Haasrode

October
2006

Electrodeionization (EDI) Technology

Outline

•Background on UPW
•Process Principles
•EDI History
•Applications and Benefits
•Ionics EDI and Performance
•Feed Water Requirements and Pretreatment
Background on UPW
Background on UPW

There have been few new technology developments in

purifying water over the past 10+ years
> UPW Systems essentially still comprise RO, DI, UV,
Degasification, and Filtration to remove TDS, TOC, O2,
Bacteria, and Particles
> Progress in purifying water has principally been a
result of utilizing new materials of construction, new
applications of technology, methods of operation, and
product improvements
Background on UPW

However, the purity requirements of Ultra Pure Water

have continued to increase pushing the envelop of
“conventional” water treatment technologies.
Specifically, new treatment technologies that cost-
effectively address Boron and Reactive Silica levels are
required
> Typical 0.25-micron and 0.18-micron geometry
specifications require:
– Boron <50-ppt
– Silica <0.1-ppb
Background on UPW

At the same time, the microelectronics industry has

heightened concerns and demands for:
> Environmental and Personnel Safety (e.g., reduction in
chemicals handled, stored, and disposed)
> Water use efficiency (Good neighbor)
> Life-cycle cost
> Space utilization (Space = Money)
> Reliability (100% Uptime)
> Water Quality consistency
Background on UPW

To meet these increased water quality

requirements, environmental and safety concerns,
water and space efficiency, reduced life-cycle cost,
and improved reliability and water quality
consistency - new technology is required!

ELECTRODEIONIZATION (EDI)
Process Principles
Process Principles

Device
•Cation exchange membrane
•Anion exchange membrane
•Spacers
•Electrodes
•Ion exchange resin
Process Principles

- - Cathode (-) - -

CO2 Cation-Exchange Membrane

Ca++
SiO2 -
Cl
Na+
SO4=
HCO3- Anion-Exchange Membrane

+ + Anode (+) + +
Process Principles

EDI System

Feed
Concentrate
Make-up

Concentrate Recycle Product

Waste
PROCESS PRINCIPLES
Ion-Exchange Membrane
Anion-Exchange Membrane Cation-Exchange Membrane

CH 3
Cl- O Na+
N+ S O-
CH 3CH 3 Mobile Counter Anions O Mobile Counter Cations
CH 3 Cl- O +
Na
N+ Water-Filled Passage S O- Water-Filled Passage
CH 3CH 3 O
CH 3 Cl- Fixed Cation Sites O Na+
Fixed Anion Sites
N+ S O-
CH 3CH 3 Polymer Support Structure O Polymer Support Structure
Process Principles

How does EDI work?

Enhanced transfer regime (high salinity)
> Remove strong ions from water

Electroregeneration regime (low salinity)

> Remove ionizable species (weak acids or weak bases)
from water
Process Principles

- - Cathode (-) - -
Ca++ Mg++ Na+ H+

CO2 Cation-Exchange Membrane High-

Ca++ Purity
SiO2 -
Cl Product
Na+
SO4= Water
HCO3- Anion-Exchange Membrane

SO4= Cl- HCO3- HSiO3- CO3= OH-

+ + Anode (+) + +
Process Principles

Electroregeneration Regime
Resin in hydrogen and hydroxide forms
Removal of weakly ionized compounds by
ionization reactions
> CO2 + OH- ---> HCO3- pKa = 6.4
> HCO3- + OH- ---> CO3= pKa =10.3
> SiO2 + OH- ---> HSiO3- pKa = 9.8
> H3BO3 + OH- ---> B(OH)4- pKa = 9.2
> NH3 + H+ ---> NH4+ pKa = 9.2
Process Principles

14
100
% of CO2 Ionized

Percent of CO2 or SiO2 in

% of SiO2 Ionized
Feed/Anion Resin pH

12
80

Ionized Form
10
60
Resin pH
8

40
6

Feed pH
4
20

0-10 30-40 60-70 90-100

INLET OUTLET
% of Flowpath
EDI History
EDI Technology History

1955 - Walters et al, radwaste work with periodic electro-

regeneration of ion exchange resin in stack.
1957 - Kollsman patent on basic EDI method and
apparatus.
1959 - Gluekauf, early EDI experimental data and theory.
1960’s - Early Ionics EDI experiments.
1970’s - Ionics EDI research continuous.
1987 - Millipore Commercialized EDI - “CDI”.
1991 - IONICS, 50 gpm EDI unit installed at GGNS.
Applications and Benefits
EDI Applications

Microelectronics
> UPW
> IWT
Power Generation
Boiler Feed
Pharmaceutical
Industrial
Others
Technology Benefits

Continuous process with constant stable product

quality.
No acid or caustic regenerants required
No upsets or downtime from regeneration
No need for high purity water rinse and backwash
Produces high purity water with high water
recovery (95%).
Additional Technology Benefits

No regeneration waste
Eliminates need for a waste treatment plant
Eliminates acid and caustic storage tank
Eliminates acid and caustic dilution skid
Reduced floor space
Safe and reliable (No chemical handling)
Additional Technology Benefits

Minimizing on-going O&M costs

> essentially no chemical usage
> minimal maintenance
Easy to install
> lower installation costs than with conventional ion-
exchange
> on-line quicker
Provide consistent high percentage boron rejection
Product Quality Comparison

RO - MB IX
RO - EDI
Product Conductivity ( S/cm)

2.5
2 Pass RO

1.5

0.5

0
0 100 200 300 400 500 600
Operating Hours
 Boron Removal by RO
• Boron removal by RO is pH dependent
• RO does not reject Boron well at neutral pHs due to:
– poor ionization of boric acid
– extremely small boric acid molecule

• Typical Boron rejection by RO:

– 30% to 60% at neutral pH
– >90% when > pH10
 Boron Removal by Ion-Exchange
• Boron is not well removed by ion-exchange due to:
– low selectivity
– poor ionization of boric acid
• Boron is the first to break through ion-exchange
• Studies show Boron breaks through 2 to 5 times
faster than silica
• Boron displacement
Ionics EDI and
Performance
Unique Product Design

Longer flow path and residence time

Patented ion-exchange membrane
Patented external resin filling method
Rugged Industrial system design for large scale
application
Patented Ion-Exchange Membrane

Homogenous Membrane Anion-Exchange Membrane

CH 3
Cl-
Lower Electrical Resistance N+
CH 3CH 3 Mobile Counter Anions
CH 3 Cl-
N+ Water-Filled Passage
Provides excellent ion CH 3CH 3
CH 3 Cl- Fixed Cation Sites
N+
transfer CH 3CH 3 Polymer Support Structure

Rugged membrane Cation-Exchange Membrane

O Na+
Long membrane life S O-
O Mobile Counter Cations
O Na+
S O- Water-Filled Passage
Chlorine stable O
O Na+
Fixed Anion Sites
S O-
O Polymer Support Structure
Homogenous
Ion-exchange Membrane

100% IX Resin
Heterogeneous
Ion-exchange Membrane

IX Resin

Plastic Substrate
Heterogeneous
Ion-exchange Membrane

IX Resin

Plastic Substrate
Homogenous
Ion-exchange Membrane

IX Resin

Fibers
Heterogeneous
Ion-exchange Membrane

IX Resin

Plastic Substrate
Heterogeneous
Ion-exchange Membrane

IX Resin

Plastic Substrate
Anion
Ion-exchange Membrane Comparison
Ionics EDI CDI E-Cell

Membrane Homogenous Heterogeneous Heterogeneous

Type
Capacity 2.0 1.5 1.5
(meq/g)
2
R (ohm-cm ) 10.6 23.4 48

Thickness 0.060” 0.069” 0.063”

Burst (psi) 275 35 20

Cation
Ion-exchange Membrane Comparison
Ionics EDI CDI E-Cell

Membrane Homogenous Heterogeneous Heterogeneous

Type
Capacity 2.3 2.3 2.3
(meq/g)
2
R (ohm-cm ) 10.9 17.8 33.8

Thickness 0.063” 0.069” 0.058”

Burst (psi) 270 35 20

Ionics EDI

Patented stack design

> External filling and emptying ion-exchange
resin
> Can replace individual spacers or membranes if
ever required:
– Low maintenance cost
– Field Serviceable
Ionics EDI
IONICS provide complete system and components
required for the EDI system
> EDI stack
– Membrane
– Spacer
– Electrode
> Electrical Control
> Hydraulic skid
Ionics EDI
Consistent high quality performance
> High product Megohm
> High rejection on weakly ionized compounds
– SiO2: 95% ~ 99+%
– H3BO3: >96%
– CO2: ~99%
Decarbonation is not always necessary
High water recovery
Ionics EDI
Ionics EDI experiences in semiconductor industry:

– MEMC – Microchip – TDK

– ST Micro – Delco – Shinko
– LSI Logic – Komatsu – Toppan
– Cherry – Sumitomo – Akita
Semiconductor – Seagate – Procomp
– SGNEC – TI – Citizen
– UMTC – HP – more….
– Komag – Ashland
– Motorola – Citizen
Ionics EDI
Standard Product Line:
> 50 gpm (11.4 M3/h)
> 100 gpm (22.7 M3/h)
> 150 gpm (34.1 M3/h)
> 200 gpm (45.4 M3/h)
> 250 gpm (56.8 M3/h)
> 300 gpm (68.1 M3/h)
> 350 gpm (79.5 M3/h)
> 400 gpm (90.8 M3/h)
Ionics EDI 50/100
Ionics EDI 200
Typical Performance
Performance after RO:

99.5% salt removal

Up to 18+ MW-cm

95% ~ 99+% silica rejection

Up to 96+% boron rejection

Up to 99+% CO2 rejection

Conclusions

50 years ion exchange membrane experience

Patented EDI Membranes
Patented EDI Stack Design
Superior Performance
Leading EDI supplier in Semiconductor Industry
Long Term Industry Track Record
Performance

EDI performance effected by:

> Feed water quality
> Stack current
> Water recovery
> Flow rate
> Temperature
EDI Performance
100%

98%
%Silica Removal

96%

94%

92%

90%

2.0 2.5 3.0 3.5 4.0 4.5 5.0

Stack Amps
EDI Performance

100%

99%
%Silica Removal

98%

97%

96%

95%
35 40 45 50 55 60 65 70 75 80

Flow Rate (GPM)

EDI Performance
25

20
Stack DP (PSI)

15

10

35 40 45 50 55 60 65 70 75 80

Flow Rate (GPM)

EDI Performance

5.0

4.5
Stack Amps

4.0

3.5

3.0

2.5

2.0

350 370 390 410 430 450 470 490

Stack Voltage
 Feed water
Requirements and
Pretreatment
Scaling in EDI

Cathode (-)
Ca++ Mg++ Na+ H+
Cation-Exchange Membrane
CO
2
Ca+
SiO2 +

Cl
Na -
+
SO4
=
HCO 3 Anion-Exchange HCO3- + OH- --> CO3= + H2O
-
Membrane ++ =
Ca + CO3 --> CaCO3

SO4= Cl- HCO3- Ca++ HSiO3- OH-

+ + + (+) +
Anode
Feed Water Requirement
Conductivity: < 40 mS/cm
Hardness: < 0.25 ppm as CaCO3
TOC: < 0.5 ppm
Pressure: 20 to 50 psi
Temperature: 10 to 35oC
pH: 4 to 10
Chlorine: < 0.1 ppm
Fe, Mn, Sulfide: < 0.01 ppm
CO2 < 8 ppm
Pretreatment

Minimum pretreatment
> TFC RO is required to minimize:
– Scaling
– Organic fouling
– Particulate and colloidal plugging
– Oxidative attack
– Chemical cleaning
Pretreatment

Optional pretreatment
> Multimedia filter
> AC filter
> Degasification
> UF
> Softener
> UV
> Organic scavenger
Some Example
UPW Plant at Central Texas

A 700 gpm EDI Plant with PVDF Piping

UPW Plant in Arizona

A 120 gpm EDI Plant with CPVC Piping