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Desalination
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Chemical Engineering Department, Kuwait University, P.O. Box 5969, 13060 Safat, Kuwait
Mechanical Engineering Department, Kuwait University, P.O. Box 5969, 13060 Safat, Kuwait
H I G H L I G H T S
G R A P H I C A L
A B S T R A C T
a r t i c l e
i n f o
Article history:
Received 24 March 2015
Received in revised form 29 July 2015
Accepted 30 July 2015
Keywords:
Maleic-anhydride
n-alkylacrylamide
CaCO3 scales
Inhibition efciency
Pipe ow system
SEM and XRD
a b s t r a c t
Novel low molecular weight copolymers (termed as YMR-series polymers) prepared through reaction of maleic
anhydride with n-alkylacrylamide monomers via nitroxide-mediated radical polymerization (NMRP), atom
transfer radical polymerization (ATRP) and free radical polymerization have shown feasibility as a new generation scale inhibitor. The scale inhibition property of these YMR-polymers towards CaCO3 in the articial cooling
water was studied in steel (316 L) and copper (90/10, CuNi alloy) pipes using a pipe ow system at various temperatures. The relationship between deposited scale mass and temperature was deduced from experimental
data. The effect on formation of CaCO3 scales was investigated with scanning electronic microscopy (SEM) and
X-ray powder diffraction (XRD) analysis. The results showed that the low molecular weight YMR-polymers
were excellent calcium carbonate scale inhibitor in copper and steel pipe ow system showing inhibition up to
98% at 60 C.
2015 Elsevier B.V. All rights reserved.
1. Introduction
Scaling is a difculty encountered in processing aqueous solutions
containing ions of sparingly soluble salts. Scale deposits can readily
form on ow surfaces when a solution is concentrated beyond the
Corresponding author.
E-mail address: yalroomi.kuniv@gmail.com (Y.M. Al-Roomi).
http://dx.doi.org/10.1016/j.desal.2015.07.028
0011-9164/ 2015 Elsevier B.V. All rights reserved.
139
140
Table 1
Conditions and results for the polymerization of YMR-series polymers in o-xylene at 140 C.
Monomers
(Mol %)
Initiator
(Mol %)
Mn GPC
YMR47
MAa
BPOb (10)
847
YMR40
MA
BPO (5)
641
YMR34
MA
AIBNc (15)
457
Antiscalant
MA
YMR44
AIBN ( )
400
AIBN (7.5)
1890
AAO (50)
BPO (7.5)
1759
AAO (50)
AIBN (10)
1725
MA (50)
AAO (50)
BPO (10)
1364
YMR82
MA (60)
AAO (40)
BPO (7.5)
1345
YMR83
MA (50)
AAO (50)
AIBN (12)
1267
1466
YMR74
MA (50)
AAOd (50)
YMR68
MA (50)
YMR63
MA (50)
YMR76
YMR 142A
MA (50)
AAHe (50)
YMR 154A
MA (50)
AAH (50)
1280
YMR 144A
MA (50)
AAB (50)
1215
YMR 152A
MA (50)
AABi (50)
1020
YMR 151A
MA (50)
AAB (50)
859
AAP (50)
610
YMR 146A
MA (50)
Reaction
Free radical
homopolymerization
Free radical
copolymerization
YMR 131S
YMR 133S
YMR 134S
YMR 121S
YMR 136S
a
MA (50)
MA (50)
MA (50)
MA (50)
MA (50)
MA (50)
AAB (50)
BPO / TEMPO
(10:10)
1116
AAPk (50)
BPO / TEMPO
(3:7)
888
AAH (50)
BPO / TEMPO
(10:5)
813
AAH (50)
BPO / TEMPO
(10:10)
680
ABAl (50)
BPO / TEMPO
(5:15)
560
AAP (50)
BPO / TEMPO
(10:5)
537
Atom transfer
radical
polymerization
YMR 135S
Nitroxide mediated
radical
polymerization
141
2
Ca antiscalant Ca2 blank
x100
Ca2 original Ca2 blank
Fig. 2. Variation of inhibition efciency versus dosage of inhibitors for different YMRseriers polymers.
CaCO3 scale inhibition efciency of the antiscalant increases the pressure drop decreases. In other words for antiscalants showing better
scale inhibition efciency, there was very little CaCO3 scale deposit in
142
Fig. 3. Effect of scale accumulation on pressure in the pipe with time (20 min.) in blank and different antiscalants in copper and steel pipe ow system for 0.15 M CaCO3 solution at 0.5 ppm
antiscalant concentration.
the sample pipe and hence a very low pressure drop of 0.007 psi was observed as compared to pipe sample containing blank solution (without
scale inhibitor) where the scaling was very high and hence the pressure
drop increased to 0.099 psi for copper pipe and 0.089 psi for steel pipe.
Based on these ve best performing antiscalants (YMR 142-A, YMR-74,
YMR-63, YMR 154-A and YMR 135-S) were selected and tried at various
temperatures.
Fig. 4. Effect of inhibition percent with temperature on scale formation for copper and
steel pipe ow system, run time = 20 min for 0.15 M CaCO3 solution at 0.5 ppm
antiscalant concentration.
Temperature
(0C)
BLANK
60
0.0627
0.0015
0.0055
0.0062
0.0041
0.0037
65
0.0701
0.0031
0.0081
0.0089
0.0062
0.0051
70
0.0771
0.0056
0.011
0.0117
0.0095
0.0076
75
0.0849
0.0106
0.0149
0.0156
0.0128
0.012
60
0.0589
0.0013
0.0043
0.005
0.0039
0.004
65
0.0621
0.0029
0.0067
0.0085
0.0065
0.006
70
0.07
0.01
0.01
0.0157
0.0099
0.01
75
0.07
0.01
0.02
0.026
0.017
0.01
YMR74
143
where,
dm/dt
Ar
T
C
k
The k constant derived from the curves in Fig. 7 are listed in graph.
It shows that as the temperature rises rate constant also increases,
showing a signicant increase from 70 C to 75 C.
Fig. 5. Plot of scale amounts against time at various temperatures for YMR-74 (0.5 ppm) in
copper pipe ow system for 0.15 M CaCO3 solution.
YMR-74 was further investigated at different time with varying temperature in 0.15 M CaCO3 solution at 0.5 ppm antiscalant concentration for
copper and steel pipe. To determine the correlation between scaling
rate and temperature the amount of calcium carbonate at different temperatures is plotted against time (Figs. 5 & 6). The plot show that the
curves are parabolic indicating scale amount is quadratic function of
run time. For copper pipe (Fig. 5) it is observed that temperature
seemed to signicantly promote the scaling of CaCO3. The scale mass
was 9 106 kg/m2 at 60 C in 20 min time but as the temperature increased to 75 C the rate of scale formation also increased and reached
Fig. 6. Plot of scale amounts against time at various temperatures for YMR-74 (0.5 ppm) in
steel pipe ow system for 0.15 M CaCO3 solution.
Fig. 7. Comparison of scaling rate at different temperatures for YMR-74 (0.5 ppm) in
(a) copper pipe ow and (b) steel pipe ow system for 0.15 M CaCO3 solution.
144
presence of the polymer are presented in Figs. 811. The crystal habit of
calcium carbonate has at least three forms: calcite, aragonite and
vaterite, depending on the temperature. The vaterite crystals are usually
formed at low temperature. The aragonite crystals are needle [28] and
ower like structures [29] while the calcite crystals are block like [28]
particles of cubic shape [29] or entangled rhombohedra [30]. In the
present study, crystals of calcite are formed in the absence of scale inhibitor which can be observed in Figs. 811 and also it's conrmed by
our previous publication [2224]. We have studied the effect of YMR
polymers on the calcite crystals and found that there is an alteration
Fig. 8. SEM images of CaCO3 scale deposited on steel pipe walls for Blank solution. From
top: (a) Blank (20 min; 60 C); (b) Blank (12 min; 65 C); (c) Blank (6 min; 75 C).
Fig. 9. SEM images of CaCO3 scale deposited on steel pipe walls for YMR-74 (0.5 ppm).
From top: (a) YMR-74 (20 min; 60 C); (b) YMR-74 (12 min; 65 C); (c) YMR-74
(6 min; 75 C).
145
Fig. 10. SEM images of CaCO3 scale deposited on copper pipe walls for Blank solution. From
top: (a) Blank (20 min; 60 C); (b) Blank (12 min; 65 C); (c) Blank (6 min; 75 C).
Fig. 11. SEM images of CaCO3 scale deposited on copper pipe walls for YMR-74 (0.5 ppm).
From top: (a) YMR-74 (20 min; 60 C); (b) YMR-74 (12 min; 65 C); (c) YMR-74 (6 min;
75 C).
20 min. for 60 C, 12 min for 65 C and 6 min for 75 C, and long needle
shaped structures are formed but as the temperature rises from 60 C to
75 C there is an absence of tubular structure and at 70 C we observe
spongy deposit. Although at lower temperature of 65 C scales contain
only aragonite crystals but at higher temperature of 75 C other forms
of CaCO3 crystals may exist (conrmed by XRD analysis) which leads
to very fast scale deposition, causing the blockage of the ow in the
test unit.
Fig. 9(ac) shows the deposition of CaCO3 scales in the presence of
antiscalant YMR-74. There is almost no scale deposition within
20 min. for 60 C, 12 min for 65 C and although a small deposition is observed in 6 min at 75 C. This lack of scale deposition shows the efciency of YMR-74 as scale inhibitor as compared to the blank which shows
blockage within the same range of time.
Similar results are observed for copper pipes also for blank and in
presence of YMR-74 antiscalant at 60 C, 65 C and 75 C at different
time shown in Figs. 1011. In blank complete blockage is observed
and almost no scaling takes place in presence of antiscalant YMR-74 at
60 C and 65 C with varying time (Fig. 11). But as the temperature
increases to 75 C slight scaling is observed.
146
Fig. 12. XRD patterns of the CaCO3 crystals at 65 C in the absence of scale inhibitor (a), in the presence of scale inhibitor (b). A: aragonite; V: vaterite; C: calcite.
147
Fig. 13. XRD patterns of the CaCO3 crystals at 75 C in the absence of scale inhibitor (a), in the presence of scale inhibitor (b). V: vaterite; C: calcite.
Fig. 13(b) it's obvious that in presence of scale inhibitor at 75 C temperature the intensity of the characteristic peak for calcite at 29.406
corresponding to crystal face 104 is greatly reduced.
This indicates that calcite is the dominant crystal formed in the absence of scale inhibitor (Figs. 12(a) & 13(a)). In the presence of scale inhibitor, the dominant crystal formed is aragonite and vaterite, and the
diffraction peaks of calcite are greatly reduced or almost invisible
(Figs. 12(b) & 13(b)). In other words the scale inhibitor delays the transformation from the less stable vaterite and aragonite phase, into the
most stable calcite phase. Whereas in the absence of scale inhibitor
the less stable aragonite and vaterite phases have managed to transform
into more stable calcite phase.
Calcite is the most thermodynamically stable and vaterite is the least
stable form in the three polymorphic forms of CaCO3 [2830]. In the absence of scale inhibitors calcite can be formed from the transformation
of aragonite or vaterite [31,32]. Vaterite is the initial phase formed in
many CaCO3 supersaturated solutions and then gradually transforms
to calcite [33]. Although calcite has the greatest thermodynamic stability under ambient conditions, however in the presence of scale
148
and unstable aragonite phase became the main crystal form in CaCO3
scale. At higher temperature of 75 C the polymers could disturb the
calcite growth and induce vaterite growth. These polymers can be safely
used up to a temperature of 75 C and up to pH 10.45 at a very low
dosage level of 0.5 ppm.
Acknowledgment
The authors wish to acknowledge Research Administration Department of Kuwait University for having provided the necessary funds
from Project RE05/06 for carrying the research work.
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