an effective
method to study oxidative mechanisms. The content of carbonyl compounds and hydroxyl compounds
decreased, and the content of hydroxyl compounds showed a slight increase at high temperature. No
organic acids or esters were generated during the oxidative process.
1.

INTRODUCTION
Compared with the conventional solvent refining lube base oil, the hydrotreated naphthenic lube base oil

provided by Kelemayi has many excellent properties, including high viscosity index, low volatility loss, and low
aromatic content, among others. However, this oil does have one serious shortcoming in that it discolors intensely
when exposed to high temperature or sunlight [1-2]; consequently, it cannot meet the stringent color requirements
of advanced white industrial products, and this greatly reduces its commercial value. Therefore, studying the
mechanism of its thermal oxidation should help to find an effective means of overcoming this disadvantage.
Modern hydrocarbon oxidative theory is based on two universally accepted theories, Bach- Englers peroxide
theory and Senmenovs radical reaction theory. The oxidative process for a hydrocarbon can be divided into three
phases: an initial oxidative phase, a medium oxidative phase, and a deep oxidative phase. In a hydrotreated
naphthenic lube base oil, alkanes account for more than 99% of its composition. Therefore, in these three phases,
lube base oil will yield peroxide, hydroxyl, and carbonyl compounds, and ester compounds of different oxide
stages. If the changes in peroxide value and oxygen-containing compounds at high temperature can be monitored,
we can determine its thermal oxidative mechanism.
____________________________________________________________________________________________________
Department of Chemical Engineering, Shanghai Institute of Technology, Shanghai, 200233, P.R. China.
Petrochina Lubricating Oil R&D Institute, Lanzhou, 730060, P.R. China.3 Petrochina Lubricating Oil R&D Institute,
Kelemayi, 934003, P.R. China. School of Chemistry and Chemical Engineering, Shanghai Jiao Tong University,
Shanghai, 200240, P.R. China. Published in revised form in Khimiya i Tekhnologiya Topliv i Masel, No.4,
pp. 30 32, July August, 2009.
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0009-3092/09/45040260 2009 Springer Science+Business Media, Inc.

In this paper, infrared spectroscopy (IR) and iodometry were used to monitor the changes in peroxide value
and in oxygen-containing compounds and the results used to formulate a proposed thermal oxidative mechanism
for hydrotreated napthenic lube base oil.
2. EXPERIMENTAL SECTION
2.1. Reagents and Apparatus
Silica gel (60/200 mesh) and neutral alumina absorbents (100/200 mesh) were purchased from Qingdao Chemical
and Engineering Plant (Qingdao, China). All other reagents were analytical grade. Petroleum ether was purified by
percolation through silica gel.
Liquid chromatography column, size:

1 cm50 cm

Hyposulfite standard solution N/1000

All infrared spectra were collected with a Nexus 670 infrared spectrometer (Nicolet Company, USA).
2.2. Hydrotreated Naphthenic Sample
The oil sample KN4010 of hydrotreated naphthenic lube base oil was provided by Kelemayi Refinery (Xinjiang
Province, P.R.China). Physical and chemical properties of the oil are given in Table 1.
2.3. Test of Peroxide Value
(1) Reagent preparation
Saturated potassium iodide: 14 kilograms potassium iodide was weighed and dissolved in 10 ml distilled water.
If necessary, it was heated to aid dissolution, and then stored in a brown bottle at room temperature.
Table 1 Physical and chemical properties of lube base oil
Indexes
Appearance at 15C
Density, kg/dm3
2

Viscosity at 40 C, mm /s

Method

Typical data

ASTM D4176

Clear bright

ASTM D4052

895.7

ASTM D4052

130.6

Viscosity index

14
2

Viscosity at 100C, mm /s

ASTM D4052

9.666

Sulfur, g/g
Nitrogen, g/g

ASTM D2622

<10

Color, Saybolt units

ASTM D156

Hydrocarbon type analysis

ASTM D2140

<10
+30

CN

45.7

CP

54.3

CA

Compositional analysis

ASTM D2007

Clay gel,% mass

saturates

95.60

aromatics

4.29

polars

0.11

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Chloroform-glacial acetic acid solution: 40 milliliters chloroform was measured and added to 60 ml of glacial
acetic acid to make a uniform 100 ml.
(2) Experimental procedure
A five gram sample was accurately weighed, then transferred to a 250 ml beaker;

50 ml of chloroform-glacial acetic acid solution was added to dissolve the sample completely;
1 ml of saturated potassium iodide was added and the beaker was covered and shaken lightly
for 30 seconds;
The solution was left in the dark for 3 minutes;

100 ml fresh distilled water was added and the solution was shaken.
The solution was titrated with a hyposulfite standard solution (N/1000) using a potentiometer.
The peroxide value was calculated by the following equation

X = (V2 V1 ) 0.011000 /M
where X represents the peroxide value; V 2 is the volume (ml) of hyposulfite standard solution added to the sample;
V 1 is the volume (ml) of hyposulfite standard solution, which was calibrated for a blank reagent; M is the amount
(g) of sample.
2.4. Separation of Polar Components
For common hydrotreated oil, many researchers have reported that an effective and simple research method to
assess the stability of an oil sample is to analyze the sediment formed at high temperature. However, for hydrotreated
naphthenic lube base oil, it is observed that, although it discolors intensely at high temperature, it does not
produce sediment like common hydrotreated oils. The reason for this is that all photo- oxidized polar compounds
tend to be soluble in an oil sample because of the inherent good solvent capacity of naphthenic base oil and they
remain as polar components of the oil sample. Therefore, researching these polar components following a thermal
oxidative process could generate similar results to those obtained for other oils by researching sediments. This
required methodology to separate and characterize these polar compounds.
The hydrotreated naphthenic lube base oil was passed over silica, and then a small volume of petroleum ether
and benzene was used to wash off the nonpolar saturates and aromatics. The materials retained by the silica were
defined as the polar components. The polar components were removed from the silica using ethanol. All fractions
were evaporated to dryness under a nitrogen atmosphere to a constant weight, which was recorded to determine
mass balance.
2.3 Test of High temperature
The test procedure employed was as follows: 100 ml of the oil sample to be tested was placed in
a 250 ml beaker. Samples were placed in an air-ventilated oven and kept at a constant temperature 160 oC1 o C.
3. RESULTS AND DISCUSSION
3.1 Change of Peroxide Value of Hydrotreated Naphthenic Lube Base Oil at High Temperature
The peroxide values were measured against time of exposure to high temperature, and the results are shown
in Fig.1.

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Fig.1. Change of peroxide value against time at high temperature

The lube base oil yielded peroxide when exposed to high temperature, indicating that its oxidative mechanism
conforms to the radical reaction theory at the initial oxidative phase. Peroxide values showed an increase at the
initial phases and then stabilized at a constant value for 4 to 8 hours.
3.2. Change of Oxygen-containing Compounds of Hydrotreated Naphthenic Lube Base Oil at High Temperature
3.2.1 Direct Analytical Method by Infrared Spectroscopy
Infrared spectroscopy (IR) is a powerful tool for investigating oil sample degradation. In general, an oil
sample will form different oxygen-containing compounds at different oxidative stages. IR was therefore used to
monitor the changes in oxygen-containing functional groups in response to high temperature, in order to determine
the thermal oxidative mechanism for the lube base oil sample [3-12].
Usually, the absorption band at 1710 cm -1 is assigned to carbonyl compounds, which would be representative
of a medium oxidative phase; the 1770 cm -1 band is assigned to organic acids or ester compounds, which are
representative of the deep oxidative phase; and the 3400 cm -1 band is assigned to hydroxyl compounds. The IR for
the direct analytical method is shown in Fig. 2, which indicates that a change in functional groups from
oxygen-containing compounds cannot be detected by IR following high temperature treatment. Consequently,
this oxidative mechanism cannot be investigated. There may be two reasons for this: one is that only a tiny
fraction of lube base oil undergoes an oxidative reaction, so that the actual production of oxidative compounds is
very low; another may lie in the relatively low sensitivity of IR spectra for detecting chemical components. Thus,
it was necessary to perform a prior separation of these polar compounds and use indirect analytical methods to
analyze the thermal oxidative mechanism.
3.2.2 Indirect Analytical Method by Infrared Spectroscopy
In order to solve the problem encountered above, and due to the presence of oxygen-containing compounds
in the polar components following high temperature treatment, we first separated polar components by

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Absorbance

Wave numbers, cm -1

Absorbance

Fig. 2. Infrared spectra of lube base oil against time at high temperature by direct
method.

Wave numbers, cm -1
Fig. 3. Infrared spectra of polar components against time at high temperature by an
indirect IR method.
liquid-solid adsorptive chromatography and then analyzed the changes of oxygen-containing functional groups
by infrared spectroscopy. The IR spectra of polar components at high temperature are shown in Fig.3.
The absorption band at 3500-3300 cm-1 is assigned to hydroxyl compounds, the 1700-1750 cm -1 band is assigned
to carbonyl compounds and the 1770 cm -1 band is assigned to organic acids or ester compounds. A characteristic
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Fig. 4. Changes in OH and C=O with time at high temperature.

absorption band at 1770 cm -1 was not observed, which indicated that no organic acids or esters were formed by the
oxidative processes. Consequently, the oxidative process giving rise to rubber oil should occur during the medium
oxidative phase, and this also, in part, can explain why there is no sediment deposition during the oxidative
process.
3.2.3. Evaluation of Changes in Carbonyl Compounds and Hydroxyl Compounds by the Peak Area Ratio Method of
Infrared Spectroscopy
In order to evaluate the change in carbonyl compounds and hydroxyl compounds of hydrotreated lube base
oil following high temperature treatment, a semi-quantitative method was used. The peak area of 1500-1414 cm -1
was chosen as a reference peak, then A

1654 1808 cm -1

/A

1405 1521 cm -1

and A

3102 3698 cm -1

/A

1405 1521 cm -1

were measured

and calculated and used to evaluate its change. The experimental results are presented in Fig. 4.
Fig. 4 indicates that carbonyl compounds decrease as the time at high temperature increased. On the basis of
the radical reactive theory, the main reason for this is possibly that the carbonyl compound may have been
transformed into other oxides, so that the content of these other oxidative compounds may have been increased.
Hydroxyl compounds showed only a slight increase as the time at high temperature increased.
4. CONCLUSION
In this paper, the oxidative mechanism for degradation of hydrotreated naphthenic lube base oil at high
temperature was studied by monitoring changes in peroxide value and in oxygen-containing compounds. The
following conclusions can be drawn:
(1) The thermal oxidative mechanism for hydrotreated lube base oil conforms to the radical reaction theory,
which is characteristic of the medium oxidative stage.
(2) The indirect analytical method of infrared spectroscopy is an effective method for studying this oxidative
mechanism.

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(3) The content of carbonyl compounds and hydroxyl compounds shows a decrease, and the content of
hydroxyl compounds shows a slight increase following treatment at high temperature. No organic acids or esters
were formed during the oxidative process.
ACKNOWLEDGMENT
The project is supported by the Innovation Program of the Shanghai Municipal Education Commission, Project
Number 09YZ387. The authors thank the R&D centre of PetroChina Lubricating Oil Company, Lanzhou for financial
support, and Dr. Xingguo Cheng for technical assistance.
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