Sulfide/Calcium Carbonate Scale

Coprecipitation

M ixed carbonate-/sulfide-scale
problems have been reported
when water is produced from carbonate
TABLE 1—BRINE COMPOSITIONS
FOR THE BASE CASE OF
TABLE 2—BRINE COMPOSITIONS
FOR CaCO3 FORMED IN THE
CaCO3 FORMED IN THE PRESENCE OF H 2S IN THE
reservoirs. This study presents
BULK SOLUTION AND BULK SOLUTION AND ON THE
interactions of lead sulfide and zinc ON THE SURFACE OF THE METAL SURFACE
sulfide coprecipitating with calcite. The METAL SPINDLE
relationship between bulk precipitation Ion Brine 1, mg/L Brine 2, mg/L
and deposition on a metal surface of Ion Brine 1, mg/L Brine 2, mg/L
Na 10 000 10 000
the mixed carbonate/sulfide scales was Na 10 000 10 000
examined when the mixed scales began Ca 1163 0
Ca 1163 0
to nucleate, agglomerate, and grow. Mg 1473 0
The nature of these mixed crystals may Mg 1473 0
K 1340 0
indicate that mixed sulfide scales tend
K 1340 0
to prefer forming in solution rather than Cl 22 989 12 491.8
adhering to metal surfaces in protected Cl 22 989 12 491.8
HCO3 0 2520
zones. Thus, the mixed sulfide scale
HCO3 0 2520
may be controlled in one zone but be S 0 500
unprotected in other regions.
carbonate- and sulfide-scale problems The principle is that, as CO2 is lost from
have been reported when water is pro- supersaturated brine, CaCO3 scale will
Introduction duced from carbonate reservoirs, and form in the bulk solution and on the
Carbonate reservoirs contain approxi- the use of scale inhibitors to control this metal surface of the spindle. The spin-
mately 60% of the world’s remaining oil problem is relatively common. dle is nonrotating, so a magnetic stirrer
and gas reserves. Scale precipitation dur- was used to accelerate scale formation
ing oil and gas production is costly. Con- Experiments on the surface of the spindle in the dy-
ventional scales, such as sulfate and car- Experiments were carried out in a namic beaker test. CaCO3 scales were de-
bonate, are well-known and have been 500‑mL acrylic-glass vessel at 20°C with posited on the active surface of the stain-
researched and reported extensively. a magnetic stirrer to accelerate bulk pre- less steel. During the experiments, an
Sulfide scales are less studied, and their cipitation. Calcium carbonate (CaCO3) insulating tape around the electrode en-
effect on conventional scales (formation was precipitated spontaneously by mix- sured that only the end surface was the
and inhibition) is relatively unknown. ing 150 mL of a base brine with 150 mL electrochemically active surface. Deposi-
The effects of carbonate/sulfide co- of a second brine containing a bicarbon- tion occurred on the active surface of the
precipitation in bulk solution and on ate. The composition varied according to electrode, which was the only surface an-
metal surfaces are presented. Sulfide the sulfide scale being formed in associa- alyzed with the environmental scanning
was coprecipitated with barium sul- tion with the CaCO3 scale. The influence electron microscope (ESEM). As the ex-
fate (BaSO4), and the effects on forma- of lead sulfate and zinc sulfate (PbS and periments progressed, the pH of the so-
tion and inhibition of the BaSO4 crys- ZnS, respectively) on CaCO3 bulk precipi- lution was allowed to increase (i.e., CO2
tals were monitored. The relationship tation and surface deposition was stud- degassing proceeded). The composition
between bulk precipitation and sur- ied. The acrylic-glass vessel was built to of the final scaling solution varied, de-
face deposition of the mixed carbonate/ simulate the formation of CaCO3-scale pending on the brine composition used
sulfide scales was examined also. Both deposition by carbon dioxide (CO2) loss. for the experiments.

Brine Compositions. Table 1 shows the

This article, written by Dennis Denney, contains highlights of paper SPE 168182, brine composition for the base case of
“Sulfide Scale Coprecipitation With Calcium Carbonate,” by C. Okocha and K.S. CaCO3 formed in the bulk solution and on
Sorbie, SPE, Heriot-Watt University, prepared for the 2014 SPE International the surface of the metal spindle. Table 2
Symposium and Exhibition on Formation Damage Control, Lafayette, Louisiana, details the brine composition for CaCO3
26–28 February. The paper has not been peer reviewed. formed in the presence of hydrogen sul-

For a limited time, the complete paper is free to SPE members at www.spe.org/jpt.

164 JPT • SEPTEMBER 2014

Fig. 1—CaCO3 produced from Table 1 brine (base case) Fig. 2—CaCO3-crystal mass formed in the bulk solution at
showing crystal coverage on the metal surface at 24 hours. 24 hours.

fide (H2S), both in bulk and on the metal portant to establish a base case of pre- tals that formed on the metal surface at
surface. This was the base case used to cipitated CaCO3 crystals in bulk and on 24 hours were 10 to 20 µm in size and
determine the influence of H2S on the the active metal surface. Bulk CaCO3 pre- covered the whole metal surface. Fig. 2
formation of CaCO3. The complete paper cipitation was carried out with the brine shows the CaCO3 crystals that formed in
contains tables with brine compositions compositions in Table 1. Fig. 1 shows the bulk solution. In the bulk solution,
used in the other experiments. an ESEM image with corresponding the size of the crystals in the precipitate
­energy-dispersive-analysis X-ray (EDAX) was less than 5 µm.
Results elemental quantifications for the CaCO3 Figs. 3 and 4 show CaCO3 crys-
Base Case (CaCO3-Crystal Formation). crystals that formed on the active metal tals deposited on the metal surface and
To investigate the influence of sulfide surface. Notice the classic trigonal rhom- precipitated in the bulk solution after 2
coprecipitation with CaCO3, it was im- bohedral crystal shape of calcite. Crys- hours, respectively. Fig. 3 shows fewer
 Fig. 3—CaCO3 crystals formed on the metal surface at 2 Fig. 4—CaCO3-crystal mass formed in the bulk solution at
hours. 2 hours.

crystals deposited on the metal surface, and ZnS were mixed in the scale in the EDAX data indicated the presence of
but the crystals are of similar size and bulk phase. However, ZnS was not iden- CaCO3. In the bulk solution, PbS formed
shape. Crystals that formed in the bulk tified on the metal surface. Although spontaneously as the brines were mixed.
solution (Fig. 4) aggregated as a CaCO3 both scales (CaCO3 and ZnS) form, The scales appeared as a brown gritty
mass. The experiment showed that the there must be a difference in the de- mix in the bulk solution. The low solu-
precipitate formed in the bulk solution gree of adhesion of these minerals to the bility of the PbS may have enhanced the
was different from the deposit formed metal surface. full formation of the crystals by a het-
on the metal surface. erogeneous precipitation process. This
CaCO3 Coprecipitation With PbS. was the only experiment in the study
CaCO3 Coprecipitation With ZnS. The Fig. 6 shows the CaCO3 crystals depos- in which fully formed PbS crystals were
CaCO3 crystals deposited on the ac- ited on the active metal surface when co- found in the bulk solution.
tive metal surface when coprecipitat- precipitated with PbS. The CaCO3 crys-
ed with ZnS varied in size but were tals are distorted, with most crystals CaCO3 Coprecipitation With Sulfide
fully formed undistorted CaCO3 crys- appearing to be quite thin, and pro- Scales in the Presence of Scale In-
tals. Fewer crystals formed on the metal jecting outward; some crystals formed hibitor. Inhibited CaCO3-deposition
surface than in the base case at 24 hours. bunched together, giving a flower-petal experiments were performed with a
EDAX data indicated that the crystals appearance. Crystals that formed in the polymeric scale inhibitor (SI)—poly-
were CaCO3. Fig. 5 shows CaCO3 crystals bulk solution were fully formed CaCO3 phosphino carboxylic acid (PPCA)—
that formed in the bulk solution, with crystals mixed with, perhaps, PbCO3 with initial PPCA concentrations of 3,
elongated crystals in a fused mass. The (not confirmed). The CaCO3 crystals 1, and 0.5 ppm in the mixed brines.
EDAX data indicated that CaCO3 crystals showed a rhombohedral shape, and A base-case experiment with Brine 2

Fig. 5—CaCO3 crystals in the bulk solution coprecipitated Fig. 6—CaCO3 deposit coprecipitated with PbS on the
with ZnS. metal surface at 24 hours.

166 JPT • SEPTEMBER 2014

Fig. 7—CaCO3 formed on the metal surface in the Fig. 8—CaCO3 formed on the metal surface in the
presence of 1-ppm PPCA at 24 hours. presence of 0.5-ppm PPCA at 24 hours.

in Table 1 indicated that at 3 ppm, no bulk were a mix of fully formed CaCO3 in the presence of sulfide scales, the bulk
CaCO3 was formed in the brine or on the (likely) with PbCO3 crystals. This result precipitation was affected less than the
surface of the metal. However, as the SI suggests that the PbS/CaCO3 scaling sys- metal-surface deposition. This study will
concentration was reduced, tiny spots tem may be more difficult to inhibit in aid in designing better scale-treatment
of CaCO3 crystals formed at 1 ppm, but bulk solutions than the ZnS/CaCO3 scal- programs as more information becomes
they had an unusual appearance, prob- ing system. The precipitation of CaCO3 available regarding which scales occur
ably because of the SI. Fig. 7 shows crys- crystals in the presence of SI (PPCA in and where and in what form these mixed
tals formed on the metal surface in the this case) demonstrated that minimum- scales occur. Such data also will help de-
presence of 1-ppm PPCA. Fig. 8 shows inhibitor-concentration levels appropri- termine the type of SIs with which to
the metal surface with CaCO3 when ate for the metal surface and the bulk so- treat different mixed sulfide/carbonate
0.5 ppm of SI was used; the CaCO3 crys- lution may be very different. However, scaling systems. JPT
tals appeared to be in the nucleation
stage and not in the same quantity as for
the base case. EDAX data confirmed that
the CaCO3 crystals were in an early stage
of formation.

Conclusions
CaCO3 crystals were deposited in bulk
solution and on a stainless-steel surface
in the absence and presence of sulfide
scales of zinc and lead. The coprecipita-
tion process for these scales was simi-
lar to field conditions in which CaCO3
scales are deposited on metal surfaces
and precipitated in the bulk solution.
Sulfide scales have different effects on
the type and medium (surface or bulk)
of CaCO3-scale deposition. Crystalliza-
tion was found to be sensitive to changes
in the brine chemistry. When CaCO3 was
coprecipitated with ZnS, fewer CaCO3
crystals were deposited on the metal
surface, while more CaCO3 crystals were
mixed with the ZnS flocculent. How­
ever, when CaCO3 was coprecipitated
with PbS, the CaCO3 that was deposited
on the metal surface exhibited distorted-
crystal forms (probably a polymorph of
those deposited in the base case). The
corresponding crystals formed in the

JPT • SEPTEMBER 2014 167