Article

pubs.acs.org/EF

Chemical Characterization of Lube Oils

Antonina Kupareva,† Paï vi Mak̈ i-Arvela,† Henrik Grénman,† Kari Eran̈ en,† Rainer Sjöholm,‡
Markku Reunanen,§ and Dmitry Yu. Murzin*,†
†
Laboratory of Industrial Chemistry and Reaction Engineering, Process Chemistry Centre, ‡Laboratory of Organic Chemistry,
§
Laboratory of Wood and Paper Chemistry, Process Chemistry Centre, Åbo Akademi University, FI-20500 Turku/Åbo, Finland

ABSTRACT: In this paper, estimation of the chemical composition of used oils collected from several European locations was
performed on the basis of a comparative analysis of chemical composition of commercially available fresh and used motor oils.
Although the motor oil undergoes a range of chemical and physical transformations during routine engine operations,
information about the structure of hydrocarbons in the fresh oil allows for an estimation of the approximate ratio of different
types of hydrocarbons in the same oil after its use. As an example, a particular type of fresh oil was used in the engine and then
reanalyzed by the same analytical techniques. Gas chromatography−mass spectrometry (GC−MS), Fourier transform infrared
(FTIR) spectroscopy, nuclear magnetic resonance (NMR) spectroscopy, and elemental analysis (CHNS/O analysis) were used
to characterize the chemical composition of the oil samples. A comparison of the obtained results showed correlations between
chemical properties of the fresh oil and the collected used oil. Both oil FTIR spectra exhibited the bands that are related to the
presence of carbonyl groups and amine-containing compounds, respectively. Opposite from the fresh oil, phenols were not found
in the used oil. According to the obtained 1H NMR spectra, the paraffinic hydrocarbons of the fresh oil are more linear and have
longer chains than those in the used oil.

1. INTRODUCTION performance properties. Likewise, the correlation between

Nowadays, globally different automotive sources generate large
amounts of used oils. To achieve maximum energy
conservation and environmental benefits, it is generally
preferable to re-refine used oils into regenerated base oils.
The regeneration industry is an important part of European
independent lubricant production, which represents one-third
of the European market for lubricant volume (1.5−2 million
tons of lubricants). On the basis of data published by the
European Re-refining Industry Section of UEIL, Groupement
Européen de l’Industrie de la Régénération (GEIR),1 today, the
European waste oil recycling industry comprises 28 plants. A
total of 17 of these plants produce base oils. The industry has a
total nameplate capacity of 1.3 million tons/year and a total
lube oil production of 400 000 tons/year and produces 500 000
tons/year of other products including fuels, asphalt, gas oil, flux
oil, etc. An approximate total turnover is between € 200 million
and 250 million/year.1
Composition of new motor oils and new oil additives is
changing because of continuous engine modification. The
variability of lubricating fluids has increased in recent years to
meet the demands of new engines having more stringent
requirements because of their operation under more severe
conditions or in challenging environments. Significant growth
in markets of synthetic and semi-synthetic oils has been
observed. Novel oil compositions are certainly known to oil
manufacturers, while this information is unavailable to re-
refineries processing used oil. For optimal and qualitative oil,
re-refining data on the used oil chemical structure is therefore
needed. The dependence of the chemical composition of crude
motor oils upon the oil refining processes was described.2 It has
been demonstrated that various process parameters and
severities of operation for lubricant refining can be optimized
in terms of structural data to obtain base oils with improved
chemical characteristics of the fresh and used motor oils can be
used for optimizing and updating technology of re-refining the
waste oils.
Motor oil analysis, being of importance for engine
manufacturers, usually includes oxidation and nitration
measurements, estimation of viscosity, total acid number,
total base number, and other general properties of motor oil,
which are useful for automobile users. There is, however, very
little information on the chemical composition of modern fresh
oils and hydrocarbon transformations during their use. A
number of literature sources provided detailed information on
the chemical and physical properties and performance
characteristics of the lube oil.3−16 Infrared spectroscopy plays
an important role in lubricant analysis to characterize various
constituents qualitatively. Fourier transform infrared (FTIR)
spectroscopy has been used for the determination of the
moisture content in a wide range of lubricants,7 viscosity
indexes, and base numbers of motor oil,8 for studies of chemical
changes occurring at the lubricant additive interface during
heating and sliding at high temperatures,9 and for estimation of
differentiation between used motor oils,10,11 fresh motor oils,12
virgin and recycled engine oils.13 Comparative physical and
chemical analyses of fresh and used gasoline engine oils with
mineral base have been performed by inductively coupled
plasma−optical emission spectroscopy (ICP−OES).14 Corre-
lations between electrical, mechanical, and chemical properties
of fresh and used aircraft engine oils have been estimated by
measuring their resistivity, permittivity, and viscosity as a
function of the temperature.15 The major part of studies
Received: June 27, 2012
Revised: December 13, 2012
Published: December 13, 2012

© 2012 American Chemical Society 27 dx.doi.org/10.1021/ef3016816 | Energy Fuels 2013, 27, 27−34
Energy & Fuels
available in the literature is devoted to the estimation of the
metal content in motor oils9,16,17 and their physical properties,
while the chemical composition of engine oils defines the key
characteristics of these oils.
In view of the complex structure of the used oils, acquiring
full information on the oil composition from single analysis is
impossible. According to our knowledge, there is only one
publication reporting the application of different methods for
comparative analysis of fresh and used oil chemical structures.
Results of several analyses of fresh, used, and weathered motor
oils by gas chromatography−mass spectrometry (GC−MS),
nuclear magnetic resonance (NMR) spectroscopy, and FTIR
spectroscopy techniques were correlated.18 These results
showed the presence of aromatic hydrocarbons, including
polycyclic aromatic hydrocarbons in the used oil, while they are
absent in the fresh oil. Furthermore, it was demonstrated18 that
various analytical techniques can be applied for the analysis of
hydrocarbon composition of motor oils as well as various
functional groups and compounds present in the used oil.
Information dealing with the general structure of the fresh oil is
helpful and, for the most part, adequate to predict the fate of
the oil after its use in the re-refining process.
The objective of the present study is to estimate the chemical
composition of used oil, which is a current feedstock for re-
refineries. The estimation was based on analytical results of
commercially available fresh motor oil, the same type of
commercially available motor oil after being used, and the used
oil from a re-refinery. The oil samples were analyzed by GC−
MS, FTIR spectroscopy, NMR spectroscopy, and elemental
analysis (CHNS/O analysis). The results were correlated to
obtain detailed information regarding the composition of the
used oil.
2. MATERIALS AND METHODS
The used lube oil investigated in the present work contained about
85−95% used motor oil, which was collected from several automobile
crankcases, with the rest (5−15%) being industrial oil. The combined
oil was dried by adding calcium chloride pellets (CaCl2) for carrying
out FTIR spectroscopy analysis. A fresh commercially available
synthetic motor oil was purchased. The fresh motor oil was added
to a 1.5 L engine and run for 7000 km, and then it was drained for
analysis. Typical physical properties of the fresh, spent, and used
samples are shown in Table 1, while oil distillation curves are depicted
Table 1. Physical Properties of Fresh and Spent Motor Oils
and Used Motor Oil from Re-refinery Storage
physical property fresh oil spent oil used oil
viscosity at 100 °C (cSt) 10.99 9.87 8.49
viscosity at 40 °C (cSt) 61.76 57.52 50.07
viscosity index 172 158 146
density at 15 °C (mg/L) 0.854 0.860 0.871
in Figure 1. In the text below, the term “used oil” corresponds to oil
delivered to a particular re-refinery from multiple European used oil
collection centers, “fresh oil” corresponds to a commercially available
motor oil, and “spent oil” denotes the same commercially available
motor oil after being used in the engine, specified above.
The fresh oil has higher viscosity and distillation temperatures. This
trend is not surprising, because higher viscosity oil generally has
heavier, less volatile components. The flatter shape of the curve for the
fresh oil indicates that the oil contains compounds with similar boiling
points. Figure 1 displays the distillation curves of the spent and used
lube oils. The first drops of the spent and used oils began to distill at
significantly lower temperatures than that of the fresh oil. This
28
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Figure 1. Distillation curves of analyzed oil samples.
suggests some gasoline contaminations in the former oils. The
temperature profile of the spent oil rapidly approaches the temperature
profile of the fresh oil after this initial low-temperature point.
The distillation temperatures of the collected used oil are lower than
the fresh and spent oils, with the average difference being 35 °C. This
indicates that the used oil contains more volatile compounds
compared to the fresh oil, with some amount of residual fuel that
distills early.
2.1. GC−MS. One drop of lube oil was diluted with hexane [high-
performance liquid chromatography (HPLC) grade] to 2 mL and
analyzed by a Hewlett-Packard 6890/5973 gas chromatograph coupled
to a mass selective spectrometer detector. The gas chromatograph was
equipped with an Agilent 19091J-002 capillary column, with a 25 m
length, 0.20 mm internal diameter, and 0.11 μm film thickness. Helium
was the carrier gas. The temperature program consisted of a heating
rate of 8 °C/min from 80 to 340 °C with a hold time of 6 min.
2.2. FTIR Spectroscopy. Potassium bromide (KBr) discs were
used to analyze oil samples by FTIR spectroscopy. Background spectra
were obtained by scanning two clean discs in the instrument. One
drop of the analyzed oil was placed on one KBr-polished disc and was
covered with a second KBr disc. Both discs were placed in a Bruker
IFS 66v/S instrument. Scans were carried out in the 4000−500 cm−1
range.
2.3. 1H NMR Spectroscopy. 1H NMR experiments were carried
out on all oil samples. Deuterated chloroform (CDCl3) was applied as
a solvent. The spectra were obtained with a Bruker AV600 NMR
instrument. NMR data and spectra were processed by Bruker’s
TopSpin NMR software.
2.4. Elemental Analysis. Carbon, hydrogen, nitrogen, sulfur, and
oxygen contents were estimated using a FlashEA 112 organic
elemental analyzer according to the standard test procedures. The
technique used for the determination of CHNS/O was based on the
quantitative “dynamic flash combustion” method.
3. RESULTS AND DISCUSSION
3.1. GC−MS. GC−MS spectra of oil samples revealed bell-
shaped curves at 18−32 min (Figure 2). The noise observed in
the chromatogram of the used lube oil hindered identification
of the observed peaks. The used oil chromatogram showed the
peaks at 6−18 min, which indicated the peaks characteristic of
gasoline components, including short hydrocarbons, cyclic
paraffins, and aromatics. The most abundant peaks were located
between 18 and 27 min. Approximate analysis of GC−MS data
demonstrated that the used lube oil contains a broad range of
aromatic and aliphatic hydrocarbons, with chain lengths ranging
dx.doi.org/10.1021/ef3016816 | Energy Fuels 2013, 27, 27−34
Energy & Fuels Article

Figure 2. GC−MS spectrum of fresh motor oil, spent motor oil, and used oil: 1, napthalene; 2, butyl-diphenylamine; 3, octyl-diphenylamine; 4,
butyl-octyl-diphenylamine; 5, 4,4′- methylenebis(2,6-di-tert-butylphenol); 6, p,p′-dioctyldiphenylamine; 7, (E)-N,N′-di-tert-butyl-2,2,7,7-
tetramethyloctane-1,8-diimine; 8, N-[1-(1-naphthyl)ethyl]-2-naphthamide; 9, 3-hexenoic acid,5-hydroxy-2-methylmethyl ester; and 10, [1,1′-
bicyclohexyl]-1,1′-diol.

from C16 to C32. Hydrocarbons were also detected in the fresh
and spent motor oils. The most abundant peaks were located
between 22 and 28 min, which showing the presence of
hydrocarbons with longer chains than those in the used oil.
Moreover, the chromatogram of the analyzed samples revealed
numerous intense peaks, which were identified as various
diphenylamine derivates and oxygen-containing organic com-
pounds. The peaks of (E)-N,N′-di-tert-butyl-2,2,7,7-tetrame-
thyloctane-1,8-diimine, N-[1-(1-naphthyl)ethyl]-2-naphtha-
mide, and 3-hexenoic acid,5-hydroxy-2-methylmethyl ester
were visible in all analyzed samples. The intensity of these
peaks declined for the spent motor oil. Imide and amide
derivates can be present in motor oil as dispersants.5 Methyl
29
esters of linear unsaturated acids provide synthetic oils with
thermal and oxidative properties.19
Alkylated diphenylamines observed in the spectra of the fresh
and spent motor oils are being used as antioxidant additives for
engine oils. Opposite from the presence of 4,4′-methylenebis-
(2,6-di-tert-butylphenol), which is the hindered phenolic
antioxidant, in the fresh motor oil, this compound was not
found in the spent motor oil. In addition, more volatile
compounds, such as naphthalene, were detected in the spent oil
sample. The presence of a light fraction was also confirmed by a
lower initial boiling point of the spent oil than of the fresh oil.
Thus, complexity of the used oil composition allows for
estimation of the carbon number range in different compounds
being present in the used oil. However, additional studies are
dx.doi.org/10.1021/ef3016816 | Energy Fuels 2013, 27, 27−34
Energy & Fuels
Figure 3. FTIR spectra of oils: I, used oil; II, spent oil; and III, fresh oil. Fresh oil spectra: (1) O−H vibrations in alcohols and phenols. Used oil
spectra: (3) Si−H vibrations and (6) NO vibrations in nitrosamines. Fresh/used oil spectra: (2) C−H vibrations in hydrocarbons, (4) CO
vibrations, (5) aromatic rings, (6) carbonates, (7 and 9) sulfonates, (9) methacrylates, (8) C−N and N−H vibrations in amines, (10) P−O−C
vibrations in ZDDPs, and (11) PS vibrations in ZDDPs.
needed to further elucidate the chemical structure of
unidentified compounds.
3.2. FTIR Spectroscopy. The chemical composition of the
fresh, spent, and used motor oils was investigated by comparing
their FTIR spectra. The hydrocarbon composition of fresh or
used automotive lubricating oils consists primarily of saturated
compounds, such as linear and branched chain paraffins. The
analyzed samples possessed multiple bands at the 2954−2856
cm−1 region (Figure 3), an intense band at 1463 cm−1, and a
less intense band at about 1376 cm−1, which correspond to the
presence of a mixture of hydrocarbon compounds with short
carbon chain lengths and C−H branching vibrations containing
−CH− groups in the sample according to Nakanishi and
Solomon.20
Lube oils are made by introducing proper additives, which
are used to enhance the natural properties of the oils and to
prevent some undesirable properties. Oxygen-containing func-
tional groups can be present in fresh oils as a part of friction
modifiers or lubricity additives, which are generally polar
molecules, composed of a polar functional group (ketone, ester,
and carboxylic acid) and a nonpolar hydrocarbon tail.5 The
spectra comprise the bands at 1747 and 1701 cm−1, which are
related to compounds with carbonyl groups from esters,
ketones, or acids. In more detail, the band at 1747 cm−1
indicated the presence of five- and seven-membered cyclic
ketones. The band at 1701 cm−1 can also be referred to as
polymethacrylate in the oil samples. Polymethacrylate is being
used as a viscosity modifier and a pour-point depressant
30
Article
additive for lube oil and typically exhibits the bands at 1701 and
1154 cm−1.12,13 The intensity of polymethacrylate peaks in the
spectrum of the fresh oil is significantly higher than in the
spectra of the used and spent motor oils. On the basis of the
study by Al-Ghouti et al.,8 which demonstrated that the band at
1701 cm−1 is an informative wavenumber for viscosity index
(VI) estimation of lube oils, the fresh oil had a higher viscosity
index than the other oils.
Several metal-containing compounds are added to oils to
improve lubricant characteristics. Some of the characteristic
infrared absorption bands of “single” additives were recognized
in the spectra of the fresh and used oils. Zinc dialkyl
dithiophosphates (ZDDPs) are organometallic compounds,
which are one of the most effective antioxidants and, therefore,
included as a key component in many oxidation inhibitor
packages for engine oils.3 Bands associated with the P−O−C
bonds of ZDDPs are located at 1050−920 cm−1.10 The
characteristic frequency of the PS bond is around 1040−950
cm−1.20 Sulfonate, phenate, and carboxylate are the common
polar groups present in detergent additives of motor oil. The
spectra of the analyzed oils showed the peaks at around 1376
and 1154 cm−1, which are associated with the presence of
sulfonate salts in the oils. Carbonates of overbased sulfonates
absorb at 1490−1410 cm−1.21
Amines are also present in the lube oils as multifunctional
additives; moreover, their presence was demonstrated by GC−
MS analysis. Different types of amine-containing compounds
have been found to provide appreciable antioxidative proper-
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Energy & Fuels Article

ties, dispersion, and anticorrosion effects to engine oils. Table 2. Chemical Shift of Different Types of Protons in 1H
Succinimides, typical dispersants, are normally difficult to NMR Spectra of Fresh and Used Oil
identify through their infrared spectra because of weak
fresh oil δ spent oil δ used oil δ
absorption bands and a possible overlapping by other proton (ppm) (ppm) (ppm)
components, e.g., carbonyl compounds. Their CO band is
CH3−C 0.9−0.8 0.9−0.8 0.9−0.8
normally located as a doublet or triplet between 1750 and 1670
−C−CH2−C 1.34−1.25 1.33−1.2 1.33−1.2
and the C−N and N−H vibration bands at 1310−1210 cm−1.21 R−CH2−NR−N<
The fresh oil spectra showed the doublet band at 1747−1709 R−CH2−COO−
2.3 2.3 2.3
cm−1 and also bands at 1305 and 1230 cm−1, which confirmed −R2−CH−COOH 2.6
the presence of succinimides in the fresh oil. In addition to −C−CH2−O−R 3.4
carbonyl compounds and metal-containing groups, amines were −C−CH2−O−H 3.6 3.6
also present in the used and spent motor oils. However, the −C−CH−O−R 3.8 3.7
bands indicating C−N and N−H vibrations in these samples of −C−CH−O−H 3.9 3.9
lube oils had less intensity than in the fresh oil. The used oil −C−CH2−O−CO−R 4.0 4.0 4.0
spectra showed the band at 1457 cm−1, which may be H2O 4.8
associated with not only the presence of a mixture of −C−CH−O−CO−R 4.8
hydrocarbon compounds, as mentioned above, but also the −R2−CH−OCOR− 5.0
formation of carcinogenic nitrosamines because of the chemical olefinic protons 5.65−5.5 5.55 5.1−5.3
transformation of amines from motor oil additives. aromatic protons 6.95−7.05 6.8−7.1 6.75−7.2
Another class of commonly used additives in industrial and phenols 7.77
automotive lubricating oils and greases is antioxidants. The
fresh oil sample possessed an absorption band at 3648 cm−1,
which indicates O−H stretching vibrations in the monomeric
alcohols and phenols. The phenols and especially the sterically
hindered phenols are being extensively used as antioxidant
additives.5 GC−MS of the fresh oil also demonstrated the peak
of 4,4′-methylenebis(2,6-di-tert-butylphenol). Opposite from
the presence of phenols in the fresh motor oil, these
compounds were not found in the used and spent motor oils.
Another difference in the FTIR spectra between analyzed
samples was the presence of silicon-containing species, as
indicated by absorption bands in the 2294−2102 cm−1 region
in the used oil, although no silicon compounds were found in
the fresh and spent oils. These compounds can be added to
industrial as well as motor lube oils as foam inhibitors.5
Even if during motor oil use the concentration of aromatic
hydrocarbons is expected to increase, FTIR spectroscopy
analysis did not show this growth. However, the NMR spectra
demonstrated the presence of aromatic compounds in both the
fresh and used oils (see below). The FTIR spectra of all
samples exhibited a low-intensity peak at 1600 (1606) cm−1
from the aromatic ring stretching vibrations. On average,
polycyclic aromatic hydrocarbons represent about 4−8% of
hydrocarbons in the used motor oils.18 Thus, it can be
concluded that the FTIR method alone is not adequate for the
determination of aromatic compounds in the oils.
3.3. 1H NMR Spectroscopy. 1H NMR spectra of the
analyzed oil samples provided more detailed information
regarding the hydrocarbon structure of the oils and also
confirmed some data obtained by FTIR spectroscopy (Table
2). The spectra of analyzed oils contained the peaks
corresponding to oxygen-containing functional groups at δ
3.4−5.0 ppm (Figure 4). The oxygen-containing compounds of
the fresh oil were esters and ethers, while the used oil contained
essentially alcohols. The fresh oil spectra demonstrated two Figure 4. NMR spectroscopy spectra of oils (8.0−2.0 ppm): I, used
high-intensity singlets at the chemical shift of δ ∼ 5.0 and 4.0 oil; II, spent oil; and III, fresh oil.
ppm and a less intense doublet at δ ∼ 4.8 ppm corresponding
to the presence of esters; thus, the oil can be qualified as a
synthetic fluid. The spent and used lube oils processed only one
singlet with low intensity at δ ∼ 4.00 ppm, corresponding to used and spent oils. Moreover, the used oil spectra exhibited a
esters. The content of esters in the fresh oil can also be broad peak at δ ∼ 2.6 ppm, corresponding to the presence of
confirmed by FTIR spectroscopy results, which showed a organic acids, which are commonly formed in lube oils via
higher amount of carbonyl groups in the fresh oil than in the chemical oxidation processes.
31 dx.doi.org/10.1021/ef3016816 | Energy Fuels 2013, 27, 27−34
Energy & Fuels Article

In addition to oxygen-containing compounds, there were a

few notable differences between the fresh, spent, and used
motor oils found in the NMR spectra. The fresh oil 1H NMR
spectrum showed the presence of phenols in the chemical shift
range δ ∼ 7.4−7.9 ppm, in line with GC−MS and FTIR
spectroscopy analyses. Opposite from it, the presence of phenol
was not found in the spent and used oils. Thus, phenolic
antioxidants were depleted during use of the motor oil. The
used oil spectrum contained a broad signal at δ ∼ 4.8 ppm,
showing the presence of water. In fact, water is one of the
contaminants in the motor oil, usually appearing in the used oil
at the stages of collection, transportation, and storage of the
used oil.
The spectra of analyzed samples exhibited a strong signal
with chemical shifts in the range δ ∼ 2.1−2.4 ppm, which could
be associated to α-methylene protons of amines, as well as
carboxylic acids and esters.22 These compounds were also
identified by FTIR spectroscopy and GC−MS. Moreover, a
reduction of the amine peaks intensity was observed in FTIR
and GC−MS spectra of the spent and used oils.
The peaks observed at the chemical shift of δ ∼ 7.0 ppm
corresponded to aromatic hydrocarbons in the samples. The
molar percentage of aromatic protons was equal to 0.27 and
0.94 for the fresh and used oil samples, respectively. Aromatic
hydrocarbons can be added to fresh motor oils as a part of
various additives. Aromatic amines are used as multifunctional
antioxidants, antiwear agents, and viscosity index improvers for
lubricants, while aromatic sulfides represent oxidation and
corrosion inhibitors.5 GC−MS fresh oil spectra also contained
several aromatic-containing compounds. In the used oil,
aromatics may arise from the formation of polycyclic aromatic
hydrocarbons, nitrogen-based compounds, i.e., nitrates, and
Figure 5. NMR spectroscopy spectra of oils (2.05−0.55 ppm): I, used
other substances, i.e., acids, esters, and peroxides, formed oil; II, spent oil; and III, fresh oil.
during engine operation.13 A comparison of NMR spectra of
the fresh and spent oils showed a 2-fold increase of aromatics in
the latter motor oil.
Estimation of the total concentration of olefinic protons
exhibiting a signal at δ ∼ 5.6 ppm in the fresh and spent oils
from NMR spectra showed that the amount of olefins
decreased with lube oil usage. However, the spectra of the
industrially collected used oil demonstrated an olefin content
almost 3-fold higher than in the fresh oil. This fact can be
explained assuming that the collected used oil was in nature
more olefinic.
The molar percentage of aliphatic protons was equal to 99.7
for the fresh oil sample, whereas it was 98.9 for the used oil
sample. Methyl and methylene proton peaks were observed
between 0.95 and 0.8 ppm and in the 1.35−1.2 ppm range,
respectively (Figure 5). A comparison of the spectra showed
that the paraffinic hydrocarbons in the fresh oil are more linear
and have longer chains than those in the used oil. No Figure 6. Carbon and hydrogen contents in the oil samples.
differences in the concentration of aliphatic hydrocarbons and
their structures in the fresh and spent oil samples were
observed. Furthermore, the analyzed oil spectra showed a sharp compared to that in the fresh oil, but the carbon content was
singlet produced by protons of the t-butyl group at the very similar in both samples. These results may be associated
chemical shift of δ ∼ 1.1 ppm. The intensity of the t-butyl with the higher concentration of olefinic and aromatic
group peak diminished with lube oil usage. The ratio between hydrocarbons in the used oil than in the fresh oil, what was
−C−CH2−C and CH3−C groups is equal to 3.1 and 2.1 for the also identified by NMR analysis.
fresh and used oils, respectively. The obtained data showed that the content of nitrogen and
3.4. Elemental Analysis. This analysis, which was oxygen in the lube oil after its use is higher than in the fresh oil.
performed for the fresh and used motor oils demonstrated The differences were 0.73 and 0.25 mol % for nitrogen and
differences in the elemental compositions (Figures 6 and 7). oxygen contents, respectively. Lube oil oxidation occurs,
The used oil contained about 4.5 molar percent less hydrogen causing the breakdown of a lubricant because of aging and
32 dx.doi.org/10.1021/ef3016816 | Energy Fuels 2013, 27, 27−34
Energy & Fuels
Figure 7. Oxygen, nitrogen, and sulfur contents in the oil samples.
harsh operating conditions. Nitration is primarily a problem in
natural gas engines. The reason for the nitration process of the
motor oil may be excessive “blow-by” from cylinder walls and
compression rings. A higher amount of oxygen in the used oil
compared to that in the fresh oil confirmed by NMR results
demonstrated a high amount of water and alcohols in the
sample of used oil. However, the elemental analysis results
regarding nitrogen content in the oils are not in line with the
FTIR spectroscopy and NMR results, which both showed more
intense peaks of nitrogen-containing compounds in the fresh
oil. Likewise, the elemental analysis did not show the presence
of sulfur in the fresh oil sample, while FTIR spectroscopy
clearly indicated the peaks, which correspond to ZDDPs being
used as antioxidant additives for lube oils. Elemental analysis is
thus not that precise in the determination of elements
contained in the oils, and obtained results should be confirmed
by other analytical techniques, such as FTIR spectroscopy,
GC−MS, and NMR.
4. CONCLUSION
The chemical composition of used oil, collected from several
European locations, was compared to the chemical composition
of the commercially available fresh motor oil. The fresh and
used motor oils were investigated via GC−MS, FTIR
spectroscopy, and NMR techniques and elemental analysis
with an organic elemental analyzer. Combined analysis of the
obtained results demonstrated that these techniques could be
applied for the determination of the chemical nature of the lube
oil and could be a helpful tool for distinguishing between
compositions of oil samples of various degrees of use.
The obtained data showed that the hydrocarbon structure of
the motor oil is changed insignificantly during its operation and
the major part of the changes is accounted for with depleted oil
additives. The modern fresh oil has the following chemical
composition: 99.7% aliphatic hydrocarbons, 0.27% aromatic
hydrocarbons, and 0.03% olefinic hydrocarbons. During its
application, oxidation processes occur, resulting in a slight
increase of aromatic hydrocarbons and sulfur contents in used
oil, although these changes can be probably related to the
presence of used industrial oil with a higher amount of the
latter compounds in the analyzed used oil. The estimation of
the hydrocarbon structure of the used oil showed the presence
of 98.9% aliphatic hydrocarbons, 0.94% aromatic hydrocarbons,
and 0.08% olefinic hydrocarbons.
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Differences in the concentration of aliphatic hydrocarbons
and their structures in the modern fresh and used motor oils
were elucidated. The used oil showed a higher content of
methyl protons than the fresh oil; thus, the used oil is more
branched.
Dependent upon the chemical structure of the used oil, it is
possible to select the type of used oil re-refining processes and
to regulate the severity of them. On the basis of the obtained
data, the process of recovery could be catalytic hydrotreating
for the removal of heteroatoms and saturation of unsaturated
hydrocarbons. The content of aromatics and olefins in the used
oil allows for the estimation of the severity of hydrogenation
and the rate of needed hydrogen for oil re-refinery. The
branched aliphatic hydrocarbons present in the used oil should
provide a sufficient pour point, and hydroisomerization of this
oil is optional.
FTIR spectroscopy results demonstrated the reduction of
carbonyl groups with lube oil use, which leads to a decrease of
the viscosity index of the oil. GC−MS and NMR results
showed the depletion of phenol-containing antioxidants.
Hence, the re-refined oil should be blended with the new
additive packages.
■ AUTHOR INFORMATION
Corresponding Author
*Telephone: 358-221-549-85. E-mail: dmurzin@abo.fi.
Notes
The authors declare no competing financial interest.
■
ACKNOWLEDGMENTS
The research was funded by the National Technology Agency
of Finland (Tekes), which is gratefully acknowledged. Ida
Rönnlund is gratefully acknowledged for the provided equip-
ment to carry out elemental analysis.
■
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