Accepted Manuscript

Mechanisms, performance optimization and new developments in

demulsification processes for oil and gas applications

Zlata Grenoble, Siwar Trabelsi

PII: S0001-8686(18)30195-7
DOI: doi:10.1016/j.cis.2018.08.003
Reference: CIS 1904
To appear in: Advances in Colloid and Interface Science

Please cite this article as: Zlata Grenoble, Siwar Trabelsi , Mechanisms, performance
optimization and new developments in demulsification processes for oil and gas
applications. Cis (2018), doi:10.1016/j.cis.2018.08.003

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 ACCEPTED MANUSCRIPT

Mechanisms, Performance Optimization and New Developments in

Demulsification Processes for Oil and Gas Applications

Zlata Grenoble, Siwar Trabelsi

Global Research & Innovation Center, Flotek Chemistry, Houston, Texas 77064 United States

Corresponding author:

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E-mail address: zgrenoble@flotekind.com

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Abstract

The present review discusses new developments and optimization of demulsification processes
in oil and gas applications, and highlights the critical parameters. Discussed are the primary
mechanisms of demulsification, as well as the strategies for developing optimum demulsifiers.
Demulsification mechanisms are presented in the context of emulsion stability principles which
are equally applicable to the destabilization of crude oil-water emulsions.

The present paper is a concise overview of the various surfactant classes and their structure-

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activity relationship. It correlates demulsification optimization with surfactant properties and

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their applications. These classes include, but are not limited to pluronic block co-polymers, as
well as amine- and siloxane based nonionic surfactants. The emphasis is on providing some

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strategies for achieving optimum crude oil-water separation efficiency by tuning the demulsifier
to the intended application and crude oil properties.

A brief overview of unconventional analytical techniques, which reach beyond the standard

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demulsifier evaluation methods, i.e., Near Infrared Spectroscopy (NIR), and in particular, low
resolution NMR relaxometry, highlights their role in monitoring demulsification processes.
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Keywords: emulsion, demulsifier, oil-water separation mechanisms.
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Contents

1. Introduction

2. Demulsification Mechanisms

2.1. Models for Assessment of Optimum Demulsifier Conditions

2.2. Effects of different Parameters on Demulsification
2.2.1. Salinity Effect
2.2.2. Effect of Non-Aqueous Solvent
2.2.3. Surfactant Molecular Weight

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2.2.4. Temperature Effect

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2.3. Branched Surfactants

3. Optimizing Demulsifier Formulations

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3.1. Hydrophilic-Lipophilic Balance and Optimum Formulations.
3.2. Surfactant Adsorption Kinetics and Displacement of Asphaltenes by Competitive

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Mechanisms
3.3. Hole Nucleation and Other Concepts
3.4. Thermodynamics and Kinetics of Surfactants at the Oil-Water Interface
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4. Demulsifier Types and Properties in Demulsifier Mixtures and Microemulsions.

4.1. Block Co-Polymeric (Pluronic) Surfactants

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4.2. Amine-Based Surfactants

4.3. Siloxane-Based Surfactants
4.4. Novel and Unconventional Surfactants
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4.4.1. Ionic Liquid Derivatives as Surfactants and Demulsifiers

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5. Novel Analytical Techniques used in Demulsification Monitoring

5.1. NMR Spectroscopic Techniques

5.2. Near Infrared Spectroscopic Techniques
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5.3. Alternative Analytical Techniques

5.4. Newly Emerging Oil-Water Separation Techniques
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6. Future Outlook

7. Conclusions

Acknowledgements
References
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1. Introduction
Crude oil is generally produced as a mixture of crude oil and water, either as water-in-
oil, oil-in-water emulsions, or multiphase mixtures. The actual fraction of water in the crude oil
(water cut) depends on the geographic location and geological condition, and the type of crude
oil recovery process. These may change in the course of crude oil production. Separation of
water from the hydrocarbon phase along with removal of inorganic salts and metals is required in
order to facilitate transportation and storage, and reduce risks of hydrocarbon processing
problems, i.e., catalyst poisoning. Surfactants with demulsifier properties are usually added to

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the crude oil-water separation process to minimize crude oil-water emulsion formation and

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enhance demulsification. A strategic approach to optimize demulsifiers will aid in achieving fast
and cost-effective separation at low demulsifier dosage [1].

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The primary difference between demulsifying surfactants and surfactants, in general, is
their affinity for the interface, combined with a large surface area occupied by the demulsifier

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molecule (nm2 /molecule). The adsorption kinetics and surface affinity of demulsifying
surfactants are competitive with naturally occurring surfactants in crude oil, i.e., asphaltenic
molecules, i.e., asphaltenes, resins, and naphthenic acids [1]. These molecules contain
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hydrophobic and hydrophilic (polar) portions, which render them amphiphilic. They have a
tendency to form aggregates or nano-aggregates, resulting in stable films or networks at the
water-oil interface.
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A good demulsifier destabilizes this interfacial layer by several mechanisms:

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competitively adsorbing at the interface, displacing asphaltenic aggregates, breaking

up/destabilizing the asphaltenic film, along with reducing interfacial tension between the
hydrocarbon and aqueous phase, leading to enhanced droplet coalescence kinetics [2]. The goal
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of a demulsifier system is to counteract the stabilizing mechanisms by competitively adsorbing at

the interfacial region, thus weakening or dispersing asphaltenic/resin layers. Specific demulsifier
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formulations can be further tailored to the type of crude oil, brine composition, and the nature
and fractions of asphaltenes and resins [3, 4].

It has been common practice to use empirical or standard performance test methods,
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i.e., bottle tests, for demulsifier performance assessment, without paying too much attention to
the exact mechanisms and underlying thermodynamics and kinetics of demulsification.
Frequently, the primary demulsifier selection criteria are based on the surfactant hydrophilic-
lipophilic balance (HLB) concept; the HLB value is solely related to the surfactant properties
based on the molecular structure and contributions from hydrophilic and hydrophobic portions.
The HLB for most commercial surfactants or demulsifiers is known; however, the value is
difficult to predict for extended surfactant with more complex molecular structures.

Empirical models are mostly based on Bancroft’s work and Bancroft’s rule, which
states that hydrophilic surfactants, preferentially soluble in the aqueous phase, will stabilize an
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oil-in-water emulsion, whereas hydrophobic surfactants will stabilize water-in-oil emulsions [5].
Both the HLB model and Bancroft’s rule provide the basic information on the surfactants’
hydrophilic-hydrophobic properties. Later developments in the study of
emulsification/demulsification have led to more advanced prediction models for improved
demulsifier selection and performance assessment [2,3]. These models exceed the scope of the
empirical models by providing demulsifier performance prediction tools on the basis of
thermodynamic aspects and phase equilibria.

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2. Demulsification Mechanisms:

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2.1 Models for Assessment of Optimum Demulsifier Conditions

Some of the later models predicting optimum conditions for demulsification are the so-
called “Hydrophilic-Lipophilic Deviation”, (HLD – a dimensionless parameter), and “Surfactant-

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Affinity Difference” (SAD) [3]. The SAD model is related to the change of the surfactants’
chemical potential after transfer from an aqueous to an oil phase, or partitioning between the two
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phases. The HLD model is related to the SAD concept; both originated in the research group of
Prof. Salager and co-workers; they were initially developed for ionic surfactants, and then
expanded to a modified form to include non-ionic surfactants [3]. The HLD expression defines a
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surfactant system at thermodynamic equilibrium correlating the HLD of a given surfactant to the
SAD of a reference surfactant. The model considers contributions from salinity, surfactant
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molecule specific properties, the type of co-solvent (alcohol), and temperature effects:

HLD = (SAD-SADref)/RT
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= ln S – k ACN + f (A) + σ – aT (T – Tref)

for ionic surfactant (1)

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HLD = (SAD-SADref)/RT
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= bS – k ACN + φ (A) + β + cT (T – Tref)

for nonionic surfactant (2)

Where S is the salinity (wt% NaCl, KCl), ACN is the alkyl carbon number, which is replaced by
the equivalent carbon number (EACN) for hydrocarbon based oil phases, f(A) is an alcohol-
specific constant, and aT is a temperature dependent constant, that vanishes when the HLD is
determined at the reference temperature of 25˚C. σ and k are surfactant specific constants. Eq.
(2) applies to nonionic surfactants, where β = α-EON, with α being related to the hydrophobic
properties of the surfactant and EON the equivalent ethylene oxide unit number.
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In contrast to simply applying the HLB or Bancroft’s rule, the model includes effects
of crude oil properties, brine salinity, temperature, and possibly pressure conditions. The
surfactant properties are related to thermodynamic equilibrium conditions of the demulsifier-
crude oil system, which are required for a stable emulsion [1-3]. Thermodynamic aspects in
emulsion stability go back to Winsor’s work. His thermodynamics-based model describes a type
III emulsion where the oil-water-system is at equilibrium. At equilibrium conditions, the
surfactant’s interaction with the aqueous phase is balanced by its interaction with the
hydrophobic oil phase and a ratio of 1[1]. System adjustments are made by changing several

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controllable parameters: one of these parameters is the selection of a surfactant or a mixture of
surfactants with HLB values that match the oil properties; another important variable is salinity

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which is used to modify the effective HLB of ionic surfactants.

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A system with an R ratio = 1 will be at its optimum for a demulsification process, which
corresponds to a net curvature = 0. By Windsor’s definition, the R ratio is given by R = (ACO-
AOO-ALL)/(ACW -AWW -AHH), where C, O, and W stand for surfactant, oil, and water, and L and H

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designate the lipophilic and hydrophilic portions of the surfactant. High values of the interaction
terms ACO and ACW promote miscibility of the mixture, whereas strong contributions from the
terms AOO, AWW , ALL, and AHH may promote phase separation [1]. If a nonionic surfactant is
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used as a demulsifier, the EON of the nonionic surfactant matches the oil phase and optimum
conditions for demulsification performance are established. Using this concept of
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thermodynamic equilibrium, Salager and coworkers identified two maxima that represent
optimum emulsion stability conditions [3]. One is found below and the second one above the
optimum value determined from salinity scans (figure 1). The two maxima are representative for
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emulsion stability, whereas the minimum in between indicates the best condition for system
separation. A scan of performance vs. surfactant HLD/SAD is one efficient tool to locate this
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optimum condition, which is relevant for water droplet coalescence. For practical purposes,
initial selection of the most suitable surfactant or surfactant combination based on the intrinsic
HLB may be a valid starting point, but should not be limiting for fine-tuning the system.
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Correlations of demulsifier types and dosage effects with experimental observations can
provide information on the demulsifier performance, as shown by Nguyen and co-workers.2 One
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example is to observe changes in the Gibbs elasticity modulus as one measurable parameter for
demulsifier efficacy and to differentiate between demulsifier types. The observed kinetic rates of
the demulsifier adsorption at the oil-water interface correlated with the separation efficiency,
indicative of the demulsification process [2]. Similar approaches can be taken to find the
optimum demulsifier dosage by testing the system’s efficiency over a range of demulsifier
concentrations. Some of the primary criteria for developing an optimum surfactant system and
good demulsification performance include [2-4]:

- Analysis/identification of the crude oil properties, i.e., composition, SARA analysis, API
gravity, equivalent alkyl carbon number (EACN), total acid number (TAN).
- Selection of suitable surfactant combinations.
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- Test separation efficiency as function of the relevant variables.

- Determination of the stability maxima and minimum by means of a salinity scan.
A salinity scan (NaCl-solution) aids to detect the minimum emulsion stability, and the
increasing (maxima) stability to the left (O/W) and to the right (W/O) of an emulsion.
(discussed in more details in section 3.1).
- Adjustment of controllable variables.
- Interfacial tension lowering properties of the demulsifier.
- Optimum concentrations of the surfactant(s).

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The hydrophobic-hydrophilic ratio of surfactants allows for initial prediction of

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preferential demulsifier partitioning between the oil and the water phase, and to some extent their
interaction with solvents and co-solvents. Using nonionic surfactants with a certain degree of

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ethoxylation, the primary contributors are the length of the alkyl-chain vs. the number of
ethylene oxide units. The ratio of the ethylene oxide units in the hydrophilic segments to the
alkyl carbon number, along with the head group properties gives a reasonable estimate of their

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partitioning behavior. The most common, conventional nonionic surfactants include triblock co-
polymers, or poloxamers, with usually known HLB values [4,6]. What is frequently difficult to
assess is the solvent-poloxamer interaction as illustrated in studies by Ivanova et al. with high
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surfactant concentrations or high molecular weight triblock co-polymers [4].

Another criterion for demulsifier assessment is the “relative solubility number” (RSN),
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which may be considered an alternative approach to the HLB parameter. The empirical method
for determination of the RSN value is defined as the volume in milliliters of distilled water
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required to give a persistent turbidity in a benzene/dioxane solvent system, using 1 g of the

surfactant per 30 mL of the solvent mixture. Low RSN numbers (index < 13) are indicative of
low or no water solubility, whereas high RSN numbers (index > 17) refer to increasing water
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solubility of the surfactants. The RSN index gives an estimate of the maximum amount of
surfactants that can be added to a given water-oil/solvent system as well as its hydrophilic/
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hydrophobic properties. Modified methods have been proposed to avoid the use of toxic
solvents, such as benzene and dioxane. Comparative studies based on toluene or xylene/ ethylene
glycol dimethyl ether (EGDME) have shown that these solvents are equally applicable [7]. Other
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external factors also might affect demulsifier performance.

2.2. Effects of different Parameters on Demulsification

2.2.1. Salinity Effect

Increasing salinity usually results in lowering of repulsive forces between adjacent

head groups in ionic surfactants, resulting in denser micellar packing (packing parameter), and
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lower critical micelle concentration (cmc) of a given surfactant system. The resulting
thermodynamic effects are decreased polar properties of the surfactant along with increased ionic
strength of the aqueous phase and repartitioning of the surfactant into the hydrophobic oil phase.
Kabalnov and co-workers identified additional mechanisms, which are related to their ability to
modulate water solubility of non-ionic surfactants, by either the salting- in or salting-out effect,
according to the Hofmeister series, or by their competing adsorption-desorption at the oil-water
interface [8]. Salts present in the interfacial region between the water and the organic phase shift
phase equilibria, with subsequent repartitioning of the surfactant between the two phases. The

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salts adsorbed at the interfacial region changed the curvature of the surfactant, depending on the
salt type, with either a positive or negative curvature ((+) or (–) sign). The salting-out strength

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and depletion of the interfacial region of the various salts was proportional to the respective salt
concentrations, dependent on the type of salt, and the polarizability of the involved ionic

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species. Besides these quantitative effects, different types of salts showed varying effectiveness,
on a molar basis, in modulating interfacial curvature. The equilibrium position may shift towards

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higher stability, or in case of demulsification, farther away from optimum stability. Salinity
contributions from external sources, i.e., brines, need to be considered in the oil recovery
process. Salinity has less impact on non-ionic surfactants.
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2.2.2 Effect of Non-Aqueous Solvent:
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The effect of non-aqueous solvent properties were illustrated in connection with the
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Pluronic surfactant, F127 (EO 100 PO70 EO100 ), with a molecular weight of approx. 12,600 g/mol,
in glycerol, propylene glycol, and ethanol solvents. Phase behavior and liquid crystal structure
studies by Ivanova et al. showed that the ratio of EO vs. PO greatly influenced their interaction
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with the co-solvents, leading to swelling of the PO block, and liquid crystal formation tendencies
[9]. Similar phenomena were observed with other high molecular weight pluronics in water. Less
polar solvents, i.e., ethanol and glycol, interact preferentially with the apolar PO block, or are
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located at the interface between EO and PO blocks. In contrast, more polar glycerol preferred the
EO sites. Pacheco et al. studied two linear and two branched EO-PO pluronic surfactants with
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varying EO/PO ratios in a variety of solvents with different polarity [9]. The more hydrophilic or
actually more polar solvent combinations of xylene/ethanol offered the highest solubility for the
surfactants with the lowest interfacial tension.

Pluronic surfactants and their interaction with solvents just point out the important
contribution of solvents in general, which apply to any type of demulsifier. Their effects are not
limited to this type of surfactants as shown in above studies. Solvent polarity relative to the
demulsifier affects the demulsifier’s solubility and solvent-demulsifier interaction, which again
directs their oil-water partitioning, phase behavior, and affinity for the interface.
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2.2.3. Surfactant Molecular Weight:

Molecular weight distributions of a demulsifier dictate to some extent its mobility and
diffusion behavior along with the resulting interfacial adsorption kinetics. Demulsifiers with high
molecular weights in the range of polymeric macromolecules may be preferred for certain
applications as flocculants, friction reducers and/or viscosity modifiers. Their slow adsorption
kinetics makes them less efficient as demulsifiers that need to compete with natural surfactants
present in crude oil. The adsorption kinetics measured for asphaltenes themselves, in particular
asphaltene aggregates found at asphaltene concentrations (> 2-4 wt%) in crude oils, are relatively

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slow, but still require a demulsifier, with dominating adsorption kinetics. Studies by Pena et al.

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confirmed that high molecular weight type demulsifiers do adsorb at the interface and interact
with other species adsorbed at the interface of nearby drops, but with slower adsorption kinetics

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[10]. Their partitioning at the oil-water interface and R values (or net curvature) is generally
unfavorable for IFT reduction, and also for water droplet coalescence enhancement. Molecular
weight effects of demulsifiers and the related kinetics were demonstrated quite successfully with

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pluronic surfactants, which are commercially available with widely varying lengths of the
hydrophobic and hydrophilic segments. The mole fraction of the hydrophobic PO block relative
to the EO portion strongly affects both their partitioning at the oil-water interface and also their
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tendencies to form micelles [6]. At a given temperature or cmc, their aggregate forming
tendencies of the studied pluronics increased with increasing mole fraction of the hydrophobic
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block. Surfactants with this property may be favorable for gel or emulsion type applications, but
not recommended in a demulsification formulation.
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2.2.4. Temperature Effect:

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Temperature may further modulate the intrinsic hydrophilic and hydrophobic properties
of the surfactants, in particular, non-ionic ethoxylated surfactants, as demonstrated by Pacecho et
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al [8]. The hydrophobic PO segment tends to adsorb along the oil-water interface, whereas the
more hydrophilic EO blocks extend into the aqueous phase. Increasing temperatures reduced the
solubility parameter of all block co-polymers, proportional to their EO chain lengths by
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weakening the hydrogen-bonds between ethylene oxide units and the surrounding water
molecules by temperature induced electronic orbital disturbances between the O-H orbitals. The
dehydrated ethylene oxide units become less hydrophilic and repartition between water and oil
phase. Alexandritis and Hatton demonstrated how complex and difficult to predict these
temperature effects during their work with pluronic triblock co-polymers [6]. Increased
temperature renders the EO blocks less hydrophilic proportional to the temperature increase and
the EO/PO ratio. The more hydrophobic PO segments of pluronics were less sensitive to
temperature induced dehydration as compared to the EO blocks. Aggregation mechanisms or
micellization in the bulk phase may be affected by temperature variations, proportional to the
number of ethylene oxide units. Micellization, in general, is more difficult for pluronics with
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increasing hydrophilic blocks, making it thermodynamically less favorable to transfer the

surfactant monomer from the hydrophilic aqueous phase to the hydrophobic oil phase. Increasing
temperature along with increasing hydrophobicity favor the aggregation mechanism in the bulk
and affinity for the oil-water interface, but negatively impact cloud point and overall phase
behavior of temperature-sensitive surfactants, as confirmed by simulation studies [11].

Adsorption kinetics, in general are influenced by temperature, including droplet

coalescence kinetics, and thermodynamically driven processes. Natural surfactant molecules and
aggregates, i.e., asphaltenes in crude oil, may not respond to temperature effects to the extent

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observed with surfactants containing hydrophilic ethylene oxide units; however, substantial

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temperature variations may modulate their intrinsic properties, solvent solubility, aggregate
forming tendencies, and interfacial asphaltenic film properties, and thus the film drainage

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dynamics [12].

New developments including in-house internal studies (Flotek Internal R&I Study) on

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temperature-induced interfacial properties and asphaltene behavior at model oil-water systems
support temperature-induced structural rearrangement and repartitioning of asphaltenes and/or
asphaltenic aggregates at the interface. Decreasing interfacial tension and the viscoelastic
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modulus with increasing temperature, modulation of surface coverage as well as surface
restructuring or rearrangement are the most prominent features. The rheological property
changes are primarily related to increasing temperature, with low or no pressure dependent
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responses of the asphaltenes adsorbed at the crude oil or model oil-water interface. The actual
magnitudes depend on the asphaltene fractions or crude oil type, and are further modulated by
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the amount or fraction of resins [13-15].

Demulsification kinetics at elevated temperature are known to increase, but more work and
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information is necessary to assess the impact of temperature-related changes of asphaltene

interfacial layers on demulsification. Predictable demulsifier properties for successful
demulsification at elevated temperature are demulsifiers with high temperature tolerance.
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2.3. Surfactant Branching:

Many surfactants, including demulsifiers, are derived from easily available hydrocarbon
raw materials, and have a branched structure. Branched alkyl chains add more hydrophobic
character to the surfactant as compared to their single-chain analogues. The increased
lipophilicity is primarily due to the extended area and volume of the hydrophobic alkyl portion,
enhancing partitioning into the oil phase as well as their response to external effects, i.e.
temperature, salinity, and water-oil ratio in binary and ternary mixtures. Systematic studies by
Wormuth and Zushma confirmed their advantage in certain microemulsion applications, i.e.,
lowering of the total surfactant requirement, and also T* (the lowest temperature at which a
microemulsion is formed [16]. However, this type of surfactant feature is not favorable in
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demulsification processes, where both equal partitioning between water and oil (HLD = 0) and
adsorption at the water-oil interface are required [17]. Substantial branching does not lead to any
significant improvement due to: (a) improved packing efficiency gives a thinner interfacial
packing density and lowers its ability/mobility to penetrate a rigid asphaltenic layer (b)
hydrophilic head groups with high surface energy can approach the interfacial regions
counteracting the initial surface energy lowering effects of the methyl groups [18]. Branching of
the tail groups have some effects on surfactants, in general, with the most prominent being an
increase in hydrophobic character. Branching in demulsifiers may not lead to the desired

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demulsification performance in most non-ionics, and to some extent, anionic surfactants.
However, this approach may be favorable for modifying other types of surfactants, i.e., silicone-

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based surfactants for different purposes [18].

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3. Optimizing Demulsifier Formulations

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3.1. Hydrophilic-lipophilic Balance and Optimum Formulation

A systematic approach to develop efficient demulsifier systems has been described by

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Salager and Rondon [17,19], and supported by experimental studies conducted within their
research groups. The HLD concept and related parameters form the basis for demulsifier
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formulation, and agree with Bancroft’s rule. If the HLD = 0, the system is at its thermodynamic
equilibrium, where the surfactant interacts equally with both water and oil, and interfacial
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tension is at its minimum value. The optimum condition for emulsion destabilization is a
demulsifier formulation which has its minimum between two emulsion stability maxima or two
optimum conditions. These two stability maxima are related to the optimum stability of
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microemulsions, where the lower stability optimum is located at an HLB < 10, corresponding to
the optimum condition for water-in-oil (W/O) emulsions. The second maximum is found at an
HLB > 10 for an optimized oil-in-water (O/W) emulsion. The optimum condition for
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demulsification is in between, with an HLD of 0, and accompanied by both ultra-low interfacial

tension and low viscosity. A salinity scan using NaCl for ionic surfactants, or alternatively, EON
(equivalent ethylene oxide number) scan for nonionic surfactants narrows down the optimum
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formulation composition, as illustrated in figure 1 for scans relative to HLB, and HLD [19].
Asphaltenes, which have more lipophilic character and HLD > 0, require a more hydrophilic
demulsifier to shift the hydrophilic- lipophilic balance towards 0. In case of surfactant mixtures,
the sum of their contributions should counterbalance the effects of naturally occurring
surfactants.
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Figure 1: (left): Emulsion stability expressed as the time required for 50% water separation as
function of HLB, EON, and salinity, for a given surfactant concentration; (right): stability as
function of HLD (copied from [19]).
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Rondon et al. reaffirmed the principle of minimum stability by blending pluronic
surfactants with two other non-ionics of known HLB values. They showed that the optimum
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condition is met “when the surfactant adsorbed at the interface exhibits the same affinity for both
oil and water phase”. Further improvement of the demulsification process is feasible by
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choosing surfactants with favorable oil-water partitioning and a wide optimum concentration
range, as illustrated in figure 2.
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Figure 2: Emulsion stability (presented as the time required for 50% water separation) vs.
demulsifier concentration at constant surfactant EON (range of EON values from 4.75 to 20).
The minimum stability is shown as black circles, the so-called optimum optimorum is designated
by a star symbol (copied from [19]).
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The demulsifier with an EON number of 10 is close to or at the minimum emulsion stability over
a wide concentration range, providing more dosing flexibility as compared to the other nonionic
surfactants with different EON values and narrower concentration range for the optimum
destabilization condition.

3.2. Surfactant Adsorption Kinetics and Displacement of Natural Compounds by

Competitive Mechanisms

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The optimum demulsifier concentration increases linearly with increasing asphaltene

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concentration up to a given threshold value [20]. The optimum surfactant concentration for
obtaining optimum instability reaches a plateau and remains constant. Below this threshold

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concentration, referred to as the T-value, the optimum demulsifier concentration is related to the
asphaltene concentration in the bulk. Above the threshold point T, demulsifier concentrations
required for optimum destabilization conditions do not increase with further asphaltene content.

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This strongly suggests that asphaltene aggregation and adsorption at the water-oil interface
remains constant and the ratio of asphaltene at the interface relative to the bulk has reached
equilibrium. Replacing the demulsifier with one from the same family with higher EON values
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(alkyl phenol with higher EON number and HLB=13.5) leads to lower optimum demulsifier
concentrations as well as lower asphaltene concentrations at the critical point T or plateau region
(Figure 3). The lower asphaltene concentration shown at the critical T point of the alkylphenol
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surfactant with 10 EO units demonstrates that using a more hydrophilic demulsifier (higher EON
values) leads to both lower asphaltene adsorption and demulsifier dosage requirement.
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Figure 3: log Cdemuls vs. log Casph plot for three nonylphenols indicating the position of
minimum stability at equilibrium conditions for three nonylphenol ethoxylates with different
EON values; (copied from [[19]).
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Substitution of the alkyl phenol demulsifier for a structurally different demulsifier (Tween 80® or
polyethylene glycol sorbitan monooleate with HLB=15) did not change the demulsifier
concentration requirements. It did, however, increase the equilibrium concentration of adsorbed
asphaltenes due to different interaction and mixing with the asphaltene fraction.

More in-depth studies of asphaltene properties revealed that only certain fractions of the
asphaltenes are interfacially active. This surface active asphaltene subfraction and its impact on
interfacial properties were studied by Yang et al. They observed that rigid asphaltenic film did

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not form when a particular subfraction was removed and only a small fraction of asphaltenes is
interfacially active [20]. However, more work needs to follow to narrow down the properties of

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this subfraction.

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3.3. Hole nucleation and other concepts:

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The parameters and thermodynamic concepts crucial for film stability have been
described in various models, and equally apply to the mechanisms of emulsion destabilization. In
the context of oil-water phase separation, these models explore the mechanisms of oil film
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drainage, including hole nucleation of the oil film. The fundamental thermodynamic parameters
for prediction of the water droplet coalescence have been proposed and discussed in the early
1960’s. Davies [ref 21] and Rideal presented a model based on thermodynamic principles for
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hole nucleation processes vs emulsion stability. The original theory has been extended and
frequently combined with additional models to predict demulsifier efficiency by including the
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physico-chemical properties of the demulsifier and the phase behavior of the emulsions.
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The fundamental principles underlying these models state that lowering the activation
energy and thus the thermodynamic free energy barrier for hole nucleation of the oil film is
favorable for hole nucleation (film drainage or rupture). Kabalnov and Weers extended the hole
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nucleation theory by including the Helfrich equation. Their extended models provide the bending
elasticity parameter for the surfactant molecule and energy penalty related to the most probably
surfactant curvature in oil/water emulsions [22]. This free energy penalty is a critical factor in
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controlling the surfactant’s spontaneous curvature at the oil-water interface and subsequent
coalescence probability of two approaching water drops. This dependence of the energy
requirement (W*) on the spontaneous curvature has its origin in the strong curvature of the
surfactant monolayer at the interfacial layer around the edges of nucleating hole. The
spontaneous curvature can be fine-tuned by varying additional parameters, i.e., salinity with
ionic surfactants. Surfactants with a large spontaneous curvature, i.e., spherical micelles, provide
lower energy barriers to overcome and promote emulsion stability. The opposite applies to the
hole nucleation process. Practical applications of this fundamental concept of favorable
spontaneous curvature in the context of macromolecules are briefly discussed in the following
section 4.3.
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Kabalnow and Wennerström [23] introduced the spontaneous curvature (Ho ) parameter
of a surfactant as part of their “oriented wedge theory” model. The spontaneous curvature, and
the resulting free energy barrier may favor either stabilization or breaking of an emulsion.
Positive values of Ho favor O/W emulsion, whereas negative values stabilize W/O emulsions,
and a Ho = 0 provides the condition for phase separation. Extension of this model and Bancroft’s
rule leads to the statement that surfactants with branched hydrophobic portions and small head
groups favor W/O emulsions, whereas surfactants with straight alkyl chains and large polar head

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groups are preferred for O/W emulsions. The primary driving mechanisms are packing
constraints at the oil-water interface. A similar approach was taken by Klaseboer et al., however,

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from the point of view of film drainage and drop coalescence [24]. The authors studied the
kinetics of drainage and coalescence processes by spectroscopic techniques. Their model

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includes physical properties of the continuous phase, i.e., viscosity, film thickness, prevailing
film pressures, and velocities.

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Experimental studies by interferometric techniques [25] presented numerical values for
micellar dimensions (including aggregation numbers) and the critical film thickness using
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interferometric techniques. The authors demonstrated that the film drainage or hole nucleation
process depends on micellar aggregates and their restructuring inside the film. Micellar
restructuring occurs due to the confined space in a thin film to maintain a balance between
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repulsive and attractive forces. Micellar volume fractions were estimated based on the individual
molecular structure and the electrical double layer formed around them. The process was
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controlled by the surfactant concentration as well as the molecular structure, and in case of ionic
surfactants, also electrolyte addition.
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One the latest and new models evolving from this hole nucleation theory has been
employed by Kiran and Acosta [26], and incorporated in their “Hydrophilic-Lipophilic
Deviation” (HLD) and “Net Average Curvature” (NAC) models. They showed that a favorable
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spontaneous curvature of the demulsifier molecules and the resulting free energy decrease is
proportional to the lowering of the interfacial tension between water and oil (γow). This concept
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may be viewed as an improved expansion of Davies and Rideal’s model for water drop
coalescence/hole nucleation prediction. The focus of their study was the phase inversion point,
and the optimum net average curvature of the surfactants for emulsion stability or instability. The
theoretically calculated curvature of the surfactant and the dynamic radii is used for predicting
several crucial parameters, i.e., viscosity, interfacial tension, density, solubilization capacity, and
also density of the system. Their model system (sodium hexyl sulfosuccinate-toluene-water)
demonstrated that the phase behavior of a system is predictable, given the information of
relevant input parameters. Introduction of an additional model, “collision-coalescence-
separation” (CCS) allows determination of the thermodynamic parameter and prediction of
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whether a hole in the film will further open or close. Similar to previous findings [22, 23], the
most critical parameters involve film thickness and interfacial tension.

3.4. Thermodynamics and Kinetics of Surfactants at the Oil-Water Interface:

Asphaltene concentrations reach a plateau at the water-oil interface [27], below which
the required demulsifier concentration is proportional to the asphaltene concentration
(“proportional regime”). Above this value, in the so-called “saturation regime”, the surfactant

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concentrations remain constant, irrespective of the asphaltene content. Excessive increase of the

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demulsifier concentrations does not improve the demulsification process, but may give rise to the
opposite effects of stabilizing the water-oil emulsion (overdosing) [27,28]. Overdosing resulted

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in increasing both adsorption and desorption kinetics, due to steric repulsive forces between the
demulsifier molecules [28]. Instead of the expected asphaltene film penetration, the demulsifiers
appeared to form three-dimensional networks and stabilize the asphaltene film. Pereira et al.

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tested a series of pluronic demulsifiers with relatively high molecular weights. They confirmed
that demulsification efficiency improves with increasing hydrophilic properties up to a certain
point, reflected by shorter separation times. However, increasing hydrophilic properties also
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means increasing molecular weight, which slows down the demulsifier’s adsorption kinetics. A
combination of optimal surfactant geometry (affinity for the interface) and low molecular
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weight, which allows fast adsorption kinetics, was found in a nonionic and slightly hydrophilic
extended surfactant, a block co-polymer with the structural formula C 12 PO14EO 20 (figure 4).
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Figure 4: Sketch of the suggested arrangements of the extended surfactants at the oil-water
interface (copied from [27]).

The extended block copolymer (low MW of 1,100) has a relatively hydrophobic poly propylene
oxide segment which is presumed to remain at the interface in a folded and loosely packed
configuration; this type of interfacial arrangement may prevent asphaltenes from forming
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aggregate networks or gels and promote faster separation kinetics (figure 4). Even better
performance was observed with its counterpart, an anionic and hydrophilic extended surfactant
C12 PO14EO2 SO4Na [28].

Recent developments and research activities in micro- and nanotechnological devices are
focusing also on surfactant and demulsifier performance in droplet coalescence kinetics, apart
from adsorption kinetics of the surfactants themselves [29, 30]. Microchannel chips with the
desired microchannel configuration allow in situ monitoring of oil droplet coalescence kinetics
of oil-in water emulsions. This type of “lab-on-a-chip” uses a combination of experimental data,

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computational methods, and statistical analysis to identify the coalescence criteria for the oil-

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water model system. The microchips are designed to study the coalescence kinetics as function of
emulsion density, viscosity, and related rheological properties i.e., film drainage efficiency,

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volume fraction of the dispersed phase, the hydrodynamic diameter of the droplets, and the flux.
Similar experimental layouts with some refinements of the microfluidic design are equally
applicable to a demulsifier system [31-33]. The use of microfluidic devices combined with

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microscopy imaging was successfully demonstrated during an in-house R&I internal study [34].
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4. Demulsifier Types and Properties in Demulsifier Mixtures and
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Microemulsions .
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4.1. Block Copolymer (Pluronic) Surfactants

A large number of demulsifier formulations include some type of pluronic surfactants,

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or tri-block copolymers. These tri-block copolymers, usually abbreviated in the short notation
EOn -PO m-EO n ., or alternatively POEn -PPOm-POEn, are known for their low toxicity, wide
application range, and relatively high salinity brine tolerance [35-38]. Disadvantages are their
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temperature sensitivity, due to dehydration effects, as discussed earlier in this review. They are
are offset by their ability to competitively adsorb at the oil-water interface, forming spacer-like
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aggregates. Adilbekova and co-workers found good demulsification efficiencies, even with
relatively hydrophobic pluronic demulsifiers and low aqueous solubility (relative solubility
numbers (RSN) < 13) [7, 39]. The significance of RSN was discussed previously in section 2.1.
The favorable demulsification efficiency may be related to the nature of the particular crude oil
used in this study, kerosene, which requires a more hydrophobic demulsifier, and also to the use
of two pluronic surfactants. One of the pluronics in the mixture had a dominating hydrophilic
block (PEO), promoting interaction with the water phase, whereas the second one reached into
the oil phase, due to more hydrophobic character from the dominant PPO block. These
mechanisms of pluronics partitioning between oil and water phases are supported by theoretical
modelling and simulation studies [39]. Their simulation models revealed the tendency of the
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hydrophobic propylene oxide chain to partition into the oil phase, with the more hydrophilic
ethylene oxide segments oriented towards the aqueous phase.

More complex behavior is seen with the extended Tetronics®. Tetronic® surfactants
are branched polyols, also known as “poloxamines” with the general formula of “2[HO-(PO)m-
(EO)n -N-CH2 -CH2 -N- 2[(EO)n -(PO)m -OH] or 2[HO-(EO)n -(PO)m-N-CH2-CH2 -N- 2[(PO)m-
(EO)n -OH”. Tetronics® offer larger structural and geometric variation as well as isomerism and
increase surfactant density at the interfacial region. One of the challenges associated with
Tetronics® are their difficult to predict phase behavior and interfacial properties. Performance

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tests of pluronic and tetronic block copolymers with PO n -EO m-POn , structures, carried out by

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Mansur and co-workers, demonstrated the correlation between structure, solubility, and
demulsification efficiency [40]. However, none of the selected and studied demulsifiers were

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competitive with a commercial product, which was used as benchmark in the study, but without
disclosing any of its properties. The superior performance of the commercial product is not
unusual since it contains most likely three or more surfactants. The impact of the hydrophilic

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segment (EO) position was demonstrated by Wu et al.in studies of sequential pluronics [41]. The
pluronics with outer EO segments improved demulsification performance as compared to their
pluronic counterparts containing equal percentage of EO units, but arranged in a reversed
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sequential geometry. Reversed sequential arrangements result in different micellization behavior,
less favorable adsorption at the interfacial regions, and ultimately less efficient enhancement of
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droplet coalescence.
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Demulsification Performance with Heavy Crude Oil

100
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% Water Separation

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60
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40
C12 cationic
C16 cationic
20 C18 cationic
Blank
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0
0 10 20 30 40 50 60 70 80 90 100 110 120

Time (minutes)

Figure 5: % water-heavy crude oil separation vs. time Fig. 6: Emulsion formation after high-shear
for three cationic demulsifier systems. mixing using condensates and hexa-
decyl alkylammonium chloride as
demulsifier.

The effects of the hydrophilic- hydrophobic ratio and alkyl chain length on surfactant
properties became apparent during an in-house study (Flotek R&I internal) of three tertiary alkyl
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ammonium chloride surfactants with varying (C 12 to C18 –alkylammonium chloride) alkyl chain
lengths. All three demulsifiers performed well with heavy crude oils at initial volume fractions of
1:1 water:oil (figure 5), but formed stable water-in-oil (W/O) emulsions with light crude oils or
condensates, containing high saturate fractions (figure 6); the emulsion volume fractions was
proportional to the alkyl chain length, and thus the hydrophobic character of the demulsifier.

4.2. Amine-based Surfactants and Additives:

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Apart from quaternized ammonium based cationic surfactants, alkylamines have

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found extensive use within the group of non-ionics. Silva and co-workers compared the effects
of short chain alkylamines, ethyl- and hexylamine, to those of acidic carboxylic acids, i.e.,

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acetic- and hexadecanoic acid as additives to demulsifier formulations [42]. They found that
addition of hexylamine, in particular, improved demulsification efficiency in admix with tri-
block copolymers as demulsifiers, whereas the less polar hexadecanoic acid had no significant

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effect on the separation process. Their proposed mechanism is: both ethylamine and hexylamine
are water soluble due to the amine function, but hexylamine tends to partition preferentially to
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the oil side (longer alkyl chain), which is the preferred phase of asphaltenic compounds. The
optimum dosage requirements were low. Polyester derivatives of in-house synthesized
ethoxylated and polyesterified aromatic amines were studied by Al-Sabagh and co-workers (with
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calculated HLB in the range of 8.9 to 10.4) [43]. As already discussed previously in context with
hydrophobic-hydrophilic properties, the demulsification process strongly depended on alkyl
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chain lengths, degree of ethoxylation, and surfactant molecular weight. Low molecular weight
amino-polyesters, paired with a high proportion of ethylene oxide units were superior to their
high molecular weight counterpart in displacing asphaltenes from the interface.
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Similar relationships between the ethoxylated segments of the amine-based

demulsifiers and their demulsification performance was noted by Xu et al [44]. The researchers
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employed diethylene triamine as the basic structure to study the effects of varying EO and PO
lengths on the demulsification efficiency. The performance of these amine-based dendrimeric
demulsifiers was good, when the PO unit numbers were either comparable to the EO length or
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lower. Introducing an amine-oxide head group increases hydrophilic properties, resulting in

higher cloud point phase behavior, and improved the demulsification process [45]. The amine
oxide based surfactants participate in the demulsification process as an ensemble with other
surfactants by modifying intermolecular interaction and surface forces. Amine-or amido-based
surfactants appear to strongly affect a demulsification formulation, when combined at the right
proportion with other demulsifiers, i.e. tri-block co-polymers. This may also apply to some
variants of betaines. Hirasaki et al. studied amphoteric amine-based demulsifiers in conjunction
with a trialkylammonium halide (n-octyl trimethyl ammonium bromide or C 8 TAB), non-ionic
linear ethoxylates, and branched alkyl ethoxylates [46]. The researchers conducted the study in
the context of chemical enhanced oil recovery. In this case, the aqueous phase contained a blend
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of anionic surfactants, alcohols, and partially hydrolyzed polyacrylamides. This mixture of

anionic surfactants and polymers has a tendency to form stable oil-in-water emulsions. The
combination of the positively charged C8 TAB, and the amine-based amphoteric demulsifier and
the overall charge neutralization effects shifted the phase behavior towards a more balanced
system, or to the point of minimum stability, as discussed in section 2.1.

Betaine effects on interfacial tension reduction in crude oil emulsions were studied
by Cao et al. [47] with focus on synergism between zwitterionic demulsifiers and various crude

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oil fractions. The presence of cationic and anionic functionalities in betaines compensates for the
high charge densities in high salinity brine-crude oil mixtures. A variant of alkylsulfobetaine

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(ASB), a xylyl-substituted alkylsulfobetaine (XSB), with a xylene ring attached to the alkyl
chain on the sulfobetaine core, reduced the interfacial tension (IFT) in the order of 10-2 mN/m vs.

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an average of 10-1 mN/m for the conventional alkylsulfobetaine. The significant effect of the
xylene group was interpreted by the authors in terms of increasing the hydrophilic character

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(relative to the hydrophobic alkylgroups) of the surfactant. However, none of the two
sulfobetaines could achieve interfacial tension values below 10-2 mN/m, with the exception of
XSB in admix with various crude oil fractions. The synergistic effects observed with ASB and
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acidic compounds in resins may have been a result of proton exchange with the acidic functions,
and thus charge density modulation in the interfacial region. No synergistic interaction could be
observed with asphaltenes in connection with ASB, but some synergism existed between XSB
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and asphaltenes and aromatic fractions. Likely mechanisms for this XSB-asphaltene interaction
are the aromatic functionality and ability to intercalate between the fused polar aromatic rings of
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asphaltenes and disrupt the asphaltenic interfacial film (figure 7).

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Figure 7: IFT values for ASB (left) and XSB (right) with aromatic/kerosene fractions (copied from
[47]).

Atta and co-workers observed high affinity of ethoxylated Schiff-base derived

polymeric surfactants for a xylene-ethanol mixture. The typical Schiff-bases belong to the
“imine” group, synthesized by using primary amines and –OH and –CHO functionalized mono-
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aromatics as starting material, The surfactant molecules were synthesized by ethoxylation at the
–OH functionality. Their favorable interaction properties with polar crude oil fractions were
attributed to the polar phenolic ring and the secondary amine functionalities, enhancing solubility
and dispersion of the demulsifier(s); faster dispersion in the solvent promoted competitive
adsorption kinetics and efficient disruption of the asphaltenic film [48]. The xylene-ethanol
mixture act both as an additive and co-solvent, which favor increased cmc with smaller
aggregation numbers (Nagg), making a larger number of demulsifier molecules available for
adsorption at the oil-water interface.

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Hao and co-workers found that the demulsification efficiency of an amido-based

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demulsifier with a dendritic molecular architecture (figure 8) was related to the compactness and
number of amido groups in the molecular core, as well as their position within the demulsifier

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molecule [49]. When dosage effects were used as a criterion, demulsifiers containing a dendritic
triethylenetetramine (TETA) core reached optimum performance at a demulsifier dosage of 200
ppm and diesel content of 50 g/L of diesel oil in water. At low oil-water ratios, i.e., 3g/L of

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diesel in water, demulsification performance dropped to the level of the control molecule. The
highly branched molecules with hydrophobic properties could not efficiently partition between
water and oil phases and adsorb at the interface. Hydrophobic effects were dominating, despite
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the polar nature of the amido functions in the molecular core. The thermodynamica lly more
favorable mechanism was to form aggregates in solution vs. adsorption at the interface, making
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them less suitable for treating water-in-oil emulsions. These demulsifiers were effective for
diesel oil fractions from catalytic cracking processes, but performed poorly in fractions from
coking processes, which leave stable coke films at the oil-water interface. Their performance
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could be improved by addition of the anionic sodium dodecyl sulfate (SDS) as co-surfactant,
which interacts favorably with the cationic amido core of TETA, and results in charge
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neutralization [49]. However, self-aggregation in the aqueous solution was still the preferred
mechanism at very low oil fractions.
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Figure 8: Dendritic demulsifiers with cores consisting of four or five amido cores and equal
number of extendable branches (copied from [49]).
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Alternative modifications to the basic molecular surfactant structure have been

studied and reported, including the effects of inserting biodegradable linkers between the alkyl
chain and the polar head group of gemini surfactants [50]. The linkers decreased both the
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surfactant packing density and the cmc proportional to increasing spacer length. The reduction in
cmc has been rationalized by: (a) increasing hydrophobicity of the molecule, and (b) different
packing density induced by steric hindrance of the alkyl chains combined with an increased total
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volume of the hydrophobic tail. However, the amide group appeared to attenuate the reduced
aggregation tendency via hydrogen bonding or by lowering repulsive forces between the
surfactant molecules. Similar structure-activity relationships of hyperbranched structures were
confirmed by Magnusson and Kelland with a group of amine oxide containing molecular
structures, which were described as crystal growth or clathrate inhibitors [51].
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4.3. Siloxane-based Surfactants

The most important surfactants of this group consist of branched copolymers with a
siloxane backbone and linear polyether side chains or pendants. They are known for their low
surface tension and unique flexibility of the siloxane backbone. The siloxane backbone may
contain either Si-O-X or Si-C linkages, produced by reacting siloxane end groups with
polyethers or alcohols [52]. The low surface tension of polysiloxane-polyether copolymer of
about 20 mN/m or even less is related to both the length and structure (linear or branched) of the
polysiloxane backbone chain, and not so much dependent on the chain length of the polyether

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segments[52]. Historically, siloxane-based surfactants were primarily used as foam destabilizers

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or antifoam agents. In combination with certain molecular structures, they also find applications
as foam stabilizers, i.e., polysiloxane-polyether block co-polymers for production of

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polyurethane foams. New research activities have discovered their favorable properties and
potential use as demulsifiers. Forny-le Follotec et al., studied a relatively small polysiloxane-
based tri-block co-polymer, PEO 12 -PDMS13 -PEO 12, which is structurally related to the pluronic

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tri-block co-polymer L64, or PEO 13 -PPO 36-PEO 13 [53]. A combination of SANS, small angle x-
ray scattering (SAXS), and dynamic light scattering (DLS) techniques confirmed the siloxane
backbone flexibility, which allows to adopt the energetically most favorable configuration or
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curvature.
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Figure 9: Proposed mechanism of hole creation and water droplet coalescence

(copied from [53]).

The authors observed small size micelles and aggregation behavior comparable to linear alkyl
ethoxylates, with a hydrophobic core and the hydrophilic segments interfacing with the aqueous
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phase; the positive surfactant curvature fits the oil/water interfacial configuration. This
thermodynamically favorable configuration lowers the energy barrier between droplets,
promoting hole nucleation in the oil film and coalescence of water droplets, as discussed in
section 3.3. (figure 9).

A study by Daniel-David and co-workers correlated changes in the interfacial elastic

modulus with the demulsifier efficiency of two tri-block copolymers with a siloxane center
segment and outer EO segments, and a third tri-block copolymer with hydrophobic PPO outer

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segments (structures shown in figure 10) [54].

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Figure 10: General structures of siloxane-based triblock co-polymers with (a) EO and (b)PPO
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outer segments (copied from [54]).

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The presence of the siloxane-based tri-block copolymer destabilized the asphaltene interfacial
layer with varying efficiency. The tri-block copolymers containing outer hydrophilic EO
segments were soluble in either oil or water or both. The EO pendants penetrate the interfacial
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layer created by native surface active molecules, i.e., asphaltenes, followed by displacement of
these native substances. In contrast, demulsification performance was poor when tri-block
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copolymers with outer hydrophobic PPO segments were used, in analogy to the structure-activity
relationship found with pluronic surfactants.
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Noïk and Dalmazzone observed synergistic effects with binary blends of either siloxane
based surfactants with different polarity indices or a mixture of a siloxane surfactant with organic
surfactants [55]. In general, low molecular weight siloxane-based surfactants and intermediate
solubility of the blends appeared superior to the remaining siloxane-based surfactants in the
demulsification test sequence. This good performance vs. solubility index may be related to the
surfactants’ ability to partition equally between water and oil phase thus favorably affecting the
water-oil interfacial properties. Total surfactant concentration at optimum performance was as
low as 50 ppm. The sudden increase in the E modulus, although not specifically pointed out in
the research article, reveals some of the constraints that are encountered with polysiloxane
surfactants: their limited water solubility paired with a delicate water-oil partitioning balance.
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This complexity in phase behavior of siloxane-based surfactants was demonstrated further by R.

Gee from the Dow Corning research group, when incorporating aminosilicones into
microemulsions [56]. Various nonionic surfactants and an aminosilicone fluid containing a
structure of (CH3)3 SiO [(CH3)2 SiO]x [CH3 (NH2 RNHR') SiO]y Si (CH)3 , amino content of 0.8
wt%, and an average MW of 7,500 (Q-8075), were mixed with the conventional nonionic
surfactants Tergitol® TMN6 and TMN10 (trimethylnonyl ether with 6 and 10 ethylene oxide
units). The particle size strongly depended on the rate of mixing, with large regions of gel-like
structures identified in the phase diagrams. Ultra-low interfacial tension, although not the

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primary factor in demulsification, were measured at silicone-oil-water interfaces only within a
narrow surfactant concentration range.

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In different emulsion formulation studies, aminosilicone, methylated aminosilicone,

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acid modified silicone, and polydimethylsiloxane gave stable emulsions at high shear stirring
conditions [57]. Undesired phase behavior due to the high shear conditions as observed in Gee’s
study did not occur [56]. However, different experimental conditions, phases and co-surfactants

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were used, which do not allow for a direct correlation. The dominating mechanism of emulsion
formation was not the expected Pickering type aggregation, but the formation of interfacial
layers, stabilized by conformational changes and interaction of the hydrophilic portions of the
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surfactant molecules with the aqueous phase. The silicone-modified surfactants rearranged at the
interface due to surface area constraints and enhanced interaction of the more hydrophilic
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functionalities with the water sub-phase.

Polysiloxanes, in general, are complex molecular structures. Their phase behavior may
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deviate from predicted behavior due to small variations in co-surfactants, co-solvents, and
mechanical treatment.
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4.4. Novel and Unconventional Surfactants:

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4.4.1. Ionic Liquid Derivatives as Surfactants and Demulsifiers:

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Ionic liquid-based surfactants have emerged as potential candidates for

demulsification processes [58]. These types of surfactants are found as the salt of cationic
species with halide anions as the counterion, or more complex inorganic salts, and even
combinations of organic-inorganic anionic species (figure 11). Ionic liquids have low vapor
pressures and high thermal stability. They have primarily been used as so-called “green”
solvents, as catalyst supports in industrial catalytic processes, and also in synthesis [58]. Ionic
liquids adopt surface active properties by extension of the hydrophobic alkyl substituents at the
ammonium or hetero-atom ring of a pyridinium or imidazolium. Ionic liquids with small sized
ammonium (polar and highly hydrophilic quaternary amine) cations, along with the optimum
alkyl chain length of eight carbons gave some promising results with extra heavy crude oil;
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however, complete water-oil separation could only be achieved by adding heat energy via a
microwave step [59].

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Figure 11: Structures of some representative cationic and anionic species in ionic liquids;
(copied from [58])
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Silva and co-workers substituted the simple halide anion by bulkier trifluoromethylsulfonate
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derived anions (figure 12) , and also enhanced the demulsification performance by applying
microwave techniques; addition of the microwave step indicates that a high energy input is
required in order to increase the intrinsically slow separation kinetics [60].
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In contrast to ionic liquids, surfactants contain polar and non-polar moieties within one
molecule. Partitioning between oil and water at the interface is controlled by the surfactant
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structural configuration. Ionic liquids, however, are cation-anion salts, bound by strong
electrostatic forces. The charge itself does not necessarily coincide with its hydrophilicity or
polar properties. Imidazolium in the cation – anion pair imidazolium and trifluoromethyl
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sulfonylimide, i.e., possesses polar character; the negatively charged trifluoromethyl

sulfonylimide contains polar and non-polar functionalities which may enable partitioning
between aqueous and hydrocarbon phase, but with the additional constraint of the cation
proximity. Similar constraints have been reported in cmc studies, where unambiguous
identification of a cmc was either complicated or occurred only with long alkyl chain containing
cationic portions with simple halide anions [61]. Dong et al. found cmc values in the range of
1mM to 0.1 or less for these ionic liquids with high surface tension values of 40 mNm-1 and
relatively low adsorption kinetics.
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Figure 12: Structures of cations and anions in ILs studied as demulsifiers including the
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commonly used abbreviations (copied from [61]).

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5. Novel Analytical Techniques Used in Demulsification Monitoring

5.1. NMR Spectroscopic Techniques
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By applying a magnetic field to a sample - along with orthogonal radio frequency

pulses of controlled intensity, duration and intermittence - one is able to investigate the
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magnetization of nuclei which exhibit a permanent magnetic moment, such as protons ( 1 H).
These principles have been exploited by a number of different techniques which vary the
sequence of the magnetic field and radio frequency pulse. Two of these techniques, CPMG
(Carr, Purcell, Meiboom and Gill) and PGSE (Pulsed Gradient Spin Echo), allow one to size
droplets in emulsions, given a number of conditions are met. Peña et al. discuss these Low
Resolution Time Domain NMR (TD NMR) techniques in more details, along with a proposed
method of using both techniques together. The combination of both allows to overcome inherent
limitations in the individual techniques for determination of non-lognormal droplet size
distributions [62].
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TD NMR is frequently used as a supporting technique along with the conventional

demulsification tests, i.e., bottle tests. Some of the benefits of using this technique to analyze the
droplet size distribution of water in crude oil emulsions include: samples do not require dilution
or intensive preparation; samples are not damaged during the measurement; it is faster than other
techniques, i.e., light microscopy, and it allows to study opaque samples. As mentioned above,
certain TD NMR techniques have restrictions in terms of the types of droplet size distributions
which can be measured, as well as the range of drop sizes which can be resolved. Peña et al.
went on to use TD NMR alongside shake bottle tests, shear viscosity and IFT, to compare the

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performance of phenolic resins versus polyurethanes [63]. This technique allowed them to
confirm that tests performed with polyurethanes resulted in water droplets flocculating at the

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bottom of the sample which they were not able to discern visually due to the opacity of the
sample. This in turn allowed them to propose a mechanism for demulsification and confirm the

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synergistic effect of combining polyurethanes and phenolic resins to treat the emulsion.

More detailed description of the principles, application areas, and limitations can be

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found in their review paper, which both provides information on the theory, and also
experimental supporting results in connection with crude oils and demulsifier agents[62]. The
preferred NMR method for demulsification assessment and monitoring is referred to as “Pulsed
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gradient spin echo”, where a magnetic field gradient is applied to the diffusing protons. Using
theoretical principles and certain algorithms allow to correlate the diffusivity in the magnetic
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field gradient to the droplet size of either oil or water. The spin relaxation with and without
magnetic field gradient is measured, and their ratio is correlated with diffusivity and ultimately
with the average droplet size of either water droplets in oil or oil droplets in water. The technique
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has found its applicability in W/O or O/W emulsions with relatively narrow droplet size
distribution.
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5.2. Near Infrared Spectroscopic Technique

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Spectroscopic techniques as monitoring methods for emulsion destabilization

mechanisms include the utilization of NIR for qualitative and quantitative analysis of asphaltenic
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compounds [64]. Characteristic vibrational frequencies are correlated to emulsion stabilizing

tendencies as function of asphaltene content and aggregation, providing additional insight into
actual mechanisms of demulsification, and the critical components of the demulsification
process. Specially designed NIR pressure cells were used for testing the dispersing capabilities of
various commonly known dispersants, i.e., alkylbenzenesulfonic acid, naphthenic acids, fatty
alcohols and fatty amines, and a proprietary inhibitor. In one particular case, the NIR technique
allowed to study efficient emulsion formation inhibitors, which was hexylamine. The work
further demonstrated that certain types of acidic compounds, i.e. dodecylbenzylsulfonic acid,
which is the conjugate base of dodecylbenzyl sulfonate, formed large aggregates with asphaltene
compounds.
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5.3. Alternative Analytical Techniques

Optical techniques, based on light scattering phenomena, have been developed to study
the efficiency of oil-water phase separation. One of these methods, frequently referred to as
“Turbiscan”, monitors the change in turbidity as function of droplet density and size, and droplet
coalescence during the separation of an O/W or W/O emulsion. It has found interest as an optical
method relying on multiple scattering of incident photons emitted by a NIR light source. The
signal intensities of both transmitted and back scattered light are proportional to the droplet

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density, and droplet shape and motion. The signals may be acquired at a local spot or over the
entire sample height. Correlations and ratios of the transmitted and backscattered signal

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intensities allow qualitative monitoring of the demulsification process, study the oil-water
separation kinetics, and define an emulsion stability index [65-67].

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5.4. Newly Emerging Oil-Water Separation Techniques

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Magnetic nanoparticles, designed and studied at the University of Texas at Austin in
collaboration with Maersk Oil R&I, showed promising results for separating residual oil droplets
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from produced water, using an externally applied magnetic field [68]. These nanoparticles attach
to the oil droplets (assumed to bear a negative charge) which can be separated from the produced
water, with subsequent recovery and potential reuse of the magnetic nanoparticles (MNPs). The
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negative charge applies specifically to the acidic components found in crude oil as resins,
asphaltenes and naphthenic acids. The particles are superparamagnetic, with average diameter of
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10nm. Separation times were reported to be as low as one minute with separation efficiencies of
99.9% oil free produced water.
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Future Outlook:
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A large number of conventional and novel surface active agents present opportunities
for designing the most effective demulsifier system. Besides cost vs. efficiency, their
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environmental footprint may need consideration. Numerous countries, i.e., Canada and the
European Union have imposed restricted use or even a complete ban on certain groups of
surfactants, i.e., ethoxylated alkylphenols. Legislative regulations of surfactant usage vary from
one country to another, depending on toxicity and health hazards, but in general are becoming
increasingly tougher and more complex. A survey of chemicals as employed in hydraulic
fracturing and EOR has been compiled by Elsner and Hoelzer [69], providing some general
insight on the classification criteria related to the most common chemical groups, field
applications, and related restrictions.
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Conclusions:

This review gives a concise description of important properties and requirements for
surfactants used as demulsifiers. These, one properties may be summarized as follows: the HLB
or hydrophilic vs. hydrophobic properties should match the crude oil; HLB’s can be adjusted by
choosing a combination of surfactant and co-surfactant, or by adjusting the ethylene oxide unit
numbers, or the alkyl chain length on the surfactant molecule. The demulsifier should partition
both in oil and water, and possess slightly hydrophilic character to counterbalance the more
hydrophobic nature of the crude oil components. It should have low to moderate molecular

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weight with fast adsorption kinetics to competitively adsorb at the oil-water interface and

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displace or weaken the rigid films/networks formed by naturally present surfactants, i.e.,
asphaltenes. A large interfacial area per molecule is desirable for optimum efficiency and low

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dosing requirements. Choosing a demulsifier system with HLD properties that match the crude
oil (EACN) and gives zero net curvature is crucial for optimum performance. In addition, an
analysis of the molecular structure and major functional groups before formulating a

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demulsification system, including a detailed crude oil analysis and practical tests, will help to
identify suitable demulsifiers for a given crude oil.
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Acknowledgements
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Andrei Zelenev and Keith Dismuke are gratefully acknowledged for their feedback and
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suggestions during the preparation of the manuscript. We also thank Trudy Boudreaux and
Danielle Rosenberg for final review of the document.
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Highlights of the manuscript entitled “Mechanisms, Performance Optimization and New Developments in
Demulsification Processes for Oil and Gas Applications”:

 A concise description of demulsifier mechanisms, basic and improved demulsification

models.
 Thermodynamic aspects of demulsification efficiency.
 The different demulsifier chemical classes and their optimum utilization.
 The effects of surfactant hydrophilic-hydrophobic ratio on demulsification efficiency and rate
kinetics.


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Novel demulsification techniques as alternatives to the conventional emulsion bottle test.

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