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Received: 18 August 2020 | Revised: 24 January 2021 | Accepted: 13 March 2021

DOI: 10.1111/wej.12704

FULL LENG TH ORIG INAL RE SE ARCH PAPER

Scale inhibition in industrial water systems using


chitosan-­alginate mixture

Essam Khamis1 | Dalia E. Abd-­El-­Khalek 2


| Mervat A. Abdel-­Kawi3 | Jilan M. Anwar4

1
Chemistry Department, Faculty of
Science, Alexandria University, Alexandria, Abstract
Egypt
The study aims to establishing the possibility of using eco-­friendly natural polymers to
2
National Institute of Oceanography and
Fisheries, NIOF, Alexandria, Egypt
formulate scale inhibitor for industrial water applications. The performance of a blend
3
Department of Environmental of two natural polymers, chitosan and sodium alginate as scale inhibitor in compari-
studies, Institute of Graduate Studies son with a commercially available inhibitor formulation, HEDP (Hydroxyethylidene,
and Research, Alexandria University,
Alexandria, Egypt 1-­Diphosphonic Acid), is carried out using electrochemical measurements, conductiv-
4
Quality Control and Environment ity and NACE test complemented with crystals morphology characterization using
Department, Water Company, Holding
optical and electronic microscopic examination. Overall results show that chitosan is
Company of Water and Wastewater,
Alexandria, Egypt more efficient for the inhibition of calcium carbonate scales formation, whilst it has
poor efficiency in the inhibition of sulfate scales, whereas sodium alginate has the
Correspondence
Dalia E. Abd-­El-­K halek, National Institute highest efficiency in inhibiting calcium sulfate scales. However, the addition of sodium
of Oceanography and Fisheries, NIOF,
alginate to chitosan, as a package, has a dual control effect on carbonate and sulfate
Alexandria, Egypt.
Email: dalia1282002@yahoo.com scale formation with good efficiency compared to HEDP. This new phosphorus-­free
package represents an effective antiscalant to have green environment.

KEYWORDS
alginate, chitosan, desalination, environmental management, HEDP, scale inhibition

1 | I NTRO D U C TI O N metal are decreasing, and their discharges are regulated in many
areas of the world (Hasson et al., 2011). Studies have identified sev-
Scaling is one of major problems in many industries including oil, and eral hypothetical mechanisms by which chemical discharge can in-
gas production, water transport (Guo et al., 2012), power genera- fluence marine ecosystems (Lattemann, & Hopner, 2008; Sadhwani
tion, batch precipitation and desalination plants (Abdel-­Gaber et al., et al., 2005; Tsiourtis, 2001). Therefore, scale-­inhibitor chemistry
2008). The presence of a scale layer can cause a progression of has moved towards “green antiscalants” that are biodegradable,
damages, for example, partial obstruction of pipes leading to a de- have minimum environmental impact, phosphrous free and are cost-­
crease in flow rate, impedance of heat transfer, increase of energy effective (Hasson et al., 2011). Plant extracts were employed as green
consumption and unscheduled equipment shutdown. (Abdel-­Gaber scale inhibitors, and the results obtained have been considered very
et al., 2008; Hasson et al., 2011). A widely used technique for limit- promising (Abdel-­Gaber et al., 2011; Abd-­El-­Khalek et al., 2016, 2019,
ing scale deposition is by substoichiometric dosage of an antiscalant Castillo et al 2009; Khamis et al., 2020; Vasyliev et al., 2020).
to the feed water. Antiscalants are classified as nonpolymeric, for Also, Poly (aspartic acid), Poly (maleic acid) (PMA) (Li et al., 2019;
example, phosphonate, phosphonocitric acid, condensed phosphate Martinod et al., 2008, 2009) and poly (carboxylic acid)-­based chem-
or polymeric additives, for example, homopolymers of methacrylic icals are considered as environmentally friendly, biodegradable an-
acid, maleic acid, acrylic acid and co polymers containing monomers tiscalants (Amjad, 2012; Li et al., 2006; Wang et al., 2013). In recent
of different functional group (Amjad et al., 2014; Zhou et al., 2019). years, some biopolymers were evaluated as scale inhibitors such
Phosphorus-­based inhibitors can serve as nutrients leading to eu- as carboxymethyl inulin (Boels & Witkamp, 2011; Kırboga & Öner,
trophication difficulties. Permissible limits of phosphorus and heavy 2012), carboxymethyl cellulose (Saleah & Basta, 2008), guar and

Water and Environment Journal. 2021;00:1–11. wileyonlinelibrary.com/journal/wej © 2021 CIWEM | 1


2 | KHAMIS et al.

xanthan gums (Elkholy et al., 2018) and starch-­based biopolymers


(Romero et al., 2007; Saleah & Basta, 2008; Yu et al., 2018).
Sodium alginate and chitosan (CS) are biodegradable polymers
which can be produced at an estimated amount of millions tons per year
from brown algae and crustacean shells, respectively (Ahmed et al.,
2012; Davies, 2002). It was reported that sodium alginate reduces the
rates of crystal growth of calcium carbonate measured under physio-
logical conditions (Manoli, & Dalas, 2002). Also, chitosan derivatives
are currently being explored intensively for their applications in water
and wastewater treatment, and various modified chitosan have been
studied as CaCO3scale inhibitor (Guo et al., 2012; Macedo et al.,2019;
Zeng et al., 2015; Zhang et al., 2015;) using conductivity and other bulk
precipitation tests. However, these tests provide a poor characteriza-
tion of antiscalant inhibitory capability because they do not provide
any information on the adhesive properties of the scale (Abdel-­Gaber
F I G U R E 1 Structural formula of (a) chitosan and (b) sodium
et al., 2012; Hasson et al., 2011). The consequences of the presence
alginate
of scale on the surface are more problematic than precipitation in the
bulk solution. Thus, the electrochemical method is a more recent way
of studying the buildup of calcium carbonate layers in different media Calcium brine: 7.5 g/L NaCl +11.0 g/L CaCl2.2H2O and sulfate brine:
(Abdel-­
Gaber et al., 2008; Abd-­
El-­
Khalek & Abd-­
El-­
Nabey, 2013; 7.5 g/L NaCl +10.66 g/L NaSO4; 50 ml of each brine solutions was con-
Marin-­Cruz et al., 2004; Marin-­Cruz & Gonzalez, 2002). nected in the test cell with different concentration of sodium alginate
This study aims to investigate chitosan and sodium alginate as and chitosan. Testing cells were placed in the water bath set at 71°C for
environmentally friendly inhibitors for carbonate and sulfate scales 72 h. After that, the concentration level of calcium ions was determined
formation using electrochemical techniques in addition to bulk in the solution by titration with EDTA and Murexide indicator.
tests and microscopic examination. Antiscalent performance of Equation (1) was employed to calculate percent of scale inhibition:
chitosan and sodium alginate was compared with the performance
of commercially available antiscalant HEDP (Hydroxyethylidene-­1,
( )
Ca − Cb
% Inhibition = 100 × ( (1)
1-­Diphosphonic Acid). As is known, phosphonates are generally con-
)
Cc − Cb
sidered as scale inhibitors for CaCO3and CaSO 4 scales because they
have a high tolerance for calcium ions. where Ca = Ca2+ concentration in the treated sample after pre-
cipitation; Cb = Ca2+concentration in the blank after precipitation;
Cc = Ca2+concentration in the blank before precipitation.
2 | M ATE R I A L S A N D M E TH O DS

2.1 | Preparation of solutions 2.3 | Conductivity test for CaCO3 scaling

The chitosan with a degree of deacetylation of at least 70% was ob- Conductivity test was performed as described formerly (Drela et al.,
tained from Chitopharm™, Norway (Figure 1). Chitosan solution was 1998). Prior each experiment, 5 ml of 0.1 M CaCl2 solution is added to
prepared by dissolving 0.5 g in 100 ml of 0.1 M acetic acid under appropriate volume of the stock solution of suggested inhibitor and
stirring at room temperature with a pH of about 4 (Ahmed et al., then the mixture is completed to 100 ml by doubly distilled water.
2012). Sodium alginate (sodium salt of alginic acid) was supplied by The conductivity of stirred solution is monitored during titration by
CDH (P) Ltd., India, with chemical structure shown in Figure 1. Stock 0.1 M Na2CO3 using HQ14d conductivity meter at 25.0 ± 0.1°C.
solution of sodium alginate was obtained by dissolving 1 g of sodium
alginate in 1 L distillated water. Double distilled water and analytical
reagent-­grade NaCl, NaHCO3, Na2CO3, Na2SO 4 and CaCl2were used 2.4 | Electrochemical measurements for
for preparing brine solutions (Lin & Dexter, 1988). CaCO3 scaling

The electrochemical measurements were carried out in a cell with


2.2 | NACE test for calcium sulfate scaling three-­electrode mode (Abd-­El-­K halek & Abd-­El-­Nabey, 2013);
platinum sheet and saturated calomel electrode (SCE) were used
The test method was described previously (Boris et al., 2007; NACE as counter and reference electrodes, respectively. The work-
Standard TM 0374-­2001, 2001). For the test, synthetic brines were ing electrode was steel that had the following chemical compo-
prepared as follows. sition (wt. %): C, 0.21; S, 0.04; Mn, 2.5; P, 0.04; Si, 0.35; balance
KHAMIS et al. | 3

Fe. Chronoamperometry and electrochemical impedance meas- Optical photographs of CaSO 4 crystals after precipitation in
urements were performed using Gamery instrument G300™ absence and presence of optimum concentrations of sodium al-
Potentiostat/ Galvanostat/ ZRA. Chronoamperometry curves were ginate and chitosan were presented in Figure 3. As seen, tubular
carried out by polarizing the steel electrode to −1 V (vs. SCE) in test structure of CaSO 4 crystals is observed in the absence of anti-
solution for 3 h. Thus, the current passing through the steel elec- scalant (Shakkthivel & Vasudevan, 2006). The addition of sodium
trode, during calcareous deposits, is recorded with respect to time. alginate and HEDP modified CaSO 4 crystals and decreased their
EIS measurements were done after scale deposition process. The size, whilst reduced crystal quantity in presence of chitosan ac-
frequency range for EIS measurements was 0.1 to 1 × 104 Hz with complished with low degree of modification of rode edges. It is
applied potential signal amplitude of 10 mV. All the measurements possible to predict that carboxylate and phosphonate groups
were done at 40.0 ± 0.1°C. To test the reliability and reproducibil- in sodium alginate and HEDP, respectively, capture Ca2+ ions in
ity of the measurements, triplicate experiments were performed in solutions or from the surface of inorganic minerals (Hoang, 2015;
each case at the same conditions. Zhang,et al., 2017). Figure 4 illustrates the interaction between
negative charge on oxygen of alginate and Ca2+ ion. This interferes
with the formation of the crystals, so the crystal growth cannot be
2.5 | Microscopic examination fully consistent with normal lattices; thus, irregular shapes were
formed. Increasing the efficiency of sodium alginate can be at-
The morphology and crystal lattices of scale were observed with tributed to the presence of hydroxyl group which coordinate sur-
optical microscope (Axioskop 40 “Ziess”) and scanning electron face cations and forming hydrogen bridges with surface anions or
microscope, SEM, (JEOL-­5300 Scanning microscope). Prior to SEM water molecules in gypsum because of its high crystalline water
examination, scale crystals were sputter-­coated with a thin film of content and being very sensitive to the hydrogen bonding facilities
gold under vacuum. (Hoang, 2015).

3 | R E S U LT S A N D D I S CU S S I O N 3.2 | Calcium carbonate scales testing

3.1 | Calcium sulfate scales testing 3.2.1 | Conductivity test

Figure 2 shows the variation of percentage inhibition of calcium sul- The conductivity test was used as a first step to test the efficiency
fate scale with concentration of sodium alginate, chitosan and HEDP. of the proposed inhibitors towards CaCO3 scale formation. In this
It is clear that sodium alginate has the highest efficiency for CaSO 4 section, the conductivity was monitored whilst calcination of cal-
scale inhibition, whilst chitosan shows poor effect towards calcium cium carbonate from the calcium chloride solution was carried
sulfate inhibition. Moreover, increasing the concentration of sodium out by adding sodium carbonate. It is known that nucleation is the
alginate increases the percentage of calcium sulfate scale inhibition first step in precipitation, and this also applies for the scaling de-
and plateau region is observed after 50 ppm (100%). posit. The super saturation point, S, is a key point in homogeneous

sodium alginate
120 chitosan
HEDP

100

80
% of scale inhibtion

60

40

20

F I G U R E 2 Variation of percentage
0
inhibition of calcium sulfate scale with
0 20 40 60 80 100 120
different concentrations of sodium
alginate, chitosan and HEDP concentration of antiscalant,ppm
4 | KHAMIS et al.

addition of chitosan or HEDP impedes the super saturation point


and consequently retards calcium carbonate scales. In addition, the
increased concentration of both inhibitors increases the value of
the super saturation point. This can be attributed to the complex
formation capacity of chitosan or HEDP with cations, thereby re-
ducing the nucleation rate and the growth of crystals. Also, chi-
tosan can react with sodium carbonate and form soluble complexes
Blank Sodium alginate (50ppm),4X (Qian et al., 2018). A carbonate is bound to either two protonated
amino groups in chitosan to form a complex, or one protonated
amino group and one sodium ion.
Figure 6 shows SEM photographs of CaCO3crystals after pre-
cipitation in the absence and presence of the suggested scale in-
hibitors. As seen, cubic structure of calcium carbonate crystals was
observed in the absence of antiscalants. Addition of chitosan mod-
ified the cubic structure into spherical shape and reduced its size.
Chitosan(10ppm),4X HEDP This is probably related to the presence of NH2+ and OH− groups
in chitosan which can bind Ca2+ through their lone pair of elec-
F I G U R E 3 Optical photographs of CaSO 4 crystals after trons. Chitosan can then occupy the growing points of the initially
precipitation in absence and presence of suggested scale inhibitors
formed crystals, and the crystal morphology is then changed, lead-
at their optimum concentration
ing to deformation and preventing further crystal growth. Also,
these functional groups can interact with calcium ions present in
the media preventing the Ca2+arrival at the surface of scale nuclei
(Elkholy et al., 2018; Macedo et al., 2019; Yang et al., 2010; Zhang
et al., 2015). Whilst in the presence of HEDP, calcium carbonate
particles lost their sharp edges and exhibited great irregularity in
the morphology of the scale and seemed as a spongy structure
(Garcia et al., 2001).
However, the addition of sodium alginate had no change in super
saturation point; the cubic shapes of CaCO3 were modified into
spherical shape. It is clear that the modification begins at low con-
centration (25 ppm) due to cross-­linking between alginate and Ca2+
cations onto CaCO3 crystal, and complete modification is observed
at 1000 ppm of sodium alginate. Interaction between Ca2+ ions and
sodium alginate led to Ca2+ being immeasurable in conductivity
test. This observation indicates that accuracy of conductivity test
depends on strength of interaction between cations and the inhibi-
tor in addition to type of complex formed. It can be concluded that
conductivity test is a screening test designed to measure the ability
of inhibitor to retard or suppress the formation of the critical nuclei
in the supersaturated fluid (Abdel-­Gaber et al., 2012) and is not ap-
plicable to all modifier antiscalants.

F I G U R E 4 Interaction of alginate with Ca2+ ion


3.2.2 | Electrochemical test

nucleation. When the ion product is beyond this point, the ho- The consequences of the presence of scale on the surface are
mogeneous nucleation rate is suddenly increased, which results more problematic than precipitation in the bulk solution. The elec-
in precipitation and scaling (Abdel-­G aber et al., 2008; Drela et al., trochemical method is a more recent way to study the buildup
1998). of calcium carbonate layers and the main component of scale on
Dependence of super saturation point of calcium carbonate metal surface. This method allows a faster evaluation of the scal-
scale at different concentrations of sodium alginate, chitosan and ing power of various industrial, natural and chemically or physi-
HEDP was illustrated in Figure 5. As seen, addition of sodium al- cally treated waters (Abd-­El-­K halek & Abd-­El-­Nabey, 2013; Garcia
ginate has no change in super saturation point. On other hand, et al., 2001).
KHAMIS et al. | 5

F I G U R E 5 Dependence of super
saturation point of calcium carbonate
scale at different concentrations of
chitosan, sodium alginate, and HEDP

3.2.3 | Chronoamperometry measurements process. The percentage of scale inhibition could be determined
from the following Equation (2):
The chronoamperometry curves for polarized steel electrode in the
[ ]
CaCl2 brine solution at 40°C in the absence and presence of differ- (Rct)0 − (Rct)i
% Scale inhibition = × 100 (2)
ent concentrations of sodium alginate and chitosan were shown in (Rct)0

Figure 7. The figure displayed that the addition of suggested inhibi-


tors to the brine solution increases the limiting value of the current where (Rct) 0 and (Rct) i are the charge transfer resistances after
which indicates that low amount of scales is formed on steel surface. It polarizing the steel electrode at −1 V (vs. SCE) in scaling environ-
can be explained by the bonding strength between cations and active ment for 3 h in the absence and presence of tested inhibitors, re-
groups in the two polysaccharides which disorders the normal lattice spectively. The data displayed that both polysaccharides sodium
structure of the calcium carbonate crystals and thus modify them to alginate and chitosan are more efficient as CaCO3 scale inhibitors
fluffy forms that cannot be attached on metal surface. than HEDP. This efficiency attributed to the presence of func-
tional groups such as NH2+, COO − and OH− which are multiple
adsorption sites and make them easily adorable (Umoren et al.,
3.2.4 | Impedance (EIS) measurements 2018). Moreover, the size of polymer chains which favors the ad-
sorption on metal surface (Benchikh et al., 2009; Darmokoesoemo
As no information about the thickness and porosity of the scale layer et al., 2018; Eduok et al., 2018; Mobin & Rizvi, 2017; Sun et al.,
is obtained from chronoamperometry curves (Safaira et al., 1999), the 2018; Umoren et al., 2018).
use of impedance technique will improve the understanding of the elec- High optimum concentration of sodium alginate indicates that
trochemical scaling process. Figure 8 shows Nyquist plots for polarized it does not interact through “threshold effect.” It was reported that
steel in brine solution in the absence and presence of different concen- doubly charged calcium ions (Ca2+) can bind two different alginate
trations of sodium alginate and chitosan, respectively. As seen, different strands simultaneously (Ibrahim et al., 2014) (Figure 4).
types of distorted semicircles are observed and their sizes decrease with
increasing the inhibitors concentrations. These observations indicate
that increasing the concentration of antiscalants reduces the insulation 3.3 | Chitosan-­alginate mixture
caused by the scaling layer. Figure 9 displays phase angle and Bode dia-
grams which show a considerable decrease of steel electrode modulus The overall results displayed that chitosan is more efficient for inhi-
impedance with the addition of chitosan and alginate. The values of bition of the calcium carbonate scales, whilst it has poor efficiency
phase angle lower than 90 in Bode theta plots indicate the presence for sulfate scales inhibition.
of nonideal capacitances that verify the inhomogeneities in the system. A mixture of chitosan and sodium alginate was tested to im-
Two equivalent circuits (Beaunier et al., 1976; Bousselmi et al., prove the efficiency of chitosan as sulfates scales inhibitor.
1997) were used to fit the experimental data of impedance plots for Table 2 shows calcium sulfate scales inhibition efficiencies at dif-
the scale formation processes in brine solution containing different ferent concentrations of sodium alginate and chitosan. Inhibition
concentrations of sodium alginate, chitosan and HEDP (Figure 10 efficiency of the mixture of 50 ppm of sodium alginate and 400
and Table 1,). The data clarified that increasing inhibitor concen- ppm of chitosan compared with HEDP were illustrated in figure 11.
tration decreases the charge transfer resistance confirming the As seen, suggested mixture has a dual effect on carbonate and sul-
inhibitive effect of these substances towards the scales formation fate scale inhibition with good efficiency reached to 88% and 87%,
6 | KHAMIS et al.

F I G U R E 6 Scanning electron microscope (SEM) micrographs of CaCO3crystals after precipitation in absence and presence of the tested
scale inhibitors

compared with HEDP which achieved 65.3 and 87.3, respectively. chitosan-­alginate mixture and some other natural polymeric scale
Chitosan and alginate have synergetic effect that besides their inhibitors are listed in Table 3. However, tested polysaccharides
functional groups, ionic bonds between chitosan and calcium algi- have high optimal concentrations; it is believable to produce prom-
nate were formed through NH2− in chitosan and COO − in alginate ising green antiscalants with regard to eutrophication caused by
(Cahyaningrum et al., 2015). The composition of isoniazid:algi- phosphorous polymers. Also, it can be considered as alternative
nate:chitosan may have additional inhibiting effect on the grow- to nongreen technologies especially in food and pharmaceutical
ing of crystals. The comparisons of the scale inhibition between industries and desalination plants.
KHAMIS et al. | 7

F I G U R E 7 Chronoamperometry curves for polarized steel electrode in CaCl2 brine solution in absence and presence of different
concentrations of (a) alginate and (b) chitosan at 40 ○C and –­1 V versus saturated calomel electrode (SCE) for 3 h

EODQN  EODQN 
 SSP   SSP 
SSP  SSP 
 SSP  SSP 

SSP  SSP 
 



] RKPFP

]RKPFP








 

  
 
 
 



         
        

]RKPFP ]RKPFP 

(a) (b)

F I G U R E 8 Impedance spectra of polarized steel in brine solution in absence and presence of different concentrations of (a) alginate and
(b) chitosan after 3 h

F I G U R E 9 Bode plots measured for polarized steel in brine solution in absence and presence of optimum concentrations of alginate and
chitosan after 3 h
8 | KHAMIS et al.

300 ppm chitosan


Blank

7 ppm HEDP 1000 ppm alginate


F I G U R E 1 0 Impedance spectra of polarized steel in brine solution with its fitting curves and equivalent circuits in the absence and
presence of scale inhibitors

TA B L E 1 Computer fit results (± error) of the impedance spectra obtained for the steel electrode that was cathodically polarized in CaCl2
brine solution containing different concentrations of tested antiscalants and HEDP after 3 h

%
Antiscalant Conc., ppm Rs ohm.cm2 Q µF n Rct Ohm.cm2 W ±(error*10 −4) inhibition

Alginate 0 5.55 ± 0.04 103.7 ± 1.5 0.78 1436 ± 13.31 —­ —­


200 5.26 ± 0.038 160 ± 2.24 0.77 1338 ± 13.73 —­ 6.8
500 17.8 ± 0.23 126 ± 0.8 0.70 1330 ± 17.5 —­ 7.4
750 5.146 ± 0.044 125.6 ± 3.02 0.77 546.9 ± 8.9 0.037 ± 1.80 61.9
1000 3.74 ± 0.035 186 ± 5.4 0.75 336.3 ± 7.99 0.03 ± 1.38 76.6
Chitosan 50 4.84 ± 0.035 169 ± 2.46 0.77 1160 ± 13.01 —­ 19.0
100 4.44 ± 0.03 191 ± 4.05 0.81 579.6 ± 10.39 0.049 ± 3.29 59.6
200 7.04 ± 0.05 209 ± 4.97 0.79 521.9 ± 9.681 0.054 ± 3.60 63.6
300 4.7 ± 0.035 286 ± 8.2 0.78 228 ± 4.32 0.064 ± 2.46 84.1
400 4.17 ± 0.033 293 ± 8.75 0.77 189.4 ± 3.48 0.071 ± 2.48 86.8
HEDP 7 3.95 ± 0.036 231 ± 5.17 0.72 497.7 ± 8.45 0.082 ± 7.24 65.3

TA B L E 2 CaSO 4 Inhibition in brine solution in absence and


3.4 | Conclusions presence of different concentrations of suggested mixture

Mixture concentration (sodium alginate: chitosan) ppm % inhibition


Chitosan shows inhibitory activity for calcium carbonate scales
50–­100 60
precipitation whilst alginate has the highest efficiency for sulfate
50–­200 74
scales inhibition. The EIS data clarified that the metallic surface
area occupied by CaCO3 scale particles decreases with increasing 50–­3 00 79

inhibitor concentrations, whilst conductivity measurements cannot 50–­4 00 87


provide any information on the adhesive properties of the scales
on the surfaces. The chitosan-­alginate blend has a good efficiency modification of their crystals. Our findings confirm that the new
with a broad poisoning effect on the crystallization of carbonate blend can be applied as green antiscalant technologies in food, phar-
and sulfate scales, compared to HEDP, which results from significant maceutical industries and desalination plants.
KHAMIS et al. | 9

F I G U R E 1 1 Comparison between
inhibition efficiencies of alginate-­chitosan
mixture and HEDP on CaSO 4 and CaCO3
scales

TA B L E 3 Comparisons of the scale inhibition between chitosan-­alginate mixture and some other natural polymeric scale inhibitors

Inhibition
Scale inhibitor Scale type Test method Dose efficiency (%) Reference

Alginate-­chitosan Mixture CaCO3 and Static test, conductivity, 400:50 ppm 88 and 87
CaSO 4 electrochemical measurements
Chitosan CaSO4 Static test 40 ppm 78 Saleah and Basta
(2008)
Copolymer modified CaCO3 Static test 0.2 g/L 95.6 Guo et al.,
chitosan (2012)
Carboxymethyl CaCO3 Static test and conductivity 50 mg/L 98.5 Zhang et al.,
quaternary ammonium (2015)
oligochitosan
Carboxymethylchitosan CaCO3 Computability and dynamic tube 170 ppm Efficient Macedo et al.,
blocking test (2019)
Poly aspartic acid/chitosan CaCO3 and Static test 8 mg/L 92 and 89 Zeng et al.,
Ca3(PO4)2 (2015)

DATA AVA I L A B I L I T Y S TAT E M E N T Abd-­El-­Khalek, D.E., Abd-­El-­Nabey, B.A., Abdel-­Kawi, M.A., Ebrahim,
S.h. & Ramadan, S.R. (2019) The inhibition of crystal growth of
The data that support the findings of this study are available on re-
gypsum and barite scales in industrial water systems using green
quest from the corresponding author. The data are not publicly avail- antiscalant. Water Supply, 19(7), 2140–­2146.
able due to privacy or ethical restrictions. Abd-­El-­Khalek, D.E., Abd-­El-­Nabey, B.A., Abdel-­kawi, M.A. & Ramadan,
S.R. (2016) Investigation of a novel environmentally friendly inhib-
ORCID itor for calcium carbonate scaling in cooling water. Desalination, 7,
2870–­2876.
Dalia E. Abd-­El-­Khalek https://orcid.org/0000-0002-1134-2511
Ahmed, R.A., Farghali, R.A. & Fekry, A.M. (2012) Study for the stabil-
ity and corrosion inhibition of electrophoretic deposited chi-
REFERENCES tosan on mild steel alloy in acidic medium. International Journal of
Abdel-­Gaber, A.M., Abd-­El-­Nabey, B.A., Khamis, E. & Abd El-­Rhmann, H. Electrochemical Science, 7, 7270–­7282.
(2012) Green anti-­scalent for cooling water systems. International Amjad, Z. (2012) Investigations on the evaluation of polymeric calcium
Journal of Electrochemical Science, 7, 11930–­11940. sulfate dihydrate (gypsum) scale inhibitors in the presence of phos-
Abdel-­Gaber, A.M., Abd-­El-­Nabey, B.A., Khamis, E. & Abd-­El-­Khalek, D.E. phonates. Desalination and Water Treatment, 37, 268–­276.
(2008) Investigation of fig leaf extract as a novel environmentally Amjad, Z., Landgraf, R.T. & Penn, J.L. (2014) Calcium sulfate dihydrate
friendly antiscalent for CaCO3 calcareous deposits. Desalination, (gypsum) scale inhibition by PAA, PAPEMP, and PAA/PAPEMP blend.
230, 314–­328. International Journal of Corrosion and Scale Inhibition, 3(1), 35–­47.
Abdel-­Gaber, A.M., Abd-­El-­Nabey, B.A., Khamis, E. & Abd-­El-­Khalek, Beaunier, L., Epelboin, I., Lestrade, J.C. & Takenouti, H. (1976)
D.E. (2011) A natural extract as scale and corrosion inhibitor for Electrochemical study and scanning electron microscopy, iron
steel surface in brine solution. Desalination, 278, 337–­3 42. coated with paint. Surf. Technol., 42, 237–­254.
Abd-­El-­Khalek, D.E. & Abd-­El-­Nabey, B.A. (2013) Evaluation of sodium Benchikh, A., Aitout, R., Makhloufi, L., Benhaddad, L. & Saidani, B.
hexametaphosphate as scale and corrosion inhibitor in cool- (2009) Soluble conducting poly (aniline-­co-­orthotoluidine) copo-
ing water using electrochemical techniques. Desalination, 311, lymer as corrosion inhibitor for carbon steel in 3% NaCl solution.
227–­233. Desalination, 249(2), 466–­474.
10 | KHAMIS et al.

Boels, L. & Witkamp, G. (2011) Carboxymethyl inulin biopolymers: a Macedo, R.G.M.A., Marquesa, N.N., Pauluccia, L.C.S., Cunhaa, J.V.M.,
green alternative for phosphonate calcium carbonate growth inhib- Villetti, M.A., Castro, B.B. et al. (2019) Water-­soluble carboxymeth-
itors. Crystal Growth & Design, 11(9), 4155–­4165. ylchitosan as green scale inhibitor in oil wells. Carbohydrate
Boris, A.M., Alla, Y.F. & Margarita, A.K. (2007) New generation of water–­ Polymers, 215, 137–­142.
treatment products for formulated from biodegradable and renew- Manoli, F. & Dalas, E. (2002) The effect of sodium alginate on the crystal
able material. NACE Corrosion, paper number 07064. growth of calcium carbonate. Journal of Materials Science: Materials
Bousselmi, L., Fiaud, C., Tribollet, B. & Triki, E. (1997) The characterization in Medicine, 13, 155–­158.
of the coated layer at the interface carbon steel-­natural salt water Marin-­Cruz, J., Cabrera-­Sierra, R., Prech-­C anul, M.A. & Gonzalez, I.
by impedance spectroscopy. Corrosion Science, 39, 1711–­1724. (2004) Characterization of different allotropic forms of calcium
Cahyaningrum, S.E., Herdyastuti, N. & Qomariah, N. (2015) synthesis carbonate scales on carbon steel by electrochemical impedance
and characerization of chitosan-­alginate for controlled release of spectroscopy. Journal of Applied Electrochemistry, 34, 337–­3 43.
isoniazid drug. Indonesian Journal of Chemistry, 15(1), 16–­21. Marin-­Cruz, J. & Gonzalez, I. (2002) Evaluation of the extent of carbon
Castillo, L.A., Torin, E.V., Garcia, J.A., Carrasquero, M.A., Navas, M. & steel surface damage by calcium carbonate scale. Journal of the
Viloria, A. (2009) PDVSA, New product for inhibition of calcium Electrochemical Society, 149, B1–­B3.
carbonate scale in natural gas and oil facilities based on aloe vera: Martinod, A., Euvrard, M., Foissy, A. & Neville, A. (2008) Progressing the
application in Venezuelan oilfields. In: Latin American and Caribbean understanding of chemical inhibition of mineral scale by green in-
Petroleum Engineering Conference. Society of Petroleum Engineers, hibitors. Desalination, 220, 345–­352.
SPE, p. 123007. Martinod, A., Neville, A. & Euvrad, M. (2009) Electrodeposition of a
Darmokoesoemo, H., Suyanto, S., Anggara, L.S., Amenaghawon, A.N. calcareous layer: Effects of green inhibitors. Chemical Engineering
& Kusuma, H.S. (2018) Application of carboxymethyl chitosan-­ Science, 64, 2413–­2421.
benzaldehyde as anticorrosion agent on steel. International Journal Mobin, M. & Rizvi, M. (2017) Polysaccharide from Plantago as a green cor-
of Chemical Engineering, 2018, 4397867. rosion inhibitor for carbon steel in 1 M HCl solution. Carbohydrate
Davies, J.C. (2002) Pathogenesis and persistence. Paediatric Respiratory Polymers, 160, 172–­183.
Reviews, 3(2), 128–­140. NACE Standard TM 0374-­2001. (2001) Item 21208, Laboratory screen-
Drela, I., Falewicz, P. & Kuczkowska, S. (1998) New rapid test for evalua- ing tests to determine the ability of scale inhibitors to prevent the
tion of scale inhibitor. Water Research, 32, 3188–­3191. precipitation of calcium sulfate.
Eduok, U., Ohaeri, E. & Szpunar, J. (2018) Electrochemical and surface Qian, J., Wang, X., Shu, J., Su, C.H., Gong, J., Xu, Z. et al. (2018) A novel
analyses of X70 steel corrosion in simulated acid pickling medium: complex of chitosan–­sodium carbonate and its properties. Marine
Effect of poly (N-­vinyl imidazole) grafted carboxymethyl chitosan Drugs, 16, 416–­428.
additive. Electrochimica Acta, 278, 302–­312. Romero, C., Bazin, B., Zaitoun, A. & Leal-­C alderon, F. (2007) Behavior
Elkholy, A.E., El-­Taib Heakal, F., Rashad, A.M. & Zakaria, K.h. (2018) Monte of a scale inhibitor water-­ in-­
oil emulsion in porous media. SPE
Carlo simulation for guar and xanthan gums as green scale inhibi- Production & Operations, 22, 191–­201.
tors. Journal of Petroleum Science and Engineering, 166, 263–­273. Sadhwani, J., Veza, J. & Santana, C. (2005) Case studies on environmen-
Garcia, C., Courbin, G., Ropital, F. & Fiaud, C. (2001) Study of the scale tal impact of seawater desalination. Desalination, 185, 1–­8.
inhibition by HEDP in channel flow cell using a quartz crystal micro- Safaira, M., Srhiri, A., Keddam, M. & Takenouti, H. (1999) Corrosion of
balance. Electrochimica Acta, 46, 973–­985. a mild steel in agricultural irrigation waters in relation to partially
Guo, X., Qiu, F., Dong, K., Zhou, X., Qi, J., Zhou, Y. et al. (2012) blocked surface. Electrochimica Acta, 44, 4395–­4 402.
Preparation, Characterization and scale Performance of scale in- Saleah, A.O. & Basta, A.H. (2008) Evaluation of some organic-­based
hibitor copolymer modification with chitosan, Journal of. Industrial biopolymers as green inhibitors for calcium sulfate scales. The
and Engineering Chemistry Research, 18, 2177–­2183. Environmentalist, 28, 421–­428.
Hasson, D., Shemer, H. & Sher, A. (2011) State of the art of friendly Shakkthivel, P. & Vasudevan, T. (2006) Acrylic acid-­diphenylamine sul-
“green” Scale control inhibitors: A review article. Journal of Industrial phonic acid copolymer threshold inhibitor for sulphate and car-
and Engineering Chemistry, 50, 7601–­7607. bonate scales in cooling water systems. Desalination, 197(1–­3),
Hoang, T.A. (2015) Mechanism of scale formation and inhibition. In 179–­189.
Amjad, Z. & Demadis, K.D. (Eds.) Mineral scales and deposits, scien- Sun, H., Wang, H., Wang, H. & Yan, Q. (2018) Enhanced removal of heavy
tific and technological approaches. Elsevier, pp. 47–­83. metals from electroplating wastewater through electrocoagulation
Ibrahim, S.M., Abou El Fadl, F.I. & El-­Naggar, A.A. (2014) Preparation and using carboxymethyl chitosan as corrosion inhibitor for steel anode.
characterization of cross linked alginate. Journal of Radio analytical Environmental Science: Water Research & Technology, 4, 1105–­1113.
and Nuclear Chemistry, 299, 1531–­1537. Tsiourtis, N. (2001) Desalination and the environment. Desalination, 141,
Khamis, E., Abd-­El-­Khalek, D.E., Abdel-­Kawi, M.A. & Anwar, J.M. 223–­236.
(2020) New application of brown sea algae as an alternative to Umoren, S.A., AlAhmary, A.A., Gasem, Z.M. & Solomon, M.M. (2018)
phosphorous-­containing antiscalant. Environmental Technology, 1–­ Evaluation of Chitosan and Carboxymethyl cellulose as Ecofriendly
10. https://doi.org/10.1080/09593​330.2020.1797898. Corrosion Inhibitors for Steel. International Journal of Biological
Kirboga, S. and Oner, M. (2012) The inhibitory effects of carboxymethyl Macromolecules, 117, 1017–­1028.
inulin on the seeded growth of calcium carbonate. Colloids and Vasyliev, G., Vorobyova, V. & Zhuk, T. (2020) Raphanus sativus L. extract
Surfaces B: Biointerfaces, 91, 18–­25. as a scale and corrosion inhibitor for mild steel in tap water. Journal
Lattemann, S. & Hopner, T. (2008) Environmental impact and impact as- of Chemistry, 2020, 5089758.
sessment of seawater desalination. Desalination, 220, 1–­15. Wang, H., Liu, G., Huang, J., Zhou, Y., Yao, Q., Ma, S. et al. (2013)
Li, C., Zhang, C. & Zhang, W. (2019) The inhibition effect mechanisms of Performance of an environmentally friendly anti-­scalant in CaSO4
four scale inhibitors on the formation and crystal growth of CaCO3 scale inhibition. Desalination and Water Treatment, 53, 8–­14.
in solution. Scientific Reports, 9, 13366. Yang, X., Xu, G., Chen, Y., Liu, T., Mao, H., Sue, W. et al. (2010) The influ-
Li, H., Ma, W., Wang, L., Liu, R., Wei, L. & Wang, Q. (2006) Inhibition of ence of O-­c arboxymethylchitosan on the crystallization of calcium
calcium and magnesium-­containing scale by a new antiscalant poly- carbonate. Power Technology, 204, 228–­235.
mer in laboratory tests and a field trial. Desalination, 196, 237–­247. Yu, W., Wang, Y., Li, A. & Yang, H. (2018) Evaluation of the structural
Lin, S.H. & Dexter, S.C. (1988) Effects of temperature and magnesium ion morphology of starch-­graft-­poly(acrylic acid) on its scale-­inhibition
on calcareous deposition. Corrosion Science, 44, 615–­622. efficiency. Water Research, 141, 86–­95.
KHAMIS et al. | 11

Zeng, D., Chen, T. & Zhou, S. (2015) Synthesis of polyaspartic acid/ Zhou, M., Gu, Y. & Yi, R. (2019) Preparation and performance evalua-
chitosan graft copolymer and evaluation of its scale inhibition tion of a new ter-­polymer scale inhibitor. Journal of Macromolecular
and corrosion inhibition performance. International Journal of Science, Part A, 56(11), 1060–­1070. https://doi.org/10.1080/10601​
Electrochemical Science, 10, 9513–­9527. 325.2019.1652544.
Zhang, A., Zhou, Y., Yao, Q., Wang, T., Li, J., Chen, Y. et al. (2017) Inhibition
of calcium carbonate and sulfate scales by a polyether-­based poly-
carboxylate antiscalant for cooling water systems. Desalination and
How to cite this article: Khamis E, Abd-­El-­Khalek DE, Abdel-­
Water Treatment, 77, 306–­314.
Kawi MA, Anwar JM. Scale inhibition in industrial water
Zhang, H., Cai, Z., Jin, X., Sun, D., Wang, D., Yang, T. et al. (2015)
Preparation of modified oligochitosan and evaluation of its scale systems using chitosan-­alginate mixture. Water and Environment
inhibition and fluorescence properties. Applied Polymer Science, Journal. 2021;00:1–11. https://doi.org/10.1111/wej.12704
132, 42518.

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