Demulsification

of Oilfield Emulsions
 Emulsion Formation

Emulsions can either be formed

➢ naturally or

➢ artificially by man

depending on the use.

 Emulsion Definition

Emulsion is a relatively stable

dispersion of one liquid in
another immiscible liquid
 Conditions for Emulsion Formation

For emulsions to form, there must be:

❖ two immiscible liquids
❖ agitation resulting in turbulence to
disperse one liquid in the other
❖ a stabilizing agent called emulsifier
which prevents coalescence of the
dispersed particles.
Satisfying These Conditions in the Oil Industry

➢Oil production is accompanied by water. Water and

oil are immiscible and their mixtures tend to segregate
into two layers.
➢The oil-water mixtures are sheared sufficiently by
turbulent flow through subsurface and surface chokes,
valves, pumps and fittings into two types of mixtures
(water-in-oil mixture or oil-in-water mixture).
➢The dispersed droplets would naturally coalesce
together and form larger droplets and segregate if
agitation is stopped over an unlimited period of time.
 Stability of Emulsions

The following substances which are found in producing formations, tend to promote
the stability of emulsions.

➢ Finely-divided solids such as:

•Drilling mud (colloidal clay)
•Produced sand
•Iron sulphide from pipe corrosion
•Precipitated minerals due to scale formation
•Asphaltenes in the crude

➢ Surface-active agents such as

•Naphthenic acids in the crude
•Injected inhibitors (for corrosion or wax deposition control)
 Stability of Emulsions

Emulsions get:
❖more stable with agitation
and
❖ less stable with rising temperature.
 Identifying the Types of Emulsion

If only oil and water are considered, we shall

have either:

❖ Water-in-oil (w/o) emulsion or

❖ Oil-in-water (o/w) emulsion which is

also called inverse emulsion
 Identifying the Types of Emulsion (Cont.)

To identify the type of emulsion, we can

perform the following simple tests:
✓A drop of w/o emulsion will easily and
rapidly disperse in oil while that of o/w
emulsion will readily disperse in water.
✓An o/w emulsion will conduct electricity
while a w/o emulsion will be more electrically
resistant.
✓Photomicrographic studies.
 Aging Effects

❖Emulsions tend to be more stable

with age

❖Its characteristic also change with

age
 Problems Of Stable Emulsion
❖The presence of water in oil results in two-phase flow which is more difficult to
transport. Pumping costs and erosion of pipeline and equipment increase.
❖Emulsion treatment is expensive. On chemical treatment alone Mkpadi and
Okonkwo (1986) estimated that about N200,000 worth of chemicals are used daily
in Nigeria.
❖They introduce salt into the crude causing corrosion and scaling problems.
❖Water causes hydrate formation in gas pipelines.
❖Water lowers the API gravity of crudes.
❖The disposal of separated water is polluting to environment.
 Theory of Emulsion Stabilizers

Emulsifiers work in a two-fold way.

➢ They create electrical charge on the droplets
making them to repel each other and prevent
coalescence.
➢ They concentrate at the oil-water interface,
toughen the surface film and prevent coalescence of
the droplets. This is so because emulsifiers are
usually partly soluble in both liquids. They have a
water soluble part called the hydrophilic part and an
oil soluble part called the lipophilic part.
 Structural Disposition

The structural disposition of a molecule at the interface illustrated with

NONYLPHENOL-POLYOXY ETHYLENE is given below:

c=c 1
// \\ 1
c-c-c-c-c-c-c-c-c-c-c-c-c-c-c-c-c-c-c c-c-c-c-c-c-c-c-c-c-c-c-c-c-c-c-c-c-c
\\ // 1
c=c 1
1
Interface
 Nature of Emulsion

❖ The nature of the emulsion depends on the

Hydrophile-Lipophile Balance (HLB).

❖ HLB is defined as the relative proportion of

hydrophilic to the lipophilic part of an
emulsifier molecule.

❖ HLB that determines whether an emulsifier

would stabilize w/o emulsion or o/w emulsion.
 Nature of Emulsion (Cont.)

➢Low HLB implies that less fraction

of it is soluble in water and thus
stabilizes w/o emulsion.
➢In the reverse, high HLB implies
that a greater fraction of the
emulsifier is soluble in water thus
stabilizing o/w emulsion.
 Bancroft’s Rule

Bancroft’s Rule states that the liquid

phase in which the stabilizer has the
greatest solubility will form the
continuous or external phase of the
emulsion while the other immiscible
liquid in which the emulsifier is less
soluble forms the dispersed or internal
phase.
 Some Available HLB Values

Solubility Characteristics HLB Range

No dispersability in water 1–4
Poor dispersion 3–6
Milky dispersion after vigorous agitation 6–8
Stable milky disperson 8 – 10
Translucent to clear dispersion 10 – 13
Clear solution 13+

Table: Required HLB Value for Emulsifying Oils in Water (Mkpadi and
Okonkwo, 1986)
 Some Available HLB Values (Cont.)
Compounds HLB
Beeswax 9
Benzene 15
Carbon tetrachloride 15
Castor Oil 14
Chlorinated paraffin 12-14
Chlorobenzene 13
Cocoa Butter 6
Corn oil 8
Cotton seed oil 6
Cyclohexane -15
Kerosene 12
Lard 5
Mineral oil, aromatic 12
Mineral oil, paraffin 10
Mineral spirits 14
Nitrobenzene 13
Palm oil 7
Paraffin wax 10
Soya bean oil 6
Tuluene 15
Xylene 14
 Theory of Emulsion Resolution

We can either:
✓prevent emulsion formation or
✓treat emulsion after it has been
allowed to form.
 Prevention
The only factor the production Engineer can control is
turbulence or agitation of the liquid mixtures through
the flow restrictions and pumps. This can be done by:
1) Avoiding the use of surface chokes.
2) Use other flow control devices such as intermitters of
automatic valves that can allow periodic wide-open
flow.
3) Lift pumps used should have high volumetric
efficiency and run at appropriate strokes and speed.
4) Gravity flow provides the least turbulence.
5) Good reservoir management to delay water coning and
breakthrough.
 Treatment

Factors important in the treatment

of emulsion include:
✓The viscosity of the oil, µo.
✓The droplet sizes, R
✓The density difference between
the liquids, |юp-юf|
 Treatment

Factors important in the treatment

of emulsion include:
✓The viscosity of the oil, µo.
✓The droplet sizes, R
✓The density difference between
the liquids, |юp-юf|
 Treatment
The essence of treatment is Stoke’s law of settling of particles in a fluid. For
spherical particles, the settling velocity is given by:

V = 2R2 (p - f)g

9 µf

Where:
 = density, gm/cc
v = settling velocity, cm/sec
g = acceleration due to gravity, 980 cm/sec2
µ = viscosity of fluid, poises
R = radius of particules, cm
P = particule
f = fluid
 Effect of Velocity

From the above relationship the velocity

increases with increase:
1) in size of particles and
2) density difference but
3) with decrease in viscosity of the fluid.
NOTE:
The higher the velocity, the easier to treat the
emulsion.
 Methods of Treating Emulsion
There are basically 7 methods.
1) Heating These four have found the
2) Gravity settling greatest application in the
3) Electrical field.
4) Chemical

The others are:

5) Filtration
6) Centrifugation and
7) Dilution
 Heat Treatment

The effect of heat treatment decreases the viscosity,

thickness and cohesion of the separating interfacial
film
1. reduces the viscosity of the continuous phase (µo)
which in turn enhances rapid settling of the disperse
phase within a certain range of temperature. Within
100oF – 200oF, increase in temperature aids gravity
settling. Above 200oF, increasing temperature has no
appreciable effect on viscosity.
2. Settling. Above 200oF, increasing temperature has no
appreciable effect on viscosity.
 Heat Treatment (Cont.)

3. Effects changes in the relationship between the

interfacial tension of the emulsifier and the
colloidal properties and ruptures the film.
4. Increases the solvency of bulk oil for the stabilizer
and the rate of diffusion of the stabilizer back into
the oil.
5. Increases the energy level and when the rate of
Brownian movement of the disperse particles,
causing coalescence and gravity settling.
6. Increases the density difference of the liquids. Oil
expands on heating.
 Heat Treatment Recommendation

❖ Heating can be done by use of heaters

but the most effective and efficient
source of heat is that of the producing
formation.

❖ It is therefore usually recommended to

treat the emulsion near the wellhead.
 Disadvantages of Heat Treatment

❖increased turbulence at high temperature

undesirable
❖vapour losses of the oil are incurred
❖loss of API, volume and revenue increases with
vapour losses.
❖Additional cost of heating involved. With the cost
of energy this could be substantial in the overall
production cost.
❖As a result of the hardness of water, scaling and
corrosion problems could be accelerated.
 Minimizing Above Problems

It is advisable to choose low

pressure steam or hot water heater-
treater to high pressure steam
 Gravity Settling Methods
The objective of this method is to afford a quiescent environment
that would effect segregation of the liquids by means of differential
densities of the phases.
▪for effective gravity segregation, density of water should be at
least 4% greater than the density of oil.
▪If this condition is not met we can dilute the oil with lighter ends to
reduce the oil density.
▪However, this condition is usually met since most wells produce
brine.
▪Any “free-water” which settles out within a period of about 5
minutes under quiescent conditions must be removed before
further treatment.
▪ Liquid knock-out vessels, Gunbarrels and wash tanks serve this
purpose.
 Electric Dehydration

▪This method is credited to Cottrel, P.G.,

Speed, H.B. and Wright A.
▪When brought within the electric field of
high alternating current, the dispersed water
droplets of the emulsion coalesce and settle
out under gravity.
▪In this process, heat can be moderately
applied to reduce the viscosity of the oil to
facilitate gravity settling
 Theory
When w/o emulsion is passed through two electrodes upon which a high potential is
impressed, the water droplets become charged by induction. Thus:
▪one side of the water globule becomes positively charged and the other negatively
charged.
▪Globules realign as adjacent unlike charges attract. This results in a chain between
the two electrodes.
▪When this occurs a discharge of electricity passes through the chain from one
electrode to the other.
▪The chain of water particles constitutes an electrical path thus coalesce and form a
large drop of water which readily settles out under gravity.
 Stages Involved

Thus essentially two stages are involved:

➢The polarization of the particles by

electrical induction, realignment by
attraction and formation of large droplets.

➢Settling out of these large particles after

electrical discharge and depolarization.
 Stages Involved (Cont.)

Both stages are facilitated by heating the

emulsion to a temperature between 120o and
180oF. Within this temperature range, the
viscosity of oil reduces, interfacial tension is
lowered and density difference of the liquids
is increased. All of these promote
demulsification. However excessive heating
must be avoided as discussed above.
 Chemical Resolution of Emulsion
➢Synthetic or organic chemicals have been discovered to modify or alter the HLB
of emulsifiers.
➢Additive is absorbed into the interface, rupture the skin and or displace the
stabilizer, forcing it back into the oil.
➢It also lowers the interfacial tension of the droplets leaving an interface covered
or partially covered with a thin film which offers little resistance for coalescence
or droplets.
➢Time and turbulence aid diffusion of the additive.
➢It is usually added at the wellhead to take advantage of well temperature,
because of the extra advantages of heat treatment as discussed earlier.
 Problems of Chemical Treatment
1. uncertain nature of emulsifiers and their HLBs.
Thus a trial-and-error method used to screen the
additives.
2. Additives are expensive and large quantities are
required
3. There is no universal demulsifier. The activity of
a single demulsifier changes with the age of the
field requiring periodic evaluation of
effectiveness.
4. Different vendors claim theirs is more effective
thus …….
Laboratory Simulation of Demulsification

A relationship of the resistance of

emulsion to resolution based on
electrical conductivity has to be
established. A linear relationship will
aid the selection of additions. It
requires skill.
 Filtration
➢Most treating plants have a filtration section made
up of either wood excelsion, glasswool, charcoal, coke
sand or alumina.
➢They are maintained water-wet such that as the
droplets are forced through, due to tortuosity of the
paths, they would be distorted and tend to coalesce,
adhere to the surface of the filter and drain.
➢Apart from coalescence, this section prevents
turbulence.
➢Filter must be inspected regularly to check for
clogging by foreign materials.
 Centrifugation

Most treating vessels are also

designed to effect centrifugation by
use of vanes, sudden changes in
direction causing impingement, etc.
 Dilution

Dilution with the continuos phase

can minimize the effects of emulsion
but not totally eliminate emulsion.
Oil Field Equipment Used for Emulsion Control

➢The ultimate action of any device is gravity settling

on the basis of Stoke’s law.
➢Water content of crude oil should be between 0.1 –
3% depending on pipeline requirement.
➢For any of the methods, chemicals may be injected
to improve emulsion resolution.
➢A free-water knock-out vessel should be upstream
of the major treating vessel.
Below are the major treating equipment used in the field.
 Wash Tank

➢A wash tank is a device in which w/o emulsion is

admitted to a large tank below the water-oil
interface. The water provides a washing action.
➢A long hold up time and absence of turbulence are
vital for effective treatment.
➢Incoming oil often heated with heated with or
without chemical injection.
➢Wash tanks are little used offshore because they
tend to be large and heavy.
VESSELS
 Heater-Treater

➢As the name implies, this uses heat

essentially.
➢It has provision for free-water
dropout, degassing and a possible
coalescing medium.
➢Washing action used and turbulence
minimized.
 Chemelectric Treater

These are heater treaters to which a

set of electrodes have been added
for electrical effect. Chemicals can
also be added upstream.
 Design of Treating Systems
1. Treating systems are expensive and troublesome
2. They are frequently under or oversized because of
insufficient data.
3. Proper selection can minimize problems and result in
cost efficiency.
4. Corrosion and scale formation control necessary
5. Reduction of energy load can lead to substantial savings.
6. Free water knockout upstream of major treating vessel
can reduce energy requirement.
7. Recent innovation is to incorporate a free water
knockout or bypass facility in the design of pressure
type treaters.
 Selection of Treating Systems
1. Tightness of the emulsion (from photomicrographs)
2. Specific gravity of the oil and produced water
3. Corrosiveness of the crude oil, produced water and
casing head gas.
4. Scaling tendencies of the produced water
5. Quantity of fluid to be treated and percent water in the
fluid
6. Availability of a sales line for the casing head gas
produced.
7. Desirable operating pressures for equipment
8. Paraffin forming tendencies of the crude oil.
 Steps for sizing of Vessels
The following procedure can be used to size treating vessels:
1. Assume an average treating temperature
2. For the selected treating temperature, determine the
specific gravities of the oil and water and the viscosity of
the oil
3. Using the appropriate relationships for either vertical or
horizontal vessels, calculate the capacity of the vessels.
4. After sizing, determine the heat requirement to raise the
inlet temperature to the treating temperature.
Remember to add possible heat loses.
5. After sizing, check to see if retention time is within
recommended limits.
6. Check valve sizing on vessels.
 Type Of Treating Systems And Recommended Applications
S/ TREATING RECOMMENDED REMARKS
N SYSTEM APPLICATION
1 Pressure-type treaters • medium to high gravity Economics of both
crudes (30oAPI+) capital investment,
• sweet and slightly operation and
corrosive crudes maintenance best.
• sales line available for
casing head gas
• normally preferred to other
systems for conservation of
oil gravity and recovery of
rich vapour.
2 Gun barrel Tanks • loose emulsions of all Designed for minimum
without heat gravity oils with inlet fluid treating temperature.
o
temperatures of 80 F or
more
3 Gun barrel Tanks • sweet or slightly corrosive Temperatures up to
with direct heaters oils of all gravities for both 120oF
loose, moderate and tight
emulsions.
4 Gun barrel tanks with • Moderate or very corrosive Temperature range: 90-
indirect heaters emulsions of all gravity oils 100oF.
• Normally used for loose or
moderate emulsions
• Also used where scaling is
likely
 Average Treating Temperatures For Various Types Of Emulsions

Emulsion Conventional Sivalls Down Gunbarrel

Characteristics Treaters Flow Treaters Tanks
Loose
Emulsion 100 – 120 85 – 100 80 – 100

Moderate
120 – 140 100 – 110 100 – 120
Emulsion

Tight
140 – 180 110 – 135 120+
Emulsion
 Values Of Constant “C” Used In Sizing Of Vessels

Emulsion Average water droplet

Characteristics diameter in Microns C
(meter x 10-6)
Free Water 200 1,101

Loose Emulsion 150 619

Moderate Emulsion 100 275

Tight Emulsion 60 99
 Heat Flux Requirement

Fluid Around Fire Box Fire Box Heat Flux Btu/hr sq. ft.
of Fire bos surface area
Crude oil 6,000 – 8,000

Salt water 10,000

Fresh water 12,000

Boiling Water 15,000

 Some Equations Used in Sizing
Vertical Treater of Gunbarrel tank
W = c(w-o) (0.785 D2)H
µo

Horizontal treater
W = c(w-o) (L) (H) ??
µo

Heat required:
Q = w(6.25 + 8.33x) (T2-T1)

Total heat required = Heat required for treating emulsion

+ expected heat losses

Q loss = K(D) H (Tt-Ta)

 Some Equations Used in Sizing (Cont.)
Check heat transfer texts for other equations. Graphs are also available for sizing in
reference texts.

W = oil capacity, bbl/d

C = constant (Table 4)
 = gravity at treating temperature
µo = Viscosity of oil at treating temperature
D = diameter of the vertical vessel, ft.
L = length of interface area in horizontal vessel, ft
H = width of interface in horizontal vessel, ft
Q = heat required, Btu/hr
X = percent water in emulsion expressed as a fraction
T2 = treating temperature, oF
T1 = inlet temperature, oF
w = water, oc oil
 Common experience in Nigeria (Mmaji, 1990)

➢ Light streams use SERVOCC Chemicals,

➢ Medium Streams use Petrolite.
➢ Heavy Streams or sludges use Acetic Acid.

Treating chemicals can be added at any point in the system from the bottom of the
hole to the stock tank. There are three basic types of treating differing in the point
of injection:

▪Downhole treatment – injection at wellbore.

▪Flowline treatment – injection at flowline before the coke or before the
separator.
▪Batch treatment – injection at the tank.
 Actual Field Report

The following is an actual field report from a service company

✓Bottle test is a test conducted to select the most efficient demulsifier and the
required dosage to enhance efficiency.

✓To select the best demulsifier we always go to the field with all our appropriate
stream demulsifiers prepared in 5% solution and bottled in 50ml bottles.

✓The test is run in the field by using the thief which is a 5 inch elbow to collect sample
from the flowline before chemical injection.

✓The sample is put into a 4 litre container.

 Actual Field Report (Cont.)
✓The container is properly shaken and the temperature of the crude noted.
✓Into 16 200 ml prescription bottles, the sample is poured up to the 100 ml mark.
✓The pipette is used to dope 15 bottles with 15 different demulsifiers with 25 ppm
each.
✓The 16th bottle is left undopped as blank.
✓The bottles are put in shaking machine for proper mixability of the crude sample
and demulsifiers for 20 minutes.
✓The bottles are transferred to a water bath and heated up to 40oC. Readings of
levels of water breakout is taken after 15 minutes, 30 min, 1 hr, 1½hrs, 2 hrs, 3 hrs up
to 6 hours.
 Actual Field Report (Cont.)

✓Note the bottle and demulsifier that gave the best

separation.
✓After that use pipette or syringe to suck 50 ml out
of the 100 ml of the upper part of the separated
emulsion and shake the remaining 50 ml in the
bottle.
✓Transfer it to the 6 inch centrifuge tube and
centrituge for 2 minutes and record the clarity of the
water as very clear, clear and not clear.
 Determination of Required Dosage
❖Again fill 6,200 ml bottles with the freshly
collected sample up to 100 ml mark.
❖Using pipette, dope 5 bottles with 10 ppm, 25
ppm, 50 ppm, 75ppm and 100 ppm of the
demulsifier selected above.
❖ The 6th bottle is left as blank. Shake with shaking
machine and heat with water bath.
❖Take recordings of water separation as before and
note the dosage that gave the best separation.
❖Centrifuge thereafter and record the clarity of
water.
 BS & W Test

Run the Basic Sediments and water (BS&W) test prior to

the bottle test.

This is done by:

➢ filling the 100 ml centrifuge bottle up to the 50 ml

mark with fresh crude sample and
➢ making it up to 100 ml mark with toluene for 5
minutes and
➢ record the BS & W to the nearest 0.1%.

This gives idea of the total water content to be separated.

 BS & W Test (Summary)

➢Runt the BS & W test

➢Run the Bottle test and select the best
demulsifier
➢Run the test with the best demulsifier at
different dosages to determine the optimum
dosage.
➢ After running all these tests,
recommendations are made to the operating
companies on the selected demulsifier and
optimum dosage to be used.
 Improved Bottle Test By Udoh (1989)
➢The bottle test is improved upon by considering certain quantitative parameters.
➢These parameters help in effectively describing demulsification.

They include:
➢settling time; which was observed to be a function of demulsifier,
➢treating temperature and quantity of demulsifier,
➢salt content is also a standard measurement.
➢Refinery and pipeline industry restriction, necessitated its inclusion in the
measurement.
➢Emulsion leg measurement is done on the observation that demulsifiers like Servo
6602 give a column of emulsion, in addition to the water and oil columns, on
treatment, although the oil is cleaned to nil BS & W%.
 Field Matching
Field matching is the process of finding the demulsifier, that treats a particular
oil field emulsion best, out of the many demulsifiers present in the market.

It is first done in the laboratory through bottle test, which simulates field
conditions in the laboratory and monitors the effect of demulsifiers on emulsion.

The result of the bottle test indicates in a small scale the effect of the
demulsifier on the emulsion and is used as the basis for choosing a demulsifier.

Field chemical treatment of emulsion can be adequately monitored to obtain

optimum efficiency using the bottle test data.
 The Bottle Test
The bottle test is described by the American
Petroleum Institute (API) and Petroleum
Extension Services Publication “Treating Oil
Field Emulsions”, 1974. It measures primarily
the following parameters:

a. The water column produced by treatment with a

demulsifier-water (BS & W%)
b. The basic sediment and water of the treated
column of oil (BS & W%).
c. The quantity needed to get the best or optimum
treatment, all done at optimum treating
temperature.
 The Bottle Test (Cont.)

The method of experiment remains the same

with slight modifications to measure the
following:

d. The settling time of the demulsifier

e. The salt content of the treated column of the
oil
f. Emulsion produced as a column: if any
Emulsion leg.
g. The effect at temperature on these parameters
 Apparatus

1) 6 ounce (200ml) prescription bottles

graduated to 100 ml with screw caps
2) Thermostatic water bath
3) Centrifuge machine
4) thermometer salt-in-crude analyser
5) measuring cylinders
6) large plastic can.
 Material

1) Demulsifier prepared in either 1

percent or 10 percent solution
2) Fresh crude without chemical addition
3) Toluene xylene
4) Mixed alcohol
5) Neutral oil.
 Conditions

1) The crude should be as fresh as possible

to eliminate rapid aging.
2) It should be representative of emulsion
treated
3) The same condition of agitation as
obtained in the leases should be
simulated.
 Procedure

1) With the large plastic can, fresh crude is

collected from the production line just before
treatment or before any chemical injection starts.
2) When brought into the laboratory, it is kept for
20 minutes and the bottom drawn off through the
can tap to remove free water. This is done until
only emulsion flows showing no free water.
3) The remaining sample is shaken vigorously to
mix properly.
 Procedure (Cont.)
4. BS & W test is carried out on the sample to determine the
water present in the emulsion.
i. A centrifuge bottle is filled to the 50 ml mark with
Toluene.
ii. 3 drops of a demulsifier are added (precisely acid
based special demulsifier such as Hoechst or tretolite.
iii. The well shaken sample is added to make up 100 ml.
iv. It is placed in a water bath at 60C for 10 minutes.
v. It is then centrifuges for another 10 minutes.
vi. When removed, the sediment and water removed is
read and multiplied by two (2) to give the BS&W%.
This gives the water content of the emulsion Wc that
needs to be removed by demulsifier treatment.
 Procedure (Cont.)
5. Each of the 6-ounce bottles are filled to the 100 ml mark
with the well shaken sample.
6. Each bottle is placed in a water bath at 80oC for 10
minutes for the crude to attain this temperature. They
are placed in a row and the demulsifier is added in
drops one drop to the first, increasing by one drop till
the eighth with 8 drops. They are shaken vigorously
and placed back in the water bath at the same
conditions for another 10 minutes.
9. It is removed after 10 minutes and the following readings
taken immediately:
i. Water column volume (water – leg Wp)
ii. Emulsion column volume (Emulsion-leg em)
 Procedure (Cont.)
10. The bottles are allowed to cool to room temperature (30oC). The reading sin (7)
are taken again i.e. water-leg, Wp and Emulsion leg, em.
11. The bottles are shaken vigorously at room temperature for 5 minutes and placed
on a table while simultaneously starting a stop clock. The water-leg and emulsion leg
are watched until they attained the initial values recorded in step (8). This time is
recorded as settling time.
12. 50 ml of the bottle’s top sample is pipetted out and the BS & W test repeated
again as stated in step (4).
13. 10ml of the bottle’s top sample is drawn and used in salt content test.
 Procedure (Cont.)
14. A 100 ml measuring cylidner is filled to the 50 ml mark
with mixed alcohol (mixed alcohol = 63%, Buthanol =
37% with 0.02 ml of water per 100 ml mixture).
a) 40 ml of xylene is added to make up 90 ml solution.
b) The test sample is added to make up 100 ml solution.
(The first test sample is usually neutral oil to give the
blank value bV). Subsequent rest samples give the
test value tV.
c) This is shaken and poured into the analyser beaker
and all bubbles removed. The beaker placed back in
the crude analyser with the electrodes placed back.
 Procedure (Cont.)
d. The analyser is calibrated to “red point” by keeping
voltage at 125 volts and adjusting ampere buffer until it
reaches the ‘red mark’. The calibration knob is
depressed to read position and the value read from the
amp-scale.
e. The test value tV minus the blank value bV gives the
needed readings for the use in the conversion table.
The actual value of the salt in PTB is read from a
conversion table the using the value (tv-bv = Q).
15. The process is repeated from steps (5) to (11) with the
water bath temperature kept at 70oC, 60oC, 50oC and
40oC respectively for each set. The experiment is done
in batches of 8 bottles.
 Combination Test

1. Two demulsifiers are combined to augment the

efficacy of each other to improve treatment.
2. The base demulsifier must be known which is
usually the demulsifier that treated the crude to
the least BS & W and has the higher optimum
treating temperature.
3. The test is done at the optimum treating
temperature of the base demulsifier. The second
demulsifier is the one to be added to improve the
qualities of the base demulsifier.
 Examples of the Base Demulsifier
Examples of the base demulsifier used in this study
were:

1) Servo 8171
2) Servo 6602

Secondary demulsifiers used were

1) Hoechst 2655
2) Tretolite RP-1656

In carrying out the test, the conditions stated earlier

are followed:
 Modifications to Conditions
Steps (1) to (2) are carried out with the following
modifications:
a. Step (6). Each of the bottles is shaken vigorously for 5
minutes and placed in a water bath at the optimum
treating temperature of the base demulsifiers for 10
minutes. After 10 minutes, it is shaken vigorously for 5
minutes and a drop of the secondary demulsifier is
added to each of the bottles. It is shaken again
vigorously for 5 minutes and placed back in the water
bath for 10 minutes. The rest of the steps from (7) are
followed precisely.
b. Ste (12). The process is repeated from (5) to (11) with
increasing number of secondary drops (one drop at a
time up to 8 drops) in step (6) above.
 Interpretation of Data
1. Waterleg, Wp
§ This is the volume of the water column produced from the
emulsion during treatment.
§ It is measure in millimeters.
§ It indicates the extent to which the aim of treatment has been
achieved with the demulsifier.
§ The aim is to remove 100% of the water content to have 100%
of the oil from the emulsion water leg value less than this means
less than 100 percent emulsion resolution.
§ The water-leg is measured at two temperatures – treating and
room temperatures.
§ These two measurements show the effect of cooling in
treatment.
§ The room temperature simulates field storage condition.
Cooling helps in separation
 Interpretation of Data (Cont.)
2. Emulsion-leg, em
This is the volume of the emulsion produced occupying a
separate column between the water and oil columns.
No emulsion treatment aims at producing an emulsion leg.
Emulsion leg formation indicates inadequacy of the
demulsifier.
It can also mean that the demulsifier has stripped the
crude of emulsion, forming a column which is quickening
the natural process that would have taken place if the crude
was allowed to rest for a long time.
Heating helps in separation, reducing emulsion leg.
 Interpretation of Data (Cont.)
3. Settling Time
The settling time is the time it takes the initially separated water, emulsion and oil
columns to settle again to the initial readings at room temperature on being vigorously
agitated for another five minutes. It is measured in minutes.
Settling time at the lowest temperature is the worst design condition.
The crude treatment process is a dynamic one and static condition cannot be
achieved.
Only quick acting and quick settling demulsifiers can withstand this condition.
Settling time is a function of the demulsifier and its ability to completely neutralize
the electrostatic and adhesive forces that exist in emulsion.
High settling time is undesirable.
 Interpretation of Data (Cont.)

➢4. Basic Sediments and Water, BS&W

➢ The BS&W is the major determinant of the efficiency
of the demulsifier.
➢ It is the amount of basic sediments, like dirt and
water still present in the tested crude.
➢ It is measured at room temperature.
➢ If the demulsifier excels in other parameters but fails
in this, then its ultimate aim is defeated.
➢ Crude treatment seeks to produce nil BS & W% i.e. a
crude that has been completely rid of water.
 Interpretation of Data (Cont.)

5. Salt Content
➢Along with other things, the refinery is concerned with
the salt content of the crude.
➢Some crude oils have high salt contents that cannot be
tolerated by the refinery equipment (- API and petroleum
Extension Services, 1974).
➢The salt content is measure in parts per thousand
bands (PTB). Where organic salts are present and soluble
in the oil, the BS & W% may be low, but the salt content
high.
➢The parameter ensures that desalting has been done.
 Interpretation of Data (Cont.)

6. Treating Temperature
➢ Temperature is considered here as a simulation
parameter.
➢ Demulsification is a chemical reaction controlled by
temperature.
➢ Heating is usually done to effect complete
demulsification.
➢ Any demulsifier that can perform effectively at low
temperature, say room temperature, would have:
i. saved the additional cost of heating and maintaining
heaters
ii. reduced vapour losses thus increasing revenue
 Interpretation of Data (Cont.)

➢The cost of heating increases with increase in the

optimum treating temperature of the demulsifier used.
➢A low temperature acting demulsifiers would have a
lower cost.
➢The demulsifiers used in the case studies had the
following as their optimum treating temperatures
Servo 8171 = 70oC, Servo 6602 = 70oC
Hoechst 2655 = 50oC, Trelolite RP-1656 = 50oC
 Interpretation of Data (Cont.)

7. Quantity
➢This is the volume of demuslifier added to 100 ml
of emulsion.
➢Its aim in this test was to help determine the ratio.
Thus, the ratio test is integrated into the test.
➢The ratio is read from a plot of BS & W against
quantity.
➢It is the optimum point where:
d(BS&W) =0
dq
 API Standard
✓In this test, the API standards and
conditions for carrying out bottle test are
strictly adhered to as published in the
standards, section 245(2).
✓The settling time is introduced as a means
of explaining the time it takes to separate as a
function of demulsifier and treating
temperature.
 Applications
The main applications of these tests are:
1. Field matching, where a mathematical
efficiency equation has been developed by
Udoh, (1989).
2. Optimization of cost of treatment
3. Treatment plant design
4. Combination test for improved treatment.
 Summary of Findings and Conclusions

1. A total of seven parameters are used to quantify the

efficiency of a demulsifier. Thus, a demulsifier activity
can be effectively described and ranked. These are:
a. water-leg
b. Emulsion-leg
c. Settling time
d. BS&W
e. Salt content
f. Temperature
g. Quantity

2. It is rare to find a demulsifier without defects in any of

the seven vital parameters. In order words there is no
universal demulsifier.
 Summary of Findings and Conclusions

3. Demulsifiers A and B are good crude cleaners but support emulsion, while C and D
are bad cleaners but good emulsion treaters.
4. A combination of demulsifiers can improve emulsion treatment
5. At high temperature, some demulsifiers react quickly and effectively. There is a
temperature above which there is no increase in BS&W of the treated oil. This is the
optimum treating temperature.
6. Cooling helps in improving the parameters of the treatment by increasing water-leg
and decreasing emulsion leg. This is why most demulsifiers break water in the
storage tanks instead of treating facility.
Measurement Of Dielectric Content
Of Oilfield Emulsions And Its
Application To Emulsion Resolution
 Definition of Emulsion

An emulsion is a mixture of two

immiscible liquids in which one liquid is
finely dispersed in the continuous phase
of the other liquid in the presence of
stabilizing agents called emulsifiers.
 Promotion of Emulsion Stability

Hausler (1978) reported that the following

substances which are found in producing
formations tend to promote emulsion stability:
a. finely – divided solids such as drilling mud
(colloidal clay), produced sand, iron sulphide
from pipe corrosion, precipitated minerals due
to scale formation, asphaltenes in the crude oil
and
b. indigenous crude oil surface-active agents or
surfactants such as naphthenic acids, injected
inhibitors for corrosion or wax deposition
control.
 Emulsifier
➢The emulsifiers concentrate at the oil-
water interface as skin, increase the
interfacial tension and prevent the
coalescence of the dispersed droplets.
➢Emulsifiers also induce electrical charges
on the droplets making them to repel each
other.
➢The stability of an emulsion thus depends
greatly on the physico-chemical
characteristics of the emulsifier.
 Types of Emulsion

1. When water is the dispersed phase,

the emulsion is called water-in-oil
emulsion and
2. when oil is the dispersed phase, the
emulsion is called oil-in-water
emulsion or invert emulsion.
 Effects of the Characteristics of Emulsion

1. The interfacial tension becomes stronger

2. the stability of the emulsion increases as
further adsorption and rearrangement of
emulsifiers occur at the interface.
3. Emulsions get more stable with agitation
and less stable with rising temperature.
 Problems of Stable Emulsion
The problems of stable emulsion are:
• increase in pumping cost
• erosion of pipeline and equipment
due to two-phase flow
• increase in corrosion rate and scaling
problems due to the salt content of
formation water and
• lowering of the API gravity of the oil
 Properties of Emulsifiers

a. Emulsifiers are partly soluble in both liquids

b. They have a water soluble part called hydrophile
and an oil soluble part called lipophile
c. The stability of an emulsion depends on the
Hydrophile-Lipophile Balance (HLB)
d. It is the HLB that determines whether an emulsifier
would stabilize water-in-oil (w/o) emulsion or oil-in-
water (o/w) emulsion
e. Low HLB (less than four) implies that less fraction
of the emulsifier is soluble in water and thus
stabilizes w/o emulsion
 Water-in-crude oil emulsions

Stockwell et al (1986) showed that:

❖The viscosity of water-in-light crude oil emulsions
increases with increasing water content and
decreasing droplet size.
❖Emulsions are pseudo plastic depending on the
water-oil-ratio and shear rate.
❖At low water content and higher temperature,
emulsions are Newtonian.
❖With increasing water content, deviations from
Newtonian behaviour occur.
 High Emulsion Stability

Gladden and Neustadter (1972)

reported that anomalous high
emulsion stability is attributed to
high interfacial viscosity.
 Interfacial Rheology of Emulsions

According to Cairns et al (1974):

➢Maximum interfacial tension occurred at pH
4-6.
➢Decrease in interfacial tension at low pH
might be due to the ionization of nitrogen
bases in the interface and that at high pH to
the formation of carboxylates.
➢The asphaltene content of crude oil does not
necessarily indicate the existence of high
interfacial viscosity.
 Electrical and Coalescence Behaviour of
Water-in-oil Emulsions

Taylor (1988) observed that when water-in-

oil emulsions was subjected to high voltage
gradients, the stability of the emulsions
depends on
➢the nature of crude oil interfacial film
compressibility or incompressibility and
➢the presence of chemical additives.
 Thermodynamics of Emulsions

An emulsion does not invert

spontaneously except as some phase
inversion temperature that a
preferentially water soluble emulsifier
at low temperature may become
preferentially oil soluble at elevated
temperature
 Characteristic Physical Parameters

To minimize the time it takes to screen

additives, there is need to investigate the
use of characteristic physical parameters
which are easy to measure. Hence dielectric
constant is investigated.
 Thesis of Measure of Dielectric Constant

✓Dielectric constant of hydrocarbon (between 2 and

6) is quite different from that of water (78.5-80), The
dielectric constant of emulsion must be between the
two limits of oil and water depending on the activity
and nature of the emulsifier.
✓Thus dielectric constant measurements can define
hydrocarbon water mixtures when oil is the
continuous phase (Allen and Roberts, 1978).
✓Thus there must be some relationship between the
dielectric constants of emulsions and demulsifiers.
 Definition of Dielectric Constant

Frank (1967) defined dielectric constant, K, of a

sample as the ratio of the capacitance of the
sample to the capacitance of vacuum (or air).

K = capacitance of material
Capacitance of vacuum (or air)
 Capacitance

➢Capacitance is a measure of the ability of a

substance to store electrical energy.
➢Thus, substances with low capacitance are called
insulators while substances with high capacitance
are conductors.
➢Non-polar substances such as crude oil have low
dielectric constants than polar substances such as
water.
➢Vacuum is arbitrarily given a dielectric constant
of one.
 Effect of Hydrogen Ions on Capacitance

➢Arthur (1973) explained that hydrogen ion neutralizes the negative charges on
the negative plate of a capacitance meter and thus allows more charges to be
stored on the negative plate.
➢That is why the K – value of water is high since it has enough hydrogen ions to
neutralize the negative charges on the negative plate.
➢On the other hand crude oil is made up of hydrogen and carbon atoms that
have little difference in electronegativity and so do not neutralize charges and so
have no room to store more charges. Hence low K-value.
 Experiments

1. Two sets of experiments were performed in

two successive years to investigate the use
of dielectric constant as a screening
parameter for demulsifiers.
2. In each case representative samples of
water-in-oil emulsions were obtained from
wellheads of different oilfields in Nigeria.
3. Samples were obtained upstream of
chemical injection facilities and are
therefore considered demulsifier-free.
 Experiments (Cont.)

4. Each emulsion sample was allowed to stand

at atmospheric condition for at least four days
before the laboratory study. This allows time for
degassing and enables free water and sediments to
settle out. Commercial demulsifiers used in this
study were obtained from service companies. The
chemical compositions of these demulsifiers were
not known.
 Experiments (Cont.)
5. Dielectric constants of the demulsifiers,
oilfield emulsions and the resolved oil and
water were measured with capacitance
meter. Then the meter is switched on and
the dielectric constant of the sample is read
off.

6. The specific gravity of the emulsion was

measured by means of hydrometer at
room temperature (25oC). The pH was
monitored with either a pH meter or pH
paper.
 Experiments (Cont.)

7. Basic Sediment and Water (BS&W)

of the emulsion was measured
according to API standard
procedure using an electric
centrifuge
 Phase 1

➢After the BS&W test, 5 graduated test tubes were each filled with 20cc of
emulsion sample A1 and labelled after the 5 demulsifiers.
➢A drop (0.008cc) of each of the 5 demulsifiers was added to the corresponding
test tubes.
➢After standing for 90 minutes at room temperature, the water that dropped off
was read off in each test tube and a syringe was used to collect some of the
remaining emulsion for dielectric measurement.
➢This quantity was carefully put back into the test tube before the second set of
drops were added.
➢The experiment was repeated for three, four, five, six and seven successive
drops.
 Calculation of Efficiency Resolution
A given emulsion sample contains 30% water and 20cc of the emulsion was taken, it
means that the volume of water, VT, in the test tube is 20 x 0.3 = 6cc. If 2cc of water
drops out, Vd, after the first drop of demulsifier, then the efficiency, E, after the first
drop is given by

E = Vd x 100%
VT
As an example, E after first drop is

E = 2 x 100% = 33.33%
6
The experiment was repeated for emulsion samples A2 to A8. The results of these
experiments are presented in Table 5.
 Phase 2

1. Another set of experiments were

conducted on 4 different w/o emulsion
samples using 4 different commercial
demulsifiers.
2. The dielectric constants of demulsifiers
and emulsions are given in Table 6 while
the results of dielectric measurements of
demulsifier treated emulsion samples
are presented in Table 7.
 Discussion of results

➢Generally it was observed that w/o emulsion is

resolved if the dielectric constant, k, of the demulsifier
is lower than that of the emulsion.
➢The lower the k value of the demulsifier (close to
that of oil K = 2) the more efficient is the demulsifier.
➢On addition of the demulsifier, the k value of the
emulsion gradually decreased with consequent
increase in emulsion resolution efficiency until an
optimum efficiency was attained at a k value of
emulsion approximately equal to that of the
demulsifier.
 Discussion of results (Cont.)

➢Beyond this critical or equilibrium k-value, there

was a reversal of trend of k-value (increasing) with
decrease in emulsion resolution efficiency.
➢Low HLB emulsifiers have greater affinity for oil
and so stabilize w/o emulsion. Thus high HLB
demulsifiers are required to destabilize them.
➢High HLB emulsifiers have greater affinity for water
and so stabilize o/w emulsion. These require low
HLB demulsifiers to destabilize them.
 HLB by Solubility Characteristics in Water

Solubility Characteristics in Water HLB Range

No dispersability 1–4
Poor dispersion 3–6
Milky dispersion after vigorous agitation 6 – 8
Stable milky dispersion 8 – 10
Translucent to clear dispersion 10 – 13
Clear solution 13+
Required HLB Value for Emulsifying Oils in Water
Compounds HLB
Beeswax 9
Benzene 15
Cartontetrachloride 15
Castor oil 14
Chlorinated paraffin 12-14
Chlorobenzene 13
Cocoa butter 6
Corn oil 8
Cotton seed oil 6
Cyclohexane -15
Kerosene 12
Lard 5
Mineral oil, aromatic 12
Mineral, paraffinic 10
Mineral spirits 14
Nitrobenzene 13
Palm oil 7
Paraffin wax 10
Soya bean oil 6
Toluene 15
Xylene 14
 Dielectric Constants of some Simple
Diatomic and Polyatomic Materials
Material Dielectric Constant At Room temperature
(25oC)
Pentane 1.84
Carbontetrachloride 2.24
Carbondesulplude 2.64
Phenol 9.74
1-Butanol 19.1
Acetic anhydride 20.7
Chloroform 4.31
1,1 Dichloroethane 100.00
benzylalohol 13.1
Bromoethane 9.39
Ethanol 24.30
Water 78.5
Formamide 109.5
Oil 2-2.2
Glass 6-10
Acetone 21.4
Castor oil 4.67
Petroleum oil 2.00
Dimethylsulfoxide 46.6
Dielectric Constants of Demulsifiers
Water-in-oil (w/o) Emulsion Samples (Phase I)

Demulsifier Dielectric Constant, KD

AA 15.9
AB 3.95
AC 65.0
AD 11.99
AE 109.0
Dielectric Constants of Demulsifiers
Water-in-oil (w/o) Emulsion Samples (Phase I)

W/O Emulsion Dielectric S.G. pH

Constant, Kem
A1 45.0 0.80 7.5
A2 25.0 0.94 7.0
A3 15.5 0.81 7.0
A4 16.5 0.90 8.0
A5 10.0 0.94 8.0
A6 4.0 0.90 6.0
A7 53.0 0.69 5.0
A8 50.0 0.63 8.5
 Summary of Results of Emulsion Resolution
• Emulsion Sample A1, Kem = 45
Demulsi KD ?K (kem- Em Krw Kro N pH at Em
fier kD
AA 15.9 29.10 80.0 70 15.0 4 8
AB 3.95 41.05 83.0 64.3 5.0 6 7
AC 65 -20.00 -- -- 43 6 9
AD 12 23.00 75 65 13.9 4 8.9
AE 109 -64.00 -- -- -- 8.5
(ii) Emulsion Sample A2, Kem = 25
AA 15.9 9.10 80 54 15 4 8
AB 3.95 21.05 80 70 4 4 7.5
AC 65 -40.00 -- -- 25 6 7.0
AD 12 13.00 60 72 13.9 4 8.0
AE 109 -84.00 -- -- 35 5 7.5
(iii) Emulsion Sample A3, Kem = 15.5
AA 15.9 -0.40 3 40 15 3 8.5
AB 3.95 11.55 60 75 3.99 6 7.5
AC 65 -49.50 -- -- 15.5 6 7.0
AD 12 3.50 60 69 12 4 8.5
AE 109 -93.50 -- -- 18 6 8.9
(iv) emulsion Sample A4, Kem = 16.5
AA 15.9 0.60 70 45 15.8 4 8.5
AB 3.95 12.55 35 71 4.5 7 7.0
AC 65 -48.50 -- -- 16.5 6 8.0
AD 12 4.50 80 71 19 5 8.6
AE 109 -92.50 -- -- 13 6 9.0
Summary of Results of Emulsion Resolution (Cont.)
• Emulsion Sample A5, Kem = 10
Demulsi KD ?K (kem- Em Krw Kro N pH at Em
fier kD
AA 15.9 -5.90 ? 40 16 6 8.5
AB 3.95 6.05 8 76 9 3 9.0
AC 65 -55.0 -- -- 10 6 8.0
AD 12 -2.0 ? 23 12.0 4 8.6
AE 109 -99.0 -- -- 13 6 9.0
*Very small
(vi) Emulsion Sample A6, Kem = 4
AA 15.9 -15.5 2 21.1 4 4 6.5
AB 3.95 0.05 70 77 4 4 8.0
AC 65 -61.00 -- -- 4 6 6.0
AD 12 -8.0 30 23 2.0 4 6.5
AE 109 -105.0 -- -- 7.0 6 7.5
(vii) Emulsion Sample A7, Kem = 53
AA 15.9 37.10 81 76.1 20 6* 6.0
AB 3.95 49.05 30 72 23 5* 7.0
AC 65 -12.00 10 -- 5.8 4 5.9
AD 12 41.00 60 70 5 6* 6.0
AE 105 -56.00 20 -- 40 6 7.5
*Better at higher drops
(viii) Emulsion Sample A8, Kem = 50
AA 15.9 34.10 80 69 15.9 5 8.9
AB 3.95 46.05 60 55 3.95 3 8.5
AC 65 -15.0 -- -- 50 6 8.5
AD 12 38.0 25 69 10 6 9.0
AE 109 -59.0 0 -- 9.0 6 7.0
 Dielectric Constants of Demulsifiers and w/o
Emulsion Samples (Phase II)

Dimulsifier KD
BA 5.4
BB 12.8
BC 40
BD 28

W/o Emulsion Kem S.G. pH

B1 50 0.95 8.5
B2 4.7 0.82 6.0
B3 35 0.84 7.5
B4 4.5 0.87 6.0
Summary of Results of Emulsion Resolution
Using Dielectric Constant Measurement (Phase II)
• Emulsion sample B1, Kem = 50
Demulsifie KD ?K Em Krw Kro N
r (kem-kD
BA 5.4 44.6 91 68 11 6
BB 12.8 37.2 88 65 14 4
BC 40.0 10.0 83 60 44 4
BD 28.0 22.0 60.5 64 30 5
(ii) Emulsion Sample B2, Kem = 4.7
BA 5.4 -0.7 0.0 -- --
BB 12.8 -0.81 0.0 -- --
BC 40.0 -35.3 0.0 -- --
BD 28.0 -23.3 0.0 -- --
(iii) Emulsion Sample B3, Kem = 35
BA 5.4 29.6 90 60 13.5 4
BB 12.8 22.2 89 50 13 7
BC 40.0 -5.0 11 -- 36 6
BD 28.0 7.0 95.5 70 27 6
(iv) Emulsion Sample B4, Kem = 4.5
BA 5.4 -.09 2.4 -- -- --
BB 12.8 -8.3 0 -- -- --
BC 40.0 -35.5 0 -- -- --
BD 28.0 -23.5 0 -- -- --
Recommended Procedure for Screening, Ranking and
Selection of Demulsifiers
Stage Consideration(s) Reason
Primary • Measure Kem, KD at room
temperature •The higher the positive
• Calculate ΔK=Kem-KD difference the better but
not absolute indicator of
efficacy.

Secondary • Determine optimum Efficiency, Em •The higher the better

• The number of drops to reach Em, N •The lower the better due to
cost considerations
• Determine Krw and Kro •The higher the Krw close to
K of water the better.
Alternatively the lower the
Kro close to pure oil the
better.

Tertiary • pH , the less Acidic, the higher the pH Risk to men and material
of the oil the better. handling acidic demulsifier.
May damage refinery
• The less significant the change of pH catalysts and accelerate
during treatment, the better. corrosion problems.

• Cost considerations from volumetric The lower the cost the better.
requirements (Number of drops, N)

• Others to be considered later would

be availability, shelf-life of
demulsifier, etc.
 Screening, Ranking and Selection of demulsifiers
Based on Dielectric Constant (Phase I)

Stage Consideration(s) Ranking of demulsifiers in Decreasing Performance in

Emulsion Samples

A1 A2 A3 A4 A5 A6 A7 A8

Primary • Coose if Δk is positive AB AB AB AB AB AB AB AB

• Magnitude of Δk (the higher, AD AD AD AD AD AD

the better) AA AA AA AA AA

Secondary • Optimum Efficiency Em AB AB

AA AA AD AD AB AB AA AA
AD AD AB AA AD AB
• No of drops to reach Em, N AA
AD AB
• Higher Krw’ lower Kro AB AA
Tertiary AD
and Final Lower Acidity at Em AB
Selection AD
• Cost of chemical AA AB AB AD AB AB AA AA
Screening, Ranking and Selection of Demulsifiers
Based on Dielectric constant (Phase II)

Stage Consideration(s)

B1 B2 B3 B4

Primary • Choose if Δk is positive BA

BB -- BA
• Magnitude of Δk (the higher BD BB --
the better) BC BD

• Em BA BD
BB -- BA BA
• N BC BB

• Krw, Kro

• pH BA
Or BD BA
• Cost of chemicals BB
 Conclusion

➢Based on this study, an electrostatic property – dielectric constant –can be

used to screen and rank demulsifiers to match oilfield water-in-oil emulsions.
➢It supplements the commonly used bottle test.
➢A three-stage cost effective procedure is recommended for screening, ranking
and selection of demulsifiers.
➢Dielectric constant is easily measurable in the field and is time-saving.
➢Results of secondary screening are similar to those of bottle test.
➢As a screening and ranking criterion, results of dielectric constant
measurement are both qualitative and quantitative.
 Nomenclature
BS&W = Basic sediments and water, cc, percent
E = Emulsion resolution efficiency, percent
Em = Optimum efficiency, percent
HLB = Hydrophile-Lipophile Balance
K - Dielectric constant
KD = Dielectric constant of demulsifeir
Kem = Dielectric constant of emulsion
Kro = Dielectric constant of remaining emulsion – approximately K of resolved
oil t optimum efficiency.
Krw = Dielectric constant of resolved water
K = Difference in dielectric constant = Kem – KD

N = Optimum number of drops to reach Em

pH = Measure of acidity or basicity
S.G. = Specific gravity (water = 1.0)
Vd = Quantity of water in test tube, cc
VT = Total quantity of water from BS&W test.
 INTRODUCTION
Types of Oilfield Emulsions

Oil-in-Water (O/W)
Droplets of Crude oil dispersed in Water
Water is the continuous phase

Water-in-Oil (W/O)
Droplets of Water dispersed in crude oil
Crude is the continuous phase

Our main focus

 INTRODUCTION
Stability of W/O Emulsion depends on
1. Type of Emulsifier or Stabilizer
2. Viscosity of the continuous phase
3. Gravity contrast of the two Liquids
4. Percent Water/Characteristics, TDS
5. Age of Emulsion
6. Level of Agitation and flow
turbulence
 INTRODUCTION
STABILIZING AGENTS
W/O Emulsion Stabilizers
•Substances that make W/O Emulsion Stable
•Two main classes of stabilizers
 finely–divided solids such  Crude oil surface–active
as agents or surfactants
• drilling mud (colloidal
clay) • naphthenic acids
• produced sand • injected inhibitors for
corrosion or wax
• iron sulphide from pipe deposition control.
corrosion
• precipitated minerals
due to scale formation
• asphaltenes in the crude
 Theory of Emulsification
Chemically, stabilizers are surfactants partially soluble
in oil and water: Hydrophile-Lipophile Balance (HLB)

Electrically, induce electric charges on entrained particles

 Hydraulically, Surface Tension

 Emulsion Treatment

HANDLING TECHNIQUES

Treatment Techniques Preventive Techniques

Combination Reduce Turbulence Down hole Production

Mechanical Thermal Chemical
of others Dehydration completion
technique
Electrical Reduce HBSW

Preventive engineering vs. Curative engineering

Proactive vs. Reactive

Principle: (prevention better than cure if cheaper)

Treatment of Emulsion
Industrial treatment uses following techniques:

 Gravity Settling (Tanks)

 Heating (Heater Treaters)

 Electrical dehydration (Chemelectrics)

 Chemical treatment (Demulsification)

 N o n-
C hemical
C hemical
51%
49%
 Chemical Treatment
 Chemical treatment most effective

 Widely used.
 Most complicated
 Chemicals used called Demulsifiers
 Demulsifiers
Demulsifiers are neutralizers of Emulsifying agents.
Typical Commercial Demulsifiers mixtures of several
components, which have various chemical structures
Some typical demulsifiers are proprietary mixtures of
compounds such as:

Esters (glycol esters) Sulfonates

Di-epoxides Polyesteramines
Urethanes Oxyalkylated phenols and
Resins polyamines
Glycols Alkanolamines
Theory of Demulsification
Demulsifier molecules occupy the empty spaces available for
adsorption in the Emulsion. (Penetration)

Due to the high interfacial activity of the demulsifier, the interfacial

tension gradient is reduced. reduce interfacial tension

This leads to a strong increase in the rate of film thinning

When the film thickness decreases below some critical value, the
film ruptures followed by

Flocculation (Attraction) and

Coalescence of droplets

Neutralize or reverse HLB + neutralize electric charges

 Problem of Selection
of Demulsifiers

Tedious Trial and Error Method of Screening and Ranking

Expensive and time consuming

Need to minimize time and resources in screening

Manual method prone to errors

Need for improvement/alternatives - Ranking

to characterize Emulsions
and Demulsifiers

Dielectric constant of a substance is ratio of capacitance of a pair of

parallel plates when dipped in the substance to the capacitance of the
parallel plates in air (or vacuum).

The value of Dielectric Constant could be read directly from meters e.g.
the Brookhaven B1-870 Dielectric Constant Meter

Dielectric Constant of
Water = 78.5 while that of
Oil = 2.2
HLB-Dielectric Constant
Relationships
Dielectric Constant (X) = Capacitance (Substance)
Capacitance (Air or vacuum) Frank(1967)

HLBem = 20*(1-SV)/AV Foster & Leslie(1979)

SV = Saponification Value, AV = Acid Value
SV=(b-a)*(N)*(56.1)/W
B= vol of HCL soln. for blank in ml, a=vol of HCL
soln. for sample in ml
N= molarity of HCL, W=sample weight in grams
AV (acid value) = (V)*(N)*(56.1) / W
V is the volume of NaOH solution required in ml
N is the molarity of the NaOH solution
W is the weight of sample in grams.

HLBem= 4.98848 – 0.22327 Xem Ajienka et al (1992)

AMA Ratio= HLBem/ Xd Ajienka-Mmaji-Airuehia (1992)

 Demulsifiers
SUMMARY OF RESULTS OF EMULSION RESOLUTION, SCREENING AND RANKING OF DEMULSIFIERS.
EMULSION SAMPLE R1: Xem = 24.3; HLBem = 2.2; BS & W = 30%; OPERATING TEMP = 25OC

SCREENING RANKING EMULSION BOTTLE TEST

Demul XD HLB Vd ΔXM ΔX ΔHL Rem AMA Ex Rem Em N Xr Xro Rem- Final
-sifier (ml (Xem- (Xem-XD B - RATIO (%) - (%) w ark Re-
D Xro) )
) HLBD- Ark ark Mark
HLBem

RA 12.8 9.6 3.4 12.3 11.5 7.4 4TH 0.171 93 4TH 56. 5 65 12 4TH Poor
6
RB 66.5 2.6 - 9.3 -42.2 0.4 F 0.033 - F - 6 - 15 F Very
poor
RC 5.40 15.4 4.8 19.3 18.9 13.2 2ND 0.407 98 2ND 80 4 70 5 2ND Very
good
RD 4.10 17.6 4.8 20.3 20.2 15.4 1ST 0.537 99.5 1ST 80 3 75 4 1ST Very
good
RE 6.60 12.6 4.2 18.3 17.7 10.4 3RD 0.333 97 3RD 70 4 70 6 3RD Good
RF 75.4 1.6 - 7.8 -51.1 -0.6 F 0.029 - F - 6 - 16. F Very
5 poor
RG 18.3 3.2 2.4 11.3 6.0 1 5TH 0.120 53 5TH 40 6 45 13 5TH poor
 Flowchart
*Measure Xem, HLBem, XD, HLBD
*Calculate ΔX, ΔHLB

1 screening
ΔX=Xem – XD

IS No
*ΔX = + ve STOP
*HLB = High or + ve
ΔHLB =HLBD - HLBem

CALCULATE
20
•AMA RATIO
(RANK) •Ex
•Xro or Xrw

30 SELECT
FINAL •Em very high
(RANKING) •N very low
•pH high, CE cost efficiency

SELECT
New Approach to Screening, Ranking and Selection of
Demulsifiers for Oilfield Emulsion Resolution
HLB vx X for Em uls ion

6
4

HLB
2
0
0 50 100 150
X, Die le ctric Cons tant

Em vs Ex

120
Em

70

20
40 60 80 100
Ex
PROGRAM DESCRIPTION

Functions:
•Viewing DB of
Demulsifier
•Go to Demulsifier
selection page
•End Program
FORM2- ACCESSING DEMULSIFIER DATABASE

Functions:
•Go to Demulsifier
selection page
•Viewing DB of
Demulsifier
•End Program
FORM3 – DATA ANALYSIS (DEMULSIFIER
SELECTION)

Functions:
•Predict HLBem
•Screen, Rank &
Select the best
Demulsifier.
•Access DB of
Demulsifier
•Generate report
APPLICATION-DEMULSISCREENER
(SOFTWARE DEMONSTRATION)

CLICK TO START DEMULSISCREENER

 RESULTS
THE RESULTS GOTTEN ARE COMPARABLE WITH THOSE GOTTEN FROM
BOTTLE TEST(EMULSION SAMPLE R1: Xem = 24.3; HLBem = 2.2; BS & W = 30%)

SCREENING RANKING EMULSION BOTTLE TEST

Demulsifier Xd HLBd ∆X ∆HLB AMA ratio Rank Em (%) N Xrw Xro Remark Final
Remark

DA 12.80 9.6 11.5 7.4 0.171 4th 56.6 5 65 12 4TH Poor

DB 66.50 2.6 -42.2 0.4 0.0330 6th - 6 - 15 F V.poor

DC 5.40 15.4 18.9 13.2 0.4074 2nd 80 4 70 5 2ND V.good

DD 4.10 17.6 20.2 15.4 0.5365 1st 80 3 75 4 1ST V.good

DE 6.60 12.6 17.7 10.4 0.3333 3rd 70 4 70 6 3RD Good

DF 75.40 1.6 -51.1 -0.6 0.0917 7th - 6 - 16.5 F V.poor

DG 18.30 3.2 6 1 0.1202 5th 40 6 45 13 5TH poor

 RESULTS(2)
THE RESULTS GOTTEN ARE COMPARABLE WITH THOSE GOTTEN FROM
BOTTLE TEST.(EMULSION SAMPLE R2: Xem = 6.2; HLBem = 4.6; BS & W = 25%)

SCREENING RANKING EMULSION BOTTLE TEST

Demulsifier XD HLBD ∆X ∆HLB AMA ratio Rank Em (%) N Xrw Xro Rem-ark Final
Remark

DA 12.80 9.6 -6.6 5.0 0.359 4TH 4 5 24 5 F Poor

DB 66.50 2.6 -60.3 -2.0 0.069 6TH - 6 - 6 F Poor

DC 5.40 15.4 0.8 10.8 0.851 2ND 68 4 50 5 2ND Good

DD 4.10 17.6 2.1 13.0 1.121 1ST 72 3 76 3.2 1ST V. good

DE 6.60 12.6 -0.4 8.0 0.697 3RD 30 5 25 4 F Poor

DF 75.40 1.6 -69.2 -3.0 0.061 7TH - 6 - 6 F Poor

DG 18.30 3.2 -12.1 -1.4 0.251 5TH 2 5 15 5 F Poor

 Experimental Data (Opara, 2003)

EMULSION SAMPLE Dielectric Constant Of BS & W (%)

Emulsion (Xem )
R1 24.3 30
R2 6.2 25
R3 16.0 26
R4 9.1 15
R5 6.7 20
R6 8.3 20
R7 51.0 35
R8 12.23 10
R9 76.50 25
R10 12.82 30
Plot of Xem vs. BS&W

100
80
60
Xem 40
20
0
0 20 40 60 80 100
BS&W(%)
Measurement range for capacitance
and inductance sensors
Inductance sensor
80

dielectric constant of
70

oil/water mixture
60
50
40 Capacitance sensor
30 Transition zone
20
10
0
0 10 20 30 40 50 60 70 80 90 100

% water in oil
RELATIONSHIP BETWEEN DIELECTRIC
CONSTANT AND BS&W ( BASE CURVE)

0.0359bsw
80 X = 2.2e

dielectric constant of
oil/water mixture(X)
70
60
50
40
30
20
10
0
0 10 20 30 40 50 60 70 80 90 100

% water in oil(bsw)
STABILIZER EFFECT ON
EMULSION
80

oil/water mixture(Xem)
dielectric constant of
70
60
X = 2.2e0.0359bsw
50
40
30
20
10
0
0 10 20 30 40 50 60 70 80 90 100

% water in oil(bsw)
 Assumptions
GAS FRACTION

That our emulsions are monophasic (no gas phase).

If we are to consider the gas fractions present in the

emulsion, then the base curve would no longer hold.

There is a relationship between dielectric constant of

Emulsion and BS&W with different gas fractions
 Assumptions
PRESSURE

The effectiveness of the demulsifiers are considered under

atmospheric pressures.

At high pressures the effectiveness of the demulsifiers

would likely be reduced.

That dielectric constant of a fluid increases with

increasing pressure.
 Assumptions
TEMPERATURE

the temperatures of the emulsions and demulsifiers are at

ambient temperatures of about 25oC.

High temperatures are likely to increase the effectiveness

of the demulsifier

emulsion stability decreases with increasing temperature

dielectric constant of a material decreases with increasing

temperature.
Effect of Gas Fractions

80

oil/water mixture(Xem)
dielectric constant of
70
Base line
60
X = 2.2e0.0359bsw
50
Increasing gas
40 f raction
30
20
10
0
0 10 20 30 40 50 60 70 80 90 100

% water in oil(bsw)
Characterization of Stabilizers:
Assumptions
Only a particular stabilizer is responsible for our emulsion
stability.

In reality we may have more than one stabilizing agent

being responsible for a particular stable emulsion.

Moreno (1998) proposed that the dielectric constant of a

mixture is an addition of the dielectric constants of the
components that make the mixture.
Characterization of Stabilizers:
Assumptions
X (mixture) =[%A*X(A) + %B*X(B) + …+ % Z*X(Z)] / 100

since it is difficult to determine the proportion of stabilizer in the emulsion

we would assume that it is unity (one).

Hence simplifying the equation to:

X (mixture)=X (stabilizer) + X (water/oil emulsion)

Stabilizer Effect On Dielectric Constant of
Emulsion (Dielectric jump)

80

oil/water mixture(Xem)
dielectric constant of
70
60
X = 2.2e0.0359bsw
50 B
40
30
20
10 A
0
0 10 20 30 40 50 60 70 80 90 100

% water in oil(bsw)
Characterization of Emulsion
Stabilizer Equation
The base curve equation is given as:

X = 2.2*e0.0359*bsw

And, Xem = X + Xs

Therefore, Xs = Xem – X

Hence, Xs = Xem – 2.2*e0.0359*bsw

Stabilizer predicted
Characterization of Emulsion
Stabilizer cont’d
If the dielectric constant and BS&W of the emulsion are known.

The dielectric constant of the stabilizer (Xs) could be calculated

Xs could then be used to match known dielectric constants of known

oilfield stabilizers.

This matching enables us to predict the probable stabilizer in the

emulsion.
Characterization of Emulsion
Stabilizer cont’d
For Example

Emulsion sample R2 (Xem=6.2 and BS&W=25%)

Calculated Xs=5.19

Hence stabilizing agent is SAND

Since known dielectric constant of sand is

between 3.0 and 5.3 Source – ASI Instrument Inc.
 DEMULSIFIER EFFECT ON
STABILIZED EMULSION
Using Emulsion sample R7 (Xem=51 and BSW=35%)

Demulsifiers Dielectric constant of Dielectric constant of

demulsifier ( XD ) resolved oil ( Xro )
RA 12.80 11.0 (high)
RB 66.50 Failed
RC 5.40 5.0
RD 4.10 4.0
RE 6.60 5.0
RF 75.40 Failed
RG 18.30 10.4 (high)
EFFECT OF DEMULSIFIER (RA) ON
EMULSION SAMPLE R7

80
70
60
A
50
40
x

30
20 B
Xd = 12.8
10
0
0 20 40 60 80 100
bsw
EFFECT OF DEMULSIFIER (RC) ON
EMULSION SAMPLE R7

80
70
60
A
50
40
x

30
20
B1
10
Xd = 5.4
0
0 20 40 60 80 100
bsw
EFFECT OF DEMULSIFIER (RD) ON
EMULSION SAMPLE R7

80
70
60
A
50
40
x

30
20
10 B2
Xd = 4.1
0
0 20 40 60 80 100
bsw
EFFECT OF DEMULSIFIER (RE) ON
EMULSION SAMPLE R7

80
70
60
A
50
40
x

30
20
B3
10
Xd = 6.6
0
0 20 40 60 80 100
bsw
EFFECT OF DEMULSIFIER (RG) ON
EMULSION SAMPLE R7

80
70
60
A
50
40
x

30
20
Xd = 18.3
B4

10
0
0 20 40 60 80 100
bsw
 DEMULSIFIER EFFECT ON
STABILIZED EMULSION
The Demulsifiers tend to draw down the dielectric jump induced by
the stabilizing agent back to the base curve.

Each Demulsifier brings down the dielectric jump to a value very

close to the dielectric constant of the Demulsifier.

Also the dielectric fall can not go below the base curve even if the
value of the dielectric constant of the demulsifier is below the base
curve at that point.

Demulsifiers with dielectric constants above the dielectric constant

of the emulsion would not have much effect on the emulsion.
 DEMULSIFIER EFFECT ON
STABILIZED EMULSION
Furthermore, you do not need to apply a Demulsifier with dielectric
constant below the base curve for a particular BSW, as it would
achieve about the same result with a Demulsifier that its dielectric
constant is on the base curve.

The quality of resolution of an emulsion depends on the dielectric

constant of the applied Demulsifier.

In other words to achieve an emulsion resolution of Xro = 4.5 a

Demulsifier with a dielectric constant of Xd = 4.5 or slightly less
could be applied on the emulsion.
 Characterization of Emulsion
Stabilizers

With Knowledge of stabilizer in emulsion, root cause of

emulsion stability addressed

Appropriate demulsifiers could be applied at short notice

Possibility of real time monitoring of emulsion stabilizers

using dielectric constant
 On Theory of Emulsification
and Demulsification
HLB vs Dielectric Permittivity

Assumption that high Hydrophile - Lipophile Balance

(HLB) demulsifiers are required to resolve oilfield water-in-
oil emulsions stabilized by low HLB emulsifiers investigated.

Results show that it is not a rule.

Assumption subject to condition that dielectric permittivity

of the demulsifier is lower than dielectric permittivity of
emulsion under treatment.
HLB vs. Dielectric Permittivity
Crossplot of delta HLB versus delta
Dielectric Permittivity

30
Not Treated despite
+ve HLB Completely treated
20

10
delta HLB
0
-15 -10 -5 0 5 10 15
-10
Not Treated
-20 Treated despite -ve HLB

-30
delta e
Emulsion Resolution Efficiency
vs. Dielectric Permittivity
Plot of Emulsion Resolution Efficiency
versus delta Dielectric Permittivity

100
90

Emulsion Resolution
80

Efficiency (%)
70
60 High Resolution
50
40
30
Poor Resolution
20
10
0
-15 -10 -5 0 5 10 15
delta Dielectric Permittivity
Emulsion Resolution Efficiency vs. Dosage,
Dielectric Permittivity and HLB

Effect of Dosage of Demulsifier

on E, e and HLB

100

80
No. of Drops
60 εem
40 E
HLBem(predicted)
20

0
1 2 3 4 5 6 7
Effect of Dosage on Dielectric
Permittivity and HLB

Effect of Dosage of Demulsifier on Dielectric

Permittivity and HLB

14
12
10
No. of Drops
8
εem
6
HLBem(predicted)
4
2
0
1 2 3 4 5 6 7
 Advances in Emulsion
Resolution Research
 New Approach to Selection of Demulsifiers

 Real Time Selection of Demulsifiers

 Understanding the Theory of Emulsification

and Demulsification

 Characterization of Emulsion Stabilizers

 Further Research
 Characterization of Emulsion Forming
Tendency of Formation Well Effluents
in the Niger Delta

 Deoiler Research

 Formulation of Demulsifiers from

Local Raw Materials
 CONCLUSIONS
 Better Understanding of the Nature
of Oilfield Emulsions

 Cost Effective Demulsifier Selection

 Real-time Application of New Technique

THANK YOU