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Abstract
Dissolver technology has been developed and applied with
varying degrees of success over the past few years to clean
carbonate and the more challenging sulphate/sulphide scales
from production tubing and process equipment. The intention
of this proposed application was to select a chemical that
could be applied into the near wellbore region of the reservoir
to recover scale induced damage while not creating any
secondary precipitation or negative wettability effects.
The impact of dissolver chemical formulation on the reservoir
formations wettability and the potential for mobilization of
fines (both reservoir silicate and scale) has not been outlined
before. In this paper reservoir condition coreflood studies are
outlined where scale is formed within the cores to allow
assessment of sulphate dissolver performance. This will form
a critical part of the technical evaluation of the dissolver
formulation suitability for field application. Results from
these coreflood studies will be compared to those generated
for the same chemicals in conventional static dissolver
studies.
The practical concerns about deployment methods within
subsea production wells are also emphasized. Specific
reference will be made to the impact of metallurgy on
chemical selection and the need to reduce corrosion risk
within developments which utilize both carbon steel and super
duplex requiring the development of higher pH non acid
carbonate dissolvers.
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Acknowledgements
The authors would like to thank BP E&P, Nalco Energy
Services for permission to publish this work. We are also
grateful for the help and co-operation of members of the asset
team, field operators and Nalco laboratory staff for their
assistance in carrying out the treatments described in this
paper.
Reference
1. Allege, D.A., Woo, G., Sharma, MM, Lake, L.W.:
Barium and Calcium Sulphate Precipitation and
Migration Inside Sand Packs, paper SPE 19765.
2. Weintritt, S.J. and Cowan, J.C.: Unique Characteristics
of Barium Sulphate Scale Deposition, JPT (October
1967) 1381; Trans., AIME, 240.
3. Cowan. J.C. and Weintritt, D.J.: Water Formed Scale
Deposits, Gulf Publishing Co., Houston, Texas (1976).
4. Carrel, K.D.: The Occurrence, Prevention and Treatment
of Sulphate Scale in Shell Expro, paper SPE 16538
presented at the 1987 SPE Offshore Europe 87
Conference, Aberdeen 8-11 September.
5. De Vries, H. and Arnaud, F.: The First Successful
Downhole Barium Sulphate Scale Dissolving operation,
paper SPE 26704 presented at the 1993 SPE Offshore
Europe Conference, Aberdeen, 7-10 September.
6. Clemmit, A.F., Hunton, A.G., and Balance, D.C.: The
Dissolution of Scales in Oilfield Systems, paper SPE
7.
8.
9.
10.
11.
12.
13.
14.
15.
16.
17.
18.
SPE 100356
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SPE 100356
Ion
Na
K
Ca
Mg
Ba
Sr
Cl
HCO3
SO4
Concentration (mg/l)
Formation Water
Seawater
47454
10800
282
400
4532
430
576
1400
108
0
205
0
82457
19754
240
145
23
2750
Table 3. Comparison of sulphate dissolver Perfoance for formulations W and N at two activities after 24 hours at
90C.
Chemical Application
Percentage of
Scale Dissolved (mass)
Percentage of
Scale Dissolved (ion)
100% Chemical N
2.26
22.60%
12.71%
35%Chemical N
1.83
18.30%
7.03%
100% Chemical W
2.68
26.80%
13.10%
35% Chemical W
1.23
12.30%
9.91%
Appearance of
Treated Barite
Smaller Grains
and Dust
Smaller Grains
and Dust
Smaller Grains
and Dust
Smaller Grains
and Dust
Table 4. Permeability measurements made during core conditioning, in-situ scale formation, dissolution and
post chemical treatments with oil, brine, chemical formulation N.
Formulation N Scale Dissolver Permeability
Test Code
Brine perm 1 following initial brine injection (Stage 4)
Brine perm 2 following initial flood to Sor (Stage 8)
Brine perm 3 following scale build up (Stage 14)
Brine perm 4 after dissolver chemical treatment (Stage 25)
K mD values % change
50.36
8.09
-83.93
6.07
-25.03
6.36
-21.44
18.64
19.82
11.43
17.53
Viscosity values
Oil at 93C
Formation Water at 93C
1.0 cp
0.5 cp
6.32
-42.33
-11.55
10
SPE 100356
Table 5. Permeability measurements made during core conditioning, in-situ scale formation, dissolution and post
chemical treatments with oil, brine, chemical formulation W.
Formulation W Scale Dissolver Permeability
Test Code
Brine perm 1 following initial brine injection (Stage 4)
Brine perm 2 following initial flood to Sor (Stage 8)
Brine perm 3 following scale build up (Stage 14)
Brine perm 4 after dissolver chemical treatment (Stage 25)
K mD values % change
68.33
12.24
-82.09
6.65
-45.67
13.05
6.63
27.46
30.28
13.88
16.39
Viscosity values
Oil at 93C
Formation Water at 93C
1.0 cp
0.5 cp
10.27
-54.18
-45.88
Table 6. Comparison of carbonate dissolver performance for four formulations after 6 hours at 90C.
Scale Dissolver Type
7.5% HCl
50% Acetic/Formic acid
pH 12.8 modified EDTA
pH 4.5 modified EDTA
% Dissolution (mass)
100
100
21.7
93.4
% Dissolution (ion)
81.47
87.57
49.92
74.14
Table 7. Carbonate dissolver corrosion performance to carbon steel and CRA after 6 hours exposure 90C (no
carbonate scale present during test)
Corrosion Rates
Coupon type
Chemical type
mmpy
Mpy
Carbon steel
68.00
2677.17
Carbon steel
27.00
1062.99
Cr 25 Super Duplex
0.02
0.79
Cr 25 Super Duplex
0.03
1.18
SPE 100356
11
Table 8. Carbonate dissolver corrosion performance to carbon steel after 24 hours exposure 90C (no scale
present during test)
Corrosion Rates
Coupon type
Chemical type
CI Concentration
mmpy
Mpy
Carbon steel
None
31.60
1244.09
Carbon steel
100 ppm
20.17
793.90
Carbon steel
1000 ppm
6.60
259.84
Carbon steel
5000 ppm
6.16
242.44
Corrosion Rates
Coupon type
Chemical type
CI Concentration
mmpy
Mpy
Carbon steel
None
16.40
645.67
Carbon steel
100 ppm
5.49
216.14
Carbon steel
1000 ppm
2.66
104.72
Carbon steel
5000 ppm
1.85
72.68
12
SPE 100356
Figure 1. Oil Production rate decline due to natural reservoir pressure and scale induced damage plus impact on oil rate of scale
inhibitor squeeze (SISQ), stimulation and a stimulation alone.
= (C+B) - A >>>(B - A)
SISQ + Stim.
B= Volume of oil
produced due to scale
inhibitor being present
Inhibition or
stimulation treatment
Pre SISQ
Decline
Decline in
BOPD due
to scale
C= Volume of oil
released due to
stimulation
Post SISQ or
SISQ stimulation
Decline
Qoil
BOPD
SISQ alone
Time
Figure 2. Calcium ion concentration within the effluent leaving a sand/carbonate pack flood after application of acid dissolver with
and without mutual solvent
2500
15% mutual solvent enhanced
2000
1500
1000
500
13
1
12
6
12
1
11
6
11
1
10
6
96
10
1
91
86
81
76
71
66
61
56
51
46
41
36
31
26
21
16
11
unenhanced
SPE 100356
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Figure 3. Barium ion concentration within the effluent leaving a sand/barite pack flood after application of acid dissolver with and
without mutual solvent
2000
unenhanced
Barium ion concentration within the effluent (ppm)
1500
1000
500
96
10
1
10
6
11
1
11
6
12
1
12
6
13
1
13
6
14
1
14
6
15
1
91
86
81
76
71
66
61
56
51
46
41
36
31
26
21
16
11
Figure 4. Rate of barium sulphate dissolution using two formulations (W and N) of sulphate dissolver at two concentration over 24
hour contact time, 90C.
10000
35% Formulation N
35% Formulation Wl
9000
8000
7000
6000
5000
4000
3000
2000
1000
0
0
10
15
Time / hours
20
25
14
SPE 100356
Figure 5. Rate of strontium sulphate dissolution using two formulations (W and N) of sulphate dissolver at two concentration over 24
hour contact time, 90C.
Static Scale Dissolver Tests
Strontium in Solution
100% Formulation N
100% Formulation W
10
35% Formulation N
35% Formulation W
9
8
7
6
5
4
3
2
1
0
0
10
15
20
25
Time / hours
Figure 6. Rate of calcium sulphate dissolution using two formulations (W and N) of sulphate dissolver at two concentration over 24
hour contact time, 90C.
Static Scale Dissolver Tests
Calcium in Solution
100% Formulation N
100% Formulation W
100
35% Formulation N
35% Formulation W
90
80
70
60
50
40
30
20
10
0
0
10
15
Time / hours
20
25
SPE 100356
15
Figure 7. Differential pressure across core plug during the formation of in siture barium sulphate scale, 25C, 90% FW : 10% SW at 60
ml flow rate.
45
40
35
60 mls/hr
30
25
20
15
10
0
0
200
400
600
800
1000
1200
1400
1600
Time (mins)
Figure 8. Differential pressure across the core plug during the dissolution of in situe barium sulphate scale with mutual solvent
preflush and formulation N, 65C, flow rate 60ml/h
70
Dead
Volume
1 Pore
Volume
3 Pore Volumes
Main Treatment
1 Pore
Volume
Preflush
Preflush
60
50
40
30
Shut-in/soak
Shut-in/soak
20
10
0
0
20
40
60
80
100
Volume (mls)
120
140
160
180
200
16
SPE 100356
Figure 9. Differential pressure across the core plug during the dissolution of in situe barium sulphate scale with mutual solvent
preflush and formulation W, 65C, flow rate 60ml/h
70
Dead
Vol
60
1PV
Pre-Flush
3 PV Main
Treatment
3 PV Main
Treatment
3 PV Main
Treatment
1 PV
Pre-Flush
50
40
30
20
10
Shut-in/soak
Shut-in/soak
0
0
10
20
30
40
50
60
70
80
90
100
110
120
130
140
150
160
170
180
190
200
Volume (mls)
Element
Element
CK
OK
NaK
AlK
SiK
SK
ClK
KK
CaK
BaL
Total
Wt %
30.97
13.94
3.83
0.46
7.14
6.33
4.23
0.43
1.07
31.6
100
At %
57.66
19.48
3.72
0.38
5.68
4.42
2.67
0.25
0.6
5.15
100
CK
OK
NaK
MgK
AlK
SiK
SK
ClK
KK
BaL
FeK
Total
Wt %
43.09
18.04
0.92
0.17
1.22
6.22
4.96
1.11
1.1
20.52
2.66
100
At %
65.95
20.72
0.74
0.13
0.83
4.07
2.85
0.58
0.52
2.75
0.87
100
SPE 100356
17
Figure 12. Rate of calcium carbonate dissolution using four formulations of carbonate dissolver over 6 hour contact time, 90C.
7.5% HCl
12000
10000
100%
100%
Ca dissolved (ppm)
8000
93.4%
6000
21.7%
4000
2000
0
0
60
120
180
240
300
360
Time (mins)
Figure 13. Carbon steel weight loss coupons following emersion in acetic/formic acid carbonate dissolver for 24 hours 90C. Coupons
were tested with and without acid corrosion inhibitor present.
No CI
Figure 14. Carbon steel coupons following emersion in modified EDTA carbonate dissolver, pH 4.7 after 24 hours 90C. Coupons
were tested with and without acid corrosion inhibitor present.
No CI