Sie sind auf Seite 1von 18

Journal of Petroleum Science and Engineering 70 (2010) 10–27

Contents lists available at ScienceDirect

Journal of Petroleum Science and Engineering


j o u r n a l h o m e p a g e : w w w. e l s ev i e r. c o m / l o c a t e / p e t r o l

Effect of pH and scale inhibitor concentration on phosphonate–carbonate interaction


S. Baraka-Lokmane ⁎, K.S. Sorbie
Department of Petroleum Engineering, Heriot-Watt University, Edinburgh EH14 4AS, Scotland, United Kingdom

a r t i c l e i n f o a b s t r a c t

Article history: In this paper, we present results from five corefloods (RC1 to RC5) from the Jurassic Portlandian limestone
Received 5 July 2007 (ф ~ 19.80% and k = 606 mD) using 5000 ppm, 10,000 ppm, 25,000 ppm and 27,000 ppm of partly neutralized
Accepted 14 May 2009 Diethylenetriamine pentamethylenephosphoric acid (DETPMP) at pH 4 and 2. The purpose of this study was
to study the effect of inhibitor concentration and pH on the inhibitor adsorption and on the evolution of the
Keywords:
inhibitor and cation (calcium and magnesium) return concentrations. These corefloods were performed
carbonate rock
scale inhibitor
using long cores (12 in.), which were treated with just 0.5 pore volume (PV) of inhibitor. Another purpose
phosphonate was to study the transport and inhibitor/carbonate rock interactions when less than 1 PV of inhibitor solution
calcium dissolution is injected. This allows for consumption of the inhibitor during propagation and return, rather than saturating
corefloods the core with many PV to full adsorptive capacity of the inhibitor/rock system. This study showed that the
higher the concentration of SI and lower the pH, the more calcium dissolution is observed (from the [Ca2+]
effluents). In all treatments there is a decrease in the [Mg2+] effluent corresponding directly to the increase
in calcium. The effluent cation results in the long corefloods which strongly support the view that both
magnesium and calcium are binding quite strongly to the DETPMP scale inhibitor. These observations lead us
to a number of conclusions on the factors that must be included in a full carbonate model. In particular, our
experimental results, along with some simple modeling, greatly clarify the role of both calcium and
magnesium in the mechanism of the scale inhibitor retention in carbonate systems.
© 2009 Published by Elsevier B.V.

1. Introduction Adsorption is often the primary mechanism of SI retention during


squeeze treatments of sandstone formations. The scale inhibitor
A common problem, in oilfield reservoirs is scale deposition. Scale retention mechanism can be more complex than simple adsorption
is an assemblage of deposits that can develop in the formation pores within carbonate reservoirs because the carbonate rock is a much
near the wellbore reducing formation porosity and permeability. It can more reactive substrate. In carbonate formations, scale inhibitors are
block flow by clogging perforations or forming a thick lining in deliberately allowed to react with the formation and precipitate as the
production tubing (Fig. 1). The build-up of scale inside well bores and slightly soluble calcium salt. This can result in longer scale protection
the surrounding reservoir causes millions of dollars in damage every times. Even fully neutralized inhibitors react with carbonates to form
year (Mackay et al., 2003). Oilfield scales are inorganic crystalline precipitates (Crowe et al., 1994).
deposits that form as a result of the precipitation of solids from brines Reactions that govern the inhibitor squeeze and return are very
present in the reservoir and production flow system. This scale complicated. Several factors, such as pH, [Ca2+], [Mg2+], temperature,
formation is the result of changes in the ionic composition, pH, rock mineralogy etc, affect the adsorption level and the shape of the
pressure and temperature of the brine. Common scales are calcium adsorption isotherm (Jordan et al., 1994; Baraka-Lokmane and Sorbie,
carbonate (CaCO3) and barium sulphate (BaSO4). When the formation 2004, 2006).
of sulphate or carbonate scale is a problem in producer wells, the most The Rice University Brine Chemistry Consortium has carried out a
common remedy is to treat the formation with scale inhibitor large number of studies on the scale inhibitor retention in carbonate-
chemicals in a “squeeze” treatment (Fig. 2) (Crowe et al., 1994; Norris rich formations during squeeze treatments (Kan et al., 1992, 2004a,b,
et al., 2001). Phosphonates are one of the most common types of non- Tomson et al., 2004; Kan et al., 2005). From these “batch” studies,
polymeric scale inhibitors, which are used commercially in oilfield some of their conclusions were:
operations. The phosphonate scale inhibitor Diethylenetriamine
pentamethylenephosphoric acid (DETPMP) is known to be amongst (1) calcite is the primary solid responsible for phosphonate retention
the strongest adsorbing scale inhibitor onto carbonate. and clay plays a secondary role in phosphonate retention;
(2) although formation mineralogy can be a factor, the primary
⁎ Corresponding author. Tel.: +44 131 451 3189; fax: +44 131 451 3539. control of inhibitor retention and return is the pill acidity and
E-mail address: salima.lokmane@pet.hw.ac.uk (S. Baraka-Lokmane). concentration; and

0920-4105/$ – see front matter © 2009 Published by Elsevier B.V.


doi:10.1016/j.petrol.2009.05.002
S. Baraka-Lokmane, K.S. Sorbie / Journal of Petroleum Science and Engineering 70 (2010) 10–27 11

Fig. 1. The build-up of scale inside a tube. Fig. 3. AFM image of the coreflood RC4 showing the morphology of the rock surface.

(3) salt forms at higher pill concentration. This is due to the calcite because they are particularly sensitive to post-depositional diagenesis,
surface poisoning that lowers the pH of phosphonate–calcite including dissolution, dolomitization and fracturing processes. Carbo-
reaction. nate mineralogy is usually simple — principal minerals are calcite,
dolomite, and minor quantities of clay (Choquette and Pray, 1970;
The current study carries over some of this work into the realm of Roehl and Choquette, 1985).
dynamic corefloods and we compare our conclusions with those of the In order to carry out a systematic study in well-characterized
Rice U. group. The purpose of this work is to study the mechanisms and carbonate cores, a permeable carbonate rock material has been sourced.
the factors that affect the retention of the phosphonate scale inhibitor Sample material was acquired from the Albion Stone Quarries Ltd, Isle of
DETPMP in carbonate formations. We present coreflooding results using Portland. This rock originates from the Portland Basebed stone and is an
DETPMP to study the effect of inhibitor concentration and pH on open textured oolitic limestone from the Jurassic Portlandian Formation.
inhibitor adsorption and on the behaviour of the inhibitor and cation The b3.5 m thick Basebed is the lower part of the Freestone series, which
(calcium and magnesium) concentration. “Contained” corefloods were comprises the Portland Roach, Portland Whitbed and Portland Basebed
performed to study the transport and inhibitor/carbonate interactions of Formations and is underlain by a cherty series.
the phosphonate inhibitor when less than 1 PV is injected. This allows In this study, five methods were used to characterize the rock
the analysis of the consumption of the inhibitor during propagation and material: X-ray diffraction (XRD), petrographic thin section, atomic force
desorption, rather than saturating the core with many PV of SI solution microscopy (AFM), scanning electron microscopy (SEM) and energy
to reach full adsorptive capacity of the inhibitor/rock system. dispersive X-ray (EDX). XRD analysis was carried out both on whole rock
and on the fine particle fractions. The results of the bulk rock XRD
2. Mineralogy of carbonate rock material analysis show that the rock material is composed mainly of pure calcite
(98 to 99.9%). Quartz constitutes between 2 and ~0.1% of the rock.
Carbonate rocks contain more than 50% of the world's hydrocarbon Analysis of the fines showed that no clay minerals are present. Figs. 3
reserves. The carbonate reservoirs have complex pore systems, mainly and 4 characterize the morphology of the rock surface showing the
calcite crystals and the shell fragments. The petrography analysis shows
that the rock material is a pure porous marine oolitic limestone

Fig. 4. AFM image of the coreflood RC4 showing the calcite crystals and the shell
Fig. 2. Squeeze treatment of producer well. fragments.
12 S. Baraka-Lokmane, K.S. Sorbie / Journal of Petroleum Science and Engineering 70 (2010) 10–27

composed of fine-grained remains of microorganisms with calcite shells,


ooids (Fig. 5) with micrite and sparite calcite cement (Fig. 6). The rock
presents a fine, dark matrix of micrite (microcrystalline calcite), which is
also present as cement in the pore space. It forms a regular coating
around grains and appears as a dark line in thin sections. The thin
sections show the presence of 3 major types of porosity: a high
intergranular porosity (Fig. 5), a moldic, secondary porosity, created by
dissolution of the carbonate shell fragments later in the diagenetic
history of the limestone (Fig. 6) and a high microporosity which occurs
between the micritic matrix of the sample (Fig. 5). The petrophysical
measurements of the rock material show that the limestone has porosity
(by helium porosimeter), Φ~ 19.80%, grain density, ρ = 2.61 g/cm3 and
permeability, k ~ 606 mD.

3. The squeeze strategy

In squeeze treatments, the objective is to retain the maximum Fig. 6. SEM photo showing cement containing micrite and sparite crystals, around the
amount of inhibitor in the formation either by ooid grains (M: micrite, C: calcite, O: ooid).

(1) adsorption on the rock substrate by a physico chemical process


or (4) Shut-in: the well will then be shut in for a specified period
(2) precipitation (or phase separation) in a controlled manner, at (usually for 6 to 24 h) in order to allow the inhibitor to interact
some distance from the near wellbore area. This is generally with the rock substrate.
achieved by adjusting the injected solution chemistry ([Ca2+] (5) Back production: the well is then put onto back production and
concentration, pH, temperature etc.). the inhibitor is then expected to return to the wellbore at a
concentration above the threshold level, minimal inhibitor
Following the treatment, the inhibitor slow release from the rock concentration (MIC), for a long period of time (squeeze lifetime).
will be governed by the inhibitor adsorption or retention process,
which is specific to the particular inhibitor, the rock matrix and the The success of the treatment, or the squeeze lifetime, can be
brine chemistry of interest (Crowe et al., 1994; Graham and Mackay, monitored either by analyzing the inhibitor concentration or by
2000; Jordan and Sjursaether, 2004). assaying the scaling ions in the return brine. As soon as the scale
In the field, the procedure for applying such a chemical treatment inhibitor return concentration falls below the minimum inhibitor
to an oil or gas producing well normally involves the following five concentration (MIC) that prevents the scale formation, the squeeze is
stages (Fig. 2): considered to be over and retreatment is recommended.
Successive squeeze treatments can be optimized either from an
(1) Preflush: a pre-flush package which generally consists of a very examination of the actual treated field return data or from a modelling
dilute solution mostly in seawater of the inhibitor eventually of the lab coreflood inhibitor return data performed under simulated
mixed with a surfactant, is injected into the well. This both field conditions. This is achieved by use of the industry standard,
cools the near wellbore formation and “prepares” the rock Squeeze VI software, developed by Heriot-Watt University, to enable
surface. to derive an adsorption isotherm from the scale inhibitor effluent
(2) Inhibitor injection: the main inhibitor slug, also dissolved in results either from the field or from the lab coreflood data. The shape
seawater, is squeezed into the near wellbore area. of the inhibitor adsorption isotherm, Г, describes the relationship
(3) Overflush: the main inhibitor slug is displaced to the required between the level of inhibitor adsorption at the rock surface (in mg/g)
distance from the wellbore by injecting seawater into the well. and the injected scale inhibitor solution. Once the scale inhibitor/rock
adsorption isotherm has been derived for the mineralogy, tempera-
ture and pressure conditions present in the specific reservoir, it may
then be used to optimize the design of the squeeze treatment for the
reservoir formation.

4. Dynamic corefloods experiments

Coreflood experiments in the laboratory are designed to simulate


the reservoir squeeze treatment. These tests are a vital tool in
understanding the mechanisms controlling scale inhibitor/rock inter-
action since: they allow complete temperature and pressure control,
they enable to determine the complete mineralogical petrophysical
characteristics of the rock, and with them it is possible to perform post-
scale inhibitor treatment petrography to quantify the magnitude of
retained scale inhibitor and its mineralogical structure and location.
The main steps in the corefloods broadly follow the field inhibitor
treatment stages and are as follows:

Fig. 5. General texture of the oolitic limestone, showing the elongated and rounded (1) seawater saturation, permeability measurement and core
ooids, which are formed from micrite resulting the rough surfaces of the ooid grains.
Note that blue epoxy resin is used to fill pore space (C: calcite, M: micrite, O: ooid). (For
characterization;
interpretation of the references to colour in this figure legend, the reader is referred to (2) injection of the main scale inhibitor slug (containing a lithium
the web version of this article.) tracer) followed by a shut-in of 24 h; and
S. Baraka-Lokmane, K.S. Sorbie / Journal of Petroleum Science and Engineering 70 (2010) 10–27 13

system. This was felt to be a more appropriate type of flood to use for
developing reactive transport models for SI/carbonate systems.
The composition of the synthetic seawater used for the coreflood
tests is presented in Table 1. The scale inhibitor (SI) used for the
corefloods RC1, RC2, RC3, RC4 and RC5 was a generic Diethylenetriamine
pentamethylenephosphoric acid (DETPMP). The partly neutralized
DETPMP was dosed with lithium tracer, in a ratio of 1:100. The scale
inhibitor solutions were filtered through a 0.45 µm membrane filter
prior to use.
The effluent samples were analyzed for the cation concentrations,
[Ca2+], [Mg2+], [Fe2+/3+], and also for [Li+], by inductively coupled
plasma (ICP). The DETPMP concentration was also determined by ICP
based upon the phosphorus content. The desired dilutions were
prepared using a Microprocessor-controlled dilutor (Gilson Dilutor
401). For the calibration, matrix matched standards were used to
suppress the interferences of the brine solution.
Fig. 7. Coreflood equipment for corefloods RC1 to RC5.

5. Permeabilities measurements

(3) seawater postflush or back production until the inhibitor Pressure drops (ΔP) between inlet and outlet of the cores were
concentration drops below 0.5 ppm (estimated MIC level). monitored throughout all of the experiments. Variable flow rate vs. ΔP
(4) Permeability measurement to check if the treatment has caused measurements were performed to determine the pre- and post-flood
any damage in the reservoir properties and a detailed petro- permeabilities. Table 2 shows the calculated values of permeability for
graphy analysis is carried out. the pre- and post-treatment stages.
In corefloods RC1, RC2, RC3, RC4 and RC5, before the scale inhibitor
The coreflooding procedures adopted in this study are designed to treatment, the permeabilities were equal to 596 mD, 606 mD, 602 mD,
study the inhibitor retention and return characteristics in a single phase 609 mD and 600 mD respectively. After the SI treatment an increase of
flow. The corefloods were conducted using a bench top assembly with a 20% (k = 718 mD), 50% (k = 909 mD), 65% (k = 992 mD), 58%
resin-coated outcrop carbonate core (Figs. 7 and 8). The line pressure for (k = 960 mD) and 63% (k = 975 mD) were observed respectively for
these floods was approximately equal to 20 psi. The corefloods were the floods RC1, RC2, RC3, RC4 and RC5. Table 2 shows that we observe
conducted at room temperature. The full experimental procedure for an increase in permeability as the concentration of the SI increases
corefloods RC1 to RC5 is outlined in Appendix A. and the pH of the SI decreases.
These floods were performed in long cores (12q length and 1q
diameter). The purpose of these corefloods is to study the transport of
the scale inhibitor (SI) solution and the SI/carbonate interactions, by 6. Inhibitor analysis
injecting less than 1 PV of SI into these cores. In fact, 0.5 PV of
5000 ppm (RC1 and RC4), 10,000 ppm (RC2), 25,000 ppm (RC3) and 0.5 PV of 5000 ppm, 10,000 ppm, 25,000 ppm and 27,000 ppm of
27,000 ppm (RC5) seawater solutions of partly neutralized DETPMP at partly neutralized DETPMP at pH 4 (RC1, RC2 and RC5) and at pH 2
pH 4 (RC1, RC2 and RC5) and at pH 2 (RC3 and RC4) were injected into (RC3 and RC4) were injected into the core but all other fluids
the respective cores but all other fluids (postflush seawater, and (postflush seawater and lithium tracer solution) were at pH 6. After SI
lithium tracer solution) were at pH 6. After SI injection through the injection from the inlet end of the core, the flow was reversed and the
inlet end of the core, the flow was reversed and the postflush was postflush was injected at the former outlet of the core with the SI
injected through the former outlet of the core with the SI being being produced from the former inlet (Fig. 9). These experiments are
produced from the former inlet (Fig. 9). This allows the evaluation of designed in order to check what is the most important factor that
the SI slug during propagation and return, rather than saturating the improves the SI adsorption, is it the high concentration of the SI or the
core with many PV to reach full adsorptive capacity of the SI/rock low pH value of the SI.

Fig. 8. Schematic diagram of the experimental set up for the resin-coated coreflooding experiments, corefloods RC1 to RC5.
14 S. Baraka-Lokmane, K.S. Sorbie / Journal of Petroleum Science and Engineering 70 (2010) 10–27

Fig. 9. Experimental procedure for the 12 inch long carbonate core (RC1).

6.1. Injection and initial postflush 6.2. Seawater postflush

Fig. 10 shows the back production with seawater at pH 6, i.e. Figs. 11 and 12 present the early (~ 100 PV) and late (~ 1800 PV)
reversed flow after the 0.5 PV SI slug injection in cores RC1 and RC2, postflush SI return profiles, for corefloods RC1 to RC5. As expected, the
followed by a shut-in period. The SI effluent profiles show an initial SI return concentrations are low and they also drop more
immediate spike in SI concentration, and then a gradual decrease in rapidly for these floods since only 0.5 PV of SI solution have been
it. In these floods, the scale inhibitor adsorption can be visualized from injected. In the early post flush, the floods RC3 and RC5 presents the
the retardation between scale inhibitor and the lithium tracer effluent highest SI returns since the corefloods have been performed with the
concentrations. In floods RC1 and RC2, the lithium effluent also shows highest DETPMP concentration i.e. 25,000 ppm active DETPMP at pH 2
a similar initial spike mirroring the SI one (they are mixed), followed and 27,000 ppm active DETPMP at pH 4, respectively. Floods RC1, RC2,
by a drop to a concentration ratio (C/Co) ~ 0.17 and 0.38 (respectively) RC3, RC4 and RC5, treated with 5000 ppm at pH 4, 10,000 ppm at pH 4,
and then a sudden rise as the injected lithium tracer from the 25,000 ppm at pH 2, 5000 ppm at pH 2, and 27,000 ppm active
seawater post flush breaks through in the reverse flow as shown in DETPMP at pH 4, respectively show lower [SI] returns. Thus after 10 PV
Fig. 10. It is clear from the RC1 and RC2 tracer results in Fig. 10 that of postflush for flood RC3 SI return concentration is ~ 780 ppm,
there is quite a high level of mixing (dispersion) in the core since the ~697 ppm for flood RC5, ~287 ppm for flood RC2, ~ 163 ppm for flood
postflush (injected at the outlet end) “catches” the leading edge of the RC4 and ~ 69 ppm for flood RC1.
tracer injected from the inlet with the SI slug. Likewise, it is evident Fig. 12 shows that the [SI] return concentration reaches a value of
that there is some level of SI adsorption since there is a long low [SI] 1 ppm after ~ 300 PV for floods RC1, RC2 and RC4, after 355 PV for flood
tail concentration with [SI] N 1 ppm for ~ 300 PV. RC3 and after 596 PV for flood RC5. The 0.70 ppm return concentration
is reached after 400PV for floods RC1 to RC4 and after 691PV for flood

Table 1 Table 2
The composition of brine solution used for the tests. Brine permeability values before and after the scale inhibitor treatment.

Component Concentration Ion Concentration Coreflood SI pH of the Permeability Permeability Increase in


(g/l) (ppm) concentration injected (k) (mD) (k) (mD) permeability
NaCl 24.08 Sodium (Na+) 10,890 (ppm) SI solution Pre-treatment Post-treatment (%)
CaCl2.2H2O 2.34 Calcium (Ca2+) 428 RC1 5000 4 596 718 20
MgCl2.6H2O 11.44 Magnesium (Mg2+) 1368 RC2 10,000 4 606 909 50
KCl 0.877 Potassium (K+) 460 RC3 25,000 2 602 992 65
NaSO4 4.38 Sulphate (SO2−
4 ) 2960 RC4 5000 2 609 960 58
Chloride (Cl−) 19,773 RC5 27,000 4 600 975 63
S. Baraka-Lokmane, K.S. Sorbie / Journal of Petroleum Science and Engineering 70 (2010) 10–27 15

Fig. 10. Normalised (C/Co) inhibitor and lithium concentration profiles obtained during initial adsorption and postflush stages, floods RC1 and RC2.

Fig. 11. Inhibitor return profiles, early postflush (− 0.40–N100 PV), Dequest 2066 (DETPMP) Aqueous for flood RC1 to RC5.

RC5. Finally the 0.5 ppm return concentration (MIC) is reached after calcium concentrations are observed, which correspond at the same
~ 700PV for all five corefloods. time with a dip in the magnesium concentration. This is an important
observation and has been explained by the binding of the magnesium
7. Cation analysis — calcium and magnesium and the calcium to the DETPMP (Baraka-Lokmane and Sorbie, 2006).
effluent concentrations During the injection of the SI, we observe a loss in magnesium
concentration, because the magnesium is adsorbed together with the
Fig. 13 presents the [Ca2+], [Mg2+], [Li+] and [SI] concentration SI. After the shut-in, we observe a spike in the magnesium concentration
profiles during the main treatment and the early postflush stages for because it is released by the rock together with the SI during the
coreflood RC5. In this figure, very distinct spikes in SI, lithium and postflush.

Fig. 12. Inhibitor return profiles, late postflush (100–N 1800 PV), Dequest 2066 (DETPMP) Aqueous [SI] = 9–N 0.40 ppm, floods RC1 to RC5.
16 S. Baraka-Lokmane, K.S. Sorbie / Journal of Petroleum Science and Engineering 70 (2010) 10–27

Fig. 13. Normalised (C/Co) inhibitor, lithium and recorded calcium, magnesium concentration profiles obtained during initial adsorption and postflush stages, flood RC5.

During the postflush, two effects influence the effluent calcium and 15 respectively. Clearly, the levels of both Ca and Mg concentra-
concentration, some calcium remains bound to the DETPMP but, in tions correlate with that of the [SI], with a larger effect being seen both
addition carbonate rock dissolution also occurs and this phenomenon at high SI concentration and at a lower injection pH. This effect will be
is predominant. This explains the increase in calcium concentration in discussed and also modelled in more detail below.
the effluents. Calculations of the amount of dissolution of calcium carbonate
A direct comparison of the evolution of the [Ca2+] and [Mg2+] from the rock matrix were carried out. Table 3 shows SI adsorption,
effluent concentrations for the five corefloods is shown in Figs. 14 calcium carbonate dissolution and gain in magnesium during the

Fig. 14. Recorded calcium concentration profiles obtained during adsorption and postflush stages, floods RC1 to RC5.

Fig. 15. Recorded magnesium concentration profiles obtained during adsorption and postflush stages, floods RC1 to RC5.
S. Baraka-Lokmane, K.S. Sorbie / Journal of Petroleum Science and Engineering 70 (2010) 10–27 17

Table 3 Table 5
Scale inhibitor adsorption, calcium carbonate (dissolution) and magnesium (gain) Percentages of SI retained by the rock.
during the main treatment and postflush stages for floods RC1 to RC5.
Coreflood % SI retained % SI retained
Coreflood Inhibitor CaCO3 dissolution Mg gain Modelling Mass balance (experiment)
adsorption (mg) (mg)
RC1 10.6 15.9
(mg/g)
RC2 6.8 4.8
MTa PFb MT PF
RC3 2.4 3.6
RC1 (SI, pH = 4 0.073 0.93 (0.003) 211.24 (0.70) 1.53 14.14 RC4 13.1 14.7
Li solution, pH = 6) RC5 4.1 2.4
RC2 (SI, pH = 4 0.075 1.27 (0.004) 248.59 (0.82) 2.07 182.34
Li solution, pH = 6)
RC3 (SI, pH = 2 0.087 1.49 (0.005) 481.23 (1.59) 2.31 198.65
Li solution, pH = 6)
RC4 (SI, pH = 2 0.080 1.15 (0.004) 420.04 (1.38) 0.82 117.33
97.60%, thus the percentage of scale inhibitor retained in the rock
Li solution, pH = 6) varies between 2.40% and 15.21%.
RC5 (SI, pH = 4 0.084 1.17 (0.004) 475.19 (1.57) 1.16 168.71
Li solution, pH = 6) 8. pH values
The values in brackets are in mg/g.
a
MT = main treatment. The effluent pH profiles for all five corefloods RC1 to RC5 are shown
b
PF = postflush. over the entire main treatment and postflush periods in Fig. 16. SI
injection is performed at pH = 4 for corefloods RC1, RC2 and RC5 and
at pH = 2 for corefloods RC3 and RC4. In all these floods, a sharp rise in
pH just after the shut-in can be observed and then the pH values
main treatment and the postflush stages, calculated using mass
stabilize at ~pH 7 until the end of the post flush. Fig. 17 shows also two
balance.
profiles of the effluent pH values for coreflood RC4: a first profile
Fig. 14 shows that for the different corefloods we observe first a
presenting pH values in the same order as for floods RC1 to RC5
spike in calcium concentration: 693 ppm (RC1), 754 ppm (RC2),
(varying between 6.7 and 8.4), and a second profile with much lower
1213 ppm (RC3), 1106 ppm (RC4) and 1261 ppm (RC5). Then the
pH values varying between 2.50 and 4.30. The lower pH values were
calcium levels drop to 412 ppm (RC1), 407 ppm (RC2), 457 ppm (RC3),
those measured immediately after elution from the core. The higher
449 ppm (RC4) and 441 ppm (RC5) and remain finally more or less
pH values were measured when the collected effluent samples had
constant until the end of the coreflood.
been protected with test tubes lids and left standing for some time
Fig. 14 and Table 3 show that coreflood RC4 (5000 ppm SI at pH 2)
after elution. For these latter samples, CO2 has escaped from the
presents a higher total calcium concentration in the effluents (ca.
effluents, thus explaining the observed high pH values.
421.19 mg or 1.38 mg/g vs. ca. 212.17 mg or 0.70 mg/g) than coreflood
Fig. 17 shows that the high pH values have been modelled with
RC1 (5000 ppm SI at pH 4). The lower pH of the injected SI solution in
MultiScale software (Table 6 and Fig. 18) (mineral scale prediction
coreflood RC4 is thus responsible for the high calcium dissolution.
software by Petrotech, Haugesund, Norway), and the low pH values
Fig. 14 and Table 3 show also that coreflood RC5 (27,000 ppm SI at
have been modelled with PHREEQC modeling (Tables 7 and 8,
pH 4) presents comparable levels of calcium elution (ca. 476.36 mg or
simulations 1 to 5) (geochemical modelling program developed by
1.57 mg/g vs. ca. 482.72 mg or 1.59 mg/g) than flood RC3 (25,000 ppm
Appelo and Gerba in 1993 for the U.S. Geological Survey).
SI at pH 2). These results show that the slightly higher SI
concentration for coreflood RC5 (27,000 ppm DETPMP) has compen-
9. Modelling of pH prediction, SI returns and Ca/Mg/SI interaction
sated the lower pH value (pH = 2) of coreflood RC3. Coreflood RC3
(25,000 ppm SI at pH 2) presents a higher calcium elution (ca.
In this study, we have carried out three types of modelling:
482.72 mg or 1.59 mg/g vs. ca. 421.19 mg or 1.38 mg/g) than coreflood
RC4 (5000 ppm SI at pH 2) thus pointing to the effect of increased SI (1) the prediction of pH evolution has been performed first with
injected concentration on the calcium release from the rock. This is the help of two softwares: MultiScale and PHREEQC;
also valid for the corefloods performed at pH 4, ca. 476.36 mg or (2) secondly we investigated whether we can reproduce the SI
1.57 mg/g for coreflood RC5 (27,000 ppm SI), ca. 249.86 mg or return concentration profiles using a simple adsorption
0.82 mg/g for coreflood RC2 (10,000 ppm SI at pH 4) and ca. 212.17 mg isotherm approach.; and
or 0.70 mg/g for coreflood RC1 5000 ppm SI). (3) finally, the behaviour of the Ca and Mg concentration in the core
Table 4 shows that all five corefloods show a very small SI eluents has been explained by a simple equilibrium SI–Mg2+
adsorption level, Γ ~ 0.073 mg/g (RC1), ~ 0.075 mg/g (RC2), ~ 0.087 mg/ binding model.
g (RC3), ~0.080 mg/g (RC4) and ~0.084 mg/g (RC5) respectively.
These values are roughly estimations as the cores have been treated
9.1. pH prediction
with only 0.5 PV of SI solution. Table 5 shows that we obtain a
percentage of scale inhibitor return varying between 84.51% and
The pH of the effluents for our corefloods have been predicted with
the help of two models: PHREEQC and MultiScale.

9.1.1. MultiScale modelling


Table 4 MultiScale is a computer program designed to calculate equilibrium
Values of scale inhibitor adsorption calculated using mass balance. in systems containing brines of different composition, gas, oil, and
solids. As the input, the user defines temperature, pressure, and the
Coreflood SI injected Total SI retained % SI return % SI retained SI adsorption
(mg) (mg) (mg/g) concentration of each compound; MultiScale then uses the appro-
RC1 73.65 15.21 84.80 15.21 0.073 priate chemical and thermodynamic equations to calculate the final
RC2 145.78 7.02 95.19 4.81 0.075 phases, which are present, and the equilibrium composition of each
RC3 364.28 13.26 96.36 3.64 0.087 phase. MultiScale can be used to predict the scaling tendency of NaCl,
RC4 80.11 11.78 85.30 14.70 0.080 BaSO4, SrSO4, CaSO4, FeS, CaCO3 and FeCO3, as well as the final pH of
RC5 527.42 12.63 97.60 2.40 0.084
the mixing of two solutions.
18 S. Baraka-Lokmane, K.S. Sorbie / Journal of Petroleum Science and Engineering 70 (2010) 10–27

Fig. 16. Measured pH values for floods RC1 to RC5.

Fig. 17. Measured pH values for flood RC4.

Fig. 18 shows Effluents pH values modelled with the help of the gas phase pressure of CO2 in equilibrium with the carbon dioxide in
MultiScale software. The input pH values are equal to 6 and 4. The solution. The Saturation Index, SI is a numeric value indicating whether
software MultiScale does not accept pH values lower than 4, in the water is scale-forming or corrosive. It takes account of factors such as pH,
case of carbonate system. Fig. 18 shows that the pH values are around total alkalinity, calcium hardness and water temperature. The ideal
7. Table 6 shows that the measured pH values are in the same order to Saturation Index range is between −3 and +3.
those predicted with the software MultiScale. Mole transfer is relative to the moles in the phase assemblage;
positive numbers indicate an increase in the volume of the phase
9.1.2. PHREEQC modelling present, that is, precipitation; negative numbers indicate a decrease in
The second software used to predict the effluent pH values from the the volume of the phase present, or dissolution. Saturation Index: “–”
different coreflooding experiments is the PHREEQC modelling, which is indicates that Saturation Index calculation not possible because one of
a powerful geochemical modelling program developed by Appelo and the constituent elements was not in solution. Mole transfer: “–” indicates
Gerba in 1993 for the U.S. Geological Survey. PHREEQC is written in the C that no mole transfer of this mineral was allowed in the simulation.
programming language and it is designed to perform a wide variety of Selected results from the output data are presented in Table 8. In
low-temperature aqueous geochemical calculations. The program is the simulation the input pH values vary between 6 and 2, the
based on equilibrium chemistry of aqueous solutions interacting with temperature is equal to 20 °C and values of CO2(g) vary between − 4
minerals, gases, solid solutions, exchangers, and adsorbing surfaces. and 4. Table 7 shows that the resulting pH values decreases as input
PHREEQC is used for simulating a variety of reactions and processes in CO2(g) increases. In the different simulations, the seawater has the log
natural waters or laboratory experiments. PCO2 specified by the input except for the simulations 5, 10 and 15
Table 7 shows the input data set. In this program, seawater is defined where the seawater has the log PCO2 equal to about 2.5. In the
by using the major-ion data, it is equilibrated with calcite, to investigate simulations 5, 10 and 15 the input CO2(g) value is equal to 4.
the chemical evolution. In Table 7, PCO2 is the partial pressure of CO2, i.e. The different simulations show that the seawater is supersaturated
with dolomite for input CO2(g) equal to −4, −2 and 0 (simulations 1 to 3,
6 to 8 and 11 to 13). This indicates that thermodynamically, dolomitization
Table 6
Measured and modelled pH values using MultiScale software. should occur, thus dolomite should precipitate. The seawater is under-
saturated with dolomite for input CO2(g) equal to 2 and 4 (simulations 4,
Input pH Measured pH values Modelled pH values (MultiScale)
5, 9, 10, 14 and 15). This indicates that dolomite should dissolve.
6 7.2600 7.0633
Table 8 shows that no mole transfer of dolomite is allowed in the
4 6.8650 7.0628
different simulations. In the simulation 1, the moles of CO2 in the
S. Baraka-Lokmane, K.S. Sorbie / Journal of Petroleum Science and Engineering 70 (2010) 10–27 19

Fig. 18. Effluents pH values modelled with the help of MultiScale software.

phase assemblage decreased by about 21 mmol, i.e. about 21 mmol The Freundlich sorption isotherm model is the following
dissolved into solution. Likewise, about 25 mmol of calcite dissolved.
n
This figure is shown in all the simulations except for simulations 11 C = k:C ð1Þ
and 12, where the input pH is equal to 2 and the values of CO2(g) are
equal to −4 and −2. In the simulations 11 and 12, about 8 mmol and where k and n are constants, Г is the mass per dry unit weight of solid
6 mmol escaped from the seawater solution. (mg/g) of the SI adsorbed, and C is the concentration in ppm of the SI
These different simulations presented in Table 8 have shown that in the brine solution.
with the help of PHREEQC modelling we can reproduce the effluents Figs. 19 and 20 show the experimental and modelled SI returns
pH values obtained in our coreflooding experiments. curves over the full SI concentration range for floods RC1 and RC3
(points = experimental [SI]; solid lines = modelling results). These
figures show a satisfactory but not perfect match between experi-
9.2. Isotherm derivation
mental and the modelling results. Flood RC1 shows a better fit
between modeling results and experimental results than flood RC3.
The SQUEEZE V software was used to derive adsorption isotherms,
This is probably because the calcium and the magnesium ions are
Γ(C) for the different corefloods, from the SI effluent concentrations
strongly involved in the SI/carbonate rock interaction, specially for the
from floods RC1 to RC5. The isotherm describes the adsorption of the
coreflood performed with high SI concentration (25,000 ppm) and
scale inhibitor on to the rock substrate. Once the SI adsorption
lower pH value (pH = 2) and in this case a single adsorption isotherm
isotherm in the carbonate rock has been derived, it may then be used
may not provide a complete description of the process.
in turn to model the coreflood. This “completes the cycle” since, where
From the modelling results in Figs. 19 and 20, we can predict the
the model calculations match the experimental coreflood concentra-
amount of SI (for example, as a % of the injected amount) retained in the
tions, then the isotherm is essentially validated. However, there is an
core at the end of the flood. These predictions are compared with the
issue in these “contained” floods since the full length of the core is not
experimental mass balance measurements in Table 5 and it can be noted
exposed to the SI solution and also the same end of the12q core is used
that both results agree extremely well. However, we cannot be satisfied
for SI injection and back production. Thus, by assuming a shorter
with this “pseudo-isotherm” approach although if it fits the experi-
“effective length” of the core, the best fits for flood RC1 (performed
mental data very well since we are aware that the SI/calcite interaction
with 5000 ppm SI at pH 4) and RC3 (performed with 25,000 ppm SI at
in the core is more complex than a simple adsorption process.
pH 2) are represented in Figs. 19 and 20 with their corresponding
In the literature, we can find three views on the precise mechanisms
Freundlich isotherms (i.e. k and n values) (squeeze V program, Heriot-
through which SI species are retained within the reservoir formation e.g.
Watt University, Scotland).
adsorption, precipitation, surface condensation, coupled adsorption/
precipitation etc.
Table 7
These three views are:
PHREEQC modeling input data set.

TITLE Example 3, part A.–Calcite equilibrium at log PCO2 = − 4.0 and 20C.
(1) the Heriot-Watt view, where retention is described in general
SOLUTION 1 Seawater
terms through an adsorption isotherm, Г(C), or alternatively by a
units ppm
pH 2.00 two parameter precipitation/dissolution model, Π(C) (solubility)
temp 20.0 and r2 (dissolution rate) (Sorbie et al., 1991a,b, 1992, 1993a,b,
Ca 428.0 1994, Sorbie and Gdanski, 2005);
Mg 1368.0 (2) the Halliburton model, which approaches adsorption from a
Na 10,890.0
K 460.0
mineralogical perspective and relates the total rock adsorption
S(6) 2690.0 to the adsorption on each mineral component of the rock
EQUILIBRIUM_PHASES (Gdanski and Funkhouser, 2001, 2002, 2005); and
CO2(g) − 4.0 (3) the Rice University view, in which for example, phosphonate
Calcite 0.0
retention is related to the solubility of a sparingly soluble
END
calcium phosphonate precipitate and refers to high, medium
20 S. Baraka-Lokmane, K.S. Sorbie / Journal of Petroleum Science and Engineering 70 (2010) 10–27

Table 8
PHREEQC modeling results.

Simulation Input data pH Log Saturation Index Mole transfer


PCO2 (mmol)
Calcite Dolomite CO2 Calcite Dolomite
1 Temperature = 20 °C 8.143 − 4.00 0.00 0.81 − 20.75 − 24.84 –
CO2 (g) = − 4.0
pH = 6
2 Temperature = 20 °C 7.113 − 2.00 0.00 0.75 − 2.312 − 1.987 –
CO2 (g) = − 2.0
pH = 6
3 Temperature = 20 °C 5.977 0.00 0.00 0.45 − 0.501 − 0.146 –
CO2 (g) = 0.0
pH = 6
4 Temperature = 20 °C 4.751 2.00 0.00 − 0.13 − 3531 − 0.885 –
CO2 (g) = 2.0
pH = 6
5 Temperature = 20 °C 4.493 2.46 0.00 − 0.28 − 10,000 − 130.2 –
CO2 (g) = 4.0
pH = 6
6 Temperature = 20 °C 8.141 − 4.00 0.00 0.81 − 0.1254 − 0.329 –
CO2 (g) = − 4.0
pH = 4
7 Temperature = 20 °C 7.112 − 2.00 0.00 0.75 − 2.225 − 2.063 –
CO2 (g) = − 2.0
pH = 4
8 Temperature = 20 °C 5.977 0.00 0.00 0.45 − 50.04 − 14.65 –
CO2 (g) = 0.0
pH = 4
9 Temperature = 20 °C 4.750 2.00 0.00 − 0.13 − 3531.0 − 88.60 –
CO2 (g) = 2.0
pH = 4
10 Temperature = 20 °C 4.493 2.46 0.00 − 0.28 − 10,000.0 − 130.3 –
CO2 (g) = 4.0
pH = 4
11 Temperature = 20 °C 8.026 − 4.00 0.00 0.58 7.853 − 8.204 –
CO2 (g) = − 4.0
pH = 2
12 Temperature = 20 °C 7.012 − 2.00 0.00 0.55 6.083 − 9.615 –
CO2 (g) = − 2.0
pH = 2
13 Temperature = 20 °C 5.926 0.00 0.00 0.35 − 40.63 − 21.18 –
CO2 (g) = 0.0
pH = 2
14 Temperature = 20 °C 4.736 2.00 0.00 − 0.16 − 3515.0 − 0.946 –
CO2 (g) = 2.0
pH = 2
15 Temperature = 20 °C 4.482 2.47 0.00 − 0.30 − 10,000.0 − 136.5 –
CO2 (g) = 4.0
pH = 2

and low solubility phases of this precipitate (Kan et al., 1992, adsorption is significantly improved by the presence of Ca2+ ions and
2004a,b; Tomson et al., 2004; Kan et al., 2005). effectively poisoned by the presence of excess Mg2+ ions. Sorbie and
Laing (2004) have shown that calcium and magnesium may bind to
These three views described above are probably all “right” under DETPMP, which was denoted by A for simplicity. The solution equilibrium
certain circumstances. Sorbie and Gdanski (2005) have published a binding reactions which occur in a Ca/Mg/DETPMP system are as follow:
detailed comparison of the Heriot-Watt and Halliburton models showing
KCa
that the two models are very similar in broad principle and differ only in Ca + A X Ca  A ð2aÞ
some details (e.g. the form of the desorption rate law). For example, both
models could match some very detailed experimental SI core effluent data KMg
with equal accuracy by changing only some model parameters. Mg + A X Mg  A ð2bÞ
In the case of a carbonate system, although the “pseudo-isotherm”
approach fits the data very well, we are aware that the SI/calcite The stability constants KCa and KMg, are given by:
interaction in the core is more complex than a simple adsorption
process. Future work will focus on improving the model for describing XCa  A
KCa = ð3aÞ
this process. The modeling presented in section 9.3 takes some initial XCa  XA
steps towards a full model for the SI/carbonate interaction taking into
account the involvement of both calcium and magnesium ions. XMg  A
KMg = ð3bÞ
XMg  XA
9.3. A simple model of the Ca and Mg behaviour

The role of calcium and magnesium ion, which are known to interact For DETPMP, these quantities are known to be KMg = 6.3 × 1010 and
directly with the DETPMP, has been studied in this work. DETPMP KCa = 5.0 × 1010. Suppose we start with initial quantities of Ca, Mg, SI
S. Baraka-Lokmane, K.S. Sorbie / Journal of Petroleum Science and Engineering 70 (2010) 10–27 21

Fig. 19. RC1 — linear coreflood model, best fit. Freundlich isotherms: k = 6000, n = 0.25.

Fig. 20. RC3 — linear coreflood model, best fit. Freundlich isotherms: k = 4500, n = 0.45.

(as A) in solution, denoted XCa0, XMg0 and XA 0. It is quite straightforward Table 9 summarizes results for the calculated ratio using Eqs. (4a
to rearrange the system of equations to obtain the following two and b) and (5) from the five experimental corefloods RC1 to RC5. The
implicit equations for XCa and XMg: numerically predicted value of (XCaA/XMgA) varies between 0.1402 and
0.1797, implying that 12 to 15% of DETPMP is bound to Ca and 85 to
XCaO 88% of DETPMP is bound to Mg. This is quite consistent with the
XCa = h XA
i ð4aÞ
1 + KCa O results we observe in our experiments where the retained SI causes a
1 + KCa XCa + KMg XMg
decrease below the stock of magnesium during the adsorption stage of
the treatment followed by a post shut-in value of magnesium
XMgO
XMg = h XA
i ð4bÞ
1 + KMg O
1 + KCa XCa + KMg XMg
Table 9
Values of percentage of SI bound to Ca and Mg using Eqs. (4a and b) and (5) for floods
Eqs. (3a) and (3b) can be solved numerically in a spreadsheet but the RC1 to RC5.
actual quantity of interest is the equilibrium value of (XCaA/XMgA), i.e. the
Coreflood (XCaA/XMgA) % SI–Ca % SI–Mg (XCaA/XMgA) % SI–Ca % SI–Mg
ratio of SI bound to Ca to SI bound to Mg. For very large values of stability
Eq. (5) bound bound Eq. (4a and b) bound bound
KCa, KMg, as is the case here, an approximate equation for this ratio is given
by: RC1 0.1402 12 88 0.1496 13 87
RC2 0.1436 13 87 0.1641 14 86
! ! RC3 0.1431 13 87 0.1797 15 85
XCaA KCa  XCaO RC4 0.1432 13 87 0.1457 13 87
e ð5Þ
XMgA KMg  XMgO RC5 0.1428 12 88 0.1796 15 85
22 S. Baraka-Lokmane, K.S. Sorbie / Journal of Petroleum Science and Engineering 70 (2010) 10–27

Table 10
XRD, XRF and XPS results.

Sample XRD analysis XPS analysis


Calcite Quartz Albite Na Microcline Phosphorus P
(CaCO3) SiO2 (AlSi3O8) K(AlSi3O8) (%)
(%) (%) (%) (%)
RC1 96.0 4.0 0.160
RC2 99.0 1.0 0.170
RC3 97.8 1.8 0.4 0.350
RC4 98.8 1.2 0.210
RC5 74.0 2.0 117.0 7.0 0.300

concentration above the stock as the SI (bound mainly to Mg) is back


produced. Further work is in progress to model more appropriately
the corefloods (RC1 to RC5) taking into account the involvement of
calcium and magnesium in the SI/carbonate rock interaction.

10. Post-coreflood petrographic analysis


Fig. 23. Image of calcite cement in core RC5. Note the undamaged calcite crystals and
The rock material used in floods RC1 to RC5 was analysed after the calcite crystals with microwormholes.
SI treatment, to check for any evidence of dissolution of the rock
matrix and/or precipitation within the rock matrix. A post-coreflood analyses include the study of the thin sections as well as the XRD, XPS,
petrography analysis has been performed on cores RC1 to RC5. These AFM, SEM and EDX measurements.
XRD analysis carried out both on the whole rock and on the fine
particle fractions has shown that the rock material is almost pure

Fig. 21. Image of calcite cement in core RC3. Note the undamaged calcite crystals.

Fig. 24. Larger magnification of Fig. 23.

Fig. 22. Image of calcite cement in core RC4. Note the undamaged calcite crystals. Fig. 25. SEM photo showing masses of SI salts on the ooids (coreflood RC1).
S. Baraka-Lokmane, K.S. Sorbie / Journal of Petroleum Science and Engineering 70 (2010) 10–27 23

Fig. 29. SEM Photo of coreflood RC4, showing SI salts occupying the void space.

Fig. 26. SEM photo showing masses of SI salts on the ooids (coreflood RC2).
these floods with 0.5PV of respectively 25,000 ppm and 5000 ppm of
DETPMP at pH 2 has not induced the formation of worm holes or micro
worm holes (Figs. 21 and 22). The SEM analysis carried out on core RC5
performed with 27,000 ppm DETPMP at pH 4 has shown that the high
concentration of the SI solution has induced the formation of micro
worm holes formed on the calcite crystals (Figs. 23 and 24). This is
probably due to the high concentration of the SI solution (27,000 ppm).
Indeed, the coreflood RC5 showed also the highest level of calcium
dissolution (Ca = 481.55 mg or 1.58 mg/g) (see section 7). SEM analysis
carried out on cores RC1 to RC5 showed the presence of SI salts
occupying the void spaces (Figs. 25 and 28) and also formed on the ooid
grain surfaces (Fig. 26). Large amount of SI salts have also been observed
on the RC3 core, 25,000 ppm SI solution at pH 2 (Fig. 27).
The EDX analysis has revealed clearly the presence of phosphorus
together with calcium, chloride and sodium (Fig. 28). The structure of
Fig. 27. Image of RC3 after the scale inhibitor treatment. Note the SI salts.
the vacuolar structure of the phosphorus calcium salt shows that the salt
has been precipitated, confirming that the mechanism of the DETPMP
calcite. Core RC1 is about 96% calcite and 4% quartz. Core RC2 is about retention in carbonate rocks is of a precipitation type (Figs. 29–31).
99% calcite and 1% quartz. Core RC3 is about 97.8% calcite, 1.8% quartz The Atomic Force Microscopy (AFM) analysis has shown the shape
and 0.4% plagioclase. Core RC4 is about 98.8% calcite and 1.2% quartz. of the calcium phosphonate crystals (Figs. 32 and 33); indeed, the
Core RC5 is about 74% calcite, 2% quartz, 17% plagioclase and 7% AFM technique allows a higher resolution than the SEM technique and
microcline (Table 10). 3-D images of the rock surfaces.
The analysis of the thin sections as well as the SEM analysis The X-ray photoelectron spectrometer (XPS) analyses have been
performed on corefloods RC3 and RC4 have shown that the treatment of carried out in order to estimate the percentages of phosphorus (from the

Fig. 28. Energy dispersive X-ray spectrum (EDX) of the SI salt showed on Fig. 31.
24 S. Baraka-Lokmane, K.S. Sorbie / Journal of Petroleum Science and Engineering 70 (2010) 10–27

Fig. 32. AFM image showing the structure of the calcite phosphate crystal in coreflood RC4.
Fig. 30. Larger magnification of Fig. 29.

The main conclusions of this study are as follows:

(1) the results from the “contained” long corefloods RC1 to RC5
scale inhibitor) retained in the cores. XPS analysis (Table 10) carried out showed that:
after the scale inhibitor treatment show that the amount of phosphorus in (a) the higher the concentration of SI and lower the pH, the
the rock matrix varied between 0.16% (RC1) and 0.35% (RC3). Thus flood more calcium dissolution is observed (from the [Ca2+]
RC3 (25,000 ppm DETPMP at pH 2) shows more retained phosphorus effluents);
(0.35%) than floods RC5 (0.30%), RC4 (0.21%), RC2 (0.17%) and RC1 (b) in all treatments there is a decrease in the [Mg2+] effluent
(0.16%). These results are in agreement with the calculated values of the SI concentration corresponding directly to the increase in the
adsorption levels reported in Table 4 (see section 7). Table 4 shows that [Ca] concentration;
the coreflood RC3 exhibits also the highest level of SI adsorption (c) the post shut-in pH in all of these floods shows a peak
(Γ~ 0.087 mg/g). These results confirm that we have more SI retention between pH 7 and 8.5 which gradually decreases to pH ~ 7;
with high SI concentration and low pH values, and the low pH parameter (d) the core permeability (k ~ 600 mD) increases in all cases
seems to be more important than the concentration of the SI solution. indicating that the stimulation effect through calcite
dissolution is greater than the permeability reducing effect
11. Summary and conclusions induced by the deposition of (Ca and Mg) phosphonate
salts; and
Detailed results are presented from a series of DETPMP scale (e) the lowering of the injected SI solution pH (i.e. pH = 2) is
inhibitor (SI) carbonate corefloods using Jurassic Portlandian chalk more important than an increase in the SI concentration
(Φ ~ 19.8% and k ~ 600 mD). Five of these were “contained” long (12q) (i.e. 27,000 ppm DETPMP) for improving the SI adsorption
corefloods injecting 0.5PV of SI as follows: in the core.
(2) The prediction of the pH evolution has been performed with
flood RC1 — 5000 ppm DETPMP at pH 4; the help of two softwares: MultiScale and PHREEQC. The future
flood RC2 — 10,000 ppm DETPMP at pH 4; work will consist of using a batch modelling in order to
flood RC3 — 25,000 ppm DETPMP at pH 2; simulate more appropriately our laboratory experiments.
flood RC4 — 5000 ppm DETPMP at pH 2; and (3) The coreflood effluent cation analysis strongly support the view
that both magnesium and calcium are binding quite strongly to
flood RC5 — 27,000 ppm DETPMP at pH 4.
the SI (i.e. Ca–A and Mg–A where A = DETPMP). The calcium
Postflush using pH 6 seawater brine was injected through the effluent concentration always shows an increase during SI
original core outlet end of the above 5 corefloods and SI was back injection since the effect of dissolution (which increases the
produced from the original inlet. effluent [Ca2+] concentration) dominates that of Ca–A reten-
tion. This is further supported by our simple model of Ca–A and

Fig. 31. Larger magnification of Fig. 30 of the SI salt containing phosphorus, calcium,
chloride, and sodium. Fig. 33. Larger magnification of Fig. 32.
S. Baraka-Lokmane, K.S. Sorbie / Journal of Petroleum Science and Engineering 70 (2010) 10–27 25

Mg–A binding which allows us to estimate the relative amounts pH = 6). measurement of permeability k1 between P1 and P2 and k2
of each of these species, as the ratio, (XCaA/XMgA). The between P2 and P3 (see Figs. 2.3 and 2.5).
numerically predicted value of (XCaA/XMgA) varies between 3. Lithium solution injection: 50 ppm lithium in brine solution
0.1402 and 0.1797, implying that 12 to 15% of the DETPMP has (pH = 6) was injected at a flow rate of 30 ml/h, 30 samples of
Ca bound to it and 85 to 88% has Mg bound to it. This is in 2 ml were collected (sample interval every 4 min).
excellent agreement with our experimental results(from the 4. Brine solution injection: brine solution (pH = 6) was injected at a
effluent data) and explains why the Mg effluent concentration flow rate of 30 ml/h, 30 samples of 2 ml were collected (sample
shows a clear dip during the SI placement and a peak during the interval every 4 min).
seawater postflush period. 5. Scale inhibitor injection: injection of 0.5 PV (15.18 ml) 5000 ppm
(4) The modelling, using the derivation of an effective pseudo- active SI-labelled with 50 ppm Li tracer — in brine solution
isotherm (with a Freundlich isotherm), is able to produce good (pH = 4) at a flow rate of 30 ml/h then shut in. The core was then
matches (not predictions) of the SI return concentration curves for shut in over 24 h.
all five core floods RC1 to RC5. We are able to predict the final %SI 6. Postflush is carried out with lithium solution injection: 50 ppm
retained in the core by modelling and this can be compared with lithium in brine solution (pH = 6) from the outlet (P3) (see
the experimental mass balance results. In fact, excellent quanti- Figs. 2.3 and 2.5) at a flow rate of 30 ml/h. Sample schedule = N80
tative agreement is seen. However, we are not satisfied by this samples of 2 ml collected (sample interval every 4 min); 60
approach since a simple adsorption model does not, in our view, samples of 10 ml collected (sample interval every 20 min);
represent all what is happening in these floods We are aware that approximately 500 samples of 20 ml collected (sample interval
the SI/calcite interaction in the core is more complex than a simple every 40 min), until the active inhibitor concentration fell below
adsorption process. Future work will focus on improving the approximately 0.5 ppm active inhibitor.
model for describing the SI/carbonate interaction taking into 7. Post-treatment brine permeability measurement: brine permeability
account the involvement of both calcium and magnesium ions. was measured at room temperature at flow rates of 30, 60, 90, 120,
(5) The petrography analysis has shown that corefloods RC3 and RC4 and 240 ml/h in forward direction of flow, 10 min each (brine with
(at pH 2) did not induce the formation of worm holes or micro pH = 6). Measurement of permeability k1 between P1 and P2 and k2
worm holes, but coreflood RC5 performed with 27,000 ppm between P2 and P3 (see Fig. 2.5).
DETPMP at pH 4 has shown that the high concentration of the SI 8. Measurement of dead volume: after completing all the steps
solution has induced the formation of micro worm holes on the described above, the core assembly was dismantled and the dead
calcite crystals. The analysis of the structure of the phosphonate- volume in the system was measured.
calcium salt shows that this salt has been precipitated, confirming
that the mechanism of the DETPMP SI retention in carbonate
Experimental procedure for coreflood RC2
rocks is of a precipitation type. The Atomic Force Microscopy
(AFM) analysis has revealed the shape of the calcium phospho-
nate crystals. Thin sections, SEM, EDX, XPS and AFM analysis of 1. Brine saturation: saturation of the core with brine solution
the cores after the different corefloods have shown the presence (pH = 6) at room temperature and at flow rates of 30, 60, and
of SI salts formed within the void space and on the ooid grains. 90 ml/h, 1 h each. The core was then shut in over 24 h.
The EDX analysis of the SI salts has revealed the presence of 2. Pre-treatment brine permeability measurement: brine permeability
phosphorus. The XPS analysis has shown that corefloods RC3 was measured at room temperature at flow rates of 30, 60, 90, and
(25,000 ppm DETPMP at pH 2) shows more retained phosphorus 120 ml/h in forward direction of flow, 30 min each.(brine with
(0.35%) than floods RC5 (0.30%), RC4 (0.21%), RC2 (0.17%) and pH = 6).
RC1 (0.16%). These results show that we have more SI retention 3. Lithium solution injection: injection of 0.25 PV (7.59 ml) 50 ppm
with both a high SI concentration and a low pH value, the low pH Lithium in brine solution (pH = 6) from the inlet at a flow rate of
parameter seeming to be more important on SI adsorption than 30 ml/h, 30 samples of 2 ml were collected (sample interval every
the concentration of the SI solution. 4 min).
4. Brine solution injection: injection of 0.25 PV (7.59 ml) brine
solution (pH = 6) from the inlet at a flow rate of 30 ml/h, 30
Acknowledgements
samples of 2 ml were collected (sample interval every 4 min).
5. Lithium solution injection: continuous injection of 50 ppm Lithium
The sponsors of the Heriot-Watt University, Flow Assurance and
in brine solution (pH = 6) from the outlet at a flow rate of 30 ml/h,
Scale Team (FAST) JIP are thanked for their support, input and
30 samples of 2 ml were collected (sample interval every 4 min).
permission to publish this work: Baker Petrolite, BG Group, BP,
6. Brine solution injection: continuous injection of brine solution
Champion Technologies, Chemtura, Chevron, Clariant, ConocoPhillips,
(pH = 6) from the outlet at a flow rate of 30 ml/h, 30 samples of
Halliburton, Hydro Oil and Energy, M I Production Chemicals, Nalco,
2 ml were collected (sample interval every 4 min).
Petrobras, REP, Rhodia, Shell, Solutia, Statoil and Total. We thank Dr
7. Scale inhibitor injection: injection of 0.5 PV (15.18 ml) 10,000 ppm
Norbert Kohler for his constructive review of the manuscript.
active SI-labelled with 50 ppm Li tracer — in brine solution
(pH = 4) from the inlet at a flow rate of 30 ml/h then shut in. The
Appendix A. Detailed experimental procedures for “contained”
core was then shut in over 24 h.
corefloods RC1 to RC5
8. Postflush is carried out with lithium solution injection: 50 ppm
lithium in brine solution (pH = 6) was injected from the outlet at
Experimental procedure for coreflood RC1
a flow rate of 30 ml/h. Sample schedule = N80 samples of 2 ml
collected (sample interval every 4 min); 60 samples of 10 ml
1. Brine saturation: saturation of the core with brine solution (pH = 6) collected (sample interval every 20 min); approximately 500
at room temperature and at flow rates of 30, 60, 90, and 120 ml/h, samples of 20 ml collected (sample interval every 40 min), until
1 h each. The core was then shut in over 24 h. the active inhibitor concentration fell below approximately
2. Pre-treatment brine permeability measurement: brine permeability 0.5 ppm active inhibitor.
was measured at room temperature at flow rates of 30, 60, 90, 120, 9. Post-treatment brine permeability measurement: brine permeabil-
and 240 ml/h in forward direction of flow, 10 min each (brine with ity was measured at room temperature at flow rates of 30, 60, 90,
26 S. Baraka-Lokmane, K.S. Sorbie / Journal of Petroleum Science and Engineering 70 (2010) 10–27

120, and 240 ml/h in forward direction of flow, 10 min each (brine Experimental procedure for coreflood RC5
with pH = 6).
10. Measurement of dead volume: after completing all the steps 1. Brine saturation: saturation of the core with brine solution (pH = 6)
described above, the core assembly was dismantled and the at room temperature and at flow rates of 30, 60, and 90 ml/h, 1 h
dead volume in the system was measured. each. The core was then shut in over 24 h.
2. Pre-treatment brine permeability measurement: brine permeability
Experimental procedure for coreflood RC3 was measured at room temperature at flow rates of 30, 60, 90, and
120 ml/h in forward direction of flow, 30 min each (brine with
1. Brine saturation: saturation of the core with brine solution (pH = 6) PH = 6).
at room temperature and at flow rates of 30, 60, and 90 ml/h, 1 h 3. Lithium solution injection: 50 ppm Lithium in brine solution
each. The core was then shut in over 24 h. (pH = 6) was injected at a flow rate of 30 ml/h, 60 samples of
2. Pre-treatment brine permeability measurement: brine permeability 2 ml were collected (sample interval every 4 min).
was measured at room temperature at flow rates of 30, 60, 90, and 4. Brine solution injection: brine solution (pH = 6) was injected at a
120 ml/h in forward direction of flow, 30 min each (brine with flow rate of 30 ml/h, 60 samples of 2 ml were collected (sample
pH = 6). interval every 4 min).
3. Lithium solution injection: 50 ppm Lithium in brine solution 5. Scale inhibitor injection: injection of 0.5 PV (15.18 ml) 25,000 ppm
(pH = 6) was injected at a flow rate of 30 ml/h, 60 samples of active SI-labelled with 50 ppm Li tracer — in brine solution
2 ml were collected (sample interval every 4 min). (pH = 6) at a flow rate of 30 ml/h then shut in. The core was then
4. Scale inhibitor injection: injection of 0.5 PV (15.18 ml) 25,000 ppm shut in over 24 h.
active SI (pH = 2) from the inlet at a flow rate of 30 ml/h then shut 6. Post flush is carried out with brine solution injection: brine solution
in. The core was then shut in over 24 h. (pH = 6) was injected from the outlet at a flow rate of 30 ml/h.
5. Post flush is carried out with iodide solution injection: 200 ppm Sample schedule = N80 samples of 2 ml collected (sample interval
Sodium Iodide in brine solution (pH = 6) was injected from the every 4 min); 60 samples of 10 ml collected (sample interval every
outlet at a flow rate of 30 ml/h. Sample schedule =N80 samples of 20 min); approximately 500 samples of 20 ml collected (sample
2 ml collected (sample interval every 4 min); 60 samples of 10 ml interval every 40 min), until the active inhibitor concentration fell
collected (sample interval every 20 min); approximately 500 below approximately 0.5 ppm active inhibitor.
samples of 20 ml collected (sample interval every 40 min), until the 7. Measurement of dead volume: after completing all the steps
active inhibitor concentration fell below approximately 0.5 ppm described above, the core assembly was dismantled and the dead
active inhibitor. volume in the system was measured.
6. Measurement of dead volume: after completing all the steps
Note: analyze Li, Ca, Mg and Fe in steps 3 and 4; analyze Li, “P”, Ca,
described above, the core assembly was dismantled and the dead
Mg and Fe in steps 5 and 6.
volume in the system was measured.
References
Experimental procedure for coreflood RC4
Baraka-Lokmane, S. and Sorbie, K.S. Scale Inhibitor Core Floods in Carbonate Cores: The
Influence of pH on Phosphonate–Carbonate Interactions, SPE 87448, SPE Sixth
1. Brine saturation: saturation of the core with brine solution (pH = 6) International Symposium on Oilfield Scale, 26–27 May 2004, Aberdeen, UK.
Baraka-Lokmane, S. and Sorbie, K.S. Scale Inhibitor Core Floods in Carbonate Cores:
at room temperature and at flow rates of 30, 60, and 90 ml/h, 1 h Chemical Interactions and Modelling, SPE 100515, SPE Sixth International
each. The core was then shut in over 24 h. Symposium on Oilfield Scale, 26–27 May 2006, Aberdeen, UK.
2. Pre-treatment brine permeability measurement: brine permeability Choquette, P.W., Pray, L.C., 1970. Geologic nomenclature and classification of porosity in
sedimentary carbonates. AAPG Bull. 54 (2), 207.
was measured at room temperature at flow rates of 30, 60, 90, and
Crowe, C., McConnell, S.B., Hinkel, J.J., Chapman, K., 1994. Scale inhibition in wellbores.
120 ml/h in forward direction of flow, 30 min each (brine with SPE 27996. Paper Presented at the University of Tulsa Centennial Petroleum
PH = 6). Engineering Symposium Held in Tulsa, OK, USA. 29–31 August.
3. Lithium solution injection: 50 ppm Lithium in brine solution Gdanski, R., Funkhouser, G.P., 2001. Successful model of the kinetic release of a
phosphonate scale inhibitor. Presented at the NIF International Oilfield Chemistry
(pH = 6) was injected at a flow rate of 30 ml/h, 60 samples of Symposium, Geilo, Norway. 1–4 April.
2 ml were collected (sample interval every 4 min). Gdanski, R., Funkhouser, G.P., 2002. Fully contained laboratory squeeze treatment.
4. Brine solution injection: brine solution (pH = 6) was injected at a Presented at the NIF International Oilfield Chemistry Symposium, Geilo, Norway.
17–20 March.
flow rate of 30 ml/h, 60 samples of 2 ml were collected (sample Gdanski, R., Funkhouser, G.P., 2005. Mineralogy driven scale inhibitor squeeze designs.
interval every 4 min). SPE 94510. Paper Presented at the SPE European Formation Damage Conference
5. Scale inhibitor injection: injection of 0.5 PV (15.18 ml) 5000 ppm Held in Scheveningen, The Netherlands. 25–27 May.
Graham, G.M., Mackay, E.J., 2000. Scale inhibitor selection criteria for downhole
active SI-labelled with 50 ppm Li tracer — in brine solution application in a chalk reservoir. 4th Chemistry in Industry Conference and
(pH = 2) at a flow rate of 30 ml/h then shut in. The core was then Exhibition. Scale and Corrosion Chemistry Session, Paper No OFC-2, pp. 1–158.
shut in over 24 h. Jordan, M.M., Sjursaether, K., 2004. Scale control within sea chalk/limestone reservoirs.
The challenge of understanding and optimizing chemical placement methods and
6. Post flush is carried out with brine solution injection: brine solution retention mechanism: laboratory to field. SPE 86476. Paper Presented at the SPE
(pH = 6) was injected from the outlet at a flow rate of 30 ml/h. International Symposium and Exhibition on Formation Damage Control, Lafayette,
Sample schedule = N80 samples of 2 ml collected (sample interval Louisiana, USA. 18–20 February.
Jordan, M.M., Sorbie, K.S., Jiang Ping, Yan Ming Dong, Todd, A.C., 1994. Phosphonate
every 4 min); 60 samples of 10 ml collected (sample interval every
scale inhibitor adsorption/desorption and the potential for formation damage in
20 min); approximately 500 samples of 20 ml collected (sample reconditioned field core. SPE 27389. Paper Presented at the SPE International
interval every 40 min), until the active inhibitor concentration fell Symposium on Formation Damage Control Held in Lafayette, Louisiana, USA. 7–10
below approximately 0.5 ppm active inhibitor. February.
Kan, A., Cao, X., Yan, P.B., Oddo, J.E., Tomson, M.B., 1992. The transport of chemical scale
7. Measurement of dead volume: after completing all the steps inhibitor and its importance to the squeeze procedure. Paper No 33 Presented at the
described above, the core assembly was dismantled and the dead NACE Annual Conf and Corrosion Show, Nashville, TN. 27 April–1 May.
volume in the system was measured. Kan, A.T., Fu, G., Tomson, M.B., Al-Thubaiti, M., Xiao, A.J., 2004a. Factor affecting scale
inhibitor retention in carbonate-rich formation during squeeze treatment. SPE J.
280–289 September.
Note: analyze Li, Ca, Mg and Fe in steps 3 and 4; analyze Li, “P”, Ca, Kan, A.T., Fu, G., Tomson, M.B., 2004b. Adsorption and precipitation of an aminoalk-
Mg and Fe in steps 5 and 6. ylphosphonate onto calcite. J. Colloid Interface Sci. 275–284.
S. Baraka-Lokmane, K.S. Sorbie / Journal of Petroleum Science and Engineering 70 (2010) 10–27 27

Kan, A.T., Fu, G., Tomson, M.B., 2005. Prediction of scale inhibitor squeeze and return in of Chemistry Publication — Chemicals in the Oil Industry: Developments and
calcite-bearing formation. SPE 93265. SPE International Symposium on Oilfield Applications.
Chemistry Held in Houston, Texas, U.S.A. In. 2–4 February. Sorbie, K.S., Yuan, M.D., Todd, A.C., 1992. Interpretation and theoretical modelling of
Mackay, E.J., Collins, I.R., Jordan, M.M., Feasey, N., 2003. PWRI: scale formation risk scale- inhibitor/tracer corefloods. SPE Prod. Eng. 307–312 August.
assessment and management. SPE 80385. Paper Presented at the 5th International Sorbie, K.S., Yuan, M.D., Chen, P., Todd, A.C., Watt, R.M.S., 1993a. The effect of pH on the
Symposium on Oilfield Scale Held in Aberdeen, UK. 29–30 January. adsorption and transport of phosphonate scale inhibitor through porous media. SPE
Norris, M., Perez, D., Bourne, H.M., Heath, S.M., 2001. Maintaining fracture performance 25615, SPE International Symposium on Oilfield Chemistry, Anaheim, CA. 20–22
through active scale control. SPE 68300. Paper Presented at the 3rd International February.
Symposium on Oilfield Scale Held in Aberdeen, UK. 30–31 January. Sorbie, K.S., Jiang, P., Yuan, M.D., Chen, P., Jordan, M.M., Todd, A.C., 1993b. The effect of
Roehl, P.O., Choquette, P.W., 1985. Carbonate Petroleum Reservoirs. Springer-Verlag, pH, calcium and temperature on the adsorption of phosphonate inhibitor onto
New York City. consolidated and crushed sandstone. SPE 26605, SPE Annual Conference and
Sorbie, K.S., Laing, N., 2004. How scale inhibitors work. Mechanisms of selected barium Technical Exhibition, Houston, TX. 3–6 October.
sulphate scale inhibitors across a wide temperature range. SPE 87470 SPE Sorbie, K.S., Yuan, M.D., Jordan, M.M., Hourston, K.E., 1994. Application of a scale
International Symposium on Oilfield Scale held in Aberdeen, UK. 26–27 May. inhibitor squeeze model to improve field squeeze treatment design. SPE 28885,
Sorbie, K.S., Gdanski, R.D., 2005. A complete theory of scale inhibitor transport and Proceedings of the SPE European Petroleum Conference (Europec 94), London, UK.
adsorption/desorption in squeeze treatments. SPE 95088 SPE International 25–27 October.
Symposium on Oilfield Scale Held in Aberdeen, UK. 11–12 May. Tomson, M.B., Kan, A.T., Fu, G., 2004. Control of inhibitor squeeze via mechanistic
Sorbie, K.S., Yuan, M.D., Todd, A.C., 1991a. The modelling and design of scale inhibitor understanding of inhibitor chemistry. SPE 87450 SPE, 6th International Symposium
squeeze treatments in complex reservoirs. SPE 21024, SPE International Sympo- on Oilfield Scale Held in Aberdeen, UK. 26–27 May.
sium on Oilfield Chemistry, Anaheim, CA. 20–22 February.
Sorbie, K.S., Watt, R.M.S., Todd, A.C., McClosky, T., 1991b. Derivation of scale inhibitor
adsorption isotherms for sandstone reservoirs. In: Ogden, P.H. (Ed.), Royal Society