COLLOIDS

AND
A
Colloids and Surfaces SURFACES
ELSEVIER A: Physicochemicaland Engineering Aspects97 (1995) 119 128

Water-in-crude oil emulsions from the Norwegian continental shelf

11. Ageing of crude oils and its influence on the emulsion stability
Hans Petter Ronningsen a,,, Johan Sj6blom b, Li Mingyuan b
a Reservoir Technology, Fluid laboratory, Statoil A/S, Forus, N-4001 Stavanger, Norway
b Department of Chemistry, University of Bergen, N-5007 Bergen, Norway
Received 27 May 1994; accepted 11 December 1994

Abstract

The stability of water-in-oil emulsions based on some North Sea crude oils has been studied with particular
emphasis on the effects of ageing, i.e. exposure of the crude oils to air (and light). It is clearly demonstrated that the
interfacial tension of a crude oil towards formation water decreases substantially as a result of ageing. This seems to
be caused by the formation of various oxidation products, mainly carbonyl compounds. In addition, the water-in-oil
emulsions in general become more stable. However, in some cases a reversal of this trend has been observed, indicating
that oxidation products still with high interfacial activity but having less beneficial film properties are formed in the
later stages of the ageing process.

Keywords: Ageing; Emulsion stability; Water-in-crude oil emulsions

1. Introduction with its content of indigenous polar compounds,

It is frequently observed in studies of the forma-
tion and breaking of water-in-crude oil emulsions
that the results may be time-dependent, in the
sense that the measured emulsion stability depends
on the age of the crude oil sample, i.e. the extent
to which it has been subjected to air and light
exposure. This may apply not only on a long time-
scale (months), but also on a short time-scale
(hours), and may thus introduce errors and poor
reproducibility even within a single series of succes-
sive measurements. Consequently, the direct rele-
vance and reliability of such tests for process design
purposes may be highly questionable.
The idea that the tendency of a crude oil to
form stable water-in-oil emulsions is correlated
* Corresponding author.
found among the resins and asphaltenes, is well
documented [1]. With this background it would
not be surprising that processes which change the
polarity of a crude oil may change its ability to
form emulsions.
Possible changes that may occur during ageing
of a stabilized (atmospheric) crude oil exposed to
air and light, are; (1) loss of light ends (evapora-
tion); (2) precipitation of heavy components such
as wax and asphaltenes (these processes occur, of
course, even without exposure to air and light);
and (3) chemical alteration (oxidation/photolysis).
Such changes may in turn lead to changes in
physical properties such as density, viscosity, sur-
face/interfacial tension and dissolving capacity.
Finally, the stability of water-in-crude oil emul-
sions depends to some extent on each of these
properties of the oil phase. Processes like those

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120 tL P. Ronningsen et al./Colloids Surfaces A: Physicochem. Eng. A,spects 97 (1995) 119 128
mentioned above have been described in connec-
tion with studies of the behaviour of oil-spill
on the sea, then called weathering processes.
Evaporation is then most often the dominating
effect, but photo-oxidation has also been shown to
contribute [2].
To our knowledge, ageing effects occurring in
crude oils and their influence on the emulsion
formation tendency or other crude oil properties
have not been studied systematically before; at
least, only a few published results appear to exist.
Tort and Andersen [3] studied interracial behavi-
our and chemical changes taking place in an
asphalt sample subjected to progressively stronger
exposure to oxygen. In parallel with increased
levels of oxidation, they observed enhanced inter-
facial activity. In fact, an increased content of
asphaltenes was observed as well. These experi-
ments are, to some extent, similar to those con-
ducted by Sj6blom et al. [4] with interfacially
active fractions separated from some of the same
North Sea crude oils that are used in the present
paper.
With this background, a project was initiated in
order to study the changes that occur in some
North Sea crude oils as a result of exposure to air
and light, and their implications for the examina-
tion of emulsion formation and stability.
2. Samples
North Sea crude oils from five different fields,
all sampled at the separator outlet during the
testing of exploration wells and stored in 201
pressurized bottles, have been used. The bottles
were heated to 60°C overnight in the laboratory,
whereafter the oils were depressurized in one stage
to atmospheric pressure. The oils had been stored
from 1 month to 3 years in the pressurized bottles
prior to testing. The first test (i.e. no ageing) was
started as soon as practically possible after depres-
surization, i.e. within a few minutes. All crude oil
samples were aged at 50°C in transparent or dark
bottles with air naturally available, i.e. the exposure
to air was not forced or accelerated in any way.
Some oils were also stored under nitrogen for
reference.
3. Experimental
For the mixing of synthetic water-in-oil emul-
sions, a Buhler HO4 propeller-type homogenizer
was used. It was operated at 8000 rev min-1 for
1 rain. The sample volume was 11 ml. The water
cut was 50% and the temperature was 50 or 70 °C.
These mixing conditions have previously been
shown by Johansen et al. [5] to create droplet size
distributions that are fairly realistic compared to
that of naturally occurring emulsions, i.e. giving
mean droplet sizes of around 10 p,m with a stan-
dard deviation of about 5 ~tm. The emulsions were
transferred from the mixing vessel to a graduated
cylinder and were kept in a thermostatted bath at
the specified test temperature for an observation
period of at least 30 min, during which the water
break-out (free water as a percentage of the original
water) was recorded.
In tests conducted with demulsifier, this was
added as a 0.1% solution in xylene by shaking for
30 s immediately after mixing of the emulsion.
The total acid numbers of the crude oils were
measured according to ASTM D-664/89.
The density was measured at 15°C using a
frequency density meter ( D M A 4 0 with a
DMA 602M measuring cell; Anton Paar).
The kinematic viscosity was measured at 50°C
using Ubbelohde glass capillary tubes.
The dynamic viscosity was measured using a
Haake RV12 concentric cylinder viscometer equ-
ipped with an NV double-gap measuring system.
The cooling rate was 12°C h -1.
The surface tension and interfacial tension
towards synthetic formation water were measured
at 50°C using a KSV Sigma 70 interfacial tensiom-
eter (Du Noi~ying method).
The IR spectra of whole crude oils were recorded
using a Perkin-Elmer 1720 X Fouriertransform-
infrared spectrophotometer.
The total wax content was measured by a slightly
modified U.O.P. method 46 64, the so-called ace-
tone precipitation technique (at - 2 5 °C) described
by Burger et al. [6].
 H.P. Ronningsen et aL/Colloids Surfaces A: Physicochem. Eng. Aspects 97 (1995) 119-128 121

The asphaltene content was determined by pre-
cipitation with pentane at room temperature.
The wax formation temperature was determined
by polarization microscopy.
More details about methods for determination
of the wax content, asphaltene content, wax forma-
tion temperature, viscosity, pour point and density
are found in the paper of Ronningsen et al. [7].
More details about interfacial tension measure-
ments and IR spectra are given by Sj6blom et al.
E43.
4. Results
4.1. Emulsion stability tests --fresh oils (no
ageing)
Some relevant chemical and physical data of the
crude oils investigated are summarized in Table 1.
Emulsions based on fresh oils D and E (directly
from pressurized bottles) exhibited the slowest
dehydration; no observable water break-out took
place within 24h without use of demulsifier
(Fig. l(a)). These were rather waxy oils (particu-
larly oil E) with the highest asphaltene contents,
i.e. 1.2-1.7 wt.%. However, oil B, which was a
waxy oil with very low asphaltene content, also
formed a very stable emulsion (only 20% of the
original water breaking out within 24 h). Like oils
D and E, oil B had a very low acid number, i.e. a
low content of organic acids. It should be empha-
sized that the tests were conducted at a temperature
far above the wax formation temperature; thus no
contribution from wax particle stabilization is
likely. Neither was the viscosity of these oils high;
at 50°C it was in fact the lowest of all the oils
investigated, and the interfacial tension towards
formation water was not particularly low.
Fresh oil C also exhibited slow dehydration
during the first 30 rain after emulsion formation,
but, in fact, complete separation took place within

Table 1
Chemical and physical data of the fresh North Sea crude oils investigated

Characteristic Oil A Oil B Oil C Oil D Oil E

Molecular weight 244 241 233 192 263

Density at 15°C (kg m 3) 883.3 856.3 887.0 847.2 865.7
Clo + (wt.%) 91.20 89.12 88.44 79.03 90.15
C10 + aromatics (wt.%) 42.4 29.0 41.3 36.2 28.8
Total wax (wt.%) 2.2 14.8 6.7 11.4 15.6
Asphaltenesa (wt.%) 0.3 0.27 0.50 1.7 1.2
Sulphur (wt.%) 0.42 0.1 0.48 0.20
Total acid number (mg K O H g-1) 0.22 0.07 2.60 0.07 0.09
Basic nitrogen (wt.%) 0.031 0.014 0.023 0.031 0.013
Wax formation temp. (°C) 30 40 41 42 40
Wax dissolution temp. (°C) 50 53 55 - 50
M i n i m u m pour point (°C) -45 13 -48 12 16
Surface tension b (raN m - 1) 27.3 26.3 27.7 25.7 28.4
Interracial tension bc (mN m - 1) 28.8 26.7 24.6 22.3 26.1
Kinematic viscosity (cSt)
At 80~C 3.65 2.86 3.31 2.40 3.84
At 5 0 ' C 7.17 5.12 6.40 3.30 7.07
Dynamic viscosityd (mPa s)
At 20°C 16.9 46.7 29.1 19.5 155
At 5~C 41.1 295 56 78.6 900

a Pentane insolubles.
b At 50 °C.
c Towards synthetic formation water.
d At shear rate 100 s i.
122 H.P. Ronningsen et al./Colloids Surfaces A: Physicochem. Eng. Aspects 97 (1995) 119 128

100 4.2. Emulsion stability tests - - aged oils

l Oils D and E: No separation
"O
= 8oJ
; J A significant increase of e m u l s i o n stability was
~. 6o o b s e r v e d a l r e a d y after 24 h e x p o s u r e of oils A
; •• Oil
o,, CB
AJ (Table 2) a n d B (Table 3) to air (and light). This
~ 40, [ ] ~i'°il ! trend c o n t i n u e d for a b o u t 1 m o n t h . Thereafter, a
reversal of the trend t o w a r d s m o r e stable emulsions
o~ 202
t o o k place. F o r oil B the same t r e n d was also
o b s e r v e d with e x p o s u r e to air only (i.e. in a d a r k
1 10 100 1000 10000 bottle) (Table 4). F o r oil C (Tables 5 a n d 6) the
(a) Time (min) emulsions were originally very stable a n d no
1oo ~ o b s e r v a b l e change seemed to take place in the first
weeks. F r o m a b o u t 3 m o n t h s ( p e r h a p s s o m e w h a t
'o 80] earlier) there was a substantial change in the
• Oii direction of less stable emulsions, a trend that
~. 60 /J I eoil B
c o n t i n u e d at 6 m o n t h s as well. I n d i c a t i o n s of the
ffl ~0, C
~ 40' ~0iI D same k i n d of reversal has been observed with
~o E m o d e l emulsions stabilized with aged interfacially
o~ 201 active fractions from oil C [ 4 ] .
Even m o r e p r o n o u n c e d effects of ageing were
1 10 1oo 1ooo 1o0oo observed with oils D a n d E. Some emulsion sta-
(b) Time (min) bility d a t a for oil D are s u m m a r i z e d in Fig. 2. This
crude, which was rather asphaltenic (1.7 wt.%
Fig. 1. Separation of water as a function of time from w/o
emulsions based on fresh North Sea crude oils: a) Without p e n t a n e insolubles) formed extremely stable emul-
demulsifier and b) With 10 ppm demulsifier. sions. All e x p e r i m e n t s therefore h a d to be per-
formed at higher t e m p e r a t u r e (80 ° C) a n d b y using
24 h (Fig. l(a)). This oil h a d r e m a r k a b l y high acid demulsifier to b r e a k the emulsions. It is seen in
n u m b e r a n d a m o d e r a t e a s p h a l t e n e content. Fresh Fig. 2 that emulsions based on fresh oil (directly
oil A, which was a low-wax, l o w - a s p h a l t e n e b i o d e - from a pressurized bottle) were quite easy to b r e a k
g r a d e d oil, showed the fastest s e p a r a t i o n with 60% with demulsifier (94% within 6 mins). A l r e a d y after
of the original w a t e r b r e a k i n g out within 30 min. 3 h e x p o s u r e to air a n d light (at 50°C), a substan-

Table 2
Emulsion stability data for oil A (aged with air and light at 50°C) 50% water

Ageing Free water separated (%)

time
After 1 min After 3 min After 6 min After 10 min After 15 min After 20 min After 30 min After 24hrs

0 11 (16) 20 (90) 38 (94) 40 (95) 45 (95) 48 (95) 60 (95) G)

2h (8) (88) (88) (90) (90) (90) (90) ()
24 h 1 (10) 8 (92) 14 (94) 14 (94) 16 (94) 20 (94) 30 (96} (-)
1 week (14) (90) (92) (92) (94) (94) (95) - (-)
1 month 0 (5) 0 (54) 0 (92) 0 (92) 0 (94) 0 (94) 1 (94) 42 (98)
1 month" 1 (24) 2 (92) 3 (96) 5 (96) 8 (96) 12 (98) 16 (98) 76 (98)
3months 0 (34) 0 (80) 2 (90) 8 (92) 24 (92) 32 (94) 60 (94) 86 (98)
3months a 0 0 0 2 3 4 4 46

Results obtained with 10 ppm demulsifier are given in parentheses.

a Crude sample stored under nitrogen in the dark at 50°C.
 H.P. Ronningsen et al./Colloids Surfaces A: Physicochem. Eng. Aspects 97 (1995) 119 128 123

Table 3
Emulsion stability data for oil B (aged with air and light at 50°C) 50% water

Ageing Free water separated (%)

time
After 1 min After 3 min After 6 min After 10 min After 15 min After 20 min After 30 min After 24 h

0 1 (6) 2 (46) 4 (98) 6 (98) 8 (98) 8 (98) 12 (98) 22 (100)

2h 0 (0) 1 (18) 2 (90) 3 (98) 3 (100) 4 (100) 6 (100) 14 (100)
24 h 0 (0) 0 (68) 1 (98) 1 (100) 1 (100) 1 (100) 1 (100) (100)
1 week 0(0) 0 (10) 0 (32) 0 (68) 0 (90) 0 (94) 0 (98) 1(100)
1 month 0 (0) 0 (2) 0 (60) 0 (90) 0 (98) 0 (100) 0 (100) 0 (100)
3months 0 (0) 0 (8) 0 (16) 0 (56) 1 (84) 1 (86) 2 (90) 24 (100)

Results obtained with 10 ppm demulsifier are given in parentheses.

Table 4
Emulsion stability data for oil B (aged with air (dark) at 50°C)-50% water

Ageing Free water separated (%)

time
After 1 min After 3 min After 6 min After 10 min After 15 min After 20 min After 30 min After 24 h

0 1 (6) 2 (46) 4 (98) 6 (98) 8 (98) 8 (98) 12 (98) 22 (100)

2h . . . . .
24 h 0 (0) 0 (40) 0 (76) 0 (98) 0 (98) 0 (98) 0 (98) 0 (100)
1 week 0 (0) 0 (60) 0 (96) 0 (96) 0 (96) 0 (98) 0 (98) 0 (100)
1 month 0 (0) 0 (10) 0 (90) 0 (98) 0 (98) 0 (98) 0 (100) 0 (100)
3 months 0 (0) 0 (0) 0 (94) 1 (96) 1 (96) 2 (96) 14 (96) 32 (96)

Results obtained with 10 ppm demulsifier are given in parentheses.

Table 5
Emulsion stability data for oil C (aged with air and light at 50°C)-50% water

Ageing Free water separated (%)

time
After 1 min After 3 min After 6 min After 10 min After 15 min After 20 min After 30 min After 24 h

0 0 (44) 2 (98) 0 (98) 0 (100) 0 (100) 0 (100) 0 (100) 100

2h 0 (32) 0 (98) 0 (98) 0 (98) 0 (98) 0 (98) 0 (100) 100
24 h 0 (28) 0 (96) 0 (98) 0 (100) 0 (100) 2 (100) 15 (100) 96
1 week 0 (58) 0 (92) 0 (96) 0 (96) 0 (98) 0 (98) 5 (100) 98
1 month (3) (90) (92) (94) (94) (94) (100)
3months 0 (6) 2 (84) 16 (88) 70 (90) 90 (90) 90 (90) 90 (98) 100
3months 0 (12) 0 (92) 0 (94) 0 (96) 0 (96j 0 (96) 0 (96) (98)
6months 0 2 16 60 90 90 90 94

Results obtained with 10 ppm demulsifier are given in parentheses.

tial i n c r e a s e o f s t a b i l i t y w a s o b s e r v e d , a n d a f t e r 1 months ageing, the behaviour had nearly returned

month no water break-out occurred within the to the original!
first 2 h a f t e r m i x i n g . A f t e r 7 m o n t h s a g e i n g , a E m u l s i o n s b a s e d o n t h e w a x y oil E w e r e h a r d
r e v e r s a l o f t h e t r e n d h a d t a k e n p l a c e a n d a f t e r 10 t o b r e a k e v e n w i t h d e m u l s i f i e r , a n d as s e e n i n
124 H.P. Ronningsen et al./Colloids Surfaces A." Physicochem. Eng. Aspects 97 (1995) 119 128

Table 6
Emulsion stability data for oil C (aged with air (dark) at 50°C) 50% water

Ageing Free water separated (%)

time
After 1 min After 3 min After 6 min After 10 min After 15 min After 20 min After 30 min After 24 h

0 0 (44) 0 (98) 0 (98) 0 (100) 0 (100) 0 (100) 0 (100) 100 (100)

2h . . . . .
24 h (8) (88) (88) (90) (90) (90) (92)
1 week (1) (90) (94) (96) (98) (98) (100)
1 month 1 (1) (86} (88) (88) (90) (90) (92)
3months 0 (6) 5 (88) 14 (96) 90 (96) 92 (96) 92 (96) 92 (98) 98
6months (1) 2 (80) 18 (92) 76 (92) 96 (94) 98 (94) 100 (96) 100 (96)

Results obtained with 10 ppm demulsifier are given in parentheses.

100
Ageing 1 ON . . . .
time: Ageing time:
'10 80
IINo "o 8 •
,= ! 0'3 hrs BBNo
60 i AZ4hrs
U) I O 1 week ~ 6 ' : '2:rhrs
40 @ 1 month • 1 week
t~ -~ 7 months 4 ~ 1 month
20 10 months I ~ 3 months
o~ 2
i V 6 months
0 [ )~t 9 months
0 10 20 30
1 10 100 1000
Separation time (min) Separation time (min)
Fig. 2. Effect of ageing with air and light at 50°C on water Fig. 3. Effect of ageing with air and light at 50°C on water
separation from emulsions based on crude oil D. Water cut; separation from emulsions based on crude oil E. Water cut;
50%; temperature; 80°C; demulsifier; 10 ppm NH-601 IX. 50%; temperature; 70°C; demulsifier; 10 ppm NH-6011X.

Fig. 3, a gradual change towards more stable emul-

sions took place. After 6 months, no water break- 100 i
Ageing time:
out was achieved within 24 h after mixing. So far, "o 80
there was no evidence of any reversal of the trend
P F INo
for this oil. ~. 60!
• 24 hrs
For oils D and E a very slight increase in i A 11 days
stability was observed even when the oils had been 40
~ • 40 days
stored under nitrogen (for several months). This is
20
illustrated for oil E in Fig. 4. For oil A as well,
slightly enhanced emulsion stability was evident 0
when the crude oil was stored in the dark under a 0 10 20 30
nitrogen atmosphere (Table 2). The same reversal Separation time (min)
after about 3 months ageing, as in the case with Fig. 4. Effect of ageing in nitrogen (in the dark) at 50°C on
exposure to air, is n o t seen to occur. This indicates water separation from emulsions based on crude oil E. Water
that although a gradual change, in fact, may occur cut; 50%; temperature; 70°C; Demulsifier; 10 ppm NH-601 IX.
 H.P. Ronningsen et al./Colloids Surfaces A." Physicochem. Eng. Aspects 97 (1995) 119-128 125

even in a nitrogen atmosphere, p r o b a b l y owing to 4.4. Density and viscosity

small a m o u n t s of oxygen dissolved in the oil during
depressurization, the ageing process is slowed For all the oils, a slight increase in density and
down, as one would expect. viscosity was observed during 3 m o n t h s ageing at
50 ° C. D a t a for crude oil A are shown in Table 7
4.3. Interracial tension as a typical example. This increase can mainly be
attributed to a certain (though small) loss of light
The interfacial tension (at 50 ° C) between crude components. The density in general increased by
oil A and synthetic formation water was measured 0.2-0.4% and the viscosity by 2-4%. These changes
regularly for a period of 50 days after depressuriza- are too small to have any significant effect on the
tion of the live separator oil. The results are emulsion stabilities.
summarized in Fig. 5. A more or less linear reduc-
tion from about 28 to about 1 6 m N m -~ was 4.5. Acid number
observed. There is a tendency of the curve to level
out at a value of about 15 m N m -1. N o significant In Table 1 it can be noted that oil C had a very
effect of using U V instead of ordinary light was high acid number, 2.60, i.e. a b o u t ten times higher
observed in this case. than n o r m a l for N o r t h Sea crude oils. This is
nicely correlated with a dominating carbonyl peak
a r o u n d 1725 cm -~ in the infrared spectrum of the
interfacially active fractions (Fig. 4 in Ref. 4), com-
3O pared to oils A and B (particularly B), which had
Temperature: 50 °C low acid numbers. Also oils D and E had very low
+uv acid numbers.
"
0
25 I
I As seen in Table 8, no significant increase in the
= -UV
-I total acid n u m b e r of oils A and C was observed
as a result of exposure to air and light for 3
months, only a very slight increase for oil C, almost
within experimental error.
C

-- 15 .... i L i i i i i

0 10 20 30 40 50 60 5. D i s c u s s i o n
Storage time (days)

Fig. 5. Interfacial tension between crude oil A and synthetic Low interfacial tension towards the water phase
formation water as a function of ageing time at 50°C. is beneficial with regard to the formation of small

Table 7
Density (15°C) and kinematic viscosity (50°C) vs. ageing time (at 50°C) for oil A

Ageing Ageing with air and light Ageing with air (dark) Ageing under nitrogen (dark)
time
Density Viscosity Density Viscosity Density Viscosity

0 881.6 6.71 881.6 6.71 882.5 6.68

2h 881.9 6.73 - -
24 h 883.2 6.91 881.7 6.68 883.6 6.72
I week 884.0 6.83 883.8 6.74 883.4 6.67
1 month 882.7 6.78 882.7 6.78 882.9 6.78
3 months 882.7 6.80 883.1 6.85 883.5 6.88
8 months 883.0 6.98 6.96 -
126 H.P. Ronningsen et al./Colloids Surjaces A. Physicochem. Eng. A~pects 97 (1995) 119-128
Table 8
Total acid number (mg KOH per gram of oil) of oils A and C
as a function of ageing in air and light
Ageing time Aged in air and light Aged in air (dark}
Oil A Oil C Oil A Oil C
No ageing 0.25 2.51 0.25 2.51
24 h 0.24 2.55 0.24 2.50
1 week 0.22 2.56 0.22 2.55
1 month 0.22 2.52 0.22 2.59
3 months 2.61 2.64
water droplets in the continuous oil phase.
However, low interfacial tension itself does not
ensure stable emulsions. The main mechanism
behind the stabilization of water droplets in a crude
oil is believed to be the formation of rigid interfacial
films (see Refs. [ 8 - 1 0 ] and others). In addition,
particle and polymer (steric) stabilization may con-
tribute. Hence, interfacially active components pre-
sent in a crude oil must also possess beneficial film
properties in order to promote stabilization of
water-in-oil emulsions. Asphaltenes are known to
possess both these properties and a correlation is
thus normally seen between the asphaltene content
and the tendency of a crude oil to form stable
emulsions [ 1,11 ].
The rather high asphaltene content of oils D
and E (compared to most North Sea oils) may
thus partly explain the stable emulsions formed by
these oils. However, like oil B, which also formed
stable emulsions, oil D and E were waxy (wax
contents between 11.4 and 15.6 wt.%). The total
wax content has previously been identified (to-
gether with the oil viscosity) by Johansen et al.
[5] as an important parameter for the prediction
of emulsion stability. Waxes may promote stabili-
zation either as particles, i.e. below the wax forma-
tion temperature, or on the molecular level as
lipids. The experiments in this study were con-
ducted at 50°C which is about 10°C above the
wax formation temperatures of the oils. Hence,
although the presence of submicron wax crystals
cannot be completely excluded, the molecular effect
of the waxes is probably the most important in
these cases.
Crude oils are known to contain acidic corn-
pounds, ranging from relatively strong carboxylic
acids to weak phenolic and naphthenic acids [ 12].
The total acid number of a crude oil is a measure
of the overall content of acidic compounds and is
determined by alkali titration. Such compounds
are known to exhibit interfacial activity [13] and
the acid number could thus be suspected to give
an indication of the tendency of a crude oil to
form stable water-in-oil emulsions, like for instance
the polarity index proposed by Brianing [14].
Moreover, the acid number might be used as an
indicator of oxidative changes taking place during
the ageing of a crude oil.
Oils B, D and E, which had the lowest acid
numbers, formed equally stable or more stable
emulsions than oil C. Other examples from our
laboratory also indicate that oils with low acid
numbers form very stable emulsions. We have seen
no examples, so far, of high-acid-number crudes
that do not form stable emulsions. No definite
correlation can thus be identified between total
acid number and tendency of a crude oil to form
stable emulsions. It appears that high-acid-number
crudes, in general, form rather stable emulsions,
whereas low-acid-number crudes may or may not
form stable emulsions. It was surprising to notice
that no increase in acid number took place as a
result of ageing, even though it was clearly demon-
strated by Sj6blom et al. [4] that ageing of inter-
facially active fractions was accompanied by a
substantial increase in the same carbonyl peak in
the IR spectrum that distinguishes oil C from the
other oils. However, since carboxylic acids and
other carbonyl compounds (ketones, aldehydes,
etc.) are not very well separated in the IR spectrum,
this fact may be taken as an indication that the
main oxidation products formed as a result of
ageing, although being highly interfacially active,
are not of the acid type.
The reduction of interfacial tension between
oil A and formation water is not very surprising
in view of the results of Sj6blom et al. [4] with a
model system with interfacially active fractions
added. They found even more pronounced reduc-
tions of interracial tensions with ageing of the
fractions. The trend seen in Figure 5, is likely to
be representative for most crude oils. This means
that in the study of phenomena that depend on
 H.P. Ronningsen et al./Colloids Surfaces A: Physicochem. Eng. Aspects 97 (1995) 119-128
the interfacial tension, such as emulsion formation,
aged crude oil samples may give a highly erroneous
impression of the real properties of that fresh
crude oil.
The clear demonstrations of ageing effects shown
in this study mean that oxidation products formed
as a result of the ageing of crude oil may not only
give rise to enhanced interfacial activity and thus
easier droplet formation. They also are able to
promote the long-term stabilization of dispersed
water droplets by the mechanisms mentioned
previously.
The mechanism behind the reversal of the trend
towards more stable emulsions with ageing
observed in several cases is not understood in
detail yet. Sj/Sblom et al. [4] found no such trend
in the interfacial activity of the pure oxidized
fractions. It is well known that surface active
compounds added to a surfactant solution can
have a film-stabilizing effect when present in low
concentrations. At higher concentrations they can
have a reverse effect. A possible explanation could
be that even though more interfacially active com-
pounds are formed all the time, the late oxidation
products have less beneficial film properties, possi-
bly due to "wrong" molecular weights. Hence,
these compounds, due to their high interfacial
activity, tend to replace other compounds present
at the oil-water interface and thereby creating a
less stable film.
In many (perhaps most) cases, emulsion stability
will be overestimated using bottle tests conducted
with aged crude oil samples. However, owing to
the possible reversal, such tests need not necessarily
be conservative. Whether they are, may depend on
the particular oil. The only way to obtain reliable
results is to conduct tests on fresh crude oil samples
as soon as possible after the flash of pressurized oil.
One should be aware of the possibility that not
only the time a crude oil has been in contact with
air, but also its total age (including storage time
in pressurized bottles) and the location of the
sampling point during well testing (i.e. bottom
hole, wellhead, separator or stock tank) might
influence the results of the emulsion formation and
stability tests. We have, in fact, observed indic-
ations that crude oil obtained from a single-phase
bottom-hole sample from a North Sea field pro-
127
duces less stable emulsions than corresponding oil
obtained from an ordinary bottom-hole sample
(which had been below its bubble point and repres-
surized into the single-phase state) and separator
samples, each collected and stored under pressure.
This could be related to differences in the state of
dissolved asphaltenes, and is also a factor that has
to be considered seriously. This will be examined
in more detail together with possible ageing effects
taking place immediately after depressurization of
live reservoir oil, and published in a subsequent
paper.
6. Conclusions
The stability of water-in-oil emulsions based on
North Sea crudes appears to be mainly correlated
with the wax and asphaltene content, in agreement
with previous studies. There appears to be no
definite correspondence between the total acid
number and the tendency of a crude oil to form
stable emulsions.
Crude oils are subjected to chemical alteration
as a result of exposure to air. In particular, car-
bonyl compounds and certain condensation pro-
ducts have been identified. Even when stored under
nitrogen, gradual changes seem to occur in the
direction of more stable emulsions, probably due
to small amounts of dissolved oxygen. When
exposed to air for several months, a reversal of the
trend towards more stable emulsions has been
observed in several cases. The reason for this
behaviour is not clearly understood, but may be
related to differences in the film properties of
oxidation products formed in earlier and later
stages of the ageing process. Ageing effects tend to
be less pronounced in tests where demulsifier is
used to break the emulsions. This is actually reas-
suring, since most emulsion tests in practice will
be conducted with demulsifiers. There are, how-
ever, examples of substantial ageing effects also in
experiments in which demulsifier has been used.
Slight increases in the density and viscosity of
the oils as a result of light end loss have been
observed. These changes are far too small, however,
to influence the emulsion stability to any great
extent.
128 H.P. Ronningsen et al./Colloids Surfaces A. Physicochem. Eng. Aspects 97 (1995) 119-128
The results emphasize the need to use oil samples
as fresh as possible when evaluating the emulsion
formation tendency of a crude oil and when evalu-
ating the performance of chemical demulsifiers.
Preferably, tests should be conducted in such a
way that contact with air is completely avoided
or, at least kept to a minimum.
Acknowledgements
Technical assistance by Brit Bjorndal and
Gunbjorg Fagerland, both of Statoil RESTEK-
Fluidlab, with the emulsion stability tests, and the
density and viscosity measurements, and by
Kjartan Sletten, Statoil SFTK at Mongstad, with
acid number measurements, is gratefully
acknowledged.
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