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SOCIETY OF PETROIEUM ENGINEERS OF AIME
6200 North Central Expressway =R SPE 1507
Dallas, Texas 75206

THIS IS A PREPRINT --- SUEJECT TO CORRECTION

Effect of Ultrasonic Irradiation on Coalescence

and Separation of Crude Oil-Water Emulsions

By

R. J. Schoeppel, Member ARJE, The U. of Tulsa, Tulsa, Okla., and

A. W. Howard, Member AIME, Marathon Oil Co., Grass Creek, Wyo.

63 Copyright 1966
Arneriesn Institute of Mining, Metallurgical and Petroleum Engineers, Inc.

This paper was prepared for the klst Annual Fall Meeting of the Society of Petroleum Engineers
of AIME, to be held In Dallas, Tex., Oct. 2-5, 1966. Permission to copy is restricted to an abstract
of not more than 300 words. Illustrations may not be copied. The abstract should contain conspicu-
ous acknowledgment of where and by whom the paper is presented, Publication elsewhere after publica-
tion in the JOURNAL OF FETROIEUM TECHNOLOGY or the SOCIETY OF PETROIEUM ENGINEERS JOURNAL is usually
granted upon request to the Editor of the appropriate ~ournal provided agreement to give proper credit
is made.

Discussion of this paper is tnvited. Three copies of any discussion should be sent to the
Society of Petroleum Engineers office. Such discussion may be presented at the above meeting and,
with the paper, may be consttieredfor publication in one of the two SPE magazines.

ABSTRACT significance of this problem is shown by an

Tne coalescing and separating te~dencies
of untreated and treated crude oil-water
emulsions when exposed to ultrasonic treatment
are experimentally investigated. Combined
ultrasonic and chemical treatment greatly
increased separation efficiency over chemical
treatment exposed only to low-frequency
mechanical agitation. Both short- and 2ong-
duration ultrasonic irradiations were effective
in proaucing coagulation: the rate 0$
separation increased as much as 700-fold over
natural settling rates.
The ultrasonic treatment technique offers
a potentially practical method of improving
natural oil-water coalescence and separation
while simultaneously decreasing chemical
requirements.
INTRODUCTION
One of the recurrhg problems which has
bonttnually plagueclthe oil i.nclustry
is
separation of water pxoduceriwith oil, The
References and illustrations at end of’paper.
estimated 15 to 20 million Clollarsexpended for
chemicals each year to treat the world’s oil
production.l This expense does not include
costs for handling the derrrulslfier,
injection
equipment, heater fuel, etc.
Current methoclsof treating oil-water
emulsions utilize natural settling, chemical
dehydration, and/or electrical dehydration
techniques to effect separation. Sonic energy
may be used ‘tocause either agglomeration or
dLsperslon of immiscible liquids, depentting
upon frequency, wave energy, geometry, etc. A
detailed literature survey revealed that, while
a considerable amount of work has been done on
sonic vibration as a coagulating force in
aerosols and dust-gas systems, relatively
little has been published on the use of this
same force in separation of iinmiscibleliquid
systems. It is the purpose of this paper to
present the results of an experimental
investigation showing the capability of ultra-
sonic treatment to [l.] increase the rate of
coalescence aniisettling of necturallyoccurring
cruae oil-water emulsions and [2] increase the
rate of dispersion of chemical tiemul.sifying ~
agents.
,
 E?ZFECTOF ULTRASONIC IRRADIATION ON COALESCENCE
AND SEPARATION OF CRtl )IL-WATEREMULSIONS
‘RIORWORK
Several phenomena occur in a liquid when
;ubjectedto ultrasonic irradiation. These
?esult from the molecular transfer of pressure
ml.ses causing a vibrating motion of the
naterialalong the directton of wave propa-
gation. Alternate high- and low-pressure
?erlods cause corresponding compressions and
~arefactionswithin the liquid with a sociated
:hanges In density and temperature.3’~ Emulsi-
~icatiou of immiscible liquids by ultrasonic
Irradiation occurs when the intensity of ultra-
sonic irrad~ations exceeds the cavitation level
Emulsions so generated are mbre stable than
those mixed by mechanical stirring or blendfng;
the stabili%y of the emulsion being a function
of the size and distrlbutton of dispersed
~roplets.5,6 WLth lower intensity irradiations
however, the equilibri~ droP1e~ size is
sufficiently large that spontaneous coagulation
occurs upon interruption of the treatment.
Depending on the viscosity of the dispersing
phase and the settling distance, a fairly rapid
coagulation with separation can be achieved
when sound intensities are below that capable
of producing emulsions.7
Experiments were carrie~ out with an oil-
in-water emulsion by Sollner( an w
in-oil emulsion by SurmnerfZ’Ucht~ ~~ ‘atex-
systems consisted of’transparent tubes to house
the suspensions with a transducer element
introduced at one end. After a few minutes Of
vibration, their suspensions were broken with
either the dispersed or dispersing phase
occupying the relatively qufescent area near
the mid-points of nodes af the standing waves -
with the other phase concentrating at the an%i-
nodes. [If the dispersed phase has a lower
density than the continuous phase? collection
has been found to occur at the nodes; other-
9]
w~se, collection occurs at the anti-uodes”
Only two field applications involving’’the
use of sonic vibrations as a coagulating force
in crude oil-water systems were found in the
literature.lO?ll One applies continuous-flow
treatment to separate oil-water emulsions
whereas the other operates in a batch system.
ti one of the batch fieltitests,11 a magneto-
strictor of high-nickel permalloy was used to
generate ultrasonic energy. The field-scale
unit had a 1,900-watt generator with an output
freauenc~
-. of 22.5 kcJsec and a 4-in. &bameter
signal aischarge plate. The unit was installet
iQ a 500-bbl vessel. Under normal operating
conditons, the unit removed from 99.0 to 99.7
per cent of the water from the emulsifiefioil.
The unit was claimeclto have given efficient
operation with a relatively small capital
investment ma a low electrical energy re-
quirement.
----
SPE-L>U(
EXPERIMENTAL
Apparatus antiMaterial
The principal equipment used in this
investigation consisted of an ultrasonic
generator preclestgnedto operate at ~0 kc/see
with a power output of 500 watts. !Ihe
generator output was equally aiviaec among
16 magnetostrictors symmetrica~y locatefias
shown in Fig. 1. Opposite magnetostrictors
were separated by 11-1/2 in. These were
immersed in water making up the ultrasonic
bath. Normal use of the bath was for ultra-
sonic cleming.
Samples to be treateclwere placed in the
center of the ultrasonic bath at a aepth equal
to the immersion fiepthof the magnetostrictor
transducers. To insure a consistent experi-
mental temperature, it was necessary to main-
tain the temperature of both the ultrasonic
bath and a settllng bath at a level above
that generateilthrough transducer operation.
The temperature selected was 118F.
To simulate natural contlitionsexisting
in produced crude oil-water emulsions,
naturally occurring oilfteld emulsions of
varying water content were uses. These were
obtainefifmm different zones of the low-
gravity high-viscosity Oregon Basin oil fiehl
in Northern Wyoming where adequate de-
mulsification is a continuing ard aifficult
problem. Table 1 presents the physical
properties of the crudes testes. Crude No. 1
represents a low-water content emulsion> where
as CrutieNo. 2 contained a rather high
emulsified water content. CrufieNo. 3 is a
difficult emulsion to break because of its
viscosity.
Procedure A
Preliminary tests Indicated the water
phase to be continuously distributed through-
out each field.sample. Nevertheless, a 500-
ml bulk sample of each emulsion was agitatecl
at high speed with a blender for five minutes
to Insure uniformity. This was then aivified
into five 100-ml samples ana placed in the
constant temperature settltng bath. Two were
used for subsequent ultrasonic irradiation, on
useclto determine the sample water content;
and two for tleterminingthe average-natural
separation characterlst~cs of the emulsion
In the A-Series 01 tests, two of the
smples were contacteciwith ultrasonic
irrafiiation”forvarying lengths of time. The~
were then placea back in the settling bath snc
the per cent free water recoxcieci
a% subsequen~
time intervals.
DC-1 m-w R.
. ..
.T. $W!!-T(M!PPF!T.
“ .
w“--------
~u-J-)- I
Procedure B
A second series of tests was conducted to
determine the effectiveness of chemical dis-
persion by ultrasonic energy. A 1,000-ml
sample of each crude was blended in the manner
previously described and divided into ten 100-III1 is believed to result from an accumulation of
samples. Two samples were used to determine
the water cut and the remainder placed in the
settling bath. T 2 reference samplesj one
untreated and one ,reatedwith one of the two
better competitive manufacturer chemicals
previously evaluated,12 were used. The other
six were similarly treated and exposed to
ultrasonic irradiation for varying lengths of
time. They were then placed in the settling
bath and the per cent free water recorded as a
function of time. This procedure was then
repeated with the chemical additive of the other
manufacturer. Since the chemical demulsifiers
are commercially available, the trade name of
each demulsifier is withheld for competitive
reasons.
RESULTS AND DISCUSSION
Demulsification by Ultrasonic Irradiation
Partial separation in all experiments using depends on the specific gravity of the dis-
sonic vibrations was effected in a shorter time
period and to a greater degree than was obtained
by natural separation. Figs 2, 3 and 4 ilhS-
trate the results of various ultrasonic contact
times for the crude oil-water emulsions tested.
Curve 1, on all three graphs, represents the
settllng efficiency of the reference samples
not subjected to ultrasonic irradiation. Curves
2 and 3 represent the efficiency of separation
after being contacted by 60 and 120 miu. of
ultrasonic vibration, respectively. By
comparing the’graphs, it can be seen that
Crude No. 1 responded most favorably to the
ultrasonic $reatment, providing nearly complete
separation within a 2&hour settling period.
Crude No. 3 responded quite differently, how-
ever, the separation efficiency barely in-
creasing w%th increasing ultrasonic treatment.
TWO distinct periods of separation may be
noted in these plots. These correspond to a
first-order or initial settling rate and a
subsequent or second-order rate. The settling
rate during the first-ordex period is apparently
due to coalescence and separation of lihe
larger droplets and is seen to be much greater
than that observed during the subsequent
settling period.
Comparing the resylts obtained from ultra- perloa of from 10 to 20 reins.appears to be
sonic irradiation to that of natural settling,
it maybe observed that an increase in settling
ra%e in the order of from 500 to 700 per cent
by volume for any given hour was o-Dtained
during the period of first-order settling for
ANTI A. W.
.-., - --- ,. .
HOWART)
--------
Crude No. 1. Application of ultrasonic
irradiation over a two-hour period produced a
faster initial settling rate but resulted in a
lower degree of total separation over the same
total the interval. This observation of an
apparent optimum in ultrasonic treatment time
most of the waker droplets in the zone where
the stationary waves were formed. When the
concentration of water droplets in the oil
and/or the concentrat~on of water in the systex
falls below a certain level, and is then sub-
~ected to additional irradiation, a condition
favorable for emulsification is produced. TM.:
condition has been described by Sollner and
Bondy indicating that after a certain period
of irradiation in a static system, additional
iiv?adiationproduces a more stable emulsion.13
Dispersion by Ultrasonic Irradiation
The use of ultrasonic irradiation to
disperse chemical demulsifiers incorporates,
at the sane time, features essential to
coalescence and separation. This coagulative
action causes migration of the dispersed phase
which enhances accumulation at the nodes and
anttnodes. The severity of the migration
persed phase.
Some of the results typical of this serie
of experiments are illustrated in Figs, 5 ad
for the crude sample No. 3 which responded
least to straight ultrasonic treatment. Fig.
presents the separation history for various
ultrasonic contact times when the best of
eight demulsiflers tested was added to the
sample to enhance separation. Fig. 6
represents a similar history for the best
chemical demulsifier tested of the competitive
brand.
These results and others show that the
degree of demulsification obtained at any time
varies with the physical properties of the
crude, the demulsifier used, and the ultrasoni
irradiation time. In all tests the effective-
ness of separation was greater with increased
ultrasonic irradiation, showing that this
technique is apparently quite effective in
increasing the rate of chemical dispersion.
A greater portion of this increase, however,
as shown by a comparison of Figs. 3 and 4 with
5 and 6, is apparently due to the coagulative
effects of ultrasonic irradiation rather than
to additional dispersion of the demulsifier.
From the plots of Figs. 5 Wd 6, an irradiation
sufficient to produce effective chemical dis-
persion for the particular irradiation system
and materials used in this study.
In agreement with the first- and
 EFFECT OF ULTRASONIC IRRADIATION ON COALESCENCE
.
AND SEPARATION OF CRUDE OTL-WATER EMULSTONS
—.. —.-—.. . ----- 150:
.RPF.- . \

second-order settilingperiods of Figs. 3 and 4, 2. Danser, H. W., and Neumann, E. P.:

these curves also show that, once initial
settling occurs, the rate of subsequent settling
3s essentially independent of irradiation time.
From this, it is apparent that the coagulative
effects of ultrasonic irradiation aided in
decreasing the time nece~sary to establish this
constant settling rate. Other experiments
designed to compare the efficiency of ultra-
sonic dispersion wi’bhlow-frequency mechanical
mixing showed that combined chemical-ultrasonic
treatment greatly increased separation
efficiency. Such a treatment appears to offer
a practical method of improving oil-water
separation while simultaneously decreasing
chemical requirements.
CONCLUSIONS
“Industrial.Sonic Agglomeration and
Collection Systems”, Ind and Ebg. Chem.
[1949] &, 2439.
3, Goldman, R.: Ultrasonic Technology,
Reinhold Publishing Corp. N.Y. [1962].
4. Carlin, B.: Ultrasonics, McGraw-Hill Book
Co., ~c., New York, N.Y., 2nd Ed. [1960].
5. Bikerman, J. J’.: “The Interface Symposium,
Pt. 6, Foams and ~ulsions”, Ind. and ?3ng.
Chem. [Jan., 1965] 57, 56.
6. ~, R. A. W. and might, J. T,: “A
Kinetic Theory of Droplet Coalescence with
Application to Rnulsion Stability”j Trans.
Faraday Sot. [Jan., 1965] 6J, 170. —
7. Sollner, K.: “Colloidal Effects or Ultra-
sonics”, Chem. Eng. Prog. [1951] ~, No. 1,
28
●

8. Su.merfrucht, J. N.: “A Study of the

Ultrasonic irradiation was found to
produce a coagulating effect on crude oil-water
emulsions which is also effective In demulsifier
r mulsions”, Thesis, U. of Oklahoma,
dispersion. The combined effects of ultra-
sonically produced coagulation smd chemical
dispersion have been shown to provide an
effective method of increasing the demulsifying
rate of crude oil-water emulsions. Both long-
and short-duration ultrasonic Irradiations are
effective in producing coagulation; in one
test, the rate of separation increased as
much as 700-fold over natural settling rates.
ACKNOWLEDGMENT
The authors wish to thank Dowell, Inc.j
Marathon Oil Co., !lketoliteDiv., Petrolite
COW., and Visco Div., Nalco Chemical Co. for
supplying the materials and equipment used in
this StNdy.
PJXERENCES
1. Steinhouff, l?.: “Modern Oil Field
lkmulsification”jpetroleum [Oct., 1962] ~ >
335.
Feasibility and Application of Ultra-
sonics to the Treatment of Crude Oil
Norman, Okla. [1962].
.
9. Bondyj C. and Sollner, K.: “Qualitative
Experiments of Emulsification by Ultra-
sonics”, Trans., Faraday Society [1936]
~, 616.
10. May, R. D.: “System for the Sonic Treat-
ment of Rnulsions and for Resolving the
Same into .TheirConstituent Parts”, U. S.
patent 3~200,567 [issued Oct. 17,419651.
11. Skripnik, E. I., Dolganov, V. 1. and
Simileiskii, A. Z., et al.: “Demulsifi-
cation of Crude Oils by Means of Ultra
sonics”, Neft. Khoz. [July, 1963] No. 7,
51.
12. Howard, A. W.: “An Investigation of
Ultrasonic Demulsification of the Crude
Oil-Water System”, Thesis, U. of Tulsa,
Tulsa, Okla. [1965].
13. Sollner, K. and Bondy, C.: “The Mechanism
of Coagulation by Ultrasonic Waves”) Trans,
Faraday Society [1936] —32, 27.

TABLE I
Field Emulsions Studied

Property Crude No. 1 Crude No, 2 Crude No. 3

API Gravity 20.8 20.9 18.7

Viscosity at 60°F, cp 15.7 9.0 70.4
Solution GOR, SCF/Bbl 107 108 33
Saturation Pressure, psig 960 520 190
Water Content of Lab.
Emulsion Samples, % 7-8 30 - 50 5-7
 ..-
MAGNETOSTRICTORS

Q SAM PLE
&

Fig. 1 - Plan View of Ultrasonic Bath

100

fi 80
+
s
-1
u
~ 60
SONIC
CONTACT TIME
% Q!m!iE (MIN)
~>e

g 40 i
e
2
w
w
E 20

0
4 8 12 16 20 24

SETTLING TIME, HRS.

Fig. 2 - Ultrasonic Demulsification Results

Crude No. 1 - No Demulsifier Added
 +El
did~
I

SETTLING TIME, HRS. SETTLING

—
TIME , HRS
15 20 24

Fig, 3 - Ultrasonic Demulsification Results Fig. 4 - Ultrasonic Demulsification Results

Crude No. 2 - No Demulsifier Added Crude No. 3 - No Demulsifier Added

SETTLING TIME, HRS,

Fig. 5 - Chemical-Ultrasonic Demulsification

Crude No. 3 - Demulsifier No, 1

$3
:
~ 60

:
#
SON,C OEM”LS,FIIR
:- 40 —- CONTACT nw mm

z
3
Id

E+!
1. 20 —

20 40 60 80 100 120 140 160

SETTING TIME, HRS.

Fig. 6- Chemical-llltrasonic Demulsification

Crude No. 3 - Demulsifier No. 2