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The Effect of pH and Mineralogy on the Retention of Polymeric Scale Inhibitors

on Carbonate Rocks for Precipitation Squeeze Treatments

Conference Paper · February 2018

DOI: 10.2118/189519-MS

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SPE-189519-MS

The Effect of pH and Mineralogy on the Retention of Polymeric Scale

Inhibitors on Carbonate Rocks for Precipitation Squeeze Treatments

Kh. Jarrahian, K. S. Sorbie, M. A. Singleton, L. S. Boak, and A. J. Graham, Institute of Petroleum Engineering,
Heriot-Watt University

Copyright 2018, Society of Petroleum Engineers

This paper was prepared for presentation at the SPE International Conference and Exhibition on Formation Damage Control held in Lafayette, Louisiana, USA, 7-9
February 2018.

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
The bulk "apparent adsorption" behavior (Γapp, vs. Cf) of 2 polymeric scale inhibitors (SI), PPCA and
PFC, onto carbonate mineral substrates has been studied for initial solution pH values of pH 2, 4 and 6.
The 2 carbonate minerals used, calcite and dolomite, are much more chemically reactive than sandstone
minerals (e.g. quartz, feldspars, clays etc.) which have already been studied extensively. In nearly all
cases, precipitates formed at higher SI concentrations were due to the formation of sparingly soluble SI/
Ca complexes. A systematic study has been carried out on the SI/Ca precipitates formed, by applying
both ESEM/EDX and particle size analysis (PSA), and this identifies the morphology and the approximate
composition of the precipitates.
For PPCA, at all initial solution pH values, regions of pure adsorption (Γ) ([PPCA] <100ppm) and coupled
adsorption/ precipitation (Γ/Π) are clearly observed for both calcite and dolomite. PFC at pH = 4 and 6
also showed very similar behavior with a region of pure adsorption (Γ) for [PFC] < 500ppm and a region
of coupled adsorption/precipitation (Γ/Π) above this level. However, the PFC/calcite case at pH 2 showed
only pure adsorption, while the PFC/dolomite case at pH 2 again showed coupled adsorption/ precipitation
at higher PFC concentrations. For both SIs on both carbonate substrates, precipitation is the more dominant
mechanism for SI retention than adsorption above a minimum concentration of ~100 – 500 ppm SI. The
actual amount of precipitate formed varies from case to case, depending on the specific SI, substrate (calcite/
dolomite) and initial pH (pH 2, 4 and 6).
Although the qualitative behavior of both PPCA and PFC was similar on both carbonate substrates, the
apparent adsorption of PPCA was higher on calcite than on dolomite; PFC apparent adsorption was higher
on dolomite than on calcite. It is discussed in the paper how these observations are related to the reactivity
of the different carbonate minerals, the resulting final pH (which affects the dissociation of the SI), Ca-SI
binding and the solubility of the resulting complex.
2 SPE-189519-MS

Introduction
The deposition of mineral scale may lead to the loss of well integrity and productivity if not properly
managed. The most common way of preventing mineral scale deposition is by the use of chemical scale
inhibitors (SI). Chemical scale inhibitors are applied to prevent or greatly reduce the occurrence of mineral
scale through inhibitor squeeze treatments. The efficiency and lifetime of a SI squeeze treatment depends
on the SI interaction with the rock minerals in the porous medium such that the SI is effectively retained
in and released from the formation [1-5]. The two main mechanisms of scale inhibitor retention within the
reservoir formation are known to be adsorption and precipitation, or a combination of the two processes,
i.e. coupled adsorption (Γ) / precipitation (Π), which we denote as (Γ/Π) [6-10]. Adsorption is thought
to occur through an electrostatic attraction or physical adsorption between the inhibitor and formation
minerals and this process is described by an adsorption isotherm (Γ) which governs the squeeze lifetime in
a pure adsorption squeeze treatment. In an attempt to increase squeeze lifetimes beyond that attainable by
adsorption, ‘precipitation’ squeezes have been trialled in the field [11].
Historically, phosphonate scale inhibitors such as Di-Ethylene Tetra-amine Penta (methylene-
phosphonic acid) (DETPMP), have been applied in scale squeezes. The performance of phosphonates is
mainly because of the presence of the phosphonate functionality (usually as an amino phosphonate), which
yields very good Inhibition Efficiency (IE) and SI retention behavior [12, 13]. In addition, phosphonates are
readily detectable (via "P" by Inductively Coupled Plasma Optical Emmission Spectroscopy (ICP)) which
allows the operator to know when the inhibitor concentration is reaching minimum inhibitor concentration
(MIC) levels which indicates when to re-squeeze the well. Scale inhibitor squeezes are expensive operations
due to equipment, time and deferred oil production costs and hence a long squeeze lifetime is the desired
outcome of a squeeze operation. In recent years, environmental restrictions on which chemical can be used
have been applied to certain areas such as the North Sea. This has limited the use of phosphonate scale
inhibitors which in turn has stimulated the interest in the development of polymeric scale inhibitors which
are thought to be more environmentally acceptable, although some of these species do have phosphorus in
their structures e.g. Phosphino Polycarboxylic Acid (PPCA) and P-Functionalized Co-Polymer (PFC) [14].
In fact, introducing phosphorus containing species into polymeric scale inhibitors improves the adsorption
capacity, squeeze lifetimes and the detectability of the inhibitors allowing analysis by ICP [15, 16].
In the literature, the mechanisms of adsorption (Γ), precipitation (Π) and coupled adsorption/precipitation
(Γ/Π) have been investigated using various approaches, but often the field observations are not accurate
enough to distinguish clearly between different mechanisms [17-20]. Sorbie et al. studied the effect of
pH, temperature and calcium on the adsorption of phosphonate scale inhibitors onto consolidated and
crushed sandstone. They showed scale inhibitor adsorption onto the crushed rock material increases at higher
temperatures. Moreover, inhibitor adsorption onto crushed rock is lower at pH4 than at pH2 or pH6; when
calcium ions are present. Finally, the adsorption of phosphonate inhibitor (DETPMP) decreased predictably
as pH increases (at 25°C) in the absence of Ca2+ ions [18]. Ibrahim et al. carried out static compatibility
and coupled adsorption/precipitation experiments using a range of phosphonate scale inhibitors (DETPMP
(a penta- phosphonate) and OMTHP (a hexa- phosphonate)) and several minerals. They concluded that for
all SI/mineral systems, pure adsorption is observed at low [SI] concentrations whilst coupled adsorption/
precipitation occurs at high concentrations. Therefore, at low SI concentration levels, an adsorption
isotherm, Γ(C) would correctly describe the SI/mineral retention mechanism but at higher concentrations a
coupled adsorption/ precipitation (Γ/Π) model would be required [21].
Most previous experimental work has not included carbonate rock substrates due to the complexity of its
geochemistry. However, over 50% of the world remaining oil reserves are located in carbonate formations.
The carbonate formation provides a much more chemically reactive substrate, where the scale inhibitor
retention mechanisms may be more complex than simple adsorption. Clearly, understanding the main
retention mechanisms for various scale inhibitors in carbonate reservoirs will help us in the selection of more
SPE-189519-MS 3

effective scale inhibitors for squeeze treatments in carbonates. The aim of this study is to investigate the most
important mechanisms governing the retention of two types of polymeric scale inhibitors in calcite (CaCO3)
and dolomite (CaMg (CO3)2) mineral substrates. This has been done by carrying out a range of "apparent
adsorption" experiments where we plot the apparent adsorption, Γapp, vs. Cf, the final SI concentration [1].
We have shown previously that when we measure Γapp, vs. Cf, as a function of (m/V) where m is the mass
of substrate (calcite or dolomite) and V is the solution volume, we can easily identify concentration regions
when pure adsorption (Γ) and where coupled adsorption/precipitation (Γ/Π) occur [21]. These apparent
adsorption plots are measured in a specific fraction size of calcite or dolomite (100- 315 μm) at two different
(m/V) ratios. All of the SI/calcium precipitates are also studied using Environmental Scanning Electron
Microscope / Energy-Dispersive X-Ray Spectroscopy (ESEM/EDX) and Particle Size Analysis (PSA).
These techniques give us direct information on the morphology of any precipitates formed, e.g. whether they
are formed as free crystalline (or amorphous) precipitates or whether they form as "coated structures" on
the surface of the calcite or dolomite grains. The EDX measurements also give us an approximate chemical
composition of the precipitates; for example, it can establish if they contain P (from the SI) and Ca and in
what approximate atomic ratios.

Experimental Studies
Static adsorption and compatibility tests were carried out to identify the pure adsorption (Γ) and coupled
adsorption/ precipitation (Γ/Π) behavior of the scale inhibitors (SIs) with Synthetic North Sea Seawater
(NSSW). For the static adsorption tests, the experiments were performed with different masses of calcite and
dolomite (m = 5 and 10 g) for a fixed volume (V= 40 ml) of solution, which allows any coupled adsorption/
precipitation behavior to be observed, i.e. for a range of (m/V) ratios. In the corresponding compatibility
tests, the experiments were performed to investigate precipitation behavior, since no mineral was used in
these tests. Hence, any lost in SI concentration during the compatibility test must be due to pure precipitation
from the NSSW, with no contribution from the substrate [1, 21].

Materials
Two polymeric scale inhibitors were used in this work, as follows: Phosphino PolyCarboxylic Acid (PPCA)
and P-Functionalized Co-Polymer (PFC). These SIs are commercial products widely used in oilfield
applications. PPCA is extensively described in the literature, and PFC was first reported in 2010 [15] and
further described in 2013 [23].
All SI solutions were prepared in NSSW that included Lithium (Li+) as a tracer and were pH adjusted
to three values, i.e. pH= 2, 4 and 6, to evaluate the effect of pH on apparent adsorption. Moreover, all
experiments were conducted at 95°C. ICP analytical method was used in this study for assaying the various
elements in solution e.g. P, Ca, Mg and Li.

Minerals
Moroccan calcite and Skye dolomite of size fraction (100-315μm) were used to study the retention of scale
inhibitors onto carbonate mineral substrates. Energy Dispersive X-Ray (EDX) analysis of these minerals
confirmed the elements which exist in the crystal structure of the solid substrates, as shown in Table 1.

Table 1—EDX signals of pure calcite and dolomite used in this work.
4 SPE-189519-MS

As shown in Table 1, for pure calcite and dolomite, the elements detected by EDX analysis are calcium,
oxygen, carbon and magnesium (dolomite only) confirming the composition of the substrates. From the
above, we can take the compositions of calcite and dolomite as CaCO3 and (approximately) CaMg (CO3)2,
respectively.

Brine
The composition of the synthetic brine used, North Sea Seawater (NSSW), is given in Table 2. Lithium
(Li+) has been added as an inert tracer to determine if any evaporation occurred during static adsorption
and compatibility tests.

Table 2—Synthetic North Sea Seawater Water Composition (NSSW).

Experimental Procedure
Both types of experiment (static adsorption and compatibility tests) were performed at a reservoir like
temperature of 95°C at pH= 2, 4 and 6. For the static adsorption tests, experiments were performed with
different concentrations of SI; blank (0), 50, 100, 500, 800, 1000, 2000 and 4000 ppm active. The pH values
of all the stock solutions were adjusted to pH= 2, 4 and 6. Then, 40 ml of each stock solution was added
to bottles containing 5 and 10g of substrate, either calcite or dolomite. After 24 hrs at 95°C, the samples
were removed from the oven and filtered through a 0.2 μm filter paper to separate the solid and supernatant
phases. ICP was used to analyze the ion concentrations (phosphorus, calcium, magnesium and lithium) in the
supernatant before and after filtration. ESEM/EDX was performed on the collected solid phases (precipitate
as well as mineral) to analyse the surface of the calcite/dolomite grains and any bulk precipitate formed.
For the compatibility tests, as no mineral was present in the solutions, all test and stock solutions were
only analyzed by ICP to measure the difference in ion concentrations. Any missing ion concentrations
between the test and stock value were assumed to be related to pure precipitation at this stage (Π only).
With substrate present, the "apparent adsorption" of SI retained by the mineral, Γapp (in mg SI/g substrate),
was calculated using the formula:

(1)

Where Co and Cf are the initial and final SI concentrations, respectively; in these experiments, we plot
the results as Γapp, vs. Cf. V is the volume of SI solution and m is the mass of mineral substrate. Note that
we refer to "apparent adsorption" since both adsorption (Γ) and precipitation (Π) are occurring together and
thus the "apparent adsorption" is in fact a combination of both mechanisms (Γ/Π); a detailed discussion of
how to analyze such experiments along with the appropriate mathematics is given in the references [1, 21].
SPE-189519-MS 5

Experimental Results
Apparent Adsorption of PPCA and PFC on carbonate rocks
In this section, we present the results of the static coupled adsorption/precipitation (Γ/Π) experiments; which
we have referred to as "apparent adsorption" experiments. Figures 1 and 2 show the apparent adsorption
level of PPCA and PFC for two different masses (m = 5g and 10g) of 100-315μm calcite and dolomite as
a function of the final scale inhibitor concentration in synthetic NSSW at initial pH values of pH = 2, 4
and 6 at 95°C, respectively.

Figure 1—Comparison of apparent adsorption for PPCA onto 2 masses (m = 5g and

10g) of calcite and dolomite at pH2 (Fig 1(a)), pH4 (Fig 1(b)), pH6 (Fig 1(c)) and T = 95°C
6 SPE-189519-MS

Figure 2—Comparison of apparent adsorption for PFC onto 2 masses (m = 5g and 10g)
of calcite and dolomite at pH2 (Fig 2(a)), pH4 (Fig 2(b)), pH6 (Fig 2(c)) and T = 95°C

The results in Figures 1 and 2 clearly show regions of both pure adsorption (where apparent adsorption
levels for different (m/V) ratios overlap) and coupled adsorption/precipitation (where different (m/V) results
diverge) for PPCA, regardless of the type of carbonate substrate and the initial solution pH. However, PFC
is retained on calcite through a pure adsorption mechanism at pH 2 (See Figure 2(a)). At the other initial pH
values (pH 4 and pH 6) both pure adsorption and coupled adsorption/precipitation are observed for PFC (like
SPE-189519-MS 7

PPCA). PPCA in NSSW has pure adsorption behavior up to [PPCA] ~100 ppm and coupled adsorption/
precipitation for [PPCA] >100ppm. PFC shows a larger region of pure adsorption (Γ only) at lower PFC
concentrations (up to [PFC] ~500ppm) compared with PPCA at pH 4 and 6. The most interesting specific
observations from these initial apparent adsorption results are that:
i. For PPCA: The apparent adsorption, Γapp, (a) is highest at pH 2, next highest at pH 4 and lowest at
pH 6, and (b) is greater on calcite than on dolomite.
ii. For PFC: The apparent adsorption, Γapp, (a) is approximately the same at pH 6 and pH 4 while in
PFC/calcite at pH2, only pure adsorption is observed, and (b) is less on calcite than on dolomite.
iii. The region of pure adsorption (Γ) is more extensive for PFC than for PPCA; the pure Γ region
extends up to [PFC] ~500 ppm and [PPCA] ~100ppm.
To explain these observations, further ancillary results will be presented below on carbonate dissolution
(changing [Ca2+] and [Mg2+] in solution) and on the final pH values of the system; further ESEM/EDX and
PSA data is also presented below on the precipitates (and carbonate substrates) themselves.

Results on final pH and [M2+] for PPCA and PFC in Γapp experiments on carbonate rocks
Final pH Values. Figures 3 and 4 present all of the final pH results for PPCA (Figure 3) and PFC (Figure
4) for both the blank and apparent adsorption experiments on calcite and dolomite given in Figures 1 and
2. Firstly, we note from the blank solution results that the pH remained at its initial value (pH = 2, 4 or 6)
for all SI concentrations in the absence of carbonate substrate for both PPCA and PFC. In the presence of
a carbonate mineral substrate, these final pH results give a good indicator of the total system response and
we can summarize these results as follows:
i. For PPCA (at the higher concs.): the final pH values for initial solution pH = 2, 4 and 6 were pH
~7, 7–7.3 and pH ~8, respectively, for calcite, and pH 7.6–8, 7.5–8.3 and pH 8–8.2, respectively,
for dolomite. That is, a somewhat higher final pH was found for dolomite than for calcite for all
initial pH values.
ii. For PFC (at the higher conc.): the final pH values for initial solution pH = 2, 4 and 6 were pH 5–5.1,
5.6–6 and pH 6–6.3, respectively, for calcite, and pH 7.6–8.2, 6.9–7.8 and pH 7.6–7.9, respectively,
for dolomite. That is, a higher final pH was again found for dolomite in comparison to calcite for
all initial pH values.
iii. Overall, PFC results in a lower final pH than PPCA under all initial conditions for both carbonate
minerals.
8 SPE-189519-MS

Figure 3—Comparison of pH for PPCA onto 2 masses (m = 5g and 10g) of calcite and dolomite at T = 95°C, pH 2, 4 and 6
SPE-189519-MS 9

Figure 4—Comparison of pH for PFC onto 2 masses (m = 5g and 10g) of calcite and dolomite at T = 95°C, pH 2, 4 and 6

Final divalent cation (mainly Ca2+) levels. The initial solution (synthetic seawater) has a calcium level
of, [Ca2+] = 428ppm (~10.7mM) and, in the following figures, it is this calcium level to which results are
normalized. Figures 5 and 6 present the final differences in normalized [Ca2+] for both compatibility and
adsorption tests for the PPCA/carbonate and PFC/carbonate systems. In summary, the final normalized
calcium results from these figures show the following:
i. Firstly, none of the blanks (i.e. with no carbonate substrate present) in Figures 5 and 6 show
any significant deviations from normalized [Ca2+] = 1, indicating that all solutions are completely
compatible and there is no loss of Ca2+ by precipitation for any of the initial pH/[SI] conditions;
ii. For both SIs (PPCA and PFC) and both carbonate minerals (calcite and dolomite), the normalized
[Ca2+] is well above unity for all initial pH = 2, 4 solutions; from normalized [Ca2+] ~ x1.8–x3
10 SPE-189519-MS

and ~x1.4–x 1.8 for PPCA/carbonate; ~x2–x3 and ~ x1.4 – x1.6 for PFC/carbonate, respectively
(although all final pH values are well above this value – see above);
iii. All initial pH = 6 cases (both PPCA, PFC and calcite/dolomite) give normalized [Ca2+] levels that
are mostly below or just above unity (PFC/calcite has a normalized [Ca2+] x1.03 – 1.07).

Figure 5—Comparison of Changes in normalized C/C0 of [Ca2+]

in calcite and dolomite systems vs final [PPCA] at pH= 2, 4 and 6
SPE-189519-MS 11

Figure 6—Comparison of Changes in normalized C/C0 of [Ca2+] in calcite and dolomite systems vs final [PFC] at pH= 2, 4 and 6

We note that initial and final levels of Mg2+ were also measured in all apparent adsorption experiments
(not presented here) but the results indicated that the role of Mg was secondary in these systems.

ESEM/EDX Analysis for PPCA, PFC-Carbonate Precipitates

ESEM-EDX analysis was used to examine the surface of the carbonates both before and after treatment in
all of the apparent adsorption experiments reported above. After filtration, all the filter papers containing
calcite/dolomite substrates and the precipitated complex (if present) for each of the PPCA and PFC
concentrations tested were dried and taken for ESEM-EDX analysis. The results are shown by presenting the
directly observed ESEM images in the figures along with some representative EDX compositions from these
images as tables of % (weight and atomic) of the various elements present; the latter results are approximate
12 SPE-189519-MS

but can be taken as "semi-quantitative". We have studied all of the precipitates where they occurred in these
experiments, but we focus here only on the highest concentration results since these are the cases for which
the most precipitate was obtained, and which show the clearest results. PSD results, however, are shown for
all cases below. Figure 7 shows the ESEM results for the 4000ppm PPCA case at pH = 2 where PPCA has
the highest Γapp in both calcite and dolomite. This figure shows significant amounts of smaller sized granular
precipitate, particularly in Figures 7(b) and 7(d), which focus specifically on this precipitate. The precipitate
occurs mainly as a separate material rather than coating the carbonate grains. From the solution ICP results,
this precipitate certainly contains both Ca and PPCA (P). However, the EDX detects no phosphorus (P) for
these cases but it does detect Ca, and so we do not show the results tables here. No P is detected mainly
because of the low content of phosphorus in PPCA (~0.5% of P) [22].

Figure 7—Morphology of 4000 ppm PPCA Samples for 100-315

μm calcite and dolomite at pH=2 on ESEM photographed samples

PFC contains a higher proportion of P than PPCA and is much more detectable by EDX. Results for the
4000ppm PFC precipitates formed at pH =2, pH =4 and pH = 6 for both calcite and dolomite are shown in
Figure 8 (pH 2), Figure 9 (pH 4) and Figure 10 (pH 6) (ESEM images) and Table 3 (pH 2), Table 4 (pH 4)
and Table 5 (pH6) (corresponding % weight/atomic by EDX).
SPE-189519-MS 13

Figure 8—Morphology of 4000 ppm PFC Samples for 100-315 μm calcite and dolomite at pH2 on ESEM Samples

Table 3—EDX analysis of 4000 ppm PFC for 100-315 μm calcite and dolomite at pH 2

As shown in the Figure 8 and Table 3, a significant amount of phosphorus was detected by EDX in the
PFC/dolomite case (~4% wt) and a small amount of P is seen around dolomite grains which may be due
to SI or SI/Ca precipitate adhering on the surface of dolomite. It should be mentioned that although PFC
has been retained by pure adsorption on the calcite grain, some phosphorus was detected by EDX in the
sublayer of the calcite grains (~2%wt) and around the calcite grains (~1% wt.); both of these levels are less
than what were found in the PFC/dolomite system.
14 SPE-189519-MS

Figure 9—Morphology of 4000 ppm PFC Samples for 100-315 μm calcite and dolomite at pH4 on ESEM Samples

Table 4—EDX analysis of 4000 ppm PFC for 100-315 μm calcite and dolomite at pH 4

As shown in Figure 9 and Table 4 for the PFC results, phosphorus is clearly detected at a high levels in
the finer PFC/Ca precipitate which forms in the bulk (P ~11% and 3% by weight for calcite and dolomite
respectively). However, in addition, there is a smaller but detectable amount of P on the calcite and dolomite
grains (~3% and 2% by weight, respectively) for the 4000ppm PFC case. This lower amount is possibly
due to some of the PFC/Ca precipitate adhering to the calcite or dolomite surface or is part of the adsorbed
SI. Some significant levels of sulphur (~2.12 % by weight) have been detected in the SI/dolomite case,
appearing as some white spots on bulk precipitate (see Figure 9 (d)), which may come from the PFC SI.
ESEM/EDX results for the 4000ppm PFC case at pH = 6 for both calcite and dolomite are shown in Figure
10 and Table 5. These results for the PFC/dolomite case show that phosphorus is again clearly detected at
a significant level (~3%) in the finer precipitate which forms in the bulk. This is similar to the phosphorus
SPE-189519-MS 15

levels detected for the PFC/Calcite case (~3%). In addition, there is a detectable amount of P (~ 3% by
weight, ~ 0.3% by weight) on the dolomite and calcite grains themselves, respectively; possibly due to
some of the SI/Ca precipitate adhering to the dolomite and calcite surfaces or may be part of the adsorbed
SI. Furthermore, as the pH of the PFC solutions increases in the dolomite case, the amount of phosphorus
detected, clearly increases (~ 3% and ~4% by weight at pH 4 and 6 respectively).

Figure 10—Morphology of 4000 ppm PFC Samples for 100-315 μm calcite and dolomite at pH6 on ESEM Samples

Table 5—EDX analysis of 4000 ppm PFC for 100-315 μm calcite and dolomite at pH 6 from ESEM

Particle Size Analysis for PPCA-Carbonate at pH2

Particle size distributions (PSDs) were measured for all precipitates which formed in the apparent adsorption
experiments. A Particle Size Analyzer (PSA) manufactured by the Malvern Company was used. Firstly,
16 SPE-189519-MS

the particle size analysis for the larger pure calcite/dolomite (100-315 μm) was performed using a 300 mm
Lens (the largest one which can only detect larger particle of order ~100+ μm) to measure the PSD and then
similar PSD measurements were performed using the smaller 75mm lens (suitable for PSD down to ~1+
μm sizes). Results are first shown for the larger particle distributions in Figure 11(a) (for PPCA/calcite) and
Figure 11(b) (for PPCA/dolomite). We show PSA for PPCA/carbonate substrates at pH2 since this is the
case for which most precipitate was observed.

Figure 11—Particle Size Analysis for 100-315 μm calcite and dolomite

residue at different concentrations and pH=2 with the 300 mm lens

The PSD results in Figure 11 show that there is good consistency in the measurement of the carbonate
particle sizes with the 300mm lens for both experiments. For these cases, we see that only large particle
sizes are observed and are broadly in agreement with the calcite/dolomite size range we expect. When these
same sample cases were examined by the smaller lens (45 mm lens) which can "see" much smaller particles
(from ~1 – 20 μm), we see no fine particles of this size for the 100ppm case; see Figure 12 – the "flat
line". However, when at increased PPCA concentrations where the system is going from a region of pure
adsorption to coupled adsorption/precipitation, we now see peaks of PSD between ~1 – 10 μm (Fig. 12).
SPE-189519-MS 17

Clearly, these populations of smaller particles are the SI/Ca precipitated material which forms as this finer
material; note that this is clearly distinguishable from the calcite/dolomite grains (which are much bigger
as shown in Figure 11 and this can also be seen directly from the ESEM results in Figures 8, 9 and 10).

Figure 12—Particle Size Analysis for 100-315 μm precipitate deposited

on filter paper at different concentrations and pH=2 with 45 mm lens
18 SPE-189519-MS

Summary, Conclusion and Discussion

Summary of Observations
In this paper, results have been presented for a range of apparent adsorption experiments for the polymeric
scale inhibitors (SIs), PPCA and PFC, on the carbonate minerals, calcite and dolomite. The results are
plotted as graphs of Γapp, vs. Cf, at different (m/V) ratios, as shown in Figures 1 and 2. In these experiments,
the initial pH was fixed (at pH =2, pH =4 or pH =6), as was the initial amount of calcium in solution
([Ca2+] = 428ppm), but both of these quantities changed at equilibrium; pH always increased and the final
normalized [Ca2+] was either above unity (initial pH = 2 and 4) or around unity (pH = 6). Both final pH and
[Ca2+] levels were measured for all experiments (i.e. for each concentration point in the apparent adsorption
curve). In addition, all precipitates were analyzed using ESEM/EDX and by PSA (particle size analysis).
These carbonate systems are much more chemically reactive than sandstone minerals (e.g. quartz, feldspar
and clays) which have already been studied extensively. The inhibitor solution reacts chemically with the
rock to change solution pH and [Ca2+] levels such that, for the higher SI concentrations, precipitation of a
sparingly soluble SI-Ca complex is formed giving a region where coupled adsorption/precipitation (denoted
Γ/Π) occurs. The detailed observations (described above) for apparent adsorption, the corresponding final
pH and normalized [Ca2+] behavior and the ESEM/EDX/ PSA results are summarized in Table 6. It is these
results that we must explain qualitatively, and in due course reproduce by modelling.

Table 6—Summary of apparent adsorption, the corresponding final pH and normalized

[Ca2+] observations and the ESEM/EDX/ PSA results from the experiments in this paper
SPE-189519-MS 19

Conclusions
The specific conclusions from this work are as follows:
1. Both pure adsorption (Γ) and coupled adsorption precipitation (Γ/Π) regions are clearly observed for
PPCA, on both dolomite and calcite, for initial pH values of pH2, 4 and 6. This is also the case for
PFC at pH2, 4 and 6 except in one case where PFC shows only pure adsorption at pH2 on calcite.
However, precipitation is more dominant for SI/carbonate retention than adsorption in the sense that
it occurs over a much wider [SI] range above a minimum concentration of ~100ppm (for PPCA) and
~500ppm (for PFC). The actual amount of precipitate formed varies from case to case, depending
on the specific SI, the substrate (calcite or dolomite) and initial pH (and temperature T, although a
fixed T = 95°C was used in this work). In the low SI concentration region (<100ppm for PPCA and
<500ppm for PFC), only pure adsorption (Γ) is observed. Hence, in a squeeze treatment in the lower
[SI] tail, the dynamic region of the return curve would be controlled by the relevant low concentration
region of the adsorption isotherm, Γ(C). However, the general "loading" of the formation with SI/
M2+ complex (i.e. the total amount retained as a "reservoir" of SI within the formation) would be as
a result of the precipitation/dissolution process.
2. For PPCA, the main observations are that the apparent adsorption (Γapp) levels are (i) higher for
lower initial pH conditions, and (ii) higher for calcite than for dolomite. Coupled with this, the final
pH values tend to be in the range pH ~7 – 8 (the lowest values are for lowest initial pH) and final
normalized [Ca2+] levels depend mainly on initial pH, being ~ x1.8 – x3 and x1.4 – x 1.8 for initial
pH 2 and 4 respectively, and just below x1 (x0.84 – x0.97) for initial pH 6.
3. For PFC, the main observations are that the apparent adsorption (Γapp) levels are (i) about the same
at pH 4 and pH 6 and (ii) higher for dolomite than for calcite. We also note that in one case, PFC on
calcite at pH 2, shows only pure adsorption. Coupled with this, the final pH values tend to be lower
than in the PPCA cases, in the range pH ~5.02 – 8.2 (the lowest values are for lowest initial pH) and
final normalized [Ca2+] levels depend mainly on initial pH, being x2– x3 and ~x1.17 – x1.66 for initial
pH 2 and 4, respectively and around x1 (x0.94 – x1.07) for initial pH 6.
4. Results from the ESEM/EDX and Particle Size Analysis (PSA) generally confirm and are consistent
with the static apparent adsorption results. For both PPCA and PFC, it is clear from the ICP results that
both Ca and P are lost from solution and form a precipitate. This precipitate can be observed directly
by ESEM where a distinct granular precipitate of size much smaller than the carbonate grains (~100
– 400μm) is observed. This is further confirmed by PSA using the smaller (45mm) lens which detects
a precipitate with a size range of ~1–10μm. EDX does not detect any phosphorus (P) in the PPCA/Ca
precipitate, due the fact that the P content of PPCA is too low to detect using this method, but it does
detect Ca. For the PFC/Ca precipitate, EDX does easily detect high P (phosphorus) concentrations
in the deposit where clear Γ/Π has occurred and the EDX levels are higher as Γapp (precipitation)
increases. Very little P is detected directly on the calcite or dolomite grain surfaces but traces are
sometimes seen.

Discussion
To understand the detailed results presented in this paper, we must consider the parts of the chemical
processes involved. This can be approached by considering the polymeric scale inhibitors as weak polyacids
of the form (HnA). The dissociation and speciation of the SI is governed by pH, which the inhibitor itself
determines although an initial pH can be set experimentally as is done here (to pH 2, 4 and pH 6). When the
SI (weak polyacid) solution contacts the carbonate mineral substrate, it reacts with it chemically generally
dissolving/chelating some calcium into solution. The SI can then form a SI/Ca (and SI/Ca/Mg) complex
20 SPE-189519-MS

which is sparingly soluble and this may precipitate, which in turn can affect pH. Thus, the entire system is
coupled and the 3 parts of the equilibrium system are
i. The dissociation of SI as a weak polyacid (HnA) to form dissociated species, such as Hn-mAm- right
up to An- at very high pH values;
ii. These dissociated SI species, which are very strong chelating agents, then bind with Ca2+ (and Mg2+)
ions to form SI/Ca complexes which are known to be sparingly soluble;
iii. The above reactions must be coupled to the carbonate system since the lower pH solution conditions
and the chelating power of the dissociated SI cause the carbonate equilibrium to change.
A model is currently under development to carry out the above program and this will be presented in the
near future. Consider any observed differences between systems e.g. the fact that for PPCA Γapp for calcite >
dolomite, but for PFC Γapp for calcite < dolomite. Clearly, this must be related to the dissociation behavior of
the different SIs, the Ca2+ (mainly) binding constants to the main functional groups on the SI, the solubility
of the SI-Ca complex which forms and the coupling of the SI (weak polyacid) to the carbonate system (and
indeed the reactivity of the carbonate system since calcite and dolomite are different). However, to explain
exactly why the example result above is as observed requires a full model which can reproduce and hence
explain the observations.

Acknowledgments
The following companies are thanked for sponsorship of the Flow Assurance and Scale Team
(FAST) at Heriot-Watt University: Halliburton Multi-Chem, NalcoChampion, Petronas, Repsol Sinopec,
Schlumberger MI Swaco, Shell, Statoil, Total and Wintershall. We are also very grateful to Dr. Jim Buckman
for his support with the use of the ESEM facility and our colleagues Wendy McEwan and Katherine McIver
in the FAST Analytical Team at Heriot-Watt University for performing the ICP-OES analysis. Finally, BWA
and Clariant service companies are thanked for supplying the PPCA and PFC scale inhibitors, respectively.

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