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Section A5 Crystallization Temperature

A5.1 A5.2 A5.3 A5.4 Introduction ........................................................................................... 2 TCT in formates what does it mean and why is it so hard to get right? 2 Crystallization mechanisms in formate brines ..................................... 2 Procedure for TCT determination in formate brines .............................3 A5.4.1 Selecting and preparing seeding material ......................................... 4 A5.4.2 TCT determination method............................................................... 4 A5.5 TCT data for formate brines ................................................................. 5 A5.5.1 TCT in single-salt sodium formate..................................................... 6 A5.5.2 TCT in single-salt potassium formate ............................................... 6 A5.5.3 TCT in single-salt cesium formates .................................................. 6 A5.5.4 TCT in blended formate brines ......................................................... 6 A5.6 Pressurized crystallization temperature PCT ...................................... 15 A5.6.1 Introduction ...................................................................................... 15 A5.6.2 Methods for determining PCT in formate brines ............................. 15 A5.6.3 PCT data for formate brines ............................................................ 15 A5.7 How to apply TCT / PCT data in the field ............................................. 18 A5.8 How to lower crystallization temperature of formate brines ............. 18 A5.8.1 Lowering TCT in single-salt formate brines ...................................... 18 A5.8.2 Lowering TCT in formate brines .................................................... 18 References .................................................................................................. 18 The Formate Technical Manual is continually updated. To check if a newer version of this section exists please visit www.formatebrines.com/manual

NOTICE AND DISCLAIMER. The data and conclusions contained herein are based on work believed to be reliable; however, CABOT cannot and does not guarantee that similar results and/or conclusions will be obtained by others. This information is provided as a convenience and for informational purposes only. No guarantee or warranty as to this information, or any product to which it relates, is given or implied. CABOT DISCLAIMS ALL WARRANTIES EXPRESS OR IMPLIED, INCLUDING MERCHANTABILITY OR FITNESS FOR A PARTICULAR PURPOSE AS TO (i) SUCH INFORMATION, (ii) ANY PRODUCT OR (iii) INTELLECTUAL PROPERTY INFRINGEMENT. In no event is CABOT responsible for, and CABOT does not accept and hereby disclaims liability for, any damages whatsoever in connection with the use of or reliance on this information or any product to which it relates. 2011 Cabot Corporation, M.A.-U.S.A. All rights reserved. CABOT is a registered trademark of Cabot Corporation. V ER S IO N 3 04/ 1 1 SECTION A5 PAGE 1

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A5.1 Introduction
Crystallization temperature is an important property of well construction and intervention fluids that are used in cold weather conditions and / or under high pressure. True crystallization temperature (TCT) has historically been used to define the performance ceiling of oilfield brines and fluids. In traditional oilfield brines and fluids there is typically only a small difference (safety margin) between the TCT as measured in the laboratory and the fluids performance ceiling in the field. Formate brines behave very differently. With a massive supercooling effect and the formation of metastable crystals, the difference between TCT as measured in the laboratory and the performance ceiling in the field is enormous, and it is questionable whether TCT is suitable for measuring the performance ceiling of the fluid. Not only is true crystallization temperature (TCT) a questionable measure of the performance ceiling of formate brines, but it is also extremely difficult to measure correctly. Measurements of TCTs in formate fluids have, over the past years, become a true stumbling block for many test laboratories. An assortment of conflicting TCT curves and mixing tables exist in the industry today. For a concentrated potassium formate brine, for example, TCT data can be found to vary from -18 to +7C / -4 to +45F.

considerations imposed by the method cause discrepancies. The API procedure is designed to be reproducible with minimal training and allows for a rapid sample throughput for traditional oilfield brines (halides). Unfortunately, formate brines were not considered when this method was developed. The API 13J guidelines are therefore currently being rewritten by an API workgroup. Two problems discovered with the current API method when applied to formate brines are supercooling and formation of metastable phase crystals. The enormous amount of supercooling that takes place in formate brines makes it impossible for most laboratories to even reach the low temperatures required to form the first crystals. TCTs of formate brines are therefore frequently reported as too low to be measured. When a low enough temperature is reached, measurements are often complicated by the formation of metastable potassium formate crystals. In order to produce meaningful TCT values for formate brines, it is therefore crucial to thoroughly understand the chemistry of these brines and their complex crystallization behavior.

A5.2 TCT in formates what does it mean and why is it so hard to get right?
The most commonly used procedure for measuring TCT in oilfield brines is the API 13J method [1]. In this procedure a brine sample is cooled at a set rate, often with a generic seed crystal of barium sulfate, until the onset of precipitation. Once precipitation starts, a small rise in temperature is usually seen due to the exothermic nature of the event. After precipitation has been noted the sample is heated until all crystals have redissolved. The data recorded from this procedure includes: First Crystal to Appear (FCTA): The temperature at which precipitation first occurs. True Crystallization Temperature (TCT): The temperature at which the sample spontaneously rises after precipitation onset. This point is only valid if there is less than a 1.5C / 3F difference between FCTA and TCT. Last Crystal to Dissolve (LCTD). The temperature at which no more crystals are present when the sample is heated. From a thermodynamic point of view, FCTA, TCT, and LCTD should be the same. In practice, kinetic

A5.3 Crystallization mechanisms in formate brines

A typical TCT curve for a brine system is shown in Figure 1. This is a phase diagram consisting of three phase equilibrium lines, an eutectic point, and a critical point. The phase equilibrium line to the left represents the brines freezing point. At conditions along this line, ice crystals are in equilibrium with the brine. The eutectic point represents the brine composition (concentration) that gives the lowest possible TCT. The center equilibrium line represents the concentration range of the brine where a hydrated version of the salt crystallizes. Along this equilibrium line the hydrated salt crystal exists in equilibrium with the brine. The right equilibrium line represents the concentration range where dry salt crystals precipitate. Along this equilibrium line, dry salt exists in equilibrium with the brine. It is difficult to measure TCT at or just around the eutectic or critical points. Metastable crystals can form along the stippled lines (shown in Figure 1). However, extrapolating the measured equilibrium lines, which intersect at the eutectic and critical points, can generate good TCT curves. All three formate brines exhibit very different TCT behavior. Sodium formate (shown in Figure 4) behaves just like the salt in Figure 1. Its TCT curve has one critical point, where hydrated and dry salt form.

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Typical TCT curve

Salt
Critical point

Temperature

Salt-H2O Ice
Eutectic point

Metastable phase TCT

Water Brine concentration

Figure 1 Typical TCT curve (or phase diagram) of brine, consisting of three phase equilibrium lines, an eutectic point and a critical point. The phase equilibrium lines represent conditions where three different solid crystals exist in equilibrium with the brine. The eutectic point represents the brine composition (concentration) with the lowest TCT, and the critical point is the point where the phase equilibrium lines of the two different salt structures join. The TCT curve of cesium formate (Figure 6) has no critical point, which means that only one salt structure forms. Since cesium formate is known to exist as a monohydrate at ambient conditions, this is the phase equilibrium line for cesium formate monohydrate in equilibrium with cesium formate brine. The critical point for the cesium formate TCT phase diagram is at a temperature so high that it is impractical to measure. Potassium formate (Figure 5) exhibits very unusual behavior as it precipitates crystals of two different hydrated phases, here referred to as metastable and stable phases: The metastable phase gives a low TCT (around -10C / 12F) for a concentrated (1.57 g/cm3 / 13.1 lb/gal) brine. This crystal phase is normally crystallized spontaneously when a certain degree of supercooling is reached or by seeding with metastable potassium formate crystals. The thermodynamically stable phase gives a rather high TCT (around 7C / 19F) for a concentrated (1.57 g/cm3 / 13.1 lb/gal) brine. These crystals form from the metastable phase crystals after some time (hours) in equilibrium with saturated brine, or by seeding with stable potassium formate crystals. The higher TCT, i.e. the one from the stable phase, is thermodynamically correct, and defined as the scientifically correct TCT. The TCT of the metastable phase, on the other hand, often contains more useful information for many applications.

A5.4 Procedure for TCT determination in formate brines

With the standard API measuring method [1], the supercooling effect can be overcome by using very low cooling rates and cycling the temperature between TCT and LCTD several times. Using low cooling rates is not feasible, however, when determining TCT of fluids with metastable phases. A kinetic conversion may take place at any time, potentially causing the measured TCT to gradually drift from the metastable phase TCT to the stable phase TCT. In many cases, there is no knowledge about which phase has been measured. Consequently, Cabot Specialty Fluids (CSF) has carried out extensive work on crystallization behavior of formate brines and on optimizing the measuring method [2], [3], [4]. From this work, it has been concluded that it is extremely important to select the correct type of seeding material, and if the correct seeding material is selected, the actual

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TCT measurement becomes relatively simple, with no need for very low cooling rates. By seeding with crystals of the same kind that crystallize from the test brine, one can make consistent and good measurements, which are not influenced by supercooling. For potassium formate brines and their blends with metastable phase TCT, the collection and storage method for seeding crystals determines which phase is measured. A5.4.1 Selecting and preparing seeding material Selection of seeding material is critical for measuring TCT in formate brines. Both the problem of supercooling and those associated with metastable phases forming in potassium formate and potassium formate blends are overcome by selecting a suitable seeding material. The rule is simple: Use the same kind of seeding crystals as those crystallizing from the test brine. The crystals should be prepared by crystallization (not drying) and kept in a freezer. Seeding material should be selected according to the following guidelines: Single-salt brines: For any low-density brines that precipitate to the left side of the eutectic point (ref. Figure 1), i.e. the part where water freezes out, no special seeding material is required. For higher density brines that precipitate to the right of the eutectic point, where hydrated or dry salts crystallize, seed with a stable crystal of this salt (see Figure 3 to Figure 5). Use a potassium formate metastable crystal to measure the metastable phase TCT of a potassium formate brine. Blended brines (e.g. a cesium / potassium formate blend, Figure 6): For brines to the left of the eutectic point, where potassium formate crystals precipitate first, seed with a stable potassium formate crystal. Alternatively, use a metastable potassium formate crystal to measure the blends metastable TCT. For higher density brines to the right of the eutectic point, use a cesium formate seeding crystal. Seeding crystals are easiest prepared in the freezer (set at -45C / -49F or lower) according to the following method: Place a sample of brine in a clean plastic sample bottle in the freezer. Add seeding crystals to the brine at any temperature lower than 10C / 50F below its expected TCT. For potassium formate brines, be aware that seeding with stable phase crystals gives stable phase crystals and seeding with metastable crystals gives metastable crystals. The seeding crystal needs to be of the same type as those

required. Crystallization time varies from a few seconds to a few hours after seeding depending on the samples TCT. If seeding crystals are prepared for the first time, i.e. no seeding crystals are available for seeding; they need to form from a brine that crystallizes along the same phase equilibrium line (ref. Figure 1), but that has a high enough TCT to overcome supercooling at freezer temperature. For potassium formate, whenever crystals are formed from such a spontaneous crystallization process, these crystals are always metastable. They can then be converted to stable crystals by leaving them for some time at higher temperature. This is tricky, so always keep a sample in the freezer once success is first achieved. Stable phase crystals remain stable forever. Metastable (potassium formate) crystals should remain metastable as long as they are kept at low enough temperature. However, always be prepared for a situation where these can transform to stable phase crystals. A5.4.2 TCT determination method The method used by CSF for determining TCT is based on the API recommended method [1]. Before TCT measurement can start, determine an approximate TCT for the sample. This is easiest completed using the information already available in Figures 4 to 6. By knowing brine type and density, TCT can be predicted with fairly high accuracy. CSF uses a Grant GR-150 cooling bath controlled by LabwiseTM software. Attached to the bath is a liquid-cooled sample cup with a stirrer. The test brine is added directly to this cup. The following procedure should be followed to measure stable phase TCT: Program the LabwiseTM temperature controller to set the first target temperature at approximately 8C / 14F below approximate TCT. When sample temperature is around 1C / 2F below its approximate TCT add a seeding crystal. As soon as the first crystals appear, note the temperature (FCTA = First Crystal To Appear). At this point, the stirring rate should be reduced and temperature should increase by 1 3C / 2 4F before falling again. The maximum temperature obtained at this stage is the first estimation of TCT. Once temperature starts to decrease, adjust the cooling bath to 2C / 4F above the first TCT estimation and switch the cooling system off. Observe the sample for the Last Crystal To Dissolve (LCTD) and note temperature. If the sample has become completely solid, temperature should rise slowly in small increments until the sample is completely crystal-free.

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Crystallized potassium formate transferring from metastable to stable phase

Stable TCT

Temperature

Metastable TCT

Time

Figure 2 Temperature as a function of time during a TCT measuring test where the crystallized potassium formate transfers from a metastable phase crystal to a stable phase crystal. Once the sample is completely crystal free, repeat this cooling / heating cycle two to three times. During the measuring process, stirring speed should be kept high, but lowered to watch for signs of FCTA and LCTD. TCT can be calculated as an average of the repeat measurements detailed above. Discrepancies of around 1C / 2F between the results are normal. However, if one result is significantly lower, this should be rejected. To measure metastable phase TCT in a potassium formate brine or a potassium formate blend the same method should be used, with the following exceptions: A metastable crystal of the brine itself should be used for seeding. During the temperature cycling steps, crystals can start converting to stable phase crystals at any time. This is represented by a sudden increase in TCT from one cycle to another. TCT eventually stabilizes again at the stable phase TCT. The correct metastable phase TCT is calculated as an average of TCTs measured before this sudden increase. How likely the brine is to convert to stable phase during the temperature cycling depends on the amount of heating applied in each temperature cycle and brine type or concentration. The activation energy required to transform crystals to the stable phase depends on brine concentration (for single salt brines) and brine composition (for blended salts). A typical temperature plot showing a transition from metastable to stable phase potassium formate crystals is shown in Figure 2.

A5.5 TCT data for formate brines

The TCT data presented in this section are a combination of TCT data measured by CSF and TCT data taken from various other sources. All curves have been verified with CSFs recommended test method. As CSFs method involves seeding with crystals of the formate brine itself, these curves are likely to be rather conservative (read higher values) than what one could expect from other methods. TCT for single-salt brines are shown in Figure 3 to Figure 6 and Table 1 to Table 3. Figures 4, 5, and 6 also show some measured points representing supercooling. This is the temperature where the brine has successfully been held for at least two weeks in the presence of traditional seeding material and other particles (barite, bentonite, rust, dust, etc.) without crystallizing. With the use of less sophisticated measuring techniques that do not use crystals of the brine itself for seeding, measured TCT values can typically be found anywhere in the range between the supercooling points and the TCT curve.

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A5.5.1 TCT in single-salt sodium formate TCT as a function of fluid density for a pure sodium formate single-salt brine is presented in Figure 4 and Table 1. The data represent a mixture of measurements completed by Shell [5] and newer measurements by Cabot Specialty Fluids and Baroid. A5.5.2 TCT in single-salt potassium formate TCT as a function of fluid density for a pure potassium formate single-salt brine is presented in Figure 5 and Table 2. Freezing point data (the phase equilibrium line to the left of the eutectic point) has been taken from OSCA [6]. Stable and metastable crystallization temperatures (the phase equilibrium lines to the right of the eutectic point) are all measured by CSF [3] according to the method described above. A5.5.3 TCT in single-salt cesium formate TCT as a function of fluid density for a pure cesium formate single-salt brine is presented in Figure 6 and Table 3. Freezing-point data (the phase equilibrium line to the left of the eutectic point) has been taken from Shell [5]. Crystallization temperatures (the phase equilibrium line to the right of the eutectic point) are all measured by CSF [2][3] according to the method described above.

A5.5.4 TCT in blended formate brines When concentrated cesium formate and concentrated potassium formate are blended, the blends TCT depends on the blend ratio. An eutectic point (minimum TCT) is achieved at around 50 / 50 blend ratio or, more exactly, at a density of 1.91 g/cm3 / 15.9 lb/gal (see Figure 7 for a blend of 1.57 g/cm3 / 13.1 lb/gal potassium formate brine and 2.20 g/cm3 / 12.9 lb/gal cesium formate brine). In winter, blends are often made from more diluted potassium formate brine (1.54 g/cm3 / 12.9 lb/gal), which lowers TCT. Some blends also retain a safe TCT even if water is removed. The TCT curve in Figure 7 should therefore not be used as a definitive guide to TCTs in blended cesium and potassium formate blends supplied by CSF.

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METRIC

TCT of formate brines

30 20 10 0 Temperature [C] -10 -20 -30 -40 -50 -60 -70 1.0 1.1 1.2 1.3 1.4 1.5 1.6 1.7 1.8 1.9 2.0 2.1 2.2 2.3 Density (g/cm3) NaFo KFo stable phase KFo metastable phase CsFo

FIELD

TCT of formate brines

100 80 60 40 20 0 -20 -40 -60 -80 8 9 10 11 12 13 14 Density [lb/gal] 15 16 17 18 19 20 NaFo KFo stable phase KFo metastable phase CsFo

Figure 3 True Crystallization Temperature (TCT) for sodium, potassium, and cesium formate brines.

Temperature [F]

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TCT sodium formate single salt

20 15 10 5 0 -5 -10 -15 -20 -25 1.00 NaFo NaFo supercooling

Temperature [C]

1.05

1.10

1.15

1.20

1.25

1.30

1.35

Density (g/cm3)

FIELD
FIELD

TCT sodium formate single salt

60 50 40 Temperature [F] 30 20 10 0 -10 -20

NaFo NaFo supercooling

8.2

8.4

8.6

8.8

9.0

9.2

9.4

9.6

9.8

10.0

10.2

10.4

10.6

10.8

11.0

11.2

Density [lb/gal]

Figure 4 True Crystallization Temperature (TCT) for sodium formate (single salt). The supercooling points represent the temperature where the fluid has been successfully kept for at least two weeks in the presence of standard seeding material.

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Table 1 True Crystallization Temperature (TCT) for sodium formate single salt. METRIC Density [g/cm ]
3

FIELD TCT [C] 1.00 1.01 1.02 1.03 1.04 1.05 1.06 1.07 1.08 1.09 1.10 1.11 1.12 1.13 1.14 1.15 1.16 1.17 1.18 1.19 1.20 1.21 1.22 1.23 1.24 1.25 1.26 1.27 1.28 1.29 1.30 1.31 1.32 1.33 0.0 -0.7 -1.6 -2.5 -3.4 -4.4 -5.4 -6.5 -7.8 -9.1 -10.6 -12.1 -13.9 -15.7 -17.8 -20.0 -22.5 -18.2 -13.9 -10.0 -6.4 -3.3 -0.5 1.9 3.9 5.5 6.7 7.6 8.0 10.7 13.6 16.2 18.6 20.7 Density [lb/gal] 8.34 8.40 8.50 8.60 8.70 8.80 8.90 9.00 9.10 9.20 9.30 9.40 9.50 9.60 9.70 9.80 9.90 10.00 10.10 10.20 10.30 10.40 10.50 10.60 10.70 10.80 10.90 11.00 11.10 TCT [F] 32.0 31.2 29.4 27.5 25.5 23.3 21.0 18.4 15.5 12.3 8.8 4.9 0.6 -4.2 -5.9 3.8 12.5 20.2 26.9 32.7 37.4 41.2 44.0 45.7 47.6 54.2 60.0 65.2 69.8

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TCT potassium formate single salt

30 20 10 Temperature [C] 0 -10 -20 -30 -40 -50 -60 1.00 1.05 1.10 1.15 1.20 1.25 1.30 1.35 1.40 1.45 1.50 1.55 1.60 1.65 TCT stable phase TCT stable phase extrapolated TCT metastable phase TCT metastable phase extrapolated KFo supercooling

Density [g/cm3]

FIELD

TCT potassium formate single salt

90 80 70 60 50 40 30 20 10 0 -10 -20 -30 -40 -50 -60 -70 -80 8.0 8.5 9.0 9.5 10.0 10.5 11.0 11.5 12.0 12.5 13.0 13.5 14.0

TCT stable phase TCT stable phase extrapolated TCT metastable phase TCT metastable phase extrapolated KFo supercooling

Temperature [F]

Density [lb/gal]

Figure 5 True Crystallization Temperature (TCT) for potassium formate (single salt). The stable phase TCT is measured by seeding with stable phase potassium formate crystals. The metastable phase TCT is measured by seeding with metastable phase potassium formate crystals. The supercooling points indicate the temperature where the fluid has been successfully kept for at least two weeks in the presence of standard seeding material.

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Table 2 True Crystallization Temperature (TCT) for potassium formate single salt. METRIC Density [g/cm ]
3

FIELD TCT (stable) [C] TCT (metastable) [C] Density [lb/gal] 8.34 8.40 8.50 8.60 8.70 8.80 8.90 9.00 9.10 9.20 9.30 9.40 9.50 9.60 9.70 9.80 9.90 10.00 10.10 10.20 10.30 10.40 10.50 10.60 10.70 10.80 10.90 11.00 11.10 11.20 11.30 11.40 11.50 11.60 11.70 11.80 11.90 12.00 12.10 12.20 12.30 12.40 12.50 12.60 12.70 12.80 12.90 13.00 13.10 13.20 13.30 13.40 13.50 TCT (stable) [F] 30.8 30.1 28.9 27.5 25.9 24.1 22.1 20.0 17.7 15.2 12.5 9.7 6.7 3.5 0.2 -3.3 -6.9 -10.7 -14.7 -18.8 -23.0 -27.4 -31.9 -36.6 -41.3 -46.3 -51.3 -56.5 -61.8 -67.2 -58.6 -49.4 -40.7 -32.3 -24.3 -16.8 -9.6 -2.9 3.4 9.3 14.8 19.9 24.6 28.9 32.8 36.2 39.3 42.0 44.2 46.0 47.4 65.6 89.3 TCT (metastable) [F]

1.00 1.01 1.02 1.03 1.04 1.05 1.06 1.07 1.08 1.09 1.10 1.11 1.12 1.13 1.14 1.15 1.16 1.17 1.18 1.19 1.20 1.21 1.22 1.23 1.24 1.25 1.26 1.27 1.28 1.29 1.30 1.31 1.32 1.33 1.34 1.35 1.36 1.37 1.38 1.39 1.40 1.41 1.42 1.43 1.44 1.45 1.46 1.47 1.48 1.49 1.50 1.51 1.52 1.53 1.54 1.55 1.56 1.57 1.58 1.59 1.60 1.61

0.0 -1.2 -1.7 -2.4 -3.1 -3.9 -4.8 -5.8 -6.8 -7.9 -9.1 -10.4 -11.7 -13.1 -14.6 -16.1 -17.7 -19.3 -21.0 -22.7 -24.6 -26.4 -28.3 -30.3 -32.3 -34.4 -36.5 -38.6 -40.8 -43.0 -45.3 -47.5 -49.9 -52.2 -54.6 -52.1 -47.8 -43.6 -39.6 -35.7 -32.0 -28.5 -25.1 -21.8 -18.8 -15.9 -13.1 -10.5 -8.1 -5.8 -3.7 -1.7 0.1 1.8 3.3 4.6 5.8 6.8 7.7 8.4 12.4 23.4

-58.6 -54.4 -50.3 -46.5 -42.8 -39.3 -36.0 -32.8 -29.8 -27.0 -24.3 -21.8 -19.5 -17.3 -15.4 -13.5 -11.9 -10.4 -9.1 -8.0 0.4 14.2

-71.9 -63.0 -54.5 -46.4 -38.8 -31.6 -24.9 -18.6 -12.7 -7.3 -2.4 2.2 6.3 9.9 13.1 15.9 22.8 41.2 59.7

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TCT cesium formate single salt

30 20 10 0 Temperature [C] -10 -20 -30 Temperature [C] -40 -50 -60 -70 1.0 1.1 1.2 1.3 1.4 1.5 1.6 1.7 1.8 1.9 2.0 2.1 2.2 2.3 2.4 2.5 Density [g/cm3] TCT CsFo TCT CsFo extrapolated CsFo supercooling

FIELD

TCT cesium formate single salt

90 80 70 60 50 40 30 20 10 0 -10 -20 -30 -40 -50 -60 -70 -80 8 9

TCT CsFo TCT CsFo extrapolated CsFo supercooling

Temperature [F]

10

11

12

13

14

15

16

17

18

19

20

21

Density [lb/gal]

Figure 6 True Crystallization Temperature (TCT) for cesium formate (single salt). The supercooling points indicate the temperature where the fluid has been successfully kept for at least two weeks in the presence of standard seeding material.

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Table 3 True Crystallization Temperature (TCT) for cesium formate single salt. METRIC Density [g/cm3] 1.00 1.05 1.10 1.15 1.20 1.25 1.30 1.35 1.40 1.45 1.50 1.55 1.60 1.65 1.70 1.75 1.80 1.85 1.90 1.92 1.94 1.96 1.98 2.00 2.02 2.04 2.06 2.08 2.10 2.12 2.14 2.16 2.18 2.20 2.22 2.24 2.26 2.28 2.30 2.32 2.34 2.36 2.38 2.40 FIELD Density [lb/gal] 0.0 -1.0 -2.3 -3.8 -5.5 -7.5 -9.8 -12.3 -15.0 -18.0 -21.2 -24.7 -28.4 -32.4 -36.6 -41.0 -45.7 -50.6 -55.8 -58.0 -57.4 -49.6 -42.5 -35.9 -30.0 -24.5 -19.6 -15.1 -11.0 -7.2 -3.8 -0.7 2.2 4.9 7.4 9.9 12.2 14.5 16.9 19.2 21.7 24.3 27.1 30.1 8.34 8.5 9.0 9.5 10.0 10.5 11.0 11.5 12.0 12.5 13.0 13.5 14.0 14.5 15.0 15.5 16.0 16.2 16.3 16.4 16.5 16.6 16.7 16.8 16.9 17.0 17.1 17.2 17.3 17.4 17.5 17.6 17.7 17.8 17.9 18.0 18.1 18.2 18.3 18.4 18.5 18.6 18.7 18.8 18.9 19.0 19.1 19.2 19.3 19.4 19.5 19.6 19.7 19.8 19.9 20.0

TCT [C]

TCT [F] 32.0 31.4 29.0 25.9 22.2 17.8 12.8 7.2 1.0 -5.9 -13.4 -21.6 -30.4 -39.8 -49.8 -60.5 -71.8 -70.4 -61.9 -53.9 -46.2 -38.9 -32.0 -25.5 -19.3 -13.5 -8.0 -2.8 2.1 6.8 11.2 15.3 19.3 23.0 26.5 29.9 33.1 36.2 39.1 41.9 44.7 47.3 49.9 52.4 55.0 57.5 60.0 62.5 65.0 67.6 70.3 73.1 75.9 78.9 82.0 85.2

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TCT and supercooling data for blended Cs and K formate

15 10 5 0 -5 Temperature [C] -10 -15 -20 -25 -30 -35 -40 -45 1.45 1.50 1.55 1.60 1.65 1.70 1.75 1.80 1.85 1.90 1.95 2.00 2.05 2.10 2.15 2.20 2.25 CsKFo stable phase CsKFo metastable phase CsFo KFo stable phase KFo metastable phase CsKFo supercooling

Density [g/cm3]

FIELD

TCT and supercooling data for blended Cs and K formate

50 40 30 20 10 0 -10 -20 -30 -40 12.0 CsKFo stable phase CsKFo metastable phase CsFo KFo stable phase KFo metastable phase CsKFo supercooling

Temperature [F]

12.5

13.0

13.5

14.0

14.5

15.0

15.5

16.0

16.5

17.0

17.5

18.0

18.5

19.0

Density [lb/gal]

Figure 7 True Crystallization Temperature (TCT) for a blend of 1.57 g/cm3 / 13.10 lb/gal potassium formate and a 2.20 g/cm3 / 18.36 lb/gal cesium formate. The stable phase TCT is measured by seeding with stable phase potassium and cesium formate crystals, whilst the metastable phase TCT is measured by seeding with metastable potassium formate crystals. Blends of potassium and cesium formate used in the field can contain more or less water than this standard blend, so field brine TCTs might be higher or lower than shown in this plot.

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A5.6 Pressurized crystallization temperature PCT

A5.6.1 Introduction In deep-water environments, crystallization can become a serious problem. High pressure and low temperature can cause the salts in high-density brine solutions to become more susceptible to crystallization. Extremely high pressure and low temperatures are normally encountered at the mud line and during pressure testing of equipment. Pressure as high as 16,000 to 18,000 psi is not unusual. Therefore, it is of great importance to know the crystallization temperature for the fluid at realistic pressure conditions. There are two major problems associated with PCT measurements in general. The first problem is the lack of a dependable standardized method. The second problem is the poor availability of high-pressure testing equipment to identify the TCT under dynamic conditions of pressure and temperature. For formate brines, with the additional difficulties of extreme supercooling and existence of metastable phases, these measurements become extremely complicated. A5.6.2 Methods for determining PCT in formate brines PCT measurements of formate brines have been carried out at two test laboratories: Westport Technology Center International and Baroid. The test methods that have been used to determine PCT in formates are: Westport Technology Center International: acoustic method Westport has chosen an acoustic method for determination of PCT. This technique was chosen due to serious limitations in standard determination techniques, such as visual detection, temperaturetime-plot, and volume change. The equipment can measure down to -30C / -22F. The pressure range is from 0.07 to 140 MPa / 10 to 20,000 psi, and the sample volume is from 5 to 350 mL. Both the arrival time of the acoustic wave and attenuation of the wave amplitude are functions of the number of solid particulate in the brine solution. To ensure temperature and composition homogeneity, the cell is rocked back and forth, which also helps reduce the supercooling effects. The acoustic cell sits in a controlled temperature chamber with a circulation system that provides uniform temperature distribution and cooling rates. Baroid: Fiber optics technique Baroid uses the following methods for determining crystallization: Visual (fiber optics) Volume change Temperature inflection point
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The cell volume is 70 mL. The cell is equipped with a stir disk. Testing starts at 10,000 psi and decreases to the base line of 100 psi in 2,500 psi increments. The test includes four cycles at each pressure stage to check for supercooling effects. Each test takes 16 to 21 hours with 0.05g of 5 micron marble used as seeding agent. A5.6.3 PCT data for formate brines By using the two measurement methods described above some limited PCT values have been determined. PCT data for a 2.195 g/cm3 / 18.3 lb/gal cesium formate brine with and without 0.5% KCl TCT was measured as a function of pressure for a 2.195 g/cm3 / 18.3 lb/gal buffered cesium formate brine with and without the addition of 5% KCl. KCl was added to reduce TCT. The tests were completed at Westport Technology Center according to its acoustic technique described above. The results are listed in Table 4 and plotted in Figure 8. PCT data for various formate brines and blends Baroid has carried out a number of PCT tests on formate fluids by using their fiber optics detection technique mentioned above. TCT as a function of pressure (up to 20,000 psi) was measured on buffered, saturated cesium formate brine (2.18 g/cm3 / 18.18 lb/gal). The test results are shown in Table 5 and plotted in Figure 8. Similar tests were carried out on several buffered formate brines: 1.32 g/cm3 / 11.01 lb/gal sodium formate, 1.58 g/cm3 / 13.17 lb/gal potassium formate, 2.18 g/cm3 / 18.18 lb/gal cesium formate, 2.2 g/cm3 / 18.34 lb/gal cesium formate, and 1.52 g/cm3 / 12.67 lb/gal potassium / cesium formate. From Figure 8 it can be seen that there is very good consistency between the two methods of PCT measurements. Also, by comparing the TCTs when no pressure is applied, it is found that the TCTs measured with these instruments are similar to the ones measured in standard TCT tests. For cesium formate and cesium / potassium formate blends, the following rule of thumb applies:

Cs & Cs/K formate: Increase in TCT ~ 1F per 1,000 psi pressure increase.

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Table 4 TCT as a function of pressure for a buffered 2.195 g/cm3 / 18.3 lb/gal cesium formate brine with and without 5% KCl. Measured at Westport Technology Center International. Pressure [MPa] 0.14 20.7 34.5 48.3 68.9 [psi] 21 3,000 5,000 7,000 10,000 PCT 2.195 g/cm3 / 18.3 lb/gal CsFo [C] 7.2 7.5 10.2 [F] 41.0 42.0 50.4 PCT 2.195 g/cm3 / 18.3 lb/gal CsFo +5%KCl [C] [F] -4.7 23.6 -2.3 27.8 -1.9 -0.33 28.6 31.4

Table 5 TCT as a function of pressure for a variety of formate brines and blends. The measurements have been carried out by Baroid. The 1.52 g/cm3 / 12.7 lb/gal potassium / cesium formate blend has been designed specifically to lower TCT / PCT. Pressure [MPa] 1.32 g/cm3 / 11.0 lb/gal NaFo 0.69 17.24 34.47 51.71 68.95 0.69 17.24 34.47 51.71 68.95 0.69 17.24 34.47 51.71 68.95 0.69 17.24 34.47 51.71 68.95 132.5 117.8 102.2 86.7 71.4 68.2 51.2 34.3 17.1 0.56 [psi] 100 2,500 5,000 7,500 10,000 100 2,500 5,000 7,500 10,000 100 2,500 5,000 7,500 10,000 100 2,500 5,000 7,500 10,000 19,221 17,086 14,830 12,574 10,352 9,888 7,433 4,969 2,476 81 [C] 10.39 12.78 12.33 16.28 17.06 -8.3 -4.3 -2.0 0.56 1.96 -6.03 -4.67 -3.42 -2.18 -2.40 5.3 6.7 8.2 9.6 11.2 15.5 13.9 12.6 11.0 9.2 10.8 8.4 7.2 5.7 4.2 PCT [F] 61.2 62.3 63.0 63.5 65.5 17.0 24.2 28.4 33.0 35.5 21.2 23.6 25.9 28.1 27.7 41.5 44.0 46.7 49.3 52.2 59.9 57.1 54.7 51.8 48.5 51.4 47.2 44.9 42.3 39.6

1.58 g/cm3 / 13.2 lb/gal KFo

1.52 g/cm3 / 12.7 lb/gal KCsFo

2.20 g/cm3 / 18.3 lb/gal CsFo buffered

2.18 g/cm3 / 18.2 lb/gal CsFo

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PCT in various formate brines and blends

22 20 18 16 14 12 10 TCT [C] 8 6 4 2 0 -2 -4 -6 -8 -10 0 10 20 30 40 50 60 70 80 90 100 110 120 130 140 1.32 g/cm3 NaFo (Baroid) 2.20 g/cm3 CsFo-buffered (Baroid) 2.12 g/cm3 CsFo (Westport) 2.18 g/cm3 CsFo (Baroid) 2.20 g/cm3 CsFo + 5% KCl (Westport) 1.52 g/cm3 KCsFo (Baroid) 1.58 g/cm3 KFo (Baroid)

Pressure [MPa]

FIELD

PCT in various formate brines and blends

80 75 70 65 60 55

TCT [F]

50 45 TCT [F] 40 35 30 25 20 15 10

11.0 lb/gal NaFo (Baroid) 18.3 lb/gal CsFo-buffered (Baroid) 18.3 lb/gal CsFo (Westport) 18.2 lb/gal CsFo (Baroid) 18.3 lb/gal CsFo + 5% KCl (Westport) 12.7 lb/gal KCsFo (Baroid) 13.2 lb/gal KFo (Baroid) 0 2 000 4 000 6 000 8 000 10 000 Pressure [psi] 12 000 14 000 16 000 18 000 20 000

Figure 8 TCT as a function of pressure for a variety of formate brines and blends.

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A5.7

How to apply TCT / PCT data in the field

A5.8 How to lower crystallization temperature of formate brines

In some applications it might be desirable to lower the crystallization temperature of formate brines and blends. A5.8.1 Lowering TCT in single-salt formate brines TCT can be lowered in single-salt formate brines by adding chloride ions. The lowering of TCT by adding 15% and 20% potassium chloride to a sodium formate brine has been demonstrated by Shell [5], and is shown in Figure 9. Care should be taken, however, when adding chloride ions to a formate brine. Chloride is known to cause localized corrosion problems, and is hard to remove. A5.8.2 Lowering TCT in formate blends In certain deepwater applications there is need for formate brine with the typical density of single-salt potassium formate brine, but with lower TCT than can be obtained by this single-salt brine alone. In this case, a blended potassium / cesium formate brine can be formulated with some additional water added.

Although the scientifically correct fluid TCT is the thermodynamically stable one, i.e. the highest one measured, this might not be the most suitable TCT value to use when formulating drilling and completion fluids. As formates supercool more than other brines, and potassium formate brines and their blends precipitate metastable phase crystals, it is impossible to apply measured TCT data in the same way as in other brines. Storage of potassium formate brine (and formate blends with a high potassium formate content) in tanks is a good example of this. In the absence of a stable-phase potassium formate seeding crystal, a thermodynamically stable phase cannot be formed before metastable crystals exist in the fluid. Therefore, this fluid can be stored safely at temperatures down to the TCT of the metastable phase, or even lower due to supercooling. In periods when temperatures outside the tank go beyond the TCT of the metastable phase, metastable crystals may form locally at the sides of the tank, although the bulk temperature in the fluid inside the tank is significantly above this temperature. The extent of this crystallization is limited, but within a few hours the transformation to thermodynamically stable crystals can occur. These stable phase crystals serve as seeding crystals for thermodynamically stable-phase crystals to form in the whole storage tank, assuming bulk temperature inside the tank is below the TCT of the stable phase. Crystallization will be substantial as the fluid can be regarded as heavily supersaturated with respect to this type of crystallization. In order to dissolve these crystals again, the temperature obviously needs to be above the LCTD value of the stable phase, which is significantly higher than the LCTD temperature of the metastable phase. Therefore, potassium formates can safely be stored down to the lower TCT of the metastable phase, and even lower due to supercooling. However, one should keep in mind that localized cooling and crystallization at the wall of the container can have drastic consequences for the extent of crystallization and the ability to dissolve the crystals afterwards.

References
[1] API RP 13J: Testing of Heavy Brines. [2] Obi, A.S.: Measurements of True Crystallisation Temperature in High Density Caesium Brines used in Drilling Fluids, MSc Thesis, Robert Gordon University, Aberdeen, September 2008. [3] Chrenowski, M.: TCT Behaviour of Formate Drilling and Completion Fluids, MSc Thesis, Robert Gordon University, Aberdeen, September 2009. [4] TCT Cesium Potassium Formate Blends, Lab Report LR-406, Cabot Operations & Technical Support Laboratory, Aberdeen, September 2010. [5] Howard, S.K., Houben, R.J.H., Oort, E. van, and Francis, P.A.: Formate drilling and completion fluids Technical Manual, Shell Report SIEP 96-5091, 1996. [6] OSCA report: Crystallization Temperatures for Potassium Formate Brines Formate Brine Project Task #1, March 1995.

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TCT sodium formate single salt

20 15 10 5 Temperature [C] 0 -5 -10 -15 -20 -25 -30 1.00 1.05 1.10 1.15 1.20 1.25 1.30 1.35 NaFo NaFo +15% KCl NaFo +20% KCl

Density [g/cm3]

FIELD

TCT sodium formate single salt

60 50 40 Temperature [F] 30 20 10 0 -10 -20 NaFo NaFo +15% KCl NaFo +20% KCl

8.2

8.4

8.6

8.8

9.0

9.2

9.4

9.6

9.8

10.0

10.2

10.4

10.6

10.8

11.0

11.2

Density [lb/gal]

Figure 9 TCT in single-salt sodium formate brine. Effect of adding 15% and 20% KCl to a sodium formate brine [5].

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