Chapter 2

Crude Oil Emulsions:

Everything You Wanted to Know
But Were Afraid to Ask
 Outline

 Emulsions
 What are emulsions?
 Types of emulsions
 Where do they form?
 Stability of emulsions
 Challenges during oil production
 Reservoir and production aspects of emulsions
 Demulsification: oil-water separation
 Emulsion treatment programs
 Recommendations
Some Examples of Emulsions
 Definitions

● Emulsion: An emulsion is a colloidal dispersion of

one liquid (disperse phase) in another (continuous
phase)
● Types of Emulsion:
 Water-in-oil
 Oil-in-water
 Complex/multiple emulsions
● Macroemulsions, size > 0.1 µm
● Microemulsions, size < 0.1 µm
Oil-field emulsions are water-in-oil macroemulsions
Emulsion
• A system containing 2 immiscible liquid phase that one of them
dispersed as droplets on the other

Classification of emulsions

W/O/W
Chemical Demulsification O/W W/O

• The addition of small amount of breaking agent to enhance the

phase separation
Emulsion Photomircrographs
Where do they form?
 Emulsion Stability
 Emulsions are inherently unstable
 Classified based on their kinetic stability
 Loose: few minutes
 medium: tens of minutes
 tight: hours, days
 Presence of emulsifying agents
 Films act as physical barriers to
coalescence
 Factors affecting emulsion stability
 W/O vs. O/W Emulsions
• Bancroft’s rule
• Emulsion type depends more on the nature of
the emulsifying agent than the relative
proportions of oil or water present or the
methodology of preparing emulsion.
• The phase in which an emulsifier is more
soluble constitutes the continuous phase.
• In O/W emulsions- emulsifying agents are
more soluble in water than in oil (High HLB)
• In W/O emulsions-emulsifying agents are more
soluble in oil than in water (Low HLB)
Hydrophilic-Lipophilic Balance (HLB)
• The balance of size and strength of
hydrophilic and lipophilic group of lipophilic hydrophilic

surfactant
• HLB characteristic
HLB <9.0 - lipophilic
HLB 9 to 11 - intermediate
HLB >11 - hydrophilic
An example of a very tight emulsion
Physical Structures of three-phase emulsions: a) Oil-in-
water-in-oil emulsion b) Water-in-oil-in-water emulsion
 Tests for Emulsion Type (W/O or O/W
emulsions)

• Based on the Bancroft’s rule, many

emulsion properties are governed by the
properties of the continuous phase
1. Dye test
2. Dilution test
3. Electrical conductivity measurements
4. Refractive index measurement
5. Filter paper test
 Phase Inversion in Emulsions
• Based on the Bancroft’s rule, it is possible to
change an emulsion from O/W type to W/O type by
inducing changes in surfactant HLB
• O/W W/O
1. W O +emulsifier W/O
2. O W + emulsifier O/W
3. Nature of emulsifier; making the emulsion more oil
soluble tends to produce a W/O emulsion and vice
versa.
4. Phase volume ration; oil/water ratio (high) W/O
emulsion and vice versa.
5. Temperature of the system
 Factors affecting stability

 Heavy polar material in crude oil

 Fine solids including organics
(asphaltenes, resins, waxes) and
inorganics (clay, scales, corrosion
products)
 Temperature
 Droplet size and droplets size
distribution
 pH of the brine
 SARA

Interfacial
Viscosity pH
Factors
influence
Emulsions
Droplet
Stability
Temperature
Size

Interfacial
Tension
Photo-micrograph of an emulsion showing
interfacial films
 Measurement of stability

 Determines the ease of separation

 Most common is the bottle test
 Used for
 water separation over time
 water separation with demulsifier
dosage
Screening demulsifiers
 Standard ASTM method for BS&W
Emulsion Challenges During Oil
Production
 Negatives:
 Water and salt in sellable crude
 Oil in disposal water… injectivity concerns
 Flow assurance concerns
 Productivity decline in wells
 Higher emulsifier
 Equipment trip and upsets
 Higher oil production costs
 Positives:
 None!!
Reservoir Aspects of Emulsions
 During drilling operations
 Acidization of wells
 Well treatments
 EOR/IOR operations
 Drilling Operations
 Drilling mud can form tight
emulsions
 May cause formation damage
 Incorrect estimation of reserves
 Most likely to form in reservoirs
with
 Lower API (< 25o)
 Lower Temperatures (< 150 oF)
 Poorer rock quality (low porosities
and permeabilities)
 Higher amount of asphaltenes
Methods of Destabilizing Emulsions

 Chemical Method
 Electrical Method
 Heating Method (Conventional or
Microwave Heating
 Mechanical Method
Schematic representation of the break-down process in
emulsions.
Emulsion Demulsification Methods

g D (  w  o )
2
vm 
18 o

qMW
hA
 Tm  Ta  
V
A
V
   dT 
Tm  273.15  Ta  273.15  C p  
4 4

 dt 