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SPE 87437 Inhibition Of Barite Scale In The Presence Of Hydrate Inhibitors

Mason B. Tomson, SPE; Amy T. Kan, SPE; and Gongmin Fu. Rice University, Brine Chemistry Consortium

Copyright 2004, Society of Petroleum Engineers Inc. This paper was prepared for presentation at the 6th International Symposium on Oilfield Scale held in Aberdeen, UK, 26-27 May 2004. This paper was selected for presentation by an SPE Program Committee following review of information contained in an abstract submitted by the author(s). Contents of the paper, as presented, have not been reviewed by the Society of Petroleum Engineers and are subject to correction by the author(s). The material, as presented, does not necessarily reflect any position of the Society of Petroleum Engineers, its officers, or members. Papers presented at SPE meetings are subject to publication review by Editorial Committees of the Society of Petroleum Engineers. Electronic reproduction, distribution, or storage of any part of this paper for commercial purposes without the written consent of the Society of Petroleum Engineers is prohibited. Permission to reproduce in print is restricted to an abstract of not more than 300 words; illustrations may not be copied. The abstract must contain conspicuous acknowledgment of where and by whom the paper was presented. Write Librarian, SPE, P.O. Box 833836, Richardson, TX 75083-3836, U.S.A., fax 01-972-952-9435.

Abstract Large volumes of hydrate inhibitors (e.g., methanol, ethanol, monoethylene glycol, and triethylene glycol as cosolvent) are added to control hydrate formation. Such practice has an adverse effect on scale formation since the mineral salts are generally less soluble in the cosolvent. Due to production from reservoirs, oilfield brines are often close to saturation as they enter a well, even a small amount of added methanol, ethanol, etc., is often sufficient to induce various minerals to precipitate, particularly the sparingly soluble minerals, e.g., barite. For example, barite solubility is reduced by as much as 20 folds, with 50% (w/w) methanol. In this paper, barite nucleation rate were studied over a wide range of concentrations, e.g., Ba (0.5-1.8 mm) SO4 (0.51.8 mm) methanol (0-40%), monoethylene glycol (0-40%) or triethylene glycol (40%). Barite nucleation rate is significantly accelerated in as little as 5% (wt/wt) methanol. The barite nucleation rate can be modeled with a modified classical nucleation theory. The inhibition of barite by two phosphonate inhibitors and a polymer inhibitor in the co-solvent/brine solution is more complex. At lower co-solvent concentrations (<30% w/w), the nucleation inhibition can be predicted with a previously derived semi-empirical model that mathematically separates the effect of added inhibitors from that of the uninhibited mineral phase. At high methanol (>30%) concentration, barite nucleation may be difficult to inhibit by scale inhibitors, due to high supersaturation and the tendency of phosphonate to be precipitated as metal salt. Introduction: Barium sulfate, BaSO4 scale, is commonly found in the oil and gas wells and the various industrial water treatment systems. It is problematic since BaSO4 is difficult to remove once formed. Furthermore, it is often enriched with radium due to co-precipitation. Therefore, the study of precipitation of

BaSO4 from supersaturated solution is of both scientific and practical importance1-5. In the oil and gas industries, methanol (MeOH) and monoethylene glycol (MEG) or simply ethylene glycol (EG) are often used to inhibit gas hydrate formation during production. Gas hydrate is a crystalline solid consisting of gas molecule surrounded by a cage of water molecules, which forms at certain high pressure and low temperature regimes. Gas hydrate formation is particularly troublesome for offshore gas wells where the producing temperature is low due to both adiabatic expansion of gas and seawater cooling. Once gas hydrate forms, it can plug up the well and prevent gas production. One economic solution to prevent hydrate formation is to inject a large quantity of methanol or ethylene glycols. However, methanol or ethylene glycols may cause adverse scaling problems in the associated brine solution, which often contains high concentrations of dissolved minerals. There is little research on the solubility of mineral salt in methanol/water/salt or ethylene glycol/water/salt solutions. The authors have studied the solubility of mineral salts in these mixed solvent systems. In Figure 1 is plotted the barite solubility in NaCl-BaSO4-hydrate inhibitor-water mixtures versus hydrate inhibitor concentrations. As shown in Figure 1, barite solubility is negatively impacted by all three hydrate inhibitors, where the effects are in the order of methanol>triethylene glycol>monoethylene glycol. The impact of methanol on barite scale formation can be predicted by ScaleSoftPitzer with a neutral species activity coefficient, 6,7 N . BaSO
4

SI

Barite

Ba 2 + SO 2 S 2 + S 2 N 2 4 BaSO 4 Ba SO 4 = log Barite K sp


4

][

(1

N where BaSO is a function of co-solvent concentration (mole

fraction) and temperature (Eqs. 2 & 3).


N log( BaSO , MeOH) = (3.022 + 1167.6 / T(o K )) x MeOH 10.89 x 2 MeOH 4

(2
N log( BaSO , EG) = 2.590 x EG 4

- 5.316 x 2 EG

(3

N In the following discussion, BaSO for triethylene glycol is 4 N assumed to be equal to BaSO for monoethylene glycol since
4

N the value of BaSO for triethylene glycol is not available. 4 While the effects of hydrate inhibitors on barite solubility are

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SPE 87437

documented, the impact of hydrate inhibitors on the nucleation kinetics of barite formation and the efficiency of common scale inhibitors has not been studied. Phosphonates and polycarboxylic acids are good inhibitors of mineral nucleation and are widely used in industries. The solution chemistry of phosphonates has been better understood than that of the polycarboxylic acids8-10. Recently, the authors have made significant progress toward the understanding of the solution chemistry of a specific polymeric inhibitor phosphino-polycarboxylic acid (PPCA)11. Equations based upon the electrostatic theory of macromolecules12 have been developed to estimate PPCA's solution speciation as a function of temperature, ionic strength, pH and Ca concentrations. A set of semi-empirical equations have been proposed to predict the nucleation time in the presence and absence of scale inhibitors and the minimum inhibitor concentration (MIC) for any specific well conditions. The overall influence of inhibition on the nucleation time is modeled by mathematically separating the effect of added inhibitors from that of the uninhibited mineral phase. The induction time for uninhibited mineral phase can be described by classical nucleation theory. This greatly simplifies how to describe new inhibitors and blends. The predictions compare favorably with both laboratory observations and field data. The objective of this report is to discuss the impact of hydrate inhibitors on barite nucleation kinetics and the prediction of inhibitor MIC. Semi-empirical model to predict barite nucleation. According to Shnel and Mullin13, the induction time ( t ind , sec), for a critical nuclei to form and for the critical nuclei to grow to detectable size, can be determined from Eq. 4: 2 2/3 3 4/3 ' 2 Vm NA 0 (4 ) = a + 2 Vm N A log(t ind + 2 4 (2.303RT ) 2 (SI ) 4 (2.303RT ) 3 (SI )
5/3 Vm and a = 0.25 + log10 0.32 + log10 8/3 4 0.5 2 N D Ksp ( 1 ) A

inhibitor concentration and blends needed for a specific well condition. Which inhibitor to use among many commercial options and the minimum effective concentration needed are often critical in scale treatment. Common inhibitor types include various aminopolyphosphonates, polyacrylates, polysulfonates, their derivatives and mixtures. The inhibition calculation is based on a semi-empirical nucleation inhibition model. The currently available prediction of inhibitors include: NTMP [nitrilotri(methylene phosphonic) acid], HDTMP [hexamethylenediamine tetra(methylene phosphonic) acid], DTPMP [diethylenetriamine penta(methylene phosphonic) acid], BHPMP [bis-hexamethylenetriamine penta(methylene phosphonic) acid], PAA (polyacrylic acid), PPCA (phosphinopolycarboxylic acid), and SPA (sulfonated polyacrylic acid)14-16. The model parameter set is presently limited to calcite and barite, the most common oilfield scales. The efficiency of inhibitors has been modeled as a function of field conditions, such as saturation index (SI), temperature (T), pH, and lattice ion ratios (R, for example [Ba2+]/[SO42-] in the case of barite scale) as in Eq. (6) to Eq. (7).
o log(t inh , s) = log(t ind , s) + f safety b inh (L / mg) C inh (mg / L) (6

log(b inh ) = 0 + 1 SI + 2 T(K ) + 3 pH + 4 log R

(7

where tinh is the time period for the system to be protected from scaling which is approximately equal to the time for the brine to travel from the bottom-hole to surface facility plus the surface detention time, binh is the inhibition efficiency, 0 to 4 are constants listed in He et al.17, Table 2. Xiao et al.18 have improved the binh equation for PPCA by considering PPCA speciation as a function of brine composition (eq. 8-11).
b inh = f u u + f Ca Ca

(8 (9

f u = 3.31 + f Ca = 0.52 SI 2

1.03 4.84 745 + 2 + SI SI T

(10 (11

In Equation 4, the second term is related to the nucleation and/or diffusional growth, either of which can not be distinguished and the third term is related to polynuclear growth or other unidentified growth mechanisms. Xiao et al. proposed to model barite induction period, in a functional form similar to Shnel and Mullin's nucleation equation (Eq. 5). 2 [ 1087 0 . 30 [ 1087 0 . 30 T ] T ]3 0.12 log10 ( t 0 , sec) = 2 . 24 + ind T 3SI 2 T 2SI (5 This prediction has been verified for over four orders of magnitude in induction time, from a few seconds to hours. The term in brackets is related to the interfacial surface tension and physical constants. Nucleation Inhibition Time And Minimum Inhibitor Concentration (MIC). Recently, the authors have made progress in estimating the inhibitor efficiency through a semiempirical nucleation inhibition model. With the nucleation inhibition model, we are able to predict the minimum effective

u + Ca + H = 1

For any solution condition, the protonated fraction (H), the deprotonated fraction (u) and the metal complexed fraction (M) can be calculated from an electrostatic polymer model11, similar to those in Tanford12, for PPCA under a wide range of ionic strength and temperature conditions. Experimental Nucleation Kinetics Experiments. A large number of experiments were done at different pH, ionic strength, Ba, SO4, Ca, scale inhibitor, and hydrate inhibitor concentrations. The induction period (tind) of BaSO4 nucleation is defined as the time elapsing between the mixing of two solutions and the onset of an increase in turbidity reading. In each experiment, cationic and anionic solutions were prepared separately: one with crystallizing cations Ba2+; another with crystallizing anions SO42-. When methanol, monoethylene glycol, or triethylene glycol was used, a portion of the co-solvent was

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SPE 87437

added into each solution the solution with crystallizing cations and the solution with crystallizing anions to well mixed. Then the two solutions were mixed and the nucleation kinetics was then tracked with turbidity measurement. The Ba2+ and SO42- concentrations were systematically varied from 0.5 to 1.8 mm and the cosolvent concentrations were systematically varied from 0 - 40% (wt) to yield a SI variation of 1.3 to 4.2 SI unit. Both solutions contained the same amount of NaCl. If Ca2+ and/or scale inhibitors were added to the solution, Ca2+ was added to the cationic solution and scale inhibitor was added to the anionic solution. The pHs of the cationic, anionic solutions were adjusted with 0.01 m NaOH solution to the desired pH. For some experiments, the solutions also contained 5 mm PIPES buffer at 6.42 pH. The two solutions (10 ml each) were then rapidly added into a polycarbonate turbidity cell (30 ml) and mixed under continuous stirring at 350 rpm by a Teflon-coated magnetic stirring bar. The turbidity of the solution was tracked by a ratio/XR turbidimeter (HACH Company) and the data acquisition was accomplished via a digital multimeter (Radio Shack) connected to a PC for data logging. At the end of the experiments, the mixed solution pH was determined with a pH meter. Once the data was collected, the turbidity reading versus time (sec) was plotted on a semi-logarithmic chart. The logarithmic induction time at the onset of turbidity changes was determined from the chart. Results and Discussion Effects Of Hydrate Inhibitors On Barite Nucleation Rate. A large number of barite nucleation kinetics studies have been done to evaluate the effect of hydrate inhibitors on barite nucleation rate. The effect of methanol and monoethylene glycol on barite nucleation, as tracked by turbidity reading, is shown in Figure 2. In Figure 2 are plotted the turbidities of solutions versus reaction time where the solutions contained 0-25% methanol (figure 2a, [Ba]=[SO4]=0.7 mm) and 0 - 11% monoethylene glycol (figure 2b, [Ba]=[SO4]=1.11 mm). Since hydrate inhibitors generally cause barite to be less soluble, it is expected to see an accelerated nucleation in the presence of hydrate inhibitors. In these experiments, the barite SI increased from 1.62 to 3.17 when methanol concentrations increased from 0 to 25%. Similarly, the barite SI for figure 2b changed from 2.17 to 2.34 due to the change in monoethylene glycol concentrations from 0 to 11%. A total of thirty six nucleation experiments with methanol were run at various ionic strength (0-4 m), Ca (0-0.1 m), Ba (0.5-1.1 mm), SO4 (0.5-1.1 mm) and methanol (0-40%) concentrations. A total of nine nucleation experiments were run with monoethylene glycol (MEG) and one with triethylene glycol (TEG) at 1 m ionic strength, various Ba and SO4 (0.761.79 mm), Ca (0-0.05 m), MEG (0-40%), and TEG (40%) concentrations. The observed nucleation time can be correlated to methanol, monoethylene glycol concentrations and barite SI by Eqs. 12 and 13. Eqs. 12 and 13 are modified from Eq. 6 to account for the change in crystal/solution interfacial energy, in the numerators of the second and third terms, due to the cosolvent effect.

0 log10 ( t ind , sec) = 2.24 + 2 [1087 0.30 T + 1695.2 x MeOH 7564.2 x 2 MeOH ] T 2SI 3 [1087 0.30 T + 1695.2 x MeOH 7564.2 x 2 MeOH ] 0.12 3 2 T SI

r = 0.95
log10 ( t , sec) = 2.24 +
0 ind 2 [1087 0.30 T + 1397.5 x EG 6350.3 x 2 EG ] 2 T SI 3 [1087 0.30 T + 1397.5 x EG 6350.3 x 2 EG ] 0.12 3 2 T SI

(12

r=0.92 (13 In Figures 3a and 3b are plotted the observed barite induction times versus the barite induction times calculated from Eqs. 12 and 13. The predicted barite induction times are generally in good agreement with the observed values. Interestingly, the barite induction time that was observed in 40% TEG can also be predicted by Eq 13, suggesting that monoethylene glycol and triethylene glycol have similar solution properties as might be expected. The coefficients in the numerator terms 2 and 3 of Eqs. 12 and 13 (for the methanol and monoethylene glycol corrections) are very similar, indicating that the crystal/solution interfacial energies of different cosolvent/brine solutions are very similar for methanol/brine and ethylene glycol/brine systems. According to Eq. 12, the crystal/solution interfacial tension is only increased by 3% at 0.2 mole fraction of methanol (31% wt). These results are certainly reasonable considering similarity of the properties of methanol versus glycols. Inhibition In The Presence Of Hydrate Inhibitors. The effect of three common scale inhibitors (BHPMP, NTMP, and PPCA) on barite-supersaturated methanol-salt-water, monoethylene glycol-salt-water, and triethylene glycol-saltwater solutions were studied. The effect of methanol on BHPMP inhibition of barite nucleation and growth is demonstrated in Figure 4. In Figure 4 are plotted the solution turbidities versus logarithmic reaction time (sec) for four groups of solution matrices, where figures 4a and 4b contained 0.75 mm Ba and SO4 and 0 and 10% methanol and figures 4c and 4d contained 1.11 mm Ba and SO4 and 0 and 10% methanol. In the absence of methanol, the solutions were completely inhibited with as little as 0.11 and 0.33 mg/L BHPMP over a period of ~24 hours (log(t) 5, see Figures 4a and 4c). With 10% methanol, 0.22 and 0.65 mg/L BHPMP were required to inhibit barite precipitation for 24 hours, i.e., the MIC is about doubled when 10% methanol is added to the brine (see figures 4b and 4d). The efficiency of NTMP versus BHPMP on barite scale inhibition was compared at 20 and 30% methanol concentrations (Figures 5 and 6). For these experiments, the salt-water matrix composition is identical to that of figures 4c and 4d, i.e., 1.11 mm Ba and SO4 concentrations. NTMP was used as the inhibitor in Figures 5a and 6a and BHPMP was used in Figures 5b and 6b. As shown in Figure 5, 2.44 mg/L NTMP or 1.90 mg/L BHPMP were needed to inhibit barite

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SPE 87437

precipitation for 24 hours at 20% methanol. The BHPMP MIC is increased by a factor of 6 in the 20% methanol concentration versus in the brine itself. Surprisingly, NTMP failed to inhibit barite precipitation, when the solution contains 30% methanol (figure 6a). The barite nucleation time appears to be shorter than that detectable by this experimental procedure (< 1 sec). With 5-7 mg/L NTMP, the barite nucleation and growth appeared to be slowed by less than 30 sec. Consistent with previous conclusions, BHPMP is more efficient than NTMP to inhibit barite precipitation from a solution of similar composition. Approximately 2.52 mg/L BHPMP was needed to inhibit barite precipitation for 24 hours in the presence of 30% methanol. Surprisingly, nucleation was observed when higher than 2.52 mg/L BHPMP concentration was used. At lower than 2.52 mg/L, the inhibitor concentration was probably below the minimum concentration needed for barite inhibition. However, there is not a good explanation why precipitation occurs at higher than 2.52 mg/L BHPMP concentration. For the experiment with higher than 2.52 mg/L BHPMP concentration, it is proposed that nucleation may be induced by Ca-BHPMP precipitation. Additional investigation on this issue of phosphonate solubility in methanol/brine solution will be discussed in the later section of this paper. In Figure 7 is plotted the efficiency of PPCA on barite nucleation ([Ba] = [SO4] = 0.9 mm) in the presence of 12% methanol. The efficiency of PPCA to inhibit barite (~1.1 mg/L for 30 minutes) appeared to be lower than that of BHPMP in the 10% methanol solution (0.22-0.65 mg/L). The relative efficiency of BHPMP, NTMP, and PPCA at low methanol concentrations is qualitatively consistent with that observed by He et al.14,16,17. In Figure 8, the inhibitions of barite nucleation by BHPMP in the presence of either 40% methanol or 40% monoethylene glycol are compared. BHPMP failed to inhibit barite nucleation and growth in the presence of 40% methanol. However, only 0.38 mg/L BHPMP was needed to inhibit barite precipitation in the presence of 40% monoethylene glycol, indicating a significant advantage in using ethylene glycol to control hydrate formation. Note that barite SI is only 2.4 in 40% monoethylene glycol solution versus SI = 4.2 in 40% methanol solution. In Figure 9, the inhibitions of barite nucleation by BHPMP in the presence of either 40% monoethylene glycol (MEG) or 40% triethylene glycol (TEG) are compared. BHPMP inhibition is more effective in the monoethylene glycol/brine solution than in the TEG/brine solution as would be expected from the solubility results (Figure 1) and nucleation inhibition equations (Eq. 5-7). In fact, most of the nucleation inhibition results observed at moderately low co-solvent concentrations appeared to be consistent with the nucleation inhibition equations (eq. 6-11) previously reported for the co-solvent free systems. In Figure 10 are plotted the corresponding predicted nucleation inhibition time (predicted from Eqs. 6-11) versus observed nucleation inhibition time for three inhibitors (BHPMP, NTMP, and PPCA). The influence of hydrate inhibitors on scale inhibitor efficiency can be qualitatively modeled with Eqs. 6-11, even though there were a few observations that were not in good agreements to that predicted by the equations. Certainly, Eqs 6-11 may have to be

modified, as was done in Eqs. 12-13 for the uninhibited mineral, to better model the effects of cosolvent on nucleation inhibition in the future. Phosphonate Solubility In Brine/Methanol Solution. The failure of phosphonate to inhibit barite precipitation at high methanol concentration may be due to kinetic limitation since barite nucleation time is very short under such condition. It is also possible that phosphonate will precipitate with a cation, e.g., calcium, at high methanol concentrations, and thereby, accelerate barite nucleation. In order to test the hypothesis that phosphonate salt may nucleate in high methanol solutions, the turbidity of sulfate free solutions, containing BaCl2 (1.1 mm), CaCl2 (0.1 m), NaCl (1 m), H2O, methanol (30-40%), and phosphonate (8-9 mg/L BHPMP or NTMP), were monitored and compared to the controlled solution in the absence of inhibitors. In Figure 11 is plotted the turbidity of the solutions versus time. Clearly, turbidity was observed shortly after the start of the experiment in the inhibitor solution, but the turbidity was absent in the inhibitor free solution. The turbidity is assumed to be due to calcium phosphonate salt formation. After 24 hours mixing, the solutions were filtered with a 0.22 m polysulfone filter and analyzed for phosphonate concentration. Analysis of phosphonate was done by first evaporating the methanol and water to near dryness in a boiling water bath. The nearly dried solid was re-dissolved in 0.24 N HCl. Phosphonate was oxidized with persulfate in an autoclave for 30 minute at 121 C. The resulting solution was neutralized and reacted with molybdate and ascorbic acid reagents according to Standard Method 4500 PE and the phosphorus concentration was measured colorimetrically. In Table 1 is listed the analysis results. The phosphonate in the methanol free solution was completely recovered, while approximately 70-80% phosphonate disappeared from the methanol containing solutions. The final phosphonate concentration is around 2 mg/L in the 30% methanol solution and 1.3 mg/L in the 40% methanol solution. Therefore, the problem of scale inhibition in the presence of methanol can be related to both the very high supersaturation state of the scaling minerals and limited solubility of phosphonates in brine. Conclusions This paper presents an extensive study of the impact of hydrate inhibitors on barite nucleation and nucleation inhibition. The following conclusions can be made from the results: (1) Barite solubility was reduced in the presence of methanol, monoethylene glycol and triethylene glycol. The solubility reduction is most strongly impacted by methanol and to a lesser degree by monoethylene glycol and triethylene glycol. (2) All three hydrate inhibitors reduce barite nucleation time, due to the increase in supersaturation and an increase in crystal/solution interfacial energy. (3) The impact of hydrate inhibitors to barite nucleation rate can be predicted by semi-empirical equations of classical nucleation theory. (4) Scale inhibitors, e.g., BHPMP, can inhibit barite nucleation at low to medium hydrate inhibitor

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SPE 87437

concentrations and the inhibitor efficiency can be predicted by previously proposed inhibition equations. (5) At high methanol concentrations, phosphonate inhibitor may form metal phosphonate salt and possibly induces other mineral salts nucleation. Nomenclature N = neutral species activity coefficient BaSO
4

(7)

(8) (9)

Vm NA R

, '

D xMeOH xEG T SI

= geometric shape factors = crystal/solution interfacial energy = molar volume of the crystals = Avogadro's number = gas constant = number of ions in a molecular unit = diffusion coefficient in a solution = supersaturation (= {Ba2+}{SO42-}/Ksp). = methanol mole fraction concentration = Monoethylene glycol mole fraction concentration = Temperature (K) = Saturation index = Nucleation induction time (sec)

(10)

(11)

(12) (13) (14)

0 ind

= Nucleation induction time in the presence of inhibitor (sec) binh = inhibitor effectiveness coefficient (l/mg) Cinh = inhibitor concentration (mg/l) fsafety = safety factor to calculate MIC 0, 1, 2, 3, 4 =constants for inhibitor efficiency calculation H, u, M =the protonated, deprotonated and metal complexed fraction of PPCA tinh Acknowledgement The financial support of the Rice University Brine Chemistry Consortium of companies: Aramco, B.J.-Unichem, BakerPetrolite, Champion Technologies, Inc., Chevron-Texaco,Inc., ConocoPhyllips, Inc., Marathon Oil, Ondeo Nalco, Shell, Center for Biological and Environmental Nanotechnology, Nanoscale Science and Engineering Initiative of the National Science Foundation and U.S. EPA Hazardous Substance Research Center/South & Southwest Region is greatly appreciated. References
(1) He, S.; Oddo, J. E.; Tomson, M. B. "The nucleation kinetics of barium sulfate in NaCl solutions up to 6m and 90 oC"; Journal of Colloid and Interface Science 1995, 174, 319-326. (2) Wojciechowski, K.; Kibalczyc, W. "Light Scattering Study of KH2PO4 and BaSO4 Nucleation Process"; Journal of Crystal Growth 1986, 76, 379-382. (3) Hartman, P.; Strom, C. S. "Structural Morphology of Crystals with the Barite (BaSO4) Structure: A Revision and Extension"; Journal of Crystal Growth 1989, 97, 502-512. (4) Allan, N. L.; Rohl, A. L.; Gay, D. H.; Catlow, C. R.; Davey, R. J.; Mackrodt, W. C. "Calculated Bulk and Surface Properties of Sulfates"; Faraday Discuss. 1993, 95, 273-280. (5) Liu, S. T.; Nancollas, G. H. "Scanning Electron Microscopic and Kinetic Studies of the Crystallization and Dissolution of Barium Sulfate Crystals"; Journal of Crystal Growth 1976, 33, 11-20. (6) Kan, A. T.; Fu, G.; Tomson, M. B. "Effect of methanol on carbonate equilibrium and calcite solubility in a

(15)

(16)

(17)

(18)

gas/methanol/water/ salt mixed system"; Langmuir 2002, 18, 9713-9725. Kan, A. T.; Fu, G.; Tomson, M. B. "Effect of methanol and ethylene glycol on sulfates and halite scale formation"; Ind. Eng. Chem. Res. 2003, 42, 2399-2408. Nikitina, L. V.; Grigor'ev, A. I.; Dyatlova, N. M.; J. Gen. Chem. USSR 1974, 44, 1568-1571. Tikhonova, L. I. "Complex Formation by Diethylenetriamine NNN'N'- penta(methylphosphonic) Acid"; Russ. J. of Inorg. Chem. 1968, 13, pp. 1384-1388. Tomson, M. B.; Kan, A. T.; Oddo, J. E. "The acid/base and metal complex solution chemistry of the polyphosphonate, DTPMP versus temperature and ionic strength." Langmuir 1994, 10, 1442-1449. Xiao, J.; Kan, A. T.; Tomson, M. B. "The acid-base and metalcomplexation chemistry of phosphino-polycarboxylic acid under high ionic strength and high temperature." Langmuir 2001, 17, 4661-4667. Tanford, C. Physical Chemistry of Macromolecules; John Wiley & Sons, Inc.: NY, 1967. Sohnel, O.; Mullin, J. W. "Interpretation of Crystallization Induction Periods"; J. Colloid Interface Sci. 1988, 123, 43-50. He, S.; Kan, A. T.; Tomson, M. B. In Book "Inhibition of Mineral Scale Precipitation by Polymers"; Inhibition of Mineral Scale Precipitation by Polymers; Amjad, Z., Ed.; Plenum Press: New York, 1997, pp 163-170. He, S. L.; Kan, A. T.; Tomson, M. B. "Inhibition of calcium carbonate precipitation in NaCl brines from 25 to 90 C." Applied Geochemistry 1999, 14, 17-25. He, S. L.; Kan, A. T.; Tomson, M. B. "Mathematical Inhibitor Model for Barium Sulfate Scale Control"; Langmuir 1996, 12, 1901-1905. He, S. L.; Kan, A. T.; Tomson, M. B. "A new interactive software for scale prediction, control and management"; In SPE Annual Technical Conference and exhibition; SPE: San Antonio, TX, 1997 Xiao, J. A.; Kan, A. T.; Tomson, M. B. "Prediction of BaSO4 precipitation in the presence and absence of a polymeric inhibitor: Phosphino-polycarboxylic acid"; Langmuir 2001, 17, 4668-4673.

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SPE 87437

Table 1. Solution phase phosphonate concentrations after 24 hours reaction in a solution matrix of 0.97 m NaCl, 0.09 m Ca, 1.1 mm Ba and 40% (wt) methanol. Inh MeOH NaCl (m) Ca B SO4 (mm) Initial Phn Final Phn Conc (wt fr) (m) (mm) Conc. after 24 hrs (mg/L) (mg/L) BHPMP 0.000 0.792 0.081 0.904 0.000 9.47 8.29 BHPMP 0.326 0.977 0.090 1.103 0.000 8.83 2.07 BHPMP 0.306 0.977 0.090 1.108 0.000 7.97 1.80 BHPMP 0.400 0.977 0.090 1.109 0.000 9.19 1.20 NTMP 0.000 0.792 0.081 0.900 0.000 9.32 9.22 NTMP 0.324 0.977 0.090 1.089 0.000 8.72 1.95 NTMP 0.300 0.976 0.090 1.112 0.000 7.76 2.12 NTMP 0.400 0.977 0.090 1.049 0.000 9.78 1.48 NTMP 0.400 0.976 0.090 1.106 0.000 8.99 1.22

BaSO4 Conc. (moles/Kg H2O)

0.00012 0.0001 0.00008 0.00006 0.00004 0.00002 0 0 20 40 60 80 100 Hydrate Inhibitor (wt%) TEG MeOH MEG

Figure 1. Plot of barite solubilities in three different hydrate inhibitors/brine combinations. The three types of solution matrices are (1) NaCl-BaSO4-H2O-Methanol, (2) NaCl-BaSO4-H2O-Monoethylene glycol; and (3) NaCl-BaSO4-H2O-Triethylene glycol.

0.71 mm Ba/SO4
20 Turbidity (NTU) 15 10 5 0 10 100 1000

a. MeOH Conc. (wt/wt)


50 Turbidity (NTU)

b.
1.11 mm Ba/SO4

0% 5% 10% 14% 18% 23% 10000

40 30 20 10 0 0.1 1 10 100

EG Conc. (wt/wt) 0% 11%

1000

Reaction Time (sec)

Reaction Time (sec)


Figure. 2. Effect of (a) methanol and (b) monoethylene glycol on nucleation rate of barite at 25 C. For the methanol experiments, the solutions contained 1 m NaCl, 0.1 m CaCl2, 0.71 mm of Ba and SO4 and 5 mm PIPES buffer at pH 6.42 and various concentrations of methanol. For the monoethylene glycol experiments, the solutions contained 1 m NaCl, 1.116 mm of Ba and SO4 and 0 and 11%(w/w) of monoethylene glycol.

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SPE 87437

a.
Pred. log(tind, sec)

5 4 3 2 1 0 -1 0.00 2.00 4.00 MeOH

b.
Pred. log(tind, sec)

3.0 2.5 2.0 1.5 1.0 0.5 0.0 0.0 1.0 2.0 3.0 TEG M EG

Obs. log(tind, sec)

Obs log (tind, sec)

Figure 3. Plots of the predicted versus observed logarithm induction time (sec) of barite at 25 C in the presence of (a) methanol and (b) monoethylene glycol and triethylene glycol. The solution matrices of the data in figure 3a contained 1-4 m NaCl, 0-0.1 m Ca, 0.48-1.11 mm Ba and SO4, and 0-40%(w/w) methanol at 6.0-6.4 pH. The solution matrices of the data in figure 3b contained 1 m NaCl, 0-0.05 m Ca, 0.76-1.81 mm Ba and SO4, and 0-40% monoethylene glycol and triethylene glycol at 6.0-6.4 pH.

a.
BHPMP Conc. 0 mg/L 0.04 mg/L 0.11 mg/L

c.
BHPMP Conc. 50 40 30 20 10 0 0 1 2 3 4 5 Ba=SO4=1.11 mm SI=2.05 No MeOH 0 mg/L 0.27 mg/L 0.22 mg/L 0.33 mg/L

50
Turbidity (NTU)

40 30 20 10 0 0

Ba=0.77 mm, SO4 =0.72 mm SI=1.67 No MeOH

Turbidity (NTU)

4
0.13 mg/L

log (t, sec)

b.

log(t, sec)

d.
0 mg/L BHPMP 0.52 mg/L Conc. 50 Ba=SO4=1.11 mm 40 SI=2.79 30 10%MeOH 20 10 0 0 1 2 3 4 5 0.43 mg/L 0.65 mg/L

Turbidity (NTU)

10 0 0 1 2 3 log(t, sec) 4 5

Turbidity (NTU)

BHPMP 0.0 mg/L Conc. 0.22 mg/L 50 Ba=0.75 mm 40 SO4 =0.72 mm 30 SI=2.27 10%MeOH 20

log(t, sec)

Figure 4. Plots of typical nucleation rate of barite in the presence of different Ba, SO4, BHPMP, and methanol concentrations. The experiments were run at 25 C and the solution matrix also contained 0.98 m NaCl, 0.09 m CaCl2, and 5 mm PIPES buffer at 6.42 pH. Plots a and b contained ~0.75 mm Ba and SO4 and 0 and 10% (w/w) methanol and plots c and d contained ~1.11 mm Ba and SO4 and 0 and 10% (w/w) methanol.

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SPE 87437

a.
NTMP Conc. 50 40 Turbidity (NTU) 30 20 10 0 0 1 2 3 4 5 log(t, sec) 0 mg/L 1.98 mg/L 2.27 mg/L 1.53 mg/L 2.11 mg/L 2.44 mg/L

b.
BHPMP Conc.
50

0 mg/L 1.28 mg/L 1.71 mg/L

0.63 mg/L 1.59 mg/L 1.90 mg/L

Turbidity (NTU)

Ba=SO4=1.11 mm SI=3.43 20% MeOH

40 30 20 10 0 0

Ba=SO4=1.11 mm SI=3.43 20% MeOH

log(t, sec)

Figure 5. Plots of nucleation rate of barite in the presence of 20% methanol (w/w) concentration and two different phosphonate inhibitors (NTMP and BHPMP). The experiments were run at 25 C and the solution matrix also contained 0.98 m NaCl, 0.09 m CaCl2, and 5 mm PIPES buffer at 6.42 pH. All solutions contained ~1.11 mm Ba and SO4.

a.

b.
NTMP Conc.

0 mg/L 4.54 mg/L 7.18 mg/L

2.29 mg/L 5.90 mg/L

BHPMP Conc.

0 mg/L 2.04 mg/L 3.02 mg/L

1.56 mg/L 2.52 mg/L 5.32 mg/L

50
Turbidity (NTU)

50 Turbidity (NTU) 40 30 20 10 Ba=SO4=1.11 mm SI=3.93 30% MeOH

40 30 20 10 0

Ba=SO4=1.11 mm SI=3.93 30% MeOH

0 0 0.5 1 log(t, sec) 1.5 2

log(t, sec)

Figure 6. Plots of typical nucleation rate of barite in the presence of 30% methanol (w/w) concentration and two different phosphonate inhibitors (NTMP and BHPMP). The experiments were run at 25 C and the solution matrix also contained 0.98 m NaCl, 0.09 m CaCl2, and 5 mm PIPES buffer at 6.42 pH. All solutions contained ~1.11 mm Ba and SO4.

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SPE 87437

PPCA Conc. 60 50 Turbidity (NTU) 40 30 20 10 0 1 10

0 mg/L 1.1 mg/L

0.27 mg/L
Figure 7. Plot of barite nucleation rate in the presence of 12%(w/w) methanol and various concentrations of PPCA. The experiments were run at 25 C and the solution matrix also contained 1.02 m NaCl, and 0.9 mm Ba and SO4.

Ba=SO4=0.9 mm SI=2.85 12% MeOH

100

1000

10000

100000

Induction Time (se c)

a.
BHPMP Conc. 50

0 mg/L 3.11 mg/L 5.83 mg/L Ba=SO4=1.1 mm SI=4.21 40% MeOH

1.58 mg/L 4.78 mg/L

b.
BHPMP Conc. 50 Turbidity (NTU)

0 mg/L 0.29 mg/L 0.38 mg/L

0.19 mg/L 0.27 mg/L

Turbidity (NTU)

40 30 20 10 0 0

Ba=SO4=1.1 mm 40 SI=2.61 40% MEG 30 20 10 0

0.5

1.5

log(t, se c) log(t, sec) Figure 8. Plots of nucleation rates of barite in the presence of 40%(w/w) methanol or monoethylene glycol and different BHPMP phosphonate concentrations. The experiments were run at 25 C and the solution matrix also contained 1.0 m NaCl, 0.045 m CaCl2, and 5 mm PIPES buffer at 6.42 pH and [Ba]=[SO4]=1.1 mm.

a.
BHPMP Conc. 50
Turbidity (NTU)

0 mg/L 1.68 mg/L

0.71 mg/L 2.36 mg/L

b.

BHPMP Conc. 50
Turbidity (NTU)

0 mg/L 1.95 mg/L

1.62 mg/L 2.27 mg/L

40 30 20 10 0 0

Ba=SO4=1.80 mm SI=3.08 40% MEG

40 30 20 10 0 0

Ba=SO4=1.80 mm SI=3.08 40% TEG

2 3 log (t, sec)

log(t, sec)

Figure 9. Plots of nucleation rates of barite in the presence of 40%(w/w) monoethylene glycol or triethylene glycol concentration and different BHPMP phosphonate concentrations. The experiments were run at 25 C and the solution matrix also contained 1.0 m NaCl, 0.045 m CaCl2, and 5 mm PIPES buffer at 6.42 pH and [Ba]=[SO4]=1.8 mm.

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10

SPE 87437

MeOH

1:1 5.0

EG BHPMP
Pred. log(t, sec)

MeOH

1:1

4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0.0 0.0

NTMP
4.0 3.0 2.0 1.0 0.0

Pred. log(t, sec)

1.0

2.0 Obs. log(t, sec)

3.0

4.0
MeOH EG

0.0 1:1

1.0

2.0

3.0

4.0

5.0

Obs. log(t, sec)

4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0.0 0.0 1.0 2.0 3.0 Obs. log(t, sec) 4.0

Figure 10. Plot of the predicted logarithmic barite nucleation inhibition time versus observed nucleation inhibition time for three inhibitors (BHPMP, NTMP and PPCA) in the presence of methanol, monoethylene glycol and triethylene glycol. The solution matrix composition are 1 m NaCl, 0-0.1 m Ca, 0.7-1.8 mm Ba and SO4, 0-30% methanol, 0-40% monoethylene glycol, pH 5-6.4.

Pred. log(t, sec)

Turbidity (NTU)

6 5 4 3 2 1 0 0 1 2 3 4 5 Log t (sec)

30% MeOH, NTMP 30% MeOH, BHPMP 30% MeOH 40% MeOH, NTMP 40% MeOH

Figure 11. Plot of the turbidity versus time following the mixing of a barium containing solution with a NaCl solution in the presence of 3040% methanol and 0 - 8 mg/L phosphonate inhibitors at 25 C.

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