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Applied Geochemistry. Vol.9. pp. 561-567.

1994
Pergamon Elsevier Science Ltd
Printed in Great Britain
088%2927/94$7.00+ 0.00

0883-2927(94)E@OlS-2

The inhibition of gypsum and barite nucleation in NaCl brines at


temperatures from 25 to 90°C

SHILIANG HE, JOHN E. ODDO and MASON B. TOMSON


Department of Environmental Science and Engineering, P.O. Box 1892, Rice University, Houston,
TX 77251. U.S.A.

(Received 26 October 1993; accepted in revised form 24 March 1994)

Abstract-The inhibition of gypsum and barite nucleation in NaCl brines by phosphonates and polycar-
boxylates was studied at 25,50,70 and 90°C in terms of the prolonged induction period. Hexamethylene-
diaminetetra(methylene phosphonic) acid (HDTMP) was found to be an effective inhibitor for the scaling
of calcium sulfate dihydrate. Hydroxyethylene-1, 1-diphosphonic acid (HEDP) and phosphinopolycar-
boxylic acid (PPPC) were found to be effective inhibitors for barium sulfate scaling. The inhibition of
nucleation through prolongation of the nucleation induction period likely resulted from an increase in the
interfacial tension between the crystal and aqueous solution due to the presence of the inhibitors. It was
observed that the inhibition of nucleation depends highly on the lattice cation/anion molar ratio and the
pH of the solution as well as the degree of supersaturation and temperature for a given inhibitor.

INTRODUCTION previous studies concerning the inhibition of sulfate


scales were limited either to very low supersaturation
CALCIUM sulfate (gypsum, hemihydrate and anhy- or to a specific brine solution or temperature. These
drite) and barium sulfate (barite) are the most com- studies are of limited use in understanding the per-
mon sulfate scales in the oil and gas industry and formance of inhibitors against sulfate scaling. More-
other industries involving subsurface waters or over, many variables have significant influences on
brines, such as geothermal energy and brine disposal the performance of scale inhibitors, such as the
(e.g. COWANand WEINTRI~, 1976; ROSENBAUERet degree of supersaturation, temperature, pH and the
al., 1992). Sulfate scales often deposit and accumu- lattice cation/anion molar ratio. Many of these para-
late in formations, production tubing and surface meters are recognized, but have not been experi-
equipment due mainly to changes in temperature mentally studied. Furthermore, the mechanism of
and/or pressure or to mixing of injected incompatible scale inhibition is not well understood.
water with formation water or formation waters from A knowledge of the precipitation kinetics (nuclea-
different zones (COWANand WEINTRIT~,1976). Once tion and crystal growth) is needed to predict scale
they are formed, sulfate scales are almost impossible formation and the correct use of inhibitors in scale
to remove chemically. In addition, barium sulfate control. The authors have studied the primary nu-
scales have the potential to contain coprecipitated cleation kinetics and seeded growth of calcium sul-
radium which results in the occurrence of naturally fate dihydrate and barium sulfate in NaCl solutions to
occurring radioactive materials (NORM) (e.g. 6 M and 90°C (HE et al., 1994a,b). The results of
SMITH, 1987; GRAY, 1993). These NORM scales are nucleation induction periods of supersaturated cal-
being regulated by governmental agencies. There- cium sulfate or barium sulfate solutions improved our
fore, prevention of sulfate scale deposition is of ability in predicting the sulfate scaling tendency and
practical significance. modeling the deposition rate.
The most economical method to control scale is to This paper presents an experimental study on the
prevent its formation and deposition by inhibiting nucleation kinetics of calcium sulfate dihydrate and
nucleation and crystal growth using threshold chemi- barium sulfate in the presence of scale inhibitors,
cal inhibitors (e.g. RALSTON, 1969, 1972; VETOER, such as phosphonates and polycarboxylates in NaCl
1972). Common threshold inhibitors include poly- solutions. The inhibition kinetics were investigated in
phosphates, phosphonates and polycarboxylates terms of the prolonged induction period which is
(COWANand WEINTRITT,1976). These inhibitors are closely related to the tendency to form scale. Also,
reported to be effective in inhibiting calcium carbon- the results of the influence of common solution
ate, calcium sulfate and barium sulfate scales (e.g. parameters, such as pH and the non-stoichiometry of
RALSTON,1969,1972; VEER, 1972; RIZKALLA,1983; lattice ions in the solution on the inhibition of sulfate
AMJAD, 1988; VAN DER LEEDENet al., 1992). Most nucleation by these inhibitors are discussed.
562 S. He er al.

Table 1. The experimental conditions and results of the


screening tests of scale inhibitors for gypsum in 3.0 M NaCl
solutions at 25°C ([Ca2’], = [SO:-I,)
0.4 -

[Ca*+] Cone. hd
(mmol/kg H20) Inhibitor (mg/l) PH (min)

140 ATMP 50 1.8 7


140 HEDP 50 1.8 2
140 HDTMP 50 5.5 >144O
0.1 - 140 DTPMP 50 1.5 29
hd
140 PPPC 50 3.9 18
0.01. 0 100 200 300 400
160 PCAP 50 4.5 25

Time (s)

Fig. 1. The variations in the turbidity (in terms of absorb-


ance) vs time plot to illustrate the determination of the Table 2. The experimental conditions and results of the
induction period (rind) for the nucleation of barium sulfate at screening tests of scale inhibitors for barite in 1.0 M NaCl
25°C. solutions at 25°C ([Ba2’lt = [SO:-],)

[Ba2+] Cont. lind


EXPERIMENTAL METHODS (mmol/kg H,O) Inhibitor (mti) PH (min)

Materials 2.79 ATMP 50 1.8 0.2


2.79 ATMP 50 6.5 4.1
Supersaturated solutions of calcium sulfate or barium 2.79 HEDP 50 1.8 0.2
sulfate with NaCI were made by mixing equal volumes of 2.79 HEDP 50 6.5 >1440
stock solutions containing the lattice cation (Ca” or Ba”) 2.79 HDTMP 50 5.5 12.1
and anion (SOd2-). The lattice cation solution consisted of 2.79 DTPMP 50 1.5 0.1
calcium chloride or barium chloride plus sodium chloride. 2.79 DTPMP 50 6.5 320.1
The lattice anion solution consisted of sodium sulfate plus 2.79 PPPC 50 3.9 3.6
sodium chloride. The stock solutions were made by dissolv- 2.79 PPPC 50 6.5 98.5
ing reagent-grade CaCl, 2H20, BaC12 . 2H20, NqSO, 2.79 PCAP 50 4.5 0.6
and NaCl in distilled and deionized water. The solution was 2.79 PCAP 50 6.5 38.7
filtered twice through 0.2pm membrane filters to minimize
the amount of insoluble particles. These stock solutions
were subsequently maintained at the desired temperature Calculation of the saturation states
before mixing. Mixing took place in a jacketed glass reactor
kept at constant temperature (fO.l”C) by circulating water
The saturation state (fI) of the solution with respect to
from a constant-temperature water bath. The supersatur-
gypsum or barite was defined as the ratio of the activity
ated solution was stirred by a Teflon-coated magnetic stir-
products divided by the thermodynamic solubility product
ring bar (300 rev/min). Generally the inhibitor was added to
of the mineral (K,,). For gypsum the reaction is as in Eqn
the lattice anion solution prior to the addition of the lattice
cation solution. (I):
A number of threshold chemical inhibitors were used in CaSO, 2H20@ CaZf + SO:- + 2H20 (1)
this study, including aminotri(methylene phosphonic) acid
(ATMP), 1-hydroxyethylidene-1, 1-diphosphonic acid and its saturation state is given in Eqn (2):
(HEDP), hexamethylenediaminetetra(methylene phos-
phonic) acid (HDTMP), diethylenetriaminepenta(methy-
lene phosphonic) acid (DTPMP), phosphinopolycarboxylic
acid (PPPC) and phosphinopolycarboxylic acid polymer where a,, mi and y, are, respectively, the activity, the molar
(PCAP). The inhibitor solution was adjusted to a desired concentrations and the activity coefficients for species i. The
pH by adding NaOH. a, term is the activity of water which can be calculated from
the osmotic coefficient (@J). The saturation index (SI) is
defined as the logarithm of the saturation state (SI = log Q).
Determination of the induction periods
The activity and osmotic coefficients as well as the satu-
ration state were calculated by Pitzer equations based on the
The method for measurement of the induction period program, EQPITZER (HE and MORSE, 1993), which is valid
(rind) was described in detail in previous papers (HE er al., for the Na-K-Ca-Mg-H-OH-Cl-S04-H20 system up to
1994a, submitted). Generally, rindwas determined by moni- high ionic strengths (6 M), 200°C and 1000 bars. The
toring the turbidity of the supersaturated solution. An program was recently updated to include the barium and
example is given for barium sulfate nucleation in 1 M NaCl strontium ions.
solution with a saturation index (defined below) of 1.75 at
25°C (see Fig. 1). The time lapse between the generation of
a supersaturated state (mixing) and the first observed tur-
bidity was taken as rind.Turbidity was measured for moder- RESULTS AND DISCUSSION
ate and slow precipitation reactions, but for fast
precipitation in the cases of highly supersaturated con- A number of inhibitors were tested for their
ditions or at elevated temperatures, that is, for an induction
period less than 10 s, rind was estimated visually. The repro-
efficiency in inhibiting gypsum and barite nucleation
ducibility of the turbidity measurement was about 1.4% and in NaCl brines at 25°C. The experimental conditions
the visual technique was about 3-4%. and test results are given in Tables 1 and 2 for calcium
Inhibition of gypsum and barite nucleation in NaCl brines 563

5 ‘1 0’ ’ . i. ‘. ’ . 0
I
a P
0
4- 0.A A

I
3
.dJ 0” A
log 6.d 3 -o
+ + + l
A +
6) + A
+’ 0
hi! tiad 2 a
(8) +

“0 10 20 30 40 50
HDTMP, Acid Active (mg/l)
60
$I::.+,
; , ,+,
.,
0 10 20 30 40 50

HEDP, Acid Active (mg/l)

3 b
0 0 0

l% tind
6)

0 A
A
0 A
log had 2- l
A +
(3)

0 5 10 15 20
PCAP, Acid Active (mgh)

Fig. 2. The inhibition of gypsum nucleation by (a) HDTMP


and (b) PCAP in 3 M NaCl solutions at a pH of 5.5 (SI of
0.72 with respect to gypsum). The open circles, solid circles,
0 10 20 30 40 50 I
triangles and crosses represent temperatures of 25, 50, 70
and 9O”C,respectively. PPPC, Acid Active (me/l)
Fig. 3. The inhibition of barite nucleation by (a) HEDP
and(b) PPPC in 1 M NaCl solutions at a pH of 6.5 (SI of 2.95
sulfate and barium sulfate, respectively. The test with respect to barite). The open circles, solid circles,
triangles and crosses represent temperatures of 25, 50, 70
results indicated that the most effective inhibitor and 90°C respectively.
against gypsum nucleation was neutralized HDTMP
and the most effective inhibitor against barite nuclea-
tion was neutralized HEDP. PCAP and PPPC were period when the HDTMP concentration exceeded 35
also effective as inhibitors for the nucleation of cal- mg/l at 90°C was interpreted as a result of the precipi-
cium sulfate and barium sulfate, respectively. tation of calcium-HDTMP.
When the most effective inhibitors were identified,
these inhibitors were studied in great detail. The
inhibition of gypsum by HDTMP and PCAP and the The inhibition of barite nucleation
inhibition of barite by HEDP and PPPC were studied
over a range of supersaturations, temperatures and The inhibition of barium sulfate nucleation by
inhibitor concentrations in order to determine the HEDP and PPPC was investigated in 1 M NaCl
critical supersaturations and temperatures at which solutions with equal total concentrations of barium
these chemical inhibitors can be applied. and sulfate at 25,50,70 and 90°C. The results of these
tests are shown in Fig. 3a and b. The saturation index
of the solution was 2.95 with respect to barite at all
The inhibition of gypsum nucleation temperatures. The pH of the solution was 6.5. The
inhibitor concentrations ranged from 0 to 50 mg/l for
The inhibition of gypsum nucleation by HDTMP both HEDP and PPPC.
and PCAP was investigated in 3 M NaCl solutions As the temperature increased from 25°C higher
with equal total concentrations of calcium and sulfate inhibitor concentration was needed to maintain the
at 25, 50, 70 and 90°C. The results of these tests are same degree of inhibition for both salts, probably due
shown in Fig. 2a and b. The saturation index of the to the higher nucleation rate at higher temperatures.
solution with respect to gypsum was 0.72. The pH of Also, much lower saturation index of the supersatu-
the solution was about 5.5. The inhibitor concen- ration solutions can be inhibited for calcium sulfate
trations ranged from 0 to 60 mg/l for HDTMP and Ck compared to barium sulfate at a given inhibitor con-
20 mg/l for PCAP. The decrease of the induction centration. Therefore, the inhibition of nucleation
564 S. He et al.

seems to be dependent on the initial nucleation rate SI

or the induction period which were controlled by the


1.0 0.82 0.71 0.63 0.56
4
interfacial tension between the crystal and aqueous
solution and the molar volume of the crystal, as well
as, temperature and saturation index of the solution
based on the classical nucleation theory (NIELSEN,
1964; SOHNEL and MULLIN, 1988).

Nucleation kinetics in the presence of inhibitors


0’ . ’ . I . ’ ’
It was observed that the nucleation induction 1.0 1.5 2.0 2,s 30
period was prolonged at a constant supersaturation l/(SIY
and temperature when trace amounts of scale inhibi-
tors were added to the solutions supersaturated with
respect to either gypsum or barite. The prolongation SI
depends on the nature and concentration of the 3.16 1.63 1 41
5 ‘I’I”.”
inhibitor (Figs 2 and 3). According to the classical
nucleation theory, the other important parameters
without regard to the saturation index and tempera-
ture affecting the nucleation rate or the induction
log had
period is the interfacial tension between the crystal (6)
and aqueous solution (a). The interfacial tension can
be estimated from the experimental data of the
induction period based on the classical nucleation
equation (for details, see SOHNELand MULLIN, 1988). -1’ ’ ’ I ’ ’
u.0 0.1 0.2 0.3 0.4 0.5
The interfacial tensions for gypsum and barite in
l&W
NaCl solutions without inhibitors have been esti-
mated previously (HE et al., 1994a, submitted) from Fig. 4. The inhibition of gypsum and barite nucleation at
the slope of the log tind vs 1/(SI)2 plot according to 25°C to illustrate the effect of inhibitors on the interfacial
Eqn (3): tension. (a) Inhibition of gypsum by HDTMP at a pH of 5.5
(b) Inhibition of barite by HEDP at a pH of 6.5. Curves A
(open circles), curve B (crosses), curve C (triangles). curve
-- B D (diamonds) and curves E (solid circles) represents inhihi-
log tind = tsI)2 c,
tor concentrations of 0.0, 0.5, I .O.5.0 and 10.0 mgil.

where C is a constant and B is the slope and is a


function of temperature and interfacial tension as in
Eqn (4) 3 Table 3. The estimated interfaciai tensions between gyp-
sum or barite and aqueous NaCl solutions in the prcscnce of
inhibitors at 25°C

NaCl Cont. a
where R is the gas constant, T is the absolute tem- Crystal (M) Inhibitor (mg/l) Slope (mJ/m’)
perature, N, is Avogadro number, V,,, is the molar
volume of the crystal, f is a correction factor for Gypsum 3.0 HDTMP (0.0) 45.5
Gypsum 3.0 HDTMP (1.0) 49.4
heterogeneous nucleation (assumed to be 0.01, see 3.0 HDTMP (5.0) 55.7
Gypsum
SOHNEL and MULLIN, 1988) and B is a geometric Gypsum 3.0 HDTMP (10.0) 69.‘)
shape factor. The geometrical factor was defined as /3
= 4S3/[27V2], where S and V are the surface area and Bar&e 1.0 HEDP WV 12.1 140.5
Barite 1.0 HEDP (0.5) 22.0 171.2
volume of the nucleus, respectively (see NIELSEN,
Barite 1.0 HEDP (1.V 26.0 181.0
1964). Barite 1.0 HEDP (5.0) 49.0 223.6
The induction period for calcium sulfate nuclea- Barite 1.0 HEDP (10.0) 67.0 248.2
tion in 3 M NaCl solution and for barium sulfate
nucleation in 1 M NaCl solution at 25°C as a func-
tion of the saturation index was experimentally It should be noted that the geometrical factor (,!?)
measured. The results are graphically presented in was assumed to be a constant with or without the
Fig. 4a and b for gypsum and barite, respectively. presence of inhibitors in the calculation. However, it
The slope and estimated interfacial tension for gyp- is well known that additives, such as scale inhibitors,
sum and barite with and without inhibitors (HEDP often change the crystal morphology (e.g. COWAN
and HDTMP) assuming a constant B (j3 = 50 for and WEINTRIT~, 1976), and therefore the geometrical
rectangular parallelepiped, see NIELSEN, 1964) are factor may be a variable. However, the assumption is
listed in Table 3. probably valid since the geometrical factor will de-
Inhibition of gypsum and barite nucleation in NaCl brines 565

crease slightly in the presence of inhibitors for gyp- increase slightly to 6 M. For barite, the induction
sum and barite and thus, the estimated interfacial period decreases with increasing NaCl concen-
tension should be even higher if the geometrical trations to 6 M. The variation trend of the induction
factor were taken into account. The crystal mor- period with ionic strength was proportional to the
phology of gypsum and barite were found to be thick, enhanced solubility of gypsum or barite in electrolyte
rounded, enlarged and less needle-like crystals in the solutions. The influence of pH and the lattice cation/
presence of inhibitors rather than small, thin, sharp anion molar ratio on the inhibition of nucleation was
and elongated needle crystals without inhibitors (e.g. investigated in this study.
LEUNC and NANCOLLAS, 1970; RALSTON, 1972;
AMJAD, 1988).
Adding inhibitors, such as HDTMP and HEDP, to The pH-dependence of inhibition
supersaturated calcium sulfate or barium sulfate
solutions will increase the interfacial tension and thus The effect of the solution pH in the range of
prolong the nucleation induction period. The in- 1.5-12.0 on the inhibition of gypsum nucleation by
crease in the interfacial tension depends on the HDTMP and PCAP was studied at 25°C in 3 M MaCl
nature and concentration of the inhibitor. In the case solutions with equal total concentrations of calcium
of gypsum inhibition, the presence of 10 mg/l and sulfate. The saturation index of the solution was
HDTMP elevated the interfacial tension from 46 to 0.73 with respect to gypsum. For barium sulfate, the
70 mJ/m’ at 25°C. In the case of barite inhibition, the pH dependence of the inhibition of nucleation by
presence of 10 mg/l HEDP elevated the interfacial HEDP and PPPC in the same range of pH was
tension from 141 to 248 mJ/m2 at 25°C. Therefore, studied at 25°C in 1 M NaCl solutions with equal total
the effect of inhibitors on the nucleation rate can be concentrations of barium and sulfate. The saturation
interpreted in terms of the elevated interfacial ten- index of the solution was 2.95 with respect to barite.
sion in the presence of inhibitors. The inhibitor concentration studied was 2.5 mg/l.
The difference between different inhibitors for The results are presented in Fig. 5a and b for gypsum
nucleation inhibition may be due to different impact and barite, respectively.
on the interfacial tension for a given crystal. The The results presented in Fig. 5a and b indicate that
different impact likely results from different molecu- at a constant temperature, saturation index and in-
lar structures of these inhibitors, such as their mol- hibitor concentration, the induction period is de-
ecular weight and size, number of functional group pendent on the solution pH. It was observed that the
and the degree of dissociation. The molecular struc- inhibition becomes generally more effective as the
ture varies widely among these polyelectrolytes. For pH of the solution increases to a point, due probably
example, there are different numbers of the phos- to the degree of ionization or dissociation of the
phonic acid group (PO,H,) in these phosphonic acids inhibitor at a given pH. In the case of PPPC and
(two for HEDP, three for ATMP, four for HDTMP PCAP, the maximum inhibition was reached when
and five for DTPMP). The functional group (COOH) the solution pH was about 3 and 4, respectively. The
in polycarboxylates also varies widely. The affinity maximum inhibition was reached at a higher pH
between the inhibitor molecule and the crystal sur- (about 7) for phosphonates HDTMP and HEDP.
face also plays an important role in determining the
efficiency of the inhibition. Although gypsum and
barite are both alkaline earth metal sulfate minerals, The dependence on the non-stoichiometry of lattice
gypsum is more selective to inhibitors probably be- ions in solution
cause of the occurrence of a water sheet around
calcium ions at the nucleus surface or because of its The effect of non-stoichiometry of lattice ions in
much higher aqueous solubility. aqueous solutions (e.g. the [Ca”]/[SO$-1 or the
The performance of nucleation inhibitors can be [Ba2’]/[SOi-] ratio) on the inhibition of nucleation
affected by many factors other than the degree of was studied at 25°C for calcium sulfate and barium
supersaturation and temperature for a given inhibi- sulfate. The calcium sulfate solutions were super-
tor. These factors need to be considered in practical saturated with respect to gypsum and maintained at
applications, for example, designing scale inhibitor the same saturation index (0.85) and ionic strength
squeezes (pumping inhibitors into reservoir forma- (5 M), but of different [Ca2’]/[SOz-] molar ratios
tions) for specific well conditions. The most import- ranging from 0.1 to 50. The induction periods for
ant parameters include ionic strength, pH and the gypsum nucleation in these solutions at 25°C were
lattice cation/anion molar ratio of the solution. The measured at a pH of 5.5 with no inhibitor and with 4.6
nucleation rate of gypsum and barite in NaCl solu- mg/l HDTMP and 10 mg/l PCAP. The results are
tions, from 0 to 6 M at 25”C, without inhibitors was shown in Fig. 6a. For barite, the supersaturated
found to be dependent on the ionic strength of the solutions were of the same saturation index (3.56)
solution (HE et al., 1994a, submitted). In the case of and ionic strength (1 M), but of different
gypsum, the induction period decreases with increas- [Ba2’]/[SO$-] molar ratios ranging from 0.005 to
ing NaCl concentrations up to 3 M and then starts to 500. The induction periods for barite nucleation in
566 S. He et al.

s- - I
l
.

4.

0 +
Stoiehiometric
log tind 10s h.. Point l l +
(s) (a) 3-
I +

2-

1.1 . ’ I ’ ’ ’ . ’ .
0 2 4 6 8 10 12 14 I-
‘-2 -1 0 1 2
Solution pH
tog tcP*+l/[soq-]

s-.
b

0
47
A

log tind 2 3-
(s) 1:
log timd *
6) * Stoicbiometric
Point 0

l-
8A 0
0 .,.,.I .,.I.,. . aId IO B p 0 00
0 2 4 6 8 10 12 14
0 I . I .
Solution pH -3 -2 -1 0 1 2 3

log rBP*+1/ISOt~l
Fig. 5. The effect of the solution pH on the inhibition of
calcium sulfate and barium sulfate nucleation at 25°C. (a) Fig. 6. The effect of lattice cation/anion molar ratios on the
Inhibition of calcium sulfate by HDTMP (circles, A) and inhibition of (a) gypsum nucleation at a pH of 5.5 by
PCAP (crosses, B) at 2.5 mg/l in 3 M NaCl solution. (b) HDTMP (4.6 mg/l, solid circles) and PCAP (10 mg/l.
Inhibition of barium sulfate by HEDP (diamonds, C) and crosses), and (b) barite nucleation at a pH of 6.5 by HEDP
PPPC (triangles, D) at 2.5 mg/l in 1 M NaCl solution. (2.5 mg/l, squares) and PPPC (2.5 mg/l, triangles) at 25°C.
The saturation index is 0.85 and 3.56 and the ionic strength
is 5.0 and 1.0 M for calcium sulfate solutions and barium
sulfate solutions, respectively. Open circles represent no
these solutions at 25°C were measured at a pH of 6.5 inhibitors added.
with no inhibitor and in the presence of 2.5 mg/l
HEDP and PPPC. The results are shown in Fig. 6b.
It was observed (Fig. 6) that the lattice ion molar
ratio of the solution has a strong effect on the effec- lattice cation, negatively charged surfaces of nuclei
tiveness of anion inhibitors, such as HDTMP, tend to repulse anionic inhibitors which results in the
HEDP, PCAP and PPPC. The degree of the inhi- weakening of anionic inhibitors.
bition of nucleation generally increases with increas-
ing lattice cation/anion ratios. However, when there
are no inhibitors present in the solution, the nuclea- IMPLICATIONS FOR SCALE DEPOSITION AND
tion induction period seems to be independent of the CONTROL
ratio in the case of calcium sulfate or slightly depend-
ent on the ratio in the case of barium sulfate. Water-formed scale minerals nucleate, grow and
The effect of the lattice ion molar ratio on the deposit due to supersaturation. Changes in the tem-
inhibition of nucleation can be explained in terms of perature and pressure of the solution generally can
nucleation theory (e.g. GUNN, 1976). In the case of result in small changes in the state of supersaturation
the dominance of lattice cation over the lattice anion, because of the small mineral solubility variation with
the surface of nuclei generated in aqueous solution temperature and/or pressure. However, mixing of
tends to be positively charged and will attract anionic incompatible waters, such as seawater and formation
inhibitors which results in adsorption of inhibitor waters, could create high states of supersaturation
anions on the surface of the nuclei. On the other with respect to calcium and/or barium sulfates.
hand, when the lattice anion is dominant over the The experimental results from this study with fairly
Inhibition of gypsum and barite nucleation in NaCl brines 567

high saturation indices for both gypsum and barite no way does this constitute an endorsement by GRI of any
suggest that both calcium sulfate and barium sulfate products or views contained herein. In addition, the work
was also supported by a consortium of companies including
scales can be controlled by trace amounts of inhibi-
Texaco, Inc., Conoco, Inc., Champion technologies, Inc.,
tors (HDTMP for calcium sulfate and HEDP for FMC Corporation-product Additives Div. and Zapata, Inc.
barium sulfate). The degree of the inhibition of The critical comments of Dr J. Bischoff, Dr W. Evans and
nucleation is relative and the prolongation of the Dr Y. Kharaka were greatly appreciated.
induction period should be compared to the resi-
Editorial handling: Yousif Kharaka
dence time of subsurface brines and the flow rate.
Also, the compatibility of scale inhibitors with the
REFERENCES
formation waters should be examined for appli-
cations in the field conditions. Most importantly, one AMJAOZ. (1988) Calcium sulfate dihydrate (gypsum) scale
must consider the compatibility with other divalent formation on heat exchanger surfaces: The influence of
ions and heavy metals present in brines, such as scale inhibitors. J. Colloid Interface Sci. 123,523-536.
Mg2+, S?’ , Fe2’, Co2+ and Pb2’. The compatibility COWANJ. C. and WEINTRI~~D. J. (1976) Water Formed
Scale Deposits. Gulf Publishing Co., Houston, Texas.
with calcium ions commonly present in brines should
GRAYP. R: (1993) NORM contamination in the petroleum
be also examined in the case of barium sulfate inhi- industrv. J. Petrol. Technol. 45. 12-16.
bition. Complexation of highly charged anionic in- GUNN D: J. (1976) Mechanism for the formation and
hibitors with metals will reduce significantly their growth of ionic precipitates from aqueous solution. Disc.
activity and efficiency. The study of the nucleation Faraday Sot. 61, 133-140.
HE S. and MORSEJ. W. (1993) Prediction of gypsum,
and inhibition of sparingly soluble alkaline metal anhydrite and halite solubility in brines under subsurface
sulfates in the presence of divalent metal ions is in conditions. Comput. Geosci. 19, l-22.
progress. HE S., 0000 J. E. and TOMSONM. B. (1994a) The nuclea-
tion kinetics of calcium sulfate dihydrate in NaCl solu-
tions up to 6 molar and 90°C J. Colloid Interface Sci. 162,
297-303
CONCLUSIONS HE S., Oooo J. E. and TOMSONM. B. (1994b) The seeded
growth of calcium sulfate dihydrate crystals in NaCl
The nucleation of calcium sulfate in NaCl solutions solutions up to 6 molar and 90°C. .I. Colloid Interface Sci.
can be inhibited by HDTMP to a saturation index of 163,372-378.
LEUNGW. H. and NANCOLLAS G. H. (1970) A kinetic study
at least 0.7 and to temperatures of at least 90°C. The of the seeded growth of barium sulfate in the presence of
nucleation of barium sulfate in NaCl solutions can be additives. .I. Inorg. Nucl. Chem. 40, 1871-1875.
inhibited by HEDP to a high saturation index (2.9 NIELSENA. E. (1964) Kinetics of Precipitation. Pergamon
below 50°C and 2.4 below 90°C). Press, New York.
RALSTON P. H. (1969) Scale control with aminomethylene-
The inhibition of nucleation through a prolonged
phosphonate. /. Petrol. Technol. 21. 1029-1036.
induction period was interpreted as a result of an RALSTON P. H. (1972) Inhibiting water formed deposits with
increase in the interfacial tension between the crystal threshold compositions. Mater. Perform. Protect. 11,39-
and aqueous solution in the presence of chemical 44.
inhibitors. For example, the interfacial tension be- RIZKALLAE. N. (1983) Kinetics of the crystallization of
barium sulfate. J. Chem. Sot., Faraday Trans. 79, 1857-
tween calcium sulfate dihydrate and the aqueous 1867.
solution increases from 46 to 70 mJ/m2 at 25°C in the ROSENBAUER R. J., BISCHOFFJ. L. and KHARAKA Y. K.
presence of 10 mg/l HDTMP. For barite, the interfa- (1992) Geochemical effects of deeo-well iniection of the
cial tension increases from 141 to 248 mJ/m2 at 25°C Paradox Valley brine into Paleozoic carbonate rocks,
in the presence of 10 mg/l HEDP. Colorado, U.S.A. Appl. Geochem. 7,273-286.
SMITHA. L. (1987) Radioactive scale formation. J. Petrol.
The degree of inhibition depends on the pH of the Technol. 39.697-706.
solution and the lattice ion molar ratio, in addition to SOHNEL0. and MULLIN J. W. (1988) Interpretation of
the degree of supersaturation and temperature. Gen- crystallization induction periods. J. Colloid Interface Sci.
erally the inhibition efficiency of anionic inhibitors 123,43-50.
VANOERLEEOENM. C., KASHCHIEV D. and VANROSMALEN
increases with increasing lattice cation/anion molar G. M. (1992) Precipitation of barium sulfate: Induction
ratios. time and the effect of an additive on nucleation and
growth. J. Colloid Interface Sci. 152,33&350.
Acknowledgements-This work was supported by the Gas VETTER0. J. (1972) An evaluation of scale inhibitors. J.
Research Institute under contract No. 5088-212-1717, but in Petrol. Technol. 24,997-1006.