Journal of Petroleum Science and Engineering 70 (2010) 1027

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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 phosphonatecarbonate 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
In this paper, we present results from ve coreoods (RC1 to RC5) from the Jurassic Portlandian limestone ( ~ 19.80% and k = 606 mD) using 5000 ppm, 10,000 ppm, 25,000 ppm and 27,000 ppm of partly neutralized 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 inhibitor and cation (calcium and magnesium) return concentrations. These coreoods were performed using long cores (12 in.), which were treated with just 0.5 pore volume (PV) of inhibitor. Another purpose was to study the transport and inhibitor/carbonate rock interactions when less than 1 PV of inhibitor solution is injected. This allows for consumption of the inhibitor during propagation and return, rather than saturating 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+] efuents). In all treatments there is a decrease in the [Mg2+] efuent corresponding directly to the increase in calcium. The efuent cation results in the long coreoods 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.

Article history: Received 5 July 2007 Accepted 14 May 2009 Keywords: carbonate rock scale inhibitor phosphonate calcium dissolution coreoods

1. Introduction A common problem, in oileld reservoirs is scale deposition. Scale is an assemblage of deposits that can develop in the formation pores near the wellbore reducing formation porosity and permeability. It can block ow by clogging perforations or forming a thick lining in production tubing (Fig. 1). The build-up of scale inside well bores and the surrounding reservoir causes millions of dollars in damage every year (Mackay et al., 2003). Oileld scales are inorganic crystalline deposits that form as a result of the precipitation of solids from brines present in the reservoir and production ow system. This scale formation is the result of changes in the ionic composition, pH, pressure and temperature of the brine. Common scales are calcium carbonate (CaCO3) and barium sulphate (BaSO4). When the formation of sulphate or carbonate scale is a problem in producer wells, the most common remedy is to treat the formation with scale inhibitor chemicals in a squeeze treatment (Fig. 2) (Crowe et al., 1994; Norris et al., 2001). Phosphonates are one of the most common types of nonpolymeric scale inhibitors, which are used commercially in oileld operations. The phosphonate scale inhibitor Diethylenetriamine pentamethylenephosphoric acid (DETPMP) is known to be amongst the strongest adsorbing scale inhibitor onto carbonate.
Corresponding author. Tel.: +44 131 451 3189; fax: +44 131 451 3539. E-mail address: salima.lokmane@pet.hw.ac.uk (S. Baraka-Lokmane). 0920-4105/$ see front matter 2009 Published by Elsevier B.V. doi:10.1016/j.petrol.2009.05.002

Adsorption is often the primary mechanism of SI retention during squeeze treatments of sandstone formations. The scale inhibitor retention mechanism can be more complex than simple adsorption within carbonate reservoirs because the carbonate rock is a much more reactive substrate. In carbonate formations, scale inhibitors are deliberately allowed to react with the formation and precipitate as the slightly soluble calcium salt. This can result in longer scale protection times. Even fully neutralized inhibitors react with carbonates to form precipitates (Crowe et al., 1994). Reactions that govern the inhibitor squeeze and return are very complicated. Several factors, such as pH, [Ca2+], [Mg2+], temperature, rock mineralogy etc, affect the adsorption level and the shape of the adsorption isotherm (Jordan et al., 1994; Baraka-Lokmane and Sorbie, 2004, 2006). The Rice University Brine Chemistry Consortium has carried out a large number of studies on the scale inhibitor retention in carbonaterich formations during squeeze treatments (Kan et al., 1992, 2004a,b, Tomson et al., 2004; Kan et al., 2005). From these batch studies, some of their conclusions were: (1) calcite is the primary solid responsible for phosphonate retention and clay plays a secondary role in phosphonate retention; (2) although formation mineralogy can be a factor, the primary control of inhibitor retention and return is the pill acidity and concentration; and

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Fig. 1. The build-up of scale inside a tube.

Fig. 3. AFM image of the coreood RC4 showing the morphology of the rock surface.

(3) salt forms at higher pill concentration. This is due to the calcite surface poisoning that lowers the pH of phosphonatecalcite reaction. The current study carries over some of this work into the realm of dynamic coreoods and we compare our conclusions with those of the Rice U. group. The purpose of this work is to study the mechanisms and the factors that affect the retention of the phosphonate scale inhibitor DETPMP in carbonate formations. We present coreooding results using DETPMP to study the effect of inhibitor concentration and pH on inhibitor adsorption and on the behaviour of the inhibitor and cation (calcium and magnesium) concentration. Contained coreoods were performed to study the transport and inhibitor/carbonate interactions of the phosphonate inhibitor when less than 1 PV is injected. This allows the analysis of the consumption of the inhibitor during propagation and desorption, rather than saturating the core with many PV of SI solution to reach full adsorptive capacity of the inhibitor/rock system. 2. Mineralogy of carbonate rock material Carbonate rocks contain more than 50% of the world's hydrocarbon reserves. The carbonate reservoirs have complex pore systems, mainly

because they are particularly sensitive to post-depositional diagenesis, including dissolution, dolomitization and fracturing processes. Carbonate mineralogy is usually simple principal minerals are calcite, dolomite, and minor quantities of clay (Choquette and Pray, 1970; Roehl and Choquette, 1985). In order to carry out a systematic study in well-characterized carbonate cores, a permeable carbonate rock material has been sourced. Sample material was acquired from the Albion Stone Quarries Ltd, Isle of Portland. This rock originates from the Portland Basebed stone and is an open textured oolitic limestone from the Jurassic Portlandian Formation. The b3.5 m thick Basebed is the lower part of the Freestone series, which comprises the Portland Roach, Portland Whitbed and Portland Basebed Formations and is underlain by a cherty series. In this study, ve methods were used to characterize the rock material: X-ray diffraction (XRD), petrographic thin section, atomic force microscopy (AFM), scanning electron microscopy (SEM) and energy dispersive X-ray (EDX). XRD analysis was carried out both on whole rock and on the ne particle fractions. The results of the bulk rock XRD 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. Analysis of the nes showed that no clay minerals are present. Figs. 3 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. 2. Squeeze treatment of producer well.

Fig. 4. AFM image of the coreood RC4 showing the calcite crystals and the shell fragments.

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composed of ne-grained remains of microorganisms with calcite shells, ooids (Fig. 5) with micrite and sparite calcite cement (Fig. 6). The rock presents a ne, 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), ~ 19.80%, grain density, = 2.61 g/cm3 and permeability, k ~ 606 mD. 3. The squeeze strategy In squeeze treatments, the objective is to retain the maximum amount of inhibitor in the formation either by (1) adsorption on the rock substrate by a physico chemical process or (2) precipitation (or phase separation) in a controlled manner, at some distance from the near wellbore area. This is generally achieved by adjusting the injected solution chemistry ([Ca2+] concentration, pH, temperature etc.). Following the treatment, the inhibitor slow release from the rock will be governed by the inhibitor adsorption or retention process, which is specic to the particular inhibitor, the rock matrix and the brine chemistry of interest (Crowe et al., 1994; Graham and Mackay, 2000; Jordan and Sjursaether, 2004). In the eld, the procedure for applying such a chemical treatment to an oil or gas producing well normally involves the following ve stages (Fig. 2): (1) Preush: a pre-ush package which generally consists of a very dilute solution mostly in seawater of the inhibitor eventually mixed with a surfactant, is injected into the well. This both cools the near wellbore formation and prepares the rock surface. (2) Inhibitor injection: the main inhibitor slug, also dissolved in seawater, is squeezed into the near wellbore area. (3) Overush: the main inhibitor slug is displaced to the required distance from the wellbore by injecting seawater into the well.
Fig. 6. SEM photo showing cement containing micrite and sparite crystals, around the ooid grains (M: micrite, C: calcite, O: ooid).

(4) Shut-in: the well will then be shut in for a specied period (usually for 6 to 24 h) in order to allow the inhibitor to interact with the rock substrate. (5) Back production: the well is then put onto back production and the inhibitor is then expected to return to the wellbore at a concentration above the threshold level, minimal inhibitor concentration (MIC), for a long period of time (squeeze lifetime). The success of the treatment, or the squeeze lifetime, can be monitored either by analyzing the inhibitor concentration or by assaying the scaling ions in the return brine. As soon as the scale inhibitor return concentration falls below the minimum inhibitor concentration (MIC) that prevents the scale formation, the squeeze is considered to be over and retreatment is recommended. Successive squeeze treatments can be optimized either from an examination of the actual treated eld return data or from a modelling of the lab coreood inhibitor return data performed under simulated eld conditions. This is achieved by use of the industry standard, Squeeze VI software, developed by Heriot-Watt University, to enable to derive an adsorption isotherm from the scale inhibitor efuent results either from the eld or from the lab coreood data. The shape of the inhibitor adsorption isotherm, , describes the relationship between the level of inhibitor adsorption at the rock surface (in mg/g) and the injected scale inhibitor solution. Once the scale inhibitor/rock adsorption isotherm has been derived for the mineralogy, temperature and pressure conditions present in the specic reservoir, it may then be used to optimize the design of the squeeze treatment for the reservoir formation. 4. Dynamic coreoods experiments Coreood 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 interaction 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 postscale inhibitor treatment petrography to quantify the magnitude of retained scale inhibitor and its mineralogical structure and location. The main steps in the coreoods broadly follow the eld inhibitor treatment stages and are as follows:

Fig. 5. General texture of the oolitic limestone, showing the elongated and rounded ooids, which are formed from micrite resulting the rough surfaces of the ooid grains. Note that blue epoxy resin is used to ll pore space (C: calcite, M: micrite, O: ooid). (For interpretation of the references to colour in this gure legend, the reader is referred to the web version of this article.)

(1) seawater saturation, permeability measurement and core characterization; (2) injection of the main scale inhibitor slug (containing a lithium tracer) followed by a shut-in of 24 h; and

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system. This was felt to be a more appropriate type of ood to use for developing reactive transport models for SI/carbonate systems. The composition of the synthetic seawater used for the coreood tests is presented in Table 1. The scale inhibitor (SI) used for the coreoods 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 ltered through a 0.45 m membrane lter prior to use. The efuent 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. Coreood equipment for coreoods RC1 to RC5.

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

6. Inhibitor analysis 0.5 PV of 5000 ppm, 10,000 ppm, 25,000 ppm and 27,000 ppm of partly neutralized DETPMP at pH 4 (RC1, RC2 and RC5) and at pH 2 (RC3 and RC4) were injected into the core but all other uids (postush seawater and lithium tracer solution) were at pH 6. After SI injection from the inlet end of the core, the ow was reversed and the postush was injected at the former outlet of the core with the SI being produced from the former inlet (Fig. 9). These experiments are designed in order to check what is the most important factor that improves the SI adsorption, is it the high concentration of the SI or the low pH value of the SI.

Fig. 8. Schematic diagram of the experimental set up for the resin-coated coreooding experiments, coreoods RC1 to RC5.

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

6.1. Injection and initial postush Fig. 10 shows the back production with seawater at pH 6, i.e. reversed ow after the 0.5 PV SI slug injection in cores RC1 and RC2, followed by a shut-in period. The SI efuent proles show an immediate spike in SI concentration, and then a gradual decrease in it. In these oods, the scale inhibitor adsorption can be visualized from the retardation between scale inhibitor and the lithium tracer efuent concentrations. In oods RC1 and RC2, the lithium efuent also shows a similar initial spike mirroring the SI one (they are mixed), followed by a drop to a concentration ratio (C/Co) ~ 0.17 and 0.38 (respectively) and then a sudden rise as the injected lithium tracer from the seawater post ush breaks through in the reverse ow as shown in Fig. 10. It is clear from the RC1 and RC2 tracer results in Fig. 10 that there is quite a high level of mixing (dispersion) in the core since the postush (injected at the outlet end) catches the leading edge of the tracer injected from the inlet with the SI slug. Likewise, it is evident that there is some level of SI adsorption since there is a long low [SI] tail concentration with [SI] N 1 ppm for ~ 300 PV.

6.2. Seawater postush Figs. 11 and 12 present the early (~ 100 PV) and late (~ 1800 PV) postush SI return proles, for coreoods RC1 to RC5. As expected, the initial SI return concentrations are low and they also drop more rapidly for these oods since only 0.5 PV of SI solution have been injected. In the early post ush, the oods RC3 and RC5 presents the highest SI returns since the coreoods have been performed with the highest DETPMP concentration i.e. 25,000 ppm active DETPMP at pH 2 and 27,000 ppm active DETPMP at pH 4, respectively. Floods RC1, RC2, RC3, RC4 and RC5, treated with 5000 ppm at pH 4, 10,000 ppm at pH 4, 25,000 ppm at pH 2, 5000 ppm at pH 2, and 27,000 ppm active DETPMP at pH 4, respectively show lower [SI] returns. Thus after 10 PV of postush for ood RC3 SI return concentration is ~ 780 ppm, ~697 ppm for ood RC5, ~287 ppm for ood RC2, ~ 163 ppm for ood RC4 and ~ 69 ppm for ood RC1. Fig. 12 shows that the [SI] return concentration reaches a value of 1 ppm after ~ 300 PV for oods RC1, RC2 and RC4, after 355 PV for ood RC3 and after 596 PV for ood RC5. The 0.70 ppm return concentration is reached after 400PV for oods RC1 to RC4 and after 691PV for ood

Table 1 The composition of brine solution used for the tests. Component NaCl CaCl2.2H2O MgCl2.6H2O KCl NaSO4 Concentration (g/l) 24.08 2.34 11.44 0.877 4.38 Ion Sodium (Na+) Calcium (Ca2+) Magnesium (Mg2+) Potassium (K+) Sulphate (SO2) 4 Chloride (Cl) Concentration (ppm) 10,890 428 1368 460 2960 19,773

Table 2 Brine permeability values before and after the scale inhibitor treatment. Coreood SI concentration (ppm) RC1 RC2 RC3 RC4 RC5 5000 10,000 25,000 5000 27,000 pH of the Permeability (k) (mD) injected SI solution Pre-treatment 4 4 2 2 4 596 606 602 609 600 Permeability (k) (mD) 718 909 992 960 975 Increase in permeability Post-treatment (%) 20 50 65 58 63

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Fig. 10. Normalised (C/Co) inhibitor and lithium concentration proles obtained during initial adsorption and postush stages, oods RC1 and RC2.

Fig. 11. Inhibitor return proles, early postush ( 0.40N100 PV), Dequest 2066 (DETPMP) Aqueous for ood RC1 to RC5.

RC5. Finally the 0.5 ppm return concentration (MIC) is reached after ~ 700PV for all ve coreoods. 7. Cation analysis calcium and magnesium efuent concentrations Fig. 13 presents the [Ca2+], [Mg2+], [Li+] and [SI] concentration proles during the main treatment and the early postush stages for coreood RC5. In this gure, very distinct spikes in SI, lithium and

calcium concentrations are observed, which correspond at the same time with a dip in the magnesium concentration. This is an important observation and has been explained by the binding of the magnesium and the calcium to the DETPMP (Baraka-Lokmane and Sorbie, 2006). During the injection of the SI, we observe a loss in magnesium concentration, because the magnesium is adsorbed together with the SI. After the shut-in, we observe a spike in the magnesium concentration because it is released by the rock together with the SI during the postush.

Fig. 12. Inhibitor return proles, late postush (100N 1800 PV), Dequest 2066 (DETPMP) Aqueous [SI] = 9N 0.40 ppm, oods RC1 to RC5.

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Fig. 13. Normalised (C/Co) inhibitor, lithium and recorded calcium, magnesium concentration proles obtained during initial adsorption and postush stages, ood RC5.

During the postush, two effects inuence the efuent calcium concentration, some calcium remains bound to the DETPMP but, in addition carbonate rock dissolution also occurs and this phenomenon is predominant. This explains the increase in calcium concentration in the efuents. A direct comparison of the evolution of the [Ca2+] and [Mg2+] efuent concentrations for the ve coreoods is shown in Figs. 14

and 15 respectively. Clearly, the levels of both Ca and Mg concentrations correlate with that of the [SI], with a larger effect being seen both at high SI concentration and at a lower injection pH. This effect will be discussed and also modelled in more detail below. Calculations of the amount of dissolution of calcium carbonate from the rock matrix were carried out. Table 3 shows SI adsorption, calcium carbonate dissolution and gain in magnesium during the

Fig. 14. Recorded calcium concentration proles obtained during adsorption and postush stages, oods RC1 to RC5.

Fig. 15. Recorded magnesium concentration proles obtained during adsorption and postush stages, oods RC1 to RC5.

S. Baraka-Lokmane, K.S. Sorbie / Journal of Petroleum Science and Engineering 70 (2010) 1027 Table 3 Scale inhibitor adsorption, calcium carbonate (dissolution) and magnesium (gain) during the main treatment and postush stages for oods RC1 to RC5. Coreood Inhibitor adsorption (mg/g) 0.073 0.075 0.087 0.080 0.084 CaCO3 dissolution (mg) MTa RC1 (SI, pH = 4 Li solution, pH = 6) RC2 (SI, pH = 4 Li solution, pH = 6) RC3 (SI, pH = 2 Li solution, pH = 6) RC4 (SI, pH = 2 Li solution, pH = 6) RC5 (SI, pH = 4 Li solution, pH = 6) 0.93 (0.003) 1.27 (0.004) 1.49 (0.005) 1.15 (0.004) 1.17 (0.004) PFb 211.24 (0.70) 248.59 (0.82) 481.23 (1.59) 420.04 (1.38) 475.19 (1.57) Mg gain (mg) MT 1.53 2.07 2.31 0.82 1.16 PF 14.14 182.34 198.65 117.33 168.71 Table 5 Percentages of SI retained by the rock. Coreood RC1 RC2 RC3 RC4 RC5 % SI retained Modelling 10.6 6.8 2.4 13.1 4.1 % SI retained

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Mass balance (experiment) 15.9 4.8 3.6 14.7 2.4

97.60%, thus the percentage of scale inhibitor retained in the rock varies between 2.40% and 15.21%. 8. pH values The efuent pH proles for all ve coreoods RC1 to RC5 are shown over the entire main treatment and postush periods in Fig. 16. SI injection is performed at pH = 4 for coreoods RC1, RC2 and RC5 and at pH = 2 for coreoods RC3 and RC4. In all these oods, a sharp rise in pH just after the shut-in can be observed and then the pH values stabilize at ~pH 7 until the end of the post ush. Fig. 17 shows also two proles of the efuent pH values for coreood RC4: a rst prole presenting pH values in the same order as for oods RC1 to RC5 (varying between 6.7 and 8.4), and a second prole with much lower pH values varying between 2.50 and 4.30. The lower pH values were those measured immediately after elution from the core. The higher pH values were measured when the collected efuent samples had been protected with test tubes lids and left standing for some time after elution. For these latter samples, CO2 has escaped from the efuents, thus explaining the observed high pH values. Fig. 17 shows that the high pH values have been modelled with MultiScale software (Table 6 and Fig. 18) (mineral scale prediction software by Petrotech, Haugesund, Norway), and the low pH values have been modelled with PHREEQC modeling (Tables 7 and 8, simulations 1 to 5) (geochemical modelling program developed by Appelo and Gerba in 1993 for the U.S. Geological Survey). 9. Modelling of pH prediction, SI returns and Ca/Mg/SI interaction In this study, we have carried out three types of modelling: (1) the prediction of pH evolution has been performed rst with the help of two softwares: MultiScale and PHREEQC; (2) secondly we investigated whether we can reproduce the SI return concentration proles using a simple adsorption isotherm approach.; and (3) nally, the behaviour of the Ca and Mg concentration in the core eluents has been explained by a simple equilibrium SIMg2+ binding model. 9.1. pH prediction The pH of the efuents for our coreoods have been predicted with the help of two models: PHREEQC and MultiScale. 9.1.1. MultiScale modelling MultiScale is a computer program designed to calculate equilibrium in systems containing brines of different composition, gas, oil, and solids. As the input, the user denes temperature, pressure, and the concentration of each compound; MultiScale then uses the appropriate chemical and thermodynamic equations to calculate the nal phases, which are present, and the equilibrium composition of each phase. MultiScale can be used to predict the scaling tendency of NaCl, BaSO4, SrSO4, CaSO4, FeS, CaCO3 and FeCO3, as well as the nal pH of the mixing of two solutions.

The values in brackets are in mg/g. a MT = main treatment. b PF = postush.

main treatment and the postush stages, calculated using mass balance. Fig. 14 shows that for the different coreoods we observe rst a spike in calcium concentration: 693 ppm (RC1), 754 ppm (RC2), 1213 ppm (RC3), 1106 ppm (RC4) and 1261 ppm (RC5). Then the calcium levels drop to 412 ppm (RC1), 407 ppm (RC2), 457 ppm (RC3), 449 ppm (RC4) and 441 ppm (RC5) and remain nally more or less constant until the end of the coreood. Fig. 14 and Table 3 show that coreood RC4 (5000 ppm SI at pH 2) presents a higher total calcium concentration in the efuents (ca. 421.19 mg or 1.38 mg/g vs. ca. 212.17 mg or 0.70 mg/g) than coreood RC1 (5000 ppm SI at pH 4). The lower pH of the injected SI solution in coreood RC4 is thus responsible for the high calcium dissolution. Fig. 14 and Table 3 show also that coreood RC5 (27,000 ppm SI at pH 4) presents comparable levels of calcium elution (ca. 476.36 mg or 1.57 mg/g vs. ca. 482.72 mg or 1.59 mg/g) than ood RC3 (25,000 ppm SI at pH 2). These results show that the slightly higher SI concentration for coreood RC5 (27,000 ppm DETPMP) has compensated the lower pH value (pH = 2) of coreood RC3. Coreood RC3 (25,000 ppm SI at pH 2) presents a higher calcium elution (ca. 482.72 mg or 1.59 mg/g vs. ca. 421.19 mg or 1.38 mg/g) than coreood RC4 (5000 ppm SI at pH 2) thus pointing to the effect of increased SI injected concentration on the calcium release from the rock. This is also valid for the coreoods performed at pH 4, ca. 476.36 mg or 1.57 mg/g for coreood RC5 (27,000 ppm SI), ca. 249.86 mg or 0.82 mg/g for coreood RC2 (10,000 ppm SI at pH 4) and ca. 212.17 mg or 0.70 mg/g for coreood RC1 5000 ppm SI). Table 4 shows that all ve coreoods show a very small SI adsorption level, ~ 0.073 mg/g (RC1), ~ 0.075 mg/g (RC2), ~ 0.087 mg/ 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 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

Table 4 Values of scale inhibitor adsorption calculated using mass balance. Coreood RC1 RC2 RC3 RC4 RC5 SI injected (mg) 73.65 145.78 364.28 80.11 527.42 Total SI retained (mg) 15.21 7.02 13.26 11.78 12.63 % SI return 84.80 95.19 96.36 85.30 97.60 % SI retained 15.21 4.81 3.64 14.70 2.40 SI adsorption (mg/g) 0.073 0.075 0.087 0.080 0.084

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

Fig. 17. Measured pH values for ood RC4.

Fig. 18 shows Efuents pH values modelled with the help of MultiScale software. The input pH values are equal to 6 and 4. The software MultiScale does not accept pH values lower than 4, in the case of carbonate system. Fig. 18 shows that the pH values are around 7. Table 6 shows that the measured pH values are in the same order to those predicted with the software MultiScale. 9.1.2. PHREEQC modelling The second software used to predict the efuent pH values from the different coreooding experiments is the PHREEQC modelling, which is a powerful geochemical modelling program developed by Appelo and Gerba in 1993 for the U.S. Geological Survey. PHREEQC is written in the C programming language and it is designed to perform a wide variety of low-temperature aqueous geochemical calculations. The program is based on equilibrium chemistry of aqueous solutions interacting with minerals, gases, solid solutions, exchangers, and adsorbing surfaces. PHREEQC is used for simulating a variety of reactions and processes in natural waters or laboratory experiments. Table 7 shows the input data set. In this program, seawater is dened by using the major-ion data, it is equilibrated with calcite, to investigate the chemical evolution. In Table 7, PCO2 is the partial pressure of CO2, i.e.
Table 6 Measured and modelled pH values using MultiScale software. Input pH 6 4 Measured pH values 7.2600 6.8650 Modelled pH values (MultiScale) 7.0633 7.0628

the gas phase pressure of CO2 in equilibrium with the carbon dioxide in solution. The Saturation Index, SI is a numeric value indicating whether water is scale-forming or corrosive. It takes account of factors such as pH, total alkalinity, calcium hardness and water temperature. The ideal Saturation Index range is between 3 and +3. Mole transfer is relative to the moles in the phase assemblage; positive numbers indicate an increase in the volume of the phase present, that is, precipitation; negative numbers indicate a decrease in the volume of the phase present, or dissolution. Saturation Index: indicates that Saturation Index calculation not possible because one of the constituent elements was not in solution. Mole transfer: indicates that no mole transfer of this mineral was allowed in the simulation. Selected results from the output data are presented in Table 8. In the simulation the input pH values vary between 6 and 2, the temperature is equal to 20 C and values of CO2(g) vary between 4 and 4. Table 7 shows that the resulting pH values decreases as input CO2(g) increases. In the different simulations, the seawater has the log PCO2 specied by the input except for the simulations 5, 10 and 15 where the seawater has the log PCO2 equal to about 2.5. In the simulations 5, 10 and 15 the input CO2(g) value is equal to 4. 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 should occur, thus dolomite should precipitate. The seawater is undersaturated with dolomite for input CO2(g) equal to 2 and 4 (simulations 4, 5, 9, 10, 14 and 15). This indicates that dolomite should dissolve. Table 8 shows that no mole transfer of dolomite is allowed in the 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) 1027

19

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

phase assemblage decreased by about 21 mmol, i.e. about 21 mmol dissolved into solution. Likewise, about 25 mmol of calcite dissolved. This gure is shown in all the simulations except for simulations 11 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 6 mmol escaped from the seawater solution. These different simulations presented in Table 8 have shown that with the help of PHREEQC modelling we can reproduce the efuents pH values obtained in our coreooding experiments. 9.2. Isotherm derivation The SQUEEZE V software was used to derive adsorption isotherms, (C) for the different coreoods, from the SI efuent concentrations from oods RC1 to RC5. The isotherm describes the adsorption of the scale inhibitor on to the rock substrate. Once the SI adsorption isotherm in the carbonate rock has been derived, it may then be used in turn to model the coreood. This completes the cycle since, where the model calculations match the experimental coreood concentrations, then the isotherm is essentially validated. However, there is an issue in these contained oods since the full length of the core is not exposed to the SI solution and also the same end of the12q core is used for SI injection and back production. Thus, by assuming a shorter effective length of the core, the best ts for ood RC1 (performed with 5000 ppm SI at pH 4) and RC3 (performed with 25,000 ppm SI at pH 2) are represented in Figs. 19 and 20 with their corresponding Freundlich isotherms (i.e. k and n values) (squeeze V program, HeriotWatt University, Scotland).
Table 7 PHREEQC modeling input data set. TITLE Example 3, part A.Calcite equilibrium at log PCO2 = 4.0 and 20C. SOLUTION 1 Seawater units pH temp Ca Mg Na K S(6) EQUILIBRIUM_PHASES CO2(g) Calcite END ppm 2.00 20.0 428.0 1368.0 10,890.0 460.0 2690.0 4.0 0.0

The Freundlich sorption isotherm model is the following C = k:C

n

where k and n are constants, is the mass per dry unit weight of solid (mg/g) of the SI adsorbed, and C is the concentration in ppm of the SI in the brine solution. Figs. 19 and 20 show the experimental and modelled SI returns curves over the full SI concentration range for oods RC1 and RC3 (points = experimental [SI]; solid lines = modelling results). These gures show a satisfactory but not perfect match between experimental and the modelling results. Flood RC1 shows a better t between modeling results and experimental results than ood RC3. This is probably because the calcium and the magnesium ions are strongly involved in the SI/carbonate rock interaction, specially for the coreood performed with high SI concentration (25,000 ppm) and lower pH value (pH = 2) and in this case a single adsorption isotherm may not provide a complete description of the process. From the modelling results in Figs. 19 and 20, we can predict the amount of SI (for example, as a % of the injected amount) retained in the core at the end of the ood. These predictions are compared with the experimental mass balance measurements in Table 5 and it can be noted that both results agree extremely well. However, we cannot be satised with this pseudo-isotherm approach although if it ts the experimental data very well since we are aware that the SI/calcite interaction in the core is more complex than a simple adsorption process. In the literature, we can nd three views on the precise mechanisms through which SI species are retained within the reservoir formation e.g. adsorption, precipitation, surface condensation, coupled adsorption/ precipitation etc. These three views are: (1) the Heriot-Watt view, where retention is described in general terms through an adsorption isotherm, (C), or alternatively by a two parameter precipitation/dissolution model, (C) (solubility) and r2 (dissolution rate) (Sorbie et al., 1991a,b, 1992, 1993a,b, 1994, Sorbie and Gdanski, 2005); (2) the Halliburton model, which approaches adsorption from a mineralogical perspective and relates the total rock adsorption to the adsorption on each mineral component of the rock (Gdanski and Funkhouser, 2001, 2002, 2005); and (3) the Rice University view, in which for example, phosphonate retention is related to the solubility of a sparingly soluble calcium phosphonate precipitate and refers to high, medium

20 Table 8 PHREEQC modeling results. Simulation Input data

S. Baraka-Lokmane, K.S. Sorbie / Journal of Petroleum Science and Engineering 70 (2010) 1027

pH

Log PCO2 4.00

Saturation Index Calcite Dolomite 0.81

Mole transfer (mmol) CO2 20.75 Calcite 24.84 Dolomite

10

11

12

13

14

15

Temperature = 20 CO2 (g) = 4.0 pH = 6 Temperature = 20 CO2 (g) = 2.0 pH = 6 Temperature = 20 CO2 (g) = 0.0 pH = 6 Temperature = 20 CO2 (g) = 2.0 pH = 6 Temperature = 20 CO2 (g) = 4.0 pH = 6 Temperature = 20 CO2 (g) = 4.0 pH = 4 Temperature = 20 CO2 (g) = 2.0 pH = 4 Temperature = 20 CO2 (g) = 0.0 pH = 4 Temperature = 20 CO2 (g) = 2.0 pH = 4 Temperature = 20 CO2 (g) = 4.0 pH = 4 Temperature = 20 CO2 (g) = 4.0 pH = 2 Temperature = 20 CO2 (g) = 2.0 pH = 2 Temperature = 20 CO2 (g) = 0.0 pH = 2 Temperature = 20 CO2 (g) = 2.0 pH = 2 Temperature = 20 CO2 (g) = 4.0 pH = 2

8.143

0.00

7.113

2.00

0.00

0.75

2.312

1.987

5.977

0.00

0.00

0.45

0.501

0.146

4.751

2.00

0.00

0.13

3531

0.885

4.493

2.46

0.00

0.28

10,000

130.2

8.141

4.00

0.00

0.81

0.1254

0.329

7.112

2.00

0.00

0.75

2.225

2.063

5.977

0.00

0.00

0.45

50.04

14.65

4.750

2.00

0.00

0.13

3531.0

88.60

4.493

2.46

0.00

0.28

10,000.0

130.3

8.026

4.00

0.00

0.58

7.853

8.204

7.012

2.00

0.00

0.55

6.083

9.615

5.926

0.00

0.00

0.35

40.63

21.18

4.736

2.00

0.00

0.16

3515.0

0.946

4.482

2.47

0.00

0.30

10,000.0

136.5

and low solubility phases of this precipitate (Kan et al., 1992, 2004a,b; Tomson et al., 2004; Kan et al., 2005). These three views described above are probably all right under certain circumstances. Sorbie and Gdanski (2005) have published a detailed comparison of the Heriot-Watt and Halliburton models showing that the two models are very similar in broad principle and differ only in some details (e.g. the form of the desorption rate law). For example, both models could match some very detailed experimental SI core efuent data with equal accuracy by changing only some model parameters. In the case of a carbonate system, although the pseudo-isotherm approach ts the data very well, we are aware that the SI/calcite interaction in the core is more complex than a simple adsorption process. Future work will focus on improving the model for describing this process. The modeling presented in section 9.3 takes some initial steps towards a full model for the SI/carbonate interaction taking into account the involvement of both calcium and magnesium ions. 9.3. A simple model of the Ca and Mg behaviour The role of calcium and magnesium ion, which are known to interact directly with the DETPMP, has been studied in this work. DETPMP

adsorption is signicantly improved by the presence of Ca2+ ions and effectively poisoned by the presence of excess Mg2+ ions. Sorbie and Laing (2004) have shown that calcium and magnesium may bind to DETPMP, which was denoted by A for simplicity. The solution equilibrium binding reactions which occur in a Ca/Mg/DETPMP system are as follow: Ca + A X Ca A Mg + A X Mg A The stability constants KCa and KMg, are given by: KCa = XCa A XCa XA XMg A XMg XA 3a
KMg KCa

2a 2b

KMg =

3b

For DETPMP, these quantities are known to be KMg = 6.3 1010 and 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) 1027

21

Fig. 19. RC1 linear coreood model, best t. Freundlich isotherms: k = 6000, n = 0.25.

Fig. 20. RC3 linear coreood model, best t. Freundlich isotherms: k = 4500, n = 0.45.

(as A) in solution, denoted XCa0, XMg0 and XA 0. It is quite straightforward to rearrange the system of equations to obtain the following two implicit equations for XCa and XMg: XCa = h XCaO
XA O 1 + KCa XCa + KMg XMg

1 + KCa

4a

XMg =

1 + KMg

XMgO

Table 9 summarizes results for the calculated ratio using Eqs. (4a and b) and (5) from the ve experimental coreoods RC1 to RC5. The 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 88% of DETPMP is bound to Mg. This is quite consistent with the results we observe in our experiments where the retained SI causes a decrease below the stock of magnesium during the adsorption stage of the treatment followed by a post shut-in value of magnesium

XA O 1 + KCa XCa + KMg XMg

4b
Table 9 Values of percentage of SI bound to Ca and Mg using Eqs. (4a and b) and (5) for oods RC1 to RC5. Coreood RC1 RC2 RC3 RC4 RC5 (XCaA/XMgA) Eq. (5) 0.1402 0.1436 0.1431 0.1432 0.1428 % SICa bound 12 13 13 13 12 % SIMg bound 88 87 87 87 88 (XCaA/XMgA) Eq. (4a and b) 0.1496 0.1641 0.1797 0.1457 0.1796 % SICa bound 13 14 15 13 15 % SIMg bound 87 86 85 87 85

Eqs. (3a) and (3b) can be solved numerically in a spreadsheet but the actual quantity of interest is the equilibrium value of (XCaA/XMgA), i.e. the ratio of SI bound to Ca to SI bound to Mg. For very large values of stability KCa, KMg, as is the case here, an approximate equation for this ratio is given by: ! ! KCa XCaO XCaA e XMgA KMg XMgO 5

22 Table 10 XRD, XRF and XPS results. Sample XRD analysis Calcite (CaCO3) (%) RC1 RC2 RC3 RC4 RC5 96.0 99.0 97.8 98.8 74.0 Quartz SiO2 (%) 4.0 1.0 1.8 1.2 2.0

S. Baraka-Lokmane, K.S. Sorbie / Journal of Petroleum Science and Engineering 70 (2010) 1027

XPS analysis Albite Na (AlSi3O8) (%) Microcline K(AlSi3O8) (%) Phosphorus P (%) 0.160 0.170 0.350 0.210 0.300

0.4 117.0 7.0

concentration above the stock as the SI (bound mainly to Mg) is back produced. Further work is in progress to model more appropriately the coreoods (RC1 to RC5) taking into account the involvement of calcium and magnesium in the SI/carbonate rock interaction.

10. Post-coreood petrographic analysis The rock material used in oods RC1 to RC5 was analysed after the SI treatment, to check for any evidence of dissolution of the rock matrix and/or precipitation within the rock matrix. A post-coreood petrography analysis has been performed on cores RC1 to RC5. These
Fig. 23. Image of calcite cement in core RC5. Note the undamaged calcite crystals and calcite crystals with microwormholes.

analyses include the study of the thin sections as well as the XRD, XPS, AFM, SEM and EDX measurements. XRD analysis carried out both on the whole rock and on the ne 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 magnication 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 (coreood RC1).

S. Baraka-Lokmane, K.S. Sorbie / Journal of Petroleum Science and Engineering 70 (2010) 1027

23

Fig. 29. SEM Photo of coreood RC4, showing SI salts occupying the void space. Fig. 26. SEM photo showing masses of SI salts on the ooids (coreood RC2).

Fig. 27. Image of RC3 after the scale inhibitor treatment. Note the SI salts.

calcite. Core RC1 is about 96% calcite and 4% quartz. Core RC2 is about 99% calcite and 1% quartz. Core RC3 is about 97.8% calcite, 1.8% quartz and 0.4% plagioclase. Core RC4 is about 98.8% calcite and 1.2% quartz. Core RC5 is about 74% calcite, 2% quartz, 17% plagioclase and 7% microcline (Table 10). The analysis of the thin sections as well as the SEM analysis performed on coreoods RC3 and RC4 have shown that the treatment of

these oods 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 coreood 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 the vacuolar structure of the phosphorus calcium salt shows that the salt has been precipitated, conrming that the mechanism of the DETPMP retention in carbonate rocks is of a precipitation type (Figs. 2931). The Atomic Force Microscopy (AFM) analysis has shown the shape of the calcium phosphonate crystals (Figs. 32 and 33); indeed, the AFM technique allows a higher resolution than the SEM technique and 3-D images of the rock surfaces. The X-ray photoelectron spectrometer (XPS) analyses have been 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) 1027

Fig. 30. Larger magnication of Fig. 29.

Fig. 32. AFM image showing the structure of the calcite phosphate crystal in coreood RC4.

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

Fig. 31. Larger magnication of Fig. 30 of the SI salt containing phosphorus, calcium, chloride, and sodium.

Fig. 33. Larger magnication of Fig. 32.

S. Baraka-Lokmane, K.S. Sorbie / Journal of Petroleum Science and Engineering 70 (2010) 1027

25

MgA binding which allows us to estimate the relative amounts of each of these species, as the ratio, (XCaA/XMgA). The numerically predicted value of (XCaA/XMgA) varies between 0.1402 and 0.1797, implying that 12 to 15% of the DETPMP has Ca bound to it and 85 to 88% has Mg bound to it. This is in excellent agreement with our experimental results(from the efuent data) and explains why the Mg efuent concentration shows a clear dip during the SI placement and a peak during the seawater postush period. (4) The modelling, using the derivation of an effective pseudoisotherm (with a Freundlich isotherm), is able to produce good matches (not predictions) of the SI return concentration curves for all ve core oods RC1 to RC5. We are able to predict the nal %SI retained in the core by modelling and this can be compared with the experimental mass balance results. In fact, excellent quantitative agreement is seen. However, we are not satised by this approach since a simple adsorption model does not, in our view, represent all what is happening in these oods We are aware that the SI/calcite interaction in the core is more complex than a simple adsorption process. Future work will focus on improving the model for describing the SI/carbonate interaction taking into account the involvement of both calcium and magnesium ions. (5) The petrography analysis has shown that coreoods RC3 and RC4 (at pH 2) did not induce the formation of worm holes or micro worm holes, but coreood 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 on the calcite crystals. The analysis of the structure of the phosphonatecalcium salt shows that this salt has been precipitated, conrming that the mechanism of the DETPMP SI retention in carbonate rocks is of a precipitation type. The Atomic Force Microscopy (AFM) analysis has revealed the shape of the calcium phosphonate crystals. Thin sections, SEM, EDX, XPS and AFM analysis of the cores after the different coreoods have shown the presence of SI salts formed within the void space and on the ooid grains. The EDX analysis of the SI salts has revealed the presence of phosphorus. The XPS analysis has shown that coreoods RC3 (25,000 ppm DETPMP at pH 2) shows more retained phosphorus (0.35%) than oods RC5 (0.30%), RC4 (0.21%), RC2 (0.17%) and RC1 (0.16%). These results show that we have more SI retention with both a high SI concentration and a low pH value, the low pH parameter seeming to be more important on SI adsorption than the concentration of the SI solution. Acknowledgements The sponsors of the Heriot-Watt University, Flow Assurance and Scale Team (FAST) JIP are thanked for their support, input and permission to publish this work: Baker Petrolite, BG Group, BP, Champion Technologies, Chemtura, Chevron, Clariant, ConocoPhillips, Halliburton, Hydro Oil and Energy, M I Production Chemicals, Nalco, Petrobras, REP, Rhodia, Shell, Solutia, Statoil and Total. We thank Dr Norbert Kohler for his constructive review of the manuscript. Appendix A. Detailed experimental procedures for contained coreoods RC1 to RC5 Experimental procedure for coreood RC1 1. Brine saturation: saturation of the core with brine solution (pH = 6) at room temperature and at ow rates of 30, 60, 90, and 120 ml/h, 1 h each. The core was then shut in over 24 h. 2. Pre-treatment brine permeability measurement: brine permeability was measured at room temperature at ow rates of 30, 60, 90, 120, and 240 ml/h in forward direction of ow, 10 min each (brine with

3.

4.

5.

6.

7.

8.

pH = 6). measurement of permeability k1 between P1 and P2 and k2 between P2 and P3 (see Figs. 2.3 and 2.5). Lithium solution injection: 50 ppm lithium in brine solution (pH = 6) was injected at a ow rate of 30 ml/h, 30 samples of 2 ml were collected (sample interval every 4 min). Brine solution injection: brine solution (pH = 6) was injected at a ow rate of 30 ml/h, 30 samples of 2 ml were collected (sample interval every 4 min). Scale inhibitor injection: injection of 0.5 PV (15.18 ml) 5000 ppm active SI-labelled with 50 ppm Li tracer in brine solution (pH = 4) at a ow rate of 30 ml/h then shut in. The core was then shut in over 24 h. Postush is carried out with lithium solution injection: 50 ppm lithium in brine solution (pH = 6) from the outlet (P3) (see Figs. 2.3 and 2.5) at a ow rate of 30 ml/h. Sample schedule = N80 samples of 2 ml collected (sample interval every 4 min); 60 samples of 10 ml collected (sample interval every 20 min); approximately 500 samples of 20 ml collected (sample interval every 40 min), until the active inhibitor concentration fell below approximately 0.5 ppm active inhibitor. Post-treatment brine permeability measurement: brine permeability was measured at room temperature at ow rates of 30, 60, 90, 120, and 240 ml/h in forward direction of ow, 10 min each (brine with pH = 6). Measurement of permeability k1 between P1 and P2 and k2 between P2 and P3 (see Fig. 2.5). Measurement of dead volume: after completing all the steps described above, the core assembly was dismantled and the dead volume in the system was measured.

Experimental procedure for coreood RC2 1. Brine saturation: saturation of the core with brine solution (pH = 6) at room temperature and at ow rates of 30, 60, and 90 ml/h, 1 h each. The core was then shut in over 24 h. 2. Pre-treatment brine permeability measurement: brine permeability was measured at room temperature at ow rates of 30, 60, 90, and 120 ml/h in forward direction of ow, 30 min each.(brine with pH = 6). 3. Lithium solution injection: injection of 0.25 PV (7.59 ml) 50 ppm Lithium in brine solution (pH = 6) from the inlet at a ow rate of 30 ml/h, 30 samples of 2 ml were collected (sample interval every 4 min). 4. Brine solution injection: injection of 0.25 PV (7.59 ml) brine solution (pH = 6) from the inlet at a ow rate of 30 ml/h, 30 samples of 2 ml were collected (sample interval every 4 min). 5. Lithium solution injection: continuous injection of 50 ppm Lithium in brine solution (pH = 6) from the outlet at a ow rate of 30 ml/h, 30 samples of 2 ml were collected (sample interval every 4 min). 6. Brine solution injection: continuous injection of brine solution (pH = 6) from the outlet at a ow rate of 30 ml/h, 30 samples of 2 ml were collected (sample interval every 4 min). 7. Scale inhibitor injection: injection of 0.5 PV (15.18 ml) 10,000 ppm active SI-labelled with 50 ppm Li tracer in brine solution (pH = 4) from the inlet at a ow rate of 30 ml/h then shut in. The core was then shut in over 24 h. 8. Postush is carried out with lithium solution injection: 50 ppm lithium in brine solution (pH = 6) was injected from the outlet at a ow rate of 30 ml/h. Sample schedule = N80 samples of 2 ml collected (sample interval every 4 min); 60 samples of 10 ml collected (sample interval every 20 min); approximately 500 samples of 20 ml collected (sample interval every 40 min), until the active inhibitor concentration fell below approximately 0.5 ppm active inhibitor. 9. Post-treatment brine permeability measurement: brine permeability was measured at room temperature at ow rates of 30, 60, 90,

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120, and 240 ml/h in forward direction of ow, 10 min each (brine with pH = 6). 10. Measurement of dead volume: after completing all the steps described above, the core assembly was dismantled and the dead volume in the system was measured. Experimental procedure for coreood RC3 1. Brine saturation: saturation of the core with brine solution (pH = 6) at room temperature and at ow rates of 30, 60, and 90 ml/h, 1 h each. The core was then shut in over 24 h. 2. Pre-treatment brine permeability measurement: brine permeability was measured at room temperature at ow rates of 30, 60, 90, and 120 ml/h in forward direction of ow, 30 min each (brine with pH = 6). 3. Lithium solution injection: 50 ppm Lithium in brine solution (pH = 6) was injected at a ow rate of 30 ml/h, 60 samples of 2 ml were collected (sample interval every 4 min). 4. Scale inhibitor injection: injection of 0.5 PV (15.18 ml) 25,000 ppm active SI (pH = 2) from the inlet at a ow rate of 30 ml/h then shut in. The core was then shut in over 24 h. 5. Post ush is carried out with iodide solution injection: 200 ppm Sodium Iodide in brine solution (pH = 6) was injected from the outlet at a ow rate of 30 ml/h. Sample schedule =N80 samples of 2 ml collected (sample interval every 4 min); 60 samples of 10 ml collected (sample interval every 20 min); approximately 500 samples of 20 ml collected (sample interval every 40 min), until the active inhibitor concentration fell below approximately 0.5 ppm active inhibitor. 6. Measurement of dead volume: after completing all the steps described above, the core assembly was dismantled and the dead volume in the system was measured. Experimental procedure for coreood RC4 1. Brine saturation: saturation of the core with brine solution (pH = 6) at room temperature and at ow rates of 30, 60, and 90 ml/h, 1 h each. The core was then shut in over 24 h. 2. Pre-treatment brine permeability measurement: brine permeability was measured at room temperature at ow rates of 30, 60, 90, and 120 ml/h in forward direction of ow, 30 min each (brine with PH = 6). 3. Lithium solution injection: 50 ppm Lithium in brine solution (pH = 6) was injected at a ow rate of 30 ml/h, 60 samples of 2 ml were collected (sample interval every 4 min). 4. Brine solution injection: brine solution (pH = 6) was injected at a ow rate of 30 ml/h, 60 samples of 2 ml were collected (sample interval every 4 min). 5. Scale inhibitor injection: injection of 0.5 PV (15.18 ml) 5000 ppm active SI-labelled with 50 ppm Li tracer in brine solution (pH = 2) at a ow rate of 30 ml/h then shut in. The core was then shut in over 24 h. 6. Post ush is carried out with brine solution injection: brine solution (pH = 6) was injected from the outlet at a ow rate of 30 ml/h. Sample schedule = N80 samples of 2 ml collected (sample interval every 4 min); 60 samples of 10 ml collected (sample interval every 20 min); approximately 500 samples of 20 ml collected (sample interval every 40 min), until the active inhibitor concentration fell below approximately 0.5 ppm active inhibitor. 7. Measurement of dead volume: after completing all the steps described above, the core assembly was dismantled and the dead volume in the system was measured. Note: analyze Li, Ca, Mg and Fe in steps 3 and 4; analyze Li, P, Ca, Mg and Fe in steps 5 and 6.

Experimental procedure for coreood RC5 1. Brine saturation: saturation of the core with brine solution (pH = 6) at room temperature and at ow rates of 30, 60, and 90 ml/h, 1 h each. The core was then shut in over 24 h. 2. Pre-treatment brine permeability measurement: brine permeability was measured at room temperature at ow rates of 30, 60, 90, and 120 ml/h in forward direction of ow, 30 min each (brine with PH = 6). 3. Lithium solution injection: 50 ppm Lithium in brine solution (pH = 6) was injected at a ow rate of 30 ml/h, 60 samples of 2 ml were collected (sample interval every 4 min). 4. Brine solution injection: brine solution (pH = 6) was injected at a ow rate of 30 ml/h, 60 samples of 2 ml were collected (sample interval every 4 min). 5. Scale inhibitor injection: injection of 0.5 PV (15.18 ml) 25,000 ppm active SI-labelled with 50 ppm Li tracer in brine solution (pH = 6) at a ow rate of 30 ml/h then shut in. The core was then shut in over 24 h. 6. Post ush is carried out with brine solution injection: brine solution (pH = 6) was injected from the outlet at a ow rate of 30 ml/h. Sample schedule = N80 samples of 2 ml collected (sample interval every 4 min); 60 samples of 10 ml collected (sample interval every 20 min); approximately 500 samples of 20 ml collected (sample interval every 40 min), until the active inhibitor concentration fell below approximately 0.5 ppm active inhibitor. 7. Measurement of dead volume: after completing all the steps described above, the core assembly was dismantled and the dead volume in the system was measured. Note: analyze Li, Ca, Mg and Fe in steps 3 and 4; analyze Li, P, Ca, Mg and Fe in steps 5 and 6. References
Baraka-Lokmane, S. and Sorbie, K.S. Scale Inhibitor Core Floods in Carbonate Cores: The Inuence of pH on PhosphonateCarbonate Interactions, SPE 87448, SPE Sixth International Symposium on Oileld Scale, 2627 May 2004, Aberdeen, UK. Baraka-Lokmane, S. and Sorbie, K.S. Scale Inhibitor Core Floods in Carbonate Cores: Chemical Interactions and Modelling, SPE 100515, SPE Sixth International Symposium on Oileld Scale, 2627 May 2006, Aberdeen, UK. Choquette, P.W., Pray, L.C., 1970. Geologic nomenclature and classication of porosity in sedimentary carbonates. AAPG Bull. 54 (2), 207. Crowe, C., McConnell, S.B., Hinkel, J.J., Chapman, K., 1994. Scale inhibition in wellbores. SPE 27996. Paper Presented at the University of Tulsa Centennial Petroleum Engineering Symposium Held in Tulsa, OK, USA. 2931 August. Gdanski, R., Funkhouser, G.P., 2001. Successful model of the kinetic release of a phosphonate scale inhibitor. Presented at the NIF International Oileld Chemistry Symposium, Geilo, Norway. 14 April. Gdanski, R., Funkhouser, G.P., 2002. Fully contained laboratory squeeze treatment. Presented at the NIF International Oileld Chemistry Symposium, Geilo, Norway. 1720 March. Gdanski, R., Funkhouser, G.P., 2005. Mineralogy driven scale inhibitor squeeze designs. SPE 94510. Paper Presented at the SPE European Formation Damage Conference Held in Scheveningen, The Netherlands. 2527 May. Graham, G.M., Mackay, E.J., 2000. Scale inhibitor selection criteria for downhole application in a chalk reservoir. 4th Chemistry in Industry Conference and Exhibition. Scale and Corrosion Chemistry Session, Paper No OFC-2, pp. 1158. Jordan, M.M., Sjursaether, K., 2004. Scale control within sea chalk/limestone reservoirs. The challenge of understanding and optimizing chemical placement methods and retention mechanism: laboratory to eld. SPE 86476. Paper Presented at the SPE International Symposium and Exhibition on Formation Damage Control, Lafayette, Louisiana, USA. 1820 February. Jordan, M.M., Sorbie, K.S., Jiang Ping, Yan Ming Dong, Todd, A.C., 1994. Phosphonate scale inhibitor adsorption/desorption and the potential for formation damage in reconditioned eld core. SPE 27389. Paper Presented at the SPE International Symposium on Formation Damage Control Held in Lafayette, Louisiana, USA. 710 February. Kan, A., Cao, X., Yan, P.B., Oddo, J.E., Tomson, M.B., 1992. The transport of chemical scale inhibitor and its importance to the squeeze procedure. Paper No 33 Presented at the NACE Annual Conf and Corrosion Show, Nashville, TN. 27 April1 May. 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. 280289 September. Kan, A.T., Fu, G., Tomson, M.B., 2004b. Adsorption and precipitation of an aminoalkylphosphonate onto calcite. J. Colloid Interface Sci. 275284.

S. Baraka-Lokmane, K.S. Sorbie / Journal of Petroleum Science and Engineering 70 (2010) 1027 Kan, A.T., Fu, G., Tomson, M.B., 2005. Prediction of scale inhibitor squeeze and return in calcite-bearing formation. SPE 93265. SPE International Symposium on Oileld Chemistry Held in Houston, Texas, U.S.A. In. 24 February. Mackay, E.J., Collins, I.R., Jordan, M.M., Feasey, N., 2003. PWRI: scale formation risk assessment and management. SPE 80385. Paper Presented at the 5th International Symposium on Oileld Scale Held in Aberdeen, UK. 2930 January. Norris, M., Perez, D., Bourne, H.M., Heath, S.M., 2001. Maintaining fracture performance through active scale control. SPE 68300. Paper Presented at the 3rd International Symposium on Oileld Scale Held in Aberdeen, UK. 3031 January. Roehl, P.O., Choquette, P.W., 1985. Carbonate Petroleum Reservoirs. Springer-Verlag, New York City. Sorbie, K.S., Laing, N., 2004. How scale inhibitors work. Mechanisms of selected barium sulphate scale inhibitors across a wide temperature range. SPE 87470 SPE International Symposium on Oileld Scale held in Aberdeen, UK. 2627 May. Sorbie, K.S., Gdanski, R.D., 2005. A complete theory of scale inhibitor transport and adsorption/desorption in squeeze treatments. SPE 95088 SPE International Symposium on Oileld Scale Held in Aberdeen, UK. 1112 May. Sorbie, K.S., Yuan, M.D., Todd, A.C., 1991a. The modelling and design of scale inhibitor squeeze treatments in complex reservoirs. SPE 21024, SPE International Symposium on Oileld Chemistry, Anaheim, CA. 2022 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

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of Chemistry Publication Chemicals in the Oil Industry: Developments and Applications. Sorbie, K.S., Yuan, M.D., Todd, A.C., 1992. Interpretation and theoretical modelling of scale- inhibitor/tracer coreoods. SPE Prod. Eng. 307312 August. Sorbie, K.S., Yuan, M.D., Chen, P., Todd, A.C., Watt, R.M.S., 1993a. The effect of pH on the adsorption and transport of phosphonate scale inhibitor through porous media. SPE 25615, SPE International Symposium on Oileld Chemistry, Anaheim, CA. 2022 February. Sorbie, K.S., Jiang, P., Yuan, M.D., Chen, P., Jordan, M.M., Todd, A.C., 1993b. The effect of pH, calcium and temperature on the adsorption of phosphonate inhibitor onto consolidated and crushed sandstone. SPE 26605, SPE Annual Conference and Technical Exhibition, Houston, TX. 36 October. Sorbie, K.S., Yuan, M.D., Jordan, M.M., Hourston, K.E., 1994. Application of a scale inhibitor squeeze model to improve eld squeeze treatment design. SPE 28885, Proceedings of the SPE European Petroleum Conference (Europec 94), London, UK. 2527 October. Tomson, M.B., Kan, A.T., Fu, G., 2004. Control of inhibitor squeeze via mechanistic understanding of inhibitor chemistry. SPE 87450 SPE, 6th International Symposium on Oileld Scale Held in Aberdeen, UK. 2627 May.