SPE 93008
The Key To Predicting Emulsion Stability: Solid Content
Michael K. Poindexter, SPE, Nalco Energy Services; Shaokun Chuai, Memorial Sloan-Kettering Cancer Center; Robert A.
Marble and Samuel C. Marsh, Nalco Energy Services
Copyright 2005, Society of Petroleum Engineers Inc.
This paper was prepared for presentation at the 2005 SPE International Symposium on Oilfield
Chemistry held in Houston, Texas, U.S.A., 2 – 4 February 2005.
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Abstract
Chemical demulsifiers are routinely added in the oilfield to
effectively resolve water-in-crude oil emulsions. As used in
the common bottle test, demulsifiers in effect probe or
interrogate emulsion stability strength. Emulsion stability in
turn is defined by no less than three parameters – water drop,
oil dryness and interface quality. All three parameters are
direct outputs of the bottle test, and collectively, all three
provide a more complete picture of emulsion stability as
opposed to the use of any singular parameter.
By selecting a wide variety of demulsifiers and
performing a standardized bottle test (as introduced in SPE
84610), emulsion stability from a variety of sites can be
quantified and compared. By coupling bottle test results with
corresponding crude oil analytical data, fundamental questions
concerning factors governing emulsion stability can be
quantified. The results show that solid content, not asphaltene
content or any other crude oil parameter investigated, is by far
the best single predictor for gauging emulsion stability.
Furthermore, statistical analysis via partition trees shows that
emulsion stability is most aptly described using several input
parameters as opposed to a single factor. This statistical
technique produces emulsion stability descriptions with
Rsquare values on the order of 0.9.
Introduction
Crude oil characterization remains a challenging proposition.
Many crude oil characterizations are based on a separation
scheme (e.g. distillation,1 chromatography,2,3 precipitation,4
etcetera), a bulk property of the fluid (e.g. viscosity, API
gravity, surface tension, etcetera) or a combination of
properties. The intent of most characterizations is to relate
some property or group of properties back to the fluid’s
behavior in production or refining. Establishing a valid cause-
and-effect relationship can lead to greater confidence when
assessing the economic and technical risks associated with
new projects or modifications to existing systems.
As related by Hopf, crude oil characterization played a
strong role in the development of organic chemistry.5 For
example, the cage hydrocarbon adamantane, a classic in
skeletal construct, was first isolated in minute amounts
(0.0004%) from petroleum in 1933, eight years before a
synthetic confirmation. The characterization of crude oil has
thus developed both one molecule at a time and by groups of
molecules. Fractionation into saturates, aromatics, resins and
asphaltenes (SARA) remains the most common method for
classifying crude oils by groups. A variety of techniques exist
for classifying crude oils by SARA analysis. Two recent
advances in SARA characterization center on the use of high-
performance liquid chromatography6 and infrared and near-
infrared spectroscopy.7 The most studied petroleum group is
the asphaltene fraction which is an ensemble of molecules
defined by both solubility and insolubility properties8 and
certain general features regarding structure and atomic
composition.9 Recently, a process for quantifying the
overwhelming molecular complexity of crude has been
illustrated by high resolution mass spectroscopy.10 Such
quantifications are providing a fingerprint with which to
compare and contrast crude oils. This technique is quite an
advancement that holds unprecedented potential. While
certain atomic arrangement information is still not possible
with mass spectroscopy, the ability to rapidly amass and store
crude oil information for any molecular parameter holds great
promise.
Additionally, Buckley pointed out that the
characterization of crude oil and asphaltenes in particular is
based not just on the output of laboratory methods but by
process conditions which influence the solubility parameter
and ultimate fate of the asphaltenes.11,12 Such an operational
definition clarifies the need to couple crude oil properties (i.e.
characterizations) with crude oil behavior in the field. The
industrial practice of establishing and managing such critical
relationships ultimately falls under the realm of flow
assurance. Flow assurance can be divided into the deposition
of solids (e.g. hydrates, waxes, asphaltenes and scales) and
disturbed fluid behavior (e.g. foaming and emulsification).13
The latter of these areas is the focus of this study.
One of the main requirements in upstream production
involves the dehydration of oil to meet pipeline water
specifications. Numerous parameters have been cited as
playing a role in emulsion stability.14 Sorting through the
influence of some of the parameters can be accomplished via
2 SPE 93008
the field bottle test. In reality, the bottle test does not
prescribe to a set procedure that is maintained for all emulsion
studies. There is no standard method for conducting a bottle
test in the literature nor should there be.14 The bottle test is as
much method as procedure. Some of the variables which are
initially examined in the field include the influence of
demulsifier chemistry, demulsifier dosage, test length,
temperature, degree of agitation, etcetera. Experimental
design can help in establishing a bottle test procedure that is
representative of field conditions (i.e. one that ultimately
produces dry oil and accurately simulates field conditions).15,16
Linking bottle test data to crude oil properties, which are
determined through extensive laboratory analyses, is a way to
further examine the factors that govern emulsion stability. As
introduced in SPE 84610, a select group of demulsifiers can be
used to probe emulsion strength.17 These chemicals act to
thoroughly interrogate emulsion stability. Emulsion stability
is quite a broad term. Oil-water resolution is often defined as
water drop (i.e. bulk separation of water from oil measured
visually) over time yet this description by itself is incomplete.
The amount of water remaining in the oil also describes a
further aspect of emulsion stability, and this aspect is not
adequately defined as a mere subtraction of the water drop
from the total water cut (i.e. water content). As detailed later
in the section on Emulsion Stability Parameters, this residual
water can be quantified using several different parameters.
Some of the residual water remaining in the oil phase remains
in an emulsified state. Quantifying this type of water provides
a more complete description of emulsion stability and helps
illustrate the differences observed among different oilfield
emulsions.
It is generally recognized that emulsions have a time
dependent nature such that aged crude emulsions are more
difficult to resolve than their fresh counterparts.18,19 For this
reason, all bottle test data reported in this study was generated
in field laboratories using fresh emulsion samples. There is
reasonable debate whether the bottle test accurately represents
field conditions.20 Once a sample is removed from the
process, sample denaturizing commences. Laboratory studies
face the same dilemma unless conducted on live-oil samples.
Conducting such studies for a large number of bottle test
conditions would be cost prohibitive in most instances. Thus,
aside from performing a field evaluation, the on-site bottle test
is probably the method most able to closely mimic the
conditions of a production facility.
To determine the crude oil properties influencing the
bottle test results, numerous analyses were conducted on
emulsions shipped back to the lab for characterization. In
effect, the crude oil characteristics serve as the independent or
input variables used to describe emulsion stability. Emulsion
stability in turn is described by the bottle test results (i.e. the
dependent or target variables). As pointed out by McLean and
Kilpatrick, it is unlikely that one independent parameter can
adequately predict emulsion stability.21 More than likely, a
combination of factors acting in tandem is responsible. A
variety of statistical techniques were used to search for cause-
and-effect relationships. In this work, the partition tree
method was found to be very useful in providing descriptions
of emulsion stability with Rsquare values on the order of 0.9.
Unlike principal component regression, another useful
technique for investigating the type of multivariate problem
posed,22 partition tree analysis does not create new latent
variables that are a linear combination of the original input
variables. Latent variables (sometimes called eigenvectors)
can serve as excellent predictors, but their exact underlying
meaning can be difficult to ascertain as they are in effect each
a mixture of variables. Instead, analysis via partition trees
uses input variable ranges most apt in describing the variance
of the target variable. Partition tree results are very
interpretable regarding what independent variables are
selected in model construction.
Experimental Procedures
Chemicals. Thirty-six different demulsifiers from Nalco
Energy Services, spanning six chemical families (see Table 1),
were used in each emulsion study. Demulsifier dosages for all
tests were held at 150 ppm (by vol) using five percent
dilutions (by wt) of chemical in heavy aromatic solvent.
Stoddard solvent or Varsol (Registry No. 8052-41-3) was used
as the diluent in determining oil dryness values.
Field Emulsions. Crude oil emulsions obtained from the field
were free of chemical demulsifier, and any free water found
was drained from each sample before the start of each test.
The thirteen emulsions under investigation are listed in Table
2 along with a basic chemical description of each oil along
with their abbreviations. To conform with production
conditions, the two Canadian emulsions (SGD-1 and SGD-2)
and two Venezuelan emulsions (EV and WV) were diluted
with field condensate after collection from the wellhead. This
was necessary to keep the bottle test emulsion identical to the
field process fluid.
Bottle Test Procedure. Methods used to determine the
theoretical oil-water interface level (commonly called a
grindout), water drop, oil dryness and interface quality were
followed according to SPE 84610.17 Additionally, for
extensive descriptions of the field bottle test, see the work of
Leopold23 as well as Manning and Thompson.24
Crude Oil Characterizations. Field emulsions were sent to a
central laboratory where oil-water separation was performed
using the demulsifiers listed in Table 1. Crude oil collected
for the SARA analyses involved removal via syringe of the
top portion of resolved crude oil (i.e. ca. 15% of the total oil
phase) from each lab bottle test. A literature procedure, based
on n-heptane as the asphaltene precipitant, was used to
separate the crude oils into their SARA fractions.25 Crude oil
viscosities were measured at both 25 °C and the bottle test
temperature using a Brookfield Programmable DV-III+
Rheometer. Total acid numbers were determined according to
ASTM D66426 while naphthenic acid numbers involved solid
phase extraction of the maltenes (i.e. the n-heptane soluble
fraction) followed by titration in an isopropyl alcohol/toluene
solution using potassium hydroxide. Both acid numbers are
reported in milligrams KOH/gram of crude oil. Solid content
determinations followed ASTM D480727 and results are
reported in pounds per thousand barrels (PTB).28 Iron, nickel
and vanadium contents were determined on a Jarrell-Ash 61E
inductively-coupled argon plasma emission spectrometer and
SPE 93008
are reported in parts per million (ppm). Elemental analyses
were conducted by Galbraith Laboratories located in
Knoxville, TN.
Statistical Analyses. All statistical analyses (spec. linear
regressions and the multivariate model partition tree) were
conducted using JMP Statistical Discovery Software Version
5.0.1 from the SAS Institute, Inc., Cary, NC.
Lab versus Field Emulsions
The study of water-in-crude oil emulsions is often conducted
in the laboratory using model systems. With such a controlled
arrangement, given amounts of a crude oil component (often
asphaltenes, resins, naphthenic acids, solids or combinations
of these components) are added to a solvent system which is
generally a mixture of heptane and toluene.21,29-33 This solvent
system acts as a substitute for the lighter, less polar crude oil
components (i.e. the saturate and aromatic fractions) and
permits adjustment of the aliphatic-aromatic balance that
contributes largely to the solubility and aggregation state of
the more polar components. Water is combined with the
synthetic organic phase followed by agitation to create the
emulsion. Generating emulsions in this fashion allows
exacting control over the factors governing emulsion stability.
The approach presented in this study uses the crude oil
emulsions as obtained from the field. Each fluid brings its
own unique inventory of material to bear on the problem,
namely emulsion stability. Comparing emulsion stability
where numerous input or crude oil parameters are changed in
basically an uncontrolled manner would seem not helpful in
unraveling the complexity. However, examining emulsion
stability in this manner becomes a multivariate problem that
can be addressed using various statistical techniques.
In field separators, all crude oil emulsion components are
present simultaneously and act in tandem, e.g. asphaltenes are
never devoid of resins. The bottle test in essence maintains
the complex interplay of crude oil components as encountered
in the field. Similar to lab studies, this multivariate approach
permits the same basic questions to be addressed regarding
factors contributing to emulsion stability. With all the crude
oil constituents simultaneously engaged, if a given parameter
or possibly group of parameters aptly describes an aspect of
emulsion stability across a wide variety of emulsions, then the
identified parameter is highly relevant. In essence, this
alternative methodology is a different yet complementary
approach to the laboratory model studies.
Furthermore, the crude oil parameters chosen for this
investigation were based in part on prior laboratory studies
that have shown how specific crude oil components or
properties either influence emulsion stability or act as major
crude oil classifiers. The bottle test approach coupled with
statistical analysis of the data allows both the influence of
each factor to be examined using linear regression analysis
(e.g. determining whether more or less of a certain component
is detrimental to emulsion stability) and the ranking of critical
factors determined to be important using partition tree
analysis. Clearly, examining the influence of each individual
crude oil parameter is partly confounded in this approach as
the parameters, as stated earlier, act collectively. However, if
3
a parameter has an overwhelming influence, then this
parameter will stand out in the analysis.
To compare and contrast the bottle test data from the
different emulsions, thirty-six different demulsifiers were
selected to probe emulsion stability (see Table 1). The
demulsifiers span six distinctly different chemical classes, and
the dosage for all chemicals used in each study was 150 ppm
by volume. To some degree, the choice of demulsifiers used
is arbitrary. Almost any group of chemicals having interfacial
activity could work in this methodology. All field bottle test
studies were conducted using fresh samples taken after the
wellhead. After distributing 100 mL of emulsion into bottles
having graduation markings, each sample was dosed with a
single demulsifier (36 demulsifiers in all). A blank and the
incumbent chemical used in the field were also included in the
field work, but this data was not included in the analyses of
this report. The main reason for running the blank and
incumbent was to ensure the test results were representative of
the field system. If the blank showed good performance or the
incumbent showed poor performance, then the test results
were suspect and discarded.
The rationale for using a range of demulsifiers was to
thoroughly probe emulsion stability. Some chemicals excel in
producing more complete water drop, others have a propensity
to produce dry oil, while some chemicals have no effect at all.
By subjecting each emulsion to the same set of chemical
probes at the same concentration, comparisons between
emulsions become possible. Such a protocol does not imply
that other factors, like test temperature or amount of agitation,
are not also important. However, some of these other
parameters are partly incorporated into the parameters under
investigation (see Table 2 for the crude oil parameters). For
example, bottle test temperature would influence the viscosity
of the crude oil, and this parameter is one of the independent
variables under study.
Statistical Parameters
Crude Oil Variables. From each field site, emulsions were
sent to a central laboratory where the emulsions were resolved
using the demulsifiers from Table 1. The top portion of
resolved oil (ca. upper 15%) was collected and used for
analysis. A variety of crude oil parameters were ascertained
regarding their possible contribution to emulsion stabilization.
Most of the variables listed in Table 2 have been used to either
study emulsion stability in the lab or classify crude oils.
Crude oil groups, determined from fractionation, include
asphaltenes, resins, aromatics, saturates, total acid content,
naphthenic acid content and solids. Bulk crude oil properties
or parameters investigated include viscosity (measured at both
room temperature and the bottle test temperature), aromaticity
(defined as the H/C ratio of the aromatic fraction)32 and the
content of three commonly reported transition metals– iron,34
nickel and vanadium.35
Emulsion Stability Variables. Bottle test results provide a
wealth of information. Water drop versus time, oil dryness
and quality of the interface are all aspects open to
investigation using the method. As mentioned, studies
reporting only one of these parameters can obscure the overall
process of water-oil separation. Good water drop does not
4 SPE 93008
necessarily imply dry oil.17 Only determining the water
content in the oil can determine whether such a relationship
holds. In this study, five of the most important bottle test
parameters were selected to define emulsion stability. Mean
values of the five bottle test parameters were calculated for
each emulsion and then the results were examined against the
crude oil parameters determined in the lab. In essence,
emulsions showing minimal water drop or wet oil are likely
stabilized by components not present in oils showing high
levels of resolution.
The five bottle test parameters consist of final water drop,
unresolved emulsion and total water remaining in a sample of
oil removed from the top oil and similarly unresolved
emulsion and total water remaining from the bulk oil phase.
Final water drop is expressed as a percentage where the last or
final water drop reading taken during the test is divided by the
water cut (or water content) of the emulsion. The procedure
for determining the water cut is often called a “grindout” and
is described in SPE 84610 as well as other references.23,24
Chemicals promoting coalescence of water droplets show high
water drop values.
The second and third bottle test parameters describe
different aspects of oil dryness. Both parameters start by
taking a small aliquot (sometimes called a thief or centrifuge
cut23) of oil via syringe at a specified level above the
theoretical oil-water interface which is another term for water
cut. In these studies, the thief was taken 15 mL above the
interface. One part of thief (about 6 mL) is added to a
graduated API centrifuge tube containing one part of cutter
solvent (typically Varsol, Stoddard solvent or some other low
aromatic, high boiling solvent) and the mixture shaken. The
cutter solvent acts to dilute the emulsion and enhance oil-
water separation. Following centrifugation of the sample,
unresolved emulsion is determined and reported as basic
sediment in the thief, BS(thief). To resolve the emulsion
completely and separate any undetected residual water still
held in the oil phase, a large dose of chemical (often called a
slug with treat levels typically at a few thousand parts per
million) is added. Most slugging chemicals have low
molecular weights with the sulfonate functionality. The
slugging agent is mixed into the solution, and the contents
centrifuged. As before, the water content is recorded and
reported as slug(thief). Demulsifiers showing low thief values
are often viewed as good flocculants.
The fourth and fifth bottle test parameters further describe
oil-water resolution. Following the two thief measurements,
the bulk resolved water in the bottles is removed via syringe
and the remaining oil, which is often wet, is shaken
thoroughly. One part of this wet oil is added to an API
centrifuge tube containing one part of cutter solvent and
processed using the same steps used in the thief
measurements. These values are often called composites, as
they quantify the water content in the final composite, and are
reported as BS(composite) and slug(composite). Composite
readings provide additional information regarding oil dryness
and interface quality. For example, the closer the composite
readings are to the thief values, the more evenly distributed is
the residual water throughout the oil phase. Conversely, if
thief measurements are much lower than the composite values,
then the unresolved water in the oil exists as a gradient where
more water resides closer to the oil-water interface. Both thief
and composite values are reported as percentages since both
values measure the amount of residual emulsion or water
remaining in the oil. To compare and contrast crude oil
emulsion stability, the mean values of the five bottle test
parameters for each emulsion were used as the dependent
variables in the statistical analyses (see Table 3).
Statistical Analyses
Linear Regressions. Linear regression is the most common
way to establish whether a relationship exists between two
variables. When regressing the independent crude oil
parameters of Table 2 with the dependent bottle test variables
of Table 3, solid content had the highest Rsquare value for
each bottle test result. For comparison, the Rsquare values for
asphaltene content, the most commonly studied crude oil
fraction, are also included (see Table 4). For both asphaltene
and solid contents, higher concentrations favored emulsion
stabilization for all five bottle test variables. Regarding the
solid content results, four of the five Rsquare values are
around 0.8. This is remarkably high as the solids are vying
with all the other crude components in stabilizing the
emulsion. Figure 1 illustrates these trends for the oil dryness
parameter having the highest Rsquare value for asphaltene
content, namely slug(thief). Final water drop gave a
noticeably lower Rsquare value (0.22) for solid content than
for the other four descriptions of emulsion stability. This
result indicates that of the crude oil properties selected no
single variable adequately describes water drop.
Upon further examination of Figure 1A, it might be worth
considering a non-linear fit to describe the influence of
asphaltene content on slug(thief). Until about 8% asphaltenes,
this oil dryness parameter remains small in value. After this
point, some of the data rises abruptly while part continues to
show little asphaltenic influence. In fact, the three most
asphaltenic crude oils (CAN, EV and WV) would seem to
have sufficient asphaltenes to stabilize an emulsion yet all
have relatively low slug(thief) values. Regarding the solid
content of these three crudes, CAN, WV and EV finish in
sixth, ninth and last place, respectively. Conversely, for the
four crudes veering upward in Figure 1A (MT-1, MT-2,
SGD-1 and SGD-2), all have lower asphaltenic contents than
CAN, EV and WV but are the most abundant in solid content.
While additional asphaltenic properties not accounted for,
such as molecular weight or heteroatom content, may play a
role in defining emulsion stability, it is clear that solid content
is playing a very critical role in predicting emulsion stability.
Partition Tree Analyses. Partition tree analysis is sometimes
referred to as decision or regression tree analysis. This
technique is based on the earlier techniques called AID
(Automatic Interaction Detection) and CART (classification
and regression trees).36 Analysis via partition trees permits
construction of highly informative multivariate models using
more than one input variable. This statistical technique
determines input variables over their most pertinent or
descriptive data range. In most regression techniques, the full
range of the input variables is regressed against the full range
of a given target variable. There are cases where a portion of
the dependent variable is not well defined by the full range of
SPE 93008
the independent variable. Partition tree analysis allows such
descriptions to be explored and identified. In effect, a virtue
of the technique is that partition trees can account for non-
linear associations which are complementary to linear
regression analysis.
Partition tree models were used to examine the collective
influences of the crude oil parameters on emulsion stability.
Partition tree analysis starts by selecting a target variable (i.e.
one of the five bottle test parameters from Table 3) and
finding the independent variable that optimally splits the target
variable. In this study, the crude oil parameters serve as the
partitions for each of the objects (i.e. the emulsions). Groups
resulting from the initial split can be partitioned further using
the first split independent variable or another independent
variable. If the same independent variable is used in
successive splits then a strong predictor has been identified.
In each instance, the partition is dictated by finding the
independent variable that best divides the data cluster under
consideration for split.
Figure 2 is representative of the technique and uses the
same output variable discussed in Figure 1, namely slug(thief).
Solid content was selected as the first split with a value of 661
PTB where more solids gave higher slug(thief) values (i.e.
more wet oil). For the second level splits, asphaltene and solid
contents were used for the left- and right-side splits,
respectively. In summary, the bottle test parameter slug(thief)
is best described by a combination of solid and asphaltene
contents where high solid and asphaltene contents both
increase the slug(thief) values.
Splits describing all five bottle test variables are
summarized in Table 5 along with the numerical value of the
splits. Solid content clearly dominates the results. This crude
oil parameter received at least one split in each analysis, four
of the five first level splits and nine of a possible fifteen splits.
In fact, solid content received all three splits used to describe
the BS(composite) parameter. No other crude oil property
was able to predict emulsion stability to this degree. For each
split involving solid content, higher levels always indicated
greater emulsion stability. Similarly, asphaltene and resin
contents always partitioned such that higher levels
corresponded to greater emulsion stability (see slug(thief) and
slug(composite) models). This agrees with much of the
literature as these more polar components are known to
contribute to emulsion stabilization. However, model studies
have also done much to shed light on the balance of
asphaltenes and resins (typically reported as the
resin/asphaltene ratio, R/A) regarding emulsion stability.
Generally, lower R/A ratios favor more stable emulsions.37
While the R/A ratios are not listed in Table 2, this quotient
was also included in all the partition tree analyses but was
never selected as a partition.
Iron content served as the first split variable for the final
water drop parameter where crudes containing higher iron
levels gave less water drop. Iron (especially ferric iron, Fe3+)
is known to have an influential role in determining asphaltene
polarity and ultimately asphaltene solubility properties.
Higher iron levels appear to promote asphaltene aggregation.34
Aromatic content received two splits in Table 5. It is difficult
to judge how this crude oil fraction influences emulsion
stability as it is rarely studied in the lab. Most model work
5
uses heptane-toluene mixtures in place of the crude oil derived
saturate-aromatic fractions. Returning to Table 5, higher
aromatic content favors greater coalescence as seen for the
water drop parameter. However, higher aromatic content
leads to higher slug(composite) values. Thus, water drop
appears not to be related to oil dryness regarding aromatic
content. A similar observation was noted in SPE 84610.
Viscosity determined at room temperature received a
secondary split for BS(thief). As expected, higher viscosity
hindered dehydration. Concerning the remaining Table 2
entrants, crude oil viscosity measured at the bottle test
temperature, both acid numbers, two of the metals (nickel and
vanadium) and the aromaticity of the aromatic fraction
received no splits in any of the models.
Of the five bottle test variables, water drop had the lowest
Rsquare value (0.70). The same trend was found in the linear
regression analyses (see Table 4). A possible explanation for
this result might be the beginning of demulsifier
overtreatment. In a related study using 50 ppm of
demulsifier38 (versus the 150 ppm used in this study), solid
content was used to make the first split of all five bottle test
parameters, and the Rsquare value for the partition tree model
describing water drop was 0.85. Thus, the drop in Rsquare
value for the higher demulsifier dosage study could indicate
that the demulsifiers are not just probing emulsion strength but
possibly contributing to emulsification.
Solid Content
The solid content reported in Table 2 is defined by ASTM
D4807. Crude oil used for the analyses was taken from the
upper or top portion of the bottles. Extremely large solid
particles are not likely to be found in this section of the bottle.
The ASTM procedure uses 0.45 µm pore size filter paper and
includes a hot toluene wash of the solids. Washing with a hot
aromatic solvent will remove most, if not all, of the organic
material associated with the solids. This would include the
heavier crude oil components such as the resins, asphaltenes
and naphthenic acids. Thus, determining the interactions
between the isolated solids and the more polar crude oil
components is not possible using the ASTM procedure.
Having such an organic-inorganic description well established
would ultimately be beneficial for defining the exact ensemble
of constituents responsible for emulsion stabilization. This
avenue of investigation was not undertaken here. For oil sand
bitumen, Kotlyar et al. demonstrated that solids and
asphaltenes are strongly associated.39
From this work, solid content proves to be an excellent
measure for describing emulsion strength. Further
descriptions using size distribution and elemental composition
were not needed. When reviewing numerous past analytical
records involving crude oils not used in this study, it was
determined that all the crude oils had some solid content as
defined by ASTM 4807. There were no crude oils with zero
solid content. Assuming this holds true for crude oils
throughout the world, then solid content should be reported in
all crude oil assays.
In related work, aliquots of emulsion were taken from the
oil-water interface for each of the emulsions studied. In other
words, these samples were taken from the bottom portion of
the oil phase, not the top. This region of the bottle likely holds
6 SPE 93008
other valuable information regarding emulsion stability as the
water content is generally higher nearer the interface. Solids
from this region were also isolated using ASTM D4807 and
further examined using scanning electron microscopy. In each
case, the dimensions of isolated inorganic solids would be
classified as clay (0-3.9 µm) or silt (3.9-62.5 µm) particles and
not the various larger sand particles.40 The importance of this
smaller size range has been discussed41 as well as other
important features of solids in contributing to emulsion
stability.42,43
The ability of solids alone in stabilizing emulsions was
firmly established years ago by Pickering.44 This work,
however, does not intend to suggest that solid content is the
only factor contributing to crude oil emulsion stability.
Numerous other factors have been shown to influence
emulsion strength. Nonetheless, solid content appears to be
the best predictive variable for describing emulsion strength.
Conclusions
Thirteen water-in-crude oil emulsions were investigated using
the field bottle test followed by crude oil characterization and
fractionation into SARA and other commonly analyzed
components (spec. solid, naphthenic acid and total acid
content). A variety of demulsifiers was used on each emulsion
to quantify and compare emulsion strength. Crude oil
properties commonly cited as influencing emulsion stability
were used to examine if one or more of the attributes could
describe emulsion stability as defined by five bottle test
parameters. The primary technique used to elucidate cause-
and-effect relationships was partition tree analysis. From the
five bottle test variables, solid content showed by far the
greatest ability to predict emulsion strength. In comparison to
the other crude oil variables used in the partition tree analysis,
solid content received at least one split to describe each of the
bottle test parameters, four of the five first splits and nine of a
possible fifteen splits. No other input parameter came close to
matching this level of importance. In each case where solid
content was found to be influential, higher solid content was
shown to be detrimental.
When considering projects involving emulsion resolution,
this study indicates that the reporting of crude oil properties
should include solid content as well as the other commonly
reported values. Without consideration of this key variable,
predictions of emulsion stability strength will likely be
lacking. Results from this study do not imply that the crude
oil parameters used herein are the only ones responsible for
emulsion stability. Beside crude oil properties, other
parameters influencing emulsion stability likely include water
chemistry as well as process conditions.
Acknowledgments
The authors thank Nalco Energy Services for permission to
publish this work as well as Becky Ramsey, Bob Pultz and
Terry Street for determining the acid numbers and the metal
and solid contents.
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Table 2. Summary of Crude Oil Properties

Bottle Test
Viscosity, Viscosity, % % % % Acid Naphthenic Fe, Ni, V, Aromatic Temperature
Crude Oil (source) Designation cP (25 °C) cP (test) Saturates Aromatics Resins Asphaltenes Numbera Acidsa Solidsb ppm ppm ppm H/Cc (°F)
Alberta CAN 47,150 360 18.8 51.9 14.6 14.3 0.9 0.4 401 6.8 64 160 1.54 194
Alberta SGD-1 8,850 144 18.6 48.9 13.7 13.1 1.0 1.0 661 3.6 66 150 1.52 195
Alberta SGD-2 7,618 168 15.9 54.7 13.6 12.3 1.8 0.6 985 14 62 150 1.52 199
California (offshore) COf 235 24 14.8 43.9 16.7 11.4 1.1 0.4 257 120 69 175 1.71 180
California Midway-Sunset MS-1 98,979 480 10.7 57.4 24.1 7.9 3.3 1.8 156 32 67 75 1.51 190
California Midway-Sunset MS-2 52,200 330 14.6 53.1 25.0 8.3 5.3 2.6 634 19 53 62 1.56 190
Eastern Venezuela EV 4,385 114 13.8 49.0 14.1 14.5 4.0 1.7 96 6.8 76 335 1.55 194
Gulf of Mexico GM-1 17 8 65.2 26.8 2.6 0 1.1 0.3 176 13 0.9 0.7 1.54 120
Gulf of Mexico GM-2 214 29 17.0 59.9 11.9 3.0 1.9 1.3 286 22 21 60 1.54 165
Montana MT-1 38 18 38.6 28.6 4.3 8.1 1.1 0.2 664 5.0 2.9 2.7 1.46 125
Montana MT-2 218 57 34.5 30.8 4.2 11.6 0.3 0.1 1,090 13 4.6 1.0 1.46 125
Western Venezuela WV 90,800 630 11.6 49.5 16.9 17.0 2.1 0.4 208 4.8 86 980 1.52 199
Wyoming WY 179 44 24.2 49.3 9.9 7.6 0.3 0.2 157 2.7 34 130 1.54 132

a
Reported as mg KOH/g of crude. b Reported as pounds/1,000 barrels of crude (PTB). c
Atomic ratio for aromatic fraction.
8 SPE 93008

Table 3. Mean Bottle Test Parameters

Water Drop Oil Dryness Oil Dryness Interface Interface
Crude Oil (Final), % BS(thief), % slug(thief), % BS(composite), % slug(composite), %
CAN 50.2 2.0 5.7 3.0 13.4
SGD-1 60.7 9.6 14.4 20.4 25.5
SGD-2 25.6 22.0 30.0 22.9 42.3
COf 62.1 3.1 3.8 4.1 13.6
MS-1 48.3 2.1 2.7 2.5 14.4
MS-2 64.9 0.9 2.6 7.9 21.6
EV 54.8 1.1 3.1 2.4 6.0
GM-1 54.9 0.4 1.5 2.6 10.8
GM-2 56.9 0.2 1.7 3.8 10.8
MT-1 57.3 15.2 16.5 15.4 19.6
MT-2 53.9 28.5 24.0 27.5 27.7
WV 75.5 1.3 7.4 4.0 10.7
WY 80.3 0.6 1.1 1.0 5.5

Table 4. Rsquare Values for Two Crude Oil

Properties versus Bottle Test Parameters
Bottle Test Parameter Asphaltenes, % Solids, PTB
Water Drop (final), % 0 0.22
BS(thief), % 0.05 0.81
Slug(thief), % 0.12 0.79
BS(composite), % 0.05 0.89
Slug(composite), % 0.04 0.81

Table 5. Summary of Partition Tree Results

Bottle Test Parameter R2 First Split Variable Second Split Variables (left - right)

iron solids - aromatics

Water Drop (final), % 0.704 ≥5/<5 ppm ≥985/<985 PTB - <49.3/≥49.3 %

solids solids - viscosity (25 °C)

BS(thief), % 0.973 <664/≥664 PTB <661/≥661 PTB - <218/≥218 cP

solids asphaltenes - solids

Slug(thief), % 0.969 <661/≥661 PTB <11.4/≥11.4 % - <985/≥985 PTB

solids solids - solids

BS(composite), % 0.970 <661/≥661 PTB <634/≥634 PTB - <985/≥985 PTB

solids resins - aromatics

Slug(composite), % 0.941 <634/≥634 PTB <14.6/≥14.6 % - <54.7/≥54.7 %
SPE 93008 9

35 35
Figure 1A Figure 1B
30 SGD-2 30 SGD-2

25 25
MT-2 MT-2
Slug(thief), %

Slug(thief), %
20 20
MT-1 MT-1
15 SGD-1 15 SGD-1

10 10
WV WV
5 CAN 5 CAN
COf EV COf
EVMS-1
GM-1 GM-2 MS-1
MS-2
WY WY
GM-1GM-2 MS-2
0 0
-5 0 5 10 15 20 0 250 500 750 1000 1250
Asphaltenes (%) Solids, PTB

Figure 1A and 1B. Plots of asphaltenes and solids versus the oil dryness parameter, slug(thief).
Each point on the plots represents a crude oil emulsion.

35
SGD-2
30
Solids, PTB>=985
25
MT-2
Slug(thief), %

Solids, PTB>=661
20
Solids, PTB<985 MT-1
15 SGD-1
10 All Rows
WV
5 Asphaltenes
CAN (%)>=11.4
Solids, PTB<661 COf
Asphaltenes
MS-2 (%)<11.4 MS-1 EV
GM-2 GM-1 WY
0
Asphaltenes (%)<11.4 Asphaltenes (%)>=11.4 Solids, PTB<985 Solids, PTB>=985
Solids, PTB<661 Solids, PTB>=661
All Rows

Figure 2. Partition tree of slug(thief) using the crude oil parameters from Table 2.