Oil/water separation technologies
Where stable emulsions cannot be removed mechanically, the application of
demulsifiers, coagulants and flocculants accelerates the separation process
BERTHOLD OTZISK
Kurita Europe
E
mulsions can cause fouling
and under-deposit corro-
sion problems in
distillation columns, heat
exchangers and reboilers.
Commercial methods for
breaking emulsions include
settling, heating, distillation,
centrifuging, electrical treat-
ment, chemical treatment and
filtration. These separation
technologies can be used in
combination to secure opti-
mum results.
Emulsions can be classified
as oil-in-water and water-in-oil
types. The type of emulsion
can be determined by adding a
drop of emulsion into a beaker
containing water and oil. If the
emulsion is of the water-in-oil
type, the drop diffuses through
the oil but remains in water.
The oil-in-water emulsion
diffuses through the water, but
not through the oil. Both types
of emulsions can co-exist in
crude oil side by side.
Separation of water-in-oil
emulsions
In this type of emulsion, water
is the internal dispersed or
discontinuous phase, while oil
is the external or continuous
www.digitalrefining.com/article/1000798
phase. Separation by the differ-
ent gravity of the two phases is
a very slow process, but can be
accelerated by the assistance of
chemicals. The chemicals used
are termed demulsifiers, emul-
sion breakers or wetting
agents. These additives are
surfactants, which migrate to
the oil/water interface. They
adsorb on the oil films
surrounding water droplets
and break the oil films. Then,
water droplets aggregate to
form water drops large enough
to gravitationally separate
them from the oil. Non-ionic
surfactants having both lipo-
philic and hydrophilic
groups are mainly used as
demulsifiers.
Typical applications in refineries
Tank farm treatment
Crude oil, intermediates and
finished products are stored in
the tank farm. It is the first
facility in a refinery where free
water can be removed by
settling from the oil. Pumped
crude oil from the well
contains water in emulsified
and free states. A crude oil
emulsion consists of small
globules of water surrounded
by oil. Water is the internal
phase and oil is the external
phase, which can easily be
detected by microscope. With
the help of gravity, small water
droplets coalesce to form
bigger droplets. An adequate
residence time is essential for
separation into two phases.
The bigger droplets finally
settle down to be removed by
drainage.
Most of the time, emulsified
water cannot be separated
effectively by gravity settling
only, as the emulsion can sepa-
rate into three phases:
Oil on the top
Water at the bottom
Persistent emulsion in the
middle or below the water
layer.
To break such a persistent
emulsion, chemicals have to be
applied. A number of demulsi-
fiers are commercially available
with varying degrees of perfor-
mance and selectivity.
Generally, demulsifiers are
diluted with an organic solvent
and injected into crude oils.
The nature of the emulsion
changes from crude to crude,
which can influence the perfor-
mance of the emulsion breaker
PTQ Q2 2013 1
 programme. This EB-4113 showed the
necessitates the evalu- highest desalting and
ation of cost dehydration efficiency
effectiveness and for this crude oil.
performance in break- EB-4110 is an oil-
ing the emulsion. soluble demulsifier,
which is typically
Crude oil desalting injected into crude oil
Crude oil fed from the in front of the desalter
tank farm to the crude mixing valve. EB-4113
distillation unit still is a water-soluble
contains water, salts, demulsifier, which is
sludge and various Figure 1 Evaluation of demulsifiers typically injected into
kinds of impurities. desalter wash water.
This can cause corrosion, foul- water droplets entrained in the
ing, plugging and catalyst temporary emulsion. The water Separation of oil-in-water
degradation in the downstream droplets coalesce into bigger emulsions
refining units. The main droplets, which can settle by In aqueous systems, the hydro-
purpose of electrostatic desalt- gravity. Therefore, sufficient carbons generally carry a
ing is therefore to remove retention time in a desalter is negative charge at their
impurities, such as inorganic required for efficient water and surface. Often, they are steady
microparticles, suspended oil separation. A suitable dispersed into small droplets
solids and water-soluble demulsifier is commonly used because of their repellent
contaminants, together with to promote the separation of forces. A cationic charged long-
the water. water and oil. The desalted chain polymer neutralises the
The major variables and crude oil is continuously fed negatively charged oil droplets.
effects on the desalter opera- from the desalter vessel to the The repellent forces are weak-
tion are: atmospheric crude distillation ened and oil droplets are
Wash water mixing column. The desalter effluent brought together. This resolves
Wash water quality and rate water is discharged from the the emulsion of water and oil.
Desalting temperature desalter vessel to the wastewa- The emulsion-breaking process
Electric field ter treatment facility. involves three steps:
Retention time Figure 1 shows the labora- Agglomeration
Use of demulsifiers. tory evaluation of demulsifiers Creaming
Wash water is added in front in comparison with an Coalescence.
of the mixing valve to the untreated crude oil sample Figure 2 illustrates the physi-
crude oil to prepare a tempo- (blank). For the evaluation of a cal process of oil-in-water
rary emulsion. A key point of demulsifier, the crude oil was emulsion breaking.
desalting is an appropriate mixed with 4 wt% wash water Agglomeration is the associa-
mixing of crude oil with the and agitated with an electric tion of small dispersed phase
wash water to obtain a suffi- stirrer. This mixture was trans- droplets (clusters). Creaming is
cient desalting rate. Heating ferred into several centrifuge the concentration of the
lowers the viscosity of crude glasses. With the exception of dispersed phase. Coalescence is
oil. This promotes demulsifica- the blank sample, 10 ppm of the drainage of the continuous
tion and the formation of large different demulsifiers were phase. The oil droplets agglom-
water droplets from the emul- added into the centrifuge erate by forming bigger
sion. An electric field is glasses and thoroughly mixed droplets and clusters, and are
induced by AC or DC current again. After 24 hours, the water collected at the surface. The
in the oil/water mixture to content and salt content was addition of an emulsion
improve water coalescence. determined to find the best breaker additive helps to accel-
The electrical field imposes an performing demulsifier. In this erate the separation process.
electrical charge on the small case, Kurita EB-4110 and Kurita These types of emulsion

2 PTQ Q2 2013 www.digitalrefining.com/article/1000798

breakers are surface active
components, which destabilise
the dispersed phase.

Typical applications in refineries

and petrochemical plants Creaming
Agglomeration
Ethylene production
Ethylene is mainly produced by
steam cracking. This process
includes thermal cracking, cool-
ing, compression and
separation. Light liquid hydro- Emulsion
carbons (naphtha) and gases are
converted mainly into unsatu-
rated smaller molecules, which
are separated by compression
and distillation. The hot gases Coalescence Creaming and
leaving the cracking furnaces coalescence
are immediately quenched in
oil quench and water quench Figure 2 Oil-in-water emulsion breaking process
columns. The purpose of the
cooling is to prevent polymeri- breaker for quench water. In hydrocarbons from water
sation and the formation of this case, no demulsifier was within 10 minutes residence
unwanted byproducts. The applied in front of the oil/water time. In this case, the emulsion
collected quench water is sepa- separator. The separated water breaker added to bottle No. 3
rated from heavy hydrocarbons still contained hydrocarbons, showed the best performance.
in the oil/water separator. which were dispersed in the Within the defined time frame,
Often, the separated quench aqueous phase. It was not an impressive hydrocarbon
water still contains hydrocar- possible to remove these hydro- layer was formed, while other
bons, which are dispersed in carbons in the oil/water samples showed no effects or
the aqueous phase. separator. The target of the poor separation. The good
Demulsifiers are usually laboratory test was to select an results of the laboratory test
applied to improve the separa- emulsion breaker that signifi- were confirmed later in a field
tion of hydrocarbons from the cantly improves the removal of trial.
quench water. It is mandatory
to provide the correct amount
of chemical to avoid
overdosing of the demulsifier,
because at higher concentra-
tions demulsifiers have the
tendency to act as emulsifiers
instead of breaking the
emulsion, they form a more
stable emulsion with hydrocar-
bons. A simple beaker test is a
good tool to check how much
demulsifier is required for the
separation of hydrocarbons
and water.
Figure 3 shows the result of a
laboratory evaluation to find
the best performing emulsion Figure 3 Quench water from oil/water separator

www.digitalrefining.com/article/1000798 PTQ Q2 2013 3

 Wastewater treatment
Water is used intensively in
refineries and petrochemical
processes, and during its use it
becomes contaminated with
hydrocarbons, increasing the
biological (BOD) and chemical
oxygen demand (COD) of the
effluent water. Cooling water,
process effluents, rain water
and surface water are collected
at the wastewater plant
together with a very briny
effluent stream from the desalt-
ing process. Typical pollutants
are hydrogen sulphide, ammo-
nia, cyanides, metals and
suspended solids. Effective
waste treatment technologies
are required to comply with all
legal requirements. The waste-
water treatment methods are
generally classified into three
categories of mechanical, chem-
ical and biological treatments,
and a wastewater plant is typi-
cally designed in three steps:
Mechanical separation
Chemical and biological
treatment
Filtration and polishing.
The main purpose of the
primary treatment is the sepa-
ration of oil and water. The
removal of oil is a very impor-
tant step to reduce the loading
to the downstream treatment
processes, because high oil
levels are toxic for the microor-
ganisms used in biological
treatment. The wastewater
typically contains oil in water
emulsions, with oil dispersed
4 PTQ Q2 2013
in the continuous water phase.
Common primary treatment
units are:
API oil/water separator
Corrugated plate interceptor
(CPI)
Dissolved air flotation (DAF)
Induced air flotation (IAF).
The function of an API oil/
water separator is based on the
difference in specific gravity of
oil and water. Suspended
heavy particles settle to the
bottom of the separator to be
scraped by a rake into the
sludge pit, which is discharged
continuously. The oil rises to
the top of the separator. The
wastewater accumulates as a
middle layer between the
settled solids and the oil phase.
It can be sent to a flotation unit
for further treatment.
Substances such as oil or parti-
cles can be separated from
water by flotation. Mechanical
flotation and dissolved air
flotation are applied to increase
the flotating velocity of parti-
cles. Fine air bubbles are
generated in water. The
upward flow of the bubbles
and the adhesion of bubbles
with particles improves the
efficiency of the flotation. The
floating oil is skimmed contin-
uously to be pumped into the
slop oil system.
Conclusions
Oil/water emulsions appear in
many areas of refineries and
petrochemical plants, and can
cause operational problems as
well as infringement of envi-
ronmental regulations. There is
a variety of separation equip-
ment available on the market
to separate the oil phase from
the water phase. In such cases,
where stable emulsions are
formed that cannot be removed
mechanically, the application
of demulsifiers, coagulants and
flocculants accelerates the sepa-
ration process and improves
mechanical performance. This
helps to fulfil legal require-
ments, reduces corrosion and
fouling risks, and results in
reduced maintenance costs and
higher equipment availability.
Further reading
1 Kurita Handbook of Water Treatment,
2nd English Ed, Kurita Water Industries
Ltd, Japan, 1999.
2 Ullmanns Encyclopedia of Industrial
Chemistry The Ultimate Reference,
Release 2012, 8th Ed, Wiley Online
Library, Wiley-VCH.
3 Hartinger L, Handbuch der Abwasser-
und Recyclingtechnik, 2nd Auflage, 1991,
Hanser, Germany.
Berthold Otzisk is a Consulting Engineer
in the Technical Department of Kurita
Europe GmbH, Viersen, Germany, where
he focuses on refinery and petrochemical
applications.
Email: otzisk@kurita.de
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