Desalination 357 (2015) 36–44

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Desalination
journal homepage: www.elsevier.com/locate/desal

Synthesis and evaluation of phosphate-free antiscalants to control

CaSO4·2H2O scale formation in reverse osmosis desalination plants
Shaikh A. Ali a, I.W. Kazi a, F. Rahman b,⁎
a
Chemistry Department, King Fahd University of Petroleum & Minerals, Dhahran 31261, Saudi Arabia
b
Center for Refining & Petrochemicals, Research Institute, King Fahd University of Petroleum & Minerals, Dhahran 31261, Saudi Arabia

H I G H L I G H T S

• Pre-treatment of reverse osmosis (RO) desalination process for seawater and brackish water
• Synthesis of phosphate-free antiscalants to control calcium sulfate scale formation
• Comparative evaluation of different antiscalants for seawater and brackish water RO plants

a r t i c l e i n f o a b s t r a c t

Article history: Polysuccinimide (PSI) of various molecular weights (MW) was synthesized from aspartic acid. The PSIs were hy-
Received 13 July 2014 drolyzed with NaOH to obtain sodium polyaspartates. Partial hydrolysis of a PSI gave the copolymer poly(SI-co-
Received in revised form 3 November 2014 sodium aspartate). PSIs were treated with one equivalent of cyclic amines: pyrrolidine, piperidine, and azepane
Accepted 5 November 2014
to afford the corresponding polyaspartamides in excellent yields. Treatment of PSI with 0.5 equivalents of the cy-
Available online xxxx
clic amines led to the formation of 1:1 copolymer poly(SI-co-aspartamide) which on basic hydrolysis gave the
Keywords:
corresponding 1:1 copolymer poly(sodium aspartate-co-aspartamide).
Reverse osmosis The antiscalant behavior of the newly synthesized compounds was evaluated at various concentrations (2.5 ppm–
Gypsum scale 10.0 ppm) for the inhibition of gypsum scale formation. The antiscalant evaluation experiments were performed by
Phosphorus-free antiscalant measuring conductivity and using concentrated brines. The study revealed the performance of low MW antiscalants
Polyaspartate to be superior to their high MW counterparts. Thus, a polyaspartate is found to be a better antiscalant than its
Brackish water corresponding copolymer of SI/aspartate, i.e. a partially hydrolyzed PSI. Derivatives of 7-membered cyclic amine
azepane performed better than their 5- and 6-membered counterparts. At the same degree of polymerization, per-
formance with decreasing order of effectiveness was found to be: polyaspartate N poly(aspartamide-co-aspartate) N
(SI-co-aspartate) N poly(SI-co-aspartamide) N polyaspartamide.
© 2014 Elsevier B.V. All rights reserved.

1. Introduction
The world desalting capacity including contracted or under construc-
tion plants as of July 2013 was 80.5 × 106 m3/d. The share of GCC countries
in the world desalting capacity is about 45–48% whereas the share of
Saudi Arabia is largest, about 18–20% of the world desalting capacity [1].
The share of reverse osmosis (RO) process has increased to 63% of the
world desalting capacity. Rapid urbanization, phenomenal industrial
growth along with high population growth and agricultural development
make water one of the most precious resources in Saudi Arabia.
Scaling is one of the major problems in both RO and MSF desalina-
tion plants. In membrane-based desalination plants, deposit of scale
on the membranes reduces product recovery and salt rejection, and in-
creases pressure drop. All these factors result in decreasing the product
water quantity as well as lowering the product water quality besides in-
creasing the pumping cost. The feed waters to the desalination plants in
the Middle East region are seawater and aquifer brackish waters, which
consist of mostly NaCl; but they also contain ionic species such as Ca2+,
−
Mg2+, Sr2+, SO2− 4 , and HCO3 which, under suitable conditions of tem-
perature, pressure, and concentration, may combine to form CaCO3,
Mg(OH)2, CaSO4·2H2O, SrSO4, etc. These salts have very low solubility;
therefore, they come out of the brine and deposit on the heat transfer
tubes in the case of thermal plants, and on membrane surfaces in case
of RO plants. In this paper, we present synthesis and performance eval-
uation of phosphate-free antiscalants to inhibit scale formation in RO
plants.
1.1. Literature review

⁎ Corresponding author. Davey [2] presented an excellent review on the mechanism of addi-
E-mail address: frahman@kfupm.edu.sa (F. Rahman). tives in precipitation processes. Logan and Walker [3] reported the role

http://dx.doi.org/10.1016/j.desal.2014.11.006
0011-9164/© 2014 Elsevier B.V. All rights reserved.
 S.A. Ali et al. / Desalination 357 (2015) 36–44 37

of additives in the prevention of scale formation. Harris [4] discussed
the effect of various additives in inhibiting the precipitation of alkaline
scale (e.g., calcium carbonate, magnesium hydroxide) and sulfate scale
(e.g., calcium sulfate, strontium sulfate) in desalination plants. Amjad [5]
presented the influence of various antiscalants such as polyphosphates,
phosphonates, polystyrene sulfonate, polyacrylamide, polyacrylate and
formulated polyelectrolytes on crystallization and crystal modification
process of gypsum scale at 25 °C. It is reported [6] that some correlation
exists between the structure of the inhibitors and the inorganic scale.
Effectiveness of inhibitors may even vary for different hydration forms
of the same scale. Dihydrate and hemihydrate forms of calcium sulfate
have markedly distinct interactions with inhibitors like polyvinyl sulfo-
nate (PVS) with respect to change of the crystal habit. The effective inter-
action among the negatively charged groups on the inhibitor and Ca2+
imparts the changes in precipitate morphologies in the crystal lattice of
calcium sulfate hemihydrates and dihydrate and scale inhibition. Carbox-
ylate antiscalants are usually less effective in the presence of multi-valent
metal ions like Ca2+. “AQUAKREEN KC-550” is reported [7] to be effective
against such multi-valent ions. Effect of polyelectrolyte architecture on
scale inhibition has been discussed by Oner et al. [8]; it was found that
polyacrylates imparting maximum surface charge density were more ef-
fective than polymethacrylates. Le Gouellec and Elimelech [9] reported
the effect of hydrodynamics and dosage of additives on inhibition of gyp-
sum scaling in a nanofiltration system. Effectiveness of several commer-
cial antiscalants against gypsum scale formation was evaluated by Shih
et al. [10]. Based on precipitation studies, Rahardianto [11] found that in-
creasing bicarbonate concentrations led to minimized membrane scaling
with gypsum. Amjad [12] examined the inhibition of gypsum precipita-
tion by a variety of polymeric materials and concluded that compared
to polymers, surfactants perform poorly against gypsum precipitation.
Polyphosphate additives added for controlling scale formation in
the reject brine of desalination plants when discharged in the sea
act as nutrient to algae, leading to their increased growth, and local
flourishing and influence over the marine biota picture at the intakes
and outfalls as compared to that of the open sea [13]. Poly(acrylic
acid) and poly(acrylamide), often used as antiscalants, do not exhibit
biodegradability [14] and as such affect the natural world and impact
the environment negatively.
Therefore, there is a demand for biodegradable water-soluble poly-
mers that would be able to solve the scaling problem in the desalination
industry without also damaging the environment. Poly(amino acids),
with amide linkage of a peptide, are completely biodegradable [15–17]
and as such have attracted considerable attention as candidates for biode-
gradable antiscalants. Sodium polyaspartate (SPASP), a poly(amino acid)
with carboxylic acid side chains, exhibits both biodegradability and func-
tionality such as chelating ability and dispersibility. Scale inhibition and
delay in deposition of precipitates onto the membrane surface have
been investigated using polyaspartic acids and their mixtures with surfac-
tants and emulsifiers in the presence of polyacrylates or phosphonates
[18–21] or 1-hydroxyethylidene-1,1-diphosphonic acid [22]. Formulated
compounds prepared by mixing scale inhibitor containing polymer and
organic phosphonic acid have been applied for water treatment [23].
A study on the function and mechanism of phosphonic acid modified
polyaspartic acid scale inhibitor has been reported by Liang et al. [24]. A
scale inhibitor composed of components such as hydroxyethylidene
diphosphonic acid, sodium polyacrylate, hydrolyzed poly(maleic
anhydride), and poly(epoxysuccinic acid) and auxiliary agents like
sodium bisulfite, chlorine dioxide, and benzotriazole have been used
[25]. Sodium hexametaphosphate is a popular additive that has been
used as a gypsum-scale inhibitor to prevent or minimize scale formation
challenging requirements in view, there is a need to develop
antiscalants that readily biodegrade and have low mobility for min-
imum environmental impact and also perform at cost-effective dos-
age of antiscalants.
2. Experimental
Poly(aspartic) based inhibitors are currently the most promising
alternative to conventional non-degradable inhibitors. In the present re-
search, we have synthesized polysuccinimide (PSI) of various molar
masses, which were converted into various homo- and copolymers of
aspartates, aspartamides, poly(SI/aspartamides), poly(SI/aspartates),
and poly(aspartates/aspartamides). The structures of newly syn-
thesized polymers along with their codes are illustrated in Table 3.
The scale inhibiting properties of these new inhibitors have been inves-
tigated using aqueous solution containing 3 times the concentration of
calcium and sulfate ions found in RO plant concentrated brine (CB) cor-
responding to the concentrations of reject brine at 70% recovery for
brackish water as feed.
2.1. Materials
L -Aspartic acid (ASP) (Fluka Chemie AG), sulfolane N,N-
dimethylformamide (Fluka Chemie AG) o-phosphoric acid (85% certified
ACS Fischer Scientific), sulfuric acid (98% certified ACS Fischer Scientific),
sodium hydroxide (Fluka Chemie AG), pyrrolidine, piperidine and
azepane (Fluka Chemie AG) were used as received. A commercially
available leading antiscalant for reverse osmosis desalination plant
applications was obtained in the local market.
2.2. General procedure for polymer synthesis
2.2.1. Polysuccinimide with degree of polymerization (n) of 100: PSI 2-100
A slightly modified procedure [28] was adapted for the preparation
of the PSI 2-100. Thus a mixture of H2SO4 (2.5 g) and L-aspartic acid
(1) (50 g, 376 mmol) was thoroughly ground in a porcelain mortar at
room temperature. The mixture was then transferred to a two-necked
round bottomed flask fitted with a large air condenser and heated in
an oil bath at 203 °C under nitrogen atmosphere. Water vapor, deposit-
ed in the condenser, was swept off by N2 purge. The mixture was stirred
continuously using a magnetic stir-bar. Clumps, formed after 30 min,
were finely ground again and heated for a further 7 h. A pale white pow-
dered product PSI 2-100 was washed with several portions (300 mL) of
hot water to remove unreacted aspartic acid as well as H2SO4. Final
wash was done by methanol (150 mL) and the product was dried
under vacuum at 85 °C for 2 h (until achieving constant weight, 33 g,
90%).
A 0.5% solution of the PSI 2-100 in dimethyl formamide (DMF)
showed reduced viscosity (ηred) of 8.57 mL/g as determined at 25
°C using an Ubbelohde viscometer. The molecular weight and the
degree of polymerization (n) were estimated to be approximately
Table 1
Percent inhibition against precipitation at various times in the presence of 10 ppm of the
synthesized polymers in 3CB supersaturated CaSO4·2H2O solution at 40 °C.
Entry Sample Percent inhibition at different times (min)

in concentrated brines [26]. 100 500 1000 1500 2000 2500 3200 3500
In accordance with the principles of responsible care, Hasson et al. 1 3-100 100 100 100 100 98 97 92 20
[27] proposed a general product profile for ecologically benign inhibitor 2 4-100 100 98 77 7 7 7 7 7
systems as follows: excellent scale inhibition, low aquatic and human 3 10-100 100 98 93 85 9 9 9 9
toxicity, high biodegradability, good price/performance ratio, and free 4 11-100 100 100 100 99 96 90 10 7
5 12-100 99 99 99 98 95 91 73 12
of phosphorus, nitrogen, and heavy metals [28]. Keeping these entire
38 S.A. Ali et al. / Desalination 357 (2015) 36–44

Table 2 with water until the washing becomes neutral and finally with metha-
Percent inhibition against precipitation at various times in the presence 10 ppm of the nol (100 mL). The residue was dried under vacuum at 90 °C (till con-
synthesized polymers in 3CB supersaturated CaSO4·2H2O solution at 40 °C.
stant weight) (24 g, 88%).
Entry Sample Percent inhibition at different times (min)

10 100 500 800 2.2.3. Polysuccinimide with degree of polymerization (n) of 600: PSI 2-600
PSI 2-600 was prepared using the procedure as described in [31].
1 3-230 100 100 98 9
2 5-100 29 23 22 22 L-Aspartic acid (1) was mixed with 30 wt.% phosphoric acid, and
3 6-100 100 99 82 9 the mixture was heated at 180 °C for 3 h under reduced pressure
4 7-100 100 50 29 20 (25 mm Hg) and then for 1 h under a higher vacuum of 1 mm Hg. The
5 8-100 100 96 47 12 mixture was cooled to room temperature and dissolved in DMF. The so-
6 9-100 100 99 94 89
7 9-230 99 4 1 2
lution was then poured into a large excess of water. The precipitated
8 9-600 100 15 4 5 polymer PSI 2-600 was filtered, washed with water and methanol and
9 Commercial 99 6 4 4 then dried to a constant weight under vacuum at 85 °C to obtain the
PSI with 85% yield.

9744 g mol−1 and 100, respectively, as calculated from the following
empirical equation [29]:
1:56
n ¼ 3:52  ηred
where n is the degree of polymerization and ηred is the reduced viscosity
of a 0.5% solution in DMF expressed in the unit of mL/g.
2.2.2. Polysuccinimide with degree of polymerization (n) of 230: PSI 2-230
PSI 2-230 was prepared using the procedure as described in [30]. A
suspension of aspartic acid (1) (37.7 g, 283 mmol) and 85% phosphoric
acid (1.62 g, 14.1 mmol) in sulfolane (120 g) was refluxed under N2 at
160 °C in an oil bath for 5 h. The reaction mixture containing the insol-
uble white product PSI 2-230 was filtered off and washed several times
Table 3
Chemical structure of synthesized polymers of different molar masses.a
Polymer Chemical structure
2.2.4. Aspartamide derivatives of PSI 2
Procedure reported for the amidation of PSI with primary amines is
used to carry out amidation reaction using cyclic amines [32]. To a stir-
ð1Þ ring solution of PSI-2 (1.95 g, 20 mmol) in DMF (10 mL) at 0 °C, pyrrol-
idine (m = 1) or piperidine (m = 2) or azepane (m = 3) (10 mmol or
20 mmol) was added drop-wise for 5 min. The mixture was stirred at
room temperature for 20 h and then poured drop-wise into a vigorously
stirred acetone (100 mL). The product was filtered and washed with ac-
etone and dried under vacuum at 70 °C to a constant weight to obtain
pale white products with yields in the range of 85–93%. Reaction of
PSI 2-100 with 1 equivalent of cyclic amines pyrrolidine (m = 1) and
azepane (m = 3) gave poly[(pyrrolidine-1-yl)aspartamide] (5-100)
and poly[(azepane-1-yl)aspartamide] (6-100), respectively. Reaction
of PSI 2 with 0.5 equivalent of cyclic amines afforded poly[(pyrrol-
idine-1-yl)aspartamide-ran-succinimide] (7-100); poly[(piperidine-1-
yl)aspartamide-ran-succinimide] (8-100); and poly[(azepane-1-yl)
aspatamide-ran-succinimide] (9-100, 9-230 and 9-600). The synthe-
sized compounds gave satisfactory elemental analyses.

Polyaspartate
2.2.5. Alkaline hydrolysis of PSI/PSI derivatives
α
Solid NaOH [103 mmol (1 equivalent) and 79.3 mmol (0.77 equiva-
lent)] for the hydrolysis of PSI 2 and 51.5 mmol of NaOH for PSI/
aspartamides 7, 8 and 9 were added portion-wise to a stirring mixture
β
of PSI 2 or PSI/aspartamide 7, 8 or 9 (103 mmol) in water (30 mL) for
Poly(aspartamide- 5–8 min at 0 °C under N2. The solution was stirred at room temperature
ran-aspartate) for 3 h. After the completion of the reaction, the mixture was poured
drop-wise onto a vigorously stirred acetone (200 mL). Hygroscopic
white sticky product of polyaspartate 3-100, 3-230, poly(aspartate-
ran-succinimide) 4-100, poly[(pyrrolidine-1-yl)aspartamide-ran-as-
partate] (10-100), poly[(piperidine-1-yl)aspartamide-ran-aspartate]
Poly(succinimide-ran- (11-100), and poly[(azepane-1-yl)aspartamide-ran-aspartate] (12-
aspartate) α 100) was precipitated out. The products were filtered and washed
with acetone and dried under vacuum at 70 °C to constant weights.
β
The yields of the hydrolysis reactions remained over 90%. The syn-
thesized compounds gave satisfactory elemental analyses.

Poly(succinimide-ran- 2.3. Evaluation of antiscalant behavior

aspartamide)

The precipitation and inhibition of calcium sulfate (gypsum) scale

formation were evaluated using a series of the newly synthesized
environmentally benign antiscalants. The concentration of reject brine
at 70% recovery and 98% salt rejection was denoted as 1CB. A mathemat-
Polyaspartamide
ical model was applied on the basis of feed water analysis to determine
α the concentrations of ions in the reject brine (1CB). Analysis of brine in
an RO Plant at King Fahd University of Petroleum & Minerals (KFUPM)
β revealed the presence of 281.2 and 943.3 ppm Ca2+ ions and 611 and
2100 ppm of SO2− 4 ions in the brackish feed water and in the concen-
trated brine (1CB) respectively [26].
a
Polymer structures are given as bold numbers and the hyphenated numbers refer to
The evaluation of the new scale inhibitors was performed in 3CB
the degree of polymerization (n) values of 100, 230 and 600 corresponding to the MW of solutions containing three times the concentrations of Ca2+ and SO2− 4
10,000, 22,000 and 58,000 g mol−1, respectively, of the precursor polymer PSI 2. in 1CB solutions. The solutions were supersaturated with respect to
 S.A. Ali et al. / Desalination 357 (2015) 36–44 39

Scheme 1. Synthesis of polysuccinimide of various molar masses.

CaSO4·2H2O as confirmed from its solubility data. Solutions containing deionized water. The solutions were filtered (0.45 μm membrane filters,
ions equal to 6 times the concentrated brine of 1CB were prepared by Millipore) and standardized by complexometric titration (EDTA)
dissolving the calculated amount of CaCl2 and Na2SO4 respectively, in (Metrohm autotitrator) and ion chromatography (Dionex ICS-3000)

Scheme 2. The monomer in different forms and protonation constants.

40 S.A. Ali et al. / Desalination 357 (2015) 36–44

for calcium (Ca2+) ions and sulfate (SO2−

4 ) ions respectively. A three 2.3.3. Calcium ion concentration measurement method
step procedure was adopted to evaluate the performance of newly syn- The antiscalants which demonstrated very good inhibition prop-
thesized antiscalants. erties in conductivity experiment measurement method were
further evaluated by measuring the Ca++ ion concentration of the
solutions with time. The percent inhibition (PI) of antiscalant against scal-
2.3.1. Visual inspection method-fast screening
ing is calculated using the following equation:
Equal volume (20 mL) of 3CB calcium chloride solutions and sodium
sulfate solutions was introduced in the glass tubes or vials and 10 ppm
h i h i
antiscalant formulations were added to each tube before mixing the two Ca2þ − Ca2þ
solutions. All these tubes were kept in the constant temperature water inhibited ðtÞ blankðtÞ
% Scale Inhibition ¼  2þ     100
bath at 50 °C equipped with continuous shaking mechanism. About 30 Ca inhibitedðt Þ − Ca2þ blankðtÞ
0
antiscalants were evaluated in the glass tubes simultaneously. Visual
inspection of each antiscalant was carried out and time was recorded h i
2þ
when the solution started to indicate turbidity or precipitation. Anti- where Ca is the initial concentration at time zero,
inhibitedðt0 Þ
scalants that showed better inhibition, meaning clear solutions or no
[Ca2 +] inhibited (t) and [Ca2 + ] blank (t) are the concentrations in the
turbidity for about 10 h were selected for further testing in stirred bea-
inhibited and blank solution (without antiscalant) at time t respec-
ker experiments. The initial fast screening method at accelerated condi-
tively [35].
tions provided performance of successful antiscalants in a qualitative
manner.
3. Results and discussion

2.3.2. Conductivity measurement method 3.1. Synthesis of aspartic acid-based antiscalants

A solution of 6CB calcium chloride (60 mL) containing (1.2 mL
of 1000 ppm) antiscalant in a round bottom flask was heated at 40
°C ± 1 °C. A preheated (40 °C) 6CB sodium sulfate solution (60 mL)
was added to the stirring solution (300 rpm) in the flask. The resultant
solution of 3CB concentration with respect to calcium ions and sulfate
ions now contained 10 ppm of antiscalant. The performance of all the
selected antiscalants from fast screening method was evaluated by re-
cording the conductivity at every 10–20 s through data-logger. These
conductivity measurements provided accurate data on performance of
antiscalants.
Polysuccinimide (PSI) 2 with degree of polymerizations of 100, 230
and 600 has been prepared from L-aspartic acid (1) using the procedure
as outlined in Scheme 1. A sample, for instance, designated as 2-100
identifies the structure by the bold number followed by the regular
number 100 as the degree of polymerization. The degree of polymeriza-
tion and molar mass of the polymers were determined using viscosity
measurements as described in the experiment [29]. Samples of 2-100
and 2-230 upon treatment with 1 equivalent of NaOH were converted
into sodium polyaspartates 3-100 and 3-230, respectively. A partially

Fig. 1. 1H NMR spectra of (a) 3-100 in DMSO-d6, (b) 9-100 in D2O, (c) 6-100 in D2O, and (d) 12-100 in D2O.
 S.A. Ali et al. / Desalination 357 (2015) 36–44 41

Fig. 2. Precipitation behavior of a supersaturated solution (3CB) of CaSO4·2H2O at 40 °C in the presence (10 ppm) and absence (blank) of (a) 9-100, 8-100, 7-100; (b) 3-100, 3-230;
(c) 9-100, 9-600, 9-230; and (d) 9-100, 6-100, 7-100, 5-100.

hydrolyzed sample of 4-100 was prepared by treating PSI 2-100 with 3.2.1. Effect of MW on CaSO4·2H2O scale inhibition
0.77 equivalent of NaOH. The effect of degree of polymerization (n) on percent inhibition (PI)
Aspartamide 5-100 and 6-100 were obtained by treating PSI is revealed by the performances of 3-100 (Table 1, entry 1) and 3-230
2-100 with one equivalent of pyrrolidine and azepane, respectively (Table 2, entry 1). Low molecular weight 3-100 demonstrates much
(Scheme 2). However, reaction of PSI 2 with 0.5 equivalent of 5-, higher PI than its higher MW counterpart 3-230 (Fig. 2b). The dramatic
6-, and 7- membered cyclic amines (pyrrolidine, piperidine and effect of MW on antiscalant performances is shown in entries 6–8
azepane) afforded the copolymers poly(SI/aspartamide) 7, 8 and 9, (Table 2); the copolymers 9-100, 9-230 and 9-600 at 100 min gave PI
respectively. Finally, the PSI part of the 1:1 poly(SI/aspartamides) of 99, 4 and 15%, respectively (Fig. 2c).
7-100, 8-100, and 9-100 was hydrolyzed with an equivalent amount
of NaOH to the corresponding poly(aspartate/aspartamide) 10-100,
11-100, and 12-100 (see Table 3).
Fig. 1 represents the 1H NMR spectra of 2, 6, 9, and 12. The 1:1 compo-
sition of the copolymers 9-100 (Fig. 1b) and 12-100 (Fig. 1d) was con-
firmed using area integration of the 8H protons (marked ‘d’ and ‘e’)
appearing in the δ range of 1.25–1.75 ppm versus the rest of the protons.

3.2. Scale inhibition properties of the synthesized polymers

In the reverse osmosis (RO) process, the inlet stream is feed water
and outlet streams are product water and reject brine. If the dissolved
salts in the reject brine stream become supersaturated due to increased
recovery ratio, then scaling occurs.
For the current work, the precipitation behavior of a supersaturated
solution of CaSO4·2H2O containing 2830 ppm of Ca2+ and 6300 ppm of
SO24 − in the absence and presence of antiscalants was investigated
based on the method used by Amjad and Zuhl [35]. Percent inhibition
(PI) of newly synthesized antiscalants at a concentration of 10 ppm is Fig. 3. Precipitation behavior of a supersaturated solution (3CB) of CaSO4·2H2O at 40 °C in
shown in Tables 1 and 2. the presence (10 ppm) and absence (blank) of 12-100, 11-100, 10-100 and 4-100.
42 S.A. Ali et al. / Desalination 357 (2015) 36–44
3.2.2. Effect of charges on the polymer backbone on CaSO4·2H2O scale
inhibition
The data reveals that a fully hydrolyzed sample 3-100 (Table 1,
entry 1) imparts higher PI than its partially hydrolyzed counterpart
4-100 (Table 1, entry 2) having the same degree of polymerization
(Figs. 2b and 3). Higher amount of negative charges on the polymer
backbone 3-100 has thus greater beneficial effect; while at 1500 min,
3-100 imparted a PI of 100%, the 4-100 displayed a PI of 7% only. A
comparison between the poly(SI/aspartamide) copolymers 7, 8 and 9
(Table 2, Fig. 2a) with the corresponding aspartamide/aspartate copoly-
mers 10, 11 and 12 (Table 1, Fig. 3) revealed the superiority of the later
antiscalants, thus yet again displaying the importance of the negative
charges on the polymer backbone in suppressing the precipitation of
CaSO4·2H2O.
3.2.3. Effect of amine ring size in the aspartamides on CaSO4·2H2O scale
inhibition
Aspartamide 6-100 (Table 2, entry 3) of 7-membered azepane
performed better than the aspartamide 5-100 (Table 2, entry 2) of
5-membered pyrrolidine (Fig. 2d); both of which, however, are out-
performed by either aspartate 3-100 (Table 1, entry 1) or 3-230
(Table 2, entry 1) (Fig. 2b). Copolymers 7-100, 8-100, and 9-100 with
a 1:1 aspartamide/SI ratio (Table 2, entries 4–6, Fig. 2a) imparted PI of
29, 47 and 94%, respectively, at 500 min. Thus, azepane derivative
9-100 demonstrated the best antiscalant behavior. Note that the
aspartamide/SI copolymers 7-100, 8-100, and 9-100 performed better
than their corresponding aspartamide homopolymers 5-100 and
6-100 (Table 2, entries 2, 3).
Fig. 4. Precipitation behavior of a supersaturated solution (3CB) of CaSO4·2H2O at 40 °C in the absence (blank) and presence of various concentrations of (a) 3-100; (b) 10-100; (c) 12-100;
and (d) a commercial antiscalant.
3.2.4. Effect of copolymer type on CaSO4·2H2O scale inhibition
As discussed under Sections 3.2.2 and 3.2.3, poly(aspartamide/SI)
copolymers 7-100, 8-100, and 9-100 performed better than their corre-
sponding aspartamide homopolymers 5-100 and 6-100 (Table 2), while
the corresponding aspartamide/aspartate copolymers 10, 11 and 12
(Table 1, Fig. 3) revealed the best performance.
3.2.5. Effect of antiscalant concentration on CaSO4·2H2O scale inhibition
The effect of dosage of antiscalant 3-100, 10-100, 12-100, and (d)
a commercial antiscalant on the gypsum scale inhibition is shown in
Fig. 4. Induction time was recorded to measure the performance of
each inhibitor. Induction time is defined as the time required for
the commencement of precipitation or it is the time elapsed until
the moment at which the onset of precipitation can be detected.
The commencement of precipitation in our experiments was detect-
ed by drop in conductivity. When the conductivity decreases rapidly,
precipitation is visible, as the solutions become turbid. It is apparent
from Fig. 4 that the induction time increases with the increase in dos-
age of antiscalants. As shown in many graphs, in the presence of co-
polymer, onset of precipitation is preceded by an induction time of
several minutes to several thousand minutes. Later on the crystal
growth recommences with a measurable rate observed by a sharp
drop in conductivity. The equilibrium inhibition percentages in almost
all experiments are low. As evident from the figures and tables, all the
synthesized compounds performed much better than the commercial
antiscalant (Fig. 4d).
In addition, the duration of the induction time depends on the con-
centration of the antiscalants. Involvement of polyaspartates into the
 S.A. Ali et al. / Desalination 357 (2015) 36–44
nucleation process during the induction period leads to the prevention
of the growth of CaSO4·2H2O by poisoning of active growing sites in
the crystal. However, a few of the growth sites of lower energy may
still be free to grow at a slow rate which leads to a very small change
in ion concentrations which are difficult to be detected by conductivity
measurement. Later on, after the adsorbed molecules are incorporated
into growing crystal, the crystal growth can resume at a rate compa-
rable to that of the un-poisoned systems. The results presented in
this study clearly show that the polyaspartates are able to prolong
the induction period and may thus minimize the fouling of mem-
branes by CaSO4·2H2O.
3.2.6. Summary of antiscalant behaviors
Low MW antiscalants are found to be superior to their high MW
counterparts. Higher amount of negative charges on the polymer
backbone is found to have a greater beneficial effect on the gypsum
scale inhibition. Derivatives of 7-membered cyclic amine azepane,
performed better than their 5- and 6-membered counterparts. At
Fig. 5. EDX and SEM images of gypsum formed from 3CB at 40 °C with (a) blank; (b) 3-100; (c) 12-100; and (d) 10-100.
43
the same degree of polymerization, performance in decreasing
order of effectiveness was found to be: polyaspartate N copolymer
poly (aspartamide-co-aspartate) N copolymer poly(SI-co-aspartate) N
copolymer poly(SI-co-aspartamide) N polyaspartamide.
3.3. EDX and SEM images
As shown in Fig. 5a, scanning electron microscopy (SEM) analysis
revealed that a monoclinic CaSO4·2H2O crystal of a regular shape and
compact structure is formed in the absence of inhibitors. In the presence
of antiscalants, crystals having irregular shapes and loose structures are
formed. Fig. 5b shows that in the presence of sodium polyaspartate
3-100, a CaSO4·2H2O crystal loses its sharp edges, and its morphology
is modified from elongated stick forms to thin flakes. In the presence
of 12-100 and 10-100 the crystal morphology also changes to smaller
fragments (Fig. 5c, d). Since various types of crystal faces have different
surfaces, inhibitor molecules are adsorbed at different rates onto each
type of face lattice structure. Consequently, alterations in crystal shape
44 S.A. Ali et al. / Desalination 357 (2015) 36–44
occur during outgrowth that is, the crystal cannot grow normally in
accordance with an array of crystal lattices strictly, causing the crystals
to become distorted or increasing the internal stress of crystals. Increase
in stress could result in crystal fractures and prevention of deposition of
microcrystalline [33].
4. Conclusions
In comparing the efficacy of the inhibitors, the performance criterion
proposed by Reitz [34] can be adopted. In RO desalination, the residence
time of the saline water inside the permeators is less than 15 min. If,
according to Reitz [34], 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 considered as an effec-
tive inhibitor at that dose level against that particular scaling.
Based on the Reitz [34] criterion, the results indicate that almost all
of the synthesized green additives in the present study are very effective
with only 10 ppm dose concentration against precipitation of gypsum at
40 °C and 3CB brine concentrations except 5-100. Hydrolyzed deriva-
tives are more efficient than unhydrolyzed PSI-derivatives. Antiscalant
3-100 was found to be the most effective with very high induction time
at a 10 ppm dose concentration. Antiscalants 3-100, 4-100, 12-100 and
10-100 can be used as effective antiscalants for CaSO4·2H2O even at a
concentration of only 2.5 ppm in brackish water RO plant.
It is planned to evaluate the most promising antiscalants using a
minimum size commercial RO unit with two-stage membrane con-
figuration according to the procedure adopted by Butt et al. [36]. Actual
brackish feed water will be used with appropriate filtration system and
results will be reported in next publication.
Acknowledgments
The authors would like to acknowledge the support provided by
King Abdulaziz City for Science and Technology (KACST) through the
Science & Technology Unit at King Fahd University of Petroleum
and Minerals (KFUPM) for funding this work through project No. 08-
WT76-04 as part of the National Science, Technology and Innovation
Plan. The laboratory facilities provided by the Chemistry Department
and Center for Refining & Petrochemicals, Research Institute, KFUPM
are also acknowledged.
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