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F O R M AT E B R INE S – COMPATI B I L I TY W I TH ME TAL S

Formate Brines
Compatibility with Metals

Photo: Courtesy of Sandvik

Authored by Siv Howard, Formate Brines Consultant

Reviewed by Derek Milliams, Advanced Corrosion Management Services


Frank Dean, Ion Science

Commissioned by Cabot Specialty Fluids

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

Purpose and Scope 3


Acknowledgements 3
Summary 3
1 Introduction to Formate Brines 4
2 Introduction to Oilfield Corrosion 4
2.1 Types of Corrosion 4
2.2 Types of CRAs and how they are chosen 5
3 HPHT Field Experience 6
4 What Makes Formates less Corrosive than Other Brines? 7
5 The Carbonate/Bicarbonate pH Buffer in Formate Brines 7
5.1 How the Carbonate/Bicarbonate Buffer Works 7
5.2 Buffer Protection against CO2 (H2S) influx 8
6 Corrosion in Formate Brines in the Absence of Corrosive Gases 10
7 Corrosion in Formate Brines Contaminated with CO2 12
7.1 CO2 Corrosion 12
7.1.1 CO2 Corrosion of C-Steel 13
7.1.2 CO2 Corrosion of 13Cr Steel 14
7.1.3 CO2 Corrosion of Higher Alloy Steels 16
7.1.4 CO2 Corrosion Rates 16
7.2 Impact of CO2 on SCC 19
7.2.1 Testing by Hydro Corporate Research Centre 19
7.2.2 Testing by Statoil at Centro Sviluppo Materiali 20
8 Corrosion in Formate Brines Contaminated with H2S 21
8.1 Impact of H2S on General and Pitting Corrosion 21
8.2 Impact of H2S on SCC and SSC 21
8.2.1 Sulfide Stress Cracking (SSC) of Carbon and Low Alloy steels 21
8.2.2 Cracking of CRAs in H2S Containing Environments 22
8.2.3 High-Temperature Testing by CAPCIS 22
8.2.4 High-Temperature Testing by Statoil at Centro Sviluppo Materiali 24
8.2.5 Low-Temperature Testing by CAPCIS 24
8.3 Use of H2S Scavengers in Formate Brines 25
9 Corrosion in Formate Brines Contaminated with O2 26
9.1 Impact of O2 on SCC 26
9.1.1 Testing by Hydro Research 26
9.1.2 Testing by CAPCIS 27
9.1.3 Testing by Statoil at Centro Sviluppo Materiali 28
9.2 Use of O2 Scavengers in Formate Brines 28
10 Catalytic Decomposition of Formates – a Laboratory Phenomenon 29
11 Hydrogen Embrittlement of Metallic Materials in Formate Brines 30
11.1 Hydrogen Embrittlement 30
11.2 Sources of Hydrogen 30
11.2.1 Hydrogen Charging from Galvanic Coupling 30
11.2.2 Hydrogen Charging from Formate Decomposition 30
11.3 Field Evidence – Total’s Elgin Wells G1 and G3 31
12 Avoid Pitfalls in the Laboratory! 32
13 Avoid Pitfalls in the Field! 33
13.1 Four Simple Rules for Avoiding Corrosion in Formate Brines 33
13.2 Examples of Incorrect Use 33
References 35

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Purpose and Scope Summary


Cabot Specialty Fluids (CSF) is in the process of writing a The corrosivity of formate brines used in drilling, completion,
formate technical manual. This manual will cover formate workover, and packer fluids for HPHT wells has been
brines and their application in well construction operations: thoroughly investigated over the past few years. One of the
chemical and physical properties, compatibilities and drivers for this activity has been a spate of costly well
interactions, applications, and Health, Safety and integrity failures that have been reported after operators have
Environmental aspects. While preparing the manual, CSF used the traditional high-density halide completion brines.
has received numerous enquiries for information about the
corrosion characteristics of formates. In response, CSF Laboratory and field experience has shown that buffered
decided to commission a seperate review on metal formate brines are considerably less corrosive than other
compatibility of formate brines. The outcome of this review is brines at high temperatures, even after exposure to large
reported in this document. The report includes some basic influxes of acid gas.
corrosion theory, a review of laboratory test results with
formate brines, best practice procedures for testing formates, Over the past 10 years, formate brines have been used in
advice on the proper field use of formates, and some more than 130 HPHT well construction operations where
examples of improper use of formates in the field. they have been exposed to temperatures of up to 216°C /
420°F and pressures of up to 117.2 MPa / 17,000 psi.
There is no record of any corrosion incidents being caused
Acknowledgements by buffered and correctly formulated formate brines under
these demanding conditions.
Some of the experimental work described in this document
was undertaken for CSF by Hydro Research and CAPCIS The low corrosivity of the formate brines is attributed to the
Ltd. Other sources of information have been SPE and NACE benign properties of the brine itself. Formate brines have a
papers, and personal communication from corrosion naturally alkaline pH and can be buffered with carbonate/
researchers and consultants. bicarbonate buffers to maintain a favorable pH even after
large influxes of acid gas. As a matter of fact, it has been
In addition to the two reviewers Frank Dean, Ion Science, and shown that the pH in buffered formate brine never drops
Derek Milliams, Advanced Corrosion Management Services, below about 6–6.5 when contacted by acid reservoir gases.
I want to thank the following people for their valuable Formate brines contain very low levels of halide ions, and are
contributions and advice: Peter Rhodes (Consultant), Salah thereby free of the corrosion problems commonly associated
Mahmoud of MTL Engineering, John Herce of MTL Engineering, with halides such as pitting and stress corrosion cracking.
Neal Magri of Technip Offshore, Inc., and Mike Billingham of Even with a significant level of chloride contamination, formate
CAPCIS. brines have been shown to outperform uncontaminated
bromide brines. And last but not least, the formate ion is an
In addition, I want to thank Cabot Specialty Fluids for anti-oxidant, which limits the need for adding oxygen
supporting the preparation of this review, and especially John scavengers, and avoids the problems that can occur when
Downs for his valuable technical contributions and editing. these scavengers become depleted.

With the growing awareness of the shortcomings of the


halide brines, it is expected that formate brines will have an
increasingly important role in future HPHT well construction
operations.

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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

Figure 1 Factors required for stress corrosion cracking (SCC).

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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].

General application limit


Group Name Cr % Ni % Mo %
[°C] [°F]
13Cr 13 -- -- <150 <300
Martensitic Modified 13Cr-1Mo (M13Cr) 13 4 1 <175 <350
Modified 13Cr-2Mo (S13Cr) 12.5 5 2 <175 <350
22Cr 22 5 3 <200 <400
Duplex
25Cr 25 7 4 <250 <480

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F O R M AT E B R IN E S – COMPATI B I L I TY W I TH ME TAL S

3 HPHT Field Experience


Over the last 10 years formate brines have been used in more Since their first use in HPHT wells, there have been no
than 130 HPHT applications at downhole temperatures as high corrosion incidents caused by formate brines when used
as 216°C / 420°F and at pressures up to 117 MPa / 17,000 psi. according to the guidelines described in this document.

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

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F O R M AT E B R INE S – COMPATI B I L I TY W I TH ME TAL S

4 What Makes Formates less 5 The Carbonate/Bicarbonate


Corrosive than Other Brines? pH Buffer in Formate Brines
There are several features of formate brines that make them Formate brines provided for field applications should be
inherently less corrosive than other brines used by the oil buffered by the addition of potassium or sodium carbonate
industry. and potassium or sodium bicarbonate. Typical recommended
levels are 6 to 12 lb/bbl of potassium carbonate or a blend of
Halide-fee potassium carbonate and potassium bicarbonate. The main
Conventional halide brines (NaCl, KCl, NaBr, CaCl2, CaBr2, purpose of this buffer is to provide an alkaline pH and to
ZnBr2, and their blends), and particularly chlorides, are known prevent the pH from fluctuating as a consequence of acid or
to promote several forms of corrosion. Localized corrosion, base influxes into the brine. The buffer also plays a very
such as pitting and SCC are promoted in halide environments, important part in encouraging the formation of the high quality
and the severity increases with increased halide concentration. protective carbonate film on the steel surfaces.
Even after contamination with moderate levels of chloride
ions (Cl-), formate brines still retain their non-corrosive 5.1 How the Carbonate/Bicarbonate Buffer Works
characteristics in most applications. A pH buffered solution is defined as a solution that resists a
change in its pH when hydrogen ions (H+) or hydroxide ions
Antioxidant (OH-) are added. The ability to resist changes in pH comes
Oxidants, such as O2 are known to cause corrosion about by the buffer’s ability to consume hydrogen ions (H+)
problems. The formate ion is a well-known antioxidant or free and/or hydroxide ions (OH-).
radical scavenger, used in many industrial and medical
applications. The carbonate/bicarbonate buffer system provides strong
buffering at two different pH levels:
Favorable alkaline pH
Formate salts dissolved in water exhibit a naturally favorable • Higher buffer level at pH = 10.2
pH (8-10).
Ÿ Ÿ P+A Ÿ
( ←
#/ #/ ( →←(#/
⎯⎯
P+A
⎯⎯ 3 (#/3

Ÿ (1)
 PKT


 PKT 

In non-oxygenated solutions, corrosivity is determined in part


Ÿ Ÿ
P+ #/ Ÿ Ÿ(#/
Ÿ
by pH. The lower the pH, the greater the tendency for where P+ A =  #/ 10.2 #/  P+ (#/ Ÿ
  ( ←⎯ → (#/3  PKT
A ⎯ A 

corrosion. In addition, pH determines the stability/solubility of #/



 A ( P+←
P+A Ÿ
⎯⎯→ (#/ Ÿ P+A Ÿ
 PKT
A #/ ( ← 3⎯ ⎯ → (#/  PK


Ÿ P+ 

(#/ 10.2
At pH=(#/
( (← Ÿ
P+ ⎯ ⎯→←(⎯
( ⎯ #/ →Ÿ ( #/


(#/ PKTŸ
PKT 3
A ) the #/


corrosion scales. buffered 


solution  contains
 the same
Ÿ Ÿ
amount of carbonate P+ P+A
Ÿ (Ÿ#/ P+ Ÿ )Aand bicarbonate (#/
#/ 

( (#/ ).
Ÿ
P+AŸ
#/ #/ P+((#/ Ÿ←⎯
A (#/ ( ⎯ A
→Ÿ(#/
(#/ ← ⎯(
P+
⎯ (
A #/
→  (P+
(#/


#/
 A Ÿ
(  PKT
#/  PKT
3 ← ⎯ ⎯ → PKT


Traditional high-density halide brines typically have pH values




   3   
Ÿ P+A Ÿ P+A
of between 2 and 6 (depending on the type of halide) and are • Lower buffer Ÿlevel at pH
(#/ ( =(#/ ← 6.35
Ÿ ⎯⎯ → ( (#/
←⎯⎯ → (#/ 
PKT PKT


#/
P+AG P+ #/#/ #/  G AQ

P+ #/ Ÿ Ÿ (#/
AQ  (#/ ŸP+A Ÿ PKT Ÿ PKT 
#/ A (#/ ( ←⎯⎯→  ( (#/  #/3  PKT
A   

therefore naturally more corrosive than formate brines. Ÿ Ÿ P+A Ÿ Ÿ


ŸP+P+ (#/ ((#/ #/

Ÿ A A #/ P+A  P+  A( ← ⎯ ⎯→  (#/( 3  #/

 PKT
P+(#/
#/  AQ #/
 (#/ (( /AQ
 Ÿ
 ← (
P+

((⎯
#/ / → AQ
← ( (
⎯#/ ⎯ #/ →  AQ Ÿ( #/

(2)
PKT
PKT Ÿ PKT
PKT PKT
 #/  AG #/ #/  (#/
Ÿ A  
 AQ


Compatibility with Carbonate-based pH buffer #/ ( ← ⎯ ⎯ → (#/ 3

 PKT
    


Ÿ
 #/  AQ (#/ PKT PKT

+ A #/ Ÿ  G  #/ P+A#/ AQ   G #/
The only truly reliable protection against corrosion from acid P+
(  #/
Ÿ where A  AQ ( ← (#/ (#/ + AŸ Ÿ
 → AQ((#/  #/ (Ÿ  ( AQ
AQ P+  PKT
P+ A = 6.35  PKT
#/ ⎯ ⎯ → AQ (#/ Ÿ


#/ P+ (  AQ(
(#/ ← ⎯⎯ ( #/Ÿ
PKT


PKT
A
Ÿ #/   AQ Ÿ( / ( #/  AAQ
P+A #/ (#/ ← ⎯ ⎯ → 

gas (CO2 and H2S) is to pre-treat the receiving brine with a


 #/ 
 ( Ÿ←⎯⎯ → (#/ P+A 3

 PKT
#/  AQ (#/
( /  #/   Ÿ(
( #/ AQ  AQ
( ←  ⎯
/  ⎯→ (
( #/
Ÿ  OKT   AQ #/  PKTPKT 
PKT
 OKT
Ÿ  

carbonate/bicarbonate buffer. The buffer not only helps to(#/ ( ←At #/
#/
P+A   G #/
pH
 AQ #/ #/


G  
( AQ
AQ

#/
((P+
#/  (  AQ
AQ
#/
→  (#/
+AAQ Ÿ→    AQ
Ÿ (#/
PKT
  AQ
PKT 
→=(6.35 A )AQ the buffered
(#/ solution
 AQ(  #/ contains the
 PKT
Ÿ
 #/ ← ⎯→ (#/ (  AQ Ÿ
#/ PKT
  
⎯ 
⎯⎯


 Ÿ 


 P+ A + A #/ Ÿ (#/ 
maintain the brine pH in the safe alkaline zone but also same amount + (of #/bicarbonate
 + AQ P+ ←⎯ ⎯→ ( #/ (#/ ((#/ Ÿ
 AQ  AQ
← ⎯
+A
⎯ ) (and
→ (#/

AQ( Ÿ#/
carbonic  AQ  PKT
(  AQ 
 PKT
(AŸ AQ
#/  AQ #/
Ÿ#/  G
((/ / G↔
AQ 
(#/
(#/ (/ ŸŸ AQAQ
AQ ((#/ #/
 AQ Ÿ(AQ
PKT
 PKT
P+A PKT
  PKT
Ÿ
 OKT
promotes metal passivation. P+A (#/acid ( (#/  #/  
 ). #/ #/ /↔
(#/  G  (
Ÿ#/
(
 AQ

#/←
#/
AQ

P+

 AQ
A
(→←
→ (#/
(⎯ #/⎯→
 AQ PKT
Ÿ (#/3 PKT
Ÿ  
 P

#/  ŸAQ #/ Ÿ  (#/ G #/  AQ →((#/   AQ (#/  OKT   OK
PKT
 #/   AQ 
Ÿ Ÿ
+A  #/ AQ →   AQ
( #/  AQ ( #/ ←⎯ ⎯  →Ÿ (#/
AQ ←
#/G ⎯
+ A  AQ (
⎯ AQ →
Ÿ( (#/
PKT
Ÿ+  AQ
 AQ


(
 AQ  PKT
( ŸAQ  PKT PKT
⋅ ; (#/ ==⋅ ;P+ = (//↔  (#/ ( #/ AQ  AQ  PKT

 Ÿ
Traditional high density completion and packer fluids based#/  G  #/ The AQ exact ; ( =levels ; ( #/ of P+A ŸŸwill (#/
Ÿ
A and+(#/ vary somewhat with
+ (#/ #/ ( + #/
+
#/0  G (#/  AQ  G ( Ÿ/  ( #/
 PKT
 AQ Ÿ  PKT
 AQ 
 PKT PKT
0#/  /↔ (#/ AQ (  PKT

on divalent halide brines (CaCl2, CaBr2, ZnBr2) cannot be #/ Ÿ
brine concentration,
 AQ
#/  AQ  Ÿ (   temperature,
#/ #/  AQ
( #/ → ⎯ 
AQ
#/(#/
+A →
 and

Ÿ(#/ AQ(  / ↔
pressure.
Ÿ  OKT
(#/

 ( P+
AQ
 OKT
(  AQ
  AQ

AQA

#/  AQ (/  (#/  AQ  ( #/
#/  AQ PKT ←
 ⎯→
(#/ Ÿ (#/
 AQ  + A ( ←
Ÿ
  AQ


( #/  PKT
PKT PKT
buffered because even small amounts of added carbonate/ ; (  =G⋅ ; (#/  #/  =
⎯ ⎯ → 

 
+ +  ( #/  ŸAQ ← ⎯ ⎯→ (#/ŸŸ  AQ (  AQ PKT  PKT


( ;/ = (#/ = ⋅ ;#/ =#/



bicarbonate buffer are precipitated out. Carbonate/bicarbonate P(
#/  ŸG LOG
P( ( ↔ LOG #/ ;; ( (
Ÿ+ 0 
Ÿ AQ
 =AQ (#/ (Ÿ AQ
( ; ( = ⋅ ; (#/
 AQ  PKT
 =
 PKT
(#/  PKT
Ÿ
 PKT
 AQ  OKT
( #/  AQ ←⎯ ⎯→ (#/  AQ  (  +
+A #/ G (
AQ  / ↔  (#/
 PKT
 (+P+
AQ  (
A (#/ (#/
 AQ →  Ÿ
( #/ 
 PKT  PKT
 PKT
  
#/   AQ 0#/ /  AQ 
buffers are soluble in formate brines, and can be formulated #/Ÿ  ŸAQ  (0#/ #/    AQ → (#/  AQ
Ÿ
  OKT
P(  Ÿ LOG P( + Ÿ Ÿ LOG LOG 0#/ +
Ÿ Ÿ LOG LOG0;#/ (#/ +
 = ; (#/
LOG
Ÿ
=  PKT  PKT
to make fluids that remain pH stable in the face of quite large = ⋅ ; (#/ P(  LOG ; ( =
 OKT

 PKT
⋅=;(#/

#/  AQ ( #/  AQ ; ( →
 (#/
; ( =#/
Ÿ
 AQ Ÿ (
  G =

 /↔ + A(#/  AQ
Ÿ 
Ÿ (  AQ

 PKT
←#/  G + #/   AQ (  AQ  PKTPKT

+ (  #/    AQ ⎯ ⎯→ (#/   AQ


influxes of CO2 . 0
+ 0
0 #/  P(
(#/
Ÿ
0
 LOGŸ  #/ ; (  GP( = ( LOG(#/
 /↔
; (  PKT
= Ÿ  AQ  PKT (  AQ  PKT  PK
 PKT
#/ #/(#/
+ #/ 
P(  
Ÿ LOG 
+ Ÿ LOG  0 LOG ; (#/
Ÿ
=  PKT  OKT
; ( = ⋅ PKT
Ÿ
#/  G ( / ↔ (#/  AQ (  AQ #/ Ÿ  AQ #/ ( Ÿ #/
 #/AQ  ( AQ / →(Ÿ#/ (#/   AQ
Ÿ
  AQ Ÿ 
PKT
; (#/  =
 PKT
In order to fully understand how the buffer in the formate P( +  ŸŸ LOG + Ÿ LOG P( 0 Ÿ LOG
#/   AQŸ (#/
LOG +;Ÿ (#/ LOG0#/ = Ÿ LOG; (#/  =
 PKT  P
(#/
P(  LOG P(AQ
( #/; ( LOG = AQ
(#//
 0 #/ ; ( (#// = AQ (#/ 0 #/ (#//(
;Ÿ( ŸAQ = ⋅ ; (#/ (#//(  =  PKT AQ   AQ (#/ Ÿ  AQ
 PKT  PKT  PK
+
 PKT
 +
brine enhances the corrosion protection provided by the ; ( = ⋅ ; (#/ =
Ÿ
0#/ #/  G (#/ (0 (
/Ÿ ↔ #/

0(#/  AQ Ÿ←  AQ⎯
+A
⎯ →
Ÿ ( (#/ Ÿ
 AQ  AQ (  AQ

 PKT

 PKT
#/  (#/
+  PKT  #/
formate brine itself, one first needs to understand how this 0#/ P+
P(   (
Ÿ #/
 P+A  (#/
LOG +
P(  Ÿ LOG Ÿ 
LOG 
(P(
0
+ #/ Ÿ LOG
 AQ 0
LOG ;
(#/
P+
(#//
Ÿ

A ; (#/
LOG =

(#//( P+
Ÿ
 AQ
Ÿ
= 
(#//(
  PKT



(#//( 

 
 PKT
 
AQ  (#/ Ÿ
 AQ 
A

#/   LOG 
#/ ;
  #/ (  =  Ÿ
 AQ  A
( #/  AQ →  PKT (#/Ÿ  AQ   O
Ÿ
buffer works and how it reacts to influxes of common acid ( #/  AQ (#//
 ŸŸ
 AQ  (#//(  AQ (#/  AQ 
0#/ ( 0 (#/
Ÿ   ; ( P( = ⋅ ; ( LOG
(#/  #/ ;= 
( AQ = (#// Ÿ
 AQ  (#//(   AQ
 PKT(#/ Ÿ
  AQ
gases such as CO2 and H2S. &E  #/&E  AQ ( P+ #/ →(#/ +&E ( Ÿ →
AQ AQ &E  ž (
0AQ


  G LOG ž ( (#/ Ÿ
Ÿ AQ Ÿ  AQ  PKT
 PKT
#/   #/    ; + G 
P+ (#//(
= (#/ 
 PKT
   PKT
P(  LOG ; ( =

P( A Ÿ LOG + 0 Ÿ
 PKT
 LOG
#/  #/  (#/ A Ÿ
(  AQ  PK

#/  G ( / ↔ (#/   AQ
P+A  ( #/ P+
Ÿ   P( ŸLOG   +(Ÿ#/ LOG0 #/P+
 LOG
 A (#//(
Ÿ ; (#/ Ÿ=P+
Ÿ
 A (#//(  PKT
 
(
&E #/ (#//(
 ( AQ
&E#/
(#//( (#//
 AQ
0 #/ → &E 
 AQAQ  
AQ Ÿ(#//(

 PKT&E A (  GAQ
ž 
AQ ž
#//( (#/
(  AQ Gž ( 
 #//(

AQ
AQ  PKT
Ÿ
 AQAQ  PKT
Ÿ  PKT  PKT
 Ÿ AQ ( (#// AQ (#//( 
&E #/ →
(#/  AQ
Ÿ
→ &E
 
 AQ (#/
 G (#/  AQ  P
P(  Ÿ LOG + Ÿ LOG 0#/ LOG ; (#/ = P( LOG  
 ; ( =
  
 PKT


&E ( #/ 0#/ AQ &E → ;


((#/
&E
(  Ÿ
#/ = ; AQ
(#/
 AQ
Ÿ
ž = ( &E  G


AQ (#/
ž
Ÿ
(  AQ 
G (#/ P
Ÿ
  AQ
⋅  →
Ÿ P+  (P+ #/ Ÿ    
+A (#//(      
 P+  PKT
  
0#/ (#/ &E A #/

&E  A ↔

(#/
&E#/
&E #/ (
Ÿ  S
 #/ (#//(
↔  AQ
&E#/ 

 
AQ S
(#// → P+ &EŸ  (#//(
A AQ
0  AQ

(#//( ž (  PKT
 
G
AQ #//(
(#/ ŸŸ
 AQ
 AQ  PK
 P 
  
P(  Ÿ LOG + Ÿ LOG 0#/
 #/ 
LOG ; (#/
Ÿ
=   PKT


&E (#//( (#/  &EAQ  AQ → &E


(#//( (#//  AQ AQ Ÿ ž AQ
→ ( &E  G(#//(  AQ #//(
ž  AQ
(
Ÿ
 AQ
G (#/  P
#//(
Ÿ
  AQ  AQ
Ÿ
( 3
&E Ÿ( G&E #/(  (( AQ 3 P+ AQ &E 
AQ AQ &E#/  ž ( PKT
ž (  G (#/
Ÿ
(#/
AQ Ÿ  AQ  PKT
 3 G
&E 0
→( 3  → PKT
 #/ AQ Ÿ &E ŸAQ
AQ ( #/  (#/     P+G PKT
 A  (#//(   PKT
 PKT

(#/ P A AQ 7(#//  AQ (#//( A #/  (#/ ↔
P( 
ŸAQ
  S 
 LOG ; ( =
GE #/ 
 P

P+↔ A &E (+#/  S ↔  &E#/Ÿ  SP+   PKT
(#//(  

 PKT

P+A &E #/ &E#/
  Ÿ
#/
&E 3
( (#//(
AQ&E (← 3P+⎯ ⎯  AQ
AQ → ←
(#//( →(3 P+ &E− A AQ


 AQ
(+&E 3 −( ž ( AQ 
 G( (
 +
#//(
PKT
 
AQ Ÿ PKT
PKT A
Ÿ  PKT
 (#//(  AQ  AQ  +  G #//(  AQ


P+A  (#/    ( &E 3 ⎯ ⎯


G ( → 
#/ →  (3    AQ
 AQ
AQ → &E ž

 AQ
AQ ž (  G PKT
(#/  AQ  
A 
 ( #/

  AQ

  (#//  AQ  (#//(
P(  Ÿ LOG + Ÿ LOG 0#/
Ÿ 
 LOG ;(#/ AQ  =
Ÿ
(#/
 Ÿ
  AQ  P 
( 3  G  &E ( 3
((  AQ3
#/  G  AQ ( → 3 &E AQ
Ÿ  G +  PKT


 AQ ž PKT
(  G (#/ Ÿ
 AQ
PK 
(#//
&E #/
Ÿ
 AQ
(#//
 Ÿ
( Ÿ /
&E#/

AQ Ÿ ←⎯→
AQ
CAT
&E#/S ( (#/   Ÿ
CAT  AQ − ( 
 PKT
  PKT
 
/ (#/   AQ + Ÿ ( P+ ( ( G G PKT
↔ ←
P+
 S⎯→  PKT
ž(&E 3  ↔  ← 
#//(  AQ  
Ÿ

&E ( #/  AQ → &E &E  #/
G(#//( ŸAQ
→ (3 &E AQ
A
 AQ (  P+ ( (#/ ⎯
#/ ⎯ 0

 AQ →  AQ (#/ PKT

ž
 AQ
A  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

P("EHAVIOROF#ARBONATE"ICARBONATE"UFFER7HEN!DDING3TRONG!CID


P+A



P(

P+A




                  
&RACTIONOFBUFFERCONSUMED

!DDITIONOFSTRONGACID

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.
Ÿ P+A Ÿ
#/
#/ 
Ÿ (
converted ←⎯
← ⎯ ⎯
P+
(to carbonic
⎯A → (#/ Ÿ
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
Ÿ Ÿ
P+ Ÿ (#/ Ÿ
A ( #/
level. amounts of CO2. Unless the influx is unusually large, the
P+A Ÿ
P+A
#/

←⎯⎯ #/
 → (#/

  PKT 3 (#/
brine will maintain a pH (at around the upper buffer level)
Ÿ Ÿ P+A Ÿ
P+A Ÿ#/ (#/ 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
Ÿ P+A
(#/ ( ←⎯⎯Ÿ→ (#/ 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 (#/Ÿ
(#/ ( #/
( #/
brines
P+
A is influx of carbon dioxide
(#/
Ÿ 
( #/  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,
 
 

meaning that this brine system cannot be “acidified” to


#/  AQ
#/
#/  AQ
( /( /
   (#/  AQ
( #/  AQ
  AQ ( /  (#/  AQ
PKT
(4) PKT
PKT any great extent by exposure to CO2.
+ A
( #/  AQ ←⎯ ⎯→+(#/  AQ (  AQ Ÿ


 PKT
 PKT
A Ÿ
(#/
#/  AQ ←⎯ +⎯A → (#/Ÿ  AQ (  AQ

(5) • Unbuffered formate brines: The pH of these brine
(  Ÿ   AQ ←⎯ ⎯→ 
(#/  AQ Ÿ (  AQ  PKT
#/  AQ ( #/  AQ → (#/  AQ   OKT systems behaves very much like halide brines when
Depending
#/
#/

  AQ
Ÿ AQ +
on(the #/
( #/ pH inAQ
 AQ the
→ brine
(#/ Ÿ
system,
  AQ
Ÿ  OKT
the dissolved CO2
  OKT exposed to CO2 gas. However, they do have a higher initial
→ (#/  AQ 
#/ 
will  Gremain ( / ↔ in(#/
Ÿ
 AQ  (
thebrine as AQ
either  PKT
carbonic acid (H2CO3) or pH, and the pH drop will be limited as the formate brine is
-
bicarbonate (HCO +
+ 3) according to the equation 5. This is a buffer in itself (pKa = 3.75). If there is any chance of an
#/;(G
#/ G =
demonstrated
; (#/

( /
( /Ÿ ↔
=
(#/
↔ (#/
  in Figure
Ÿ
  AQ
Ÿ AQ (  AQ
  3. more
As (  AQCO gas enters  PKT
 PKT
into the acid gas influx, the use of unbuffered formate brines is not
+   PKT
2
0#/
brine, the carbonic acid concentration builds up and the pH recommended.
drops ;((and =⋅;
allows
(#/Ÿunbuffered
Ÿ
= brines to acidify.
+
P(  ; LOG = ⋅ ; (#/
 ; ( =  =  PKT PKT
+ 0#/  PKT
0 #/ 
P(  Ÿ LOG + Ÿ LOG 0#/ LOG ; (#/ =
Ÿ
 PKT

 ;( =
0#/  LOG
P(
P( (#/
 LOG

Ÿ

 ; ( =
 PKTP A G E
 PKT
8

( #/  AQ (#//Ÿ  AQ  (#//( AQ Ÿ (#/Ÿ  AQ  PKT


P(

Ÿ
ŸLOG
LOG+
+ŸŸ LOG
LOG00#/ LOG ; (#/Ÿ =  PKT
 PKT
P(  #/  LOG ; (#/ =
P+A  (#/   P+A  (#//(  
Ÿ
F O R M AT E B R INE S – COMPATI B I L I TY W I TH ME TAL S

P(IN6ARIOUS"RINE3YSTEMSASA&UNCTIONOF#/)NFLUX6OLUME



"UFFEREDFORMATE P(

#/MAINLYCONVERTEDTO
 BICARBONATE(#/
WHICHDOESNOTPROMOTECORROSION
P( 
5NBUFFEREDFORMATE


 P(
#/MAINLYCONVERTEDTO
 CARBONICACID(#/
#ALCIUMBROMIDE WHICHPROMOTESCORROSION

          
"",'ASI NFLUX"",BUFFEREDFORMATEBRINE#/  ª#ª& ATM

)NCREASINGTIMEOF#/INFLUX

Figure 3 pH as function of CO2 influx in a typical halide brine, an unbuffered formate brine, and a buffered formate brine.

Influx of CO2 into a wellbore is often accompanied by


hydrogen sulfide (H2S). H2S is a very weak acid with a pKa1 at
around 7. H2S corrosion is generally suppressed in alkaline
scenarios by the formation of non-soluble sulfide films.
Therefore sustained corrosion by hydrogen sulfide in the
presence of buffered formate brines is unlikely to occur.

In order to get the full benefit of the carbonate/bicarbonate


buffer in the formate brine, both the buffer level and buffer
capacity need to be maintained during field use. Over-
treatment with potassium carbonate is most often not a
problem.

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

6 Corrosion in Formate Brines in


the Absence of Corrosive Gases
In the absence of corrosive gasses and within the operating The general corrosion rates of C-steel and CRAs in formate
envelope of the specific metal (as defined in Table 1 and its brines are negligible regardless of the temperature. Localized
associated text), formate brines are essentially non-corrosive to corrosion and SCC have never been observed. The use of
all forms of steels used in oil and gas well construction, even corrosion inhibitors in formate brines is neither necessary nor
when contaminated with chloride ions. Table 3 and Table 4 list recommended.
general corrosion rates for a variety of formate brines at
temperatures up to 218°C / 425°F, collected from various
published and unpublished sources [3].

Table 3 General corrosion rates of C-steel in formate brines.

Density pH Temp. days P-110 C-110 Q-125


Fluid (diluted
s.g. ppg 1:10) °C °F mm/y MPY mm/y MPY mm/y MPY
NaFo 1.26 10.5 10.0 163 325 7 0.008 0.3
CsFo 12.0 163 325 7 0.000 0.0
CsFo + 5% KCl 2.18 18.2 10.5 177 350 40 0.076 3.0 0.065 1.0 0.051 2.0
CsFo 12.0 177 350 7 0.003 0.1
CsFo 10.0 191 375 ? 0.005 0.2
CsFo 10.0 204 400 17 0.008 0.3
CsFo 1.94 16.2 218 425 30 0.177 7.0

Table 4 General corrosion rates of CRAs in formate brines.

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
Ÿ
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
#/ GŸ  #/   AQ P+A Ÿ
PKT
#/Ÿ ( ←⎯ P+⎯ → (#/Ÿ3 
 PKT
#/Ÿ ( ←⎯ ⎯ A
→ (#/3Ÿ 
 PKT
#/  AQ (/  (P+
#/ ( ←⎯ #/
Ÿ ⎯→ (#/3

A
  AQ
Ÿ

PKT
 PKT
7 Corrosion in Formate Brines P+A acid
Carbonic #/will Ÿ then be consumed
(#/Ÿ by the carbonate buffer
P+A #/ (#/ Ÿ
Contaminated with CO2 according
(
P+ #/  AQ ←
A Ÿ #/
to⎯ +A
⎯ the →Ÿfollowing
(#/ P+A
Ÿ

 AQ (#/ reaction:
(  AQ

 PKT
(#/Ÿ ( ←P+ ⎯⎯ → (#/ 
PKT
(#/ Ÿ  Ÿ ( ← ⎯ ⎯ A

P+A AQ → (#/
( #/  Ÿ

PKT
 OKT
Carbon dioxide (CO2) influxes emanating from leakage of #/  AQ
(#/ ( ←Ÿ⎯⎯→ (#/
 ( #/
    AQ


PKT(6)
reservoir gases into the well environment are common P+A (#/ #/ #/
Ÿ ( ←
Ÿ Ÿ
(( #/
P+
← ⎯
P+
⎯ (#/ → (#/
Ÿ Ÿ
 PKT
 PKT
A
A

Ÿ (#/
P+A case +  P+
 ⎯
 ⎯
( #/ favorable→  3 3
Ÿ
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
#/ / ↔← Ÿ⎯
(#/ ⎯Ÿ→  AQ ( #/ (3  AQ  PKT
P+  ŸŸ Ÿ Ÿ Ÿ Ÿ P+ Ÿ
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 #/   Ÿ
carbonate
3
(#/
component

Ÿ 
PKT
of the pH buffer is


#/;( GA = ⋅#/
; (#/

Ÿ AQ
(#/

Ÿ Ÿ
= Figure Ÿ( 3). ←
(Ÿ⎯
P+  P+
⎯→ (→ #/( #/ PKT PKT Ÿ
A
Ÿ
(#/ PKT (#/
A
sub-surface equipment and tubulars. P+
overwhelmed #/ (see (#/ ←⎯⎯ P+ #/
+#/ 
A  AQ
#/(#/  AQ 0
 ( /
Ÿ( /  ( #/
 ( ←
 ( 
 ⎯
#/ P+

  AQ
 AQ
 → ( #/

PKT
 A
 PKT
PKT
PKT
A
 

 #/ Ÿ 
#/  AQ Ÿ (  / P+ ( A#/ (#/
P+ AQ  Ÿ ( #/ PKT Ÿ 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
Ÿ
has
 #/
Ÿ
Ÿ

 AQ


 been
AQ
(



 AQ #/ (

(  AQ
overwhelmed
 AQ  PKT
or PKT
consumed,
PKTtheŸ
;( A =


P(  LOG +
#/  G  
Ÿ
#/  (AQ  AQ

 PKT
 PKT
P+A

PKT
equations, (#/ ( #/
( #/
P+   AQ ←
(#/ ⎯ ⎯Ÿ→ (#/ (

AQ
#/
some years it was thought that the incidence of localized pH will
A decrease according to the following
   which
 OKT
 

#/#/ Ÿ  AQ G  #/ #/   AQ  OKT


PKT
 Ÿ Ÿ
#/  AQ ((
#/  #/
AQ
 AQ (AQ / → →
( #/ (#/(#/
 AQ Ÿ  AQ  AQ  PKT
corrosion of CRAs would be restricted to wells where are also valid for  unbuffered 
brines:  

 PKT
 

P( 
#/
#/

Ÿ LOG
G  AQ#/ + Ÿ( LOG#/
  AQ 
0#/
#/  AQ LOG (; (#/
 AQ → (#/
/  ( #/
Ÿ
= Ÿ AQ
  AQ
PKT #/ OKT PKT
  G  #/  AQ
   
chloride brines became contaminated with oxygen. More #/  AQ ( (  /
++ #/ (#/ AQŸ Ÿ←  AQ
⎯⎯ → (#/  AQ
 (  AQ PKT

+ A
 PKT Ÿ

 PKT

#/  G ( / (#/  AQ (  AQ

recent research has revealed that bromide brines may cause 0#/AQG (((#/ / ↔

+ (#/
Ÿ
( #/   AQ
AQ +(  AQ Ÿ
←⎯

⎯→ (#/  AQ ((7)  PKT
#/  PKT
 AQ  AQ ( /
A
 ( #/  AQ 
#/
#/  G ( / ↔
/ ( #/
+ (#/
 AQ 
Ÿ
(  AQ PKT  PKT
   
AQ  AQ AQ → (#/
    
pitting and SCC in the presence of CO2 as well [5].   OKT
Ÿ Ÿ
( #/  AQ ←#/  (#/ Ÿ (
 AQ #/   AQ
 PKT
A
 ⎯⎯→ (  AQ 

  OKT
Ÿ Ÿ
#/  AQ +(
((#//(
 #/
  AQ  PKT
→ (#/ ŸAQ ← ⎯
+ A
(( #/
 #/ AQ  AQ
; (
( =←
+A
;⎯
=⋅⋅;⎯ →(#//
(#/
(#/ (#/
Ÿ
==  Ÿ  AQ
Ÿ Ÿ AQ

AQ AQ ((#/
 #/ AQ
 AQ ⎯ Ÿ
→ (#/ PKT
  AQ (  AQ 
Buffered formate brines are very different from halide brines + #/ Ÿ  AQ #/ (Ÿ #/
G (AQ /↔ →
Ÿ
(#/   AQ (
(8)(#/ Ÿ  AQ  OKT
 PKT

  AQ  PKT
 PKT
;( =0 ⋅0;#/
(#/  = 
in the way their corrosivity is influenced by a CO2 influx. The + Ÿ
#/  AQ #/ 
( #/#/  AQ
 G → ( (#/
+
Ÿ
 OKT
(  PKT
#/ Ÿ
( #/  AQ → (#/Ÿ  AQ
AQ   AQ  PKT 
  AQ  AQ 
Ÿ
0#/ / ↔ (#/
P+A  (#/   ;
+   Ÿ P+ A  (#//(  
difference is mainly due to the influence of the carbonate/ #/  G ( / ↔ ( = ⋅ Ÿ; (#/
(#/  AQ =(  AQ  PKT
+  
 PKT
+
+ 0
bicarbonate pH buffer. P(
P(
#/ G

 LOG
LOG
( /  ; ((#/

=
 ; ( =  ; ( = ⋅ ; (#/ =
Ÿ
(9)
 AQ #/ (  AQ Ÿ
 PKT
#/
 PKT
Ÿ
  G ( / ↔ (#/  AQ (  AQ
 PKT
Ÿ

&E
P( (  #/
LOG   AQ +→
 ; ( = Ÿ
&E  AQ ž (  G (#/   AQ
 PKT  PKT
; ( = ⋅ ; (#/ = 0 #/  PKT
+ P(  LOG ; ( =  PKT
 PKT
P(
P( ;
(Ÿ LOG +0Ÿ LOG 0  LOG  ; (#/
; (#/
Ÿ
=Ÿ  PKT
 PKT
 =(  G #//(
; (Ÿ = ⋅ ; (#/ =
Ÿ

&E Ÿ=LOG
⋅ ; (#/+ #/ŸŸLOG
=
00#/ LOG Ÿž  AQ  PKT
 (#//( + ŸLOG AQ → #/&E  AQ  PKT
+
#/  LOG ; (#/  =
7.1 CO2 Corrosion +P( Ÿ LOG 
  PKT
(10) 0 
0#/ P(  Ÿ LOG + Ÿ LOG 0 LOG ; (#/ =

ŸP(
Ÿ
 LOG ; (  PKT
#/ =  PKT
0
Ÿ P+ Ÿ#/  

In the oilfield, aqueous fluids that have been acidified by an #/ 0#/ ( (#/ ← ⎯ ⎯ŸA → (#/  PKT


(#/

#/ 3
Ÿ ; (Ÿ=

0
P(


 LOG (#/  PKT
 PKT
#/&E  ( Ÿ#/ A0 &E#/
 (#/Sbe Ÿ Ÿseen
 P+
influx of CO2 are known to cause high rates of general Ÿ#/
From Equation ↔ 10 P+A
it(#/can Ÿ
that the pH PKT
at
#/ ← ( ⎯
⎯ ← →
⎯ ⎯ → (#/  PKT Ÿwhich the fluid

#/
 PKT


P(  LOG ( Ÿ ; = P(  Ÿ LOG

3 + Ÿ3LOG Ÿ 0#/  LOG ; (#/P(
 PKT  =  LOG ; ( =


corrosion and pitting corrosion. P+eventually
( #/  AQ #/ stabilizes
(#// doesn’t
Ÿ
(#/
AQ ;only
 (#//( depend  AQon the
(#/
 PKT partial Ÿ
 AQ  PKT
Ÿ =
A Ÿ

( (
(
 #/P( ŸAQ
3 G

 Ÿ( (
LOG +
 Ÿ
3
LOG
(#//
Ÿ#/ AQ
0#/Ÿ LOG
  AQ
Ÿ
AQ AQ
(#//Ÿ 
(#/
 (#//(
Ÿ  AQ  (#//(
Ÿ  AQ
 AQ PKT
(#/ (#/
AQ (#/

Ÿ
Ÿ
 AQ
Ÿ
  AQ
 PKT
 PKT
 PKT
P+AP( #/
pressure
P+ #/   AQ of#/ CO (#// 2 ( 0#/(#/ ), but (#/ Ÿ(#//(
also
(#/ on the concentration ofAQ 
+ Ÿ LOG 0#/ LOG ; (#/ =
Ÿ
 AŸ LOG Ÿ + Ÿ LOG 0#/ P+A LOG ; (#/ 
 =
  PKT P(  ŸLOG
Corrosion rates of carbon and low alloy steels in aqueous (#/
bicarbonate
P+ŸA #/ 0 (#/P+ ( ((#/
P+ ← ⎯
 A
Ÿ
⎯ ). In→ (
buffered #/


  P+ brines
  (#//(   the PKT
effect of high
P+ ( #/  P+  (#//(    
AQ ( #/  ⎯Ÿ A→
P+3Asubsequent A P+  +  (#//(
P+  0  
 A
(  A  (Ÿ #/ A − 
(#/ ( #/ PKT
A
← ⎯ a(3 AQ AQ + (  AQ Ÿ

(#/
P+ ( ( ⎯ ⎯  ⎯ (influx #/ PKT
Ÿ
environments containing CO2 can reach high levels (thousands 0 ← →
to( large P+ is
Aoffset
A  (#//( AQby PKT
a(#//(
very  high


#/

    (#/  Ÿ
← ⎯

#/ →

 
(#// #/ 
 AQ(#/ (#/ 
Ÿ
  AQ  PK
of mils per year), but the corrosion can be effectively reduced by P+ A(#/  AQ &E
concentration. (#/ pH (#//
measurements
( #/ (
Ÿ
 #/
AQ
AQ  → (#//(&E on

 AQ  AQ
formate
ž (  (#/brines
 G
Ÿ
(#/
Ÿ AQ   AQ  PKT
 exposed Ÿ
 PKT
&E (Ÿ#/Ÿ AQ Ÿ → &ECAT  AQ žŸ (  G (#/  PKT
 
ŸAQ  PKT
the formation of a protective layer of iron carbonate on the P+A( &E
toP+
(#//
 #/
&E a Awide(
((#/
 AQ  #/ (#/
 temperature
AQ  
 AQ
(#// (P+ / → (
Ÿ
A← AQ &E
 #/( (
⎯→
range#/ #/AQ
 (#//( (#/
and   ž
at žCO
 ( AQ( 2 G
AQ partial
G (#/ (P+ (#/(#/Ÿ
G
(  (#//(
#/
pressures
A AQ
Ÿ AQ
 AQ of  PKT
 PKT
(#//

up
Ÿ
 AQ  (#//( AQ (
 PKT
 #/  AQ  → &E  AQ 
 
  AQ Ÿ
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 ž PKT
( formate
of G #//( Ÿ brines
 AQ  PKT
&E (#//(  
 AQ → &E   AQ ž(  G #//(  ŸAQ   PKT
#/P+#/
&E G A
(#//(
does
&E #/
 ((#//(
G #/
(#//(
not ←
drop#/
AQ
 ⎯
CAT
 below
AQ
→ AQ
AQ
 #/
&E →6–6.5 ( &E #/
Ÿ ( 
 P+ AAQ
AQ →
G (#//(
(diluted ž ž
and&E ( PKT
G AQ
G
undiluted),
PKT
 
#//( P+
ž(
#//( A regardless
 PKT (ŸG #/  
 AQ
(#/ Ÿ
 PKT
 PKTAQ P+A  (#//( 
 PKT
 → &E AQ (  AQ
 

#/ &E

 AQ ((#/ /  (AQ &E #/

→#/
  AQ 
&E ↔

 &E#/
AQ  S
 ž (  G

PKT
(#/ Ÿ
 AQ PKT
 PKT
There are two factors determining whether or not a completion of the initialŸlevel of carbonate/bicarbonate
   buffer [7]. 
&E  (#/ &E#/  S ž  PKT

/↔ (&E (#//(  AQ → &E(#/ 
 AQ  &E ž ((G#/  PKT
#//(
 AQ → &E
Ÿ
 PKT
AQ  AQ
(  G PKT PKT
#/&E AQ
#/ ( AQ  /
#/ (  (
AQ #/   AQ
#/ AQ
Ÿ
 
ž (  G (#
brine will inhibit CO2 corrosion. These are: &E
&E  #/#/+ŸA↔
Ÿ
↔ (→ 
3 &E
&E#/
&E#/ G Ÿ  AQ 
S(S  3  AQ
AQ
 PKT
 PKT ŸPKT
( #/ &E  AQ(#//( ←⎯ ⎯→ (#/ 
 AQ →AQ &E (  AQ AQ

ž(  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 3Ÿ AQ
AQ
(#/
⎯ ( →  3
→&E AQ
(#/

&E ←
 Ÿ P+ Ÿ
AQ #/ (
 AQ⎯ AQ⎯ →
A AQ ↔(ž (3 (AQ
&E#/ −  G  S+ #//(
  AQ  PKT AQPKT
(+  PKT &EŸ
like AQ (#//(
PKT  AQ → &E  AQ ž(  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 3Ÿ AQ GG 


#/ 
( ( (
 
Ÿ 3
 #/
↔ 3  AQ
&E#/

AQ
 AQ  →S  (#/ 
Ÿ
 AQ   OKT PKT
PKT
 PKT
protective layer on exposed metal surfaces in the case the on contact P+A CO
with 2Ÿ gas, as they +cannot be buffered with


#/&E(
Ÿ  Ÿ
#/AQ 3  #/
AQ  AQ (
 ←

 ↔ #/
⎯ (⎯  #/
(#//
&E#/ →( (3
AQ 3→SAQ
 G−   (#/
AQ 
→((

AQ /+ 3
Ÿ  AQ
 (
(#/ ←AQ CAT
⎯→ Ÿ  (#/

 AQ AQ   OKT
Ÿ
 
 PKT AQ  OKT
(
PKT
&E
  #/G  PKT
Ÿ
PKT
↔ &E#/  S 
CO2 influx is significant enough to lower the pH. carbonate/bicarbonate.
( 3  G  P+
+P+AA
( 3  AQ −−Upon a typical CO2PKT influx the rapid
#/(3  G AQ AQ ( ← ←/⎯ ↔⎯ ⎯ ⎯ →
(#/ →(3 Ÿ
(3 AQ CAT

AQ AQ
(  +

AQ + ( ++
( AQ  AQ  PKT PKT
PKT
move toŸ the left + in the ← carbonate P+A bicarbonate (equilibrium  PKT
Ÿ(  3Ÿ
/ ← AQ ←  3 G  (PKT
 3 AQ
(#//( ⎯ →⎯ #/  Ÿ (  −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 ŸŸAQ ←⎯
 AQ
 AQ ⎯
(
Ÿ =( /
A
→ / (3 
CAT
←Ÿ⎯→ (#/ 
CAT AQ
(#/ + ( Ÿ ŸAQ
AQ ( PKT
 G  PKT
2
← ⎯→    AQ (   Ÿ 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← Ÿ Ÿ⎯→
CAT
Ÿ #/ CAT (  G  PKT
 PKT  PKT
; = =
overwhelm the buffer is very low. Nevertheless, substantial pH
; ( (#//
of= ;⋅ ( (#/ ⋅acidified
= #/ (#/
AQ  ( halide
/ ←⎯→ brine
 (#/ will  therefore
Ÿ
AQ (  Gmainly depend
+  (#//(
+ Ÿ ←
(#//( ⎯CAT
CAT → #/#/  ( (⎯  GG
 Ÿ→
 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
(#// Ÿ
 AQlower ( / ←⎯→ CAT
(#/Ÿ  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  Ÿ LOG + Ÿconcern LOG 0#/ voiced LOG ; (#/ by new users PKT of formate brines is
 =
Ÿ
P(
protective layer of iron carbonate forms very quickly (within a  
P( that corrosive formic ;acid will= always be present
 PKT  PKT with the
Ÿ
Ÿ LOG
P( +
Ÿ LOG Ÿ LOG +0 Ÿ#/ LOG
Ÿ  #/ 
0 LOG (#/LOG ; (#/

Ÿ
=
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#/ (#/(#/
 
Ÿ

Ÿ


presence of the carbonate/bicarbonate buffer therefore not (#/  AQ (#//Ÿ  AQ  (#//( AQ (#/Ÿ  AQ (11) PKT
only reduces the level of brine acidification in the presence of (#/ (#/ AQ   AQ (#// (#//
Ÿ
 AQ Ÿ  AQ (#//(  (#//(  AQ  AQ (#/ (#/
Ÿ
  AQ   AQ
Ÿ
 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 (#/Ÿ  AQ
ž (  G amounts
even  PKT
when
 Ÿ
occurs. When CO2 enters into the buffered formate brine, &E the
( #/
&E (#/
formate AQ brine
→ AQ&E
→ is &E
AQ
exposed ž (
 AQ to
 
ž G
a(
high
  (#/
G CO
(#/
2  AQ
concentration.

Ÿ
 AQ  PKT
 PKT
carbonic acid will be formed according to Equations 3 and 4. &E
In (#//(
order to obtain AQ → &E  AQ ž
a substantial (  G #//(
conversion
Ÿ
of formate  AQ to PKT
&E &E
(#//(
(#//(  AQ →  AQ&E

→ &E AQ  AQ
ž (  ž
 G(  #//(
G #//(
Ÿ
 AQ Ÿ  AQ PKT
 PKT
&E #/ ↔ &E#/  S

 PKT
PA G E 
&E1 2&E
#/ ↔ &E#/
 #/
Ÿ 
  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
 
Ÿ P+ Ÿ
#/ ( ←⎯⎯
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

Ÿ Ÿ
P+A #/ (#/
Ÿ P+A
(#/
formic
#/ 

Ÿ acid, (a stronger
( ←

P+A⎯ ⎯→acid ( #/
→ (#/3  PKT
Ÿ (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
Ÿ P+ Ÿ
#/
P+AA #/
P+
hydrochloric ((#/ ←
Ÿ ⎯
acid
Ÿ A
⎯→(#/
 (HCl). ((#/
 #/
The Ÿ
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
ŸP+A Ÿ
#/
P+
(#/
the G Ÿ  #/
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.
Ÿ P+
P+AAQ Ÿ
#/
(#/ (#/
( /  (
( ← #/
⎯⎯ (→
 #/
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 (#/
Ÿ Ÿ
  AQ (  AQis to maintainPKT
 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
Ÿ 2 ( /  (#/  AQ
#/  AQ ( #/  AQ → (#/  AQ 

Ÿ
 OKT
PKT
#/  G  #/
likelihood that aAQ
buffered formate brine wouldPKT ever receive a Buffered formate brines that are exposed to a large amount
CO
( #/ 2 gas  AQ 
influx

+A
⎯⎯ + large
→ (#/ Ÿenough to overwhelm the buffer is low.
 AQ (  AQ  PKT of CO2 form a higher quality protective layer than other
 PKT
 
#/  G ( / ↔ (#/Ÿ  AQ (  AQ
(Figure
#/  AQ 3). ( Traditional
/  (#/  AQ
high-density halide-based brines do not
PKT acidified completion brines because they provide both a
#/Ÿ this
have  AQ advantage,
( #/  AQand → CO (#/ Ÿ
  AQ
2 corrosion
 OKT
will commence after higher amount of carbonate (see bullet point 2 above – effect
even
( ; (a
#/  AQ ←⎯minor
= ⋅ ; (#/
 +influx
+⎯→
A Ÿ
= of COŸ
 (#/  AQ (  AQ 2 .
 PKT of buffer) and a higher rate of initial corrosion (see bullet point
+  PKT
#/  G (0 / ↔ (#/Ÿ  AQ (  AQ
#/   PKT 3 above – the additional small amounts of formic acid seem
Even
#/Ÿif AQ a CO influx is sufficient enough   OKT
to overwhelm the not only to slightly increase the initial high corrosion rate but
Ÿ
2 (  #/  AQ → (#/  AQ
carbonate
; ( LOG component
= ⋅ ; (#/
; =
=
Ÿ
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 Ÿ
 PKT
efficiently in a buffered
P(  Ÿ LOG + Ÿ LOG 0#/ LOG ; (#/ = formate Ÿ than in other high density
 PKT
completion
P(  LOG ; (brines.
= Here is why: 7.1.1 CO2 Corrosion of C-Steel
 PKT
0#/ ; ( = ⋅(#/ ; (#/ Ÿ Ÿ
= If the carbonate component of the buffer in a formate brine is
+  
 PKT
Both
P(  ŸcarbonicLOG + 0#/ Ÿ LOG
acid
0 #/ 
and
LOG ;formic
(#/ 
Ÿ
= acid are  PKT
known to be corrosive overwhelmed by CO2 influx, the pH will start decreasing and
to
(C-steel
#/  AQ and (#// lower Ÿ
alloyed
 AQ  steels
(#//( and AQ to
some
(#/ Ÿ
CRAs,
 AQ such CO
 PKT 2 corrosion will take place according to Equations 12 and 13.
0  (#/
Ÿ 
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 (#//Ÿ  AQ  (#//(  AQ (#/Ÿ  AQ  PKT
For C-steel this initial phase of high rates of general corrosion
P(  Ÿ LOG + Ÿ LOG 0#/  LOG ; (#/ =
Ÿ
 PKT
Ÿ
&E ( #/
P+A  (#/  
   AQ → &E  AQ ž (
P+A  (#//(     G (#/   AQ (12)
 PKT is readily measured by short-term weight loss tests. There are


0#/ Ÿ cases in the oilfield literature where exaggerated and


(#/
&E
&E
and to (#//(
(a#/ lesser  AQextent;
→ &E 

 AQ ž(  G #//( Ÿ
Ÿ
 PKT misleading CO2 corrosion rates have been reported with
 AQ  PKT
  AQ → &E  AQ ž (  G (#/  AQ
formates as a consequence of measuring the short-term
(13)  PKT
Ÿ Ÿ
( #/#/   AQ Ÿ (#//  AQ  (#//(  AQ Ÿ(#/  AQ
 PKT
&E (#//(  ↔ AQ&E#/ → &E   S  AQ ž(  G #//(  AQ   PKT weight loss and then extrapolating this rate linearly over time
to create annual corrosion figures. It has therefore been
P+   ( #/ 3 AQ  P+A  (#//(  up in solution
(
&E 3
FerrousA G #/ iron



(
↔  &E#/
liberated
  S by these reactions PKT
 PKT
builds advised [6][7] not to use standard short-term weight loss
and eventually reaches a level at which the solubility of iron methods to predict long-term CO2 corrosion rates for C-steel
((3 3 G (  #/ ←(⎯ P+3 A  AQ
 GPKT
  AQ
−  + Ÿ
&E
carbonate exceeded
is⎯

AQ → → (3&E  AQ  AQ
locally + (on ž AQ
the(  corroding
(#/
PKT   AQ
surface.  PKT
in formate brines.
FurtherŸcorrosion P+A will− then cause the build-up of an iron
( 3 AQ ←  PKT
+
AQ⎯

⎯ → (3 ⎯→AQ  +(#/
CAT (  AQ Ÿ PKT
(#//
&E (#//(
carbonate layer (AQ on
 / → ←
the &E steel  AQ  ž
surface: AQ (  ( G   G#//( Ÿ
 AQ  PKT Compared with halide brines, formate brines have been
(#//  AQ CAT Ÿ CAT
( / ←⎯→ (#/  AQ (  G Ÿ  PKT shown to be much less aggressive to C-steel, even in tests
(#//(
&E #/←
⎯Ÿ → #/ (  G
↔ &E#/   S  (14)
 PKT
 PKT where high CO2 additions have decreased the pH to the
 

(#//( ←⎯ 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 Ÿ
 AQ efficient
( / ←in⎯→ CAT
inhibiting
(#/Ÿfurther (  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#/#ORROSIONIN&ORMATESAND"ROMIDES


+&OSG ª#

 


#ORROSIONRATE;MMY=



#ORROSIONRATE;-09=

+#S&OSG ª#


#A"RSG)NHIBITEDª#


#A"R SG5NINHIBITED ª#




+#S&OSGª#

 
      

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.

When using measured CO2 corrosion rates for formate


22Cr brines, which have been measured after the buffer has been
overwhelmed; one would need to consider the timing aspect
of these rates.
Figure 9 SEM photo of iron carbonate protective layer formed
on 22Cr in a potassium/cesium formate brine where pH was
pulled down to the lower buffer level by a large influx of CO2.
The thickness of the layer is about 50–100 μm.

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

#/CORROSIONRATEOF# 3TEELIN"UFFERED&ORMATE"RINES
4EMPERATUREª&
       


 &ORMATEBRINESWITHINTACTBUFFER 
#ORROSIONRATEMMY

#ORROSIONRATE-09
!FTEREXTENDEDTIMEPERIODWITH#/(3 INFLUX
 







 
          
4EMPERATUREª#

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.

#/CORROSIONRATESTANDARD#RIN"UFFERED&ORMATE"RINES
4EMPERATUREª&
       

4YPICAL/PERATING7INDOW
 
#ORROSIONRATEMMY

#ORROSIONRATE-09
 &ORMATEBRINESWITHINTACTBUFFER

!FTEREXTENDEDTIMEPERIODWITH#/(3 INFLUX






 
          
4EMPERATUREª#

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

#/CORROSIONRATEOFMODIFIED#RIN"UFFERED&ORMATE"RINES
4EMPERATUREª&
       
 
4YPICAL/PERATING7INDOW
  
#ORROSIONRATEMMY

#ORROSIONRATE-09
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  !FTEREXTENDEDTIMEPERIODWITH#/(3 INFLUX

 

 


 
          
4EMPERATUREª#

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.

#/CORROSIONRATEOF#RIN"UFFERED&ORMATE"RINES
4EMPERATUREª&
       
 
4YPICAL/PERATING7INDOW
  
#ORROSIONRATEMMY

#ORROSIONRATE-09
  &ORMATEBRINESWITHINTACTBUFFER

!FTEREXTENDEDTIMEPERIODWITH#/(3 INFLUX
 

 

 

  
          
4EMPERATUREª#

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.

#/CORROSIONRATEOF#RIN"UFFERED&ORMATE"RINES
4EMPERATUREª&
       
 

  
#ORROSIONRATEMMY

#ORROSIONRATE-09

  &ORMATEBRINESWITHINTACTBUFFER

!FTEREXTENDEDTIMEPERIODWITH#/(3 INFLUX
 

 

 

  
          
4EMPERATUREª#

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

7.2.2 Testing by Statoil at Centro Sviluppo Materiali Modified 13Cr-2Mo


Centro Sviluppo Materiali used the four point bent beam No SCC failures were observed with modified 13Cr-2Mo in
(fpbb) test to evaluate the SCC susceptibility of modified cesium formate and fresh water solutions. However, cracks
13Cr-2Mo steel (5 different grades of 110 ksi) and alloy 718 at the initiation stage were observed on modified 13Cr-2Mo
in buffered cesium formate brine saturated with chloride at after 2 months at 140°C / 284°F. The results are shown in
165°C / 329°F [10]. The test was run for 1 month with a CO2 Table 10.
headspace pressure of 4 MPa. The amount of acid gas
added to the autoclaves was sufficient to drop the brine pH The fact that Centro Sviluppo Materiali observed cracks at
to 8.3–8.5, but did not totally overwhelm the buffer. This the initiation stage on modified 13Cr-2Mo after 2 months at
study concluded that the susceptibility to SCC and localized 140°C / 284°F, and Hydro Research did not on modified
corrosion was negligible in both metals (Table 9). There was 13Cr-1Mo after 3 months at 160°C / 320°F could be related
no evidence of embrittlement in any of the test metals. to the difference in the chloride levels of the two brines (four
times higher in Statoil’s brine) or it could be related to the
difference in the test methods (Hydro Research opened the
Table 9 Centro Sviluppo Materiali – fpbb testing in a 1.94 s.g. / test cell for visual inspection after each month).
16.2 ppg cesium/potassium formate brine contaminated with
65 g/L Cl- at 165°C / 329°F. PCO2 = 4 MPa / 580 psi. Alloy 718
The results are taken from [10]. No failures were observed with alloy 718, but significant loss
of ductility was experienced. This phenomenon is discussed
Results in Section 11.
Test specimen
Pitting SCC
Modified Submerged No No
13Cr-2Mo Liquid/vapor interface No No
Submerged No No
Alloy 718
Liquid/vapor interface No No

Statoil and Centro Sviluppo Materiali have also reported


some more extensive testing of a cesium/potassium formate
brine saturated with chloride and exposed to CO2 [11]. The
CO2 partial pressure was also 4 MPa / 580 psi. The final pH
of the brine was not reported, and it is therefore uncertain if
the buffer was overwhelmed or not. In addition to the four
point beam testing, this program also included slow strain
rate tensile (SSRT) testing performed in air at ambient
temperature to look for evidence of hydrogen embrittlement.
The testing gave the following results:

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

• crack • cracks at the initiation stage • no cracking

PA G E 2 0
P+AA #/ (#/
ŸŸ P+
P+AA 
(#/ (
(#/ ( ←
←⎯⎯

 →(
⎯→ (#/
#/ PKT
PKT
Ÿ
P+
P+AA (#/ Ÿ
(#/ (
(#/
#/ 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
Ÿ
Both Statoil (Centro Sviluppo Materiali) [10][11] and Hydro
 PKT

A
( #/  AQ ←⎯ 
⎯→ (#/Ÿ  AQ (  AQ Research [15] have included H2S in some of their corrosion
Hydrogen sulfide, H S, is highly Ÿaggressive towards
 OKT metallic experiments with CO2 in formate brines. Hydro Research
AQ   OKT
ŸŸ
#/
#/ AQ AQ ( (#/#/AQ AQ →
2
→ (#/ (#/ AQŸ

materials. Depending upon the material, H2S can cause concluded that the presence of H2S had very little impact on
general
#/ corrosion, ++
Ÿpitting corrosion,
sulfide stress cracking
 PKT the quality of the protective iron carbonate film that forms on
#/GG ( (/ /↔ ↔(#/ (#/ŸAQ AQ ( ( AQAQ  PKT
(SSC), stress corrosion cracking (SCC), hydrogen induced carbon and 13Cr steel surfaces in formate brines, even in the
cracking (HIC),Ÿ stress oriented HIC (SOHIC), and hydrogen case where pH is reduced to the lower buffer level by
( ==⋅⋅;;(#/ (#/ ==

;;( Ÿ
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 ; (#/ Ÿ=
Ÿ
P(
P( ŸŸLOG LOG++ ŸŸLOG 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
ŸŸ
(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 (#//
ŸŸ
(for example
(#// AQ
AQ (#//(
thiocyanates).
(#//( AQ
AQ (#/
ŸŸ
 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 Ÿ
[13][14]. amount of pitting corrosion that was reported by Statoil [11]
&E
&E ( (#/#/AQ AQ → → &E&E AQ AQ ž ž( (GG (#/ (#/ŸAQ 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,ŸŸand when
 PKT chloride contamination level in their test brine (saturated).
&E (#//(  AQ &E  AQ ž
&E (#//( AQ → &E  AQ ž(  G #//(  AQ  PKT
→ (  G #//(  AQ
introduced into an aqueous solution, the following equilibrium
will
&E  establish: ŸŸ
 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
(#// ŸŸ CAT  PKT
 PKT
ŸŸ
(#// 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

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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#2EGIONSOF%NVIRONMENTAL3EVERITY
PSI

REGION
 P(RANGEOFBUFFEREDFORMATES .ORMALLY NOSPECIALPRECAUTIONS
 WITHINTACTBUFFER
AREREQUIREDFORTHESELECTIONOF
 STEELSFORUSEUNDERTHESE
 CONDITIONS.EVERTHELESS HIGHLY
 P(RANGEOFBUFFEREDFORMATES SUSCEPTIBLESTEELSCANCRACK
 WITHOVERWHELMEDBUFFER
 33#REGIONS AND
 3PECIFICGUIDELINESNEEDTOBE
P(  FOLLOWEDFORSELECTIONOFMATERIAL

  
 

 

P(RANGEOFHALIDEBRINES


     
(3PARTIALPRESSURE;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

Modified 13Cr-2Mo SM13CRS-110ksi / 3/3 3/3 CsKFo: Cracks on cross-


UNS S41426 sections 0.11 mm

Duplex 22Cr EN 1.4462 / No No


UNS S31803

Duplex 25Cr EN 1.4410 / No No


UNS S32760

Alloy 718 UNS N07718 1/3 No

• crack • cracks at the initiation stage • no cracking

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.

Yield stress (Rp0.2) Tensile strength % Elongation % of Hydrogen uptake


Test specimen % of initial value of initial value initial value [ppm]
CaBr2 KCsFo CaBr2 KCsFo CaBr2 KCsFo CaBr2 KCsFo
Modified 13Cr-2Mo 100 100 101 99 99 100 0.9 1.0
Duplex 22Cr 105 95 102 92 101 95 3.1 3.2
Duplex 25Cr 107 95 106 94 88 99 2.4 6.8
1)
Alloy 718 112 94 106 97 96 97 6.0 4.8

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].

H2S Modified 13Cr-2Mo Alloy 718


Fluid Position in test cell
[kPa] [psi] Pitting SCC Pitting SCC
1 Month
CsKFo + 20 g/L Cl- Submersed No No No No
3 0.44 Liquid/vapor interface No No No No
CsKFo + 65 g/L Cl- Submersed No No No No
Liquid/vapor interface No No No No
CsKFo + 75 g/L Cl- Submersed No No No No
3 0.44 Liquid/vapor interface No No No No

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.

Results [SCC] Comment


Test specimen
CaBr2 CsKFo
1 month
Modified 13Cr-2Mo SM 13CRS-110ksi /UNS S41426 3/3 No CaBr2: cracks on cross sections 1.8 mm
Duplex 22Cr EN 1.4462 / UNS S31803 No No
Duplex 25Cr EN 1.4410 / UNS S32760 No No
Alloy 718 UNS N07718 No No

• crack • cracks at the initiation stage • no cracking

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.

Yield stress (Rp0.2) Tensile strength Elongation Hydrogen uptake


Test specimen % of initial value % of initial value % of initial value [ppm]
CaBr2 KCsFo CaBr2 KCsFo CaBr2 KCsFo CaBr2 KCsFo
Modified 13Cr-2Mo 100 102 101 99 93 98 1.3 1.0
Duplex 22Cr 104 109 101 104 93 92 1.2 1.7
Duplex 25Cr 102 104 103 105 96 92 1.3 1.4
Alloy 718 104 107 106 108 96 103 3.0 2.7

8.3 Use of H2S Scavengers in Formate Brines


The carbonate/bicarbonate buffer that is normally added to Another iron based scavenger, compatible with high
formate brines when they are used as well construction fluids concentration formate brines, is iron gluconate [19], a Fe(II)
provides useful protection against corrosion by H2S. The complex, which is water-soluble at high pH. In addition to
alkaline pH helps to push the chemical equilibrium (Equation being solids free, this scavenger has the added benefit of
16) towards the formation of bisulfide (HS-) from H2S (aq). reacting very rapidly on a quantitative basis with sulfide.
8.5 kg/m3 / 3 lb/bbl of iron gluconate has been tested in a
The capacity of the carbonate/bicarbonate buffer is enormous buffered 2.2 s.g. / 18.3 ppg cesium formate brine (pH=11).
(as demonstrated in Figure 3), and large amounts of acid gas The added scavenger was shown to be compatible with the
can be converted to HCO3- and HS- before the pH starts brine; it dissolved completely within 5 minutes without any
dropping. The likelihood that a buffered formate brine would change in pH.
ever receive a CO2 gas influx large enough to overwhelm the
buffer during field use is low, but as can be seen from the A third iron based scavenger that may be compatible with
previous section (8.2.4), this could result in some loss of formate brines is iron oxalate. Compatibility testing still needs
ductility in CRAs and the addition of an H2S scavenger could to be carried out with this scavenger.
be beneficial since the impact of H2S on lowering pH would
be reduced and less bisulfide ion, that might stimulate Another group of zinc-free H2S scavengers that is expected
hydrogen uptake, would be dissolved in the formate brine. to be compatible with formates are the electrophilic organic
inhibitors that bind up sulfur in an organic form. These have
The addition of H2S scavengers has additional benefits over the advantage that they do not form any solids when reacting
the use of the buffer alone as the scavengers tie up the with H2S. These will also require compatibility testing.
sulfide rather than changing the equilibrium. Additionally, the
use of an additional H2S scavenger will help to remove any
bisulfide from the formate brine.

A zinc-free, iron based H2S scavenger, Ironite Sponge®, has


been tested in formate brines, and is shown to have some
positive effect in scavenging the H2S. But Ironite Sponge® is
a solid, which limits its application in clear completion fluids.

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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:

1. Low solubility of oxygen in formate brines. 9.1 Impact of O2 on SCC


The solubility of oxygen in low-salinity aqueous solutions at Extensive testing has been carried out by Hydro Corporate
surface temperature and pressure is about 9 ppm. The Research Centre, Porsgrunn, CAPCIS, and Statoil (at Centro
solubility decreases in high salinity formate brines, as shown Sviluppo Materiali) to see if formate brines contaminated with
in Figure 16, and at elevated temperatures [20]. oxygen can cause stress corrosion cracking in alloy steels.

2. Formate brines are antioxidants. 9.1.1 Testing by Hydro Research


Formate is a strong reductant, anti-oxidant, and free radical Hydro Corporate Research Centre, Porsgrunn has tested
scavenger. As this is a property of the formate ion itself, CRAs for SCC after exposure to buffered 1.7 s.g. / 14.2 ppg
which is present in massive quantities in high-density formate potassium/cesium formate brine. They used the “U-bends and
brines, it will never be depleted. C-rings, prestressed to yield” method [12]. A 1.7 s.g. / 14.2 ppg

3OLUBILITYOF/IN&ORMATE"RINES



3OLUBILITY;PPM=


3OLUBILITY;PPM=



        
&ORMATECONCENTRATION;WEIGHT=

Figure 16 Solubility of oxygen in potassium formate at 21°C / 70°F.

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.

Modified 13Cr-2Mo + Alloy 718


Fluid
Pitting SCC
-
CsFo + 3 g/L Cl No No
CsFo + 87 g/L Cl- No No

PA G E 2 8
P(  Ÿ LOG + Ÿ LOG 0#/ LOG ; (#/ =  PKT

0#/ Ÿ
(#/
Ÿ

F O R M AT E B R INE S – COMPATI B I L I TY W I TH ME TAL S


(#/  AQ (#//Ÿ  AQ  (#//( AQ (#/Ÿ  AQ  PKT

P+A  (#/   P+A  (#//(  


10 Catalytic Decomposition bore, after modest formate decomposition, the hydrogen
&E ( #/  AQ → &E  AQ ž (  G (#/  AQ
 Ÿ
 PKTpartial pressure may rise to a level where the equilibrium for
of Formates – a Laboratory
   

the formate decomposition reaction shifted towards the


Phenomenon
&E (#//(  AQ → &E  AQ ž(  G #//( Ÿ  AQ  PKT reactants, opposing further formate decomposition. By
The technical
ŸŸ
literature contains extensive experimental contrast, most laboratory experiments have been carried out
the decomposition PKT

&E #/(e.g.
evidence &E#/
↔[23])   S
for
 of formate and at low pressure using autoclaves containing a gas-filled
formic acid at high temperatures to molecular hydrogen and headspace (the gases are typically nitrogen, air, or CO2).
( 3 G  ( 3 AQ PKT
other products. The two decomposition mechanisms most Under these artificial conditions more substantial formate
commonly cited P+A are: decomposition will occur before a sufficient hydrogen partial
( 3 AQ ←⎯⎯→ (3  AQ + (  AQ

 − +
PKT pressure can exist. One way to create a high partial pressure
 PKT of hydrogen in a laboratory reactor is to make a highly
(#//Ÿ  AQ ( / ←⎯→
CAT
(#/Ÿ  AQ (  G (17)
pressurized gas cap of pure hydrogen.
(18)  PKT
CAT
(#//( ←⎯ → #/ (   G
Such an experiment was carried out by Hydro Corporate
 Research Centre, Porsgrunn, Norway. They used a
Note that both these reactions produce molecular hydrogen. 35 MPa / 5,076 psi gas cap of hydrogen to simulate a
Equation 17, leading to the formation of bicarbonate and realistic partial pressure of hydrogen that would immediately
hydrogen gas, is the one cited most frequently in alkaline exist if decomposition took place at the bottom of a well at a
solutions of formates heated to high temperatures [23]. moderate depth [24]. The experiments were run with buffered
Equation 18 requires the presence of formic acid and might formate brines with a high pH level, and buffered formate
be more likely to occur in acidic formate solutions. As a brines in which the buffer had been overwhelmed with CO2
buffered formate brine is almost always alkaline, and can only and thereby dropped the pH to the lowest level possible
assume a slightly acidic state of pH = 6–6.5 after a massive (6–6.5). In both cases, the presence of the high partial
acid gas influx, this reaction is unlikely to ever be dominating. pressure of hydrogen in the reactor significantly increased the
Both of these decomposition reactions can be catalyzed by temperature threshold at which decomposition of formate
metal surfaces. Nickel, an alloying component in commonly brine was initiated. In fact, the temperature threshold for
used Cr-steel oilfield tubulars, is known to be a good catalyst initiation of catalytic decomposition of formate was reported
for formate decomposition. to be raised to the sort of level normally required to initiate
bulk decomposition of the brine.
Against this background of laboratory data showing
hydrogen evolution from formate decomposition, new users Another factor that has to be considered when going from a
sometimes express reservations about the suitability of laboratory environment to a field environment is the possible
formate brines for HPHT application despite the fact that formation of thin layers of corrosion products on service
formates have been in daily use in HPHT wells since 1996. steels or the presence of chemicals that poison the catalytic
sites on metal surfaces that might drive formate decomposition
Cabot Specialty Fluids have provided formate brines to more reactions.
than 130 high pressure high temperature (HPHT) well
operations, and they are in routine use in HPHT wells every We conclude that whilst surface-catalyzed decomposition of
day of the year. Cesium formate brines have a long history of buffered formate brines is well described in laboratory
being exposed to high well temperatures for long periods. experiments, it is not likely to occur substantially in the field,
During a well suspension job in Total’s Elgin Franklin field in and has certainly not been detected in the field. At the
the North Sea a buffered cesium formate brine was left moment the highest temperature to which a formate brine
downhole for 450 days at temperatures close to 200°C / has been exposed in the field is 216°C / 420°F (at 10,000 psi)
405°F. Despite close monitoring with specialist equipment, no during the completion of a Mobile Bay well. Again, there was
gaseous or soluble formate decomposition products were no evolution of hydrogen gas from the brine over the 16 days
detected either during or after the operation. Similarly, no the brine was in the well.
formate decomposition products were detected in a Mobile
Bay well in which a buffered cesium formate brine was
exposed to 216°C / 420°F for 20 days during a completion
operation. As a matter of fact, there are no reports of formate
decomposition from any of the approximately 130 HPHT
wells drilled and/or completed with buffered formate brines
since 1996 (Table 2). If formates substantially decomposed
on metal surfaces in wells at temperatures as low as 100°C /
212°F then reports of hydrogen evolution from HPHT wells
should be commonplace.

A possible explanation for why decomposition of formate


brines is not detected in field applications is that in the well

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11 Hydrogen Embrittlement In summary: a specific material’s susceptibility to hydrogen


of Metallic Materials in embrittlement depends on hydrogen solubility, diffusivity, and
the concentration threshold at which the material might be
Formate Brines
damaged. All these factors are temperature dependent.

11.1 Hydrogen Embrittlement In practice, hydrogen embrittlement failures are seldom


Hydrogen embrittlement of metallic materials is the result of observed in the field, for one or more of the following
hydrogen uptake into the metal. Hydrogen solubility reasons:
increases with temperature, so that far more hydrogen
uptake is needed at high temperature to achieve the same • the hydrogen activity at the surface of the metallic material
level of hydrogen embrittlement as may be caused at a lower is insufficiently high to exceed the threshold of hydrogen
temperature with less hydrogen uptake. uptake for significant embrittlement to occur at the service
temperature
Metallic materials exposed to brines at wellbore temperatures • the equipment is not exposed for a long enough time
will, under some conditions, absorb hydrogen. Typically for • corrosion-resistant alloys are passive, such that the
some materials, e.g. carbon and low alloy steels, the level of corrosion rate is very low. This results in low levels of
hydrogen uptake will be greater than that necessary to cause hydrogen (NB. galvanic couples are a special case, see
embrittlement at low temperatures and the consequences of below).
the (rapid) cooling of the material, when it is recovered from a
well, or when temperature variations occur because of 11.2 Sources of Hydrogen
production shut-in, must be considered. Corrosion processes generating atomic hydrogen provide the
most common source of hydrogen that can diffuse into
Little evidence has been found that relates hydrogen uptake metallic alloys. Sulfide ions poison the recombination of
at the in-service temperature to the degree of embrittlement atomic hydrogen to molecular hydrogen reaction. This further
caused by this hydrogen at the same temperature. increases the atomic hydrogen available for diffusion (see
Section 8). Another common source of hydrogen charging of
For carbon and low alloy steels embrittlement may result corrosion-resistant alloys (CRA) is the cathodic reaction that
from intense hydrogen entry due to corrosion at low occurs on the CRA surface as a result of galvanic coupling to
temperatures in the presence of a ‘hydrogen promoter’. At a less noble material. The catalytic decomposition of organic
temperatures above about 150°C / 300°F it is known that acid has been suggested as another source of hydrogen in
hydrogen embrittlement of carbon and low alloy steels does organic brines.
not occur because the hydrogen mobility in the steel
becomes very high, allowing hydrogen to escape from the 11.2.1 Hydrogen Charging from Galvanic Coupling
material. Hydrogen charging of alloy 718 has been observed both in
the field and in the laboratory for several brine systems
For martensitic stainless steels, such as 13Cr alloys, the including formates. As alloy 718 is mainly used for packers
situation seems likely to be similar to that for carbon and low and liner/tubing hangers, this material is normally coupled
alloy steels. galvanically to other metals, often C-steel. In any given
solution, galvanic coupling will tend to contribute to an
For other CRAs the situation is less clear. As an example, for enhanced propensity for hydrogen embrittlement.
nickel alloys some hydrogen uptake can take place over the
whole temperature range with, for a given set of environmental 11.2.2 Hydrogen Charging from Formate Decomposition
conditions, the level of uptake increasing with temperature. Catalytic decomposition of formate and formic acid has been
The higher the hydrogen concentration in the alloy the higher found to be a source of hydrogen charging of metallic alloys
is the potential degree of loss of ductility and embrittlement. (e.g. alloy 718) in the laboratory environment [11].
The ability of nickel alloys to retain the hydrogen once
absorbed (lower hydrogen diffusivity) can make these effects There is some evidence, however, that this might not occur in
particularly marked when these alloys are cooled from the field. In Total’s Elgin well G3, the 25Cr tubing was
elevated temperatures. Some recent cases exist where well exposed to a formate brine at about 200°C / 392°F for 16
components made of alloy 718 (a nickel-based alloy) have months. Laboratory testing [25] has shown that 25Cr will
been found to be embrittled after retrieval from the well. serve as a catalyst for decomposition of formate at this
Alloy 718 is frequently used in packers and tubing/liner temperature, and the 25Cr tubing should, according to this
hangers in HPHT wells, and the susceptibility of this material theory, be charged with hydrogen. When the tubing was
to hydrogen embrittlement has raised a concern in the retrieved, no increased hydrogen levels were measured (see
industry [26], though no fresh evidence of in-service failures Section 11.3 below). The measured hydrogen levels were
in brines was found during this review. indeed lower than those measured in the section of the same
tubing that had been exposed to SBM (Synthetic Based Mud).

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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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13 Avoid Pitfalls in the Field! temperatures. The corrosion is a result of interactions


between formate and zinc, which is present in the coating of
The correct use of buffered formate brines will avoid corrosion galvanized steels. It cannot be mitigated through the use of
problems in HPHT wells. Here are four simple rules that must carbonate/bicarbonate buffer. Fortunately, galvanized steel is
be followed to ensure success: normally not used in any critical sub-surface equipment
required for well construction operations.
13.1 Four Simple Rules for Avoiding Corrosion
in Formate Brines 13.2 Examples of Incorrect Use
Never use Corrosion Inhibitors in Formate Brines! There are a couple of examples of corrosion incidents
Buffered formate brines are naturally protective towards reported from field operations as a result of using formate
C-steel and CRAs. Adding a corrosion inhibitor to a formate brines incorrectly. These are:
brine is not only unnecessary and costly, but can actually
cause localized corrosion: Wireline Failure I
• In the event that the upper buffer level in a buffered The failure of a galvanized wireline has been reported
formate brine is overwhelmed by a massive CO2 influx, following use in a formate brine. Failure analysis concluded
no corrosion inhibitors can give better protection against that the galvanized coating around the wire body had been
CO2 corrosion than the protective iron carbonate layer that removed by mechanical abrasion and the underlying C-steel
is formed by the buffered formate brine itself. If the upper was subsequently exposed to hydrogen sulfide and attacked
buffer level is not overwhelmed, the corrosion rates will by localized pitting corrosion.
remain low, and no further protection is needed anyway.
• Sulfur-containing corrosion inhibitors are known to cause In this case, the galvanized coating was removed mechanically.
cracking of susceptible metals at high temperatures in a However, galvanized coating is not compatible with formates
zinc-free environment [28]. In formates, the use of any form and would probably have been breached by the formate
of corrosion inhibitor is unnecessary and should be brine without the assistance of mechanical removal.
avoided. The use of thiocyanate-based inhibitors was once
recommended to suppress the catalytic decomposition of In contrast to halide brines, buffered formates are compatible
formates. It is now believed that catalytic decomposition with C-steel exposed to large influxes of sweet and sour gas.
does not occur in formate brines under realistic wellbore However, this only applies to cases with a relatively low fluid
conditions (Section 10) and the addition of thiocyanate is volume-to-metal surface ratio, and does therefore not apply
not recommended. to wireline applications.

Be Cautious with C-steel or standard 13Cr Wireline! Wireline Failure II


In the event that a very large CO2 influx (large enough to Corrosion damage occurred in a C-steel wireline during the
overwhelm the upper buffer level and pull the pH down to the recompletion of a Hydro operated gas-condensate well in the
lower buffer level) should occur during use of wireline, North Sea. The C-steel wireline was immersed in unbuffered
significant CO2 corrosion can be expected. This is because potassium formate brine inside a modified13Cr-2Mo
the metal surface area-to-fluid volume presented by the production tubing at about 131°C / 268°F. The fluid was
wireline is very low, and a significant amount of corrosion can exposed to an acid gas influx, and was acidified due to the
take place before the fluid becomes saturated with iron lack of a buffer. Failure analyses concluded that a significant
carbonate and allows a protective film to be formed on the amount of corrosion had taken place, and that the color of
wireline surface. Use of C-steel and standard 13Cr wireline the cable had changed to black. The black color is likely to
material is therefore not recommended in formates if there is have been a protective iron carbonate layer. A large amount
any chance of receiving a very large CO2 influx into the of corrosion must have occurred before the iron carbonate
wellbore. Be also aware that a positive laboratory test result layer was formed. The absence of bicarbonate (no buffer)
might be misleading if the metal surface-to-fluid volume ratio and the very high fluid volume-to-metal surface ratio are
used in the test is unrealistic. factors that are known to slow down the formation of the
protective layer.
Never leave out the Buffer!
Unbuffered formate brines have been used in a few special Two lessons were learnt from this incident:
applications [29]. If formate brine is being used without a 1. Formate brines should always be buffered. In this case,
buffer, one should be aware of the consequences this could if this brine would have been buffered, the amount of acid
have in the event of a CO2 influx. In this case, the formate gas influx that was experienced would most likely not have
brine will behave in a similar fashion to a halide brine: been high enough to lower the pH and the wireline would
corrosion will commence after just a small influx of CO2, and not have corroded. In the situation that the acid gas influx
the protective layer will form more slowly and be of poorer would have been large enough to overwhelm the upper
quality. buffer level, the huge amount of bicarbonate would
contribute to limiting he corrosion by preventing further
Keep Formate Brines away from Galvanized Steel! acidification and also assisting in the faster formation of
Formate brines are corrosive to galvanized steel at high the iron carbonate protective layer.

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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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References
[1] Sumitomo: “Applications to Corrosive Wells. The new SM series and their applications to corrosive wells. Concept of Material
Selection according to Gas (CO2 and H2S) Partial Pressure.”
[2] NACE MR0175/ISO 15156-3: “Petroleum and natural gas industries – Materials for use in H2S containing environments in oil
and gas production” – Part 3: “Cracking-resistant CRAs (corrosion-resistant alloys) and other alloys”.
[3] Mahmoud, S.: “Report # MTL 03-115-Corrosion of Steels and CRAs in Formate Based Fluids. Part I. Review and Interpretation
of Available Corrosion/Cracking Data.”
[4] Unpublished data from Cabot Specialty Fluids.
[5] Craig, B., Webre, C.M.: “Stress Corrosion Cracking of Corrosion Resistant Alloys in Brine Packer Fluids”, SPE 93785, April 2005.
[6] Leth-Olsen, H.: “CO2 Corrosion of Steel in Formate Brines for well Applications”, NACE 04357, 2004.
[7] Leth-Olsen, H.: “CO2 Corrosion in Bromide and Formate Well Completion Brines”, SPE 95072, May 2005.
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