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Membrane Separation Processes

Reverse Osmosis (RO)

Topics covered in Reverse Osmosis (RO) include the following:

 Basic Concepts of Osmosis, Osmotic Equilibrium and Reverse Osmosis


 Reverse Osmosis Membranes and Materials

 Process Design and Membrane Selectivity

 Factors affecting Membrane Performance

 Operation of Reverse Osmosis Systems

 Membrane Fouling Control and Cleaning

 Advantages and Disadvantages of Reverse Osmosis Systems

Basic Concepts

Consider the 2 tanks connected as shown in the Figure. The 2 tanks are joined by a pipe this
contains a semi-permeable membrane. A pure solvent, such as water, is contained in one tank
and a saline solution (ordinary salt dissolved in water) in the other tank. The semi-permeable
membrane will allow the passage of the water molecules, but not the salt ions.

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Because the water molecules are less concentrated in the saline solution (due to the presence
of the salt ions), a water concentration gradient will exist across the membrane between the
pure water and the saline solution. This water concentration gradient will cause the flow of
water molecules from the pure water side across the membrane to the saline solution side.

A similar salt concentration gradient will exist in the opposite direction that will cause the
flow of salt ions across the membrane from the saline solution side to the pure water side.
Although the concentration gradient exists, the membrane will prevent the flow of the salt
ions across it.

This process of osmosis will stop when the pressure created by the elevated level of saline
solution is equal to the driving pressure of the water concentration gradient, known as the
osmotic pressure. The condition is known as osmotic equilibrium. This is shown in the
Figure.

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To reverse the flow of water molecules, an external pressure greater than the osmotic pressure
must be applied to the saline solution side. This results in the reverse flow of water molecules
across the membrane back to the pure water side. See the Figure. This flow is termed the
reverse osmosis, and forms the basis of separation whereby a solution can be concentrated by
forcing out the solvent.

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RO Membranes and Materials

Spiral wound membranes 8-in in diameter and 40-in in length are the type most commonly
used for RO. RO membranes can be grouped into 3 main categories:

Seawater membranes operated with 3 - 5 wt% salt solutions at pressures of 800 - 1000 psi.

Brackish water membranes operated with 2,000 - 10,000 ppm salt solutions at pressures
200 - 400 psi.

Ultrapure water low-pressure nanofiltration membranes operated with 200 - 500 ppm salt
solutions at pressures 100 - 150 psi.

The fluxes and rejection rates of cellulose acetate membranes are inferior compared to
composite membranes, but they can tolerate up to 1 ppm chlorine, so chlorination can be used
on cellulose acetate membranes for sterilizing the feedwater. Thus cellulose acetate
membranes are suitable for feedwater having significant biological loading. Because their
properties change on heating, cellulose acetate membrane are generally not used above about
35 oC. The membranes also slowly hydrolyse over time, so the feedwater is usually adjusted
to pH 4 - 6, the range in which the membranes are most stable.

Polyamide membranes offer good seawater salt rejection up to 99.5%, but the fluxes are low,
in the range of 1 - 3 gal/ft2.day. Polyamide membranes are susceptible to degradation by
chlorine because of their amide bonds. Loeb-Sourirajan membranes based on sulfonated
polysulfone and substituted polyvinyl alcohol are used in water softening applications
because their divalent ion rejection is high.

Composite membranes have significantly higher salt rejections and fluxes than cellulose
acetate membranes. At 3.5% NaCl solution, they have a salt rejection of 99.5% and a water
flux of 30 gal/ft2.day at 800 psi. A major drawback is the rapid, permanent loss in selectivity
that results from exposure to even ppb levels of chlorine. Thus, composite membrane is not
suitable for treating seawater.

Process Design

Reverse osmosis operation usually involves 2 components: water (A) and salt (B). The water
flux permeates the reverse osmosis membrane according to the equation:

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where

Thus, the water flux is proportional to the applied pressure.

· when DP < Dp, water flows from the dilute to the concentrated salt solution side of the
membrane by normal osmosis
· when DP = Dp, no flow occurs
· when DP > Dp, water flows from the concentrated to the dilute salt solution side of the
membrane by reverse osmosis

The salt flux across a reverse osmosis membrane is given by:

where: B = salt permeability constant


CBO = salt concentration on the feed side of membrane
CBL = salt concentration on the permeate side of membrane

The salt flux is independent of pressure. The salt concentration on the permeate side is
usually very small compared to the feed side, i.e. CBO >> CBL.

Membrane selectivity increases as the pressure increases. Selectivity can be measured in a


number of ways, but conventionally it is measured as the salt rejection coefficient, defined as:

????

Membrane rejection can be expressed as:


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where rW is the density of water (g/cm3).

Membrane Selectivity

Some general guidelines are provided below:

Multi-valent ions are retained better than monovalent ions. The order of rejection of
cations by RO membranes is as follows:

For anions, the order of rejection is:

Dissolved gases such as ammonia, carbon dioxide, sulfur dioxide, oxygen, chlorine, and
hydrogen sulfide always permeate well.

Rejection of weak acids and bases is highly pH-dependent. In non-ionized form,


rejection is low.

Rejection of neutral organic solutes generally increases with the MW of the solute.
Solutes with MW > 100 are well rejected by all RO membranes.

Factors affecting Membrane Performance

The effect of feed pressure on membrane performance is shown below in the Figure.

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The water flow is zero at a pressure equal to the osmotic pressure of the feed (350 psi). The
water flux increases with feed pressure. The salt rejected is also zero at feed osmotic pressure,
but increases very rapidly with pressure to each more than 99% salt rejection at 700 psi.

The effect of increasing feed salt concentration on membrane performance is shown in the
Figure.

Increasing salt concentration increases the osmotic pressure. At a constant feed pressure
(1000 psi), the water flux falls with increasing salt concentration. The water flux approaches
zero when the salt concentration is about 10wt%, at which point the osmotic pressure equals
the hydrostatic pressure. The salt rejection also falls with increasing salt concentration.

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The effect of temperature on salt rejection and water flux is shown in the Figure.

The water flux doubles as the temperature is increased by 30 oC. Salt rejection declines
slightly as the temperature increases.

Operation of Reverse Osmosis (RO) Systems

A simple schematic of an RO system is shown in the Figure. The feedwater is pumped into a
pressure vessel containing the semi-permeable RO membranes. The RO device is also known
as a permeator. The pressurized concentrated liquid, called brine or reject, is let down to
atmospheric pressure through a flow-regulating valve. The purified water, called permeate or
product water, is recovered at low or atmospheric pressure.

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In its simplest design form, an RO system consists of a pump to pressurized the feedwater, an
RO device, and a throttling (flow control) valve on the brine outlet to control the conversion.
A typical RO plant uses this basic design in modular form to achieve the desired product flow
and water quality.

The basic expanded design of a single RO system is shown in the Figure, and includes the
following additional items:

Cartridge filter to remove large particulate matter that could damage the high-pressure
pump or cause plugging and fouling

Safety devices for protection of the permeator, such as high temperature switch, high
pressure shutdown switch (or pressure relieving device)

Low pressure switch to protect the pump

Flowmeters for product water and brine flow rates

Pressure gages for pressure drop measurement: across filter, between feed and product
water, between feed and brine, etc

Sampling points for various streams, including feed, product water and brine

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There are 2 basic types of pumps used in RO systems - centrifugal pumps and positive-
displacement pumps. The piping configuration for both pump systems is shown in the Figure.

For the centrifugal pump, a throttling valve on the discharge line controls the feed pressure to
the RO system. A back-pressure valve for re-circulation of about 10% of the flow can be used
when the pump capacity is greater than needed to supply the RO system.

For the positive-displacement pump, a relief valve is required for protection again high
pressure. Flow restrictions, such as a shutoff valve, must never be used between the pump
and the relief valve.

The back-pressure valve controls the system pressure and allows for re-circulation of about
10% of the flow when the pump capacity is greater than needed to supply the RO system.
Pulsation dampeners are required on the pump inlet and outlet lines to minimise pressure
fluctuations.

For large-scale RO plants, continuous monitoring is used for such factors as temperature, feed
pH, feed conductivity, brine and product conductivities, feed chlorine content, energy
consumption, etc.

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Multiple RO Units

The modular design concept is used to expand the single-unit system when the desired
product flow is greater than the output of an individual unit. The Figure showed several RO
permeators connected in parallel where the feed, product and brine lines formed manifolds.

The system conversion is controlled by a single valve on the brine manifold. For hollow-fibre
modules, because of slight variations in pressure drop among them, conversion in individual
units is kept equivalent by using flow-balancing tubes, installed between brine ports and the
brine manifold.

When higher conversion is required, brine staging is used. Brine-stage systems can have 2, 3
or more stages. In general, depending on water temperature, feed pressure and concentration,
minimum brine flow, etc, 2-stage systems can operate at about 75 - 80% conversion. 3-stage
systems can operate at about 85 - 90% conversion. An example of a 2-stage 4:2 arrangement
is shown in the Figure. There are 4 units in the first stage, and 2 units in the second stage. The
equipment used for this system is the same as for a single-stage parallel system, with the
addition of gages, meters and sampling points necessary to monitor the performance of each
stage.
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Brackish water plants usually consist of 1, 2 or 3 brine-staged systems. Because seawater
plants operate between 20 and 40% conversion, only single-stage parallel systems are used.

Membrane Fouling Control

For optimal performance, feedwater to the RO system should be treated to remove gross
amounts of solids, and to prevent fouling of the RO system.

Various unit operations - collectively called pretreatment - upstream of the RO system, must
be carried out on most waters. The types of unit operations used in the pretreatment system
are determined by the chemical nature of the membrane as well as the system configuration.

Typically, pretreatment will consist of filtration to remove large particles, and one or more of
the following operations:

Adjustment of solubility parameters to prevent precipitation of sparingly soluble salts


(scaling) as a result of concentrating action of the RO process

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Coagulation of colloidal matter

Chemical treatment to prevent biological growth

The need for pretreatment is determined from the feedwater composition, the conversion of
the RO system and the solubility of the particular salt.

Membrane fouling is the main cause of permanent flux decline and loss of product quality in
RO systems. The cause and prevention of fouling depends greatly on the feedwater being
treated, and appropriate control procedures must be devised for each plant. Fouling control
involves pretreatment of the feedwater to minimize fouling control as well as regular cleaning
to handle nay fouling that still occurs.

If pretreatment is inadequate, fouling will occur rapidly, cleaning will be less effective and
the need for cleaning will increase. In any case, frequent cleaning (more than once a month)
should not be substitute for pretreatment if long life and efficient operation are desired.

In general, fouling can be divided into 4 principal categories: scale, silt, bacteria, and organic
compounds. More than 1 category may occur in the same plant.

Scale

Scale is caused by precipitation of dissolved metal salts in the feedwater on the membrane
surface. As water is removed from the feed into the permeate, the concentration of salts in the
feed increases until its solubility limit is exceeded. The salt then precipitates out on the
membrane surface as scale. A measure of the tendency of a particular feedwater to produce
scale is the concentration factor, as given by:

where the Recovery Rate is the ratio of the product water flow rate to feedwater flow rate:

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The relationship between the brine solution concentration factor and the water recovery rate
is shown in the Figure.

Pretreatment for scale prevention is usually used for all membranes and RO configurations.
With plants that operate below a concentration factor of 2 (i.e. 50% recovery rate), scaling is
not normally a problem. For many brackish water RO systems, the recovery rate is normally
80 - 90%. The salts that most commonly form scale are: calcium carbonate, calcium sulfate,
silica complexes, barium sulfate, strontium sulfate and calcium fluoride.

Calcium carbonate scaling is by far the most common, and it is easily controlled. Acid
addition to prevent calcium carbonate scaling is used for both brackish water and seawater.

Brackish water may also require addition of anti-scalant such as sodium hexametaphosphate.
Anti-scalant interfere with the precipitation of the salt and maintain the salt in solution even
when the solubility limit is exceeded. Alternatively, ion exchange softening can be used to
prevent scaling by precipitation of calcium sulfate, barium sulfate, strontium sulfate and
calcium fluoride.

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For some brackish RO systems, lime softening (with lime or soda ash) is used in the
pretreatment to prevent scaling and permit operation of RO system at high conversion (85 -
90%).

Silica (SiO2) scaling may be a problem with some brackish waters because once formed,
silica scale is difficult to remove by cleaning.. Typical pretreatment include conversion
control, increasing temperature to increase solubility, and lime/soda ash softening.

All RO devices are very sensitive to fouling by ion corrosion products, so materials of
construction must be carefully considered. The most effective way to minimize corrosion in
an RO plant is to limit the use of metal. Non-metallic materials should be employed on all
wetted parts wherever they are practical and economical. For low pressure piping, plastic
materials such as polyvinyl chloride, polyethylene, fibre-reinforced polyester and epoxy
fibreglass are frequently used. Stainless steels (304, 316) are commonly used for high-
pressure pumps and pipings in brackish water RO systems.

Silt

Silt is formed by suspended particulates of all types that accumulate on the membrane
surface. Typical sources include organic colloids, iron corrosion products, precipitated iron
hydroxide, algae, and fine particulate matter.

An indicator of likelihood of silt fouling in feedwater is the silt density index (SDI) of the
feedwater. The SDI is an empirical measurement of the time required to filter a fixed volume
of water through a standard 0.45-mm pore size microfiltration membrane. Suspended
material in the feedwater that plugs the filter increases the sample filtration time, producing a
higher SDI.

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The maximum tolerable SDI varies with membrane module design. Spiral wound modules
generally require an SDI of less than 5, whereas follow fine-fibre modules are more
susceptible to fouling and require an SDI of less than 3.

To avoid fouling by suspended solids, some form of feedwater filtration is required.


Groundwater usually has very low SDI values, and cartridge filtration is often sufficient.
However, surface water or seawater may have an SDI of up to 200, requiring flocculation,
coagulation, and deep-bed multimedia filtration before RO treatment.

Biofouling

Biological fouling is the growth of bacteria on the membrane surface. If biological fouling is
a problem, the feedwater is usually chlorinated. This is normally required for surface waters
(brackish as well as seawater). Well waters are not chlorinated unless Cl2 is required to
prevent biological degradation of the membrane. The susceptibility of membranes to
biological fouling is a strong function of the membrane composition.

Cellulose acetate membranes are easily attacked by bacteria. Feedwater for such membranes
needs to be sterilized. Polyamide membranes are also susceptible to bacterial attack, but thin-
film composite membranes are generally quite resistant. Chlorination can be used for
cellulose acetate membrane, but be followed by dechlorination for polyamide and other
membranes, usually by addition of sodium metabisulfate. In ultrapure water production,
sterility is often maintained by UV sterilizers.

Organic Fouling

Organic fouling is the attachment of materials such as oil or grease to the membrane surface.
It is common in RO systems used for treating industrial effluent streams. Filtration or carbon
adsorption can be used to remove organic materials from feedwater.

An example of a complete pretreatment flow scheme for seawater RO plant is shown in the
Figure where the water is controlled for pH, scale, particulates and biological fouling.

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The feedwater is first treated with chlorine to sterilize the water and to bring it to a pH of 5 -
6. A polyelectrolyte is added to flocculate suspended matter, and 2 multi-layer depth filters
then removed the suspended matters. The water is dechlorinated by dosing with sodium
bisulfite, followed by an activated carbon bed. The water is then filtered through a 1 - 5 mm
cartridge filter before being fed to the RO modules.

Membrane Cleaning

Generally cleaning is done once or twice a year, but more often if the feedwater is
problematic. The specific cleaning procedure is a function of the feedwater chemistry, the
type of membrane used, and the type of fouling encountered. A typical cleaning regimen
consists of flushing the membrane modules byre-circulating the cleaning solution at high
speed through the module, followed by a soaking period, and a second flux, and so on. The
chemical cleaning agents commonly used are acids, alkalis, chelatants, detergents, formulated
products and sterilizers.

Acid cleaning agents such as hydrochloric, phosphoric or citric acids effectively remove
common scaling compounds. With cellulose acetate membranes, the pH of the solution
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should not go below 2.0, or else hydrolysis of the membrane will occur. Oxalic acid is
particularly effective for removing iron deposits. Citric acid is not very effective with
calcium, magnesium or barium sulfate; in this case a chelatant such as ethylenediamine
tetracetic acid (EDTA) may be used.

To remove bacteria, silt, or precipitates from the membrane, alkalis combined with surfactant
cleaners are often used. Detergents containing enzyme additives are useful for removing
biofoulants and some organic foulants.

Sterilization of a membrane system is also required to control bacterial growth. For cellulose
acetate membranes, chlorination of the feedwater is sufficient to control bacteria. Polyamide
and interfacial composite membranes do not normally require sterilization, as they are usually
fairly resistant to biological attack. Periodic shock disinfection using formaldehyde or
peroxide is usually enough to prevent biofouling.

Repeated cleaning gradually degrades reverse osmosis membranes. As membranes approach


the end of their useful life, the water flux will normally have dropped by at least 20% and the
salt rejection will have begun to fall.

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Advantages and Disadvantages of RO Systems

Advantages:

1. RO performs a separation without a phase change. Thus, the energy requirements are
low.
2. RO systems are compact, and space requirements are less than with other desalting
systems, e.g. distillation.

3. RO equipment is standardized - pumps, motors, valves, flowmeters, pressure gages,


etc. Thus, the learning curve for unskilled labour is short.

4. Many RO systems are fully automated and designed to start-up and shutdown
automatically through interlocks. Thus, RO plants usually require little labour.

5. Due to their modular design, maintenance is easy. Scheduled maintenance can be


performed without shutting down the entire plant.

6. The modular design also makes expansion an easy option.

Disadvantages:

1. The applied pressure must exceed the osmotic pressure to obtain product flow and to
separate the solute from the solvent. The maximum feed pressure for seawater devices
varies from 800 - 1000 psig, while the limit for brackish water varies from 400 - 600
psig. Due to the high pressure requirement (about 200 psig or more above the osmotic
pressure) RO is usually not applicable for concentrated solutions.
2. Because all RO membranes and devices are susceptible to fouling, the RO process
usually cannot be applied without pretreatment.

3. RO feed streams must be compatible with the membrane and other materials of
construction used in the devices. If the feed stream contains incompatible compounds,

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these must be removed in pretreatment, or another compatible device and/or
membrane must be considered.

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