Strontium Sulfate Scale Control by
Inhibitor Squeeze Treatment in the Fateh Field
Alain J. Essel, * SPE, Dubai Petroleum Co.
B.L. Carlberg, Conoco Inc.
Summary
Strontium sulfate scale in the Fateh field results from
mixing incompatible waters. Precipitation squeezes with
phosphonate scale inhibitors were shown to be effective
in laboratory studies and field use of precipitation
squeezes confirmed this. Continued use has resulted in
additional operating and performance data.
Introduction
In May 1974 Dubai Petroleum Co. started the injection
of seawater in the Fateh Mishrif reservoir. The first in-
dication of the strontium sulfate precipitation problems
to come was seen in laboratory compatibility studies be-
tween Arabian Gulf and Mishrif waters. These results
were confirmed several years later when strontium
sulfate deposits were identified in Fateh producing
wells.
Strontium Sulfate Solubility
Solubility of strontium sulfate in waters and brines as
reported in the literature varies rather markedly. For in-
stance, solubilities in sodium chloride solutions as deter-
mined by Lucchesi 1 are significantly less than results
reported by Collins and Davis,2 Culberson et al., 3 and
Brower and Renault. 4 Similarly, solubility product data
collected by Sillen s scatter widely as a function of
temperature. Nancollas and Campbell 6 suggest that
problems in determining true solubility can be attributed
to impurities in the water. Enustun and Turkevich 7
credit interfacial tension between the water and the
crystallite with responsibility for the problem. Under the
latter explanation, minute crystals tend to be more highly
soluble than larger crystals of strontium sulfate. The
solubility data reported by Collins and Davis,2 even
though limited to 109°F (77°C), seem to be most
• Now with Total Co. Fran~aise des petroles.
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Copyright 1982 Society of Petroleum Engineers of AIME
1302
generally accepted. Brower and Renault's data 4 as a
function of temperature can be combined with
solubilities reported by Booth and Bidwell 8 to give a
solubility-temperature curve in water (Fig. 1).
Laboratory Studies
With the expectation of strontium sulfate scale deposi-
tion in producing wells as a result of waterflood opera-
tions, laboratory studies were initiated. These included
evaluation of scale inhibitors as well as adsorption
isotherms for possible application to the inhibitor
squeeze treatment.
Scale Inhibitor-Performance of
Commercial Treating Chemicals
Scale inhibitor evaluations were carried out in glass-
lined stainless steel bombs containing a 50/50 mixture of
Arabian Gulf water and Mishrif formation water. Scale
inhibitor at 0- to 30-mg/L concentrations was added
before the two waters were mixed. The bombs then were
closed and maintained at the bottomhole temperature of
230°F (110°C) for 24 hours. At the end of this time, the
liquid from the bomb was filtered hot under pressure to
remove any precipitated strontium sulfate. The filtrate
then was analyzed for residual strontium concentration.
Loss of strontium during the test was used to calculate
the effectiveness of the inhibiting chemical. A minimum
effectiveness of 95 % protection at 5 mg/L chemical was
requested before an inhibitor was considered for further
use.
Inhibitor Adsorption/Desorption
Normal squeeze techniques rely on a physical adsorption
of chemical onto the rock. Adsorption isotherms were
prepared with the procedure outlined by Kerver and
Heilhecker 9 -e.g., Fig. 2. Very few phosphate ester
compounds were used in these tests because of the reser-
voir temperature limitations [230°F (l100C)]. Phos-
JOURNAL OF PETROLEUM TECHNOLOGY
phonates and polymers were predominant. In each case,
crushed limestone from the Mishrif formation was used
for the test. Several such compounds were recommended
for field tests in a formation squeeze application.
Precipitation Squeeze Treatments
Squeeze treatments in these wells were complicated by
the very thick producing zones [approximately 150 ft (46
m)] and the high volume of produced fluids [8,000 BID
(1270 m 3 /d)]. Normal adsorption squeeze procedures
resulted in limited squeeze life. The precipitation
squeeze process 10 offered promise of success under
these unfavorable conditions. In this process, the in-
hibitor is precipitated within the interstices of the forma-
tion. When the well is returned to production, re-solution _'c
of the precipitate takes place slowly over an extended
period of time to provide the necessary active inhibition Fig. 1-Strontium sulfate solubility in water.
as these incompatible waters are mixed within the
wellbore. The phosphonate inhibitor in acid solution is
injected into the producing zone. Once there, the acid is
allowed to spend itself on the limestone, thus bringing 110

the necessary calcium ions into solution. When the acid 100 -. ROOM TEMP.

is neutralized, the combination of calcium and ---0 170·F

phosphonate is precipitated as desired. 90

Cowan and Weintritt 11 have listed typical calcium 80

phosphonate solubility curves. Such a curve, as deter-

70
mined in our laboratory, is shown in Fig. 3. Our in-
hibitor concentrations for precipitation squeezes have 60

been approximately 10% of the chemical as received. 50

For the typical scale inhibitor phosphonate, this results
40
in a concentration of approximately 2 % active ingredient
in the treating solution. Precipitation then requires a 30 _-- 8
minimum of "" 320 mg/L calcium in solution. This con-
centration is increased slightly by acidic conditions
within the treating area. For preparation of the curves we
used the Hach 2100 N turbidimeter to detect the limits
M

of solubility. FINAL CONCENTRATION. mo/l11er

Much of our laboratory work has been based on the

use of limestone columns within which the precipitate Fig. 2-Adsorption on Mishrif core, Inhibitor D (phosphate
ester).
has been formed. These columns, V2 in. (l cm) in
diameter and usually 30 in. (75 cm) long, were filled
with crushed limestone, sieved to limits of 0.04 to 0.09 IOQOOO

in. (1 to 2.4 mm). Inhibitor solutions were pumped into

these columns at rates varying from 2 to 5 mUmin [ "" 1
to 5 B/min (0.16 to 0.79 m3/min)] in Mishrif wells.
Reaction of the acidic system with the limestone caused
precipitation within the column. Effectiveness of this
precipitation then was verified in two separate ways. The
first procedure was to flood the treated column with
brine and to measure the phospho nate concentration in
the discharge liquid. This is, of course, similar to :;OLU8l~ II<i'>Oll8LE

desorption curves run when the squeeze is based on an

10,000
•
adsorption technique. A typical curve is shown in Fig. 4.
The second and most frequently used technique in our
work was the analysis of the rock itself. Following the
squeeze, the column was divided into I-in. (2.5-cm)
segments of crushed limestone, which then were ana-
lyzed to determine the amount of precipitated
phosphonate. A typical curve of precipitated
phosphonate vs. penetration of the column is shown in
Fig. 5. It is to be expected that the life of a precipitation ',0001-----------'0,..-----------::::"'0
COl, ..",., Concenl.ohon (QU"Olenls/M,U,on
squeeze would be a function of the distance from the
well bore at which precipitation takes place. Within cer- Fig. 3-Solubility curve in calcium solutions [pH 6, 109°F
tain limits, the greater the distance from the wellbore (77°C)).

JUNE 1982 1303

 where precipitation takes place, the longer should be the
period of returns. On this basis, we studied techniques
TABLE 1-WATER ANALYSIS
by which precipitation could be moved further into the
Seawater Mishrif Water column. Injection rates were varied from 1 to 5 mLimin.
(mg/L) (mg/L) We varied inhibitor concentrations from 1 to 10%, using
Total dissolved solids 44,000 141,000 a chemical as received. Various methods for controlling
Chloride 24,500 86,900 pH were used, and the total volume of chemical injected
Sulfate 3,400 340 into the column was varied over a wide range. From this
Bicarbonate 159 244
Sodium 13,700 43,700
we found that (1) injecting rapidly caused greater
Magnesium 1,670 2,010 penetration before precipitation and (2) the greatest
Calcium 576 7,920 quantity of inhibitor precipitated resulted when the
Strontium o 610 greatest quantity was injected. The greatest peak concen-
Barium o 13 tration within the column resulted when injection rate
pH 7.8 5.6
was slow but a substantial quantity of chemical was in-
jected.
Then, within limits, we could control the placement of
the chemical and the quantity precipitated. However, in-
jection rate is not always a controllable factor. Thus we
looked for other methods for improving this penetration.
One of these was to substitute weak acids for the
hydrochloric previously used in conjunction with the
phosphonate inhibitor. The best combination was the un-
neutralized phosphonate inhibitor available from the
chemical supplier. The process of manufacturing
phosphonate inhibitors results in an acidic product, a
phosphonic acid that normally is neutralized with caustic
to provide the common phosphonate inhibitor. By using
this phosphonic acid material, we had the somewhat
weaker acid desired for better penetration. Squeezes
based on this material have been used with success not
only in the Arabian Gulf area but also within the con-
tinental U. S. In some cases, this acidic squeeze product
Fig. 4-lnhibitor in effluent following laboratory precipitation
has been combined with acid retarders to enhance further
squeeze test. the penetration of the chemical into the producing zone.
Field Problems
When a tubing is scaled up with SrSO 4 scale, the chance
of cleaning it by solvent treatment is limited. Scale in-
hibitor squeeze jobs are expensive; current costs are
about $60,000 for chemicals and boat charges, and 4
days' production loss. Our goal is to reduce these
squeeze jobs to a minimum to minimize downtime and
operating costs. We are faced with the problems of (1)
when to start squeezing a well, (2) how to squeeze, (3)
how to monitor the squeeze efficiency, and (4) when to
stop squeezing.

• Basic Parameters
• •• The incompatibility problem and the resulting scale
deposition is not surprising when the analyses of the for-
•
••
mation water and of the seawater are considered (Table
1). Mishrif water contains approximately 600 mg/L
strontium, while the seawater includes 3500 mg/L
• sulfate. On the basis of solubility data, theoretical scal-
I • ing tendencies have been calculated (Fig. 6). IO Normal-
ly all water mixtures from 0 to 98 % seawater are poten-
tially scale-forming. The total amount of scale is, of
10
course, also a function of the water production. A low
CQuJ,... PENETRATION ItlcI'l~S scaling index associated with a high water production
may be as dangerous as a lower water production
Fig. 5-lnhibitor precipitated in Column. associated with a high scaling tendency. The ratio of the
actual strontium value to the calculated saturated value
has been plotted on Fig. 6. This curve presents a max-
1304 JOURNAL OF PETROLEUM TECHNOLOGY
 SrS04 SCALING POTENTIAL
0.6
0.5 4 60
~ Start
~ 0.4
8'
'"_ E~
3 <II
0.3
"'~
0'" 0.2
c
.
;r 0.1
'"
100% 50% 100%
Formation Sea Water
Water
Fig. 6-Supersaturation and potential scale as a function of
injection water cut.
imum for a 50% seawater/50% formation water mixture
that corresponds approximately to the beginning of our
scale problem.
History on the wells currently producing formation
water/ seawater mixtures is another parameter that is used
as a guideline and contradicts somewhat the ther-
modynamic calculations. A typical well, Well F-1 in
Fateh field (Fig. 7), began to produce 500 BID (80
m 3 /D) water in June 1976, when SrS04 was detected
for the first time in the producing tubing. The well was
producing a mixture of 60% seawater and 40% Mishrif
water. The first squeeze job was implemented in Dec.
1976 and the tubing was pulled in July 1977. Scale
thickness was 0.5 in. (1.3 cm) at the bottom of the tubing
[at 8,000 ft (2438 m)] and decreased progressively to nil
at 5,500 ft (1676 m). Analysis indicated that the scale
was pure strontium sulfate. Since that time, the well has
been squeezed regularly and scale buildup is under con-
trol. Another Fateh well, Well D-3, followed the same
pattern as Well F-1 as far as seawater/formation water
ratio and daily water production are concerned but has
never scaled up. Water analysis of Well D-3-produced
water for strontium content indicates that no scale
buildup is occurring in the formation. No variation of the
skin factor has been detected in any of the wells produc-
ing seawater. Fateh and Southwest Fateh fields contain
54 Mishrif producers, all of which are potential scale
problem wells. Currently, 13 of them are producing
seawater. Of these, three are producing around 10%
water and are not scaling up; three are producing about
25 % seawater with one being squeezed; five are produc-
ing about 75 % seawater with two being squeezed; and
the remaining three do not indicate scale buildup. Two of
them are producing more than 90% seawater and are no
longer producing scale, although they have in the past.
In conclusion it seems (1) that scale buildup starts
when a mixture of 50% seawater/50% formation water is
reached and that not all wells are affected by this prob-
lem, and (2) that skin factor measurements and water
analysis indicate that we have no scale deposition on the
formation face or in the formation. Scale buildup is max-
imum at the bottom ofthe tubing.
JUNE 1982
M!5HRIF
WOler Wo••
100 Cu.
"to'"
Totol
90 FluuS.
80
70
Wot.,Flood
50
c 40
~
0
,
0
30
..<>,
0
20
10
1974 1975 1976 1977 1978 1979 1980
Fig. 7-Well F-1 water production history.
When to Stop Squeezing
On the basis of the theoretical scaling tendency, scale in-
hibitor squeeze treatments were stopped on two wells
when the produced water contained 92 % seawater.
These wells started to build up SrSO 4 scale when we had
a 50/50 seawater/formation water mixture. Since then,
gauge ring runs have indicated no further scale buildup.
When to Start Squeezing
Since the basic thermodynamic and kinetic data fail to
explain why all seawater-producing wells do not build up
scale and since unnecessary jobs should be avoided,
regular gauge ring runs and water analyses are con-
ducted. From the chloride value of the produced water,
the seawater/formation water ratio and the theoretical
strontium value for this mixture can be calculated.
Samples of the produced water are taken at the wellhead,
Versene'" is added to redissolve all SrS04 scale that may
have formed and did not stick on the tubing, and stron-
tium content is measured by atomic absorption. From
these analyses and the consideration of the basic
parameters, a gauge run schedule is established to check
for scale building. Gauge ring run frequency varies from
1 to 6 months. In order to minimize downtime, a
schedule is established incorporating all wireline work
including scale determination, gas lift valve modifica-
tions, subsurface safety valve checks, etc. Though im-
perfect, this method is quite reliable and no tubing
strings have had to be pulled during the past 3 years.
Squeeze Jobs
A typical squeeze job procedure is given in Table 2.
Three types of chemicals have been tested.
Phosphate Esters
The first squeeze jobs implemented without spearhead
lasted approximately 3 weeks. Formation of 'emulsion
preventing good adsorption of the chemical on the for-
mation was suspected. By incorporating a spearhead of
surfactant, we increased the squeeze life to- 2 months.
The squeeze procedure was modified to include a wet-
ting agent in the treating solution to enhance the adsorp-
1305
--40
'"
20
10
20
DAYS
Fig. 8-Chemical return-polymer squeeze.
tion of the scale inhibitor. This extended the squeeze life
to 3 months.
Phosphonate Salts
Phosphonate salts were injected after acidification with
HCI to form phosphonic acids. This method has been
termed the precipitation-type squeeze treatment. Three
different chemicals were tested in this manner. Consis-
tent squeeze life of3 to 3.5 months was obtained.
Polymer
Polymers were found to be very effective in laboratory
experiments and are stable at high temperature. The first
results in squeeze jobs with this type of chemical were
disappointing because only 2 months' protection was ob-
tained. Then it was decided to inject the polymer with
acid. By this method a polymer network can be formed
in situ by pseudoreticulation with the calcium ion, and
therefore the effect of adsorption can be combined with
the slow redissolution of the precipitated polymer. More
than 4 months' protection was obtained by this method
(Fig. 8)
Squeeze Monitoring
These chemicals work on a threshold basis-i.e., over a
limited concentration we are fully protected, and under
this limit scale deposition is no longer inhibited. Water
samples are taken daily and checked for chemical return
and strontium concentration. Gauge rings are run on a
3-month basis to crosscheck for analysis.
Future Development
Phosphonic acids with acid retarders are being tested. A
better control of the chemical placement should be ob-
tained.
Until now wells have been resqueezed when the
chemical return concentration was below the threshold.
A recent study 12 indicated that the onset of precipitation
started 1 hour after the mixing of the two waters with
I-mg/L scale inhibitor, the threshold for this chemical
being 5 mg/L. As the retention time in our producing
tubings is around 30 minutes, the threshold limit may be
too stringent a factor. Field tests will be implemented to
determine the lowest acceptable limit.
Conclusions
Close cooperation between laboratory and field people
resulted in a squeeze life increase from 1 to more than 4
months.
1306
Spearhead
TABLE 2-SQUEEZE PROCEDURE
500 bbl seawater + surfactant 0.1 %
Treatment Scale inhibitor 5% solution in seawater
Chemical amount: 1 % of daily water production
Overflush Seawater + surfactant 0.1 %
Total volume: 100% of daily water production
Shut-in period 24 hours
Cost $25,000 chemicals + boat charges
4 to 5 days' production loss
Scale does not form in all wells that are potential scale-
formers. A scientific explanation for this phenomenon
has not been found. Therefore a constant monitoring by
water analysis and gauge ring runs is necessary.
We have concluded that when produced water contains
more than 90% seawater, SrS04 precipitation is no
longer a problem.
References
I. Lucchesi, P.J.: "Radiochemical Investigation of the Dissolution
of Strontium Sulfate in Aqueous Media," PhD dissertation, New
York U., New York City (1954).
2. Collins, A.G. and Davis, J.W.: "Solubility of Barium and Stron-
tium Sulfates in Strong Electrolyte Solutions," Env. Sci. and
Tech. (Oct. 1971)5,No. 10, 1039-1043.
3. Culberson, e.H., Latham, G., and Bates, R.G.: "Solubilities and
Activity Coefficients of Calcium and Strontium Sulfates in Syn-
thetic Seawater at 0.5 and 25°C," 1. Phys. Chern. (1978) 82, No.
25,2693-2699.
4. Brower, E. and Renault, J.: "Solubility and Enthalpy of the
Barium Strontium Sulfate Solid Solution Series," Circular 116,
New Mexico State Bureau of Mines and Mineral Resources,
Socorro, NM (1971) 13-17.
5. Sillen, L.G.: "Stability Constants of Metal-Ion Complexes,"
Special Publication No. 17, The Chemical Society, London
(1964).
6. Nancollas, G.H. and Campbell, J.R.: "The Crystallization and
Dissolution of Strontium Sulfate in Aqueous Solutions," J. Phys.
Chern. (June 1969)23, No.6, 1735-1740.
7. Enustun, B.V. and Turkevich, J.: "Solubility of Fine Particles of
Strontium Sulfate, ,,' J. American Chern. Soc. (Sept. 5, 1960) 82,
4502-4509.
8. Booth, H.S. and Bidwell, R.M.: "Solubilities of Salts in Water at
High Temperatures," J. American Chern. Soc. (June 1950) 72,
2567-2575.
9. Kerver, J.K. and Heilhecker, J.K.: "Scale Inhibition by Squeeze
Technique," J. Cdn. Pet. Tech. (Jan.-March 1969) 15-23.
10. Nassivera, M. and Essel, A.: "Fateh Field Seawater Injection,
Water Treatment Corrosion and Scale Control," paper SPE 7765
presented at the SPE Middle East Oil Technical Conference and
Exhibition, Bahrain, March 25-29, 1979.
II. Cowan, J.C. and Weintritt, D.J.: Water Formed Scale Deposits,
Gulf Publishing Co., Houston (1976) 360-361.
12. Jacques, D.F., Gollberg, B.J., and Whiteside, W.e.: "Strontium
Sulfate Solubility and the Effects of Scale Inhibitors," paper
presented at the BSE/NACE Middle East Corrosion Conference,
Bahrain, April 15-17, 1979
SI Metric Conversion Factors
bbl x 1.589873 E-Ol = m3
OF (OF-32)/1.8 = °C
in. X 2.54* E+OO = cm
L x l.0* = dm 3
*Conversion factor is exact. JPT
Original manuscript received in Society of Petroleum Engineers office Jan. 21, 1981.
Paper accepted for publication Dec. 8, 1981. Revised manuscript received AprilS,
1982. Paper (SPE 9628) first presented at the SPE Middle East Oil Technical Con-
ference held in Manama, Bahrain, March 9-12,1981.
JOURNAL OF PETROLEUM TECHNOLOGY