SPE Annual Technical

Conference & Exhibition

October 8-10, 2012
70.0
Emulsion Viscosity

Viscosity,cP
60.0
50.0
40.0
30.0
20.0
10.0
0.0
0 10 20 30 40 50 60 70 80 90 100

Water cut ( % v/v )

Oil-Water
Properties,
Emulsions and
Chemicals
Oil & Water Properties

OIL: WATER:

Viscosity
Viscosity

Density
Density (salinity)

Conductivity
pH

TAN

Oxygen

IFT EMULSION:

Viscosity
Zeta Potential
WAT

Density
Solids

Solids
GOR
Acronyms
TAN Total Acid Number, mg KOH/g
GOR Gas to Oil Ratio, vol/vol
Typically, scf/bbl.
WAT Wax Appearance Temperature
Typically, Cloud Point WAT = 9oF.
BS&W Basic Sediment & Water
% by volume of oil/water mixture.
IFT Interfacial Tension, dyne/cm
Oil Gravity
Light Oils - associated with high salinity water
usually large density differential
rapid water separation rate
low viscosity
Heavy Oils - associated with low salinity water
small density differential
hindered water separation rate
high viscosity
Oil Viscosity vs.
Temperature
~15 API Crude Oils

Typical

x3

/3
Emulsion Viscosity
Inversion Point

Oil continuous below the inversion point.

Water continuous above the inversion point.

Ranges from 20% to 70%, lowest in heavy oils.

Emulsion Viscosity
70.0

60.0
Viscosity,cP

50.0

40.0

30.0

20.0
Inversion Point
10.0

0.0
0 10 20 30 40 50 60 70 80 90 100

Water cut ( % v/v )

Interfacial Tension

Numerous Dependencies
 Temperature > Water-Soluble Organics
 Fine Solids > Chemical Additives
 Water pH > Hydrocarbon Composition

Ranges from 15 to 45 dynes/cm

Average ~ 24 - 28 dynes/cm
 Reduced by demulsifiers
 Reduced by DC electrostatic forces
Oil Conductivity
 Emulsion Stability is not dependent on
Oil Conductivity

 Critical Parameter for power unit sizing

on dehydrators and desalters

 Modest Oil Conductivity may promote

droplet charge and coalescence

 High Oil Conductivity may limit

electrostatic field strength
Conductivity vs. Temperature
1800
1600
Conductivity, nS/m

1400 Typical
1200 High
1000
800
600
400
200
0
50 100 150 200 250 300
Temperature, F
Emulsion Types

Mechanically formed emulsion
Formed by high shear devices, pumps, valves, etc.
Easily reversed by electrostatics

Surfactant formed emulsion
Formed by the presences of in-situ chemicals
Requires an effective chemical program to reverse
Benefits obtained by synergy with electrostatic field

Solids formed emulsion
Created by the in-situ solids very stable emulsion
May be handled by use of chemicals and electrostatic
Water-in
Water-in--Oil Emulsion
Typical
Oil--in
Oil in--Water Emulsion
Typical
Complex Emulsions
16 API SAGD DilBit

H2O in Oil in H2O

vs.

H2O in Oil

vs.

Oil in H2O
Emulsion Breaking

Heat

Removal / dilution of emulsifiers

Forced coalescence

Electrostatic fields

Chemicals

Centrifugal forces
Water pH
Low Water pH: Aids Water Quality
<6 Neutralizes Surfactants
Destabilizes Emulsion

High Water pH: Activates Surfactants

> 7.5 Weakens Asphaltene Films
Stabilizes Emulsions
Salinity
High Water Salinity: High Oil API Gravity
High Density Differential
Rapid Water
separation
Possible Salt Crystals

Low Water Salinity: Low Oil API Gravity

Low Density Differential
Slow Water Separation
Poor Water Quality
Total Suspended Solids

Production Sands

Water Scales, Contaminants

Corrosion Products

Bacteria

Iron Oxides and Sulfates

Asphaltenes

Paraffins
Chemicals

Demulsifiers

Clarifiers

Biocides

Scale inhibitors

Corrosion inhibitors

Wax inhibitors

Asphaltene stabilizers

Organic acids

Etc.
Process Synergies
Chemicals Electrostatic Fields Hydraulics

Coagulation
Requires Chemical Reaction

Flocculation
Assisted by Electrostatic Forces

Sedimentation
Depends Upon Vessel Flow Regime,
Drop/floc Size & Viscosity
Types of Chemicals
Employed

Demulsifiers
Provide Film Destabilization of Water Drops
in Oil (Coagulation)

Wetting Agents
Aid in Separation of Solids from Oil

Reverse Emulsion Breakers
Aid in Separation of Oil Drops from Water

Specialty Chemicals
Paraffin Inhibitors, Asphaltene Solvents, Etc.
Chemical Demulsifiers/Clarifiers
Demulsifiers/Clarifiers

Accumulate at the droplet interface

Enhance coalescence

Reduce oil/water interfacial tension

Improve gravity separation

May interfere with electrostatic coalescence

Selection Methods for
Demulsifiers

Bottle Tests Most Common Method
Measure Sedimentation Rate
Estimate Resultant Oil Quality
Vary Chemical Type and Dosage

Electrostatic Bench Tests
Measure Response of Emulsion to
Electrostatic Field
Measure Resultant Oil Quality
Vary Chemical Type & Dosage and
Electrostatic Field Type
Partnership for Drop Growth

Chemicals Remove the Barriers

Electrostatics Provide the

Muscle

Hydraulics Provide the

Environment
Comparative Results
19.5API Brazilian Crude
Chemical Bottle Test Electrostatic
Bench Test
Best Water in Oil BS&W
Performanc % By Difference Measured %
e
A 2.2 2.12
B 4.6 2.01
C 5.3 1.62
D 5.7 1.20
E 6 2.35
Chemical Treatment
Droplet size: Volume vs.
Surface

Volume and buoyancy grow with D3

Surface and drag grow with D2

Conclusions

Accurate physical properties improve vessel
sizing and performance prediction.

Emulsion resolution is critical to achieving

maximum separation performance.

Chemical selection must be conducted in an

appropriate separation environment gravity
versus electrostatic.

Specialty chemicals may be required for solids,

Asphaltenes, and reverse emulsions.