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A Case Study of Seawater Injection

Incompatibility
John Chapin Lindlof, SPE, Arabian American Oil Co.
Kenneth G. Stoffer, SPE, Arabian American Oil Co.

Summary
One of the primary concerns in the implementation of an in the literature were limited. This work sup~lemented
effective waterflood is the compatibility between the for- the available strontium sulfate solubility data. -7 Results
mation water and the water to be injected. The Arabian of this testing have been reported in Ref. 8.
American Oil Co. (ARAMCO) and the Saudi Arabian Additional phases of the evaluation program, which
Ministry of Petroleum and Mineral Resources Technical are the subject of this paper, included extensive
Branch recognized a potential incompatibility problem laboratory analyses and water system evaluations, reser-
and embarked on a comprehensive program to evaluate voir simulation studies, field tests, and other procedures.
possible strontium sulfate and calcium sulfate scaling
associated with the injection of seawater into the Arab-D Theory
reservoir in the northern areas of Ghawar field. The solubility of calcium sulfate is an order of magnitude
greater than that of strontium sulfate, which in tum is
Introduction about one and one-half orders of magnitude greater than
Waterflooding of the northern areas of the Ghawar field, that of barium sulfate (Fig. 1). Such data, however, can
the world's largest known oil field, with the Wasia be misleading. Fig. I indicates, for example, that the
aquifer as the source water began in 1965. As the reser- solubility of strontium sulfate can be greater than 950
voir pressure-maintenance program continued, a deci- mg/L (mg/dm 3). This solubility, however, is true only
sion was made to replace Wasia water injection in the when the solution is stoichiometrically balanced-i.e.,
north 'Uthmaniyah area of the field with seawater injec- when the number of strontium ions equals the number of
tion. To meet this requirement, a 4.2-million BID (0.67 sulfate ions. If an excess of either ion is introduced, the
X 10 6 _m 3 ) seawater-treatment plant, with associated solubility is depressed markedly. This is known as the
distribution and injection facilities, was placed in opera- "common ion effect."
tion in June 1978. As the solubility of strontium sulfate is decreased by
The initial Wasia waterflood and the subsequent the common ion effect, the supersaturation becomes a
seawaterflood in the north 'Uthmaniyah area, together disproportionately higher percentage of total strontium
with the connate Arab-D formation water, represented a sulfate in the solution. The supersaturation represents the
three-water system with a possible incompatibility prob- amount of strontium sulfate present in excess of the
lem. Basic to the understanding of water incompatibility solubility and thus represents the amount available for
in this instance was knowledge of the solubilities of the precipitation from solution and possible scaling. The
sulfates of barium, calcium, and strontium, and how supersaturation exists in a metastable state and, as such,
their solubilities are affected by changes in salinity, the manner in which it exists in solution or comes out of
temperature, and pressure. Particular emphasis was solution by crystallization and precipitation is entirely
placed on laboratory work to determine the solubility of unpredictable.
strontium sulfate, since strontium sulfate solubility data Fig. 2 illustrates the common ion effect for mixtures of
Arab-D formation water and seawater. In these mixtures
0149-2136/83/0007-9626$00.25 the maximum strontium sulfate solubility is reached at
Copyright 1983 Society of Petroleum Engineers of AIME Point C, where the strontium ions of the formation water
1256 JOURNAL OF PETROLEUM TECHNOLOGY
TABLE 1-ANALYSES OF WATERS ASSOCIATED WITH
SEAWATER FLOOD AT 'UTHMANIYAH

Low-Salinity High-Salinity
Arab-O Arab-O Wasia Seawater
Na + 29,680 51,187 1,504 18,043
Ca++ 13,574 29,760 392 652
Mg++ 1,575 4,264 66 2,159
Ba + + 8 10 0 0
Sr + + 557 1,035 5 11
HC0 3 369 351 192 119
C1 - 73,861 143,285 2,577 31,808
S04-- 404 108 700 4,450
C0 3 - - 0 0 0 27
TOS, mg/dm 3 120,000 230,000 5,436 57,269

in stoichiometric balance with the sulfate ions of the


seawater. If a'n excess of either ion exists (either side of ~

~
COS04
Point C), the common ion effect causes a dispropor-
tionate decrease in the solubility of strontium sulfate, u
o
resulting in a relatively high level of supersaturation in 10
~
comparison with the total strontium sulfate a:: 10 3
concentration. ...
w
SrS04
Since the solubility of the sulfates of calcium, stron-

/
..J

tium, and barium can all be estimated, the amount of a::


w
Q.
supersaturation of each can be predicted for any given
system of different waters. Caution, however, must be :g
~
10 2
exercised when working with estimated values of BOS04
solubility and supersaturation. Many different variables, 1

including temperature, pressure, other ions, pH, tur-


~
bulence, rate of kinetics of precipitation, and seeding or
nucleation all have an effect on the behavior of mixtures ~
of incompatible waters. Some of these variables are
beyond the scope of definition in an oilfield situation.
They introduce unknown factors that make any estimate
of solubility, supersaturation, and the likelihood of NoCI SOLUTION
precipitation and scaling uncertain. 2 3
IONIC STRENGTH
Ghawar Field Waters
Fig. 1-Relative solubilities of three sulfates in brine.
An evaluation of possible incompatibility in the northern
Ghawar field involves the consideration of four different
source waters. These are the native Arab-D formation
water, seawater, and two aquifer waters that have been
used previously as source waters for water injection, the
Wasia and the Biyadh. Since the Biyadh has had only
1000
minor use, the greatest concern was for the three-water
systems composed of Arab-D water, seawater, and
Wasia water. The Wasia water has been injected into the a:
north area of the Ghawar field since 1965, and in most '"...:::i
areas a large bank of Wasia water exists behind which
the seawater either is already being, or was proposed to ...
a:
'" AREA A Sr > SO,
be, injected. o<f) 500 AREA B SO, > Sr
Vi POINT C Sr AND SO, BALANCED
Representative analyses of these three waters illustrate STOICHIOMETRICALLY
the high concentration of calcium and strontium in '",.'" SUPERSATURATION
Arab-D water and the high concentration of sulfate in
seawater (Table 1). Note that the barium concentration is
comparatively low. The formation of barium sulfate -/. SEAWATER
scale has not been a concern except for any role it might 50 100
I
playas a seeding agent in initiating the crystallization of 50
% BRINE (WITH STRONTIUM)
strontium sulfate and calcium sulfate.
The areal variation in the composition of Arabian Gulf Fig. 2-Effects of common ions on SrS0 4 solubility,
seawater and Wasia aquifer water is small, whereas the
areal variation in Arab-D water composition is signifi-

JULY 1983 1257


cant (Fig. 3). Throughout the Ghawar field, the Arab-D
I0 C 10 70 30 40
I.. : fonnation water exhibits a nearly constant ratio of stron-
KILOMETERS tium to total dissolved solids (TDS). This ratio is about
0.004. Whereas the strontium concentration of the
Arab-D water varies from <400 to > 1,125 mg/L
«400 to > 1125 mg/dm 3 ) in the north 'Uthmaniyah
area, the strontium concentration in the 'Ain Dar and
Shedgum areas of Ghawar is unifonnly high, varying on-
ly between about 1,000 and 1,125 mg/L (1000 and 1125
mgt dm 3 ). Thus, although there is a small portion of the
north 'Uthmaniyah area that has high strontium concen-
trations, all the 'Ain Dar and Shedgum areas have
unifonnly high strontium levels. Although there was
some concern for possible scaling in the high-salinity
area of north 'Uthmaniyah, the planned expansion of
seawater injection to the 'Ain Dar and Shedgum areas
became a primary concern because of their higher poten-
SHEOGUM tial for possible strontium sulfate and calcium sulfate
scaling.
A generalized ternary diagram for the three-water
system comprising Arab-D fonnation water, seawater,
and Wasia water illustrates the expected direction a
seawaterflood would take when following an earlier
Wasia flood (Fig. 4). The initial condition would be pure
Arab-D water, represented at the top of the figure. As
Wasia water sweeps the reservoir, the produced-water
composition analysis shows a mixture of Arab-D and
Wasia waters, moving along the Arab-D/Wasia axis in
the direction of lower Arab-D and higher Wasia com-
position. As seawater injected behind the Wasia bank
breaks through into the producing well, the produced-
water composition leaves the Arab-D/Wasia axis and
moves toward the seawater apex as the seawater com-
position increases and eventually becomes the primary
constituent of the produced water.
In tenns of incompatibility, the changing water com-
position controls the scaling tendencies of the produced
water. The water compositions with the highest levels of
both strontium and calcium sulfate supersaturation have
low levels of Wasia water concentration. The maximum
HARAOH strontium sulfate supersaturations occur with a relatively
small percentage of seawater and a high percentage of
Arab D (Fig. 5), whereas the maximum calcium sulfate
supersaturation occurs with a relatively smaller percen-
tage of Arab-D and a higher percentage of seawater (Fig.
6). Thus, the produced-water composition of a particular
well could pass through an area of high strontium sulfate
supersaturation, an area of high calcium sulfate super-
saturation, both, or neither, depending on the relative
Fig. 3-Ghawar field strontium content of Arab-O formation size of the Wasia flood bank ahead of the seawater and
water.
how fast seawater breaks through into the producing
wellbore.
The composition of Arab-D water was shown earlier
to vary considerably in the 'Uthmaniyah area. Doubling
both the salinity and the strontium content of Arab-D
water more than doubles the maximum level of super-
saturation (Figs. 7 and 8). Thus, areas of Ghawar, and
most notably north 'Uthmaniyah with its lower levels of
Arab-D salinity, would not be expected to be as suscepti-
ble to scaling as areas with higher Arab-D salinity ( e.g.,
'Ain Dar and Shedgum).

1258 JOURNAL OF PETROLEUM TECHNOLOGY


100 % ARAB D

100% ARAB D BRINE (TDS=245,OOO mgs/U

WASIA WATER PRE


DOMINANT TDS
5000 my I

100% 100%
100%WASIA SEAWATER WASIA
Fig. 4-Ternary representation of north 'Uthmaniyah Fig. 5-SrSO 4 supersaturation of north 'Uthmaniyah ternary
waterflood. water system.

Kinetics Consideration of these theories and their application to


Some comment on kinetics of strontium and calcium strontium sulfate and calcium sulfate crystallization in-
sulfate precipitation illustrates the application of this fac- dicates that there is a potential for scaling if seawater is
tor to the three-water systems of this discussion. injected into areas of higher-salinity Arab-D water
The kinetics of the chemical reactions of concern in- without an adequate Wasia buffer.
clude the two aspects of supersaturation-how
much-and the degree of supersaturation-how fast. Laboratory Tests
Supersaturation represents the amount of a compound Tests were conducted in the laboratory to substantiate
that is in excess of its solubility and is available for further that these potentials for scaling exist. Both
precipitation and possible scaling. natural Arab-D formation water and synthetic water
The degree of supersaturation is defined as the ratio of simulating Arab-D formation water were mixed with
supersaturation to solubility for any given water mixture. seawater and Wasia water in various proportions. These
The degree of supersaturation (squared) has been shown tests demonstrated that strontium sulfate could be
to be directly proportional to flux, or the rate of precipitated in amounts approaching theoretical calcula-
crystallization. 9,10 tions. Also, the dilution effects of Wasia water were
The relative importance of these two factors, super- demonstrated either to reduce or to eliminate precipita-
saturation and degree of supersaturation, varies for stron- tion altogether.
tium sulfate and for calcium sulfate. For strontium Although an extensive literature search indicated that
sulfate, the region of highest flux is lower on the precipitation and plugging in the reservoir caused by in-
Arab-D/seawater axis than is the region of highest super- jection of incompatible water could be expected to be
saturation (Fig. 9). The significance of this is that the minimal, 11 additional independent laboratory work was
region of maximum flux or driving force for strontium performed. Injection tests with cores involved sequential
sulfate crystallization does not coincide with the region displacement of cleaned Arab-D cores with gas, distilled
of maximum supersaturation. water, formation water, and seawater. Permeability to
The same concept, when applied to calcium sulfate for each of these fluids was measured after flow conditions
the same three-water system, indicates something dif- had stabilized. The data showed no measurable reduction
ferent. Here, the region of highest supersaturation more in permeability as a result of incompatibility effects be-
nearly coincides with the region of highest flux (Fig. tween Arab-D formation water and seawater when the
10). The flux gradient is also steeper, so that relatively two waters mix in the pore channels during displacement
small changes in water composition can result in of one water by the other. These test results confirmed
disproportionate changes in the rate of precipitation. other similar test results published in the literature.
Because the supersaturation and flux gradients nearly
overlie one another, and because the flux gradient is Reservoir Simulation Studies
steeper for calcium sulfate, a small change in the Cross-sectional reservoir simulation studies were con-
Arab-D/Wasia relative composition can have a signifi- ducted to evaluate the effects of various conditions on
cant influence on the amount and rate of calcium sulfate potential scaling. These model studies confirmed that a
precipitated. A similar small change in water composi- Wasia water bank previously injected ahead of seawater
tion has much less effect on strontium sulfate precipita- would act as a buffer to separate the Arab-D formation
tion because of the offset between the areas of higher water from the seawater and thus would reduce the
supersaturation and highest flux and because of the lower potential for scaling. The relative size of the Wasia water
flux gradient. bank had a significant effect on the potential for scaling,
JULY 1983 1259
100 % ARAB 0
(TDS = 245,000 mgs/L) - - DEGREE OF SUPERSATURATION
(SQUARED)

- - - - SUPERSATURATION, PTB
(LBs PER 1000 BBLS)

I
I
I
..,"
-100-
./
100% 100%
SEAWATER WASIA --------~----- ----
100"'/0 SEAWATER 100% WAStA

Fig. 6-CaSO 4 supersaturation of north 'Uthmaniyah ternary Fig. 9-SrSO 4 supersaturation and degree of supersatura-
water system. tion (squared).

- - DfGREf ()F SUPEHSATURATI')N


100% BRINE I SQUARED)

- - - SUPERSATURATII)N I PTB
: LBs PER 1000 BBLS)
120.000 mgs.
TDS/L

50
I
~

ot-______________-----------,o ----- ..,"

100'" SE/WIATER 100'" WASIA 100% Sf AWATER 100% WAStA

Fig. 7-SrSO 4 supersaturation for low-salinity Arab-O brine. Fig. 10-CaS0 4 supersaturation and degree of supersatura-
tion (squared).

SDGM131 FIELD TEST


100% BRINE WATER SAMPLE
COMPOSITION
AND 400
230.000 mgs. SCALING POTENTIAL A SEPTEMBER
TDS/L DATA *• OCTOBER
NOVEMBER
• DECEMBER
o JANUARY

1001-_ _ _-~ 2001-------~'.


tE

" .
• • :"••• , . . . . .

.::.--:---

100/-_______________________- - - -

100% SEAWATER 100% WASIA 100% SEAWATER 100% WASIA

Fig. 8-SrS0 4 supersaturation for high-salinity Arab-O brine. Fig. 11-Ternary representation of typical field test results.

1260 JOURNAL OF PETROLEUM TECHNOLOGY


as did the relative location of the produced well, either gram was developed that used linear programming
high or low on structure, and the degree to which wet techniques to determine the produced-water composition
wells are produced and the Wasia water buffer is mix given possible source waters of known composition.
depleted. In these tests, the known possible source-water analysis
Perhaps the most significant effect, though, was that used for the computer program are Arab-D formation
of reservoir heterogeneity. The Arab-D reservoir in ' Ain water, seawater, and Wasia water. Four key components
Dar and Shedgum has a relatively uniform horizontal are used in this program to determine the proportion of
permeability of about 630 md. However, over large the source waters in the sample of unknown composi-
areas of the Arab-D reservoir, superpermeability zones tion: calcium, sulfate, chloride, and TDS.
on the order of magnitude of 3,000 md have been After the relative proportion of each source water in a
documented. These zones of superpermeability dominate given produced water sample is determined, the com-
reservoir and well bore flow and have a significant bear- position can then be plotted as a discrete point on a ter-
ing on scaling potentials by causing injected seawater to nary for the three-water system. As discussed previous-
break through early in the producing wells. Seawater ly, various overlays on the ternary diagram can then
would in these instances be mixed in the well bore with allow the supersaturation and degree of supersaturation
Arab-D water being produced from the more for both strontium sulfate and calcium sulfate to be deter-
homogeneous section of the reservoir. The resulting mined readily (Fig. 11). This technique has been tested
seawater and Arab-D mixtures could cause high scaling on prepared samples of known proportions and been
potentials, in both downhole tubulars and surface proved accurate and reliable.
facilities.
Results
Field Tests
The results of the first three well tests were
Design negative-i.e., predicted scaling did not occur. The first
All the preceding indications of a potential seawater- field test was an annulus-injection test conducted over a
incompatibility problem in the well bore are based on period of 100 days. Total theoretical strontium sulfate
laboratory and theoretical observations. Further supersaturation during the test was estimated at 46,000
evidence based on producing conditions was needed to Ibm (21 Mg). At the end of the test, the 4Vz-in.
evaluate this potential better. (ll.4-cm) tubing was pulled and inspected. The surface
To this end, a series of four field tests were conducted. producing facilities were also inspected. There were no
Since seawater injection had not begun in north indications of any scale accumulation. ,
'Uthmaniyah until mid-1978, seawater breakthrough had The second field test was also an annulus-injection
not been experienced in any producing wells. To test, and was conducted for 120 days. The total
simulate conditions of seawater breakthrough, lines were theoretical strontium sulfate supersaturation during the
laid to supply seawater to four wells. Three of these test was estimated at 110,000 Ibm (50 Mg). Again, when
wells were selected on the basis of ease of access to a the test was ended, there was no indication of any scale,
seawater supply and, more important, on the basis of the either in the tubing or in the surface facilities.
salinity of the produced water. Wells having the highest The third field test completed was the accelerated
possible ratio of Arab-D to Wasia waters were selected field-flood test conducted with the pair of wells, a pro-
to test areas of high scaling potential. In these three tests, ducer and a closely offset injector. This test, terminated
4Vz-in. (11.4-cm) tubing was run open ended inside after 182 days, was estimated to have produced 26,000
9¥S-in. (24.5-cm) casing with a 7-in. (17.8-cm) liner set Ibm (12 Mg) supersaturated strontium sulfate. When the
to the top of the Arab-D. The actual Arab-D producing test was completed and the tubing and surface facilities
intervals in all four test wells and most other producing inspected, no indication of scaling was evident.
wells are openhole completions below the 7-in. The fourth field test involved the third annulus-
(17.8-cm) liner. The seawater was injected down the injection test well. This test was conducted over a period
tubing-casing annulus, allowing the injected seawater of 44 days, with estimated total production of 52,000
and produced Arab-D and Wasia waters to mix as they pounds (24 Mg) supersaturated strontium sulfate. When
were produced up the 4Vz-in. (11.4-cm) tubing. the test was terminated and tubing pulled, a uniform
The fourth test was designed to simulate an actual layer of scale about 0.4 in. (1 mm) thick was evident on
seawaterflood operation more closely. A producing well the bottom 6,000 ft (1830 m) of tubing. The top 1,000 ft
was selected with a high Arab-D/Wasia ratio in the pro- (300 m) of tubing was still clean. The scale was analyzed
duced water and an injection well was drilled, closely and found to contain 73 % strontium sulfate, 11 %
offsetting the producing well. Seawater was injected into calcium sulfate, and 11 % barium sulfate.
the Arab-D formation in the injection well. The close Testing was continued in the fourth well, and to date
well spacing resulted in seawater breakthrough in the three additional tests have been completed in this well.
producing well slightly more than 1 month later. Not on- Each of the subsequent tests involved running various
ly was there opportunity for Arab-D water and seawater configurations of bare-steel and internally plastic-coated
to mix in the well bore of the producing well, but there (I PC) tubing. In each test, massive amounts of scale up
was the opportunity for them to mix in the formation. to 1 in. (27 mm) thick were found from the bottom of
each tubing string up to near the surface. The massive
Analytical Technique scale was predominantly calcium sulfate. Underlying the
Throughout the field tests, samples of produced water massive layer of calcium sulfate scale in all the last three
were routinely collected and analyzed. A computer pro- tests was a thin, primary layer of predominantly stron-

JULY 1983 1261


tium sulfate scale less than 0.04 in. (1 mm) thick. This References
primary scale layer is similar to that encountered during !. Lambert, B. and Hume-Rothery, W.: "Studies of Precipitated
the first test in this well. These tests showed that, Solids, Part I, Strontium Sulfate," J. Chern. Soc. (1926),
although the IPC tubing delayed scale buildup, massive 2637-48.
scale buildup progressed rapidly once begun. 2. Eniistiin, B.V. and Turkevitch, J: "Solubility of Fine Particles of
Strontium Sulfate," J. Arner. Chern. Soc. (Sept. 5, 1960) 82,
4502-09.
Further Testing 3. Solubilities of Inorganic and Metallo-organic Cornpounds, Gallo
Plans are to extend testing in the one well in which scal- (ed.), fourth edition, D. Van Nostrand Co., Princeton, NJ (1958)
1519.
ing has been encountered. The primary objective of 4. Lucchesi, P.J. and Whitney, E.D.: "Solubility of Strontium
future testing is to demonstrate the effectiveness of Sulfate in Water and Aqueous Solutions of Hydrogen Chloride,
chemical scale inhibitors in controlling scale deposition. Sodium Chloride, Sulfuric Acid and Sodium Sulfate by the
The inhibitor injection technique has not been deter- Radiotracer Method," J. Appl. Chern., London (1962) 12,
277-79.
mined. This phase of testing will evaluate the use of dif- 5. Davis, J.W. and Collins, A.G.: "Solubility of Barium and Stron-
ferent scale inhibitors at different. concentrations. The tium Sulfates in Strong Electrolyte Solutions," Envir. Sci. (1971)
alternatives of squeeze (batch) inhibitor treatment vs. 5, 1039.
continuous downhole inhibitor injection treatment will 6. MacDonald, R.W. and North, N.A.: "The Effects of Pressure on
also be considered. the Solubility of CaCO 3, CaF 2' and SrSO 4 in Water," Cdn. J.
Chern. (1974) 52, 318!.
Additionally, all other wet producing wells in the 7. Jacques, D.F., Gollberg, J.B., and Whiteside, W.e.: "Strontium
north 'Uthmaniyah area where seawater is currently be- Sulfate Solubility and the Effects of Scale Inhibitors," paper
ing injected are being monitored for seawater presented at the 1979 NACE Middle East Corrosion Conference,
breakthrough. Wells with seawater breakthrough will be Bahrain, April 15-17.
8. Jacques, D.F. and Bourland, B.l.: "A Study of Solubility of
evaluated on an individual basis, and those wells that are Strontium Sulfate," Soc. Pet. Eng. 1. (April 1983) 292-300.
conducive to scaling will be closely monitored. The 9. Doremus, R.H.: "Crystallization of Slightly Soluble Salts from
criteria for selection of wells to be closely monitored are Solution," J. Phys. Chern. (1970)74, No.7, 1405-08.
(1) high water cut, >40%; (2) low Wasia water propor- 10. Packter, A. and Sahay, S.: "The Precipitation of Sparingly Solu-
ble Alkaline-Earth Metal and Lead Salts with Slow Development
tion, <30%; (3) a high natural Arab-D water salinity of Supersaturation (Slow Anion and Hydroxyl Ion Addition):
(i.e., high calcium and strontium content); (4) proximity Kinetics of Nucleation and Induction," Kristall und Technik
to a permanent wet-crude handling facility; and (5) (1974) 9, Part 1,485-86.
heterogeneous formation with openhole completion. 11. Bernard, G.G. : "Effective Reactions Between Interstitial and In-
jected Waters on Permeability of Rocks," Producers Monthly
(Dec. 1955) 20, No.2, 26.
Conclusions
On the basis of positive evidence of scaling encountered SI Metric Conversion Factors
in one of the four field tests, it is concluded that a poten- bbl x 1.589 873 E-01
tial exists for precipitation and scale formation in the OF (OF-32)/1.8
wellbore where seawater and Arab-D formation water L x 1.0* E+OO
can mix intimately under turbulent flow conditions. Ibm X 4.535 924 E-01

* Conversion factor is exact. JPT


Acknowledgments
We thank the Saudi Arabian Ministry of Petroleum and Original manuscript received in Society of Petroleum Engineers office Jan. 13, 1981.
Mineral Resources and ARAMCO for permission to Paper accepted for publication June 9, 1982. Revised manuscript received April 11.
1983. Paper (SPE 9626) first presented at the 1981 Middle East Oil Technical Con·
publish this paper. ference held in Manama, Bahrain, March 9-12.

1262 JOURNAL OF PETROLEUM TECHNOLOGY

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