Paper No.

CORROSION2004
04365
EFFECT OF OIL-IN-WATER EMULSIONS ON THE PERFORMANCE
OF CO2 CORROSION INHIBITORS

Egil Gulbrandsen, Jon Kvarekvål

Institute for Energy Technology (IFE),
NO-2007 Kjeller, Norway

ABSTRACT

Corrosion inhibitor performance tests showed that dispersions (emulsions) of oil droplets in
water could reduce inhibitor performance. Surface active, amphiphilic inhibitor molecules have a high
affinity for accumulation at the oil-water interface. The dispersed droplets may constitute a very large
2
surface area. When the surface area exceeds 1 m /liter (order of magnitude) they can deplete a critical
amount of corrosion inhibitor from the corrosive aqueous phase. This “parasitic” consumption of
inhibitor constitutes a potential corrosion risk and leads to increased inhibitor demand.

Key words: corrosion, inhibition, carbon dioxide, carbon steel, dispersions, emulsions.

INTRODUCTION

Corrosion inhibition is the most common way to mitigate CO2 and H2S corrosion of carbon steel
in oil field applications. CO2 corrosion inhibitors are mostly composed of surface-active molecules
that form a protective layer at the pipe wall. In order to form a protective film the inhibitor has to be
present in a critical minimum concentration in the aqueous phase. Experience shows that much higher
doses of corrosion inhibitor are often needed in the field, compared to what is shown to be minimum
effective dose in the laboratory. It is important to identify the factors that lead to this increased
inhibitor demand in the field, since they constitute a risk of uncontrolled and detrimental corrosion.
Understanding of these interactions may aid the optimization of doses, and may contribute to the
development of improved inhibitor products. It may facilitate the analysis of test results and of failure
cases, and potential problem areas may be identified at an early stage. Furthermore, the environment
may benefit from reduced emissions to the sea if the dosage can be reduced.

Copyright
2004 by NACE International. Requests for permission to publish this manuscript in any form, in part or in whole must be in writing to NACE
International, Publications Division, 1440 South Creek Drive, Houston, Texas 77084-4906. The material presented and the views expressed in this paper are
solely those of the author(s) and not necessarily endorsed by the Association. Printed in U.S.A.

1
Publication Right
Government work published by NACE International with permission of the author(s). Requests for permission to publish this manuscript in any form, in part
or in whole must be made in writing to NACE International, Publications Division, 1440 South Creek Drive, Houston, Texas 77084-4906. The material
 The present paper deals with the (parasitic) consumption of corrosion inhibitor molecules by
emulsion droplets. CO2 corrosion inhibitor performance tests and theoretical calculations were used to
study the phenomenon.

Being amphiphilic, surface-active compounds, the corrosion inhibitors have a high affinity for
the oil-water interface. When water is dispersed (emulsified) in the oil, or vice versa, the small
droplets form a large interface area that could also accumulate critical amounts of corrosion inhibitor.
Furthermore, corrosion inhibitor may facilitate emulsion formation and stabilization, and thus
contribute to subsequent separation problems.

EXPERIMENTAL

The corrosion test solutions were prepared from technical or analytical grade chemicals and distilled
water or reverse osmosis water. The test solutions were purged with CO2 grade 4.0. This gas contains
less than 10 ppm of O2, corresponding to less than 0.5 ppb in the test solutions at equilibrium. The
actual concentration of dissolved O2 in the test brine was measured with an Orbisphere Model 3600
( )
Oxygen Analyzer. 1 The dissolved O2 concentration was normally 5-10 ppb, but were in a few shorter
periods up to 30 ppm. A low-aromatic white spirit product was used as the model oil in the tests. The
o
oil had a density of 0.788 kg/L and boiling point range 193-245 C, corresponding to kerosene.

Four different corrosion inhibitor products were tested, see Table 1.

Table 1. Commercially available inhibitor products tested.

Inhibitor Active ingredients Type Preferential solubility

INH A Amines, surfactants Cationic Oil soluble - water dispersible

INH F Amines, surfactants Cationic Oil soluble - water dispersible

INH H Quaternary ammonium Cationic Water soluble

chlorides

INH E Phosphate ester Anionic Water soluble

The corrosion test with emulsion formation were performed in a small recirculating loop system
with the specimen in the submerged impinging jet geometry, see Figure 1. The jet system was built
into a 25-liter titanium autoclave. The system was filled with 18 or 20 liters of fluid (water + oil). A
gear pump was used to pump the fluid through the 3 mm diameter jet nozzle. The jet stream was
perpendicular to the specimen surface. In all the tests the distance (H) between the nozzle and the
specimen was 15 mm, i.e. the distance to nozzle diameter (d) ratio H/d equalled 5. The flow
1-2
characteristics of the submerged impinging jet have been described elsewhere. In the periods where

1
Trade name of Orbisphere, Geneva, Switzerland

2
oil was added to the jet stream, the oil was pumped into the nozzle inlet pipe ca. 150 mm upstream of
the nozzle (Fig. 1) by means of a high-pressure injection pump.

Rotameter
6/4 CO2 in
O2

6/4
pH Safety valve

Bypass 8/6

Relief valve PI Manometer

Heating
Gear pump medium
10/8

Drain Drain Thermoelement

8/6

Tor Blakseth -10.98

CO2 out
S4
EM.D
YST
\TIS
E\KIP
D\:IF

Flow meter
8/6

Jet nozzle
CO2 /oil
Drain Corrosion
specimen
Drain

Figure 1 Schematic drawing of jet impingement system used for inhibitor tests with
emulsion formation.

The corrosion test specimens were machined from X65 ferritic-pearlitic low carbon pipeline
steel (Element analysis (wt%): C, 0.08; Mn, 1.54; Ni, 0.03; Si, 0.25; Cr, 0.04; P, 0.019; S, 0.001;
V, 0.045; Mo, 0.01; Al, 0.038; Nb, 0.04; Sn, 0.001). The jet specimens were prepared by machining
the steel into cylinders and tubular pieces of different diameters. These pieces were mounted
concentrically and moulded into epoxy resin. The end surface of this cylindrical assembly constituted
the test electrode surface. The design of the specimens is shown in Figure 2. A stationary cylinder
specimen (10 mm D x 10 mm H) made of the same steel was included in some tests. The cylinder
specimen was mounted on a rod that was inserted through a nozzle in the lid of the test autoclave.
This specimen was located in the water phase ca. 8 cm above the jet nozzle, away from the direction
of the jet flow. All the test specimens were pre-treated by grinding with 1000 mesh SiC paper wetted
with isopropanol, degreasing in acetone and finally flushing with ethanol.

Corrosion rates were determined by means of the linear polarization resistance (LPR) technique
(scanning 0.1 mV/s from –5 to +5 mV vs. the open circuit potential, Ecor). A three-electrode

3
configuration was used in all the tests. The corrosion current density Icor was calculated from
polarization resistance Rp as Icor = B/(RpA), where A is nominal specimen surface area, and B is the
LPR-constant. The value of B (20mV) was based on previous mass loss measurements. The average
2
penetration rates (v) were calculated as v(mm/y) = 1.16Icor(A/m )). All the reported results were
corrected for uncompensated electrolyte resistance determined by electrochemical impedance
measurements.

1 mm 3 mm
Disc

Ring #1 Epoxy
X-65 steel
Ring #2
AISI 316

Ring #1
O.D. 6.5 mm
I.D. 2.5 mm

Ring #2
O.D. 19 mm
I.D. 15 mm
7 mm (tor) D:/IFE/KIP/RINGPRVR.DSF Page 2

15 mm Sleeve
O.D 25 mm
I.D. 22 mm
Specimen A Specimen B

24 mm
Oxidised X-65 steel surface

Shield
Specimen
Jet Nozzle

7 mm 15 mm
(tor) D:/IFE/KIP/RINGPRVR.DSF

Specimen D

Figure 2 Schematic drawing of the test specimen surfaces. The drawing in the lower right
corner shows the setup in the test where a shield was located between the jet
nozzle and the specimen.

RESULTS

Most of the tests were performed at 60 oC, 1 bar CO2, pH 4.5-5 with 0.1 % or 1 % NaCl. The jet
flow velocity was varied between 0 and 12 m/s, corresponding to wall shear stresses up to ca. 350 Pa
at 60 oC.

Figure 3 shows baseline LPR corrosion rates at 60 oC in absence of inhibitor. First the jet flow
velocity was increased successively from 0-9 m/s. The corrosion rate showed an increasing trend with

4
increasing flow velocity, from ca. 3 mm/y at 0 m/s to about 8 mm/y at 9 m/s. The difference between
the ring electrodes was negligible. For comparison, the corrosion rate in straight pipe flow at 9 m/s
under the given conditions is 4-6 mm/y. After 4.5 hours the flow velocity was decreased to 5 m/s, and
oil was injected into the jet flow. The volume fraction of oil in the jet stream was 0.5%. The oil
injection continued for 2 h and the corrosion rate showed a slightly increasing trend during this
period. After the oil flow was stopped, the exposure was continued at 5 m/s flow velocity. The
corrosion rate continued to increase during the next 20 h, which is normal during the first days of a
3
CO2 corrosion experiment. The brine became turbid during the period of oil injection.

100
no oil oil in jet no oil c
0 3 6 9 5 5 m/s
Corrosion rate / (mm/y)

Inner ring
10 Outer ring
Cylinder

1
0 5 10 15 20
Time / h

Figure 3 Corrosion rate vs. time during tests with impinging jet flow with no inhibitor
present. Experimental conditions: 60 oC, 1 bar CO2 , pH 5, 1% NaCl. Specimen B.

Inhibitor A

In the first test, the specimens were exposed to a solution with 30 ppm INH A for 20 h before
jet flow was started. No oil was present. In this period the corrosion rate dropped to
0.04 mm/y, Figure 4a. The jet flow velocity was increased stepwise to 10 m/s. The inhibition was not
significantly affected by this flow, as the corrosion rate continued to decrease with time throughout
the test.

In the next test, Figure 4b, the specimens were again exposed to a solution with 30 ppm
INH A. No oil was present from the start of the test. The jet flow velocity was now 5 m/s from the
start. The corrosion rates dropped to 0.02- 0.04 mm/y in 20 hours, showing that the inhibition process
was not significantly affected by the flow. Oil was then pumped from a CO2 purged bottle into the jet
stream at a volume fraction of 0.5% in the jet stream. The pumping continued for 3 hours, thus adding

5
2 liters of oil to the system. In this way, the water-cut in the system was decreased from 100 to 90%.
A water sample taken from the tank was turbid, indicating emulsion formation. The sample remained
turbid for many hours, and a thin layer of oil appeared at its surface. The separated oil constituted
about 1-2 % of the volume. The corrosion rate increased slowly during the period of oil pumping, but
did not exceed 0.1 mm/y. After the oil flow had been stopped, the corrosion rate decreased slowly
again. A small drop in corrosion rate was seen when the jet flow was turned off.

In a similar test with 30 ppm INH A at 90 oC, Figure 4c, the corrosion was reduced below
0.1 mm/y before oil was injected in the jet stream. The injection of oil into the jet stream caused a loss
of inhibition, but the corrosion rate did not increase to more than 0.3-0.4 mm/y, and the corrosion was
inhibited once the oil injection stopped. In this test, the oil (10 %) was present in the system from the
start of the test, and the oil was pumped from the oil layer at the top of the test brine into the jet
stream. The results of Fig. 4c indicated that the reduced inhibitor performance observed when oil was
injected in Fig. 4b was not caused by partitioning of inhibitor to the oil phase.

1
a
Jet velocity: 0 m/s 3 5 7 10 12
Corrosion rate / (mm/y)

0.1

0.01

Centre
1st ring
2nd ring
0.001
0 10 20 30 40 50 60 70
Time / h

Figure 4 a Caption overleaf

6
 1
Jet velocity: 5 m/s 0 m/s b

Oil (%): 0 0.5 0

Corrosion rate / (mm/y)

0.1

0.01

Centre
1st ring
2nd ring
0.001
0 10 20 30 40 50 60 70 80
Time / h

10
Jet velocity 5 m/s
c
Oil (%): 0 0.5 0

1
Corrosion rate / (mm/y)

Inner ring
Outer ring

0.1

0.01

0.001
0 10 20 30 40 50
Time / h

Figure 4 Corrosion rate vs. time during impinging jet tests with 30 ppm INH A.
(a) Effect of flow velocity, 100 % water-cut. 60 oC (Spec. A). (b) Effect of injecting
oil in the jet stream (emulsion formation). 100-90 % water-cut. 60 oC (Spec. A).
(c) Effect of oil in the jet stream at 90 oC, 90 % water-cut. (Spec. B).
All tests: pH 4.5-5, 1 bar CO2.

7
Inhibitor F

In the first test the specimens were exposed to a solution with 30 ppm INH F for 19 hours with a
jet flow velocity of 5 m/s. Oil was not yet added to the system. The results are shown in Figure 5a.
The corrosion rate decreased to 0.1 mm/y during this period. After 19 hours the oil injection into the
jet stream (0.5 vol%) was started. The corrosion rate increased immediately to 1 mm/y and then
increased further to about 10 mm/y. (The high peak values may be an artifact of the compensation of
the high solution resistance in 0.1 % NaCl). The oil pumping was stopped at t = 23 hrs. The corrosion
rate decreased slowly to 3-4 mm/y, and remained constant at this rate for the next 15 hours. No sign of
inhibition could be seen. A cylinder specimen was also exposed during this experiment. It was placed
ca. 8 cm above the jet nozzle, and was thus not directly exposed to the jet stream. During the period of
oil injection, the specimen slowly lost inhibition and reached a corrosion rate of 2-4 mm/y.

A freshly ground cylinder specimen was inserted at t = 40 hrs (not shown). The specimen was
not protected. The loss of inhibitor performance after oil injection in the jet stream was accordingly
3
not caused by the strong corrosion of the specimens (precorrosion effect ). In a replicate test it was
found that the inhibition recovery was facilitated in 1 % NaCl solution, compared to 0.1 %.

In order to shed more light on the effect of emulsion formation versus the droplet impingement a
test was performed with a shield placed between the jet nozzle and the test specimen. The shield was
located ca. 7 mm away from the jet specimen surface, as illustrated in the lower right corner of Fig. 2.
This shield thus prevented the water jet stream from hitting the specimen surface directly, while the
specimen still was exposed to the test solution. The test was performed with 30 ppm INH F at 60 oC.
The water-cut was 90 % from the start of the test. The results of this test are displayed in Figure 5b. A
measurement problem occurred in the first part of the test, and data before 32 h data are therefore not
shown. A water jet flow of 3 m/s was applied. The corrosion rate decreased to 0.01 mm/y in the
period of jet flow without oil injection. At 46 h the jet flow velocity was decreased to 1 m/s, and oil
was injected at a rate of 0.24 vol-% in the stream. The corrosion rate remained low. After 7 hours the
oil injection rate was increased to 0.7 vol% at 1 m/s jet velocity. The corrosion rate increased to 1
mm/y. When the oil injection was stopped (55 h) the corrosion was inhibited again. During the
periods of oil injection the aqueous solution became turbid.

Inhibitor H
o
The performance of INH H was tested at 60 C with 90 % water-cut. The test was performed
with 100 ppm inhibitor, since 30 ppm did not provide inhibition under these conditions. Figure 6
shows the results of this test. The corrosion rate decreased to 0.1-0.4 mm/y during the initial 19 hours
exposure with only water jet flow. When injection of oil into the jet stream started at 19 h the
corrosion rate increased and reached a level of about 2 mm/y at 25 h. The corrosion rate continued to
increase slowly when the oil injection was stopped (25 h). This increase was caused by an increasing
3
cathodic rate, probably a result of exposure of cementite. The jet flow was stopped at 47 h, but the
corrosion was not inhibited during the next 20 h.

The corroded specimens were replaced by fresh ground specimens at 75 h, and the jet flow was
restarted. The corrosion rate increases with time. The specimens were removed and again replaced by

8
fresh ground specimens at 96h. A shield was placed between the jet nozzle and the specimen. No
inhibition was obtained in this case neither.

100
Jet velocity 5 m/s a
no oil oil no oil
Corrosion rate / (mm/y)

10

1
Centre
1st ring
2nd ring
Cylinder
0.1
0 10 20 30 40 50
Time / h

10
Jet velocity (m/s): 3 1
b
Oil (%): 0 0.24 0.7 0
Corrosion rate / (mm/y)

0.1

0.01

Inner ring
Outer ring
0.001
30 40 50 60 70 80
Time / h

Figure 5 Corrosion rate vs. time during impinging jet test with 30 ppm INH F at 60 oC,
pH 4.5, 1 bar CO2. (a) 0.1 % NaCl. 100-90 % water-cut. (b) 90 % water cut with
shield in front of specimens, 1% NaCl.

9
 100
Jet velocity (m/s): 3 0 3

Oil (%): 0 0.86 0 0 0 0

0

Corrosion rate / (mm/y)

10

Fresh Fresh
1 specimen specimen
with shield

0.1

Inner ring
Outer ring
0.01
0 20 40 60 80 100 120 140
Time / h

Figure 6 Corrosion rate vs. time during impinging jet test with 100 ppm INH H. 60 oC,
pH 4.5, 1 bar CO2, 1 % NaCl. 100-90 % water-cut.

Inhibitor E

At a dose of 30 ppm of the anionic inhibitor INH E the corrosion rate decreased below 0.1 mm/y
after 10 h exposure, Figure 7a. Oil injection into the jet stream started after 19 hours exposure. The
corrosion potential immediately started to fluctuate strongly. The fluctuations can be attributed to
fluctuating oil wetting of the specimens when exposed to the oil containing jet stream. These
fluctuations made LPR-measurements impossible in the period of oil injection. Water samples were
again turbid, indicating emulsion formation. When the oil injection was stopped at 25 hrs the
corrosion potential stabilized, and corrosion measurements could be continued. The low corrosion
rates were probably caused by oil wetting of the specimens.

The test was repeated with a shield between the jet nozzle and the specimen. The corrosion rate,
Figure 7b, decreased to around 0.1 mm/y after 20 h exposure. When oil injection into the jet stream
started (24 h) the corrosion rate rapidly decreased to very low values, indicating oil wetting of the
specimen. The corrosion potential was stable when the shield protected the specimen from the oil
containing jet stream. LPR-measurement could thus be performed during the period of oil injection.
The corrosion potential went up to–0.54 V. The corrosion rate and corrosion potential remained stable
for at least 15 h after the oil injection was stopped.

10
 10
Water: 3 m/s
a
Oil (%): 0 0.86 0

Corrosion rate / (mm/y)

1

0.1

0.01

Inner ring
Outer ring
0.001
0 20 40 60 80 100 120
Time / h

1
Water: 3 m/s
b
Oil (%): 0 0.86 0
Corrosion rate / (mm/y)

0.1

0.01

0.001

Inner ring
Outer ring
0.0001
0 10 20 30 40 50
Time / h

Figure 7 Corrosion rate vs. time during impinging jet test with 30 ppm INH E. 60 oC, pH 5,
1 bar CO2, 90% water-cut, 1 % NaCl. (a) No shield. (b) With shield.

11
 DISCUSSION

The results indicated that the tested inhibitors were resistant to jet flow in purely aqueous
solutions at 60 oC. When oil was injected into the jet flow, INH F and INH H immediately lost
protection, whereas INH A was resistant to failure over a period of several hours under the same
conditions. Furthermore, with INH E the corrosion rate decreased when oil was injected into the jet
stream. This shows that inhibitor formulation is an essential factor.

The oil in the jet stream seemed to be destructive to the inhibition (INH F, H) by some yet
unidentified process. Several hypotheses could be proposed to explain the effect of the oil.
Tentatively, the loss of inhibition observed could be connected to the formation of oil-in-water
emulsions in the jet stream. The inhibitor removal could potentially be caused by mechanical action of
the oil droplets on the inhibitor film, or by depletion of inhibitor from the brine by accumulation of
critical amount of inhibitor onto the oil emulsion droplet surface. Erosion of the metal surface was
less probable, since the inhibition was not lost with INH A and INH E.

In order to discriminate between the effect of emulsion formation and droplet impingement,
tests were performed with a shield placed between the jet nozzle and the test specimen (Figs. 5b, 6
and 7b). This shield thus prevented the water jet stream from hitting the specimen surface directly,
while the specimen still was exposed to the test solution. The inhibition was lost with INH F and INH
H when the emulsion was formed. The improved protection with INH E that occurred during oil
injection was also reproduced with the shielded specimen. This indicate that solution chemistry, rather
than flow effects dictated the behavior.

The results thus indicate that the loss of inhibition was caused by the formation of an unstable
oil-in-water emulsion, rather than the impingement of oil droplets at the surface. Also, it can be ruled
out that the rise in corrosion rate was caused by O2, due to the low O2 concentration in the system and
the low convection near the specimen surface with the shield installed.

The amount of emulsion in the system is determined by the balance between its formation and
breakdown rates. Furthermore, the droplet size is an important factor contributing to the total interface
area. These parameters are discussed below.

Emulsion formation rate

In order to emulsify the oil, the water in the jet nozzle must be sufficiently turbulent. The
emulsification is caused by the shear forces of the turbulent flow, while the oil-water interfacial
4
tension tend to counteract droplet formation. Both the level of turbulence and the concentration of
surfactants in the system may influence the droplet size distribution. The droplet sizes are thus
expected to decrease with increasing turbulence and decreasing interfacial tension. It was noted,
however, that emulsions were formed in the jet both with and without inhibitor present in the system.

Furthermore, the formation rate is co-determined by the oil injection rate and the concentration
of surface-active agents. The rate of emulsion build-up will also depend on the test solution volume.
In the tests with the shield installed the test specimens were exposed to an environment reflecting the
bulk of the solution. When the jet stream hits the specimen directly, the specimen is exposed to the
actual environment in the jet stream, where the emulsion concentration probably is higher from the
start of the oil injection.

12
Emulsion breakdown rate

The breakdown of oil-in-water emulsions can be discussed in terms of two consecutive

4-5
processes:

- The first step is flocculation, where oil droplets collide and stick together to form flocs, i.e.
aggregates of individual droplets.

- The following step is coalescence, whereby the flocculated droplets combine to form one larger
droplet. This process thus reduces the area-to-volume ratio of the emulsion. Accumulated inhibitor
will not be released before this step takes place.

Either of these steps can be rate limiting. The test conditions, like convection (turbulence),
temperature, salt content, pH, properties of the oil and properties of the corrosion inhibitor and other
chemicals, may influence the rate of either of the steps in the breakdown process. (Other mechanisms
of emulsion breakdown exist (e.g. Ostwald ripening), but they will not be discussed here).

Flocculation rates

The theoretical minimum half-life of an emulsion can be calculated from fast flocculation
5-6
theory, see Table 2. It is assumed that all the droplets flocculate when they collide (i.e. the
flocculation probability is unity) and coalesce immediately. This is a rather unrealistic scenario, but it
is still useful for this discussion, since it defines the minimum lifetime of an emulsion. Collision
5
between oil droplets are caused by three phenomena:

- Brownian motions

- Liquid shear (the relative motion between droplets in a shear field increases encounter rates)

- Differential sedimentation (caused by differences in density)

The maximum collision rates of these three processes can be calculated from fundamental
5-6 6
theory. In practice, Brownian motion is the dominating term. Approximate half-life times of
5
emulsion subject to fast flocculation by Brownian motion at room temperature are given in Table 2.

Table 2 Approximate half-life times of emulsion subject to fast flocculation by Brownian

5
motion at room temperature.
Droplet radius Volume fraction of oil-in-water emulsion
(µm)
0.1 % 1% 10 %

0.1 760 ms 76 ms 7.6 ms

1 760 s 76 s 7.6 s

10 210 h 21 h 2.1 h

13
 This tabulation shows that emulsions with low volume fractions and droplets sizes in the range
1-10 µm can posses considerable life times even without any surfactant stabilization. This fact is in
agreement with the observation done on actual water samples from the test systems during oil
injection in the jet stream. The water samples remained turbid for many hours after they were taken.
Furthermore, the oil fraction in the water samples was low, in the order of 1-2%, as evaluated from
the oil that separated from the samples.

In practice, the flocculation rates are considerably lower than indicated by the fast flocculation
5-6
theory. One reason is the electrical double layer that forms at the droplet surface. This creates a
repulsive electrostatic barrier that must be overcome before a stable floc is formed, and thus reduces
the number of successful droplet collisions. A second reason is that the water between two droplets
need time to escape before they collide. This hydrodynamic effect, which is not included in fast
flocculation theory, strongly reduces the flocculation rate of larger droplets.

Flocculation rates increase with temperature. Increasing salt concentration reduces electrostatic
forces between droplets and thus increases flocculation rates. Surfactants in general increase the
stability of emulsions. The improved recovery of inhibitor performance of INH F observed in 1 %
NaCl compared to 0.1 % NaCl, can probably be connected to increased emulsion breakdown rate.

Estimate of the emulsion’s capacity to accumulate inhibitor

Amphiphilic inhibitor molecules have a strong affinity to accumulate at the oil-water interface.
The inhibitor molecules will orient themselves with the hydrophobic hydrocarbon tails into the oil,
and the hydrophilic head groups into the water. Figure 5 gives a rough indication of the emulsion’s
capacity to accumulate corrosion inhibitor. The volume fraction (V) of the emulsion needed to
accumulate a given concentration of inhibitor [cacc] is plotted as a function of the droplet radius (R),
according to the following equation:

N Aa
V = [cacc ]R (1)
3

where NA is Avogadro’s number. The area a occupied per inhibitor molecule was assumed to be
60 Å2. Typical adsorption areas of surfactant molecules are 20 – 100 Å2 (ref. 4). Equation 1 assume
that the emulsion droplets are mono-disperse.

The results suggest that, for example, a 1 % emulsion of 10 µm radius droplets can accumulate
10 ppm inhibitor from the water phase. Such an emulsion has a considerable life-time, and the
inhibitor therefore has time to diffuse to the droplets. The conclusions of a parallel study on this
7
subject were in agreement with these estimates.

If the right conditions are present, the oil droplets impinging at the steel surface may coalesce at
the surface. The test with INH E (Fig. 7) indicated that this inhibitor created a hydrophobic steel
o
surface at 60 C. Furthermore the emulsion was able to coalesce at the steel surface. These conditions
caused quite persistent oil wetting of the steel surface. This effect dominated over a possible depletion
of inhibitor by the emulsion formation. In this way, emulsification could contribute to corrosion
protection under certain conditions.

14
 Recent work in our laboratory has confirmed the presented jet impingement results using two
other techniques of emulsion formation (homogenizer and gas spray nozzle technique).

Depletion of inhibitor by accumulation at emulsion droplets is a flow related phenomenon. In

the field, emulsion formation is very likely to occur in the choke valve. The flow conditions may
(co-)determine the emulsion concentration further downstream in the line. Furthermore, in laboratory
loop tests, the high shear rates encountered in a centrifugal pump could maintain a constant level of
fine emulsion droplets. This should be taken into account in the evaluation of results from loop tests
where oil is included.

The results of the tests with INH F and INH H indicated that the inhibitor performance depends
strongly on the emulsion history of the test fluids. The consequence for inhibitor testing in the
presence of oil is that operations involving mixing and flow must be carried out in a controlled and
reproducible manner.

1E+0
Volume fraction of oil in water

1E-1

1E-2

1E-3

30 ppm
1E-4 10 ppm
3 ppm
1E-5
1E-7 1E-6 1E-5 1E-4
Oil droplet radius / m

Figure 5 Volume fraction of oil-in-water emulsion needed to accumulate a given amount of

inhibitor blend (in ppm) plotted as a function of droplet radius. Assumptions:
Inhibitor blend with 30 % active compound with molar mass 300 g/mol. Mono-
disperse droplets. 100 % coverage of inhibitor molecules at the oil droplet surface,
each molecule occupying an area of 60 Å2.

15
 SUMMARY AND CONCLUSION

Depletion of inhibitor by accumulation on w/o emulsion was studied by impinging jet

o
experiments. Experimental conditions were 60 C, pH 5, 1 bar CO2, 100-90 % water-cut,
0.1-1% NaCl. A refined, low-aromatic white spirit product was used as oil phase. Jet flow velocities
in the range 0-12 m/s were employed. Corresponding wall shear stresses were 0-350 Pa. Oil-in-water
emulsions were formed by injection of small amounts of oil in the impinging jet stream. This created
small amounts of emulsion (order of 1 % oil) that broke down in a few hours. The conclusions drawn
from the experimental results are:

• Corrosion inhibitor can accumulate on the oil-water interface of emulsion droplets and
significantly reduce the effective inhibitor concentration in the water phase. Theoretical estimates
indicate that inhibitor can be depleted from the water phase if the total oil droplet surface area
2
exceeds 1 m /liter (order of magnitude). Emulsification can be critical for inhibition, causing
increased corrosion risk and excessive inhibitor consumption. The sensitivity of the inhibitor to
oil-in-water emulsions was dependent on the inhibitor formulation.

• Emulsions need not be stable in order to accumulate inhibitor, since unstable emulsions at low
volume concentrations may have half-lives of the order of hours.

• Depletion of inhibitor by accumulation at emulsion droplets is a flow related phenomenon.

• Under certain conditions oil-in-water emulsions may promote oil wetting and thus contribute to
improved corrosion protection.

• The mixing of oil and water should be carefully controlled in laboratory inhibitor tests.

ACKNOWLEDGEMENT

The present work was carried out in Institute for Energy Technology's joint industry project
"Kjeller Inhibitor Project - Phase I" (1997-2000). The project was sponsored by BP, Chevron,
Conoco, DST Group (Dalmine, Siderca, Tamsa), Elf, Eni Agip, Shell, Total, TR Oil Services, and the
Research Council of Norway. The authors acknowledge the sponsors for their technical advice and
financial support.

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