Water Contaminants

Class Typical Example

MEMBRANE Suspended solids Dirt clay,

Dirt, clay colloidal materials

FILTRATION Dissolved organics Trihalomethanes, synthetic

organic chemicals, humic
acids
Dissolved ionics (salts) Heavy metals, silica, arsenic,
nitrate

Microorganisms Bacteria, viruses, protozoan

cysts, fungi, algae

Gases Hydrogen sulfide, methane

Conventional Filtration Crossflow Filtration

Feed
Feed Concentrate

Barrier media
Membrane

Permeate or Permeate
Filtrate

2 3

1
 Membrane Separation Membrane Separation

• Removal of particulate & colloidal matter

f
from li id
liquid
• Removal of dissolved solids (0.0001µm to
1 µm)
• Selective barrier allows passage of certain
constituents & will retain other
constituents.

4 5

Membrane Process Terminology

Membrane Schematic
• Feed Stream (Feed water)- Influent to
membrane module Feed Permeate

• Permeate (Product stream / Permeating Pump

stream) – The liquid that passes through
the semipermeable membrane
• Concentrate (Retentate / reject / retained
phase
h / waste stream)) – Liquid
Li id containing
i i
the retained constituents Concentrate

6 7

2

8 9
Key Terms in Membrane Process
• Array or train- Multiple interconnected stages in series
• Concentrate – The portion of feed stream that does not pass
g the membrane that contains higher
through g TDS than feed
stream
• Feed Stream- Input stream to the membrane array
• Flux/Feed Flow – Mass or volume rate of transfer through
the membrane surface
• Fouling – Deposition of existing solid material in the element
on the feed stream of the membrane
• Lumen – The interior of a hollow fiber membrane
• Mass Transfer Coeff. (MTC) – Mass or volume unit transfer
through membrane based on driving force 10
Key Terms in Membrane Process
• Membrane- A phase act as a barrier to flow of molecular or
ionic species between other phases that it separates.
• Membrane Element – A single membrane unit containing
bound group of spiral-wound or hallow fine fibre
membranes to provide a nominal surface area
• Module – A complete unit comprised of the membranes,
the pressure support structure for the membranes, the
feed inlet and outlet permeate and retenant ports, and an
overallll supportt structure
t t
• Permeate – The “purified” product water exiting the
system, that contains lower TDS than the feed stream
• Reject ion – Percent solute concentration reduction of
permeate stream relative to feed stream
Key Terms in Membrane Process
• Pressure vessel – A single tube that contains several
membrane elements in series
• Scaling – Precipitation of solids in the element due to
solute concentration on the feed stream of the membrane
• Solvent – Liquid containing constituents (TDS)
• Solute – Dissolved constituents (TDS) in raw, feed,
permeate and concentrate stream
• Stage or blank – Pressure vessel arranged in parallel
• System arrays – Number arrays needed to produce the
required flow
11
3
Definition Sketch for Membrane Process
Feed Water (f)
Qf=Feedwater flowrate
Cf =Feedwater concentration
Pf =Feedwater pressure
membrane
Container for
membrane module
Kf-water mass transfer coefficient
Ki-Solute mass transfer coefficient
Types of Membranes
Common Types of Membrane Processes
Permeate (p)
Qp= Permeate flowrate
Cp = Permeate concentration •Microfiltration
•Ultrafiltration
Pp = Permeate pressure
kw
•Nanofiltration
ki
• Reverse Osmosis
Concentrate (c) • Dialysis
• Electrodialysis
Qc= Concentrate flowrate
Cc = Concentrate concentration
Pc = Concentrate pressure
12 13
Membrane Process Classification
•Membrane Materials
•Driving Force
•Removal Mechanism
•Size of Separation
p
14 15
4
 Membrane Materials Membrane Materials
• Skin – 0.2-0.25 µm – organic or inorganic materials
• Support – porous structure of 100 µm thick Principle type of membranes-
• Flat sheet, fine hollow fibers, tubular Polypropylene, cellulose acetate, aromatic
polyamides and thin film composite (TFC).
Flat Sheet
The selection of membrane and system
configuration is based on minimizing
Asymmetric- cast in Thin film membrane clogging and deterioration
one process Composite
b
basedd on pilot
il t plant
l t studies
t di

Thin Layer < 1 µm Bonding thin cellulose acetate,

Thicker support layer = polyamide – 0.15-0.25 µm
100 µm Thicker support layer + 100 µm
16 17

Driving Force
Microfiltration
Ultrafiltration Hydraulic Pressure
Nanofiltration Difference

Reverse Osmosis
Dialysis Concentration Difference
Electrodialysis Electromotive Force with
ion selective membrane
18 19

5
 Removal Mechanisms
Removal Mechanism
• Principle mechanism in MF & UF is by straining
• In NF & RO small p
particles are rejected
j byy the
water layer adsorbed on the surface of the
membrane which is known as dense
membrane
• Ionic species are transported across the
membrane by diffusion through the pores of
macromolecule comprising the membrane.
• NF can be used to reject solids < 0.001µm

20
• RO can be used to reject solids < 0.0001µm 21

Removal Mechanism Size of Separation

Membrane Process Typical Separation Mechanism Membrane Process Operating Structure
Microfiltration Sieve (straining) (Pore Size)
Microfiltration Macropores (> 50 nm)
Ultrafiltration Sieve
Ultrafiltration Mesopores (2 to 50 nm)
Nanofiltration Sieve + Solution/ Diffusion +
Exclusion
Nanofiltration Micropores (< 2 nm)
Reverse Osmosis Solution/ Diffusion + Exclusion Reverse Osmosis RO membrane is defined as
Dense (< 2 nm)
Dialysis Diffusion
Dialysis Mesopores (2 to 50 nm)
Electrodialysis Ion Exchange with Selective Electrodialysis Micropores (< 2 nm)
Membranes
22 23

6
 Filtration Range Particle Size

Yeast Cell =
3 00 microns
3.00

Bacteria =
0.45 microns

Ferric Iron
Molecule =
0.001 microns

Human Hair ~
24 75 microns
25

Relative Sizes of Particles Size of Separation

Substance xxx Microns Membrane Typical Operating
Grain of table salt 100 Process Range µm
Range,
Human hair 80 Microfiltration 0.08 - 2.0
Lower limit of visibility 40 Ultrafiltration 0.005 - 0.2
Nanofiltration 0.001 - 0.01
Milled flour 25
R d bl
Red blood
d cells
ll 8 Reverse 0.0001 - 0.001
Osmosis
Bacteria 2
Dialysis -
Electrodialysis -
26 27

7
 Membrane Configuration Tubular Modules
•Membrane in cast on the inside of
Support tube
support tube
•A
A number of tubes (singly or in a
bundle ) are placed in pressure
vessel
•Feed water is feed through feed
tube and collected on outside of the
tube
•Used for water with high SS / having
Annular space for flow
high plugging potential
•These units are easier to clean – done by circulating chemicals &
pumping a foamball or spongeball through to mechanically wipe the
28 29
membrane

Hollow Fiber Spiral Wound

•Hollow fiber membrane module consists of a bundle of hundred to •A flexible permeate
thousands of hollow fibers. spacer is placed two flat
•The
The entire assembly is entered into pressure vessel. membrane sheets
•The feed can be to the inside of the fiber (inside outflow) or outside •The membranes are
of the fiber (outside inflow) sealed on 3 sides
•The open side is attached
to perforated pipe

•A flexible feed spacer is added

•Flat sheets are rolled into a tight circular configuration
•Thin film composites are used in this modules
•The flow in rolled-up arrangement follows spiral flow pattern
30 31

8
 Plate & Frame
•Plate & frame membrane modules consists of series of flat
membrane sheets & support plates
•Water to be treated passes between the membranes of two
neighboring membrane assemblies
•The plate supports membranes and provides a channel for
permeate to flow out of the unit
•Used for electrodialysis

32 33

Membrane Separation Membrane Operation

Technologies Features • Pump is used to pressurize the feed water and to
circulate it through the module
• Continuous process resulting in automatic and
uninterrupted
i t t d operation
ti • A valve is used to maintain the pressure of retentate
• Low energy utilization involving neither phase nor (concentrate)
temperature changes • The permeate is withdrawn at atmospheric pressure
• Modular design – no significant size limitations • As constituents in the feed water accumulate on the
• Minimal moving parts with low maintenance membrane (fouling), the pressure buildup on feed side,
requirements the flow through membrane (flux) starts to decrease,
• No effect on form or chemistry of the contaminant and % rejection also starts to decrease
• Discrete membrane barrier to ensure physical • When performance has deteriorated to a given level,
separation
the membrane modules are taken out of service
• No chemical addition requirements
• Modules are backwashed and cleaned chemically

9
 Membrane Operation modes for Membrane Operation modes for MF and UF
MF and UF Cross flow operation
• Three process configurations used with Bleed & backwash
MF & UF waste
t R i
Recirculation
l ti Loop
L

1. Cross flow Permeate

Raw Water
2. Cross flow with reservoir
3. Direct feed Feed
Pump
Screen or Recirculation
Filter Pump
Membrane Filter Air &/or liquid
backwash

• Feed water is pumped with cross flow tangential to the

membrane
• Water not passing through membrane is re-circulated
through the membrane after blending with additional
36 37
feed water

Membrane Operation Modes for MF and UF Membrane Operation Modes for MF and UF
Cross flow operation with reservoir
Bleed & backwash Direct Feed / Dead End
waste
Recirculation Loop

Bleed & backwash

Permeate waste

Raw Water Permeate

Membrane Filter Raw Water
Air &/or liquid
backwash
Screen or
Filter Influent Screen or Feed Membrane Filter Air &/or liquid
Pump Filter Pump b k
backwash h

• There is no cross flow

Feed • All the water applied to the membrane passes through
Pump
• Feed water is pumped with cross flow tangential to the membrane membrane
• Water not passing through membrane is re-circulated to storage 38 • Raw feed water is used periodically to flush the 39
reservoir accumulated material from the membrane surface

10
Transmembrane pressure for cross flow mode is given by-
Overall pressure drop across the filter module
for direct feed mode operation is given by-

[ ]
Pf Pp
Pf+Pc Pp
Ptm= - Pp Pf
Ptm = Pf - Pp
2
Pc
Ptm= transmembrane pressure gradient, kPa Total permeate flow from a membrane system
Pf = inlet pressure of feed stream, kPa is given by-
Pc = pressure of concentrate stream, kPa
QP = FW A
Pp = pressure of permeate stream, kPa

Overall pressure drop across the filter module QP = permeate stream flow rate, kg / s
for cross flow mode operation is given by- FW = transmembrane water flux rate, kg / m2. s
P = Pf - Pp
A = membrane area, m2
P = pressure drop across module, kPa 40 41

Transmembrane water flux rate is a function of- Rate of rejection (of solute)
•the quality of feed stream,
•the degree of pretreatment,
•the characteristics of membrane, Cf - Cp
•the system
y operating
p gpparameters R%= x100
The recovery rate is defined as Cf

Qp
r%= x100 The corresponding mass balance equations are
Qf
Qf = Qp + Qc
Qp = permeate stream flow, kg / s. Qf Cf = Qp Cp + Qc Cc

Qf = feed stream flow, kg / s.

42 43

11
Operating Modes w.r.t. Flux and TMP Microfiltration
(Transmembrane pressure)

Flux Flux Flux

TMP TMP TMP

Time, min Time, min Time, min

Constant flux TMP is fixed Flux rate & TMP
rate
t and
d TMP isi and flux rate is are allowed to
allowed to vary allowed to vary vary with time
(increase) with (decrease) with
time time
44

Ultrafiltration Nanofiltration

12
 Definition of RO Osmosis
• Osmosis is spontaneous transport of a
solvent from dilute solution to a
Higher Lower
concentrated solution across an ideal semi- concentration concentration

permeable membrane which rejects the

passage of solute but allows solvent to flow.

• Solvent flow can be reduced by exerting

pressure on the solution side. Semi-permeable
Membrane

Osmosis

Level rises
Difference in
level is Higher Lower
Osmotic Concentration Concentration
Lower Potential Higher Potential
Pressure

Water Flow

13
 Reverse Osmosis Reverse Osmosis Applied
Pressure Pressure
Feed Water
Can force (reverse)
osmotic flow to
lower-concentration
side
Concentrate
Flow Fresh water

Semi-permeable Semi-permeable
Membrane Membrane

Reverse Osmosis
Semipermeable
Membrane
Pressure

Ö Sea Sea
Fresh Water Fresh Water
Water Water
Fresh Sea (diluted)
Water Water

H2O H2O H2O H2O

Initial Condition Equilibrium Reverse Osmosis

The Osmotic Pressure, π, is defined as: π = MRT
M = molarity, R= gas constant ,T =absolute temperature

14
 Determination of Surface Area
RO Fundamentals
for RO Membrane
• Semi-permeable membrane uses two Fw = Kw (∆Pa – ∆ Π )
QP
=
A
mechanisms
h i ffor removall off iimpurities:
iti
Fw = Water flux rate, kg /m2.s
• Rejection (repels mineral salts involving Kw = Water mass transfer coefficient, s/m

dielectric and molecular forces) ∆Pa = average imposed pressure gradient, kPa

• Sieving
Si i (does
(d nott allow
ll particulate
ti l t matter
tt tot
pass on a small scale ~0.0005 microns. Tiny
∆Pa =
[ ] Pf+Pc
2
- Pp

∆ Π = osmotic pressure gradient, kPa

organics and gas molecules can pass.) ∆Π=
[ ] Πf+Πc
2
- Πp
57

• Some solute passes through the Recovery rate and rate of rejection are same as
membrane in all cases. described for MF & UF
• Solute flux can be described by -
Qp
QP Cp r%= x100
Fi = Ki x ∆Ci = Qf
A
Fi = flux of solute species i, kg /m2.s Cf - Cp
Ki =Solute mass transfer coefficient, m-s R%= x100
∆Ci = solute concentration gradient, kg/m3 Cf

∆Ci =
[ ]Cf+Cc
2
- Cp

58 59

15
 Membrane Fouling Fouling issue
• Fouling is potential deposition & accumulation • Traditional membrane technology is
of constituents in the feed stream on
membrane
generally
g y affected byy fouling.
g
• Fouling has significance in design & operation • This long-term loss in throughput
of membrane capacity is basically due to the
• Pretreatment needs formation of a boundary layer which
• Cleaning requirements
builds up naturally on the membrane
• Operating conditions
• Cost
surface during the filtration process.
• Performance
60 61

Constituents affecting performance of

Fouling issue
membrane through mechanism of fouling
• In addition to reduction in the flux Type of Responsible Remarks
performance of the membrane, this membrane Constituents
fouling
boundary or gel layer acts as a
secondary membrane, reducing the Fouling Metal oxides Damage to
(cake Organic & membranes can
original design selectivity of the formation inorganic colloids be limited by
membrane in use. sometimes Bacteria controlling
g these
identified as Microorganisms substances (by
• This inability to handle the buildup of biofilm Concentration use of
solids has also limited the use of formation) polarization microfiltration
membranes to low-solids feed streams. before RO)
62 63

16
 Constituents affecting performance of Constituents affecting performance of
membrane through mechanism of fouling membrane through mechanism of fouling
Type of Responsible Remarks Type of Responsible Remarks
membrane Constituents membrane
fouling Constituents
f li
fouling
Scaling Calcium sulfate Scaling can be
Damage to Acids Damage to
(Precipitation) Calcium carbonate reduced by limiting
membrane Bases membranes can
Calcium fluoride salt content, by
pH extremes be limited by
Barium sulfate adding acid to limit
Free chlorine controlling these
Metal oxide formation of
B t i
Bacteria substances.
b t
formation calcium
Free Oxygen Extent of damage
Silica carbonate, and by
depends on the
antiscalants
nature of the
addition
64 membrane 65

Membrane Fouling Caused by

Control of Membrane Fouling
Buildup Solids
• Mechanisms resulting in resistance to flow due to • Approaches used to control membrane
accumulation of material within lumen fouling (reduce TSS & bacterial content
Filtration
1. Pore narrowing of feed water)
Thin Thin
2. Pore plugging membrane
skin
membrane
skin
1. Pretreatment of the feed water
3. Gel / cake formation, caused by concentration 2. Membrane back flushing with water
Backwash
polarization (when majority of the solid matter &/or air
in the feed is larger than the pore size or
molecular weight cutoff of the membrane) 3 Chemical Cleaning of the membrane
3.
Filtration
Thin Thin Thin Thin
membrane membrane membrane membrane
skin skin skin skin
66 67
Backwash

17
 Pretreatment for NF & RO
• Pretreatment options for NF & RO
9 Pretreatment of secondary effluent by chemical
clarification & multimedia filtration or by
multimedia filtration & UF to remove colloidal
matter
9 Cartridge filters (pore size 5 to 10 µm) to
reduce suspended solids
9 Water disinfection with chlorine / UV / Ozone to
limit bacterial activity
9 Removal of O2 to prevent oxidation of Fe, Mn,
H2S and to decrease scaling potential of Fe &
Mn. 68
Assessing Need for Pretreatment
for NF & RO
• Three main fouling indexes used to asses
treatabilityy of g
given water with NF & RO are
1. Silt Density Index (SDI)
2. Modified Fouling Index (MFI)
3. Mini Plugging Factor Index (MPFI)
70
Pretreatment for NF & RO
• Pretreatment options for NF & RO
9 Removal of chlorine (dechlorination) (with
sodium bisulfite) and ozone may be necessary
for some type of membranes
9 pH of the feed water should be adjusted (with
H2SO4) to reduce scale formation (4.0 to 7.5)
9 Regular (once in a month) chemical cleaning of
membrane element to restore membrane flux flux.
69
Assessing Need for Pretreatment
for NF & RO
• Silt Density Index (SDI) is static measurement of resistance
determined by samples taken at start & end of test
• SDI does not measure the rate of change g of resistance during
g
the test
• Sample is passed through a 0.45 µm Millipore filter with a 47
mm internal diameter at 210 KPa gage to determine index
• Time required for test is 15 min to 2h
ti =time to collect initial sample of 500 ml
tf =time to collect final sample of 500 ml 71
t = total time for running the test
18
Assessing Need for Pretreatment Approximate Values for Fouling
for NF & RO Indexes
• MFI is determined using same equipment &
procedure used for SDI Membrane Fouling Index
• Volume is recorded every 30 s for 15 min P
Process SDI MFI, s/L2
filtration
Nanofiltration 0-2 0-10
RO Hollow Fiber 0-2 0-2
RO spiral wound 0-3
0 3 0-2
0 2
Q =average flow, L/s
a =constant
V = Volume, L
72 73

Application of Membranes Applications of MF & UF

• Replacement for depth filtration to reduce
• Microfiltration turbidity.
• Ultrafiltration • Remove residual suspended solids.
solids
• Nanofiltration • To reduce bacteria to condition the water for
• Reverse Osmosis effective disinfection.
• Pretreatment step for NF & RO.
• Separation of active biomass from aerobic
biological treatment.
• Separation of active biomass from
anaerobic complete mix reactors.
74 75

19
Applications of MF & UF in Wastewater Treatment
• Aerobic Biological Treatment – Separation of biomass
in activated sludge process
• Anaerobic Biological Treatment – Separation of
biomass in an anaerobic complete mix reactor
• Membrane Aeration Biological Treatment- Transfer
pure oxygen to biomass attached to outside of
membrane
• Membrane Extraction Biological Treatment – Extract
degradable organic molecules from inorganic
constituents such as acids, bases and salts
• Ultrafiltration is also used for removal of high
molecular weight dissolved solids (colloids, proteins,
carbohydrates) 76
Disadvantages of MF & UF
• High pressure system needs more electricity
• Pretreatment requires to prevent fouling
• Pretreatment facilities mayy need additional space
p • Can remove small 0.001 µm particles
& cost
• Requires residual handling & disposal of
concentrate
• Membrane replacement after every 3 to 5 years
• Scaling may create serious problem
• Flux rate declines with time. Recovery rate may be
considerably less than 100%
• Lack of reliable low cost method for performance
monitoring 78
Advantages of MF & UF
• Can reduce amount of treatment chemicals.
• 50 to 80 % less space requirements than
conventional process.
• Reduced labour requirement due to automation
• New membrane design allows use of lower
pressure.
• System cost may be competitive with
conventional treatment.
• Removes protozoan, cysts, oocysts, helminth
• May also remove few bacteria & viruses.
77
Application of Nanofiltration
• Also known as ‘loose’ RO.
• Nanofiltration is used for removal of
multivalent metallic ions from wastewater
(softening)
• Disinfection requirements are reduces as it
removes organic & inorganic solids as well
as bacteria & viruses.
79
20
 Application of RO Advantages of RO

• Main use of RO is for desalination • Can remove dissolved solids

• Removal of dissolved solids from • Can disinfect treated water
wastewater after depth filtration / • Can remove NDMA
microfiltration (nitrosodimethylamine) & other related
organic compounds
• Can remove natural organic matter &
inorganic matter

80 81

Electrodialysis
Disadvantages of RO
• Electrodialysis is an electro membrane
• Works best on ground water / low
solids surface water / pretreated process in which ions are transported
wastewater effluent through ion permeable membranes from
• Lack of reliable low cost method for one solution to another under the influence
performance monitoring
of a potential gradient.
• Requires residual handling & disposal
• The electrical charges on the ions allow
of concentrate
• Expensive compared to conventional them to be driven through the membranes
treatment 82 fabricated from ion exchange polymers. 83

21
 Electrodialysis
• Applying a voltage between two end electrodes
generates the potential field required for this.
• The membranes used in electro dialysis have
the ability to selectively transport ions (semi-
permeable barrier) having positive (cations) or
negative
g charge
g ((anions)) and reject
j ions of the
opposite charge, useful concentration, removal,
or separation of electrolytes can be achieved by
electro dialysis. 84 85

Electrodialysis

86 87

22
 Removal of solids depends on

• Wastewater temperature
• Amount of electric current passed
• Type and amount of ions
• Permselectivity of membrane
• Fouling and scaling potential of wastewater
• Wastewater flowrates
• Number and configuration of stages

88 89

• Current required for electrodialysis can be Current required in amps for a stack
estimated using Faraday’s law of electrolysis. of membranes:
• One Faraday of electricity will cause one gram FQNή
I=
equivalent of a substance to migrate from one n Εc
electrode to another, the number of gram
I = current, amp
equivalents removed per unit time is given by
F = Faraday’s constant
Gram equivalents per unit time = QNή = 96,485 amp.sec / equivalent
Q = flowrate,
flowrate L/s n = number of cells in the stack
N = normality of solution, eq/L ή = electrolyte removal as a fraction
ή (Eta) = electrolyte removal as a fraction
Ec = current efficiency (typically 0.8 to 0.9)
90 91

23
 Power required is calculated using Ohm’s law
• Capacity of membrane to pass an electric current is
related to P=ExI
CD/N = current density to normality ratio P= power, W
CD – current density (current in milli- amperes that flows E = Voltage, V
through a cm2 of membrane perpendicular to current Voltage required is determined by:
direction)
N - normality of feed solution E = RxI
High CD/N – Localized deficiency of ions on the surface of
membrane (polarization) causes excessive power
P = R x I2
consumption
R = resistance across unit (all cells + feed and
Practical Range of CD/N – 500-800 mA/cm2
product water), ohms. Generally in range
of 4 – 8 ohms.
I, in amps, as determined in previous
92
calculation. 93

Application of ED Treated water

Membrane stack
• Batch mode or continuous mode
• Units in parallel to provide hydraulic capacity
• Units
U it iin series
i tto provide
id d
desired
i dddegree off Raw Water Pretreatment
Cartridge
filters

treatment if required

• Makeup water @ 10% of feed volume to

Low pressure
circulation pump

wash membrane Concentrated

DC power
• A portion of concentrate stream is recycled supply
brine

to maintain equal flowrate & pressure on

both sides of membrane
• H2SO4 is fed to concentrate stream to Flow diagram for ED membrane process with
maintain low pH thus minimize scaling pretreatment
94 95

24
 Disposal of Concentrated Waste Stream
Typical Operating Parameters
Sr. Parameter Unit Range Concentrate may contain hardness, heavy metals, high
molecular weight organics, microorganisms, H2S, high
No.
pH due to concentration of alkalinity which may cause
1 Detention time in stack d 10 - 20 precipitation of metals

2 CD/N ratio mA / cm2 500 - 800 No. Disposal option

1 Ocean discharge
3 Membrane resistence Ω ohms 4-8
2 Surface water discharge
4 Salt-removal efficiency % 40 - 60 3 Land application
5 Current efficiency % 85 - 95 4 Di h
Discharge to
t wastewater
t t collection
ll ti
system
6 Concentrate stream flow % of 10 - 20 5 Deep-well injection
feed 6 Evaporation ponds
96 7 Controlled thermal evaporation 97

THANK
YOU 98

25