Naske PDF

Characterisation of Crude Oil Components,
Asphaltene Aggregation and Emulsion Stability

by means of Near Infrared Spectroscopy
and Multivariate Analysis

by

Narve Aske

Thesis Submitted in Partial Fulfilment of the
Requirements for the Degree of

DOKTOR INGENIR

Department of Chemical Engineering
Norwegian University of Science and Technology
Trondheim, June 2002

I
Preface
This thesis is submitted in partial fulfilment of the requirements for the degree of dr.ing. at
the Norwegian University of Science and Technology, NTNU. It consists of five papers that are
based on work performed at Statoil R&D Centre from January 2000 to June 2002. In addition,
some of the work is a result of a shorter stay at Norsk Hydro Research Park in Porsgrunn,
Norway.

After finishing my siv.ing. degree in chemical engineering in 1998, I was introduced to the
field of surface and colloid chemistry by joining the research programme Flucha II (Fluid
Characterisation at Elevated Pressures and Temperatures). The programme is supervised by
Professor Johan Sjblom, and is a joint event between Statoil R&D Centre and Department of
Chemical Engineering at NTNU in Trondheim. The programme is financed by The Research
Council of Norway and the oil industry, represented by Statoil, Norsk Hydro, TotalFinaElf and
ABB. The sponsors have acted as a reference group by evaluating the programme progress
twice a year. The project has involved three doctoral students and one post doc.

In addition to the five papers presented in this thesis, a sixth paper has been accepted for
publication in Journal of Dispersion Science and Engineering. Parts of the work contained in
this thesis were presented at the 3
rd
International Conference on Petroleum Phase Behavior
and Fouling in New Orleans, USA in March 2002. I have also contributed to an invited series
paper in a special issue of Advances in Colloid and Interface Science on the occasion of
Professor Overbeeks 90th birthday.

II
Acknowledgements
I would like to express my sincere gratitude to

Professor Johan Sjblom, for taking on the challenging task of teaching a process engineer the
fine art of surface and colloid chemistry, and not at least for his skills in Finnish
teambuilding.

Dr. Harald Kallevik, for his valuable contributions to this thesis, and also for his genuine
interest and insightful comments to my work.

Dr. Harald Frdedal, for first introducing me to the fascinating, yet sometimes very
frustrating, world or asphaltene chemistry, and Dr. Robert Orr, for interesting discussions on
interfacial rheology and for taking good care of me during my stay in Porsgrunn.

Trond Erik Havre, Inge Harald Auflem and the rest of my Flucha-colleagues, for participating
in quite a few fruitful coffee breaks, and for providing some invaluable memories from
Trondheim by night.

Statoil R&D Centre, for providing access to not only office space and laboratory facilities, but
also for letting me exploit some of their highly skilled employees during my work. The rest
of the Flucha-sponsors and The Research Council of Norway are thanked for their financial
support.

Tove, for her love and support, and simply for being the best reason in the world to go home
from work from time to time.

III
Abstract
Effective separation of water-in-crude oil emulsions is a central challenge for the oil industry
on the Norwegian Continental Shelf, especially with the future increase in subsea and even
down-hole processing of well-fluids. The mechanisms and properties governing emulsion
stability are far from fully understood, but the indigenous surface-active crude oil components
are believed to play a major role.

In this work a thorough physico-chemical characterisation of a set of crude oils originating
from a variety of production fields has been performed. Crude oil properties responsible for
emulsion stability were identified by use of multivariate analysis techniques like partial least
squares regression (PLS) and principal component analysis (PCA). Interfacial elasticity along
with both asphaltene content and asphaltene aggregation state were found to be main
contributors to emulsion stability. Information on a crude oils ability to form elastic crude oil-
water interfaces was found to be especially crucial when discussing emulsion stability.
However, measured values of interfacial elasticity were highly dependent on asphaltene
aggregation state.

Several experimental techniques was utilised, and partly developed, for the crude oil
characterisation. A high pressure liquid chromatography (HPLC) scheme was developed for
SARA-fractionation of crude oils, and an oscillating pendant drop tensiometer was used for
characterisation of interfacial rheological properties. For emulsion stability a cell for
determining the stability as a function of applied electric fields was used. In addition, near
infrared spectroscopy (NIR) was used throughout the work both for chemical and physical
characterisation of crude oils and model systems.

High-pressure NIR was used to study the aggregation of asphaltenes by pressure depletion. A
new technique for detection of asphaltene aggregation onset pressures based on NIR
combined with PCA was developed. It was also found that asphaltene aggregation is
reversible, but highly time-dependent. Finally, the size of asphaltene aggregates in model
systems was estimated by fitting NIR spectra to Rayleigh scattering theory.

IV
List of Papers

I. Narve Aske, Harald Kallevik, Johan Sjblom.
Determination of Saturate, Aromatic, Resin and Asphaltenic (SARA)
Components in Crude Oils by means of Infrared and Near Infrared
Spectroscopy.
Energy & Fuels, 15 (5) 1304-1312, 2001.

II. Narve Aske, Robert Orr, Johan Sjblom.
Interfacial Properties of Water-Crude Oil Systems using the Oscillating Pendant
Drop. Correlations to Asphaltene Solubility by Near Infrared Spectroscopy.
Submitted, Colloid and Polymer Science 2002.

III. Narve Aske, Harald Kallevik, Johan Sjblom.
Water-in-Crude Oil Emulsion Stability Studied by Critical Electric Field
Measurements. Correlation to Physico-Chemical Parameters and Near Infrared
Spectroscopy.
In press, Journal of Petroleum Science and Engineering.

IV. Narve Aske, Harald Kallevik, Einar Eng Johnsen, Johan Sjblom.
Asphaltene Aggregation from Live Crude Oils and Model Systems Studied by
High Pressure NIR Spectroscopy.
Accepted, Energy & Fuels 2002.

V. Narve Aske, Harald Kallevik, Johan Sjblom.
Asphaltene Aggregate Size by Near Infrared Spectroscopy.
Submitted, Applied Spectroscopy 2002.

V
Additional publications

VI. Narve Aske, Robert Orr, Johan Sjblom.
Dilatational Elasticity Moduli of Water-Crude Oil Interfaces using the Oscillating
Pendant Drop.
Accepted, Journal of Dispersion Science and Technology 2002.

VII. Johan Sjblom, Harald Kallevik, Narve Aske, Inge Harald Auflem, Trond Erik Havre,
ystein Sther, Robert Orr.
Recent Development in the Understanding of the Stability and Destabilization of
Water-in-Crude Oil Emulsions.
Presented at: "The 3
rd
International Conference on Petroleum Phase Behavior
and Fouling", New Orleans, USA, March 10-14, 2002.

VIII. Johan Sjblom, Narve Aske, Inge Harald Auflem, ystein Brandal, Trond Erik
Havre, ystein Sther, Arild Westvik, Einar Eng Johnsen, Harald Kallevik.
Our Current Understanding of Water-in-Crude Oil Emulsions. Recent
Characterization Techniques and High Pressure Performance.
Advances in Colloid and Interface Science, Special Issue: A Collection of Invited
Papers in Honour of Professor J. Th. G. Overbeek on the Occasion of his 90th
Birthday, In press, 2002.

VI
Contents
Preface ...................................................................................................................... I
Acknowledgements..................................................................................................... II
Abstract................................................................................................................... III
List of Papers............................................................................................................ IV
1 Introduction........................................................................................................1
2 Crude Oil Properties.............................................................................................2
2.1 Chemical composition..................................................................................2
2.2 Structure...................................................................................................5
2.3 Emulsions..................................................................................................8
3 Crude Oil Characterisation .................................................................................. 11
3.1 SARA Separation ...................................................................................... 11
3.2 Interfacial Rheology .................................................................................. 14
3.3 Near Infrared Spectroscopy........................................................................ 18
3.4 Critical Electric Field.................................................................................. 21
4 Multivariate Data Analysis................................................................................... 23
4.1 Principal Component Analysis (PCA) ............................................................ 23
4.2 Partial Least Squares Regression (PLS) ........................................................ 24
5 Main Results ..................................................................................................... 26
Paper I ............................................................................................................ 26
Paper II ........................................................................................................... 29
Paper III .......................................................................................................... 33
Paper IV........................................................................................................... 37
Paper V............................................................................................................ 42
6 Concluding Remarks .......................................................................................... 46
7 References ....................................................................................................... 48

1
1 Introduction
Subsea and down-hole processing of well fluids will be a central challenge on the
Norwegian Continental Shelf in the years to come. This type of processing presumes
more efficient separation of water / gas / oil, together with more cost-effective transport
of well fluids over long distances. More efficient separation requires more knowledge of
the mechanisms governing the separation process, and in this respect the indigenous
crude oil surfactants are known to play a major role. However, at the present our
knowledge of how these components influence separation processes is lacking in several
respects. Of special importance is knowledge of separation mechanisms at high pressures
and temperatures.

The Flucha II programme, a direct continuation of the first Flucha programme, aims to
increase the basic knowledge related to these issues. Central topics are physico-chemical
characterisation of crude oils and their indigenous surface-active components, like
asphaltenes, resins and naphthenic acids. The chemical composition and physical
characteristics of the crude oils are linked to emulsification and foamability at relevant
pressures and temperatures. The programme also aims at mapping the performance of
chemical additives acting as demulsifiers / inhibitors at operational conditions.

My contribution has been the build-up of a data matrix of over 20 crude oils, including
both North Sea and African production fields. Experimental techniques have been
developed to include characterising data such as SARA-fractions, interfacial rheology and
emulsion stability. The aggregation behaviour of asphaltenes at elevated pressures and
temperatures has also been studied. Near infrared spectroscopy in combination with
multivariate analysis has been used as an efficient tool throughout most of the work.
Crude Oil Properties

2
2 Crude Oil Properties
2.1 Chemical composition
Even though crude oils are a continuum of tens of thousands of different hydrocarbon
molecules, the proportions of the elements in crude oils vary over fairly narrow limits.
Nevertheless, a wide variation in properties is found from the lightest crude oils to the
highly asphaltenic crudes. The carbon content normally is in the range 83-87%, and the
hydrogen content varies between 10 and 14%. In addition, varying small amounts of
nitrogen, oxygen, sulfur and metals (Ni and V) are found in crude oils [1].

Due to the complex composition of crude oils, characterisation by the individual
molecular types is not possible, and elemental analysis is unattractive because it gives
only limited information about the constitution of petroleum due to the constancy of
elemental composition. Instead, hydrocarbon group type analysis is commonly employed
[2-9]. Knowledge of the distribution of major structural classes of hydrocarbons in crude
oils is needed in various fields in the petroleum industry. Examples are studies related to
reservoir evaluation, migration and maturity, degradation processes, processing, and
environmental effects [10].

The SARA-separation is an example of such group type analysis, separating the crude oils
in four main chemical classes based on differences in solubility and polarity. The four
SARA-fractions are the saturates (S), aromatics (A), resins (R), and the asphaltenes (A).
Instead of molecules or atoms, certain structures are here considered the components of
the crude oil, and the SARA-separation can be seen to give information somewhat
between that obtained by elemental analysis and analysis for individual molecules [1].
Figure 2-1 demonstrates the SARA-separation scheme developed for Paper I of this
thesis [11]. The chemical composition of crude oils will in the following be discussed on
the basis of the SARA-fractions. More information on the SARA-separation technique is
given in Chapter 3.


3
Crude oil
Asphaltenes
Maltenes
Resins Aromatics Saturates
n-hexane
precipitate solution
silica
trichloro-
methane
n-hexane n-hexane

Figure 2-1: SARA-separation scheme.

Saturates: The saturates (aliphatics) are non-polar hydrocarbons, without double bonds,
but including straight-chain and branched alkanes, as well as cycloalkanes (naphtenes).
Cycloalkanes contain one or more rings, which may have several alkyl side chains. The
proportion of saturates in a crude oil normally decreases with increasing molecular
weight fractions, thus the saturates generally are the lightest fraction of the crude oil.
Wax is a sub-class of the saturates, consisting primarily of straight-chain alkanes, mainly
ranging from C
20
to C
30
. Wax precipitates as a particulate solid at low temperatures, and
is known to effect emulsion stability properties of crude oil systems [12-14].

Aromatics: The term aromatics refer to benzene and its structural derivates. Aromatics
are common to all petroleum, and by far the majority of the aromatics contain alkyl
chains and cycloalkane rings, along with additional aromatic rings. Aromatics are often
classified as mono-, di-, and tri-aromatics depending on the number of aromatic rings
present in the molecule. Polar, higher molecular weight aromatics may fall in the resin or
asphaltene fraction.

Resins: This fraction is comprised of polar molecules often containing heteroatoms such
as nitrogen, oxygen or sulphur. The resin fraction is operationally defined, and one
common definition of resins is as the fraction soluble in light alkanes such as pentane and
heptane, but insoluble in liquid propane [1, 15, 16]. Since the resins are defined as a
solubility class, overlap both to the aromatic and the asphaltene fraction is expected.
Despite the fact that the resin fraction is very important with regard to crude oil

4
properties, little work has been reported on the characteristics of the resins, compared to
for instance the asphaltenes. However, some general characteristics may be identified.
Resins have a higher H/C ratio than asphaltenes, 1.2-1.7 compared to 0.9-1.2 for the
asphaltenes [16]. Resins are structural similar to asphaltenes, but smaller in molecular
weight (< 1000 g/mole). Naphthenic acids are commonly regarded as a part of the resin
fraction.

Asphaltenes: The asphaltene fraction, like the resins, is defined as a solubility class,
namely the fraction of the crude oil precipitating in light alkanes like pentane, hexane or
heptane. This precipitate is soluble in aromatic solvents like toluene and benzene. The
asphaltene fraction contains the largest percentage of heteroatoms (O, S, N) and
organometallic constituents (Ni, V, Fe) in the crude oil. The structure of the asphaltenes
has been the subject of several investigations, but is now believed to consist of polycyclic
aromatic clusters, substituted with varying alkyl side chains [15]. Figure 2-2 shows a
hypothetical asphaltene monomer molecule. The molecular weight of asphaltene
molecules has been difficult to measure due to the asphaltenes tendency to self-
aggregate, but molecular weights in the range 500-2000 g/mole are believed to be
reasonable [17-21]. Asphaltene monomer molecular size is in the range 12-24 [1, 18].

Figure 2-2: Hypothetical asphaltene molecule [22].

It is important to keep in mind that knowledge about the chemical composition of crude
oils, gained from for instance a SARA-analysis, cannot fully explain the crude oil

5
behaviour with regard to emulsion stability, asphaltene deposition etc. Equally important
is information of the structure of the crude oil, which is a result of interactions between
the continuum of chemical constituents in the oil. The interactions between the heavy
end molecules, the asphaltenes and resins, play the most significant role in this sense.
2.2 Structure
Asphaltenes are believed to be suspended as a microcolloid in the crude oil, consisting of
particles of about 3 nm [15]. Each particle consists of one or more aromatic sheets of
asphaltene monomers, with adsorbed resins acting as surfactants to stabilise the colloidal
suspension. The molecules are believed to be held together with -bonds, hydrogen
bonds, and electron donor-acceptor bonds [20]. Under unfavourable solvent conditions
resins desorb from the asphaltenes, leading to an increase in asphaltene aggregate size,
and eventually precipitation of large asphaltene aggregates. This asphaltene aggregation
model is the so-called steric stabilisation model developed by Leontaritis and Mansoori
[23-25], based on the earlier work by Nellensteyn and others [26-28]. On the basis of
this model, resins are necessary to suspend the asphaltene aggregate, thus the
aggregate is an asphaltene-resin complex. Figure 2-3 shows a model of an asphaltene
aggregate stabilised by resin molecules.

Figure 2-3: Resin solvated asphaltene aggregate [29].

An alternative model of asphaltene stabilisation exists, referred to as the thermodynamic
model, and first reported by Hirscberg et al. [30]. In this approach the resins are not
considered explicitly, but are treated as an integrated part of the solvent medium. This
view implies that the asphaltene monomers and aggregates are in thermodynamic
equilibrium, solvated by the surrounding medium. Thus, the critical distinction between

6
the thermodynamic and steric stabilisation models lies in whether the asphaltene colloids
are solvated or suspended in the hydrocarbon media [15]. The main advantage of using
the thermodynamic approach when modelling asphaltene aggregation is that it utilizes
conventional thermodynamic methods for phase equilibra, like equations of state.
However, since the resins are not considered explicitly it does not sufficiently take into
account the resin-asphaltene interaction, which is based on experimental observations
[24]. Different thermodynamic asphaltene aggregation models have been reviewed by
Andersen and Speight [31], with the conclusion that they are lacking in several respects
and are not quantitatively correct.

The pronounced tendency of asphaltenes to self-aggregate is one of their most
characteristic traits, and responsible for a large proportion of the problems encountered
during crude oil processing and refining. Aggregation and precipitation of asphaltenes
may cause a large variety of problems, from formation damage, equipment plugging,
catalyst deactivation etc. In addition, asphaltene aggregation has a great influence on
emulsion stability of crude oil-water systems, as will be discussed in section 2.3. The
parameters that govern aggregation and precipitation of asphaltenes are both solvent
conditions, pressure and temperature; their effects have been studied in detail by
numerous authors [32-47].

The solubility of the heaviest crude oil fraction, the asphaltenes, depends on a delicate
balance between this fraction and the lighter fractions of the crude oil. Any unfavourable
disturbance in this balance may induce asphaltene aggregation. For instance, the
addition of light, paraffinic components to an asphaltene containing solution will lower
the solubility power with respect to the asphaltenes. As already stated, resin molecules
will react to the addition by desorbing from the asphaltenes in an attempt to re-establish
thermodynamic equilibrium, thus increasing the probability of asphaltene self-
aggregation [45]. Figure 2-4 illustrates increasing asphaltene aggregation due to
increasing amounts of straight-chain aliphatics relative to aromatics in the solution.
Mixing of crude oils from different sources during production or refining may cause such
aggregation effects, and the consequences can be severe asphaltene deposition on all
types of processing facilities [24].


7

Figure 2-4: Formation of larger asphaltene aggregates under unfavourable solvent conditions [29].

Asphaltenes are also known to aggregate by pressure depletion alone [30, 45, 48]. By
decreasing the pressure, the relative volume fraction of the light components within the
crude oil increases. This causes an increase in the solubility parameter difference
between the crude oil and the asphaltenes, reaching a maximum at the bubble point
pressure. Below the bubble point asphaltenes are more soluble again due to evaporation
of light crude oil components. The relative change in asphaltene solubility has been
shown to be highest for light crude oils that are undersaturated with gas, and which
usually contain only a small amount of asphaltenes. This means, somewhat surprisingly,
that heavy crudes will usually present fewer problems with asphaltene aggregation and
precipitation, despite their higher asphaltene content. Of course, heavy crude oils
generally possess higher resin amounts, which can explain some of this behaviour.

Temperature has a less pronounced effect on aggregation than crude oil composition and
pressure, but an increase in the temperature generally affects the aggregation of
asphaltenes by decreasing the solvating power of the crude oil [49]. However, some
controversy regarding the temperature effect exists in the literature. Some authors state
that the asphaltene aggregate size decreases with increasing temperature [50], while
others state that the precipitation of asphaltenes increases with temperature [1] .

The reversibility of the asphaltene aggregation is also a subject of some controversy.
Hirscberg et al. [30] assumed that the aggregation was reversible, but probably very
slow. Joshi et al. [51] found the precipitation from a live crude oil to be reversible in the
matter of minutes, except for a subtle irreversibility observed for the first
depressurisation of the crude oil. They also discussed the different behaviour of
Asphaltene
aggregate
Aliphatic solvent
Aromatic solvent

8
asphaltenes precipitated from crude oils with excess n-alkanes and by asphaltenes
contained in the original crude oil. Hammami et al. [45] also found that the aggregation
was generally reversible, but that the kinetics of the redissolution varied significantly
depending on the physical state of the system. Peramanu et al. [52] reported differences
in the reversibility of solvent- and temperature-induced aggregation.

In Papers IV [53] and V [54] of this thesis near infrared spectroscopy is used to study
asphaltene aggregation behaviour both at ambient and at high-pressure conditions.

2.3 Emulsions
The concept of emulsions has been defined by IUPAC (1972) as [55]:

An emulsion is a dispersion of droplets of one liquid in another one with which it is
incompletely miscible (..). In emulsions the droplets often exceed the usual limits for
colloids in size.

For the petroleum industry the usual emulsions encountered are water droplets dispersed
in the oil phase (W/O), although the reverse situation is also possible. In addition to the
usual emulsion types, multiple emulsions of for instance oil droplets dispersed in water
droplets that are in turn dispersed in a continuous oil phase (O/W/O) can occur. Water
droplets in crude oil emulsions might be up to 100 micrometers in diameter, which is
large compared to the common definition of the upper limit of colloidal size (1 m) [56].
The emulsion formation is a result of the co-production of water from the oil reservoir.
During processing, pressure gradients over chokes and valves introduce sufficiently high
mechanical energy input (shear forces) to disperse water as droplets in the oil phase
[57].

All emulsions, perhaps with the exception of microemulsions, are thermodynamically
unstable. However, the destabilisation may take considerable time, and a stable emulsion
is unable to resolve itself in a defined time period without some form of mechanical or
chemical treatment [56]. Water-in-crude oil emulsion destabilisation basically involves
three steps, namely flocculation, followed by sedimentation of water droplets due to
density differences, and finally coalescence of the individual water droplets, as illustrated
in Figure 2-5. Large droplet sizes, high density difference between the oil and the
aqueous phase, and low continuous phase (oil) viscosity causes high sedimentation rates.
Flocculation is the aggregation of two or several droplets, touching only at certain points,

9
and with virtually no change in total surface area. Coalescence is the process of droplets
fusing together and forming larger and larger droplets, until the oil and water is
separated into two discrete phases.

Flocculation Sedimentation Coalescence

Figure 2-5: Emulsion separation by flocculation, sedimentation, and coalescence.

In crude oil emulsions, emulsifying agents are present at the oil-water interface,
hindering this coalescence process. Such agents include scale and clay particles, added
chemicals or indigenous crude oil components like asphaltenes, resins, waxes and
naphthenic acids [57]. The mechanism by which indigenous crude oil components
stabilise a droplet interface is by producing a physical barrier for droplet-droplet
coalescence. The lighter resins act as individual monomers, in a similar manner to
traditional surfactants. The resins have a tendency to be more interfacially active than
the asphaltenes, thus be the first to reach and cover a fresh water-oil interface. This
lowers the interfacial tension, but is not regarded as a sufficient step to stabilise against
coalescence [57]. The main stabilising effect is believed to be caused by interaction with
the asphaltenes. This effect is very dependent on the aggregation state of the
asphaltenes; monomeric asphaltenes do not stabilise interfaces to the same extent as
nanosized asphaltene aggregates accumulating at the interface.

Kilpatrick and coworkers [20, 37, 38] postulate that the primary mechanism of
asphaltene stabilisation of water-in-oil emulsions is through the formation of a viscous,
crosslinked, three-dimensional network of asphaltene aggregates with high mechanical
strength. The importance of interactions between asphaltenes and resins in the
stabilisation of crude oil emulsions has also been pointed out by others [58-65]. Figure
2-6 illustrates the accumulation of asphaltene aggregates at an oil-water interface.
Kilpatrick and Spiecker [20, 29] used a biconical bob rheometer to probe the strength of
such asphaltenic films at the interface. We have in Paper II [66] employed an oscillating
pendant drop tensiometer for measuring the interfacial rheological properties of crude

10
oil-water systems. in Paper III [67] these results have been correlated to emulsion
stability.

Figure 2-6: Accumulation of asphaltene aggregates at the oil-water interface [29].
Crude Oil Characterisation

11
3 Crude Oil Characterisation
Crude oils from different sources exhibit a wide range of physical and chemical
properties. To predict the behaviour of any crude oil with regard to for instance emulsion
stability, knowledge of these properties is of utmost importance. Such properties include
characterising parameters like density, viscosity, interfacial tension, molecular weight
etc.

Predicting emulsion stability behaviour from characterising data is a difficult task due to
the fact that emulsion stability is the result of a complex interplay between the different
crude oil constituents. For instance, the amount of the interfacially active fractions, resins
and asphaltenes, are known to be important for emulsion stability, but equally important
is knowledge of their interaction behaviour.

In the following sections some of the main characterising techniques used throughout
this thesis are described. This includes methods for determining both the chemical
composition of crude oils and the interfacial properties of crude oil-water systems. In
addition, the application of near infrared spectroscopy (NIR) with regard to crude oil
characterisation is described. The use of NIR has been found to be especially useful since
the technique can be applied for both chemical and physical characterisation of crude oil
systems.
3.1 SARA Separation
3.1.1 Background
Traditionally chromatographic techniques have been extensively used for hydrocarbon
group type determinations like for instance the SARA-separation. Standard ASTM
procedures for SARA separation are available [68, 69]. However, these techniques, which
are based on liquid chromatography (LC), are lengthy, tedious, and laborious as well as
expensive to run on routine basis [7]. High performance liquid chromatography (HPLC)
has been demonstrated to be a very efficient alternative to the standard ASTM
procedures for SARA separation [4-7, 9].

No HPLC method is applicable to all types of hydrocarbon samples, therefore specific
methods for each type of sample are used [3]. For crude oils, deasphalting of the sample
is usually the first step. This is done by a standard asphaltene precipitation by alkanes

12
like pentane, hexane or heptane. The remaining SAR fractions are then separated by
HPLC using silica or bonded phase columns, and an alkane as the mobile phase. The
complexity of the material in a crude oil, and the lack of an aromatic/resin selective
column makes it impossible to draw a clear distinction between aromatics and resins.
Therefore, a method specific definition of aromatics and resins is usually employed.

Separation of saturates and aromatics, with backflushing of the resins, have been
obtained on amino columns, cyano columns and aminocyano columns. However, two
coupled columns such as cyano/aminocyano or silica/cyano are often employed. In this
case the purpose of the first column is to retain the resins, while the second retains the
aromatics. The saturate fraction has no retention on such columns, and is therefore
eluted directly through the columns. The resins and aromatics have to be eluted from
their respective columns with appropriate solvents.

3.1.2 Experimental
A SARA separation system was developed to characterise crude oils of interest. The main
components of the system are an HPLC-pump, two 7.8 x 300 mm Bondapak NH
2
-
columns in series, and an ultraviolet (UV) and a refractive index (RI) detector. The
system is shown schematically in Figure 3-1. The separation scheme was presented in
Chapter 2.1.

Figure 3-1: HPLC-system


13
The first step of the procedure is to remove the asphaltenes by n-hexane precipitation.
The rest of the oil is then diluted in n-hexane and injected onto the system through the
injection valve ahead of the separation columns. Hexane is also used as mobile phase.
The saturates, having no retention on the column material, elutes first and are detected
on the RI-detector. This fraction is followed by the aromatics which are detected both on
the UV- and the RI-detector. Both fractions are collected in separate vials after the
detectors. The resins must be eluted with a more polar mobile phase. This is
accomplished by reversing the flow through the columns by a backflush valve, and by
using trichloromethane as mobile phase. The solvent is evaporated from all three
collected fractions, and by including the asphaltene yield the SARA distribution may be
calculated.

Figure 3-2 illustrates typical detector response for a SARA fractionation. The example
shows a case where only one column is in use. The reason for employing two columns in
series was to achieve a better separation of the saturate and aromatic fraction. Using
only one column, one single RI-detector peak is detected, indicating overlapping between
the saturate and aromatic fraction. This problem was solved when introducing a second
column. The RI-detector response is seen to fall off rapidly, while the UV-detector
response of the aromatics continues to over 20 minutes. This is due to the much higher
sensitivity of the UV-detector. The B at 40 minutes indicates the start of
trichloromethane backflushing, and the resin fraction is seen to elute immediately after
this.

Saturates
Aromatics
B
Resins
Saturates
Aromatics

Figure 3-2: Detector response during SARA separation.


14
The total yield of the fractions for crude oils is good, typically ranging from 92-100%.
Some light condensates display somewhat lower yields. The main reason for the material
loss is the solvent evaporation procedure, where nitrogen is blowed over the samples.
Radke et al. [8] studied the effect of evaporation using the same solvent evaporation
procedure applied in the present method. They showed that the loss was primarily due to
evaporation of saturates, and to some extent, the aromatics. The reported SARA-values
of the low-yield samples in this study are corrected to 100 % by adjusting the saturate
and aromatic values. Hence, the evaporation loss from the resin fraction is considered to
be negligible.

Further experimental details may be found in Paper I [11].

3.2 Interfacial Rheology
3.2.1 Background
The interfacial rheology of surfactant solutions influences the stability of many
technologically important systems such as foams, froths and emulsions [70]. The
mechanisms by which resins and asphaltenes stabilise crude oil emulsions by forming a
protective layer at the interface have already been discussed. Here the principles for the
measuring of the elastic and viscous properties of such a layer will be presented.

Generally, when an interface with adsorbed interfacially active molecules is stretched,
interfacial tension gradients are generated. The tension gradients will oppose the
stretching and try to restore the uniform interfacial tension state, i.e. the interface will
behave elastically. This is the so-called Gibbs-Marangoni effect. This is illustrated in
Figure 3-3 where a water drop in oil is being stretched either by shear forces or drop
collisions.


15
High interfacial tension
Low interfacial tension
Surfactants move to reduce the
gradient in interfacial tension
Surfactants
Water
Oil
Shear forces or collisions
thin the interfacial film

Figure 3-3: Gibbs-Marangoni effect at oil-water interface.

The main function of interfacially active molecules is not the interfacial tension lowering
they produce, but that their presence can lead to such gradients in interfacial tension
able to resist tangential stresses. In practice, emulsion droplets being stretched can
resist coalescence due to the elastic membrane, providing the droplet interfaces with a
self-healing mechanism [71]. Physical cross-linking of asphaltenic aggregates will also
contribute to this resistance to coalescence.

Interfacial rheological properties can be measured through the so-called interfacial
dilatational modulus. This property gives a measure of resistance to the creation of
interfacial tension gradients, and the rate at which such gradients disappear after the
deformation. The interfacial dilatational modulus, , is defined as the increase in
interfacial tension for a unit of relative increase in surface area [72]

A d
d
ln
= (1)

where is the interfacial tension and A is the interfacial area. For a small deformation of
the area, the change in interfacial tension can be written as a sum of an elastic and a
viscous contribution

dt
A d
A viscous elastic
d
d
ln
ln + = + = (2)

where
d
and
d
is the interfacial dilatational elasticity and viscosity, respectively. The two
contributions can be measured separately by subjecting the interface to small, periodic
oscillations at a given frequency. In an oscillatory experiment the interfacial area is
varied with time, t, according to

16

) exp( ln t i A (3)

where is the frequency of the oscillations. Based on the above equations the interfacial
dilatational modulus can be written as a complex number

d d
i + = (4)

where the first term is equal to the elastic contribution, and the second term is
proportional to the viscous contribution.

The interfacial dilatational modulus is a complex function of both oscillation frequency
and concentration of interfacially active components in the bulk phase. The viscous part
of the interfacial dilatational modulus will represent a combination of internal relaxation
processes, and relaxation due to diffusion of matter between the interface and bulk
phases.

3.2.2 Experimental
Numerous techniques have been employed for the determination of interfacial rheological
properties, including canal surface viscometers, knife-edge and disc surface viscometers,
including the biconical bob viscometer [29, 59, 73-75]. These techniques measure the
interfacial shear rheological properties. We have measured the interfacial dilatational
rheological properties by using an oscillating pendant drop tensiometer. The system is
illustrated schematically in Figure 3-4. It operates by oscillating an oil drop in an aqueous
phase at constant frequency. Images are continuously taken of the drop profile, and by
knowing the densities of the two phases, the interfacial tension is calculated by use of
the Laplace equation [76]. The technique is known as axisymmetric drop shape analysis
(ADSA).


17
1
2
3
4
5
6 7
8
9

Figure 3-4: The pendant drop tensiometer consisting of an optical bench (1) with an halogen lamp
as light source (2), a cuvette containing the oil drop in the water phase (3), a CCD camera (7)
attached to a telecentric lens (6), a syringe (4), and a DC motor (5). The drop profile (9) is analysed
on the personal computer (8).
Since both the changes in interfacial area and interfacial tension are known, the absolute
value of the complex dilatational modulus, ||, can be calculated according to Eq. 5

) / ( A A = (5)

In addition, the phase angle, , between the changes in interfacial tension and interfacial
area is determined. The elastic and viscous contributions to the complex modulus may
then be distinguished by introducing this angle, so that

cos =
d
(6a)

sin =
d
(6b)

For emulsion systems the interfacial concentration of surfactants is low due to the large
interfacial area created by the formation of many small droplets. Therefore the oil
systems under study was diluted with some solvent to better simulate the interfacial
concentrations encountered in real systems. The oil drop was oscillated with a frequency
of 0.1 Hz in all our studies.

Further experimental details may be found in Paper II [66].

18
3.3 Near Infrared Spectroscopy
Over the last 30 years near infrared spectroscopy has been increasingly used as an
analytical tool, particularly by the food and agricultural industries, but also by the textile
and polymer industries in addition to the petroleum industry [77]. The increasing
popularity is due to the four principal advantages of the method, namely speed,
simplicity, multiciplicity of analysis from a single spectrum and the non-consumption of
the samples. The main disadvantages of NIR spectroscopy have always been the
insensitivity to minor constituents and the broad absorption bands [78]. The latter
drawback is compensated by the rapid development of advanced and user-friendly
software for multivariate analysis.

The near infrared spectroscopic region lies between the visible and the mid infrared
regions of the electromagnetic spectrum. It is defined by ASTM as the spectral region
spanning the wavelength range 780-2526 nm. In mid infrared spectroscopy diatomic
molecules will vibrate as a harmonic oscillator, and the energy, E
v
, will be given by [79]

0
2
1
hc v E
v
|
.
|
\
|
+ = (7)

where h is Plancks constant, v is the vibrational quantum number,
0
is the frequency of
vibration and c is the speed of light. However, vibrations in polyatomic molecules involve
complex movement of their constituent atoms. In practice, such molecular vibrations
tend to be anharmonic, i.e. vibrations about the equilibrium position are non-symmetric.
This anharmonicity introduces overtones and combinations of the fundamental vibration
bands in the mid infrared region. These absorption bands can be found in the near
infrared region. The energy levels for anharmonic vibration may be written as

e v
x hc v hc v E
0
2
0
2
1
2
1
|
.
|
\
|
+ |
.
|
\
|
+ = (8)

where x
e
is the anharmonicity constant. The intensity of the overtone and combination
bands is markedly lower than for the fundamental bands. When dealing with organic
compounds, as for crude oils, the most prominent NIR bands are those related to O-H,
C-H and N-H groups. Main absorption bands of NIR spectra are given in
Table 3-1.


19

Table 3-1: Near infrared absorption bands.
Absorption band Wavelength region [nm]
O - H First overtone 1400 - 1450
O - H Combinations 1900 - 1975
C H Second overtone 1125 - 1225
C H Combinations first overtone 1350 1450
C H First overtone 1625 1775
C H Combinations 1950 - 2450

One of the main advantages of near infrared spectroscopy when working with colloidal
systems like crude oils is the ability to also gain information on the physical state of the
system. In addition to absorption, near infrared spectra will display a baseline elevation
due to light scattering by aggregates or particles in solution. For small particles relative
to the wavelength (r/ 0.05), Lord Rayleigh derived an expression for the total energy
scattered by a particle. The basic premise for Rayleigh scattering is that the particle is so
small that the electromagnetic field it experiences is uniform over the particle. By also
assuming that the particles were slightly lossy and dielectric, Rayleigh deducted an
expression for the scattering cross section of a particle [80]

2
2
2
4
6 5 7
2
1
3
2
|
|
.
|
\
|
+
=
n
n r
sc
(9)

where r is the particle radius, the wavelength of the incident light and n is the ratio of
the discrete phase to the continuous phase index of refraction. In the absence of multiple
scattering, and in the Rayleigh limit (r/ 0.05), fewer, but larger spheres are much
more efficient scatterers than the same mass of smaller particles.

Within the Rayleigh limit the light extinction can be considered a sum of the absorbance
and scattering contribution, represented by the following particle cross-sections [81]

abs sc tot
+ = (10)

where
tot
,
sc
and
abs
are the total, scattering and absorption cross-sections,
respectively.

20

The light extinction depends exponentially on the number of particles and the total cross-
section

) exp(
0
tot
N
I
I
= (11)

where I and I
0
are the intensities of the transmitted and incident light respectively, and N
is the number of particles. The relation between optical density (OD), light intensity,
number of particles and particle cross section is then given by

tot
N
I
I
OD 434 . 0 log
0
= |
.
|
\
|
= (12)

The measured optical density is thus a combination of absorption and scattering
contributions. The effect of multiple scattering is not accounted for in this equation.
Absence of multiple scattering implies that radiation scattered by a single particle
proceeds directly to the detector without any further scattering encounters. In case of
multiple scattering, the scattering and absorption cannot be treated separately.
Conditions for single scattering can usually be attained by working with dilute systems
and with small volumes.

Figure 3-5 demonstrates the effect of particle size on NIR spectra. During a sol-gel
preparation of silica particles, NIR spectra were taken at intervals. The increasing optical
density due to increasing particle size is clearly seen.


21
Wavelength [nm]
O
p
t
i
c
a
l

D
e
n
s
i
t
y

Figure 3-5: NIR spectra of silica particles formed by sol-gel process.

Several authors have used NIR spectra for particle size determinations [82-85]. NIR
spectroscopy has also found widespread use in the determination of both physical and
chemical properties of crude oils and related materials [77, 86-91]. Throughout this
thesis the ability of NIR spectroscopy to gain both chemical and physical information on
crude oils and model systems will be demonstrated. In Papers IV [53] and V [54] near
infrared spectroscopy was used specifically for the detection of asphaltene aggregation
onset pressures, and aggregate size determinations.
3.4 Critical Electric Field
Demulsification by electrocoalescence is common in the petroleum industry. Water is
separated from the emulsion by applying an electric field of 1-10 kV/cm to cause
flocculation and coalescence of water droplets in the continuous oil phase [92]. The
electric field strength needed to cause such coalescence can be used as a measure of the
emulsion stability. In low electric fields water droplets surrounded by a rigid interfacial
film will attain a chain-like configuration. When increasing the electric field the droplets
will bridge the gap between the electrodes. Ultimately, an irreversible rupture of the
interfacial films between the droplets will increase the conductivity through the emulsion
sample [63, 93]. This critical electric field, E
critical
, may then be defined as a measure of
the emulsion stability. Figure 3-6 demonstrates the effect on the water droplets when
increasing the electric field over an emulsion.

22

0
0.5
1
1.5
2
2.5
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7
Electric field [kV/cm]
C
u
r
r
e
n
t

[
m
A
]
Water cut 30%

Figure 3-6: Emulsion droplets in an increasing electric field.

In paper III [67] a newly developed electric field cell was used for the determination of
emulsion stability. The method is similar to the one employed by Kallevik et al. [94]. The
cell is depicted schematically in Figure 3-7. It consists of a Teflon plate with a 10 mm
diameter hole in the centre, with a brass plate on each side. The distance between the
plates is 0.5 mm, and the upper brass plate has two small holes for sample injection. The
brass plates are connected to a power supply, which can increase the applied voltage in
user-defined steps. The system is held together with isolating plexiglass plates. The
power supply delivers a maximum of 100 V DC, corresponding to a maximum electric
field of 2.0 kV/cm. Emulsions are injected into the cell volume, and the electric field over
the emulsion sample is increased until E
critical
is reached, as seen by a sudden increase in
conductivity.

<100 V
Plexiglass
Brass (3.0 mm)
Teflon (0.5 mm)
50 mm
Sample volume

Figure 3-7: Electric field cell for emulsion stability measurements.
Multivariate Data Analysis

23
4 Multivariate Data Analysis
Many of the scientific problems encountered are multivariate in nature. For instance, the
phenomenon of emulsion stability depends on the complex interplay of a number of
variables. Multivariate analysis is a tool for extracting the essential information related to
some properties of interest from a large data set. The use of multivariate analysis on
chemical problems is often termed chemometrics, and has been defined by Wold [95] as
How to get chemically relevant information out of measured chemical data, and how to
represent and display this information. Several review articles on chemometrics have
been published [96, 97].
4.1 Principal Component Analysis (PCA)
The main purpose of PCA is to extract the essential information contained in a large data
set of m samples, each characterised by n variables (m x n data matrix, often termed X).
PCA decomposes the data by finding combinations of variables that best describe the
main trends in the data set. The idea is that these main trends are more or less directly
related to the main phenomena that describe the data set [98]. Because the variables in
a large data set usually co-vary to a large extent, the effective dimension of the data set
can be reduced from n to fewer dimensions that are combinations of the original
variables. These combined variables are called principal components (PC) because they
are particular relevant for the data set. The principal components can be seen as a
projection of the original data set in n dimensions onto a new co-ordinate system of the
principal components. Each sample will have a value along these new axes, and the value
of the sample along any given PC is termed the score for the sample. The scores describe
how the samples relate to each other. Every PC is a linear combination of n coefficients
based on the original n variables. These coefficients for each PC are called the loadings
for the principal component. Loadings thus constitute a bridge between the original
variable space and the PC space.

Mathematically, PCA is based on an eigenvector decomposition of the covariance matrix
of the variables in the data set. Given a data matrix X with m rows of samples and n
columns of variables, the covariance matrix of X is defined as

1
) cov(
T
=
m
X X
X (13)


24
The result of the PCA procedure is a decomposition of the data matrix, X, into principal
components of score and loading vectors

m n k k i i m n
+ + + + + = E p t p t p t p t X
T T T
2 2
T
1 1
... (14)

Here t
i
is the score vector, p
i
is the loading vector and E is the residual matrix. The
direction of the first principal component (t
1,
p
1
) is the line in the variable space that best
describes the variation in the data matrix X. The direction of the second principal
component is given by the straight line that best describes the variation not described by
the first principal component, and so on. This implies that PC2 is orthogonal on PC1.
Thus, the original data set can be adequately described using a few orthogonal principal
components instead of the original variables, with no significant loss of information. The
result is that the original data set of n variables is decomposed to a structured part (the
principal components) and a residual part. The residual part can be considered noise that
contains little information of interest.

One of the most powerful tools offered by the principal component analysis is the score
plot. A score plot is any two pairs of score vectors plotted against each other. The score
plots can be viewed as particularly useful two-dimensional windows into the PC-space,
where relations between the samples are easily observed. Often over 90% of the
information contained in the original n-dimensional data set can be found in a plot of the
two first principal components. Thus PCA performs a dual purpose: a transformation into
a more relevant co-ordinate system (the PC-space), and a dimensionality reduction. The
number of principal components needed to describe the system must be evaluated from
case to case, and depends on which principal components contain the information of
interest.
4.2 Partial Least Squares Regression (PLS)
Regression between a large data set (X matrix) and a response (y vector) is often
impossible by ordinary least squares methods due to strongly correlated and redundant
information in the data set. This problem is especially prominent for spectral data sets.
One solution to this is to decompose the X matrix by PCA as shown in Equation 13, and
perform the regression between the resulting score vectors and the response. Such PCA
decomposition followed by regression is called principal component regression (PCR). The
PLS regression is an alternative multivariate regression method. In PCA and PCR
decomposition the scores and loadings are the vectors that best describe the variance of

25
the X matrix. In PLS decomposition the scores and loadings are the vectors that have the
highest covariance with the response vector y. The PLS decomposition is followed by a
regression between these score vectors and the response.

Due to the risk of overfitting the regression model, i.e. modelling noise, the optimum
number of principal components to be used must be determined. One way of doing this is
the cross validation technique. Cross validation checks a model by repeatedly taking out
different sub-sets of calibration samples from the model estimation, and instead using
them as temporary, local sets of secret test samples. If the model parameter estimates
are stable against these repeated perturbations, this indicates that the model is reliable
[99]. In the simplest case each subset contains only one sample, which is called full cross
validation. Alternatively the test set method may be used for validation. Here a
completely new data set is used exclusively for validation purposes. This method requires
that enough samples are available both for regression and validation.
Main Results

26
5 Main Results

This section summarises the main findings from the five papers of this thesis. Paper I
described the characterisation of 18 crude oils and condensates by the HPLC SARA-
fractionation procedure. It was then shown that the SARA values could be predicted by
multivariate analysis from infrared and near infrared spectroscopy. Paper II used the
oscillating pendant drop tensiometer to characterise the interfacial rheology of the same
crude oils as used in Paper I. Paper III first extended the characterisation work on the
samples by introducing more data, including emulsion stability properties. Then the crude
oil characterisation work done in Papers I and II was summarised by investigating which
crude oil parameters determined the emulsion stability. In Papers IV and V the attention
was turned to the aggregation of asphaltenes. In Paper IV the aggregation onset as a
function of pressure and temperature was studied by high-pressure near infrared
spectroscopy. In Paper V the size of asphaltene aggregates was determined by Rayleigh
scattering theory of near infrared light.
Paper I
The intention of Paper I was to investigate the possibility of predicting SARA-values from
infrared and near infrared spectra of crude oils by multivariate regression. A set of 18
crude oils and condensates were characterised by IR and NIR, and by the SARA-
procedure. Table 5-1 shows the SARA-distribution for the samples along with the origin
and density. The samples are seen to reflect a broad range in SARA-properties. For
instance, the value of saturates range from 24.4 wt% for sample 18 to 82.7 wt% for
sample 4. Sample 18 is a highly asphaltenic crude oil, while sample 4 is a light
condensate.
Main Results

27

Table 5-1: SARA-distribution and density.
SARA fractionation results
Crude oil
no.
Origin Saturates
(wt%)
Aromatics
(wt%)
Resins
(wt%)
Asphaltenes
(wt%)
Density
(g/cm
3
)
1 West Africa 47.9 36.5 15.2 0.4 0.914
2 North Sea 48.0 37.5 14.2 0.3 0.916
3 West Africa 41.2 36.4 20.4 2.1 0.916
4 North Sea 82.7 13.4 3.9 0.0 0.839
5 North Sea 62.7 23.6 12.2 1.5 0.844
6 North Sea 35.3 36.8 24.5 3.5 0.945
7 North Sea 41.8 38.8 18.7 0.6 0.914
8 North Sea 50.9 34.6 14.0 0.5 0.885
9 West Africa 40.6 32.1 20.6 6.6 0.888
10 North Sea 79.8 16.5 3.6 0.1 0.796
11 West Africa 57.3 27.9 13.5 1.3 0.873
12 North Sea 60.6 30.0 9.2 0.2 0.857
13 West Africa 42.4 36.1 20.5 1.0 0.921
14 North Sea 65.0 30.7 4.3 0.0 0.796
15 North Sea 50.3 31.4 17.5 0.7 0.898
16 North Sea 55.4 28.3 12.9 3.4 0.840
17 West Africa 54.5 28.8 14.9 1.8 0.873
18 France 24.4 43.4 19.9 12.4 0.939

A principal component analysis was first performed on both the IR- and the NIR-spectra.
This revealed that the IR-spectra of samples 15 and 17 were outliers, and these two
samples were therefore left out of the IR-calibration models. A total of four models based
on the IR-spectra were built, one for each of the four SARA-parameters. The same was
done for the NIR-spectra, producing a total of 8 prediction models. In order to obtain
robust prediction models from the spectroscopic data, a broad calibration range was
required. The sample set contained samples ranging from light condensates to heavy
crude oils, and should be well suited for calibration purposes. One drawback, however,
was the asphaltene distribution. Most samples were low in asphaltene content, and only a
few had high asphaltene contents.

Partial least squares regression (PLS), using the spectroscopic data as X-data, was used
for the modelling, and full cross validation was utilised to validate the models. For the IR-
spectra the original spectra were used, while the NIR-spectra were first-order
differentiated before modelling since this produced better models. Figure 5-1 shows
Main Results

28
example spectra used in the modelling, while Figure 5-2 shows the measured vs.
predicted plot for one of the calibration models.

0
0.2
0.4
0.6
0.8
1.0
1750 1671 1591 1512 1433 1354 1275 1196 1117 1038 959. 880. 801. 722.
-0.02
-0.01
0
0.01
0.02
1000 1200 1400 1600 1800 2000 2200
4
13
18
Wavenumber [cm
-1
]
A
b
s
o
r
b
a
n
c
e
13
18
Wavelength [nm]
IR NIR
0
0.2
0.4
0.6
0.8
1.0
1750 1671 1591 1512 1433 1354 1275 1196 1117 1038 959. 880. 801. 722.
-0.02
-0.01
0
0.01
0.02
1000 1200 1400 1600 1800 2000 2200
0
0.2
0.4
0.6
0.8
1.0
1750 1671 1591 1512 1433 1354 1275 1196 1117 1038 959. 880. 801. 722.
-0.02
-0.01
0
0.01
0.02
1000 1200 1400 1600 1800 2000 2200
4
13
18
Wavenumber [cm
-1
]
A
b
s
o
r
b
a
n
c
e
13
18
Wavelength [nm]
IR NIR
4
13
18
Wavenumber [cm
-1
]
A
b
s
o
r
b
a
n
c
e
13
18
Wavelength [nm]
4
13
18
Wavenumber [cm
-1
]
A
b
s
o
r
b
a
n
c
e
4
13
18
4
13
18
Wavenumber [cm
-1
]
A
b
s
o
r
b
a
n
c
e
13
18
Wavelength [nm]
13
18
13
18
Wavelength [nm]
IR NIR

Figure 5-1: IR-spectra and first-order differentiated NIR-spectra.

13
7
3
2
1
15
16
17
12
14
10
4
18
9
8
11
5

Figure 5-2: PLS prediction model for saturates from NIR spectra.

Main Results

29
In Table 5-2 the predicted uncertainty in the eight models are compared to the
experimental uncertainty of the HPLC-procedure. RMSEP (Root Mean Square Error of
Prediction) is a measure of the average prediction error that can be expected, expressed
in the same units as the original response values (wt%). The main conclusion is that the
models based on infrared and near infrared spectroscopy have the same levels of
uncertainty as the original HPLC-procedure. One exception is the asphaltene models, and
this is probably due to the unfavourable sample set with regard to asphaltene content.
The SARA-values can thus be predicted in a fast and simple manner from spectroscopic
techniques as an alternative to the traditional and more tedious HPLC-procedure.

Table 5-2: Uncertainty in HPLC procedure compared to IR and NIR PLS predictions.
Experimental (wt%) RMSEP, IR (wt%) RMSEP, NIR (wt%)
Saturates 2.2 2.5 2.8
Aromatics 2.5 2.2 2.4
Resins 1.4 1.4 1.4
Asphaltenes 0.2 1.3 1.0

Paper II
This paper investigated the interfacial rheology of water-crude oil systems. An oscillating
pendant drop tensiometer was utilised to characterise 21 crude oils and condensates in
contact with a common aqueous phase. 18 of the samples were the same as those
characterised in Paper I. All crude oils and condensates of this study were diluted in a
heptane/toluene solvent before measuring. Both the effect of oil concentration and
solvent composition was investigated. For the concentration study all 21 samples were
diluted with a 50/50 vol% heptane/toluene solution (heptol50) at three oil
concentrations, namely 0.002, 0.01 and 0.02 ml oil/ml solvent. For the solvent
composition study, two crude oils were diluted in heptane/toluene solutions containing 0,
50, 90, 95 and 100 vol% heptane (heptol(0)-heptol(100)).

In another paper on the oscillating pendant drop tensiometer the interfacial dilatational
elasticity modulus of the samples was discussed [100]. This modulus incorporates both
an elastic and a viscous contribution. Since the viscous component was found to be
insignificant for the majority of the samples, only the interfacial elasticity was discussed
in detail in Paper II. In this paper the interfacial rheology data was in addition
supplemented by near infrared spectroscopy data in order to offer a better explanation to
the effects of varying oil concentration and solvent composition.

Main Results

30
Figure 5-3 shows the measured interfacial elasticity of the samples. Two distinct groups
of samples could be separated, the ten samples of decreasing elasticity from the
intermediate to the highest oil concentration (left) and the ten samples of increasing
elasticity in the same interval (right). The last sample, crude oil 13, was not included in
these plots due to difficulties measuring the interfacial elasticity at the lowest oil
concentration.

2
6
10
14
18
22
26
30
34
-3 -2.8 -2.6 -2.4 -2.2 -2 -1.8 -1.6 -1.4
log (oil concentration)
I
n
t
e
r
f
a
c
i
a
l

e
l
a
s
t
i
c
i
t
y

[
m
N
/
m
]
1
2
3
5
6
11
15
19
20
21
-2
0
2
4
6
8
10
12
14
16
18
-3 -2.8 -2.6 -2.4 -2.2 -2 -1.8 -1.6 -1.4
I
n
t
e
r
f
a
c
i
a
l

e
l
a
s
t
i
c
i
t
y

[
m
N
/
m
]
4
7
8
9
10
12
14
16
17
18

Figure 5-3: Interfacial elasticity plotted against oil concentration.

It was observed that the concentration dependence could not be explained by the SARA-
determined amounts of interfacially active fractions in the crude oils, resins and
asphaltenes. Some kind of crude oil component interactions was the most likely
explanation. To find an explanation to the differences in oil concentration dependence on
the elasticity, the crude oils were characterised by NIR spectroscopy. In Figure 5-4 the
optical density at 1600 nm from the NIR spectra of the crude oil solutions is plotted
against the relation (Resins/Asphaltenes) as determined from the SARA-analysis. Since
resins are believed to disperse asphaltene aggregates, small values of this relation should
indicate larger asphaltene aggregates. This was confirmed from the figure where low R/A
values generally produced high values of optical density. High values of optical density
implied larger aggregates in the solution. It was also seen that at low oil concentrations
the aggregate size was small, and more or less the same for all crude oils, while
especially at the highest oil concentration very high values of optical density was found
for the low R/A crude oils.

Main Results

31
0.070
0.075
0.080
0.085
0.090
0.095
0.100
0.105
0.110
0 5 10 15 20 25 30 35 40 45 50
(wt% resins)/(wt% asphaltenes)
O
D

1
6
0
0

n
m
0.002 ml/ml
0.01 ml/ml
0.02 ml/ml
2 8 14
1 12 9 10 17 18 15 6 3 19 7 20 11 21
High OD samples Low OD samples

Figure 5-4: Optical density at 1600 nm of the samples as a function of the R/A number.

It was further noted that most of the samples that displayed decreasing elasticity at high
oil concentrations (left hand side of Figure 5-3) were the same samples displaying high
optical density at high oil concentrations. The right hand side samples of Figure 5-3
corresponded to the low optical density samples (small aggregates). The only exceptions
to this correlation were samples 1, 2 and 7. In addition, samples 4 and 16 were not
included in the R/A plot due to lack of asphaltenes, but they naturally belong to the high
R/A group. Sample 5 was not characterised by NIR due to lack of sample material.

The main conclusion from this part was that the decreasing values of interfacial elasticity
at high oil concentrations were caused by the formation of large, apparently weaker
interfacially active, asphaltene aggregates. To further verify this the solutions of one of
the two crude oils studied at several solvent compositions were also characterised by NIR
spectroscopy, and compared with the values of interfacial elasticity. Figure 5-5 shows the
elasticity values and corresponding optical density as a function of crude oil concentration
and solvent composition.

Main Results

32
0
0.01
0.02
0.03
0.04
0.05
0.06
-3 -2.8 -2.6 -2.4 -2.2 -2 -1.8 -1.6
n
e
t

O
D

1
6
0
0

n
m
8
10
12
14
16
18
20
22
24
-3 -2.8 -2.6 -2.4 -2.2 -2 -1.8 -1.6
Log (oil concentration)
l
n
t
e
r
f
a
c
i
a
l

e
l
a
s
t
i
c
i
t
y

[
m
N
/
m
]
heptol(0)
heptol(50)
heptol(95)
heptol(100)

Figure 5-5: Interfacial elasticity and optical density of crude oil 15.

In poor solvents (high heptane content) the interfacial elasticity decreased with
increasing oil concentration. In good solvents the interfacial elasticity generally increased
with oil concentration. From the optical density results the formation of larger aggregates
is seen to be much more dominating in poorer solvents. Again, the lowering of the
interfacial elasticity appeared to be caused by the formation of larger asphaltene
aggregates. At the lowest oil concentration, the highest elasticity values were obtained in
the poorest crude oil surfactant solvents. In such solvents the interfacial activity of resins
and asphaltenes is high, and more or less no aggregation was taking place, as seen from
the optical density values. At higher oil concentrations this effect of interfacial activity
seemed to be opposed by the formation of asphaltene aggregates.

Paper II demonstrated that measuring interfacial rheological properties of crude oil
systems is highly dependent both on the oil concentration and what solvent is used for
dilution. The effect of high interfacial activity in aliphatic solvents is quickly opposed by
asphaltene aggregation when increasing the oil concentration. When comparing the
interfacial rheological properties of different crude oils, both these effects have to be
taken into consideration. The findings of this study are consistent with the asphaltene
aggregation model proposed by Kilpatrick and coworkers [20, 37, 38]. They found that
precipitated asphaltenes had a lower ability to form elastic interfaces. This was attributed
to lower interfacial activity of such precipitated aggregates and possibly high amounts of
defects in films of precipitated material.
Main Results

33
Paper III
In Paper III the characterisation work presented in Papers I and II was taken advantage
of. The critical electric field cell was developed to measure the emulsion stability of the
same 21 crude oils and condensates used in the earlier papers. By multivariate analysis
the emulsion stability was then correlated to the physico-chemical properties of the
samples. In addition to SARA-data and interfacial elasticity, properties like density,
interfacial tension, molecular weight, total acid number (TAN) and viscosity were added
to the data matrix. The aim of this study was to gain insight into which parameters
govern the emulsion stabilising properties of the crude oils. In addition, NIR spectra of
the crude oils were used as input data.

Table 5-3 shows the data matrix, including E
critical
values for water cuts of 20% and 30%.
t1 and t2 are the first and second score vector from a principal component analysis of the
NIR spectra. The elasticity values used were the values for the lowest oil concentration,
0.002 ml oil/ml solvent (see Paper II).

Table 5-3: Data matrix on crude oil and condensates.
Origin
WC20
[kV/cm]
WC30
[kV/cm]
S
[wt%]
A
[wt%]
R
[wt%]
Asph.
[wt%]
(S+Asph)/
(R+A)
R/(R+Asph)
1 West Africa 0.58 0.47 47.9 36.5 15.2 0.4 0.93 0.97
2 North Sea 0.87 0.61 48.0 37.5 14.2 0.3 0.93 0.98
3 West Africa 2.00 0.68 41.2 36.4 20.4 2.1 0.76 0.91
4 North Sea 0.00 0.00 82.7 13.4 3.9 0.0 4.78 1.00
5 North Sea 1.00 0.64 62.7 23.6 12.2 1.5 1.79 0.89
6 North Sea 0.91 1.03 45.5 37.1 16.0 1.4 0.88 0.92
7 North Sea 2.00 1.50 35.3 36.8 24.5 3.5 0.63 0.88
8 North Sea 0.55 0.45 56.0 29.6 14.1 0.3 1.29 0.98
9 North Sea 0.84 0.59 41.8 38.8 18.7 0.6 0.74 0.97
10 North Sea 0.53 0.33 50.9 34.6 14.0 0.5 1.06 0.97
11 West Africa 2.00 1.85 40.6 32.1 20.6 6.6 0.90 0.76
12 North Sea 0.00 0.00 79.8 16.5 3.6 0.1 3.98 0.97
13 West Africa 0.61 0.45 57.3 27.9 13.5 1.3 1.42 0.91
14 North Sea 0.59 0.08 60.6 30.0 9.2 0.2 1.55 0.98
15 West Africa 0.85 0.40 42.4 36.1 20.5 1.0 0.77 0.95
16 North Sea 0.00 0.00 65.0 30.7 4.3 0.0 1.86 1.00
17 North Sea 0.47 0.42 44.1 41.6 13.8 0.5 0.81 0.97
18 North Sea 0.93 0.43 50.3 31.4 17.5 0.7 1.04 0.96
19 North Sea 2.00 2.00 54.5 28.8 14.9 1.8 1.29 0.89
20 West Africa 0.91 0.72 55.4 28.3 12.9 3.4 1.43 0.79
21 France 2.00 1.70 24.4 43.4 19.9 12.4 0.58 0.62

Main Results

34
Table 5-3, continued
Origin t1 t2 OD,
1600 nm
Elasticity
[mN/m]
Density
[g/cm
3
]
IFT
[mN/m]
Mw
[g/mole]
Visc.,25C
[kg/m s]
TAN
[mg KOH]
1 West Africa -5.45 0.11 0.168 11.5 0.914 20.5 234 18.7 1.10
2 North Sea -3.16 0.26 0.240 7.3 0.916 24.8 279 57.4 3.10
3 West Africa 8.91 0.16 0.659 7.8 0.916 26.4 310 143.0 1.50
4 North Sea -7.42 0.17 0.107 -1.1 0.839 37.1 166 1.8 0.69
5 North Sea -3.62 -0.43 0.236 16.5 0.844 12.8 201 5.4 0.18
6 North Sea -0.39 0.52 0.332 3.7 0.862 31.9 244 14.5 0.02
7 North Sea 5.99 0.81 0.544 11.7 0.945 27.4 333 386.6 2.30
8 North Sea -5.02 -0.10 0.185 6.7 0.850 24.7 216 6.6 0.17
9 North Sea -3.53 0.28 0.229 8.4 0.914 11.8 284 51.0 3.10
10 North Sea -4.54 0.12 0.197 5.0 0.885 22.8 234 11.6 2.70
11 West Africa 17.50 -0.49 0.991 10.6 0.888 29.0 260 27.8 0.49
12 North Sea -5.84 -0.60 0.165 -1.4 0.796 34.2 157 1.7 0.01
13 West Africa -2.87 -0.05 0.257 - 0.873 24.6 235 17.7 0.50
14 North Sea -5.11 -0.39 0.186 0.2 0.857 22.9 227 10.5 0.04
15 West Africa 1.33 -0.02 0.395 9.2 0.921 16.2 295 105.8 3.60
16 North Sea -7.36 0.18 0.107 -0.6 0.796 27.6 142 1.2 0.02
17 North Sea -4.94 -0.37 0.192 8.1 0.847 19.9 223 11.7 0.15
18 North Sea -4.24 0.14 0.206 14.8 0.898 19.5 249 19.1 1.20
19 North Sea 9.54 0.11 0.684 24.9 0.840 27.4 298 63.1 0.36
20 West Africa 4.91 -0.41 0.525 5.6 0.873 19.0 248 15.3 0.44
21 France 15.31 0.00 0.893 12.9 0.939 13.4 303 278.9 0.20

A PLS regression model was built using the average E
critical
values at water cuts of 20%
and 30% as response. Due to a skewed distribution the E
critical
values were logarithmically
transformed before modelling. This excluded the condensates from the model since these
samples did not form stable emulsions (zero E
critical
values). Figure 5-6 shows the
regression coefficients and the predicted vs. measured plot for the resulting model. The
R
2
value of the model is 0.93. From the regression coefficients the amount of asphaltenes
and interfacial elasticity are seen to be main contributors to emulsion stability. In
addition, the NIR spectra (through the scores t1) seem to contain much information with
regard to emulsion stability properties. High values of aromatics and the relation
Resins/(Resins+Asphaltenes) seem to be the two main variables decreasing emulsion
stability.

Main Results

35
-1.2
-1
-0.8
-0.6
-0.4
-0.2
0
0.2
0.4
0.6
0.8
-1.2 -1 -0.8 -0.6 -0.4 -0.2 0 0.2 0.4 0.6 0.8
14
10
17
8
1
13 15
18
9
2
5
20
6
3
11
7
21
19
Measured (ln E
critical
)
P
r
e
d
i
c
t
e
d

(
l
n
E
c
r
i
t
i
c
a
l
)
S
a
t
u
r
a
t
e
s
A
r
o
m
a
t
i
c
s
R
e
s
i
n
s
A
s
p
h
a
l
t
e
n
e
s
t
1
,

N
I
R
t
2
,

N
I
R
(
S
+
A
s
f
)
/
R
+
A
)
R
/
(
R
+
A
s
f
)
E
l
a
s
t
i
c
i
t
y
D
e
n
s
i
t
y
I
F
T
M
W
T
A
N
V
i
s
c
o
s
i
t
y
R
e
g
.

C
o
e
f
f
.

(
l
n

E
c
r
i
t
c
a
l
)

Figure 5-6: Regression coefficients and predicted vs. measured plot for the emulsion stability model.

Based on the full model, a reduced model was built, containing only a few of the most
important variables. Five parameters from the full model were kept, the four SARA-
parameters and the interfacial elasticity. All four SARA-parameters were kept since they
are determined in the same experiment. This model produced a R
2
value of 0.82. This
means that data from only two experimental procedures, the SARA-separation and the
interfacial elasticity determination, are able to give a reasonable estimate of the emulsion
stability properties of a crude oil. Earlier attempts to correlate the emulsion stability to
SARA-data and some of the other variables in the data matrix were not successful,
underlining the importance of knowing the interfacial properties of crude oils when
discussing emulsion stabilisation/destabilisation.

The NIR spectra appeared to contain information on the emulsion stability properties of
the crude oils due to the high value of the t1 regression coefficient. t1, the scores of PC1,
was closely correlated to the baseline elevation caused by increasing aggregate size in
the crude oils. Based on this, a third PLS model with NIR spectra of the crude oils as X-
data, was constructed. Wavelengths from 1300-2200 nm were used to predict the same
E
critical
values as in the other two models. Figure 5-7 shows example NIR spectra and the
predicted vs. measured plot of the resulting model. The model produced a R
2
value as
high as 0.95, confirming that near infrared spectroscopy is a very good source of
information for crude oil properties. In Paper I it was demonstrated that SARA-
parameters could be predicted from NIR spectra, and we showed in this paper (through
t1) that NIR spectra contain information on the aggregation state of the asphaltenes in
Main Results

36
the crude oils. These are all factors contributing to emulsion stability, and explains some
of the good predictive power of near infrared spectroscopy.

-1.2
-1
-0.8
-0.6
-0.4
-0.2
0
0.2
0.4
0.6
0.8
-1.2 -1 -0.8 -0.6 -0.4 -0.2 0 0.2 0.4 0.6 0.8
14
17
10
8
1
13
15
18
9
2
20
6
3
19
11
7
21
P
r
e
d
i
c
t
e
d

(
l
n
E
c
r
i
t
i
c
a
l
)
Measured (ln E
critical
)
0
0.5
1.0
1.5
2.0
1300 1400 1500 1600 1700 1800 1900 2000 2100 2200
1
15
7
21
O
p
t
i
c
a
l

d
e
n
s
i
t
y
Wavelength (nm)
0
0.5
1.0
1.5
2.0
1300 1400 1500 1600 1700 1800 1900 2000 2100 2200
1
15
7
21
O
p
t
i
c
a
l

d
e
n
s
i
t
y
Wavelength (nm)
1
15
7
21
O
p
t
i
c
a
l

d
e
n
s
i
t
y
Wavelength (nm)

Figure 5-7: Example NIR spectra and predicted vs. measured plot for the NIR model.

One of the problems associated with the prediction of emulsion stability from single
parameters like SARA, elasticity, viscosity etc. is that detecting the effect of constituents
of very low concentration in the crude oil may be difficult. However, such constituents
may have a dramatic effect on the emulsion stability properties. One example is chemical
demulsifiers added at ppm-levels during crude oil production. A SARA-determination is
not able to distinguish between a crude oil sample with and without such additives. An
indirect analytical procedure like near infrared spectroscopy on the other hand, can be
able to detect such additives by measuring the effect they have on the crude oil. Figure
5-8 shows two NIR spectra of the same North Sea crude oil, the only difference being the
addition of 10-15 ppm of demulsifier. This crude oil was not included in the sample set
published in Papers I-III. It is seen that this addition has an adverse effect on the NIR
spectra, a difference that a SARA-analysis would not have revealed. The differences in
the spectra are due to smaller asphaltene aggregates in the sample with added
demulsifiers. The emulsion stability of the crude oil with no added demulsifier (as
measured by E
critical
) was twice as high as for the sample with addition. The interfacial
elasticity of the two samples was also measured, and it was found that the sample
without added demulsifier displayed higher values of interfacial elasticity than the treated
sample (15.3 mN/m vs. 11.8 mN/m). This again demonstrates the close correlation
between asphaltene aggregation, interfacial elasticity and emulsion stability.
Main Results

37
0.2
0.4
0.6
0.8
1.0
1.2
1.4
1000 1200 1400 1600 1800 2000 2200
No demulsifier added
Demulsifier added
Wavelength [nm]
O
p
t
i
c
a
l

D
e
n
s
i
t
y

Figure 5-8: Effect on NIR spectra of crude oil with addition of demulsifier.

Paper IV
In Papers II and III the importance of asphaltene aggregation state was discussed both
in relation to interfacial rheology and emulsion stability. In addition, near infrared
spectroscopy was shown to contain information on this aggregation state through the
baseline elevation caused by light scattering. In Paper IV the asphaltene aggregation
behaviour was studied in more detail by use of a high-pressure NIR system shown in
Figure 5-9. The system combined the accurate pressure and temperature control offered
by a PVT rig, in which a high-pressure transmittance NIR cell was connected. Specially
designed software enabled direct principal component analysis (PCA) of the spectra in
order to easily detect asphaltene aggregation.

Main Results

38
x
x
x x
x x
x
Air cabinet
Personal computer
NIR spectrometer
Fibre optics
NIR
cell
Cell 1
Cell 2
V1
V2
V3 x
x
x x
x x
x
Air cabinet
Personal computer
NIR spectrometer
Fibre optics
NIR
cell
Cell 1
Cell 2
x
x
x x
x x
x
Air cabinet
Personal computer
NIR spectrometer
Fibre optics
NIR
cell
Cell 1
Cell 2
V1
V2
V3

Figure 5-9: High-pressure near infrared spectroscopy setup.

Both a recombined crude oil and model systems of pentane, toluene and asphaltene were
studied. The model systems were constructed such as to be at the verge of asphaltene
precipitation. Two systems of 1.2 wt% asphaltene in 35 wt% and 40 wt% pentane-in-
toluene solvents were made. The crude oil contained 0.8 wt% asphaltenes, had a
reservoir bubble point pressure of 155 bar and was known to be susceptible to
asphaltene precipitation by pressure depletion. The systems were pressurised to 100 or
300 bar and charged to the high pressure rig at temperatures from 100C to 150C. The
systems were then depressurised in steps, and the resulting NIR spectra at each
pressure level were analysed by the PCA routine. The system was allowed about 20
minutes to equilibrate at each pressure level. It was found that at the asphaltene
aggregation onset pressure a distinct shift in the PCA score plots could be seen. Lowering
the pressure even further, the bubble point was detected by NIR spectra displaying low
absorbance due to gas evolution. In Figure 5-10 the procedure of asphaltene aggregation
onset detection (for the crude oil) from the NIR spectra, via the principal component
analysis, to the impact on the phase envelope is demonstrated. Starting from 300 bar,
first a decrease in optical density with pressure depletion due to the compressibility of
the crude oil was seen. As soon as aggregates started to grow the optical density
increased due to increased light scattering. Although this was difficult to see directly from
the spectra, it was clearly seen from the score plot to occur around 180 bar. In the phase
envelope for the crude oil the pressure depletion path is indicated along with the
detected asphaltene aggregation onset pressure at 180 bar. By performing the same
type of experiments at several temperatures the full asphaltene aggregation onset
envelope can be determined.

Main Results

39
0.4
0.6
0.8
1.0
1.2
1.4
1300 1400 1500 1600 1700 1800 1900 2000 2100 2200
Wavelength [nm]
O
p
t
i
c
a
l

D
e
n
s
i
t
y
300 bar
160 bar
155 bar (bubble point)
0.4
0.6
0.8
1.0
1.2
1.4
1300 1400 1500 1600 1700 1800 1900 2000 2100 2200
Wavelength [nm]
O
p
t
i
c
a
l

D
e
n
s
i
t
y
300 bar
160 bar
Wavelength [nm]
O
p
t
i
c
a
l

D
e
n
s
i
t
y
300 bar
160 bar
-0.08
-0.04
0
0.04
0.08
0.12
-0.2 -0.1 0 0.1 0.2 0.3 0.4 0.5 0.6
Scores PC1
S
c
o
r
e
s
P
C
2
300
280
260
240
220
200
190
180
170
165
160
150 (liquid phase)
-0.08
-0.04
0
0.04
0.08
0.12
-0.2 -0.1 0 0.1 0.2 0.3 0.4 0.5 0.6
Scores PC1
S
c
o
r
e
s
P
C
2
300
280
260
240
220
200
190
180
170
165
160
150 (liquid phase)
0
40
80
120
160
200
240
280
320
-50 50 150 250 350 450 550
Temperature [C]
P
r
e
s
s
u
r
e

[
B
a
r
]
o Asphaltene aggregation onset
Critical point
0
40
80
120
160
200
240
280
320
-50 50 150 250 350 450 550
Temperature [C]
P
r
e
s
s
u
r
e

[
B
a
r
]
Critical point
Critical point
PCA
To phase
envelope

Figure 5-10: Detection of asphaltene aggregation onset pressure from high-pressure NIR
spectroscopy and PCA.
Main Results

40

Performing the same type of experiments on the model systems (containing only
asphaltenes in addition to solvents) produced the same type of results, thus confirming
that the shift in the score plot indeed was caused by asphaltene aggregation.
Depressurisation of a model system without asphaltenes showed no shift in the score
plot. Table 5-4 summarises the experimental conditions, detected onset pressures and
bubble points for the systems studied. The bubble point pressures for the low
temperature model systems were too low to be detected. As expected, the onset
pressure for the 40 wt% pentane solvent was higher than for the 35 wt% pentane
system. In addition, the onset pressure at 150C was found to be higher than that at
100C.

Table 5-4: Bubblepoint and asphaltene aggregation onset pressures.
System Temperature
[C]
Bubblepoint
[bar]
Onset pressure
[bar]
Crude oil 125 155 180
35 wt% pentane 100 <2.5 20
35 wt% pentane 150 10 30
40 wt% pentane 100 <2.5 40
40 wt% pentane, no asphaltene 150 14 -

The reversibility of the asphaltene aggregation was also studied for the crude oil system
and the 35 wt% pentane system at 150C. This was done by repressurising the systems
stepwise from the bubble point to 100 bar and 300 bar for the model system and the
crude oil respectively. When the original pressure was reached, the systems were left to
stand and NIR spectra were recorded in intervals until no further spectral change was
observed. In Figure 5-11 the optical density at 1600 nm for both the depressurisation
and the repressurisation for the two systems are shown.
Main Results

41

0.39
0.40
0.40
0.41
0.41
0.42
0.42
140 160 180 200 220 240 260 280 300 320
Pressure [bar]
O
p
t
i
c
a
l

D
e
n
s
i
t
y

@

1
6
0
0

n
m
Depressurisation
Repressurisation
300
300
72h
0.39
0.40
0.40
0.41
0.41
0.42
0.42
140 160 180 200 220 240 260 280 300 320
Pressure [bar]
O
p
t
i
c
a
l

D
e
n
s
i
t
y

@

1
6
0
0

n
m
Depressurisation
Repressurisation
300
300
72h
300
300
72h
0.48
0.50
0.52
0.54
0.56
0.58
0.60
0.62
0.64
0 20 40 60 80 100 120
Pressure [bar]
O
p
t
i
c
a
l

D
e
n
s
i
t
y

@

1
6
0
0

n
m
Depressurisation
Repressurisation
100
100
23h
0.48
0.50
0.52
0.54
0.56
0.58
0.60
0.62
0.64
0 20 40 60 80 100 120
Pressure [bar]
O
p
t
i
c
a
l

D
e
n
s
i
t
y

@

1
6
0
0

n
m
Depressurisation
Repressurisation
100
100
23h
100
100
23h

Figure 5-11: Asphaltene aggregation and reversibility of crude oil and model system.

For the crude oil (upper plot) considerable redissolution of the aggregation was seen
when increasing the pressure from 150 to 170 bar, as seen by the decrease in optical
density at 1600 nm. However, no significant redissolution was then observed until the
crude oil was left at the original pressure of 300 bar. After 72 hours the aggregate size
had practically returned to its original state. For the model system on the other hand, the
Main Results

42
aggregates seemed to redissolve steadily during repressurising, but the redissolution
came to a stop after approximately 23 hours of equilibration at the original pressure of
100 bar. Thus, while the asphaltene aggregation of the crude oil was more or less
completely reversible, the model system asphaltene aggregation appeared to be only
partial reversible. The asphaltenes of the model system were stripped for the resin
fraction when they were being prepared. The lack of dispersing resins during the
repressurisation was believed to explain the different behaviour of the crude oil and the
model system. The possibility of full reversibility for the model system by allowing even
more time for equilibration could however not be ruled out.

Using NIR spectroscopy in combination with multivariate analytical techniques like
principal component analysis was shown to be a very efficient tool in studying asphaltene
aggregation behaviour. Very small spectral changes are detected in a score plot, enabling
an accurate determination of the onset pressure. In addition, bubble points are easily
detected from the spectral features.
Paper V
In several of the earlier papers of this thesis the ability of near infrared spectroscopy to
detect particle formation in crude oils has been emphasised. However, no quantitative
measure of the size of the particles could be given. In this last paper the possibility of
getting a measure of the asphaltene aggregate size was explored. The idea was to exploit
the equations for Rayleigh scattering by small, dielectric spheres.

In this paper the NIR measurements were performed at ambient conditions with a
transflectance probe with path length of 0.5 mm. The measured optical density from the
NIR spectra depended both on the particle radius, r, and the number of particles, N,
contained in the cell volume, as seen from the Rayleigh scattering expression

(
(
|
|
.
|
\
|
+
= =
2
2
2
4
6
2
1
84 . 13056 434 . 0 434 . 0
n
n r
N N OD
sc
(15)

This equation follows from Equations 9-12 in Chapter 3. To use Equation 15 to predict
particle size, r, from the optical density, a measure of the number of particles contained
in the cell volume had to be found. For this purpose dilute aqueous solutions of
monodisperse polystyrene particles of known particle size were used. Since the radius of
the polystyrene particles was known, the experimental optical density curve of the
Main Results

43
particles could be fit to Equation 15 by only varying N, the number of particles. The
number of particles was determined indirectly by adjusting the cell volume in Equation 16
when fitting experimental optical density curves to Equation 15

100
3
4
%
3
,
= =
part part
part solv cell
part
tot part
r
wt V
M
M
N

(16)

where M
part, tot
and M
part
is the total mass of particles and the mass of a single particle,
V
cell
is the volume containing the particles,
solv
and
part
is the density of the solvent and
particles, wt%
part
is the weight percent of particles in solution, and r
part
is the radius of
the particles.

The cell volume, a measure of the volume exposed to the NIR light, was found to be
approximately 0.31 cm
3
. To verify this value, the size of another set of polystyrene
particles was predicted by only varying the radius in Equation 15. The fit of Equation 15
to the experimental optical density curve gave a radius of 70.5 nm, which was considered
close enough to the known radius of 65 nm. It is important to note that the experimental
optical density curves used were net scattering curves, with the optical density of pure
water subtracted. This isolated the scattering contribution, assuming that the absorption
contribution of the particles was negligible. Figure 5-12 shows the fit of the experimental
and the calculated optical density curves for the volume calibration (115 nm radius) and
the verifying of the volume (65 nm radius).

0.018
0.022
0.026
0.030
0.034
0.038
1100 1140 1180 1220 1260 1300
Wavelength[nm]
O
p
t
i
c
a
l

D
e
n
s
i
t
y
Rayleigh (115 nm, adjusted)
Experimental (115 nm)
0.004
0.005
0.006
0.007
0.008
0.009
1100 1140 1180 1220 1260 1300
Wavelength [nm]
O
p
t
i
c
a
l

D
e
n
s
i
t
y
Rayleigh (70.5 nm)
Experimental (65 nm)

Figure 5-12: Cell volume estimation by monodisperse polystyrene particles.

Main Results

44
For the determination of asphaltene aggregate size, pentane-precipitated asphaltenes
were first dissolved in toluene (0.19 wt%). To induce asphaltene aggregation this
solution was titrated with pentane, and NIR spectra were recorded after each pentane
addition. The optical density was seen to first decrease due to the pentane dilution,
before increasing due to light scattering by asphaltene aggregates forming at around 40
wt% added pentane. To predict the aggregate size the scattering contribution had again
to be isolated. To remove the solvent absorption the optical density of reference solutions
with the same amount of added pentane to toluene, but without asphaltenes, was
subtracted from all spectra. This isolated the asphaltene contribution (scattering and
absorption). The asphaltene absorption contribution was removed by assuming that
asphaltenes in pure toluene displayed no scattering. Therefore the first spectrum, of
asphaltenes in pure toluene, was subtracted from all spectra. The subtraction of this
spectrum had to be volume corrected since the asphaltene concentration continuously
decreased with pentane addition. Figure 5-13 shows the optical density at a single
wavelength, 1300 nm, for the pentane titrated asphaltene solutions. The absorption +
scattering curve is the net asphaltene contribution to the optical density. For the
scattering curve the asphaltene absorption in pure toluene is subtracted, leaving only the
scattering contribution. This curve is corrected for the dilution by pentane addition in the
corrected scattering curve. The first sign of aggregation is seen at around 40 wt%
pentane. These corrected scattering NIR spectra were used for the subsequent aggregate
size estimations.

-0.01
0.00
0.01
0.02
0.03
0.04
0.05
0 10 20 30 40 50 60
weightpercent pentane
O
p
t
i
c
a
l

D
e
n
s
i
t
y
absorption + scattering
scattering
corrected scattering

Figure 5-13: Optical density at 1300 nm for the pentane titrated asphaltene-in-toluene solutions.
Main Results

45

With the light scattering from the asphaltene aggregates isolated, the optical density in
the region 1200-1600 nm was used to fit the experimental NIR curves to the Rayleigh
theory in Equation 15. The minimum aggregate size detected was for the 41.4 wt%
added pentane solution, which gave an aggregate radius of 32 nm. For aggregates larger
than approximately 100 nm in radius (52.3 wt% added pentane) the Rayleigh theory was
found to no longer be valid. The fit to the Rayleigh theory for these two systems is shown
in Figure 5-14.

0.006
0.010
0.014
0.018
0.022
0.026
1200 1300 1400 1500 1600
Wavelength [nm]
O
p
t
i
c
a
l

D
e
n
s
i
t
y
Rayleigh (100 nm)
Experimental (52.3 wt% pentane)
0.0000
0.0002
0.0004
0.0006
0.0008
0.0010
0.0012
1200 1300 1400 1500 1600
Wavelength [nm]
O
p
t
i
c
a
l

D
e
n
s
i
t
y
Rayleigh (32 nm)
Experimental (41.4 wt% pentane)

Figure 5-14: Estimation of aggregate radius for two solutions of asphaltenes in pentane and
toluene.

46
6 Concluding Remarks
The stabilisation/destabilisation of water-in-crude oil emulsions is a complex field that
have great implications on petroleum processing. Despite the huge economical and
environmental consequences caused by the failure to properly resolve such emulsions,
the mechanisms and factors controlling the process is still far from fully understood. This
work has tried to contribute to this understanding by correlating the physico-chemical
properties of very different crude oils to their emulsion stability properties. In addition,
asphaltene aggregation both at ambient and high-pressure conditions has been studied.

Techniques have been developed in order to determine parameters thought to influence
emulsion stability. This includes the build-up of a SARA-separation scheme by HPLC, and
application of the oscillating pendant drop technique on crude oils for interfacial rheology
measurements. In addition to establishing a data matrix of characterising parameters,
the use of indirect characterising by spectroscopic techniques has been utilised. This has
resulted in the observation that crude oil SARA-data can be determined both from
infrared and near infrared spectra in a fast and simple manner compared to the more
tedious traditional HPLC-method (Paper I). The oscillating pendant drop technique was
found to be well suited for measurements on crude oil systems, and the elasticity of a
crude oil-water interface was found to not be directly correlated to any of the SARA-
fractions of the crude oils (Paper II). This emphasised the fact that interfacial rheological
properties must be viewed as a result of complex interactions between the indigenous
crude oil components. This was confirmed from near infrared spectroscopy data, which
suggested that asphaltene aggregation had a great influence on the interfacial rheology.

A new cell for measuring emulsion stability, based on the application of electric fields,
was used as an alternative to traditional bottle tests. The technique was demonstrated to
give very reproducible data that was easily obtained (Paper III). The characterising data
on the 21 crude oils collected through Papers I and II was added to a data matrix that
already contained parameters like viscosity, density, molecular weight etc. The data was
then correlated to the obtained emulsion stability data. It was found that amount of
asphaltenes, interfacial elasticity and asphaltene aggregation was the parameters
contributing most to high stability. Near infrared spectroscopy was also found to produce
good estimates of emulsion stability. This was attributed to the fact that NIR contain both
chemical information (SARA, Paper I) and information on the asphaltene aggregation
state. Both these factors were shown to have a great influence on the emulsion stability.

47
As described, the level of asphaltene aggregation was found to influence both interfacial
rheology and emulsion stability (Papers II and III). Asphaltene aggregation, and
subsequent deposition, is also known to cause other problems like plugging of reservoirs
and processing equipment. In this respect the onset pressure of asphaltene aggregation
is an important parameter. In Paper IV the combination of a high-pressure NIR cell and
multivariate analysis was demonstrated to be a very efficient tool in the early detection
of this aggregation onset pressure. The system was also used to demonstrate the full
reversibility of crude oil asphaltene aggregation by repressurisation, although the kinetics
of the process was slow.

In the discussions of asphaltene aggregation level (Papers II-IV) no quantitative measure
of the size of the aggregates was given. In Paper V the near infrared spectral data was
coupled to the Rayleigh theory of light scattering to produce a measure of this size. It
was found that aggregate sizes down to about 30 nm in radius could be detected by NIR.
This further confirmed the usefulness of near infrared spectroscopy when working with
colloidal systems like crude oils. Throughout the work of this thesis NIR has been shown
to contain both chemical (SARA) and physical information (size of aggregates). By also
utilising the benefits of multivariate analysis tools like PCA and PLS, the data contained in
the NIR spectra has been extracted in a simple and efficient way.

48
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Characterisation of Crude Oil Components,

Asphaltene Aggregation and Emulsion Stability

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