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Experimental Analysis of Scale Inhibitors Retention in Carbonate

Formations for Application in Squeeze Treatments
Khosro Jarrahian,* Morteza Aminnaji, Alexander Graham, and Kenneth Sorbie

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ABSTRACT: In this work, static adsorption/precipitation (Γ/Π) experiments were conducted for two widely used scale inhibitors
(DETPMP and VS-Co) using two different size fractions of Moroccan calcite (315−500 and 125−250 μm) to study the effect of
particle size on the “apparent adsorption” of these SIs onto carbonate. The reason for performing these experiments at two particle
size ranges was to determine whether the relative surface area to volume ratios (as presented as particle size) would affect whether
the precipitating SI−Ca complex forms as a “skin” on the mineral surface and, if so, to determine whether this “skin” could affect the
further interaction between the SI and the carbonate mineral by a “surface poisoning” effect. The results of both environmental
scanning electron microscopy/energy dispersive X-ray analysis (ESEM/EDX) and direct particle size analysis (PSA) clearly showed
that no (or very little), such surface deposition or coating around calcite grains occurred for either of these SIs. Essentially, the
results for both particle sizes were qualitatively the same for each of the SIs. The DETPMP retention showed coupled Γ/Π behavior,
which was predominantly precipitation at [DETPMP] > 100 ppm and was quantitatively almost the same for both calcite particle
sizes. Likewise, the results for VS-Co were quantitatively almost identical for both particle sizes and the retention was predominantly
via adsorption up to [VS-Co] ≈ 3000 ppm, with some small degree of precipitation at higher concentration observed. The rather
different behavior of DETPMP and VS-Co may be ascribed to different functional groups having different pKa values and strengths
of SI−Ca binding. Both sets of static adsorption/precipitation experimental results for DETPMP and VS-Co on each calcite particle
size fraction were also predicted using a previously published model.

1. INTRODUCTION solvent in some applications), followed by the selected scale

One of the common problems in oil production systems is the inhibitor (normally in the concentration range of 5% to 20% v/v
deposition and buildup of various inorganic scale precipitates in KCl or injection quality seawater), and finally, an overflush
(e.g., BaSO4, CaCO3, etc.).1−7 These scale deposits can have a stage (using inhibited seawater or KCl) into the well.18,19
highly damaging effect on production performance if they are When the SI is injected into the formation rock near the
not properly treated and can be formed in the oil/gas reservoir wellbore, it is retained within the porous medium. Once the well
itself or anywhere in the production system, including upstream, is brought back onto production, the retained SI is desorbed/
midstream, and downstream, for example, production tubing,
pumps, heat exchangers, chokes, and valves.8−11 One of the most
common ways of preventing mineral scale deposition is by the Received: August 7, 2021
deployment of chemical SIs in a process called a “squeeze” Revised: January 21, 2022
treatment.12−17 In general, the squeeze process (Figure 1) Published: February 4, 2022
involves the cessation of flow at a production well and the
pumping of a preflush solution (0.1% v/v inhibitor in KCl or
injection quality seawater, also containing 20% v/v of a mutual

© 2022 American Chemical Society https://doi.org/10.1021/acs.energyfuels.1c02691

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(methylene-phosphonic acid) (DETPMP) depends both on the

state of SI dissociation and Ca2+-bridging. Tantayakom et al.44
studied a Ca-ATMP (a phosphonate scale inhibitor) precip-
itation in the presence of magnesium ion. They concluded that
the molar ratio of divalent cations to ATMP molecules in the
precipitate increased with increasing pH of the precipitating
solution. In addition, they found that squeezing pH0 7 brines
containing ATMP and high Ca ions would generate a desirable
precipitated product, but precipitation likely would occur faster
than desired.
Tomson et al.39 presented results on the interactions between
SI and carbonate-rich formation rocks in which they described
the two main mechanisms governing the SI retention in
carbonate reservoirs: (a) the precipitation of SI−Ca2+ because
of the increase/decrease in [Ca2+] generated through calcite
dissolution and (b) the formation of a surface “skin” of the SI−
Ca complex, which then led to a reduction in carbonate
dissolution. Kahrwad et al.23 developed a model that shows the
dependence on the m/V ratio if coupled adsorption/
precipitation is occurring in the sandstone/DETPMP system
and showed that apparent adsorption increases as the pH of
DETPMP solutions increases. At pH0 4, only pure adsorption is
observed, whereas, at pH0 6, coupled adsorption/precipitation is
the dominant mechanism of DETPMP retention. Ibrahim et
Figure 1. Schematic of the three principal scale squeeze treatment al.34 carried out a series of static adsorption/compatibility
stages. Reproduced with permission from ref 18. Copyright 2020 experiments for a range of phosphonate SIs on various mineral
American Chemical Society. substrates present in sandstones, for example, quartz, kaolinite,
siderite, etc. They showed that pure adsorption occurred at low
redissolved, depending on the retention mechanism, into the [SI] and the “adsorption isotherm” could be used to correctly
stream of produced water. To avoid consuming high volumes of describe the SI/mineral retention mechanism, while the coupled
chemical, the SI must prevent or reduce scale formation at Γ/Π retention mechanism was dominant at high [SI] (and
substoichiometric levels, that is, at the operating threshold elevated Ca2+ concentrations) and a coupled Γ/Π model would
concentration of the SI, which is known as the minimum be used for most phosphonate SI/mineral systems.
inhibitor concentration (MIC). As a general rule, the greater the Carbonate rocks provide a much more chemically reactive
SI retention in the near-wellbore region, the longer the potential substrate than sandstone reservoirs and so the scale inhibitor
squeeze lifetime (measured in the volume of water produced retention mechanism can be more complex than simple
with a [SI] ≥ MIC) that can be achieved.10,20−26 In scale adsorption.9,33,45,46 In carbonate formations, scale inhibitors
inhibitor squeeze treatments, the main mechanisms of SI such as DETPMP (which are often deployed in an acidic form)
retention within the reservoir formation are through adsorp- may react with the formation and form precipitated complexes,
tion,27−30 precipitation,31,32 or a combination of these two, that that is, as sparingly soluble calcium salts of the SI as reported by
is, coupled adsorption/precipitation (denoted Γ/Π). Tomson et al.39 Precipitating of the SI in this way can result in
Adsorption occurs through an electrostatic attraction or longer scale squeeze lifetimes and, hence, can give an improved
physical adsorption between the inhibitor and formation efficiency of SI deployment. Indeed, even fully neutralized
mineral surface. This process is described by an adsorption inhibitors react with carbonates to form precipitates since the SI
isotherm, Γ(C), and this governs the squeeze lifetime in an species are generally strong chelators for divalent ions, such as
adsorption squeeze treatment. Recently “precipitation” squeezes Ca2+. Baraka-Lokmane and Sorbie9 studied scale inhibitor/
have been proposed and trialed in the field to increase squeeze carbonate systems by performing a series of core floods in
lifetimes beyond that attained by pure adsorption.33−35 carbonate cores with DETPMP as the SI. They concluded that
The mechanisms of adsorption (Γ), precipitation (Π), and the higher the concentration of SI and lower the pH, the more
coupled adsorption/precipitation (Γ/Π) have been investigated calcium dissolution was observed (from the [Ca2+] effluents),
using various modeling approaches by many researchers.36−42 and there was a decrease in the [Mg2+] effluent concentration
The early mechanistic investigation on SI retention was corresponding directly to the increase in the [Ca2+]. In addition,
performed by Vetter,36 who concluded that the “adsorption the core permeability (k ∼ 600 mD) increased in all cases
isotherms” of SI on sand particles at various pH values and low indicating that the stimulation effect through calcite dissolution
temperature were more or less indistinguishable, and that there was greater than the permeability reducing effect induced by the
was a small increase in the amount of adsorption as the solution deposition of (Ca and Mg) phosphonate salts and finally the
pH was raised. Sorbie et al.43 studied the effect of pH, lowering of the injected SI solution pH was more important than
temperature, and [Ca2+] on the retention of phosphonate SIs in an increase in the SI concentration for improving the SI
both crushed and consolidated sandstone. They observed an adsorption in the core. Jarrahian et al.46 carried out coupled Γ/Π
increasing of SI adsorption on the crushed rock with experiments for two types of widely used polymeric SI on two
temperature. In addition, the adsorption of inhibitor was common carbonate rocks (calcite and dolomite). It was found
shown to clearly depend on both the [Ca2+] and the solution that poly phosphino carboxylic acid (PPCA) retained more on
pH, since the adsorption of diethylene tetra-amine penta- calcite than on dolomite and that the PPCA retention reduced as
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Figure 2. Scheme of static adsorption and compatibility experiment.

the solution pH was lowered. In the P-functionalized copolymer conditions (temperature and pH) and mineralogy compositions
(PFC)/carbonate system the behavior was the opposite to that (sandstones and carbonates). However, there is still a gap in our
for PPCA, that is, PFC showed higher retention on dolomite knowledge on the effect of particle size of the carbonate mineral
than calcite. Jarrahian et al.33 summarized the Γ/Π experimental fractions on the retention of scale inhibitors. The aim of this
results for 5 widely used SIs (DETPMP, PPCA, PFC, polyhydric study is to investigate the impact of particle size on the retention
alcohol phosphate ester (PAPE), and sulfonated polyacrylic acid of different scale inhibitors (DETPMP and VS-Co as
copolymer (VS-Co)) on three common carbonate mineral representatives of phosphonate and polymeric scale inhibitors,
substrates (calcite, dolomite, and limestone). The findings from respectively) in carbonate porous media. This has been done by
this work were as follows: (a) in the polymeric SI (PPCA, PFC, performing a range of “apparent adsorption” experiments, where
and VS-Co) cases, greater retention was observed for all 3 we plot the apparent adsorption (Γapp) versus final SI
carbonates at lower solution pH values. This was because of the concentration (Cf).23 It has been shown here conclusively
increase in divalent cations concentration (Ca2+ and Mg2+) where the system is in pure adsorption (Γ) and where it is
generated in situ through rock dissolution, which enhanced the coupled adsorption/precipitation (Γ/Π).47−50 When the
complexation process of SI with divalent cations (SI-M2+ apparent adsorption results (Γapp) are plotted versus final scale
complex), and (b) for phosphonate (DETPMP) and a inhibitor concentration (Cf) as a function of mass/volume ratio
phosphate ester (PAPE) SIs, a higher retention of SI was (m/V, where m is the mass of substrate (carbonate mineral) and
found at higher solution pH levels. This was due to the greater V is the solution volume), at low concentrations, scale inhibitor
level of SI dissociation and also more functional groups available is retained dominantly by pure adsorption and the adsorption
for precipitation of SI with M2+. (c) The polymer VS-Co/ results simply “move along” the adsorption isotherm and do not
dolomite system mostly showed pure adsorption with only a depend on the (m/V) ratio. However, at higher concentrations,
very low amount of precipitation; this was attributed to the the adsorption results are clearly deviating from the adsorption
presence of sulfonate groups (low pKa), and (d) polymeric isotherm, the inhibitor is retained mostly by precipitation. In
inhibitors retained at their highest level on calcite (highest other words, the scale inhibitor interacts with divalent cations,
relative calcium content), followed by limestone and then mainly Ca2+, and the SI_Ca complex is precipitated out. This
dolomite; (e) for the phosphonate and phosphate ester SIs method was applied in this work to analyze such apparent
cases, the highest retention levels were observed on dolomite adsorption experiments.23,33,34 The current experiments in this
(higher final solution pH and more SI dissociated), followed by paper are carried out deliberately in the “initial stages” of a
limestone and calcite. (f) For all SI types, higher retention (more squeeze to determine the precise balance of adsorption (Γ) and
precipitation, Π) was observed at elevated temperatures. At precipitation (Π), which cannot be determined directly in flow
lower temperatures, the pure adsorption region was larger for all experiments.
SIs. A range of apparent adsorption results (Γapp vs Cf as functions
Extensive research has been conducted on the apparent of m/V) is presented for two SIs (DETPMP and VS-Co) on
adsorption of scale inhibitors under different operational calcite substrates with different particle sizes. These results also
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show the corresponding levels of final [Ca2+] and pH for every 9. After 24 h in the oven, remove the test bottles and immediately
apparent adsorption experiment. This information is supple- filter through individual 0.22 μm membrane filters; keep the
mented by the study of the formed precipitates using ESEM/ labeled mineral/precipitate on their filter papers and the
EDX and particle size analysis (PSA).46 These techniques separate supernatant solutions.
revealed direct information on the morphology of any 10. Leave the filtered supernatant solution to cool to room
precipitates formed, that is, whether they are formed as free temperature for approximately 24 h.
crystalline (or amorphous) precipitates or whether they form as 11. Measure the post-test pH.
“coated structures” on the surface of the calcite grains. The EDX 12. Sample the filtered supernatant using a pipet and dilute the
sample volume in a known matrix volume ready for analysis
measurements also yield an approximate chemical composition
alongside the associated stock solutions by inductively coupled
of the precipitates; for example, establishing the presence of plasma-optical emission spectrometry (ICP-OES) for
phosphorus (P from the SI) and Ca, and in what approximate [DETPMP], [Ca2+], and [Mg2+]. Analyze the [SI] of the VS-
(P/Ca) atomic ratios.33,45 Co samples by the wet chemical matrix-matched Hyamine
technique instead of ICP-OES.51
2. EXPERIMENTAL METHODS AND MATERIALS 13. Perform ESEM/EDX analysis and PSA on the collected and
2.1. Experimental Procedure. Static adsorption/compatibility dried solid phases (precipitate/mineral combined and separate)
experiments were carried out to differentiate between the pure to analyze the morphology and particle size of the mineral-
adsorption (Γ) and coupled adsorption/precipitation (Γ/Π) behavior substrate grains and any bulk precipitate formed.
of SIs on carbonate mineral in a North Sea seawater (NSSW) brine. A It should be mentioned that, in the environment in which the
stock solution of SI with 10 000 ppm was initially prepared and used to experiment was performed (our laboratory), the carbon dioxide
make the different SI concentrations in the experiments. Initial SI concentration was negligible. So, there is no need to control the
concentrations of 50, 100, 500, 2000, and 4000 ppm were used in all the small amount of CO2. Moreover, the plastic bottles were capped tightly,
experiments for DETPMP. Higher initial concentrations of VS-Co were so CO2 could not get out of the system. When the bottles were put in
used at 1000, 2500, 5000 and 10 000 ppm; this was done since the VS- the oven, the caps were checked after an hour to ensure no evaporation
Co was analyzed by a matrix-matched Hyamine method using an (CO2 liberation) happens during the experiment. Li+ was also added as
ultraviolet spectrophotometer that requires higher concentrations for an inert element into the solution and [Li+] was analyzed before and
better accuracy. The pH was measured for all the stock solutions and after the static adsorption test. This is the way we trace the evaporation
while it was later adjusted to an initial pH of 4 for the solution with of solution (CO2 liberation) at high temperatures and consequently the
DETPMP, the experiment with VS-Co was conducted at natural pH error of our experiment.
(no pH adjustment to specific value) of the [VS-Co] solution. In the bulk compatibility tests, no mineral was present, and all test
For the static apparent adsorption tests, the experiments were and stock solutions were analyzed by ICP-OES to measure the
conducted using two different masses of carbonate mineral (Moroccan difference in ionic compositions. Any difference in concentrations
calcite) (m = 5 and 10 g) for a fixed volume of solution (V = 0.04 L), between the test and stock values were assumed to be related to pure
which result in two different values of the m/V ratio. Corresponding precipitation at this stage (Π only). In the presence of mineral substrate,
compatibility experiments (with no mineral present) were carried out the apparent adsorption of SI retained by the mineral, Γapp (in mg SI/g
to establish whether the inhibitor is fully compatible with the test brine substrate), was calculated using the following equation:45
(in this case, with NSSW). Thus, any reduction in SI concentration for
this test is due to the incompatibility between SI and NSSW, that is, it V (Co − Cf )
results in the formation of SI/Ca2+ precipitation.32,34,45 Γapp =
m (1)
While Figure 2 presents a simple schematic of the static adsorption/
compatibility test, the main steps with their details in the experimental where C0 and Cf are the initial and final SI concentrations, respectively,
procedure are as follows: V is the volume of SI solution, and m is the mass of mineral substrate. In
these experiments, the results were plotted as Γapp versus Cf. Note that
1. Prepare NSSW brine by dissolving the relevant salts in distilled apparent adsorption is used because both adsorption (Γ) and
water, and subsequently, filter this brine through a 0.45 μm filter precipitation (Π) may be occurring simultaneously, and thus the
paper. apparent adsorption is a combination of both mechanisms (Γ/Π). It
2. Prepare a 10 000 ppm of SI stock solution in the test brine and should be noticed that the adsorption is expressed as mg SI/g substrate
further dilute to appropriate SI concentrations for the apparent here, as mentioned above. Because the surface area of the mineral
adsorption test in the same test brine in which result in initial substrate (i.e., in m2/g) in this reactive system is actually changing since
concentrations of 50, 100, 500, 2000, and 4000 ppm for there is some degree of preferential dissolution of the smaller fraction of
DETPMP, and 1000, 2500, 5000, and 10 000 ppm for VS-Co. the carbonate mineral which has the higher area/mass ratio. Moreover,
3. Record the pH and then adjust the pH of all stock solutions the mass of substrate at all times is actually an absolute value, even in
(blanks and SI/SW samples) to the required initial test pH this chemically reacting system (SI/carbonate systems).45 Finally, our
value: that is, pH0 4 for DETPMP and leave VS-Co at its natural mathematical model, on which the entire (Γ/Π) theory is based,23,52−54
solution pH. directly uses the mass/mass formulation; hence, the first part of the
4. Prepare two sets of plastic bottles: one for apparent adsorption analysis if we expressed Γapp in mol/area or mg/area would be to
(contains mineral substrate, calcite) and the other set for convert to mass/mass.
compatibility testing (no mineral present). Prepare duplicate 2.2. Analysis Methods. 2.2.1. Inductively Coupled Plasma−
sample bottles for each test condition for adsorption but only Optical Emission Spectrometry (ICP-OES). ICP-OES was used to
one for compatibility. analyze for the specific ions of interest (phosphorus, calcium,
5. Weigh samples of mineral substrate into appropriately labeled magnesium, and lithium) in the supernatant, before and after filtration,
bottles (m = 5 and 10 g) for each size fraction (125−250 μm and using a Thermofisher dual view iCAP 6500 system.45
315−500 μm). 2.2.2. Environmental Scanning Electron Microscopy−Energy
6. Pipette 40 cm3 of the appropriate SI solution into each bottle (V Dispersive X-ray (ESEM-EDX). ESEM-EDX analysis was used to
= 0.04 L) slowly. examine the surface of the crushed calcite before and after the apparent
7. Cap the bottles and shake for 5 s thoroughly, to ensure the adsorption experiments. This was performed to investigate the possible
system was mixed properly, before placing in an oven at a test morphology of the precipitated complex in the presence of calcite
temperature (95 °C) and atmospheric pressure. substrate and, in particular, to establish if the precipitate was formed as a
8. Check the bottle caps for tightness after 1 h and tighten if loose, grain coating around the calcite particles or whether it formed
to avoid evaporation. independently as a bulk precipitate. Therefore, after filtration, all the

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Figure 3. Specifications of the scale inhibitors (SI) used in this work. Reproduced with permission from ref 45. Copyright 2020 American Chemical
Society.

filter papers containing calcite substrate and (in some cases) the
precipitated complex for each of the SI concentrations tested were dried
and examined by ESEM-EDX analysis. For this study, a Philips XL30
ESEM system, with an Oxford Instruments cryo-stage and an EDX
detector, was used for the analysis.34,45
2.2.3. Particle Size Analysis (PSA). Particle size distributions (PSDs)
were measured for all precipitates using a Malvern Instruments
MasterSizer for all precipitates that formed in the apparent adsorption
experiments. The PSD for the SI-divalent cation precipitate (SI/M2+)
(size fractions of 1 μm and larger) was obtained using a 45 mm lens
(size range from 0.1 to 80 μm). PSA was further used to explain the
apparent adsorption results by confirming the formation of the SI/M2+
complex in the mixtures.46
2.3. Materials. 2.3.1. Scale Inhibitors. Two scale inhibitors were
used in this work, which are (1) diethylene triamine penta (methylene
phosphonic acid) or DETPMP, DETA-phosphonate, and (2)
sulfonated polyacrylic acid copolymer or VS-Co. These SIs are Figure 4. Morphology of pure calcite on ESEM photographed sample.
commercial chemicals, which are commonly used in oilfield
applications, and the structures of these SIs are presented in Figure Table 1. EDX Signals on the Pure Calcite from ESEM
3.45,55 DETPMP and VS-Co were supplied by Italmatch and
ChampionX (previously Nalco Champion) companies, respectively. element pure calcite (weight %) pure calcite (atomic %)
In the case of VS-Co, the chemical supplier did not provide us with the C 17 25
specifications of the inhibitors, including molecular weight and the O 57 63
percentage of sulfonation.
Ca 26 12
2.3.2. Substrate. The substrate used was Moroccan calcite, which
was sourced from the UK Geology Company (UKGE). This rock was
crushed and sieved down to the desired size fractions (125−250 and This carbonate rock was further characterized by dissolving them in
315−500 μm), before being washed with distilled water to remove any 100 mL of 10% HCl solution, and the solutions were analyzed by ICP-
fines. Prior to use, the materials were allowed to air-dry. We have OES to determine cation concentrations (Ca, Mg, and Fe); the results
checked the effect of particle size (i.e., specific surface area) of the are presented in Table 2.
crushed carbonate, and results are not dependent on this, indicating For the Moroccan calcite studied, there was negligible magnesium
impurity observed, and the chemical formula was confirmed as CaCO3.
that the effect is controlled by the extent of chemical reaction rather
than surface effects (although the kinetics is a little faster for the smaller
particle size).18,32,45 ESEM/EDX analysis was used to characterize the Table 2. Characterization of the Carbonate Substrates
morphology and elemental compositions of the pure calcite,32,46 as
shown in Figure 4 and Table 1. The elements detected by EDX analysis calcium magnesium
were calcium, oxygen, and carbon, confirming the composition of the carbonate type (mole) (mole) iron (mole) Mg/Ca ratio
−6 −9 −8
substrates (three different parts of the examined surface were analyzed Moroccan 9 × 10 3 × 10 2.5 × 10 3.3 × 10−4
to make sure that the EDX results are precise and accurate). calcite

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2.3.3. Brine. The brine solution used was synthetic North Sea In fact, eq 3 is just a parametrized “solubility model”, which
seawater (NSSW). This brine was made by dissolving the appropriate tries to capture the fact that the higher the [SI] or [Ca] then the
salts in distilled water as listed in Table 3. The brine solution was filtered more precipitate that is formed.
Some additional notation is introduced in Figure 5 as follows:
Table 3. Synthetic NSSW Composition
• C1,0 and C1,finitial (t = 0) and final equilibrium (t → ∞)
ion concentration (ppm) salt used mass of salt(g/L) of SI with the unit of molar concentration (M)
Na+ 10 890 NaCl 24.08 • C2,0 and C2,finitial (t = 0) and final equilibrium (t → ∞)
Ca2+ 428 CaCl2·6H2O 2.34 of Ca with the unit of molar concentration (M)
Mg2+ 1368 MgCl2·6H2O 11.44 • Γthe adsorption, which depends on C1,f, Γ = Γ(C1,f)
K+ 460 KCl 0.88 (mg/g)
SO42− 2960 Na2SO4 4.38 • Πis the precipitation process depending on both C1,f
Li+ 50 LiCl 0.3055 (SI concentration) and C2,f (Ca concentration) through
Cl− 19 766 Ksp as Ksp = (C1,f). (C2,f)n in this notation when the system
is in equilibrium; units of Ksp → Mn+1
through a 0.45 μm filter to remove any undissolved solids before use, in • mpthe actual mass of precipitate that forms
accordance with normal industry practice. 50 ppm lithium (Li+) was
added as an inert tracer to determine whether any evaporation occurred According to the definition of the parameters, the coupled
during static adsorption and compatibility tests. adsorption/precipitation model reported by Kahrwad et al. is as

ij yz
As shown in Table 3, Iron was not added into the NSSW water follows:

F(C1f ) = C1f + jjj zz·Γ(C )

j V ·MSI ·1000 zz
sample because iron is easily oxidized and is used up in the system
m
k {
instantly. In addition, silica was not also included in the synthetic
1f
NSSW. Because the aqueous fluid typically had less than 2 ppm, which
i ij K yz yzz
1 jj
+ jjjC20 − jjj SP zzz zzz − C10
would have no effect on the results. So, silica plays a negligible role in

n jj j C z zz
1/ n
this system.

3. COUPLED ADSORPTION/PRECIPITATION MODEL k k 1f { { (4)

A coupled adsorption/precipitation model reported by Kahrwad where, at equilibrium adsorption/precipitation, one must solve
et al.23 was used to predict the experimental results of coupled
1i
1/ n y
this equation for C1,fthat is, find the root of F(C1f) = 0. Note that
the term n jjjjC20 − CSP zz describes precipitation, where n is
zz
adsorption/precipitation (Γ/Π) processes. Kahrwad et al.23

k {
used this model for similar DETPMP Γ/Π processes but on
different substrates: sand, clays, and siderite, which are much less
( )
K
1f

chemically reactive than calcium carbonate. the stoichiometry of Ca2+ ions involved in precipitation reaction
As discussed, the apparent adsorption of SI (Γapp) retained by (eq 2) or precipitation factor.
the mineral is described using eq 1 and it is shown schematically Note: The SI adsorption isotherm is based on Freundlich
in Figure 5, where the precipitation is shown to occur by the isotherm (the adsorbate (SI) forms a monomolecular layer on
the surface of the adsorbent (calcite in this case)). Here, the
Freundlich form is assumed, as follows:
Γ(C1f ) = α(C1f )β (5)
where α and β are constants. In this work, these constants are
determined based on the experimental results of SI−calcite
system with 5 g of calcite, that is, a trial-and-error process for α
and β was performed to achieve the optimal match with the
experimental results. Once the best constants have been chosen,
the adsorption isotherm could be predicted for other amounts of
substrate, that is, in this work, the results of adsorption isotherm
for the SI−calcite system with 10 g of calcite were predicted and
compared with the experiments as reported in the next section.
Figure 5. Schematic showing how both coupled adsorption and
precipitation can occur showing how this could be interpreted as an 4. RESULTS AND DISCUSSION
“apparent adsorption”, Γap.
4.1. DETPMP−Calcite. 4.1.1. Adsorption/Compatibility
Test. The scale inhibitor DETPMP was used at initial
concentrations of 50, 100, 500, 2000, and 4000 ppm for the
formation of the calcium salt of the SI, that is, by precipitation of compatibility and apparent adsorption experiments. Figure 6
SI_Can. In general, the stoichiometry of this precipitation shows the apparent adsorption of scale inhibitor, Γapp (mg SI/g
reaction is as follows: rock), as a function of final SI concentration, Cf (ppm), for two
different masses of calcite with size fractions of 125−250 and
SI + nCa F SI−Ca n (2)
315−500 μm in synthetic NSSW at pH0 4 at 95 °C.
where n Ca ions may bind to a single SI molecule. The solubility The regions of both pure adsorption (Γ) and coupled
of this sparingly soluble salt would be described by an adsorption/precipitation (Γ/Π) are observed at lower and
equilibrium solubility product, Ksp, of the form: higher initial SI concentrations respectively as shown in Figure 6.
Only pure adsorption (Γ) is seen for [SI] up to ≈100 ppm
K sp = [SI]·[Ca]n (3) DETPMP, i.e., before the curves with different (m/V) start to
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Figure 6. Apparent adsorption (Γapp vs Cf,) for DETPMP onto 2 masses Figure 7. Comparison of pH trend for different masses of calcite (315−
(m = 5 and 10 g) of calcite for two size fractions of calcite (315−500 μm 500 and 125−250 μm) versus final [DETPMP]
and 125−250 μm) at pH0 4 and T = 95 °C. Solid lines are matched to
calculate β and n in eqs 4 and 5. Dashed lines are predicted using the
model. Inset: Pure adsorption region.

deviate from each other due to coupled adsorption/

precipitation occurring.18,34 The pure adsorption region is
shown in the inset of Figure 6 with much higher resolution. In
this pure adsorption region, all curves almost overlap and locally
plateau at a level of Γ ∼0.09−0.16 mg/g; this is a reasonable
level if the mechanism is purely adsorption. However, above ca.
100 ppm of DETPMP, not only do the curves with different (m/
V) diverge, but also, they lead to levels of apparent adsorption of
Γapp ∼ 1−22 mg/g. Therefore, both the divergence of the Γapp vs
Cf curves and the levels of “apparent” adsorption indicate that
both pure adsorption (Γ) and precipitation (Π) mechanisms are
involved above ca. 100 ppm of DETPMP, indicating coupled Figure 8. Normalized [Ca2+] (C/C0) versus final [DETPMP] for the
size fractions of 315−500 and 125−250 μm.
adsorption/precipitation. It is also noted that, within exper-
imental accuracy, there was very little quantitative difference
between the two size fractions of calcite 125−250 μm and 315− formed. Figure 7 shows the pH changes versus final [DETPMP]
500 μm. That is, the coupled Γ/Π effect is driven by the for each of the points in Figure 6.
DETPMP/calcite chemistry and, the particle size range does not As shown in Figure 7, no significant change in pH was
affect the coupled Γ/Π results. In other words, the particle size observed in the compatibility test (the test without calcite).18,45
does not affect the final (equilibrium) amount of apparent Therefore, DETPMP could be considered as a fully compatible
adsorption, although it has an impact on the kinetics of system SI with NSSW in the solution without mineral and at pH0 4.
(the smaller particles in the system, the quicker interaction they However, when the calcite substrate was added into the solution,
have with the scale inhibitors), and the SIs chemistry has the pH increased from pH0 4 to around pH 8. This was
governed the interaction of SI with calcite grains. attributed to the dissolution of calcite in the scale inhibitor
Figure 6 also shows that there was a reasonable match solution and the consequent generation of in situ calcium. As the
between experimental results and prediction using the model initial [SI] was increased, the in situ calcium generated will
described in Section 3. As discussed, the data both for the pure interact with the phosphonate groups in the DETPMP and a
adsorption and coupled Γ/Π regions for m = 5 g was used to sparingly soluble Ca-DETPMP complex will be formed. This, in
tune the model to find α, β, and n which are 245, 0.85, 0.17 and turn, will result in loss of calcium and phosphorus from the
230, 0.82, 0.195 for the size fraction of 315−500 μm and 125− solution (by Ca-DETPMP precipitation) with a consequent
250 μm, respectively. Having these parameters, as shown in decline in solution pH from pH ∼8 to pH ∼ 5. This reduction in
Figure 6, the results for the case with m = 10 g could be predicted pH starts just above 100 ppm is consistent with the onset of the
without any additional parameters. As expected, for pure coupled adsorption/precipitation region for both size fractions
adsorption, the data for m = 5 and 10 g fall on the same as shown in Figure 6.
adsorption isotherm, which is described here very well by the Figure 8 shows the normalized [Ca2+] (relative to the initial
Freundlich form (Γ(C1f) = α (C1f)β).23 value of [Ca2+] in NSSW which is 428 ppm) for both
To support the results of static apparent adsorption/ compatibility and adsorption tests in calcite for the two size
compatibility test in Figure 6, the results of pH and final fractions of 315−500 and 125−250 μm. As shown in Figure 8,
[Ca2+] were investigated as shown in Figures 7 and 8, no noticeable change in normalized [Ca2+] was observed for the
respectively. Changes in the final solution pH can be attributed compatibility test, implying no precipitation in the absence of
to the loss of [Ca2+] and [Phosphorus] because of the precipitate calcite substrate. This particularly shows that DETPMP is
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compatible with NSSW at pH0 4.18,45 Figure 8 shows that, in the As shown in Figure 9 and Table 4, for pure calcite, most
presence of calcite substrate, the normalized [Ca2+] increases by elements detected by EDX analysis are calcium, oxygen, and
20% (Δ[Ca2+] ≈ 100 ppm) in which reaches a plateau in the carbon, indicating the substrate is mainly calcite. For the 100
adsorption/precipitation region. While the precipitation of the ppm DETPMP case, which is in the pure adsorption region,
Ca2+-DETPMP complex occurs, an increased normalized [Ca2+] there are no traces of phosphorus (P) on the calcite grains and
is observed due to calcite dissolution as shown in Figure 8, that no significant changes in the elements compared with pure
is, the final effect is a net increase of Ca2+ in the solution. Similar calcite. The Na and Cl detected here have come from seawater
to pH analysis, Figure 8 indicates analogous results for both size deposited on the filter paper. Pieces of evidence form the results
fractions of calcite. An interim conclusion from the apparent of Figure 9 and Table 4 confirm that phosphorus is clearly
adsorption results (Γapp vs Cf) and the supporting [Ca2+] and the detected at a high level (∼14% by weight) in the finer precipitate
pH analysis is the calcite particle size has no effect and that the which forms mainly in the bulk phase. However, there is a small
DETPMP−calcite interaction is governed by the chemistry. but detectable amount of phosphorus (∼0.39% by weight) on
4.1.2. ESEM/EDX Analysis for DETPMP−Calcite. ESEM/ the calcite grains themselves for the 2000 ppm DETPMP case
EDX analysis was used to examine the surface of the crushed (no P can be detected on the calcite at 500 ppm DETPMP).
calcite before and after SI treatment in all apparent adsorption This lower amount is possibly some of the SI/Ca precipitate
experiments.18,32,45 ESEM images for the 315−500 μm size adhering to the calcite surface or is part of the adsorbed SI. As
fraction are presented in Figure 9 and the corresponding EDX the concentration of DETPMP increases from 500 to 2000 ppm,
the amount of phosphorus detected clearly increases.33,34 No
“surface coating” of the SI/Ca complex around calcite grains was
observed in these experiments, even for the highest concen-
tration of SI. Thus, we see no evidence for the hypothesis of
“surface poisoning” by the Ca-DETPMP complex.
4.1.3. Particle Size Analysis for DETPMP−Calcite. Particle
size distribution (PSD) of the SI/Ca2+ complex was measured
using a 45 mm lens (to see small particles (from ∼1−20 μm) and
the results are presented in Figure 10. The PSD results indicate
the absence of any fine particles in the Blank and 100 ppm cases,
as no fine particles (precipitate of SI with Ca2+) of this size are
formed in the pure adsorption region. However, for the cases
with higher DETPMP concentration (500 and 2000 ppm),
where the system was in a region of coupled adsorption/
precipitation, the peaks of PSD was observed between ∼1−10
μm.31,51 Clearly, these populations of smaller particles are the
SI/Ca precipitated material which forms as this finer material.
These observations agree very well with the direct visual results
observed in the ESEM (e.g., Figure 9) and confirm that both
retention mechanisms (pure adsorption and precipitation) are
occurring in the DETPMP/calcite system.
4.2. VS-Co−Calcite. 4.2.1. Adsorption/Compatibility Test.
Another set of static adsorption/compatibility test was carried
out for VS-Co as a polymeric SI at the natural pH (no pH
adjustment) and temperature of 95 °C, that is, the scale inhibitor
was used at different concentration of 1000, 2500, 5000, and
10000 ppm. Figure 11 shows the “apparent adsorption” results
(Γapp vs Cf) of VS-Co (mg SI/g rock) for two different masses of
calcite with size fractions of 125−250 and 315−500 μm in
synthetic brine solution (NSSW).
In contrast to DETPMP, the results of apparent adsorption
Figure 9. Morphology of samples for pure calcite, 100, 500, and 2000 for VS-Co show an extensive region of pure adsorption (Γ only)
ppm DETPMP for 315−500 μm calcite from ESEM photographed
samples.
up to the concentration of ∼3000 ppm for both size fractions.
Similar to DETPMP, beyond the pure adsorption region, the
apparent adsorption curves for VS-Co diverge ([VS-Co] > 3000
analysis is presented in Table 4 (the ESEM/EDX analysis for the ppm), indicating coupled adsorption/precipitation (Γ/Π).33
125−250 μm size fraction is almost the same). The ESEM/EDX The pure adsorption region is much more significant than was
analysis was utilized to explore the nature of the SI−M2+ observed for DETPMP, and this is clearly evidenced by both the
complex precipitated in the presence of calcite. In particular, clear shape of the adsorption isotherm (Γ (C)) and the
this analysis is used to establish whether the SI−M2+ complex reasonable level of adsorption (i.e., Γmax plateaus at a level of up
was formed as a grain coating around the calcite particles or to Γ ∼0.40−0.47 mg/g which is a very typical value for this SI).
whether it formed separately as a bulk precipitate.18,32 Hence, It should be noticed that the Freundlich isotherm does not have
after filtration, all the filter papers containing calcite grain and, in a plateau. This was referring to the apparent behavior of the
some cases, the precipitated complex for each of the SI experimental adsorption data. All that was meant was that it was
concentrations tested were dried and examined by ESEM/EDX showing adsorption type behavior rather that the rapidly rising
analysis. characteristics of precipitation.
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Table 4. EDX Analysis of the Samples for Pure Calcitea

calcite grains pure bulk precipitate, bulk precipitate,
sample calcite 100 ppm calcite grains 500 ppm 500 ppm calcite grains 2000 ppm 2000 ppm
element % weight % atomic % weight % atomic % weight % atomic % weight % atomic % weight % atomic % weight % atomic
C 14 21 13 24 17 26 17 26 37 44
Na 1 2 3 2 3 2 3 2
Mg 2 2 2 2 5 4
P 5 3 5 3 1 1 14 9
Cl 1 2 6 3 6 3 6 3
Ca 29 13 31 13 21 10 21 10 17 7 21 18
O 57 66 54 59 46 54 46 54 45 48 51 64
a
100, 500, and 2000 ppm DETPMP for 100−315 μm of calcite at pH0 = 4 and T = 95 °C.

regions of pure adsorption (Γ) and coupled adsorption/

precipitation (Γ/Π), however, the extent and importance of
these two regions differ.33 The effect of precipitation is expected
to be much more important than adsorption for DETPMP (and
other phosphonates) as discussed in the previous section. In
contrast, the results for VS-Co indicate that although some
precipitation does occur, adsorption is more important. As
shown in Figure 11, the results of apparent adsorption for VS-Co
for both calcite size fraction are quite similar qualitatively and
almost quantitatively. In this respect, the results for VS-Co/
calcite system are quite similar to those for the DETPMP/calcite
system (i.e., identical quantitative results are observed for both
size fractions). Conclusively, it confirms that particle size does
not have any significant effect on the equilibrium apparent
adsorption results.
Like DETPMP, the coupled adsorption-precipitation model
Figure 10. Particle size distribution for precipitate deposited on filter was used to predict the results of VS-Co/calcite apparent
paper in different concentrations of DETPMP using 45 mm lens. adsorption experiment. The data, both for the pure adsorption
and coupled Γ/Π regions in VS-Co/calcite system for m = 5 g,
was used to tune the model to find α, β, and n, which are 680,
0.88, 0.01077 and 690, 0.86, 0.01077 for the size fractions of
315−500 and 125−250 μm, respectively. As shown in Figure 11,
apparent adsorption could be well predicted (based on above
coefficients) for the VS-Co/calcite systems with 10 g of calcite
for both size fraction.
The prediction results of these two scale inhibitors (DETPMP
and VS-Co) shows that the model for analyzing apparent
adsorption experiments which includes both pure adsorption
(Γ) and coupled adsorption/precipitation (Γ/Π) regions works
reasonably well for SIs on carbonate (calcite) mineral substrates.
Therefore, this model could predict the apparent adsorption for
both DETPMP/calcite and the VS-CO/calcite systems,
although the former is hugely dominated by precipitation (Π)
and the latter is mostly dominated by pure adsorption (Γ).
Final pH values as a function of final concentration of VS-Co
Figure 11. Apparent adsorption (Γapp vs Cf) for VS-Co onto 2 masses have also been measured which are shown in Figure 12. As
(m = 5 and 10 g) of calcite for two size fractions of calcite (315−500 μm
shown in Figure 12, the blank sample (no scale inhibitor) has a
and 125−250 μm) at natural pH and T = 95 °C. Solid lines are matched
to calculate n, α, and β in eqs 1 and 2. Dashed lines are predicted using pH value of 5.89 and it decreases to pH 4.69 at 10000 ppm of
the model. Inset: Pure adsorption region. VS-Co SI. This reduction of pH is due to the acidic nature of VS-
Co scale inhibitor, that is, the pH value of VS-Co decreases as
[VS-Co] increases. So, the nature pH of solution means that the
At higher concentrations of VS-Co (Final [SI] > 3000 ppm), pH of solution has not been adjusted and it varies from 5.89 to
there was clearly a coupled adsorption/precipitation region 4.69 depending on the [VS-Co]. The results show that the final
which was confirmed by the direct observation of a precipitate pH tends to flatten out around pH ≈ 8, which is due to the
using ESEM analysis, discussed in the next section. Although calcite.33 The presence of calcite in the brine solution leads to
precipitation does occur in the VS-Co/calcite system, it is much being buffer of solution at final pH ≈ 8. Moreover, the VS-Co
lower than in the DETPMP/calcite system (Γapp ∼ 1−4 mg/g (initial pH ∼ natural pH (no pH adjustment)) like DETPMP
for VS-Co and Γapp ∼ 4−20 mg/g for DETPMP). Therefore, (initial pH ∼ adjusted pH ∼ 4) is fully compatible with NSSW
these two SI−calcite systems both show qualitatively similar without mineral in the solution. So, we conclude these two types
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Figure 14 and the corresponding EDX analysis is presented in

Table 5.

Figure 12. Comparison of pH trend for different masses of calcite

(315−500 and 125−250 μm) versus final concentration of VS-Co.

of scale inhibitors do not have incompatibility issue with

NSSW.31
Figure 13 shows the changes of normalized [Ca2+] (C/C0) in
solution before and after the experiments for both adsorption

Figure 14. Morphology of samples for (a) pure calcite, (b) 2500, (c)
1000, and (d)10 000 ppm VS-Co for 315−500 μm calcite from ESEM
photographed samples.

The results of pure calcite are similar to those reported in the

previous section for DETPMP. The results in Table 5 also
indicate that there was no S (Sulfur) signal in the pure calcite,
that is, sulfur was not observed on the surface or precipitate. As
discussed, the evidence shows coupled adsorption/precipita-
tion, as shown in Figure 11. In this region, some small amount of
sulfur on the calcite grain was detected, however, these results
cannot specify certainly whether it is related to VS-Co, because
there are two sources of sulfur, which are seawater (SO42−) and
VS-Co.
Figure 13. Normalized [Ca2+] (C/C0) vs final [VS-Co] for the size 4.2.3. Particle Size Analysis for VS-Co−Calcite. Particle size
fractions of 315−500 and 125−250 μm. analysis (PSA) has been carried out for all the VS-Co apparent
adsorption experiments using the smaller (45 mm) lens to detect
and compatibility tests for both size fractions of calcite. As smaller particles if they are present, as shown in Figure 15. Note
shown in Figure 13, the normalized [Ca2+] increased gradually that smaller particles are in the size range of 1−20 μm and are
up to ∼2.2 (normalized [Ca2+] in NSSW is 428 ppm) for the VS- only detected for the highest concentration of VS-Co (10 000
Co/calcite system. This behavior contrasts with the DETPMP/ ppm) case. For this case, these particles could be identified
calcite system, that is, the normalized [Ca2+] does not change visually in the ESEM micrographs as shown in Figure 14d. No
significantly and remains at the level of ∼1.1−1.2 (Figure 8). such particulates were observed in the pure adsorption region, as
This different behavior implies that for the VS-Co/calcite we expect.
system, the increase of [VS-Co] does indeed leach more Ca2+
from the calcite into the solution, but this is not all precipitated, 5. ANALYSIS OF KEY OBSERVATIONS
as is the case for the DETPMP/calcite system. It is well-known To understand the details and characteristics of the above
that the acidic (high dissociation constant (Ka) or low pKa) results, it is necessary to investigate the various stages of the
sulfonate groups in the VS-Co structure are very tolerant to high chemical processes which are involved. This can be approached
levels of divalent ions such as Ca2+. In contrast, the phosphonate by considering the SIs as weak polyacids of the form (HnA).45,57
groups in DETPMP bind very much more strongly to Ca2+ and The dissociation and speciation of the SI are governed by pH,
the complex formed has a lower solubility.33,56 which the inhibitor determines, although an initial pH can be set
4.2.2. ESEM/EDX Analysis for VS-Co−Calcite. Similar to experimentally, as was done here (pH0 4) for DETPMP. When
DETPMP/calcite system, all solids which were collected from the SI solution contacts the carbonate mineral substrate (calcite
the static adsorption test for the VS-Co/calcite system have been here), a chemical reaction occurs between them, generally
examined using ESEM/EDX analysis. The ESEM results for the dissolving/chelating some Ca2+ into the solution. The SI can
VS-Co/Calcite system with the size fraction of 315−500 μm for then form an SI/Ca (and SI/Mg) complex that is sparingly
pure sample, 2500, 1000, and 10 000 ppm VS-Co are shown in soluble, and this may precipitate, which also affects the final pH
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Table 5. EDX Analysis of Pure Sample, 2500, 1000, and 10000 ppm VS-Co Samples for 315−500 μm Calcite at Natural pH, T = 95
°C from ESEM
pure sample calcite grains 2500 ppm calcite grains 10 000 ppm bulk precipitate 10 000 ppm
element % weight % atomic % weight % atomic % weight % atomic % weight % atomic
N 17 22
C 15 26 19 24 27 38
Na 1 1 1 1 4 3
Mg 1 1
S 1 1
Cl 1 1 7 4
K 1 1
Ca 43 22 29 27 22 10 10 4
O 41 51 52 49 49 50 59 64

CO2 + H 2O F HCO3− + H+

HCO3− F CO32 − + H+

CaCO3 F Ca 2 + + CO32 −

H 2O F OH− + H+
A model describing this overall process is currently under
development to perform this program,58 although we could get a
good match between experimental results and the model
described above in section 3. This new model requires knowing
the pH of the solution and quantities of Ca2+ generated by rock
dissolution, for example, how much is involved in complexation
(to form SI−Can) and how much remains in solution (as free
Ca2+ or as soluble SI−Can complex).46 With this understanding
Figure 15. Particle size analysis for 5 g of 125−250 μm calcite residue in of the mechanisms involved in the carbonate/SI/Ca/Mg
different concentrations with 45 mm lens. systems, an outline of the mechanistic schematic of the coupled
processes (adsorption and precipitation) is presented for
DETPMP and VS-Co.
of the solution. Thus, the SI/carbonate system comprises the 5.1. Mechanistic Process in DETPMP/Carbonate Sys-
three parts of the equilibrium system as follows:45 tem. As shown in Figure 16, at the first stage, the calcite
(I) Dissociation of scale inhibitor as a weak polyacid: SI
dissociates like weak polyacid (HnA) to form dissociated
species, such as Hn−1A− 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+) to form
SI/Ca complexes that are barely soluble. The stoichiom-
etry, shown by parameter n here, is the ratio of Ca ions to
SI molecules. The chelation process of SI with divalent
cations, mostly Ca2+, is described as45
i2y
Ca 2 + + jjj zzzHn − 1A−i F Ca 2 +[Hn − 1A−i]2/ i
ki{ Figure 16. Schematic diagram of the mechanistic for calcite substrate,
i = 1, 2, ..., n which is dissolved in seawater.

i2y
Mg 2 + + jjj zzzHn − 1A−i F Mg 2 +[Hn − 1A−i]2/ i
substrate is dissolved in seawater and Ca2+ and CO32− are
ki{
released out of the system. Thus, the pH of solution raised from
the initial pH, in this DETPMP case pH0 4, to around 7.46 In
i = 1, 2, ..., n addition, Ca2+ is also increased. As it was mentioned, this
carbonate system is governed by the carbonate equilibrium
(III) The above reactions must be coupled to the carbonate equations.
system. That is, the CO2/bicarbonate/carbonate coupled At the second stage, the adsorption of DETPMP on the calcite
aqueous and the rock dissolution of the calcite as substrate occurs. Figure 17 illustrates the schematic diagram of
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5.2. Mechanistic Process in VS-Co/Carbonate System.

In VS-Co/carbonate system, like the DETPMP/carbonate
system, calcite is dissolved in NSSW and calcium concentration
and pH of the solution is increased due to carbonate release as
shown in Figure 16 (the first stage in carbonate equilibrium
equations).
In the presence of VS-Co, the SI dissociates and the negatively
charged species is generated. The VS-Co has been synthesized
from a 50/50% mix of vinyl sulfonate and acrylic acid
monomers. Sulfonated polymers, for example, VS-Co, are least
affected by changing of pH because an extremely low pH (e.g.,
pH < 1) is required to associate the highly acidic sulfonate
functional groups. So, the VS-Co has a higher tolerance to
chelate Ca2+ from solution (lower stability constants between
SO3H group and Ca2+ and Mg2+).56 However, it has also a
Figure 17. Schematic diagram of the mechanistic for DETPMP carboxylic acid functional group which pH has much more effect
dissociation which results in adsorption of DETPMP on calcite on its speciation than that of the sulfonic acid functional group.
substrate (at lower concentration, for example, [DETPMP] < 100 So, carboxylic acid functional group dissociates, and the negative
ppm) because of the increasing pH in seawater.
charge species is generated.61 As a result of this negative charge
species, electrostatic attraction causes the physical adsorption of
VS-Co on the calcite substrate. This mechanistic of VS-Co
the mechanistic for DETPMP adsorption on calcite. The SI dissociation and adsorption on calcite substrate is illustrated in
(DETPMP in this case) dissociates as the pH increases which is Figure 19.
due to calcite dissolution. DETPMP has five phosphonate
functional groups which are susceptible to pH and they are easily
deprotonated due to higher pKa (pKa ≈ 0.5−1.5).59 When
deprotonation (dissociation) occurs, the negatively charged
species are produced and they adsorb on the positive charge
surface of calcite through electrostatic interaction. This
retention mechanism of SI happens at low [SI] ([DETPMP]
∼ 100 ppm). It is worth to mention that DETPMP also reacts
with calcite substrate as it has acidic pH (≈4) and calcium and
bicarbonate are leached out.
At higher concentration of DETPMP ([DETPMP] > 100
ppm), Ca2+ from solution is chelated by DETPMP and the SI/
Ca complex precipitates out, that is, in other words, Ca2+ binds
with dissociated DETPMP. The schematic diagram of the
mechanistic for this process is shown in Figure 18. As Ca2+ and
DETPMP are eliminated from the solution, the final pH of
solution decreases, as shown in Figure 7. It should be noticed
that Mg2+ may be chelated by DETPMP but the solubility Figure 19. Schematic diagram of the mechanistic for VS-Co
product (Ksp) of DETMPM−Mgn is higher (more soluble) than dissociation which results in adsorption of VS-Co on calcite substrate
that of DETPMP−Can.60 (at lower concentration, e.g., [VS-Co] < 3000 ppm) in seawater.

As the concentration of VS-Co increases, the dissociated R-

COO− group chelates Calcium from the solution and the
precipitate of VS-Co/Ca2+ forms. This Schematic diagram of the
mechanistic for VS-Co precipitation is shown in Figure 20. It
should be mentioned that VS-Co forms a polyanionic species
after it dissociates as it is a polymeric scale inhibitor. Thus, it can
adsorb on the positive surface charge calcite much better than
DETPMP. This claim is confirmed by the apparent adsorption
results presented in Figures 6 and 11, that is, dominant retention
mechanism for VS-Co is pure adsorption (Γ), whereas for
DETPMP is precipitation (Π), although both (Γ/Π) mecha-
nisms were observed for both SIs.
To sum up, we can point out that the change of the Gibbs free
energy from the metastable condition to the stable (equili-
brium) condition is defined as the thermodynamic driving force,
Figure 18. Schematic diagram of the mechanistic for DETPMP that is, the system is prone to go to the state with the minimum
dissociation which results in adsorption/precipitation of DETPMP on Gibbs free energy. In terms of chemical potential, which is
calcite substrate (at higher concentration, e.g., [DETPMP] > 100 ppm) defined as molar Gibbs free energy (Gibbs free energy per mole
in seawater. of substance), a difference in chemical potential between two
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1. For the DETPMP/calcite system, a domain of pure

adsorption (Γ) is observed at lower SI concentration of
[DETPMP] ≤ 100 ppm, as well a much more extensive
region of coupled adsorption/precipitation (Γ/Π)
behavior at [DETPMP] > 100 ppm. Qualitatively similar
regions (i.e., pure Γ and coupled Γ/Π) were found for the
VS-Co/calcite system, but in this case, the pure
adsorption mechanism dominated up to [VS-CO] ≈
2000 ppm, and only above this did some smaller amount
of precipitate appear. For both SI/calcite systems, the
calcite substrate is much more reactive than say quartz or
clays since much more Ca2+ is leached into solution by the
scale inhibitor. These differences between DETPMP and
VS-Co in their behavior with calcite are due to the
different SI−Ca binding strengths of the different
functional groups present in each of these SIs.
Figure 20. Schematic diagram of the mechanistic for VS-Co
dissociation which results in adsorption/precipitation of VS-Co on
2. When different particle size ranges of calcite were used
calcite substrate (at higher concentration, e.g., [VS-Co] > 3000 ppm) in (315−500 and 125−250 μm in this work) in the apparent
seawater. adsorption experiments for each SI (DETPMP and VS-
Co), the overall behavior for each SI was broadly the
same. That is, there was no strong effect of particle size
conditions is also defined as driving force. In the scale inhibitor and the Γapp versus Cf plots were very similar. The Γapp vs
retention processes (pure adsorption and precipitation) on the Cf plots for VS-Co were rather more closely reproduced
rock surface,62 those inhibitors (DETPMP and VS-Co) have quantitatively than those of DETPMP probably because
different chemistries and hence different adsorption behavior on the latter system was much more reactive and so was a
the reservoir rocks. As mentioned above, phosphonate func- little more difficult experimentally to reproduce exactly.
tional groups in DETPMP SI are susceptible to pH and they are This indicates that it is the fundamental SI−calcite
easily deprotonated due to higher pKa. When deprotonation chemistry that governs the Γapp versus Cf behavior (i.e., the
(dissociation) occurs, the negatively charged species are regions of pure Γ and coupled Γ/Π) and not a surface
produced and they adsorb on the positive charge surface of deposition reaction (see 3 below).
calcite through electrostatic interaction. But this pure adsorption 3. The experimental finding that the particle size was not of
region is negligible somehow in the DETPMP/calcite system, as major importance in governing the Γ app versus C f
DETPMP actively reacts with calcite substrate and easily chelate behavior, indicated that a possible poisoning reaction
Ca2+ in situ produced through rock dissolution. While, in the VS- was not occurring at the calcite grain surface. This was
Co/calcite system, sulfonated functional groups are least further confirmed experimentally by carrying out ESEM/
affected by changing of pH because of an extremely low pH EDX analysis along with particle size analysis (PSA) of the
(e.g., pH < 1). So, the VS-Co has a higher tolerance to chelate calcite and the SI/Ca complex precipitates. No significant
Ca2+ from solution (lower stability constants between SO3H surface precipitation/coating of the SI/Ca complex on the
group and Ca2+ and Mg2+). Thus, the pure adsorption region is calcite was observed by ESEM. Instead, a clear SI/Ca
more extended to higher [VS-Co] in comparison with complex could be observed in ESEM for all DETPMP
[DETPMP]. It confirms that the adsorption driving force in cases for [DETPMP] ≥ 500 ppm; this was shown by EDX
VS-Co (greater difference in chemical potential) is higher than to contain a significant amount of phosphorus (P) and Ca
in DETPMP. and particle size analysis showed that it consisted of a
much finer particulate precipitate with size ∼1−20 μm.
6. SUMMARY AND CONCLUSIONS Likewise, a precipitate of VS-Co/Ca was also observed
The “apparent adsorption” behavior (Γapp vs Cf) of two common but only for high concentrations of [VS-Co] ≈ 10 000
commercially available scale inhibitors (SI = DETPMP and VS- ppm in which sulfur (S) was detected, although this S
Co) on the carbonate mineral substrate, calcite, has been could be from the seawater (sulfate) or the sulfonate
studied. This extends earlier work by including calcium groups in the VS-Co polymer. We note that no finer
carbonate (calcite) mineral substrate which is much more precipitate was observed for either SI (DETPMP or VS-
chemically reactive than sandstone minerals which we have Co) in the pure adsorption region of the Γapp versus Cf
studied in previous work (e.g., quartz, siderite, and clays).23,33 A curves.
systematic study has been carried out of the effects of particle 4. All of the Γapp versus Cf, experimental results were
size of the calcite to test between two possible effects of the modeled using a model developed and published some
reaction of the SI with the calcite surface, namely, does the time ago.21 Apparent adsorption plots were constructed
interaction occurs by (i) forming a coating on the calcite grain for various values of (m/V) ratio; m = mass of calcite
which “poisons” the continuing reaction or (ii) is it simple substrate and V = scale inhibitor solution fluid volume. If
dominated by the bulk chemistry. In addition to the direct these plots coincide for different (m/V) ratios over a
measurement of the (Γapp vs Cf) curves, ancillary measurement range of final SI concentration values, then this indicates
of final pH and solution [Ca2+] are also presented, along with pure adsorption (Γ). Alternatively, if the Γapp curves
corresponding detailed ESEM/EDX and particle size analysis diverge for different (m/V) ratios, then this shows that
(PSA) of the calcite/precipitated complex. coupled adsorption/precipitation (Γ/Π) is occurring.
The specific conclusions from this work are as follows: The procedure in applying this model involves matching
1788 https://doi.org/10.1021/acs.energyfuels.1c02691
Energy Fuels 2022, 36, 1776−1791
Energy & Fuels pubs.acs.org/EF Article

the Γapp versus Cf curve for a given (m/V) value (the m = 5 Moieties As Green Oilfield Scale Inhibitors. Ind. Eng. Chem. Res. 2021,
g case in this work) and then predicting the results for the 60, 8331.
other (m/V) ration (m = 10 g here). If both the match and (5) Dietzsch, M.; Barz, M.; Schüler, T.; Klassen, S.; Schreiber, M.;
Susewind, M.; Loges, N.; Lang, M.; Hellmann, N.; Fritz, M.; Fischer, K.;
prediction agree well with the experimental data, then our
Theato, P.; Kühnle, A.; Schmidt, M.; Zentel, R.; Tremel, W. PAA-
analysis of the retention mechanism (pure Γ, or coupled PAMPS Copolymers as an Efficient Tool to Control CaCO3 Scale
Γ/Π) is certainly correct both qualitatively and Formation. Langmuir 2013, 29 (9), 3080−3088.
quantitatively. Very good agreement between the model (6) Mirzaalian Dastjerdi, A.; Kargozarfard, Z.; Najafi, B.; Taghikhani,
and the experimental results was observed for both the V.; Ayatollahi, S. A Microscopic Insight into Kinetics of Inorganic Scale
DETPMP/calcite and the VS-Co/calcite systems. Thus, Deposition during Smart Water Injection Using Dynamic Quartz
the model can capture the main features of coupled Crystal Microbalance and Molecular Dynamics Simulation. Ind. Eng.
adsorption/precipitation in a reactive system such as in Chem. Res. 2020, 59, 609.
the SI/calcite cases for both DETPMP and VS-Co. (7) Chao, Y.; Horner, O.; Vallée, P.; Meneau, F.; Alos-Ramos, O.; Hui,

■
F.; Turmine, M.; Perrot, H.; Lédion, J. In Situ Probing Calcium
Carbonate Formation by Combining Fast Controlled Precipitation
AUTHOR INFORMATION Method and Small-Angle X-Ray Scattering. Langmuir 2014, 30 (12),
Corresponding Author 3303−3309.
Khosro Jarrahian − Flow Assurance and Scale Team (FAST), (8) Hasson, D.; Shemer, H.; Sher, A. State of the Art of Friendly
Institute of GeoEnergy Engineering (IGE), Heriot-Watt “Green” Scale Control Inhibitors: A Review Article. Ind. Eng. Chem. Res.
University, Edinburgh EH14 4AS, U.K.; orcid.org/0000- 2011, 50 (12), 7601−7607.
(9) Baraka-Lokmane, S.; Sorbie, K. S. Effect of PH and Scale Inhibitor
0001-7933-7607; Phone: +44 (0) 131 451 4583; Concentration on Phosphonate−Carbonate Interaction. J. Pet. Sci. Eng.
Email: [email protected] 2010, 70 (1−2), 10−27.
(10) Khormali, A.; Petrakov, D. G.; Nazari Moghaddam, R. Study of
Authors
Adsorption/Desorption Properties of a New Scale Inhibitor Package to
Morteza Aminnaji − Department of Chemical Engineering and Prevent Calcium Carbonate Formation during Water Injection in Oil
Analytical Science, The University of Manchester, Manchester Reservoirs. J. Pet. Sci. Eng. 2017, 153, 257−267.
M1 3AL, U.K.; orcid.org/0000-0002-5837-1336 (11) Liu, C.; Zeng, X.; Yan, C.; Zhou, C.; Li, M.; Wang, Z. Effects of
Alexander Graham − Flow Assurance and Scale Team (FAST), Solid Precipitation and Surface Corrosion on the Adhesion Strengths of
Institute of GeoEnergy Engineering (IGE), Heriot-Watt Sintered Hydrate Deposits on Pipe Walls. Langmuir 2020, 36, 15343.
University, Edinburgh EH14 4AS, U.K. (12) Heath, S. M.; Juliussen, B.; Chen, P.; Chen, T.; Benvie, R. Novel
Kenneth Sorbie − Flow Assurance and Scale Team (FAST), Scale Squeeze Technology and Treatment Designs for Improving Scale
Institute of GeoEnergy Engineering (IGE), Heriot-Watt Inhibitor Retention and Treatment Lifetimes-Use of Ionic Polymers in
University, Edinburgh EH14 4AS, U.K. the Overflush. In SPE International Conference on Oilfield Scale; Society
of Petroleum Engineers, 2012.
Complete contact information is available at: (13) Jordan, M. M.; Mackay, E. J.; Vazquez, O. The Influence Of
https://pubs.acs.org/10.1021/acs.energyfuels.1c02691 Overflush Fluid Type On Scale Squeeze Life Time-Field Examples And
Placement Simulation Evaluation. In CORROSION 2008; NACE
Notes International, 2008.
The authors declare no competing financial interest. (14) Zhang, P.; Liu, Y.; Kan, A. T.; Tomson, M. B. Laboratory

■
Evaluation of Synergistic Effect of Transition Metals with Mineral Scale
ACKNOWLEDGMENTS Inhibitor in Controlling Halite Scale Deposition. J. Pet. Sci. Eng. 2019,
175, 120−128.
The following are thanked for their support of the FAST 6 Joint (15) Zhang, P.; Liu, Y.; Zhang, N.; Ip, W. F.; Kan, A. T.; Tomson, M.
Industry Project at Heriot-Watt University: Halliburton Multi- B. A Novel Attach-and-Release Mineral Scale Control Strategy:
Chem, Nalco Champion, Petronas, Repsol Sinopec, Schlum- Laboratory Investigation of Retention and Release of Scale Inhibitor
berger MI Swaco, Shell, Statoil, Total, and Wintershall. We also on Pipe Surface. J. Ind. Eng. Chem. 2019, 70, 462−471.
appreciate the Institute of GeoEnergy Engineering, Heriot-Watt (16) Yan, F.; Zhang, F.; Bhandari, N.; Wang, L.; Dai, Z.; Zhang, Z.;
University for support with the ESEM/EDX facility, and our Liu, Y.; Ruan, G.; Kan, A.; Tomson, M. Adsorption and Precipitation of
colleague Wendy McEwan in the FAST Analytical Team at Scale Inhibitors on Shale Formations. J. Pet. Sci. Eng. 2015, 136, 32−40.
Heriot-Watt University for conducting the ICP-OES analysis. (17) Pairat, R.; Sumeath, C.; Browning, F. H.; Fogler, H. S.
Precipitation and Dissolution of Calcium− ATMP Precipitates for
Finally, Italmatch and Nalco Champion Companies are
the Inhibition of Scale Formation in Porous Media. Langmuir 1997, 13
gratefully acknowledged for providing the DETPMP and VS- (6), 1791−1798.
Co scale inhibitors, respectively.

■
(18) Jarrahian, K.; Sorbie, K. S. Mechanistic Investigation of
Adsorption Behaviour of Two Scale Inhibitors on Carbonate
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