SPE 87468 Measurment and Prediction of Salt Formation in the Presence of Hydrate Organic Inhibitors

R. Masoudi SPE, B.Tohidi SPE, A. Danesh SPE, A.C. Todd SPE, and J. Yang, Centre for Gas Hydrate Research, Institute of Petroleum Engineering, Heriot-Watt University Introduction Flow assurance is an essential aspect of safe and economical production of hydrocarbons over the lifetime of a field. Gas hydrate and scale control are two of the key aspects of flow assurance. Gas hydrates, or clathrates, are ice-like crystalline compounds consisting of low molecular diameter gases inside cavities formed by water molecules, which can form at certain pressure and relatively low temperature conditions. Gas hydrate formation is particularly troublesome for offshore drilling and production due to low seabed temperature, high residence time and high operating pressure. Hydrates can block pipelines, subsea transfer lines, and, in the event of a gas kick during drilling, form in the wellbore, risers, BOPs (BlowOut Preventers) and choke-lines [1]. Common practice for preventing gas hydrate formation involves the injection of large quantity of thermodynamic inhibitors (e.g. methanol, ethanol, ethylene glycol, triethylene glycol). However, the addition of organic inhibitors may adversely affect salt solubility in the associated brine solutions, which often contain high concentrations of dissolved minerals, leading to potential salt precipitation, commonly termed salting-out [2,3]. The deposition of salt may result in flow restriction due to salt plug formation, as well as hydrate formation (as a result of neglecting the effect of salt deposition on reducing the overall hydrate prevention characteristics of the system). In the open literature, there is a little research on the solubility of mineral salts in hydrate organic inhibitor/water/salt solutions, which are only applicable to the studied systems and limited range of temperature and pressure [2,4-6] and no accepted methodology for correlating the effects of hydrate organic inhibitors on scale formation/inhibition. Therefore, a better experimental and theoretical understanding of the salt formation as a function of both electrolyte and organic inhibitor concentrations in the presence or absence of scale inhibitors over a wide range of temperature and concentration is crucial to the success of any flow assurance strategy. The work in this communication is the results of a systematic experimental and modelling research on the effect of three hydrate organic inhibitors (i.e., methanol, ethanol, ethylene glycol) on various mineral salt formation (i.e., halite, sylvite and antarcticite) over a wide range of temperature and

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 Organic inhibitors (e.g. methanol, ethanol, ethylene glycol, triethylene glycol) are generally used to reduce the risk of gas hydrate formation in drilling and production operations. The addition of organic inhibitors has a significant adverse effect on the solubility of salts, increasing the risk of salt deposition. A better understanding of salting-out problems is necessary for effective design and implementation of flow assurance strategies in such complex systems. In this communication we present an experimental investigation on the effect of methanol, ethanol and ethylene glycol on the solubility of several salts, including halite, sylvite and antarcticite. The results show that ethylene glycol has a much lesser adverse impact on salt deposition than methanol and ethanol. The details of an experimental set-up used for measuring salt solubility and salting out are described. The set-up could also provide valuable information on the effectiveness of various inhibitors used for preventing salt deposition in the presence or absence of gas hydrate organic inhibitors. In addition, a novel predictive numerical approach is proposed to model salt formation in brine solutions with or without hydrate organic inhibitors. The model is based on the equality of the fugacity of salt in the solid phase and aqueous phase, which are calculated by an equation of state. The validity of the new developed model is demonstrated over a wide temperature range (i.e., 20 to 125 C), salt concentration up to saturation point and hydrate inhibitor concentration up to 50 mass%.

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concentration. The applied experimental set-up and its capability in determining salt solubility data in the presence or absence of hydrate organic inhibitor are first described. The development of a new thermodynamic approach capable of predicting salt formation in electrolyte solutions with or without hydrate organic inhibitors is then detailed for the studied systems in this work. Experimental For salt solubility measurements and salting-out effect, the procedure selected was the one utilised by Chiavone-Filho and Rasmussen [7], based on the original technique of Babinets and Polishchuk [8]. In this method, the solute concentration is accurately determined by simply weighing the residue produced after evaporation of a known weight of the solution. Precise control of solution temperature is maintained throughout the operation, with an insulated, water-jacketed glass cell ensuring isothermal conditions while equilibrium is achieved, controlled to within 0.1 K. Also, pre-warming of the sampling syringe to 5 K above cell temperature is used to prevent solute precipitation during sample withdrawal. The key part of the solubility apparatus, as illustrated in Figure 1, is a jacketed glass cell. There is a glass-cooling coil, which is fitted on the lid of the cell and immersed in the solution. The coolant from a thermostat circulates through the glass coil and then the jacket to reach the required temperature. A magnetic stirrer bar is used to mix the solution. A PRT thermal probe is inserted into the solution to measure the temperature, and an accuracy of 0.1 K is expected. The salt is added into in small quantities, giving adequate time to the system to reach equilibrium, until slight excess of salt appeared. During the measurement the cell is closed to minimize solvent evaporation, hence any change in the composition of the system. Once the system is saturated a sample of the solution is taken and the concentration of salt in the solution is measured by evaporating the solvent in a high temperature oven. At each measurement point, the solution is stirred for more than 1.5 hours and allowed to settle for more than 0.5 hours before sampling. Sometimes, for a high concentration of the solution with a high viscosity longer stirring time and settling time may be needed. The glasscooling coil is applied to make the temperature even while the magnetic stirrer is stopped to allow settling down (I assume this is necessary to see salt coming out of solution, i.e., saturation). The reliability and repeatebility of the measurement techniue was assessed by carrying out a series of solubility tests on potassium chloride in two aqueous ethylene glycol mixtures, at several temperatures, for which Chiavone-Filho and Rasmussen [7] reported data. Authors reported KCl solubility for six different aqueous ethylene glycol solutions at various temperatures. Two of the mixtures used in their study, were exactly reproduced gravimetrically here, 85.58 % and 44.42 % by mass of ethylene glycol in water. As can be seen from Table 1, good agreement has been obtained in all cases, and furthermore, measurement were found to be very repeatable over several days, at different temperatures, and with

recharges of test fluids between experiments (for example, the two sets of replicated measurements at 298.15 k were performed ten days apart, and those at 348.15 K were separated by two days). The set-up has been used in measuring various salt solubilities in the brine solutions in the presence or absence of hydrate organic inhibitors. It should be noted that the experimental setup has the capability of being used in determining the salting out properties in the presence of hydrate and/or scale inhibitors. Therefore the effectiveness of various scale inhibitors in the presence or absence of hydrate organic inhibitors can also be investigated. Numerical approach In a recent publication, we presented a rigorous thermodynamic model for predicting phase behaviour and salt precipitation in aqueous electrolyte solutions, and this was successfully applied to the prediction of hydrate stability for such systems. A comprehensive description of the model is given elsewhere [9]. The developed model was then extended to include ethylene glycol and to investigate the phase behaviour of aqueous solutions containing both salt and hydrate organic inhibitor [5]. The numerical model has considered the thermodynamic equilibria between all possible phases namely: vapour, liquid hydrocarbon, water-rich phase (with the possible presence of hydrate organic inhibitors and salts), ice, gas hydrates (structure-I, II, and H), and salts. In summary, the developed model uses the Valderrama modification of the Patel and Teja equation of state (VPT EoS) for fugacity calculations in all fluid phases [10]. Nondensity dependent (NDD) mixing rules are applied to model polar-nonpolar and polar-polar interaction [11]. Salts are considered as entity pseudo-components in a modified VPT EoS by defining their critical properties and acentric factors [9]. The hydrate phase is modelled by using the solid solution theory of van der Waals & Platteeuw [12], as implemented by Parrish & Prausnitz [13]. The Kihara model for spherical molecules is applied to calculate the potential functions for compounds forming the hydrate phase [14]. Salt Formation Petroleum production is commonly associated with the production of formation water. NaCl, KCl, and CaCl2 are of the principal electrolyte components of almost all produced water. The salinity of produced water varies in different reservoirs, but high water salinities, in some cases very close to saturation, are not uncommon. This can pose a serious flow assurance problem due to the potential for salt deposition in the well-bore, tubing and pipelines. During production, pressure/temperature changes may result in salt supersaturation in the produced water, resulting in salt precipitation [15]. Excluding chemical reactions that can result in scale deposition (for example, injection of sea water into the formation for pressure maintenance and resulting interaction between sulphate ions in the sea water with barium ions in the formation water), several other processes could lead to salt precipitation, including:

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Temperature reductions as fluids are transported from the reservoir to the surface reduce salt solubility. Salt concentration of brine increases as produced gas strips water, leaving the salt behind (assisted by a reduction in the system pressure, resulting in an increase in water partial pressure). The addition of hydrate organic inhibitors (methanol, glycol) may reduce salt solubility in the aqueous phase. A reduction in CO2 concentration in the aqueous phase can result in the deposition of bicarbonates as carbonates.

For this purpose, first the heat capacity change, l s , and volume change on melting, Vi f , for Cp = C P CP the salt should be calculated, as well as the fugacity of the pure subcooled liquid salt. The latter can be calculated using an EoS for the pure salt. The fugacity of the salt in the solid phase is calculated from Eq. (2) by substituting the fugacity of pure liquid salt, Vi f , and Cp in Eq. (2). The detailed calculations of the parameters Vi f and Cp for three salts, NaCl, KCl and CaCl2, are presented elsewhere [9,16]. Then, from the fugacity equality conditions, we get the equilibrium relations that equate the fugacity of the pure solid and the fugacity of the salt in the aqueous phase (which was calculated from the EoS). This will enable the prediction of the potential salt precipitation conditions. Results and discussion As earlier noted, in this approach, salt is treated as an entity pseudo component by defining its critical properties and acentric factor. The objective was to develop a model cable of predicting the phase behaviourof water-salt solutions over a wide range of temperature, pressure, and concentrations, as well as saturation and salt precipitation. Hence, three sets of experimental data on aqueous saline solutions, i.e., freezing point depresssion, boiling point elevation and salt solubility, were used in determining the interaction parameters between water and salts. The complete atmospheric binary phase diagrams consisting freezing point depression line (AB), boiling point elevation line (CD), and salt precipitation line (BD) for three binary H2O-NaCl, H2O-KCl, and H2O-CaCl2 systems are presented in Figures 2 to 4, respectively. The figures present the available experimental data [16-21] and the models calculations. It is worth mentioning that the pressure doesnt have a significant effect on the freezing point depression (AB) and salt formation (BD) lines, therefore, these figures, excluding boiling point elevation lines (CD), could be applied to other pressures. A similar procedure was used for determing the interaction parameters between organic inhibitors and salts. Figure 5 shows experimental [5,17] and calculated NaCl solubility in aqueous ethylene glycol (EG) as a function of temperature and EG concentration. As shown in the figure, NaCl solubility is reduced considerably as EG concentration increases, although there is a slight increase in the solubility at high temperature conditions. Figure 6 presents the experimental [7] and calculated dependency of KCl solubility on ethylene glycol concentration in aqueous solutions at various temperatures. As with sodium chloride, the results show that the solubility of potassium chloride in aqueous ethylene glycol solutions decreases significantly with increasing ethylene glycol concentration, and it increases with an increase in the system temperature. Figure 7 illustrates experimental [16] and calculated CaCl2 solubility in aqueous ethylene glycol (EG) solutions as a function of temperature and EG concentration. As can be seen, unlike sodium chloride and potassium chloride, CaCl2 solubility is reduced slightly with increasing EG concentration. The solubility of CaCl2 increases at high temperature conditions. Figures 5 to 7 essentially show the

As noted earlier, in addition to preventing salt formation and plugging, it is necessary to evaluate the hydrate inhibition characteristics of the system to ensure the effectiveness of the hydrate prevention strategies. Considering the above, it is vital that the salt and hydrate free region of reservoir fluids in the presence or absence of organic inhibitor, can be accurately predicted. In this study, the earlier mentioned model is applied to develop an approach capable of predicting salt formation in the electrolyte solutions with or without various hydrate organic inhibitors. The approach is based on the equality of fugacities for salt in the salt phase and in the aqueous phase, which are calculated from an EoS. The modelling procedure and predictive capabilities for aqueous solutions of hydrate organic inhibitors and salts are detailed here. In order to predict salt deposition in the liquid phase, it is necessary to examine the Solid-Liquid Equilibria (SLE). In isothermal systems the equality of chemical potentials can be expressed as:
l

fi = fi

(all i )
s

(1)

Where f i and f i are the fugacity of species i in liquid and solid phases, respectively. As the solvent does not enter the solid phase, the fugacity of the solid phase (i.e., salt) remains that of the pure solid. The ratio of fugacity of pure solid at subcooled condition to that of solid at the same temperature, considering the effect of pressure and assuming that the volume change on melting is independent of pressure, is expressed as:
i f l h f T 1 T V f 1 T Cp = ln is = i 1 + Cp.dT .dT + i (P P Tm ) RT RT Tm RT Tm R Tm T RT fi

(2) where Vi f and PTm are volume change on melting and pressure at the melting point (normally equal to 1 bar), respectively. Eq. (2) shows the relationship between the fugacities of pure subcooled liquid and that of solid state. Potential salt precipitation can be predicted by the above approach, where salts are considered as pseudo components and their fugacities in solid and aqueous phases are calculated.

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SPE 87468

maximum concentrations of NaCl, KCl, and CaCl2 that can exist with EG in aqueous solutions without any salt precipitation. In all cases, the agreement between experimental data and the models calculations is good, demonstrating the accuracy of the developed model. Figure 8 shows the experimental [6,22] and calculated NaCl solubility in aqueous methanol (MeOH) as a function of temperature and MeOH concentration. As can be seen, NaCl solubility is reduced considerably as MeOH concentration increases. The solubility increases slightly with increase in temperature at all concentrations of MeOH. Figure 9 presents experimental [6,22] and calculated dependency of KCl solubility on methanol concentration in aqueous solutions at various temperatures. The data show that the solubility of potassium chloride in aqueous methanol solutions decreases significantly with increasing methanol concentration, but it increases with an increase in the system temperature. Figure 10 illustrates the experimental [22] and calculated CaCl2 solubility in aqueous methanol (MeOH) as a function of temperature and MeOH concentration. As can be seen, unlike sodium chloride and potassium chloride, increasing methanol concentration doesnt have any significant effect on CaCl2 solubility. The solubility increases markedly with temperature. Figures 8 to 10 essentially show the maximum concentrations of NaCl, KCl, and CaCl2 that can exist with MeOH in aqueous solution without any salt precipitation. Figure 11 shows experimental [6] and calculated NaCl solubility in aqueous ethanol (EtOH) as a function of temperature and EtOH concentration. As can be seen, NaCl solubility is reduced considerably as EtOH concentration increases. There is a slight increase in solubility at higher temperatures. To our knowledge, there is still no predictive model in the open literature capable of predicting salt precipitation behaviour in the aqueous multi-salt systems in the presence or absence of organic inhibitors. Figure 12 presents an independent set of experimental data [22] and the predictions of this model on salt precipitation behaviour in quaternary NaCl-CaCl2-EG-H2O systems at various concentrations of EG. An acceptable agreement is observed. It should be mentioned that, as experimental data and model predictions show, the precipitation region in this system is halite. The model predictions presented in this figure shows the reliability of the developed model. Analysing the above figures and comparing the effect of various hydrate organic inhibitors for each individual salt (i.e., halite, sylvite and antarcticite), the results could be summarised as: Ethylene glycol has a much lesser adverse impact on salt formation than methanol and ethanol. The effect of temperature on halite precipitation in the presence or absence of hydrate organic inhibitors is not significant.

Sylvite precipitation is significantly affected by both temperature and hydrate organic inhibitor concentration. Addition of the hydrate organic inhibitors (investigated in this work) to calcium chloride aqueous solutions doesnt have a significant impact on antarcticite precipitation.

Conclusions An integrated experimental and modelling study has been presented on the effect of three hydrate organic inhibitors (i.e., methanol, ethanol, and ethylene glycol) on the formation of three salts (i.e., halite, sylvite and antarcticite). Novel experimental data on the freezing point depression, boiling point elevation, and salt precipitations on the above systems have been described. A novel salt precipitation approach capable of predicting salt formation in the brine solutions with or without hydrate organic inhibitors has been detailed. The model is based on the equality of the fugacities of salt in the salt phase and the aqueous phase, which are calculated from an EoS. The model has been shown to be successful in modelling salt precipitation in multi electrolyte solutions with or without organic inhibitors. The results show that ethylene glycol has a much lesser adverse impact on salt deposition than methanol and ethanol and also the addition of the hydrate organic inhibitors (studied in this work) to calcium chloride aqueous solutions doesnt have a significant impact on antarcticite precipitation. In addition, the effect of temperature on halite formation is negligible. The experimental set-up and procedures used in this work could easily be adopted for determining the effectiveness of various inhibitors used for preventing salt deposition in the presence or absence of gas hydrate organic inhibitors. Acknowledgements This work is part of a Joint Industrial Project (JIP) conducted at the Institute of Petroleum Engineering, Heriot-Watt University. The JIP was supported by ABB, Petrobras, Shell, TOTAL and the DTI, which is gratefully acknowledged. Mr Rahim Masoudi wishes to thank the National Iranian Oil Company (NIOC) for financial support. Nomenclature , f i =Fugacity of species i in liquid and solid phases l f i , f i s =Fugacity of pure species i as a liquid and solid at T and P of the mixture f =Volume change on melting at solids melting point Vi
f
i l s

hi
PTm

(cm3/mol) =Enthalpy change of melting at solids melting

point (J/mol) =Pressure at solids melting point (bar) =Heat capacity change between liquid and solid states (J/(mol K))

Cp

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SPE 87468

T Tm R

=Temperature (K) =Melting point (K) =Ideal gas constant (=8.314 J/(mol K))

Greek symbols = Chemical potential change between liquid and i solid states (J/mol) References
1. 2. Barker, J. W., and Gomez, R. K., Formation of Hydrate During Deep-water Drilling Operations, Journal of Petroleum Technology, 41(3) (1989), 297-301. Amy, T.K., Gongmin, F., Malene, A.W., and Mason, B.T., Effect of hydrate inhibitors on oilfield scale formation and inhibition, Paper SPE 74657 presented at the SPE Oilfield Scale Symposium, Aberdeen (2002), January 30-31. Matthews, P. N., Subramanian, S., and Creek, J., High Impact, Poorly Understood Issues with Hydrate in Flow Assurance, Proceeding of the 4th International Conference on Gas Hydrates, Yokohama (2002), May 19-23, 899-905. Tomson, M.B., Kan, A.T., Fu, G., and Al-Thubaiti, M., Scale formation and prevention in the presence of hydrate inhibitors, SPE 80255 presented at the SPE International Symposium on Oilfield Chemistry, Houston, Texas (2003), February 5-7. Masoudi, R., Tohidi, B., Anderson, R., Burgass, R.W., and Yang, J., Experimental measurement and thermodynamic modelling of clathrate hydrate equilibria and salt solubility in aqueous ethylene glycol and electrolyte solutions, Fluid Phase Equilibria, Accepted for publication. Pinho, S.P. and Macedo, E.A., "Representation of salt solubility in mixed solvents: A comparison of thermodynamic models", Fluid Phase Equilibria, 116 (1996), 209-216. Chiavone-Filho, O. and Rasmussen, P., Solubilities of Salts in Mixed Solvents, Journal of Chemical and Engineering Data, 38 (1993), 367-369. Babinets, D.M., and Polishchuk, A.G., Device for solubility determination of salts in mix-solvent, Zhurnal Fizicheskoi Khimii, 55(2) (1981), 535-537. Masoudi, R., Tohidi, B., Danesh, A., and Todd, A.C., A new approach in modelling phase equilibria and gas solubility in electrolyte solutions and its applications to gas hydrates, Fluid Phase Equilibria, 215 (2004) 163-174. Valderrama, J. O., A Generalized Patel-Teja Equation of State for Polar and Nonpolar Fluids and Their Mixtures, Journal of Chemical Engineering of Japan, 23(1) (1990), 87-91. Avlonitis, D., Danesh, A., and Todd, A. C., Prediction of VL and VLL Equilibria of Mixtures Containing Petroleum Reservoir Fluids and Methanol With a Cubic EoS, Fluid Phase Equilibria, 94(1994), 181-216. Van der Waals, J. H., and Platteeuw, J. C., Clathrate Solutions, Advances in Chemical Physics, 2(1959), 1-57. Parrish, W.R. and Prausnitz, J.M., Dissociation pressure of gas hydrates formed by gas mixtures, Industrial and Engineering Chemistry, Process Design and Development, 11(1972), 26-35. Kihara, T., Virial Coefficient and Models of Molecules in Gases, Reviews of Modern Physics, 25(4) (1953), 831-843. Joseph, W.K. and James, B.D.," A Protocol to Inhibit the Formation of Natrium Chloride Salt Blocks", SPE 74662 presented at the SPE Oilfield Scale Symposium, Aberdeen (2002), January 30-31. Masoudi, R., Tohidi, B., Danesh, A., Todd, A.C., Anderson, R., Burgass, R.W., and Yang, J., Measurment and prediction of gas hydrate and hydrated salt deposition in aqueous ethylene glycol and electrolyte solutions, Chemical Engineering Science, submitted for publication.

17. CRC Hand Book of Chemistry and Physics, CRC Press Inc., Boca Raton, Florida, U.S.A, (1989). 18. Washburn. "International Critical Tables (ICT) of numerical data, physics, chemistry and technology", National Research council, (1926-30). 19. Stephen, H., Stephen, T., Solubilities of Inorganic and Organic Compounds, Pergamon Press, Oxford. London. New York. Paris, (1963). 20. Breton, A.M. Postgraduate thesis in Physical Sciences. University of Pau, France, June 6th, (1967). 21. Potter, R.W., and Clynne, M.A., Solubility of Highly Soluble Salts in Aqueous Media Part 1, NaCl, KCl, CaCl2, Na2SO4, and K2SO4 solubilities to 100C, Journal of Research of the U.S. Geological Survey, 6(6) (1978), 701-705. 22. Parrish, W.R. Thermodynamic Inhibitors in Brine. Personal Communication (2000).

3.

4.

Table 1: Solubility of potassium chloride in aqueous ethylene glycol mixtures: comparison of measured and literature values Chiavone-Filho and Rasmussen [7].
KCl Solubility (mass%) Ethylene Crucible Crucible Measured, Temperature Literature glycol No. 1 No. 2 mean (K) (mass%) 85.58 323.15 7.74 7.70 7.72 7.78 44.42 298.15 14.66 14.61 14.64 14.75 44.42 298.15 14.62 14.58 14.60 14.75 44.42 323.15 17.62 17.53 17.58 17.61 44.42 44.42 348.15 348.15 20.25 20.10 20.26 20.11 20.26 20.11 20.30 20.30 AAD

5.

0.06 0.11 0.15 0.03 0.04 0.19

6. 7. 8. 9.

AAD = Absolute Average Deviation

Coolant
PRT Septum Seal For Sampling

10. 11.

Insulated Jacket

12. 13. 14. 15.

Cooling Coil

Stirrer Bar

Coolant
Supply Insulating Cork Mat

16.

Stirrer Unit

Figure 1: Schematic measurement apparatus.

illustration

of

solubility

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SPE 87468

390 375 C 360 345 330 Liquid + NaCl Liquid Liquid + Vapour Vapour +NaCl D

30

25

NaCl / mass%

20

T/K

315 300 285 270 Liquid + Ice 255 240 0 10 20 30 40 Ice + NaCl.2H2O B A Liquid + NaCl.2H2O

15 0 mass% EG [17] 10 mass% EG [5] 10 25 mass% EG [5] 40 mass% EG [5] Predictions 5 270 290 310 330 350

NaCl / mass%

T/K

Figure 2: Phase diagram of binary NaCl-H2O at atmospheric pressure. Experimental data: freezing point () [17]; boiling point () [18]; salting out () [19,20]. The solid lines are model calculations.

Figure 5: Experimental and calculated maximum soluble mass of NaCl in aqueous ethylene glycol solutions as a function of temperature and EG concentrations. EG concentrations are shown on a salt-free basis.

35

390 370 350 330 310 290 A 270 Liquid

Vapour +KCl D C Liquid + Vapour

30

KCl / mass%

273.15 K, [7] 298.15 K, [7] 323.15 K, [7] 348.15 K, [7] Predictions

25

T/K

20

Liquid + KCl Liquid + Ice

15

Ice + KCl 250 0 5 10 15

B 20 25 30 35 40

10 0 5 10 15 20 25 30 35 40 45

EG / mass%

KCl / mass%

Figure 3: Phase diagram of binary KCl-H2O at atmospheric pressure. Experimental data: freezing point () [17]; boiling point () [18]; salting out () [19]. The solid lines are model calculations.
440 420 400 380 360 340 C Liquid Liquid + CaCl2.4H2O Liquid + CaCl2.2H2O Vapour + Liquid Vapour + CaCl2 D

Figure 6: Experimental and calculated KCl solubility as a function of ethylene glycol concentration in aqueous solutions. EG concentrations are shown on a salt-free basis and salt concentrations are in the solution (i.e., Mass%KCl=100xMassKCl/(MassH2O+MassKCl+MassEG).

60

50

T/K

CaCl2 / mass%

320 300 280 260 240 220 200 0 5 10 15 20 25 30 35 Liquid + Ice Ice + CaCl2.6H2O B A

40

CaCl2.4H2O +CaCl2.2H2O Liquid + CaCl2.6H2O

30 273.15 K [16] 20 288.15 K [16] 303.15 K [16] 10 Predictions

CaCl2.6H2O +CaCl2.4H2O

40

45

50

55

60

65

70

75

CaCl2 / mass%

0 0 5 10 15 20 25 30 35 40

Figure 4: Phase diagram of binary CaCl2-H2O at atmospheric pressure. Experimental data: freezing point () [17]; boiling point () [18]; salting out () [16,19-21]. The solid lines are model calculations.

EG / mass%

Figure 7: Experimental and calculated CaCl2 solubility as a function of ethylene glycol concentration in aqueous solutions. EG concentrations are shown on a salt-free basis.

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SPE 87468

30

30

25

25

NaCl / mass%

15

NaCl / mass%

20

20

15

10

0 mass% MeOH [6,22] 10 mass% MeOH [6,22] 20 mass% MeOH [6,22] 40 mass% MeOH [6,22] Predictions

10

0 270

0 mass% EtOH [6] 10 mass% EtOH [6] 20 mass% EtOH [6] 40 mass% EtOH [6] 50 mass% EtOH [6] Predictions

275

280

285

290

295

300

305

310

315

320

325

T/K

0 295

305

315

325

335

345

T/K

Figure 8: Experimental and calculated maximum soluble mass of NaCl in aqueous methanol solutions as a function of temperature and MeOH concentrations. MeOH concentrations are shown on a salt-free basis.

Figure 11: Experimental and calculated NaCl solubility as a function of temperature and EtOH concentration. EtOH concentrations are shown on a salt-free basis.
30

30
25

0 mass% EG [22] 10 mass% EG [22] 25 mass% EG [22]

25

KCl / mass%

20

NaCl / mass%

20

Predictions

15 Halite

15

10

10 273.15 K [22] 298.15 K [6] 5 323.15 K [6] Predictions 0 0 10 20 30 40 50

0 0 5 10 15 20 25 30 35 40 45 5

CaCl2 / mass%

MeOH / mass%

Figure 9: Experimental and calculated KCl solubility as a function of methanol concentration in aqueous solutions. MeOH concentrations are shown on a salt-free basis.

Figure 12: Experimental and predicted NaCl solubility in quaternary NaCl-CaCl2-EG-H2O system as a function of CaCl2 and EG concentrations at 288.71 K. In this system, NaCl is the salt to initially come out of solution.

50 273.15 K [22] 280.37 K [22] 45 288.71 K [22] Predictions

CaCl2 / mass%

40

35

30 0 5 10 15 20 25 30

MeOH / mass%

Figure 10: Experimental and calculated CaCl2 solubility as a function of methanol concentration in aqueous solutions. MeOH concentrations are shown on a salt-free basis.

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