Desalination 238 (2009) 109116

Behaviors of dissolved organic matter in membrane desalination

Sangho Leea*, Jun-Seok Choia, Chung-Hak Leeb
a

Department of Environmental Research, Korea Institute of Construction Technology, Gyeonggi-do, Korea Tel. +82 (31) 910-0320; Fax +82(31) 910-0291; email: s-lee@kict.re.kr b School of Chemical Engineering, Seoul National University, Seoul, Korea Received 15 November 2007; Accepted 31 January 2008

Abstract The significance of dissolved organic matter (DOMs) in membrane fouling has been also increasingly noted in desalination plants using reverse osmosis (RO) and nanofiltration (NF). Nevertheless, little information is available on the interactions between DOM and other foulants such as inorganic scale. This study sought to gain a fundamental understanding of the complicated fouling phenomenon by scale formation in the presence of DOM. Experimental studies with model solutions were conducted in a small batch filtration device. Humic acid and calcium sulfate were used as model DOM and scale-forming salts. The fouling of RO/NF membranes by scale formation was observed to be greatly affected by DOM and there appeared to be a strong link between the rate of fouling and DOM concentrations. Although DOM itself is a foulant to membranes, it acted like an antiscalant to lessen fouling due to scale formation. It is likely that the adsorption of DOM on crystal-growing sites on membranes as well as crystal surfaces diminished the sites for crystal growth and subsequently retarded the rate of crystallization. Image analysis of crystal particles grown in the presence of DOM also supported this hypothesis. Keywords: Desalination; Reverse osmosis; Nanofiltration; Humic acid; Scale formation; Calcium sulfate; Membrane fouling

1. Introduction Reverse osmosis (RO) and nanofiltration (NF) membranes are now considered a promising technology for desalination, water purification, and wastewater treatment. RO/NF membrane
*Corresponding author.

technology offers many advantages such as high removal of target pollutants, ease of operation, and a small footprint. Nevertheless, the main limitation to the use of RO/NF membranes is membrane fouling that is expensive for design and operation of membrane plants.

Presented at the First International Workshop between the Center for the Seawater Desalination Plant and the European Desalination Society, November 1516, 2007, GIST, Gwangju, Korea. 0011-9164/09/$ See front matter 2008 Elsevier B.V. All rights reserved. doi:10.1016/j.desal.2008.01.041

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The significance of dissolved organic matters (DOMs) in RO/NF membrane fouling has been also increasingly noted in recent studies. Among the total DOMs in seawater 8090% is represented by the humic materials or substances, which have been regarded to cause fouling by organic adsorption or biofilm growth. To date, significant efforts have been dedicated to investigating the mechanisms and control methods for RO/NF fouling by DOMs [13]. Scale formation is another serious problem in RO/NF membrane systems. Scale formation has been recognized as a serious constraint in designing and operating membrane systems because scale formation not only lowers the flux and rejection of permeate but also shortens the membrane life. Many studies have attempted to investigate scale formation mechanisms [46] and reduce scale formation in membrane systems [5 12]. However, few works have been done to reveal the interactions between DOMs and inorganic salts that can cause scale formation in membrane systems. Since DOMs are ubiquitous in surface water and seawater, they can act as background organics to interfere with kinetics of scale formation. This study aims at a fundamental understanding of the complicated fouling phenomenon by scale formation in the presence of DOMs. Experimental studies with model solutions were conducted in a small batch filtration device to study the effect of DOMs on membrane fouling and scale formation rate. The mechanism for the interaction was suggested based on the filtration data and image analysis results.

Fig. 1. Schematic diagram of experimental set-up: stirred cell RO device.

2. Experimental The test system shown in Fig. 1 was used to measure filtration characteristics for NF membranes. The stirred cell was made of stainless steel to improve chemical stability. The diameter of the stirred cell was 54 mm and the working

volume was 100 ml. A magnetic stirrer (Stirrer assembly 8200, Millipore, USA) was positioned just above the membrane. The length of the stirring bar was 52 mm. The working pressure was controlled by a high pressure nitrogen cylinder and by a gas pressure regulator. The stirring speed was controlled by a magnetic stirrer plate. The temperature of the feed solution was adjusted to 2025EC and the effect of temperature on viscosity and density was corrected. Since the experiment was performed in a short time (normally less than 30 min), the variations of the temperature during an experiment were smaller than 1EC. A commercially available RO membrane (Filmtec, USA) of the thin film composite (TFC) type was used for the filtration tests. The pure water flux was measured to be 6070 L/m2-h at 1000 kPa and the ion rejection was over 98%. All experiments were performed using new membranes. Prior to the filtration all membranes were

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thoroughly cleaned to remove remaining organic and inorganic materials by successively filtering 0.1 M sodium hydroxide and 0.1 M hydrochloric acid solution at 10 bar. Finally the membrane was cleaned with ultrapure water. The permeate flux was expressed in terms of the concentration factor (VCF). The concentration factor, defined as a ratio of the feed volume to concentrate volume, indicates the extent of concentration:

VCF

Vf Vc

Vp Vc

(1)

determined by ion chromatography (Dionex 4000I, USA) and by a conductivity meter (Model 170, Orion, USA). The turbidity measurement for the feed and retentate was made on a turbidimeter (HF, DRT-100B, USA). The digital image analysis programs were used to obtain information concerning CaSO4 crystal particle formed during RO filtration. An optical microscope (Eclipse E 600W, Nikon) was used to obtain images of CaSO4 particles. A commercial program (Image-Pro Plus, Media Cybernetics, USA) was used to analyze the shape of CaSO4 particles.

where Vf, Vc, and Vp are defined as the volume of feed, concentrate, and permeate, respectively. VCF is proportional to permeate recovery. Humic acid (Aldrich, USA) was obtained from Aldrich Chemical and used as a model DOM. Water-borne humic and fulvic acids (Swannee River, USA) obtained from the International Humic Substance Society were also used for comparison. In each compound, the powders were dissolved in water without further purification and the concentration of 35 ppm as TOC stock solutions were made. The stock solutions were kept in a refrigeratior at 4EC before use. Hydrochloric acid and sodium hydroxide (Ajax Chemical) were used to adjust pH of the solution. The concentration of DOMs was measured using a total organic carbon analyzer (DC-180, Rosemount, USA), which is based on a persulfateultraviolet light oxidation method 13. To determine the molecular weight of DOMs, the feed solution was divided into the four fractions using three cellulose acetate hydrophilic ultrafiltration membranes (Amicon, USA) with different molecular weight cut-offs: 30,000, 10,000 and 5,000 Dalton. A saturated solution of CaSO4 (2000 mg/L) was used as a model scale-forming salt. Prior to filtration test, the solution was prefiltered using a 0.45 m filter. The concentrations of CaSO4 were

3. Results and discussion 3.1. Membrane fouling by humic acid Fig. 2 shows the flux in batch cell filtration of a feed solution containing Aldrich humic acid as a function of VCF. The transmembrane pressure was 600 kPa, and the stirring speed was 170 rpm. As expected, the rate of flux decline increases with increasing humic acid concentration in feed solution. In all cases, a significant loss in flux was observed at the beginning of filtration. Based on this result, a linear relationship between flux decline ratio and humic acid concentration was obtained:

FD 1

Jf Jw

0.0519chumic

(r2 = 0.985) (2)

where FD is the flux decline ratio, Jw is the pure water flux (L/m2-h), Jf is the final flux after RO filtration (L/m2-h), and chumic is the humic acid concentration in feed solution (mg/L). This relationship suggests that the flux decline ratio is almost proportional to the humic acid concentration. Membrane fouling by humic acid is closely related with divalent ion concentrations. The adsorption of humic acid onto the membrane

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Fig. 2. Effect of humic acid on permeate flux (operating conditions: P = 600 kPa; = 170 rpm; feed solution, humic acid in DI water).

Fig. 3. Effect of background ions on permeate flux decline by humic acid (operating conditions: P = 600 kPa; = 170 rpm; feed solution, humic acid in DI water).

Fig. 4. Effect of humic acid on permeate flux decline due to scale formation (operating conditions: P = 600 kPa; = 170 rpm; feed solution, saturated CaSO4 solution (2000 mg/L) with humic acid).

Fig. 5. Effect of DOM characteristics on permeate flux decline due to scale formation (Operating conditions: P = 600 kPa; = 170 rpm; feed solution, saturated CaSO4 solution (2000 mg/L) with humic acid)

increases with increasing calcium ion concentration. Thus, the effect of calcium ion on permeate flux decline by humic acid was examined as shown in Fig. 3. Addition of calcium ion to humic acid solution increases the rate of flux decline at early stage. Nevertheless, the final flux values were similar for both cases. This result indicates that the calcium ion affects the rate of flux decline but did not change the steady-state flux.

3.2. Effect of humic acid on membrane fouling by scale formation Fig. 4 shows the flux in batch cell filtration of saturated CaSO4 solutions with various humic acid concentrations. It is clear that permeate flux loss by CaSO4 scale formation was much more serious than that by humic acid adsorption/ deposition. For instance, without the addition of humic acid, the flux continuously decreased with

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(a)

(b)

Fig. 6. Effect of pH on permeate flux decline due to scale formation (operating conditions: P = 600 kPa; = 170 rpm; feed solution, saturated CaSO4 solution (2000 mg/L) with humic acid). (a) Flux decline due to scale formation without humic acid. (b) Flux decline due to scale formation in the presence of humic acid.

VCF and became lower than 1 L/m2-h at VCF = 5.5. This is attributed to the characteristics of CaSO4 crystals formed on the membrane surface. Since these crystals have very low porosity (less than 0.1% [14]), they block the membrane surface, leading to a decrease in effective membrane area. At high VCF, the membrane surface is completely blocked and the flux became almost zero. As shown in Fig. 4, the rate of flux decline significantly decreases with increasing humic acid concentration in feed solution. For instance, with the addition of only 0.5 mg/L of humic acid to the feed solution, the flux at VCF = 4 was two times higher than that without humic acid. This result indicates that humic acid acts as a strong antiscaling agent for CaSO4 scale formation. Fig. 5 compares the scale inhibition effect of Aldrich humic acid with SW humic and fulvic acids. All these humic substances showed the antiscaling effects. The antiscaling effect seems to be relevant to the characteristics of humic substances. The order of the hydrophobicity was fulvic acid < Aldrich humic acid < SW humic acid, which is roughly coincident with the trend of scale inhibition effect.

In general, the solubility and crystallization rate of CaSO4 are independent of pH. Thus, the rates of flux decline by CaSO4 scale formation were similar at different pH as shown in Fig. 6(a). However, the rate of flux decline can be changed with pH in the presence of humic acid [Fig. 6(b)]. This is because pH affects the characteristics of humic acid, thereby changing the antiscaling effect. This will be further discussed later on. 3.3. Mechanism of antiscaling effect by humic acid The mechanism of antiscaling by humic acid may be (1) complexation of calcium in solution [15] or (2) covering the active sites of crystal nucleation and growth [16]. First, the possibility of calcium complexation was theoretically examined. This mechanism proposes that humic acid complexing free-calcium ions reduces the saturation state of the solution and consequently decreases the reaction rate. If this mechanism is dominant, substantial amount of calcium ions should be bound to humic acid. The calcium binding capacity of humic acid has been reported to be below 2 meq/g humic acid 17. The amount

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(a)

(b)

Fig. 7. Effect of HA on the shape of CaSO4 crystals (magnification: 200 times). (a) CaSO4 crystals formed without HA. (b) CaSO4 crystals formed with HA (2 mg/L).

of humic acid for batch filtration test was 0.2 mg at chumic = 2 mg/L while the amount of calcium ion was 58.9 mg. Assuming that the calcium binding capacity is 2 meq/g humic acid, the amount of calcium that can be bound to humic acid is less than 0.01 mg. Therefore, it is likely that the calcium complexation has little effect on scale formation in our case. The pH dependency of the antiscaling effect also suggests that complexation is not an important mechanism. As shown in Fig. 5, the inhibition of scale formation by humic acid is stronger at low pH than that at high pH. If the mechanism of antiscaling is the calcium complexation by acid sites on the humic acid molecule, the rate of scale formation should be lower at high pH. The antiscaling mechanism other than the calcium complexation may be the coverage of active sites of crystal surface. This mechanism proposes that humic acid is adsorbed onto the active sites to inhibit nucleation and growth of crystals. An evidence of this mechanism is morphological changes because humic acid adsorp-

tion alters the shape of crystals. Fig. 7 compares the crystal particles grown with and without added humic acid. Needle-like crystals were obtained in the absence of humic acid while plate-like crystals were grown in the presence of humic acid. This result suggests that the coverage of active sites may be a dominant mechanism for antiscaling effect. Fig. 8 shows the distribution of shape factor for crystal particles with and without added humic acid, which was obtained from image analysis of microscopic photographs. As the concentration of humic acid increases, the shape factor increases. For instance, the average shape factor of crystal particles without added humic acid was 0.68 and it increased up to 0.8 at chumic = 10 mg/L. This also supports our conclusion that the coverage of active sites by humic acid adsorption is important. Fig. 9 compares the molecular weight distributions for humic acid in DI water and saturated CaSO4 solution. Because of high calcium concentration, the molecular weight is changed in the

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Fig. 8. Analysis of shape factor for CaSO4 crystals formed under different humic acid concentrations (operating conditions: P = 600 kPa; = 170 rpm; feed solution, saturated CaSO4 solution (2000 mg/L) with humic acid).

Fig. 10. Effect of humic acid and antiscalant on permeate flux decline due to scale formation (operating conditions: P = 600 kPa; = 170 rpm; feed solution, saturated CaSO4 solution (2000 mg/L) with humic acid and/or SHMP).

Fig. 9. Distribution of molecular weights for humic acids in DI water and saturated CaSO4 solution.

saturated CaSO4 solution. The interaction between calcium ions and humic acid is likely to increase the adsorption of humic acid onto the crystal surfaces, thereby affecting the rate of scale formation. 3.4. Interaction between humic acid and antiscalant In most RO/NF membrane plants, antiscaling chemicals are widely used to prevent scale formation on membrane surface. Thus, it is important to

examine the role of humic acid in the presence of antiscalants. Fig. 10 compares the effect of humic acid and sodium hexametaphosphate (a typical antiscalant) on scale formation rate. Similar effects of scale inhibition were obtained for chumic = 2 mg/L and cSHMP = 10 mg/L. When both humic acid and sodium hexametaphosphate were added to the feed solution, the scale formation rate was slightly lower and the flux was somewhat higher (less than 5 L/m2-h at VCF = 10). However, the inhibition effect of the mixture was smaller than expected. Further studies are required to elucidate the interactions between humic acid and antiscalants.

5. Conclusions In this work, the effect of humic acid on scale formation in RO membrane system was investigated using a laboratory scale filtration device and synthetic feed solution. The following conclusions can be drawn from this work: C Fouling of RO/NF membrane by scale formation significantly was affected by humic acid. As the concentration of humic acid

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S. Lee et al. / Desalination 238 (2009) 109116 procedure schedules in reverse-osmosis systems operation. Desalination, 83 (1991) 77118. S. Lee, J. Kim and C.H. Lee, Analysis of CaSO4 scale formation mechanism in various nanofiltration modules. J. Membr. Sci., 163 (1999) 6374. S. Lee and C.H. Lee, Effect of operating conditions on CaSO4 scale formation mechanism in nanofiltration for water softening. Water Res., 34 (2000) 38543866. G. Belfort, Synthetic Membrane Processes Fundamentals and Water Applications, Academic Press, New York, 1984. D.L. Kronmiller, What every reverse osmosis water system manager should know. Desalination, 98 (1984) 401411. B.W. Watson, High recovery reverse osmosis. Desalination, 78 (1990) 9197. R. Rautenbach and R. Habbe, Seeding technique for zero-discharge processes, adaption to electodialysis. Desalination, 84 (1991) 153161. W. Pulles, G. Juby and R. Busby, Development of the slurry precipitation and recycle reverse osmosis (SPARRO) technology for desalinating scaling mine waters. Water Sci. Tech., 25 (1992) 177192. I. Bremere, M.D. Kennedy, A. Johnson, R.V. Emmerik, G.-J. Witkamp and J.C. Schippers, Increasing conversion in membrane filtration systems uisng a desupersaturation unit to prevent scaling. Desalination, 119 (1998) 199204. APHA, AWWA, and WEF, Standard Methods for the Examination of Water and Wastewater, 21st ed., APHA, Washington, DC, 2005. J. Gilron and D. Hasson, Calcium sulfate fouling of reverse osmosis membranes: Flux decline mechanism. Chem. Eng. Sci., 42 (1987) 23512360. Y.A.L. Gouelleca and M. Elimelech, Calcium sulfate (gypsum) scaling in nanofiltration of agricultural drainage water. J. Membr. Sci., 205 (2002) 279291. P. Zuddas, K. Pachana and D. Faivre, The influence of dissolved humic acids on the kinetics of calcite precipitation from seawater solutions. Chem. Geol., 201 (2003) 91101. S.H. Yoon, C.H. Lee, K.J. Kim, and A.G. Fane, Effect of calcium ion on the fouling of nanofilter by humic acid in drinking water production. Water Res., 32 (1998) 21802186.

increases, the scale formation was retarded and higher flux was obtained. Not only humic acid but also fulvic acid exhibited the inhibition effect. C The dominant mechanism of scale inhibition by humic acid was not complexation of calcium but coverage of active sites on crystal particles by humic acid adsorption. C The image analysis results indicated that the morphology of crystals grown in the presence of humic acid was significantly changed. Plate-like crystal particles were obtained at high concentration of humic acid.

[5]

[6]

[7]

[8]

[9]

Acknowledgements This research was supported by a grant (code# C106A152000106A085700220) from the Plant Technology Advancement Program funded by the Ministry of Construction and Transportation of the Korean Government and a grant entitled, Development and application of Me-TsPc nanocatalysts for detoxification of endocrine disrupting chemicals and pharmaceuticals, funded by the Korean Ministry of Environment.

[10]

[11]

[12]

[13]

References
[1] S. Lee, S. Kim, J. Cho and E.M.V. Hoek, Natural organic matter fouling due to foulantmembrane physicochemical interactions. Desalination, 202 (2007) 377384. [2] N. Park, B. Kwon, S.-D. Kim and J. Cho, Characterizations of the colloidal and microbial organic matters with respect to membrane foulants. J. Membr. Sci., 275 (2006) 2936. [3] J. Cho, G. Amy and J. Pellegrino, Membrane filtration of natural organic matter: comparison of flux decline, NOM rejection, and foulants during filtration with three UF membranes. Desalination, 127 (2000) 283298. [4] A.G. Pervov, Scale formation prognosis and cleaning [14]

[15]

[16]

[17]