Desalination 126 (1999) 267280

Effects of water quality on silica fouling of desalination plants

R. Sheikholeslami*, S. Tan
School of Chemical Engineering and Industrial Chemistry, The University of New South Wales, Sydney 2052, Australia Tel. +61 (2) 9385-4343; Fax +61 (2) 9385-5966; email: r.sheikholeslami@unsw.edu.au

Abstract Laboratory tests with simulated waters in the range of those in a prospective desalination plant were carried out to determine the water quality effects on silica precipitation both in batch and dynamic tests using RO membranes. In this study the effect of cations on silica polymerization was investigated. Previous investigations established that the best operating pH range is below 6.5, which precludes polymerization as well as precipitation of silicates. Thus this pH was adopted for this study. Results indicated that magnesium hardness was more effective than Ca hardness in silica polymerization rate. At a given hardness, decreasing the ratio of calcium to magnesium was found to increase the polymerization rate. This was apparent in batch tests and during the initial period of dynamic tests. Also batch tests showed that polymerization increases with the degree of supersaturation. However, in dynamic tests the flux decline was higher at low feed concentrations and higher Ca:Mg ratio after a period of operation. This inflection on the effect of Ca:Mg ratio and silica concentration in dynamic tests is possibly due to precipitation of monomeric silica and deposition at the surface resulting in a less permeable scale. While at high concentrations or when polymerization is rapid (at high Ca:Mg) bulk polymerization results and deposits are of more porous colloidal silica. Membranes, retentate and batch precipitates were analyzed using electromagnetic dispersion spectroscopy and an electron microscope. It was found that the batch precipitates consisted only of silica and oxygen, whereas those of dynamic tests had minor amounts of Ca and Mg in addition to many contaminants, most notably iron which was possibly due to corrosion in the pump. Keywords: Silica fouling; RO fouling; Desalination; Fouling

1. Introduction Fouling has become a major barrier in achieving efficient use of energy in desalination plants where pure water is produced from
*Corresponding author.

seawater and brackish water. Silica fouling has been described as the major unresolved problem in desalination units. The consequence of such fouling is reduced reverse osmosis (RO) efficiency due to high pressure drops thus

Presented at the Conference on Desalination and the Environment, Las Palmas, Gran Canaria, November 912, 1999. European Desalination Society and the International Water Association. 0011-9164/99/$ See front matter 1999 Elsevier Science B.V. All rights reserved

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increasing the energy losses and costs. Other costs, associated with fouling, are maintenance due to the increased need for cleaning equipment, materials costs if anti-foulants are used, and production losses during plant shut-downs for cleaning.

3. Background 3.1. Different forms of silica Silica, with a molecular formula of SiO2, is one of the most abundant minerals on earth [2] and has many crystalline and amorphous forms. Crystalline silica usually takes the form of quartz, tridymite, or cristobalite, and has a low solubility in water, of the order of 6 ppm SiO2 [3]. Amorphous silica, a general term for any silica lacking crystal structure, has a higher solubility of 100140 ppm SiO2 [4]. The dissolution of silica involves a chemical reaction that can be represented by: SiO2 + 2H2O Si(OH)4

2. Objective This study investigates the relative effects of calcium and magnesium that are dominant in feed waters on solubility limits of silica; the experimental range used simulates the conditions encountered in a prospective desalination plant. The results will be used to guide modifications to the pretreatment technology and/or to the RO modules operating conditions to mitigate silica fouling. The plant raw water mainly consists of calcium, magnesium, carbonates, sulfates, iron and chloride ion. Solution pH and temperature are being adjusted in the pretreatment stage. Previous studies assessed the effects of pH, temperature and silica and calcium concentration in batch tests. Therefore, a series of experiments was conducted to determine the effect of total hardness and calcium to magnesium ratio on the solubility of silica in both batch and dynamic systems. The dynamic system will involve the use of Osmonics SEPA CF flat-sheet RO unit with a MS-19 polyamide membrane. This membrane was chosen because its fouling propensity had been previously investigated [1]. The effect of initial silica concentration on fouling will be investigated, as will the effect of hardness and varying the ratio of calcium to magnesium. The experiments were carried out with recycling the retentate and determining the flux as a function of recovery. The dynamic runs will be carried out for extended periods of time (in excess of 72 h) to simulate the industrial conditions a bit more closely.

Thus the soluble form of silica is initially monomeric, as it contains only one silicon atom. In this form it is often called monosilicic acid. Monosilicic acid is generally deionized at most natural pH levels. At a pH of 8.5 only 10% of the monosilicic acid is ionized and, as the pH reaches 10, 50% is ionized. Polymerization of monosilicic acid is initiated in the presence of hydroxyl groups when only fractional ionization exists. High degrees of ionization prevent polymerization. Monosilicic acid remains in the monomeric state for long periods in water at 25 C, as long as the concentration remains less than about 2 10 3 M [5]. At higher concentrations the monosilicic acid polymerizes, usually rapidly, initially to form polysilicic acids of low molecular weight and then larger polymeric species which are in colloidal forms. The colloidal species can also be formed by silicon bonding loosely with organic compounds or with other complex inorganic compounds, usually aluminum and calcium oxide [6]. Amorphous silica is classified in terms of its reactivity. It can be in the form of dissolved silica (also referred to as reactive silica) or in

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the form of a colloid (also referred to as unreactive silica), or as particulate (also known as suspended silica). To avoid ambiguity, the following terminology will be used in this text: Silica SiO2 in any of its crystalline or amorphous forms. Crystalline silica Quartz, tridymite, or cristobalite. Amorphous silica A general term for any silica lacking crystal structure. Dissolved silica Silica in the form of monosilicic acid; the silica that reacts with ammonium molybdate within 2 min after the solutions are mixed. Strictly speaking, dissolved silica should include polysilicic acids with molecules smaller than the colloidal range, but for convenience we will restricts the term to the monomer. Monosilicic acid Si(OH)4; the principal form of silica in dilute solutions (less than 100 ppm) and in freshly prepared solutions of higher concentrations. Polysilicic acid Silicic acids containing two or more atoms of silicon per molecule. The simpler polysilicic acids react slowly with ammonium molybdate (or dissociate slowly to the monomer) and are usually less than about 50 in diameter. Colloidal silica More highly polymerized species or particles larger than about 50 , although sometimes down to 1020 . Particulate silica Silica larger than colloidal, such as sand. Silica sol A broad term for polysilicic and colloidal silica. 3.2. Common silica-reduction methods Several different treatment approaches used for removing silica from high-purity water are [7,8]: For dissolved silica (reactive): Lime softeners with elevated pH with the use of magnesium hydroxide

Hot process softeners Reverse osmosis Desilicisers For colloidal silica (non-reactive): Lime softeners Hot process softeners Macroreticular anion resin Upflow filters with chemical feed Cross-flow microfiltration with chemical feed Ultrafiltration 3.3. Solubility of amorphous silica Much research has been done to investigate the solubility of amorphous silica in water at temperatures between 0 and 100 C. Alexander et al. [4] found that amorphous silica exhibits a range of solubility of 100 to 140 ppm at 25 C. This was confirmed by Krauskopf [3], Okamoto et al. [9], and Comb [6]. The pH effects and the effects of some ions have also been studied to some extent [35,1012]. However, not much work has been carried out to investigate the interactive effects under the conditions encountered in desalination plants. 3.4. Deposition of silica from water The mechanism of SiO2 formation from Si(OH)4 is the reverse of the dissolution of solid silica. This condensation reaction is catalyzed by hydroxide ions and accelerated by the presence of salts such as MgCl2 and CaCl2 that are being studied in this investigation. Dissolved silica comes out of supersaturated solution in three ways: 1. As a deposit on a solid surface where the Si(OH)4 condenses with any solid surface which has OH groups it can react with. If the receptive surface is MOH, where M is a metal that will form a silicate at the pH involved, the reaction that takes place can be represented as:

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Once the entire receptive surface has been covered, all further deposition is on silica, which results in a film of silica build-up. 2. As colloidal particles remaining in suspension. This occurs if there is insufficient area of receptive solid surface for deposition, and if the concentration of silica is above 200 ppm (depending on pH). The monosilicic acid polymerizes firstly to low polymers, and these further condense to form small three-dimensional polymers termed colloidal particles. 3. As biogenic amorphous silica by living organisms. This is not relevant to current study, as it usually occurs in natural waters. The deposition of colloidal silica on solid surfaces occurs when the colloidal particles collide and combine with the solid surface. The concentration of colloids must be sufficiently low because a concentrated sol under these conditions would be rapidly gelled and no coating obtained. This is analogous to the deposition of dissolved solution in that the silica concentration must not be so high that the particles collide and adhere to each other rather than to the solid surface. The deposition from monosilicic acid forms an impervious glasslike film, whereas colloidal particles form a more porous film, which is often white and opaque when dried. 3.5. Silica fouling and reverse osmosis Fouling occurs in RO systems when the dissolved silica exceeds its solubility limit and precipitates with other compounds. Any polysilicic acid formed will form silicates in the presence of metals and at suitable pH. The

silicate gets more viscous as it sits on the membrane surface and as it dehydrates becomes hard like cement. This formation of silica scale in RO systems leads to limited recovery in many installations and unnecessary increase in costs. The two categories of fouling relevant to this investigation are precipitation fouling and particulate fouling. The former occurs when monomeric silica polymerizes at the membrane surface; this is also called scaling. The latter refers to the accumulation of colloids, formed in the bulk solution, at the membrane surface. So the main distinction between the two is whether the polymerization occurs at the interface causing molecular deposition or in the bulk solution causing colloidal deposition. When using RO one must be aware of the effect that the relative insolubility of silica can have on the membrane as the feed solution becomes more concentrated. The standard industry guideline has been to limit the maximum silica concentration to about 120 mg/L in the retentate at 25 C [13], although systems operating with brine silica concentrations of 180 mg/L have been reported. 4. Experimental procedures Analytical grade chemicals and reagents were used in this study. Water was distilled and microfiltered with a 0.22 m Millipore filter prior to use. All the test tubes and containers were washed with concentrated hydrochloric acid and thoroughly rinsed with distilled water. Silica solutions were prepared using a soluble salt of metasilicate (Na2SiO3.9H2O). Standard solutions were prepared using 1000 ppm commercial analytical grade silica solution. All containers used were made of plastic to prevent possible leaching from glass containers. Prepared solutions were analytically tested for all components immediately after preparation to establish the base line and were monitored during experimentation.

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Batch tests were carried out to determine the precipitation characteristics of silica at different Ca, Mg and SiO2 concentrations. For each run the required mass of sodium metasilicate was dissolved in distilled and micro-filtered water. When calcium and/or magnesium were present, the pH was first adjusted to 6.5 and then the calcium chloride and magnesium chloride salts were added. The solution was then diluted to achieve the required concentration. The solution was poured into small containers of equal volume to insure a constant-volume batch reactor. The solution hardness and silica and calcium concentrations were monitored throughout each run that lasted over 3 weeks. A minimum of 20 to 30 water samples was taken during each run and analyzed for all chemical constituents. The analyses for SiO2 were carried out using the molybdosilicate method and a UV spectrophotometer (Cary 1E UV-Visible Spectrophotometer) as our previous experimentation has shown [14] that this is the only appropriate method for the experimental conditions. Calcium concentration was determined by titration with EDTA using Murexide or Eriochrome Blue Black R as the indicator. The total calcium and magnesium hardness was determined by EDTA titration using Eriochrome Black T as the indicator. Each run was initially sampled three times daily when the greatest concentration change was occurring and then less frequently as the concentrations stabilized. For each dynamic test between 20 and 30 L of solution was prepared in 5 L batches. For each run the required mass of sodium metasilicate was dissolved in 4.5 L distilled water. The pH was adjusted to 6.5 and then the calcium and magnesium chlorides were added. The solution was diluted to 5 L, and this process repeated until the required run volume was prepared. The solution was pumped through the Sepa CF flatsheet RO unit; schematics of the unit are shown in Fig. 1.

Fig. 1. Schematics of RO unit.

Operating pressure for each run was held constant at 350 psig and cell pressure maintained at 850 psig. The permeate was measured over time by a computerized data acquisition system and the flux was computed accordingly. The silica concentration in the feed vessel was measured by the molybdosilicate method at the beginning and end of each run, and periodically as the run progressed. 5. Results and discussion 5.1. Batch tests All batch tests were carried out at room temperature and at pH 6.5. Table 1 summarizes the experimental conditions. As indicated previously, hardness and silica, calcium and magnesium concentrations were monitored with time. Figs. 2 and 3 are representative of typical concentration profiles obtained for batch runs with high and low silica concentrations, respectively. Both figures show that calcium and magnesium concentrations remain constant while silica concentrations drop with time. The drop in silica concentration is significant for high silica

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Table 1 Summary of experimental conditions for the batch runs Run 1 2 3 4 5 6 7 8 Silica concentration (mg SiO2/L) 500 500 500 500 200 200 200 200 Calcium concentration (mg CaCO3/L) 450 200 450 200 200 450 450 200 Magnesium concentration (mg CaCO3/L) 400 400 150 150 400 400 150 150 Ca/Mg 1.125 0.5 3 1.33 0.5 1.125 3 1.33 Total hardness (mg CaCO3/L) 850 600 600 350 600 850 600 350

Fig. 2. Typical concentration profiles for batch run B3, concentration over time.

Fig. 3. Typical concentration profiles for batch run 6, concentration over time.

concentrations while for low concentrations of silica the drop is not significant enough to conclude that the solutions of 200 ppm silica are unstable. There seems to be a very minor drop from the original value of 200 ppm; however, this can be due to the measurement errors as the initial value (at time zero) is obtained from weight of the sodium metasilicate used in solution preparation while the remainder of

values are obtained from the UV-SPM measurements. In addition, our previous investigations [14] confirm that silica solutions of 200 and 250 ppm were stable even in the presence of Ca concentrations of 400 and 625 ppm. Figs. 2 and 3 also suggest that neither Ca nor Mg have precipitated out of the solution. This is confirmed by EDS analysis of the precipitate as discussed later.

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5.2. Effect of Ca:Mg ratio Runs B2 and B3 are compared in Fig. 4 to examine the effect of varying the Ca:Mg ratio. For an initial starting concentration of 500 ppm SiO2 and total hardness of 600 ppm, it is evident the concentration of dissolved silica drops more rapidly for a Ca:Mg ratio of 0.5 than for a ratio of 3.0. After about 20 h there is no appreciable difference in dissolved silica concentration of either run. Runs B5 and B7 show a similar trend (Fig. 5). The dissolved silica concentration of run B5 (Ca:Mg = 0.5) drops more rapidly initially

than does run B7 (Ca:Mg = 3.0). However, here after 120 h there is no appreciable difference in dissolved silica concentration for either run. Again, even though there seems to be a minor drop in silica concentrations (Fig. 5), it might merely be due to experimental error as explained above. These results indicate that within the experimental range, Ca/Mg ratio does not affect the solubility limit but influences the rate of polymerization. This may indicate that these cations only catalyze polymerization and do not participate in the polymerization process.

Fig. 4. Effect of Ca:Mg ration on dissolved silica (500 ppm initially, Si 600 ppm hardness).

Fig. 5. Effect of Ca:Mg ratio on dissolved silica (200 ppm Si initially, 600 ppm hardness).

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5.3. Effect of total hardness Runs B1 and B4 show the effect of total hardness on dissolved silica for a given Ca/Mg ratio when the initial silica concentration is 500 ppm (Fig. 6). Run B1, with a total hardness of 850 ppm, shows a more rapid drop in dissolved silica than run B4, which has less than half the amount of hardness with 350 ppm. Fig. 7 with an initial silica concentration of 200 ppm confirms that increased hardness leads to a faster drop in dissolved silica in solution; however, after about 30 h the concentration of silica in both solutions is very similar. 5.4. Amorphous silica solubility The dissolved silica content of Runs B1 to B4 drops to an equilibrium concentration of around 130 ppm after about 50 h from an initial starting concentration of 500 ppm SiO2. Runs B5 to B8 reacted more slowly with the concentration of dissolved silica still greater than 150 ppm after 300 h. This is consistent with the literature [15] where it has been found that the concentration of dissolved silica in solution decreases more rapidly as the degree of supersaturation increases. Of course, the magnesium and calcium ions in the solution would have catalyzed the rate of polymerization somewhat; the fact that after 300 h the silica concentration for runs B5B8 remained above 150 ppm is a reflection of the relatively small degree of supersaturation of the solution initially as at 25 C, and solubility of amorphous silica is around 130 ppm. Thus, supersaturation for Runs B1B8 is not sufficient for the concentration drop to reach the solubility limit at that temperature. As mentioned before, considering the experimental error, runs B5B8 seem to be stable supersaturated solutions. 5.5. Analysis of precipitate One hundred milliliter samples from each of runs B1B4 were filtered using 0.22 millipore

Fig. 6. Effect of hardness on dissolved silica (500 ppm initially, Ca:Mg ~1.2).

Fig. 7. Effect of hardness on dissolved silica (200 ppm Si initially, Ca:Mg ~1.2).

filter paper. Each yielded roughly 0.035 g of precipitate which was analyzed using an electron microscope and electromagnetic dispersion spectroscopy (EDS). From the spectrum it is apparent that the precipitate consists of silica and oxygen only, with no calcium or magnesium present in the filtered solid. This is confirmed by hardness and calcium tests performed on the solution before and after filtration where there was no discernible difference in concentration. 5.6. Dynamic tests All dynamic runs were carried out at room

R. Sheikholeslami, S. Tan / Desalination 126 (1999) 267280 Table 2 Summary of dynamic runs Feed concentrations Run D1 SiO2, ppm Ca, ppm Mg, ppm pH Feed volume, L Run duration, h Feed spacer Initial flux, L/m2.h Final flux, L/m2.h Water recovery, % 100 200 150 6.5 30 118 No 17.0 3.3 81.8 Run D2 200 200 150 6.5 20 53 Yes 18.3 16.0 75.1 Run D3 50 200 150 6.5 30 114 Yes 14.5 8.0 78.1 Run D4 150 200 150 6.5 25 94 Yes 15.3 9.7 82.6 Run D5 150 100 250 6.5 25 85 Yes 16.8 12.4 85.7

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temperature and at pH 6.5 (Table 2). The initial flux varied widely between runs, as the membrane permeability is not uniform and identical in membrane samples used. The instantaneous flux was normalized in order to compare flux profiles between runs in terms of fractional flux. 5.7. Effect of feed spacer Dynamic Run D1 was performed with no feed spacer as difficulties were encountered with membrane perforations. Upon completion of the run the membrane was found to have significant silica scales. The feed spacer (Run D3) increased turbulence on the feed side, and thus reduced silica deposition on the membrane. A comparison between Run D1 and D3 confirms the unusually rapid flux decline of Run D1. Run D3 had the higher silica content initially, and so the flux was expected to show a more rapid decline than Run D1; this clearly was not the case (Fig. 8). A comparison between the membrane from Run D1 with those of Runs D2 to D4 reveals the lack of a feed spacer leads to a very heavily fouled membrane. Inspection of fouled

membranes indicated that the actual membrane from Run D1 was hardly visible due to the thickness of the deposited silica. 5.8. Effect of initial silica concentration Dynamic Runs D2, D3 and D4 are compared in Fig. 9. The initial flux decline is more rapid for higher initial concentrations of silica as expected. As recovery increases, the concentration of the solution also increases. As the run progresses and silica and cations concentrations increase, silica will either deposit monomerically at the membrane or polymerize to colloidal silica prior to attaching to the membrane as scale; both forms of deposition lead to a decrease in flux but the relative effect would be different. The exact nature of the membrane scale (monomeric or colloidal) is difficult to determine. It is of interest to note that of the three runs, the run with the lowest initial silica concentration of 50 ppm exhibited the greatest flux decline for about 75% recovery. At this recovery, the flux was 77% and 71% of initial flux respectively for Runs D2 (200 ppm SiO2) and D4 (150ppm SiO2) and 55% of initial flux

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Fig. 8. Effect of feed spacer. Normalized flux vs. recovery (200 ppm Ca, 150 ppm Mg).

Fig. 9. Effect of initial silica concentration. Normalized flux vs recovery (200 ppm Ca, 150 ppm Mg).

for Run D3 (50 ppm SiO2). Although flux decrease for Run D4 was initially more gradual, after about 50% recovery the flux dropped quite dramatically. This is bad news for desalination plants, as the current convention is to keep silica

concentrations low initially in the hope that less fouling will occur. These results seem to suggest that perhaps the effect of fouling is less for higher initial silica concentrations, as it is more likely that the silica will polymerize in the

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solution and colloidal silica will deposit on the membrane which seems to be more porous than the monomeric deposit. The effect of initial silica concentrations is also reflected in the relative lengths of runs; Run D2 (200 ppm SiO2) took 53h to achieve 75% recovery, Run D4 (150 ppm SiO2) had achieved this after 82 h, while it took run D3 (50 ppm SiO2) about 107 h to process threequarters of its feed. 5.9. Comparison between actual and theoretical dissolved silica The concentration of dissolved silica in the reservoir was measured periodically as the runs progressed. The theoretical silica concentration was computed as a function of initial concentration and recovery (e.g., at 50% recovery of a 100 ppm initial silica, the theoretical silica concentration would be 200 ppm). Fig. 10 shows that the dissolved silica concentration increases until around 400 ppm and then starts to decrease as the monomer polymerizes in the solution to colloidal silica. Unexpectedly, in Run D3 the theoretical value is lower than the measured value of silica, and it

appears that silica is to have been picked up from some source. The only explanation is that as the runs were performed consecutively; since the feed reservoir was only rinsed with distilled water between runs, it is possible that silica deposited on the reservoir and cooling tubes from previous runs and redissolved in the 50 ppm solution. Regardless of this anomaly, Fig. 10 confirms that low concentrations will result in formation of less colloidal silica in the solution and the fouled deposit is made mostly by precipitation of monomeric silica at the surface which is more resistant to mass transport. It is expected that actual silica concentrations in the solution in Run D3 would follow the same trend (reach a maximum) as the other runs once the silica concentration is approached 400 ppm. The location corresponds to a run time of 73 h for Run D4 (150ppm SiO2), 50 h for Run D2 (200 ppm SiO2). Even Run D1 (100 ppm SiO2),

Fig. 10. Actual and theoretical silica concentrations. Dissolved silica vs. time.

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which exhibited the great flux drop due to increased scale as there was no feed spacer, took only 100 h before the maximum dissolved silica concentration was reached. After a 115 h run D3 (50 ppm SiO2) did not seem close to reaching a maximum concentration of dissolved silica. This means that the deposits at the membrane surface must have been monomeric, not colloidal, and so were probably less porous than the deposits for runs D4 and D2. 5.10. Effect of calcium:magnesium ratio The effect of altering the ratio of calcium to magnesium can be seen in Fig. 11. Runs D4 and D5 had the same initial dissolved silica concentration of 150 ppm and total hardness of 350 ppm, but the ratio of Ca:Mg in Run D4 was 1.3 whereas the ratio in Run D5 was 0.4. The effect was that run D4 exhibited a slower flux decrease initially (until about 50% recovery), then the drop was significantly more rapid than that of Run D5. As a way of comparing run

performance, Run D4 took 90 h to recover 80% of its solution, whereas run D5 took only 78 h. From the batch results and literature, we would expect the lower ratio of calcium to magnesium to lead to a faster drop in concentration of dissolved silica and a corresponding faster rise in the concentration of colloidal silica. Thus the scaling mechanism for run D5 probably favoured colloidal deposition, whereas run D4 probably exhibited more monomeric deposition. This result seems to support our theory that colloidal deposition is more favourable than monomeric deposition in RO systems, as the flux decrease, although greater initially, is less rapid as the run progresses, and less time is needed to achieve the same recovery. 5.11. Analysis of retentate and membranes After each dynamic run the membrane was allowed to air dry and then photographed. Small samples from the used membranes were analyzed using an electron microscope and EDS. The

Fig. 11. Effect of Ca:Mg ratio on flux. Percent maximum flux vs. recovery (SiO2 = 150 ppm, hardness = 350 ppm).

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retentate from Run D4 was filtered using 0.22 m Millipore filter paper, and the resultant solid was also analyzed. From the spectra it is apparent that these deposits mainly consists of silica and oxygen, with minor amounts of other elements consisting of sodium, magnesium, sulfur, chlorine, potassium, copper, calcium, and/or iron. Only the presence of chlorine, calcium and magnesium (and sodium) can be explained in terms of the salts added, the appearance of iron and copper and potassium might be attributed to impurities in the salts and outside contamination. Though iron contamination and leaching in the solution may have occurred as the solution came into contact with the pump, which is not made of stainless steel and with most of the piping in the equipment which is stainless steel, the result of 31% iron on membrane from Run D3 is very surprising and inexplicable.

6. Conclusions and recommendations Increasing the initial concentration of silica in the dynamic runs was found initially to cause a greater drop in flux; however, the flux decrease as the run progressed was found to be inversely related to the initial concentration of silica. The run with the lowest initial silica concentration of 50 ppm suffered the greatest flux decline after 60% recovery, dropping to almost half the initial flux. This means that the current convention of keeping silica concentration in RO feed solutions low to minimize fouling may not be effective in avoiding flux decrease and increased run times. Surprisingly, operating RO systems with higher

initial silica concentrations appears to be more favourable. The results indicate this is due to the increased polymerization to colloidal silica that occurs at the higher dissolved silica concentrations, which leads to a more porous colloidal deposit on the membrane. The monomeric deposit, which occurs at lower dissolved silica concentrations, may be less permeable, hence resulting in a more significant flux decline. More dynamic tests at low silica concentrations should be carried out to confirm the effects of decreased RO performance at low concentrations of dissolved silica. Calcium and magnesium salts were found to catalyze the polymerization reaction of dissolved silica, with higher concentrations of total hardness leading to a faster drop in dissolved silica in solution. In batch runs, magnesium was found to affect silica concentrations more than calcium, as the runs with a given hardness and lower ratios of calcium to magnesium exhibited the faster decline in dissolved silica. In dynamic runs, having a higher proportion of magnesium to calcium was found to result in a higher flux decline initially, but a slower flux decline as the run progressed. These results support the theory that colloidal silica scale on the membrane is more porous than monomeric silica scale. Again, more runs should be performed to confirm this theory. The EDS analysis of the precipitate from the batch tests did not contain Ca or Mg, indicating that these cations were only catalyzing the polymerization. However, the analysis of deposits on the membranes and those loosely remained in the retentate indicate presence of minor elements such as Mg, Ca, Cl and Fe. Iron

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R. Sheikholeslami, S. Tan / Desalination 126 (1999) 267280 [7] M. Henley, Ultrapure Water, 9(9) (1992) 13. [8] A. Marsawa, D. Meyerstein, F. Daltrophe and O. Kedem, Desalination, 113 (1997) 73. [9] G. Okamoto, T. Okura and K. Goto, Geochim. Cosmochim Acta, 12 (1957) 123. [10] W.L. Marshall and J.M. Warakomski, Geochim. Cosmochim. Acta, 44 (1980) 915. [11] C.-T.A. Chen and W.L. Marshall, Geochim. Cosmochim. Acta, 46 (1982) 279. [12] S.H. Chan, H. Rau, C. Debellis and K.F. Neusen, J. Heat Transfer, 110(3) (1988) 841. [13] S.D.N. Freeman and R.J. Majerle, Desalination, 103 (1995) 113. [14] R. Sheikholeslami, R. Yeung, T. Koo and P.K.R. Yadem, Chemeca 99. [15] H.P. Rothbaum and A.G. Rohde, J. Colloid Interface Sci., 71(3) (1979) 533.

can be leached out of pipings but why Ca, Mg and Cl are present in dynamic runs but not detectable in batch runs is inexplicable. The precipitates from batch tests were white while those of dynamic tests were yellowish, indicating the presence of impurities to a different extent (i.e., yellow to light brown). Further analysis of used membranes would be useful to determine if this is a major factor affecting the flux profile, as it was noticed that some membranes (particularly D1 and D3) were quite brown, suggesting the presence of iron oxides. Acknowledgements The support of the Middle East Desalination Research Centre (MEDRC) is gratefully acknowledged. References
[1] P.K.R. Yadem and R. Sheikholeslami, Chemeca 98. [2] S. Sjoberg, J. Non-Crystalline Solids, 196 (1996) 51. [3] K.B. Krauskoph, Geochim. Cosmochim. Acta, 10 (1956) 1. [4] G.B. Alexander, W.M. Heston and R.K. Iler, J. Phys. Chem., 58 (1954) 453. [5] R.K. Iler, The Chemistry of Silica, Wiley, New York, 1979. [6] L.F. Comb, Ultrapure Water, 13(1) (1996) 41.