Lecture 4

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MEMBRAN

PROCESSES
Introduction to Membrane Processes
MEMBRANE PROCESSES
 Membrane: A perm-selective barrier or interface

Phase 1 Membrane Phase2

Feed Permeate

Performance of a membrane process can be evaluated via its


selectivity and/or its flux
2
DRIVING FORCE
J= -A (dX/dx)

J: flux
A: constant
X: gradient (T,P,C)
x: coordinate

3
DRIVING FORCE
Types of Fluxes

Mass Flux Jm = -D (dC/dx) Fick


Volume Flux Jv = -Lp (dP/dx) Darcy
Heat Flux Jh = -λ(dT/dx) Fourier
Momentum Flux Jn = - ν(dv/dx) Newton
Electrical Ji = -I/R (dE/dx) Ohm

D: diffusion constant
Lp: Permeability constant
λ: thermal diffusivity
ν: η/ρ kinematic viscosity
I/R: electrical conductivity
4
SOME MEMBRANE PROCESSES AND
DRIVING FORCES
Membrane Process Phase 1 Phase 2 Driving Force
Microfiltration Liquid Liquid ΔP
Ultrafiltration Liquid Liquid ΔP

Nanofiltration Liquid Liquid ΔP


Reverse Osmosis Liquid Liquid ΔP

Gas Separation Gas Gas ΔP


Pervaporation Liquid Gas ΔP
Electrodialysis Liquid Liquid ΔE

Dialysis Liquid Liquid ΔC

5
TRANSPORT IN MEMBRANED

Liquid Liquid Gas Phase 1

Driving Membrane
Force
Liquid Gas Gas Phase 2

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1)Pressure Driven
Membrane Processes

2)Concentration Driven MEMBRA


Membrane Processes
NE
PROCESS
3)Temperature Driven ES
Membrane Processes

4)Electrical Potential
Driven Membrane
Processes
PRESSUR
Microfiltration (MF) E
DRIVEN
Ultrafiltration (UF)
MEMBRA
Nanofiltration (NF) N
PROCESS
Reverse Osmosis (RO) ES
OPERATION MODES OF MEMBRANE PROCESSES

Dead-end Filtration
Feed

Filter Cake Membrane

Permeate
Crossflow Membrane Process

Feed
Retentate

Membrane

Permeate

Notes: The retentate may be recirculated to the feed


A “dynamic” membrane may be created by adding Lime or KMnO4 to
the feed, to precipitate MnO2 on membrane
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MEMBRANE OPERATION
100% 50% !

Feed Concentrate
Suspended Solids Suspended Solids
Colloids Colloids
Dissolved Solids Dissolved Solids

Membrane

Permeate
Low molecular
weight dissolved 50% !
solids
Liquid

To River, Sewer or Re-use


ADVANTAGES OF MEMBRANE
PROCESSES
 They are usually continuous
 Comparatively low energy utilisation
 No phase change of contaminants
 Small temperature change
 Modular design
 Minimum of moving parts
 Physical separation of contaminants
Properties of Pressure Driven Membrane Processes
Membrane Membrane Applied Pressure Applications Membrane
Process Type Thickness

Mikrofiltration Symetric or Hidrostatik Separation of Particles 10-150 μm


Asymetric pressure (<2 bar)
microporous

Ultrafiltration Symetric or Hidrostatic Separation of 0.1-1 μm


Asimetric pressure (1-8 bar ) Macromolecules
microporous

Nanofiltration Asymetric Hidrostatic Small Organic


pressure (10-30 bar) Compounds and Selected 0.1-1 μm
Salts

Reverse Asymetric, Hidrostatic Small molecular weight


Osmosis composite pressure (10-100 bar) soluble compounds 0.1-1 μm
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MICROFILTRATION
Removal of particles in the fluid by means of pressure through
the microporous membrane
Microfiltration is basically the same processes as reverse
osmosis, ultrafiltration and nanofiltration, only the size range of
the separated material is different.

P (Pressure)
0.7-7 bar
Suspension solids,
sand, clay,
Membrane bacteria, oil
0.1 – 3 μm emulsions
Viruses, multivalent,
monovalent ions,
water
 It is used to hold particles larger than 0.6 μm.

 The pressure difference between feed and


filtrate in microfiltration is 0.7-2 bar.

 Only porous membranes are used in


microfiltration.
MIKROFILTRATION

 Microfiltration membranes are characterized by


the "Nominal Pore Diameter".

 Nominal Pore Diameter is the most abundant


pore size in the pore size distribution.

 The majority of microfiltration membranes are


symmetrical.
 While selecting microfiltration membranes, properties

such as mechanical strength of the membrane,


resistance to temperature, chemical compatibility of the
membrane, hydrophobicity, hydrophility and permeability
should be taken into consideration.

 Tubular and capillary membrane modules are mostly

preferred.
MATERIALS USED IN
THE PRODUCTION OF
MICROFILTRATION
MEMBRANES
cellulose nitrate

natural and synthetic polymers


such as; cellulose nitrate or
acetate, polyamides, polyvinylidene
fluoride, polysulfone,
polycarbonate, polypropylene etc.

polypropylene

polyvinylidene fluoride
APPLICATIONS OF MICROFILTRATION

 Food, pharmaceutical, nuclear, chemical and beverage


industry

 Separation of particles to get


pure water

Separating oil-water emulsions


Metal ion recovery etc.
 Ultrafiltration is similar to microfiltration in terms of
operation.

 It is used to hold particles between 0.1-0.01 μm.

 The UF top layer is supported by a high permeability


ULTRAFILTRATION and selectivity substrate with a thickness of 50-250 μm.
(asymmetrical membrane)

 UF membranes are used to separate dissolved


substances and small particles.

 Usually tubular, capillary and spiral-wound modules are


used
 Since determining the pore size
distribution in ultrafiltration membranes is
expensive, "molecular weight" is used as
the characteristic separation size.

 In a membrane filtration, the molecular


weight area MWCO (Molecular Weight
ULTRAFILTRATION Cut Off) in which 90-95% of the
molecules are kept is given as the
"SEPARATION LIMIT".

 Typical molecule separation limit for


ultrafiltration membranes is around 1,000-
100,000 D (Dalton) = kg / kmol.

 This value has been determined for each


type of membrane.
 Food and dairy industry
 Pharmaceutical industry (crushes,
antibiotics)
 Textile industry
 Chemical industry (oil-water
ULTRAFILTRATION
mixtures, paint recovery)
APPLICATIONS
 Paper industry
 Leather industry
 For pre-treatment purposes before
RO and NF
 Advanced purification in drinking
water
 It is located between reverse osmosis and
ultrafiltration membranes in terms of pore diameter.
 Nanofiltration membranes are operated at lower
pressures than reverse osmosis.
 Spiral wound membrane modules are widely used
in NF devices.
NANOFILTRATION
 It is used for the removal of molecules with a
diameter greater than 0.001 μm.
 The removal of divalent ions with nanofiltration
membranes is higher than the removal of
monovalent ions.
 The MWCO value of nanofiltration membranes
varies between 100-300 Da.
 Whey solution

 In the recovery of dairy industry


wastewater

 Color and TOC removal in the textile


NANOFILTRATION industry
APPLICATIONS
 Concentration and desalination of
organic substances in food and
pharmacy
 Surface waters hardness, pesticide

Water production cost with NF


membrane is lower than RO membrane.
REVERSE OSMOSIS
Water is forced to pass through the
pores on the membranes under high WORKIN
pressure.
G
PRINCIP
During this process, water LE OF
molecules and some inorganic
molecules can pass through these
pores, while most of the substances
REVERS
in the water cannot pass through
these pores and are thrown out as E
concentrated water.
OSMOSIS
SYSTEM
This process allows to obtain much
better water quality in the desired
capacity compared to other filtration
systems.
FACTORS AFFECTING REVERSE
OSMOSIS PERFORMANCE:

Operation
Temperature
Pressure

Feed Water
Dissolved Mineral Membrane Type
Concentration
 Drinking water production

 Fruit juice and beverage industry

 Steam boiler feed water

 Steam generator feed water


INDUSTRIAL  Power plants

APPLICATIO  Chemical industry

NS OF  Pharmaceutical industry

REVERSE  City and utility water production from sea


water
OSMOSIS  Waste water recovery
COMPARISON OF MEMBRANE
PROCESSES
Ultrafiltration Reverse Osmosis Microfiltration

Operates on difficult Requires extensive pre- Rapidly fouled by colloids


colloidal water treatment of colloids giving high replacement costs

Low pressure (2-6 bar) High pressure (10-30 bar) Low pressure (2-4 bar)

Low energy consumption High energy Low energy

High recovery (up to 95%) Low recovery (50-80%) 100% recovery

Chemical tolerance pH 1-13 pH 2-11 pH 1-13

High temperature up to 80oC 45oC max. High temperatures possible


High resistance to oxidising Limited resistance to High resistance to oxidising
agents oxidising agents agents

Stream sterilisable Stream sterilisation not Stream sterilisation possible


membranes available possible

Hygienic module designs Modules not as hygienic Hygienic designs available


available
SIZE OF MATERIALS THAT ARE REMOVED BY VARIOUS
SEPARATION PROCESSES
PARAMETERS EFFECTING
MEMBRANE SELECTION
Temperature Resistance

Chemical Compatibility

Pressure Resistance

pH resistance

Mechanical Stability
RESISTANCE TO
TEMPERATURE

Temperature is the main factor affecting the performance of the


polymeric material.
Membrane technology can be used at temperatures from 0 oC to
82oC.
Ultrafiltration system is more sensitive than microfiltration.

Cellulose acetate membranes, which are the most used


membrane type and have a lower cost than others, have a
resistance up to 35-40oC.
The temperature applied to ceramic membranes, which is
another type of membrane, can reach up to 800 oC.
CHEMICAL
COMPATIBILITY
 Membrane polymers must be chemically
solution-compatible and durable.

 Depending on the chemical substances in


the solution, performance degradation
may occur in the membrane.

 Cellulose acetate membranes are


particularly not resistant to chlorine.
pH is important for the life of
the membrane.

pH range 2-8 PH
RESISTAN
CE
Cellulose acetate membranes
are very sensitive to pH.

Membrane usage is limited in


high pH.
It is less important than
other features.
MECHANI
CAL
STABILIT
Y
The mechanical strength of
the membranes where high
pressures are used must
also be high.

37
MEMBRANE
FOULING

 This loss of performance in the


membrane as a result of the
clogging or narrowing of the pores
as a result of the accumulation of
particles or other contaminants on
or inside the membrane is called
membrane fouling.
 causes a decrease in membrane
permeability
 The decrease in flux affects the cost
of membrane plants.
There are two types of fouling

Reversible fouling: Membrane washing done hydraulically or with


chemicals can remove some contaminants that accumulate on the
membrane surface. If the amount of flux after cleaning is the same as
the initial flux, it is reversible clogging.

Non-reversible fouling: If the flux value at the end of the wash is


different from the initial flux value, non-reversible fouling
METHODS APPLIED TO REDUCE
MEMBRANE FOULING

 Pretreatment
 Membrane Properties
 Module and process conditions
 Washing: 1. Hydraulic Washing
2. Chemical Washing
3. Mechanical Washing
4. Electrical Washing
HOW SHOULD AN IDEAL
MEMBRAN BE?
 High permeability to solvent (solvent)
 Suitable filtering property
 Mechanical durability
 Chemical Stability
 Thermal Stability
 Reproducibility
 Cheap
 Easy to produce
 Easy to clean

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