Formate Brines - What's New - Siv Howard

Latest formate
developments
Siv Howard
R&D Manager
Houston
siv.howard@cabotcorp.com
August 2016
Cabot Publications 2016
Ridge Study
Independent Study by Ridge

Time - Cost Risk Benefit Analyses
Objective
Perform high level time-cost-risk-benefit analyses for well construction

comparing OBM and cesium/potassium formate drilling and completion
fluids (HPHT and non-HPHT)
Work scope
Collect and analyze reservoir drilling time data and completion time data for
North Sea wells
Available data from reliable sources were collected and sorted according to fluid
type (formates or OBM fluids / UB completion brine)
89 wells included (56 HPHT)
Drilling time and completion time included
Net ROP used for drilling performance = average hole-making progress,
including tripping, circulating, flow checks and conditioning, but excluding time
spent on underreaming, coring, logging, WOW and NPT
6
Predicted time for a 500 m 8" reservoir section
Reservoir compatibility with clear completion

brines
Completion brines are often incompatible with reservoir fluids due to presence
of divalent ions
High density halide brines contain divalent cations: Zn2, Ca2+

These can react with divalent anions and form scale, CaCO3, CaSO4
Phosphate brines contain divalent and trivalent anions: HPO42- / PO43Formate brines themselves have no divalent ions, and cannot form any scale:
Na+ / K+ / Cs+ / HCOOCO32- buffer in formate brines can react with formation water with high
concentration of divalent cations and form scale, e.g. CaCO3
Very low concentration compared to an ion that is part of the brine

Also, the buffer concentration can be reduced in critical wells
Basic formate brine properties that help

corrosion control
Slightly alkaline pH
Compatible with carbonate pH buffer
(buffers at pH=9.5)
Formate ion = antioxidant
Contains no halide ions that promote
localized corrosion
10
Carbonate/bicarbonate buffer
How does it work?
pH in various brine systems as function of CO2 influx volume

12
11
10
Buffered formate
pH
9
8
7
Unbuffered formate
6
5
Calcium bromide
4
0
50
100
150
200
250
300
350
400
450
500
BBL Gas influx/BBL buffered formate brine (2% CO2, 21C / 70F, 1 atm)
Increased amount of CO2 influx
11
CO2-corrosion Formation of Iron Carbonate

Self-repairing Protective Layer
12
Corrosion: comparison of cesium/potassium

formate and potassium phosphate
Corrosion study 1:
compatibility of C-steel with phosphate and formate brines. C-steel (JFE95S)
for 30 days at 180C
Corrosion study 2:
Compatibility of 13Cr with phosphate and formate brines for 30 days at
177C / 180C /200C.
Corrosion study 3:
For Tarim completion job. Compatibility of 13Cr tubing material (JFE-13Cr
and BG-13Cr) with phosphate and formate brine after30 days at 170C and
C-steel casing material (TP140) after 30 days at 190C.
13
Corrosion study 1
Formate brine: 1.8 s.g. cesium / potassium formate brine blend from Cabot
Specialty Fluids central stock in Aberdeen, UK. buffered with standard
buffer 6.25 ppb K2CO3 and 3.75 ppb KHCO3
Phosphate brine 1: 1.73 s.g. potassium hydrogen phosphate brine, sourced
from a service company at a rig site in China. Contained large amounts of
chromium
Phosphate brine 2: 1.8 s.g. potassium hydrogen phosphate brine sourced
from a service company in Indonesia
Metal: JFE-95S, which is a sour service grade C-steel
14
Corrosion study 1
Formate brine purged with N2 gas for 3-4 minutes to remove oxygen.
Formate brine purged with CO2 gas for 3-4 minutes to simulate an acid gas
influx.
Phosphate brine 1 (rig-site sample) purged with N2 gas for 3-4 minutes to
remove oxygen.
Phosphate brine 1 (rig-site sample) purged with CO2 gas for 3-4 minutes to
simulate an acid gas influx.
Phosphate brine 2 (laboratory sample) purged with N2 gas for 3-4 minutes to
remove oxygen.
Phosphate brine 2 (laboratory sample) purged with CO2 gas for 3-4 minutes
to simulate an acid gas influx.
15
Corrosion study I
Green sludge in phosphate

Brine exposed to 180C
for 30 days
16
Corrosion study 1 Results

C-steel, 30 days at 180C
Corrosion rate
Corrosion rate
[mm/y]
[MPY]
Formate brine
0.0037
0.15
Formate brine + CO2
0.0044
0.17
Phosphate brine 1
1.150
45.3
Phosphate brine 1 + CO2
1.274
50.2
Phosphate brine 2
1.297
51.1
Phosphate brine 2 + CO2
1.403
55.3
Test description
17
Corrosion test 1 C-steel

SEM photos
Formate
Phosphate
Phosphate
18
Corrosion test 2
Fluids:
Formate 2.0 g/cm3, buffered to pH 10.0 10.5

Formate 2.0 g/cm3, buffered to pH 7.75 (not possible in field)
Potassium phosphate 1.63 g/cm3, pH 9.65
Metal: Standard 13Cr alloy tubing material
Exposure time: 30 days
Exposure temperature: 177, 180, 200 C
19
Corrosion study 2 - Results

13Cr, 30 days
pH 7 not feasible downhole

Phosphate
Formate
20
Corrosion test 3
Fluids
Metals
Buffered cesium/potassium formate blend 1.80 g/cm3, pH 10.2

Buffered cesium formate brine 2.20 g/cm3, pH 10.2
Potassium phosphate brine, 1.63 g/cm3, pH 9.7
BG-13Cr tubing material

JFE-13Cr tubing material
TP140 C-steel casing material
Temperature:
170C for 13Cr tubing material

190C for C-steel casing material
21
Corrosion test 3 Results
= 7 MPY
22
Corrosion test 3 Results
Unexposed
Formate
Phosphate
Black protective layer
No protective layer
Pitting corrosion
23
Reservoir compatibility with clear completion

brines
Completion brines can be incompatible with reservoir fluids due to presence of
multivalent ions
High density halide brines contain divalent cations: Zn2+, Ca2+

These can react with divalent anions and form scale: CaCO3, CaSO4
High density nitrate brine contain divalent ion: Ca2+
This can react with divalent anions and form scale: CaCO3, CaSO4
Phosphate brines contain divalent and trivalent anions: HPO42- / PO43These can react with divalent cations and form scale
Formate brines themselves have no divalent ions, and cannot form any scale:
Na+ / K+ / Cs+ / HCOOCO32- buffer in formate brines can react with formation water with high
concentration of divalent cations and form scale, e.g. CaCO3
Buffer is added in relatively small concentrations
Also, the buffer concentration can be reduced in critical wells
24
Impact of brine type on formation damage

a laboratory study
25
HPHT laboratory core flooding test with

phosphate brine
Objective
Find out if potassium phosphate brine is compatible with sandstone gas
reservoirs under HPHT conditions
To determine the effect of potassium phosphate brine invasion on the gas

permeability of sandstone under HPHT conditions
To determine the cause/mechanism of any change in the gas permeability
of sandstone after exposure to the phosphate brine
Use cesium formate brine (a standard HPHT well completion fluid) as a control
substance, for comparison
26
HPHT core flood test results with potassium

phosphate brine Brine injection phase
Pressure development across core during injection of 10 PV of
phosphate brine @ 1ml/min (frontal advance rate of 80 cm/hour)
Differential pressure (psi)
160.00
140.00
120.00
100.00
80.00
60.00
40.00
20.00
0.00
0
2
3
4
5
6
Cumulative brine throughput (pore volumes)
10
Differential pressure did not stabilise

27

a laboratory study
Drawdown with humidified N2 gas
Small gain in return permeability
91.6% reduction in return permeability
28

phosphate and cesium formate brines - Result
Exposing the core to phosphate brine reduced its permeability to
gas by > 90%
Completion brine
system
Test
Temperature
o
( C)
Initial
Permeability
(mD)
Final
permeability
(mD)
Change in
permeabilit
y
(%)
Phosphate
175
10.2
0.86
-91.6
Formate
175
23.0
24.8
+7.8
29

phosphate and cesium formate brines - Result
Appearance of core face under SEM before and after exposure to phosphate
brine and gas drawdown
Before test
After test
Sand grains and pore throats covered in blanket of

phosphate scale after test EDS analysis of the scale shows
potassium, phosphorus, sodium and chloride
30

a laboratory study
Results:
Phosphate brine forms insoluble scales on contact with multivalent cations

in formation water. For example, in a very typical formation water
containing soluble calcium and iron:
tricalcium phosphate [Ca3(PO4)2] hard bonelike deposit

hydroxylapatite [Ca5(PO4)3OH] hard bonelike deposit
ferric hydroxide [Fe(OH)3] gel
strengite [FePO42H2O] - hard bonelike deposit
Potassium phosphate brine absorbs strongly onto mineral surfaces where

they can form precipitates and complex insoluble salts from exposure to
multivalent cations. These absorption reaction products block pore throats
and reduce formation permeability
31
New study removal of phosphate damage
32
33
SPE-179021-MS
Solubility of Barium Sulfate in Formate Brines
- New Insight into Solubility Levels and Reaction Mechanisms
Siv Howard and Zhao Anderson, Cabot Specialty Fluids, and Stuart
Parker, Aberdeen University
34
Slide 35
PREVIOUS WORK BY SHELL

Shell [SPE 30498] measured high levels of barium in potassium formate
brines after 16 hours exposure at 85C / 185F
Dissolved Water NaFo NaCl
Ba2+
40% 26%
[mg/L]
NaBr
46%
KFo
75%
KCl
24%
KBr
34%
CsFo Cs2SO4
82%
BaSO4
47
3,413
353
Barite
94
29
12
1,530
47
29
412
BaSO4
scale
nd
47
29
4,119
29
18
471
SPE-179021-MS Solubility of Barium Sulfate in Formate Brines - New Insight into Solubility Levels and Reaction Mechanisms Siv Howard
35
Slide 36
FIELD OBSERVATIONS
Cabot has used cesium formate brines and cesium/potassium formate
blends extensively since the 1990s.
All fluid has been returned to the Cabot site for analyses and
reclamation
High levels of barium has NEVER been measured in any brines
returned to Cabot
Surprising, considering that formate drilling and completion fluids
have been in contact with other fluids weighted with barite and with
barite filtercake downhole
36
Slide 37
EXPECTED REACTIONS
Important observations:
BaSO4 is slightly soluble in formate brine, whilst it is barely soluble in
fresh water
BaCO3 is barely soluble in formate brine and in water
K2SO4 is only slightly soluble in formate brine, whilst it is soluble in
fresh water
Cs2SO4 is soluble in formate brine and in water
With these observations in mind, one can predict how various buffered
and unbuffered formate brines react with BaSO4
37
Slide 38
DISSOLUTION OF BARIUM SULFATE IN BRINE

When BaSO4 is exposed to any brine, there will be some very slight
dissolution:
BaSO4(s) Ba2+(aq) + SO42-(aq)
Solubility product constant: Ksp [Ba2+][SO42-]
38
Slide 39
HYPOTHESIS
Unbuffered single-salt potassium formate brine:
2K+(aq) + SO42-(aq) K2SO4(s)
The removal of SO42- ions from the solution drives the further dissolution
of BaSO4 and a build-up of soluble Ba2+
39
Slide 40
HYPOTHESIS
Buffered single-salt potassium formate brine:
2K+(aq) + SO42-(aq) K2SO4(s)
Ba2+(aq) + CO32-(aq) BaCO3(s)

The removal of SO42- and Ba2+ ions from the solution drives the further
dissolution of BaSO4, but no build-up of soluble ions.
40
Slide 41
HYPOTHESIS
Unbuffered single-salt cesium formate brine:
No precipitation reactions are expected to take place as cesium sulfate is

very soluble in formate brines.
41
Slide 42
HYPOTHESIS
Buffered single-salt cesium formate brine:
BaSO4(s) = Ba2+(aq) + SO42-(aq)
Ba2+(aq) + CO32-(aq) BaCO3(s)
The removal of Ba2+ ions from the solution drives the further dissolution
of BaSO4 and a build-up of soluble SO42-
42
Slide 43
HYPOTHESIS
Blended cesium and potassium formate brines:
Expected to behave the same way as potassium formate brines since
there is K+ ions available to react with dissolved SO42-
43
Slide 44
EXPERIMENTAL
Hypotheses to be verified
Parameters to be investigated:
brine composition
brine concentration
carbonate/bicarbonate buffer concentration
exposure temperature
Exposure time
All barium measurements were performed after the fluid had cooled
down to simulate field conditions
Analytical grade BaSO4 was used more Ba2+ dissolution than barite
44
Slide 45
EXPERIMENTAL
Brines with excess BaSO4(s) were aged
dynamically in hot-rolling cells
Cooled 2 hours at ambient temperature
Ba2+ was analyzed using an Agilent 4100
MP-AES optical emission spectrometer
SO42- was analyzed using a Metrohm Ion
Chromatograph
1,000 times dilution
Solid analyses were performed externally
by FTIR
45
Slide 46
RESULTS UNBUFFERED FORMATE BRINES

Unbuffered formate brines after 16 hours exposure to BaSO4 at 100C
46
Slide 47
RESULTS EFFECT OF TEMPERATURE

Cs/K blends after 16 hours exposure to BaSO4 at variable temperature
47
Slide 48
RESULTS EFFECT OF TIME AND TEMPERATURE

Buffered blends after 6.7 days exposure to BaSO4 at variable temp.
48
Slide 49
RESULTS EFFECT OF LONG-TERM EXPOSURE

Buffered blends after 1,2, 3 weeks exposure to BaSO4 at room temp.
49
Slide 50
CONCLUSIONS
Unbuffered KFo: Soluble Ba2+ levels increased with brine
concentration above 50 wt%. At 75 wt% 3,500 mg/L was measured.
Unbuffered CsFo only slightly dissolves BaSO4 (like other brines)
Buffered formate brines: Only low levels (<10 mg/L) of soluble Ba2+
can exist due to precipitation of BaCO3.
Buffered CsFo: levels of soluble SO42- slightly elevated (< 1,330 mg/L)
Increased exposure temperature and time only slightly increased the
measured level of soluble Ba2+
At ambient conditions no effect found by increasing the exposure
time from 1 week to 3 weeks.
50
Slide 51
RECOMMENDATIONS
Although the Ba2+ level can be kept at an acceptable level in buffered
formate brines, it is not recommended to use barite weighting
material in formate brines containing potassium as dissolution and
precipitation reactions are continuously taking place
Barite weighting material could be added to pure cesium formate
brine, but elevated sulfate levels will be observed if the brine is
buffered
51
Slide 52
PREVIOUS WORK BY SHELL

Shell [SPE 30498] measured high levels of barium in potassium formate
brines after 16 hours exposure at 85C / 185F
Dissolved
Ba2+
[mg/L]
Water
NaFo NaCl NaBr

KFo
KCl
KBr
CsFo
(40%) (26%) (46%) (75%) (24%) (34%) (82%)
BaSO4
47
3,413
353
Barite
94
29
12
1,530
47
29
412
BaSO4
scale
nd
47
29
4,119
29
18
471
Unbuffered
Cs2SO4
Unbuffered, contains potassium
52
Slide 53
APPLICATIONS
Can this new understanding of dissolution and precipitation mechanisms
taking place in these highly concentrated brine systems open doors for
new technology?
Barium sulfate scale dissolution
Barite filtercake removal
53
www.formatebrines.com/manual
www.cabotcorp.com/formatemanual
54

Formate Brines - What&#39;s New - Siv Howard

Încărcat de

Informații document

Descriere originală:

Drepturi de autor

Formate disponibile

Partajați acest document

Partajați sau inserați document

Opțiuni de partajare

Vi se pare util acest document?

Este necorespunzător acest conținut?

Drepturi de autor:

Formate disponibile

Formate Brines - What&#39;s New - Siv Howard

Încărcat de

Drepturi de autor:

Formate disponibile

Latest formate

Cabot Publications 2016

Independent Study by Ridge

Perform high level time-cost-risk-benefit analyses for well construction

Predicted time for a 500 m 8" reservoir section

Reservoir compatibility with clear completion

High density halide brines contain divalent cations: Zn2, Ca2+

Very low concentration compared to an ion that is part of the brine

Basic formate brine properties that help

How does it work?

pH in various brine systems as function of CO2 influx volume

Increased amount of CO2 influx

CO2-corrosion Formation of Iron Carbonate

Corrosion: comparison of cesium/potassium

Green sludge in phosphate

Corrosion study 1 Results

Formate brine + CO2

Phosphate brine 1 + CO2

Phosphate brine 2 + CO2

Corrosion test 1 C-steel

Formate 2.0 g/cm3, buffered to pH 10.0 10.5

Metal: Standard 13Cr alloy tubing material

Exposure time: 30 days

Exposure temperature: 177, 180, 200 C

Corrosion study 2 - Results

pH 7 not feasible downhole

Buffered cesium/potassium formate blend 1.80 g/cm3, pH 10.2

BG-13Cr tubing material

170C for 13Cr tubing material

Corrosion test 3 Results

Corrosion test 3 Results

Black protective layer

Reservoir compatibility with clear completion

High density halide brines contain divalent cations: Zn2+, Ca2+

Buffer is added in relatively small concentrations

Also, the buffer concentration can be reduced in critical wells

Impact of brine type on formation damage

HPHT laboratory core flooding test with

To determine the effect of potassium phosphate brine invasion on the gas

HPHT core flood test results with potassium

Differential pressure (psi)

Differential pressure did not stabilise

Impact of brine type on formation damage

91.6% reduction in return permeability

HPHT core flood test results with potassium

HPHT core flood test results with potassium

Sand grains and pore throats covered in blanket of

Impact of brine type on formation damage

Phosphate brine forms insoluble scales on contact with multivalent cations

tricalcium phosphate [Ca3(PO4)2] hard bonelike deposit

Potassium phosphate brine absorbs strongly onto mineral surfaces where

New study removal of phosphate damage

PREVIOUS WORK BY SHELL

DISSOLUTION OF BARIUM SULFATE IN BRINE

Ba2+(aq) + CO32-(aq) BaCO3(s)

No precipitation reactions are expected to take place as cesium sulfate is

RESULTS UNBUFFERED FORMATE BRINES

RESULTS EFFECT OF TEMPERATURE

RESULTS EFFECT OF TIME AND TEMPERATURE

RESULTS EFFECT OF LONG-TERM EXPOSURE

PREVIOUS WORK BY SHELL

NaFo NaCl NaBr

Unbuffered, contains potassium

Formate Brines - What's New - Siv Howard

Formate Brines - What's New - Siv Howard