Membrane Separation & Desalination

December 1

2013
Desalination Using Reverse Osmosis

Sea Water all around the world is having a High salt content in it. This Salt is removed From the Water using the Desalination Process using Different Techniques, reverse Osmosis is Discussed Here with factors affecting it.

Submitted To: Dr. Mustafa Nasser

Submitted By: Adeem Ghaffar Rana g201206480

King Fahd university of Petroleum and Minerals

Contents
1. Water and Its Importance ..................................................................................................................... 4 Facts ........................................................................................................... Error! Bookmark not defined. Why are we discussing desalination? ....................................................................................................... 5 What is the definition of water stress?..................................................................................................... 5 2. Desalination .......................................................................................................................................... 5 Stages of the desalination process ........................................................................................................... 6 What are the benefits of a desalinated water supply?............................................................................. 7 Why are minerals added to the pure water?............................................. Error! Bookmark not defined. Where does the left over salt go?............................................................................................................. 7 Application of desalination processes ...................................................................................................... 8 3. Description of Desalination Plant ......................................................................................................... 9 Source water intake facilities .................................................................................................................... 9 General description............................................................................................................................... 9 . Pretreatment processes ........................................................................................................................ 10 General description............................................................................................................................. 10 Post-treatment.................................................................................................................................... 11 4. Reverse osmosis .................................................................................................................................. 12 Characteristics of Reverse Osmosis Process ........................................................................................... 14 5. Terms and Equations of Reverse Osmosis .......................................................................................... 15 OSMOTIC PRESSURE ............................................................................................................................... 15 WATER TRANSPORT ................................................................................................................................ 15 SALT TRANSPORT .................................................................................................................................... 15 SALT PASSAGE ......................................................................................................................................... 16 SALT REJECTION ...................................................................................................................................... 16 PERMEATE RECOVERY RATE (CONVERSION) .......................................................................................... 16 SALINE CONCENTRATE ............................................................................................................................ 16 6. Factors Affecting RO Membrane Performance................................................................................... 17 Definitions ............................................................................................................................................... 17 Recovery...................................................................................................................................... 17 Rejection ..................................................................................................................................... 17 Passage........................................................................................................................................ 17 Permeate..................................................................................................................................... 17

Flow ............................................................................................................................................. 17 Flux .............................................................................................................................................. 17 Dilute solution: ............................................................................................................................ 17 Concentrated solution: ............................................................................................................... 17

Effect of pressure .................................................................................................................................... 18 Effect of temperature ............................................................................................................................. 19 Effect of salt concentration..................................................................................................................... 20 Effect of recovery .................................................................................................................................... 21 Effect of pH ............................................................................................................................................. 22 7. 8. 9. Mass Transfer for reverse osmosis ..................................................................................................... 23 Flux ...................................................................................................................................................... 24 Critical Flux .......................................................................................................................................... 26 Factors effecting the critical flux............................................................................................................. 27 Ionic Strength ...................................................................................................................................... 27 PH ........................................................................................................................................................ 27 Zeta potential ...................................................................................................................................... 28 Particle concentration and size, and nature and concentration of organic materials ........................... 28 Membrane surface characteristics ..................................................................................................... 28 Hydraulic conditions ........................................................................................................................... 28 10. Membrane fouling .......................................................................................................................... 30

Foulants................................................................................................................................................... 32 Chemical foulants................................................................................................................................ 32 Particulate fouling ............................................................................................................................... 32 Biofouling ............................................................................................................................................ 33 Organic foulants .................................................................................................................................. 34 Key parameters ....................................................................................................................................... 34 11. What is red tide? ............................................................................................................................. 35

Effect of Red Tide .................................................................................................................................... 37 Controls Parameters to be Taken ........................................................................................................... 37

Figure 1

Why are we discussing desalination?

97.5% of all water on Earth is salt water, and of the remaining 2.5%, more than two thirds is inaccessible ice and permanent snow cover. Water is acutely, unevenly distributed and large parts of the world are already experiencing either water stress or water scarcity. According to the UN, by 2030 under a business as usual scenario, water demand will exceed supply by 40%, with up to two thirds of the global population inhabiting areas that are officially defined as water stressed.[5]

1. Desalination
Production of drinking water from seawater is technologically achievable for several decades. Until now, however, application of seawater desalination ("desal") on a large scale is primarily limited to arid regions of the world that have a cheap supply of energy, such as in the Middle East. Saudi Arabia uses this technology and produces 30% of the world's output of desalinated seawater. Desalination is a technology that is used to separates dissolved salts and other minerals from seawater or other salty water. It provides clean drinking water. The Desalination Plant uses reverse osmosis process, which removes the salts and other minerals from the water as it passes through the layers of extremely thin membranes under high pressure. The pure water is then further mixed with other drinking water supplies and sends directly towards the users. [6]

In this process, Fresh water, which has a very small quantity of salt, is passed through the membrane. After passing through the membrane, it leaves a concentrated salt stream which is then discharged back to the ocean. Approximately, 40 to 45 liters of drinking water is produced from 100 liters of raw seawater. The advantage of the desalination process is that the raw water source is independent of rainfall, so we are capable of providing water throughout the year and produces drinking water. [7]

Figure 2

Figure 3

Where does the left over salt go?

The unused seawater (about 55%), containing dissolved salts and minerals, is returned to the ocean via an outlet tunnel, and dispersed 1. 2 kilometers out to sea in water approximately 20 meters deep. The salty concentrated water, called brine, is released through a one meter diameter pipeline containing eight diffuser heads. The brine then mixes with the surrounding seawater and

is dispersed by strong tidal currents in the ocean. The increased salinity level does not cause stress to marine life. In fact the outlet structure has created an artificial reef which is a new habitat for sea creatures. [6]

Application of desalination processes

The proper choice of a desalination technology will depend on the feed water quality, which is mainly characterized by its total dissolved solids content (TDS value). Different feed water qualities and their corresponding salt content are given in Table.

Figure 4

2. Description of Desalination Plant

Source water intake facilities
General description

Figure 5

Pretreatment processes

General description The pre-treatment process improves the quality of the raw feedwater to ensure consistent performance and the desired output volume of the desalination process. Almost all desalination processes require pre-treatment of some kind. The level and type of pretreatment required depends on the source and quality of the feedwater and the chosen desalination technology. For source water of poor quality, pretreatment can be a very significant portion of the overall plant infrastructure. The potential influences on public health and the environment from the pretreatment process operations are associated with the chemical conditioning (addition of biocides, coagulants, flocculants, antiscalants, etc.) of the source water prior to pre-treatment and with the disposal of the residuals formed during the pre-treatment process. Pretreatment, when required, normally involves a form of filtration and other physical-chemical processes whose primary purpose is to remove the suspended solids (particles, silt, organics, algae, etc.) and oil and grease contained in the source water when membrane desalination is used for salt separation. For thermal desalination processes it protects downstream piping and equipment from corrosion and from formation of excessive scale of hard deposits on their surface (scaling). Biofouling is most often mitigated using an oxidant although non-oxidizing biocides are also utilized. Potential public health effects associated with pre-treatment are typically associated with the by-products

formed during the chemical conditioning process and their potential propagation into the finished fresh water. Post-treatment Product water from desalination plants is characteristically low in mineral content, alkalinity, and pH. Therefore, desalinated water must be conditioned (post-treated) prior to final distribution and use. Typically, post-treatment of product water includes one or more of the following processes: Stabilization by addition of carbonate alkalinity; Corrosion inhibition; Re-mineralization by blending with high mineral content water; Disinfection; Water quality polishing for enhanced removal of specific compounds (i.e., boron, silica, NDMA, etc.). Post-treatment of permeate produced by the desalination system is needed for two key reasons: to protect public health (by disinfection and mineral addition) and to safeguard the integrity of the water distribution system. In some cases the same post-treatment process and conditioning chemicals allow achievement of both goals. For example, addition of calcium and magnesium salts to permeate provides not only essential minerals but also stabilizes the product water and thereby protects the water distribution system against corrosion. Usually, the ultimate application dosage of any multi-purpose chemical is determined by the minimum dosage needed to achieve all purposes for which the conditioning chemical is added. If the use of the same chemical is not found to be cost effective to achieve both the public health and the corrosion protection goals, than a combination of chemicals that yield the lowest overall cost of water production may be used to meet all post-treatment goals. For example, typically calcium hypochlorite addition for disinfection meets the public health goals for pathogen inactivation and also adds some calcium. Therefore, calcium hypochlorite addition is typically combined with the feed of corrosion inhibitor to the desalination plant permeate, thereby achieving both public health and corrosion protection goals at a minimal life-cycle cost.

3. Reverse osmosis

Figure 6

In seawater desalination it commonly ranges from 55 to 68 bars [13, 14]. Operating pressures for the purification of brackish water are lower due to the lower osmotic pressure caused by lower feed water salinity. A flow sheet of a reverse osmosis based desalination plant is shown in Fig. The process includes the following stages: Water abstraction Pre-treatment Pumping system Membrane separation unit Energy recovery system

Post-treatment Control-system

Figure 7

The abstraction (1) of feed water can be realized either through coast- and beach wells or through open seawater intake systems. Coast- and beach wells provide better quality water with less turbidity, algae and total dissolved solids than open seawater intakes [15,16], but require more space. In brackish water desalination, wells are used to abstract feed water. Pre-treatment (2) includes all activities to adjust the intake water in constitution and pH-value. Particulate matter is removed from the feed-water and chemicals are added to prevent scaling and fouling. The pumping system (3) is required to overcome height differences within the distribution chain and to apply the necessary pressure to the feed. The membrane is capable of separating salt from water with a rejection of 9899.5%, depending on the membranes in use [15]. The energy recovery system is responsible for the transfer of potential energy from the concentrate to the feed. Current energy recovery systems such as work exchangers operate with efficiencies of up to 96% [13]. In post-treatment (6) permeate is re-mineralised, re-hardened, disinfected by chlorination and adjusted to drinking water standards. A control system maintains a continuous and reliable production. Fig. shows a simplified reverse osmosis scheme with energy recovery system and open seawater intake

Figure 8

Characteristics of Reverse Osmosis Process

Figure 9

4. Terms and Equations of Reverse Osmosis

There is a set of terms and equations used to define the parameters governingtransport across a membrane. This paper presents the concepts of Reverse Osmosis and the equations used to describe them. [18]

OSMOTIC PRESSURE
The osmotic pressure, Posm, of a solution can be determined experimentally by measuring the concentration of dissolved salts in solution:

W molal concentration of all constituents in a solution. An approximation for Posm may be made by assuming that 1000 ppm of Total Dissolved Solids (TDS) equals about 11 psi (0.76 bar) of osmotic pressure. [18]

WATER TRANSPORT
The rate of water passage through a semi permeable membrane is defined in Equation 2. S/d (2)

membrane, Kw is the membrane permeability coefficient for water, S is the membrane area, and d is the membrane thickness. This equation is often simplified to: Qw = A * (NDP) (3) Where A represents a unique constant for each membrane material type, and NDP is the net driving pressure or net driving force for the mass transfer of water across the membrane. [18]

SALT TRANSPORT
The rate of salt flow through the membrane is defined by Equation 4:

where Qs is the flow rate of salt through the membrane, Ks is the membrane permeability coefficient for salt, delC is the salt concentration differential across the membrane, S is the membrane area, and d is the membrane thickness. This equation is often simplified to:

force for the mass transfer of salts. [18]

SALT PASSAGE
Salt passage is defined as the ratio of concentration of salt on the permeate side of the membrane relative to the average feed concentration. Mathematically, it is expressed in Eq. 7: SP = 100% * (Cp/Cfm) (7) Where SP is the salt passage (in %), Cp is the salt concentration in the permeate, and Cfm is the mean salt concentration in feed stream. [18]

SALT REJECTION
Salt rejection is the opposite of salt passage, and is defined by Equation 8. SR = 100% - SP (8) Where SR is the salt rejection (in %), and SP is the salt passage [18]

PERMEATE RECOVERY RATE (CONVERSION)

Permeate recovery is another important parameter in the design and operation of RO systems. Recovery or conversion rate of feed water to product (permeate) is defined by Equation 9. R = 100% * (Qp/Qf) (9) where R is recovery rate (in %), Qp is the product water flow rate, and Qf is the feed water flow rate. The recovery rate affects salt passage and product flow. As the recovery rate increases, the salt concentration on the feed-brine side of the membrane increases, which causes an increase in salt flow rate across the membrane as indicated by Equation 5. Also, a higher salt concentration in the feed-brine solution increases the osmotic pressure, reducing the NDP and consequently reducing the product water flow rate according to Equation 2. [18]

SALINE CONCENTRATE
While reverse osmosis produces fresh water, the process also creates water with a higher concentration of salts. This saline concentrate is dispersed about 1km offshore through specially designed diffusers where it is very quickly and efficiently mixed with the neighboring seawater. The proportion of saline concentrate dispersed is tiny compared to the large volume of seawater in the receiving waters of the Gulf, so the concentration of salt in the Gulf does not change. Salinity levels in the surrounding seawater are regularly monitored to ensure there are no environmental impacts on the marine environment. [18]

5. Factors Affecting RO Membrane Performance

Reverse osmosis (RO) technology can be a complicated subject, particularly without an understanding of the specific terminology that describes various aspects of RO system operation and the relationships between these operating variables. This bulletin defines some of these key terms and provides a brief overview of the factors that affect the performance of RO membranes, including pressure, temperature, feedwater salt concentration, permeate recovery, and system pH. [19]

Definitions

Recovery: the percentage of membrane system feedwater that emerges from the system as product water or "permeate". Membrane system design is based on expected feedwater quality and recovery is fixed through initial adjustment of valves on the concentrate stream. Recovery is often fixed at the highest level that maximizes permeate flow while preventing precipitation of super-saturated salts within the membrane system.

Rejection: the percentage of solids concentration removed from system feedwater by the membrane.

Passage: the opposite of "rejection", passage is the percentage of dissolved constituents (contaminants) in the feedwater allowed to pass through the membrane.

Permeate: the purified product water produced by a membrane system. Flow: Feed flow is the rate of feedwater introduced to the membrane element, usually measured in gallons per minute (gpm). Concentrate flow is the rate of flow of nonpermeated feedwater that exits the membrane element. This concentrate contains most of the dissolved constituents originally carried into the element from the feed source. It is usually measured in gallons per minute (gpm).

Flux: the rate of permeate transported per unit of membrane area, usually measured in gallons per square foot per day (gfd).

Dilute solution: purified water solution, RO system product water. Concentrated solution: brackish water solution such as RO system feedwater.

Effect of pressure
Feed water pressure affects both the water flux and salt rejection of RO membranes. Osmosis is the flow of water across a membrane from the dilute side toward the concentrated solution side. Reverse osmosis technology involves application of pressure to the feedwater stream to overcome the natural osmotic pressure. Pressure in excess of the osmotic pressure is applied to the concentrated solution and the flow of water is reversed. A portion of the feedwater (concentrated solution) is forced through the membrane to emerge as purified product water of the dilute solution side please see Figure. [19]

Figure 10

As shown in Figure water flux across the membrane increases in direct relationship to increases in feedwater pressure. Increased feedwater pressure also results in increased salt rejection but, as Figure demonstrates, the relationship is less direct than for water flux. Because RO membranes are imperfect barriers to dissolved salts in feedwater, there is always some salt passage through the membrane. As feedwater pressure is increased, this salt passage is increasingly overcome as water is pushed through the membrane at a faster rate than salt can be transported. However, there is an upper limit to the amount of salt that can be excluded via increasing feedwater pressure. As the plateau in the salt rejection curve (Figure) indicates, above a certain pressure level, salt rejection no longer increases and some salt flow remains coupled with water flowing through the membrane.

Figure 11

Effect of temperature
As Figure demonstrates, membrane productivity is very sensitive to changes in feedwater temperature. As water temperature increases, water flux increases almost linearly, due primarily to the higher diffusion rate of water through the membrane. [19]

Figure 12

Increased feedwater temperature also results in lower salt rejection or higher salt passage. This is due to a higher diffusion rate for salt through the membrane.

The ability of a membrane to tolerate elevated temperatures increases operating latitude and is also important during cleaning operations because it permits use of stronger, faster cleaning processes. This is illustrated by the comparison of the pH and temperature ranges of thin-film composite (TF) membrane and a cellulose acetate (CA) membrane in Figure.

Figure 13

Effect of salt concentration

Osmotic pressure is a function of the type and concentration of salts or organics contained in feedwater. As salt concentration increases, so does osmotic pressure. The amount of feedwater driving pressure necessary to reverse the natural direction of osmotic flow is, therefore, largely determined by the level of salts in the feedwater. Figure demonstrates that, if feed pressure remains constant, higher salt concentration results in lower membrane water flux. The increasing osmotic pressure offsets the feedwater driving pressure. Also illustrated in Figure is the increase in salt passage through the membrane (decrease in rejection) as the water flux declines.

Figure 14

Effect of recovery
As shown in Figure, reverse osmosis occurs when the natural osmotic flow between a dilute solution and a concentrated solution is reversed through application of feedwater pressure. If percentage recovery is increased (and feedwater pressure remains constant), the salts in the residual feed become more concentrated and the natural osmotic pressure will increase until it is as high as the applied feed pressure. This can negate the driving effect of feed pressure, slowing or halting the reverse osmosis process and causing permeate flux and salt rejection to decrease and even stop (please see Figure).

Figure 15

The maximum percent recovery possible in any RO system usually depends not on a limiting osmotic pressure, but on the concentration of salts present in the feedwater and their tendency to precipitate on the membrane surface as mineral scale. The most common sparingly soluble salts are calcium carbonate (limestone), calcium sulfate (gypsum), and silica. Chemical treatment of feedwater can be used to inhibit mineral scaling.

Effect of pH
The pH tolerance of various types of RO membranes can vary widely. Thin-film composite (TF)membranes are typically stable over a broader pH range than cellulose acetate (CA) membranes and, therefore, offer greater operating latitude (please see Figure ). Membrane salt rejection performance depends on pH. Water flux may also be affected. Figure shows that water flux and salt rejection for Thin Film membranes are essentially stable over a broad pH range.

Figure 16

As illustrated in Figure the stability of TF membrane over a broad pH range permits stronger, faster, and more effective cleaning procedures to be used compared to CA membranes [19]

6. Mass Transfer for reverse osmosis

There are two basic types of mass-transport mechanisms in membranes. In the first type, using tight membranes, which are capable of retaining solutes of about 10 oA in size or less, diffusiontype transport mainly occurs. Both the solute and the solvent migrate by molecular or Fickian diffusion in the polymer, driven by the concentration gradients set up in the membrane by the applied pressure difference. In the second type, a sieve-type mechanism occurs where the solvent moves through the micropores in viscous flow, and the solute molecules small enough to pass through the pores are carried out by convection with the solvent. For diffusion-type membranes, the steady-state equations governing the transport of solvent and solute are given below:

Figure 17

Where Nw and Ns are the solvent and solute fluxes in kg/s m2; Pw the solvent membrane permeability, kg/s m atm; Lm the membrane thickness in m; Aw and As the solvent and solute permeability constants, kg/s m2 atm; P = P1 - P2 (hydrostatic pressure difference with P1 as the pressure exerted on feed and P2 on product solution), atm; = 1- 2 (osmotic pressure of feed solution - osmotic pressure of product solution), atm; Dw and Ds are the diffusivity of

solvent and solute in membrane, m2/s; cw the mean concentration of solvent in membrane, kg solvent/m3; Vw the molar volume of solvent, m3/kg mol solvent; R the gas constant, 82.057x103 m3 atm/kg mol K; and T the temperature, K. Note that the subscript 1 is the feed or upstream side of the membrane and 2 the product or downstream side of the membrane; Ks (distribution coefficient). At steady state, the solute diffusing through the membrane must equal the amount of solute leaving in the downstream or product (permeate) solution, cm / c

where cw2 is the concentration of solvent in stream 2, kg solvent/m3. If the stream 2 is dilute in solute, cw2 is approximately the density of the solvent. In reverse osmosis, the solute rejection R is defined as the concentration difference across the membrane divided by the bulk concentration on the feed or concentrate side (fraction of solute remaining in the feed stream):

c2/c1 can be obtained by substituting Eqs. (2) and (5) to (7). Then we have

where B is in 1/atm, which must be determined experimentally. Usually, Pw / Lm or Aw and DsKs / Lm or As are given in the literature.[20]

7. Flux
The total resistance at the end of filtration test (Rf) was calculated with the permeate flux and TMP at the end of each permeate test. The resistance at the end of filtration test (Rf) includes the resistance by concentration polarization, cake layer and adsorbed layer. The membrane rinsed with deionized water was used for another pure water flux (PWF) test to evaluate the resistance after hydraulic rinse (Rhy). The membrane was operated for 3 minutes before the PWF test to stabilize the permeate flux and pressure [21].

Then, the third pure water flux test was performed to determine the resistance after chemical cleaning (Rch). The relationship between TMP and operating parameters (time or permeate flux) were illustrated in Figure 5. Theoretically, the relationship among the flux, the driving force and resistances can be expressed by Darcys law as shown in Equation

Where, J is the flux, P is the transmembrane pressure, is the viscosity of the permeate solution, and R is the resistance [21].

Figure 18

Figure 19

Figure 19- Schematic diagram of the filtration protocol employed (fluxes and resistances involved). J0 is the initial flux of the membrane system after compaction of membrane, J is the flux at the end of the test. (a) Hydraulic resistances of the system under constant pressure operation mode (after Kilduff et al., 2000), (b) Hydraulic resistances of the system with constant step-wise increased flux [8]. After the membrane is fouled, the equation can be changed as Equation

,where is the osmotic pressure by concentration polarization, Rm is the intrinsic membrane resistance, Rcp is the resistance by concentration polarization, Rcl is the resistance by cake layer, and Ra is the resistance by adsorbed layer. In ultrafiltration and microfiltration of drinking water, the effect of the osmotic pressure by concentration polarization on the flux was neglected due to low concentration of solute in surface water treatment applications. Although it depends on the definition of authors, it can be said that Rch is closely related with Ra, Rhy with Rcp, and Rf with Rcl [21].

8. Critical Flux Critical flux is defined as the permeate flux of a membrane system under which no or little fouling is observed. Higher critical flux with low resistance to filtration results in lower capital and operating costs [21].

Critical flux has been proposed as a method for measuring the maximum flux or TMP that can safely be applied and still keep the system running effectively, i.e. with no or little fouling and with reduced frequency of chemical cleaning. Field et al. (1995) introduced the concept of critical flux, working on constant flux filtration of yeast cells with MF. They defined the critical flux as the flux below which an increase of TMP with time did not occur. Howell (1995) defined the critical flux as the flux below which there is no deposition of colloids on the membrane. All the definitions of critical flux are related with fouling of the system. Based on theoretical definitions of mass transport, the critical flux can be defined more generally as the flux at which the hydrodynamic force transporting the particle towards the membrane pore is exactly balanced by the opposing back transport forces (Bowen et al. 1999). It should be recognized, however, that diffusion is a statistical process and that not all particles in a population will follow the same path. As a result, conditions that are believed to prevent the average particle from depositing on a membrane surface will not guarantee that all particles of a particular size and density will remain detached from a surface. This also leads to the inference that there is no such thing as a critical flux at which there will be zero fouling. Rather, critical flux should be considered to be the operating condition that separates slow fouling from rapid fouling. Factors effecting the critical flux Ionic strength PH Zeta potential Particle concentration and size, and nature and concentration of organic materials
Membrane surface characteristics Hydraulic conditions

Ionic Strength Ionic strength and especially multi-valent ions affect electrostatic interactions between particles (DLVO theory) and the molecular size of polyelectrolytes such as humic materials [8]. PH In general, an increase in pH increases the electrostatic repulsion between the membrane and particles, which are typically negatively charged in natural waters. As a result, higher flux is

often observed with an increase in pH (Mnttri and Nystrm, 2000; Metsmuuronen et al., 2002; Chen, 1998). Yuan and Zydney (2000) reported increased hydraulic resistance of humic acid deposited at lower pH. Zeta potential Conversely, Huisman et al. (1999) investigated critical flux as a function of zeta potential. They found that the critical flux was affected neither by membrane zeta potential nor by particle zeta potential. The size of particle that they used was too large to be affected by zeta potential (0.53 m silica particle). Particle concentration and size, and nature and concentration of organic materials In general, the critical flux decreased with increasing concentration of particles. However, addition of larger particles resulted in higher critical flux. Generally, the critical flux decreased with increasing concentration of dissolved organic materials are reported that the role of dissolved matter in determining critical flux was small since the difference in fouling resistance was only about 5% for the DOC variation of 300 ~ 1200 mg/L. It has been noted that addition of particles reduced the amount of adsorbed NOM on membrane and this could have an impact on critical flux. Membrane surface characteristics Membrane surface characteristics can affect the critical flux. The critical flux was larger for hydrophilic than for hydrophobic membranes. Mnttri and Nystrm (2000) reported significant irreversible fouling of the most hydrophobic membrane due to sorption of the organic solutes by hydrophobic interaction with the membrane. Hydraulic conditions Critical flux is affected by hydraulic conditions. The critical flux increased as crossflow velocity increased due to the erosion of the deposited layer. The impact of Reynolds number and wall shear stress can be understood in same way, i.e. higher Reynolds number (Wu et al., 1999) and wall shear stress (Gsan-Guiziou et al., 2002) resulted in higher critical flux. Interestingly, Bacchin et al. (1996) reported that crossflow was useless when filtering a destabilized colloidal suspension.

Although sub-critical flux operation can improve system performance by reducing fouling, the operation can still encounter problems. Operation at a very low flux may not be economical. Operation at constant permeate flux can result in local fluxes that are too high in some regions of a filter (Cho and Fane, 2002). However, it seems clear that systems with a high critical flux and with significantly larger particles can benefit from operating below the critical flux (Vyas et al., 2002) [21].

Critical Pressure
The effect of the gel layer on the flux through an ultrafiltration membrane at different feed pressures is illustrated in Figure 6.9. At a very low pressure p1, the flux Jv is low, so the effect of concentration polarization is small, and a gel layer does not form on the membrane surface. The flux is close to the pure water flux of the membrane at the same pressure. As the applied pressure is increased to pressure p2, the higher flux causes increased concentration polarization, and the concentration of retained material at the membrane surface increases. If the pressure is increased further to p3, concentration polarization becomes enough for the retained solutes at the membrane surface to reach the gel concentration cgel and form the secondary barrier layer. This is the limiting flux for the membrane. Further increases in pressure only increase the thickness of the gel layer, not the flux. Experience has shown that the best long-term performance of an ultrafiltration membrane is obtained when the applied pressure is maintained below the pressure p3 shown in Figure 6.9. We can call this the critical pressure. Operating at higher pressures does not increase the membrane flux but does increase the thickness and density of retained material at the membrane surface layer. Over time, material on the membrane surface can become compacted or precipitate, forming a layer of deposited material that has a lower permeability; the flux then falls from the initial value. When constant flux operatio became common in the 1990s, the term critical flux was coined [22]. This flux is shown in Figure 6.9. It is the flux at which the first gel layer forms on the membrane surface. The best long-term performance of an ultrafiltration/microfiltration fixed flux system is obtained when the fixed flux is set below the critical flux.

Figure 20

9.

Membrane fouling

Two fouling mechanisms are generally observed for membrane processes: surface fouling and fouling in pores. However, RO membranes do not have distinguishable pores and are considered to be essentially non-porous. Thus, the main fouling mechanism for RO membranes is surface fouling. Surface fouling can occur from a variety of contaminants, including suspended particulate matter (inorganic or organic), dissolved organic matter, dissolved solids, and biogenic material. [23] In addition, fouling can develop unevenly through a membrane module or element and can occur between the membrane sheets of a module, where spacers are located to create space for the concentrate stream. [24] Overall, seawater RO plants, particularly those treating water from an open water intake, are primarily fouled by organic and particulate material, while brackish water RO plants are fouled by dissolved inorganic salts and precipitation. However, both types of RO can experience both general groups of contaminants. In addition, the types of problematic foulants are site-specific, particularly for brackish water RO, and can depend on pretreatment processes. The capacity of water to foul RO membranes is often described using the silt density index, or SDI. The SDI of water is determined from the fouling rate of a 0.45 mm filter at a pressure of 207 kPa (30 psi) and is described in the AST standard method D4189 [25]. The equation used to calculate SDI is as follows:

Where t is the total elapsed flow time, and t1 and t2 are the times (in seconds) required to filter 500 mL of water initially and after t minutes, respectively. [25, 26] The experiment is setup as a dead-end filtration with continuous flow under pressure, and the membrane is perpendicular to the permeate flow. The total time t is chosen (the standard is 15 min), and the sample flows though the filter during the entire 15 min. As water flows through the membrane, foulants will continuously accumulate on and foul the membrane; therefore, t1 is expected to be smaller than t2. Both conventional and membrane pretreatment lower the SDI of feed water, but each pretreatment choice may have negative and positive aspects (technologically and financially). An SDI of 3 or less is preferred for RO influent. However, many plants tolerate SDI values between 4 and 5, which is often the achievable range through conventional pretreatment . Kremen and Tanner (1998) showed the relationship between SDI and water fouling propensity by relating the SDI to a total flow resistance. The total flow resistance (Rt) is the combination of two resistances, the resistance of the filter (RP) and the resistance of the foulant (on the filter) (RF). The theoretical relationship between SDI and Rt, shown in Fig. 6, displays an exponential relationship between increasing SDI and increasing foulant resistance (or increasing foulant accumulation on the membrane).

Figure 21

This relationship indicates far greater fouling resistance between SDI values of 4 and 5 than between SDI values of 1 and 4. Therefore, ideally, a pretreatment scheme that can lower the SDI

to below 2 (membranes) will provide a water with a lower fouling propensity than a pretreatment scheme that provides an SDI of 35 (media filtration).

Foulants
Rejected constituents by the RO membrane pose a general fouling risk to plant operation. Foulants can be classified into four categories [27]:

Chemical foulants, which cause scaling Physical foulants or particulate matter, which is related to deposition of particles on the membrane surface Biological foulants, which can either deteriorate the membrane or form a biofilm layer, which inhibits flux across the membrane. Organic foulants, which can interact with the membrane

Chemical foulants Scaling of a reverse osmosis membrane occurs if concentrations of sparingly soluble salts, i.e. divalent and multivalent ions exceed their solubility level. Concentrations in the feed channel inside a module increase, and with increasing recovery, the risk of scaling grows. However, solubility levels only define the minimum concentration level at which scaling might occur. In practical operation, even at higher concentrations scaling may not occur due to the long induction times of crystallisation. However, it is common practice not to exceed solubility limits. Dissolved inorganics most likely to cause scaling are Ca2+, Mg2+, CO3 2!, SO4 2!, silica and iron. Particulate fouling Particulate matter in natural waters can be classified according to Potts et. al. [44] into four different categories depending on particle size: Settable solids > 100 m Supra-colloidal solids 1100 m Colloidal solids 0.0011 m Dissolved solids <10 A

Particles larger than >25 m can be easily removed by various treatment options such as screens, cartridge filters, dual-media filters etc. The most common inorganic particles are aluminum

silicate clays (0.31 m) and colloids of iron, e.g. iron oxide, aluminum oxide and silica. The most problematic feeds are those containing colloidal particles not easily removed by granular beds either because of their minute size or because of electrostatic repulsion effects of the media. In such cases it is necessary to add a coagulant or flocculating agent. The most frequently used coagulants are ferric chloride, alum and cationic polymers. The polymeric coagulants are effective in very small dosages but can cause membrane fouling difficulties [43]. The presence of suspended solids can be monitored by the silt density index (SDI) test, turbidity analysis, zeta potential measurement and particle counting. For prevention of colloidal fouling, membrane manufacturers require a turbidity NTU <0.2, zeta potential > !30 mV and SDI <35 [43]. Waters from wells are much less loaded with colloidal material and often no further reduction of colloid content is needed. Biofouling All raw waters contain microorganisms such as bacteria, fungi, algae, viruses and higher organisms such as protozoa, living or dead, or biotic debris such as bacterial cell wall fragments. At the large membrane surface dissolved organic nutrients of the water are concentrated due to concentration polarisation. Microorganisms entering a RO system therefore find ideal growth conditions resulting in possible formation of a biofilm [28]. Biofilm formation consists of three stages: Transport to the membrane surface Attachment to the surface and Biofilm growth

Biological fouling can influence the performance of an RO system, resulting in increased pressure loss along the feed channel and significant flux decline. Biofouling cannot be easily removed because microorganisms are protected from shear forces and disinfectants by a gel like layer. If the gel layer is partly removed by disinfection, e.g. chlorination, dead cellular matter serves as additional nutrient leading to intensive biologic re-growth. It is therefore essential for good RO performance to reduce biological fouling to a minimum by effective pre-treatment [29]. The potential for biofouling is higher with open intake water than with well water with its higher water quality. Pre-treatment is generally required for surface water to prevent biofouling. For a bacterial count higher than 106 CFU/ml significant biofouling problems have to be expected [48].

Organic foulants Degradation of organic matter such as plants produces a matrix of macromolecules called humic acids. Organics in natural waters are usually humic substances in concentrations between 0.5 and 20 mg/L in BW and up to 100 mg/L in surface seawater TOC [29]. Humic acids are of polymeric phenolic structure and have the ability to form chelates with metal ions, most importantly with iron ions; a gel like fouling layer is formed by complexation of multivalent ions. The adsorption of theses organics on the membrane surface results in permeability decline, which even can be an irreversible process. At high pH values (>9) fouling can be prevented since membrane and organic substances assume a negative charge. The resulting repulsion is used for cleaning of the membranes [29]. Irreversible fouling is mostly due to complexation of calcium. Calcium complexes form a highly compactable floc-like structure which also causes the highest flux decline compared to other chelates. It was found that mainly the hydrophobic humic substances are deposited on the membrane surface [31] and that the adsorption process is favoured with positively charged, high molecular mass compounds. Similarly, the most hydrophilic membranes have been found less prone to fouling by organic colloids, i.e. humic acids [30]. In RO operation it is recommended that humic acids are removed prior to filter pre-treatment by flocculation, coagulation with hydroxide flocs, ultrafiltration or adsorption on activated carbon. Other organic foulants in natural waters are oil and grease droplets.

Key parameters
Scaling and fouling are the main problems in seawater and brackish water desalination and the potential for scaling and fouling will strongly depend on the water composition. The abundance of water constituents can never be fully integrated in a process designing exercise. However, water quality can be characterized by certain key parameters which are used to gain information about the tendency of the feed water to cause scaling and fouling. Parameters that are commonly used to characterize the feed water are: The SDI Index (Silt Density Index), which describes the fouling potential of the feedwater and is determined in filtration tests with the feed or raw water using porous microfiltration membranes.

The content of Ca2+ and Mg2+ in the feedwater gives information about the hardness of the water, which causes calcinations of pipes. Total hardness is defined by the content of calcium, magnesium, barium and strontium in solution. However, in general only the amount of calcium and magnesium are used to characterize the hardness of a feedwater.

The solubility product, which gives information about the limiting salts and the potential for scaling. The conductivity is directly proportional to the content of dissolved salts in the water and is also used to determine the amount of dissolved salts in the feed. Conductivity of sea water depends strongly on temperature. Therefore, if salinity is to be calculated from conductivity, temperature must be measured at the same time as conductivity, to eliminate the temperature effect and obtain salinity.

The TDS (total dissolved solids) characterizes the content of dissolved solids in the feed, butdoes not differentiate between different salts.

10.

What is red tide?

Algal can refer to either microscopic (seen only under a microscope) plant-like cells or larger aquatic plants that can be seen with the unaided eye, such as sea lettuce. Both types of algae can be found in seawater, brackish water, or fresh water. The term algal suggests plants that

Approximately 70 percent of HAB species are dinoflagellates, and some of these produce toxins that are among the most potent known to man. Diatoms are organisms with a cell wall of glass (silica) that can be individual cells or attached in chains. They can float at the waters surface or sink to the depths of the ocean. Blue-green algae (also called Cyanobacteria) are among the oldest bacteria found on earth. They have plant pigments like algae, but they do not have an internal microstructure like that of the diatoms and flagellates. Individual cells, filaments, or colonies often float at the surface of the water and generally appear blue-green.

Effect of Red Tide

Red tide is a complex phenomenon involving many different types of creatures with different characteristics covering large areas. They disrupt the ecosystems causing large scale environmental damage. Most of the red tides cause large scale fish kill and the killed fish will be washed to the shores resulting with a bad smell on the beaches. It is also not safe to eat the fish caught in the red tide areas, which will result in loss of livelihood to fishermen during the red tide. The below picture shows about 70 tons of fish killed in Asmak fish farm, Quriyat, Oman during 2008 red tide.

Controls Parameters to be Taken

MEDRC believes that some of the needed research activities to develop strategies to understand the reasons for outbreak of red tide and its control could be the following;

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