Silica Scale Inhibition

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Silica Scale Inhibition

Chapter November 2013
DOI: 10.1201/b15606-15
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Konstantinos D Demadis
University of Crete
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12 Untangling the Gordian

Knot of Scale Formation in

Industrial Water Systems
Melina Preari, Anna Tsistraki, and
Konstantinos D. Demadis
CONTENTS
12.1 Introduction................................................................................................... 215
12.2 Growth of Amorphous Silica: A Polymerization Event................................ 215
12.3 Silica Scale Formation and Inhibition........................................................... 216
12.3.1 Cationic Inhibitors............................................................................. 216
12.3.2 Neutral Inhibitors............................................................................... 220
12.4 Mechanism of Silica Inhibition..................................................................... 222
12.5 Conclusion.....................................................................................................224
Acknowledgments...................................................................................................224
References............................................................................................................... 225
12.1INTRODUCTION
Fouling is a general term that describes the interference of solid materials with fluid
flow [1]. One of its most challenging aspects is the in situ formation of inorganic salts
or colloids. Severe fouling at times forces system operators to discard critical equipment components. Even if mechanical or chemical cleaning are viable options, they
require several work hours, total system shut downs, and high costs [2]. Foulants
could be organic or inorganic. Organic foulants are a result of poor system biocontrol
and are beyond the scope of this chapter [3]. Inorganic foulants include mineral salts
of alkaline earth metals such as calcium, barium, and strontium. Amorphous and
colloidal deposits are considered to be special cases. One such case is colloidal
silica, which will be the subject of this chapter [4].
12.2GROWTH OF AMORPHOUS SILICA:

A POLYMERIZATION EVENT
Formation of amorphous silica in aqueous systems is a highly complex process [5,6].
It usually occurs at a pH of less than 8.5. Available data suggest that silica solubility
215
216
Mineral Scales in Biological and Industrial Systems
Downloaded by [Kostas Demadis] at 10:09 15 November 2013
is rather independent of pH in the range of 68. This is the pH region where silicic
acid condensation has a maximum rate. Silica exhibits normal solubility characteristics, meaning that its solubility increases as temperature increases. Silica formation
is actually a polymerization event. Silicic acid ions condense and polymerize, thus
forming various structural motifs [7]. The product of this polymerization (polycondensation) is amorphous. Silicic acid polymerization starts with an attack of a deprotonated silanol to a neighboring silicic acid molecule, thus forming an initial dimer
(disilicic acid), which then goes on to undergo further attack by neighboring silicic
acid molecules. This produces a random polymer and eventually silica nanoparticles. These, in turn, can further grow (by incorporation of silicic acid onto the silica
particle surface) or agglomerate with other nanoparticles to give larger particles.
12.3 SILICA SCALE FORMATION AND INHIBITION

Current approaches to control silica scale growth in industrial waters include operation at low cycles of concentration, prevention of other scale formation, pretreatment [812], and chemical intervention (inhibitor use). The use of inhibitors relates
to the prevention of silicic acid oligomerization or polymerization [1322]. Hence,
silicic acid remains soluble, and therefore, formation of colloidal silica is avoided.
Recent research in our research group has demonstrated that small molecules
(cationic or anionic) are not active silica inhibitors, at least under conditions and
dosages pertinent to water treatment systems. In contrast, cationic or even neutral polymers (to a lesser extent) have been discovered as effective silica inhibitors
[1322,23]. Therefore, polymeric additives were sought that possess neutral moieties
or contain some degree of cationic charge.
12.3.1 Cationic Inhibitors

In Figure 12.1, the schematic structures of inhibitors are shown. The polymers displayed in Figure 12.1 are polyethylene glycolbased oligomers (PEGs) grafted with
phosphonium cations on each end.
The selected polymers show a variety of structural features. They all contain
dicationic charge. The three members (PEGP+-200, PEGP+-1000, and PEGP+-4000)
possess variable length polyethylene chain. The numbers 200, 1000, and 4000 denote
the molecular weight of the polyethylene chain. Figures 12.2 through 12.4 present
silicic acid stabilization results with variable dosage (in ppm) for all polymers.
In the absence of additives, silicic acid, condensation takes place readily at pH 7
to yield amorphous silica. The first measurement at 24 h indicates that its equilibrium
concentration (180 ppm) is reached. The presence of PEGP+-200 essentially does not
alter polymerization of silicic acid (Figure 12.2). Various concentrations of the additive were tested (40150 ppm), but no stabilization effect was noted. PEGP+-1000 was
then tested by the same methodology and at the same concentrations (40150 ppm)
(Figure 12.3). A strong silicic acid stabilization effect was observed, even at its lowest
concentration (40 ppm). It is worth noting that in this case the stabilization effect of
PEGP+-1000 is concentration dependent, as it increases as PEGP+-1000 concentration
increases. At 150 ppm, PEGP+-1000 stabilizes 430 ppm silicic acid.
217
P+
P+
O
9
(a)
P+
P+
O
21
(b)
P+
P+
O
91
(c)
FIGURE 12.1 Schematic structures of the three phosphonium-based silica inhibitors

PEGP+-200 (a), PEGP+-1000 (b), and PEGP+-4000 (c).
Furthermore, the strong stabilizing effect of PEGP+-1000 is supported by the

48 and 72 h measurements. For example, after 48 h (at 150 ppm concentration),
405 ppm silicic acid are stabilized, and after 72 h, 395 ppm silicic acid remains
soluble. This is remarkable, as after 72 h, only 105 ppm (from the initial 500 ppm)
silicic acid is lost to polymerization. The effect of PEGP+-4000 is similar to that of
PEGP+-1000 (Figure 12.4). One major difference is that PEGP+-4000 induces silicic
acid stabilization (365 ppm at 24 h) even at low concentrations (40 ppm). Upon
concentration increase, there is a minor increase in stabilizing effect. Finally, PEGP+4000 at 150 ppm concentration can stabilize 410 ppm silicic acid, after 24 h.
The previously described long-term silicification experiments reveal valuable information about the stabilizing effect exerted by the PEGP+ additives at a
218

500
24 h
48 h
72 h
400
350
300
250
200
150
100
50
0
Control
40
60
80
PEGP+200 concentration (ppm)
100
150
FIGURE 12.2 The effect of various concentrations of PEGP+-200 (40150 ppm) on silicic
acid stabilization during a period of 3 days.
500
24 h
48 h
72 h
450
Soluble silicic acid (as ppm SiO2)
450
400
350
300
250
200
150
100
50
0
Control
40
60
80
PEGP+-1000 concentration (ppm)
100
150
time scale >24 h. However, useful information can be extracted from short-term (8 h)
silicification runs at the early stages of silicic acid condensation. During these studies,
aliquots from the working solution are drawn every hour for the first 8 h. First, PEGP+200 was tested, at concentrations 100 and 150 ppm. The results (not shown) confirm a
negligible stabilization effect, as with the 3 day runs. Therefore, PEGP+-200 is unable
to stabilize silicic acid, even during the first stages of the condensation reaction.
219

500
24 h
48 h
72 h
400
350
300
250
200
150
100
50
0
Control
40
60
80
PEGP+-4000 concentration (ppm)
100
150
When PEGP+-1000 is tested in 8 h runs, at concentrations 40, 80, and 100 ppm,
a concentration-dependent stabilization effect is observed (Figure 12.5). First, at
40 ppm, PEGP+-1000 does not exert any stabilization beyond the control. At the end
of the 8 h period, 280 ppm silicic acid remains soluble (compare these to the measurement of 244 ppm observed at 24 h during the 3 day experiments [Figure 12.3]).
600
Soluble silicic acid (ppm as SiO2)
450
500
100 ppm
400
80 ppm
40 ppm
300
Control
200
100
0
5
Time (h)
FIGURE 12.5 The effect of PEGP+-1000 (at 40, 80, and 100 ppm levels) on silicic acid
stabilization during an 8 h period.
220

600
150 ppm
500
100 ppm
400
40 ppm
300
Control
200
100
0
5
Time (h)
FIGURE 12.6 The effect of PEGP+-4000 (at 40, 100, and 150 ppm levels) on silicic acid
stabilization during an 8 h period.
Increase in PEGP+-1000 concentration to 80 ppm has a notable increase in its stabilizing ability. Now, there is a clear increase in soluble silicic acid (360 ppm, after 8 h).
Further PEGP+-1000 concentration increase to 100 ppm causes additional stabilization improvement (400 ppm after 8 h). The observed concentration dependence of
the stabilizing ability of PEGP+-1000 in these short-term runs is consistent with that
observed during the long-term runs (see previous text).
Finally, PEGP+-4000 was tested (at 100 and 150 ppm levels) for silicic acid stabilization in 8 h runs (Figure 12.6). A strong stabilization effect is observed at 100 ppm
PEGP+-4000 concentration, causing 380 ppm silicic acid to remain soluble. Upon
PEGP+-4000 concentration increase to 150, 440 ppm silicic acid are stabilized.
12.3.2Neutral Inhibitors
The results described earlier prompted us to investigate polyethylene glycol oligomers, in order to delineate the role of the cationic phosphonium groups in silica
inhibition. Hence, the polyethylene glycol (PEG) oligomers shown in Figure 12.7
were tested. PEG-1000 (Figure 12.8) showed a very minor stabilization effect (23
ppm silicic acid stabilization above the control) at 150 ppm concentration, after
24 h. However, PEG-4000 exhibited remarkable inhibitory activity, comparable to
PEGP+-4000, as shown in Figure 12.9. The comparative results between PEGP+-4000
(Figure 12.3) and PEG-1000 (Figure 12.8) strongly indicate that the phosphonium
cationic groups play a significant role in silica inhibition. However, we need to note
that when molecular weight increases (from PEG-1000 to PEG-4000), it appears that
221

HO
H
O
(a)
21
HO
(b)
91
HO
H
(c)
227
FIGURE 12.7 Schematic structures of the three PEG-based silica inhibitors PEG-1000 (a),
PEGP+-4000 (b), and PEGP+-10000 (c).
500
Soluble silicic acid (as ppm SiO2 )
24 h
48 h
72 h
450
400
350
300
250
200
150
100
50
0
Control
40
80
150
PEG-1000 concentration (ppm)
FIGURE 12.8 The effect of various concentrations of PEG-1000 (40150 ppm) on silicic
the major determinant of silica inhibition is the ethylene oxide (EO) groups. Further
comments will be put forth when the mechanism of silica inhibition is discussed.
Lastly, the inhibitory efficiency of PEG-10000 was investigated and the results
are shown on Figure 12.10. It appears that PEG-10000 is an effective silica inhibitor even at dosages as low as 20 ppm. It also becomes evident that inhibitor dosage
increase from 20 to 40 ppm has a positive effect on inhibition. A level of 300 ppm
silicic acid is stabilized (an additional 70 compared to 20 ppm dosage). However,
further dosage increase has no additional effect, and the dosages 40, 80, and 100 ppm
stabilize 300 ppm silicic acid.
222

500
24 h
48 h
72 h
400
350
300
250
200
150
100
50
0
Control
40
80
150
PEG-4000 concentration (ppm)
450
500
450
400
350
300
250
200
150
100
50
0
24 h
48 h
72 h
Control
20 ppm
40 ppm
60 ppm
80 ppm
100 ppm
PEG-1000 dosage
12.4 MECHANISM OF SILICA INHIBITION

Amorphous silica formation is governed by several important equilibria. Some of
these are given in Figure 12.11.
As mentioned previously, silica deposition results from silicic acid selfcondensation. This reaction is first order and is catalyzed by OH in the pH range of
510. Reports have shown that the reaction yielding a silicic acid dimer is kinetically
slow in contrast to the reactions giving a trimer, tetramer, pentamer, etc., which are
very fast [2427]. All these equilibria are sensitive to pH and tend to be accelerated
by metal ions that form hydroxides, for example, Fe2+/3+, Mg2+, or Al3+.
223

Si(OH)4
[SiO(OH)3]+ H+
Si(OH)4
[SiO2(OH)2]2+ 2H+
2Si(OH)4
Si2O(OH)6 + H2O
2Si(OH)4
[Si2O2(OH)5]+ H 2O + H+
2Si(OH)4
[Si2O3(OH)4]2+ H2O + 2H+
FIGURE 12.11 Some basic equilibrium reactions in silica chemistry.
Polymerization of silicic acid is believed to occur through a SN2-like mechanism

involving a deprotonated silicic acid monoanion ((HO)3SiO ) and the Si center of
silicic acid, Si(OH)4. Inhibition of this step should be critical in the inhibition of silica scale formation. Some reports indicate that orthosilicates hydrolyze more rapidly
than other silicate species such as disilicates, chain silicates, cross-linked oligomers,
and polymers, suggesting that bridging oxygens are much more resistant to attack
than non-bridging oxygens. Above a pH of 2, this mechanism involves polymerization with condensation, catalyzed by OH.
Electrostatic interactions between a cationic polymeric inhibitor and monodeprotonated silicic acid have been invoked. These interactions stabilize soluble silicate
and prohibit the condensation reaction. Alternatively, a cationic polymer whose positive charge is primarily based on protonated amine moieties can stabilize silicic acid
molecules and/or silicate ions by hydrogen bonds. Most likely, a combination of the
previous interactions occur simultaneously for polymeric inhibitors with protonated
amine groups, whereas electrostatic interactions are responsible for the stabilizing
effect for polymers that have no NH moieties but possess NR+4 groups. In the present results, it becomes obvious that phosphonium groups PR+3 contribute substantially to inhibition.
To prove that the phosphonium cationic charges PR3+ at the endings of the PEGP+
oligomer backbone are responsible for the silicic acid stabilizing effect, experiments
were performed including phosphonium-free PEG oligomers as silica inhibitors.
When PEG-1000 is used, inhibitory efficiency drops dramatically (Figure 12.8). This
is direct proof that the presence of phosphonium cationic charges PR+3 at the endings of the PEGP+-1000 oligomer backbone are fundamentally responsible for the
measured silica inhibition.
Nevertheless, upon increase of molecular weight when PEG-4000 is used as
inhibitor, the results obtained are intriguing (Figure 12.9). PEG-4000 is nearly as
effective as PEGP+-4000 (Figure 12.4). This is a strong indication that at higher
molecular weights, the responsible moieties for inhibitory activity are the EO groups
(CH2CH2O). To further confirm the argument, we also tested a longer PEG
oligomer, namely, PEG-10000 (Figure 12.10). Although PEG-10000 appears to be an
effective inhibitor, its efficiency is somewhat lower than that of PEG-4000. Hence, it
seems that the optimal PEG molecular weight is 4000.
The precise mechanism of silica formation is only partially understood. As a
consequence, the exact mechanism of silica scale inhibition is not fully delineated.
224

HO
91
HO
Si
HO
H
O
OH
HO
Si
OH
OH
FIGURE 12.12 Schematic representation of possible silicic acid stabilization by PEG

oligomers through hydrogen bonding.
However, it is now certain that any interference with the condensation reaction could
lead to silica scale growth inhibition. Based on our results, the cationic phosphonium groups contribute to inhibition when they are grafted to the PEG chain of
molecular weight of 4000. The demonstrated silicic acid stabilization must be due to
electrostatic interactions between the PR3+ groups and surrounding silicate anions.
Also, the neutral PEG-4000 and PEG-10000 stabilize silicic acid through hydrogen
bonding between silanol groups and the O atoms of the PEG chain. This is presented
schematically in Figure 12.12.
12.5CONCLUSION
Based on the results presented in this chapter, the following conclusions can be
drawn:
Phosphonium-containing cationic oligomers are capable of stabilizing
silicic acid in circumneutral pH.
Neutral (phosphorus-free) PEG oligomers are effective inhibitors but at
selected molecular weights (MWs).
When the PEG chain is too short (MW 200), neither the cationic PEGP+200 nor the neutral PEG-200 shows inhibition capability.
At intermediate MWs (e.g., 1000), cationic PEGP+-1000 is effective, but
phosphorus-free, neutral PEG-1000 is not.
At higher MWs (e.g., 4000), both cationic PEGP+-4000 and neutral PEG4000 are effective inhibitors.
When PEG MW is 10,000, PEG-10000 is an effective inhibitor but worse
than PEG-4000. Hence, increase of MW seems to be detrimental for silica
inhibition.
ACKNOWLEDGMENTS
This research was funded by the General Secretariat of Science & Technology
(Ministry of Education) under Grant GSRT 170c and The University of Crete
Research Office under Grant KA 3517.
225
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