Summary of Crude Oil Emulsion

Elan Patria Nusadi 201030119190081

Introduction

A disperse system is made of a dispersed phase in a continuous flow. There are three major
types of dispersions based on the physics of dispersed phase, namely the following: foams of
a gas in a liquid mixture; suspensions of a solid in a liquid blend; and emulsion of a liquid in
a liquid system.

Emulsion can be defined as a system, whereby one immiscible liquid phase is dispersed as
globules (dispersed phase) in the second phase of immiscible liquid (continuous phase).
There are three types of emulsions: they are, water-in-oil (W/O) emulsion, oil-in-water (O/W)
emulsion and multiple emulsion. O/W emulsion is formed when the oil globules are dispersed
throughout the water continuous phase.

Emulsification is the process of formation of emulsions. In the oil and gas industries,
emulsification problem faced by the industries are mostly due to W/O emulsions. W/O
emulsion is also known as “chocolate mousse” or “mousse” among oil spill workers

Description of oil emulsion

Crude oil is a blend of hydrocarbons with different sizes that can have various applications in
the chemical and energy industries. The type and composition of crude oils (as vital factors)
play important roles in the development of emulsions. Water-in crude oil emulsions are stable
dispersions of water droplets in a continuous flow of oil, stabilized by heavy
particles/components (naturally occurring emulsifiers) present in the oil. Due to
emulsification, the properties and characteristics of oil spills will alter to a significant extend,
especially in the volume of spilled materials, density and viscosity of oil

oil emulsions, one of the liquid phases is crude oil and the other liquid is an aqueous phase or
water. The percentage of water, which emulsifies the crude oil, broadly differs, so it can be
greater than 70 % or less than 2 %, in a few cases. oil-in-water emulsion is an effective
mixture in sealing unconsolidated samples for long periods of time.
Classification of oil emulsion

Water-in-oil mixtures can be divided or grouped into four classes: they are, stable water-in-
oil emulsions, mesostable water in-oil emulsions, entrained water, and unstable water-in-oil
emulsions, states of water-in-oil can be classified into four classes by studying the stability,
the appearance as well as the rheological measurements of different water-in-oil samples.

the stable water-in-oil emulsions are the emulsions that remain unbroken for more than a
week in the laboratory and those emulsions remain intact for at least four week. Emulsions
remain unbroken means that the emulsions do not break or separate into water and free oil.
Stable emulsions appear as brown or reddish semi-solid materials.

Characteristic of crude oil emulsion

three criteria for crude oil emulsion to form:

i. The contact of two immiscible liquids, such as oil and water

ii. The presence of surface active component as emulsifying agent, which is usually
contributed by asphaltenes and resins
iii. Availability of sufficient turbulence or mixing energy to disperse one liquid into
another, so that there will be liquid droplets in a continuous liquid phase.

Fig. Modified crude oil process flow diagram

Researchers in the 1970s concluded that the primary reason leading to the emulsion
formation was the increase in turbulence or mixing energy. turbulence plays an important
role in the distribution and mixing of the phases in the pipeline flow of water/oil system.
Coalescence, as well as break up of emulsions, is affected by turbulence energy. Turbulence
suppression results in the turbulent flow of emulsions when the emulsions/droplets interact
with the liquid (continuous phase). Turbulence suppression is the occurrence where the local
kinetic energy in single-phase flow becomes larger than that in two-phase flow at the same
averaged liquid flux.

Experimental study on the effects of phase ratios, effects of temperature and effects of
stirring speed to the viscosity and the average droplet diameter of W/O emulsions. Three
types of crude oil obtained from Petronas Refinery Melaka with API gravity of 29.27°,
33.82° and 26.48° respectively were tested in their study. The experimental parameters tested
in the study were phase ratios of 20–80% and 50–50% W/O emulsions, temperature of 25–
90 °C and stirring speed of 500–2000 rpm. viscosity of W/O emulsions increased with the
increased in the phase ratio, decreased in the temperature and increased in the stirring speed.

Properties of the starting oil needed for the formation of a stable emulsion are: viscosity 15–
10,000 mPa s; density 0.85–0.97 g/ml; asphaltene content 3–20%; resin content 5–30%;
asphaltene-to-resin ratio 0.74; and average increase in apparent viscosity, 1100 mPa s at day
of emulsion formed and 1500 mPa s a week later

Emulsions remain unbroken for less than three days in laboratory conditions as the
mesostable water-in-oil emulsions. The mesostable water-in-oil emulsions are separated into
water and free oil in around one to three days of time mesostable emulsion displayed the
properties between stable and unstable emulsion. Mesostable emulsions appeared as black or
brown liquid. On the first day the mesostable emulsions formed, they have an average water
content of about 70% and reduced to around 30% after one week. properties of the starting oil
needed for the formation of a mesostable emulsion are: viscosity 6–23,000 mPa s; density
0.84– 0.98 g/ml; asphaltene content 3–17%; resin content 6–30%; asphaltene-to-resin ratio
0.47; and average increase in apparent viscosity, 45 mPa s at day of emulsion formed and 30
mPa s a week later.

Stability of oil emulsions

From a thermodynamic perspective, an emulsion is an unstable system due to its natural

tendency for a liquid/liquid mixture to minimize its interfacial interactions (and/or interfacial
energies).However, most emulsions demonstrate kinetic stability after a period of time. Oil-
field emulsions are usually categorized based on their degree of kinetic stability. The
interactions between the surface-active agents and water/oil interfaces are primarily
responsible for emulsion stability

The stability of water-in-crude oil emulsion is described as the dispersed water droplets
resistance against coalescence. Coalescence means that diverse particles/droplets unite
together and form a larger droplet. The factors that affect the stability of emulsions are the
total mass percentage of asphaltenes and resins, the total mass percentage of volatile
aromatics components, the elastic modulus (G′) and viscous modulus (G″), and the duration
of time after the emulsions have been formed. increased in the concentration of asphaltenes
caused the emulsions stability to be increased. Meanwhile for resins, they will not stabilize
the emulsions without the presence of asphaltenes. This means that stable emulsions will only
be formed with the presence of both asphaltenes and resins. the adsorption of surface active
molecules such as asphaltenes and resins at the interface has been found to determine the
emulsion stability. with the presence of resins alone, they cannot stabilize the emulsions.

Apart from asphaltenes and volatile aromatic compounds, the storage or elastic modulus (G′)
and loss or viscous modulus (G″) are found to be the factors affecting the stability of
emulsions. Ortega et al., (2010) reported that when the viscous behaviour of the fluid is less
than the elastic behaviour (G″oG′) of the fluid, the emulsions are said to be comparatively
stable, providing that both of the parameters are independent of the frequency in the linear
viscoelasticity region. Linear viscoelasticity region (LVER) is the region where a system
does not breakdown due to applied stress.

The larger the linear viscoelasticity region, the higher is the system's stability. When the
elastic modulus (G′) and viscous modulus (G″) do not change with respect to frequency and
they are within LVR, the system is said to be independent of the frequency in the linear
viscoelasticity region. Elastic modulus is directly affected by natural surfactants of crude oil,
such as asphaltenes, resins and naphthenates. This statement is based on the results done by
Maia Filho et al. (2012) which reported that adsorption of those surfactants on water–oil
(emulsion) interface will lead to intermolecular interactions, which will work against any
strain on the water–oil emulsion interface (Gibbs–Marangoni Effect), and hence increasing
the elastic behaviour of the emulsions. This finding is supported by Derkach (2009) study
which concluded that when shear stress is applied onto the emulsion, the surfactants adsorbed
on the surface of the emulsion will generate a stress gradient, resulting in the elastic
component (G′) in the complex modules (G*) of the emulsion got increased.
In other words, it can be said that increases in elastic behaviour will lead to decreases in
coalescence mechanism among the emulsions, and thereby producing the stable emulsions.
Next factor affecting the stability of emulsion is the period of time after the emulsions have
been formed. Fingas and Fieldhouse (2003) reported that about one week after the emulsions
were formed, the water content was found to be more reliable because emulsions that are less
stable will separate. Fingas and Fieldhouse (2003, 2004) also stated that in indicating the
stability of water-in oil emulsions, water content at formation is not a decisive aspect. This is
because the initial water content is prone to error due to the “excess” water that may exist.

Sources

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classification and stability of water-in-oil emulsions. Journal of Petroleum Science and
Engineering, 135, 498–504. doi:10.1016/j.petrol.2015.10.006 

Goodarzi, F., & Zendehboudi, S. (2018). A Comprehensive Review on Emulsions and

Emulsion Stability in Chemical and Energy Industries. The Canadian Journal of Chemical
Engineering, 97(1), 281–309. doi:10.1002/cjce.23336