Demulsifier Technology
March 24, 2004
Unocal
Curtis Conkle
Baker Petrolite
Baker Petrolite
Demulsification Techniques
Baker Petrolite
Mechanisms For Destabilizing Emulsions
Gravity or Settling Time.
Heat Energy
Electrostatic Energy
Chemical Demulsifiers
© 1999 Baker Petrolite
All rights reserved.
Demulsification Technology
Baker Petrolite
Chemical Demulsifiers - act to deactivate the emulsifying
agents; the surface active nature of the chemicals allows
them to move to the interface where they can act upon the
emulsifiers and promote “drainage".
© 1999 Baker Petrolite
All rights reserved.
Demulsifier Technology
Baker Petrolite
Steps in the demulsification process when using a chemical
demulsifier
Addition of proper demulsifier at proper dosage in the oil
phase of the emulsion.
Sufficient agitation in produced fluid to allow demulsifer to
migrate to the oil / water interface.
The demulsifier displaces the emulsifier at the interface
The barrier at the interface is disrupted promoting water droplet
collision
Sufficient quiet time to promote coalescence of the enlarged
water droplets resulting in settling of the bulk water phase
© 1999 Baker Petrolite
All rights reserved.
Demulsifier Chemistry
Baker Petrolite
Demulsifier schematic
[Backbone] - [Backbone]n - [Backbone]
(EtO) (EtO) (EtO)
nand/or
nand/or nand/or (EtO)
(PrO) (PrO) nand/or
(PrO)
n n (PrO) n
Each contains an oil soluble and water soluble portion,
making them surfactants similar to emulsifiers.
© 1999 Baker Petrolite
All rights reserved.
Baker Petrolite
Chemical Nature of
Emulsion Breakers
O H
HO O
n m
© 1999 Baker Petrolite
All rights reserved.
Baker Petrolite
Emulsion breakers tend to be polymeric
polyethers
Higher MW = better performance
© 1999 Baker Petrolite
All rights reserved.
Demulsifier Chemistry
Baker Petrolite
Chemical Types Typical Characteristics
Polyol Block Polymers Coalescence & Interface Control
High MW Crosslinked Polyols Polishing Top Oil
High MW Crosslinked Esters Polishing Top Oil
Amine Polyols Water Drop & Wetting Agents
Phenolic Resins Water Drop, Polishers, Very Versatile
Sulfonates and Sulfates Interface Control & BS Resolution
© 1999 Baker Petrolite
All rights reserved.
Polyol Block Polymers
Baker Petrolite
Polymers can be built by reacting alkylene oxides (like propylene
oxide) with alcohols:
CH3
O
ROH + CH3 CH CH2 RO CH2 CH OH
, Base Cat.
More PO
CH3
RO CH2 CH O H
x
© 1999 Baker Petrolite
All rights reserved.
Polyol Block Polymers
Baker Petrolite
A “Block Polyol” can be built by reacting ethylene oxide with the
propylene oxide polyol:
CH3 O
RO CH2 CH O H + H2C CH2
x
CH3
RO CH2 CH O CH2 CH2 O H
x y
© 1999 Baker Petrolite
All rights reserved.
Polyol Block Polymers
Baker Petrolite
Oxide reactions slow as the reactive OH groups become diluted in bulk
polymer. At ~ 2000 MW per OH equivalent, PO rearrangements become
significant because they generate fresh OH groups (contamination):
O OH OH
C H3 C H CH 2 C H2 C C H 2 + CH 2 C H C H 2
, Base Cat.
© 1999 Baker Petrolite
All rights reserved.
High MW Crosslinked Polyols
Baker Petrolite
To overcome MW limitations on simple polyols,
crosslinking is used to link polymer strands together:
• Diepoxides
• Dicarboxylic acids (Esters)
© 1999 Baker Petrolite
All rights reserved.
High MW Crosslinked Polyols
Baker Petrolite
Diepoxides have two epoxy groups which react with polyols to link
them together
O O
H2C CH CH2 O R O CH2 CH CH2
Polyol
Pol
y
ol
Good top oil polisher
© 1999 Baker Petrolite
All rights reserved.
High MW Crosslinked Polyols
Baker Petrolite
Dicarboxylic acids can also react with polyols to link them
together (polyesters)
O O
OH OH Polyol
ol y ol
P Adipic Acid
Good top oil polisher
© 1999 Baker Petrolite
All rights reserved.
Amine Polyols
Baker Petrolite
Similar to regular polyols, except that the amine center can carry a
charge and imparts different behavior to the polymer
CH3 R CH3
H O CH CH2 N CH2 CH O H
x x
Good for solids wetting
Interface Control
© 1999 Baker Petrolite
All rights reserved.
Phenolic Resins
Baker Petrolite
A “Phenolic Resin” can be built by reacting alkylphenols with
formaldehyde:
OH H2O OH OH
O
OH - + +
R R R n
© 1999 Baker Petrolite
All rights reserved.
Phenolic Resins
Baker Petrolite
Phenolic resins can be reacted with oxide to make a finished
demulsifying polymer:
R'
O H R = C4-12
O x
H R’ = H or CH3
H
y = 4-15
R y
Good water drop
© 1999 Baker Petrolite
All rights reserved.
Sulfonates Baker Petrolite
Sulfonates are usually smaller molecules
SO3H SO3H
R CH2SO3H
C12H23
Usually neutralized to avoid corrosion
Primarily used in slop oil treatment
Adversely affect water quality
© 1999 Baker Petrolite
All rights reserved.
Demulsifier Selection
Baker Petrolite
Chemical Considerations
Solubility in the oil
Solubility (dispersability) in the water
Overtreat Tendency
Compatibility with other chemicals
Bottle Test Design
Needs to model the system
Samples must be representative of the fluids to be treated
Relative Test
Do everything the same way
© 1999 Baker Petrolite
All rights reserved.
Demulsifier Selection
Baker Petrolite
Modeling System
System Diagram (type of treating system)
Temperatures and pressures of vessels
Production Rates (oil/gas/water)
Residence times of all vessels
Chemical injection points
Export/Shipping Specifications
Any limitations on Chemical (Flash point, Pour Point)
All chemicals used upstream of test
© 1999 Baker Petrolite
All rights reserved.
Demulsifier Selection
Baker Petrolite
Samples
Extreme care follow all safety protocols
Samples must be representative of fluids to be treated
All wells if possible, (especially high GOR)
Choose sample point at turbulent flow (if possible)
Open sample valve fully to minimize shear
Sample should be taken in a clean, sealed container
Beware of aging
© 1999 Baker Petrolite
All rights reserved.
Demulsifier Selection
Baker Petrolite
Relative Test
Always run a standard
Always run a blank
Keep the number of bottles at reasonable level
If a chemical fails in the system it should fail in the bottle.
Repeat the tests
Determine minimum and maximum treating levels
Vary other treating parameters (heat, settling time, agitation)
to determine impact on chemical treating.
© 1999 Baker Petrolite
All rights reserved.
Demulsifier Selection
Baker Petrolite
Critical Performance Characteristics
Water Drop Speed
Top Oil Dryness
Good Mixed Grind
Interface Sharpness
Water Clarity
Temperature/ Agitation
Solids Wetting
Treating Rate/Range
© 1999 Baker Petrolite
All rights reserved.
Demulsifier Application
Baker Petrolite
Improving Chemical Performance
Minimize shear before chemical injection.
Inject chemicals further out into the system
Temperature should be above the pour point of the crude
Vessel Fluid Levels
Inject chemical into the emulsion.
Dilute product vs Concentrated product
© 1999 Baker Petrolite
All rights reserved.
Demulsifier Application
Baker Petrolite
Trouble Shooting Treatment Problems
System Changes
Vessel Levels
Well Shut-Ins
New Well Start-ups
Vessel Temperatures
Acid flowbacks
Recycling of Fluids
Chemical Pump Failures
Chemical Interaction(s)
© 1999 Baker Petrolite
All rights reserved.
Why Chemicals Fail
Baker Petrolite
System
New production
System surges
Changes in configuration/operating parameters
Chemical
Gradual accumulation of BS pad at interface
Accumulation of solids at interface
Chemical contamination
Chemical change in the product over time (shelf life)
© 1999 Baker Petrolite
All rights reserved.
Summary
Baker Petrolite
Most demulsifiers are polymers
Polyether structures make them surface active
Inert, oil soluble.
Synergistic blends of different polymers give the best
performance. (3-4 intermediates)
Bottle tests must model system behavior
Injection location is important
Most systems have multiple parameters which can greatly
affect demulsifier performance.
© 1999 Baker Petrolite
All rights reserved.
Baker Petrolite
Baker Petrolite Corporation
Worldwide Headquarters
12645 West Airport Blvd.
Sugar Land, TX 77478
Toll Free: 1-800-231-3606
Fax: 281-275-7395
Internet: www.bakerhughes.com/bakerpetrolite
Disclaimer of Liability: The information included in this document is based on data which is considered to be accurate. Baker
Petrolite Corporation (BPC) make no warrantees or guarantees, either expressed or implied of the accuracy or completeness of
the information. Further, Baker Petrolite assumes no responsibility to update this information.
© 1999 Baker Petrolite
All rights reserved.
