SPE 80211
The Chemistry of Formate Brines at Downhole Conditions
Paul H. Javora, SPE, BJ Services Company; Mingjie Ke, SPE, BJ Services Company; Richard F. Stevens, SPE, BJ
Services Company; Sandra L. Berry, SPE, BJ Services Company
Copyright 2003, Society of Petroleum Engineers Inc.
This paper was prepared for presentation at the SPE International Symposium on Oilfield
Chemistry held in Houston, Texas, U.S.A., 5–7 February 2003.
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
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Abstract
Sodium, calcium and zinc bromide and chloride brines have
been used successfully as clear completion and packer fluids
for more than 20 years, and their chemistry and applications
have been evaluated and reported. Sodium, potassium and
cesium formate brines are relatively new brines being
explored for use as clear completion and packer fluids.
However, relatively little information has been published
about their chemistry in oilfield usage, especially under hostile
conditions of temperature and CO2 environments. This paper
describes the chemistry of formate brines used in the oilfield
not previously published.
Extensive research and laboratory data was developed to
understand the effects of pH, buffer capacity, CO2 content and
temperature on the corrosion potential and decomposition of
formate brines. Results from thermal stability testing and
corrosion testing are presented which identify conditions for
thermal decomposition of the formate ion and conditions for
significant corrosion of oilfield tubulars at typical downhole
conditions. Conditions for hydrogen gas generation, carbon
monoxide gas formation, scale formation and corrosion
potential are described. Understanding the results derived
from this work could be critical to the selection of formate
brines used for downhole conditions.
Introduction
An impressive body of literature concerning the use of formate
based drill-in fluids has been accumulated over the last ten
years1-6 (and references cited therein). The primary factor for
the success of these low-solids, non-damaging drill-in fluids
(DIFs) is related to the thermal stability of the polymer
systems to 300°F or more, due to high concentrations of
formate salt. An important secondary benefit is related to the
ability of concentrated formate brines, especially potassium
formate, to stabilize active shales7.
Detailed studies on the corrosion and thermal
decomposition of formate based brines have undoubtedly been
conducted, but only a few details are reported in the SPE
literature. One reference1 described electrochemical corrosion
results for AISI 4145 steel in 45% sodium formate as less than
39.4 mpy (1.0 mm/y). Furthermore, no evidence for stress
corrosion cracking (SCC) was found for AISI 4145 from slow
strain rate SCC tests in the presence of high-density formate
brines. Another reference2 described the concern for retorting
high-density formate brines due to its potential decomposition
to produce hydrogen gas. Laboratory tests with remote
controlled retorts indicated no problems. None-the-less, the
retort thermostats at the rig were set to 392°F for safety
reasons, and no problems indicating the presence of hydrogen
were ever noted. Bungert5 described the appearance of
hydrogen gas in a potassium formate DIF after a gas kick. The
influx of CO2 lowered the pH of the unbuffered DIF and
produced formic acid, which thermally decomposed and
generated hydrogen. The addition of carbonate/bicarbonate
buffer adjusted the pH and eliminated the problem.
This paper presents detailed information about the
corrosion and thermal stability of formate base brines.
Background
Sodium formate brine salts can be prepared by the reaction of
sodium hydroxide with carbon monoxide according to the
equilibrium Equation (1). By replacing sodium with potassium
or cesium, these formate salts can be prepared.
NaOH + CO HCO2Na (1)
This basic reaction can be conducted in molten sodium
hydroxide8, in aqueous sodium hydroxide9 or in methanolic
sodium hydroxide10. Furthermore, the reaction conditions can
be relatively mild, 200°F and 220 psi.
Sodium formate can also be made by the reaction of
hydrogen and carbon monoxide with sodium carbonate
according to Equation 2. Potassium and cesium formate can
be prepared from their respective carbonates.
H2 + CO + Na2CO3 2 HCO2Na (2)
2 SPE 80211
Alternatively, formate brine salts can be prepared by the
neutralization of formic acid at relatively low temperatures
according to Equation 3. By using potassium or cesium
hydroxide, their respective formate salts can be prepared.
NaOH + HCO2H HCO2Na + H2O (3)
Sodium, potassium and cesium formate compounds are
salts of the weak acid, formic acid. Formic acid is known to
decompose at relatively low temperatures to form hydrogen
gas, H2, especially when catalyzed by metals such as
palladium11. Various ratios of formic acid and sodium formate
were tested, and based on the experimental data obtained, that
author proposed that the catalyzed reaction proceeded via a
formate ion and absorbed formate intermediate.
Thermal decomposition studies on formate salts have been
conducted for over 60 years12. The solid phase thermal
decomposition of sodium formate was determined to proceed
via two reaction paths, as shown in Equations 4 and 5.
2 HCO2Na Na2C2O4 + H2 (4)
2 HCO2Na Na2CO3 + H2 + CO (5)
Addition of ground glass to the sodium formate was found
to accelerate the reaction velocity. The addition of certain
amounts of solid sodium carbonate or solid sodium oxalate
also increased the reaction velocity. That author concluded
that the reaction is of chain character, related to a
heterogeneous process on the container walls, and related to
the autocatalytic effect of the reaction products.
The reaction pathways described by Equations 4 and 5
have been supported by recent work and expanded to include
potassium13, 14 and cesium14 formate, and the additional
reactions depicted by Equations 6, 7 and 814.
Na2C2O4 Na2CO3 + CO (6)
Na2CO3 Na2O + CO2 (7)
2 CO CO2 + C (8)
Note that the formate decomposition Equation 5 is the
reverse of the synthesis Equation 2. While studying the
chemistry of formate on ruthenium surfaces, Weisel et.al.15
varied the amount of hydrogen and carbon monoxide, and
determined that sodium formate was in equilibrium with
sodium carbonate. In another experiment, these authors were
2 HCO2Na Na2CO3 + H2 + CO (5)
able to introduced labeled C18O into the reaction mixture, and
were able to observe and measure the rapid uptake of the 18O
labeled compound into the formate. Both experiments
demonstrate the equilibrium nature for these reactions and the
labile nature of formate salts, especially under
catalytic conditions.
In the presence of hydrogen, other decomposition
pathways were postulated by Weisel et.al., including the
formation of methane and methanol15 according the Equations
9 and 10.
2 HCO2K + 2H2 K2CO3 + H2O + CH4 (9)
2 HCO2K + 2H2 K2CO3 + CH3OH (10)
The thermal decomposition of various transition metal
formates was also studeid16 in air and under vacuum. In each
case, the formate salts of copper II (Cu2+), colbolt (Co2+),
nickel II (Ni2+), manganese II (Mn2+) and iron II (Fe2+)
decomposed at temperatures significantly less than the
decomposition temperatures for sodium formate and
potassium formate.
Experimental
Sodium formate and potassium formate were obtained from
commercial sources supplying formates to the oil industry and
used without further purification. Adjustments to pH were
made with reagent grade sodium or potassium hydroxide,
except as noted when the fluid was buffered. Values of pH
were measured on the neat solution according to internal
standards. Metal coupons and U-bends appropriate for oilfield
use were obtained from commercial sources. Handling and
measurements of metal coupons were conducted according to
NACE Standards. Brine volume to coupon surface area was
kept at about 20cc per square inch. No attempt was made to
remove oxygen from the formate brines before conducting
corrosion or thermal stability tests; only the head space gas
was purged from the pressure cells with N2. When CO2 was
required, it was pressured into the nitrogen-purged cell in
order to minimize CO2 solubility into the formate brine.
Except when specifically noted, formate brines were contained
in Teflon cups placed within 316SS pressure cells. Cells
were aged in fan-forced air-circulated ovens. Commercial
laboratories performed analytical measurements of the
headspace gas, and of the solution carbonate and oxalate ions.
Metal analyses were determined in-house by ICP
Spectroscopy.
Testing included standard single coupon weight loss
corrosion measurements, stress corrosion cracking using U-
bends, bi-metallic corrosion, and thermal stability
measurements for the formate brine.
Results
One of the first corrosion tests was conducted with the brine
contained in glass cups, but the cups were found to etch very
quickly when in contact with the formate brine. As a result,
the coupons were randomly covered with white surface
crystals, below which the metal surface was marred. Because
of this observation and similar results with core material, the
plan was to conduct corrosion tests with used formate brine
exposed to the formation, but these tests were not conducted.
Service companies routinely measure the pH of high-
density brines most often by the direct measurement of the
SPE 80211 3

neat brine. Direct pH measurement is the most common An interesting variation in pH as a function of brine
standard suitable for all brines. In this particular case, direct density was observed, that is independent of the metal type
pH measurement avoids the effect of corrosion byproduct and temperature. Data for pH versus time and density are
precipitation and shifting equilibria among carbonate, presented in Tables 4 and 5 for the metals 420 and Cr22,
bicarbonate, formate and its acid. respectively. While minor changes in pH are observed after 7
days, the major trend occurs after 30 days. A slight to
Weight Loss Corrosion moderate downward trend is observed for the 10.5 ppg sodium
The normal corrosion of potassium formate was studied at two formate, but a significant increase is observed for the
different densities and temperatures under nitrogen. The potassium formate. This behavior may be an indication that
results for C4130 and 410 are presented in Table 1. Similar the mechanism for pH change is probably
tests were conducted for Cr22, but their corrosion rates were concentration dependent11.
found to be zero. As expected, all of the Cr22 coupons retained their original
Increased corrosion at 365°F was noted for the C4130 in shinny character, but all of the C4130 coupons were coated
10.5 and 13.1 ppg brines, and therefore, second sets of with a light gray coating (150°F tests) or charcoal gray coating
duplicate tests were conducted. Similar results were obtained, (365°F tests). The 420 coupons followed the trend for the
and these points may be approaching a defining limit. In C4130 coupons, with the exception of a shinny coupon for
general, one would conclude that these corrosion rates tests conducted in 13.1 ppg brine at 150°F.
are acceptable.
Table 4
Table 1 Change in pH versus Density
Single Coupon Weight Loss Corrosion Bi-Metallic Corrosion – 420/C4130
HCO2K, pH 9.8, 300 psi N2, Duplicate Tests HCO2K, 300 psi N2, Duplicate Tests
Densityp Temp. Initial After 7 After 30
Densit Temp. 7 day 30 day 7 day 30 day pg °F pH days days
yppg °F C4130 C4130 410 410
10.5 150 9.8 9.0 9.3
10.5 150 0.1 mpy 0.0 mpy 0.0 mpy 0.0 mpy 13.1 150 9.8 9.5 10.7
13.1 150 0.5 0.5 0.0 0.0 10.5 365 9.8 8.9 8.6
10.5 365 1.5 0.3 0.0 0.0 13.1 365 9.8 10.1 11.0
13.1 365 4.4* 1.0* 1.7 1.7
* Average of 3 tests; fourth test results for C4130 were 22.8 Table 5
and 5. 2 mpy, respectively. Change in pH versus Density
Bi-Metallic Corrosion – Cr22/C4130
Bi-Metallic Corrosion HCO2K, 300 psi N2, Duplicate Tests
Bi-Metallic (galvanic) corrosion test results are presented in Densityp Temp. Initial After 7 After 30
Tables 2 and 3. As observed in Table 2, the 13.1 ppg brine at pg °F pH days days
365°F deviates from expectations, and the 30 day corrosion 10.5 150 9.8 9.1 9.7
rate for C4130 was slightly lower than the more noble 420SS. 13.1 150 9.8 9.2 11.1
Corrosion rates for Cr22 were very low as expected. 10.5 365 9.8 9.1 9.4
13.1 365 9.8 10.5 11.5
Table 2 Stress Corrosion Cracking
Bi-Metallic Weight Loss Corrosion – 420/C4130 Standard U-bends of Cr22, 420 and C4130 were tested in 10.5
HCO2K, pH 9.8, 300 psi N2, Duplicate Tests and 13.1 ppg potassium formate at 150 and 365°F. No
Density Temp. 7 day 7 day 30 day 30 day cracking was observed for all of the test samples.
ppg °F 420 C4130 420 C4130
The variation in pH as a function of brine density is similar
10.5 150 0.7 mpy 2.6 mpy 0.1 mpy 2.7 mpy to that observed in the bi-metallic tests, but was less
13.1 150 0.5 2.7 0.0 1.3 pronounced under stress conditions.
10.5 365 0.5 1.8 0.1 0.6
13.1 365 3.3 1.2 1.4 0.8 Table 6
Change in pH versus Density
Table 3 U-Bend Stress Tests
Bi-Metallic Weight Loss Corrosion – Cr22/C4130 HCO2K, 300 psi N2, Initial pH = 9.8
HCO2K, pH 9.8, 300 psi N2, Duplicate Tests Metal 150°F 10.5 150°F 13.1 365°F 10.5 365°F 13.1
Density Temp. 7 day 7 day 30 day 30 Type ppg ppg ppg ppg
ppg °F Cr22 C4130 Cr22 day C4130
C4130 7days 9.8 9.8 9.8 9.8
10.5 150 0.0 mpy 1.9 mpy 0.0 mpy 2.2 30 days 9.51 10.3 8.7 10.11,2
mpy 420, 9.8 9.8 9.8 9.8
13.1 150 0.1 0.2 0.0 1.3 7days
30 days 9.2 9.7 8.6 10.51
10.5 365 0.4 0.5 0.0 0.2
13.1 365 0.1 0.9 0.0 0.7 Cr22
7days 10.1 10.2 8.9 9.7
30 days 9.6 9.7 8.7 10.2
1 2
Gray coating Slight pitting
4 SPE 80211

Surprisingly, the surface of the C4130 coupon from the
test with 13.1 ppg brine at 365°F was observed to be
somewhat pitted. This coupon was also one observed to have
a gray coating. The 420 coupon at 365°F and the C4130
coupon at 150°F also were observed to have a gray coating.
CO2 only experiment but not in the experiment containing
H2S. This experiment, however, generated significantly more
hydrogen (Table 9), and demonstrated one decomposition
pathway. Significantly more H2 was generated than could be
accounted for based only on a corrosion process.

Carbon Dioxide and Hydrogen Sulfide Environments Carbon Dioxide Environments

Two seven-day tests were conducted with 12.5 ppg HCO2K at A series of tests were conducted to further understand and
325°F with an initial pH of 9.8. The brine was placed directly control the formate system under more stringent conditions.
into a C-276 pressure cell and the electrically isolated coupons The first series studied: two 12.5 ppg potassium formate
were suspended from a C-276 rack. Due to the limitation in brines at pH 10.2 under 300 psi N2, one with and without
equipment required to conduct these tests, the brine volume to C4130 coupon; Two 12.5 ppg potassium formate brines at pH
surface area was considerably more than 20cc/square inch. 9.0 under 300 psi CO2, one with and without C4130 coupon;
One cell was pressured with 250 psi CO2 and 0.5 psi H2S and two 12.5 ppg potassium formate brines at pH 10.2 under
while the other cell was pressured with only 250 psi CO2. 300 psi CO2, one with and without C4130 coupon. The
Corrosion data and analytical results are presented in Tables 7, corrosion results are presented in Table 10, along with the
8 and 9. corresponding soluble iron contents. Analytical results are
presented in Tables 11 and 12.
Table 7
Seven Day Corrosion Tests Table 10
12.5 ppg HCO2K, 325°F Seven Day Corrosion Tests
Head C4130 420 Cr 2205 12.5 ppg HCO2K, 340°F
Space mpy mpy mpy Test # Head Initial Final C4130 Solub
Gas C4130 Space pH pH Corrosion le
H2S & Coupon Gas Rate Iron
CO2 72 66 59 mpy mg/L
CO2 171 307 --- 1 (yes) N2 10.2 10.8 5.2 30.9
300psi
3 (yes) CO2 9.0 7.8 53.5 6770
Table 8 300psi
Solution Chemistry & Precipitates (ppt) 5 (yes) CO2 10.2 7.8 47.7 6240
12.5 ppg HCO2K, 325°F, Seven Day Corrosion Tests 300psi
2- 2- 2+ 3+
Head CO3 C2O4 Fe Cr ppt
Space mg/L mg/L mg/L mg/L mg/L Table 11
Gas Head Space Gas Analyses
H2S & 12,136 Not 628 111 199 Seven Day Corrosion Tests
CO2 detected 12.5 ppg HCO2K, 340°F
CO2 10,799 67.5 4,159 300 11 Test # N2 Mol% CO2 H2 Meth
Head
C4130 Space Mol% Mol% ane
Table 9 Coupon Gas Mol%
Hydrogen Gas Liberated
12.5 ppg HCO2K, 325°F, Seven Day Corrosion Tests 1 (yes) N2 99.34 0.66
300psi
Head H2 H2 Due to H2 Due to 2 (no) N2 97.44 2.52 0.01
Space Measured, Corrosion, Decompositi 300psi
Gas Mol% Mol% on Mol% 3 (yes) CO2 12.12 40.16 47.68 0.05
H2S & 300psi
1
CO2 89.7 16.0 73.7 4 (no) CO2 35.66 61.44 2.89 0.01
2
CO2 54.1 20.0 34.1 300psi
1
Pressure increased to 750 psi 2x and was released to 500 psi 5 (yes) CO2 13.56 50.20 36.23 0.01
2 300psi
Pressure increased to 640 psi and was released to 500 psi 6 (no) CO2 30.04 58.28 11.45
300psi
Corrosion rates for all of the metal coupons detailed in
Table 7 were unacceptable, and attributed to the reduction in Surprisingly, a relatively high corrosion rate (5.2 mpy) was
solution pH to about 8. The presence of a small amount of observed for the first experiment under N2. Even more
H2S noticeably reduced the metal corrosion rates, most likely surprising were the detection of H2 and a trace amount of
due to the formation of a more passive surface film. At the methane for the experiment under N2 without metal coupon,
end of seven days, the residual headspace H2S was reduced to most likely due to the thermal decomposition of the 12.5 ppg
1/10 its initial value. Part of the H2S contributed to the solids potassium formate. Under CO2 conditions, H2 was the
content, probably in the form of metal sulfur compounds. preferred decomposition pathway in the presence of C4130,
The formate brine was found to solubilize a large amount and without C4130, oxalate was preferred.
of iron and chromium in solution. Oxalate ions (C2O42-), one The second series studied Cr13 coupons in 10.4 ppg
of the decomposition pathways for formate, was found in the sodium formate for seven days: one test at pH 9.1 under N2;
SPE 80211 5

one test at pH 9.1 under CO2; and one test at pH 9.1 with Of all the corrosion inhibitors evaluated and not reported,
corrosion inhibitor (CI) under CO2. The results are shown in the material tested in Experiment 3 above was the best CI for
Tables 13 and 14. CO2 environments and remains the most promising.
Table 15
Table 12 Headspace Gas Analyses
Solution Chemistry Seven Day Corrosion Tests
Seven Day Corrosion Tests 12.5 ppg HCO2K, 275°F, No Metal Coupons
2-
12.5 ppg HCO2K, 340°F Test Head CO2 H2 Carbon C2O4
Test # Head CO3
2-
C2O4
2-
Mol CI Space Mol% Mol% Monoxide mg/L
C4130 Space mg/L mg/L Ratio Gas Mol% a
Coupon a a 1 N2 0.09 0.00 0.04 Broke in
Gas H2/Fe none 300psi transit
1 (yes) N2 4.081 8.04 0.62 2 CO2 84.47 1.48 1.24 10.15
300psi none 300psi
2 N2 5,336 7.24
300psi
a) Base fluid oxalate = 5.86 mg/L
3 (yes) CO2 14,311 6.69 3.94
300psi The third series studied 12.5 ppg HCO2K at 275°F without
4 CO2 16,666 31.16 metal coupons and without the addition of corrosion inhibitor
300psi (CI). Two tests were conducted, one under 300 psi N2 and the
5 (yes) CO2 14,133 7.25 3.29
300psi other under 300 psi CO2. The headspace gas analyses are
6 CO2 13,657 29.94 presented in Table 15, above. Again a trace amount of carbon
300psi monoxide was observed for the sample at 275°F under
a) Uncorrected Concentrations (base line data for potassium nitrogen. Unfortunately, the corresponding sample for oxalate
formate: 5.86 mg/L oxalate and 4607 mg/L carbonate) analysis was lost in transit to the analyst.

Table 13 Carbon Dioxide Environments - Buffered Formate

Seven Day Corrosion Tests Brines
10.4 ppg HCO2Na, 275°F, Cr13 Coupons Two series of tests were conducted at 275°F with buffered and
Test # Head Initial Final Cr13 Soluble pH adjusted 12.5 ppg HCO2K brines. The first series included
CI Space pH pH Corrosion Iron
two tests where the pH was adjusted only with KOH, and two
Gas Rate mg/L
mpy tests where the pH was adjusted with 5 pounds per barrel of a
1 N2 9.1 7.8 0.9 4.6 KHCO3 and K2CO3 buffer. Results are given in Tables 16
none 300psi and 17. Unacceptable corrosion was observed, with the
2 CO2 9.1 6.1 202 2670 generation of trace amounts of carbon monoxide.
none 300psi
3 CO2 7.6 5.7 10.8 279
0.20% 300psi Table 16
Seven Day Corrosion Tests
Table 14 12.5 ppg HCO2K, 275°F, 300 psi CO2
Headspace Gas Analyses Test # pH Metal Initial Final Corrosion
Seven Day Corrosion Tests CI additive Coupon pH pH Rate
mpy
10.4 ppg HCO2Na, 275°F, Cr13 Coupons 1 KOH C4130 11.0 7.7 142
2-
Test Head CO2 H2 Carbon C2O4 none
# CI Space Mol% Mol% Monoxide mg/L 2 KOH Cr13 11.0 7.4 388
Gas Mol% a none
1 N2 0.02 0.0 0.02 2.28 3 5 ppb C4130 11.0 7.5 115*
none 300psi none KHCO3/
2 CO2 80.42 10.30 0.53 Not K2CO3
none 300psi detecte 4 5 ppb Cr13 11.0 7.7 462
d none KHCO3/
3 CO2 78.16 0.63 0.94 Not K2CO3
0.20% 300psi detecte * Slight pitting observed
d
a) Total oxalate in base brine = 3.95 mg/L The second series of tests for 12.5 ppg HCO2K at 275°F
were conducted with excess quantities of the KHCO3/K2CO3
The pH values for each of the relatively low-density 10.4 buffer system for seven days. The headspace gas consisted of
ppg HCO2Na brines was observed to decrease, as was noted either 300 psi N2 or 200 psi CO2 plus 100 psi N2. The results
for the 10.5 ppg HCO2K brines. The oxalate levels decreased are presented in Table 18. Unacceptably high corrosion rates
from the base values of the stock brine, and carbon monoxide were observed for the Cr13 coupons. Headspace gas analyses
was now observed in the headspace gas, indicating yet another and solution chemistries were not available for this series
pathway to formate decomposition. of tests.
6 SPE 80211

Table 17 Without doubt, significant thermal decomposition was evident

Headspace Gas Analyses for both the HCO2Na and HCO2K at 325°F under N2
Seven Day Corrosion Tests without CO2.
12.5 ppg HCO2K, 275°F, 300 psi CO2
Test pH CO2 H2 Carbon Mol
# Mol% Mol% Monoxide Ratio
CI
additive
Mol% H2/Fe Discussion
1 KOH 48.9 39.1 1.9 0.97 Many observations and correlations have been formulated
none during the course of this work, but this discussion will focus
2 KOH 62.4 28.0 1.8 0.93 on four main areas of importance. For obvious reasons, the
none
3 5 ppb 61.7 30.1 0.3 0.92 first will focus on the potential low pH applications of formate
none KHCO3/ brines. Next, the thermal decomposition of formate brines
K2CO3 will be discussed, followed by the interaction between various
4 5 ppb 46.3 42.4 1.8 1.09 metals and formate brine. Finally, the importance of formate
none KHCO3/
K2CO3 salt saturation will be touched upon. As with most work, more
questions were raised and the authors appreciate the desire for
Table 18 continued investigation
Seven Day Corrosion Tests
12.5 ppg HCO2K, 275°F, Buffered Low pH Applications with Formate Brines
Test pH Metal Initial Final Corrosion The consequences associated with failure to control the pH of
HS additive Coupon pH pH Rate formate brine in CO2 environments are significant. Corrosion
Gas mpy rates of 200, 300 or 400 mpy can easily and rapidly be
1 43.7 ppb Cr13 11.7 11.5 21.6 achieved when the brine becomes more acidic. Other things
N2 KHCO3/
K2CO3 being equal, very high corrosion occurs even when the brine is
2 43.7 ppb C4130 11.7 10.7 2.7 basic, at pH values of 7.5 (Tables 13, 16). As the pH
N2 KHCO3/ increases, lower corrosion rates were observed. While it is
CO2 K2CO3 difficult to establish the desired pH value from the data
3 43.7 ppb Cr13 11.7 10.8 50.8*
N2 KHCO3/
reported herein, pH values above 9.5 seem reasonable.
CO2 K2CO3 When this data is reviewed, it becomes obvious that
* Slight pitting observed extreme care is required when formate brines are to be used in
CO2 environments or in low pH environments. Low pH
Nitrogen Environments - Buffered Formate Brines environments can be encountered during several
Two tests were conducted to evaluate the effect of long- oilfield operations.
term heat-aging on formate brines placed directly in 316SS During completion operations there are opportunities for
cells at 325°F under 300 psi N2. The first system was 10.7 the working brine to come into contact with acid
ppg sodium formate treated with 3 pounds per barrel sodium environments. When the working brine is formate based,
carbonate (Na2CO3) and 3 pounds per barrel sodium special attention is required in order to avoid the extremely
bicarbonate (NaHCO3). The second system was an unbuffered high corrosion rates reported herein due to low pH. Low pH
12.5 ppg potassium formate brine at pH 9.5. After nine applications can occur from pickling pipe, breaker recipes for
months, the headspace gas was analyzed. DIF filter cake removal, acid stimulation, simple dilution with
formation water especially in CO2 environments, and intrusion
Table 19 of CO2 and/or H2S from the formation. Any fluid that is
Headspace Gas Analyses trapped in contact with the formation or at the bottom of the
Nine Month Corrosion Tests well is subject to pH drift, especially with an acid gas
325°F, C4130 Metal Coupons, 300 psi N2 environment. Usually, completion brine will be lost to the
Test # CO2 N2 H2 Methane Carbon formation and later will be produced back with a pH different
Brine Mol% Mol% Mol% Mol Monoxide than the original working brine. Since it may not be possible
System % Mol %
to treat lost brine in all circumstances, pre-planning will help
1 1.304 3.440 94.938 0.137 0.085
10.7 identify and eliminate potential problem areas, especially for
ppg formate brine.
HCO2N The same considerations are required for selecting a
a packer fluid.
2 16.265 27.317 54.237 0.623 0.680
12.5
ppg Thermal Decomposition of Formate Brine
HCO2K The experiments conducted and reported herein clearly
demonstrate the decomposition potential for both sodium and
The headspace gas analysis for the two experiments potassium formate. Long term data for both brines at 325°F
described above are presented in Table 19. Large quantities of under N2 (Table 19) indicated that significant decomposition
H2 and the appearance of methane were observed and are occurred over nine months. In addition to thermal
diagnostic for the thermal decomposition of formate brines. decomposition, decomposition by reaction of formate with H2
SPE 80211
to form methane was also occurring. Short-term results at
340°F indicate the same decomposition pathways (Table 11).
Hints that both sodium and potassium formate thermally
decompose at a lower temperature, 275°F, is evidenced by the
generation of CO after only seven days reported in Tables 14
and 15.
The decomposition observed could be due strictly to
thermal degradation, or as referenced in the literature, assisted
by an active surface. Additional comments can be found in
the “Formate Decomposition and Metal Type” section below.
Based on the results obtained, the long-term thermal
stability for both sodium and potassium formate may be
significantly lower than previously thought, and requires
further evaluation. The actual temperature may well depend
upon the specific metals and well conditions that contact the
formate brine.
Formate Decomposition and Metal Type
Differences in behavior between C4130 and chrome metals
towards potassium formate were clearly identified during this
study. The data reported in Tables 7, 16 and 18, and data not
reported in this paper, illustrated these differences for a variety
of fluid environments. In each case, the corrosion rate for the
chrome material was found to be much greater than for C4130.
The differences ranged from about 2 times to well over
10 times.
The increased activity of chrome metal towards formate
brines strongly indicates that the formate brine could be less
stable in the chrome environment. The concern for this type
of behavior is related to the fact that transition metal formate
salts are know to have lower thermal decomposition
temperatures than sodium or potassium formates. During their
use, and as corrosion continues, the concentration of transition
metal ions also increases in the formate brine, albeit at very
low concentrations. Their fate and affect on the long-term
stability of formate brines requires significantly
more evaluation.
Low Density versus High Density Formate Brines
As noted earlier, there is a trend in pH values for the low
density versus the higher density formate brines. For the
lower density brines, around 10.5 ppg, the trend upon heat
aging is to maintain or slightly reduce the final pH value. On
the other hand, the trend for the more saturated brines is to
increase its pH value. These differences could indicate that
the low-density brines have different reaction pathways than
the higher density brines.
Conclusions
1. Under nitrogen environments, the corrosion rates for mild
steel, 13 chrome and 22 chrome in formate brines are low.
2. Hydrogen sulfide and/or carbon dioxide exert a strong
negative impact on both corrosion and decomposition of
formate brines.
3. Buffer additives mitigate the impact of acid gases on the
corrosion aspects of formate brines to a certain extent.
7
4. Significant amounts of hydrogen, methane, and carbon
monoxide are produced as a result of the thermal
decomposition of formate brines during long-term heat
aging under an inert atmosphere.
5. Chrome 13 materials were found to corrode in formate
brines to a much greater extent than C4130 in the
preponderance of cases studied.
6. Decomposition and corrosion for formate brines will most
likely depend strongly on the metal types in contact with
the brine.
Acknowledgements
The authors wish to thank the management of BJ Services
Company for permission to publish this work.
Nomenclature
CI = Corrosion Inhibitor
HS = Head Space
mpy = mils per year
ppg = pounds per gallon
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Metric Conversion Factors

°F (°F-32) x 5 / 9 = °C
Lb/gal x 1.198 26 E+02 = kg/m3
mpy x 2.538 07 E-02 = mm/y
psi x 6.894 76 E+00 = kPa