SPE 80212

Chemistry of Formate Based Fluids

SPE, William Benton, Cabot Specialty Fluids Inc., SPE, Mike Harris, Cabot Specialty Fluids North Sea Ltd., SPE,
Neal Magri, Westport Technology Center International, John Downs, Hydro Formates, SPE, Jostein Braaten,
Hydro Formates
and are typified by sodium formate brines with densities up to
Copyright 2003, Society of Petroleum Engineers Inc.
1.3 SG (11.3 ppg), potassium formate brines with densities up
to SG 1.57 (13.1 ppg) and cesium formate brines with
This paper was prepared for presentation at the SPE International Symposium on Oilfield
Chemistry held in Houston, Texas, U.S.A., 58 February 2003.
densities up to SG 2.3 (19.2 ppg). The formate brines have a
This paper was selected for presentation by an SPE Program Committee following review of
comprehensive range of beneficial properties that make them
information contained in an abstract submitted by the author(s). Contents of the paper, as
uniquely suited for use as the basis of a new generation of
presented, have not been reviewed by the Society of Petroleum Engineers and are subject to
correction by the author(s). The material, as presented, does not necessarily reflect any
high performance drilling and completion fluids designed to
position of the Society of Petroleum Engineers, its officers, or members. Papers presented at
SPE meetings are subject to publication review by Editorial Committees of the Society of
meet the demanding well construction challenges faced by the
Petroleum Engineers. Electronic reproduction, distribution, or storage of any part of this paper
st
1
oil industry in the 21 century . In fact, as predicted in 1994,
for commercial purposes without the written consent of the Society of Petroleum Engineers is
prohibited. Permission to reproduce in print is restricted to an abstract of not more than 300
field experience with formate brines has confirmed that for the
words; illustrations may not be copied. The abstract must contain conspicuous
first time in its history the oil industry at last has access to a
acknowledgment of where and by whom the paper was presented. Write Librarian, SPE, P.O.
Box 833836, Richardson, TX 75083-3836, U.S.A., fax 01-972-952-9435.
brine-based fluid that has almost all of the technical attributes
required for formulating the ideal universal drilling and
2
Abstract
completion fluid .
Monovalent salts of formic acid provide a range of solids free,
noncorrosive and environmentally sound fluids for use
Shell was the first oil company to field test a formate
primarily as drilling or completion fluids. These fluids range
brine, starting in 1993 with the use of a drilling fluid
from 1.3 s.g. (11.3 ppg) for sodium formate to 1.57 s.g. (13.1
formulation based on sodium formate brine to carry out a
ppg) for potassium formate, and 2.3 s.g. (19.2 ppg) for cesium
coiled-tubing drilling job in the Berkel field in The
1
formate. This paper will focus on the requirements of formate
Netherlands . This successful field trial was followed by the
with respect to initial solution preparation, measurement of
use of a drilling-in fluid based on sodium formate brine to drill
fluid properties, thermal stability, corrosivity, as well as
a series of horizontal wells in Shells Draugen field in
material and chemical compatibility.
Norway3. Statoil was the first oil company to field test
potassium formate brine, using it is as the basis of a drilling-in
4
Fluid property measurement requirements unique to
fluid for accessing the Gulfaks reservoir in Norway in 1994 .
formates include pH measurements of buffered solutions, and
accurate determination of crystallization temperatures.
Since these promising beginnings both sodium formate
Techniques for monitoring and maintaining formate fluids in
and potassium formate brines have been successfully used as
the field will be presented. Results of tests on the thermal
drilling and completion fluids in more than 150 onshore and
5 -15
stability of formates up to 425F (218C) will include reaction
offshore wells in 14 countries around the world . The
pathway, rates and extent of reaction with respect to pH and
primary uses for formate brines over the past 8 years have
the presence of catalytic surfaces. Also results of both field
been in demanding applications where conventional drilling
and laboratory data will be presented on the effects of CO2, its
and completion fluids have not been able to meet the required
solubility in formates, pH and corrosivity.
performance specifications. The applications where formate
brines have been used include:
The corrosivity, including stress corrosion cracking, of
formate fluids, as a function of initial fluid preparation, pH,
Reservoir drilling and completion to improve
and halide contamination will be presented. As with thermal
production rates and minimize corrosion
stability, laboratory and field data will be correlated.
Narrow bore drilling to improve circulating
Examples of weighted stimulation fluids, including those
hydraulics in slim hole and CT operations
capable of dissolving hydrates, are presented.
Shale drilling to minimize environmental impact
High temperature/high pressure drilling to avoid
Introduction
barite sag and stuck pipe
Formate brines are aqueous solutions of alkali metal formates

BUNGERT, D., MAIKRANZ, S., SUNDERMANN, R., DOWNS, J., BENTON, W. & DICK, M.

High temperature/high pressure completions and

workovers
Cesium formate brines only became commercially
available in late 1997, but in the past 5 years they have been
used as solids free or ultra low solids drill-in, completion and
workover fluids in over 60 high temperature/high pressure
(HT/HP) field applications. These operations have included
completion and kill pill applications in Elgin/Franklin wells
where the cesium formate brines have been exposed to down
hole temperatures as high as 400F (204C) for periods up to
450 days in the presence of acid gases
Prime users of cesium formate brines have been Shell,
TotalFinaElf, BP, Statoil 16 and Norsk Hydro. The driver that
has prompted these oil companies to use cesium formate
brines in such challenging well conditions has been the wish
to avoid the well control (barite sag), corrosion and HSE risks
created by conventional well construction fluids in HT/HP
acid gas wells. In fact the oil companies would have been hard
pressed to drill and/or complete certain wells in the
Elgin/Franklin, Shearwater, Huldra and Devenick fields
without cesium formate brine.
In creating the technical justification for using cesium
formate brines in these difficult wells it has been necessary to
explore the nature of the chemistry of the brines under HT/HP
conditions in the presence of steel surfaces and acid gases.
The main objective of this paper is to make available new
insights into the chemistry and behavior of potassium formate
and cesium formate brines gained from studying these fluids
in the laboratory under conditions designed to simulate
downhole HT/HP environments.
The paper also compares the observed behavior of
formate brines in the laboratory under simulated downhole
conditions with the actual behavior observed in the field. One
of the key findings emerging from the on-going laboratory
studies on formate brines under extreme conditions is that it is
difficult to accurately reproduce in the laboratory the exact
downhole environment that the brine experiences in real life.
Without taking great care it is easy to create artificial
conditions in the laboratory that can produce confusing
experimental artifacts including laboratory results that are
typically much more aggressive than found in the field.
Formate Properties
Alkali metal salts of formates show high solubility in water
that gives rise to the high densities achievable with these
fluids. Cesium formate fluids are the densest of the series of
alkali metal formates ranging from sodium formate brines (up
to 1.3 s.g. or 11.3 ppg) to potassium formate (to 1.57 s.g. or
13.1 ppg) to cesium formate (to 2.3 s.g. or 19.2 ppg). Sodium
and potassium formate based fluids were the first of the
formate brines to be applied due to their commercial
availability, and have been successfully applied in many

IADC/SPE 59191

onshore and offshore applications for the past 10 years. The

newer cesium formate fluids that have only been
commercially available since 1999 on the other hand have
seen the most severe field conditions. While still relatively
new, cesium formate brines have been used as solids free or
ultra low solids clear drill-in, completion and workover fluids
without the additions of inhibitors in over 60 field
applications. These operations have included drill-in,
completion, and kill pill applications under conditions as
extreme as 400F (204C) for 450 days. This paper will
correlate important laboratory and field data concerning the
chemical and physical behavior of high density cesium
formate based fluids along with data and results from the full
family of formate based fluids.
Cesium formate is manufactured at the Cabot Specialty
Fluids site at Bernic Lake, Manitoba. The cesium containing
ore is pollucite, Cs2Al2 Si4O12 .(H2O), and the majority of the
worlds recoverable cesium reserves are found at Bernic Lake.
As manufactured, a saturated 77F (25C) cesium formate
brine will consist of 83% dissolved solids and 17% water.
The major cations present, other than cesium, are sodium
(10,000 - 20,000 ppm, 23,000 92,000 mg/L), potassium (500
- 5,000 ppm, 1,150 11,500 mg/L), and rubidium (800010,000 ppm, 18,400 23,000 mg/L). The only major anions
present other than formate are chloride (<1000 ppm, <2,300
mg/L) from the cesium ore, and carbonate/bicarbonate, which
are added as pH buffering agents.
Compared with monovalent cations in more traditional
halide-based brines, the cesium cation is heavier and more
electropositive. Cesium is the heaviest of the stable group I
elements, with an atomic weight of 132.9. Cesium is also the
most electropositive of all the stable elements making cesium
formate the most ionic of the formate salts. The formate anion
is the most hydrophilic carboxylic acid anion yet still retains
significant organic characteristics when contrasted with the
halides. This organic character is seen in the solubility of
formate salts in organic solvents such as methanol or ethylene
glycol.
Use of cesium formate in drilling and completions require
the dissolution of additives, especially water-soluble
polymeric materials. This dissolution was initially considered
potentially problematic, as the molar ratio of ions to water in
saturated cesium formate is approximately 1:1. While brines
are typically thought of as solutions of salts in water, cesium
formate brine might also be thought of as a solution of water
in salt. As will be discussed in this paper, even with relatively
little or no free water present cesium formate brines can
effectively dissolve these polymers. Research, including
inelastic neutron scattering studies, is ongoing to determine
the behavior of water in high density formate solutions.
The formate anion is also an anti-oxidant or reductant,
readily reacting with hydroxyl free radicals, and formate
brines in general can provide solutes such as water-soluble

IADC/SPE 59191 THE EVOLUTION AND APPLICATION OF FORMATE BRINES IN HIGH-TEMPERATURE/HIGH-PRESSURE OPERATIONS

polymers with considerable protection against oxidative

degradation at high temperatures. The alkali metal formates in
solution also exert a structuring effect on surrounding water
molecules, making water more ice-like in nature. This waterstructuring behavior has a beneficial effect on the
conformation of dissolved macromolecules such as xanthan
gum, making them more ordered, rigid and stable at high
temperatures. The combination of anti-oxidant and waterstructuring properties imparts formate brines with the potential
to extend the thermal stability ceiling of common drilling fluid
polymers up to around 330o F.
Due to its high maximum density an important area of
application for cesium formate is in HTHP wells. Therefore
two major areas of interest in cesium formate chemical
behavior have been; compatibility with metals and fluid
stability when exposed to high temperatures.
The corrosivity generated for the range of traditional
inorganic heavy brines and zinc bromide in particular is of
concern from two aspects. Firstly the low pH that these fluids
exhibit causes pitting corrosion unless mitigated. And
secondly the presence of halide ions is suspected of being a
prime cause of stress cracking in tubulars when oxygen is
available. In contrast the organic formate brines exhibit
neutral to high pH and contain very low levels of chloride
ions. They have been shown not to induce stress corrosion
cracking (SCC) and general corrosion at very low acceptable
levels. Even when the chloride ion content is deliberately
elevated SCC has been shown to be suppressed in formates.
Organic acids and their salts are known to undergo
decarboxylation reactions at high temperature. Defining the
upper temperature limits of cesium formate based brines with
respect to stability was therefore critical in developing field
applications. Of particular importance was determining the
stability of formate in the temperature range 350F (177C) to
425F (218C).
However, to verify that formate fluid and the higher
density cesium formates in particular could be used with
minimal corrosion under extreme conditions they were
thoroughly tested in the laboratory. Details of extensive
testing under extreme conditions are presented and the results
from these tests are correlated with data from the field. But
first we present some features of the field results which
demonstrate the differences in behavior and characterization
than found in other fluids. It is this behavior of their unique
properties which have allowed their successful application
under these extreme high temperature and high pressure
conditions. Secondly the paper details some of the laboratory
studies on the chemistry and resultant thermal stability of
formates, carbon dioxide effects with formates and corrosivity
and then finally discuss results of general corrosion and stress
corrosion cracking issues related to formate based fluid
behavior.
Field Characterization and Case Histories of Formates

First and foremost the case histories and field experience in

using formatebased fluids have demonstrated their excellent
record with respect to health, safety and environment. The
formate family of fluids has been applied without any known
H,S & E incidents or concerns. The formate family of fluids
has been awarded the highest ratings and licensing has been
granted for offshore use in the United Kingdom, Denmark,
Norway, The Netherlands and Australia.
Formate case histories have provided a clear picture of
the performance of formates with regard to the following key
physical and chemical properties:
Temperature stability and corrosivity
Polymer mixing and stability
Fluid density and compressibility - PVT
performance
Field testing procedures
Hydrate plug dissolution
Downhole corrosion ring coupon tests
Temperature Stability and Corrosion
Cesium formate has been used in completions and workovers
on TotalFinaElfs (TFE) Elgin field on ten separate occasions.
Elgin reservoir conditions were as follows; bottom hole
temperature (BHT) = 400F (204C), bottom hole pressure
(BHP) = 16,700 psi (1151 bar), Carbon Dioxide (CO2) = 4%,
Hydrogen Sulphide (H2S) = 50 ppm.
In the most recent application coil tubing was used to reenter and abandon a well, G3, which had been suspended for
450 days with a mixture of SBM and cesium formate fluids in
the production tubing. Although no pressure build-up had
been measured on the well which might have indicated
hydrogen generation from a decarboxylation reaction in the
formate, hydrogen levels were monitored throughout the
operation by fixed sensors in the header box, the mud gas
separator (MGS) and with hand held sensors. The highest
recording of all the sensors was 7.3% of the lower explosive
limit (LEL) in the header box. However this did not agree
with the zero level readings from the (calibrated) hand held
sensors, (it was suspected that the problem with the gas
sampling unit in the header-box was unable to cope with the
quantity of sticky solids and much of the sampling was on
the solids instead of the fluid). In conclusion the hydrogen
monitoring program revealed negligible to zero hydrogen
levels.
During the course of the well abandonment the production
tubing (25 Cr) was recovered and subsequently subjected to a
detailed metallurgical examination to determine the suitability
for reuse.
The report from this examination states the following:
Results of the analysis of tubing recovered from G3

BUNGERT, D., MAIKRANZ, S., SUNDERMANN, R., DOWNS, J., BENTON, W. & DICK, M.

IADC/SPE 59191

after 15 months downhole exposure to cesium

formate indicates very low levels of hydrogen
charging at 180 deg C.
Analysis of G3 tubing exposed to SBM in another
part of the string showed surprisingly higher
hydrogen levels on two of the three removed
samples.
Mechanical tests on removed G3 material confirmed
compliance with the originally specified properties of
the tubing material. Therefore all the recovered
tubing from G3 is considered to be fit for further use
for HPHT well conditions.

from a PWD tool and the Densicalc software, further

confirming the stability of formate based fluids under
downhole conditions and the accuracy of the laboratory
generated PVT data.

Polymer Mixing and Stability

Formates have been used as drilling fluids at temperatures up
to 150 C and viscosified fluid loss pills have been used at 204
C. Mixing of normal polysaccharide polymers has proven
trouble free with normal rig hopper systems used. Initial
shipments of mud contain a reduced quantity of polymers to
allow for the viscosity hump encountered in fresh mud. As
the mud is sheared and heated the polymers yield so in use
additional polymers are added to maintain the properties at the
desired levels. Subsequent reuse of the mud is a simple
process. In some cases new mud is pre-sheared onshore to
provide the fully formulated mud from the start of the section.

Two simple tests were used to replace the retort test for
solids. To calculate the total amount of solids in the mud, the
density of the whole mud and the mud filtrate were measured.
Using a mud balance and gravity bottles respectively, the
difference between the two measurements was assumed to be
due to solids, which were assigned a density of 2.5 s.g.

Once mixed and sheared at the desired properties the

formate muds exhibit excellent polymer stability, with
polymer maintenance treatment levels extremely low even at
high temperatures. In fact the average polymer consumption
for a series of six reservoir sections with a BHT of between
140 C and 150 C was essentially zero due to thermal
degradation. The numbers shown in Table 1. are the data from
these six wells and a horizontal well with a BHT of 135C
which had a section duration time of 53 days. These numbers
also include regaining the concentration after dilution as well
as polymers used in spacer fluids.(Table1.)
Pressure Volume Temperature (PVT) Effects
Laboratory formate PVT data from which the fluid densities
and compressibilities are calculated was incorporated into a
simple software (Densicalc) package to enable calculation of
static downhole pressures given the effects of temperature and
pressure. During a workover, a Pressure Logging Tool (PLT)
run was performed with a 2.188 s.g. cesium formate fluid
(measured at 60F) in the well, to measure downhole pressures
and temperatures. The PLT results, together with the
calculations using the Densicalc program (based on a 10C
surface and 190C downhole temperatures), are tabulated in
Table 2. for comparison.
The PLT logging tool measured bottom hole pressure at
16,719 psi, which compares very favorably with the 16,750
psi calculated using the Densicalc program. A similar
correlation, which compared very favorably to within a few
psi was obtained while drilling a hole section with readings

Field Testing Procedures

Field mud testing in general followed API RP13B for water
based mud. However certain tests have been found not to be
valid for formate based fluids including the use of a retort for
solids and pf/mf and pm tests for alkalinity. pH was measured
on a 10:1 diluted mud sample using standard pH papers, which
proved simple and reliable.

Additionally a sample of mud was treated with

hydrochloric acid followed by potassium hydroxide and then
titrated with EDTA to measure the amount of calcium. The
calcium concentration measured in the whole mud was then
subtracted and the amount of calcium carbonate in the mud
was calculated. This test proved extremely simple and
accurate when used to calculate the calcium carbonate levels
in known laboratory standard muds.
The results from these two tests enabled the level of
calcium carbonate used for pore throat bridging to be
controlled at the desired level. Monitoring of the remaining
drill solids allowed the efficiency of the solids removal
equipment to be checked.
Formates and Hydrate Plug Dissolution
In two separate instances during completion and workover
operations hydrate plugs formed, once from a formation fluid
leak in the annulus filled with an inhibited aqueous packer
fluid and in the second instance when the production tubing
had not been completely displaced by the cesium formate kill
fluid, leaving a column of water and a light oil column above
it.
In the first instance with the tubing filled with 2.19 s.g.
cesium formate brine, and while pressures were being
monitored it was noticed that the annulus pressure increased
from 7,478 psi to 7,597 psi while the tubing pressure fell from
37 psi to 24 psi. At this point, a Vetco Riser was installed on
the Christmas-Tree and wireline equipment was rigged-up in
preparation for determining the location of the leak. While
injecting brine to pressure-up the annulus confirmed that only
part of the annulus volume was being pressurized this did
indicate that the blockage was in the upper part of the annulus.
This suggested that hydrates might be responsible, since the
combination of formation fluids migrating up the annulus
through inhibited water at low riser temperatures provides

IADC/SPE 59191 THE EVOLUTION AND APPLICATION OF FORMATE BRINES IN HIGH-TEMPERATURE/HIGH-PRESSURE OPERATIONS

ideal conditions for hydrates formation. An effective way of

dealing with hydrates is to raise the prevailing temperature so
preparations were made to circulate pre-heated brine down
coiled-tubing in an attempt to heat-up and melt the hydrates in
the annulus.
A combination of circulating heated cesium formate
through coiled tubing and pressurizing the annulus with a
50:50 cesium formate methanol mixture while continuously
monitoring pressures allowed the dissolution of the annulus
fluid hydrate plug to take place until the pressures equalized.
Communication between the annulus and the tubing confirmed
that the hydrate plug had melted.
In the second instance the production tubing had not been
completely displaced to cesium formate leaving a water
column at the sub-surface safety valve with an oil column
above the water column. A leak of formation fluids mainly
consisting of methane gas migrated up through the formate
column and once contacting the water column and with the
lower temperatures higher up the column provided the
conditions for hydrates to form. Once it was realized that a
hydrate plug had formed a mixture of formate and methanol
was injected from the top of the column so by gravity, being
heavier than the oil column on top, reached the hydrate plug,
which then dissolved.
Downhole Corrosion Ring Coupon Tests
Corrosion ring coupons were included at depths of between
4904 meters and 5174 meters during a drilling operation in the
North Sea. The wellbore temperature averaged of 275F
(135C) in a gas condensate reservoir and the coupons were
placed about 50 meters behind the drillbit. The coupon
wellbore time averaged 96 hours and the fluid was a 1.65 s.g.
cesium-potassium formate mud.
The coupons were
subsequently tested for rate of corrosion. The conclusions
from analysis indicated that erosion (scuff marks, etc.) or
mechanical damage of the coupons contributed to the bulk of
the weight loss reported and that the coupons suffered from
only light general corrosion at an acceptably low level. Not
much material has to removed via mechanical damage in such
tests to significantly affect the estimated corrosion rate.
However the acceptably low level of corrosion under
downhole conditions confirms the typically low levels (<1.0
mpy) measured under laboratory controlled conditions.
Chemistry of Formate Based Fluids
Organic molecules such as formates have surface-catalyzed
decomposition temperatures that can vary up or down
depending on the presence or absence of appropriate catalytic
surfaces. A review of the literature shows that a variety of
reaction pathways are available for the decomposition of
formate under high temperature. The primary reactions are (1)
an oxidative coupling of formate to produce oxalate and
hydrogen and (2) a reaction in which two formate molecules
react, one producing carbonate and one carbon monoxide
along with hydrogen. It has been reported that oxalate can
further decompose to yield elemental carbon and carbon

monoxide.
(1) 2HCO2- -OCOOCO- + H2
2(2) 2HCO2- CO3 + CO + H2
It is not possible to predict the reactivity or fate of
formate brines in an HT/HP wellbore from these experiments
with solid formates.
While the surface-catalyzed decomposition of formate in
aqueous solution has not been well studied the reverse reaction
of one decomposition mechanism has, i.e. the hydrogenation
of bicarbonate to produce formate. This reaction has been
shown to be highly susceptible to metal surface catalysis. The
decomposition reaction by this mechanism therefore must also
be equally susceptible to these same catalysts. These
particular catalysts (such as palladium and platinum) would
not occur in the oil field. Formate is also produced
commercially from the hydrogenation of carbon monoxide.
In most possible formate decomposition reactions the end
products include one or more gases. By heating formate brines
in laboratory autoclaves and monitoring for gas production it
is possible to roughly estimate the catalytic effect of the
autoclave surface on the initiation and rate of formate
decomposition at high temperatures at the fluid/metal
interface. Unfortunately the picture can be confused by
hydrogen gas production from corrosion processes, and by
reactions taking place in the autoclave headspace at the
gas/liquid/metal interfaces, so that in some cases the evolution
of gas might not be indicative of decomposition of formate in
bulk solution or at the liquid/metal interface.
The catalytic effect of the laboratory autoclave surface
was detected in early experiments when it was observed via
gas production that cesium formate brine was 13%
o
o
decomposed over a period of 12 days at 400 F (204 C) in a
surface-contaminated Hastalloy vessel. When this vessel was
sandblasted clean however, decomposition fell to less than 3%
over the same period.
This type of surface-catalyzed
decomposition behavior was seen in numerous initial
experiments, and consistent methods were subsequently
applied to make certain surface conditions were reproducible.
The main products of surface-catalyzed decomposition
appeared to be bicarbonate and hydrogen gas. Elemental
carbon was also often deposited on the autoclave surfaces as a
product of another decomposition route, and this coating of
catalytic surfaces was seen to terminate any further formate
decomposition after 24-48 hours experimental run time.
Typical results of thermal stability testing of s.g. 2.2
cesium formate brine, buffered with 1% sodium carbonate and
1% sodium bicarbonate, in 500 ml autoclaves of various
metallurgies (0.9ml brine/cm2 surface) at 400F (204C) are
shown in Figure 1. It is evident that the amount of gas
evolved, approximating to the degree of thermal
decomposition of the cesium formate brine, is a strong
function of the metallurgy and surface condition of the

BUNGERT, D., MAIKRANZ, S., SUNDERMANN, R., DOWNS, J., BENTON, W. & DICK, M.

autoclave vessel. The brine in the Teflon coated vessel did not
exhibit any significant gas evolution as long as the Teflon
coating maintained its integrity. The pressure build-up inside
a 25Cr steel autoclave was not significant. Clean Hastelloy C276 was found to be the most active catalytic surface,
followed by cleaned 25Cr and carbon steel.
When the carbon steel autoclave surface was first cleaned,
and then subjected to an oxygen environment to form a
magnetite surface, no detectable reaction and no appreciable
gas pressure build-up was seen. It is thought that the majority
of the carbon steel surfaces exposed to formate brines in a
downhole environment will be coated with a layer of natural
magnetite and will therefore not be available to catalyze
formate decomposition at high temperatures. Any catalytic
surface that is exposed to formate brine appears to become
coated and passivated with a layer of elemental carbon within
24-48 hours. This is supported by gas monitoring studies
during field applications of formate brines in HT/HP wells that
have failed to show any evidence of gas evolution that could
be associated with formate decomposition reactions.
It should be emphasized that in those experiments with
cesium formate brine which showed gas evolution in the
reaction vessel it was not possible to rule out the possibility
that the gas had been produced from corrosion processes or
from chemical reactions taking place in the autoclave
headspace. The presence of a headspace in the laboratory
reaction vessel is clearly not reproducing real-life downhole
circumstances and may give rise to misleading experimental
artifacts.
CO2 Solubility
Preliminary experiments to determine the solubility of carbon
dioxide in neutral 71% potassium formate brine have been
carried out. Results are shown in Table 3 along with modeled
CO2 solubility in deionized water. Results indicate that at
175F (79.6C) the solubility of CO2 solubility in formate is
approximately 20% greater than in deionized water, but at
119.7C the solubility in formate is one third less than in
deionized water. Buffered formate brines would be expected
to absorb enough additional carbon dioxide to convert all
carbonate present to bicarbonate. (Table 3.)
CO2 Effects on Formate Stability
Wells being drilled or completed in HT/HP reservoirs
containing an acid gas phase might on occasion experience gas
influxes containing carbon dioxide as a result of swabbing. To
examine the possible influence of the influx of a large bubble
of carbon dioxide gas on the initiation and rate of formate
decomposition, experiments were carried out. These tests,
with a CO2 headspace in Hastalloy autoclave held at 375F
(190.5C) for 10 days produced results showing evidence of
significant gas evolution, indicating that up to 25% of the
formate in solution had decomposed to mainly (>95% reaction
pathway) bicarbonate and hydrogen gas. As shown in Figure
4, the rate of gas pressure build-up dropped away to zero after

IADC/SPE 59191

24-48 hours, probably as result of the coating of the catalytic

surface by elemental carbon. The final pH of the formate
brines, after degassing at the end of the runs, was 7.0-7.1. The
decomposition of cesium formate under a pressurized pure
CO2 headspace in a Hastalloy autoclave contrasted sharply
with results obtained when the same test was run without a
CO2 headspace. In that case, over a ten-day period, the
quantity of formate decomposed was just 1.3%, as indicated
by gas evolution, and analysis for bicarbonate.
These results indicate that, in the presence of a catalytic
surface, contact with a headspace bubble of carbon dioxide
over a long period can reduce the pH of formate brines and
accelerate formate decomposition. At low pH, trace amounts
of formic acid are expected to be present. This formic acid
can, in effect, act as a catalyst for formate decomposition, by
decomposing to carbonic acid and regeneration of formic acid.
These initial tests suggested that for optimal thermal stability
formate brines should be maintained at high pH.
The chemical equilibrium (3) defining the pH level of a
formate fluid exposed to a headspace of CO2 gas may be
written as:
(3) CO2 (g) + H2 O + HCOO- = HCOOH(aq) + HCO3From this it is clearly seen that the formation of formic
acid will be suppressed by initial addition of
carbonate/bicarbonate as this will move the equilibrium to the
left. If the carbonate buffer is overwhelmed due to long term
exposure to CO2 gas, the pH will drop and increase the
presence of formic acid. However, the carbonates also
contribute to form a protective film of iron carbonate (Fe2CO3)
on carbon steel. This has been shown in laboratory tests in
formate brine exposed to high levels of CO2 (40 bar, 160 0C).
It should be stressed that cesium formate brines are
initially formulated at high pH, and then monitored and
maintained at a high pH throughout the well construction
operations whenever the brine is circulated. The low pH
conditions experienced by formate brines in laboratory
autoclave experiments should not be encountered in the field
as they could only occur in practice as a result of massive,
undetected CO2 influxes in a static column of brine. Likewise
it is difficult in a simple laboratory autoclave to reproduce the
specific surface conditions, and importantly the surface
area/volume ratio conditions as well as the gaseous
environments encountered by formate brines during use in
well construction operations.
A characteristic feature of these formate decomposition
tests was that after 24-48 hours of run time at temperatures of
less than 375F (190.5C) no further gas evolution was
observed regardless of the vessel metallurgy, added coupons,
brine pH or presence of CO2 in the headspace. It is probable
that this termination of further formate decomposition is a
result of coating or passivation of any catalytic surfaces

IADC/SPE 59191 THE EVOLUTION AND APPLICATION OF FORMATE BRINES IN HIGH-TEMPERATURE/HIGH-PRESSURE OPERATIONS

responsible for the decomposition process. It seems likely that

the elemental carbon produced as a formate decomposition byproduct is the surface coating agent, at least for Cr based
alloys and it is this agency that might be responsible for
inhibiting formate decomposition in HT/HP well operations.
pH, CO2 and Corrosion
As discussed above it is critical for HTHP operations that the
pH is monitored, maintained and controlled throughout an
operation. There are, though, four categories of conditions in
which formate field brines could exist. These four conditions
and corrosivity consequences are listed below.
1.

2.

3.

4.

Formates treated with a carbonate/bicarbonate buffer

- These fluids are maintained at pH 9-10 and produce
very minimal corrosion with no corrosion inhibitor
other than pH control. No significant corrosion has
been seen in the field with Cabot formate fluids.
Carbonate/bicarbonate buffered fluids in which CO2
influx has overwhelmed the buffer - Tests have been
carried out at 375F (191C) in which 6 times the
amount of CO2 needed was added to overcome the
carbonate/bicarbonate buffer.
Under these
conditions, corrosion in P-110 carbon steel was
within acceptable limits.
Again no corrosion
inhibitor was added. Even though the buffer is
overwhelmed, i.e. all the carbonate is converted to
bicarbonate, the bicarbonate present keeps the pH
from dropping below 6.
Nonbuffered formates with massive CO2 influx (600
psi (41 bar) CO2 30% headspace) - With no buffer,
and large amounts of CO2, pH will drop below 5. At
these pH levels corrosion starts to become
problematic, general corrosion as well as pitting.
Mixtures of formic acid and formate - Mixtures of
formic acid and formate that have at least 10% of
each component will have a pH of 3.75 +1 and the
pH alone makes these very corrosive conditions.

With good practice the formate fluid described as 1)

above is the only one that will be present in the field. Even
with poor field practice as in the second set of conditions are
the most corrosive that will be seen; but formate brines
themselves will not generate any acid and hence only
acceptably low levels of corrosion. The last two sets of
conditions, which entail unbuffered solutions, should never
occur. Formates from Cabot Specialty Fluids are buffered at
points of manufacture and blending and, except for special
stimulation situations, always the recommended practice for
field application. This buffering will ensure the high pH of the
fluid during operation, but will also enhance the formation of
iron-carbonate film on the metal surface.
Recent tests have shown that for both carbon-steel and
13Cr steel the protecting layer is formed within hours after the
formate solution has been exposed to CO2 atmosphere. A
typical Linear Polarization Resistance (LPR) plot is shown in

Figure 3, which is an intepretation of the corrosion rate. Here

it is clearly seen that the corrosion rate is rapidly decreasing
with time as a protective film is formed. This ensures low
corrosion rates even at severe CO2 pressures. Higher alloys as
S13Cr ,22 Cr steels etc shows remarkable greater resistance to
corrosion in CO2 environments using formates.
There are stories of the corrosivity of formates and it is
possible to speculate on why someone might think that
formates are corrosive. Prior to 1996 it appears that the
industry was not fully aware of the importance of buffering
formate based fluids and we believe that this is the reason for
the stories of high corrosivity in a couple of instances. Sacks
of formate salts have been received, from various suppliers
that were contaminated with formic acid. Making a fluid
directly from the fourth category of formates discussed above,
shows low pH and high corrosivity. However, measuring pH
on a concentrated formate brine with a pH probe will give an
erroneous reading at least 2 pH units too high. pH probes are
not designed to handle the 50-83% salt content of formate
brines; the brines have to be diluted to give an accurate
reading.
So it is possible to make a formate brine
contaminated with formic acid, measure the pH, and it appears
you have a nearly neutral brine with no formic acid. It is
possible that this is what happened in the field and gave rise to
the stories that formate ions themselves are corrosive, which
as discussed only occurs under low pH conditions.
Crystallization Studies
It has been observed that cesium formate and indeed the
sodium and potassium formate brines undergo significant
subcooling when subjected to the standard API RP 13J
crystallization tests. Typical results of these studies are shown
in Figure 4. Data represented by the first crystal to appear
line (FCTA) was obtained by monotonically cooling the brine
samples at less than 1F/minute. The higher crystallization
temperatures shown by the true crystallization curve (TCT)
were obtained by temperature cycling the brine or by the
addition of a seed crystal of cesium formate contained in a
capillary cell. Seed crystals other than those obtained from
cesium formate brine were found to be ineffective. The last
crystal to disappear line (LCTD) was obtained by heating
brine/crystals mixtures at less than 1F per minute. In
laboratory tests it has been observed that crystallization of
cesium and potassium formates, containing at least
approximately 20% of each salt, will not crystallize without a
mixed seed crystal regardless of degree of subcooling. Similar
behavior is seen with blends of sodium and potassium
formate.
Pressure crystallization studies (TCT) of a 2.19 s.g.
cesium formate brine up to 10,000 psig (689 bar) showed an
increase in TCT of 0.97F/1000 psi, as shown in Figure 5.
The lower curve shows the suppression of the TCT by
addition of 5% KCl. The effect of raising the TCT with
increasing pressure is not unexpected behavior and a close
approximate rule of thumb for formates is that the TCT will

BUNGERT, D., MAIKRANZ, S., SUNDERMANN, R., DOWNS, J., BENTON, W. & DICK, M.

IADC/SPE 59191

rise by 1.0F for each 1000 psi.

Ongoing structure studies being carried out at the
University of Warwick have yielded information on the
structures of the first crystals to precipitate from cesium
formate brines. X-ray diffraction studies have shown that a
1:1 mixture of cesium and sodium occur in these crystals. The
sodium is present (10,000 20,000 ppm) in the pollucite ore
from which the cesium formate is produced. The differing
size of the sodium and cesium cations enables a more compact
crystal structure to occur than that seen with cesium alone as
shown in Figure 6. Conversely the addition of potassium ions
to a cesium solution enables a less compact crystal structure
and hence the observed eutectic behavior of these blends, with
TCTs no higher than -15
C at a density of 1.9.
Formates and General Corrosivity
Extensive corrosion testing has been carried out with formates
and a variety of metals from 350F (177C) to 400F (218C),
with the conclusion that formates are noncorrosive, including
general corrosion and pitting.
Early in the development of formate brines an extensive
corrosion testing program was carried out by OSCA, Inc for
Forbrico Ltd. on a variety of carbon and chrome steels
exposed for up to 30 days to unbuffered and uninhibited
potassium formate brines at temperatures up to 365oF (185 oC).
The main conclusion from the study was that potassium
formate brines at 1.26 s.g. (10.5 ppg) and 1.57 s.g. (13.1 ppg)
density are only slightly corrosive to carbon and chrome
steels, and the corrosion rates mostly reduced by at least 50%
between the 7-day and 30 day measurements (see Table 4.),
supporting the idea that any reactions take place rapidly such
as the formation of an inhibiting or passivation layer on the
metal surface.
OSCA also made the important discovery that corrosion
tests with formate brines should only be conducted in Teflon
containers. Initial corrosion tests in glass containers produced
corrosion rate results that were an order of magnitude greater
than results obtained in Teflon containers. The coupons
recovered from corrosion tests in glass vessels appeared to be
coated in silicate, suggesting that the formate brine might have
been leaching corrosive silica compounds from the glass. The
addition of silica-containing sand to a Teflon vessel did not
result in increased corrosion rates, so the corrosion
amplification effect seems to be specifically associated with
glass.
Lowering the pH of the potassium formate brine from 9.8
to 7.2 in a 1.26 s.g. (10.5ppg) potassium formate brine
appeared to have little effect on the corrosion rate of C4130
steel, but the same experiment conducted with a 1.57 s.g. (13.1
ppg) potassium formate brine showed a doubling of 30-day
corrosion rates with a reduced pH. (Table 4)

A similar picture of low corrosion rates was observed in

our experiments with buffered pH 10.0, 1.3 s.g. (10.8 ppg)
o
o
sodium formate brine at 325 F (163 C) using P110 and a
selection of chrome steels up to 22Cr (see Table 5.). A sodium
bromide brine of the same density showed general corrosion
rates that were on average an order of magnitude higher.
The overall impression obtained from corrosion tests with
formate brines is that uninhibited formate brines exhibit
general corrosion characteristics that are at least comparable
and in some instances superior with fully inhibited
conventional brines based on chlorides and bromides. The
important difference is that formate brines, unlike the chloride
and bromide brines, do not induce stress corrosion cracking in
chrome steels. It is also probable that uninhibited formate
brines may cause considerably less general and pitting
corrosion than inhibited bromide brines under extreme HT/HP
well conditions, but this still needs to be verified by laboratory
experiment. (Table 5)
Cesium Formate Field Corrosion and Stability Behavior
The most severe conditions cesium formate has encountered to
date have been during use as a completion/kill fluid twice, as
mentioned above in the same problematic well on
TotalFinaElfs Elgin field. In the first instance the brine (2.19
s.g.) was placed below the packer, against the perforations
with coiled tubing and remained in the wellbore for about 256
days. Elgins bottomhole conditions are 400F (204C) and
16,500 psi (1138 bar). The original fluid density was 2.19 s.g.
The formulation included 5% KCl for crystallization
suppression as a safety precaution for transporting the fluid to
the rig in the winter months in the North Sea and with mudline
temperatures being around 38F (3C). The recovered sample
was obtained from a test separator when the well was flowed
and subsequently analyzed. Compositional and pH analyses
of the recovered sample are shown in Table 6.
With respect to thermal stability of cesium formate the
most important analyte in Table 6. is combined carbonate and
bicarbonate.
The increase in carbonate/bicarbonate
corresponds to transformation of 3% of the formate originally
in solution into bicarbonate and hydrogen. This represents the
maximum amount of formate decomposition possible, not
taking into account buffering added on site, or any influx of
CO2 , which would convert one mole of carbonate into two
moles of bicarbonate.
Very low levels of chromium (17 ppm, 37 mg/L) and iron
(134 ppm, 293 mg/L) were seen in the post production sample.
Even if these amounts were due to corrosion in the presence of
cesium formate they represent very low corrosion rates. A
second possibility for these metals in solution is that the iron
and chromium salts were already present when the cesium
formate was introduced into the wellbore and cesium formate
is known for its excellent solvency of metal salts. (Table 6.)

IADC/SPE 59191 THE EVOLUTION AND APPLICATION OF FORMATE BRINES IN HIGH-TEMPERATURE/HIGH-PRESSURE OPERATIONS

In the second instance on the same well as the first

instance cesium formate (2.19 s.g.) based brine was in place,
bottom hole, for 450 days after which the 25Cr duplex tubing
was recovered and tested. No evidence of hydrogen charging
was seen in the 25Cr duplex tubing in contact with formate.
In contrast 25Cr duplex tubing in contact with synthetic based
drilling fluid did show low levels of hydrogen charging. The
lack of hydrogen when the tubing was in contact with formate
indicates no corrosion or decomposition of formate took place.
Subsequent mechanical testing, stress and impact, of the
tubing in contact with formate showed no change from the
material as manufactured. Due to the lack of any adverse
effect from contact with cesium formate brine, the recovered
tubing was determined to be fit for use in further high
temperature, high pressure applications.

with potassium chloride added to a saturation level and under

o
oxidizing conditions (0.25M hydrogen peroxide) at 375 F
o
(190 C). In contrast our repeated testing of 1.36 s.g. calcium
chloride brine resulted in a time-to-failure ratio of 0.58 for
P110 carbon steel, indicating significant chloride-induced
stress corrosion cracking. Results from C-band testing were
consistent with those shown below, i.e. no indication of SCC
was seen with cesium formate brines. (Table 7.)

Formates and Stress Corrosion Cracking

Shell have previously published results of Stress Corrosion
Cracking (SCC) tests on 4145 steel with sodium formate and
o
o 1
potassium formate brines at 80 C and 150 C . Shell reported
no evidence of SCC or pitting corrosion, and negligible
general corrosion.

Under a hydrogen atmosphere (500 psi, 34 bar) in a

separate series of experiments P-110 was shown to be
moderately susceptible to embrittlement but 13Cr was not.
Additional testing with Sumitomo 13 Cr showed that the TTF
decreased to about 0.85 when oxidizing conditions (i.e. H2O2
which quickly decomposed to O 2) were used. This indicates a
condition of being practically immune to cracking.

Three different susceptibility indicators are generally

employed for determining the susceptibility of the materials to
(SCC): Time-to-failure (TTF) ratio, embrittlement index (RA
Ratio) and percent Strain-to-Failure. Of these three criteria
the TTF ratio is considered the least susceptible to
experimental uncertainty, easy and simple to measure,
whereas the reduction of area ratio (RA or Embrittlement
Index) requires additional microscopic examination that may
promote data scattering. RA is also susceptible to data scatter
from differences in machining of coupons. The % Strain-toFailure measures the stretching of the coupon during the test.
Time-to-failure in environment
TTF Ratio = Time-to-failure in air
% Embrittlement Index = Area reduction in solution/Area
reduction in air x 100
Various classification schemes are used, one of which is
widely recognized and shown below for the TTF Ratio:
Values of 0.85 -1.0
= immune to cracking
Values of 0.65 - 0.85 = practically immune to cracking
Values of 0.5 - 0.65 = moderately susceptible to cracking
Values of <0.5
= susceptible to cracking
This work has been extended by testing cesium formate
brine for its susceptibility to stress corrosion cracking, with
and without chlorides present. Typical results from this
testing are shown in Table 7. below. One of the techniques
used Slow Strain Rate Test (SSRT) - is a screening
technique. Extensive testing has also been carried out using
the more rigorous C-band method. In all of our SSRT tests
cesium formate brines were shown to not promote SCC, even

When hydrogen peroxide was used as an oxidizing agent

in tests it was seen that pressure levels did not increase
significantly in formate brines but did with calcium chloride or
calcium bromide. This further indicates that formate fluids act
as oxygen scavengers, being oxidized to bicarbonate in the
process.

Through over 60 completion or drilling operations with

cesium formate based fluids, at temperatures up to 400 F no
significant evidence of corrosion has been seen. In particular,
no hydrogen has been observed during on site monitoring.
Conclusions
Monovalent salts of formic acid provide a range of solids
free, noncorrosive and environmentally sound fluids.
Formate brines are particularly applicable to:
Reservoir drilling and completion to improve
production rates and minimize corrosion
Narrow bore drilling to improve circulating
hydraulics in slim hole and CT operations
Shale drilling to minimize environmental impact
High temperature/high pressure drilling to avoid
barite sag and stuck pipe.
High temperature/high pressure completions and
workovers
Despite low water contents formate fluids have excellent
abilities to dissolve and add temperature stability to
polymers.
Properly buffered formate brines in the field are stable to
at least 400 F
Uninhibited formate brines exhibit general corrosion
characteristics that are at least comparable and in some
instances superior with fully inhibited conventional brines
based on chlorides and bromides

10

BUNGERT, D., MAIKRANZ, S., SUNDERMANN, R., DOWNS, J., BENTON, W. & DICK, M.

Acknowledgements:
The authors would like to thank Cabot Specialty Fluids, Inc.
and Hydro Formates ASA for permission to present the
content of this paper.
References:
1. Howard, S.K.: "Formate Brines for Drilling and Completion:
State of the Art," SPE 30498 presented at the 1995 SPE Annual
Technical Conference, Dallas, 22-25 October 1995.
4. Nooner, D.W.: "Reservoir Stabilization by Treating Water
Sensitive Clays, US Patent 4,164,979 (21 August 1979).
5. Loftin, R.E. and Son, A.J.: "Well Drilling and Completion Fluid
Composition," US Patent 4,536,297 (20 August 1985).
6. Van Oort, E., et al.: Critical Parameters in Modelling the
Chemical Aspects of Borehole Stability in Shales and in
Designing Improved Water-Based Shale Drilling Fluids, SPE
28309 presented at the SPE Annual Technical Conference, New
Orleans, Louisiana, 25-28 September 1994.
7. Van Oort, E., et al.: Transport in Shales and the Design of
Improved Water-Based Shale Drilling Fluids, SPE Drilling &
Completion (September 1996) 137.
8. Van Oort, E.:Physico-Chemical Stabilisation of Shales, SPE
37263 presented at the 1997 SPE International Symposium on
Oilfield Chemistry, Houston, 18-21 February 1997.
9. Frenier, W.W., Grannan, S.E. and Hill, D.G.: Process and
Composition for Inhibiting Iron and Steel Corrosion, European
patent EP 276 879-A (3 August 1988).
10. Clarke-Sturman, A.J. and Sturla, P.L.: "Aqueous Polysaccharide
Compositions, European patent 259 939 (16 March 1988).
11. Downs, J.D.: High Temperature Stabilisation of Xanthan in
Drilling Fluids by the Use of Formate Salts, in Physical
Chemistry of Colloids and Interfaces in Oil Production, Editions
TechNet, Paris (1991).
12. Ramsay, M.S., et al.: Cesium Formate The Beneficial Effects
of Low Viscosity and High Initial Fluid Loss on Drilling Rate
A Comparative Experiment, SPE 36398 presented at the
IADC/SPE Asia Pacific Drilling Technology Conference, Kuala
Lumpur, Malaysia, 9-11 September 1996.
13. Mese, A. & Benton, W.J.: Unpublished Results.
14. Downs, J.D.: "Formate Brines: New Solutions to Deep Slim
Hole Drilling Fluid Design Problems, SPE 24973 presented at
the 1992 European Petroleum Conference, Cannes, France, 1618 November 1992.
15. Downs, J.D.: "Formate Brines: Novel Drilling and Completion
Fluids for Demanding Environments, SPE 25177 presented
at the 1993 SPE International Symposium on Oilfield
Chemistry, New Orleans, Louisiana, 2-5 March 1993.

Ref.. Horton, R., Potassium Formate Brine Corrosion Tests

for C4130, 410 and 22-Cr Steels, OSCA/Forbrico Formate
Brine Project Task #11, 12th October 1995.

IADC/SPE 59191

16. Downs, J.D., et al.: Development of Environmentally Benign

Formate-Based Drilling and Completion Fluids, SPE 27143
presented at the 2nd International Conference on Health, Safety
& Environment in Oil & Gas Exploration & Production, Jakarta,
Indonesia, 25-27 January 1994.
17. Lord, D., et al.: Shell Expros First Application of Coiled
Tubing Drilling, World Oil (June 1997) 119.
18. Svendsen, O., et al.: Optimum Fluid Design for Drilling and
Cementing a Well Drilled With Coil Tubing Technology, SPE
50405 presented at 1998 SPE International Conference on
Horizontal Well Technology, Calgary, 1-4 November 1998.
19.Brinkhorst, J.W.: Optimisation of Drilling Fluid and Clean-Up
Operations in Rogan South, Draugen Field, Norway, presented
at the Horizontal Well Technology Forum, Aberdeen, 24-25
January 1994.
20. Svendsen, O., et al.: Use of a Novel Drill-In/Completion Fluid
Based on Potassium Formate Brine on the First Open Hole
Completion in the Gullfaks Field, SPE/IADC 29409 presented
at the SPE/IADC Drilling Conference, Amsterdam, 28
February-2 March 1995.
21. Hands, N., et al.: Drill-In Fluid Reduces Formation Damage,
Increases Production Rates, Oil & Gas Journal (13 July 1998)
65.
22. Hands, N., et al.: Optimising a Long Multi-Lateral Gas Wells
Inflow Performance, World Oil (April 1999) 73.
23. Gallino, G., et al.: New Formulations of Potassium Acetate and
Potassium Formate Polymer Muds Greatly Improved Drilling
and Waste Disposal Operations in South Italy, SPE 37471
presented at SPE Production Operations Symposium, Oklahoma
City, Oklahoma (9-11 March 1997) and SPE Drilling &
Completion (March 1999) 64.
24. Abou-Sayed, I.S., Chambers, M.R. and Mueller, M.W.: Mobil
Completes Deep, Tight, Horizontal Gas Well in Germany,
Petroleum Engineer International (August 1996) 42.
25. Sundermann, R. and Bungert, D.: Potassium-Formate-Based
Fluid Solves High Temperature Drill-In Problem, Journal of
Petroleum Technology (November 1996) 1042.
26. Dick, M.A. et al.: Optimizing the Selection of Bridging
Particles for Reservoir Drilling Fluids SPE 58793 presented at
SPE International Symposium on Formation Damage, Lafayette,
Louisiana, 2324 February 2000.
27. Sundermann, R., Bohr- und Komplettierungssplmittel,
Deutsches Patentamt, DE 196 09 194 A1 (11 September 1997).
28. Hand, N. et al.: Optimising Inflow Performance of a Long
Multi-Lateral Offshore Well in Low Permeability, Gas Bearing
Sandstone: K14-FB 102 Case Study, SPE 50394 presented at
SPE International Conference of Horizontal Well Technology,
Calgary, 1-4 November 1998.

SPE 80212

Chemistry of Formate Based Fluids

11

Table 1. Polymer consumption for seven drill-in operations including spacer pills.
Number of Wells

140 C 150 C

135 C

Average Section Days

19

53

Xanthan Based Consumption (25kg sx)

35

19

Pac ULV Consumption (25kg sx)

50

39

BHT Range

HT Modified Starch Consumption (25kg sx)

95

29

Average sacks of polymer per day

9.5

1.6

Table 2. Measured and Predicated 2.188 s.g. Cesium Formate Brine Pressures
True Vertical Depth
(m)

Measured Temperature
(C)

Measured Pressure
(psi)

Predicted Pressure
(psi)

Pressure Difference
(psi)

987.67

41.6

3,090

3,069

21

997.64
1,984.97

41.8
87.3

3,121
6,163

3,100
6,120

21
43

1,994.91

87.5

6,192

6,151

41

2,982.29
2,993.14

127.3
127.5

9,185
9,215

9,137
9,170

48
45

3,979.70

152.1

12,180

12,157

23

3,989.58

152.2

12,208

12,187

21

5,505.74

188.9

16,719

16,750

31

Table 3. CO2 Solubility in 71% Potassium Formate

Temperature (C)

Pressure (bar)

79.6
119.7
161.4

3.08
4.36
6.26

Solubility in 71% Potassium Formate

(moles/L)
3.60
2.22
0.89

Solubility in Deionized
Water (moles/L)
3.03
3.35
NA

12

William Benton, Mike Harris, Neal Magri, John Downs, Jostein Braaten

SPE 80212

Table 4. Corrosion Rates for C4130, 410 and 22-Cr steels in unbuffered and uninhibited potassium formate
brines
Metal

Brine
Density(ppg)

Temp.( oC)

pH

7-day Corrosion
Rate (mpy)

30-day Corrosion
Rate (mpy)

C4130

10.5

65

7.2

0.1

0.0

C4130

10.5

65

8.5

0.0

0.0

C4130

10.5

65

9.8

0.1

0.0

C4130

10.5

185

8.5

1.6

0.5

C4130

10.5

185

9.8

1.2

0.2

C4130

13.1

65

7.2

9.1

3.3

C4130

13.1

65

8.5

1.2

0.9

C4130

13.1

65

9.8

0.5

1.5

C4130

13.1

185

8.5

4.4

1.4

C4130

13.1

185

9.8

6.6

3.0

410*

10.5

65

8.5

0.0

0.0

410*

10.5

65

9.8

0.0

0.0

410

10.5

185

8.5

0.3

0.1

410

10.5

185

9.8

0.0

0.0

410*

13.1

65

8.5

0.0

0.7

410*

13.1

65

9.8

0.0

0.0

410

13.1

185

8.5

2.8

0.9

410

13.1

185

9.8

1.7

1.7

22Cr*

10.5

65

8.5

0.0

0.0

22Cr*

10.5

65

9.8

0.0

0.0

22Cr

10.5

185

8.5

0.0

0.0

22Cr

10.5

185

9.8

0.0

0.0

22Cr*

13.1

65

8.5

0.0

0.0

22Cr*

13.1

65

9.8

0.0

0.0

22Cr

13.1

185

8.5

0.0

0.0

22Cr

13.1

185

9.8

0.0

0.0

Table 5. - Corrosion Rates for P110, 13Cr and 22-Cr steels in saturated buffered pH 10.0 sodium formate and
sodium bromide brines. All tests run at 325F (162C).
SAMPLE

Weight Loss in Sodium

Formate (A) (g)

Weight Loss in Sodium

Bromide (B) (g)

mpy in Sodium Formate

(A)

mpy in Sodium Bromide

(B)

P110 (1)
P110 (2)

0.0014
0.0011

0.0056
0.0059

0.28
0.22

1.13
1.19

13 Cr (1)

0.0002

0.0030

0.04

0.61

13 Cr (2)
Super 13 Cr (1)

0.0001
0.0001

0.0047
0.0037

0.02
0.02

0.95
0.75

Super 13 Cr (2)

0.0001

0.0032

0.02

0.65

Duplex 22 Cr (1)

-0.0011*

0.0012

-0.22 *

0.24

Duplex 22 Cr (2)
* Weight gain

-0.0006*

0.0019

-0.12 *

0.38

SPE 80212

Chemistry of Formate Based Fluids

13

Table 6. Analysis of recovered cesium formate sample after 256 days at 400F and 16,500 psi conditions.
ppm

Original
Cesium Formate

Recovered Sample

K
Na

20000
12000

22890
13133

Cl

5600

7300

Ba Ca Mg Sr

50

43

Al

20

<1

Cr

<1

17

Ni
Cu

<1
<1

<1
<1

Mn

<1

P
SO4

1
100

13
2289

Pb

<1

Fe
Carbonate + Bicarbonate

<1
6500

134
14800

pH

10.5

9.24

Table 7. Stress Corrosion Cracking Screening Testing of Formate and Halide Brines (375 F, 250 rpm)
Material

Solution (ml)

Elastic/Plastic
Deform. Pt. (mm)

Peak Stress
Time-toPt.(mm)
Failure (mm)
143.25

P110*
Air
13Cr**
Air
25Cr
Air
25Cr
Cs Formate 2.13sg
74
84.5
P110
Cs Formate 2.13sg
73.5
95.5
25Cr
Cs Formate/5% KCl
77.5
89
13 Cr**
Cs Formate/5% KCl
25Cr
Cs Formate/10% KCl
80
89
25Cr
CaCl2 1.362sg
84
90
13 Cr**
14 ppg CaBr2
P110
CaCl2 1.362sg
74
88
P110
Cs Formate/10% KCl
74
88
P110
Cs Formate/5% KCl
83.5
93.5
P110
Cs Formate/10% KCl
81
93.5
P110*
CaCl2 1.362sg
99
97.5
P110*
CaCl2 1.362sg + 2.8g H Peroxide
87
83
13 Cr**
CaCl2 1.362sg + 2.8g H Peroxide
25Cr*
Cs Formate 2.13sg + 5% KCl + 2.8g H Peroxide
96
97.5
13 Cr**
Cs Formate 2.13sg + 5% KCl + 2.8g H Peroxide
25Cr
CaCl2 1.362sg + 2.8g H Peroxide
92
89
Coupons pre-equilibrated at temperature for 24 hours prior to start of stress ramp.
**

Sumitomo Super 13 Cr

143.25
141
138.75
137.25
143.25
144
141
144
141
141
101.25
83.55
143.25
83.1

Time-toFailure (hr)
19.10
19.70
19.10
18.80
18.50
18.30
18.98
19.10
19.20
17.32
18.93
19.20
18.00
18.93
13.50
11.14
17.06
19.10
16.67
11.08

Time-to-Failure
Ratio
1.000
1.000
1.000
0.984
0.969
0.958
0.963
1.000
1.005
0.897
0.989
1.005
0.989
0.991
0.707
0.583
0.866
1.000
0.846
0.580

14

William Benton, Mike Harris, Neal Magri, John Downs, Jostein Braaten

Figure 1. Metallurgical Effect on Formate Stability

#87-Carbon Steel
#90-Carbon Steel
#93(Teflon)
Pr ess ur e (ps ig)

#137(magnetiteC-0-18:1)
100 psig equivalent to
0.63% formate
Decomposition
Y axis = 200 psi per line

100

#117-Hastelloy C-276
#140-25Cr

200

300
Time (hr)

400

500

600

Figure 2. Effect of CO2 (600 psi initial) on Cesium Formate Stability at 375 F
2500.00
2250.00

Pressure (psig)

2000.00
1750.00
1500.00
1250.00
1000.00
Pressure (psig)

750.00
500.00
0.00

50.00

100.00

150.00

200.00

250.00

Time (hours)

Figure 3. Linear Polarization Resistance of Formate Brine with CO2

X65 - Formate Solution 5 Barg CO2, 7 Days @ 120 C
5cm volume:area ratio

C or rosion R ate mm/yr

4.5
4
3.5
3
2.5
2
1.5
1
0.5
0
0.0

20.0

40.0

60.0

80.0

100.0

Time in Hours
mm/yr

120.0

140.0

160.0

180.0

SPE 80212

SPE 80212

Chemistry of Formate Based Fluids

Figure 4. Ceium Formate Crystallization

2.6

Density, SG

2.5
2.4

TCT

2.3

FCTA

2.2

LCTD

2.1
2
1.9
-60

-40

-20

20

40

60

80

100

120

Temperature (F)

Figure 5. Pressure Crystallization Temperature with and without 5% KCl for a 2.195 s.g. Cesium Formate
60
y = 0.0009x + 40.75
R 2 = 0.9929
50

Temperature (F)

40
y = 0.0007x + 24.341
2

R = 0.9093
30

20

PCT (F) 'Virgin'

PCT (F) 5% KCl
Linear (PCT (F) 'Virgin')
Linear (PCT (F) 5% KCl)

10

0
0

2000

4000

6000

8000

10000

12000

Pressure (psi)

Figure 6. Crystal Structures of Sodium Formate, Potassium Formate and Cesium Formate
Sodium Formate
Potassium Formate
Cesium Formate

Crystalline
a axis

15