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Emulsion Control Using Electrical Stability Potential


J, U. MESSENGEi
MEMBER AIME

carbon, graphite, or asplmlk which collect at the interface


and are preferentiai~ wet by one of these pbases56 Unrefined crude oils oan contain both types of emulsitlers. A
populur theory is that, of the two phases in an emulsion,
the dispersed phase will be the one contributing most tn
the interfacitil tension. UeuailY tis ph=e cont~m fie
least amount of emadsitier.
The stabdity of a water-in-oil emulsion is affected by
the folimving:8 (1) viscosity (2) particle or ~opkt size;
(3) iuterfacial tension between the phaseq (4) phasevohrme ratios; and (5) the dit%ence in density between
the phases. A stable emuI.4on is usually characterized by
high-viscasity, smaii droplek+ low intertkial
tensions,
small ditlerences in density between its phases, and slow
separation of the phases. It also has low conductivity
(high electrical stability potential).
Water-in-oil and oil-in-water gmulsiorrsa are both commotx however, oil field emulsions are predominantly wtier-in-ail emulsions. The emulsions which commonly occur
during completion and stimulation operations contain a
combination of several of the following: acids, fracturing
fluids (oii, water, acid), and formation water and oil., Produced emulsiorts usually contain formation water and oil.
Emulsions form in oilwells because oil and water are ,
mixed together at a high rate of shear in the presence of
a naturally occurring or unavoidably produced emulsifier,
During the completion and stimulation of productive
zones, and while formation fluids are being produced, OH
and water are ve~ often commingled. These mixtures are
formed inta emulsmns by agitation which occurs when the
fhdds are pumped from the surfw into the matrfx of the
formation or produced through the formation tc. the surfac~ Restrictions to flow (such as perforations, pumps,
and chokes) u increase the level of agitation; tight emulsions are more likely to form under these condhions. Often
an enudsifled droplet is an emulsion itself. Therefore,
eumkdon-breaking probiems can be quite complex. The
complexity can be even greater if a third phase (gas) is
,,,
included,,
J3em&dtlers operate by tending ta reverse the form of
the emtilon. Durirqj this process, droplets of water bkcome bigger, viscosity is lowered, color becomes darker,
separation of the phases faster and electrical stabiiitj potential approaches zero, Any of these effects could be followed as a -rn~ns of determining emukion stabiii@. However, electrical stabiiii potential is the most reproducible
and most easily measured parameter for following the stai@i~. of a waier-in-oil
emulsfon.

. .- A -.

AESTRAH
A technfque is desccibed whereby the resistance o~ an
emuisian to breaking can be quantitatively deternrined.
Produced ailfield emulsions ave usually the wate~irt-oll
type and, accordingly, do not conduct an electrical current. However, the~e is a tirreshold af A-C voitlrge pressure
above which an emrdsion will iweak and cuwerat U@ flow.
The more stable an emulsion, the hfgher the required wdtage. A Fawn Emulsion Tester, modified so that low voltages (0 to FO v) can he accurate~ measu~ed, is suitable. ;
This technique has dpplicatiran in evaluating the eficz
af a demuis!j?er on the stability af an emulsion. Emulsions
can, in essencej be titmrted with demulsifirs by adding a
quantity of demulsifier, stirring, and meawring the vahlzge
required ta cause current to jiow. Any synergistic eflect
of .!WOor mare mate~hts added simuitaneousfy can be
followed accurately. A demulsifier that significant~ towers
the threshold voltage fjrom 100 to 400 v to O to IO v for
the emulsions in this study) is effective and can cause
the emulsion to break. A demuisi$er that will brhrg about
this drop in the threshohi voltage at low wntwntratian is
very desirable. The technique is also weU adapted jor rapidly screening demulkifiers.
f
INTRODUCTION
Stable quulsiona in produced reservoir fluids resulting
from certain well stimulation and completion proqdurea
are common problems. The use of suitable demukdfiera
can often mitigate these difilcukies. At the present time,
a rapid ahd etllcient method for selecting satisfactory demuk+ifiers is not available. It is badly needed. Reliance is
new placed primarily on trial-and-error procedures.l
A new test method has been developed which permits a
more rapid and precise selection of demulsifiers. It involves fneasuring the electrical stability potential* of an
emulsion before and after a demulsifier has been added.
This paper describes this method and shows where it
should have application ir, field emulsion problems.
NATURE OF OILFIELD

sacoNY MoBIL ou co,, hfc.


DAiLAS, 7EX,

E-MULSIONS

Two immkwible components must be present for aq


ernufsion to fmrG we are. eancerned here with crude oil
and wrtter. An emulsifier must be present for em emulsion
to be strtbla= Emulaiiers can be substances wkdch are
b
soluble in oil and/or water and which [ower interfaciaI
.-_LardmLThQY
can be colloidal solids.s~h. w bertto@e,
mee- ofllee

)t. 4, 1966,
wer, (MO.,

O@, 8-6, 1S65.


s&en at end of DUD&%s
*T& paranieter ektrieai etabIlit powatlal has been used in the
nwbatenance and control Of hldi?illdshl
aqd.e, but has not b~n
aDPikd to enmk.lon datmbUIzsUcm
?lkf$wdme

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EXPERIMENTAL
r

OFPETROLFJJM
. . . . . . . . . . . .TECHNOLOGY
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AF+ARATUS

T
A water-imoil emulsion is a paor conductor of electrical
atrrettr, However, when WI hwreasing A-C voltag~ is im-

[SW ~~b~r.
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fiers were usually added in 0.1 vol-per cent increments.


Results are summarized in Table 2. In some tests, the demulsifier was added to the water before attempting to
form the emulsion. In all, 141 such tests were run, using
66 different emulsifiers. Forty-two tests showing typical
results are reported in Tables 1 and 2.
A separation test: presently in common use for screening dernulsitlers, was run, once the stability of the emulsion was lowered into the O to 10-v range, In this test the
emulsion was poured into a 250-ml graduate which was
~immersed in a water bath at 130F. The amount of water
separating from the oil was determined at 5, 10, 15 and
30-minute intervals. These data are p~esent+ in Tables J
and 2, also.

posed across two electrodes immersed in such an emub


sion, the emulsion will break and current will flow. The
potential required to just break the emulsion and make
current flow is defined as the electrical stability potential
of the emulsion. An, instrument which will provide this
information is already commercially available* This instrument would be more suitable if it were more sensitive
in the lower voltage range, A Farm Emulsion Tester, modified so that low voltages (O to 15 v) could be measured
accurately, was used in most of this work.
EXPERIMENTALWORK
The following procedure was used to evaluate the use
of electrical stability potential in destabilizing oilfield
emulsions. Emulsions were formed by stirring 1OO-CCportions of Padre Canyon crude oil and synthetic Padre Canyon formation water* * together ushig a blenrfer. After
stirring one minute, the blender was stopped and silver
electrodes were inserted, into the emulsion to measure the
electrical stability potential. Demulsifiers were then added
in 0.025 vol-per cent increments. After each addition, the
emulsion was stirred 30 seconds and the stability again
measured. In effect, the stability of the emulsion was titrated against a quantity of demulsifier. The results of
these tests are shown in Table 11A second series of emulsions was studied where 15 wt per cent HCI was substituted for the formation water; in these tests the demulsi-

...

DISCUSSION OF RESULTS
The electrical stability potential of the base enmlsion.~
(prepared from Padre Canyon crude and forn]ation water)
was reproducible within 57 per cent. The electrical stability potential of the base emulsions which contained acid
was higher than those containing formation water. The
amount of demulsifier required for the effective breaking
of an emulsion was only slightly dependent on whether
it was added to the oil or water phase or to the emulsion.
Agents 2a, 2c, 5a, 5c, 10a and 10c (Table 1) were added
to the water, &d agents 2b, 5b, and 10b were added td
the emulsion.

4A Model WA Rim
Emulsion Tester based on Mobiis US Patent
2?,SS9,404(Nov. 4, 1968) (avaSEabiethrough the Frmn Instrument Carp.
and driilinzz mud service companies].
**Composition
(sndiiter):
25,666, NNCl; 2,000,
OaOI:;
6,000,
NRHCOO; and enowb HtX to adjust the PH ta 6.86.

SCR13ENfNGDRMULSIFIERS
Electrical stability potential appears to be an effective

TABLE IEFFECTS. OF DEMULSIFIERS ON THE ELECTRICAL STA8111TY POTENTIAL OF AN EMUISION*


Electrical SIabillty

Agent
No.
iu**

,0.00
164
-

0.025
--Q&
146
-

Patential (A-C Volis) at Varlow

0.10
,

0.075
7

0.15

0.125

Amount$ of D*mul$lfier

0.175

-_ 020

0.225

Waler Separation with Time,


[VOI % @ 130FI

[VOI %)

_0.25

0,50

1.0

~.

10 ml..

1:(I

100

.95
Iqo

g
:
se
5b

5C*
6
7
1

176
172
1(62

I=

J66
165
160

100**
10b
lo&*
11

172
~j~

112
~a:

130

161
170
i 170
I.I.m.
172
1
161
I

15(
i

:2.

?6:
--173
190

11

33

190

230

180-200

IG

206
6.1

-i
117

212
202
200
2
220

--

208
2
204
215

,.~

1%

89
71
72
39
55
10

--

lZ

13
-

13 min.

35

4%

20:
220
13

2:

:$
91
53

Ss

5:

,.
25

36

1%
93
S3
11

*Contained 100 cc Padre Canyon Crude and \OO cc Padre CanVOn Water}
..parf ar ail of demuldtle? added to the water.

1%

100

la
100
S7
52

::
;!
99
97

1%
99

E
98

Iz
99

demql$lflers added after 6mulsi0n was formed.

TABLE 2EFFSCTS OF 12EMULSJFIERS ON THE EIECTR ICA1 SIASILt TY POTENTIAL

lx

l%
.96
100
l;:

7.3

7.2

_30 min.

100
9s

OF AN EMULSION*

Wafer 8reakautwith time


Electrical Slablllly
0.025

0.90

400

430 +
4s0+
4s0+
4s0+
4$o+
4s0+
j:;:

480 +.
and+
4s0+
4s0+
480+
480+

..

4s0+

...
..

480+
AW+
4s0+
-_t4---T.~--~
- X&
4s2s+
fgg~

---- .
400+

4s0+

.0.05
x
370
-

,
~

0.10

196

=
.=.

S9
4s6
&

2Z

:;:

4AS
-

1=
226
120

.2g

la
_
-

373
96

2s2
26
87
-

F
67-

:;?

2s6
ASO
262
S.s
147
20
::2
2<;
34
440

[Vol % @ 130FI

Potential (A-C VOltS) at VarIDus Amounts of Demulsifier [VOI %]


0.25
0.20
0.30
0.40
0.50
0.75
1.0

=
12

---

2.0

3.0

5 min.
.

10 min.

15 min.
.

9!:
30

G
83

z
73

.4:

9.5

s%
74

85

88

83

S3

1%
. .

4s0
!----80

2G.

340
193

296
250

220

S3

o?:

%:
2Z

32
n

112
116
.7
255
:0%

l=

4s
_

49
f.i
.

5s

6A

04

i%
..

50
--

-L-

192

141

69

62

5.4

9.$

<
x
=
-~--------

;i$z 34@

296
404

272
3s

G.

30 min.

,,

;$;
.::
104
29

6.2
2$

Contclned 100.cc Padre Canyon. crude and 100 cc Of 15 wt.por cent HC1; dwirul&s
* *OIW
enlulalefi farms,
$* Vale$ ~xceed lo@ bEclluSOof all In the Watof phrm.

20

10

addad after ainuifan WC$ farmtd.


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means of screening demulsitlers. Of the 2S agents shown


in Table 2 there is little doubt that agents 23 and 34 are <
among the most effective.
TITRATIONOF EMULSIONS
WITH JYEMULSIFIERS
Data in Tables 1 and 2 show that emulsions can be titrated with demulsifiers by measuring the stability of the
emulsion after the addition of each incremental amount
of demulsifier, The optimum treatment level can thus be
easify found.
cORRELATION OF RESULTSWITH THOSE
FROM T1lE SEPARATION TEST
The most cbmmon method in use for testing demtrlsitiers is the separation test. A separation ,of 90 vol-per cent
of the water phase in 15 minutes is generally accepted as
proof that the emulsion has been satisfactorily destabilized. This test was run on all samples in this study after
titration with demulsifier had significantly lowered the
stability of the emulsion (from 100 to 400 v to 10 v or
below for emulsions formed from Padre Canyon crude).
It can be seen in Tables 1 and 2 that the emulsions studied did break if their electrical stability potential was
brought into this range. Accordingly; the correlation between the two methods is very good,

..

.. . . .

procedures for breaking very persistent field emulsions;


two examples are given below.
FIELD EMULSION A
Limestone formations in several wells were acidixed using 15 wt-per cent HC1 plus addhives. After being cleaned
up, the wells were shut in. Marked decreases in production occurred when the wells were put on production.
They were then re-acidized. After this treatment the weils
produced an acid-formation water-oil emulsion which
could not be broken by conventional means, Using the
electrical stability potential method, a procedure was
worked out which would break the emulsion and prevent
it from forming during future stimulation attempts with
acid.
,.
FIELD EMULSION

During the design of an acid fracturing treatment it


was found that a very persistent emulsion and sludge
wouId form between 15 wt-per cent HC1 and the crude
oil. The electrical stability potential method was used in
selecting a satisfactory demulsifier and antisiudge agent.
Ordy a small sample .ol~the crude was avaiiable for these
tests; it proved to be more than adequate because more
information is gained from a single sample using this
technique.

CONCLUSIONS

,. REFERENCES

1. Electrical stability potentiaI vahres can be duplicated


in emulsions of like composition.
2. The amount of demulsifier required to break an
emulsion was not dependent on whether it was added to
the oil or water phase or to the emulsion.
3. The results obtained by using .enmlsion stability potential correlatw with those obtained in separation tests.
4. The electrical stability potential can be effectively
used: (a) for screening dqmulsitlers; (b) for determining
optimum demulsifier concentration by titrating the @mulsion; (c) for following the synergistic effect of two or
more additive+ (d) for identifying materiafs which have
no effects on emulsion stability; and (e) as a rapidly accessible criteria of demulsifier performance.

1. Staudard Procedure for the Evaluation

of Hydraulic Fractur.
ing Fluids? Section VII, Compatibility
oj Fracturing IVuifs
with Formation Fluids, RF 93, API (July, 1960) 14-15.
2, Brxkman, S, and Egloff, G.: Ertdsions and Foams, Reinhold
t,
.
Publishing Corp., New York (1941 ) 24.
3. ~9~?) eSting Oil Field Emulsions, U. of ~exas (Revised
4, Becher,,. Paul: EmuLrions; Theory and Practice,
Reinhold
Publishing Corp., New York (1957) 166.182.
5. Becher, Paul: Principles of Emulsion Zeclurology, ReinhoId
, Publishing Corp., New York (1955) 71.
6. Becher: Emulsions: Theory and Practice, 127.
~. Ibid., 07.
8. Becher: Principles o~ Emulsion ~echtmlog~, 53.
,

9, Bechrr: Emulsions: Theory and Practice, 77.


10. Becher: Principles of Ernrd-sio&Technology, 2-5.
11. API, op. cit.; 21.22.
12, Becher: Emtt&ians: Theory and Praciice, 287.
13. Berkman et al,, op. cit., 220.
*
14. Ibid,, 285.

FIELD API%JCATIONS
The electrical stability potential.,method has excellent
application for treatment of emulsions which develop under field conditions. This method has been used to develop
.

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