Nalco's advanced separations training covers oilfield emulsions including:
- Emulsion theory, types, formation, and stabilization mechanisms
- Bottle testing procedures to evaluate emulsion breaker performance
- Field trial preparation and troubleshooting tips
- Key equipment and materials needed for effective bottle testing
The document provides an in-depth overview of emulsion science and testing methods to resolve oil and water emulsions through chemical treatment optimization.
4. Equipment and
chemical treatment
are necessary to resolve
these emulsions
Sales grade crude
must be dehydrated
• 0.35% to
<1% BS&W
Water and crude can
be produced
as an emulsion
Introduction to Oilfield Emulsions
Water, solids, and gas
are normally
produced together
with the crude
• Retention time
• Heating
• Emulsion breakers
6. Emulsion Theory
An emulsion is a suspension of small droplets of one liquid in a
second liquid with which the first will not mix.
Requirements for emulsion
formation
• Two immiscible liquids
• Agitation
- Pumps
- Turbulent flow
• Surface-active component
- Asphaltenes
- Napthenic acids
- Solids
GOM Crude Oil Emulsion
40x Magnification
7. Emulsion Theory
An emulsion is a suspension of small droplets of one liquid in a
second liquid with which the first will not mix.
Alcohol + Water Emulsion
Milk (Fat + Water) = Emulsion
Oil continuous phase
Dispersed water droplets
8. Types of Emulsions
Regular Emulsion - Water in Oil
• Oil is continuous phase
• Treat using emulsion breakers
• Droplet floats when poured
into water
Reverse Emulsion - Oil in Water
• Water is the continuous phase
• Treat using reverse emulsion
breakers & water clarifiers
• Disperses into water
10. Emulsion Formation : Agitation
• Turbulent flow
• Chokes
• Pressure drops (e.g. gas
evolution)
• Pumps
• Gas bubble point/gas
lift system
• Dump valves
11. Natural Surfactants in Crude Oil
saturates
asphaltenes
aromatics
resins
SARA concentrates
• Napthenic acids
• Calcium napthenates
12. ca. 90 m
Factors Affecting Emulsion Stability
Emulsifying
Agent
Strength of
Interfacial Film
Temperature Droplet Size
Liquid Density
Differences
Solids Content Viscosity of
Continuous Phase
Age
18. Solids Stabilization
Fine solids can help promote and stabilize emulsions
ca. 90 m
Scale (salts)
Sand
Iron sulfide (corrosion)
Clays
Paraffin particles
19. Emulsion Stabilization Mechanism
Adsorption of Oil-wet Solid Particles
Emulsion stabilization by solid particle
Solids prevent coalescence of water droplets
Surfactant
Water wet
Oilw
+
Sub-micron
particle
20. Factors Affecting Emulsion Stability
Chemical Factors
• Emulsifying agent
• pH
– High pH generates soap-like
surfactants in the oil
• Water chemistry
– Fluid density difference
Physical Factors
• Solids content
• Droplet size
– Agitation
• Water cut
• Temperature
• Viscosity
• Separator residence time
• Recycling slop oil
Combinations of the above (“the Perfect Storm”)
21. Stokes Law
V = velocity of droplet separation
g = gravitational acceleration
r = radius of water droplet
d1 = density of continuous phase
d2 = density of droplet
= viscosity of continuous phase
Microns Settling Time
Sand 100.0 125 sec.
Silt 10.0 108 min.
Colloids 0.1 755 days
9
)
(
2 1
2
2
d
d
gr
V
22. Effects of Shear on Emulsion Viscosity
Low viscosity High viscosity
Shaker Fast
~49-103µm
Handshake Fast
~13-56µm
Blender 3,500 rpm
~13-36µm
Blender 13,500 rpm
~14µm
24. The following chemistries are used in the formulation of
emulsion breakers
Sulfonates
• Mediocre performance; good
wetting agents; no overtreat
Oxyalkylated Phenols
• Wetting agents
Resins (low oxide)
• Fast drop; general demulsifier;
can overtreat
Resins (high oxide)
• Strong wetting properties;
fair demulsifier
Polyol Esters
• Fast oil brightener; slow drop;
some overtreat
Crosslinked Polyols
• Slow drop; good drier; can sludge;
bridges droplets
Crosslinked Resin/Polyol
• Fast drop and overall EB;
agglomeration
Polyamine Oxyalkylates
• Often excellent EB; slow drop
25. Demulsification Process
Droplet film drainage
Allow droplets agglomeration /coalescence
Weakens the emulsion film
Surface tension alteration
Demulsifier interaction on emulsion film
Demulsifier migration onto oil-water interface
26. Benefits of Chemical Treatment
Cost effective production
• Lower treatment temperatures
– Cost savings
• Faster & more efficient water drop/dehydration
– Consistently meet pipeline BS&W spec.
• Shorter separator residence times
– More efficient operation
– Greater production capacity
27. Benefits of Chemical Treatment
• Improve Fluid Quality
• Lower BS&W
– Operators meet sales oil pipeline spec.
• Reduce oil in water
– Operators meet overboard/discharge water spec.
• Eliminate/control emulsion pads
– Efficient system operation
• Remove solids from oil
– Pipeline specs
29. Importance of Understanding
Production System
• Successful bottle test is dependent on accurately
duplication the following field conditions
– Representative emulsion/proper well production ratios
– Retention time/calculate retention time of each vessel
– Agitation/Shear-pressure drops, dump valves, and pumps
– Chemical mixing/injection points
– Heat/temperature of each vessel
30. Define the Criteria for Success: What Does
the Customer Want?
Lower BS&W content
More cost effective product
Lower oil in water phase
Eliminate/control emulsion pad
Lower treatment temperatures
Water wet solids
31. EB Bottle Testing Procedure
• Bottle test is preformed in three separate sections
Ratio
test
Elimination
test
Confirmation
test
33. Ratio Test
Purpose
• Determine appropriate bottle testing dose range of
incumbent chemical
Process
• Dose incumbent chemical at varying dosages above and
below current field treatment rate
– Example:
• Current field treatment rate = 100ppm
• Bottle testing = 50, 100, 150, 200, 250, 300ppm
Payoff
• Create benchmark bottle testing dose rate and define
parameters at remaining experimental.
– Agitation
– Dosage
– Temperature
– Retention time
34. Elimination Test
Purpose
• The elimination test is used to screen all the available products
at the dosage rates determined in the ratio test
Process
• Run bottle test with entire kit at the dose rate determined in
the ratio test
• Use parameters determined in the ratio test
– Temp, retention time, and agitation
• The test is completed when all the desired compounds have
been screened and potential products have been identified
Payoff
• Select the best candidates for confirmation test
35. Confirmation Test
Purpose
• Run ration test with candidates selected during
elimination test
Process
• Each product is tested at several ratios above and below the
dosage used in the elimination test
– Example: assuming that ratio test dose was 300ppm
• Run confirmation test on each product at: 200, 300,
and 400ppm
Payoff
• Identify optimum dose rate of selected candidate(s) for
field trial
36. Bottle Tests Observations:
What Am I Looking For?
Water drop rate
Interface quality
Oil color
Water clarity
Grindout Readings
Residual emulsion in bulk oil
Residual free water in bulk oil
37. Bottle Test Basics
Emulsified
crude
“demulsified”
crude
Water drop is
measured
over time
a top sample
(thief) is removed
to determine oil
dehydration.
Chemical
(ppm)
Heat
agitation time
Water
quality
Interface
quality
Remove water
for composites
38. The Grindout
Purpose: identify the water and emulsion content of the oil
• Is the oil meeting BS&W spec?
• Variations in BS&W can indicate other potential problems in
the system
Process: collect representative system sample
Payoff: to gain a better understanding of the BS&W to use in
optimization of EB chemical program and oil quality.
40. BS + W = Slug
BS + W > Slug
• Common result: BS is part oil and part water
BS + W = Slug
• Common results: may mean that the slugging compound did not
resolve emulsion completely and/or centrifuging was not sufficient
BS + W < Slug
• Common result: undesired difficult to resolve secondary
emulsion (fine emulsion that defies chemical treatment,
dilution and centrifugation)
?
BS
W
The Grindout
42. Bottle Test Sheet Sample
water drop
coalescence
thief,
dryness
“flocculation”
take good notes
system reference
point, complete
the grindout!
composites,
interface
control,
where
solids
often
accumulate
field info
chemicals
43. Why Run a Complete Bottle Test?
Missing potential dryer
& interface control
candidates
49. Field Trial
Preparation – Planning Ahead
• Adequate amount of product delivered
on-site
• Sufficient field support for continuous
monitoring for duration of trial
• Adequate pumping, tanks, injection
systems
• Discovery agreement for KPIs, cost of
products, manpower/equipment, and
plant test parameters
• Establish control of the system and
then optimize chemical treatment
program
• Produce field test report to document
results
Define Criteria for Success
• Lower BS&W content
• More cost effective
• Faster water drop/dehydration
• Lower oil in water phase
• Eliminate/control pad
• Lower treatment temperatures
• Water wet solids
50. Field Application Tips
• Confirm performance of test kit sample vs. drum sample
• Check compatibility of incumbent and new chemical
• Profile or benchmark all treating vessels
– BS&W, OIW, interface shakeout readings in and out of all vessels
• Place chemical as far as possible from the initial separation unit and
close to the problem*
• Consider chemical injection at:
– Problem wells
– Downhole
– Ahead of choke, header, free water knock out, treater
• Two point injection program could be necessary
• Begin chemical injection rate at 120% of incumbent product
• Allow sufficient testing time to visualize effect of new chemical
application i.e. interface control
*exception - fast dropper may re-emulsify
54. Glossary
Emulsion
A dispersion of droplets of one liquid in another, immiscible liquid, in which
the droplets are of colloidal or near-colloidal sizes. This class will focus on
w/o (“normal”) emulsions.
Colloidal
Particles, droplets or bubbles dispersed in another phase and have at least
one dimension between 1 and 1,000 nm.
Intermediate
Demulsifier components in a finished product.
Dropper
i.e. water dropper, a chemical(s) that rapidly drops water.
Dryer–
A chemical(s) that produces dry oil.
55. Glossary
Emulsion breaker
A chemical(s) that resolves unwanted emulsion (results in low BS values).
Interface or pad-buster
A chemical(s) that effectively resolves the rag layer.
Rag layer
Unresolved emulsion residing mostly at the oil-water interface.
Slop
Unresolved emulsion that is often chemically over treated and laden with
solids.
Thief
n. A sample removed by syringe for w/o analysis; v. to remove.
Composite – BS&W for the resolved oil phase.
56. Glossary
BS&W
Basic sediment, bottoms sediment or base sediment; water.
Slug
n. A chemical used to resolve untreated emulsion; v. a chemical often used
to treat slop oil. The most common Nalco slugging compound is EC2003A.
Grindout
Determining the BS, W and Slug values for a field or lab sample.
Secondary emulsion
Unresolved and undetected (hidden) emulsion before slug addition.
Secondary emulsion should be avoided.
Rag, bag, web, fish eyes
Terms used to describe the quality or appearance of an oil-water interface.
57. Glossary
Free water
Non-emulsified water that separates within minutes of sample collection.
PTB
Pounds-per-thousand barrel, a common unit of measure for inorganic solid
content (ppm x 0.35 = PTB).
Karl Fisher (KF)
A titration method used to quantify the water content in a hydrocarbon.
LACT unit
Lease automatic custody transfer, where the “official” w/o value and oil
volume is measured & where the transfer of ownership of oil/condensate
between buyer & seller occurs.
58. • Field system
survey
• Customer
interviews-
discover
technical/cost
challenges
• Review
production data
• Develop bottle
test reflecting
system
performance
Nalco bottle testing
procedure
Crude oil
characterization
Statistical analysis of
critical demulsifier
and crude oil
interactions
Interpretation of
results via factors
such as water drop,
interface quality,
water clarity, low
BS&W, other
Blend optimization –
identifying synergy
among demulsifier
components
-new formula creation
Review product for
cost-performance
optimization
opportunities
Logistics and storage
considerations
assessed
Agree upon field trial
process steps and
trial key performance
indicators
Review System Bottle Test Evaluate Candidates Recommend Field Implementation
Commercial scale-
up (if new product is
being introduced)
Field evaluation of
product and system
performance
Conduct periodic
system analysis to
drive improvement
on technical and
cost performance
Emulsion Breaker Evaluation Process