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Inhibition of Lead and Zinc Sulphide Scale Deposits Formed during Production from
High Temperature Oil and Condensate Reservoirs.
M.M Jordan Nalco/Exxon, K. Sjursaether Nalco/Exxon, M.C. Edgerton Texaco North Sea UK, R. Bruce Nalco/Exxon
Abstract
Carbonate and sulphate scales are the most common types of
mineral deposit associated with the recovery and processing of
hydrocarbon and associated produced water. In three high
temperature fields (>140C) within the North Sea more usual
scale types have been observed namely zinc and lead sulphide.
Conventional inhibitors cannot control these scale types and
their removal by chemical means can result in the generation
of toxic gas (H2S). The conditions for the formation of these
unusual scale types is described and well as the economic
impact these deposit had on hydrocarbon production of these
fields. In this paper the development of a novel scale inhibitor
package and its successful application in these fields is
described.
Field evaluation of the inhibitor types used to control
sulphide scale is described in this paper as well as the details
on how the field trials were planned, carried out and
evaluated.
Mechanical and chemical removal are also
discussed as an alternative to inhibition.
The finding of this paper significantly increase the industries
understanding of sulphide scale deposits in terms of mode of
formation and mechanism of inhibition. The paper stresses
the critical factors to be evaluated within produced water at
the early stage of field appraisal/development that can aid in
the assessment of the risk of sulphide scale deposition. The
development of a novel zinc and lead sulphide inhibitor gives
a cost effective, environment friendly alternative to chemical
or mechanical removal of such deposits.
Introduction
The most common scales encountered in oil field operations
are sulphates such as calcium sulphate (anhydrite, gypsum)
barium sulphate (barite), strontium sulphate (celestite) and
carbonates (calcite). Numerous studies on scale inhibition
have been published over the past few years with regard to
controlling such scale within the reservoir and in production
equipment (downhole and topside).1-8 Other less common
scales have also been reported such as iron oxides, iron
sulphides and iron carbonate. These scale types are most
commonly associated with iron generation from corrosion
products although iron carbonate scale has been reported
forming from produced water drawn from formations where
iron containing authigenic minerals are present within the
formation.9,10,11 As with the sulphate and carbonate scale
types described above even iron carbonate scale is able to be
controlled by inhibitor molecules.12
Lead and zinc sulphide scale has recently become a concern
in a number of North Sea oil and gas fields. These deposits
have occurred within the production tubing and within the
topside process facilities. Investigation of the literature lead to
a number of references where such scale had been
observed13,14,15,16,17 but very little information was available on
their inhibition by chemical means. This paper will outline
formation mechanisms of both lead & zinc sulphides and also
reviews the data from the literature before describing how a
chemical inhibition program has been effectively deployed
within a North Sea field and the next planed field deployment.
Potential sources of Lead and Zinc sulphide. Several
sources of zinc/lead ions and sulphide ions are possible within
produced fluids.
Potential sources of zinc and lead ions include
Reaction products of formation minerals (sphalerite ZnS
and Galena PbS) during connate and aquifer water contact
over many millions of years could result in partial mineral
dissolution.13,14,15 Zinc ion concentration within high
pressure/temperature fields within the Gulf coast of
Mexico16 were reported as high as 70 ppm Pb and 245
ppm Zn.
Reaction of injected water used for pressure support into
the aquifer or oil leg can result in the fresh or seawater
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INHIBITION OF LEAD AND ZINC SULPHIDE SCALE DEPOSITS FORMED DURING PRODUCTION
FROM HIGH TEMPERATURE OIL AND CONDENSATE RESERVOIRS
Chemical Inhibition
The prevention of scale formation via the use of inhibitor
chemicals is a very extensive subject with respect to the
prevention of sulphate and carbonate scales1-8 but little has
been published on the inhibition of lead and zinc sulphide.
Scale inhibitors function at substoichiometric concentrations
with respect to the scaling compound by a number of
mechanisms, such as preventing scale nuclei formation,
adsorbing on scale nuclei once formed, inhibit further crystal
growth and dispersing growing scale nuclei so reducing
adherence. Chelating agents while not used for conventional
sulphate/carbonate scale inhibitors work by forming a stable
water soluble complex with metal ions and effectively prevent
reactions with other ions within the brine.
Laboratory testing of scale inhibitors for application is the
most common way of product selection when controlling
sulphate and carbonate scale deposition. The issue of handling
hydrogen sulphide gas makes such testing for zinc sulphide
more difficult. Kaplan 20 describes a laboratory method of
screening products and the effectiveness of these products is
substantiated with field test data. Emmons and Chestnut21
also outline field test data which shows that zinc sulphide
scale control was possible by application of polymer based
scale inhibitors.
Investigation into conventional scale inhibitor performance
against lead and zinc sulphate by field trialing a range of
products revealed that it was possible to control the formation
of these scales. It was found that polymer based scale
inhibitors were far more effective than phosphonate based
chemicals and that the treat rates were much lower for scale
inhibitor than for chelating agents such as EDTA (Ethyl
diameter tetra acetic acid) and as a result offered a more cost
effective treatment mechanism.
Field A within the UK sector of the North Sea. Field A is a
high temperature/high pressure field in the UK sector of the
central North Sea. The field consists of High pressure and
temperature gas condensate fluids contained within 3 separate
Jurassic reservoirs. One of these accumulations is supported
by a natural aquifer. The field is produced from 5 wells drilled
to a depth of 4,880 meters TVD. Only two of the five wells are
expected to produce formation water.
Initial reservoir pressure was 14,000 Psi and Temperatures
are 174C. The wells produce onto a Normally Unattended
Installation were flowrates are measured and chemicals are
added to aid flow assurance. From here the fluids are
transported via a 30Km multi-phase pipeline to a hostprocessing platform. The majority of scale issues to date have
been reported on the host-processing platform. The field has
been on production for three years and produces at a rate of
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INHIBITION OF LEAD AND ZINC SULPHIDE SCALE DEPOSITS FORMED DURING PRODUCTION
FROM HIGH TEMPERATURE OIL AND CONDENSATE RESERVOIRS
Conclusions
1. Lead and zinc sulphide scales are extremely insoluble at
typical formation brine pH, and salinity. Their solubility
increases with increasing brine salinity, temperature and
falling pH.
2. The source of lead and zinc ion in many cases is not from
heavy completion fluid but from the formation water itself
as it reaches thermodynamic equilibrium with authigenic
or detritial formation mineral such as galena and
sphalerite. The source of the sulphate ion is from
hydrogen sulphide within reservoir water or gas phases.
3.
4.
5.
6.
7.
8.
2.
3.
4.
5.
6.
7.
8.
9.
10.
Acknowledge
The authors would like to thank Texaco UK, BP Amoco
Norge and Nalco/Exxon Energy Chemicals for permission to
publish this work. We also acknowledge the help and cooperation of members of the asset teams, and Nalco/Exxon
laboratory staff for their assistance in carrying out the
evaluations and treatments described in this paper in particular
Stuart Holt and Stuart Kemp who carried out much of the
laboratory work described.
References
1.
SPE 64427
11.
12.
13.
14.
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INHIBITION OF LEAD AND ZINC SULPHIDE SCALE DEPOSITS FORMED DURING PRODUCTION
FROM HIGH TEMPERATURE OIL AND CONDENSATE RESERVOIRS
15. Kharaka, Y.K., Lico, M.S., Wright, V.A and Carothers, W.W.
Geochemistry of Formation Waters from Pleasant Bayou No.2
Well and Adjacent Areas in Coastal Texas. Proc. Geo
pressured Geothermal Energy Conf. 4th Austin, Texas, pp 168193. 1980.
16. Kharaka, Y. K., Maest, A. S., Carothers, W. W., Law, L.W.,
Lamothe, P.J., Fries, T.L., Geochemistry of Metal-Rich Brines
from Central Mississippi Salt Dome Basin, USA, Applied
Geochemistry, Vol. 2, 1987, pp 543-561.
17. Biggs, K.D., Allison, D., Ford, W.G.F., Acid Treatments
Removes Zinc Sulfide Scale Restriction, Oil and Gas Journal,
Aug. 31, 1992, Page 17.
18. Barrett,T.J., Anderson, G. M., The Solubility of Sphalerite and
Galena in 1-5M NaCl Solutions to 300C, Geochim.
Cosmochim. Acta, Vol. 52, 1988, pp 813-820.
19. Coleman, M., Novel Methods for Determining Chemical
Composition of Oil-Zone Waters and Relevance to Scale
Prediction. SPE Oilfield Scale Symposium. 27-28th January,
1999, Aberdeen, UK.
20. Kaplan, R., I Scale Deposition Inhibitor United States Patent
5,171,459, December 15, 1992.
21. Emmon, D., and Chesnut, G.R., The Utilization of
Hydroxyethylacrylate/acrylic Acid Copolymer as Zinc Sulfide
Scale Inhibitor in Oil Well Production Process, United States
Patent 4,762,626, August 9, 1988.
Composition
Production
Fluids 29/09/99
DST
15,797
Pentland
Process platform
Wells P1, P2
148,930
1.108
0.084
7.53
N/D
N/D
N/D
N/D
Sodium
Potassium
Calcium
Magnesium
Barium
Strontium
Manganese
Total iron
Chloride
Sulphate
Bicarbonate
Carbonate
Boron
Silicon
Phosphorus
Hydrogen sulphide
41,590
345
11,790
955
1,690
680
N/D
8
91,200
16
625
NIL
52
16
1.8
20
29,300
209
8,875
745
1,475
560
N/D
169
59,491
11
N/D
N/D
N/D
N/D
N/D
<30
SPE 64427
HP sep LCV
% Wt
Loss on solvent
Dried Residue
15.7
84.3
Location
Flange Deposit
Pig Receiver
HP sep LCV
% Wt
Loss on ignition
Acid insoluble
39.11
48.86
12.05
9.94
16.61
54.71
Acid soluble
Fe
Mn
Zn
Pb
Ca
Ba
Na
SiO2
SO4
S
0.57
N/D
0.56
0.91
0.14
3.22
N/D
N/D
3.42
N/D
51.56
N/D
1.16
1.08
0.21
0.5
0.64
N/D
2.05
N/D
0.81
6.93
11.31
0.02
0.02
N/D
N/D
6.8
N/D
0.05
26.38
0.15
19.13
0.62
0.03
Non magnetic
7.06
N/D
N/D
N/D
N/D
N/D
N/D
Magnetic
0.18
27.53
0.26
16.16
0.16
0.06
Non magnetic
Acid insoluble
Ca
Ba
Sr
SO4
SiO2
Fe
Magentic
Table 3. Produced water compositions from water samples taken across the process facilities on the same day of production, Field A.
Note: a correction has been made to LP hydrocyclone and LP separator due to the dilution effect that happens in the LP fluid stream.
Location
HP Sep
HP
Hydrocyclone
LP
Hydrocyclone
Dilution
Corrected LP
Hydrocyclone
LP
Separator
Dilution
Corrected LP
Separator
Degasser
K
pH
Fe
Ba
Sr
SO4
HCO3
ppm
375
5.1
215
2260
855
3
21
ppm
355
5.16
230
2230
865
<1
22
ppm
200
5.69
135
1230
500
3.5
31
ppm
352.8
238.14
2169.7
882
6.174
54.684
ppm
200
5.66
130
1210
500
2.8
31
ppm
359.2
233.48
2173.16
898
5.0288
55.676
ppm
360
5.16
225
2190
840
3.3
22
Cr
Zn
Pb
< 0.02
8.1
0.09
< 0.02
8.2
0.07
< 0.02
4.6
< 0.05
< 0.02
8.1
< 0.05
< 0.02
4.4
< 0.05
< 0.02
7.9
< 0.05
< 0.02
7.7
< 0.05
Date
06/12/99
INHIBITION OF LEAD AND ZINC SULPHIDE SCALE DEPOSITS FORMED DURING PRODUCTION
FROM HIGH TEMPERATURE OIL AND CONDENSATE RESERVOIRS
SPE 64427
Field B (ppm)
Field C (ppm)
Na
K
Mg
Ca
Sr
Ba
Cl
SO4
CO3
HCO3
52555
3507
2249
34675
1157
91
153025
44
0
134
65340
5640
2325
30185
1085
485
167400
0
0
76
10890
460
1368
428
8
0
19700
2960
0
124
pH
Zn
Pb
H2S
Res. T
Res. P
WHFT
WHFP
5.4
10 40
<1
< 20
143
410 bar
110
20 bar
5.46
40 70
<1
20 25
150
450 bar
68
25-60
8
0
0
0
-
100000
10000
1000
FeS
100
10
ZnS
1
PbS
0.1
0.01
0.001
0
Brine pH
Figure 1. Comparison of zinc, lead and iron sulphide solubility in 1m NaCl brine at 25C.
10
SPE 64427
5m NaCl solution
0
0
50
100
150
200
250
300
350
1m NaCl solution
-2
-4
1m NaCl
2m NaCl
-6
3m NaCl
4m NaCl
5m NaCl
-8
Temperature Degree C
Figure 2. Calculated zinc sulphide solubility at 25C to 300C in 1m, 2m, 3m, 4m and 5m NaCl solutions, pH 4.0
2
5m NaCl solution
0
0
50
100
150
200
250
300
350
-2
1m NaCl solution
-4
1m NaCl
2m NaCl
-6
3m NaCl
4m NaCl
5m NaCl
-8
Temperature Degree C
Figure 3. Calculated lead sulphide solubility at 25C to 300C in 1m, 2m, 3m, 4m and 5m NaCl solutions, pH 4.0
INHIBITION OF LEAD AND ZINC SULPHIDE SCALE DEPOSITS FORMED DURING PRODUCTION
FROM HIGH TEMPERATURE OIL AND CONDENSATE RESERVOIRS
SPE 64427
11
110
100
90
15% HCl
25% HCl
80
Zn concentration (ppm/v)
50% HCl
50% organic acid
70
60
50
40
30
20
10
0
0
200
400
600
800
1000
1200
1400
1600
Figure 4. Zinc sulphide scale dissolver performance tests for hydrochloric acid and mixed organic acid at 20C using 1mm diameter
Sphalerite chips
2000
1500
1000
2500
3000
3500
4000
4500
500
0
16-Nov-97
24-Feb-98
4-Jun-98
12-Sep-98
21-Dec-98
31-Mar-99
9-Jul-99
17-Oct-99
Time
Figure 5. History of scale deposition within field A as water production rates increase. The figure shows the trace amounts of
scale observed during the low water production rates which become more significant in amount as water production rates rises
sharply in late 1999.
12
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14
12
Blank Scale
10
12000
13000
0
0
1000
2000
3000
4000
5000
6000
7000
8000
9000
10000
11000
14000
Time (seconds)
Figure 6. Low molecular weight phosphonate scale inhibitor tested under topside choke conditions. T=130 C, P=1500psi with and
without 250 ppm iron (II).
12
300ppm VS-Co
200ppm VS-Co
300ppm PVS
200ppm PVS
Blank Scale
10
0
0
1000
2000
3000
4000
5000
6000
7000
Tim e (seconds)
Figure 7. Poly vinyl sulphonate (PVS), vinyl sulphonate co polymer (VS-Co) and low molecular weight polymer scale inhibitors
tested under topside (choke) conditions with 250ppm Fe(II) present. T=130 C P=1500psi.