SPE 164910

Effects of Brine on Crude Oil Viscosity at Different Temperature and Brine

Composition - Heavy Oil/Water Interaction
Heron Gachuz-Muro, Heriot Watt University/Pemex E&P; Mehran Sohrabi, Heriot Watt University

Copyright 2013, Society of Petroleum Engineers

This paper was prepared for presentation at the EAGE Annual Conference & Exhibition incorporating SPE Europec held in London, United Kingdom, 1013 June 2013.
This paper was selected for presentation by an SPE program committee following review of information contained in an abstract submitted by the author(s). Contents of the paper have not been
reviewed by the Society of Petroleum Engineers and are subject to correction by the author(s). The material does not necessarily reflect any position of the Society of Petroleum Engineers, its
officers, or members. Electronic reproduction, distribution, or storage of any part of this paper without the written consent of the Society of Petroleum Engineers is prohibited. Permission to
reproduce in print is restricted to an abstract of not more than 300 words; illustrations may not be copied. The abstract must contain conspicuous acknowledgment of SPE copyright.

Abstract
For decades, it has been observed that temperature has a significant impact on viscosity reduction, mainly, in heavy and
extra-heavy oils where increasing the temperature will improve the flow of oil through the reservoir. Austad and his group
have reported that three main ions (SO42-, Mg2+, Ca2+) are potential determining ions for improving oil recovery in carbonate
rocks. Both of them must act together. Their studies focused on studying light oils. At the same time, they pointed out the
importance of injected fluid/crude oil/rock interactions.
Water injection is the most widely used oil recovery technique which has been extensively applied globally in both light and
heavy oil reservoirs for decades. Historically, the composition of injection water is dictated by the source of water available
for injection. However, recent investigations have shown that the composition of the flood water can have a significant
impact on oil recovery achived by water flood. Both total salinity and individual ions content of water have been shown to
affect the performance of water flood. It has also been observed that interactions between water and crude oil may affect the
oil viscosity. Most of the available research results are on light oil systems but the impact of water composition and its
interactions with heavy oil have not been investigated.
In this paper, we have experimentally investigated the interactions between brine and heavy oil. The focus of the study was
largely on the impact of brine on heavy crude oil viscosity. Four different heavy oil samples were selected from a group of
reservoirs and tested in this study. Experiments were conducted using different types of water at different temperatures.
Synthetic seawater, formation water, normal brine and distilled water were used as selected brines. The heavy oils were
brought in contact with selected brines such that each sample (system) consisted of 80/20 (brine/heavy oil) volume percent.
The viscosity and water contact of the each oil was measured before and after the oil had been in contact with brine.
The results of this paper indicate the crude oil viscosity may be altered due to contact with brine. The composition of brine as
well as crude oil affect whether the oil viscosity increases, decreases or remains unchanged. The results are important for
water injection and handling both on the surface and also in the reservoir.

Introduction
For decades, water has been injected in oil reservoirs as an efficient and cost effective way to prolong the productive life of
an oil reservoir. Although from practical point of view water flooding is relatively straightforward, interactions between
injected water and reservoirs rock and fluids can be quite complicated and sometimes unexpected behaviours are observed.
This indicates that, despite extensive research and field applications of water injection, to date, our understanding of the
process remains incomplete. Nonetheless, there is no doubt that the injection of water has helped oil recovery in many
favourable ways throughout the oil industry.

SPE 164910

In general, for heavy and extra-heavy oils, it has mainly been observed that temperature has a significant impact on the oil
viscosity. Increasing the temperature reduces viscosity and may improve the flow of oil from the reservoir to the wells and
then finally to the surface. The effect of temperature on the oil viscosity has been extensively studied; however, very few
laboratory studies have been performed o investigate the possibility of reducing the viscosity of a crude oil by simply putting
it in contact with water.
In recent years, particularly in the last 10 years, many research results have shown that smart water obtained by designing
or varying water composition and salinity may improve oil recovery. Austad et al., (2005, 2006 and 2011) have
systematically studied and verified that seawater is able to alter the wettability of some carbonate rocks. The presence of
SO42-, Mg2+, Ca2+ ions in seawater helped to improve oil recovey at temperatures above 90 oC. Most of their reported studies
were focused on fluids/rock interactions. According to Zahid and al. (2011 and 2012), crude oil/brine interactions (i.e.,
fluid/fluid interactions) at different temperatures and pressures may also contribute to improving oil recovery using seawater.
Zahid and als suggestion of the link between sulphates and crude oils have been of considerable interest. In one article
(2011) they observed how some microemulsions were formed with the rise in sulphate concentrations at high pressure and
temperature but no important viscosity changes was reported. They also observed that the measured water content in the
crude oils after interacting with brines did not cause significant change in the viscosity of the oil. Such observations raise
questions as to the effect of the interactions between injection and formation fluids on reducing the viscosity for certain crude
oils.
The purpose of this work was to investigate experimentally whether heavy oil viscosity could be affected possible crude
oil/brine interactions. We also aim to explore if the benefits of certain components of brine such as Ca2+, Mg2+ and SO42- that
have been shown to influence the viscosity of light oils can be seen in heavy oil systems.

Experimental work
Crude oil- Four Heavy crude oil samples taken different reservoirs were used in the experiments reported here. Some of the
crude oil properties measured at 20 oC are listed in table 1.
Table 1. Crude Oil Properties

Crude

Density

Viscosity

Acid Number

Base Number

Oil

(0API)

(cp)

(mg KOH/g)

(mg KOH/g)

12.55

53,484

1.00

3.50

15.44

295,328

0.35

4.60

16.62

1,686

1.35

3.40

20.96

739

Brine- Three brine solutions with different compositions were prepared for this study. A synthetic Seawater (SW) and a
synthetic Formation Water (FW) were prepared and used in the experiments. In order to have a reference system without
sulphates and Mg2+, Distilled Water (DW) and another synthetic brine, refered here to as Normal Brine (NW), were used.
The seawater used for the experiments represents that of the Gulf of Mexico. Table 2 depicts the composition of each brine.
Brines were reformulated from the original compositions in the laboratory using distilled water and salts. SW brine contains
significant amounts of Ca2+, Mg2+ and SO42- ions but the FW brine only contains small amounts of Mg2+ and SO42-.

SPE 164910

Table 2. Brine Compositions

Ion

SW (mg/L)

FW (g/L)

NW (g/L)

DW (g/L)

Na+

11,429.38

9,614.97

3,147.00

Ca2+

429.60

320.36

365.00

Mg2+

1361.60

218.94

K+

351.10

Ba2+

0.01

Sr2+

8.37

Cl-

20,040.00

15,117.25

5,498.73

SO42-

3,500.00

550.63

HCO3-

47.58

1,135.9

Equipment- A temperature-controlled viscometer (VISCOlab 3000) was used for viscosity measurements at different
temperatures, Figure 1. The device is equipped with an integrated heater that allows this precision viscometer to accurately
deliver measurements at user-defined temperatures from slightly above ambient to 180 oC. It provides continuous viscosity,
temperature readings with an accuracy of 1.0 %. Additionally, we employed a DM 40 density meter which measured the
density of the crude oil samples accurately. The instrument is able to calculate the density at temperatures between 15 and 60
o
C. It requires a small sample volume and is suitable for very viscous fluids. We also made use of a C20 Compact KF
Coulometer for measuring the water content of crude oil samples before and after the experiments. In all tests, the
measurements were repeated to verify the accuracy and repeatability of the measurement.

Figure 1. Fluid chamer of the temperature controlled viscometer used in this study.

SPE 164910

Experimental Procedure- The procedure for preparation of each sample was as follows:

Prepare brines with different compositions, Table 2.

Centrifuge the crude oil samples at 600 rpm for at least 4 hrs at 60 oC to remove any water or solids particles.
Contact oil and water with the ratio of 20% oil and 80% water (20/80 volume %).
The temperature of the oven is set to 92 oC (working temperature).
The samples were in contact (aged) for one week at working temperature.
Gently rock the sample container periodically (three times per day).
Take the sample out of the oven and leave them on the bench either overnight or for one week.
The sample was centrifuged to fully separate oil and brine.
Measure both viscosity and density at various temperatures.
Finally, measure the water content of the crude oil and compare with its value before the test (before contacting with
brine).

The viscosity measurements were repeated to determine the accuracy and reliability of the results. From each crude sample
separated after being in contact with brine, three smaller samples were taken for which viscosity and density were measured.
The error of the measurement ranged from 1 to 3% which is regarded as low. The measurements estimations of the values
were performed at room temperature, 20 oC. Figure 2 shows tests procedure and stages schematically. In order to be able to
make a sound comparison, all parameters of the tests were kept constant with brine composition being the only variable
which was changed in this set of experiments.
92 oC

20 oC

Overnight

Selected Brine

Sample

Crude Oil
System

Equilibrium

Viscosity
Measurements

One week

Figure 2. Procedure for the systems at 92 C

Results and Discussions

Viscosity Reduction
Crude Oil A- The oil viscosity was reduced after interacting with certain brines. The results, as summarized table 4,
indicate that the concentration of some ions played a role in the observed variation of the viscosity. As can be seen from table
2, a reduction in the concentration of Na+, Mg2+, HCO3-, SO42- and Cl- ions in the brine (FW or NW) would seem to have
caused a reduction in the viscosity of crude oil A. However, in our experiments, the same trend was not observed when SW
was used. On the contrarily, this brine (SW) increased the oil viscosity by 2.89 %. Table 4 also shows the density of the crude
oil A measured before and after contacting the oil with different brines. As can be seen, in addition to viscosity, the density
of the oil has also been affected differently by different brines.

SPE 164910

Table 4. Oil viscosity values for crude oil A

System

Viscosity

Viscosity
at 20 oC

Reduction

(cp)

(%)

Density
(API)

Viscosity
at 40 oC (cp)

Viscosity
at 65 oC (cp)

Viscosity
at 90 oC (cp)

Viscosity at
115 oC (cp)

Crude oil A

53,484.31

14.12*

3,224.43

450.90

120.61

44.67

Crude oil A/SW

55,030.43

22.44

3,516.54

512.21

140.81

53.24

Crude oil A/FW

30,158.71

43.61

12.89

2,310.97

382.27

114.44

46.14

Crude oil A/NW

36, 314.00

32.10

3,614.21

495.19

151.27

61.92

Crude oil A/DW

253,198.00

10,936.84

1,210.86

276.98

91.17

Crude Oil B- Significant reduction in viscosity was observed for this crude oil. However, the contribution of the ions in
influencing the oil viscosity reduction was not the same as that observed for crude oil A and therefore the results, table 5,
are not consistent with those of the previous crude oil. For instance, the observed variation of viscosity of the oil in this case
could not be completely attributed to the interactions with Na+, Mg2+, HCO3-, SO42- and Cl- ions or to the reduction of Ca2+
ions. This indicates that, in affecting the viscosity of the oil, not only the brines composition is important but also oil
constituents play a role. This observation may indicate that different oil constituents, such as resins and asphaltenic
compounds in heavy oils, may be causing atypical rheological behaviour. Such components, in contact with a brine, may
affect the viscosity of crude oils.

Table 5. Oil viscosity values for the crude oil B

Viscosity

Viscosity

Density

(cp)

Reduction (%)

(API)

Viscosity Viscosity Viscosity Viscosity

at 40 oC at 65 oC at 90 oC at 115 oC
(cp)
(cp)
(cp)
(cp)

295,328.67

15.44*

11,260.33 1,142.35

246.44

77.62

Crude oil B/SW 101,639.06

65.58

14.93

8,005.66

1,349.57

409.20

166.56

Crude oil B/FW

62,829.70

78.72

20.41

5,705.58

1063

344.66

147.55

Crude oil B/NW 140,071.30

52.57

14.39

8,988.10

1313

361.67

136.94

System
Crude oil B

Crude oil B/DW

To further investigate the effect of brine composition on crude oil viscosity and density, two other crude oil samples were
tested using exactly the same procedure that had been followed for Crude A and B.
Crude Oil C- The results of the measurements performed on this crude oil are shown in Table 5. Unexpectedly, it was
observed that crude oil C/FW system did not exhibit a reduction in the oil viscosity, unlike what had been observed with the
previous two crude oil samples. Previous results obtained for crude oil A and crude oil B were consistent with regards to
the effect of FW, which in both cases resulted in reduction of the oil viscosity. The measurements showed a small reduction
of the crude oil viscosity after being treated with seawater which again was not consistent with previous observations. In
contrast to crude oils A and B, the density of crude oil C remains the same when contacted with different brines and
the observed difference in density values for the systems of crude oil C was practically negliglable. Comparison of the
results presented in tables 4, 5, and 6 shows a considerable difference in density values.

SPE 164910

Table 6. Oil viscosity values for the crude oil C

Viscosity

Viscosity

Density

(cp)

Reduction (%)

(API)

System

Viscosity
Viscosity
Viscosity
at 40 oC (cp) at 65 oC (cp) at 90 oC (cp)

Viscosity
at 115 oC (cp)

Crude oil C

1,686.60

16.48*

225.95

55.27

21.51

10.56

Crude oil C/SW

1,562.47

7.35

16.57

231.46

60.75

24.78

12.61

Crude oil C/FW

1,790.74

16.56

243.25

60.09

23.53

11.62

3.82

16.61

215.37

52.35

20.29

9.93

Crude oil C/NW 1,622.18

Crude oil C/DW

Crude Oil D- The viscosity of this crude oil responded positively (reduced) upon contact with all brines, as shown in table
7. It can be seen that the difference of the values between the crude oil/FW and crude oil/NW systems is small for this oil.
The reason for this may be either a higher amount of Ca2+ ions in the NW brine or the 3 times higher concentrations of Na+
and Cl- or the rise of Mg2+, HCO3- and SO42- in the FW brine.

Table 7. Oil viscosity value for the crude oil D

Viscosity
Density

Viscosity
System

Reduction
(API)

(cp)

Viscosity
Viscosity
Viscosity
Viscosity
at 40 oC (cp) at 65 oC (cp) at 90 oC (cp) at 115 oC (cp)

(%)
Crude oil D

739.45

20.96*

115.76

32.05

13.55

7.08

Crude oil D/SW

648.13

12.34

20.99

100.99

27.46

11.47

5.94

Crude oil D/FW

508.78

31.19

21.21

90.75

27.13

12.07

6.56

Crude oil D/NW

499.95

32.38

20.96

89.98

27.07

12.10

6.60

Crude oil D/DW

Discussion- It can be said that two trends have been observed for the oil densities so far. On the one hand, for crude oils A
and B systems (after contacting the brines), compared to the original oil density, the values were changed. On the other
hand, the values for the last two crude oils (crude C and D) showed a minimal difference compared to the original oil
viscosities. Despite this, the oil viscosity of all crude oils showed significant changes before and after contacting with brines
with different compositions. Some researchers have found that heavy oil viscosity depends on the combined asphaltenes and
resin concentration. These literetures suggest that viscoelastic properties of heavy oils are linked to their composition and the
effect of the temperature.
Viscosity of oil is usually affected by both pressure and temperature. The flow characteristics of crude oil in a reservoir and
its effects on the production of heavy oils have been extensively investigated by many researchers (Abdul-Majeed, 1990;
Alomair, 2011; Hossain, 2005; Khan, 1987). The majority of the viscosity correlations assume that the fluid can be
considered Newtonian but this is not always true, especially where high values of viscosity are concerned. Different oil
constituents such as resins and asphaltenes in heavy oils could cause the oil to become a non-Newtonian fluid, either pseudoplastic or dilatants. Therefore, crude oil containing resin, asphaltenes and paraffin often exhibit pseudo-plastic and
viscoelastic behaviors (Argillier, 2001-2002; Dealy, 1979; De Ghetto, 1994-1995; Henaut,2003; Pierre,2004).

SPE 164910

As was mentioned above, so far, for all the measurements, the oil was in contact with brine at 92 oC. It is clear from the
results that different crude oils behaved differently when in contact with the brines. None of the crude oils tested so far
showed viscosity reduction for all brine tested. To explore the impact of treatment temperature, a new series of tests were
carried out similar to the above but this time the oil and brine contact and ageing took place at 20 oC. The results of this series
of experiments may allow us to confirm that, at least, for the cases with SW (crude oli B, C and D), where the oil
viscosity was reduced, temperature may be playing an important role.
For carbonates rocks, mainly chalks and limestones, it has been observed that the Ca2+, Mg2+ and SO42- present in seawater
are responsible for affecting the wettability. The wettability variation was seen to be more effective as the temperature
increasd, usually, above 90 oC. The reactivitiy of these ions (Ca2+, Mg2+ and SO42-) increases as the temperature increases.
Table 8 sumarises the results of the measurements performed on the crude oils in contact with different brines for a week at
20 oC (instead of 92 oC which was the case in the previous tests). As can be seen, for two of the cases tested, oil viscosity
reduction was observed. The results suggest that crude oil D was affected by the composition of the seawater (SW).
Nonetheless, in comparison with the same crude oil treated with brine at 92 oC, the same system (crude oil D/SW) at 20 oC
showed more reduction in viscosity. The results of this comparison indicate that the observed viscosity reduction is not due to
the increase in temperature.

Table 8. Oil viscosity values for the crude oil A at room temperature

Viscosity
Sample
(cp)

Viscosity
Reduction

Density
(API)

Crude oil A

32,537.99*

(%)
-

Crude oil A/SW

42,055.92

Crude oil A/NW

66,757.90

Crude oil C

1,325.68*

16.62

Crude oil C/SW

1,550.61

16.59

Crude oil C/NW

1,1136.00

14.30

16.62

Crude oil C/FW

1,467.21

16.56

Crude oil D

739.45*

20.96

Crude oil D/SW

478.37

35.30

20.96

12.55

*the oil was exposed to the same temperature.

According to the results shown in table 7 and 8, the viscosity of each specific system (crude oil/brine) does not reduce as
temperature increases. Temperature seems to have an influence but it is not completely clear to what extent the oil viscosity
may be reduced in response to a rise in temperature of the system. It seems that the crude oil/brine interactions contribute
more to viscosity reduction of the oil compared to temperature.

In addition to these experiments in which crude oil components in contact with brines seem to play an important role in
reducing the oil viscosity, we also examined both water content of crude oils and variations of ions of the brines. Water
contents in some crude oils showed a decrease when there were also reductions of viscosity. Table 9 shows the results of the
water content measurements. The results suggest that the oil viscosity decreased as its water content decreased.

SPE 164910

Table 9. Water contents for crude oil C at 20 and 92 C (measured temperature)

System

Viscosity

Viscosity

Density

(cp)

Reduction (%)

(API)

Water Content

Water Content

(mg/L)

Reduction (%)

20 C
Crude oil C

1,325.68

1,550.61

16.59

2,841.60

Crude oil C/SW

Crude oil C/FW

1,467.21

16.56

3,178.30

Crude oil C/NW

1,136.00

14.30

16.62

346.90

87.80

16.62

92 C
Crude oil C

1,686.60

16.48

1,147.1

Crude oil C/SW

1562.47

7.35

16.57

215.1

81.24

Crude oil C/NW

1,622.80

3.82

16.61

236.80

79.35

In addition to the measurements performed on the oil, samples of brines were also collected and analysed. However, the brine
composition analysis did not reveal any major changes or modifications in ion concentration of the brines. The concentrations
of Ca2+ and Mg2+ did not change and the SO4 ion concentrations showed a very small variation at the higher temperature (i.e.,
o
92 C). Figure 3 shows the concentration of Cl- and Na+ in the NW brine before contacting with crude oil C and after the
contact at both 20 oC and 92 oC. As can be seen, the concentration of these ions stays the same at 20 oC and shows only
minimal variation at 92 oC.

Figure 3. Changes in concentrations of some ions after interacting with crude oil C at two temperatures.

Viscosity Reduction at Different Temperatures, Impact of brines. Figure 4, illustrates the data that was presented in table
5 with horizontal axis showing the temperature and the vertical axis provide oil viscosity. The graph compares the viscosity
values between 20 and 150 oC for the systems made by crude oil B (table 5). It is evident that the oil viscosity decreased for
all brines until around 60 oC. We refer to this temperature as critical temperature. At that point, a change in the oil viscosity
trends occurs and the trend is reversed.

SPE 164910

Viscosity Measurements
CrudeOil"B"/BrinesSystems
1000000

crude oil/NW

100000

crude oil/SW

Viscosity(cp)

10000

1000

crude oil/FW

100

basecase

10

1
0

20

40

60

80

100

120

140

160

Temperature(oC)

Figure 4. Behaviour of the crude oil B with different brines

Figure 5 shows the results of the viscosity of crude oil A measured at different temperatures. As can be seen, the values of
viscosity for all systems increased slightly, measurements above 90 oC. It is interesting to observe that crude oil/NW and
crude oil/FW systems had two critical temperatures for crude oil A. Each crude reached the same oil viscosity at 52 oC
and 105 oC, compared to their own base case, respectively.
Viscosity Measurements
CrudeOil"A"/BrinesSystems
1000000

crudeoil/DW
100000

crudeoil/FW

Viscosity(Cp)

10000

1000

100
crudeoil/NW
crudeoil/SW
basecase

10

1
0

20

40

60

80

100

120

140

160

Temperature(oC)

Figure 5. Behaviour of another crude oil in contact with different brines

As a matter of fact, there is a contrast between all systems depending on the crude oil we use and the working temperature. It
is worth mentioning that at least the crude oil D in contact with SW brine remained with low values. On the basis of these
observations and outcomes with water content, it is reasonable to believe that selected brines will be able to interact and
change the behaviour of the crude oil. However, each brine will then affect one heavy oil either rising or dropping its
viscosity at different temperatures. These graphs denote the importance of having the whole behavior throughout
temperature.

10

SPE 164910

Conclusions

Based on the measurements reported in this paper, the following conclusions can be drawn:

The viscosity of the heavy oils can be significantly afected as a result of being in contact with certain brines. The
effect was greatest in high viscosity oils, whereas the effect was less significant when the magnitude of the viscosity
decreased. Although the mechanisms of interaction are still uncertain, there is a notable interaction between the oil
components and the brines.

All crude oil/ brine systems were sensitive to the working temperature, either 20 oC or 92 oC. One set of
measurement shows better reduction of oil viscosity using SW after interacting for a week at 20 oC. Moreover, all
crude oil were markedly affected by the NW brine. Lower changes were only obtained for the crude C. The
contribution of the sulphates ions appeared to be small compared to others mechanisms or contacts as the observed
decrease of viscosity can not be totally explained by high sulphates concentrations.

Some elements from crude oils may be migrating into brine solutions. It is not possible to come to a definitive
conclusion about the role of certain ions such as Ca2+, Mg2+ and SO42- for the improvement in viscosity.

In some heavy oils, and probably in light oils too, seawater may act as modifier of viscosity improving the flow of
the fluids in the reservoirs.

The water is present as a second phase. Viscosity decreased as water content decreasesd.

It may also be seen that the viscosity measurements depend strongly on the procedure used. Specifically, it was
observed that the period of stability is quite important and affects the measurements.

It was found that there is a critical temperature where a change of behaviour is present for some systems.

The results also reveal that at reservoir temperature, the viscosity of crude oils may increase or decrease by
becoming in contact with brine.

Further investigation need to be carried out on this subject. Additional experiments will be carried out to validate the
observations presented here to gain a better understanding of this effect and its mechanisms.

Acknowledgements
The authors acknowledge the financial support for this project provided by the National Council for Sciencie and Technology
and the Ministry of Energy of Mexico (Conacyt-SENER-Hidrocarburos). We are also very grateful to Luis A. Amador, Juan
M. Berlanga and Juan D. Yanez for their unfailing courtesy, support and enthusiasm to make this research possible.

SPE 164910

11

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