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SPE 87468

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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

Copyright 2004, Society of Petroleum Engineers Inc.

This paper was prepared for presentation at the 6 th 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 ºC), salt concentration up to saturation point and hydrate inhibitor concentration up to 50 mass%.

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 (Blow- Out 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

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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 glass- cooling 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 set- up 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]. Non- density 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 CaCl 2 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 super- saturation 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 CO 2 concentration in the aqueous phase can result in the deposition of bicarbonates as carbonates.

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

f

i

=

s

f

i

(all i )

(1)

Where

l

f

i

and

s

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:

µ

i

=

ln

f

i

=

h

i

1

l

f

T

+

1

T

T m
T
m

1

T

T m
T
m

Cp

V

i

f

RT

f

i

s

RT

T

m

RT

R

T

.

RT

CpdT

.

dT +

(

P

P

T

m

)

(2)

where

V

i

f

and

P

T

m

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.

For

this

purpose,

first

the

heat

capacity

l

Cp = C C

P

s

P

, and volume change on melting,

change,

V

i

f

,

for

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,

V

i

f

,

and

Cp

in Eq. (2). The detailed

calculations of the parameters

V

i

f

and Cp for three salts,

NaCl, KCl and CaCl 2 , 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 H 2 O-NaCl, H 2 O-KCl, and H 2 O-CaCl 2 systems are presented in Figures 2 to 4, respectively. The figures present the available experimental data [16-21] and the model’s calculations. It is worth mentioning that the pressure doesn’t 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 CaCl 2 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, CaCl 2 solubility is reduced slightly with increasing EG concentration. The solubility of CaCl 2 increases at high temperature conditions. Figures 5 to 7 essentially show the

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maximum concentrations of NaCl, KCl, and CaCl 2 that can exist with EG in aqueous solutions without any salt precipitation. In all cases, the agreement between experimental data and the model’s calculations is good, demonstrating the accuracy of the developed model.

  • - 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 doesn’t have a significant impact on antarcticite precipitation.

Figure 8 shows the experimental [6,22] and calculated NaCl solubility in aqueous methanol (MeOH) as a function of

Conclusions

temperature and MeOH concentration. As can be seen, NaCl solubility is reduced considerably as MeOH concentration

An integrated experimental and modelling study has been presented on the effect of three hydrate organic inhibitors (i.e.,

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

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.

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 CaCl 2 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 doesn’t have any significant effect on CaCl 2 solubility. The solubility increases markedly with temperature. Figures 8 to 10 essentially show the maximum concentrations of NaCl, KCl, and CaCl 2 that can exist with MeOH in aqueous solution without any salt precipitation.

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

Figure

11

shows experimental [6] and calculated NaCl

 

in this work) to calcium chloride aqueous solutions doesn’t

solubility in

aqueous

 

ethanol

(EtOH)

as

a

function

of

have a significant impact on antarcticite precipitation. In

temperature and EtOH concentration. As can be seen, NaCl

addition, the effect of temperature on halite formation is

solubility

is

reduced

considerably

as

EtOH

concentration

negligible.

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-CaCl 2 -EG-H 2 O 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.

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

l

i

,

s

f

i

=Fugacity of species i in liquid and solid phases

f

i

l

,

f

i

s

=Fugacity of pure species i as a liquid and solid at T and P of the mixture

V

i

f

=Volume change on melting at solid’s melting point (cm 3 /mol)

h

f

  • i =Enthalpy change of melting at solid’s melting point (J/mol)

P

T m

=Pressure at solid’s melting point (bar)

Cp

=Heat capacity change between liquid and solid states (J/(mol K))

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5

T

T m

R

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

Greek symbols

µ

i

= Chemical potential change between liquid and

solid states (J/mol)

References

  • 1. Barker, J. W., and Gomez, R. K., “Formation of Hydrate During Deep-water Drilling Operations”, Journal of Petroleum Technology, 41(3) (1989), 297-301.

  • 2. 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.

  • 3. Matthews, P. N., Subramanian, S., and Creek, J., “High Impact, Poorly Understood Issues with Hydrate in Flow Assurance”, Proceeding of the 4 th International Conference on Gas Hydrates, Yokohama (2002), May 19-23, 899-905.

  • 4. 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.

  • 5. 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.

  • 6. 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.

  • 7. Chiavone-Filho, O. and Rasmussen, P., “Solubilities of Salts in Mixed Solvents”, Journal of Chemical and Engineering Data, 38 (1993), 367-369.

  • 8. Babinets, D.M., and Polishchuk, A.G., “Device for solubility determination of salts in mix-solvent”, Zhurnal Fizicheskoi Khimii, 55(2) (1981), 535-537.

  • 9. 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.

    • 10. 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.

    • 11. 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.

    • 12. Van der Waals, J. H., and Platteeuw, J. C., “Clathrate Solutions”, Advances in Chemical Physics, 2(1959), 1-57.

    • 13. 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.

    • 14. Kihara, T., “ Virial Coefficient and Models of Molecules in Gases”, Reviews of Modern Physics, 25(4) (1953), 831-843.

    • 15. 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.

    • 16. 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 6 th , (1967).

    • 21. Potter, R.W., and Clynne, M.A., “Solubility of Highly Soluble Salts in Aqueous Media Part 1, NaCl, KCl, CaCl 2 , Na 2 SO 4 , and K 2 SO 4 solubilities to 100°C”, 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). Table 1: Solubility of potassium chloride
22. Parrish, W.R. Thermodynamic Inhibitors in Brine. Personal
Communication (2000).
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 AAD
glycol
No. 1
No. 2
mean
(K)
(mass%)
85.58
323.15
7.74
7.70
7.72
7.78
0.06
44.42
298.15
14.66
14.61
14.64
14.75
0.11
44.42
298.15
14.62
14.58
14.60
14.75
0.15
44.42
323.15
17.62
17.53
17.58
17.61
0.03
44.42
348.15
20.25
20.26
20.26
20.30
0.04
44.42
348.15
20.10
20.11
20.11
20.30
0.19
AAD = Absolute Average Deviation
↑ Coolant
Septum Seal
For Sampling
PRT
Insulated
Jacket
Cooling Coil
Stirrer Bar
← Coolant
Supply
Insulating
Cork Mat
Stirrer Unit
Figure
1:
Schematic
illustration
of
solubility

measurement apparatus.

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SPE 87468

390 D 375 C Vapour +NaCl Liquid + Vapour 360 345 Liquid + NaCl 330 Liquid
390
D
375
C
Vapour +NaCl
Liquid + Vapour
360
345
Liquid + NaCl
330
Liquid
315
300
285
A
270
Liquid + NaCl.2H 2 O
255
Liquid + Ice
Ice + NaCl.2H 2 O
B
240
0
10
20
30
40
T / K

NaCl / mass%

Figure 2: Phase diagram of binary NaCl-H 2 O at atmospheric pressure. Experimental data: freezing point
Figure
2: Phase diagram
of binary NaCl-H 2 O at atmospheric
pressure. Experimental data: freezing point (○) [17]; boiling point
(∆)
[18];
salting
out
(□)
[19,20].
The
solid
lines
are
model calculations.
390
Vapour +KCl
D
370
C
Liquid + Vapour
350
Liquid
330
310
Liquid + KCl
290
Liquid + Ice
A
270
Ice + KCl
B
250
0
5
10
15
20
25
30
35
40
KCl / mass%
Figure
3:
Phase
diagram
of
binary
KCl-H 2 O
at
atmospheric
pressure. Experimental data: freezing point (○) [17]; boiling point
(∆)
[18];
salting
out
(□)
[19].
The
solid
lines
are
model calculations.
440
420
D
Vapour + CaCl 2
400
Vapour + Liquid
380
360
C
Liquid +
CaCl 2 .2H 2 O
340
Liquid
Liquid +
CaCl 2 .4H 2 O
320
300
CaCl 2 .4H 2 O
A
280
+CaCl 2 .2H 2 O
260
Liquid +
Liquid + Ice
240
CaCl 2 .6H 2 O
CaCl 2 .6H 2 O
+CaCl 2 .4H 2 O
220
Ice + CaCl 2 .6H 2 O
B
200
0
5
10
15
20
25
30
35
40
45
50
55
60
65
70
75
T / K
T / K

CaCl 2 / mass%

Figure 4: Phase diagram of binary CaCl 2 -H 2 O at atmospheric pressure. Experimental data: freezing point () [17]; boiling point

()

[18];

salting

out

()

[16,19-21].

The

solid lines are

model calculations.

 
30 25 20 15 0 mass% EG [17] 10 mass% EG [5] 10 25 mass% EG
30
25
20
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 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.

35 273.15 K, [7] 298.15 K, [7] 323.15 K, [7] 30 348.15 K, [7] Predictions 25
35
273.15
K, [7]
298.15
K, [7]
323.15
K, [7]
30
348.15
K, [7]
Predictions
25
20
15
10
0
5
10
15
20
25
30
35
40
45
KCl / mass%

EG / mass%

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 =100xMass KCl /(Mass H2O +Mass KCl +Mass EG ).

60 50 40 30 273.15 K [16] 20 288.15 K [16] 303.15 K [16] 10 Predictions
60
50
40
30
273.15
K [16]
20
288.15
K [16]
303.15
K [16]
10
Predictions
0
0
5
10
15
20
25
30
35
40
CaCl2 / mass%

EG / mass%

Figure 7: Experimental and calculated CaCl 2 solubility as a function of ethylene glycol concentration in aqueous solutions. EG concentrations are shown on a salt-free basis.

SPE 87468 7

SPE 87468

7

30 25 20 15 10 0 mass% MeOH [6,22] 10 mass% MeOH [6,22] 20 mass% MeOH
30
25
20
15
10
0 mass% MeOH [6,22]
10
mass% MeOH [6,22]
20
mass% MeOH [6,22]
5
40
mass% MeOH [6,22]
Predictions
0
270
275
280
285
290
295
300
305
310
315
320
325
NaCl / mass%

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.

30 25 20 15 10 273.15 K [22] 298.15 K [6] 5 323.15 K [6] Predictions
30
25
20
15
10
273.15
K [22]
298.15
K [6]
5
323.15
K [6]
Predictions
0
0
10
20
30
40
50
KCl / 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.

50 273.15 K [22] 280.37 K [22] 288.71 K [22] 45 Predictions 40 35 30 0
50
273.15
K [22]
280.37
K [22]
288.71
K [22]
45
Predictions
40
35
30
0
5
10
15
20
25
30
CaCl 2 / mass%

MeOH / mass%

Figure 10: Experimental and calculated CaCl 2 solubility as a function of methanol concentration in aqueous solutions. MeOH concentrations are shown on a salt-free basis.

30 25 20 15 10 0 mass% EtOH [6] 10 mass% EtOH [6] 20 mass% EtOH
30
25
20
15
10
0 mass% EtOH [6]
10
mass% EtOH [6]
20
mass% EtOH [6]
5
40
mass% EtOH [6]
50
mass% EtOH [6]
Predictions
0
295
305
315
325
335
345
NaCl / mass%

T / K

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 0 mass% EG [22] 10 mass% EG [22] 25 25 mass% EG [22] Predictions 20
30
0 mass% EG [22]
10 mass% EG [22]
25
25 mass% EG [22]
Predictions
20
15
Halite
10
5
0
0
5
10
15
20
25
30
35
40
45
NaCl / mass%

CaCl 2 / mass%

Figure 12: Experimental and predicted NaCl solubility in quaternary NaCl-CaCl 2 -EG-H 2 O 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.