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Formate Brines
Compatibility with Metals
This document reports accurate and reliable information to the best of our knowledge.
Neither the author nor the reviewers assume any obligation or liability for the use of the information presented herein.
December 2006
F O R M AT E B R IN E S – COMPATI B I L I TY W I TH ME TAL S
Contents
PA G E 2
F O R M AT E B R INE S – COMPATI B I L I TY W I TH ME TAL S
PA G E 3
F O R M AT E B R IN E S – COMPATI B I L I TY W I TH ME TAL S
1 Introduction to 2 Introduction to
Formate Brines Oilfield Corrosion
High-density formate brines have been available to the 2.1 Types of Corrosion
industry for use in drilling, completion, workover, and packer The aqueous corrosion of metals involves two electro-chemical
fluids since the mid 1990s. This family of non-corrosive, reaction zones in close proximity: a cathodic reaction zone, in
high-density, monovalent brines offers clear advantages over which electrons are taken from the metal to reduce a reactant
the traditional halide family of brines in that their use is not (e.g. protons, water, or oxygen) in an electrolyte (often a
just limited to completion and packer fluids, but includes solution of salts) which is in contact with the metal, and an
solids-free drilling fluids, which offer exceptionally good flow anodic reaction zone, in which the metal is oxidized
characteristics over the whole density range. (corroded), liberating electrons into the metal. Electrons move
through the metal from the anodic to cathodic zone
The primary uses for formate brines over the past 10 years balancing the electro-chemical reactions. The effects of
have been in demanding applications where conventional corrosion most commonly encountered in the sub-surface
drilling and completion fluids have not been able to meet the oilfield environment fall broadly into the following categories:
required performance specifications. The applications where
formate brines have been used include: General corrosion: General corrosion is a relatively slow
process where the metal loss is relatively uniform over the
• HPHT completions and workovers – to provide exposed surfaces and typically occurs over long time scales.
compatibility with completion materials and reservoir Carbon steel and low alloy steels are particularly susceptible
• HPHT drilling – to avoid well control problems and to general corrosion in acid environments.
differential sticking
• Reservoir drilling and completion – to improve production Pitting corrosion: Pits are typically millimeter-sized zones of
• Narrow bore and extended reach drilling – to improve anodic corrosion commonly associated with high chloride
circulation hydraulics concentrations in solution. Pitting commences with the
• Shale drilling – to minimize environmental impact localized breakdown of a passivating scale on a metal. This
exposes small areas of oxidizable metal. Chloride preferentially
Cesium formate, the highest density brine in the formate migrates to these local anodic zones, and assists in removal
family, has proven to be an excellent replacement for the of anodically oxidized metal, to form pits. The metal surface
traditional high-density zinc bromide brine, and is now the outside the pits is cathodic and supports the reduction of, for
high-density completion fluid of first choice in the North Sea. example, dissolved oxygen from the electrolyte. Pitting
corrosion is characterized by a high cathodic to anodic area
To date, cesium formate has been used in more than 130 ratio. Metal dissolution is confined to pits that deepen much
HPHT well operations, at temperatures as high as 216°C / faster than the rate of average wall loss associated with
420°F, at pressures up to 117 MPa / 17,000 psi and in the general corrosion.
presence of corrosive gases such as CO2, H2S, and O2.
Indeed, field experience has shown that formate brines have Stress Corrosion Cracking (SCC) is a destructive and fast-
given operators the ability to drill and complete challenging acting effect of corrosion that can cause catastrophic failure
HPHT wells with a degree of success, economy, and security of Corrosion Resistant Alloy (CRA) oilfield tubulars and
that would have been difficult to achieve using conventional equipment, sometimes within a matter of days. SCC cracks
fluids. develop from local defects in the surface oxide film, often
from sites of active pitting corrosion. For SCC to occur, tensile
Field experience has also shown that buffered, uninhibited stresses in the material are required in addition to the presence
formate brines exhibit low corrosivity towards all types of of a corrosive environment and a susceptible material (Figure 1).
steel tubulars used in well construction and production Increasing stress, temperature, and concentration of, for
operations, even when contaminated with corrosive gases example, halide ions, together with corrosive oilfield gases,
and chlorides. This compatibility with carbon and low alloy and increase the risk of metal failure from SCC.
stainless steel goods has been an important consideration for
the oil companies who have chosen formate brines for use in
their HPHT well constructions.
3USCEPTIBLE 4ENSILE
MATERIAL STRESS
3##
%NVIRONMENT
PA G E 4
F O R M AT E B R INE S – COMPATI B I L I TY W I TH ME TAL S
Hydrogen damage is a term used to refer to a variety of alloy steels, is the physical result of high levels of hydrogen
deleterious phenomena – for example SSC, SOHIC, HIC, and uptake into the metal. Hydrogen is much more soluble
hydrogen embrittlement – which affect metals when they and diffusible in metals at high temperatures than at low
contain atomic (diffusible) hydrogen. The causes are broadly temperatures (defined as below 100°C / 212°F). Embrittlement,
two-fold. Either the hydrogen is dissolved into the metal at therefore, normally occurs as a consequence of corrosion at
high temperature (the higher the temperature, the less specific high temperature, followed by sufficiently rapid cooling of the
the source of hydrogen has to be) then the metal is rapidly metal to entrap the hydrogen at low temperature. It may also
cooled to a low temperature leading to hydrogen over- result from intense hydrogen entry due to corrosion at low
saturation, or the hydrogen enters the steel directly at a low temperature in the presence of a ‘hydrogen promoter’.
temperature (less than about 100°C / 212°F) due to corrosion
involving ‘hydrogen promoters’, the most important oilfield 2.2 Types of CRAs and how they are chosen
‘hydrogen promoter’ being hydrogen sulfide. Well engineers select the metallurgy of their sub-surface tubulars
according to the composition of the produced fluids/gases and
Sulfide Stress Cracking (SSC) occurs during corrosion of steel the downhole temperature profile. If there is any risk of CO2
under tensile stress in the presence of water and hydrogen production during the lifetime of the well they will tend to select
sulfide. It is generally accepted that SSC is in part caused by the Corrosion Resistant Alloy (CRA) steels that contain chromium,
promotion of hydrogen entry into the steel by hydrogen sulfide. nickel, and sometimes molybdenum. High downhole tempera-
This causes steel embrittlement which, under tensile stress, tures and the presence of H2S and Cl- necessitate the selection
causes the steel to crack. High strength carbon and low alloy of more expensive CRAs with high alloy metal content. Given
steels and hard weld zones are particularly prone to SSC. the high cost of the types of CRA tubulars being used in HPHT
wells and the cost of a well intervention and loss of production
Hydrogen Induced Cracking (HIC) occurs in carbon and if the material should fail, it is important to maximize their life
low alloy steels, when atomic hydrogen diffuses into the steel expectancy. The cost of a rig for an offshore HPHT well
and then combines to form molecular hydrogen, particularly intervention can run into several million dollars and the waiting
in the vicinity of steel inclusions, such as manganese sulfide. time for both the rig and new CRA material might be up to a
The build up of hydrogen pressure at inclusions leads to the year. It is therefore particularly important that the integrity and
formation of planar cracks. The linking of these cracks, internally life expectancy of the tubulars is not compromised by adverse
or to the surface of the steel, results in Step Wise Cracking interactions with completion, workover, and packer fluids.
(SWC) that can destroy the integrity of the component. Near
the surface of the steel the cracks can lead to the formation of Table 1 lists some CRAs commonly used in tubulars. The
blisters. HIC damage is more common in components made recommended temperature ranges for the various CRAs vary
from rolled plate than in those made from seamless material. between the OTG producers, and no universally accepted
limits exist. The temperature limits shown in Table 1 are taken
HIC generally occurs at temperatures below 100°C / 212°F from the Sumitomo selection guide [1] and apply when CO2 is
and in the presence of certain corrodants called hydrogen present. The recommended applicability limits of the alloys in
promoters, such as hydrogen sulfide. No externally applied Table 1 are also dependent upon chloride concentration and,
stress is needed for the formation of HIC. when present, upon the levels of H2S.
Stress oriented hydrogen induced cracks (SOHIC) is There are also quite a few austenitic alloys that, because of their
related to SSC and HIC/SWC. In SOHIC, staggered small corrosion resistance properties, are commonly used in well
cracks are formed approximately perpendicular to the applications. These alloys are characterized by their high content
principal stress (residual or applied) resulting in a ladder-like of chromium and nickel. They are mainly used as material for
crack array linking (sometimes small) pre-existing HIC cracks. packers, safety valves, hangers, etc. In some cases they can be
The mode of cracking can be categorized as SSC caused by sensitive to hydrogen embrittlement and other forms of attack
a combination of external stress and the local straining often associated with H2S. The industry standard for sour service
around hydrogen induced cracks. materials [2] provides more information on the sensitivity of
austenitic and other corrosion resistant alloys to this common
Hydrogen Embrittlement (HE) of metals, particularly of high contaminant of oil and gas production environments.
Table 1 Martensitic and Duplex steels commonly used in oilfield tubulars. The application limits apply in the presence of CO2 and are
further restricted by the level of CO2, H2S, and Cl- [1].
PA G E 5
F O R M AT E B R IN E S – COMPATI B I L I TY W I TH ME TAL S
Table 2 HPHT field experience with formate brines provided by CSF over the past seven years.
Total
BP Rhum Shell Marathon BP Statoil
Elgin/
3/29a Shearwater Braemar Devenick Huldra
Franklin
No. of wells 3 6 1 1 10 6
Hydrocarbon Gas Gas Gas Gas Gas Gas
condensate condensate condensate condensate condensate condensate
°C 149 182 135 146 204 149
Max. temp
°F 300 360 275 295 400 300
Completion material CRA S13Cr 25Cr 13Cr 13Cr 25Cr S13Cr
Liner material CRA S13Cr 25Cr 22Cr VM110 P110 S13Cr
Packer material CRA 718 718 718 718 718 718
Brine density g/cm3 2.00 – 2.20 2.05 – 2.20 1.80 – 1.85 1.60 – 1.65 2.10 – 2.20 1.85 – 1.95
MPa 84.8 105.6 74.4 72.4 115.3 67.5
Reservoir pressure
psi 12,300 15,320 10,800 10,500 16,720 9,790
CO2 % 5 3 6.5 3.5 4 4
H2S ppm 5 – 10 20 2.5 5 20 – 50 10 – 14
Exposure time days 250 65 7 90 1.6 yrs 45
Workover
Well kill
Perforation Completion Drilling
Application CT Workover Drill
Completion CT Completion
Workover Perforation Completion
Workover Well kill Screens
Perforation Perforation
Devon Devon
BP Walter O&G
Statoil Statoil West West
High Island Mobile Bay
Kvitebjørn Kristin Cameron Cameron
A-5 862
165 A-7, A-8 575 A-3
No. of wells 7 to date 7 to date 1 1 1 1
Hydrocarbon Gas Gas Gas
Gas Gas Gas
condensate condensate condensate
°C 155 171 163 149 135 216
Max. temp
°F 311 340 325 300 275 420
Completion material CRA S13Cr S13Cr S13Cr 13Cr 13Cr G-3
Liner material CRA 13Cr S13Cr S13Cr 13Cr 13Cr G-3
Packer Material 718 718 718 718 718 718 G-3
2.11
Brine density g/cm3 2.00 – 2.06 2.09 – 2.13 2.11 1.03 1.14 1.49 packer
MPa 81 90 99 80 74 129
Reservoir pressure
psi 11,700 13,000 14,359 11,650 10,731 18,767
CO2 % 2–3 3.5 5 3 3 10
H2S ppm Max 10 12 – 17 12 5 5 100
Exposure time 4 20
days 57 57 2 and 1.3 yrs 1.4 yrs
3 yrs packer 1.5 yrs packer
Drilling Drilling Well kill Well kill
Application Completion Completion Completion Packer Packer Completion
Screens Screens Packer Packer
Liners
PA G E 6
F O R M AT E B R INE S – COMPATI B I L I TY W I TH ME TAL S
PKT
P+
(#/ 10.2
At pH=(#/
( (←
P+ ⎯ ⎯→←(⎯
( ⎯ #/ → ( #/
(#/ PKT
PKT 3
A ) the #/
#/
A
( PKT
#/ PKT
3 ← ⎯ ⎯ → PKT
3
P+A P+A
of between 2 and 6 (depending on the type of halide) and are • Lower buffer level atpH
(#/ ( =(#/ ← 6.35
⎯⎯ → ( (#/
←⎯⎯ → (#/
PKT PKT
#/
P+AG P+ #/ #/ #/ G AQ
P+ #/ (#/
AQ (#/ P+A PKT PKT
#/ A (#/ ( ←⎯⎯→ ( (#/ #/3 PKT
A
#/ P+ ( AQ(
(#/ ← ⎯⎯ ( #/
PKT
PKT
A
#/ AQ ( / ( #/ AAQ
P+A #/ (#/ ← ⎯ ⎯ →
carbonate/bicarbonate buffer. The buffer not only helps to(#/ ( ←At #/
#/
P+A G #/
pH
AQ #/ #/
G
( AQ
AQ
#/
((P+
#/ ( AQ
AQ
#/
→ (#/
+AAQ → AQ
(#/
PKT
AQ
PKT
→=(6.35 A )AQ the buffered
(#/ solution
AQ( #/ contains the
PKT
#/ ← ⎯→ (#/ ( AQ
#/ PKT
⎯
⎯⎯
P+ A + A #/ (#/
maintain the brine pH in the safe alkaline zone but also same amount + (of #/bicarbonate
+ AQ P+ ←⎯ ⎯→ ( #/ (#/ ((#/
AQ AQ
← ⎯
+A
⎯ ) (and
→ (#/
AQ( #/
carbonic AQ PKT
( AQ
PKT
(AAQ
#/ AQ #/
#/ G
((/ / G↔
AQ
(#/
(#/ (/ AQAQ
AQ ((#/ #/
AQ (AQ
PKT
PKT
P+A PKT
PKT
OKT
promotes metal passivation. P+A (#/acid ( (#/ #/
). #/ #/ /↔
(#/ G (
#/
(
AQ
#/←
#/
AQ
⎯
P+
⎯
AQ
A
(→←
→ (#/
(⎯ #/⎯→
AQ PKT
(#/3 PKT
P
#/ AQ #/ (#/ G #/ AQ →((#/ AQ (#/ OKT OK
PKT
#/ AQ
+A #/ AQ → AQ
( #/ AQ ( #/ ←⎯ ⎯ → (#/
AQ ←
#/G ⎯
+ A AQ (
⎯ AQ →
( (#/
PKT
+ AQ
AQ
(
AQ PKT
( AQ PKT PKT
⋅ ; (#/ ==⋅ ;P+ = (//↔ (#/ ( #/ AQ AQ PKT
Traditional high density completion and packer fluids based#/ G #/ The AQ exact ; ( =levels ; ( #/ of P+A will (#/
A and+(#/ vary somewhat with
+ (#/ #/ ( + #/
+
#/0 G (#/ AQ G ( / ( #/
PKT
AQ PKT
AQ
PKT PKT
0#/ /↔ (#/ AQ ( PKT
on divalent halide brines (CaCl2, CaBr2, ZnBr2) cannot be #/
brine concentration,
AQ
#/ AQ ( temperature,
#/ #/ AQ
( #/ → ⎯
AQ
#/(#/
+A →
and
(#/ AQ( / ↔
pressure.
OKT
(#/
( P+
AQ
OKT
( AQ
AQ
AQA
#/ AQ (/ (#/ AQ ( #/
#/ AQ PKT ←
⎯→
(#/ (#/
AQ + A ( ←
AQ
( #/ PKT
PKT PKT
buffered because even small amounts of added carbonate/ ; ( =G⋅ ; (#/ #/ =
⎯ ⎯ →
+ + ( #/ AQ ←⎯ ⎯→ (#/ AQ ( AQ PKT PKT
influxes of CO2 . 0
+ 0
0 #/ P(
(#/
0
LOG #/ ; ( GP( = (
LOG(#/
/↔
; ( PKT
= AQ PKT ( AQ PKT PK
PKT
#/ #/(#/
+ #/
P(
LOG
+ LOG 0 LOG ; (#/
= PKT OKT
; ( = ⋅ PKT
#/ G ( / ↔ (#/ AQ ( AQ #/ AQ #/ ( #/
#/AQ ( AQ / →(#/ (#/ AQ
AQ
PKT
; (#/ =
PKT
In order to fully understand how the buffer in the formate P( + LOG + LOG P( 0 LOG
#/ AQ (#/
LOG +; (#/ LOG0#/ = LOG; (#/ =
PKT P
(#/
P(
LOG P(AQ
( #/;(
LOG = AQ
(#//
0 #/ ; ((#// = AQ (#/ 0 #/ (#//(
;( AQ = ⋅ ; (#/ (#//( = PKT AQ AQ (#/ AQ
PKT PKT PK
+
PKT
+
brine enhances the corrosion protection provided by the ; ( = ⋅ ; (#/ =
0#/ #/ G (#/ (0 (
/ ↔ #/
0(#/ AQ ← AQ⎯
+A
⎯ →
( (#/
AQ AQ ( AQ
PKT
PKT
#/ (#/
+ PKT #/
formate brine itself, one first needs to understand how this 0#/ P+
P( (
#/
P+A (#/
LOG +
P( LOG
LOG
(P(
0
+ #/ LOG
AQ 0
LOG ;
(#/
P+
(#//
A ; (#/
LOG =
(#//( P+
AQ
=
(#//(
PKT
(#//(
PKT
AQ (#/
AQ
A
#/
LOG
#/ ;
#/ ( =
AQ A
( #/ AQ → PKT (#/ AQ O
buffer works and how it reacts to influxes of common acid ( #/ AQ (#//
AQ (#//( AQ (#/ AQ
0#/ ( 0 (#/
; ( P( = ⋅ ; (
LOG
(#/ #/ ;=
( AQ = (#//
AQ (#//( AQ
PKT(#/
AQ
gases such as CO2 and H2S. &E #/&E AQ ( P+ #/ →(#/ +&E ( →
AQ AQ &E (
0AQ
G LOG ( (#/
AQ AQ PKT
PKT
#/ #/ ; + G
P+ (#//(
= (#/
PKT
PKT
P(
LOG ; ( =
P( A LOG + 0
PKT
LOG
#/ #/ (#/ A
( AQ PK
#/ G ( / ↔ (#/ AQ
P+A ( #/ P+
P( LOG +(#/ LOG0 #/P+
LOG
A (#//(
; (#/ =P+
A (#//( PKT
(
&E #/ (#//(
( AQ
&E#/
(#//( (#//
AQ
0 #/ → &E
AQAQ
AQ (#//(
PKT&E A ( GAQ
AQ
#//( (#/
( AQ G (
#//(
AQ
AQ PKT
AQAQ PKT
PKT PKT
AQ ( (#// AQ (#//(
&E #/ →
(#/ AQ
→ &E
AQ (#/
G (#/ AQ P
P( LOG + LOG 0#/ LOG ; (#/ = P(
LOG
; ( =
PKT
P( "EHAVIOR OF #ARBONATE"ICARBONATE "UFFER 7HEN !DDING 3TRONG !CID
P+A
P(
P+A
&RACTION OF BUFFER CONSUMED
!DDITION OF STRONG ACID
Figure 2 The pH of water buffered with carbonate as a function of added strong acid (H+). The x-axis shows the fraction of the buffer
that is consumed by the added acid. As can be seen, carbonate will buffer twice, first at pH pKa2 = 10.2 (upper buffer level) and then at
pH = pKa1 = 6.35 (lower buffer level). If the added acid is carbonic acid (from CO2 influx), the pH can never drop much below pKa1.
Figure 2 demonstrates how the carbonate buffer works when The three different brine systems in Figure 3 will react in the
a strong acid is added. The carbonate will react with added following way to a CO2 influx:
acid until all the carbonate is consumed. As long as there is
still carbonate left in the solution, the pH will remain high, • Conventional divalent halide brines cannot be buffered
around the “higher buffer level” = 10.2±1. As soon as the with carbonate/bicarbonate because the corresponding
carbonate is consumed, the pH will drop down to the “lower metal carbonate (CaCO3, ZnCO3) will precipitate out of
buffer level” where it will remain as long as bicarbonate is solution resulting in the formation of solids in the clear
available to react with the added acid and be converted to packer/completion fluid. These divalent brines have a
carbonic acid. In order for the pH to drop down below this naturally low pH (2–6) and the influx of CO2 will, dependent
second buffer level, an acid would need to be added that is on the partial pressure of CO2, further lower the pH. The
stronger than the carbonic acid that is formed. As any CO2 CO2 will largely be converted to carbonic acid, which is
gas influx into the buffered solution will dissolve and be very corrosive.
P+A
#/
#/
(
converted ←⎯
← ⎯ ⎯
P+
(to carbonic
⎯A → (#/
acid,
→ (#/ a CO PKT
3 2 influx is therefore
not
PKT
3
capable of pulling the pH much below this second buffer • Buffered formate brines are capable of buffering large
P+ (#/
A ( #/
level. amounts of CO2. Unless the influx is unusually large, the
P+A
P+A
#/
←⎯⎯ #/
→ (#/
PKT 3 (#/
brine will maintain a pH (at around the upper buffer level)
P+A
P+A #/ (#/ which is high enough to prevent carbonic acid being
(#/ ( ← (#/#/ PKTP+
←⎯
⎯⎯
⎯→→(
(#/ (Protection CO2 (H2S) PKT
A
5.2 Buffer against
influx present in the fluid. With a large influx of CO2, the pH will
P+A
(#/ ( ←⎯⎯→ (#/ PKT completion
The major cause of acidification of conventional drop down to the lower buffer level (pH = 6.35) where it will
P+
P+ A (#/
(#/ ( #/
( #/
brines
P+
A is influx of carbon dioxide
(#/
( #/ gas (CO2) into the wellbore: stabilize. Measurements of pH in formate brines exposed
A
to various amounts of CO2 have confirmed that the pH
#/ G G
#/
#/ G #/
#/
AQ AQ
#/ AQ PKT
(3)
PKT
PKT never drops below 6–6.5. This pH is still close to neutral,
;( =
0#/
LOG
P(
P( (#/
LOG
; ( =
PKTP A G E
PKT
8
P( IN 6ARIOUS "RINE 3YSTEMS AS A &UNCTION OF #/ )NFLUX 6OLUME
"UFFERED FORMATE P(
#/ MAINLY CONVERTED TO
BICARBONATE (#/
WHICH DOES NOT PROMOTE CORROSION
P(
5NBUFFERED FORMATE
P(
#/ MAINLY CONVERTED TO
CARBONIC ACID (#/
#ALCIUM BROMIDE WHICH PROMOTES CORROSION
"", 'AS I NFLUX"", BUFFERED FORMATE BRINE #/ ª# ª& ATM
)NCREASING TIME OF #/ INFLUX
Figure 3 pH as function of CO2 influx in a typical halide brine, an unbuffered formate brine, and a buffered formate brine.
PA G E 9
F O R M AT E B R IN E S – COMPATI B I L I TY W I TH ME TAL S
pH Modified
Density Temp. days 13Cr 22Cr 25Cr
Fluid (diluted 13Cr
s.g. ppg 1:10) °C °F mm/y MPY mm/y MPY mm/y MPY mm/y MPY
KFo 1.26 10.5 9.8 66 150 30 0 0 0 0
KFo 1.57 13.1 9.8 66 150 30 0 0 0 0
NaFo 1.26 10.5 10.0 163 325 7 0 0.0 0 0.0
CsKFo 1.95 16.2 10.4 165 329 30 0.01 0.39
+ 3 g/L Cl-
KFo 1.26 10.5 9.8 185 365 30 0 0 0 0
KFo 1.57 13.1 9.8 185 365 30 0.043 1.7 0 0
CsFo 10.0 191 375 ? 0 0.0 0.03 1
CsFo 10.0 204 400 17 0.003 0.1 0.03 1
CsFo 204 400 7 0.076 3
CsFo 1.94 16.2 218 425 30 9.25 364 0.41 16
• Shaded area = outside the operating envelope of the specific CRA
PA G E 1 0
F O R M AT E B R INE S – COMPATI B I L I TY W I TH ME TAL S
Corrosion comparison: Pressure build-up in the headspace of the test vessels was
Cesium formate brine versus zinc bromide brine monitored in these tests, and the bromide brine was shown
Traditional high-density halide brines are known to cause or to create higher pressures at 204°C / 400°F than the formate
facilitate pitting corrosion due to their low pH and high brine. The pressure build-up with the bromide brine, resulting
content of halide ions (Cl -, Br-). A comparative corrosion test from the evolution of hydrogen gas, is thought to have been
[4] has been carried out at 204°C / 400°F with C-steel caused by the corrosion reactions.
exposed to a high density cesium formate brine and in a
blend of zinc bromide and calcium bromide brines, both with
a density of 2.18 s.g. / 18.2 ppg. The mixed bromide brine Table 5 General and localized corrosion on C-steel (P-110)
was tested with and without a corrosion inhibitor. The testing exposed to inhibited and uninhibited calcium/zinc bromide and
was carried out in 100 mL C-steel pressure vessels. The cesium formate brines at 204°C / 400°F.
corrosion of the walls of the vessels was determined by
measuring the weight loss of the vessels after 12 days of General Rate of
exposure to the brines. The results are shown in Table 5. The corrosion maximum
Test Fluid rate penetration
CaBr2/ZnBr2 brine promoted severe localized corrosion at the
interface between the liquid and vapor. The presence of a mm/y MPY mm/y MPY
corrosion inhibitor marginally reduced the general corrosion Uninhibited CaBr2/ZnBr2 0.84 33 7.72 304
rate but seemed to amplify the localized corrosion. The Inhibited CaBr2/ZnBr2 0.66 26 13.1 517
weight loss of C-steel in the bromide brine was found to be Cs formate 0.008 0.3
about 100 times higher than in the uninhibited formate brine
and the depth of the localized metal corrosion in the bromide
was about 1,000 times higher than in formate. No significant
localized corrosion or pitting corrosion and only negligible
general corrosion was experienced in the formate brine.
PA G E 1 1
(#/ ( ←⎯⎯→ (#/ PKT
P+A (#/ ( #/
F O R M AT E B R IN E S – COMPATI B I L I TY W I TH ME TAL S
#/ G #/ AQ P+A
PKT
#/ ( ←⎯ P+⎯ → (#/3
PKT
#/ ( ←⎯ ⎯ A
→ (#/3
PKT
#/ AQ (/ (P+
#/ ( ←⎯ #/
⎯→ (#/3
A
AQ
PKT
PKT
7 Corrosion in Formate Brines P+A acid
Carbonic #/will then be consumed
(#/ by the carbonate buffer
P+A #/ (#/
Contaminated with CO2 according
(
P+ #/ AQ ←
A #/
to⎯ +A
⎯ the →following
(#/ P+A
AQ (#/ reaction:
( AQ
PKT
(#/ ( ←P+ ⎯⎯ → (#/
PKT
(#/ ( ← ⎯ ⎯ A
→
P+A AQ → (#/
( #/
PKT
OKT
Carbon dioxide (CO2) influxes emanating from leakage of #/ AQ
(#/ ( ←⎯⎯→ (#/
( #/
AQ
PKT(6)
reservoir gases into the well environment are common P+A (#/ #/ #/
( ←
(( #/
P+
← ⎯
P+
⎯ (#/ → (#/
PKT
PKT
A
A
(#/
P+A case + P+
⎯
⎯
( #/favorable→ 3 3
sources of corrosion in carbon and low alloy steels. The In this the
pH will remain at PKT
about the upper
P+#/ A G ((#/ ( (#/ A
#/ / ↔← ⎯
(#/ ⎯→ AQ ( #/ (3 AQ PKT
P+ P+
consequences of a CO2 leakage into a halide-based buffer
#/
#/
G
level
( #/
(= P+
←⎯ AQ
AQ
⎯ P+
A→ =A10.2)(#/ #/#/ and A
CO (#/#/
corrosion
2(#/ PKT
will not
PKT ( ←⎯⎯→ (#/3
take A
completion fluid can be catastrophic for the integrity of #/
place G
P+until
#/the #/
carbonate
3
(#/
component
PKT
of the pH buffer is
#/ ;( GA = ⋅#/
; (#/
AQ
(#/
= Figure (3). ←
(⎯
P+ P+
⎯→ (→ #/( #/ PKT PKT
A
(#/ PKT (#/
A
sub-surface equipment and tubulars. P+
overwhelmed #/ (see (#/ ←⎯⎯ P+ #/
+#/
A AQ
#/(#/ AQ 0
( /
( / ( #/
( ←
(
⎯
#/ P+
⎯
AQ
AQ
→ ( #/
PKT
A
PKT
PKT
PKT
A
#/
#/ AQ ( / P+ ( A#/ (#/
P+ AQ ( #/ PKT P+
Both pitting and stress corrosion cracking (SCC) can occur in (#/
Once the ( carbonate←⎯
+A
P+
⎯ →Aportion( #/ (#/ of
A
the
formate ( #/
PKT(#/buffer
brine’s ((the ←⎯⎯→ (#/ A
CRAs that have been exposed to CO2 and halide brines. For
( #/
(#/
upper
P+AbufferAQ
AQ ←⎯ ← (#/
+⎯
⎯⎯A → (#/
level)
#/ → (#/ G
has
#/
AQ
been
AQ
(
AQ #/ (
( AQ
overwhelmed
AQ PKT
or PKT
consumed,
PKTthe
;( A =
P(
LOG +
#/ G
#/ (AQ AQ
PKT
PKT
P+A
PKT
equations, (#/ ( #/
( #/
P+ AQ ←
(#/ ⎯ ⎯→ (#/ (
AQ
#/
some years it was thought that the incidence of localized pH will
A decrease according to the following
which
OKT
PKT
P(
#/
#/
LOG
G AQ#/ + ( LOG#/
AQ
0#/
#/ AQ LOG (; (#/
AQ → (#/
/ ( #/
= AQ
AQ
PKT #/ OKT PKT
G #/ AQ
chloride brines became contaminated with oxygen. More #/ AQ ( ( /
++ #/ (#/ AQ ← AQ
⎯⎯ → (#/ AQ
( AQ PKT
+ A
PKT
PKT
#/ G ( / (#/ AQ ( AQ
recent research has revealed that bromide brines may cause 0#/AQG (((#/ / ↔
↔
+ (#/
( #/ AQ
AQ +( AQ
←⎯
⎯→ (#/ AQ ((7) PKT
#/ PKT
AQ AQ ( /
A
( #/ AQ
#/
#/ G ( / ↔
/ ( #/
+ (#/
AQ
(AQ PKT PKT
AQ AQ AQ → (#/
pitting and SCC in the presence of CO2 as well [5]. OKT
( #/ AQ ←#/ (#/ (
AQ #/ AQ
PKT
A
⎯⎯→ ( AQ
OKT
#/ AQ +(
((#//(
#/
AQ PKT
→ (#/ AQ ← ⎯
+ A
(( #/
#/ AQ AQ
; (
( =←
+A
;⎯
=⋅⋅;⎯ →(#//
(#/
(#/ (#/
== AQ
AQ
AQ AQ ((#/
#/ AQ
AQ ⎯
→ (#/ PKT
AQ ( AQ
Buffered formate brines are very different from halide brines + #/ AQ #/ ( #/
G (AQ /↔ →
(#/ AQ (
(8)(#/ AQ OKT
PKT
AQ PKT
PKT
;( =0 ⋅0;#/
(#/ =
in the way their corrosivity is influenced by a CO2 influx. The +
#/ AQ #/
( #/#/ AQ
G → ( (#/
+
OKT
( PKT
#/
( #/ AQ → (#/ AQ
AQ AQ PKT
AQ AQ
0#/ / ↔ (#/
P+A (#/ ;
+ P+ A (#//(
difference is mainly due to the influence of the carbonate/ #/ G ( / ↔ ( = ⋅ ; (#/
(#/ AQ =( AQ PKT
+
PKT
+
+ 0
bicarbonate pH buffer. P(
P(
#/ G
LOG
LOG
( / ; ((#/
↔
=
; ( = ; ( =⋅ ; (#/ =
(9)
AQ #/ ( AQ
PKT
#/
PKT
G ( / ↔ (#/ AQ ( AQ
PKT
&E
P(( #/
LOG AQ +→
; ( =
&E AQ ( G (#/ AQ
PKT PKT
; ( = ⋅ ; (#/ = 0#/ PKT
+ P(
LOG ; ( = PKT
PKT
P(
P(;
( LOG +0 LOG 0 LOG ; (#/
; (#/
= PKT
PKT
=( G #//(
; ( = ⋅ ; (#/ =
&E =LOG
⋅ ; (#/+ #/LOG
=
00#/ LOG AQ PKT
(#//( + LOG AQ → #/&E AQ PKT
+
#/ LOG ; (#/ =
7.1 CO2 Corrosion +P( LOG
PKT
(10) 0
0#/ P( LOG + LOG 0 LOG ; (#/ =
P(
LOG ; ( PKT
#/ = PKT
0
P+ #/
In the oilfield, aqueous fluids that have been acidified by an #/ 0#/ ( (#/ ← ⎯ ⎯A → (#/ PKT
(#/
#/ 3
; (=
0
P(
LOG (#/ PKT
PKT
#/&E ( #/ A0 &E#/
(#/Sbe seen
P+
influx of CO2 are known to cause high rates of general #/
From Equation ↔ 10 P+A
it(#/can
that the pH PKT
at
#/ ← ( ⎯
⎯ ← →
⎯ ⎯ → (#/ PKT which the fluid
#/
PKT
P(
LOG ( ; = P( LOG
3 + 3LOG 0#/ LOG ; (#/P(
PKT =
LOG ; ( =
corrosion and pitting corrosion. P+eventually
( #/ AQ #/ stabilizes
(#// doesn’t
(#/
AQ ;only
(#//( depend AQon the
(#/
PKT partial
AQ PKT
=
A
( (
(
#/P( AQ
3 G
( (
LOG +
3
LOG
(#//
#/ AQ
0#/LOG
AQ
AQ AQ
(#//
(#/
(#//(
AQ (#//(
AQ
AQ PKT
(#/ (#/
AQ (#/
AQ
AQ
PKT
PKT
PKT
P+AP( #/
pressure
P+ #/ AQ of#/ CO (#// 2 ( 0#/(#/ ), but (#/ (#//(
also
(#/ on the concentration ofAQ
+ LOG 0#/ LOG ; (#/ =
A LOG + LOG 0#/ P+A LOG ; (#/
=
PKT P( LOG
Corrosion rates of carbon and low alloy steels in aqueous (#/
bicarbonate
P+A #/ 0 (#/P+ ( ((#/
P+ ← ⎯
A
⎯ ). In→ (
buffered #/
P+ brines
(#//( the PKT
effect of high
P+ ( #/ P+ (#//(
AQ ( #/ ⎯ A→
P+3Asubsequent A P+ + (#//(
P+ 0
A
( A ( #/ A −
(#/ ( #/ PKT
A
← ⎯ a(3 AQ AQ + ( AQ
(#/
P+ ( ( ⎯ ⎯ ⎯ (influx #/ PKT
environments containing CO2 can reach high levels (thousands 0 ← →
to( large P+ is
Aoffset
A (#//( AQby PKT
a(#//(
very high
#/
(#/
← ⎯
#/ →
(#// #/
AQ(#/ (#/
AQ PK
of mils per year), but the corrosion can be effectively reduced by P+ A(#/ AQ &E
concentration. (#/ pH (#//
measurements
( #/ (
#/
AQ
AQ → (#//(&E on
AQ AQ
formate
( (#/brines
G
(#/
AQ AQ PKT
exposed
PKT
&E (#/ AQ → &ECAT AQ ( G (#/ PKT
AQ PKT
the formation of a protective layer of iron carbonate on the P+A( &E
toP+
(#//
#/
&E aAwide(
((#/
AQ #/ (#/
temperature
AQ
AQ
(#// (P+ / → (
A← AQ &E
#/( (
⎯→
range#/ #/AQ
(#//( (#/
and
at CO
( AQ( 2 G
AQ partial
G (#/ (P+ (#/(#/
G
( (#//(
#/
pressures
A AQ
AQ
AQ of PKT
PKT
(#//
up
AQ (#//( AQ (
PKT
#/ AQ → &E AQ
AQ
metal surfaces, particularly at elevated temperatures. #/
to 4P+ MPa
G A ( #//580#/ AQ&E (#//(
psi shown
have AQ → P+ that &E
A (#//(
AQ pH
the PKT
( formate
of G #//( brines
AQ PKT
&E (#//(
AQ → &E AQ ( G #//( AQ PKT
#/ P+#/
&E G A
(#//(
does
&E #/
((#//(
G #/
(#//(
not ←
drop#/
AQ
⎯
CAT
below
AQ
→ AQ
AQ
#/
&E →6–6.5 ( &E #/
(
P+ AAQ
AQ →
G (#//(
(diluted
and&E ( PKT
G AQ
G
undiluted),
PKT
#//( P+
(
#//( A regardless
PKT (G #/
AQ
(#/
PKT
PKTAQ P+A (#//(
PKT
→ &E AQ ( AQ
#/ &E
AQ ((#/ / (AQ &E #/
→#/
AQ
&E ↔
&E#/
AQ S
( G
PKT
(#/
AQ PKT
PKT
There are two factors determining whether or not a completion of the initiallevel of carbonate/bicarbonate
buffer [7].
&E (#/ &E#/ S PKT
/↔ (&E (#//( AQ → &E(#/
AQ &E ((G#/ PKT
#//(
AQ → &E
PKT
AQ AQ
( G PKT PKT
#/&E AQ
#/ ( AQ /
#/ ( (
AQ #/ AQ
#/ AQ
( G (#
brine will inhibit CO2 corrosion. These are: &E
&E #/#/+A↔
↔ (→
3 &E
&E#/
&E#/ G AQ
S(S 3 AQ
AQ
PKT
PKT PKT
( #/ &E AQ(#//( ←⎯ ⎯→ (#/
AQ →AQ &E ( AQ AQ
( G PKT #//( AQ PKT
1. The ability of the brine to maintain an alkaline pH. Conventional completion/packer fluids based on divalent
&E
( #/ ( ( #/3(#//(
AQ ←G AQ +⎯A
⎯ →←( ⎯
+ A 3 AQ
AQ
(#/
⎯ ( → 3
→&E AQ
(#/
&E ←
P+
AQ #/ (
AQ⎯ AQ⎯ →
A AQ↔( (3 (AQ
&E#/ − G S+ #//(
AQ PKT AQ PKT
(+ PKT &E
like AQ (#//(
PKT AQ → &E AQ ( G #/
PKT
PKT
2. The ability of the brine to facilitate the quick formation of a halide brines are expected to behave almost pure water
#/&E(
#/AQ 3 #/
AQ AQ (
←
↔ #/
⎯ (⎯ #/
(#//
&E#/ →( (3
AQ 3→SAQ
G− (#/
AQ
→((
AQ /+ 3
AQ
(
(#/ ←AQ CAT
⎯→ (#/
AQ AQ OKT
PKT AQ OKT
(
PKT
&E
#/G PKT
PKT
↔ &E#/ S
CO2 influx is significant enough to lower the pH. carbonate/bicarbonate.
( 3 G P+
+P+AA
( 3 AQ −−Upon a typical CO2 PKT influx the rapid
#/(3 G AQ AQ ( ← ←/⎯ ↔⎯ ⎯ ⎯ →
(#/ →(3
(3 AQ CAT
AQ AQ
( +
AQ + ( ++
( AQ AQ PKT PKT
PKT
move to the left + in the ← carbonate P+A bicarbonate (equilibrium PKT
( 3
/ ← AQ ← 3 G ( PKT
3 AQ
(#//( ⎯ →⎯ #/ ( −G AQ +
PKT
#/( 3 ( GG /↔ ((#/ 3 P+AQ
(#//
+
(AQ ( CAT
((#/
⎯→ (3
+ AQ PKT ( PKT
PKT
+( AQ
In field environments the likelihood that a buffered formate
G
#/
(Equation /
5) ↔
will
AQ
(#/
cause
AQ(⎯→
a
AQ
− drop AQ
in pH, sufficient G for CO PKT
(#//
(#// ( 3 AQ ←⎯
AQ
AQ ⎯
(
=( /
A
→ / (3
CAT
←⎯→ (#/
CAT AQ
(#/ + ( AQ
AQ ( PKT
G PKT
2
← ⎯→ AQ ( G
brine would ever receive a CO2 gas influx large enough to ( corrosion
+ 3; AQ ( =← ⋅ ; (#/
to
⎯ P+Aensue.
⎯ → (#//
(3 −Due AQ to AQ+ the (+ (lack AQ/ ← of⎯→CAT
bicarbonate,(#/
PKT ( 3 AQ
AQ the ← (final
⎯
P+A
⎯G → PKT
(3 − AQ + (+ AQ
(#//( ;the 0← ⎯→
CAT
#/ CAT ( G PKT
PKT PKT
; = =
overwhelm the buffer is very low. Nevertheless, substantial pH
; ( (#//
of= ;⋅ ( (#/ ⋅acidified
= #/ (#/
AQ ( halide
/ ←⎯→ brine
(#/ will therefore
AQ ( Gmainly depend
+ (#//(
+ ←
(#//( ⎯CAT
CAT → #/#/ ( (⎯ GG
→
PKT PKT
PKT PKT
0← ⎯ → PKT PKT
CAT
research has been concerned with looking at the consequences on
(#// the 0#/ CO
AQ 2 #/ pressure
( / (#//(
←⎯→ (Equation
CAT
(#/← 10),
AQ
#/and ((be G G significantly
(#//
AQlower ( / ←⎯→ CAT
(#/ AQ ( G
of a CO2 influx sufficient to overwhelm the upper buffer level of than (#//( in buffered ←
CAT
⎯formate → #/ brines. ( G
PKT
P(
LOG ; ( = PKT
buffered formate brines [6][7]. Leth-Olsen, of Hydro Corporate (#//( ← ⎯→
CAT
#/ ( G PKT
(#//( ←⎯ → #/ ( G
CAT
P( P(
LOG
LOG ; ( = ; ( = PKT PKT
Research Centre, Porsgrunn, discovered in 2002 that a A common LOG + concern LOG 0#/voiced LOG ; (#/ by new users PKT of formate brines is
=
P(
protective layer of iron carbonate forms very quickly (within a
P( that corrosive formic ;acid will= always be present
PKT PKT with the
LOG
P( +
LOG LOG +0 #/ LOG
#/
0 LOG (#/LOG ; (#/
=
couple of days) on both C-steel and 13Cr steels in a buffered 0formate
#/
in(#/ solution because of the following equilibrium:
formate brine exposed to a massive CO2 challenge. The 0#/ 0#/ (#/(#/
presence of the carbonate/bicarbonate buffer therefore not (#/ AQ (#// AQ (#//( AQ (#/ AQ (11) PKT
only reduces the level of brine acidification in the presence of (#/ (#/ AQ AQ (#// (#//
AQ AQ (#//( (#//( AQ AQ (#/ (#/
AQ AQ
PKT
PKT
CO2, but also plays a very important part in the formation of P+ A (carbonic
Since #/ acid is a weaker P+A (#//(
acid than formic
acid
the high quality protective carbonate film on the steel P+A(P+
(A#/
(
#/
< P+ A (#//(
P+ A (#//(
),
formic acid
surfaces as the acidification progresses and initial corrosion &E
can only
( #/ AQin
exist →very
&Esmall AQ equilibrium (#/ AQ
( G amounts
even PKT
when
occurs. When CO2 enters into the buffered formate brine, &E the
( #/
&E (#/
formate AQ brine
→ AQ&E
→ is &E
AQ
exposed (
AQ to
G
a(
high
(#/
G CO
(#/
2 AQ
concentration.
AQ PKT
PKT
carbonic acid will be formed according to Equations 3 and 4. &E
In (#//(
order to obtain AQ → &E AQ
a substantial ( G #//(
conversion
of formate AQ to PKT
&E &E
(#//(
(#//( AQ → AQ&E
→ &E AQ AQ
(
G( #//(
G #//(
AQ AQ PKT
PKT
&E #/ ↔ &E#/ S
PKT
PA G E
&E1 2&E
#/ ↔ &E#/
#/
S
↔ &E#/
S
PKT
PKT
( 3 G ( 3 AQ PKT
( 3(G 3 G( 3(AQ
3 AQ PKT
PKT
P+A
( 3 AQ ←⎯ ⎯→ (3 − AQ + (+ AQ PKT
P+A P+A −
( 3(AQ3 ←AQ⎯ ⎯←→ ⎯⎯ (3 AQ− +AQ( ++ AQ
→(3 (+ AQ PKT
P+
#/ ( ←⎯⎯
A
→ (#/3
F O R M A T PKT
E B R INE S – COMPATI B I L I TY W I TH ME TAL S
P+A #/ (#/
P+A
(#/
formic
#/
acid, (a stronger
( ←
←
P+A⎯ ⎯→acid ( #/
→ (#/3 PKT
(one with a lower pKa) would • Amount of carbonate in the fluid. The build-up of iron
⎯⎯
PKT
need to be introduced. An example of this would be carbonate depends on the solubility product of iron
P+
#/
P+AA #/
P+
hydrochloric ((#/ ←
⎯
acid
A
⎯→(#/
(HCl). ((#/
#/
The
presence
3
PKT
of a very small amount carbonate. This means that as more carbonate ions are
of formic acid has actually proven to be a benefit in promoting present in the fluid, the less dissolved iron (corrosion
P+A
#/
P+
(#/
the G #/
formation
A #/
( ←AQ
of
⎯
iron
⎯→ ((#/
#/ films that
carbonate
PKT
PKT
protect steel product) is needed to saturate the fluid close to the metal
surfaces against CO2 corrosion [7]. surface and start film formation.
P+
P+AAQ
#/
(#/ (#/
( / (
( ← #/
⎯⎯ (→
#/
AAQ ( #/
PKT
PKT • Rate of initial corrosion. A high rate of corrosion
It is important to keep in mind that the main purpose of the immediately before the iron carbonate layer forms is
#/
( #/ G #/+⎯
AQ ←⎯
AAQ→ in (#/
AQ ( AQis to maintain PKT
PKT
P+ (#/ (brines
#/
buffer A provided
formate
a high pH so
known to increase the quality of the layer.
that CO corrosion is prevented. In a realistic field situation the
#/
AQ
2 ( / (#/ AQ
#/ AQ ( #/ AQ → (#/ AQ
OKT
PKT
#/ G #/
likelihood that aAQ
buffered formate brine would PKT ever receive a Buffered formate brines that are exposed to a large amount
CO
( #/ 2 gas AQ
influx
←
+A
⎯⎯ + large
→ (#/ enough to overwhelm the buffer is low.
AQ ( AQ PKT of CO2 form a higher quality protective layer than other
PKT
#/ G ( / ↔ (#/ AQ ( AQ
(Figure
#/ AQ 3). ( Traditional
/ (#/ AQ
high-density halide-based brines do not
PKT acidified completion brines because they provide both a
#/ this
have AQ advantage,
( #/ AQand → CO (#/
AQ
2 corrosion
OKT
will commence after higher amount of carbonate (see bullet point 2 above – effect
even
( ; (a
#/ AQ ←⎯minor
= ⋅ ; (#/
+influx
+⎯→
A
= of CO
(#/ AQ ( AQ 2 .
PKT of buffer) and a higher rate of initial corrosion (see bullet point
+ PKT
#/ G (0 / ↔ (#/ AQ ( AQ
#/ PKT 3 above – the additional small amounts of formic acid seem
Even
#/if AQ a CO influx is sufficient enough OKT
to overwhelm the not only to slightly increase the initial high corrosion rate but
2 ( #/ AQ → (#/ AQ
carbonate
; (
LOG component
= ⋅ ; (#/
; =
=
of the powerful pH buffer, a protective also to significantly further promote the formation of the iron
P(
+ (
PKT
PKT
iron carbonate 0#/ +layer will form much faster and much more carbonate layer).
#/ G ( / ↔ (#/ AQ ( AQ
PKT
efficiently in a buffered
P( LOG + LOG 0#/ LOG ; (#/ = formate than in other high density
PKT
completion
P(
LOG ; (brines.
= Here is why: 7.1.1 CO2 Corrosion of C-Steel
PKT
0#/ ; ( = ⋅(#/ ; (#/
= If the carbonate component of the buffer in a formate brine is
+
PKT
Both
P( carbonicLOG + 0#/ LOG
acid
0 #/
and
LOG ;formic
(#/
= acid are PKT
known to be corrosive overwhelmed by CO2 influx, the pH will start decreasing and
to
(C-steel
#/ AQ and (#// lower
alloyed
AQ steels
(#//( and AQ to
some
(#/
CRAs,
AQ such CO
PKT 2 corrosion will take place according to Equations 12 and 13.
0 (#/
as#/13Cr, at elevated temperatures. The corrosion takes place An initial period of high general corrosion will be experienced
P(
LOG ; ( =
PKT
P+A (#/
according the
to following mechanisms, P+A (#//( respectively: prior to the build-up of the protective iron carbonate layer.
(#/ AQ (#// AQ (#//( AQ (#/ AQ PKT
For C-steel this initial phase of high rates of general corrosion
P( LOG + LOG 0#/ LOG ; (#/ =
PKT
&E ( #/
P+A (#/
AQ → &E AQ (
P+A (#//( G (#/ AQ (12)
PKT is readily measured by short-term weight loss tests. There are
(#//( ←⎯ CAT
→ #/ ( G PKT lower buffer level [8]. Figure 4 shows photos of 1.5 mm thick
( 3 G (or 3additionally
Alternatively AQ to the formation of PKT
this iron C-steel coupons that have been exposed to 1.53 s.g. / 12.8
carbonate layer a magnetite (Fe3O4) layer can be formed. ppg calcium bromide and potassium formate brines acidified
P+A
( 3 AQ ←⎯
⎯→ (3 − AQ + (+ AQ PKT with CO2 at temperatures varying between 120°C / 248°F and
Both the iron carbonate and the magnetite films are known to 180°C / 356°F [7]. The coupon to the left shows severe
be
(#// extremely
AQ efficient
( / ←in⎯→ CAT
inhibiting
(#/further ( G PKT
AQ corrosion. localized corrosion attacks on the coupon that was exposed
to the bromide brine, and the coupon to the right shows that
Factors
(#//( that←⎯ will→influence
CAT
#/ (the G quality
of the film are [7]:
PKT only general corrosion has taken place in the potassium
formate brine. A SEM photo of an iron carbonate layer
• Volume to surface ratio. The ratio between the solution formed on C-steel in a formate brine is shown in Figure 5.
volume and the area of steel exposed to the fluid. This is The film is very dense, of thickness 5 to 20 µm. By comparison,
not a variable in an annular well environment, and it is the surface layer that was formed in the calcium bromide
therefore important to accurately reproduce this in a brine was found to be of a duplex structure with a thickness
laboratory test environment. 2–4 mL/cm2 is an acceptable of 100 to 200 µm. Table 6 shows weight loss data and actual
range. Using higher ratios will generate misleading local corrosion rates for the same coupons. Adding a
corrosion predictions. As an example, increasing this ratio commonly used corrosion inhibitor to the bromide brine did
by a factor of 10 (typical ratio used for corrosion testing = not improve the performance or stop the localized corrosion.
20 mL/cm2), has been shown to double the measured No additional chloride was added to the brines used in these
corrosion rate of 13Cr steel at 120°C. tests.
PA G E 1 3
F O R M AT E B R IN E S – COMPATI B I L I TY W I TH ME TAL S
Corrosion
film
C-steel
CaBr2 K formate
Figure 4 C-steel test specimens after exposure to inhibited Figure 5 SEM photo of iron carbonate protective layer formed
calcium bromide and potassium formate (both 1.53 s.g. / 12.8 on C-steel in a potassium/cesium formate brine where pH was
ppg) with a large CO2 influx at 120°C / 248°F, with an excursion pulled down to the lower buffer level by a large influx of CO2.
to and from 180°C / 356°F [7]. Severe localized corrosion The thickness of the layer is about 5-20 μm.
attacks are seen in the calcium bromide brine. The potassium
formate brine only caused general corrosion. (The CO2 influx
was large enough to overwhelm the upper buffer level and drop
the pH to the lower buffer level in the formate brines.)
Table 6 Average corrosion rate and rate of the deepest attack 7.1.2 CO2 Corrosion of 13Cr Steel
for C-steel in 1.53 s.g. / 12.8 ppg bromide brine and buffered 13Cr steel has been shown to behave in a similar manner to
KFo brine exposed to a large CO2 influx. The experiments were C-steel when exposed to formate brines that have received a
commenced at 120°C / 248°F, with an excursion to and from large influx of CO2. A protective layer is formed during a short
180°C / 356°F [7]. initial period of high general corrosion activity.
Corrosion rate As with C-steel, formate brines in which the pH has been
Fluid Average rate Deepest attack substantially decreased to the lower buffer level by a large
influx of CO2 appear to be much less aggressive towards
mm/y MPY mm/y MPY 13Cr than acidified halide brines. Figure 7 (see left-hand
1)
CaBr2 0.39 15.4 >8.7 >3421) photo) shows severe localized corrosion of a 13Cr steel
CaBr2 – coupon exposed to calcium bromide brine acidified with CO2
inhibited 0.34 13.4 >8.71) >3421)
at temperatures varying from 120°C / 248°F to 180°C / 356°F.
KFo 0.30 11.8 --- --- A 13Cr coupon exposed to formate brine under the same
test conditions shows only general corrosion (see right-hand
1) Perforated, i.e. attack > coupon thickness = 1.5 mm photo in same figure). Weight loss corrosion rates for the
same coupons are shown in Table 7 along with the maximum
depths of pits caused by localized corrosion.
Real-time corrosion rates for C-steel in various formate and
bromide brines exposed to a large amount of CO2 are shown A SEM photo of the film formed in the formate brine is shown
in the plot in Figure 6. This plot is based on Linear Polarization in Figure 8. This film is thicker (100 μm) than the one seen on
Resistance (LPR) measurements that have been calibrated C-steel, and the film quality and ability to inhibit corrosion are
against weight loss. As can be seen, a protective layer was not quite as good.
formed on the metal surfaces exposed to the formate brines
within the first 20–30 hours of exposure to CO2. The scatter in
the bromide data during the initial period with high corrosion
rates indicates that localized corrosion was taking place.
PA G E 1 4
F O R M AT E B R INE S – COMPATI B I L I TY W I TH ME TAL S
)NITIAL #/ #ORROSION IN &ORMATES AND "ROMIDES
+&O SG ª#
#ORROSION RATE ;MMY=
#ORROSION RATE ;-09=
+#S&O SG ª#
#A"R SG )NHIBITED ª#
#A"R SG 5NINHIBITED ª#
+#S&O SG ª#
4IME ;HOURS=
Figure 6 LPR plot showing initial corrosion of C-steel in potassium formate potassium/cesium formate and calcium bromide brines at
various temperatures. All brines were exposed to a large CO2 influx. The time scale starts from the time of acidification with CO2. An initial
short period of high corrosion rates can be seen in the formate brines before the protective iron carbonate layers are formed. No distinct
peak can be seen in the bromide brines. The corrosion inhibitor in the bromide brine appears to have no impact on the CO2 corrosion.
Corrosion
film
13Cr
CaBr2 K formate
Figure 7 13Cr test specimens after exposure to inhibited Figure 8 SEM photo of iron carbonate protective layer formed
bromide (1.53 s.g. / 12.8 ppg) and potassium formate (1.53 s.g. / on 13Cr in potassium/cesium formate brine where pH was
12.8 ppg) with a large influx of CO2 where pH had been pulled pulled down to the lower buffer level by a large influx of CO2.
down to the lower buffer level. Severe localized corrosion The thickness is about 50–100 μm.
attacks are seen in the calcium bromide brine. The potassium
formate brine only caused general corrosion.
PA G E 1 5
F O R M AT E B R IN E S – COMPATI B I L I TY W I TH ME TAL S
Table 7 Average corrosion rate (weight loss) and corrosion rate for the deepest attack for 13Cr-steel in the two 1.53 s.g. / 12.8 ppg
bromide brines, the 1.53 s.g. / 12.8 ppg potassium formate brine, and the 1.70 s.g. / 14.2 ppg potassium/cesium formate brine.
Corrosion rate
Fluid Temp [°C] days Average rate At deepest attack
mm/y MPY mm/y MPY
CaBr2 120 – 1801) 62 0.061 2.4 2.1 83
CaBr2-inhibited 120 – 1801) 62 0.055 2.2 2.6 103
KFo 120 – 1801) 50 0.72 28.3 --- ---
KCsFo 150 34 0.249 9.8 --- ---
KCsFo 175 34 0.119 4.7 --- ---
1) These tests were run at 120°C / 248°F, with a quick ramp-up to 180°C / 356°F and down again after 1,000 hours in the bromides and 700 hours in the
formates.
7.1.3 CO2 Corrosion of Higher Alloy Steels 7.1.4 CO2 Corrosion Rates
A protective layer also forms on the surfaces of higher alloy General corrosion rates in formate brines as a function of
steels in the formate brines where the higher buffer level has temperature and level of CO2 influx are shown in Figure 10 to
been overwhelmed by a massive influx of CO2 (Figure 9 for Figure 14 for C-steel, 13Cr, modified13Cr (1Mo and 2Mo),
22Cr). The layers formed on these metals are of the thicker 22Cr, and 25Cr respectively. The data are taken from various
variety (about 50–100μm). In spite of the slightly lower quality sources [6][7][8][9][10][11]. The data points represent
of these films, the corrosion rates are very low due to the measurements done with and without H2S in the headspace
resistance of these metals to both carbonic acid and formic and with and without chloride contamination in the formate
acid. No signs of pitting corrosion have been observed in any brine. Neither H2S nor chloride contamination appear to have
of these materials exposed to buffered formate brines even any significant impact on the CO2 corrosion rates. For C-steel
with a large amount of CO2 influx. and 13Cr steel, only the corrosion rates that were determined
by LPR or long term (≥30 days) weight loss tests have been
included. These are the “true” corrosion rates at which the
system will stabilize over time, and are not heavily influenced
by the short-duration high corrosion rates that are measured
before the protective layer is formed. Rates that are known to
have been measured with unrealistic volume-to-surface
Corrosion ratios are also excluded.
film
For Alloy 718 (not plotted), the measured corrosion rates are
negligible, in the order of 0.035 mm/y / 1.4 MPY after
overwhelming the buffer with CO2.
Buffered formate brines do not allow corrosion of downhole components unless and until the carbonate buffering
effects are overcome. This will normally take an extended period, or it might never happen during the life of
the well. When, due to CO2 influx, the pH does drop to a point where corrosion can occur the formation of a
protective iron carbonate layer is promoted, particularly on carbon steels, and pitting of CRAs is not seen.
Influx of CO2 into halide brines causes an immediate (further) drop in pH and increased corrosion occurs. The
formation of a protective iron carbonate layer on carbon steels is hindered or prevented and the pitting of CRAs
promoted by the presence of halide ions.
PA G E 1 6
F O R M AT E B R INE S – COMPATI B I L I TY W I TH ME TAL S
#/ CORROSION RATE OF #
3TEEL IN "UFFERED &ORMATE "RINES
4EMPERATURE ª&
&ORMATE BRINES WITH INTACT BUFFER
#ORROSION RATE MMY
#ORROSION RATE -09
!FTER EXTENDED TIME PERIOD WITH #/ (3 INFLUX
4EMPERATURE ª#
Figure 10 Measured general corrosion rates for C-steel in buffered formate brines with various levels of CO2 influx and in some cases
H2S. Most rates are taken from long term LPR plots. Formate brines contaminated with chloride are also included. (See Figure 3; an
“intact buffer” is considered to correspond to a pH of about 9.5 and above.) No localized/pitting corrosion has been reported in any of
these tests.
#/ CORROSION RATE STANDARD #R IN "UFFERED &ORMATE "RINES
4EMPERATURE ª&
4YPICAL /PERATING 7INDOW
#ORROSION RATE MMY
#ORROSION RATE -09
&ORMATE BRINES WITH INTACT BUFFER
!FTER EXTENDED TIME PERIOD WITH #/ (3 INFLUX
4EMPERATURE ª#
Figure 11 Measured general corrosion rates for 13Cr in buffered formate brines with various levels of CO2 influx and in some cases H2S.
Most rates are taken from long term LPR plots. Formate brines contaminated with chloride are also included. (See Figure 3; an “intact
buffer” is considered to correspond to a pH of about 9.5 and above.) No localized/pitting corrosion has been reported in any of these tests.
PA G E 1 7
F O R M AT E B R IN E S – COMPATI B I L I TY W I TH ME TAL S
#/ CORROSION RATE OF MODIFIED #R IN "UFFERED &ORMATE "RINES
4EMPERATURE ª&
4YPICAL /PERATING 7INDOW
#ORROSION RATE MMY
#ORROSION RATE -09
&ORMATE BRINES WITH INTACT BUFFER
!FTER EXTENDED TIME PERIOD WITH #/ (3 INFLUX
4EMPERATURE ª#
Figure 12 Measured general corrosion rates for modified 13Cr (1Mo and 2Mo) in buffered formate brines with various levels of CO2 influx and
in some cases H2S. Most rates are taken from long term LPR plots. Formate brines contaminated with chloride are also included. (See Figure 3;
an “intact buffer” is considered to correspond to a pH of about 9.5 and above.) No localized/pitting corrosion has been reported in any of these
tests, apart from a couple of tests reported by Statoil and CSM [11] where the brine was contaminated with a very high level of chloride.
#/ CORROSION RATE OF #R IN "UFFERED &ORMATE "RINES
4EMPERATURE ª&
4YPICAL /PERATING 7INDOW
#ORROSION RATE MMY
#ORROSION RATE -09
&ORMATE BRINES WITH INTACT BUFFER
!FTER EXTENDED TIME PERIOD WITH #/ (3 INFLUX
4EMPERATURE ª#
Figure 13 Measured general corrosion rates for 22Cr in buffered formate brines with various levels of CO2 influx and in some cases H2S.
Most rates are taken from long term LPR plots. Formate brines contaminated with chloride are also included. (See Figure 3; an “intact buffer”
is considered to correspond to a pH of about 9.5 and above.) No localized/pitting corrosion has been reported in any of these tests.
#/ CORROSION RATE OF #R IN "UFFERED &ORMATE "RINES
4EMPERATURE ª&
#ORROSION RATE MMY
#ORROSION RATE -09
&ORMATE BRINES WITH INTACT BUFFER
!FTER EXTENDED TIME PERIOD WITH #/ (3 INFLUX
4EMPERATURE ª#
Figure 14 Measured general corrosion rates for 25Cr in buffered formate brines with various levels of CO2 influx and in some cases H2S.
Most rates are taken from long term LPR plots. Formate brines contaminated with chloride are also included. (See Figure 3; an “intact buffer”
is considered to correspond to a pH of about 9.5 and above.) No localized/pitting corrosion has been reported in any of these tests.
PA G E 1 8
F O R M AT E B R INE S – COMPATI B I L I TY W I TH ME TAL S
7.2 Impact of CO2 on SCC The metal coupons were galvanically coupled to the loading
Until quite recently, it was widely believed that SCC of CRAs in bolts (C-276) and stressed to beyond yield. All oxygen was
completion and packer fluids was only likely to be a problem if thoroughly removed by flushing at least 6 times with 1 MPa /
the fluid was contaminated with oxygen and contained some 145 psi of test gas before testing and after each inspection.
chloride. Recently, new laboratory data emerged, suggesting All of the test metal samples were inspected with an optical
that some CRAs were also susceptible to SCC in bromide microscope after the first and second months. At the end of the
brines containing no added chlorides [5]. This discovery was exposure period the crack patterns in the specimens that had
soon followed by the revelation that SCC of CRAs could take failed were studied in cross-section under an optical
place in oxygen-free bromide brines contaminated with CO2 [12]. microscope.
SCC has never been experienced with formate brines in the Table 8 shows the test results. At the end of the 3-month test
field. In the laboratory, SCC has never been experienced in period none of the metal samples exposed to the formate
30-day tests in the presence of CO2. Only limited evidence of brine showed any signs of stress corrosion cracking. In the
SCC has been experienced in modified 13Cr steel at an bromide brine, both modified 13Cr-1Mo and Duplex 22Cr
extended test period or with presence of H2S. Extensive SCC showed signs of cracking after only 1 month, and Super
testing has been carried out on formate brines by two research Duplex 25Cr showed evidence of cracks at the initiation
groups: Hydro Corporate Research Centre in Norway [12] and stage in the third month. This clearly demonstrates that under
Centro Sviluppo Materiali SpA in Italy [10][11]. the conditions used in this test program, oxygen is not
required for SCC to take place in bromide brines; the
7.2.1 Testing by Hydro Corporate Research Centre presence of CO2 is enough.
Hydro Research tested CRAs for SCC after exposure to
buffered 1.7 s.g. / 14.2 ppg potassium/cesium formate brine. To our knowledge, there are no additives that can prevent the
They used the “U-bends and C-rings, pre-stressed to yield” SCC failures in the halide brines containing CO2. No additives
method. A 1.7 s.g. / 14.2 ppg calcium bromide brine was are currently available to scavenge CO2 from divalent halide
included in the testing for comparison. Both brine types were brines, and if such an additive did exist, it would deplete over
contaminated with 1% Cl-. No oxygen scavengers or time if the CO2 influx was persistent. Also, commonly used
corrosion inhibitors were added to either brine. The fluids corrosion inhibitors are known to be ineffective in preventing
were tested at 160°C / 320°F over a period of three months the onset of SCC.
with visual inspection after each month. Testing was done
with 1 MPa / 145 psi CO2 in the headspace, which immediately The formate brine was tested under the most aggressive
overwhelmed the upper buffer level (the carbonate portion) of conditions, i.e. the upper buffer level was overwhelmed
the carbonate/bicarbonate buffer in the formate brine and (depleted), representing the very worst case where CO2 had
allowed pH to drop to the second buffer level. The CRAs that leaked into the brine over a very long period of time. The results
were tested included triplicate specimens of modified 13Cr-1Mo, show that no additives or treatments other than buffering are
Duplex 22Cr, and Super Duplex 25Cr. required in formate brines to prevent SCC from a CO2 influx.
Table 8 Hydro Corporate Research Centre – Long term SCC testing on a 1.7 s.g. / 14.2 ppg potassium/cesium formate brine and a
1.7 s.g. / 14.2 ppg calcium bromide brine, with CO2 headspace. Temperature = 160°C / 320°F, and PCO2 = 1 MPa / 145 psi. The upper
buffer level in the formate brine was immediately overwhelmed and the pH was allowed to drop to the lower pH level. The tests were
run for three months with visual inspection of the specimens after each month.
Results [SCC]
Test specimen
CaBr2 + 1% Cl- KCsFo +1% Cl-
1 month 1)
Modified 13Cr-1Mo LC80-130M 3/3 No
Duplex 22Cr EN 1.4462 3/3 No
Duplex 25Cr EN 1.4410 No No
2 months 1) 2)
Modified 13Cr-1Mo LC80-130M 3/3 No
Duplex 22Cr EN 1.4462 3/3 No
Duplex 25Cr EN 1.4410 No No
3 months 2)
Modified 13Cr-1Mo LC80-130M 3/3 No
Duplex 22Cr EN 1.4462 3/3 No
Duplex 25Cr EN 1.4410 2/3 No
• crack • cracks at the initiation stage • no cracking
1) For the first and second month the cracking evaluation is only based on visual inspections and optical microscopy.
2) These tests are not “true” 2 and 3 months tests as the cell has been opened for inspection. They do however provide a valuable comparison of the
cracking susceptibility of the two brines.
PA G E 1 9
F O R M AT E B R IN E S – COMPATI B I L I TY W I TH ME TAL S
Table 10 Centro Sviluppo Materiali – SSRT testing and fpbb testing of modified 13Cr-2Mo in 1.95 s.g. cesium/potassium formate brine
saturated with Cl- and exposed to CO2. PCO2 = 4 MPa / 580 psi [11].
Temperature
Test duration (months) RA [%] EL [%] Cracks (fpbb) testing
°C °F
No exposure (reference) 52 21 --
100 212 1 74 20 No
140 284 1 nd nd No
140 284 2 nd nd Cracks at the initiation stage
165 329 1 nd nd No
170 338 1 nd nd No
PA G E 2 0
P+AA #/ (#/
P+
P+AA
(#/ (
(#/ ( ←
←⎯⎯
⎯
→(
⎯→ (#/
#/ PKT
PKT
P+
P+AA (#/
(#/ (
(#/
#/ F O R M AT E B R INE S – COMPATI B I L I TY W I TH ME TAL S
#/
G
#/ G #/
#/AQ
AQ PKT
PKT
8 Corrosion in Formate
#/
#/AQ
AQ ((/
/ ((#/
#/AQ
AQ Brines
PKT
PKT 8.1 Impact of H2S on General and Pitting Corrosion
Contaminated
( #/ AQ ←⎯
++A
⎯→ (#/ AQ ( AQ
with H 2S
PKT
Both Statoil (Centro Sviluppo Materiali) [10][11] and Hydro
PKT
A
( #/ AQ ←⎯
⎯→ (#/ AQ ( AQ Research [15] have included H2S in some of their corrosion
Hydrogen sulfide, H S, is highly aggressive towards
OKT metallic experiments with CO2 in formate brines. Hydro Research
AQ OKT
#/
#/ AQ AQ ( (#/#/AQ AQ →
2
→ (#/ (#/ AQ
materials. Depending upon the material, H2S can cause concluded that the presence of H2S had very little impact on
general
#/ corrosion, ++
pitting corrosion,
sulfide stress cracking
PKT the quality of the protective iron carbonate film that forms on
#/GG ( (/ /↔ ↔(#/ (#/AQ AQ ( ( AQAQ PKT
(SSC), stress corrosion cracking (SCC), hydrogen induced carbon and 13Cr steel surfaces in formate brines, even in the
cracking (HIC), stress oriented HIC (SOHIC), and hydrogen case where pH is reduced to the lower buffer level by
( ==⋅⋅;;(#/ (#/ ==
;;(
embrittlement,
++ and can promote corrosion fatigue. H2S
PKT
PKT exposure to a massive influx of CO2. Only when an extremely
00#/
#/
concentrations of only 50 ppmw dissolved in drilling and high concentration of H2S was applied or at very low CO2 /
completion fluids can cause highly stressed steel to fail in a H 2S ratios, was localized corrosion experienced. Testing with
P(
P(
LOG
LOG ;;((== PKT
PKT
matter ofminutes. PH2S = 2 kPa / 0.29 psi and PCO2 / PH2S = 500 on C-steel
PKT (covering the acid gas content and composition of all
LOG ; (#/ =
P(
P( LOG LOG++ LOG LOG00#/ #/ LOG ; (#/ = PKT
H2S can enter the completion or packer fluid either with production wells in the Gulf of Mexico and the North Sea),
00#/
reservoir
#/
gas
(#/
(#/ influxes
(along with CO 2) or from decomposition standard 13Cr, and modified 13Cr-1Mo showed no impact
of sulfur-containing additives used as corrosion inhibitors in from the presence of H2S. At PH2S = 100 kPa / 14.5 psi and
(
(#/
halide#/brines
AQ
AQ (#//
(for example
(#// AQ
AQ (#//(
thiocyanates).
(#//( AQ
AQ (#/
AQ
A number
(#/ PKT
AQ of recent
PKT PCO2 / PH2S = 4, some localized corrosion was experienced.
failures of subsurface well equipment in halide brines have Corrosion rate results with H2S from both laboratories are
P+AA (
P+
been
( #/
#/
attributed to the H2SP+
P+ AA(#//(
formed (#//( from the
thermal decom- included in the plots in Figure 10 to Figure 14. The small
position of sulfur-based
corrosion inhibitors
[13][14]. amount of pitting corrosion that was reported by Statoil [11]
&E
&E ( (#/#/AQ AQ → → &E&EAQ AQ ( (GG (#/ (#/AQ AQ PKT
PKT in the presence of H2S could be promoted by the rather high
H2S is a very weak acid with pKa1 of about 7,and when
PKT chloride contamination level in their test brine (saturated).
&E (#//( AQ &E AQ
&E (#//( AQ → &E AQ ( G #//( AQ PKT
→ ( G #//( AQ
introduced into an aqueous solution, the following equilibrium
will
&E establish:
PKT
&E #/ #/ ↔ ↔&E#/ &E#/SS PKT 8.2 Impact of H2S on SCC and SSC
(
(33GG (
(33AQ
AQ (15) PKT
PKT The following provides an outline of the cracking of metallic
materials in contact with H2S in the aqueous environments
P+
(
(33AQ
AQ ←
←⎯⎯⎯
P+
⎯
AA
→(3
→ −
(3 −AQ
+
AQ ++ ((+AQ
AQ PKT
(16)
PKT found in oil and gas production systems. It is thought that the
behavior described also provides an indication of the likely
(#// CAT PKT
PKT
(#// AQ
AQ in
Therefore, an
((/
/← ⎯→(#/
←⎯→
alkaline (#/ AQ
AQ solution,
aqueous (
( GG such
CAT
as buffered
cracking behavior of such materials in completion brines
formate brines, the dissolved H2S gas will largely exist as contaminated by H2S influx.
(#//(
(#//(← ←⎯
CAT
⎯CAT→ #/ ( G
-→ #/ ( G
PKT
PKT
bisulfide (HS ).
The service variables temperature, H2S partial pressure,
In non-oxygenated solutions, corrosivity is determined in part chloride concentration, and pH, and the presence of sulfur in
by the pH. The lower the pH the greater the tendency for the environment can, depending upon the material, affect its
corrosion. In addition, pH determines the stability/solubility of cracking behavior. Produced sulfur is relatively rare in oil and
corrosion scales. gas production environments. It can, however, also occur as
a result of the reaction of oxygen contamination, introduced
Low general corrosion is expected in view of the high pH of via surface facilities, with any H2S that is present.
formate brines buffered with carbonate/bicarbonate, even in
the presence of high concentrations of hydrogen sulfide The metallurgical state of an alloy and the total stress in a
(which will chiefly exist as HS-). At this pH, since little material (the sum of both applied and residual stresses) are
corrosion that could lead to hydrogen uptake can occur, also important variables in both these forms of cracking.
SSC is unlikely.
8.2.1 Sulfide Stress Cracking (SSC) of Carbon
By contrast, in high-density halide brines, the pH is low and Low Alloy steels
(typically 2–6), and the H2S gas will be solubilized directly as SSC can affect susceptible carbon and low alloy steels at
H2S. Soluble H2S in acidic brines can cause severe SSC. very low H2S partial pressures.
As an additional benefit, the formate brines do not require Figure 15 (taken from NACE MR1075/ISO 15156-2 [16])
corrosion inhibitors of any kind, thus removing a potential defines the boundaries within which various strengths of
man-made source of hydrogen sulfide and atomic hydrogen. steels (often expressed in terms of hardness) remain crack
resistant when exposed to various H2S partial pressures and
There is a remote possibility that H2S could flow into a formate environmental pH values at room temperature. Materials
completion or packer fluid together with an influx of CO2 large suitable for use in region 3 are also suitable for use in regions
enough to overwhelm the upper buffer level so that pH will drop 0, 1 and 2 but not vice-versa.
to 6–6.5. Hydro Corporate Research Centre, Porsgrunn and
Statoil (at Centro Sviluppo Materiali SpA) have investigated As the temperature of the environment increases the
the possible consequences of such a scenario (see 8.2.4). susceptibility of carbon and low alloy steels to SSC
PA G E 2 1
F O R M AT E B R IN E S – COMPATI B I L I TY W I TH ME TAL S
K0A 33# 2EGIONS OF %NVIRONMENTAL 3EVERITY
PSI
REGION
P( RANGE OF BUFFERED FORMATES .ORMALLY NO SPECIAL PRECAUTIONS
WITH INTACT BUFFER
ARE REQUIRED FOR THE SELECTION OF
STEELS FOR USE UNDER THESE
CONDITIONS .EVERTHELESS HIGHLY
P( RANGE OF BUFFERED FORMATES SUSCEPTIBLE STEELS CAN CRACK
WITH OVERWHELMED BUFFER
33# REGIONS AND
3PECIFIC GUIDELINES NEED TO BE
P( FOLLOWED FOR SELECTION OF MATERIAL
P( RANGE OF HALIDE BRINES
(3 PARTIAL PRESSURE ;K0A=
Figure 15 Regions of environmental severity with respect to SSC of carbon and low alloy steels at room temperature. The limits are
taken from NACE MR0175 / ISO 15156-2 [16].
decreases and above about 100°C / 212°F cracking is not important with respect to the SSC of martensitic stainless
normally observed. steels.
The other environmental variables listed above are much less The likely importance of pH suggests that the cracking
important with respect to SSC. behavior of these alloys in relation to brines of different types
will be similar to that of carbon and low allow steels.
As can be seen, pH is an important factor in cracking
behavior of these steels and hence the pH of buffered Stress Corrosion Cracking of other CRAs
formate brines (normally > 6.5 even after significant influx of The stress corrosion cracking of austenitic and duplex
acid gases) is expected to make this form of attack much less stainless steels is dependent in a complex way upon
likely than in other completion brines (halide brines) whose temperature, H2S partial pressure, and chloride concentration.
pH falls quickly when affected by the influx of CO2 / H2S. For nickel based alloys the role of chloride concentration
appears less important than the other variables. The role of
8.2.2 Cracking of CRAs in H2S Containing Environments pH in the cracking of all these alloys is less clear. Many alloys
More detail on the limits of applicability of CRAs in oil and are made more susceptible to cracking by the presence of sulfur.
gas production environments containing H2S is given in the
industry standard NACE MR0175/ISO 15156-3 [2]. The The relatively low level of chloride in buffered formate brines
information below refers to a primary mechanism of cracking when compared to halide brines would be expected to make
for the alloys discussed. More details on possible cracking some of these alloys less susceptible to SCC in the presence
mechanisms are given in Reference [2], Annex B, Table B.1. of H2S.
Sulfide Stress Cracking of Martensitic Stainless Steels In the laboratory data, reported in 8.2.3 to 8.2.5 below, little
Martensitic stainless steels, such as the standard 13Cr and or no evidence for SCC has been seen in formate brines.
modified 13Cr alloys are also subject to SSC as a mechanism
of cracking failure in H2S containing media. The H2S partial 8.2.3 High-Temperature Testing by CAPCIS
pressure limit set by the industry for the more widely used CAPCIS tested CRAs for SCC after exposure to buffered
alloys is 10 kPa (1.5 psi) at a pH no lower than 3.5. 1.7 s.g. / 14.2 ppg potassium/cesium formate brine at high
It is believed, given the involvement of hydrogen uptake in temperature (160°C / 320°F) [18]. “U-bends and C-rings,
SSC, that at a higher pH, and/or a higher temperature, a pre-stressed to yield” method was used in accordance with
higher level of H2S would be acceptable and that it may be previous test programs performed by Hydro Research (Section
possible to construct a diagram similar to that in Figure 15 for 7.2.1 and 9.1.1). A 1.7 s.g. / 14.2 ppg calcium bromide brine
these alloys. was included in the testing for comparison. No oxygen
scavengers or corrosion inhibitors were added to either brine.
The other environmental variables listed above appear less The fluids were tested at 160°C / 320°F over a period of
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1 month. Testing was done in Hastalloy vessels with buffer level of the carbonate/bicarbonate buffer was
1 MPa / 145 psi CO2 and 10kPa / 1.45 psi H2S in the overwhelmed. The pH in the bromide brine dropped slightly
headspace. The CRAs that were tested included triplicate from 3.41 to 3.30 (undiluted).
specimens of modified 13Cr-2Mo, Duplex 22Cr, Super
Duplex 25Cr, and alloy 718. The metal coupons were Table 11 shows the test results. At the end of the 4-week
galvanically coupled to the loading bolts (C-276) and test period only the modified 13Cr-2Mo test specimens
stressed beyond yield. In addition to the U-bend test pieces, showed cracks at the initiation stage in the formate brine
pre-machined, unloaded, tensile test pieces of each material (0.11 mm cracks on cross sections). In the bromide brine, all
were added to assess the effect of any hydrogen uptake on modified 13Cr-2Mo samples and one of the alloy 718
tensile properties. Coupons of each material were also samples were fractured. The tensile test pieces were tested
included for measurement of dissolved hydrogen. After the for changes in ductility within 6 hours after removal from the
specimens were added to the test vessel the vessel was test vessel to minimize loss of any absorbed hydrogen.
sealed and pressurized 5 times with 1 MPa CO2. The test Samples were stored in liquid nitrogen after cleaning and
solutions were de-aerated by purging with nitrogen for at warmed up shortly before tensile testing. Coupons for
least 12 hours prior to transfer to the test vessel. The test hydrogen measurement were brushed clean and analyzed
solutions were purged with CO2 in the test vessel for 30 by vacuum hot extraction (VHE). Results of tensile tests and
minutes before introducing the test gas mixtures. At the end hydrogen measurements are listed in Table 12. Some of the
of the exposure period the crack patterns in the specimens samples that were exposed to the two brines, CO2 and H2S,
that had failed were studied in cross-section under an optical contained probably slightly elevated levels of hydrogen. They
microscope. were not affected significantly by hydrogen embrittlement
apart from one anomalously high yield strength value from
During the test, the pH dropped from 11.9 to 7.60 (undiluted) Alloy 718 in CaBr2.
in the buffered formate brine, which indicated that the upper
Table 11 CAPCIS testing of 1.7 s.g. / 14.2 ppg calcium bromide and 1.7 s.g. / 14.2 ppg potassium/cesium formate brines exposed to
CO2 (1 MPa / 145 psi) and H2S (10 kPa / 1.45 psi) at 160°C / 320°F for 30 days.
Results [SCC]
Test specimen Comment
CaBr2 CsKFo
1 month
Table 12 CAPCIS room temperature tensile test data (EN10002-1) and hydrogen measurements after exposure to 1.7 s.g. / 14.2 ppg
calcium bromide and 1.7 s.g. / 14.2 ppg potassium/cesium formate brines at 160°C / 320°F for 30 days. PCO2 = 1 MPa / 145 psi and
PH2S =10 kPa / 1.45 psi. The tensile data are the average of measurements done on two test specimens. The hydrogen levels are based
on one single test.
1) One sample showed 103% change; the other showed 121% change.
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Table 13 Centro Sviluppo Materiali – fpbb testing of modified 13Cr-2Mo and alloy 718 in a 1.94 s.g. / 16.2 ppg CsKFo brine at 165°C / 329°F.
PCO2 = 4 MPa / 580 psi. The results are taken from [10].
8.2.4 High-Temperature Testing by Statoil at stressed to yield” method, were used. A 1.7 s.g. / 14.2 ppg
Centro Sviluppo Materiali calcium bromide brine was included in the testing for
Statoil completed some four point bent beam (fpbb) testing comparison. No oxygen scavengers or corrosion inhibitors
at Centro Sviluppo Materiali, in 1.95 s.g. buffered cesium were added to either brine. The fluids were tested at 40°C /
formate brine exposed to CO2 and H2S [10]. In this testing, 104°F over a period of 1 month. Testing was done in
the acid gas exposure was sufficient to overwhelm the upper Hastalloy vessels with 1 MPa / 145 psi CO2 and 10kPa / 1.45
buffer level (the carbonate part) and drop the pH to the lower psi H2S in the headspace. The CRAs that were tested
buffer level. Table 13 shows the results from these tests and included triplicate specimens of modified 13Cr-2Mo, Duplex
a test with only CO2. The addition of H2S did not cause any 22Cr, Super Duplex 25Cr, and alloy 718. The metal coupons
cracking of the modified 13Cr-2Mo over the 1 month were galvanically coupled to the loading bolts (C-276) and
exposure period. There was some evidence of embrittlement stressed beyond yield. In addition to the U-bend test pieces,
of the modified 13Cr-2Mo and alloy 718 used in the tests pre-machined, unloaded, tensile test pieces of each material
with H2S. were added to assess the effect of any hydrogen uptake on
tensile properties. Coupons of each material were also
Statoil and Centro Sviluppo Materiali also included the same included for measurement of dissolved hydrogen. After the
amount of H2S (PH2S = 3 kPa / 0.44 psi) in their four point bent specimens were added to the test vessel the vessel was
beam and SSRT testing [11] reported in Table 10 in the sealed and pressurized 5 times with 1 MPa CO2. The test
previous chapter (modified 13Cr-2Mo, given 1 month of solutions were de-aerated by purging with nitrogen for at
exposure to cesium formate brine at 170°C / 338°F in the least 12 hours prior to transfer to the test vessel. The test
presence of 4 MPa CO2). This showed cracks at the initiation solutions were purged with CO2 in the test vessel for 30
stage and some absorption of hydrogen into the steel. Under minutes before introducing the test gas mixtures. At the end
the same test conditions, in the absence of H2S, there was of the exposure period the crack patterns in the specimens
no cracking and no absorption of hydrogen into the steel that had failed were studied in cross-section under an optical
during the 1 month exposure. The paper does not state if the microscope.
cracks were caused by SCC or if it was SSC occurring during
cooling of the test sample. For alloy 718, there were no During the test, the pH dropped from 11.9 to 7.63 (undiluted)
failures but loss of ductility with and without H2S. This is in the buffered formate brine, which indicated that the upper
discussed further in Section 11. buffer level of the carbonate/bicarbonate buffer was
overwhelmed. The pH in the bromide brine increased slightly
There are no results listed for similar tests in halide brines from 3.41 to 3.65 (undiluted).
with H2S. The paper does, however, state that the presence
of CO2 and H2S created severe SCC in modified 13Cr-2Mo Table 14 shows the test results. At the end of the 4-week
metal samples immersed in ZnBr2/CaBr2/CaCl2 and CaBr2/ test period no sign of cracking was seen on any of the test
CaCl2 brines, and that transgranular cracks were also found specimens in the formate brine. In the bromide brine, all
in one of the tests. modified 13Cr-2Mo samples showed signs of cracks at the
initiation stage. The tensile test pieces were tested for
H2S formed by the thermal decomposition of sulfur- changes in ductility within 6 hours after removal from the test
containing corrosion inhibitors is another well-known cause vessel to minimize loss of any absorbed hydrogen. Samples
of SSC and SCC in completion/packer fluids. Corrosion were stored in liquid nitrogen after cleaning and warmed up
inhibitors are not required in formate brines, and so one shortly before tensile testing. Coupons for hydrogen
troublesome source of corrosion is eliminated. measurement were brushed clean and analyzed by vacuum
hot extraction (VHE). Results of tensile tests and hydrogen
8.2.5 Low-Temperature Testing by CAPCIS measurements are listed in Table 15. Some of the samples
CAPCIS tested CRAs for SSC after exposure to buffered that were exposed to the two brines, CO2, and H2S contained
1.7 s.g. / 14.2 ppg potassium/cesium formate brine at low probably slightly elevated levels of hydrogen, but were not
temperature (40°C / 104°F) [18]. “U-bends and C-rings, pre- affected significantly by hydrogen embrittlement.
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Table 14 CAPCIS testing of 1.7 s.g. / 14.2 ppg calcium bromide and 1.7 s.g. / 14.2 ppg potassium/cesium formate brines exposed to
CO2 (1 MPa / 145 psi) and H2S (10 kPa / 1.45 psi) at 40°C / 104°F for 30 days.
Table 15 Room temperature tensile test data (EN10002-1) and hydrogen measurements after exposure to 1.7 s.g. / 14.2 ppg calcium
bromide and 1.7 s.g. / 14.2 ppg potassium/cesium formate brines at 40°C / 104°F for 30 days. PCO2 = 1 MPa / 145 psi and
PH2S =10 kPa / 1.45 psi. The tensile data are the average of measurements on two test specimens. The hydrogen levels are based
on one single test.
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9 Corrosion in Formate Brines present in the brine was apparently not able to cope with the
Contaminated with O2 new influx of oxygen.
Oxygen is generally accepted as a cause of general Concentrated formate brines contaminated with oxygen and
corrosion, where the oxygen serves as an oxidant for without added oxygen scavenger have never caused pitting
corrosion reactions. Concentrated formate brines have or SCC in the field. Laboratory testing with these brines
beneficial properties that should help protect metals against confirm their superior performance over halide brines.
corrosion damage caused by oxygen:
3OLUBILITY OF / IN &ORMATE "RINES
3OLUBILITY ;PPM=
3OLUBILITY ;PPM=
&ORMATE CONCENTRATION ;WEIGHT=
Halide brines have no anti-oxidant properties. Therefore, if calcium bromide brine was included in the testing for
oxygen is not removed from halide based drilling and comparison. Both brines were deliberately contaminated with
completion fluids, the soluble oxygen can cause several 1% Cl-. In addition, the formate brine was tested with 0.3%
forms of corrosion in sub-surface well equipment and chloride contamination and the bromide brine was tested
tubulars. For this reason, it is essential to add an oxygen without any added chloride. No oxygen scavengers or
scavenger to halide brines. These scavengers are generally corrosion inhibitors were added to either brine. The brines
quite effective until they become depleted (consumed) or were tested at 160°C / 320°F over a period of three months.
degraded, at which point further contamination with oxygen Testing was done with 1 MPa N2 and 20 kPa O2 in the
could cause a problem. However, the standard bisulfite- headspace. The CRAs that were tested included triplicate
based oxygen scavengers are not particularly soluble in specimens of modified 13Cr-1Mo, Duplex 22Cr, and Super
calcium brines because they form solid calcium bisulfite. A Duplex 25Cr. The metal coupons were galvanically coupled to
recent well tubular failure [21] was caused by oxygen (air) the loading bolts (C-276) and stressed to beyond yield. All of the
ingress into a CaCl2 packer fluid during an annular pressure test metal samples were inspected with an optical microscope
bleed-off operation. In this instance, the oxygen scavenger after the first and second months. At the end of the exposure
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Table 16 Hydro Research / CAPCIS – Long term SCC testing over a 3-month period in 1.7 s.g. / 14.2 ppg formate and bromide brines
in the presence of oxygen. Temperature = 160°C / 320°F, PN2= 1 MPa, / 145 psi and PO2 = 20 kPa / 2.9 psi.
Results [SCC]
Test Specimen Calcium bromide Formate
No added Cl - 1% added Cl - No added Cl - 0.3% added Cl - 1% added Cl -
1 Month 1)
Modified 13Cr-1Mo LC80-130M 3/3 3/3 -- No No
22Cr EN 1.4462 ? 1/3 -- No No
25Cr EN 1.4410 No No -- No No
2 Months 1)
Modified 13Cr-1Mo LC80-130M 3/3 3/3 -- ? 2/3
22Cr EN 1.4462 3/3 3/3 -- No No
25Cr EN 1.4410 1/3 1/3 -- No No
3 Months
Modified 13Cr-1Mo LC80-130M 3/3 3/3 3/3 ? 2/2 2/3
Modified 13Cr-2Mo SM13CRS-110ksi -- -- 3/3 -- --
22Cr EN 1.4462 3/3 3/3 No No No
25Cr EN 1.4410 2/3 2/3 No No No
• crack • cracks at the initiation stage • no cracking
1) For the first and second month the cracking evaluation is only based on visual inspections and optical microscopy.
Table 17 CAPCIS – Short term SCC in 1.7 s.g. formate and bromide brines contaminated with 1% Cl- in the presence of oxygen.
Temperature = 160°C / 320°F, PN2= 1 MPa / 145 psi, and PO2 = 20 kPa / 2.9 psi. The bromide brine was tested by CAPCIS and the
formate brine by Hydro Formates (Chapter 9.1.1).
Results [SCC]
Test specimen Calcium bromide Formate
1% added Cl - 1% added Cl -
1 Week 1)
Modified 13Cr-1Mo LC80-130M 1/3 No
22Cr EN 1.4462 1/3 No
25Cr EN 1.4410 No No
2 Weeks
Modified 13Cr-1Mo LC80-130M 3/3 No
22Cr EN 1.4462 3/3 No
25Cr EN 1.4410 No No
• crack • cracks at the initiation stage • no cracking
1) For the first week the cracking evaluation is only based on visual inspections and optical microscopy.
period the crack patterns in the specimens that had failed were 9.1.2 Testing by CAPCIS
studied in cross-section under an optical microscope. The CAPCIS carried out some additional short-duration tests at
results of the testing are shown in Table 16. At the end of the 160°C / 320°F with CRAs in chloride contaminated calcium
first month none of the metal samples exposed to the bromide brines to find out how quickly they cracked in the
chloride-contaminated formate brines showed any signs of presence of oxygen (1 MPa / 145 psi pressure; 20 kPa /
stress corrosion cracking. In the bromide brines with and 2.9 psi O2) [12]. The tests were carried out by exactly the same
without chloride contamination, samples of both modified method as the oxygen tests done by Hydro Research (9.1.1).
13Cr-1Mo and Duplex 22Cr had cracked after only one The results of this testing are shown in Table 17. It is clear
month. After three months of testing, none of the 22Cr and that the modified 13Cr-1Mo and Duplex 22Cr metal samples
25Cr metal samples had cracked in the chloride-contaminated exposed to chloride- and oxygen-contaminated bromide
formate brines, but some cracks at the initiation stage were brines were beginning to crack within 7 days. The 25Cr was
evident in the modified 13Cr-specimens. In the bromide brines, more resistant to cracking in the contaminated bromide
all of the metals had cracked after two months even in the brine, but Hydro Research had previously shown that
bromide brines that were not contaminated with added cracking would eventually take place after 2 months.
chloride.
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CAPCIS also repeated the long term (3-month test) in 9.2 Use of O2 Scavengers in Formate Brines
formate with oxygen, but without chloride contamination [not The corrosive properties of oxygen are related to its strong
yet published]. The results from this test are shown in Table oxidizing properties.
16 together with the long term testing done by Hydro
Corporate Research Centre, Porsgrunn (9.1.1). The results of Due to the strong antioxidant properties of concentrated
this showed that the cracking seen by Hydro Research (9.1.1) formate brine, it has never been thought necessary to
is unlikely to be related to the chloride contamination. As scavenge soluble oxygen from high density formate brines. It
similar crack initiation was not observed in the same has not been normal practice to add an oxygen scavenger to
experiments carried out in a CO2 contaminated formate brine formate brines prior to field use.” The big difference that has
(7.2.1), the oxygen contamination seems likely to be the been seen when cracking takes place in the formate brine
cause of the cracking. and the bromide brine (9.1), supports the fact that formate
brines do have antioxidant properties. Whether the slight
9.1.3 Testing by Statoil at Centro Sviluppo Materiali cracks at the initiation stage that were seen in modified 13Cr
Centro Sviluppo Materiali used four point bent beam (fpbb) after three months of exposure at high temperature could be
tests to evaluate the SCC susceptibility of modified avoided by pre-treating the brine with an oxygen scavenger
13Cr-2Mo steel and Alloy 718 in a buffered 1.95 s.g. cesium/ is still unknown. Until experimental evidence is available it
potassium formate brine with some oxygen present in the would be advisable to pre-treat the brine with an oxygen
headspace of the reaction vessel [10][11]. Their test scavenger in case of long exposure of modified 13Cr to
temperature was 165°C / 329°F, and the pressure in the formate brines at high temperature.
headspace was 0.7 MPa. The partial pressure of oxygen was
low (about 100 ppb). The tests were run for 1 month. One Low-density formate brines, containing more water than
brine sample was contaminated with 3g/L of Cl- and the formate, may not offer the same corrosion protection as their
other was saturated with NaCl (85 g/L Cl-). Testing was higher density cousins. A 1.06 s.g. / 8.84 ppg potassium
conducted on alloy 718 and 4 different grades of modified formate brine was recently shown to cause severe under
13Cr-2Mo. None of the metal samples showed any signs of deposit corrosion damage initiated from pits of 1%Cr and
pitting or stress corrosion cracking. 3%Cr C-steel [22]. Such a diluted brine would probably have
benefited from the addition of an oxygen scavenger.
Table 18 Centro Sviluppo Materiali – 1 month fpbb testing at Sodium ascorbate has been proposed as an effective oxygen
165°C / 329°F on modified 13Cr-2Mo and Alloy 718 in a scavenger in formate brines.
cesium/potassium formate brine contaminated with chloride.
PN2 = 0.7 Pa + 100 ppb O2.
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P( LOG + LOG 0#/ LOG ; (#/ = PKT
0#/
(#/
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11.3 Field Evidence – Total’s Elgin Wells G1 and G3 204°C / 400°F, there was some concern that formate
Total’s Elgin and Franklin fields in the central part of the UK decomposition might occur and possibly cause hydrogen
North Sea comprise the largest HPHT development ever charging and embrittlement of the 25Cr tubing. Hydrogen
undertaken anywhere in the world. The reservoir gas from detectors were therefore installed on both wells during the
these fields contains 4% CO2 and 20-50 ppm H2S. The entire exposure period, but no hydrogen was ever detected.
bottom hole static temperature in the development wells was
initially about 204°C / 400°F, and the pressure 110 MPa / After their retrieval from the G1 and G3 wells, both sets of
16,000 psi. 25Cr tubulars were analyzed for hydrogen content at several
points along their length. The measured hydrogen levels in
In 1999, TotalFinaElf drilled the first two production wells in both tubulars that had been exposed to cesium formate brine
the Elgin field, G1 and G3, which were completed with 25Cr were found to be in the range 2.15–3.92 ppmw, which is only
tubing in inhibited seawater. The wells were drilled with slightly higher than the levels that are normally found in a
SBM (Synthetic Based Mud). Both wells were produced for typical manufactured 25Cr tubing (1.5–3.5 ppmw). For
about a day before they were suspended: comparison, the hydrogen levels found in the lengths of
tubing that had been exposed to the SBM were much higher,
Well G1: The well was initially shut in with hydrocarbons at up to 7.23 ppmw.
below the SCSSV. Due to a leak in the production packer, the
well was killed with cesium formate brine. After 21 days Independent mechanical testing by Bodycote on both sets of
exposure to cesium formate the tubing was cut and retrieved, tubulars concluded that the properties of the steel that had
the packer was milled out, and the well cemented. been exposed to cesium formate were still within specification,
and suitable for further use in HPHT wells [27].
Well G3: This well was initially shut in with hydrocarbons
below the SCSSV. The well was later killed and suspended Cesium formate brines have since been used very success-
with SBM from bottom hole to 3,900 meters and cesium fully in another 8 wells over a period of 7 years in the Elgin/
formate from 3,900 meters to surface. After 15 months of Franklin fields as workover, completion, coil tubing, well kill,
exposure to these fluids, the well was worked over and the and perforation fluid. In a later well, G5, a full analysis was
tubing retrieved. made on the cesium formate brine that was recovered after
being left below the packer for 9 months at 204°C / 400°F.
Total had previously carried out laboratory testing at low The analysis showed no signs of decomposition products in
pressures with buffered cesium formate brine where the the brine, and the low levels of soluble chromium and iron
buffer had been overwhelmed by exposure to high levels of found in the brine indicated that corrosion had been minimal.
acid gas. Total found that at temperatures above 170°C / 338°F,
this brine could suffer significant catalytic decomposition and
release hydrogen gas. As both of the Elgin wells would be
exposed to cesium formate brine at temperatures up to
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12 Avoid Pitfalls in the Laboratory! • Never use borosilicate (e.g. Pyrex) glass containers for
corrosion experiments with formate brines. Corrosive
Correctly formulated formate brines do not cause corrosion chemicals are released from borosilicate glass by formate
problems in the field, and when tested under realistic brines. These corrosive substances will cause unrealistically
downhole conditions, they also don’t cause corrosion high corrosion rates that do not simulate what will happen
problems in the laboratory. Formate brines are, however, in field environments.
much more sensitive to the laboratory test environment than • Never use corrosion inhibitors in concentrated formate
other oilfield brines. Some standard corrosion test procedures brines. Corrosion inhibitors interfere with the formation of
provide such unrealistic conditions and their use creates natural protective films on metals in formate brines and
artifacts that for many years have lead researchers to draw may cause localized pitting corrosion.
misleading conclusions about the corrosivity of formate • Be aware that the use of laboratory reactors with gas-
brines. filled headspace volumes does not simulate downhole
well conditions. Due to the powerful pH buffering action
These are the major pitfalls that should be avoided when of formate brines, a very large amount of CO2 must be
carrying out laboratory corrosion experiments with formates: introduced into a laboratory reactor in order to overwhelm
• Always include an appropriate dose of carbonate/ the upper buffer level and initiate CO2 corrosion. Most of
bicarbonate buffer in the formulation. Even though the corrosion rates reported here have been measured
corrosion tests may sometimes be carried out under after exposing metals to a very high partial pressure of CO2
conditions in which the upper buffer level is completely (e.g. 1 MPa) in the headspace above the formate brine,
overwhelmed (i.e. large amounts of CO2 in the head which is large enough to decrease pH to the lower buffer
space), the buffer should never be left out. This is because level. It is important to keep in mind that this laboratory
the buffer not only serves as a pH stabilizer, but also environment represents absolutely the worst case
contributes to the quality of the iron carbonate protective scenario, simulating a massive and prolonged influx of CO2
film that is formed under these conditions. into a wellbore. More often than not in real life, the upper
• Use a realistic fluid volume-to-metal surface area ratio. buffer level will not be overwhelmed and actual corrosion
Using a realistic ratio of around 2–4 mL/cm2, as typically rates in the well will be more realistically projected from
found in a cased hole, has shown to be critical when corrosion experiments with formate brines that are not
testing C-steel and standard 13Cr steel with formate exposed to CO2. This is not true for halide brines where
brines exposed to acid gas in the laboratory. If the ratio is even a minor CO2 influx will be enough to cause carbonic
made unrealistically large, a lot of corrosion will take place acid to form and CO2 corrosion to commence. The
before the protective iron carbonate film can be formed. If presence of an unrealistic gas cap might also be the
the corrosion rates are then measured by weight loss of cause of catalytic decomposition of formate brines,
metal test coupons over a short time period the results will which is frequently experienced in the laboratory, but not
be unrealistic and misleading. Testing with higher fluid in the field.
volume-to-surface metal area should not be necessary
unless the material tested is destined for use in wirelines.
• Avoid short term weight loss measurements. Even
when realistic fluid volume-to-metal surface ratios are used
in the laboratory, there will usually be an initial peak in
corrosion rate in formate brines exposed to large amounts
of acid gases while a protective film is formed. Short
duration weight loss measurements with C-steel and
standard 13Cr test coupons under these conditions yield
misleadingly high apparent corrosion rates if extrapolated
linearly over time. Continuous LPR (Linear Polarization
Resistance) measurements calibrated against weight loss
are recommended instead. The LPR measurements should
continue until the protective film has formed and the
corrosion rates have stabilized to a steady state value.
The required time for the film to form depends on
temperature and metal type. If weight loss measurements
are to be used, a minimum of at least 30 days of testing is
recommended. If unrealistically high rates are measured by
this method, one should re-measure over a longer time
period or by use of the LPR method (calibrated against
weight loss).
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2. Be cautious with C-Steel and standard 13Cr wirelines gas influx. In any event, the buffer would have prevented the
in formates. Due to the high fluid volume-to-metal surface brine pH from dropping any lower than 6–6.5. With proper pH
ratio normally seen in wireline operations, extreme care buffering the degradation of biopolymers by acid hydrolysis
should be taken if a large acid gas influx is expected. Even is minimized and the amount of formic acid formed following
buffered formate brines might, in the case of a high an acid gas influx would be significantly lower than in an
volume-to-surface ratio, allow excessive corrosion to take unbuffered formate brine.
place before the protective layer forms.
No Packer Failure
Thiocyanate Back in 2000 it was reported that a SAB3 packer with a
Thiocyanate was added to a formate-based packer fluid in a manufacturing fault that had been pulled from Total’s Elgin
well in Brazil, causing failure in the Duplex 22Cr tubing [30]. G1 well in the North Sea showed signs of cracking in the
Thermal degradation of this sulfur-containing corrosion Alloy 718 component when examined at the surface.
inhibitor in a sodium formate packer fluid caused pitting
corrosion of the string, which was charged with hydrogen as The SAB3 packer failed to seal shortly thereafter and a
a result of galvanic contact with the steel casing. The pits workover operation was initiated within a few weeks.
provided a sufficient stress intensity factor to cause brittle The manufacturer of the packer incorrectly blamed the
fracture of the couplings. Just as in halide brines, the thermal cracking on the cesium formate brine that had been used to
decomposition of thiocyanate at high temperature causes complete the well.
environmental cracking of CRAs. Thiocyanates or other
corrosion inhibitors are not required in formate brines and An investigation carried out by Total into the sequence of
should never be used. events concluded that the cracking incident had not been
caused by cesium formate:
Use of Unbuffered Formate Brine
It is reported [31] that during the period 1996-2000, Mobil 1. The FB3 packer was successfully set and pressure tested
Germany drilled a series of 15 wells in the HPHT gas fields of in a clear cesium formate brine.
North Germany with unbuffered sodium/potassium formate 2. During circulating bottoms up, a hydrogen detector
based drill-in fluids. The BHST of these wells was around showed only trace levels of hydrogen (0.012–0.030%).
150°C / 300°F. For three years Mobil had no problems while Based on this, it was concluded that there was no
drilling these HPHT gas wells with formate brines but in 1999, evidence of any formate decomposition and that corrosion
while tackling a gas kick in their Soehlingen Z 13 well, a was either nonexistent or minimal. pH was also monitored
routine gas analysis showed the presence of measurable throughout and was within the range of 9.5 to 10.0 at all
levels of molecular hydrogen in the unbuffered formate brine times.
[31]. It was suggested at the time that the hydrogen gas 3. The completion was then run in cesium formate with an
could have originated from the decomposition of formic acid integral SAB3 packer. Once this had tagged the FB3
in equilibrium with formate ions at the low fluid pH temporarily packer the string was spaced out for the hanger and the
created by the influx of a gas kick containing CO2. After the well was displaced firstly to potassium formate, and then
addition of potassium carbonate, to raise the pH and create to water inhibited with sodium thiocyanate. (Prior to this,
some pH buffering in the fluid, no further dissolved hydrogen tests were successfully run in a flow loop using cesium
gas was detected. formate brine to check a) the feasibility of circulating the
brine under HPHT conditions without causing damage to
With the benefit of new understanding created by Hydro the SAB3 packer and b) the ability of the packer to seal
Research’s decomposition testing on formate brines under afterwards.)
realistic hydrogen pressures (Section 10), we can now be 4. The SAB3 packer failed to seal shortly thereafter and a
fairly sure that the cause of hydrogen evolution in the workover operation was initiated within a few weeks.
Soehlingen well (maximum temperature of 150°C / 300°F) During the kill operation the well was again displaced to
was not the decomposition of formic acid. At the low pH cesium formate. In all, the SAB3 packer was exposed to
levels that can be temporarily created downhole in an cesium formate for no more than a couple of days.
unbuffered formate brine under static conditions during a
CO2 influx, it is more likely that other reactions (e.g. corrosion, The operator believes that the cracking of the faulty packer
or polymer degradation) could have generated the hydrogen was caused by the presence of thiocyanate in the inhibited
gas seen in the Soehlingen well. Without the protection water. Thiocyanates are known to decompose to H2S at high
against CO2 corrosion provided by a carbonate/bicarbonate temperatures and cause cracking of CRAs in HPHT wells
buffer, corrosion rates in the formate brine following an acid [28]. Over the past 6 years similar packers constructed of
gas influx could have been significant. alloy 718 have successfully been exposed to cesium formate
brines in a further 8 Elgin wells, under essentially the same
Regardless of the actual cause of the hydrogen evolution in downhole conditions, but without sodium thiocyanate added
this well; it was shown to disappear with proper buffering. to the packer fluid.
Had the formate brine been properly buffered from the start,
it is unlikely that the pH would have dropped during the acid
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