OILFIELD CHEMICALS
TRAINING MANUAL
PART2 )
2. EMULSION BREAKING
e 2.1 Problem
The most important objective of any oil production facility is the separation of water and
other foreign materials from the produced crude. The breaking of these “crude oil and
water emulsions” constitutes one of the more challenging problems in today’s oil
producing industry,
During the productive life of an oil or gas well, a stage is reached when water will be co:
produced in unacceptable quantities. This water coexists with the hydrocarbons in the
reservoir and gradually infiltrates into the hydrocarbon bearing region of the formation.
Eventually water becomes part of the production from the wells regardless of the method
of recovery.
Figure 1 shows a simplified view of how water may be produced. In the early life of the
producing field some wells that are drilled close to the oil/water contact level will begin to
produce water. Other wells drilled higher in the reservoir will produce dry oil. Later, as
the oil in the reservoir becomes depleted and the water expands upward, the oil-water
interface level rises until the wells higher in the reservoir begin to produce water. In some
‘ cases it is possible to exclude some or most of the water by plugging back the lower part
of the wellbore with cement and perforating an interval higher up in the formation. This
can at least delay water encroachment for a time.
Secondary or tertiary recovery methods are another cause of water encroachment. These
recovery methods are employed to increase the amount of oil recovered from the
reservoir, and they involve many different techniques. A number of these methods require
the injection of water or steam into the reservoir, and of course, the water is often
produced again with the oil
April 15, 1997 ‘Naleo/Exxon Energy Chemicals, LP.Emulsion Breaking _6
2.23.4 Age of Emulsion
Crude oil emulsions are systems that are not in stable equilibrium. According to the laws
} of thermodynamics, such systems change continually in an effort to attain equilibrium. As
2 result, emulsions increase in stability with age, which generally increases their resistance
to dehydration.
2.3 Theories of Demulsification .
There are many theories that have been advanced regarding the problem of resolving crude
oil emulsions. Unfortunately, these are as diverse as the emulsions they concern and no
one theory is equally applicable in all emulsions.
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2.3.1 Reverse Phase ~ vent wt 0g
In some cases, the breaking of emulsions has been based on the theory that the addition of
a reagent which would produce an oil-in-water emulsion will break a water-in-oil emulsion
by attempting to reverse the phases; and that in so acting, the intermediate condition of
complete demulsification will be accomplished. Though this may sometimes be true, it is
not always the case.
2.3.2. Rigid Film
There is one school of thought that the emulsion breaking reagent may have the action of
making the interfacial film rigid, or to convert it from a plastic, somewhat disterisible
envelope, to a glass-like one which has a relatively low coefficient of expansion. When the
enclosed water is expanded by heating, the envelope is shattered and the emulsion is
broken, To extend this suggestion and assume that the reagent has not only the power of
rigidifying the film but actually of contracting it slightly, is to supply an explanation of the
efficacy of such reagents in the absence of heat,
23.3 pH
Other schools of thought postulate that the emulsifier is rendered inactive by the addition
of the demulsifier through neutralization, change in pH or loss of solubility.
¢ 2.3.4 Electronic Charge
Still others believe that the emulsifying agents are polar bodies and function because of
their electronic charges, and any disturbance of these charges by electron carrying
molecules, will result in breaking the emulsion,
2.3.5 Temperature
Another possible explanation of the great effect of small temperature increases in some
cases is that such added heat is sufficient to cause a change of state in the film, ie
converts it from a solid to a liquid and thereby affects its stability greatly.
effects of reagents in thé'absence of added heat have been asserted to be de
" their power to cause'such a change of state in the substance ‘comprising the
dissolving it from the interface
‘April 15, 1997 Naleo/Exxon Energy Chemicals, LP.Emulsion Breaking _7
2.3.6 Surface Tension
: The theory that petroleum emulsion breaking is caused by a reduction in surface tension is
} Probably the most common. This phenomenon is often referred to without any suggestion
as to what constituent is having its surface tension lowered. It is likewise generally
predicated on a two-component system, whereas petroleum emulsions are definitely three-
component systems. The reagents used may have the incidental effect of reducing the
surface tension of either the water or the oil or both, but it is not identical with predicting
any emulsion resolution on such reduction as a cause
In any case, the most widely accepted general explanation is that the interfacial surface
between the dispersed component and the continuous component is modified in some
manner. It is generally recognized that the liquid having the greater surface tension will
form the inner, or dispersed, phase. Hence, a change in the surface tension of either
component could result in resolution, provided that the surface tension lowering is stopped
short of the point of reversing the emulsion,
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( 2.4 Treating Methods io tro mmc in ofeld ” es
The factors involved in treating water-in-oil emulsions include: 4 omy
1. breaking the film surrounding the small water droplets and coalescing the droplets GQ \
to produce larger drops
“= 2. settling the water drops during or after their coalescence
Theoretically, all emulsions separate into oil and water if allowed to settle for an unlimited
time, Much of the water produced with petroleum does separate without the assistance of
heat, chemicals or other devices. However, the small water droplets in water-in-oil
emulsions are usually surrounded by a tough film that gives the appearance of a plastic
‘wrap when viewed under a microscope. This film resists being broken, and until the film is
broken, the water droplets do not merge together into coalescence (at least in any
reasonable length of time).
The higher the ALESSAY of a water-in-oil emulsion, the slower is the settling rate ofthe
water in it, Thus, if the emulsion is at a low temperature, its viscosity i high, the
< separation of water‘from the oil is slow. Also, the smaller the water droplets are in the oil,
the longer it takes for them to separate out. In addition, if the difference in gravity
between the oil and the water in the emulsion is not great (a small gravity differential), then
their separation is slow, All the various treating practices are directed at increasing the
size of the water droplets, increasing the gravity difference between the water and oil, and
decreasing the viscosity of the oll. Therefore, heat, electricity, mechanical devices,
chemicals and various combinations of them are normally required to cause the film around
the water droplet to break and allow coalescence, resulting in improved dehydration,
It should also be emphasized that no two oil field emulsions are alike. The progédures