Article

pubs.acs.org/EF

Multivariate Analysis of Crude Oil Composition and Fluid Properties

Used in Multiphase Flow Metering (MFM)
Andreas L. Tomren,*,†,§ Tanja Barth,†,§ and Kjetil Folgerø‡,§
†
Department of Chemistry, University of Bergen, Bergen, Norway
‡
Christian Michelsen Research AS, Bergen, Norway
§
Michelsen Centre, Bergen, Norway

ABSTRACT: Crude oil characterization by infrared (IR) spectroscopy and whole oil gas chromatography (GC) has been used
to provide data for establishing multivariate prediction models for physical properties of crude oils. The parameters of interest are
used in multiphase flowmeters (MFMs) for monitoring production and transport of petroleum fluids, and permittivity
parameters are of special interest. Data for 20 crude oils and condensates has been acquired and modeled using partial least
squares (PLS) modeling. Good quality predictions were obtained for density, velocity of sound, and static and high frequency
permittivity. Biodegradation of crude oil is the main cause of variation in the modeled variables. The data required are obtained in
standard analytical procedures, and thus the approach has a considerable potential for use in on-site quality assurance.

1. INTRODUCTION Quality control based on monitoring the fluid composition using

Modern, sophisticated analytical techniques generate large
amounts of data that reflect both the composition and properties
of crude oils and crude oil fractions. This opens up possibilities
for estimating a wide range of important properties and quality
parameters for such complex mixtures based on a few, or even a
single, set of analytical data. Conventionally, the values of the
physical properties of interest are mostly used in the form of
simpler numerical scales or expressions, that is, the density,
permittivity, or octane number. Such parameters have tradition-
ally been individually determined, but applications based on
estimations or calibrations using complementary data have been
increasing. Typically, the potential for estimating a number of
conventional classification parameters based on near infrared
(NIR) spectral data using multivariate statistical methods has
recently been reported,1,2 and this approach is already extensively
used in modern refinery operations (e.g., ref 3). Similar strategies
have also been used previously to predict more limited sets of
parameters.4−9
Determining the permittivity of mixed oil−water−gas (OWG)
fluid flow is a typical example of a measurement where cali-
bration models could be useful. In crude oil production moni-
toring, multiphase flowmeters (MFMs) are used for online
monitoring of the OWG flow in pipelines, where the output of
the measurement is the volume or mass of each phase passing
the flowmeter in a given time. Data from multiphase meters help
in optimizing petroleum production, increasing the oil recovery
and lowering the investments and operational costs.10,11
Permittivity measurements provide input for the determination
of flow rates and relative distributions of the fluids in several well
established measurement technologies.12 Such systems are, how-
ever, calibrated to the initial oil composition and may loose
precision over time due to changes in the fluid compositions that
result in changes in the actual permittivities relative to the incor-
porated calibration values. Monitoring the permittivity regu-
larly is one approach to quality assurance of the meter readings,
but the necessary instrumentation is often not easily available.
standard crude oil analytical data provided by generally available
analytical instrumentation in combination with multivariate esti-
mation of the required parameters is thus an attractive alternative.
A MFM measures the permittivity of oil−water−gas mix-
tures, and it is important to know the permittivity of each phase
(oil, water, and gas) in order to calculate the ratio of the
different phases in the mixture. The topic of this work is to
determine the permittivity, in addition to other important
variables for MFM metering such as density and velocity of
sound, of the crude oil phase, and to investigate which
compounds in the oil are important for the variation in the
different variables.
Permittivity of liquids is normally measured using dielectric
spectroscopy, and the spectra are described by the parameters
of a Cole−Cole model13 fitted to the dielectric spectrum. When
predicting the permittivity of a crude oil, either the parameters
of the Cole−Cole equation or the whole spectrum can be
modeled.14 This work presents models for prediction of the
Cole−Cole parameters for the permittivity spectra based on
compositional analysis of crude oils. Some additional param-
eters that are relevant for the permittivity and flow monitoring
in general are also modeled. Both spectral profiles and com-
pound based compositional data are tested for their potential to
provide reliable estimates of the parameter values. Standard
IR spectra comprise the spectral data, while individual hydro-
carbon distributions are determined using whole oil gas chro-
matography. For both analytical techniques, the analytical data
is so extensive that direct bivariate correlation is not feasible,
and data treatment procedures that can handle large data sets
are needed. PCA (principal component analysis) of the whole
data set is therefore used initially to explore the systematic
variation in the analytical data,15 while partial least squares
Received: April 12, 2012
Revised: July 27, 2012
Published: August 2, 2012

© 2012 American Chemical Society 5679 dx.doi.org/10.1021/ef300620r | Energy Fuels 2012, 26, 5679−5688
Energy & Fuels
(PLS) is used to establish the multivariate calibration models.16
The quality of the models is determined by evaluating the
accuracy of the prediction of samples not included in the
initially modeled data. Simple data pretreatment is applied to
make the data set internally comparable.
2. MATERIAL AND METHODS
2.1. Crude Oil Samples. Twenty crude oils, originating
mainly from the North Sea, have been analyzed for physical and
electrical properties and chemical composition. The types of
measurements performed and the number of variables pro-
duced are specified in Table 1. The data have also previously
Table 1. Types of Analytical Data and Number of Variables
from Each Procedure
analysis no. of variables units
density 1 g/mL at 20 °C
velocity of sound 1 m/s at 30 °C
whole oil GC 82 normalized peak area
FTIR 1738 absorbance
dielectric spectroscopy 5 as specified for eq 2, 20 °C
been used in a preliminary presentation of some models for an
extended range of parameters.9 The data set consists of 4
condensates, which are light crude oils with a clear yellow to
brown color, while the rest of the 16 crude oils are black and
opaque. The biodegradation level of all the crude oils in the
data set have been determined on the qualitative scale of Peters
and Moldowan17 by visual inspection of the hydrocarbon
distribution as observed in the GC traces.
All oils, prior to all measurements, have been placed in an
oven at 60 °C for 4 h, to dissolve waxes that may have
precipitated during storage. They have also been shaken and
turned upside down multiple times, to homogenize the oils
thoroughly.
2.2. Infrared (IR) Spectrospcopy. A Nicolet Protegè 460
FTIR (Fourier transform infrared) spectrometer with an ATR
(attenuated total reflection) measuring cell, equipped with a
diamond crystal, has been used for obtaining FTIR spectra
of the oils. One drop of oil is placed on the crystal, and
measurements (32 scans, giving an averaged spectrum) are
taken. For quality assurance, 5 drops has been measured for
each oil to eliminate differences due to lack of homogenization,
and the average of the resulting five spectra has been used in
the modeling. The data is given as absorbance: A = log(1/R),
where R is the percentage reflectance divided by 100. Percent
reflectance shows the amount of infrared energy reflected from
the sample: %R = (IS/IB)100, where IS is the intensity of
infrared energy reflected from the sample and IB is the intensity
of the infrared energy passing through the reflection accessory
without a sample in place.
2.3. Whole Oil Gas Chromatography (WOGC). The oils
have been analyzed on a ThermoFinnigan Trace GC
instrument equipped with a flame ionization detector (FID).
The stationary phase is a HP-PONA dimethylpolysiloxane column
(50 m × 0.20 mm × 0.5 μm) from Agilent technologies. The
mobile phase is helium. The temperature program is as follows:
30 °C for 15 min, 1.5 °C/min 60 C, 4 °C/min 320 °C, 320 C for
35 min. The injector temperature is 300 °C while the FID is kept
at 350 °C. Warm, homogenized crude oil (1 μL) is introduced
manually into the GC system through a syringe, using split in-
jection. The assignment of chromatographic peaks and quality
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assessment are based on the Norwegian Standard Oil (NSO-1),18
in which the compounds have been identified in a GC-MS, and by
manual inspection, the compounds in the chromatograms have
been identified and quantified for all the oils, assuming a constant
response factor. The quantified values for two gas chromatograms
for each oil are averaged, giving the quantified values used in the
modeling.
2.4. Velocity of Sound. The velocity of sound of the oils
was measured by the technique described by Bjørndal et al.
(2008),19 where the measurement cell was modified to include
a pressure seal and a pressure transmitter. As eq 1 shows, the
velocity is dependent on the density of the given fluid.
K
c fluid =
ρ (1)
Equation 1: Velocity of sound in a given fluid. cfluid = speed of
sound in given fluid, K = bulk modulus of given fluid, and ρ =
density of the given fluid.20
2.5. Dielectric Spectroscopy. The dielectric spectra were
measured on a measurement system for complex permittivity
measurements at 20 °C, based on a system developed by
Christian Michelsen Research AS in 1996.21
2.6. Density. The density of the oils has been obtained by
using an Anton Paar K.G. DMA 60 densitometer with DMA
602 measuring cell. Air and distilled water is first measured
for calibration, then the oil. Five measurements for each oil
have been averaged, and the resulting value is used in the
modeling.
2.7. Data Set for the Multivariate Analysis. The values
for density and velocity of sound are used directly as variables
in the data set. A total of 82 compounds have been quantified
from the GC analysis, all of them compounds containing only
carbon and hydrogen. 1738 variables have been collected from
the FTIR, corresponding to the absorbance at each wave-
number. Five variables have been derived from the dielectric
spectroscopy, corresponding to the 5 variables in the Cole−
Cole equation obtained from curve fitting of the spectra (eq 2).
The data available for the analysis are summarized in Table 1.
εs − ε∞ σ
ε* = ε∞ + 1−α
−j
1 + (j ϖ τ ) ϖε0 (2)
Equation 2: Cole−Cole equation, for curve fitting of dielectric
spectroscopy. ε* = relative permittivity (dimensionless), ε∞ =
high frequency permittivity (dimensionless), εs = static
permittivity (dielectric constant at low frequencies, dimension-
less), ω = angular frequency (radians/second), τ = macroscopic
relaxation time (seconds), σ = finite conductivity (Siemens/
meter), α = empirical factor (distribution factor, dimension-
less), ε0 = permittivity in vacuum (Farads/meter).
3. MULTIVARIATE ANALYSIS
3.1. Data Pretreatment. Data collected directly from an
instrument is termed raw data. Raw data can contain noise,
baseline drift, scattering effects, and other factors that may
influence the significant information in the data set. Therefore,
it may be necessary to pretreat the raw data, in order to remove
effects that do not represent chemical, physical, electrical,
or biological properties in the sample. To find the variation
between the objects, the raw data needs to be centered. This
can be done by calculating the average value for each variable,
and then, subtracting this from each of the original variables.
dx.doi.org/10.1021/ef300620r | Energy Fuels 2012, 26, 5679−5688
Energy & Fuels
Table 2. Range of Measured Physical Properties
static high frequency
permittivity permittivity α τ (s)
range 2.017−2.270 1.996−2.337 0.0318−0.9210
standard dev. 0.02 0.02 0.03
exptl 0.05 0.04 0.06
uncertainty
By doing this, the origin of the coordinate system is placed at
the center of gravity in the data set.
N B2, ..., BN are regression coefficients for variable 1, 2, ..., N. X1,
1 X2, ..., XN is variable 1, 2, ..., N.
Xcentred(i , j) = X(i , j) − ∑ x(i , j)
N i=1 (3)
Equation 3: Centring of the data set. X = full matrix, i = column
in matrix, j = row in matrix, N = total number of objects.
Pretreatment of GC Data. When injecting samples onto the
GC column, it is not certain that the amount of sample is
exactly the same in every injection. To eliminate any effects
from this, the quantified amounts have been normalized to
constant sum. This is done by dividing the selected variables of
each object with the sum of the objects to obtain the relative
distribution of the variables in each object. This procedure is
normal for GC.22,23 For models based on GC, the data sets has
been centered and normalized to constant sum.
Pretreatment of IR Data. For the models based on FTIR,
the raw data has been centered, but no further pretreatment has
been done.
3.2. Modeling. Multivariate data analysis has been
performed using the SIRIUS program package, version 7.0.24
PLS models have been built, based on GC and FTIR data, in
order to investigate the possibility of predicting the other physical
and electrical properties that have been measured.
The data sets are first investigated as PCA models to deter-
mine the degree of systematic variation in the data. The prin-
cipal components (PCs) provide a system of orthogonal axes
that each describe a maximum of the systematic variation
remaining in the data set.
The PLS models are then established. PLS models generate
Latent Variables (LVs) that are orthogonal and describe the
maximum covariation between the independent data matrix (the
analytical data) and the dependent data (the predicted properties).
Each model is based on 17 of the 20 oils in the data sets.
Three oils in each data set have been omitted from the models
in order to use them as validation objects. It is important to
balance the number of validation objects against the total number
of samples, as the model might be less robust if too many oils are
omitted from the model building. The predictive quality of the
models can be examined by testing the apparently unknown
objects against the models. For each model, one biodegraded oil,
one nonbiodegraded oil, and one condensate has been omitted
from the data set, as these oils in general are chemically different.
These validation objects have been chosen based on their values
for each variable; for each model, there is one validation object
with high value, one validation object with low value, and one vali-
dation object with medium value. This is done in order to validate
the predictive quality of the model, given unknown samples with
high, low, and medium values of the modeled variable.
When building a PLS model, you get a model in the form of
eq 4.
Y = B0 + B1 × X1 + B2 × X2 + B3 × X3
+ ...BN × XN (4)
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velocity of sound
σ (S/m) density (g/mL) (m/s)
0−5.7 × 10−7 0−1 × 10−7 0.7300−0.940 1141−1447
7.29% 0.007
0.013
Equation 4: Regression model for PLS modeling. N is the total
amount of variables in the model. B0 is the starting point, B1,
By evaluating the regression coefficients for a given model,
you can detect which variables have the most significant effect
on the model, be it positive or negative effect and, hence, which
variables are most important for the variation in the model.
Nevertheless, the effect of the total amount of coefficients usually
is more important than the effect of one single coefficient.
In the modeling stage, the goal was to find the models that
gave as low deviations as possible for the validation objects. The
number of latent variables (LVs) giving the lowest deviations is
chosen for each model. Based on this, the number of LVs in the
different models is not necessarily the same, causing some of
the models to be more robust than the others. The number of
LVs has been chosen bearing in mind that if too many LVs are
chosen, there is a possibility that noise is modeled as well as the
significant signal, causing the model to give poor predictions for
unknown samples. Also, if too few LVs are chosen, there is a
possibility that some of the significant information remains
unmodeled and gets categorized as noise, also causing the
model to give poor predictions for unknown samples.
4. RESULTS
4.1. Initial Data Evaluation. The ranges for the measured
physical properties for all the oils are given in Table 2. The
measurements span a reasonable range of values for most of the
parameters, with the exception of τ, dielectric relaxation time,
and σ, finite conductivity, where the value is zero for 3 and 10
of the samples, respectively. This lack of variation can represent
a problem for establishing robust models. The uncertainty in α
and τ is high because they are based on the curve fit of the
Cole−Cole model, while σ is close to zero for oils in general.
This means that, among the parameters extracted from the
Cole−Cole model, static permittivity and high frequency
permittivity are easier to determine than α, τ, and σ.
The standard deviations in Table 2 are based on replicate
experiments. For the permittivity variables, the standard devia-
tion is based on two replicates, density is based on three repli-
cates, while for velocity of sound no replicates were measured.
The experimental uncertainty in Table 2 is the standard
deviation multiplied by 2, as ±1.96 of the standard deviation
about the mean marks the range within which, when a sample
exists, there is a 95% chance that it is a part of the population.
Standard deviations for σ and velocity of sound could not be
obtained because of the insufficient number of measurements.
The standard deviation for τ is given in %, as the standard
deviation varies relatively with size.
PCA performed on GC data of the sample set of crude oils
show that three groupings occur, separating biodegraded oils,
nonbiodegraded oils and condensates, as shown in Figure 1.The
two first PCs explain 67.6% of the total variance in the data set,
dx.doi.org/10.1021/ef300620r | Energy Fuels 2012, 26, 5679−5688
Energy & Fuels Article

coordinate system. Condensates are partly clustering with the

Figure 1. PCA score plot of GC data. Brown circles = biodegraded oils.
Blue squares = nonbiodegraded oils. Light blue triangles = condensates.
Figure 2. PCA score plot of IR data. Brown circles = biodegraded oils.
Blue squares = nonbiodegraded oils. Light blue triangles = condensates.
which shows that there is a high degree of systematic variation in
the data, as opposed to unsystematic noise.
Figure 1 shows that biodegraded oils span out in one direc-
tion from the origin of the coordinate system, while the non-
biodegraded oils span out in a different direction of the
nonbiodegraded oils and partly spanning out a different direc-
tion than biodegraded and nonbiodegraded oils. This indicates,
as expected, that biodegraded and nonbiodegraded oils are
chemically different, based on GC data.
PCA performed on IR data of the same set of crude and
model oils show similar groupings (Figure 2), though with a
tendency to less variation within each group. The two first PC’s
explain 93% of the total variance in the data set, which show
that the systematic variation in the data is high.
Figure 2 shows that biodegraded oils span out in one direc-
tion from the origin of the coordinate system, while the non-
biodegraded oils span out a different direction of the coordinate
system. Condensates also span out a different direction of the
coordinate system. This indicates that biodegraded oils,
nonbiodegraded oils, and condensates are different based on
IR data.
The presence of such systematic variation indicates that the
models for each data type describe variations due to chemical
compositional factors. If this variation is connected directly or
indirectly to the properties to be modeled, there is a potential
for generating prediction model for the parameters in question
and to use them to predict unknown physical properties of new
oils based on GC and IR data.
Some objects in the data set might be classified as outliers,
but since all of the oils in the data set are representative
samples, they cannot be excluded from the model. If they are
excluded, the range in which the model is valid might be
reduced. A larger data set would most likely expand the range
of the model, in addition to reducing the impression that some
objects are outliers.
3.2. Prediction Models by PLS. Table 3 gives an overview
of the established models, presented at a qualitative scale
ranging from poor, via OK for distinguishing between high and
low value, via OK, via good, to very good. This is done by com-
paring the experimental uncertainty of the measurements (shown
in Tables 4 and 5) with the prediction error of the validation
objects; if the error is much lower than the experimental
uncertainty, then the predictive quality of the model is rated as
very good, if the error is similar to the experimental uncertainty,
then the predictive quality of the model is rated as good. If
the difference between the experimental uncertainty and the
prediction error is larger, the prediction errors are more closely
examined. If the validation objects are predicted to be of high
value, while the measured values are low, the model is rated as
poor. If the validation objects are predicted to be of high value,
and the measured values are of high value, the model is rated as

Table 3. Overview of Established Models with Qualitative Evaluation

GC IR
no. no.
modeled variable coding quality LVs explained variancea quality LVs explained variancea
static permittivity permvar e_st good 8 99.29% (99.32%) good 4 96.93% (98.52%)
high frequency permvar e_inf good 8 99.77% (99.36%) good 5 97.38% (98.29%)
permittivity
α permvar a OK 6 96.56% (83.24%) OK 4 96.87% (77.51%)
τ permvar t OK for distinguishing 7 98.68% (96.94%) OK for distinguishing between 6 98.78% (91.75%)
between high and low level high and low level
σ permvar s poor OK for distinguishing between
high and low level
density eensity good 6 95.49% (97.66%) good 3 89.80% (96.03%)
velocity of sound velocity of sound good 5 94.43% (96.38%) very good 5 99.57% (99.95%)
a
Total explained variance from Independent block, and total explained variance from dependent block in ().

5682 dx.doi.org/10.1021/ef300620r | Energy Fuels 2012, 26, 5679−5688

 Table 4. Overview of the Quantitative Predictive Quality of the Established Models for IR
low value object medium value object high value object
avg. dev. val. exptl.
modeled variable coding meas. pred. dev. meas. pred. dev. meas. pred. dev. obj.a unc.b
static permittivity permvar e_st 2.08 2.04 0.04 2.22 2.15 0.07 2.43 2.39 0.04 0.05 0.05
Energy & Fuels

high frequency permvar e_inf 2.04 2.03 0.01 2.14 2.12 0.02 2.22 2.24 −0.02 0.02 0.04
permittivity
α permvar a 0.33 0.26 0.07 0.51 0.43 0.08 0.72 0.62 0.1 0.08 0.06
τ permvar t 0 −2.79 × 10−7 2.79 × 10−7 4.20 × 10−9 9.24 × 10−8 −8.82 × 10−8 4.24 × 10−7 2.54 × 10−7 1.7 × 10−7 1.79 × 10−7
σ permvar s 0 7.70 × 10−9 7.70 × 10−9 9.80 × 10−9 4.30 × 10−9 5.5 × 10−9 7.70 × 10−8 6.75 × 10−8 9.5 × 10−9 7.57 × 10−9
density density 0.766 0.762 0.004 0.824 0.833 −0.009 0.926 0.940 −0.14 0.009 0.013
velocity of sound velocity of sound 1266 1268 −2 1347 1344 3 1398 1397 1 2
a
Average deviation of the validation objects. bStandard deviation for measured values (see Table 2) multiplied with 2, as ±1.96 of the standard deviation about the mean marks the range within which,
when a sample exists, there is a 95% chance that it is a part of the population.

5683
Table 5. Overview of the Quantitative Predictive Quality of the Established Models for GC
low value object medium value object High value object
avg. dev. val. exptl.
modeled variable coding meas. pred. dev. meas. pred. dev. meas. pred. dev. obj.a unc.b
static permittivity permvar e_st 2.08 2.05 0.03 2.22 2.22 0 2.43 2.41 0.02 0.02 0.05
high frequency permvar e_inf 2.04 2.05 −0.01 2.14 2.14 0 2.22 2.22 0 0.003 0.04
permittivity
α permvar a 0.27 0.42 −0.15 0.50 0.48 0.02 0.59 0.68 −0.09 0.09 0.06
τ permvar t 0 −9.00 × 10−10 9.00 × 10−10 4.00 × 10−9 4.20 × 10−9 −2 × 10−10 7.70 × 10−9 8.60 × 10−9 −9 × 10−10 3.37 × 10−9
σ permvar s 0 1.92 × 10−8 −1.92 × 10−8 9.70 × 10−9 3.16 × 10−8 −2.19 × 10−8 7.70 × 10−8 6.24 × 10−8 1.46 × 10−8 1.86 × 10−8
density density 0.766 0.788 −0.022 0.824 0.847 −0.023 0.904 0.902 0.002 0.016 0.013
velocity of sound velocity of 1157 1189 −32 1324 1329 −5 1423 1387 36 24
sound
a
Average deviation of the validation objects. bStandard deviation for measured values multiplied with 2, as ±1.96 of the standard deviation about the mean marks the range within which, when a sample
exists, there is a 95% chance that it is a part of the population.
Article

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Energy & Fuels
Figure 3. Predicted value plotted against measured for (a) density based on GC, (b) velocity of sound based on GC, (c) static permittivity (e_st)
based on IR data, (d) high frequency permittivity (e_inf) based on IR data, (e) density based on IR data, (f) velocity of sound based on IR data.
Brown squares = biodegraded oils. Blue squares = nonbiodegraded oils. Light blue squares = condensates. Red squares = validation objects.
either OK for distinguishing between high and low value, or
OK, depending on how close to the experimental uncertainty
the prediction errors are.
The number of LVs for the different models are also given in
Table 3.
Figure 3 shows modeling results for density and velocity of
sound based on GC data, and static permittivity, high frequency
permittivity, density, and velocity of sound based on IR data, all
presented as predicted value plotted against measured value.
These figures represent the best modeling results for each
variable for GC and IR. As the models for the permittivity
variables α, τ, and σ at best give “OK” results, the results for
these models are not shown here. In addition, the modeling
for static and high frequency permittivity based on GC data
give good quality models, which already have been presented
in ref 9.
Figure 3a and b shows that prediction of density and velocity
of sound based on GC data are possible with good results
within the range of oil compositions represented in the data.
Figure 3c−f shows that prediction of static permittivity, high
frequency permittivity, density, and velocity of sound, all based
on IR data, are possible with good results within the range of oil
compositions represented in the data. No standard deviation is
obtained for velocity of sound, since there was only made one
measurement for each oil, so the quality of these models is
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evaluated based on a modeling perspective. As clearly shown in
Figure 3e and f, the validation objects do not stand out in
comparison to the model objects, and with a maximum error of
0.22% for the model for IR, it is difficult to argue against the
statement that the model is very good. However, since no
replicate measurements of velocity of sound are done, this
cannot be verified completely.
4.3. Chemical Significance of the Models. Figure 4a−f
shows the regression coefficients for the same set of models,
giving an overview of which variables are important for building
the model, and therefore, the most important variables when
looking at variation in the different properties.
Figure 4 shows that positive effect on the model for density
based on GC data originates almost exclusively from branched
alkanes and the higher molecular weight straight chained alkanes,
while negative effect originates almost exclusively from low to
medium molecular weight straight chained alkanes. This indi-
cates that biodegradation of crude oil has an important effect
on the variance of density in crude oils, since the smallest
straight chained alkanes are the first to be removed or altered
during biodegradation.17
Similar trends are observed for the model for velocity of
sound, as shown in Figure 4b. Positive effects on the model
originate almost exclusively from branched alkanes and the
higher molecular weight straight chained alkanes, while negative
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Energy & Fuels Article

Figure 4. Regression coefficients for model for (a) density based on GC data, (b) velocity of sound based on GC data, (c) static permittivity (e_st)
based on IR data, (d) high frequency permittivity based on IR data, (e) density based on IR data. The biodegradation effect is more evident for the
model for density than for the models for static and high frequency permittivity, as there are fewer effects that might be considered as noise. (f)
Regression coefficients for the model for velocity of sound based on IR data. Coding for the variables is given in Appendix 1.

effects originate almost exclusively from small to medium
molecular weight straight chained alkanes. Thus, biodegrada-
tion has an important effect also on the variance of the velocity
of sound in crude oils.
For static permittivity modeled from IR, the area between
2800 cm−1, which corresponds to the signals originating from
CH3 stretch, have a positive effect, while signals originating
from CH2 stretch have a negative effect. This is an indication of
biodegradation, as a high amount of CH3 indicates a high
amount of branched alkanes and a high amount of CH2
indicates a high amount of straight chained alkanes.4 As straight
chained alkanes are the first compounds to be attacked during
biodegradation, the branched alkanes will dominate the
composition increasingly. Other regions having a positive effect
are the CH3 bend at around 1375 cm−1 and CO at around
1450 cm−1; these signals also indicate biodegradation, as the
CO might origin from carboxylic acids formed during bio-
degradation.4 From 800 cm−1 to 694 cm−1, there are signals
having both positive and negative effects, these signals are in
the fingerprint region and are not very easy to assess, but it is
likely that they originate from C−H bonds in aromatic com-
pounds. The positive effects are due to the fact that bio-
degraded oils have more absorbance in these regions.
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The coefficients for high frequency permittivity looks very
similar as for static permittivity, with a positive effect from
CH3, both stretch and bend, and a negative effect from CH2
stretch. In addition, there is a negative effect from CH2 bend at
around 1465 cm−1, enhancing the indication that biodegrada-
tion is the most important effect on the model.
For velocity of sound, the same trends for CH3 and CH2 as
for the models for density and e_inf are present, but there are
also a lot of effects that looks like noise. However, the predic-
tive quality of the model is very good.
4.4. Precision of Prediction. Figure 5 shows the predicted
and measured values for the three validation objects for the
models for static permittivity, high frequency permittivity, per-
mittivity variable α, and density, all based on IR data, and Table 3
summarizes the quantitative modeling results. It is clear that the
deviations are small for most of the models and validation
objects. Exceptions are the permittivity variables α, τ, and σ,
where α is considered to give the best results of these three
variables.
For the variables static permittivity and α, all validation ob-
jects are predicted with a value that is lower than the measured.
It is not possible using PLS to determine whether this is a bias
or due to the choice of validation objects. A larger data set
dx.doi.org/10.1021/ef300620r | Energy Fuels 2012, 26, 5679−5688
Energy & Fuels
Figure 5. Predicted and measured values for PLS models for static
permittivity, high frequency permittivity, permittivity variable α, and
density based on IR data. (a) High value validation objects; (b)
medium value validation objects; (c) low value validation objects.
might clarify this, as more validation objects can be used in the
model validation.
Compared to the deviations that Satya et al.1 achieved for
density based on NIR spectral data, we see that the results are
somewhat better; Satya et al. achieved deviations of 1.6% and
5.3% for their two validation objects, while the three validation
objects in this work have deviations of 0.5%, 1.1%, and 1.5%.
Figure 6 shows the predicted and measured values for the
three validation objects for the models for static permittivity,
high frequency permittivity, permittivity variable α, and density,
all based on GC data, and Table 4 summarizes the quantitative
modeling results. It is clear that the deviations are small for
most of the models and validation objects. Exceptions are the
permittivity variables α, τ, and σ, where α is considered to give
the best results of the three variables.
Compared to the deviations that Satya et al.1 achieved for
their model of density based on NIR, we see that the deviations
for the model for density based on GC in this work are in the
same range; Satya et al. achieved deviations of 1.6% and 5.3%
for their two validation objects, while the three validation
objects in this work have deviations of 2.9%, 2.8%, and 0.3%.
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Figure 6. Predicted and measured values for PLS models for static
permittivity, high frequency permittivity, permittivity variable α, and
density based on GC data. (a) High value validation objects; (b)
medium value validation objects; (c) low value validation objects.
5. DISCUSSION
As Figures 3−6 and Tables 4 and 5 show, PLS calibration
models for prediction of several properties of crude oil based
on both GC data and IR data can be built with good results.
The results are comparable or even better in some cases than
previously established models.1 The reason for the improved
quality of the models in this work is uncertain, as the basis for
the models in Satya et al.1 is not possible to identify precisely.
The improvement may be due to more consistent experimental
data, since all measurements were performed by one operator
during a short time period. The sample quality may also be
relevant. In addition, the distribution of the sample properties
over a reasonable range may contribute, since the sample sets are
not very large.
Overall, the values estimated for the experimental uncertainties
and the model uncertainties lie in the same range, indicating that
the data give a good basis for accurate predictions.
The model for velocity of sound based on IR data is in fact
very good, at least from a modeling perspective, with an average
dx.doi.org/10.1021/ef300620r | Energy Fuels 2012, 26, 5679−5688
Energy & Fuels Article

Table A1. Variable Coding and Variable Names for the GC Data
variable coding variable name variable coding variable name
iC5 iso-pentane nC8 n-octane
nC5 n-pentane e-cyC6 ethylcyclohexane
22dm-C4 2,2-dimethylbutane i-C9 iso-nonane
cyC5 cyclopentane e-benzene ethylbenzene
23dm-C4 2,3-dimethylbutane m-xylene meta-xylene
2 m-C5 2-methylpentane p-xylene para-xylene
3 m-C5 3-methylpentane 4 m-C8 4-methyloctane
nC6 n-hexane 2 m-C8 2-methyloctane
22dm-C5 2,2-dimethylpentane 3 m-C8 3-methyloctane
m-cyC5 methylcyclopentane o-xylene orto-xylene
24dm-C5 2,4-dimethylpentane nC9 n-nonane
223tm-C4 2,2,3-trimethylbutane i-C10 iso-decane
benzene benzene nC10 n-decane
33dm-C5 3,3-dimethylpentane i-C11 iso-undecane
cyC6 cyclohexane nC11 n-undecane
2 m-C6 2-methylhexane nC12 n-dodecane
23dm-C5 2,3-dimethylpentane i-C13 iso-tridecane
11dm-cyC5 1,1-dimethylcyclopentane i-C14 iso-tetradecane
3 m-C6 3-methylhexane nC13 n-tridecane
1c.3dm-cyC5 cis-1−3-dimethylcyclopentane i-C15 iso-pentadecane
1t.3dm-cyC5 trans-1−3-dimethylcyclopentane nC14 n-tetradecane
1t.2dm-cyC5 trans-1−2-dimethylcyclopentane i-C16 iso-hexadecane
nC7 n-heptane nC15 n-pentadecane
m-cyC6 methylcyclohexane nC16 n-hexadecane
113tm-cyC5 1,1,3-trimethylcyclopentane i-C18 iso-octadecane
e-cyC5 ethylcyclopentane nC17 n-heptadecane
25dm-C6 2,5-dimethylhexane pristane pristane
223tm-C5/24dm-C6 2,2,3-trimethylpentane/2,4-dimethylhexane nC18 n-octadecane
1c.2t.4tm-cyC5 cis-1-trans-2−4-trimethylcyclopentane phytane phytane
33dmC6 3,3-dimethylhexane nC19 n-nonadecane
1t.2c.3tm-cyC5 trans-1-cis-2−3-methylcyclopentane nC20 n-icosane
234tm-C5 2,3,4-trimethylpentane nC21 n-henicaosane
Toluen/233tm-C5 toluene/2,3,3-trimethylpentane nC22 n-docosane
23dm-C6 2,3-dimethylhexane nC23 n-tricosane
2 m-C7 2-methylheptane nC24 n-tetracosane
4 m-C7 4-methylheptane nC25 n-pentacosane
3 m-C7 3-methylheptane nC26 n-hexacosane
1.c3dm-cyC6 cis-1−3-dimethylcyclohexane nC27 n-heptacosane
1.14dm-cyC6 trans-1−4-dimethylcyclohexane nC28 n-octacosane
11dm-cyC6 1,1-dimethylcyclohexane nC29 n-nonacosane
1t.2dm-cyC6 trans-1−2-dimethylcyclohexane nC30 n-triacontane

error of 0.12% for the validation objects, while the models for τ
(dielectric relaxation) and σ (conductivity) are more inaccurate.
For quality assurance purposes for the flowmeters, the
models for static permittivity, high frequency permittivity,
density, and velocity of sound, based on GC and IR, respec-
tively, are considered precise enough to be useful. As a minimum,
the prediction of significantly different values than used in the
initial calibration of the MFM will indicate that a new calibration
of the system is required.
The models also give information on the chemical basis for
the variations in the sample set.
For most of the models, the regression coefficients that build
up most of the models, both for GC and IR, strongly indicate
that biodegradation of crude oils is the main cause of variation in
the modeled variables. For models based on GC, the main
positive contributors to the model are branched alkanes and long,
straight chained alkanes. As low to medium molecular weight
straight chained alkanes are the first molecules to be depleted by
5687
biodegradation, the branched and large molecular weight straight
chained alkanes will have a proportionally higher relative
abundance in the crude oil mixture. The small to medium mole-
cular weight alkanes are mostly negative contributors, further
supporting that biodegradation is the main cause of variation in
the modeled variables.
The permittivity of a pure compound increases with increas-
ing number of carbon atoms in the compound;25 hence, biode-
graded oils generally have a higher permittivity than non-
biodegraded oils, since they have a higher relative abundance of
higher molecular weight straight chained alkanes. This is also
observed in the measurements for this data set.
For the models based on IR, the biodegradation effect is also
observed since significant values for the regression coefficients
tend to originate from areas in the IR spectra that are
influenced by the biodegradation process. For all models, CH3
stretch regions are positive contributors, while CH2 stretch
regions are negative contributors, reflecting that biodegraded
dx.doi.org/10.1021/ef300620r | Energy Fuels 2012, 26, 5679−5688
Energy & Fuels
oils have higher absorbance in the CH3 regions than non-
biodegraded oils, while they have lower absorbance in the CH2
regions. A strong absorbance in the CH3 regions indicates a
high amount of branched alkanes, while a strong absorbance in
the CH2 regions indicates more straight chained alkanes.
Biodegradation also causes increased contents of polar com-
pounds in crude oils, either due to production of, for example,
organic acids as metabolites in the microbial processes, or due
to the partial removal of nonpolar bulk hydrocarbons. The IR
spectra can reflect this increase directly in the parts of the
spectra that reflect carbon−oxygen bonds. This is observed in
the regression coefficients as having a positive effect on the
model, and the trend is that the biodegraded oils have stronger
absorbance in those areas than the oils that are not biodegraded,
which further supports the interpretation that biodegradation is
the major cause of variation in the modeled variables.
The condensate samples are strongly dominated by hydro-
carbons in the low molecular range, so the differences in the
hydrocarbon composition will be dominant in these samples.
A larger sample set consisting of condensates only might reveal
patterns of variation that are not obvious in the sample set used
here.
Overall, GC- and IR-based PLS calibration models of
properties that are important in MFM operation have shown
good predictive quality, supporting their usefulness in oil
production and transport facilities. A typical application would
be to detect changes in oil composition during the production
lifetime of an oil field and highlight the need for updating
calibration values. Both analytical techniques provide data that
give good model results. If MFM calibration is the major
purpose, IR spectroscopy is the best approach. It is a much
faster and easier measuring technique; also, portable measuring
devices for IR spectroscopy already exist. GC measurements
take several hours but are already in use for quality control in
other contexts, and may therefore be a good choice in a com-
bined flow assurance perspective.
■
APPENDIX A
Table A1 shows the variable coding and variable names for the
gas chromatography data, as used in Figure 4.
■
AUTHOR INFORMATION
Corresponding Author
*E-mail: andreas.tomren@kj.uib.no.
Notes
The authors declare no competing financial interest.
■ ACKNOWLEDGMENTS
The funding for this work comes from the Norwegian Research
Council through the Michelsen Centre for Research Based
Innovation and from Norwegian industrial partner Roxar.
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