DESALINATION

ELSEVIER Desalination 109 (1997) 323-332

Evaluation of SHMP and advanced scale inhibitors for control

of C a S O 4, S r S O 4, and C a C O 3 scales in RO desalination

F.H. Butt*, F. Rahman, U. Baduruthamal

Research Institute, King Fahd University of Petroleum and Minerals, Dhahran 3126I, Saudi Arabia
Tel./Fax +966 (3) 860-6934

Received 12 April 1996; accepted 28 February 1997

Abstract
Sodium hexa-meta-phosphate (SHMP), inhibitor-A (acrylic polymer), and inhibitor-B (polyacrylate+
phosphonate), each at a dose level of 1 ppm (on active basis) were evaluated at 25 C for their efficacy against CaSO 4,
SrSO4, and CaCO 3 scales in a synthesized brine which corresponded to 80% recovery from the locally available
aquifer brackish water. At periodic time intervals brine pH was measured and samples were withdrawn and analyzed
for Na , Ca 2, Sr2, SO 2-, and total alkalinity (TA). The total time of equilibration was 168 h (7 days). The criterion
adopted in comparing efficacy of the inhibitors was that if an inhibitor could achieve an induction period of at least
15 min, it would be considered an effective inhibitor at that dose level against that particular scalant. In the control
experiment (no inhibitor added), there was an immediate drop in Ca2, Sr2, and TA levels and the solution became
turbid much earlier than 15 min, suggesting that the brine was highly supersaturated and scale-forming with respect
to CaCO 3 and SrCO 3 scales and would require injection of an inhibitor. In 168 h, there was no drop in SO42-
concentration suggesting that the brine possessed no potential to form CaSOa.2H20 and SrSO 4 scales. SHMP was
able to keep the scale-forming constituents (Ca2, Sr2, and TA) in solution for 91 h, inhibitor-A for 50h, and
inhibitor-B for all of 168 h, suggesting that the inhibitors at 1 ppm gave completely scale-free operation up to 80%
product recovery and that performance of inhibitor-B was the best.

Keywords: Scale inhibitors; Polyphosphates; Acrylic polymers; Polyacrylates; Phosphonates; Scaling; Reverse
osmosis; Desalination

1. I n t r o d u c t i o n residual alkalinity from depositing CaCO 3 scale.

But there are well-documented problems
From the early stages o f the RO desalination,
associated with the use of acid+SHMP treatment.
acid (usually H2SO4) was used to control alkaline
These problems include acid-induced corrosion of
scale and sodium hexa-meta-phosphate (SHMP)
the metal piping carrying the pressurized saline
to control sulfate-based scales and to prevent any
feed, reversion of SHMP to the sludge-forming
orthophosphate, and its short shelf-life because it
*Corresponding author.

0011-9164/97/$17.00 1997 Published by Elsevier Science B.V. All rights reserved.

PH S0011-9164(97)00078-7
324 F.H. Butt et al. / Desalination 109 (1997) 323-332
acts as food for microorganisms. These problems
and an ever-growing demand for scale inhibitors
by the rapidly expanding RO desalination
industry created an enormous potential market for
better scale inhibitors--the ones which would
have none of the problems typical of SHMP+
H2SO 4 treatment. Some of the advanced
inhibitors that became available to the RO
industry as possible substitutes for acid+SHMP
treatment are listed below:
Original Commercial name of the
manufacturer inhibitor
1. Pfizer, USA FLOCON- 100
2. Calgon, USA EL-5500, EL-5600
3. BFGoodrich, USA AF-100, AF-400, AF-600
4. Betz, USA Betz-604
5. Houseman, UK PermaTreat 191, 391
Unlike SHMP, these inhibitors are in a liquid
state and thus are easy to apply. Also, they are
claimed to be safe to handle, non-corrosive, have
a long shelf-life, are good dispersants and iron
sequestrants, and are cost effective. The advanced
inhibitors have found widespread usage in the RO
industry where they are claimed to reduce and, in
some cases, replace the addition of acid.
In the present study, two well known broad-
based inhibitors known to be effective against
CaCO3, CaSO4, and SrSO 4 scales, good iron
sequestrants and possessing dispersancy
properties were chosen for the screening study.
One o f them was an acrylic polymer which we
call inhibitor-A and the other was a blend of
polyacrylates and a phosphonate which we call
inhibitor-B. Static experiments, also known as
beaker experiments, were used to evaluate their
efficacy. The advanced inhibitor which exhibited
superior performance in these tests was selected
for evaluation against the H2SO4+SHMP treat-
ment in an RO pilot plant. Results of this pilot
evaluation were presented earlier by Butt et al [1 ].
This paper describes the beaker evaluation of
SHMP and the two advanced inhibitors.
2. Review of previous work
The only real test of the efficacy of a scale
inhibitor is its evaluation in a pilot or a
commercial RO plant. However, such an
evaluation is expensive, highly involved and is
usually the last step in the evaluation process.
Beaker tests are an inexpensive way of
conducting a preliminary screening of inhibitors,
commonly using synthetic brines possessing
scaling potentials with respect to one or several
scale-formers such as CaSO4, SrSO4, CaCO3,
SrCO3, etc. No doubt the laboratory conditions
under which the beaker tests are carried out do
not represent the conditions that prevail in a real
RO plant. Hence, the results of such tests are not
directly applicable to the real RO operation.
However, since the evaluation is conducted in
parallel tests under carefully controlled
conditions, these tests do yield useful information
on the relative efficacy of the inhibitors.
Therefore, the beaker tests have been used widely
and the body of literature available on these tests
is very large. Some of the previous work is
reviewed in the following.
2.1. Inhibitors for control o f CaSO4.2H20
(gypsum) scale
Smith and Sweet [2] studied eight acrylic
polymers as CaSO 4 scale inhibitors at 30 and
90C. The polymers acted by inhibiting
crystallization of the scale-forming salts. Crystal-
lization kinetics was studied by recording the
electrolytic conductivity of the supersaturated
solutions. The effectiveness of the polymers as
scale inhibitors was interpreted in terms of
reduction in the growth rate constant. The
polymers were found to be more effective at
30C and when their molecular weight was low.
Yeatts et al. [3] synthesized the brackish water
feeds of the Gillette (Wyoming, USA) and
Webster (South Dakota, USA) RO plants, and
that of the saline irrigation water from the
Wellton-Mohawk Canal (Arizona, USA), and the
 F.H. Butt et al. /Desalination 109 (1997) 323-332
brine concentrates up to eight times the normal
concentrations of these brackish waters. The
authors determined C a S O 4 "2H Q solubility in
these waters both in the absence and presence of
5 ppm and 20 ppm of SHMP and discovered that
SHMP at a 5ppm dose level resulted in a
significant increase in the C a S O 4 '2H20
solubility. However, increasing the SHMP dosage
to 20ppm did not result in a corresponding
increase in the solubility.
Reddy et al. [4] investigated the inhibiting
action of SHMP and several other inhibitors at
ambient temperature by exposing a fiat
membrane to a saturated solution of gypsum in
distilled water at 600 psi in a recirculating system.
They observed that even without any anti-scalant,
the gypsum solution remained stable up to 40 h at
supersaturation levels as high as 150%. With
addition of SHMP, supersaturation of gypsum
increased from 162% at 5ppm to 400% at
40 ppm, i.e., more and more gypsum could be
maintained in solution by increasing the SHMP
dosage up to 40ppm. Following the onset of
precipitation after about 34 h, the supersaturation
returned to the baseline level. The scale formed in
this case was gypsum, as expected. Between
60ppm and 100ppm dose levels, SHMP was
totally ineffective, and the resultant scale on the
membrane was found to be calcium phosphate,
indicating that the polyphosphate had hydrolyzed
to orthophosphate. The performance of other
inhibitors (crystalline polyphosphate NALCO
918, polymethylacrylic acid Darex 41, Calgon's
crystalline pentasodium tripolyphosphate, etc.)
was inferior to that of SHMP.
Tsuge et al. [5] synthesized a 5640ppm
brackish water and six concentrates with a
maximum concentration factor of 6.3 and studied
the degree of CaSO 4 supersaturation that could be
maintained in solution with various dose levels of
SHMP. The crystallization of C a S O 4 from
supersaturated solutions was preceded by an
induction period which was found to increase
with the dose level of SHMP. Eventually, the
325
gypsum concentration was reduced to its
saturation level.
Reitz [6] carried out an excellent bench scale
study to investigate a number of anti-scalants to
control SrSO 4 (also CaSO 4 and CaCO3) scales in
RO systems. He used beaker experiments and
laboratory cell testing in the screening process.
The anti-scalants studied were the phosphonates
such as hydroxyethylidene diphosphonic acid
(HEDP), maleic mono and copolymers,
polyacrylates (e.g., FLOCON-100), and SHMP.
FLOCON-100 and SHMP at a 10ppm dose level
were able to maintain the CaSO 4 supersaturation
at or near the original level for periods up to 6 h.
HEDP, which is so effective against CaCO 3 scale,
showed very little activity against CaSO 4. Reitz
also compared the effectiveness of FLOCON-100
and SHMP against CaSO 4 scales in terms of their
solubilities and found that, compared with
SHMP, FLOCON-100 increased the apparent
solubility product constant (Ksp) of C a S O 4 in
15,000ppm NaCI solution by 200%. In laboratory
cell testing, Reitz exposed a fiat plate RO
membrane to two synthesized brackish waters,
one corresponding to 65% recovery of Rosweil
(New Mexico, USA) brackish water and the other
to 90% recovery of Riyadh (Saudi Arabia)
brackish water. In the Roswell brackish water
tests at 25C and 1 ppm dose level, the amount of
CaSO 4 scale collected on the disc membrane was
10 mg when using FLOCON-100 compared with
about 21 mg with SHMP. At 3 ppm, both SHMP
and FLOCON-100 were equally effective with
CaSO 4 scale which was about 1 mg. In the Riyadh
brackish water tests at 35 C and a 1 ppm dose
level, the amount of C a S O 4 scale on the disc
membrane was about 4mg with FLOCON-100
vs. more than 20 mg with SHMP. At 5 ppm, the
C a S O 4 scale collected with both SHMP and
FLOCON-100 was about 1 mg.
Amjad [7] compared the effectiveness of a
polyelectrolyte-based anti-scalant, commercially
known as AF-400, with SHMP for the control of
gypsum scale. He found the induction period to
increase as the dose level of AF-400 was
326 F.H. Butt et al. / Desalination 109 (1997) 323-332
increased. At 2 ppm, the crystallization of gypsum
was completely inhibited for at least 2h. At
0.5ppm, the induction period achieved with
AF-400 was about twice as long as that with
SHMP.
Logan and Kimura [8] investigated four
advanced anti-scalants by exposing a disc
membrane to 2000ppm NaC1 solution super-
saturated with gypsum at 400psi. At gypsum
supersaturation between 2 and 3, the EL-2438
additive, a blend of phosphonate and
polycarboxylates, at a 7.2ppm dose level
significantly increased the induction period
whereas 9.4 ppm of SHMP had no noticeable
effect. The authors studied three other additives:
EL-4010 (polyacrylate-based), EL-5500 (a blend
of polycarboxylates), and EL-5600 (a blend of
polycarboxylates and a phosphonate). In the fiat
membrane tests, these additives at an 8 ppm dose
level helped achieve 70% product recovery at a
C a S O 4 supersaturation level of about 3.2.
Smith et al. [9] conducted a comprehensive
evaluation of EL-5600 for the control of gypsum
(also CaCO3) scales encountered in brackish RO
systems. They used the laboratory scale disc of
fiat membrane similar to that used by Reddy et al.
[4]. The addition of 8ppm of EL-5600 to a
2000 ppm NaCI solution saturated with gypsum,
doubled the soluble gypsum level (2300 ppm
Ca 2+ vs. 1100 ppm for the control experiment).
2.2. lnhibitors for control o f SrSO 4 scale
In the desalination literature, the inhibition of
SrSO 4 has received much less attention than
CaSO 4 and CaCO 3. In seawaters and most
brackish waters, the concentration of Sr2 is quite
small compared with Ca 2. Accordingly, in
situations where there is a potential for both
calcium-based and strontium-based scales, the
amount of CaSO4/CaCO 3 scale formed is so large
compared to SrSO4/SrCO 3 scale that the latter is
not a significant factor in scale inhibition. In oil
field operations, however, the brines associated
with oils usually have significant concentrations
of Sr z+ and SrSO 4 becomes as significant a
problem as C a S O 4 and C a C O 3. Jacques et al. [ 10]
conducted a laboratory comparison of two
inhibitors, a commercially available phosphate
ester and Exxon Chemical Company's low
molecular weight polymer, COREXIT 7647, for
control of SrSO 4 scale. Most of the experiments
were done with 50,000ppm NaC1 at 25C.
Various degrees of SrSO 4 supersaturation were
achieved by co-precipitation of equi-molar
solutions of SrCI2 and Na2SO 4. The onset of
SrSO 4 precipitation was found to be a strong
function of degree of supersaturation. Compared
with phosphate ester, COREXIT was more
effective with SrSO4, but its effectiveness
decreased with increase in the degree of SrSO 4
supersaturation. In other words, the higher the
degree of supersaturation, higher the dose level of
the additive required to inhibit precipitation of
SrSO 4.
Reitz [6] investigated a number of anti-
scalants to control SrSO 4 (also CaSO a~d
CaCO3) scales in RO systems. He compared the
effectiveness of FLOCON-100 and SHMP
against SrSO 4 scale in terms of its solubility and
found that, compared with SHMP, FLOCON-100
increased the Ksp of SrSO 4 in 15,000 ppm NaC1
solution by 300%.
2.3. lnhibitors for control o f CaCO 3 (calcite)
scale
Reddy and Nancollas [11] studied CaCO 3
(calcite) crystal growth inhibition at 25C by
using four phosphonate-based scale inhibitors. At
the same supersaturation of CaCO 3 and same ppm
dosage of the inhibitors, they found HEDP to be
most effective against CaCO 3 scale. Wilken [ 12]
studied the effectiveness of four scale inhibitors
(ethylene maleic anhydride, acrylate, acrylic acid,
and phosphonate) in modifying crystal growth of
CaCO 3. The presence of these inhibitors in ppm
quantities significantly altered crystal growth of
calcite; the normal rhombohedral form was
changed to a needle-like structure. The inhibitor
 F.H. Butt et al. / Desalination 109 (1997) 323-332
was believed to have inhibited the crystal growth
by adsorbing on to the fast growing crystal face.
Mitsoyannis et al. [13] studied precipitation of
CaCO 3 on laboratory scale cellulose acetate
membranes at 580 psi pressure using three
synthetic brackish waters as feed: (1) a 2000 ppm
NaCI solution, (2) a solution containing 2000 ppm
NaCI and 360 ppm NaHCO 3 expressed as CaCO 3,
and (3) a solution containing 2000 ppm NaC1 and
600ppm NaHCO 3 expressed as CaCOy The
authors observed that the NaHCO3-containing
solutions caused scale formation and that the
solution containing 600ppm NaHCO 3 caused
more scale than the one containing 360 ppm. The
study concluded that the CaCO 3 scale was caused
because of (1) high permeability of CO 2 through
the membrane which increased the brine pH and
created a favorable condition for precipitation of
CaCO3, and (2) enrichment of brine with Ca 2+
due to its very high rejection by the membrane,
causing crystallization and deposition of CaCO 3.
Reitz [6] investigated a number of anti-
scalants to control CaCO 3 (also CaSO 4 and
SrSO4) scales in RO systems. The anti-scalants
studied were the phosphonates (e.g. HEDP),
maleic mono and copolymers, polyacrylates (e.g.,
FLOCON-100), and SHMP. The effectiveness of
HEDP, SHMP and FLOCON-100 against CaCO 3
scale was studied using a supersaturated solution
of CaCO 3 with a positive Langelier Index of 2.1.
All three inhibitors at 3 to 6 ppm dose levels were
found effective in inhibiting the CaCO 3 precipi-
tation for over 15 min.
Kleinstuck and Sicius [14] evaluated two
phosphonates [HEDP and phosphono butane
tricarboxylic acid (PBTC)] and two acrylates
[polyacrylate (PA) and polymaleinate (PMA)] for
their efficacy against CaCO 3 scale in cooling
water systems. At >_2ppm dosage, PBTC and
HEDP provided nearly 100% inhibition. But as
the TA increased or the dose level of HEDP was
increased, the efficacy of HEDP declined. Also,
in the presence of chlorine, which represents a
disinfection step in the RO process, HEDP
appeared to lose its inhibiting action completely.
327
The PMA performed well against C a C O 3. But in
the presence of chlorine or when the TA was
increased, higher dosages of PMA were required
to maintain its efficacy. The performance of PA
was consistently poor.
Amjad and Pugh [ 15] evaluated 13 advanced
inhibitors (containing various functional groups)
at 30C and a pH of 8.5 using a constant
composition (CC) method. The authors found
that, among other things, the effectiveness of
polyacrylic acid (PAA) inhibitor was strongly
dependent upon molecular weight (MW)
distribution and that its performance was
maximum at MW of about 2000. Of the various
inhibitors tested, the investigators found AF-600,
a proprietary anionic polymer inhibitor, to be
most promising which at only a 0.2 ppm dose
level was able to inhibit the CaCO 3 crystal
growth for about 3.3 h.
3. Synthesis of 80% brine
A typical analysis of the brackish water which
was used as feed in the pilot plant study has been
reported earlier [ 1]. Based on this feed water and
salt rejection typical of brackish RO, a brine
corresponding to 80% recovery was synthesized.
In preparing this brine, K was replaced by Na +
and NO~ and Br- were replaced by CI-, etc. But
concentrations of the ions important from the
scaling point of view ( C a 2+, M g 2 + , 51`2+ , S O 42- ,
Table 1
Composition of the 80% synthetic brine
Parameter Conc. (mg/l)
Na+ 3,237
Ca2+ 1,320
Mg2+ 420
Sr2 34.0
CI- 6,060
SO2- 2,640
HCO3 984
TDS 14,695
Ionic strength, mol/l 0.3200
328 F.H. Butt et al. / Desalination 109 (1997) 323-332
Table 2
Types and dosages of inhibitors used in beaker tests
Inhibitor Active Dosage on active
ingredients basis (ppm)
None (blank) None 0 periods of time without precipitation. In real
SHMP Polyphosphate 1 systems the presence of impurities and scale
Inhibitor-A Acrylic polymer 1 crystals accelerates precipitation. Therefore, to
Inhibitor-B Polyacrylate + 1
phosphonate
HCO3) were left unchanged. Ionic composition
of the synthetic brine is listed in Table 1. The
brine was synthesized using solutions of
analytical grade salts (NaCI, Na2SO4, NaHCO 3,
CaCI2.2H20 , MgC12.6H20, and SrCI2.6H20 ). The
dosages used of SHMP and the advanced
inhibitors A and B are listed in Table 2.
4. Experimental procedure
Borosilicate bottles each containing known
volumes ofNaC1, Na2SO 4 and NaHCO 3 solutions
were placed in an oil-bath. The laboratory air-
conditioning temperature was controlled at
approximately 22C. A Fisher (model no. 73)
temperature controller--an immersion circulator
capable of providing temperature control of the
oil bath to within +0.02C--was used to
maintain the solutions temperature at 25+0.5C.
A Fluke (model no. 2190A) digital temperature
indicator with type K (chromel-alumel)
thermocouple (TC) was used as the oil-bath
temperature sensor and another TC was immersed
in a flask containing only 14,631 ppm NaCI
solution (no inhibitor) as a true temperature
indicator of the test brines. Complete mixing was
achieved by a vigorous rocking motion of the
bottles. When the temperature was stabilized at
25~-0.5C, known volumes of CaC12, MgC12, and
SrCI 2 solutions and fine crystals of CaSOa.2H20
(gypsum), SrSO 4, and CaCO 3 (calcite) were
added to each bottle. This represented the start of
the experiments at which time pH of the brine
was 7.7. The bottle containing no inhibitor
(blank) immediately became turbid.
Ours was a clean system with modest, if any,
degrees of CaSO 4 and SrSO 4 supersaturation; the
supersaturated solutions could exist for long
simulate the real system as much as possible, fine
crystals of CaSO4.2H20, SrSO 4 and C a C O 3 (cal-
cite) were added to each bottle to provide
nucleating sites.
The total time of equilibration was 168 h (7 d)
during which a number of samples were taken at
pre-determined time intervals. Glass syringes
with 0.45-~m cartridge-type filters and Teflon
tube attachments were used to take samples. The
sampled solution from each bottle was transferred
to a flask containing 10 ml of chilled and acidified
distilled water to ensure instant dilution and
undersaturation. These diluted and acidified
samples were analyzed for cations (Na , Ca 2,
Sr 2+) and anion (SO42-). For total alkalinity (TA),
a separate 25ml sample was taken from each
bottle (no acidification or dilution) and directly
titrated for TA. The cations were determined by
using inductively coupled plasma (ICP)
spectrometer model ARL 3580 (uncertainty
1%), the anion by ion chromatography (IC)
using a Dionex ion chromatograph model 4500i
(uncertainty +2%), and TA by a Metrohm auto-
titrator, model 682 (uncertainty 1%).
S. Criterion for inhibitor evaluation
In comparing the efficacy of the inhibitors, the
inhibitor performance criterion proposed by Reitz
[6] was adopted. In RO desalination, the
residence time of the saline water inside the
permeators is much less than 15min. If,
according to Reitz, a scale inhibitor at a certain
dose level can keep a scale-forming salt in
solution for at least 15 min (i.e., if it can help
achieve an induction period of 15 min), it can be
 F.H. Butt et al. / Desalination 109 (1997) 323-332 329

considered an effective inhibitor at that dose level Fig. l(a) shows that, in the absence of an
against that particular sealant. inhibitor, there was an immediate drop in Ca 2+
and TA levels. The solution became turbid much
earlier than 15 rain. Most of the CaCO 3
6. Results and discussion precipitation had occurred in the first 48 h. As the
percent supersaturation of Ca 2+ and TA
Analytical results of the induction time
decreased, so did the rate of CaCO 3 precipitation.
experiments are listed in Tables 3-6, and Fig. 1
After 120h, the drop in Ca 2+ and TA con-
showstime variations in concentrations of Na ,
centrations, if any, was negligibly small. Fig. 1(a)
Ca2, Sr2+, SO 2- and TA. The Na which was
also shows that in 168h of equilibration time,
monitored only as a check was fairly constant
there was no drop in SO42- concentration. This
during the experiments, confirming the reliability
suggests that even in the absence of an
of the data.

3500 Sa* 3500 NB '~

3000
SO, 2" g SO~~
E
Z 25O0 Z 2500
_o (a) o_
2000
~
OC
2000-
(phosphate)
I
I
I--
Z 1500 Z 1500.
O .. ~N Ca =.
0
Z Z
O 1000 1000.
O

500 ~ TA 500.
. . . . . ,F'Sr~
I ' I I I ' I ; ,,-Sr_*.2. 0
0 20 40 60 80 100 120 140 160 180 20 40 60 80 100 120 140 160 180
TIME (HRS) TIME (HRS)

3500 Sa*
3500 - Ha*

) 3000.
~ 3000-
SO, r
g SO, 2" E
Z 2500- 2500,
O (c) o (d)
.~. [ INHIBITOR-A [ ,~ 2000'
IIC
I INItlBITOR-B ]
(acrylic polymer) I- (polyaclylate+phosphotmte)
Z~I 15011- ~ 1500. CUz~
~..,~_ c~'--~ Z
Z TA
O 1000- 1000,
O
TA
500 -
500

o I I I I I .
v" st",
. 0
20 40 60 80 100 120 140 160 180 0 20 40 60 80 100 120 140 160 180
T I M E (HRS) TIME (HRS)

Fig. 1. Inhibition experiments with 80% reject brine using (a) blank, (b) SHMP, (c) inhibitor-A, and (d) inhibitor-B.
330 F.H. Butt et al. / Desalination 109 (1997) 323-332

Table 3
Induction time experiments with synthetic brine and without inhibitor (blank)

Exp. no. Time, h pH Na+, rag/1 Ca2+, mg/I Sr2+, mg/l SO42-, mg/l TA, mg/l

20RR-1 .25 7.50 3243 1291 33.9 2534 863

20RR-2 1 7.30 3290 1290 34.2 2555 857
20RR-3 2.5 7.21 3270 1280 33.3 2540 783
20RR-4 6 7.11 3275 1265 32.3 2555 696
20RR-5 20 7.03 3255 1265 30.7 2535 608
20RR-6 29 7.04 3260 1230 30.1 2540 569
20RR-7 43 7.06 3260 1220 29.3 2550 529
20RR-8 50 7.17 3265 1177 29.0 2535 498
20RR-9 91 7.18 3260 1160 27.8 2530 469
20RR-10 114 7.12 3305 1165 27.3 2565 436
20RR-11 168 7.02 3265 1140 26.5 2550 394

Table 4
Induction time experiments with synthetic brine and SHMP inhibitor

Exp. no. Time, h pH Na+, mg/1 Ca2+, mg/l Sr2+, mg/l SO42-, mg/l TA, mg/l

21RR-1 .25 7.67 3260 1320 34.5 2535 992

21RR-2 2.5 7.72 3270 1355 34.8 2550 988
21RR-3 6 7.80 3265 1350 34.8 2560 985
21RR-4 20 7.88 3275 1355 34.8 2560 995
21RR-5 30 7.93 3265 1345 34.8 2550 988
21RR-6 44 7.97 3255 1460 34.7 2540 986
21RR-7 50 8.07 3290 1340 35.0 2565 991
21RR-8 91 8.11 3295 1345 35.1 2575 985
21RR-9 114 N.D. 3310 1225 32.0 2580 605
21RR-10 138 7.10 3255 1190 30.2 2545 549
21RR-11 168 7.10 3280 1190 29.8 2555 531

inhibitor, the 80% brine did not possess the
potential to form SO42--based scales such as
CaSOa.2HaO and SrSO 4. Even though Sr 2+
dropped by 22% from 34.0 to 26.5 ppm (Table 3),
this drop is hardly perceptible in Fig. 1(a). This is
because the concentration o f Sr2 was negligible
compared with Ca 2. Compared with Sr2+-based
scale (SrCO3), the CaCO 3 scale will form earlier
and in such massive quantities that in a real RO
plant it will render the SrCO 3 scale of little
consequence.
Fig. 1(b) shows that SHMP was able to keep
all scale-forming constituents in solution for at
least 91 h (Ca 2, Sr 2, SO 2-, and TA concen-
rations did not drop in this period). Following
this, there was precipitation o f C a C O 3 and SrCO 3
which reached equilibrium after about 140h.
These data suggest that in the beaker
experiments, 1 ppm of SHMP gave completely
scale-free operation up to 80% product recovery.
Fig. l(c) shows the performance of inhibitor-
A which was able to keep Ca 2+, Sr2+, and TA in
solution for at least 50h. Following this, there
was drop in Ca 2+, Sr 2+, and TA, suggesting
precipitation of both CaCO 3 and SrCO 3. The
solution in the bottle at this stage was more turbid
 F.H. Butt et al. / Desalination 109 (1997) 323-332 331

Table 5
Induction time experiments with synthetic brine and inhibitor-A

Exp. no. Time, h pH Na+, mg/l Ca2+, mg/l Sr2+, mg/l SO42-, mg/l TA, mg/l

23R-1 .25 7.72 3300 1340 35.0 2565 985

23R-2 2.5 7.72 3285 1335 34.9 2560 992
23R-3 6 7.84 3275 1340 34.9 2565 987
23R-4 20 7.92 3270 1345 34.8 2565 992
23R-5 29 7.97 3260 1340 34.8 2560 976
23R-6 43 7.99 3265 1440 34.9 2585 978
23R-7 50 8.09 3275 1335 34.8 2550 975
23R-8 91 7.23 3290 1225 31.4 2580 556
23R-9 114 7.07 3285 1200 29.9 2560 535
23R-10 138 7.02 3260 1175 29.0 2560 489
23R-11 168 7.02 3280 1170 28.6 2560 461

Table 6
Induction time experiments with synthetic brine and inhibitor-B

Exp. no. Time, h pH Na+, mg/l Ca2+, mg/i Sr2+, mg/l SO4z-, mg/l TA, mg/l

22R-1 .25 7.67 3305 1345 35.2 2590 986

22R-2 2.5 7.72 3240 1445 34.6 2530 984
22R-3 6 7.80 3290 1345 35.1 2570 987
22R-4 20 7.89 3275 1340 35.1 2560 986
22R-5 29 7.93 3265 1340 34.9 2550 985
22R-6 43 7.98 3245 1340 34.8 2535 985
22R-7 50 8.08 3270 1335 34.8 2540 985
22R-8 91 8.12 3260 1330 34.7 2550 989
22R-9 114 8.11 3280 1335 34.8 2555 982
22R-10 168 8.09 3250 1320 34.5 2545 982

than that being treated with SHMP, suggesting
that the amount o f scale formed with inhibitor-A
was more than that in the case o f SHMP.
Fig. l(d) shows that for 168h inhibitor-B
permitted no precipitation o f any o f the scalants.
In the beaker evaluation, therefore, performance
o f inhibitor-B was the best.
7. Conclusions
1. The 80% recovery brine was highly
supersaturated with respect to CaCO 3 and SrCO 3
and would, therefore, require the injection o f a
carbonate scale inhibitor.
2. CaCO 3 was the predominant type o f scale.
3. The brine had no potential to form SO42-
based scales such as CaSO 4 and SrSO 4.
4. The beaker experiments showed the three
inhibitors at a 1 ppm dose level to be satisfactory,
having inhibited precipitation o f the scalants far
beyond the required 15 min time period.
5. The relative performance o f the three
inhibitors could be characterized as: Inhibitor-B>
SHMP>Inhibitor-A.
332 FH. Butt et al. / Desalination 109 (1997) 323-332
Acknowledgments
The work reported in this paper was sponsored
by King Abdulaziz City for Science and
Technology (KACST), Riyadh. The authors wish
to express their sincere thanks to KACST for its
financial support o f the project, No. AR- 10-055,
K F U P M Research Institute, for its manpower,
administrative, and analytical support; and
Khurshid Kamal and Khurshid Alam, both of the
Institute, for their assistance in the experimental
work.
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