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DIALYSIS and

ELECTRODIALYSIS
Maretva Baricot
Ronnie Juraske
Course: Membrane Separations
December, 2003
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Dialysis
What is dialysis?
Dialysis is a membrane process where solutes (MW~<100 Da)
diffuse from one side of the membrane (feed side) to the
other (dialysate or permeate side) according to their
concentration gradient. First application in the 70s.

General Principles
Separation

between solutes is obtained as a result of


differences in diffusion rates.
These are arising from differences in molecular size and
solubility.
This means that the resistance increases with increasing
molecular weight.
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Dialysis
A typical concentration profile for dialysis with boundary layer
resistences

contains low-molecular-weight solute, A


intermediate size molecules, B , and a colloid, C

Dialysis
In order to obtain a high flux, the membrane should be as thin
as possible
membrane
feed

Purifed
feed

dialysate

Schematic drawing of the dialysis process


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Dialysis
The solutes separate by passing through the membrane that
behaves like a fibre filter and separation occurs by a sieving
action based on the pore diameter and particle size
(i.e. smaller molecules will diffuse faster than larger molecules).

Transport proceedes via diffusion through a nonporous


membranes.

Membranes are highly swollen to reduce diffusive resistence.

Dialysis
Transport
Separation of solutes is determined by the concentration of the molecules on either side of the membrane; the molecules
will flow from a high concentration to a lower concentration.
Dialysis is a diffusion process and at steady-state transport can be described by :

D K
P
J i i i ci i ci
l
l
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Dialysis
Membranes
homogeneous
Thicknes: 10 100 m
Membrane material: hydrophilic polymers (regenerated cellulose such as cellophane, cellulose acetate, copolymers of ethylene-vinyl alcohol and ethylene-vinyl acetate)
Membrane application: optimum between diffusion rate and swelling

Dialysis
Applications
Dialysis is used in varying circumstances such as: when a large
pressure difference on the sides of the membrane is impractical,
in heat sensitive areas, and when organic solvents are not
feasible. In areas such as the bloodstream, a pressure difference
would rupture blood cells. Dialysis is not a function of pressure;
therefore a pressure difference is not needed.
By far the most important application of dialysis is the therapeutic
treatment of patients with renal failure. The technique is called
hemodialysis and attempts to mimic the action of the nephron of
the kidney in the separation of low molecular weight solutes, such
as urea and creatinine, from the blood of patients with chronic
uremia.
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Dialysis

Dialysis
Further applications
Recovery of causic soda from colloidal hemicellulose during viscose manufacture
Removal of alcohol from beer
Salt removal in bioproducts (enzymes)
Fractionation (pharmaceutical industry)

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Dialysis
Diffusion dialysis
Diffusion process in which protons and hydroxyl ions are removed from an aqueous stream across an ionic membrane due to a concentration difference
Similar to dialysis but due to the presence of ions and an ionic membrane => Donnan equilibria build up => electrical potential has to be included into the
transport (flux) calculation.

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Dialysis
Diffusion dialysis
Membranes: ion exchange membranes (cation and anion) similar to electrodialsis
Thickness: ~few hundreds of m (100 - 500 m)
Separation principle: Donnan exclusion mechanism
Main applications: acid recovery from eaching, pickling and metal refining; alkali recovery from textile and metal refining processes.

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Dialysis
Diffusion dialysis
Example: HF and HNO3 are often used as etching agents for stainless steel. In order to recover the acid,
diffusion dialysis can be applied since the protons can pass the membrane but the Fe 3+ ions can not.

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Dialysis
Share of the market
Although the application range of dialysis is limited and the industrial interest
is low, it would be silly to claim that dialysis is not important.

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Dialysis

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ELECTRODIALYSIS (ED)
What is electrodialysis?
Electrodialysis is a membrane process in which ions are
transported through ion permeable membranes from one
solution to another under the influence of an electrical
potential gradient. First applications in the 30s.

General Principles
Salts

dissolved in water forms ions, being positively


(cationic) or negatively (anionic) charged.
These ions are attracted to electrodes with an opposite
electric charge.
Membranes can be constructed to permit selective passage
of either anions or cations.
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ELECTRODIALYSIS (ED)
How the process takes place?
Electrodialysis cell

Module
Hundreds of anionic and cationic
membranes placed alternatively

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ELECTRODIALYSIS (ED)
Ion Permeable Membranes
Non porous

Sheets of ion-exchange resins and other polymers


Thickness 100 - 500 m

Are divided in
Anion - exchange
Positively charged groups
E.g. Quarternary ammonium salts
NR3 or C5H5N-R

Cation - exchange
Negatively charged groups
E.g. Sulfonic or carboxylic acid groups
- SO3 -

Chemically attached to the polymer chains


(e.g. styrene/divinylbenzene copolymers)
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ELECTRODIALYSIS (ED)
Types of Ion - Exchange Membranes
Heterogeneous

Ion - exchange resines + Film - forming polymer


High Electrical resistance
Poor mechanical strenght

Homogeneous

Introduction of an ionic group into a polymer film

Crosslinking

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ELECTRODIALYSIS (ED)
Requirements for Ion - Exchange Membranes
High electrical conductivity
High ionic permeability
Moderate degree of swelling
High mechanical strength
Charge density 1 - 2 mequiv / g dry polymer
Electrical Resistance 2 - 10 .cm2
Diffusion coefficient 10-6 - 10-10 cm2/s
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ELECTRODIALYSIS (ED)
How the process takes place?
Donnan exclusion
Electrostatic repulsion

Osmotic flow

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ELECTRODIALYSIS (ED)
Equations involve in the process
k
t
i
k
J
zF

dC
J D
dx
b
D

k = m, b

(1)

In Steady State

J J J
m

b
D

(3)

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(2)

ELECTRODIALYSIS (ED)
Equations involve in the process
Boundary conditions

x0

C C

C Cb

Operational i

i Current density [A/m2


(4)

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zDF C C
i
b m

t t
m

ELECTRODIALYSIS (ED)
Equations involve in the process
Limiting current density

ilim

ilim

Cm

zDF
Cb

m b

t t

0
(5)

Required membrane area

Vc C in C out z F
Am
i

(8)

At Am N

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(9)

ELECTRODIALYSIS (ED)
Equations involve in the process
Required membrane area

V C in C out z F
At
i

(10)

Required energy
Vc C in C out z F
Rc
P N

(15)

P Required power [J/s

Rc Total resistance in a cell

()
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ELECTRODIALYSIS (ED)
Designing of an electrodialysis desalination plant
Desalination 142 (2002) 267-286

Parameters:
Stack Construction
Feed and product concentration
Membrane permselectivity
Flow velocities
Current density
Recovery Rates

Optimized in terms of

Width of the cell


Length of the stack
Thickness of the cell chamber
Volume factor
Shadow effect
Safety factor

Component design and properties


Operating Parameters

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ELECTRODIALYSIS (ED)
Electrodialysis desalination costs
Costs

Amount of ionic species

Operating costs
Energy consumption
Maintenance

Electrical energy
Energy for pumps

Plant size
Feed salinity

Capital costs
Depreciable items (ED stacks, pumps, membranes, etc.)
Non-depreciable items (land, working capital)
Membrane Costs

Properties
Feed concentration

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ELECTRODIALYSIS (ED)
Electrodialysis
desalination costs as a
function of the
limiting current
density at a feed
solution concentration
of 3500 mg/l NaCl

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ELECTRODIALYSIS (ED)

Electrodialysis desalination costs


as a function of the Feed solution
concentration

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ELECTRODIALYSIS (ED)
Applications

Potable from brackish wate


Reduce
Electrolyte
Content

Food products - whey, milk, soy sauce, fruit juice


Nitrate from drinking water
Boiler feed water
Rinse water for electronics processing
Effluent streams
Blood plasma to recover proteins
Sugar and molasses
Amino acids
Potassium tartrate from wine
Fiber reactive dyes

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ELECTRODIALYSIS (ED)
Recover Electrolytes

Pure NaCl from seawater


Salts of organic acids from fermentation broth
Amino acids from protein hydrolysates
HCl from cellulose hydrolysate

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ELECTRODIALYSIS (ED)
Electrodialysis Reversal Process (EDR)
The polarity of the electrodes is reversed, so the
permeate becomes the retentate and viceversa.

Electrodialysis at high temperatures


Electrodialysis with electrolysis

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