SPE 114075

Performance of Scale Inhibitors Under Carbonate and Sulfide

Scaling Conditions
J. Kevyn Smith, SPE, Julie Hammons, Galyn Boyd, SPE, and Qiang Fu, SPE, Baker Petrolite

Copyright 2008, Society of Petroleum Engineers

This paper was prepared for presentation at the 2008 SPE International Oilfield Scale Conference held in Aberdeen, UK, 28–29 May 2008.

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

Abstract

This paper compares the scale inhibition efficiencies of a phosphate ester, two phosphonate and two
polymer chemistries in the presence of ferrous iron, calcium carbonate, barium sulfate, iron sulfide and
iron carbonate scales, as well as combinations therein. The results show that as the scale speciation of
the precipitating solids change so does the scale inhibition efficiency. These changes in efficiency were
attributed to the cumulative effects of crystal matrix distortion by either exogenuous scale specie or
effect of metal complexation to the scale inhibitor chemistry. The ultimate conclusion of this study is
that because of the relationship between the scale inhibitor performance and ferrous iron concentration,
it is important to consider this relationship when determining the minimum inhibitor concentration
(M.I.C.) for the inhibition of scale growth in oilfield production systems.
Introduction

Oilfield scales are a conglomeration of several different scales, i.e. calcium carbonate, barium sulfate,
iron carbonate, iron sulfide, zinc sulfide, and lead sulfide. Rarely do these scales precipitate as pure
solids; rather they precipitate as a mixture. The complex composition of oilfield scales has been proved
by data generated from by X-ray Fluorescence (XRF) and x-ray diffraction (XRD) analysis of samples
that have been collected throughout the world (data not shown). The factors affecting the precipitation
of these complex mixtures of scales can be partly attributed to temperature, pressure, ionic composition
of the brine, and fluid turbulence. While a unified explanation to the origin of these complex scale
mixtures is outside of the scope of the present study, it is certain that the presence of the wide variety of
solids does impact scale inhibition efficiency. This is realized in the fact that scale inhibitor chemistries
have different inhibition efficiencies for different scales. These inhibition efficiencies for different scale
inhibitor chemistries have been shown to be influenced by absorption rate of the scale inhibitor to a
particular scale, agglomeration tendency of the particular scale, and zeta potential of the scale nucleons.1
To protect oilfield production equipment from the choking effects of scale precipitation, scale
inhibition programs are ideally designed to provide protection at the locations upstream of the primary
scale formation point. Scale program design can take two courses, (i) the program is based on empirical
field data (i.e. scale coupon analyses, water chemistry analyses, production data, oil production
operational conditions such as temperature and pressure) or, (ii) the program is devised from data
generated through laboratory based performance testing to select the proper scale inhibitor chemistry for
a given application. There are many successful scale inhibition programs that have been designed
without the aid of laboratory study. The increasing risk of capital loss due to scale related flow
2 SPE 114075

assurance problems and the severity of the operational conditions of new and planned oil production
plants requires that laboratory investigations become standard practice prior to the launch of new
operations or shortly thereafter.
The laboratory evaluation of scale inhibitor chemistries provides several advantages to the
aforementioned empherical method. Firstly, large number of scale inhibitor chemistries can be screened
to determine which chemistries are compatible in the produced water. Compatibility screening identifies
chemistries that will not precipitate as their calcium or magnesium salts thus rendering them ineffective.
Secondly, laboratory testing can provide performance information for each candidate scale inhibitor
chemistry. Static inhibition tests, and/or dynamic “tube blocking” tests can be conducted to select the
most efficient scale inhibitor chemistry, as well as to determine the Minimum Inhibitor Concentration
(MIC) required to arrest the formation and precipitation of scale during the test period.2-6
In the laboratory, both static and dynamic tests have been shown to be effective, not only as a
performance evaluation tool, but as a method to discern the effect of extraneous factors on scale
inhibitor performance.3-5 Dynamic tests have been used to describe scale inhibitor performance as
affected by the presence of calcium, magnesium, and ferrous ions in the bulk solution.7,8 Dynamic tests
have been used to determine the MIC against exotic scales (FeS, ZnS and PbS) in combination with the
common oil field scales (CaCO3, BaSO4, CaSO4).9-11 Static tests have been used to determine the effect
of aqueous calcium and magnesium ions against scale inhibitor performance.1,12

Outline of the Current Study. The purpose of this study seeks to address the effect of scale inhibitor
efficiency against calcium carbonate (CaCO3), barium sulfate (BaSO4), iron carbonate (FeCO3), and iron
sulfide (FeS) scales by systematically evaluating the performance of five unique scale inhibitor
chemistries against individual scale specie, as well as combinations therein. To this aim, four test stages
were designed to investigate the scale inhibition efficiency of the candidate chemistries:

• aerobic single component scaling brine (CaCO3 or BaSO4)

• aerobic dual scaling brine (CaCO3 and BaSO4)
• anaerobic single/dual scaling brine (either CaCO3/FeCO3, FeCO3 only, or BaSO4 with Fe2+)
• anaerobic tetra scaling brine (CaCO3, BaSO4, FeCO3, FeS).

In all tests, the concentrations of the relevant ions were adjusted to yield approximately equal saturation
indices, as well as predicted amounts of each scale studied (Table 1).
Scale inhibition was probed by first investigating the effect of scale inhibitors against the scales
in each test stage. DETPMP and PPCA were selected because of previous work by other researchers.3, 13
Additionally, a phosphate ester, a proprietary co-polymer, henceforth denoted Polymer, and a
proprietary phosphonate, henceforth referred to as Phosphonate, were selected for study. The Polymer
and Phosphonate were selected because of their proven performance in iron rich brines (data not shown).
All scale inhibitor chemistries were compared on an equal activity basis.

Experimental

Brine chemistry was not based on any particular field; rather it was constructed from the average from
numerous fields around the world which are known to have complex scale precipitation issues. Table 2
contains the ionic composition of each test interval which was run in this study. Magnesium, potassium,
strontium, and manganese were intentionally left out of the brine formulations. The ionic composition
of each test brine was separated into one containing all the cations (CW) and one containing all the
anions (AW). The CW was prepared by dissolving the appropriate amount of sodium chloride, ascorbic
acid (reducing agent), barium chloride (if required) and calcium chloride dihydrate (if required) into
clean filtered distilled water. The CW solution was allowed to sparge with Ultra High Purity (UHP) N2
for a period of at least four hours prior to the incorporation of the ferrous iron. Addition of ferrous iron
SPE 114075 3

was accomplished in two steps. First, the ferrous iron amount required for the test was weighed as
ferrous chloride tetrahydrate then placed in an air tight Pyrex jar. This air tight jar was connected via a
closed loop manifold to the CW solution. The air tight jar containing the ferrous chloride tetrahydrate
was sparged with UHP N2 for approximately 1 hour to ensure the removal of any oxygen then, using the
manifold, CW was introduced in the air tight jar containing the ferrous chloride tetrahydrate to dissolve
this salt, called the concentrated iron brine. Once dissolved, the concentrated iron brine was
reintroduced back into the bulk CW reservoir for use in the dynamic tests. Throughout the tests, the CW
was continuously sparged with UHP N2. Dissolved oxygen (DO) concentration in the CW without the
ferrous iron was periodically tested by using CHEMetrics test kit. Fluid for the dissolved oxygen testing
was connected via the closed loop manifold. The average DO concentration that was found to occur in
the CW was 5 ppb. Due to the fast reaction time between ferrous to ferric iron, DO was not determined
in the CW with ferrous iron.
For the preparation of the AW, sodium chloride, sodium bicarbonate, and sodium sulfate (if
required) were dissolved in filtered distilled water and allowed to purge with a mixture of CO2/UHP N2
to achieve the desired pH of 6.0 (+/- 0.1). The ratio CO2 to UHP N2 was automatically adjusted by the
aid of an automated pH/deareation system which continuously supplied either gas. Once deaearated,
sodium sulfide nonahydrate was weighed and placed in a separate air tight jar and purged of atmosphere
by applying 3-4 cycles of evacuation/ UHP N2 purge. Once sufficiently purged, the deaerated AW
fluids were introduced through a closed loop manifold to the air tight jar containing the sodium sulfide.
Once the sodium sulfide salts were dissolved, they were re-introduced back into the bulk AW. To
minimize the loss of H2S gas in the AW, the solution was immediately moved (via the manifold) into
collapsible high density polyethylene bags. DO was determined in the bagged AW by sampling from
them via the closed loop manifold. The average DO concentration that was found in the AW was 5 ppb.
The dynamic tube blocking tests employed for this studied utilized a three pump system to
deliver, CW, AW, and dosed AW. The dosed AW contained the candidate scale inhibitor or chelator or
both. Both the AW and dosed AW were mixed prior to heating. All solutions were heated in two 1m x
2 mm ID thermal equilibration columns. All the dynamic tests that were conducted in pursuit of this
study were run at 107°C. The combined flowrate was held at 10 mL/min for all tests referenced herein.
At the termination of these equilibration columns, the fluids were mixed and then forced through a 1 m x
1 mm ID column. Scale deposition was inferred by monitoring the differential pressure across the
scaling column. All the tubing for the dynamic tube blocking apparatus was constructed of either nickel
or PEEK. The fittings used were constructed of stainless steel. Specific schematics for the setup of the
dynamic tube blocking apparatus can be found in the literatures.10-11

Results

CaCO3 only study. Using the CaCO3 only brine, each candidate scale inhibitor was run at 5 and 10
ppm (Figures 1 and 2, Table 2). At 5 ppm, DETPMP, Phosphonate, and the Phosphate Ester were
observed to have a decreased scale uptime, relative to the blank. PPCA was observed to have an
increased scale up time relative to the blank, while 5 ppm of the Polymer was flat indicating no
recordable scale precipitation. A lack of pressure build was observed across the scaling coil when the
concentration of the scale inhibitor chemistries was increased to 10 ppm. Subsequent testing with the
Polymer at 2.5 ppm revealed that this chemistry had a MIC of 5 ppm (data not shown).
The results from the CaCO3 only scaling brine (brine 1, table 1) illustrate an interesting point.
The faster scaling rates relative to the blank, with sub-MIC concentrations of DETPMP, Phosphonate
and Phosphate Ester demonstrate a breakdown in the scale inhibitor functionality. At sufficient
quantities in the bulk solution, scale inhibitors can interact with scale particles in a number of ways to
disrupt scale growth/agglomeration. The literature has confirmed that phosphonate and phosphate ester
based scale inhibitors can function by complexation, adsorption on growth sites, and incorporation into
the crystal matrix.2,5,12,18 At sub-MIC concentrations, the multifunctionality of these scale inhibitors
4 SPE 114075

likely degrades and absorption by scale inhibitors on formed scale particles is likely low (as a percentage
of scale surface area) and therefore ineffective. At sub-MIC concentrations, the results from these
experiments suggest that these distortions result, not in crystal retardation, but crystal growth
acceleration. This is not unexpected since other researchers have shown that DETPMP exists in
equilibrium as a complex with Ca, Ca-SI.12 With BaSO4, scale this complexation has been used to
explain the calcium ion concentration in these solids. Interestingly, PPCA has also been shown in the
literature to exist as a calcium salt in the bulk solution. In these experiments, the top sub-MIC
performers were observed to be the polymeric based chemistries. It is well documented that polymeric
scale inhibitors functions by nucleation inhibition and dispersion.

CaCO3 and BaSO4 study. The next step was to establish the MIC for each product in the presence of
both CaCO3 and BaSO4 (Figures 3 and 4). For these tests, brine 3 was used (table 2). The first
observation that can be made is the difference in the scale up times between the experiments with only
CaCO3 (Figures 1 and 2) and CaCO3/BaSO4 (Figures 3 and 4). This decrease in the scale up time is
consistent with data that has been observed in static tests where Sorbie, et al showed that calcium ions
incorporate themselves into the barium sulfate scale matrix thereby distorting the crystal matrix.6,12,13-14
The MIC for the Polymer increased from 5 ppm (CaCO3 only) to 10 ppm with the inclusion of BaSO4.
The MIC decreased for DETPMP and the Phosphonate from 10 ppm with CaCO3 only to 5 ppm with
CaCO3/BaSO4. There was no change in the MIC for the Phosphate Ester and PPCA. The observation
for DETPMP is consistent with the two step mechanism that is purposed by Sorbie and Laing where
they prescribe that there must first be sufficient Ca ion concentration (100s of ppm) for there to be
sufficient enough inclusion into the crystal matrix to distort the crystal lattice enough to facilitate facile
inhibition.13 Inclusion of DETPMP occurs as the Ca-SI complex which explains why there are a greater
concentration of Ca in the BaSO4 in the presence of DETPMP. 13, 15-16 The lack of change in the MIC for
PPCA has been attributed in other research to be based on the number of coordination sites available for
metal coordination: PPCA, 5 –PO3H2 groups, relative to DETPMP, 2 POOH group which reduces the
effect of calcium complexation.13
The most interesting observation from this experiment was the performance of these chemistries
at sub-MIC concentrations. The results showed that DETPMP, Phosphonate and the Phosphate Ester
did not have scale up time less than the blank while these chemistries were observed to have scale up
times of less than the blank in the presence of CaCO3 brine.

Carbonate Brine without Ca, with Fe study. Complexation with iron has been shown in the literature
to reduce the scale inhibition efficiency due to the formation of an Fe-SI complex.7,8 In the extreme
case, the Fe-SI can form in sufficient quantities to precipitate out of solution. To determine the extent of
the iron impact on the complexation of the candidate scale inhibitors, the calcium ion was removed from
the solution. Dynamic tube blocking tests were run with brine 7 (table 2) which was spiked with 10-50
ppm, in 10 ppm increments, of each candidate scale inhibitor chemistry. The blank did not show an
increase in the differential pressure across the scaling coil. This is not unexpected since the scale
prediction indicates that driving force for the precipitation of FeCO3 is mild, 1.24, with only 96 mg/L
predicted to form. The results indicated that there was no pressure build up with DETPMP, PPCA,
Phosphonate, and the Phosphate Ester. With the Polymer, no pressure build up was observed for the 10-
30 ppm tests, but a pressure build up was observed for the 40 and 50 ppm tests (Figure 5). Whether the
solids precipitated in the 40 and 50 ppm Polymer dosed solutions are the Fe-SI or incorporation of the
Polymer into the FeCO3 matrix is unclear at this time.

CaCO3 and FeCO3 study. When CaCO3 scale was added back into the test brine (brine 4, table 1 and
2) in the presence of 50 ppm ferrous iron, the scale inhibitor efficiency was observed to increase from 10
ppm (CaCO3 only) to 25 ppm (CaCO3 and FeCO3). Refer to Table 3 and Figures 6-10 for a conscience
explanation of the cumulative dynamic tube blocking results. The sub-MIC performance of all the
SPE 114075 5

candidate chemistries was similar in both the CaCO3 only and the CaCO3/FeCO3 with one exception,
PPCA. In the presence of iron, sub-MIC concentrations of PPCA are shown to increase the precipitation
rate of the mixed CaCO3/FeCO3 scale. Whether this performance characteristic is due to the
incorporation of the Ca-PPCA and/or Fe-PPCA complexes into the complex scale matrix or whether
PPCA is semi-irreversible bound to FeCO3, is not known at this time. Other researchers have shown
that for DETPMP, this molecule has a preferential absorption on different minerals.21 Although this
research was with a completely different chemistry than PPCA; it is not unrealistic to expect that PPCA
would demonstrate similar adsorption characteristics.

CaCO3, FeCO3 and FeS study. Increasing the scale load in the test brine by the incorporation of FeS
yielded unexpected results. The MIC for each product was observed to be 5 ppm for all the candidate
chemistries which was half of the MIC that was observed in the aerobic CaCO3 tests (brine 1, table 2
and Figure 11). When the scale up times for the undosed blanks for each of the three CaCO3 blanks are
compared striking comparisons appear. The aerobic CaCO3 only (brine 1) was recorded to have a scale
up time and pressure of 19 minutes and 1.2 psi, respectively. When iron was added to the brine as with
the CaCO3/FeCO3 brine (4), it was recorded to have a scale up time and pressure of 60 minutes and 1.2
psi, respectively. When sulfide was added in the presence of iron as with the CaCO3/FeCO3/FeS, (brine
10), it was recorded to have a scale up time and pressure of 60 minutes and 0.9 psi, respectively. This
increase in scale up time between the CaCO3 only and CaCO3/FeCO3 tests is not unexpected as it has
been reported by Graham, et al.8 The authors attribute this difference to a change in the scale
morphology whereby the inclusion of FeCO3 acts as a crystal growth modifier. When FeS is added to
the brine, the blank scale up time remains the same as compared to the tests without FeS
(CaCO3/FeCO3), but the scale up pressure is decreased from 1.2 (without FeS) to 0.9 (with FeS). The
scale up pressure decreases even though the total predicted scale amounts are calculated to increase from
448 to 500 mg/L, without FeS to with FeS, respectively. The further increase in the scale up time and
decrease in scale up pressure suggest that the integrity of the scale matrix is comprised by both the
FeCO3 and FeS which, in turn, decreases the scale inhibitor demand. This distortion of crystal matrices
appears to the contributing factor to the decrease in recorded MIC for the CaCO3/FeCO3/FeS scale
versus to CaCO3/FeCO3 and CaCO3 only.

BaSO4 only study. Figures 12 and 13 illustrate the results from the dynamic tests with BaSO4 scale.
The best performing chemistry was shown to be the Phosphonate which had an MIC of 20 ppm.
DETPMP, the Polymer, and the Phosphate Ester were observed to have an MIC of 30 ppm. The most
inefficient scale inhibitor chemistry was shown to be PPCA having an MIC of 35 ppm. By comparison,
PPCA was shown to be the second most efficient chemistry against CaCO3. Furthermore, the relative
ranking against BaSO4 of DETPMP and PPCA is consistent with the literature.13

BaSO4 and FeCO3 study. Unlike the analogous experiments with CaCO3 and FeCO3, the
BaSO4/FeCO3 blank scale up time and pressure were not changed relative to the BaSO4 only brine
(Table 4). The primary change that was observed was the relative ranking of scale inhibitor efficiency.
Without iron, the Phosphonate was shown to be the most efficient against BaSO4 scale. When iron was
introduced, the Polymer was observed to be most efficient scale inhibitor chemistry inhibiting this
mixed scale at 20 ppm, 10 ppm less than without iron (Figure 14). The worst scale inhibitor was
determined to be the Phosphate Ester which was observed to have an MIC of 40 ppm, 10 ppm higher
than without iron. An increase in efficiency was also observed for PPCA which was recorded to have an
MIC of 30 ppm with iron and 35 without iron (Figure 15). No observable changes in efficiency were
recorded for DETPMP. A number of authors have shown variable performance against BaSO4 scale in
the presence and absence of iron which is confirmed by results from tests with PPCA, Phosphonate,
Polymer, and the Phosphate Ester.8, 19-20
6 SPE 114075

FeCO3 in the presence of sulfate study. Subsequent experiments were run where the barium ions were
left out of the brine composition leaving only iron, sulfate, and 100 ppm of bicarbonate ion for buffering
(brine 8, table 2). The aim of this experiment was to confirm the results from the similar tests with the
carbonate scaling brine without calcium and with iron. As expected, none of the candidate scale
inhibitor chemistries were observed to produce a pressure build up when added into this brine at a
concentrations of up to 50 ppm, in 10 ppm increments. Interestingly, the pressure build up with the
Polymer in the carbonate scaling brine was not observed with equal amounts of iron in the sulfate
scaling brine. These results suggest that the complexation of this chemistry with iron and the Polymer
could be mediated by sulfate or bicarbonate.

BaSO4, FeCO3, and FeS study. The inclusion of FeS was observed to have the opposite effect on the
scale up time and pressure that it did when added to the CaCO3 brine (Table 4). In the BaSO4 brine, FeS
actually accelerated the scale precipitation rate. The subsequent performance testing of the candidate
scale inhibitor chemistries revealed that none of them were capable of inhibiting this complex scale at a
concentration of 80 ppm, highest concentration tested (data not shown). The lack of calcium ions which
have been shown to accentuate scale inhibitor performance could be one reason for the reduction in
inhibition efficiency. 2,5,12,15 The increase in the scale up time and pressure are suggestive of larger
scaling potential than in the analogous CaCO3 tests.

BaSO4, CaCO3, and FeCO3 study. The blank scale up times was observed to be greater for the
BaSO4/CaCO3/FeCO3 scale versus the BaSO4/CaCO3 scale, 25 vs. 60 minutes, respectively (Table 4).
In the BaSO4/CaCO3 scaling tests, the CaCO3 appeared to be distorting the crystal matrix thereby
reducing the scaling severity as inferred by the longer scale up time (Table 4). In the
BaSO4/CaCO3/FeCO3 scaling tests, the inclusion of FeCO3 appears to accelerate scale growth with a
greater effect than the mitigatory effects of CaCO3.
For the first time during this study, there appeared to be scale building outside the heated zone at
the backpressure regulator which was thought to be BaSO4 scale. The scale that formed when the brine
was dosed with the Phosphate Ester was insoluble to the acid and EDTA used to clean the scaling coil
in-between runs. It was observed that these solids were forming in the brine spiked with 5 ppm of the
Phosphate Ester. Since the Phosphate Ester contains ortho-phosphate, it is thought that this solid was
FePO4.
Scale inhibitor chemistry efficiency for the remaining candidates was determined to be 10 ppm
for all the products except the Phosphate Ester and PPCA (Figure 16 and 17). For all products, except
the Phosphate Ester, the MIC is less than that observed in the BaSO4/FeCO3 tests. These results suggest
that crystal distortion by CaCO3 along with performance enhancement due to the formation of the Ca-SI
complexes likely is the key contributor to the decrease in the MIC. This runs countercurrent with effect
of FeCO3 on the blank scale up time and pressure between the BaSO4/CaCO3 and BaSO4/CaCO3/FeCO3
experiments. Based on these results, the data suggests that the performance enhancement on the scale
inhibitor performance in the presence of calcium (Ca-SI) is greater than the crystallization effect of the
FeCO3 on the combined scale precipitation rate.

BaSO4, CaCO3, FeCO3, and FeS study. The scale up time and pressure were observed to be consistent
with the observations that the presence of calcium (and CaCO3) reduces the scale severity (Figure 18).
The scale up pressure was observed to be less than the CaCO3/BaSO4/FeCO3 tests which suggests that
FeS is also acting as a crystal distorter (Table 4). Interestingly, FeS in the presence of BaSO4/FeCO3
was shown to accelerate the scale up time and pressure (Table 4). As was shown in the
CaCO3/BaSO4/FeCO3 tests, the pressure build up resulting from treatment with the Phosphate Ester was
the greatest, indicating the likely precipitation of FePO4. Again, the resulting precipitant was insoluble
in both acid and EDTA. The remaining chemistries were tested to 40 ppm and were found to not
completely inhibit scale (Figure 18). The most efficient product, as inferred by the lowest differential
SPE 114075 7

pressure build up across the scaling coil, was determined to be DETPMP which has been shown by other
researchers to be one of the most iron intolerant scale inhibitor chemistries.8

Conclusions

Under dymanic laminar flowing conditions, the results from this study have provided empirical evidence
that scale inhibition in complex scaling evirons are affected complex scale matrices, the effect of the
metal salts of these scale inhibitor chemistries, crystal distortion effects of both the scale inhibitors and
their associated salts, crystal distortion effects of the metals, and the scale seed particles. The effect of
seed particles can best be described by the following points:

FeCO3
• Increased the scale up time and pressure in CaCO3
• Had no effect on BaSO4
• Decreased the scale up time in CaCO3/BaSO4

CaCO3
• Increased the BaSO4 scale up time

FeS
• Increased the scale up time for BaSO4/FeCO3
• Decreased the scale up time for CaCO3/FeCO3
• Decreases the scale up time for BaSO4/CaCO3/FeCO3

Acknowledgments
The authors would like to thank Baker Petrolite for supporting and funding this project.
8 SPE 114075

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SPE 114075 9

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paper 94510, presented at the SPE European Formation Damage Conference, Scheveningen, The
Netherlands, 25-27 May, 2005.
22. Yuan, M.D., Stoppelenburg, L.S., “The Performance of Barium Sulfate Inhibitors in Iron
Containing Waters in both Aearted and Anaerobic Systems”, Paper No. 114, present at the NAC
International CORROSION 2000 Conference and Exhibition, March 2000.\
23. Dyer, S.J., Graham, G.M.”The Influence of Iron on Scale Inhibitor Performance and Carbonate
Scale Formation”, Proceedings of the 11th NIF International Oilfield Chemical Symposium,
Fargenes, Norway, 19-22 May, 2000.
10 SPE 114075

Table 1. Calculated Saturation Indices and Predicted Precipitation Amounts for the Test Matrices Used in this Study. Conditions used for the calculations were 107°C and 200 psi.

50 ppm Fe2+ 50 ppm Fe2+, No Ca or Ba

CaCO3/BaSO4/FeCO3/FeS
Aerobic Tests, No Iron

CaCO3/FeCO3/FeS
BaSO4/FeCO3/FeS
CaCO3/BaSO4/FeCO3

Carbonate Brine
CaCO3/FeCO3
CaCO3/BaSO4

BaSO4/FeCO3

Sulfate Brine
Metric CaCO3

BaSO4
ID 1 2 3 4 5 6 7 8 9 10 11
CaCO3 SI 1.17 - 1.16 1.16 - 1.07 - - - 1.15 1.12
mg/L CaCO3 351 - 349 350 - 334 - - - 348 342
BaSO4 SI - 1.97 1.9 - 1.97 1.93 - - 1.97 - 1.9
mg/L BaSO4 - 337 335 - 337 336 - - 337 - 335
FeCO3 SI - - - 1.27 0.48 1.1 1.32 0.49 0.31 1.15 1.12
mg/L FeCO3 - - - 95 27 74 96 27 18 75 74
FeS SI - - - - - - - - 2.07 1.75 2.2
mg/L FeS - - - - - - - - 44 25 60
Total mg/L 351 337 684 445 364 744 96 27 399 448 811

Table 2. Brine Chemsitry used in this study.

Aerobic Tests, No Iron 50 ppm Fe2+ 50 ppm Fe2+, No Ca or Ba

CaCO3/BaSO4/FeCO3/FeS
CaCO3/FeCO3/FeS
BaSO4/FeCO3/FeS
CaCO3/BaSO4/FeCO3

Carbonate Brine
CaCO3/FeCO3
CaCO3/BaSO4

BaSO4/FeCO3

Sulfate Brine
CaCO3

BaSO4

Ion

ID 1 2 3 4 5 6 7 8 9 10 11
Na 19872 19872 19872 19872 19872 19872 19872 19872 19872 19872 19872
Ca 2500 0 2500 2500 0 2500 0 0 0 2500 2500
Ba 0 202.5 202.5 0 202.5 202.5 0 0 202.5 0 202.5
Fe 0 0 0 50 50 40 50 50 50 40 40
Cl 34701 30553 34607 34765 30552 34657 30279 30447 30553 34752 34657
HCO3 625 100 625 625 100 625 625 100 100 625 625
SO4 0 270 270 0 270 270 0 270 270 0 270
H2S 0 0 0 0 0 0 0 0 20 10 30
pH 6 6 6 6 6 6 6 6 6 6 6
TDS 58134 51273 58411 58174 51076 58462 51078 51150 51266 57911 58197
SPE 114075 11

Figure 1. Dynamic tube blocking test results where the CaCO3 scaling
brine was spiked with 5 ppm of each scale inhibitor chemistry
2.2
6 2 5 1
3
2.0 Blank(1)
5 ppm DETPMP(2)
Differential Pressure (psi) 5 ppm PPCA(3)
1.8 5 ppm Polymer(4)
5 ppm Phosphonate(5)
5 ppm Phosphate Ester(6)
1.6

1.4

1.2

4
1.0

5 10 15 20 25 30 35 40 45 50 55 60
Time (min)

Figure 2. Dynamic tube blocking test results where the CaCO3 scaling
brine was spiked with 10 ppm of each scale inhibitor chemistry
2.2
1
Blank (1)
2.0
10 ppm DETPMP (2)
10 ppm PPCA (3)
Differential Pressure (psi)

10 ppm Polymer (4)

1.8 10 ppm Phosphonate (5)
10 ppm Phosphate Ester (6)

1.6

1.4

1.2

2,3,4,5,6
1.0

5 10 15 20 25 30 35 40 45 50 55 60
Time (min)
12 SPE 114075

Figure 3. Dynamic tube blocking test results where the CaCO3/BaSO4 scaling
brine was spiked with 5 ppm of each scale inhibitor chemistry
2.2
Blank(1)
5 ppm DETPMP(2)
2.0
5 ppm PPCA(3)
Differential Pressure (psi)

5 ppm Polymer(4)
1.8 5 ppm Phosphonate(5)
5 ppm Phosphate Ester(6) 1

1.6

1.4

1.2 3,4,6

1.0 1,5

5 10 15 20 25 30 35 40 45 50 55 60
Time (min)

Figure 4. Dynamic tube blocking test results where the CaCO3/BaSO4 scaling
brine was spiked with 10 ppm of each scale inhibitor chemistry
2.2
Blank (1)
10 ppm DETPMP (2)
2.0
10 ppm PPCA (3)
10 ppm Polymer (4)
Differential Pressure (psi)

10 ppm Phosphonate (5)

1.8
10 ppm Phosphate Ester (6)
1
1.6

1.4

1.2
2,3,4,5,6

1.0

5 10 15 20 25 30 35 40 45 50 55 60
Time (min)
SPE 114075 13

Figure 5. Dynamic tube blocking tests where carbonate scaling

brine (FeCO3) was spiked with Polymer
2.2

2.1 Blank (1)

2.0 10 ppm Polymer (2)
20 ppm Polymer (3)
Differential Pressure (psi)

1.9
30 ppm Polymer (4)
1.8 40 ppm Polymer (5)
50 ppm Polymer (6)
1.7

1.6

1.5

1.4

1.3
5,6
1.2

1.1
1,2,3,4
1.0

10 20 30 40 50 60
Time (min)

Table 3. Cumulative list of the determined MICs for each test sequence.
Aerobic Tests, No Iron 50 ppm Fe2+ 50 ppm Fe2+, No Ca or Ba

CaCO3/BaSO4/FeCO3/FeS
CaCO3/FeCO3/FeS
BaSO4/FeCO3/FeS
CaCO3/BaSO4/FeCO3

Carbonate Brine
CaCO3/FeCO3
CaCO3/BaSO4

BaSO4/FeCO3

Sulfate Brine
Metric
CaCO3

BaSO4

DETPMP 10 30 5 25 30 10 0 0 90 5 >40
PPCA 10 35 10 25 30 20 0 0 80 5 >40
Polymer 10 30 10 25 20 10 >50 0 80 5 >40
Phopshonate 10 20 5 25 30 10 0 0 80 5 >40
Phosphate Ester 10 30 10 25 40 >10 0 0 >60 5 >40
Brine Used 1 2 3 4 5 6 7 8 9 10 12

Figure 6. Dynamic tube blocking tests where CaCO3/FeCO3 brine

was spiked with DETPMP
2.2
Blank (1) 3 4 5 1
5 ppm DETPMP (2)
10 ppm DETPMP (3)
2.0
15 ppm DETPMP (4)
20 ppm DETPMP (5)
Differential Pressure (psi)

25 ppm DETPMP (6)

1.8 30 ppm DETPMP (7)

1.6

1.4

1.2

6,7
1.0

10 20 30 40 50 60
Differential Pressure (psi)
14 SPE 114075

Figure 7. Dynamic tube blocking tests where CaCO3/FeCO3 brine

was spiked with PPCA
2.2
Blank (1) 34 5 2 1
5 ppm PPCA (2)
2.0 10 ppm PPCA (3)
Differential Pressure (psi)

15 ppm PPCA (4)

20 ppm PPCA (5)
1.8 25 ppm PPCA (6)

1.6

1.4

1.2

6
1.0

10 20 30 40 50 60
Time (min)

Figure 8. Dynamic tube blocking tests where CaCO3/FeCO3 brine

was spiked with Polymer
2.2
Blank (1) 2,3,4 5 1
5 ppm Polymer (2)
2.0 10 ppm Polymer (3)
Differential Pressure (psi)

15 ppm Polymer (4)

20 ppm Polymer (5)
1.8 25 ppm Polymer (6)

1.6

1.4

1.2

6
1.0

10 20 30 40 50 60
Time (min)
SPE 114075 15

Figure 9. Dynamic tube blocking tests where CaCO3/FeCO3 brine

was spiked with Phosphonate
2.2
Blank (1) 2 3,4 1
10 ppm Phosphonate (2)
2.0 15 ppm Phosphonate (3)
20 ppm Phosphonate (4)
Differential Pressure (psi)

25 ppm Phosphonate (5)

1.8

1.6

1.4

1.2

1.0
5

10 20 30 40 50 60
Time (min)

Figure 10. Dynamic tube blocking tests where CaCO3/FeCO3

was spiked with Phosphate Ester
2.2
Blank (1) 3 2 1 5
5 ppm Phosphate Ester (2)
10 ppm Phosphate Ester (3)
2.0
15 ppm Phosphate Ester (4)
Differential Pressure (psi)

20 ppm Phosphate Ester (5)

25 ppm Phosphate Ester (6)
1.8

1.6 4

1.4

1.2

6
1.0

10 20 30 40 50 60
Time (min)
16 SPE 114075

Figure 11. Dynamic tube blocking tests where the CaCO3/FeCO3/FeS

brine was spiked with 5 ppm of each candidate scale inhibitor chemistry
2.2
Blank (1)
5 ppm DETPMP (2)
2.0
5 ppm PPCA (3)
Differential Pressure (psi)

5 ppm Polymer (4)

5 ppm Phosphonate (5)
1.8
5 ppm Phosphate Ester (6) 1

1.6

1.4
6
3 5
1.2

1.0 4
2
5 10 15 20 25 30 35 40 45 50 55 60
Time (min)

Figure 12. Dynamic tube blocking tests where the BaSO4

brine was spiked with 20 ppm of each candidate chemistry
2.2
1 6 32 4
Blank (1)
2.0 20 ppm DETPMP (2)
Differential Pressure (psi)

20 ppm PPCA (3)

20 ppm Polymer (4)
1.8 20 ppm Phosphonate (5)
20 ppm Phosphate Ester (6)
1.6

1.4

1.2

5
1.0

5 10 15 20 25 30 35 40 45 50 55 60
Time (min)
SPE 114075 17

Figure 13. Dynamic tube blocking tests where the BaSO4

brine was spiked with 30 ppm of each candidate chemistry
2.2
1
Blank (1)
30 ppm DETPMP (2)
2.0 30 ppm PPCA (3)
Differential Pressure (psi)

30 ppm Polymer (4)

30 ppm Phosphonate (5)
1.8
30 ppm Phosphate Ester (6)

1.6

1.4

3
1.2

2,4,5,6
1.0

5 10 15 20 25 30 35 40 45 50 55 60
Time (min)

Figure 14. Dynamic tube blocking tests where the BaSO4/FeCO3

scaling brine was spiked with 20 ppm of each scale inhibitor chemistry
2.2
1 3
2 Blank (1)
6 20 ppm DETPMP (2)
2.0 5
20 ppm PPCA (3)
Differential Pressure (psi)

20 ppm Polymer (4)

1.8 20 ppm Phosphonate (5)
20 ppm Phosphate Ester (6)

1.6

1.4

1.2
4

1.0

5 10 15 20 25 30 35 40 45 50 55 60
Time (min)
18 SPE 114075

Figure 15. Dynamic tube blocking tests where the BaSO4/FeCO3

scaling brine was spiked with 30 ppm of each scale inhibitor chemistry
2.2
1 6
Blank (1)
2.0 30 ppm DETPMP (2)
Differential Pressure (psi)

30 ppm PPCA (3)

30 ppm Polymer (4)
1.8 30 ppm Phosphonate (5)
30 ppm Phosphate Ester (6)
1.6

1.4

1.2
2,3,4,5

1.0

5 10 15 20 25 30 35 40 45 50 55 60
Time (min)

Figure 16. Dynamic tube blocking tests where the BaSO4/CaCO3/FeCO3

scaling brine was spiked with 10 ppm of each scale inhibitor chemistry
2.2

Blank (1)
2.0 10 ppm DETPMP (2)
Differential Pressure (psi)

1 10 ppm PPCA (3)

10 ppm Polymer (4)
1.8
10 ppm Phosphonate (5)
10 ppm Phosphate Ester (6)
1.6

1.4

3
1.2

6 2,4,5
1.0

5 10 15 20 25 30 35 40 45 50 55 60
Time (min)
SPE 114075 19

Figure 17. Dynamic tube blocking tests where the BaSO4/CaCO3/FeCO3

scaling brine was spiked with 20 ppm of each scale inhibitor chemistry
2.2
Blank (1)
20 ppm DETPMP (2)
2.0
20 ppm PPCA (3)
Differential Pressure (psi)

1 20 ppm Polymer (4)

1.8
20 ppm Phosphonate (5)

1.6

1.4

1.2
2
3,4,5
1.0

5 10 15 20 25 30 35 40 45 50 55 60
Time (min)

Figure 18. Dynamic tube blocking tests where the BaSO4/CaCO3/FeCO3/FeS

scaling brine was spiked with 40 ppm of each scale inhibitor chemistry
2.2
Blank (1)
40 ppm DETPMP (2)
6
2.0 40 ppm PPCA (3)
Differential Pressure (psi)

40 ppm Polymer (4)

40 ppm Phosphonate (5)
1.8 40 ppm Phosphate Ester (6)
4,5

1.6

1.4 1
3

1.2

2
1.0

5 10 15 20 25 30 35 40 45 50 55 60
Time (min)

Table 4. Comparison of the scale up times and pressures.

50 ppm Fe2+ 50 ppm Fe2+, No Ca or Ba
CaCO3/BaSO4/FeCO3/FeS

Aerobic Tests, No Iron

CaCO3/FeCO3/FeS
BaSO4/FeCO3/FeS
CaCO3/BaSO4/FeCO3

Carbonate Brine
CaCO3/FeCO3
CaCO3/BaSO4

BaSO4/FeCO3

Sulfate Brine
CaCO3

BaSO4

Metric

DP 1.2 1.2 0.8 1.2 1.2 0.9 0 0 1.2 0.9 0.3

Scale Up Time (min) 19 12 60 60 14 25 Did Not Scale Did Not Scale 4 60 60