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

mulsions can cause fouling and

under-deposit corrosion problems in distillation columns,
heat exchangers and reboilers.
Commercial methods for breaking
emulsions include settling, heating,
distillation, centrifuging, electrical
treatment, chemical treatment and
filtration. These separation technologies can be used in combination to
secure optimum 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 phase. Separation by
the different 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, emulsion
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
lipophilic
and
hydrophilic

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groups are
demulsifiers.

mainly

used

as

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 exter-

The nature of the

emulsion changes
from crude to crude,
which can influence
the performance of
the emulsion breaker
programme
nal 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 separate into
three phases:
Oil on the top

Water

at the bottom
emulsion
in
the
middle or below the water layer.
To break such a persistent emulsion, chemicals have to be applied.
A number of demulsifiers are
commercially available with varying degrees of performance 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 performance of the
emulsion breaker programme. This
necessitates the evaluation of cost
effectiveness and performance in
breaking the emulsion.

Persistent

Crude oil desalting

Crude oil fed from the tank farm to

the crude distillation unit still
contains water, salts, sludge and
various kinds of impurities. This
can cause corrosion, fouling, plugging and catalyst degradation in
the downstream refining units. The
main purpose of electrostatic
desalting is therefore to remove
impurities, such as inorganic
microparticles, suspended solids
and water-soluble contaminants,
together with the water.
The major variables and effects
on the desalter operation are:
Wash water mixing
Wash water quality and rate
Desalting temperature
Electric field
Retention time
Use of demulsifiers.
Wash water is added in front of
the mixing valve to the crude oil to
prepare a temporary emulsion. A
key point of desalting is an appropriate mixing of crude oil with the

PTQ Q2 2013 87

wash water to obtain a

sufficient desalting rate.
Heating lowers the viscosity of crude oil. This
promotes demulsification
and the formation of large
water droplets from the
emulsion. An electric field
is induced by AC or DC
current in the oil/water
mixture to improve water
coalescence. The electrical
field imposes an electrical Figure 1 Evaluation of demulsifiers
charge on the small water
droplets entrained in the temporary glasses. With the exception of the
emulsion. The water droplets blank sample, 10 ppm of different
coalesce into bigger droplets, which demulsifiers were added into the
can settle by gravity. Therefore, centrifuge glasses and thoroughly
sufficient retention time in a mixed again. After 24 hours, the
desalter is required for efficient water content and salt content was
water and oil separation. A suitable determined to find the best
demulsifier is commonly used to performing demulsifier. In this
promote the separation of water case, Kurita EB-4110 and Kurita
and oil. The desalted crude oil is EB-4113 showed the highest desaltcontinuously fed from the desalter ing and dehydration efficiency for
vessel to the atmospheric crude this crude oil. EB-4110 is an oildistillation column. The desalter soluble demulsifier, which is typieffluent water is discharged from cally injected into crude oil in front
the desalter vessel to the wastewa- of the desalter mixing valve.
ter treatment facility.
EB-4113 is a water-soluble demulsiFigure 1 shows the laboratory fier, which is typically injected into
evaluation of demulsifiers in desalter wash water.
comparison with an untreated
crude oil sample (blank). For the Separation of oil-in-water emulsions
evaluation of a demulsifier, the In aqueous systems, the hydrocarcrude oil was mixed with 4 wt% bons generally carry a negative
wash water and agitated with an charge at their surface. Often, they
electric stirrer. This mixture was are steady dispersed into small
transferred into several centrifuge droplets because of their repellent

Agglomeration

Creaming

Coalescence

Creaming and
coalescence

Emulsion

Figure 2 Oil-in-water emulsion breaking process

88 PTQ Q2 2013

forces.
A
cationic
charged long-chain polymer
neutralises
the
negatively charged oil
droplets. The repellent
forces are weakened and
oil droplets are brought
together. This resolves
the emulsion of water
and oil. The emulsion-breaking
process
involves three steps:
Agglomeration
Creaming
Coalescence.
Figure 2 illustrates the physical
process of oil-in-water emulsion
breaking. Agglomeration is the
association of small dispersed
phase droplets (clusters). Creaming
is the concentration of the dispersed
phase. Coalescence is the drainage
of the continuous phase. The oil
droplets agglomerate by forming
bigger droplets and clusters, and
are collected at the surface. The
addition of an emulsion breaker
additive helps to accelerate the
separation process. These types of
emulsion breakers are surface
active components, which destabilise the dispersed phase.

Typical applications in refineries and

petrochemical plants
Ethylene production

Ethylene is mainly produced by

steam cracking. This process
includes thermal cracking, cooling,
compression and separation. Light
liquid hydrocarbons (naphtha) and
gases are converted mainly into
unsaturated smaller molecules,
which are separated by compression and distillation. The hot gases
leaving the cracking furnaces are
immediately quenched in oil
quench and water quench columns.
The purpose of the cooling is to
prevent polymerisation and the
formation of unwanted byproducts.
The collected quench water is separated from heavy hydrocarbons in
the oil/water separator. Often, the
separated quench water still
contains hydrocarbons, which are
dispersed in the aqueous phase.
Demulsifiers are usually applied
to improve the separation of hydrocarbons from the quench water. It
is mandatory to provide the correct

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amount of chemical to avoid

overdosing of the demulsifier,
because at higher concentrations
demulsifiers have the tendency to
act as emulsifiers instead of
breaking the emulsion, they form a
more stable emulsion with hydrocarbons. 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 breaker
for quench water. In this case, no
demulsifier was applied in front of
the oil/water separator. The separated
water
still
contained
hydrocarbons, which were dispersed
in the aqueous phase. It was not
possible to remove these hydrocarbons in the oil/water separator. The
target of the laboratory test was to
select an emulsion breaker that
significantly improves the removal
of hydrocarbons from water within
10 minutes residence time. In this
case, the emulsion breaker added to
bottle No. 3 showed the best performance. Within the defined time
frame, an impressive hydrocarbon
layer was formed, while other
samples showed no effects or poor
separation. The good results of the
laboratory test were confirmed later
in a field trial.

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
desalting process. Typical pollutants are hydrogen sulphide,
ammonia, cyanides, metals and
suspended solids. Effective waste
treatment technologies are required
to comply with all legal requirements. The wastewater treatment
methods are generally classified
into three categories of mechanical,
chemical and biological treatments,
and a wastewater plant is typically
designed in three steps:

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Figure 3 Quench water from oil/water separator

Mechanical

separation
and biological treatment
Filtration and polishing.
The main purpose of the primary
treatment is the separation of oil
and water. The removal of oil is a
very important step to reduce the
loading to the downstream treatment processes, because high oil
levels are toxic for the microorganisms used in biological treatment.
The wastewater typically contains
oil in water emulsions, with oil
dispersed 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 particles can be separated
from water by flotation. Mechanical
flotation and dissolved air flotation
are applied to increase the flotating
velocity of particles. Fine air
bubbles are generated in water. The
upward flow of the bubbles and the
adhesion of bubbles with particles
Chemical

improves the efficiency of the flotation. The floating oil is skimmed

continuously 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 environmental
regulations. There is a variety of
separation equipment 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 separation
process and improves mechanical
performance. This helps to fulfil
legal requirements, 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

PTQ Q2 2013 89