Petroleum Technology

Chevron Petroleum Technology Company

Reservoir Performance Optimization Business Line
Houston, Texas

RESTRICTED TO COMPANY USE

Technical Memorandum 2000-19
CPTC Project No. YWAT20023100

Analysis of Crude Oil Emulsion: Well No. 84-24

Kungulo Field, Cabinda

Syed A. Ali – CPTC

Frank T. Lang – NEEC
Mike A. Kendrick– CPTC
June 28, 2000

This material is CONFIDENTIAL and the property of

Chevron Petroleum Technology Company. This material
also may be subject to the Export Control Laws of the
United States Department of Commerce and should not
be distributed outside Chevron Corporation and its
wholly-owned affiliates without prior concurrence of the
Corporate Law Department.

1
 Petroleum Technology

Houston, TX
June 28, 2000

Technical Memorandum 2000-19

ANALYSIS OF CRUDE OIL EMULSION: WELL NO. 84-24, KUNGULO FIELD,

CABINDA

Syed A. Ali – Chevron Petroleum Technology Co.; Frank T. Lang – Nalco/Exxon Energy
Chemicals, and Mike A. Kendrick – Chevron Petroleum Technology Co.
________________________________________________________________________

SUMMARY

During a 1999 rig workover in the subject well, approximately 2500 bbls of filtered seawater and
several LCM pills were lost to the formation. After the workover, the well produced
approximately 2000 bbls of a very stable emulsion. The purpose of this study was to answer the
following questions: 1) What is the emulsion? 2) How it is formed? 3) How can it be treated?
4) How to prevent its occurrence in future workovers.

The data generated from this study show that emulsion was an oil-external emulsion, comprised
of 30% water and 70 % oil. The crude oil from the 84-22 Lola reservoir is sensitive to
completion brines and yields stable emulsion upon mixing under high shear conditions. The
emulsion can be effectively treated with 0.3% EC-2027A (Nalco/Exxon product). Treatment of
completion brines with 0.8% ECF-611 (M-I product) can prevent the oil-brine emulsion problem
in future workovers. Effort should also be made to minimize the fluid loss to the formation.

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INTRODUCTION

A rig workover was performed in the Kungulo Field AAWF Lower Vermelha producer Well 84-
24 in August 1999, in which perforations were added in the Upper Vermelha. During the
workover approximately 2500 bbls of filtered seawater were lost in this low-pressured reservoir
(officially called the 84-22 Lola). During attempts to control these losses, significant amounts of
lost circulation materials (LCM) were pumped, including HEC-CaCO3 pill, sized salt pill,
Halliburton’s K-Max, and other materials (Table 1). After the workover, the well produced
approximately 2000 bbls of a very stable emulsion with the consistency of peanut butter. An
attempt to break the downhole emulsion with 6000 gals of a modified Chevron Sweep was
unsuccessful.

Table 1 - Fluid Losses and LCM Pumped

Pre-Pill Post-Pill
FSW
Date FSW* LCM pumped FSW
Chaser
losses losses
5-Aug N/A 25 bbls of HEC-CaCO3 pill w/30#/bbl each of 25 bbls 100 bph
coarse, medium and fine CaCO3
100 bph 35 bbls as above 25 bbls 60 bph
60 bph 50 bbls as above w/ only 50#/bbl of fine CaCO3 20 bbls 15 bph
70 bph 40 bbls as above with 75#/bbl of CaCO3 (size?) ? 55 bph
6-Aug 10-15 bph 9 bbls K-Max 35 bbls 50 bph
50 bph 18 bbls K-Max 31 bbls 30 bph
30 bph 50 bbls of HEC-CaCO3 pill w/ 70# each of coarse 21 bbls 12-15 bph
and medium CaCO3.
? Circulated 20 bbls of HEC Hi-Vis pill to clean mill ? ?
cuttings.
? 30 bbls of HEC-CaCO3 pill w/ 50#bbl each of 35 bbls 5-10 bph
coarse and medium CaCO3,
7-Aug 4 bph Circulated 45 bbls of HEC Hi-Vis pill to clean mill ? 10 bph
cuttings
8-Aug 40-45 bph 25 bbls of sized salt containing 55#/bbl each of ? 30 bph
after Bridgesal Plus, Plugsal, and Plugsal X.
perforating
30 bph 25 bbls as above ? 15 bph

9-Aug 15-20 bph Set packer and completed well. Total losses to
formation 2533 bbls.
* Filtered seawater

The purpose of this study was to answer the following questions:

1. What is the emulsion?

2. How is it formed?
3. How can it be treated?
4. How to prevent its occurrence in future workovers?

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EXPERIMENTAL

The field collected several gallons of oil and water samples for testing and shipped them to the
Nalco/Exxon laboratory in Sugar Land, Texas. These included:

1. An emulsion sample from Well 84-24.

2. A “clean” oil sample from Well 84-22 in the same 84-22 Lola reservoir.
3. An oil sample from Well 83-05 with 25% water-cut.
4. A representative filtered seawater brine.

Several sets of emulsion experiments were conducted at the Nalco/Exxon laboratory under
CPTC supervision. Experiments conducted in the laboratory included:

1. Resolution and separation of the field emulsion sample.

2. Characterization of 84-22 Lola crude oil using SARA (saturates, aromatics, resins
and asphaltenes) analysis.
3. Investigation of various factors/materials, such as temperature, shear, brine
composition, LCM pills, and their influence on the emulsion stability.
4. Selection of a demulsifier that can effectively resolve this water-in-oil emulsion.
5. Selection of an appropriate chemical that can be added to completion brines to
mitigate the occurrence of brine-induced emulsion in future workovers.

TEST RESULTS

Resolution of the Well 84-24 Emulsion

The Well 84-24 sample received from the field was a very stable, “pasty-like” emulsion. The
emulsion was water-in-oil as evidenced by its dispersibility in xylene and its non-dispersibility in
water. Several demulsifiers (Table 2) were screened. Demulsifier EC 2027A was found to be
effective in resolving the field emulsion sample. Measurement showed that emulsion sample
contained 30% water and 70% oil, with oil being the external phase.

Table 2 – Chemical screening on the emulsion sample

Water Separation (ml)

Chemical PPM 60 minutes 24 hours
1 Blank ------ 0 0
2 EC2003A 500 0 0
3 EC2003A 1000 0 0
4 99VZ090 500 0 10
5 99VZ090 1000 3 20
6 99VZ090 2000 11 20
7 99VZ090 4000 20 20
8 99VZ030 500 0 0
9 99VZ030 1000 0 0
10 EC2027A 2000 12 20
11 EC2025A 2000 3 15
12 EC2032A 2000 10 18
13 EC2072A 2000 11 20
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SARA Analysis of Crude Oil

SARA (saturates, aromatics, resins and asphaltenes) analysis was conducted to characterize the
84-22 Lola clean crude oil from Wells 84-22 and 83-05. The results are shown in Figure 1. The
asphaltene value reported was obtained by n-pentane method.

The data show that 84-22 Lola crude is paraffinic (43.2%) and contains surprisingly a large
percentage of resins (36.9%) and a moderate amount of asphaltenes (5.9%). Asphaltene and resin
fractions are known to cause emulsion problems and act as emulsion stabilizers.1, 2

Composition

80.0

60.0

42.3
40.0 36.9

20.0
14.9

5.9
0.0
CABINDA 84-24

S AT (%) ARO (%) NSO (%) ASPH (%)

Sat = saturate hydrocarbons; Aro = aromatic hydrocarbons; NSO = nitrogen, sulfur and oxygen compounds (resins); Asph = asphaltenes

Figure 1 - Bulk composition data for the 84-22 Lola crude oil.

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Effect of Temperature on Emulsion Stability

The effect of temperature on emulsion stability was investigated with Well 84-24 emulsion
sample. Experiments were conducted at 76°F, 86°F, 120°F, and 180°F. Viscosity was measured
using a Brookfield viscometer with a small sample adapter connected to a circulation bath. The
results are presented in Table 3. As the temperature increased, emulsion viscosity decreased.
However, the temperature by itself was unable to resolve the emulsion, even at higher
temperatures. Higher temperatures are effective in breaking emulsions only when demulsifiers
are added.2

Table 3 - Effect of temperature on Well 84-24 emulsion viscosity

Temperature (°F) Viscosity (cp)

76 Pasty
86 1800
120 96
180 54

Investigation of Factors Responsible for Crude Oil Emulsification

Several experiments were conducted to investigate the effects of various factors on crude oil
emulsification. The clean oil from the 84-22 Lola was mixed with various fluids in the same
proportion as was observed in Well 84-24 emulsion sample (i.e., 30% water and 70% oil). The
oil-water mixture was then shaken either on a horizontal shaker or homogenized in a Waring
blender for a set time before conducting the water separation tests. All experiments were done at
120°F.

Every effort was made to keep all the variables constant (shaking, heating, method of
preparation, etc.) to eliminate any errors due to operator or method sensitivities.

Effect of Shear. Shearing of crude oil-water mixture has an important effect on emulsion
stability. Shearing or mixing can occur when fluid is lost through perforations into low-pressured
reservoirs. Two experiments were conducted by mixing 70 ml crude oil from the 84-22 Lola with
30 ml filtered seawater (completion brine) at different shears:

1. Low shear in which the crude oil and seawater were shaken on a horizontal shaker
for 5 minutes.
2. High shear in which the crude oil-seawater mixture was sheared in a Waring
blender at 1250 RPM for 30 seconds.

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After mixing, the emulsion was transferred into a screw-capped, graduate bottle and placed in a
water bath at 120°F. The separation of water phase was recorded by visual inspection for a set
period. The results are shown in Table 4 and Figure 2.

Table 4 - Effect of shear on emulsion stability

(70 ml crude oil + 30 ml seawater)

Water Separation (ml)

Shear
1 Hour 2 Hours 24 Hours
Low Shear 5 15 25

High Shear 0 0 2

In the low shear case, 83% of water separated after 24 hours. However, only 6.6% water
separation was realized for the higher shear case. Data show that an increase in shear resulted in
a tighter emulsion. High shear results in smaller water droplet size dispersed in the oil phase that
is more difficult to separate.2

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 15 minutes

2 hour

24 hour

#1=High shear #2=Low shear

Figure 2 - Effect of shear on emulsion stability

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Effect of Polymer and CaCO3. Since several polymer and polymer-CaCO3 pills (Table 1) were
pumped in the Well 84-24 to control fluid losses, experiments were conducted to investigate the
effects of filtered seawater (FSW), polymer and/or CaCO3 (LCM) on emulsification of 84-22
Lola crude oil. Five tests were conducted and results compared with the field emulsion sample.
All tests were conducted with 84-22 Lola clean crude oil that was mixed with fluid-loss pill
components and blended at 1200 RPM for 50 seconds and placed in a water bath at 120°F.
Polymer and/or CaCO3 mixtures were prepared in filtered seawater. The test sequence was:

1. 70 ml clean oil + 30 ml FSW

2. 70 ml clean oil + 30 ml HEC (1%) solution
3. 70 ml clean oil + 30 ml HEC (2%) solution
4. 70 ml clean oil + 30 ml HEC (1%) + CaCO3 (1%)
5. 70 ml clean oil + 30 ml HEC (2%) + CaCO3 (2%)

The results are presented in Table 5 and Figure 3. Test data show that the addition of HEC
polymer and/or CaCO3 apparently increased the emulsion viscosity but decreased emulsion
stability. The emulsion made with crude oil and filtered seawater (FSW) was more tenacious and
stable than the ones that were made with polymer and/or CaCO3.

Table 5 - Effects of brine, polymer and CaCO3 on crude emulsification

Water Separation (ml)

No Mixture Viscosity
30 min 2 hr 24 hr 42 hr
(cp)
1 Field Emulsion Sample 0 0 0 0 --
2 70 ml Oil + 30 ml FSW 0 0 0 0 --
3 70 ml Oil + 30 ml HEC (1%) Solution 0 0 6 12 340
4 70 ml Oil + 30 ml HEC (2%) Solution 2 2 20 20 5300
5 70 ml Oil + 30 ml HEC (1%) + CaCO3 2 2 8 12 350
(1%)
6 70 ml Oil + 30 ml HEC (2%) + CaCO3 0 2 20 25 6470
(2%)

The field emulsion sample appeared to have the highest stability. The reason for apparent
tightness (i.e., stability) of the field emulsion sample could be aging. The field emulsion sample
was analyzed after several months of storage. Emulsions are known to become more stable with
time.1

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 1 2 3 4 5 6
30 minutes

1 2 3 4 5 6

2 H o u rs

Figure 3 - Effects of FSW, polymer and CaCO3 on crude oil emulsification (for details, refer to Table 5).

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 1 2 4 5
3 6
24 H o u rs

1 2 3 4 5 6

42 H o u rs

Figure 3 - Effects of FSW, polymer and CaCO3 on crude oil emulsification (continued).

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Effects of Completion Brines. A systematic study was conducted to investigate the effects of
various completion brines on the emulsification of 84-22 Lola crude oil. All experiments were
conducted at 120°F with blended oil-brine mixtures:

1. 70 ml oil + 30 ml freshwater
2. 70 ml oil + 30 ml of 2% KCl
3. 70 ml oil + 30 ml of 5% NaCl
4. 70 ml oil + 30 ml of 5% CaCl2
5. 70 ml oil + 30 ml FSW

The results (Figure 4) show that completion brines, regardless of composition, were responsible
for the Well 84-24 emulsion problem. The resulting emulsions were stable up to 48 hours.
Apparently the 84-22 Lola crude is very sensitive to completion brines. This sensitivity may be
due to interaction of resin and asphaltene fractions of 84-22 Lola crude with completion brines.

This tendency to form emulsions has significant implications for this reservoir because it is being
flooded with filtered seawater as part of the Area A Waterflood project. The very stable
emulsions that were seen in the Well 84-24 were probably due to the high-shear mixing of fluids
in the immediate wellbore vicinity while fluids were being lost into the formation. These tests
also indicate that a less stable emulsion forms as a result of low-shear mixing. This would be
more typical of a low-energy mixing which might occur at a flood front, and might actually be
beneficial to the displacement or sweep efficiency.

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6.

1 2 3 4 5

0 hr

1 2 3 4 5

48 hr

Figure 4 - Effects of completion brine type on the emulsification of crude oil. Note the lack
of water separation.

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Selection of an Emulsion Breaker

To evaluate the performance of the emulsion breaker, EC-2027A (Nalco/Exxon product), several
additional tests were performed. All experiments were performed on emulsions made with crude
oil (84-22 Lola) and various completion brines. The field emulsion sample was used as a control.
The completion brines tested were:

1. Freshwater
2. Filtered seawater
3. 5% CaCl2
4. 2% KCl

Each emulsion sample was spiked with 0.3% of EC-2027A, and water separation was noted. The
results are shown in Table 6 and Figure 5. The EC-2027A was able to resolve and separate
emulsions within 2 hours, with the exception of field emulsion sample that partially separated
(66.6 %) after 24 hours. The performance of EC-2027A was the best among all the products
tested (see Table 2).

Table 6 - Effect of EC-2027A on the resolution of brine-induced emulsions

Water Separation
No. Mixture EC-2027A (conc.) (ml)
2 hr 24 hr
1 Field emulsion sample 0.3% 10 20
2 70 ml crude oil + 30 ml freshwater 0.3% 30 30
3 70 ml crude oil + 30 ml FSW 0.3% 30 30
4 70 ml crude oil + 30 ml of 5% CaCl2 0.3% 30 30
5 70 ml crude oil + 30 ml of 2% KCl 0.3% 30 30

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 2 hour 1 2 3 4 5

24 hour

Figure 5 - Effect of EC-2027A on the resolution of brine-induced emulsions (for details, see
Table 6).

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Selection of an Emulsion Preventer

Since the crude oil from 84-22 Lola is sensitive to completion brines, attempts were made to find
a suitable chemical that can be added to completion brines to mitigate brine-induced emulsions.
We limited our evaluation to M-I products, since M-I is the fluid company of choice in Cabinda.
M-I product, Safe-Break CBF has been widely used as a completion-brine additive for preventing
crude oil emulsification.3 Several sets of experiments were conducted to evaluate the effect of
Safe-Break CBF on emulsions made from various completion brines. Safe-Break was added to
completion brines prior to mixing with crude oil under high shear conditions. The completion
brines tested were:

1. 0.3% Safe-Break in FSW

2. 0.3% Safe-Break in 5% NaCl solution
3. 0.3% Safe-Break in 2% KCl solution
4. 0.3% Safe-Break in 5% CaCl2 solution
5. 0.3% Safe-Break in freshwater
6. 1% Safe-Break in FSW
7. 1% Safe-Break in 5% NaCl solution
8. 1% Safe-Break in 2% KCl solution
9. 1% Safe-Break in 5% CaCl2 solution
10. 1% Safe-Break in freshwater

The results are presented in Table 7 and Figures 6 and 7. These results show that with 0.3%
Safe-Break, only partial demulsification occurred after 72 hours. Even at 1% Safe-Break, there
was only partial oil-brine separation after 72 hours. These results were less than desired or
expected.

Table 7 - Effect of Safe-Break on oil-brine separation

Safe-Break Water Separation (ml)

No Mixture (conc.) 2 hr 24 48 72
hr hr hr
1 70 ml crude oil* + 30 ml FSW 0.3% 0 7 10 13
2 70 ml crude oil + 30 ml of 5% NaCl 0.3% 0 10 13 17
3 70 ml crude oil + 30 ml of 2% KCl 0.3% 0 10 13 15
4 70 ml crude oil + 30 ml of 5% CaCl2 0.3% 0 8 11 18
5 70 ml crude oil + 30 ml freshwater 0.3% 0 12 20 23
6 70 ml crude oil + 30 ml FSW 1% 0 7 11 15
7 70 ml crude oil + 30 ml of 5% NaCl 1% 0 10 15 21
8 70 ml crude oil + 30 ml of 2% KCl 1% 0 8 20 22
9 70 ml crude oil + 30 ml of 5% CaCl2 1% 0 10 20 21
10 70 ml crude oil + 30 ml freshwater 1% 0 12 19 19
* Crude oil from 84-22 Lola

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 24 hours 48 hours

1 2 3 4 5
1 2 3 4 5

1 2 3 4 5

72 hours

Figure 6 - Effect of 0.3% Safe-Break on oil-brine separation (for details, see Table 7).

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 24 hours 48 hours

6 7 8 9 10 6 7 8 9 10

6 7 8 9 10

72 hours

Figure 7 - Effect of 1% Safe-Break on oil-brine separation (for details, see Table 7).

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After disappointing results with Safe-Break, additional tests were conducted with a newly
identified chemical, ECF-611 (M-I product). The results of brine separation with ECF-611 are
shown in Table 8 and Figure 8. These results show that 0.8% ECF-611 provided a complete oil-
brine separation within 30 minutes. The performance of ECF-611 (emulsion preventer) was
superior to that of Safe-Break.

Table 8 - Effect of ECF-611 on oil-brine separation

ECF-611 Water Separation (ml)

No Mixture (conc.) 5 min 30 120 min
min
1 70 ml crude oil* + 30 ml FSW 0.8% 10 30 30
2 70 ml crude oil + 30 ml of 5% NaCl 0.8% 30 30 30
3 70 ml crude oil + 30 ml of 2% KCl 0.8% 3 30 30**
4 70 ml crude oil + 30 ml of 5% CaCl2 0.8% 25 30 30
5 70 ml crude oil + 30 ml freshwater 0.8% 22 30 30**
* Crude oil from 84-22 Lola
** Brine phase-hazy

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 5 minutes

30 minutes

120 minutes

Figure 8 - Effect of 0.8% ECF-611 on oil-brine separation (for details, see Table 8).

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CONCLUSIONS

The following conclusions can be drawn based on the data presented in this study:

• The resolved field emulsion sample from Well 84-24 contained 30% water and 70%
oil, with oil being the external phase.

• Temperature alone was unable to resolve and separate the emulsion, even at higher
temperatures.

• An increase in shear resulted in a tighter emulsion.

• There may be a link between resins and asphaltenes and emulsion tightness. The higher
the amount of resins and asphaltenes in the crude oil, tighter the resulting emulsion.2

• Addition of polymer and/or CaCO3 (LCM) had little effect on emulsion stability.

• 84-22 Lola crude oil is sensitive to completion brines, regardless of the brine
composition.

• The crude oil-brine emulsion can be treated with 0.3% EC-2027A (Nalco/Exxon
demulsifier).

• Addition of 0.8% ECF-611 (M-I emulsion preventer) to a completion brine can mitigate
crude oil-brine emulsion.

RECOMMENDATIONS

Based on this study, specific recommendations are:

• Since 84-22 Lola crude is sensitive to completion brines, efforts should be made to
minimize the fluid loss to the formation during workovers. This includes the use of
CaCO3-based fluid-loss control pills.4

• All completion brines should be treated with 0.8% ECF-611 prior to their use to avoid
brine-induced emulsion problems in future workovers.

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REFERENCES

1. Strassner, J.E.: “Effect of pH on Interfacial Films and Stability of Crude Oil-Water

Emulsions”, JPT (March 1968) 303-312.

2. Kokal, S. and Al-Juraid, J.: “Reducing Emulsion Problems by Controlling Asphaltene

Solubility and Precipitation”, paper SPE 48995, 1998.

3. Ali, S.A. et al.: “New Test Identifies Completion Fluid Compatibility Problems”, Oil &
Gas Journal (August 25, 1997) 95-101

4. Ali, S. et al.: “Completion and Workover Fluids – Recommendations for Cabinda Gulf
Oil Company (CABGOC) – Addendum, March 4, 2000”, CPTC Tech. Memo 2000-04,
19 p.

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