Electrodeionization (EDI) - desalacion.org · EDI Technology History • 1955 - Walters et al, work with periodic electro-regeneration of ion exchange resin in stack. • 1957 - Kollsman

Electrodeionization (EDI)

Outline

• Process Principles • EDI History • Applications and Benefits • Performance • Feed Water Requirements and Pretreatment

Process Principles

Device

Process Principles

• Cation exchange membrane • Anion exchange membrane • Spacers • Electrodes •  Ion exchange resin

HCO3-

- - - - Cathode (-)

+ + + + Anode (+)

SiO2

CO2

Na+ SO4

= Cl- Ca++

Anion-Exchange Membrane

Cation-Exchange Membrane

Process Principles

Feed

Product Concentrate Recycle

Concentrate Make-up

Waste

EDI System

Process Principles

How does EDI work?

Process Principles

• 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

Anion-Exchange Membrane Cation-Exchange Membrane

CH 3

N +

CH 3

CH 3

CH 3

N +

CH 3

CH 3

CH 3

N +

CH 3

CH 3

Cl -

Cl -

Cl -

Mobile Counter Anions

Water-Filled Passage

Fixed Cation Sites

Polymer Support Structure

Mobile Counter Cations

Water-Filled Passage

Fixed Anion Sites

Polymer Support Structure

S O -

O

O

S O -

O

O

S O - O

O Na +

Na +

Na +

Ion-Exchange Membrane

HCO3-

Ca++ Na+

SO4= Cl-

Mg++

OH-

H+

HSiO3- CO3

=

High-Purity Product Water HCO3

-

- - - - Cathode (-)

+ + + + Anode (+)

SiO2

CO2

Na+ SO4

= Cl- Ca++

Anion-Exchange Membrane

Cation-Exchange Membrane

Process Principles

Enhanced transfer regime

Ions are transferred from solution to resins by diffusion. Ions move inside resins by means of electricity Ions reach the membranes and pass to the brine flow.

Process Principles

Polarization

Concentrado

Cationic Membrane

Anionic Membrane

Concentrate

Concentrate

FEED

H+ + HCO-3 CO2 + H2O

H2O H+

OH-

OH- + HCO-3 CO3

-- + H2O CO--

3 + Ca++ CaCO3

Electro regeneration Regime

Process Principles

• 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

Polarization

µ S/cm

EDI History

EDI Technology History

•  1955 - Walters et al, 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. •  1987 - Millipore Commercialized EDI - “CDI”.

Applications and Benefits

EDI Applications

• Microelectronics • 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

Weakly Ionized Species Removal By EDI

0

0.5

1

1.5

2

2.5

3

0 100 200 300 400 500 600 Operating Hours

Prod

uct C

ondu

ctiv

ity (

S/cm

) RO - MB IX RO - EDI 2 Pass RO

Product Quality Comparison

Boron Removal by EDI

• Boron present at very low concentrations in many waters

• Presence of Boron often unchecked • Boron can cause problems in semiconductor

manufacturing

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: –  50% to 80% 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 at 20% to 50% of silica run-length

• Boron displacement produces Boron spikes in product water

Performance of Mixed-Bed Ion-Exchange

Undetected Boron Invasion Zone

0 2 4 6 8

10 12 14 16 18 20

Operating Time

Meg

ohm

-cm

0

2

4

6

8

10

12

14

ppb

Effluent Resistivity (monitored) Influent Boron Effluent Boron Effluent Silica (monitored) EDI Effluent Boron

(Boron Break-through could effect wafer yield)

Boron Removal By EDI

• One of the most effective process to removal boron

• Well designed EDI will provide 96% to 99% boron rejection consistently

Feed B(ppb)

Product B(ppb)

B Removalby EDI (%)

B Removalby RO (%)

SemiconductorPlant #2 71 2.75 96.8 39.3

SemiconductorPlant #3 83.5 2.8 96.1 24.1

SemiconductorPlant #4 64.4 0.74 96.6 24.1

SemiconductorPlant #5 2.5 <0.1 >96.0 34.2

Boron Levels and Removal by RO and EDI

EDI Boron Removal at Varying Current Density

70

75

80

85

90

95

100

0 0.2 0.4 0.6 0.8 1 1.2 1.4I/Io

Boro

n Re

mov

al (%

)

Silica Removal by EDI

Silica removal is critical for semiconductor manufacturing

•  high silica levels lead to expensive chip failures

•  spec. limited by the ability of instrumentation

Silica Levels and Removal by EDI

Feed SiO2

(ppb)Product SiO2

(ppb)SiO2 Removal

(%)SemiconductorPlant #1 642 3.1 99.5SemiconductorPlant #2 181 2.8 98.5SemiconductorPlant #3 393 <2 >99.5SemiconductorPlant #4 274 2.6 99.1SemiconductorPlant #5 650 <5 >99.2

Study 2: EDI Performance at Varying Current Density

90

92

94

96

98

100

0,5 0,7 0,9 1,1 1,3

Sili

ca R

emov

al

(%)

I / Io

Feed Conductivity=20 micros/cm, CO2=6 ppm

Study 3: Current Densities Required to Maintain >98.5% Silica Removal

0

0,5

1

1,5

2

2,5

3

3,5

4

0 50 100 150 200 250

I/Io

Feed$Conduc*vity$(µS/cm)$

Carbon Dioxide Removal by EDI

• Carbon dioxide is often largest load on ion-exchange beds, especially after an RO

• Not effectively removed by other membrane demineralization processes such as RO or ED unless chemical adjustments are made

• Removed >99% by EDI

CO2 Levels and Removal by EDI

Feed CO2

(ppm)Product CO2

(ppb)CO2 Removal

(%)SemiconductorPlant #1 2.80 10 99.6SemiconductorPlant #2 4.48 29 99.4SemiconductorPlant #3 6.52 25 99.6SemiconductorPlant #4 6.05 10 99.8SemiconductorPlant #5 6.50 22 99.7

Summary of Weakly Ionized Species Removal

• > 99% Silica removal

• > 99% CO2 removal

• > 96% Boron removal

• > 98% Ammonia removal

Feed pH

Perc

ent o

f CO

2 or S

iO2 i

n Io

nize

d Fo

rm

% of SiO2 Ionized

% of CO2 Ionized

100

80

60

40

20

14

Resin pH

Feed

/Ani

on R

esin

pH

8

12

10

6

4

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

% of Flowpath INLET OUTLET

Process Principles

EDI Performance

EDI Stack Design

EDI Performance and Pretreatment

Performance

• EDI performance effected by: –  Feed water quality –  Stack current –  Water recovery –  Flow rate –  Temperature

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

Scaling in EDI

Cathode (-)

+ + + + Anode (+) SO4

= Cl- HSiO3-

H+ Ca++ Na+ Mg++

HCO3-

HCO3-

SiO2

CO2

Na+

SO4=

Cl-

Ca++

OH-

Anion-Exchange Membrane

HCO3- + OH- --> CO3

= + H2O Ca++ + CO3

= --> CaCO3

Ca++

Cation-Exchange Membrane

Feed Water Requirement

Non-Scaling Area

Water Recovery Decrease

Total CO2 Concentration

Har

dnes

s

PERFORMANCE

• Stack Current –  Controlled by

•  Stack voltage •  Brine & electrode stream conductivity

–  Optimum current •  Too high current

– Higher scaling potential – CO2 back diffusion – Higher power consumption –  Shorter membrane life

PERFORMANCE

• Temperature

–  Better performance at higher temperature

–  Stack pressure drop is sensitive to temperature

Feedwater Requirements and Pretreatment

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

Testing - Organics • What is removed?

–  Organic acids (acetic acid) –  TMAH(tetramethyl ammonium hydroxide) –  NMP(N-Methyl Pyrollidone)

• What may be removed? –  Waco(601?) surfactant

• What isn’t removed? –  IPA

• What may not be removed? –  Anti-forming agent –  Ethylene glycol

EDI Operation and Maintenance

STACK MAINTENANCE

• Routine Maintenance • Scaling and Scaling Control • Fouling and Fouling Control • Bacteria Control • Cleaning-In-Place

STACK MAINTENANCE

• Routine Maintenance –  Daily log sheet –  Visually inspect the stack weekly –  Hose down any chemical buildup outside the

stack –  Check the stack torque for the first three month,

and twice a year thereafter

STACK MAINTENANCE

• Stack Scaling

–  Increasing stack resistance

–  Reducing brine flow rate

–  Decreasing silica rejection

–  Product resistivity decline

STACK MAINTENANCE

• Scaling Control

–  Brine stream pH control •  pH3 or lower

–  Softener addition ahead of EDI

–  Reduce water recovery

–  Reliable RO

STACK MAINTENANCE

• Stack Fouling

–  Increasing stack resistance

–  Decreasing silica rejection

–  Product resistivity decline

–  Stack pressure drop increase

STACK MAINTENANCE

• Fouling Control

–  AC filter

–  UV

–  Organic scavenger

–  Reliable RO

STACK MAINTENANCE

• Bacteria Grow in Brine Stream

–  Brine flow decrease

–  High bacteria count in brine stream

• Bacteria Control

–  Sanitize the brine stream periodically •  0.1 to 0.2 ppm level of chlorine

STACK CLEANING

• Cleaning-in-place (CIP)

–  Continuous (in-flight) brine stream acid CIP •  pH 1.5 for hours

–  Batch brine stream acid CIP •  pH1 or lower for more than 30 min.

–  Dilute stream salt & caustic CIP •  10% salt •  pH11 •  40 C