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C ABOT SP E C I A LT Y F L U I D S F O RM ATE TECH N ICAL M AN UAL

C OMPATIBILITIE S AN D IN T E R ACT IO N S

Section B12
Solubility of Minerals
and Salts in Formate Brines
B12.1 Introduction.............................................................................................2
B12.2 Solubility of alkaline earth metal sulfates in formate brines...................2
B12.2.1 Effect of brine type...........................................................................2
B12.2.2 Effect of temperature.......................................................................2
B12.2.3 Effect of formate concentration.......................................................2
B12.2.4 Effect of exposure time....................................................................3
B12.2.5 Effect of pH......................................................................................3
B12.2.6 Effect of precipitation reactions........................................................3
B12.2.7 Practical significance of increased alkaline earth metal sulfate
solubility in formate brines................................................................3
B12.3 Solubility of salts in formate brines......................................................... 7
B12.3.1 Solubility of potassium sulfate in potassium formate brine.............. 7
B12.3.2 Solubility of sodium chloride (NaCl) in potassium formate brine...... 7
B12.3.3 Solubility of magnesium chloride (MgCl2) in formate brines............. 7
B12.4 Solubility of clays in formate brines....................................................... 11
B12.5 Solubility of silicates in formate brines.................................................. 11
B12.6 Solubility of galena, hematite, and ilmenate in formate brines............. 11
B12.7 Solubility of calcium carbonate in formate brines................................. 11
References............................................................................................ 12

The Formate Technical Manual is continually updated.


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V ER S IO N 1 – 05/ 1 1 SECTION B12 PAGE 1


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B12.1 Introduction B12.2 Solubility of alkaline earth


metal sulfates in formate
Oil and gas wells are drilled through thousands of brines
meters of various minerals to access hydrocarbon-
bearing reservoirs. While being drilled and completed, Shell Research has measured solubility of some
well construction fluids circulating in the wellbore alkaline earth metal sulfates in a variety of concentrated
are in contact with these minerals under conditions brines [3]. The solubility measurements were made
of high temperature and pressure. Therefore, it is after exposure of solid samples of alkaline earth
important to have a detailed knowledge of how metal sulfate to the brines. The following factors
drilling and completion fluids interact with minerals were varied to study their effect: brine type, brine
under down-hole conditions. In wells where it is concentration, temperature, exposure time, and pH.
necessary to drill extended sections through thick
layers of salt and anhydrite, it is particularly important Shell’s procedure was to mix the brines with solid
to know if fluids solubilize these minerals. samples of alkaline earth metal sulfates, heat at
the given temperature for the desired time in a
Oilfield brines (completion fluids and filtrates of rotating oven and quickly filter the warm fluid.
reservoir drilling fluids) are also in contact with The concentration of dissolved cations in the clear
reservoir fluids. Formation waters contain a lot of filtrate was determined by atomic absorption
different ions, which are often divalent and can spectroscopy (AAS).
easily form insoluble scales when in contact with
other divalent ions. This is why it is important to Since Shell carried out these tests, it has been
know how various formation waters react when in shown that some precipitation of alkali metal
contact with oilfield brines. sulfates takes place when alkaline earth metal
sulfates dissolve in concentrated formate brines.
Well completion brines with high electrolyte content Therefore in potassium formate brine, precipitation
are known to increase solubility of alkaline earth- of potassium sulfate occurs and in cesium formate
metal sulfate minerals, like calcium sulfate (gypsum brine some cesium sulfate precipitation takes
and anhydrite) and barium sulfate, which have low place. This precipitation is not considered in the
solubility in water. Shell solubility data as only soluble alkali earth metal
ion levels were measured (Ba2+, Sr2+, Ca2+).
For example, Templeton shows that aqueous
solutions of chloride brines can dissolve barium B12.2.1 Effect of brine type
from barite [1]. This is supported by Monnin [2] who Solubilities of sulfate minerals in the different brines
shows that at atmospheric pressure saturated are listed in Table 1 and shown graphically in Figure 1.
sodium chloride brine solubilizes 50 – 100 mg/L These tests were performed after 16-hour exposure
of barium from barite at 50 – 100°C / 122 – 212°F. at 85°C / 185°F. All fluids were tested at pH = 9.5
At higher temperatures and pressures, barium (measured in undiluted brines).
solubility levels can increase to 200 – 400 mg/L.
The same author demonstrates that barite is even Concentrated potassium and cesium formate
more soluble in calcium chloride brine, another brines dissolve significantly higher levels of alkaline
common well completion fluid. earth metal sulfates than any other tested brines.
Potassium formate brine dissolves more barium
This section of the Formate Technical Manual looks sulfate than cesium formate brine, whilst cesium
at what is known about the solubility of minerals formate brine dissolves more strontium sulfate.
and salts in formate brines. Data have been Concentrated sodium formate brine generally
collected from various known and unknown sources dissolves more alkaline earth metal sulfates than
and full descriptions of measuring methods are concentrated halide brines, but significantly less
not always available. Considering the difficulties than potassium and cesium formate brines.
associated with performing good solubility
measurements in brines, the data reported here B12.2.2 Effect of temperature
should only be used as a rough guide. The temperature dependence of barium and
strontium sulfate solubility in concentrated potassium
formate brine has been measured and reported by
Shell [3]. See Figure 2. Solubility increases significantly
with rising temperature.

B12.2.3 Effect of formate concentration


Shell also measured the influence of formate
concentration on barium and strontium sulfate

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SECTION B: COMPATIBILITIES AND INTERACTIONS CABO T S P ECIALTY FLUIDS

solubility in concentrated potassium formate brine [3]. B12.2.7 Practical significance of


See Figure 3. Solubility increases with greater formate increased alkaline earth metal
concentration. sulfate solubility in formate brines
The increased solubility of alkaline earth sulfate
B12.2.4 Effect of exposure time minerals (‘scales’) in concentrated formate brines
Shell measured influence of contact time on barium has certain implications and consequences in well
and strontium sulfate solubility in concentrated construction operations. Concentrated formate
potassium formate brine. See Figure 4. The results brines dissolve some barium and strontium from
show that strontium sulfate dissolves significantly common oilfield scales and barite at high temperatures
faster than barium sulfate. At 85°C / 185°F, 90% of and pressures. This may cause some simultaneous
strontium sulfate dissolved after about three hours precipitation of alkali metal sulfates in concentrated
and 100% after around 12 hours. Ninety percent of formate brines after contact with sulfate scales or
the barium sulfate dissolved after about 13 hours barite. These precipitated products, such as
and 100% after around 19 hours. potassium sulfate, are not scales. They easily
dissolve as soon as the formate concentration
B12.2.5 Effect of pH lowers or temperature increases, and therefore are
Shell measured the influence of pH on barium and of no significant threat to well productivity.
strontium sulfate solubility in concentrated potassium
formate brine. See Figure 5. In the pH range tested When formate brine filtrate enters the reservoir the
(pH = 7 – 13, measured in undiluted brine), no significant high solubility of alkaline earth metal sulfate affects
pH effect was observed. the ability of sulfate scales to form from contact
between formation water and contaminants in the
B12.2.6 Effect of precipitation reactions brine. This high solubility of sulfate scale in formate
Testing has been carried out to evaluate the extent brines is not allowed for in most scale prediction
other precipitation mechanisms take place when software packages used widely in the industry to
alkali metal earth sulfates dissolve in formate brines. predict incompatibilities between oilfield brines and
Tests were completed by measuring both cation formation waters.
(Ca2+) and anion (SO42-) concentrations in the brine.
The low solubility of potassium sulfate in concentrated
For anhydrite (CaSO4), it was found that this mineral potassium formate can also cause some precipitation
dissolved quite readily in high-concentration potassium of potassium sulfate if the formate fluid is in contact
formate brine (71%wt = 1.53 g/cm3 / 12.8 lb/gal). with seawater for example. This precipitation is
However, some dissolved sulfate precipitated out likely to take place at the surface, over the shakers,
as K2SO4, resulting in a correspondingly low sulfur where fluid temperature is lowered. These crystals
concentration in the liquid phase. At lower concentration re-dissolve at higher temperatures and dissolve
potassium formate (30%wt = 1.19 g/cm3 / 9.9 lb/gal), completely if the formate concentration is brought
formation of syngenite, K2Ca(SO4)2·H2O, was observed down by contact with reservoir water for example.
in addition to K2SO4. The sulfur concentrations in
solution were similar to those measured when A second precipitation mechanism takes place in
dissolving K2SO4 in the brine (see B12.3). buffered formate brines when alkali earth metal
sulfates dissolve. This is precipitation of alkali earth
For barium sulfate (BaSO4) with lower concentrations metal carbonates. Barium carbonate (BaCO3) is
of potassium formate, i.e. 10%wt = 1.06 g/cm3 / insoluble in formate (under alkaline pH conditions)
8.8 lb/gal and 30%wt = 1.19 g/cm3 / 9.9 lb/gal, the and also consumes carbonate buffer added to the
sulfate concentration in solution matched K2SO4 formate brine. For this reason, it is important to
solubility (see B12.3), indicating that precipitation had avoid contaminating formate brines with barite.
not taken place. For higher formate concentration
(71%w = 1.53 g/cm3 / 12.8 lb/gal), solubility (calculated The occurrence of precipitation also greatly
on sulfur determination) was significantly lower than complicates laboratory solubility testing. To gain a
corresponding BaSO4 solubilities measured by Shell full understanding of the dissolution / precipitation
and determined by analysis of barium content in the process, preferably both cations and anion levels
liquid phase, which indicates that some precipitation in the liquid should be determined, the solid
of K2SO4 takes place. phase analyzed, and a mass balance carried out.
Solubility figures also look different for buffered and
unbuffered brines.

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Table 1 Solubility of alkaline earth sulfates and scales after 16-hour exposure to various saturated brines at 85°C / 185°F. Some precipitation
of sodium, potassium, and cesium sulfates takes place in all of these tests, so brine sulfate levels do not correspond to levels of dissolved
alkali earth metal sulfates.

Dissolved Sodium salts Potassium salts Cesium salts


minerals/scales Water NaFo NaCl NaBr KFo KCl KBr CsFo
[mg/L] Cs2SO4
(40%w) (26%w) (46%w) (75%w) (24%w) (34%w) (82%w)
BaSO4 2 80 8 3 5,800 16 14 600 2
Barite 1 160 50 20 2,600 80 50 700 8
SrSO4 26 2,700 300 250 110,000 700 500 180,000 350
CaSO4·2H2O 1,200 2,800 9,000 9,000 90,000 15,000 10,000 80,000 600
Scale (BaSO4) nd 80 50 14 7,000 50 30 800 1
Scale (SrSO4) nd nd nd nd 600 nd nd nd nd

Solubilities in saturated salts


1,000,000

BaSO4
100,000 Barite
SrSO4
CaSO4·2aq
10,000
Solubility [mg/L]

1,000

100

10

H 2O NaCOOH NaCl NaBr KCOOH KCl KBr CsCOOH Cs2SO4


(40%w) (26%w) (44%w) (75%w) (24%w) (34%w) (82%w) (60%w)

Figure 1 Solubility of alkaline earth sulfates after 16 hours at 85°C / 185°F in various saturated brine systems with pH of 9.5 (measured
on undiluted brines). The bar chart shows the amount of dissolved sulfate salt calculated from measured barium / strontium / calcium
concentrations in the brine after exposure. Some precipitation of sodium, potassium, and cesium sulfates have taken place in all of these
brines, so brine sulfate levels do not correspond to levels of dissolved alkali earth metal sulfates.

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SECTION B: COMPATIBILITIES AND INTERACTIONS CABO T S P ECIALTY FLUIDS

METRIC

Solubility in 75% potassium formate vs. temperature


100,000

10,000
Solubility [mg/L]

1,000 Dissolved BaSO4


Dissolved SrSO4

100
20 30 40 50 60 70 80 90 100 110
Temperature [°C]

FIELD

Solubility in 75% potassium formate vs. temperature

100,000

10,000
Solubility [mg/L]

1,000 Dissolved BaSO4


Dissolved SrSO4

100
70 80 90 100 110 120 130 140 150 160 170 180 190 200 210 220

Temperature [°F]

Figure 2 Influence of temperature on the dissolution of alkaline earth metal sulfates in a concentrated potassium formate brine (75% =
1.57 g/cm3 / 13.1 lb/gal). Contact time = 16 hours. pH = 9.5 (measured in undiluted brine). The graphs show amounts of dissolved
sulfate salt calculated from measured barium / strontium concentrations in the brine after exposure. Some precipitation of potassium
sulfate has taken place, so brine sulfate levels do not correspond to levels of dissolved barium and strontium sulfates.

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Solubility vs. potassium formate concentration


100,000

Dissolved BaSO4
Dissolved SrSO4
10,000
Solubility [mg/L]

1,000

100

10

1
0 5 10 15 20 25 30 35 40 45 50 55 60 65 70 75 80

KFo concentration [%wt]

Figure 3 Influence of formate concentration on the dissolution of alkaline earth metal sulfates in potassium formate brine. Temperature =
85°C / 185°F. pH = 9.5 (measured on undiluted brine). Contact time = 16 hours. The graph shows the amount of dissolved sulfate salt
calculated from measured barium / strontium concentrations in the brine after exposure. Some precipitation of potassium sulfate has
taken place, so brine sulfate levels do not correspond to levels of dissolved barium and strontium sulfates.

Solubility in 75% potassium formate vs. exposure time

11,000

10,000

9,000

8,000

7,000
Solubility [mg/L]

6,000

5,000

4,000

3,000 Dissolved BaSO4


2,000 Dissolved SrSO4

1,000

0
0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24

Exposure time [hours]

Figure 4 Influence of contact time on the dissolution of alkaline earth metal sulfate salts in concentrated potassium formate brine
(75% = 1.57 g/cm3 / 13.1 lb/gal). pH = 9.5 (measured on undiluted brine). Temperature = 85°C / 185°F. The graph shows the amount
of dissolved sulfate salt calculated from the measured barium / strontium concentrations in the brine after exposure. Some precipitation
of potassium sulfate has taken place, so brine sulfate levels do not correspond to levels of dissolved barium and strontium sulfates.

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Solubility in 75% potassium formate vs. pH

100,000
Solubility [mg/L]

10,000

Dissolved BaSO4
Dissolved SrSO4

1,000
6.5 7.0 7.5 8.0 8.5 9.0 9.5 10.0 10.5 11.0 11.5 12.0 12.5 13.0 13.5

pH (undiluted)

Figure 5 Influence of pH on the dissolution of alkaline earth metal sulfate salts in concentrated potassium formate brine (75% = 1.57 g/cm3 /
13.1 lb/gal). Contact time = 16 hours. Temperature = 85°C / 185°F. The graph shows the amount of dissolved sulfate salt calculated
from the measured barium / strontium concentrations in the brine after exposure. Some precipitation of potassium sulfate has taken
place, so brine sulfate levels do not correspond to levels of dissolved barium and strontium sulfates.

B12.3 Solubility of salts in potassium formate brine. Figure 7 shows the


formate brines concentration of soluble chloride in the liquid phase
as a function of temperature and formate
B12.3.1 Solubility of potassium sulfate concentration. Increasing temperature did not have
in potassium formate brine a significant effect on solubility of NaCl.
Some data are available on the solubility of potassium
sulfate (K2SO4) in potassium formate brines [4]. B12.3.3 Solubility of magnesium
Solubility is about 176 mg/L in 71%wt potassium chloride (MgCl2) in formate brines
formate brine (1.53 g/cm3 / 12.8 lb/gal) at 25°C / 77°F, Magnesium chloride has very low solubility in
but this increased with decreasing formate high-density potassium formate brine and
concentration. For comparison, solubility of potassium saturated sodium chloride brine. A low MgCl2
sulfate in fresh water is 120,000 mg/L at 25°C / 77°F. solubility is important when drilling through salt
No precipitation was observed in the formate brine. formations containing magnesium chloride, such as
Figure 6 shows the soluble sulfate concentration Zechstein bischofite.
measured in three potassium formate brines as a
function of temperature. Shell [1] measured solubility of magnesium chloride
(MgCl2·6H2O) in saturated brines of potassium
B12.3.2 Solubility of sodium chloride formate, sodium formate, potassium chloride, and
(NaCl) in potassium formate brine sodium chloride as a function of temperature.
Some solubility test results are available for solubility Testing also included an oversaturated magnesium
of sodium chloride in potassium formate brine [4]. chloride brine, which was previously used as a
The solubility of sodium chloride in 71%wt potassium drilling fluid when drilling through Zechstein
formate brine is about 14,000 mg/L at 25°C / 77°F, bischofite sections. The results, shown in Figure 8,
compared with about 218,000 mg/L in fresh water. indicate a very low solubility of magnesium chloride
Solubility of NaCl increases in brines with lower in potassium formate and sodium chloride compared
potassium formate content. Additions of excess with the other brines.
NaCl led to precipitation of solid potassium chloride.
Some traces of sodium formate solid were also
precipitated at the lowest temperature in the 71%wt

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METRIC

Solubility of potassium sulphate in potassium formate

1,000,000

100,000
SO4- solubility [g/mL]

10,000

1,000

KFo 1.54 g/cm3


100
KFo 1.19 g/cm3
KFo 1.06 g/cm3
Water (Wikipedia)
10
20 30 40 50 60 70 80 90
Temperature [°C]

FIELD

Solubility of potassium sulphate in potassium formate

1,000,000

100,000
SO4- solubility [g/mL]

10,000

1,000

100 KFo 1.54 g/cm3


KFo 1.19 g/cm3
KFo 1.06 g/cm3
Water (Wikipedia)
10
70 80 90 100 110 120 130 140 150 160 170 180

Temperature [°F]

Figure 6 Dissolution of potassium sulfate in three concentrations of potassium formate brine. The figures show measured concentration
of sulfate in liquid. Open symbols represent dissolution type experiments; closed symbols represent precipitation type experiments.

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SECTION B: COMPATIBILITIES AND INTERACTIONS CABO T S P ECIALTY FLUIDS

METRIC

Dissolution of sodium chloride in potassium formate

250,000

200,000
Cl- solubility [mg/L]

150,000

100,000 Water (Wikipedia)


KFo 1.06 g/cm3
KFo 1.20 g/cm3
KFo 1.54 g/cm3
50,000

0
20 30 40 50 60 70 80 90
Temperature [°C]

FIELD

Dissolution of sodium chloride in potassium formate

250,000

200,000
Cl- solubility [mg/L]

150,000

100,000 Water (Wikipedia)


KFo 1.06 g/cm3
KFo 1.20 g/cm3
KFo 1.54 g/cm3
50,000

0
70 80 90 100 110 120 130 140 150 160 170 180 190

Temperature [°F]

Figure 7 Dissolution of NaCl in three potassium formate brines. The figures show the amount of Cl - in liquid phase as a function of
temperature and formate concentration.

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METRIC

Solubility of MgCl2· 6H2O in concentrated brines

800

KFo concentrated
700
KCl concentrated
NaCl concentrated
600
Solubility MgCl2·6H2O [g/L]

Heated MgCl2 (sat at 60°C)

500

400

300

200

100

0
20 30 40 50 60 70 80 90 100 110 120
Temperature [°C]

FIELD

Solubility of MgCl2· 6H2O in concentrated brines

800

KFo concentrated
700
KCl concentrated
NaCl concentrated
600
Heated MgCl2 (sat at 60°C)
Solubility MgCl2·6H2O [g/L]

500

400

300

200

100

0
70 80 90 100 110 120 130 140 150 160 170 180 190 200 210 220 230 240

Temperature [°F]

Figure 8 Solubility of MgCl2·6H2O in various saturated brine systems.

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Saturated sodium formate brine also reduced B12.5 Solubility of silicates in


solubility of magnesium chloride significantly, but formate brines
precipitation problems made measurements
difficult. There is no information about how these Solubility data for quartz and amorphous silicate
measurements were completed and a possibility (glass) in concentrated formate brines and water
that some precipitation could also have taken place are shown in Table 3. Apart from slightly elevated
in the other brine systems. levels of silicate dissolved from amorphous silica by
cesium formate there is little practical difference
Further investigation of magnesium chloride between water and formate brines.
solubility in potassium formate has concluded that
some precipitation takes place. MgCl2·6H2O was
added in excess to three concentrations of potassium B12.6 Solubility of galena,
formate (70%, 31.6%, and 10.7%). In the highest hematite, and ilmenate in
concentration potassium formate brine (70%), formate brines
potassium chloride mainly precipitated. Some
magnesium formate Mg(COOH)2·2H2O was Galena (PbS), ilmenate (TiO2, FeO), and hematite
also identified in the precipitates, increasing in (Fe2O3) are all insoluble in formate brines.
concentration in brines with lower formate content. Measurements show solubilities of less than <10 ppm,
which is the detection limit of the instrument (ICP).

B12.4 Solubility of clays in B12.7 Solubility of calcium


formate brines carbonate in formate
brines
Some solubility data are available for certain common
shales in concentrated sodium, potassium, and cesium Calcium carbonate is the most commonly used
formate brines [3]. The shales tested were sodium bridging material in formate fluids. Its solubility in
montmorillonite [(Na,Ca)0.33(Al,Mg)2Si4O10(OH)2· formate brines is dependent on pH. At the alkaline
n(H2O)], Kaolinite [Al2Si2O5(OH)4], and Manco shale. pH of commercial formate brines used in the field,
solubility of calcium carbonate is negligible. This is
The extent of solubilization was estimated by particularly true of formate brines buffered with
measuring levels of soluble Al and Si in the brine carbonate / bicarbonate.
phase after 16-hour contact of the brine with shale
at 85°C / 185°F. The results of the soluble Al and Si
analyses shown in Table 5 indicate that little shales
are dissolved or leached by formate brines.

Table 2 Solubility of clays in concentrated formate brines. NaFo (46%wt = 1.33 g/cm3 / 11.1 lb/gal), KFo (75%wt = 1.57 g/cm3 / 13.1 lb/gal),
CsFo (82%wt = 2.26 g/cm3 / 18.9 lb/gal). T = 85°C / 185°F. Exposure time = 16 hours.

Solubility 45%w NaFo 75%w KFo 82%w CsFo


[mg/L] Al3+ Si4+ Al3+ Si4+ Al3+ Si4+
Montmorillonite 45.0 45.0 4.0 77.0 4.0 8.5
Kaolinite 7.5 8.0 1.0 7.0 8.5 8.5
Manco shale 4.0 7.0 4.0 5.0 -- 4.0

Table 3 Solubility of silicates in concentrated formate brines. NaFo (46%wt = 1.33 g/cm3 / 11.1 lb/gal), KFo (75%wt = 1.57 g/cm3 / 13.1 lb/gal),
CsFo (82%wt = 2.26 g/cm3 / 18.9 lb/gal). Temperature = 85°C / 185°F. Exposure time = 16 hours.

Solubility of SiO2 [mg/L]


pH Water NaFo KFo CsFo
8 45 20 30 40
Quartz 10 55 60 55 35
12 175 360 125 35
8 350 255 940 1,600
Amorphous silicate (glass) 10 430 255 940 1,600
12 500 245 930 1,650

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References

[1] Templeton, C.C.: “Solubility of barium sulphate in


sodium chloride solutions from 25°C to 95°C”,
Journal of Chemical and Engineering Data, 5
(October 1960), 514–516.

[2] Monnin, C.: “A thermodynamic model for the


solubility of barite and celestite in electrolyte
solutions and seawater to 200°C and to 1 kbar”,
Chemical Geology, 155 (1999) 187–209.

[3] Howard, S.K., Houben, R.J.H., Oort, E. van,


Francis, P.A.: “Report # SIEP 96–5091 Formate
drilling and completion fluids – technical manual”,
Shell International Exploration and Production,
August 1996.

[4] Unknown source.

PAGE 12 SECTION B12 V E R SION 1 – 0 5 / 1 1

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