SPE 100356

The Evaluation of Enhanced (Carbonate/Sulfate) Scale-Dissolver Treatments for

Near-Wellbore Stimulation in Subsea Production Wells, Gulf of Mexico
M.M. Jordan and D. Marlow, Nalco; T.L. Johnson, BP America; and C. Johnston, Nalco
Copyright 2006, Society of Petroleum Engineers Inc.
This paper was prepared for presentation at the 2006 SPE Oilfield Scale Symposium held in
Aberdeen, UK, 31 May - 1 June 2006.
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Abstract
Dissolver technology has been developed and applied with
varying degrees of success over the past few years to clean
carbonate and the more challenging sulphate/sulphide scales
from production tubing and process equipment. The intention
of this proposed application was to select a chemical that
could be applied into the near wellbore region of the reservoir
to recover scale induced damage while not creating any
secondary precipitation or negative wettability effects.
The impact of dissolver chemical formulation on the reservoir
formations wettability and the potential for mobilization of
fines (both reservoir silicate and scale) has not been outlined
before. In this paper reservoir condition coreflood studies are
outlined where scale is formed within the cores to allow
assessment of sulphate dissolver performance. This will form
a critical part of the technical evaluation of the dissolver
formulation suitability for field application. Results from
these coreflood studies will be compared to those generated
for the same chemicals in conventional static dissolver
studies.
The practical concerns about deployment methods within
subsea production wells are also emphasized. Specific
reference will be made to the impact of metallurgy on
chemical selection and the need to reduce corrosion risk
within developments which utilize both carbon steel and super
duplex requiring the development of higher pH non acid
carbonate dissolvers.

This paper shows that simple dissolver tests can give

misleading performance information as they only show
dissolution rates, impact of concentration of active chemical or
the increased dissolution possible with solvents. The use of
pre scaled reservoir cores to assess the impact of dissolver
performance and the potential for secondary formation
damage allows the most effective dissolver with minimum
formation damage potential to be selected for field application.
Introduction.
Oilfield scale formation and control. The precipitation of
insoluble mineral scale deposits (scaling) is a common cause
of near wellbore formation damage during the production of
hydrocarbons and associated produced water. Precipitation of
scale can occur within the formation, near wellbore or in the
production tubing. The physical obstruction/restriction caused
when scale is deposited within the near welbore and
production tubing can lead to sever reduction in near wellbore
permeability and reduce the internal diameter (ID) of the
production tubing.
The reduction in flow area can
significantly increase flowing bottom hole pressure and reduce
production rates.
Two mechanisms of scale formation are commonly
encountered. Carbonate scales (Calcite CaCO3, Siderite
FeCO3) can be formed when pressure or temperature changes
in a flowing fluid leads to the break out of dissolved carbon
dioxide which is accompanied by the scale deposition. The
mixing of incompatible brines can lead to the formation of
sulphate scales. The common sulphate scales include Barite
BaSO4, Celestite SrSO4, Anhydrite CaSO4 and Gypsum
CaSO4.2H2O though of most concern with seawater injection
is Barite owing to its very low solubility1-4.
Carbonate/sulphate scale control is normally managed by the
application of scale inhibitors, which work by preventing
nucleation, crystal growth and dispersion. The particular
mechanism of inhibition is a function of the generic type of
scale inhibitor used. For scale control within a production
reservoir the scale inhibitor is normally applied in a squeeze
treatment. In this process the inhibitor is injected into the
formation and via the process of adsorption/desorption it
returns with the produced water over a period of time. When
the chemical concentration within the produced water falls
below the minimum inhibitor concentration, there would be no

inhibition and then the well would need to be re treated. There

are a number of scenarios when scale inhibition alone is not
sufficient to prevent production decline resulting from scale
deposition and scale removal using dissolver chemicals may
be required. Scenarios where inhibition alone may not be
totally effective at scale prevention include (1) when a scaling
problem has not been accurately predicted in advance owing
to poor water analysis, (2) when placement of a scale inhibitor
within a well has been less than optimal owing to reservoir
heterogeneity, different pressure regimes within the well, or
cross flow, (3) the well has a very low scaling tendency such
that it is more economic to remove the scale with infrequent
application of dissolver rather than inhibit the scale itself.
Scale removal methods via chemical means such as dissolver
chemistry has been extensively published in the literature5-16.
Mechanical scale removal has focused on two methods for
removal of the scale with such methods as jetting, milling and
blasting the deposits on the surface of pipes and tubulars or
secondary penetration of the reservoir using perforation or
fracturing to break through the damage to undamaged zones
within the reservoir.
The utilization dissolver treatments prior to a scale squeeze
into wells with known impaired production due to scale is a
well documented process within the North Sea17. During a
typical scale squeeze treatment there is a period of time
associated with a period of well clean up during which the
fluids pumped into the reservoir during the treatment are
displaced back to surface by the produced fluids; this period
can be anything from 24 hours to 3 months before the presqueeze oil rate is re-established. Whilst the oil production
rate decline owing to scale formation is arrested there is no
production enhancement due to the squeeze treatment (Figure
1, B-A). In combining a scale inhibitor with a stimulation
package (acid or alkaline) the economic benefit of the
stimulation (production enhancement) given by the dissolver
is maintained by the presence of the scale inhibitor (Figure
1); this gives a significant improvement in the economics of
later life fields, (C+B-A)18.
Scale dissolvers how they work. This paper will focus on
chemical removal and inhibition of scale during the early
stages of a field life cycle. Prior to discussion of the detail of
the chemical treatments a brief outline of dissolver chemistry
is essential. Scale dissolvers are typical aqueous solutions of
either acids/chelants (for carbonate scales17,19,20,21) or alkaline
chelating agents (for sulphate scales17,22,23).
In this paper both sulphate and carbonate dissolvers will be
discussed but much of the data will relate to the application of
dissolvers for barium sulphate which is the most difficult to
remove, being thermodynamically more stable.
Slow
dissolution rates and the need for temperature to enhance
performance are key factors for sulphate dissolvers.
Commercial based sulphate scale dissolvers are in many cases
based on amino-carboxylic acid chemistry such as EDTA and
DTPA which when combined with an activator have shown
successful dissolution of mixed sulphate scale when applied

SPE 100356

appropriately7,10,12,14, 16, 17.

Carbonate scale can be removed much more rapidly due to is
higher solubility in either acids or chelants at low pH. The
principle challenge with carbonate removal is corrosion on
metallurgy with the dissolver chosen. Carbonate scale can be
removed by either corrosion inhibited hydrochloric acid (5 to
15% wt/v), mixed organic acid formulations or low pH
chelants which, depending on the service environment may
need addition of corrosion inhibitor.
Impact of solvents on dissolution performance. Publications
in the use of mutual solvent preflush chemicals17,24,25 have
suggested that wettablity changes could be possible during
scale squeeze treatment so that enhanced chemical adsorption
could occur when scale squeeze treatments are applied.
Publication on the use of preflush treatments to enhance the
performance of dissolvers26 has shown that the application of
mutual solvent can do more than simply remove hydrocarbon
coating scale deposits and appear to enhance dissolution of
both carbonate and sulphate scale within cores/sandpack,
Figures 2 and 3, Table 1. These findings have been used to
help improve scale dissolver treatments. The application of
mutual solvent in the preflush to remove any oil film followed
by application of the dissolver with mutual solvent also
present has shown great promise in laboratory studies where
dissolver performance has been further enhanced.
The Field in Question
The field where these dissolvers are intended to be deployed is
located 150 miles south East of New Orleans within the Gulf
of Mexico. The reservoir is completed with deviated wells
producing via a subsea manifolds back to the semi
submersible facility capable of processing 250 mbd of oil and
140 mbd of produced water. Based on the brine chemistry the
potential for early carbonate scale was identified with scale
prediction modeling along with sulphate scale formation on
injection seawater breakthrough.
Water chemistry. Variation in the formation water chemistry
is present from the different wells within the field which are
completed. This variation reflects the slightly different zones
in which each well is completed. Typically the salinity of the
formation water is 35,000 mg/l TDS but can rise to as much as
63,500 mg/l. The barium and strontium levels within the prebreakthrough seawater are in the range of 10 to 110 ppm
barium 20 to 210 ppm strontium, 200 to 4,500 ppm calcium
and 200 to 1,200 ppm bicarbonate. The maximum mass of
barium sulphate scale is predicted to be deposited at < 5%
seawater breakthrough: however, the maximum mixed brine
supersaturation is predicted to occur at about 50% seawater.
A typical formation water analysis is presented in Table 2.
Carbonate scale formation is also expected based on the
formation water composition and the operating temperature
and pressure of the field and process system. If uninhibited,
production of a mixture of seawater/formation water will
result in the deposition of sulphate scale. Carbonate scale is
also probable when water is produced. The deposition of scale

SPE 100356

could occur in perforation tunnels or production tubing. Scale

deposition causes flow restrictions and could possibly
compromise the effectiveness of subsurface safety valves.
Downhole chemical injection is planed for initial water
production with scale squeeze treatments prior to seawater
breakthrough. As a remediation method in case of downhole
chemical injection failure or ineffective chemical treatment via
scale squeeze, bullhead deployable scale dissolvers were
required that could remove carbonate and sulphate scale.
Scale Dissolvers How Are They Normally tested?
Static tests are normally carried out to screen the most suitable
chemical and find the optimum soak period prior to field
application8. This type of test is quite suitable for application
of removing scale from production tubing and if there is little
risk of the chemical entering the formation itself. Some tests
have been published which show an assessment on the
formation damage potential of the chemicals27 if the intention
is to apply the dissolver into the formation but there is no
published work on combined scale dissolution in core and
formation damage assessment. The development of a method
to achieve is outlined in this paper.
Static Scale Dissolver Assessment Procedures and
Results.
The following section outlines the test work carried out on two
formulation of sulphate dissolver, product code N and product
code W. Both were assessed as 100% (as supplied) and as a
35% dilution in 2 wt% KCl. In the case of formulation N a
pre soak of the barite sample was carried out using EGMBE.
Both formulation N and W are based on ethylene diamine tetra
acetic acid (EDTA) and diethylene triaamine penta acetic acid
(DTPA) with other chelant additives and modification of the
pH.
Static Dissolver Procedure
1. 100 ml of solution containing the scale dissolver at the
appropriate concentration (neat scale dissolver or diluted
in distilled water / application brine) added to 150 ml
HDPE plastic bottle and placed in an oven at the
required temperature (up to 90oC) for one hour to
equilibrate.
2. 10 g of the prepared mineral chips (see below)
accurately weighed into a second polypropylene bottle.
3. The scale dissolver solution is then added to the bottle
that contains the mineral chips, and shaken vigorously.
The bottles are subsequently replaced in the oven at test
temperature and a stop clock is started (t=0).
4. At t = 30 minutes the sample bottles are shaken (inverted
c.a. 10 times).
5. At t = 1 hours, 1 ml sample of the supernatant is
withdrawn using an automatic pipette and added into a
test tube containing 9 ml of stabilising solution as
described in the sampling procedure below. Note: care
was taken to ensure that particulate matter is not
withdrawn in the sample.

6.
7.

Following sampling, the bottles are shaken as described

above, and replaced in the oven.
Step 5 was then repeated at t = 2, 4, 6, 8 and 24 hours.
For the samples collected at 24 hours, the test bottles are
shaken 1 hour prior to sampling as described above.

Mineral substrates: It is recognised that other workers

examining scale dissolvers have employed alternative forms of
barite8. In our procedure mineralogical specimens, rather than
pure (Analar grade) samples, were examined. This was
selected for the following two reasons: (i) any downhole scale
is unlikely to form as a pure sulphate mineral; (ii) since
dissolution processes are surface controlled, very high surface
areas associated with powdered samples, would be expected to
incur very high, non-representative levels of dissolution.
Substrate preparation: Mineralogical crystalline barite was
broken into small pieces (sieved to 421-1470m across). Any
discoloured pieces removed prior to further size reduction.
These pieces were then gently broken into small chips using
an agate ball and pestle, at which point any fresh discoloured
chips are also removed. The small chips are then sieved, and a
fraction in the size range 1-2 mm collected. These chips were
then rinsed through the sieve with distilled water in order to
remove dust from the surface of the chips. Following this, the
chips were dried overnight at 105C.
Sampling and analysis. The sampling procedure is carried
out as follows: The stabilizing/dilution solution contains
10,000 ppm commercial polyvinyl sulphonate scale inhibitor
PVS and 3,000 ppm potassium (as KCl) in distilled water.
The solution of 10,000 ppm PVS has been shown to
effectively stabilize (or quench) the sample and thus prevent
any post sampling re-precipitation. After the required time
interval, 1ml of the particular test supernatant waters is
collected and immediately added to the 9 ml of
potassium/PVS solution. The diluted samples are then
analyzed by Inductively Coupled Plasma Spectroscopy, ICP
for the particular ions of interest, e.g. barium, strontium,
calcium.
The rate and level of dilution is then determined in terms of
[Ba] / [Sr] / [Ca] present in solution as a function of residence
time. In this manner the relative effectiveness of different
scale dissolver formulations can be compared.
This
information can help to design the soak period of the dissolver
treatment as well as the most economic activity of the product
to be applied.
Sulphate Dissolver Static Results
Mass of scale dissolved. The scale remaining after 24 hours
reaction time was filtered to 0.45um and washed prior to
drying and weighting. Table 3 shows the percentage of
dissolution based on this method for the two formulations (N
and W). It is clear that product W at 100% is the most
effective dissolver with product N at 100% showing only
marginal better performance than the 35% of product N.

Based on these results its clear that activity of the chemical

has an influence on product performance and over treatment is
possible. At dissolver concentrations of 100% non of the
tested products show a three fold increase in total dissolved
scale relative to the 35% dilution of the same chemical.
From this test it is clear that a three stage soak period (with
fresh chemical applied at each soak) using formulation N at
35% would give more effective dissolution than a single soak
formation N or W at 100% product concentration.
Observation of the mineral barite samples post exposure to
the dissolver showed that formulation W caused the scale to
breakup in smaller fragments to a greater extent than
formulation N.
Rate of scale dissolution. Evaluation of the concentration of
the principle scale ions with time can be used to assess the
optimum shut-in or soak time for a dissolver application.
Figures 4, 5 and 6 show the concentration of ions released as
a function of time for the two formulations at 100% and 35%.
It is clear that at approximately 8 hours the rate of dissolution
slows for all formulations and activities. The higher active
formulation show a more rapid rate of dissolution and as with
the mass of dissolved scale measured formulation W is the
best overall performing chemical in terms of barium/strontium
sulphate dissolved. It is also clear that there is a disagreement
between the mass of scale dissolved measured by weight loss
and that mass of scale calculated from ion concentration,
Table 3
Why do mass of dissolution from gravimetric not agree with
ion measured mass? This discrepancy is a common feature of
dissolver testing and is due to the filter size used to retain
undissolved solids. Even a 0.45um filter will allow some
colloidal solids through thus resulting in a difference in the
data to emerge.
Dynamic Sulphate Dissolver Assessment Procedure
and Results
In terms of screening dissolvers the static tests were the most
common method of ranking chemicals before they were
applied to either tube cleaning or near wellbore stimulations.
The effectiveness of the chemicals at removing scale formed
within a core and any resulting formation damage to that core
by the chemical had not be published. The following test
program outlines the test method and procedure used to
evaluate both formulations N and W in Berea outcrop core
(analogues to the field reservoir) using filtered (<10um) field
crude oil and synthetic field brines (Table 2). The coreflood
program was designed to simulate the impact of scale
formation due to early seawater breakthrough (90% Formation
water & 10% seawater) on injectivty and then assess the
impact of the sulphate dissolver to recover that loss of
injectivty in terms of both oil and brine permeability.
Dissolver and preflush chemicals. Treatment program
formulation N used a mutual solvent chemical preflush
applied at a concentration of 20% in 2% KCl scale dissolver

SPE 100356

chemical, N as the main treatment applied as a 35% solution

in 2% KCl.
Treatment program formulation W used a mutual solvent
preflush applied at 100% and scale dissolver W as the main
treatment also applied at 100%.
Coreflood Program
1. Assemble 1.5 inch diameter Berea sandstone core plugs in
hasseler type cell (length 3 inch), 500 psi back pressure,
1,500 psi overburden.
2. Inject synthetic formation brine at 60 ml/hour for 3 hours
raise to reservoir temperature of 93oC.
3. Carry out lithium chloride tracer flood, 50 ppm of Li in
synthetic formation brine, flood at 60 ml/h for 2 hours,
collecting 2ml sample for analysis, displace lithium rich
brine with FW for 1 hour at 120 ml/h. At reservoir
temperature.
4. Measure synthetic formation brine permeability at the
following rates 0, 30ml/h, 60ml/h, 90ml/h, and 120 ml/h.
At reservoir temperature.
5. Flood with filtered crude oil to Swi (60 ml/h for 2 hour,
120 ml/h for 30 min) (measure differential pressure). At
reservoir temperature.
6. Measure crude oil permeability at reservoir temperature
(rates 0, 30ml/h, 60ml/h, 90ml/h, 120ml/h).
7. Flood core with synthetic formation water to Sor (60 ml/h
for 2 hour, 120 ml/h for 30 min) (measure differential
pressure). At reservoir temperature.
8. Measure brine permeability at reservoir temperature (rates
0, 30ml/h, 60ml/h, 120ml/h).
9. Carry out 50 ppm Li tracer to measure pore volume, flood
with 90 ml of Li tracer in formation water, collect
samples every 2 ml, flood at 60 ml/h. At reservoir
temperature.
10. Flood core with crude oil to Swi (60 ml/h for 2 hour, 120
ml/h for 30 min) (measure differential pressure). At
reservoir temperature.
11. Measure oil permeability at reservoir temperature (rates 0,
30ml/h, 60ml/h, 90ml/h, 120ml/h).
11.5 Cool the core to room temperature (20oC) while flowing
synthetic formation water at 60ml/h for a minimum of 12
hours and logging differential pressure.
12. Inject a mixture of 90% formation water and 10%
seawater to induce sulphate scale formation within the
core. Once over 25% permeability reduction has been
observed heat core to reservoir temperature and carry out
step 13 onwards.
13. Flood core with synthetic formation water to Sor (60 ml/h
for 2 hour, 120 ml/h for 30 min) (measure differential
pressure). At reservoir temperature of 93oC.
14. Measure brine permeability at reservoir temperature (rates
0, 30ml/h, 60ml/h, 120ml/h).
15. Carry out 50 ppm Li tracer to measure pore volume, flood
with 90 ml of Li tracer in formation water, collect
samples every 2 ml, flood at 60 ml/h. At reservoir
temperature.
16. Flood core with crude oil to Swi (60 ml/h for 2 hour, 120

SPE 100356

17.
18.
19.
20.
21.
22.
23.
24.
25.

26.

ml/h for 30 min) (measure differential pressure). At

reservoir temperature.
Measure oil permeability at reservoir temperature (rates 0,
30ml/h, 60ml/h, 90ml/h, 120ml/h).
Inject proposed dissolver chemical system preflush (1
PV), main treatment (3 PV) at 60oC, measure differential
pressure.
Shut in core at a designed temperature 60oC less than
reservoir due to fluid cooling effects in the near wellbore,
for 12 hours (over night).
Injected 3 PV of fresh dissolver (measure differential
pressure) and shut-in for 12 hours.
Inject the chemical stage in reverse flow direction order
of injection main treatment and preflush.
Flood core with crude oil to Swi at reservoir temperature,
(60 ml/h for 2 hour, 120 ml/h for 30 min) (measure
differential pressure).
Measure crude oil permeability at reservoir temperature
(rates 0, 30ml/h, 60ml/h, 90ml/h, 120ml/h).
Flood core with formation water to Sor, (60 ml/h for 2
hour, 120 ml/h for 30 min) (measure differential
pressure). At reservoir temperature.
Measure brine permeability at reservoir temperature (rates
0, 30ml/h, 60ml/h, 90ml/h, 120ml/h).
Carry out environmental scanning electron microscopy
(ESEM) on core sample (sections along the core from the
inlet face to the outlet face).

Dissolver Coreflood Test Results

Formulation N was evaluated following the test program
outlined. Following a series of brine and oil permeability
cycles the core was cooled from reservoir temperature to 20C
to ensure maximum sulphate supersaturation when the
formation water and seawater mixed prior to injection into the
core. Mixing of the formation water and the seawater occurs
within 3 cm of the core face.
Figure 7 shows the differential pressure across the core as a
mixture of 90% formation water and 10% seawater is injected.
The differential pressure increases exponentially which is
indicative of scale growth restricting flow paths within the
core. An increase of 18 psi was generated over a period of 25
hours of combined brine injection resulting in a reduction in
permeability of about 45%, Table 4.
Brine and oil permeability were then measured prior to
injection of the dissolver package (preflush solvent and main
treatment dissolver). Figure 8 shows the differential pressure
profile across the core during displacement of oil from the
core caused by the chemical package injection, shut-ins and
backflow stages. There is a general trend of reducing
differential pressure following the mutual solvent preflush
injection. This declining pressure suggests that the sulphate
scale is being dissolved from the inlet face of the core. After
the first shut in, the initial differential pressure is higher and
the profile is very spiky which suggests movement of
partially dissolved scale particles within the core.

Detailed permeability measurements were made throughout

the coreflood program and are presented in Table 4. The
initial permeability to brine was calculated at 50mD (Stage 4),
which fell to 8.1mD after injection of crude and subsequent
flooding to Sor (Stage 8). After scale deposition had been
achieved, the permeability to brine at Sor fell by 25% to
6.1mD. After the chemical package had been applied to the
core and following a crude oil / brine saturation cycle, the
permeability to brine was calculated at 6.4mD (Stage 25)
which was a 21% reduction in permeability from the value
calculated before scale build up and the subsequent dissolution
treatment.
The initial permeability to crude at Swi was calculated at
19mD (Stage 6), which increased to 20mD after subsequent
flooding to Sor then back to Swi (Stage 11). This 6% increase
shows that cycling brine and crude through the core does not
affect the permeability significantly. After scale deposition
had been achieved, the permeability to crude at Swi fell by
42% to 11mD. After the chemical package had been applied
to the core, the permeability to crude was calculated at 18mD
(Stage 23) which was a 12% reduction in permeability from
the value calculated before scale build up and the subsequent
dissolution treatment.
From these permeability calculations, it can be shown that the
chemical package using mutual solvent and formulation N
almost brought the permeability to oil back to pre-scale values
and did not have much effect on the cores permeability to
water.
Formulation W was evaluated on a separate core which was
cut from within a few cm of the core used for evaluation of
formulation N. Differential pressure profiles of the chemical
package application are shown in Figure 9. The differential
pressure experienced here is higher than the chemical
dissolver package N which is due to the higher viscosity of
formulation W which was applied as 100% chemical. It is
clear from the pressure profile that there does not appear to be
the same reduction in differential pressure as the chemicals are
flowed through the core (Figures 8 and 9). A possible reason
for the observed pressure rises rather than decline during
dissolver injection is due to mobilization of scale and possible
non soluble material (clays).
Detailed permeability measurement were made throughout
the coreflood program and are presented in Table 5. The
initial permeability to brine was calculated at 68mD (Stage
4), which fell to 12mD after injection of crude and
subsequent flooding to Sor (Stage 8), which are similar
values to those during conditioning of formulation Ns core
plug. After scale deposition had been achieved, the
permeability to brine at Sor fell by 46% to 6.7mD, which is a
larger decline than the value for formulation Ns core. After
the chemical package had been applied to the core and
following a crude oil / brine saturation cycle, the permeability
to brine was calculated at 13.05mD (Stage 25) which was a

6.6% increase in permeability from the value calculated

before scale build up and the subsequent dissolution
treatment.
The initial permeability to crude at Swi was calculated at
27mD (Stage 6), which increased to 30mD after subsequent
flooding to Sor then back to Swi (Stage 11). This 10%
increase shows that cycling brine and crude through the core
does not affect the permeability significantly. After scale
deposition had been achieved, the permeability to crude at
Swi fell by 54% to 14mD. After the chemical package had
been applied to the core, the permeability to crude was
calculated at 16mD (Stage 23) which was a 46% reduction in
permeability from the value calculated before scale build up
and the subsequent dissolution treatment.
From these permeability calculations, it can be shown that
formulation W slightly stimulated the permeability to water
and did not achieve the same level of stimulation on the
permeability to oil as was observed for formulation N.
In summary it can be concluded that formulation N returned
89% of oil permeability and 79% of the brine permeability
back to pre-scale values. Formulation W slightly stimulated
the brine permeability above that of the pre scaled core and
did not achieve the same level of stimulation to the oil
permeability as was observed for formulation N with only
54% of the lost permeability recovered.
Environmental Scanning Electron Microscope (ESEM) core
evaluation following sulphate dissolver. ESEM evaluation
was carried out on the pre treated and post treated core
samples to further investigate the permeability results. From
this evaluation it was also possible to observe any difference
in the performance of the dissolver formulations.
Evaluations of the cores were made at locations along their
length. Inlet face and a 1 cm intervals along the cores length
to the outlet face were analyzed.
Core treated with formulation N showed no scale on the inlet
face of the core but some very small, party dissolved (etched
grain surfaces) scale particles near the outlet face, Figure 10.
This suggests that the dissolver had removed all the scale from
the inlet face and what was not fully dissolved was reduced in
size such that it was carried though (and out) the core
Core treated with formulation W showed scale still present on
the inlet face of the core and within 1 cm of the inlet face
(Figure 11) but no scale was observed near the outlet of the
core. This observation would suggest that the dissolver was
not as effective at dissolving the scale and what was partially
dissolved was carried into the body of the core were it logged
causing a reduction of permeability.
Neither core showed any signs of emulsions, clay swelling or
clay fines mobilization following the application of both
dissolver formulations. Any changes is oil permeability
relative to brine permeability (formulation W) within the core
must be due to wettability effects on the mineral surfaces
caused by the chemicals being applied.

SPE 100356

Development of New Carbonate Scale Dissolver

Assessment of the scale risk within the field suggested that
along with sulphate scale during seawater breakthrough, there
was also a risk of downhole carbonate scale during formation
water production and early seawater breakthrough. The
completions within this field are made of corrosion resistant
alloy (Cr25) and the flow lines that connect the subsea
wellheads to the production facility are made of carbon steel.
While the sulphate dissolver formulations have a pH 10-11
the conventional carbonate dissolvers available have a much
lower pH and are commonly either hydrochloric acid or
acetic/formic acid formulations. To reduce the corrosion
rates within both alloy types through which the dissolvers
would flow evaluation of the dissolution rates of
conventional formation was carried out along side test work
to assess a novel formulation designed to remove carbonate
scale by at a high pH than conventional dissolvers. This
novel dissolver is based on ethylene diamine tetra acetic acid
(EDTA) with a pH 4.5 and is termed modified EDTA in the
body of the text.
Carbonate Scale Dissolver Performance Assessment
Carbonate test program. The same test program as outlined
for the sulphate dissolver was utilised with 100ml of scale
dissolver solution being prepared at a concentration reflecting
what would be used in the field and 2.5g of crushed mineral
calcite (Iceland spar sieved to 421-1470m) was added. Upon
mixing the samples were shaken vigorously and replaced in
the oven at 90C for a period of 6 hours. Samples were taken
at 0, 10, 30, 45, 60, 90, 120, 180, 240 and 360 minutes and
preserved using the same solution as for the sulphate scale
tests before analysis of the calcium ion concentration was
carried out via ICP-AES. At the end of the test the solutions
were filtered and the mass of calcite remaining undissolved
determined.
Carbonate scale dissolver solutions assessed were as follows:
7.5% Hydrochloric acid
50% acetic/formic acid scale dissolver
50% unmodified pH 12.8 modified EDTA chemistry
50% modified EDTA type chemistry at pH 4.7
Carbonate results. Table 6 presents the percentage dissolution
from the dissolver evaluation tests. It is clear that over the 6
hour period the hydrochloric and acetic/formic acid
formulation are very effective with the pH 4.7 modified
EDTA formation giving over 90% dissolution.
Closer evaluation of the calcium ion concentration within the
dissolver solution over this 6 hour period (Figure 12) shows
that the hydrochloric acid and acetic/formic acid formulations
display very fast dissolution kinetics . It can be seen that the
alkaline version of the modified EDTA dissolver (pH 12.8)
shows the poorest performance both in terms of rate of
dissolution and of mass dissolved at the end of the test. The
acidic version (pH 4.7) of the modified EDTA dissolver shows
a much better rate of calcite dissolution. The initial rate of

SPE 100356

dissolution of the acidic EDTA solution is almost twice the pH

12.8 version at around 4,000ppm calcium compared to less
than 2,000ppm calcium dissolved at 60 minutes.
The static carbonate dissolver results suggest a modified
EDTA with a pH of 4.7 is an effective calcium carbonate
scale dissolver during a time period of 5-6 hours, but at pH
12.8 performance and rate of dissolution is impaired. The
longer exposure time and the repeated soak periods required
for the modifiered EDTA to achieve the same dissolution
performance as acetic/formic acid formulations may have an
detrimental impact on corrosion for this formulation.
Carbonate dissolver corrosion rate assessment. Tests were
conducted on the acetic acid and pH adjusted EDTA
formulations such that via weight loss coupon tests where pre
weighted coupons were immersed at reservoir temperature in
test solutions of the dissolver chemicals with and without an
acid corrosion inhibitor for exposure times of 6 hours and 24
hours. It is important to note that the expected contact time
for the dissolver soak period is 1-2 hours but assessment of
the corrosion rates were made at up to 24 hours to estimate
the impact of the fluids being stuck in the well due to an
operational issue.
On carbon steel it is clear that the chelant EDTA based
chemical has a much lower rate than the acetic formic acid
formation, Table 7. The corrosion rate on the corrosion
resistant alloy shows both have much lower corrosion rates
but this test cannot simulate the potential loss of mechanical
strength due to hydrogen ion embrittlement which is of
concern for the acetic/formic acid chemical. Table 8 shows
the reduction in the corrosion rate for carbon steel by addition
of a corrosion inhibitor (acrylated imidazoline) to the
formulations. From the data in Table 8 and the images of the
coupons Figures 13 and 14 it is clear that the addition of an
acid specific corrosion inhibitor (1,000 to 5,000 ppm) can
reduce the corrosion risk of both dissolver types significantly.
Based on the encouraging dissolution characteristics of the
modified EDTA type dissolver and its reduced risk of
hydrogen ion embrittlement this is the preferred dissolver
option for the field and is currently undergoing evaluation for
embrittelment to downhole completions metallurgy prior to
final field sanction for use.
Conclusions
1. Total mass of scale dissolved and dissolution rate tests
based on ion data are complementary methods to help
screen both sulphate and carbonate dissolver chemicals
for application to clean scaled production tubing.
2. Repeated 6-8 hour soaks periods using lower active
sulphate dissolver formulations (35% rather than 100%)
can be more effective in terms of chemical usage than
high concentration formulations.
3. Dynamic dissolver tests evaluate the rate of dissolution

4.

5.

6.
7.

8.

and any formation damage potential such as fines

mobilization and wettability alteration that a dissolver
formulation may pose when applied to the near wellbore
region.
Assessment of both oil and brine permeability prior to and
following scale dissolver application linked with ESEM
evaluation of the core improves understanding of the
interaction of the chemicals with the rock minerals and
scale.
Utilization of mutual solvent packages in the preflush of
dissolver treatments have been demonstrated to improve
scale removal by increasing dissolution rate, mass of scale
dissolved and only add a small additional cost to the
treatments.
A good understanding of the type and location of
deposited scale within the well or wellbore region are
critical to designing an effective dissolver treatment.
Carbonate dissolver corrosion risk in carbon steel and
high Chromium alloys can be overcome with chelant
based formulations rather than acids such as hydrochloric
and acetic/formic acids for use in high temperature and
CRA completed production wells.
While dissolver treatments have proved effective in
stimulating some of the production lost due to the
formation of scale within production wells it is still more
effective to squeeze wells on time rather than trying to
remove material deposited while flowing below the
minimum inhibitor concentration (MIC).

Acknowledgements
The authors would like to thank BP E&P, Nalco Energy
Services for permission to publish this work. We are also
grateful for the help and co-operation of members of the asset
team, field operators and Nalco laboratory staff for their
assistance in carrying out the treatments described in this
paper.
Reference
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Barium and Calcium Sulphate Precipitation and
Migration Inside Sand Packs, paper SPE 19765.
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of Barium Sulphate Scale Deposition, JPT (October
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of Sulphate Scale in Shell Expro, paper SPE 16538
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Conference, Aberdeen 8-11 September.
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Downhole Barium Sulphate Scale Dissolving operation,
paper SPE 26704 presented at the 1993 SPE Offshore
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SPE 100356

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Putnis, A., Putnis, C.V., and Paul, J.M.: The Efficiency
of a DTPA-Based Solvent in the Dissolution of Barium
Sulphate Scale Deposits, paper SPE 29094 presented at
the 1995 SPE Intl. Symposium on Oilfield Chemistry, San
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and Scale Inhibitor Squeeze Treatments to Repair ad
Prevent Formation Damage in Two Statfjord Field
Wells, paper SPE 31126 presented at the 1996 SPE Intl.
Symposium on Formation Damage Control, Lafayette,
Louisiana, 14-15 February.
Benson, C.W., Keatch, R.W., and Ray, S.K: Mineral
Scale Dissolution: Chemistry and Application, Proc.,
IBC Solving Oilfield Scaling Conference, The Airport
Skean Dhu Hotel, Aberdeen (1997).
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Formation Damage at Prudhoe Bay, SPE 11188.
presented at SPE Annual technical conference and
Exhibition, New Orleans, Louisiana 25-27 September
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Klepaker, J., Andrews, J., Vikane, O., and Hagen, T.H.
Successful Scale Stimulation Treatments of a Subsea
Open Hole Gravel-packed Well in the North Sea. SPE
73715, presented at SPE International Symposium on
Formation Damage, Lafayette, Louisiana, 20-21 February
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Mota, R.O., Bezerra, M. C. M., Rosario, F.F., Prais, F.:
Forecasts and Alternative Analysis for Sulfate Removal
or Chemical Treatments for Barium and Strontium Scale
Deposition Offshore Brazil SPE 87464, presented at
the SPE International Symposium on Oilfield Scale,
Aberdeen, UK, 26-27 May, 2004.
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Waldie, A.D. Application of Scale Dissolver and
Inhibitor Squeeze Through the Gas Lift Line a Subsea
Field SPE 95100, presented at SPE International
Symposium on Oilfield Scale, Aberdeen, UK, 11-12 May
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Jordan, M.M., Hiscox, I., Dalton, J.F., Mackie, J., and
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Scale Dissolver /Squeeze Treatment in Subsea Horizontal
Production Wells, North Sea Basin. SPE 73717
presented at SPE International Symposium on Formation
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Jordan M.M, Sjuraether K, Collins I.R., Feasey N.D and

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D. Emmons. Life cycle Management of Scale Control

within Subsea Fields and Its Impact on flow Assurance,
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Fredd, C. N., and Fogler, H.S., The Influence of
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Fredd, C. N., and Fogler, H.S., The Kinetics of Calcite
Dissolution in Acetic Acid Solutions, Chem. Eng. Sci.,
22, 3863-3874, (1998).
Frenier, W.W., Novel Scale Removers Are Developed
for Dissolving Alkaline Earth Deposits SPE 65027
presented at SPE International Symposium on Oilfield
Chemistry, Houston, Texas, 13-16 February 2001.
Lakatos, I., Lakatos, J., Potential of Different Polyamino
Carboxylic Acids as Barium and Strontium Sulfate
Dissolvers SPE 94633. presented at SPE European
Formation Damage Conference, Scheveningen, The
Netherlands, 25-27 May 2005.
Nasr-El-Din, H.A., Al-Mutairi, S.H., Lynn, J.D.:
Evaluation of a New Barite Dissolver: Lab Studies
SPE 86501, presented at the SPE International
Symposium and Exhibition on Formation Damage
Control, Lafayette, Louisiana, 18-20 February 2004.
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Hewartson, J.A., Deignan, S.D.: Extending Scale
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Laboratory to the Field, presented at the 1997 Solving
Oilfield Scaling Conference, 23-24 January.
Collins, I.R., Cowie, L.G., Nicol, M., and Stewart, N.J.:
Field Application of a Scale Inhibitor Squeeze
Enhancing Additive, paper SPE 54525 presented at
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Williams, G.D, Collins, I.R. and Wade, S.R.: Enhancing
Mineral Scale Dissolution in the Near-Wellbore Region,
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Tomlins, R. and Bunney, J.: Scale Dissolver
Application: Production Enhancement and FormationDamage Potential, SPE 66565, Published in SPE
Production & Facilities November 2000, Volume 15, no.
4, pages 288 295.

Table 1. Comparison of Dissolver performance in

dynamic sandpack with and without mutual solvent
(William et al., 1999).
Scale type
Barite
Calcite

Dissolution enhancement Range

25% to 150%
55% to 100%

SPE 100356

Table 2. Typical Field formation water and injection seawater composition.

Ion
Na
K
Ca
Mg
Ba
Sr
Cl
HCO3
SO4

Concentration (mg/l)
Formation Water
Seawater
47454
10800
282
400
4532
430
576
1400
108
0
205
0
82457
19754
240
145
23
2750

Table 3. Comparison of sulphate dissolver Perfoance for formulations W and N at two activities after 24 hours at
90C.

Chemical Application

Mass (g) of Barite

Dissolved in 24 hours

Percentage of
Scale Dissolved (mass)

Percentage of
Scale Dissolved (ion)

100% Chemical N

2.26

22.60%

12.71%

35%Chemical N

1.83

18.30%

7.03%

100% Chemical W

2.68

26.80%

13.10%

35% Chemical W

1.23

12.30%

9.91%

Appearance of
Treated Barite
Smaller Grains
and Dust
Smaller Grains
and Dust
Smaller Grains
and Dust
Smaller Grains
and Dust

Table 4. Permeability measurements made during core conditioning, in-situ scale formation, dissolution and
post chemical treatments with oil, brine, chemical formulation N.
Formulation N Scale Dissolver Permeability
Test Code
Brine perm 1 following initial brine injection (Stage 4)
Brine perm 2 following initial flood to Sor (Stage 8)
Brine perm 3 following scale build up (Stage 14)
Brine perm 4 after dissolver chemical treatment (Stage 25)

K mD values % change
50.36
8.09
-83.93
6.07
-25.03
6.36
-21.44

Oil perm 1 following initial flood to Swi (Stage 6)

Oil perm 2 following 2nd flood to Swi (Stage 11)
Oil perm 3 following scale build up (Stage 17)
Oil perm 4 following dissolver chemical treatment (Stage 23)

18.64
19.82
11.43
17.53

Viscosity values
Oil at 93C
Formation Water at 93C

1.0 cp
0.5 cp

6.32
-42.33
-11.55

10

SPE 100356

Table 5. Permeability measurements made during core conditioning, in-situ scale formation, dissolution and post
chemical treatments with oil, brine, chemical formulation W.
Formulation W Scale Dissolver Permeability
Test Code
Brine perm 1 following initial brine injection (Stage 4)
Brine perm 2 following initial flood to Sor (Stage 8)
Brine perm 3 following scale build up (Stage 14)
Brine perm 4 after dissolver chemical treatment (Stage 25)

K mD values % change
68.33
12.24
-82.09
6.65
-45.67
13.05
6.63

Oil perm 1 following initial flood to Swi (Stage 6)

Oil perm 2 following 2nd flood to Swi (Stage 11)
Oil perm 3 following scale build up (Stage 17)
Oil perm 4 following dissolver chemical treatment (Stage 23)

27.46
30.28
13.88
16.39

Viscosity values
Oil at 93C
Formation Water at 93C

1.0 cp
0.5 cp

10.27
-54.18
-45.88

Table 6. Comparison of carbonate dissolver performance for four formulations after 6 hours at 90C.
Scale Dissolver Type
7.5% HCl
50% Acetic/Formic acid
pH 12.8 modified EDTA
pH 4.5 modified EDTA

% Dissolution (mass)
100
100
21.7
93.4

% Dissolution (ion)
81.47
87.57
49.92
74.14

Table 7. Carbonate dissolver corrosion performance to carbon steel and CRA after 6 hours exposure 90C (no
carbonate scale present during test)
Corrosion Rates
Coupon type

Chemical type

mmpy

Mpy

Carbon steel

50% Acetic/Formic acid

68.00

2677.17

Carbon steel

Modified EDTA pH 4.5

27.00

1062.99

Cr 25 Super Duplex

50% Acetic/Formic acid

0.02

0.79

Cr 25 Super Duplex

Modified EDTA pH 4.5

0.03

1.18

SPE 100356

11

Table 8. Carbonate dissolver corrosion performance to carbon steel after 24 hours exposure 90C (no scale
present during test)
Corrosion Rates
Coupon type

Chemical type

CI Concentration

mmpy

Mpy

Carbon steel

50% Acetic/Formic acid

None

31.60

1244.09

Carbon steel

50% Acetic/Formic acid

100 ppm

20.17

793.90

Carbon steel

50% Acetic/Formic acid

1000 ppm

6.60

259.84

Carbon steel

50% Acetic/Formic acid

5000 ppm

6.16

242.44

Corrosion Rates
Coupon type

Chemical type

CI Concentration

mmpy

Mpy

Carbon steel

Modified EDTA pH 4.5

None

16.40

645.67

Carbon steel

Modified EDTA pH 4.5

100 ppm

5.49

216.14

Carbon steel

Modified EDTA pH 4.5

1000 ppm

2.66

104.72

Carbon steel

Modified EDTA pH 4.5

5000 ppm

1.85

72.68

12

SPE 100356

Figure 1. Oil Production rate decline due to natural reservoir pressure and scale induced damage plus impact on oil rate of scale
inhibitor squeeze (SISQ), stimulation and a stimulation alone.

Total Incremental Oil Protected

= (C+B) - A >>>(B - A)

A= Deferred oil volume

SISQ + Stim.

B= Volume of oil
produced due to scale
inhibitor being present

Inhibition or
stimulation treatment

Pre SISQ
Decline

Decline in
BOPD due
to scale

C= Volume of oil
released due to
stimulation

Post SISQ or
SISQ stimulation
Decline

Qoil
BOPD

SISQ alone

Time

Clean up post sqz

Clean up post stimulation or SISQ Stim.
Squeeze Life (std sqz or stimulation sqz)

Figure 2. Calcium ion concentration within the effluent leaving a sand/carbonate pack flood after application of acid dissolver with
and without mutual solvent

2500
15% mutual solvent enhanced
2000

1500

1000

500

Time/ 5 minute intervals

13
1

12
6

12
1

11
6

11
1

10
6

96
10
1

91

86

81

76

71

66

61

56

51

46

41

36

31

26

21

16

11

Calcium ion concentration within the effluent (ppm)

unenhanced

SPE 100356

13

Figure 3. Barium ion concentration within the effluent leaving a sand/barite pack flood after application of acid dissolver with and
without mutual solvent

2000

unenhanced
Barium ion concentration within the effluent (ppm)

15% mutual solvent enhanced

1500

1000

500

96
10
1
10
6
11
1
11
6
12
1
12
6
13
1
13
6
14
1
14
6
15
1

91

86

81

76

71

66

61

56

51

46

41

36

31

26

21

16

11

Flood time/ 5 min intervals

Figure 4. Rate of barium sulphate dissolution using two formulations (W and N) of sulphate dissolver at two concentration over 24
hour contact time, 90C.

Static Scale Dissolver Tests

Barium in Solution
100% Formulation N
100% Formulation W

10000

35% Formulation N
35% Formulation Wl

9000

Barium Concentration / ppm

8000
7000
6000
5000
4000
3000
2000
1000
0
0

10

15

Time / hours

20

25

14

SPE 100356

Figure 5. Rate of strontium sulphate dissolution using two formulations (W and N) of sulphate dissolver at two concentration over 24
hour contact time, 90C.
Static Scale Dissolver Tests
Strontium in Solution
100% Formulation N
100% Formulation W

10

35% Formulation N
35% Formulation W

Strontium Concentration / ppm

9
8
7
6
5
4
3
2
1
0
0

10

15

20

25

Time / hours

Figure 6. Rate of calcium sulphate dissolution using two formulations (W and N) of sulphate dissolver at two concentration over 24
hour contact time, 90C.
Static Scale Dissolver Tests
Calcium in Solution
100% Formulation N
100% Formulation W

100

35% Formulation N
35% Formulation W

90

Calcium Concentration / ppm

80
70
60
50
40
30
20
10
0
0

10

15

Time / hours

20

25

SPE 100356

15

Figure 7. Differential pressure across core plug during the formation of in siture barium sulphate scale, 25C, 90% FW : 10% SW at 60
ml flow rate.
45

40

Differential Pressure (psi)

35
60 mls/hr

30

25

20

15

10

0
0

200

400

600

800

1000

1200

1400

1600

Time (mins)

Figure 8. Differential pressure across the core plug during the dissolution of in situe barium sulphate scale with mutual solvent
preflush and formulation N, 65C, flow rate 60ml/h
70
Dead
Volume

1 Pore
Volume

3 Pore Volumes Main

treatment

3 Pore Volumes
Main Treatment

1 Pore
Volume
Preflush

3 Pore Volumes Main Treatment

Preflush

60

Differential Pressure (psi)

50

40

30
Shut-in/soak

Shut-in/soak

20

10

0
0

20

40

60

80

100
Volume (mls)

120

140

160

180

200

16

SPE 100356

Figure 9. Differential pressure across the core plug during the dissolution of in situe barium sulphate scale with mutual solvent
preflush and formulation W, 65C, flow rate 60ml/h

70
Dead
Vol

60

1PV
Pre-Flush

3 PV Main
Treatment

3 PV Main
Treatment

3 PV Main
Treatment

1 PV
Pre-Flush

Differential Pressure (psi)

50

40

30

20

10
Shut-in/soak

Shut-in/soak

0
0

10

20

30

40

50

60

70

80

90

100

110

120

130

140

150

160

170

180

190

200

Volume (mls)

Figure 10. ESEM image and EDX analysis

Outlet of treated core (few very small grains)
of barium sulphate still present in the core)

Figure 11. ESEM image and EDX analysis

Within 1-2 cm of core inlet face (aggregate of grains not a single grain)
significant amount of barium sulphate within a few cm of inlet face

Element
Element
CK
OK
NaK
AlK
SiK
SK
ClK
KK
CaK
BaL
Total

Wt %
30.97
13.94
3.83
0.46
7.14
6.33
4.23
0.43
1.07
31.6
100

At %
57.66
19.48
3.72
0.38
5.68
4.42
2.67
0.25
0.6
5.15
100

CK
OK
NaK
MgK
AlK
SiK
SK
ClK
KK
BaL
FeK
Total

Wt %
43.09
18.04
0.92
0.17
1.22
6.22
4.96
1.11
1.1
20.52
2.66
100

At %
65.95
20.72
0.74
0.13
0.83
4.07
2.85
0.58
0.52
2.75
0.87
100

Nomenclature of EDX analysis

Element such as Carbon are denoted by C and the associated letter K is the electron energy band used to measure the amount of the
element. Wt % = weight percent of the element, At % = Atomic percent of the element.

SPE 100356

17

Figure 12. Rate of calcium carbonate dissolution using four formulations of carbonate dissolver over 6 hour contact time, 90C.

7.5% HCl

50% acetic/formic acid

50% ECTA type pH 12.8

50% EDTA Type pH 4.7

% Mass dissolved

12000

10000

100%
100%

Ca dissolved (ppm)

8000

93.4%

6000

21.7%
4000

2000

0
0

60

120

180

240

300

360

Time (mins)

Figure 13. Carbon steel weight loss coupons following emersion in acetic/formic acid carbonate dissolver for 24 hours 90C. Coupons
were tested with and without acid corrosion inhibitor present.

No CI

100ppm 1000ppm 5000ppm

Figure 14. Carbon steel coupons following emersion in modified EDTA carbonate dissolver, pH 4.7 after 24 hours 90C. Coupons
were tested with and without acid corrosion inhibitor present.

No CI

100ppm 1000ppm 5000ppm