Colloids and Surfaces, 34 (1988/89) 353-370

Elsevier Science Publishers B.V., Amsterdam - - Printed in The Netherlands

353

Water-in-Crude Oil Emulsions from the N o r w e g i a n

Continental Shelf
Part I. Formation, Characterization and Stability
Correlations
EINAR J. JOHANSEN 1, I. MAGNAR SKJ~,RV01'*, TORGEIR LUND I,
JOHAN SJOBLOM TM,HELENA S~)DERLUND 2 and GUN BOSTR()M 3

IStatoil A/S, Prolab, Box 300, N-4001 Stavanger (Norway)

2Institute for Surface Chemistry, Box 5607, S-114 86 Stockholm (Sweden)
3Department of Physical Chemistry, .4bo Akademi, SF-20500.4bo (Finland)
(Received 6 April 1988; accepted in final form 22 August 1988)

ABSTRACT
Properties of different crude oils from the Norwegian continental shelf, together with their
emulsions (with synthetic formation water), are reported. The crude oils, in most cases, are characterized by a high amount of saturated hydrocarbons, a varying amount of waxes (2-15%) and
a low content of asphaltenes (0-1.5% by weight). The crude oils (from 32 different wells) have
been characterized by means of density, viscosity, surface and interracial tension measurements.
The ability to form stable emulsions varies very much, depending on the crude oil. Emulsion
stability has been evaluated by means of visual inspection at normal gravitation and by means of
ultracentrifugation at 650-30 000g. The reproducibility in the stability sequence by these two
independent methods is satisfactory. Mean droplet sizes in the interval 10-100/nn were considered to represent realistic laboratory preparation conditions. It was found that higher mixing rates
reduced the droplet size, while a prolongation of the emulsification time gave a narrower distribution of droplet sizes. Increased temperature was found to cause instability, while extreme pH
values gave restored or even enhanced stability. This last observation was taken as an indication
of a low surface charge density, a strengthening of the interfacial film by the binding of hydration
water and a lack of stabilizing particles.
A correlation between emulsion stability and measured physicochemical parameters showed
that the emulsion viscosity, the crude oil viscosity and the content of waxes were the most significant parameters (R2=0.71, when comparing observed and calculated stability).

INTRODUCTION
I n t h e o f f s h o r e p r o d u c t i o n o f c r u d e oil, t h e p r o b l e m o f c r u d e o i l e m u l s i o n s is
encountered at an early stage. In the planning and construction of the platform
*Present address: Jotun A/S, Box 400, N-3201 Sandefjord, Norway.
**To whom correspondence should be addressed. Present address: Institute for Chemistry, Department of Physical Chemistry, University of Bergen, N-5014 Bergen-U, Norway.

0166-6622/89/$03.50

1989 Elsevier Science Publishers B.V.

354
enough space must be reserved for emulsion destabilization equipment, such
as separators and coalescers. With reliable information about crude oil and its
tendency to form emulsions, this space could be reserved for other more useful
purposes. The crucial step will hence be to predict emulsion stability from
measured analytical or physicochemical properties of crude oil samples or prepared synthetic crude oil emulsions.
Crude oil emulsion stability has been the subject of intense debate and research during the last eighty years [1-10]. There is a lack of a fundamental
understanding of the mechanisms governing the stability of oil-continuous
emulsions. The reason for this is that the most important stabilizing mechanisms are different from those of water-continuous emulsions, so that direct
parallels cannot be drawn. The direct application of an electrostatic model for
stabilization, in order to prevent flocculation of the water droplets dispersed
in the oil, does not seem to be justified. For crude oil emulsions, the importance
of a rigid and protective film surrounding the water droplets is usually pointed
out [11-14]. The detailed properties of this film, together with a fundamental
knowledge of the chemistry of the interfacially active components in the crude
oil, are far from understood. However, empirical studies have shown the importance of components like asphaltenes, porphyrines and waxes for the stabilization [ 15-22 ]. The first two components are believed to possess surfaceactive properties and hence to accumulate at the interface of water and oil.
Waxes can act either on a molecular level as lipids, or as particles (often together with clays) in the interfacial film, or alternatively as viscosifiers in the
continuous oil phase. Formation of an interfacial film possessing certain surface-rheological properties, in combination with a particle a n d / o r steric stabilization, is obviously of fundamental importance for the stability of crude oil
emulsions. In addition, the hydrodynamic behaviour of emulsions when stirred
or pumped also affects the stability. This aspect will not be covered in this
investigation.
In the first part of our study we report on the formation, characterization
and stability correlations of water/oil (w/o) emulsions based on North Sea
crude oils. In subsequent parts we will report on chemical destabilization
mechanisms (Part 2), and synthetic w/o emulsion model systems possessing
similar properties to natural crude oil emulsions based on North Sea crude oils
(Part 3 ).
EXPERIMENTAL

Analytical and physicochemical properties of the crude oils investigated

Of a total experimental matrix of 32 crude oil samples from the continental
shelf, we present in this report data of selected samples. The oil samples cover
a large geographic area, extending from the Edda field in the south to the SnSh-

355
vit field in the north. The crude oils have been selected in such a way that a
large variety of emulsion stabilities were obtained.
The analytical procedure involves determination of the content of aromatic
compounds, saturated hydrocarbons, polar compounds, waxes and asphaltenes. The following experimental procedure has been adopted:
(i) Asphaltenes were precipitated by diluting the crude oil with n-pentane
( 1 : 40, v/v) at room temperature. The suspension was filtered through a 0.45/lm filter. (Modified IP method 143.)
(ii) Wax components were precipitated in acetone at - 2 0 C and isolated
by filtering the suspension through a glass-fibre filter. The wax fraction was
further purified on a silica adsorbent in hexane solution. The procedure was a
slight modification of a method described by Burger et al. [23].
(iii) Saturated, aromatic and polar components were isolated and quantified
by preparative high-pressure liquid chromatography (HPLC). Both silica- and
cyano-columns were included in the chromatographic system. The separations
were obtained by backflushing techniques, involving both hexane and tetrahydrofuran as mobile phases.
(iv) Molecular weights were determined on a 'Cryette A' (Precision Systems
Inc. ) through measuring the freezing point depression of benzene.
The physicochemical procedure involves a determination of the pour point,
wax appearance point, density, viscosity (at 100 s -1 ), surface (Yo/a) and interfacial tension (Yo/w). These quantities were determined as follows:
(i) Wax appearance points were determined by transmission microscopy
using polarized light.
(ii) Pour points were measured according to standard procedures [IP method
15/67 (75)].
(iii) Measurements of crude oil densities were performed at 40 C with an
Anton Paar DMA602H instrument, using air and distilled water as reference
materials.
(iv) Surface a n d interfacial tensions were measured at 20 and 40 C with a
MGM Lauda Ring Tensiometer connected to a HP-1732A Recorder. Sample
thermalization time was long enough to ensure interfacial equilibrium before
measurement.
(v) Viscosity measurements were performed at 40C on a Contraves Low
Shear 30 Rotational Viscometer. A time of 10 min was allowed for thermal
stabilization before initiating the measuring programme. Readouts were taken
at a shear rate of 100 s- 1.

Physicochemical properties of the water-in-crude oil emulsions investigated

In all emulsifications we used an aqueous phase with the composition:

356

Ion

Concentration (mg 1-1)

Na +
K+
Ca 2+
Mg 2+
Ba 2+
CI-

13 844
193
1275
335
50
24 775

The density of the aqueous phase was 1.0264 g cm -~ and its surface tension
73.3 mN m -1 at 20C.
The emulsions investigated were prepared under different conditions. Either
100 ml emulsion {with 50% synthetic formation water) was emulsified with a
standard propellar rotor for 2 h at 650 rpm (A), or 12 ml emulsion was prepared
with an Ultra-Turrax equipment at 20,000 rpm for 5 min (B). In the legends
to the figures, emulsification procedures A or B are specified.
When checking the influence of pH on the crude oil emulsions, a buffer
solution was used, 1 litre of which contained 6.008 g citric acid, 3.893 g potassium sulphate, 1.796 g boric acid, 5.266 g diethyl barbituric acid and 58.440 g
sodium chloride. The final pH was adjusted with HCI or NaOH.
Viscosities of the emulsions were determined in an analogous way to the
crude oil samples. Ultracentrifugations were carried out with a Beckman
ultracentrifuge.
RESULTS

This study contains an analytical and physicochemical characterization of

crude oils from the Norwegian continental shelf and their water-in-oil emulTABLE1
Analytical chemical properties of appropriate representatives of crude oils from the Norwegian
continental shelf
Crude Aromatics
oils
(%, w/w)

Saturates
(%, w/w)

Polar
compounds

Waxes
(%, w/w)

Asphaltenes
(%, w/w)

M.W.
(g tool -1)

3.9
4.3
4.5
10.1
14.5
2.9
8.6
3.6
4.6
2.4

0.2
0.7
0.6
0.4
0.4
0.0
1.5
0.8
0.2
0.4

190
200
240
260
210
150
260
240
200
240

(%,w/w)
A
B
C
D
E
F
G
H
I
J

11.2
17.4
36.4
28.5
36.0
29.2
36.1
47.7
32.9
40.6

84.7
78.2
50.7
66.3
59.1
68.2
58.2
46.0
61.0
53.0

4.0
4.4
12.9
5.2
4.9
2.6
6.0
6.2
6.1
6.4

357

I
V

vm

III
VV

358
Crude
Crude
Crude
Crude
Crude
Crude

0
o

100 -

No water
.

off
oil
oil C
oil
oil

oil I

Crude oil
Crude oil E
D
.

l G

80-

60-

4o-

2o-

20

40

60

80

100

120

Time (min}

Fig. 1. Separation of water from emulsions based on different crude oils from the Norwe~an
continental shelf. Emulsification conditions according to procedure A described in Experimental.
Separation is at room temperature. The original content of synthetic formation water was 50%

(v/v).
16

14

12

I0

Ultracentrifugation, 50C {A]

~]

Ultracentrifugotion, 20C {A)

Grovity seporotion, 50C (S}

F
8

,/
//
/i
//

D
CRUDE

OIL

Fig. 2. A comparison of stability numbers obtained by ultracentrifugations and gravity separation

at different temperatures. Emulsification conditions as specified in the figure, A or B. The aqueous
phase was 50% ( v / v ) .

sions. Altogether, our experimental matrix of crude oils includes 32 samples.

Of these, we have chosen categories with values covering the broadest possible
interval experimentally. Table 1 gives some fundamental analytical chemical
properties of the crude oils. The amount of aromatic compounds varies from
10 to 50% (w/w), and saturated hydrocarbons from 50 to 85%. The amount of

359
non-specified polar components is between 4 and 13%. The content of waxes
precipitating in acetone varies from 2 to 15%. Finally, the amount of asphaltenes is strikingly low, ranging from 0 to 1.5% (w/w). Molecular weights determined by means of freezing point depression are all in the interval 150-260
g mol- 1.
Table 2 gives some physicochemical properties of the same crude oils at 2040C. The densities vary from 0.79 to 0.89 g cm -~, viscosities (measured at
100 s -1 ) from 2 to 41 mPa s, surface tensions are all in the narrow interval 2430 mN m -1, while the interfacial tensions (towards synthetic formation water)
are between 23 and 36 mN m-1. The table reveals a clear correlation between
a high content of wax particles and a high viscosity. In two cases it can be seen
that the interfacial tension significantly exceeds the surface tension. This is
also the case for high amounts of waxes. The table also gives the pour points
and the wax appearance points, both expressed in degrees centigrade.
The ability of each category of crude oils to form stable w/o emulsions was
checked by visual inspection and is reported in Fig. 1. It is quite obvious that
the different crude oils have varying emulsion-stabilizing properties. In order
to obtain a stability sequence, we have compared two independent methods.
First, an ordinary visual evaluation was carried out to see how long it takes for
a fixed volume of water to separate from the emulsions. In this case we measured the time it takes for 20% (v/v) of the emulsified amount of water to
separate. The stability number has been calculated from In (t.g), where t is the
separation time and g is gravity. Under normal room conditions, normalized
g = 1. The stability numbers obtained are summarized in Fig. 2. As an alternative and independent method, ultracentrifugation was used in order to speed
up the separation process. In this method, one determines the time at which
the separation of water levels out, as in Fig. 1. Since this time will be a function
of centrifugal force, we have performed ultracentrifugations at different g values. As previously, the stability number is calculated from In (t'g). In order to
show the influence of increased temperature, the visual determinations were
performed at 50C, while the ultracentrifugations were carried out at room
temperature. For the sake of comparison, one ultracentrifugation was performed at 50 C. The stability number obtained from this experiment gives
good agreement with visual inspection at the same temperature. The gravity
separation in Fig. 2 gives a stability sequence of G > M > N > D, while the sequence obtained from ultracentrifugations is G > N > M > D. Considering the
experimental conditions, this is considered to be a good reproducibility. A lower
stability of each crude oil emulsion at the higher temperature is to be expected,
especially for those crude oils which contain wax particles that melt at these
higher temperatures. Crude oil D seems to be especially sensitive to this.
In order to create realistic laboratory conditions for the emulsion tests, different emulsification conditions must be examined. An acceptable measure of
the approprite emulsification conditions is the size of the emulsion droplets.

360

From the literature it is known that naturally occurring water-in-crude oil

emulsions are built up by droplets with a diameter of 10-100 #m [15,24]. In
Fig. 3 we summarize the influence of different emulsification conditions on the
mean droplet size. The mixing time ranges from 0.5 to 120 min, and the emulsions are based on crude oil G.
In summary, higher mixing rates will reduce the mean droplet size while a
prolongation of the emulsification time will mainly give rise to more equidimensional droplets. This latter trend is manifested in Fig. 4, where the standard deviation (SD) of the mean droplet size is presented. A longer emulsification time generally results in smaller SD values. However, all emulsions are
characterized by a high level of polydispersity.
30

-i

25

2O

10

s
0

IO 30 8 0 9 0 120

5 I03080

0.5 1

MIXING TIME (min)

Fig. 3. Mean droplet size of water-in-crude oil emulsions based on crude oil G for different preparation conditions. For the lower mixing rates procedure A was used, while procedure B was used
for the two highest rates. The aqueous phase was 50% (v/v).
30

650
rpm
rpm 8000rpm 20000rpm
I~~~~ I~~~
CRUDE OIL G

"~

25

Z
o

2O

1400

e~

s
10308090

120

5 103080

0.5 1

MIXING TIME (rain)

Fig. 4. Standard deviation for mean droplet sizes in Fig. 3.

361
lOO

OIL C

90

[-.,
.<
.<

OIL D

[]

OIL E

OIL G

8O
7o
60

[]

[]

10

5O

[...,
.<

4O
3O
20
lO
0

12

14

pit

Fig. 5. Separationof waterfromcrudeoil emulsionsbasedon crudeoils C, D, E and G as a function

of pH in bufferedsystems. Preparationaccordingto procedureA. The aqueousphase was 50%
(v/v).
A water-in-oil emulsion is built up by water droplets surrounded by an interfacial film where the polar compounds are accumulated. The properties of
this stabilizing film will be highly decisive for the stability of the whole system.
In order to give a qualitative picture of the acid-base properties of this film,
we report on emulsion stability as a function of pH. Figure 5 summarizes the
results from the pH adjustments in buffer solutions on the stability of different
crude oil emulsions based on four different crude oils. The influence is not
uniform. Only one emulsion (based on crude oil E) shows a complete separation in the pH interval 5-7. Two others, i.e. C and D, show some instability
around pH 6 and 9. The influence of pH on emulsions based on crude oil G is
rather negligible. Summarizing, one can conclude that at very high and very
low pH values, the emulsions seem to be stable, while intermediate pH values
seem to cause instability. The range and degree of instability, however, is very
dependent on which crude oil the emulsion is based on.
It is commonly known that temperature changes will affect the stability of
emulsions. Especially for crude oil emulsions, a temperature increase is generally considered to destabilize the system. This is mainly due to the fact that
the viscosity of the continuous phase will substantially decrease, hence facilitating a collision between aqueous droplets. If this enhanced collision rate of
droplets results in an increased coalescence and separation, a destabilization
of the emulsion is accomplished. Figure 6 summarizes the separation process
at three different temperatures as a function of time. The separation process
has been observed for 24 h. A rise in temperature from 20 to 70 C causes a
separation of water, which is, however, not complete at 50 C. Even at 70 C,
the emulsions based on crude oils B, D and E show a low tendency to separate.
For the other emulsions investigated, the separation process is almost complete for the highest temperature.
An important individual parameter for the stability of the crude oil emul-

362
tO0
v ~
I~

70 a C

80,

//f"
40.

20-

12

16

20

24

(hours)

tOO
50 ~ C
e-~

8O

C~

6o

4o

2o
_

_~$
,
4

,
8

,
12

,
16

20

oo
,

24

[hours)

tO0
22~ C
e'~

8O

6O
.<

~,o
r.1

2o

o.~---o

o
[]
V
A

f . _ m
8

1'2

1'8

20

24

Crude
Crude
Crude
Crude
Crude
Crude
Crude
Crude

off
off
oil
oil
oil
oil
oil
oil

A
B
C
D
E
H
I
J

(hours)

Fig. 6. Separation of water from crude oil emulsions based on different crude oils as a function of
time and at different temperatures. Preparation took place according to procedure B. The aqueous
phase was 50% (v/v).

sions seems to be the emulsion viscosity. We have characterized the emulsion

viscosity for different contents of water in the emulsion. This was performed
at low shear rates of 100 s-1. At these conditions the emulsion was observed
to follow an equation of Richardson type [25], i.e.
~_e= en'~+k

0o
where ~e and 0o are the viscosity of the emulsion and the crude oil, respectively,
is the volume fraction of water emulsified, and n and k are constants. The
deviation from an ideal Richardson equation is the introduction of an intercept
different from zero ( k 0) in a logarithmic plot. Table 3 summarizes the values
of the constant n, together with R 2 values and the m a x i m u m amount of water
(~H20.ma~) that can be emulsified into each crude, without immediate separa-

363
TABLE3

Richardson's constant (n) as determined by linear regression (least squares method), and
~H._,o.... (%, v/v), the maximal amount of water that can be emulsified into the crude oil without
separation or inversion
Crude oil

CH~O. . . .

R2

3.7
4.7
2.4
2.5
4.7
3.1
3.9
3.6

0.97
1.0
0.98
0.94
0.99
0.99
0.97
0.99

(%,v/v)
A
C
D
E
G
H
I
J

80
70
70
70
80
60
80
70

tion of water or inversion of emulsion. The linearity between ln(~/e/t/o) and @

is shown in Fig. 7. At low shear rates, many of the emulsions investigated do
not show Newtonian behaviour.
In the final correlation of analytical and physicochemical properties of the
32 crude oils and their emulsions with regard to emulsion stability, the following parameters were selected: the content of wax, polar compounds and asphaltenes, the viscosities of the crude oil and the prepared emulsion, and, finally, the interfacial tension (crude oil/formation water). The selection was
based on a preliminary detailed characterization (14 parameters) of eight crude
oils and their corresponding emulsions.
Emulsion stabilities were expressed as the separation time (in minutes) at
20% water break-out. The very broad range to separation times was compressed on a logarithmic scale (log rain) for convenience.
The observed single-parameter correlations are presented in Table 4. As
mentioned previously, there seems to be a significant relationship (R2=0.59)
between emulsion stability and emulsion viscosity, as illustrated in Fig. 8. For
all other parameters, less significant correlations were observed.
A great number of multiparameter models were also investigated by regression analysis. The model types can be described by the following three generalized equations:

Y=ao +alX1 +a2X2 +a3X3+a4X4 +asXs +a6X6

Y = log ( e a. X~I- X~3. X~3. X ~ - X ~ . X ~ )

(I)
(2)
(3)

Here, Y represents the emulsion stability,Xi the six crude oil parameters and
ai the regression coefficients.

364
4.0

(a)

C R U D E OIL D

3.0

~"

2.0

1.0

O.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

VOLUME FRACTION WATER, ~b

4..0
(b]

CRUDE OIL J

3.0

xf

~'2.o

1.0

L
O, 1

0.2

0.3

0.4

0.5

0.6

0,7

0.8

VOLUME FRACTION WATER, ~b

Fig. 7. The viscosity of crude oil emulsions (#e) normalized to that of the pure crude oil (#o) as a
function of varying water contents (~). (a) Crude oil D, (b) crude oil J. Emulsification according
to procedure A.

365
TABLE 4
Definitions of parameters, symbols, measuring conditions and the significance of each individual
parameter in the stability correlationa
Parameter
(conditions/units)

Symbol

R2

Content of wax (%, w/w)

Content of polar compounds (%, w/w)
Content of asphaltenes (%, w/w)
Oil viscosity (T=40C, D= 100 s -i) (mPa s)
Emulsion viscosity (T=40C, D= 106 s -1) (mPa s)
Interfacial tension oil/water (T= 20 C ) (raN m- 1)
Emulsion stability (T=50C, water sep.) (log min)

X1

0.13

x2
X3

o.oo
0.11

X4

0.06

X5
Xe
Yw

0.59
0.19

aThe content of synthetic formation water is 50% (v/v) and the emulsions were prepared according to procedure B (see the Experimental).

''

..... i-----i

.~
.~

.....

12

10

..... !----':-----'---.:

i-----~ .....

,----,----'----,--.,----,

.....

.....
,

i----4-----i
,

.....

.....

.....

.....

,.-,-----,---,'---,-----,---,----,
. . . . .

..... i T ~ I "

._. '..~_...,:

"---!----!

. . . . .

....

:___

.....

.... ,----,-"'"'"'"---"-'""'"'

.... '----'---'----'----"---'----'

! o:

....

ioiO!

~----'J-

--i'----~

! el

-o--=--T---~i--i

20

.....

---'---'----'----'-----'----'----'

i
i

~____L--..~

..... [ [ i
i

40
EMULSION

"----'----"

.....

. . . . . }-----t----~ . . . . . I-----~----~ . . . . .

..... i....4....i._..i_.+.___!__.i_.....~-___b__i-----!----!----4

',_..." ..... ;.._.}..._" .....

.... ~----4----~-o-'----.~----,---,----,----,----,

.....

..... ~----~ .....

.-,.

.....
,

L----!----"

..... [--T---i

..... , , - , - , , , - - , " , - - , , , ,
. . . . .

,"-',

'----'----'-.--'----'--"

S0

i
,

~----:----~'
.....
!
i
i

.....

~---.,

"----'----"

.....

~ - - - . , . . . ~

.....

'----'----'-----'----'----'

..... VT---i
~

80

VISCOSITY

i
i

.....

.....

.....

..........

..... [ T i
,

100
ImPs.

120

.....

i
,

.....
140

s]

Fig. 8. Correlation between stability number and viscosity of emulsions based on 32 crude oils
from the Norwegian continental shelf. Emulsification according to procedure B.
T h e statistical analysis revealed a t h r e e p a r a m e t e r m o d e l capable o f predicting 71% o f t h e t o t a l v a r i a n c e in e m u l s i o n stability:
Y = log (e - 9.61. X}.91 oX 4 - 3.63. X55.06 )

(4)

T h i s is i l l u s t r a t e d in Fig. 9. T h e m o d e l i n p u t was limited t o wax c o n t e n t (X1),

crude oil viscosity (X4) a n d e m u l s i o n viscosity (Xs). O n l y insignificant imp r o v e m e n t s o f p r e d i c t i v e ability could be o b t a i n e d b y including m o r e
parameters.

366
14

..... i + - i - i

.~.

..... i---t---i--i----"---i---!

..... i----fff---iti-.i

.....

..... i - - 1 - t i - - T - - ~ i

..... ; ~ T ~ I

.....

..... i--i

.....

r~

, .....

. . . . . " " , _ _ _ _" , . . . _ _ ,"_ _ . . , _"_ _ _ . , . ", _ , _ _ _"_ ,

:

lO

.....

~-,.......~

4-----I-----~----4,
,
,

~'

.....

t-----~----q-----4

.....

',

F----I-----4

.....

I""-T-'";----I""--,'-'"'U---I

.....

..... i- i--

,----,----,-----,----,----,
I
',
',

i
4

i
6

.....
I

T-''"~

.....

.....

..... ~----i----'-----~----i----~ .....

~ ..... i..._.i..__L...i._...i____

.....

F---'T----I"'---F'"-

i-,i .....

, .....

L____L---" .....

i..._i_...T-y.-y..T---i~.~--i...-t----y-T---i

.............

..... l t - - i

. . . . . L _ _ A . . . . . .~. .
I

.... ~.t ~_____P.__'...--,~...-i----~

ea

F - i o - i .....

.....
.....

i-+-

..... i--i---i---i-oi-----~--i---i*-i----!---i

,----,-----,----,-----,----,----,,
,
,
,

--i - i - - i - ~ -

L__i...__L...L.-!

i
S

I
10

.....

~
12

i
14

CALCULATED STABILITY [ l o g e m i n u t e s ]

Fig. 9. Observed stability number versus calculated stability number derived from a base set of
three single parameters, i.e. wax content, crude oil viscosity and emulsion viscosity (R2= 0.71 ).
Experimental conditions as in Fig. 8.
DISCUSSION

The stability of water-continuous emulsions has been the subject of fundamental research for a long period of time. It is by now well recognized that the
surface forces involved in the stability of these emulsions are electrostatic repulsion between the oil droplets, steric effect originating from adsorbed polymer layers, particles adsorbed at the oil/water interface and the specific association tendency of the surfactants to form liquid crystals with a lamellar
geometry. The electrostatic repulsion in the aqueous environment is generally
created by the stabilizer (the surfactant). In order to screen this stabilizing
mechanism, the emulsions are normally destabilized by the addition of multivalent electrolytes. For oil-continuous emulsions, the importance of a repulsion of electrostatic origin is no longer discussed in a serious way. The basic
reason for this is that the low permittivity medium will cancel the electrostatic
repulsion and any importance of multivalent counter-ions as destabilizers.
When discussing the role of particles as stabilizers for crude-oil-continuous
emulsions, one generally restricts the discussion to clays and waxes. Of these,
at least for the conditions studied here, waxes should be considered to be more
important. The size of wax particles has been correlated to the stability of
crude oil emulsions. It was found that too large particles do not enhance the
stability of the emulsion. Hence, the melting and crystallization (and recrystallization) sequence of the waxes is of importance for the stabilizing properties of these compounds [22 ]. If the melting point is exceeded, the waxes will
mainly act as a component in the crude oil bulk and their activity at the oil/

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water interface is normally substantially reduced. This is clearly one reason
why an increase in the temperature normally destabilizes a crude oil emulsion.
The existence of natural polymers in these crude oils can be questioned and,
hence, also the importance of a steric stabilization as a mechanism dependent
on indigenous polymers. However, due to the addition of polymer-based production chemicals in different steps in the recovery of the crude oil, a steric
stabilization of the crude oil emulsions can be made possible.
The association of surface-active agents and the importance of structures
formed should be considered to have significant importance when discussing
the stability of oil-continuous emulsions [26-28]. One normally speaks of a
rigid and protective film as a result of the accumulation of surface-active material at the oil/water interface. A more detailed knowledge of the properties
of this film and of the detailed mechanisms involved in its effect on stability
is, however, mostly lacking. It is, though, obvious that one category of chemical
compounds of importance for the formation of an interfacial film in crude oil
emulsions is the asphaltenes. In a recent publication, some experimental evidence was given on the association of asphaltenes at the water/oil interface
[29 ]. It was pointed out that asphaltene particles appear to be regularly stacked
in lamellar structures, resembling the structure of the lamellar liquid crystalline mesophase D, which occurs in surfactant systems and enhances significantly the emulsion stability.
Useful information can be extracted from the pH dependence. Figure 5 clearly
indicates that very high and low pH values give a restored, or even enhanced,
stability as compared to intermediate pH values. Considering the stabilizing
mechanisms earlier presented, the observation in Fig. 5 reveals some extra
details not accounted for earlier. The polar groups originally present in the
interfacial film will most likely be ionized at these extreme pH values. Despite
this fact, the emulsions maintain, or even increase, their stability. No conversion to water-continuous emulsions will take place. This should be taken as an
indication of a low number of ionizable groups. Hence, extreme pH values are
not capable of creating high surface charge densities that would drastically
change the film properties by introducing an internal repulsion in the film,
destroying the mechanical properties that give rise to protection against coalescence. A possible mechanism for enhanced stability is the weak hydration
of the dissociated polar interfacial groups at the very high and low pH values.
This hydration of the few available charged endgroups will further enhance
the rigidity of the interfacial film. Furthermore, the stability at extreme pH
values reveals the absence of particles stabilizing the emulsions based on these
crude oils. Mineral particles would, at these extreme pH values, have different
wetting properties, which would be reflected in a dislocation at the interface
and, as a consequence, emulsion instability. This has been observed for emulsions based on crude oils and stabilized by Si02 particles [30].
Increased temperature is known to destabilize crude oil emulsions. This ef-

368

fect is a sum of the changes in many parameters. Trivially, it holds that the
bulk viscosity of the crude oil will decrease with increasing temperature, hence
facilitating an increased collision between the water droplets. A higher thermal
energy will of course enhance the collision frequency of droplets. This trend is
not sufficient to explain the separation of water (the coalescence of droplets),
since the system could remain in a flocculated state. Essential for the coalescence will be the changes taking place in the interfacial film as the temperature
increases. The interfacial viscosity is known to be temperature sensitive. But
contrary to bulk crude viscosity, which falls with increasing temperature, the
interfacial viscosity may decrease, increase or remain unchanged, depending
on the type of interface [14 ]. Another parameter of significance is the compressibility of the interfacial film. It has been reported that a coalescence of
water droplets in a water-in-crude oil emulsion is accompanied by a reduction
in surface area and, hence, a compression of the adsorbed indigenous crude oil
surfactants [ 14 ]. Formation of an incompressible and non-relaxing interfacial
film at high temperatures is indicative of a high emulsion stability. The compressibility of the film should be regarded as the result of altered solubility
properties of the crude oil surfactants or the result of a degassing process in
the film [14]. In addition to these mechanisms, one should also be aware of
the changes occurring in the association pattern of the crude oil surfactants as
a result of increasing temperature [31 ]. Essentially, the packing conditions of
the molecules will be different, and hence a destabilization of the emulsion will
Occur.

Our present study shows that the correlation between observed and calculated stability is described acceptably by an equation containing three crude
oil parameters. These parameters are the content of waxes, the crude oil viscosity and the emulsion viscosity, in order of increasing significance.
That useful information cannot be extracted on parameters like the content
of polar compounds and asphaltenes does not imply that these are insignificant
for emulsion stability. It can, however, be concluded that the properties of
active constituents, whether they are surface active a n d / o r aggregate-forming,
is not reflected by the gross weight of these operationally defined petroleum
fractions.
To some extent, the same argument also applies to the wax fraction, although wax amounts in excess of about 6% can be shown empirically to contribute to emulsion stability. However, the most important stabilizing contribution from wax components is associated with wax particle number and
morphology and, hence, closely related to wax molecular structure and the
temperature history of the crude oil.
Although the interracial tension measured by the ring method only weakly
correlates with emulsion stability, the importance of interracial film properties
should not be underestimated. In fact, at 50% water cut, implying a small mean

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droplet distance, coalescence must really be the rate limiting step in the separation process. Actually, the correlation study has been performed under conditions focusing on film properties, with a minimal contribution from Stokes
sedimentation processes. This explains the relative insignificance of crude oil
viscosity by itself. The water droplet coalescence rate seems to be related clearly
to emulsion viscosity, especially when measured in terms of the crude oil viscosity, as indicated by Eqn (4). The full implications of this observation are
yet to be understood, but further experimental efforts, including carefully designed model systems, may be of great value, especially when discussing a correlation between interfacial properties and emulsion viscosity.
In order to show the importance of changes in the interfacial film, we report
in subsequent works on the influence of demulsifiers on film properties and,
further, on the stability of model crude oil emulsions built up by surfactants
with different types of association patterns.
ACKNOWLEDGEMENTS

The Institute for Surface Chemistry (YKI) acknowledges the financial support from Statoil A/S (Contract no. T.9015), which made the work at the
institute in the area of crude oil emulsions possible. Valuable comments by
Professor Per Stenius on a preliminary manuscript are also acknowledged.
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