Mitigation of Silica Scaling by Closed-Circuit Reverse Osmosis

Abstract

Reverse osmosis (RO) is considered the most reliable and cost-effective membrane desalination technologyworldwide. However, it suffers significant performance limitations due to mainly inorganic foulinggenerated in the highly concentrated brine. Especially, scaling caused by silica and silicates depositionsresults in irreversible damages with considerable economic implications. Recently, a different ROconfiguration, termed as closed-circuit reverse osmosis (CCRO), has been claimed to exhibit substantialbenefits over conventional RO in terms of both energy savings as well as higher scaling resilience.CCRO is operated in batches, during which the generated brine is continuously recycled inside theclosed loop until a desired recovery has been accomplished, after which the brine is released and replacedby fresh feed. Regarding CCRO scaling resistance superiority, an experimental-based proofis missing from the relevant literature. The current thesis was realized in collaboration with LenntechB.V., aiming at investigating the intrinsic propensity of CCRO to withstand and delay silica scaling. Tothat end, a campaign of filtration tests was carried out by means of a single-module CCRO pilot setup,during which two scaling indicators were periodically monitored. The used indicators were the masstransfer coefficient (MTC) and the applied feed pressure (Pfeed). Prior to the filtration trials, preliminarybatch tests, of 4-hour duration each, were carried out in order to simulate and more thoroughly examinethe circulated brine conditions. Various synthetic brines were prepared and silica polymerization wasmonitored. The effects of silica supersaturation level, pH and hardness ions were investigated. Of greatimportance was whether silica existed in its monomeric or polymeric form, since this greatly impactsthe scaling occurrence probability. Batch tests results revealed that at high pH conditions (pH>10)monomeric silica concentration remained unchanged in pure silica solutions (even at high supersaturationlevels), owing to the great silica solubility level. Nevertheless, when Mg2+ and/or Ca2+ werepresent in the solution, the quantity of silicic acid rapidly reduced. This was the result of the instantaneousformation of metal-silicate precipitates. Batch tests at pH 7 were also performed. In that case,monomeric silica concentration in pure silica solutions remained constant up to initial concentrations ofabout 450 mg/L SiO2 for the examined 4-hour duration. However, at higher SiO2 concentrations, suchas at 750 mg/L, rapid polymerization occurred. When hardness cations were included in the neutral pHsolutions, they showed an accelerating effect on silica polymerization process, but they did not reactwith either monomeric or polymeric silica. This effect relates to the suppression of the silica colloidsdiffuse double layer by the hardness cations, which subsequently facilitates colloids agglomeration.Regarding the CCRO filtration tests, they were conducted in sequences with duration of 20 or 40 min,which in its turn determined the achieved sequence recovery. For most of the carried out sequencesthe initial feed composition was: 120 mg/L SiO2 and 24 mg/L Mg2+. Only the final 5 out of the total40 sequences were realized in the absence of magnesium in the feed solution. All the filtration runswere performed at pH 7, at ambient temperature and at constant flux 15 L/m2h. The outcome was ascaling-free desalination process for a total cumulative operational period of approximately 11 hours,during which recoveries as high as 90.9% were reached, whereas severe scaling took place only afterabout 14 hours of total operation. The obtained results were contrasted with filtration tests results ofconventional RO received from literature resources and in that way the higher efficiency of CCRO towithstand and delay silica scaling was proved. Additionally, through silica mass balance calculations itwas shown that during all filtration tests significant silica polymerization took place. Also, cations analysisbe means of IC excluded the participation of Mg2+ ions in the formed scale layer. It was concludedthat the scale development was the result of an initial attachment of silica colloids to the membranesurface followed by monomeric units adsorption onto them. Finally, a simple customized method forthe prediction of silica scaling potential in CCRO operations based on batch tests was proposed.