Energy & Fuels 2007, 21, 3477–3483 3477

Chemical Composition of Group II Lubricant Oil Studied by

High-Resolution Gas Chromatography and Comprehensive
Two-Dimensional Gas Chromatography
Frank Cheng-Yu Wang* and Lei Zhang
Corporate Strategic Research, ExxonMobil Research and Engineering Company, 1545 Route 22 East,
Annandale, New Jersey 08801

ReceiVed July 15, 2007. ReVised Manuscript ReceiVed August 21, 2007

A detailed chemical composition analysis of group II type lubricant oil has been accomplished by high-
resolution gas chromatography (HRGC) and comprehensive two-dimensional gas chromatography (GCxGC).
The major advantage of these techniques is the ability to obtain the detailed fingerprint of major paraffin
components. To achieve the superior low-temperature property in lubricant oil via dewaxing processes, it is
critical to monitor the change of key components (paraffins) in order to understand the effect of paraffins on
the low-temperature property of base oil and the mechanism of each dewaxing process as well as the effectiveness
of each process. Comprehensive two-dimensional gas chromatography (GCxGC) provides a better separation
between the paraffins and naphthenes in the lubricant oil. Based on the quantitative analysis of GCxGC results,
a formula has been developed to correlate the paraffin chemical composition to one of the low-temperature
property, viscosity measured by a mini-rotary viscometer (MRV). The ability of correlating the paraffin chemical
composition to MRV viscosity makes the better understanding of the role of various paraffin molecules in
MRV viscosity. This knowledge is important in managing this MRV viscosity under different applications. In
addition, this knowledge can be used in the lubricant base oil formulation, in the additive package development,
as well as a model to predict MRV viscosity from the chemical composition.

1. Introduction and environments.4 One of the viscosity measurements related

Lubricant oils are an essential component of our modern
society as they are a key element for the proper function of
machines with moving parts. The majority of lubricant oils is
produced directly or indirectly from petroleum refining and is
composed of a complex mixture of hydrocarbon.1 Lubricant oils
are classified into several groups by American Petroleum
Institute (API) based on how they produced.2 Normally, group
II lubricant oils contain mostly saturated aliphatic compounds
that include paraffins and naphthenes.
One of the major applications of lubricant oil related to our
daily life is the lubrication of automobile engines by an
automotive engine oil.3 There are many critical properties
required for an automotive engine oil to meet performance
standards set by API or SAE (Society of Automotive Engineers)
for proper engine protection. Low-temperature performance is
an important one of them. The engine oil should remain in a
liquid form with relative low viscosity under all climatic
conditions including very cold winter days or at high latitudes.
There are several different types of viscosity designed to
measure fluid performance under different operating conditions
* Corresponding author. E-mail: Frank.C.Wang@exxonmobil.com.
(1) Klamann, D. Production of Petroleum Based Lubricanting Oils. In
Lubricants and Related Products; Verlag Chemie GmbH: Weinheim, 1984;
pp 51–83.
(2) Pirro, D. M.; Wessol, A. A. Refining Processes and Lubricant Nase
Stocks. In Lubrication Fundamentals; Marcel Dekker: New York, 2001;
pp 14–15.
(3) Pirro, D. M.; Wessol, A. A. Refining Processes and Lubricant Nase
Stocks. In Lubrication Fundamentals; Marcel Dekker: New York, 2001,
pp 257–292.
to engine oil pumping capability at low temperature is the
viscosity measured by a “mini-rotary viscometer” or MRV.5
This measurement is reported in units of centipoises (cP), 1 cP
equal to 1 mPa · s (millipascal · second); the lower the value, the
better the low-temperature flow.
“Engine oil” is a formulated oil product, which is a mixture
of “base oil” and a specific designed “additive package” for a
specific operating environment. In general, the engine oil
performance properties are measured for the fully formulated
lubricant oil. However, many of the critical performance
properties are mostly determined by the quality of the base oil
used in the formulation. Therefore, it is generally acceptable to
analyze the base oil compositions and correlate a specific
performance property to the chemical compositions of the base
oil before formulated with additive package to the finished
engine oil performance. The purpose of directly analyzing base
oil is to minimize any possible interference from additive
package during the quantitative composition analysis.
Paraffins, especially the normal paraffins and monomethyl
isoparaffins, play an important role in the low-temperature
properties of lubricant oils. Normal paraffins will be the first
class of chemical compounds to crystallize out from the oil
mixture at low temperature since their straight chain structure
favors crystal formation with decreasing temperature. Mono-
methyl isoparaffins have the similar crystallization tendency,
(4) Caines, A. J.; Haycock, R. F. Crankcase Oil Testing. In AutomotiVe
Lubricants Reference Book; Society of Automotive Engineers, Inc.: War-
rendale, PA 1996; pp 97–174.
(5) Caines, A. L.; Haycock, R. F. Crankcase Oil Testing. In AutomotiVe
Lubricants Reference Book; Society of Automotive Engineers: Warrendale,
PA, 1996; pp 99–123.

10.1021/ef700407c CCC: $37.00  2007 American Chemical Society

Published on Web 09/28/2007
3478 Energy & Fuels, Vol. 21, No. 6, 2007
although slightly better. When these waxy paraffins crystallize,
they form a gel-like network in the oil body, preventing any
fluid flow and degrading lubricant’s protective function. Hence,
a reduction of normal paraffins contents improves the low-
temperature properties of engine oil. The refining process to
reduce these waxy paraffins is called dewaxing.
There is long history of dewaxing of the lube base oil. There
are two major dewaxing processes. The first one is the solvent
dewaxing process6 that applies various solvents or mixed
solvents to extract paraffins. The second one is catalyst
dewaxing7 that utilizes a catalytic reaction to selectively crack
or isomerize the paraffins to other lower molecular weight
paraffins or branched isomers. Each process has its advantages
and disadvantages. The choice of the dewaxing process depends
on the type and quality of the feedstock, the final requirement
of the paraffin content, facility design, and process economics.
In order to effectively and efficiently managing the paraffins in
the base oils, it is necessary to have an analytical method to
qualitatively detect and identify the normal paraffins and other
paraffin isomers in various base oils. Ideally, the same analytical
method should be capable of monitoring the paraffins to evaluate
the efficiency and effectiveness of the dewaxing process.
Several different analytical approaches have been used to
detect/identify the paraffins in base oil. The most common
approaches are infrared spectroscopy (IR),8 thin layer chroma-
tography,9 thermal analysis,10 nuclear magnetic spectroscopy
(NMR),11 and X-ray spectroscopy.12 Although each technique
has its advantages and disadvantages, they are all able to provide
certain specific information to address specific scientific ques-
tions. Among the analytical techniques, high-resolution gas
chromatography (HRGC)13 has the advantage to effectively
separate paraffins from the complex engine oil mixture, to
further identify the individual component using a mass spec-
trometry detector (MSD), and to semiquantitatively determine
the component with a flame ionization detector (FID). None
other methods offer such a degree of detail analysis.
In this study, a high-resolution gas chromatography method
was developed to study the composition of paraffins in the
engine oil. This method can separate the major waxy paraffin
components (normal paraffins and methyl branched isoparaffins)
from other lube oil components. The separated paraffin com-
ponents are qualitatively identified and semiquantitative deter-
mined on the basis of the model compound studied and
information from the literature.14 The method can distinguish
base oil produced from different crude oil sources and can
monitor the changes in paraffin isomer content during various
dewaxing processes, either as individual or combined composi-
tion. Although the conventional high-resolution gas chroma-
tography approach can be used to detect the normal paraffins
(6) Sequeria, A., Jr. Solvent Dewaxing and Wax Deoiling Processes.
In Lubricant Base Oil and Wax Processing; Marcel Dekker: New York,
1994; pp 153–193.
(7) Sequeria, A., Jr. Catalytic Dewaxing Processes. In Lubricant Base
Oil and Wax Processing; Marcel Dekker: New York, 1994; pp 194–224.
(8) Lima, F. S. G.; Araujo, A. S.; Borges, L. E. P. J. Near Infrared
Spectrosc. 2004, 12, 159–166.
(9) Cebolla, V. L.; Membrado, L.; Domingo, M. P.; Henrion, P.; Garriga,
R.; Gonzalez, P.; Cossio, F. P.; Arrieta, A.; Vela, J. J. Chromatogr. Sci.
1999, 37, 219–226.
(10) Wesolowski, M. J. Therm. Anal. 1987, 32, 1781–1784.
(11) Stipanovic, A. J.; Kiemle, D. J. Prepr.—Am. Chem. Soc., DiV. Pet.
Chem. 1999, 44, 288–290.
(12) Wolska, J.; Verbos, B.; Brouwer, P. ASTM Spec. Publ. 2005, 98–
107. STP 1468 (Elemental Analysis of Fuels and Lubricants).
(13) Kaplan, I. R.; Lu, S.-T.; Alimi, H. M.; MacMurphey, J. EnViron.
Forensics 2001, 2, 231–248.
(14) Claude, M. C.; Vanbutsele, G.; Martens, J. A. J. Catal. 2001, 203,
213–231.
Wang and Zhang
and monomethyl isoparaffins, these compounds coelute with a
complex mixture of other compounds, such as multimethyl
isoparaffin isomers and the naphthene isomers, thus limiting
the HRGC as a semiquantitative method for the normal and
monomethyl isoparaffin contents.
Comprehensive two-dimensional gas chromatography
(GCxGC)15,16 can provide the better chromatographic resolution
of lubricant base oil. GCxGC employs a single GC unit
containing two separation columns of different selectivity. A
modulation unit situated in between these two separation
columns performs solute focusing and reinjection into a short,
high-speed second column. The modulation mechanism is the
key to accomplish this two-dimensional separation.17 GCxGC
may be considered as a “continuous” heart-cutting form of a
conventional single heart-cutting multidimensional GC that has
been established for many years. The other unique advantage
of GCxGC technique is its enhanced sensitivity due to the
refocusing process during the modulation operation.
The greater separation and enhanced sensitivity of the GCxGC
technique provide a unique capability for the analysis of
extremely complex mixtures. When coupled with a universal
FID, GCxGC enables the quantitative analysis of both major
and minor components as many coelution problems are reduced
or eliminated. New visualization and data processing techniques
have been developed to display and analyze the two-dimensional
retention matrix. The number of peaks that can be qualitatively
and quantitatively analyzed in the GCxGC chromatogram has
been dramatically increased.
These advances have enabled GCxGC to become an ideal
technique for analyzing complex mixtures, such as lubricant
base oil. The key advantage of the GCxGC technique is the
near complete separation of paraffins from naphthenes. Hence,
the accuracy of quantitation of the paraffins is greatly improved.
As a result, a correlation between the paraffin chemical
composition and the measured MRV viscosity can be estab-
lished. This model allows the lube refinery engineers to optimize
lube operation based on predicted MRV viscosity from paraffin
compositions by this analytical method.
2. Experimental Details
2.1. Lubricant Base Oils. The lubricant base oil samples are
obtained from ExxonMobil refinery sources produced by different
refining processing.
2.2. High-Resolution Gas Chromatography (HRGC). The
HRGC system consists of an Agilent 6890 gas chromatograph
(Agilent Technology Inc., Wilmington, DE) configured with a split/
splitness inlet, capillary column, and multiple detectors. The column
was a BPX-5, 30 m, 0.25 mm i.d., 1.0 µm film (SGE Inc., Austin,
TX). The detection system contains a flame ionization detector
(FID) (Agilent Technologies Inc.) and a mass spectrometry detector
(MSD Model 7672, Agilent Technologies Inc.) The FID and MSD
setup and the analysis conditions follow recommendations from
the manufacturer’s specifications. The carrier gas was helium in
the constant flow mode at 6.0 mL/min.
A 0.2 µL sample was injected at 300 °C, with a 50:1 split. The
oven temperature was ramped from 210 °C, with 1.5 °C/min
increment, to 315 °C. The total run time was 70 min. Chemstation
(from Agilent Technology Inc.) was used for data acquisition.
Qualitative analysis was performed by matching retention time with
standard reference compounds, MSD data, and comparison to
information from the literature.14 Semiquantitative analysis was
(15) Liu, Z.; Phillips, J. B. J. Chromatogr. Sci. 1991, 29, 227–231.
(16) Marriott, P. J. J. Sep. Sci. 2004, 27, 357.
(17) Wang, F. C.; DiSanzo, F. P.; McElroy, F. C. ACS Prepr.—Symp.
2004, 49, 4–8.
Group II Lubricant Oil
Figure 1. HRGC chromatogram of typical lubricant oil feedstock.
accomplished by peak area integration after appropriate background
subtraction using the Chemstation program.
2.3. Comprehensive Two-Dimensional Gas Chromatogra-
phy (GCxGC). The GCxGC system consists of an Agilent 6890
gas chromatograph (Agilent Technology, Wilmington, DE) con-
figured with a split/splitness inlet, capillary columns, and detector.
The capillary column system contains a first-dimensional column,
which is a BPX-5, 30 m, 0.25 mm i.d., 1.0 µm film, and a second-
dimensional column, which is a BPX-50, 9 m, 0.25 mm i.d., 0.25
µm film. Both columns are manufactured by SGE Inc. (Austin, TX).
There is a dual jet thermal modulation assembly (Zoex Corp.,
Lincoln, NE) located in between the first and the second dimension
columns. This modulator assembly contains liquid nitrogen cooled
“trap-release” dual jets thermal modulator. The detection is achieved
by a flame ionization detector (FID) (Agilent Technologies Inc.).
A 0.2 µL sample was injected at 300 °C at a 50:1 split ratio. The
carrier gas was helium in the constant flow mode at 6.0 mL/min.
The oven temperature was ramped from 210 °C, at 1.5 °C/min
increment, to 315 °C. The modulation period was 10 s. Data
acquisition was completed using Chemstation (from Agilent
Technology Inc.) at a sampling rate of 100 Hz.
Acquired data were processed further for qualitative and
quantitative analysis. For qualitative analysis, the data were
converted to a two-dimensional image that was processed by a
program called “Transform” (Research Systems Inc., Boulder, CO).
The two-dimensional image was further treated by “PhotoShop”
program (Adobe System Inc., San Jose, CA) to generate publication-
ready images. The identifications of normal paraffins and mono-
methyl isoparaffins are based on the match of the retention time
position with reference compound standards in the chromatogram
as well as from literature14 reported results. A proprietary data
processing program developed internally was used for the quantita-
tive analysis.
3. Results and Discussion
3.1. Interpretation of Base Oil Gas Chromatogram. Figure
1 is a HRGC chromatogram of a typical refinery lubricant base
oil prior to dewaxing process. The chromatogram contains a
large envelop of unresolved compounds close to baseline, which
is a complex mixture of isomers of multibranched paraffins and
naphthenes (saturated cyclic with a long alkyl attached). The
partially resolved components that are visible above the
unresolved envelope consist mostly of normal and monomethyl
paraffins. The normal paraffins are predominating (∼20 wt %)
and have a carbon chain length distribution from C20 to C34.
The smaller and partially resolved peaks between the normal
paraffins are mostly monomethyl isoparaffins with equivalent
carbon numbers. For example, C28 monomethyl isoparaffins
elute between C27 normal paraffin (n-C27) and C28 normal
paraffin (n-C28). The elution order of the monomethyl isoparaffin
isomers has been reported.14 If the position of methyl substitu-
Energy & Fuels, Vol. 21, No. 6, 2007 3479
Figure 2. Two superimposed chromatograms corresponding to the base
oil before the solvent dewaxing (blue trace) and after solvent dewaxing
(red trace).
Figure 3. Two superimposed chromatograms corresponding to the base
oil before the catalytic dewaxing (blue trace) and after catalytic
dewaxing (green trace).
tion is close to the end of the chain, it will elute closer to n-C28
while monomethyl isomers with midchain methyl substitutions
will elute closer to n-C27. As shown in Figure 1, this HRGC
approach does not resolve every monomethyl isoparaffin isomer,
and the peaks between the normal paraffins are really groups
of isoparaffin isomers.
3.2. Dewaxing Process Monitoring and Phenomenon
Explanation. This HRGC analytical method may be used to
monitor the dewaxing process.6 The effect of the solvent
dewaxing process is shown in Figure 2 by superimposing
chromatograms corresponding to before solvent dewaxing (blue
trace) and after solvent dewaxed base oil (red trace). It clearly
shows that solvent dewaxing removes mainly the higher
molecular weight of normal paraffins and relatively small
amount of higher molecular weight monomethyl isoparaffins.
The higher the molecular weight of normal paraffins, the better
the solvent dewaxing efficiency.
In comparison, the effect of catalytic dewaxing7 on the base
oil composition is illustrated in Figure 3. Unlike the solvent
dewaxing based on the physical separation/extraction, the
catalytic dewaxing is a chemical conversion process. It mainly
converts the waxy normal paraffins to its branched isomers along
with small percentage of lower boiling products. On the basis
of HRGC analysis, the majority of normal paraffins have been
converted to monomethyl substituted isoparaffins with ap-
proximately equally distribution to all possible isomers. As
mentioned previously, the larger peak among isoparaffins is the
lump of many isoparaffin isomers with methyl branched away
3480 Energy & Fuels, Vol. 21, No. 6, 2007
Figure 4. Superimposed chromatograms of base oil after solvent
dewaxing (red trace) and base oil after solvent dewaxing followed by
catalytic dewaxing (green trace).
from the edge of the chain. The conversion of the normal
paraffins exhibits no discrimination by molecular weight or
straight chain length.
Because a lower viscosity value measured by MRV is
required for engine oil in cold weather, the base oil will need
to have more severe dewaxing. The deep dewaxing can be
accomplished in many different ways, depending on the
available refining resources and process economics. In many
occasions, the combination of solvent and catalytic dewaxing
has been chosen to best accommodate the manufacture processes
and cost effectiveness. However, the order of applying the
dewaxing process influences the low-temperature performance
of base oil, since the different starting composition affects the
dewaxing mechanism and dewaxing capacity/efficiency. For
example, a solvent dewaxing process followed by a catalytic
dewaxing process resulted in a base oil MRV viscosity changing
from 38 118 to 13 999 cP, which is the desired viscosity. In a
different approach, when the same base oil was treated first by
a catalytic dewaxing process followed by a solvent dewaxing
process, the resulting base oil MRV viscosity increased to 42 101
cP.
The HRGC method may be used to qualitatively explain this
unexpected result by characterizing the chemical composition
of this base oil in different dewaxing stages. Figure 4 shows
superimposed chromatograms of base oil after solvent dewaxing
(red trace) and base oil after solvent dewaxing followed by
catalytic dewaxing (green trace). As discussed previously, the
mechanism of solvent dewaxing is the removal (removed out
from the base oil) of high molecular weight normal paraffins
and some monomethyl isoparaffins. When followed by the
catalytic dewaxing, the remaining normal paraffins and mono-
methyl isoparaffins have been converted mainly to multiple
methyl branched isoparaffins. Normal paraffins and monomethyl
isoparaffins, which are responsible for low-temperature crystal-
lization, are depleted. This two-stage dewaxing is successful
and effective with reducing the MRV viscosity which can be
predicted by the qualitative compositional prediction.
Figure 5 shows superimposed chromatograms of base oil after
catalytic dewaxing (green trace) and base oil after catalytic
dewaxing followed by solvent dewaxing (red trace). In the
catalytic dewaxing process step, the majority of normal paraffins
have been converted to monomethyl isoparaffins, which are now
the chemical compounds most responsible for influencing the
MRV viscosity value. In the subsequent solvent dewaxing step,
there is only little amount of normal paraffin available to be
removed, and this solvent dewaxing process is not very effective
in the removal of monomethyl isoparaffin isomers. The com-
Wang and Zhang
Figure 5. Superimposed chromatograms of base oil after catalytic
dewaxing (green trace) and base oil after catalytic dewaxing followed
by solvent dewaxing (red trace).
bined processes resulted in the same or slightly higher MRV
viscosity and poor cold weather performance.
3.3. Interpretation of Lubricant Oil Comprehensive
Two-Dimensional Gas Chromatogram. Figure 6 illustrates a
GCxGC chromatogram of a typical lubricant base oil. The X-axis
is the first column separation based on the boiling point, and
the Y-axis is the second column separation based on the polarity
of the compounds. The purpose of these two column separation
is to separate the compounds to reach a degree of paraffins and
naphthenes separation in addition to separate by their boiling
point. Two major compound groups can be seen in this two-
dimensional chromatogram: a solid yellow line circles the
paraffins region, and a dashed yellow line circles the naphthene.
Although the paraffins and naphthenes may not be completely
separated, they are mostly resolved to be allowed to do a
reproducible peak integration and quantitative analysis.
One way to demonstrate the advantage of paraffin and
naphthene separation by GCxGC is to project this separation
into a traditional one-dimensional chromatogram. The GCxGC
chromatogram can be converted to a traditional one-dimensional
chromatogram when the entire signal along Y-axis is summed
and plotted as one data point along the X-axis. The paraffins
(with a little naphthenes due to not complete resolved paraffins
and naphthenes) in the GCxGC chromatogram can also be
selected, summed, and plotted in the same way to obtain a
unique paraffin-only one-dimensional chromatogram. Figure 7
demonstrates the GCxGC chromatogram plotted as one-
dimensional chromatogram of whole sample in blue trace and
paraffins only chromatogram in the red trace. The advantage
of GCxGC is obvious, as the large coelute envelope along the
baseline has been significantly reduced and the quantitative
analysis of paraffins in the sample will have a better accuracy
due to of the effective reduction of coelution interferences.
The carbon number of paraffin molecules in the lubricant oil
starts approximately at 20. Boiling points based chromatographic
separation split/resolve all the monomethyl isomers into three
chromatographic peak groups. Figure 8 is an enlargement of
the GCxGC chromatogram showing the separation of the C28
paraffins. On the basis of the literature,14 the IPC is the
monomethyl substitution on position 3, the IPB is the mono-
methyl substitution on position 2, 4, 5, and/or 6, and IPA is the
other monomethyl substitution that is closer to the center of
the chain. The N assign to the normal paraffin peak.
In order to have a better understanding of the distribution of
multimethyl-branched isoparaffin isomers based on the retention
time, it is necessary to perform a model compound study to
effectively account for those multimethyl-branched isoparaffin
Group II Lubricant Oil
Figure 6. GCxGC chromatogram of a typical lubricant base oil. Although the paraffins and naphthenes are not completely separated, however, they
have been separated to a great extent as shown in the second dimension of chromatographic elution.
Figure 7. GCxGC chromatogram plot as one-dimensional chromato-
gram of whole sample in blue trace and paraffins only chromatogram
in the red trace.
Figure 8. GCxGC chromatogram with C28 paraffins as an example of
detailed separation of normal paraffin and monomethyl isoparaffins.
isomers in the quantitative analysis and further physical property
correlation study. A pure C28 normal paraffin compound was
chosen as the model feed and was catalytically dewaxed or
isomerized to branched isoparaffins. Figure 9 is a HRGC
chromatogram of a catalytically isomerized and dewaxed C28
normal paraffin compound plotted between the C27 and C29
region. The red reference trace is the same red trace in Figure
Energy & Fuels, Vol. 21, No. 6, 2007 3481
7 as paraffin compounds distribution in a real lube base oil. On
the basis of the retention time, the dimethyl-branched C28
isoparaffin isomers are coeluted with normal C27 paraffin and
monomethyl-branched C27 isoparaffins; the majority of them
are located in the retention region of N (C27), IPB (C27), and
IPC (C27). The trimethyl-branched C28 isoparaffin isomers are
coeluted with other monomethyl-branched C27 isoparaffins and
normal C26 paraffin; the majority of them are located in the
retention region of IPA (C27) with only a little overlap in the N
(C26), region. The peak volume of every area indicated as normal
paraffin (N) and IPA, IPB, and IPc isoparaffin group can be
measured from the GCxGC and converted to quantitative values
as the weight percent of the total sample. When a base oil had
been heavily dewaxed, the normal paraffin and monomethyl
isoparaffins are almost completely removed; the peak volumes
of N, IPA, IPB, and IPc are the concentration measurement of
dimethyl-substituted isoparaffins and trimethyl-substituted iso-
paraffins. The quantitative compositional analysis for the sample
shown in Figure 6 is listed in Table 1.
3.4. Physical Property: MRV Viscosity Prediction via
Isoparaffin Index. In order to find the correlation between the
MRV viscosity and paraffin compounds, it is critical to
understand the degree of sample dewaxed and what kind (degree
of methyl branched) of paraffin compounds in the sample. The
correlation between MRV viscosity and paraffin composition
in this study is built based on the feed and the first two stages
of dewaxing. The majority of paraffin compounds are normal
paraffins and monomethyl isoparaffins with a small amount
dimethyl isoparaffins.
For dewax process quality control purpose, it is useful to
develop an index based on the paraffin chemical composition
to predict that the MRV viscosity of formulated oils will exceed
a predefined MRV viscosity. Our studied suite contains 30
samples, as listed in Table 2, with a variety of formulated
samples having a wide range of measured MRV viscosity values,
both within and out of specification. Using the same GCxGC
approach, an index, the “isoparaffin index”18 was developed to
perform this “critical level” MRV viscosity screening.
For any given sample, the isoparaffin index is calculated as
the ratio of the sum of isoparaffins IPA over the range of
compounds with different numbers of carbon from n to m to
(18) Wang, F. C.; Zhang, L. Two-dimensional gas chromatography of
engine lubricating oils to assess low-temperature properties. PCT Int. Appl.,
2006;WO 2006055502 A1 20060526, 48 pp.
3482 Energy & Fuels, Vol. 21, No. 6, 2007 Wang and Zhang

Figure 9. Retention position of all C28 paraffin isomers.

Table 1. Paraffin Composition (in wt %) of a Lubricant Oil

Based on GCxGC Chromatogram as Shown in Figure 6a
carbon
number 23 24 25 26 27 28 29 30 31
N 0.98 2.10 3.58 3.66 3.36 2.60 1.89 1.11 0.57
IPA 0.16 0.47 1.33 1.70 1.86 1.52 1.18 0.88 0.57
IPB 0.31 0.85 1.61 1.82 1.70 1.50 1.18 0.75 0.35
IPC 0.08 0.16 0.38 0.44 0.35 0.40 0.27 0.16 0.06
a N ) normal paraffin, IP ) monomethyl isoparaffin group A, IP
A B
) monomethyl isoparaffin group B, and IPC ) monomethyl isoparaffin
group C. Carbon number is the compound expressed by the number of
carbon in the compound.

Table 2. Isoparaffin Index along with Their Measured Viscosity

(MRV) for the 30 Samples Studied
isoparaffin isoparaffin
name index MRV name Index MRV
Figure 10. Correlation between the isoparaffin index and MRV for 26
sample 01 0.7323 36211 sample 16 0.5561 17300
sample 02 0.7269 33700 sample 17 0.5566 17004 base oil samples studied.
sample 03 0.6668 31400 sample 18 0.5670 16130 measurable amount of monomethyl isoparaffins, the isoparaffin
sample 04 0.6843 30874 sample 19 0.5506 16100
sample 05 0.7033 29600 sample 20 0.5665 14800
index will never be less than one; because the number of
sample 06 0.7108 27876 sample 21 0.5541 12700 monomethyl-substituted isoparaffin isomers included in the
sample 07 0.6899 26870 sample 22 0.5472 12675 numerator term, IPA will always larger than the number of
sample 08 0.7008 26050 sample 23 0.5429 12675 monomethyl-substituted isoparaffin isomers included in the
sample 09 0.6201 25600 sample 24 0.8357 73186 denominator term (sum of IPB and IPC). However, if the normal
sample 10 0.6504 25306 sample 25 1.0117 85446
sample 11 0.6587 23170 sample 26 0.8869 92649 paraffin and monomethyl isoparaffins are almost all removed/
sample 12 0.5992 23000 sample 27 0.9260 102578 dewaxed, the numerator term IPA represents the trimethyl-
sample 13 0.5737 19536 sample 28 0.8943 103488 substituted isoparaffins and the denominator term (sum of IPB
sample 14 0.5835 19100 sample 29 0.8918 143773 and IPC) represents some of the dimethyl-substituted isoparaf-
sample 15 0.5539 17300 sample 30 0.9790 219684
critical level 0.8000 40000
fins. The isoparaffin index will be less than one, and the value
will reflect the relative concentration of di- and trimethyl-
substituted isoparaffins.
the sum of isoparaffins IPB plus IPC over the range of carbon
The correlation between the isoparaffin index and measured
numbers from n to m:
MRV viscosity is plotted in Figure 10 with measured MRV
m viscosity being the X-axis and isoparaffin index being the Y-axis
∑ (IP ) A L for the set of samples (only 26 samples shown; the other four
isoparaffin index )
L)n
(1) with high MRV are missing due to the MRV scale in the figure).
m m If the “critical level” of formulated base oil MRV viscosity were
∑ (IP ) + ∑ (IP )
B L C L set as 40 000 cP, the target base oil isoparaffin index would be
L)n L)n set as 0.8. For any given sample of formulated oil, if the
For example, for the data from the sample listed in Table 1, n isoparaffin index for the base oil is less than 0.8, then it can
) 23 and m ) 31, ∑ L)2331 (IPA)L is 9.67, ∑ L)23
31 (IPB)L is 10.07, be formulated into finished lubricant oil having a MRV viscosity
and ∑ L)23 (IPC)L is 2.30. The isoparaffin index is calculated as
31 of 40 000 cP or less.
9.67/(10.03 + 2.30) or 0.7843. The isoparaffin indexes for the 3.5. Physical Property: MRV Viscosity Prediction via
30 samples are listed in Table 2 along with their measured MRV Isoparaffin Index. The finished lubricant oil MRV viscosity
viscosities of the formulated oils. can be further modeled by base oil paraffin composition. A
The physical meaning of the isoparaffin index can be as a subset of the first 23 lubricant base oil samples from our studied
“degree of dewaxing” indicator. If a base oil contains a suite was examined (those that qualified for the isoparaffin index
Group II Lubricant Oil Energy & Fuels, Vol. 21, No. 6, 2007 3483

the reproducibility uncertainty range. Therefore, this new MRV

viscosity correlation tool developed by the GCxGC technique
provides an acceptable accuracy for prediction of MRV viscosity
of the base oil samples studied.
3.6. Naphthenes Contribution to Viscosity (MRV). In this
study, the naphthene contribution to the MRV viscosity is not
included. There are two reasons to put off the study on this
topic at the current time. The first one is the lack of qualitative
understanding and the quantitative measurement of them. The
second reason is that a general assumption has been made on
the basis of accumulated experience that naphthene compounds
behave similarly to paraffins in terms of structures (especially
alkyl side chain), isomers distributions, and response to different
types of dewaxing processes. A correlation between composition
Figure 11. Correlation between the isoparaffin index and MRV for 23
base oil samples studied. and physical property without naphthenes will certainly be
incomplete; however, the error is unavoidable, and the source
Table 3. Measured, Predicted (Based on the Isoparaffin Index), of error is well understood and manageable.
and the Variation of Formulated Engine Oil MRV of the 23
Samples Studied
4. Conclusion and Future Development
isoparaffin MRV measured MRV predicted difference
sample index (cP) (cP) (%) A simple HRGC technique has been successfully applied for
the analysis of the chemical composition of lubricant base oil.
sample 01 0.7323 36211 33350 8
sample 02 0.7269 33700 32816 3 This method can be used as a general tool to qualitatively and
sample 03 0.6668 31400 26877 14 semiquantitatively determine the paraffin chemical composition.
sample 04 0.6843 30874 28607 7 It can be further used to estimate the efficiency of various
sample 05 0.7033 29600 30484 3 dewaxing process, such as solvent dewaxing with various
sample 06 0.7108 27876 31231 12
sample 07 0.6899 26870 29158 9 solvents or their combination, or catalytic dewaxing with
sample 08 0.7008 26050 30234 16 different types of catalysts, or dewaxing using sequential
sample 09 0.6201 25600 22252 14 multiple steps involving solvents and catalysts.
sample 10 0.6504 25306 25257 0 The HRGC technique does not resolve all components of
sample 11 0.6587 23170 26072 13
interest in the lubricant base oil. Hence, all measurements are
sample 12 0.5992 23000 20191 12
sample 13 0.5737 19536 17667 10 considered qualitative or semiquantitative. Without a precise
sample 14 0.5835 19100 18640 2 quantitative measurement of individual component, it is difficult
sample 15 0.5539 17300 15711 9 to establish any accurate correlation between the chemical
sample 16 0.5561 17300 15925 8 composition and physical property. An improved separation
sample 17 0.5566 17004 15975 6
sample 18 0.5670 16130 17001 5 technique is required to better characterize the unresolved
sample 19 0.5506 16100 15378 4 components.
sample 20 0.5665 14800 16954 15 A GCxGC method has been developed to quantitatively
sample 21 0.5541 12700 15727 24 characterize paraffin molecules in lubricant base oils. The
sample 22 0.5472 12675 14623 15
paraffins information has been further used to find the correlation
sample 23 0.5429 12675 15044 19
between the paraffin chemical composition and the low-
temperature property, viscosity, measured by MRV. A model
test), and the MRV viscosity predictions were compared to their
has been developed to predict MRV viscosity based on paraffin
measured MRV viscosity. A correlation is found between the
chemical composition to qualify certain “critical level” of preset
measured MRV viscosity with the isoparaffin index. This
MRV viscosity.
correlation is shown in Figure 11 along with the linear regression
The correlation between the paraffin chemical composition
line that yields a coefficient of variation, R2, equal to 0.883.
and the MRV viscosity can be successfully developed due to a
From this least-squares fit, MRV viscosity can be calculated
set of better quantitative paraffin results provided by the GCxGC
by
technique. The remaining key challenges for the analytical
viscosity (MRV) ) 98904 × isoparaffin index - 39705 (2) separation is how to reduce or complete eliminate the structural
isomers interferences during the chromatographic separation.
The isoparaffin index, measured MRV viscosity, predicted
In addition to the GCxGC technique, the future development
MRV viscosity, and the percent difference between the measured
will need to focus on exploring other possible hyphenated
and predicted MRV viscosity are listed in Table 3. According
techniques and/or multidimensional separation/identification
to the MRV viscosity test method (ASTM D4684-02a), the
approaches to further separate the paraffins and naphthenes to
statistical repeatability of MRV viscosity measurement is 13.2%
achieve a better quantitative analysis of each individual com-
from mean at test temperature of -35 °C. In addition, the
pound in the lubricant base oil and to correlate with its actual
reproducibility of MRV viscosity test is 35.8% from mean at
performances.
test temperature of -35 °C. As seen in Table 3, all variations
between predicted and measured MRV viscosity are well below EF700407C