Membrane Separation Processes

DEPARTMENT OF CHEMICAL ENGINEERING

Reverse Osmosis
 Introduction
• When miscible solutions of different concentration are
separated by a membrane that is permeable to the
solvent but nearly impermeable to the solute, diffusion
of the solvent occurs from less concentrated to the more
concentrated solution, where solvent activity is lower.

• The diffusion of solvent is called Osmosis.

• Osmotic transfer of water occurs in many plant and

animal cells
 Introduction
• The transfer of solvent can be stopped by increasing the
pressure of the concentrated solution until the activity of
solvent is same on both sides of the membrane.

• If pure solvent is on one side of the membrane, the

pressure required to equalize solvent activities is the
osmotic pressure of the solution.

• If pressure higher than the osmotic pressure is applied,

solvent will diffuse from concentrated solution to dilute
solution. This Phenomenon is called Reverse Osmosis
Osmosis and Reverse Osmosis Illustration
 Basic Terminology
• Feed water: Supply water that is fed into the RO system to be
treated

• Permeate: A portion of the feed water that passes through a series

of membranes and is returned as purified water.

• Concentrate: A portion of the feed water that is rejected by the

membrane and contains the solution of impurities that have been
filtered out of the permeate.

• Water flux: The rate of permeate production typically expressed as

the rate of water flow per unit area of membrane (e.g., gallons per
square foot per day)

• Recovery rate: The ratio of permeate flow to feed water flow, which
indicates the overall water efficiency of the system
Basic Information
 RO Membrane Properties
• More than 50% of RO modules use cellulose acetate
membrane.
• It has high permeability for water and low permeability for
dissolved salts.
• Its limitation are:
I. Smaller allowable pH range of 4.5-7.5 (beyond this range, cellulose
acetate becomes prone to hydrolysis)
II. Susceptibility to biological attack (degradation due to growth of
microbes)
III. Reduction of solvent flux because of compaction or mechanical
compression of membrane at high pressure difference
 RO Membrane Properties
• Another common membrane materials in RO systems
are thin film composite (TFC) membranes.

• TFC membranes are not chlorine-tolerant but can

tolerate harsh chemical environments and wide ranges in
water temperature and pH, and are less vulnerable to
compaction than CA membranes.

• TFC membranes generally have higher water flux than CA

membranes because the layers are extremely thin, which
creates more water transport through the membrane
material.
 Membrane Configuration

• Spiral Wound

• Plate and Frame

• Hollow fibre

• Tubular
 Applications
• Potable water from sea or brackish water
• Ultra pure water for food processing and
electronic industries
• Pharmaceutical grade water
• Water for chemical, pulp & paper industry
• Wastewater treatment
• Municipal and industrial waste treatment
 Mechanism
• The mechanism of water and salt transport in
reverse osmosis is not completely understood.

• One theory is that water and solutes diffuse

separately through the polymer by a solution-
diffusion mechanism.

• In this mechanism concentration of water in dense

polymer is assumed to be proportional to the activity
of water in the solution
 Mechanism
• On the low-pressure side of the dense layer, activity is
essentially unity if nearly pure water is produced at 1 atm.

• On the high-pressure side, activity would be

 slightly less than 1.0 at atmospheric pressure
 1.0 at atmospheric pressure
 slightly greater than 1.0 at higher pressures

• The upstream pressure is generally set at 20 to 50 atm above

the osmotic pressure of the feed solution.

• At these pressures, activity of water “aW“ is only a few percent

greater than for pure water at 1 atm and change in activity
and concentration across the membrane are small
• The Driving force for water transport is the difference
in activity, which is proportional to pressure
difference in osmotic pressures of feed and product.

• The equation for water flux is

Dw is the diffusivity in the membrane

Cw is the average water concentration (g/cm3)
Vw is the partial molar volume of water (cm3/gmol)
• The flux of solute is assumed proportional to the
difference in solution concentration, the diffusivity
and a solubility or distribution coefficient.
 Concentration Polarization
• Nearly complete rejection of solute by the membrane
leads to a higher concentration at the membrane surface
than in bulk solution and this effect is called
Concentration polarization.

• Concentration polarization reduces the flux of water

because the increase in osmotic pressure reduces the
driving force for water transport.

• The solute rejection decreases both because of the lower

water flux and the greater salt concentration at the
surface increases the flux of solute
 Concentration Polarization
• Equations for concentration polarization have been derived for simple
cases such as laminar flow of feed solution inside hollow fibres.

• Consider a membrane with a water flux Jw when the bulk solute

concentration is cs and f is the fraction of solute rejected.
Diffusion of solute away from membrane surface is characterized by mass
transfer Coefficient kc and driving force csi – cs .
At steady state, diffusional flux equals the amount of solute rejected per
unit area
Jw cs f = kc (Csi – Cs)

• Polarization factor is defined as

Jw f (Csi – Cs)
Г= =
kc Cs
 Factors that impact on RO performance

Basic effects of:

• Temperature

• Pressure

• Recovery rate
 Temperature Effects

• RO permeate flow is strongly dependent on the

temperature of the feed water.
• The higher the temperature the higher the permeate
flow rate.
• Why? Lower viscosity makes it easier for the water to
permeate through the membrane barrier
• RULE OF THUMB – for every 1˚C the permeate flow
will increase ~ 3%
 Temperature Variation on Salt flux

• Solute rejection declines with a temperature rise because

of the osmotic pressure increase with temperature.

• Increasing temperature increases salt passage more than

water passage

• Generally you will get better rejections at lower

temperatures

• RULE OF THUMB – salt flux increases 6% for 1˚C increase

 Pressure Effects

• Water passage increases with pressure. Solute

rejection rises with pressure, since solvent flux
increases and solute diffusion does not.

• Higher flow of water through the membrane will tend

to promote more rapid fouling, the single greatest
cause of membrane failure.

• Membrane element manufacturers usually provide

limits with regard to the maximum applied pressure to
be used, as a function of feed water quality.
 Recovery rate Effects

• As recovery is increased, concentration of solute in the

concentrate stream increases, resulting in increased
osmotic pressure which must be overcome.

• Membrane flux declines with increasing solute

concentration at high recovery rate.

• Large systems typically have recovery rates between

40% and 60%. In other words, for every 10 gallons of
feed water entering the system, 4 to 6 gallons of
purified permeate water are produced
 Steps to design RO membrane system

1. System Design Information and Feed Water

2. Selection of Element Type and Average Permeate
Flux
3. Calculation of Number of Total RO Elements
4. Decision of Recovery Rate
5. Decision of Number of Stages
6. Decision of Number of RO Elements per Pressure
Vessel
7. Decision of Element Arrangement
1. System Design Information and Feed Water

• The RO membrane system highly depends on the available

feed water.

• Therefore, the system design information (required product

flow rate, expected recovery rate, annual water temperature,
water source, application, pretreatment, required product water
quality, operating pressure limit, etc.) and the feed water
analysis should be thoroughly studied and considered in
selection of the RO system design.

• If the required permeate water quality is so high that the

quality cannot be achieved by 1pass RO system, and then a
2 pass RO system should be considered
2. Selection of Element Type and Average
Permeate Flux
• According to the feed water source, pretreatment and feed water
salinity, the type of RO membrane element is selected.

• Consider the following characteristics while selecting particular

membrane for an application:

 Membrane fouling rates

 Water flux specification
 Solid rejection rate
 System pressure requirements
 Membrane response to cleaning operations and tolerance of
cleaning procedures
 Tolerance of pH
 Temperature range
 Chemical abrasion resistance
 Contd…

• Once the water source, pretreatment and RO

element type are fixed by the designer, the
recommended value of the average permeate flux
(also called “design flux”) is given.

• In some cases, the design flux value is determined by

pilot experiment data or customer’s experience.
 3. Calculation of Number of Total RO Elements

• The relationship between the number of total elements, the product

flow rate and the average permeate flux is expressed as follow equation:

In which:
NE = total element numbers
Qp = product flow rate
JV, ave = average permeate flux
(MA)E = membrane area of element

• The calculated number of RO elements may be a slightly changed based on the

decision of element arrangement, that is, the number of pressure vessel and RO
elements per pressure vessel.
4. Decision of Recovery Rate

• In an RO membrane system, a recovery rate as high as

possible is desirable, but a high recovery rate can also cause
some problems as follows

 Possibility of scale formation increase because of the increase

of concentration factor
 Osmotic pressure increase because of the increase of
concentration factor
 Concentrate flow rate decrease
 Permeate water quality deterioration because of average feed
concentration increase
 Contd…
• The relationship between recovery rate and concentration
factor is shown in Table

• Usually in brackish water desalination, the recovery rate is

decided by scale formation, and in seawater desalination, by
feed pressure limit.
 5. Decision of Number of Stages

• The number of RO stages defines how

many pressure vessels are in series in
the RO membrane system.

• Every stage consists of a certain

number of pressure vessels in parallel

• The number of stages is a function of

the system recovery rate, the number
of elements per vessel, and the feed
water quality as shown
6. Decision of Number of RO Elements per
Pressure Vessel

• RO membrane elements can be coupled together in series

in the pressure vessel, typically 1-8 elements per one
pressure vessel.

• In deciding the number of RO elements per pressure vessel,

plant size is usually considered first.

• In a large-scale plant (> 40 m3/h), 6-8 elements per

pressure vessel are usually adopted, and in a smaller plant,
3- 5 elements per pressure vessel.

• In all cases, the space required to install or remove the RO

elements should be considered in the plant design.
 Contd…
• By increasing the number of RO elements per pressure vessel,
almost all RO design parameters will change.
• Table shows RO system design parameters and the correlation
between an increase in number of RO element per pressure vessel,
and change in RO system design parameters.
7. Decision of Element Arrangement

• The RO element arrangement (array) means element

numbers per vessel, vessel numbers per stage and stage
numbers per pass.

• For the decision of element arrangement, the system

design parameters should be consistent with the design
flux guideline.

• In the case that not every parameter is in accordance with

the design guideline, it is necessary to make a priority in
the parameters. Usually average permeate flux,
concentrate flow rate and pressure drop per vessel should
be of higher priority.
 Contd…

• To decide the array, several calculations for case study

should be done by computer program and these results
should be compared.

• Some case studies should be done with the consideration

of different operating conditions (feed concentration,
temperature, etc.) or performance changes with time.

• For each typical case, a comparison should be done in

consideration of value of design parameter, the numbers of
RO elements or pressure vessel, and satisfying the
customers demand (product water quality, limit of feed
pressure etc.).
 RO System Components
RO systems consist of the following basic components, which are
common to every RO system. The specifications for each
component vary by application, source water quality, and the
required permeate quality.

• Pre-filter(s): It is common for pre-filters to pretreat the feed

water supply before it enters an RO system. Multiple pre-
filters may be used in an RO system. The most commonly used
pre-filters are sediment filters used to remove sand, silt, dirt,
and other sediment. Carbon filters also may be used to
remove chlorine and organic compounds
 RO System Components
• Reverse osmosis membrane: The RO membrane is the heart of the
system. The membrane is where the contaminants are trapped in
the concentrate and purified water is produced.

• Pressure vessels: A pressure vessel is a sealed hollow tube that

houses the RO membrane elements. To force water through a semi-
permeable membrane, pressure must be applied to overcome the
feed water’s osmotic back pressure and permeate back pressure

• Pumps: Pumps are required to push the water through the RO

system. They must be sized to meet the required operating
pressure and flow rate of the system and they constitute largest
energy consuming component in the system
 RO System Components
• Valves: Valves are required to control the flows and pressures
of an RO system for the system to operate correctly and
optimally. There are generally two valves in an RO unit on the
feed water piping and on the concentrate piping.

• Storage tank: Permeate is stored in tanks. Industrial and

commercial storage tanks may hold up to 9000 gallons of
water.

• Drain line: This line runs from the outlet end of the RO
membrane housing to the drain. This line is used to dispose of
the concentrate rejected by the membrane element
Diagram of an RO System with Basic
Components
 REVERSE OSMOSIS WATER TREATMENT PLANT

• The largest scale applications of membrane separation processes

are those which form the key step in the desalination, or more
generally demineralization, of brackish water in the production of
drinking water.

• An outline is given of such a plant capable of producing 70,000

m3/day of drinking water for a large city in the Middle East

• The water to be processed is obtained from a deep well with a total

dissolved solids (TDS) content of 1.4 kg/m3; that is, it is of moderate
salinity and hardness.

• The plant specification required that the product water should have
a maximum TDS of 0.5 kg/m3
Flow diagram of reverse osmosis plant for
demineralization of Brackish water
 Main Process Steps
Pretreatment

a. Evaporative cooling to reduce the feed water temperature from

50–55◦C to 30–35◦C which is more compatible with satisfactory
operation of the reverse osmosis unit and more suitable for final
use.

b. Precipitation softening by addition of slaked lime (Ca(OH)2) and

sodium aluminate or ferric chloride. The net result is part-removal
of calcium, silica and especially colloids. The clarifiers used ensure
completion of these processes within the tank.

c. Acidification to optimise removal of residual coagulant.

d. Prechlorination to ensure a disinfected supply to the reverse

osmosis plant
Pretreatment
e. Rapid gravity filtration to reduce further the content of particulate
material.

f. Acidification to reduce the pH to 5.0 for optimum life of the

reverse osmosis membrane.

g. Sequestering, addition of sodium hexametaphosphate to retard

the precipitation of calcium sulphate which otherwise will exceed
its solubility limit in the reject stream.

h. Cartridge filtration with elements rated at 25 μm to protect the

high pressure pumps and reverse osmosis membranes in the
event of a break-through of particulate material.
Demineralization by reverse osmosis

• Reverse osmosis was chosen for the demineralization step as

it gave an economic solution in terms of both capital and
running costs.

• It allowed a high water recovery rate, was modular in

construction and so could be easily extended, could cope with
reasonable variations in feed salinity.

• The pre-booster pumps, cartridge filters and high pressure

pumps are arranged in seven parallel streams, one of which is
on standby

• A total of thirteen reverse osmosis stacks is installed, any

twelve of which will meet the required throughput
Demineralization by reverse osmosis

• Each stack contains 210 reverse osmosis modules

accommodated in 35 pressure vessels arranged in a
series–parallel array of 20–10–5 to achieve the desired
water recovery

• These modules are of the spirally wound type.

• The permeate from the unit is blended with the

slipstream flow, with pH adjustment if necessary, to
maintain a final water TDS < 0.5 kg/m3.

• The reject is discharged to evaporation ponds.