International Flemion Seminar 2012

Effect of Impurities on
Membrane Performance
& Recovery of Performance

June, 2012
Contents

General Information
1) Model of Impurity Deposits
2) Classification of Impurity Influences

Investigated Results; Influential Factor

1) Investigation Method
2) Influential Operation Factors
3) Most Influential Impurities on Cell Voltage
4) Recovery method

Performance of new F-8080 Series

1
Model of Ion Channel

Normal State
Hydrophobic Area

Hydrophilic Area COO- COO- OH-

H 2O
H 2O H 2O
H2O Na+ H 2O H 2O
Na+
H 2O Na+
H 2O H 2O H 2O
COO- H 2O H 2O
COO-

It is hard for anions to pass through the membrane due

to the repulsive force of fixed negative charge.

2
Basic Structure of Flemion Membrane

Sulfonic Carboxylic Layer

Layer (High Selectivity)

(High
Conductivity)

Woven Cloth

Flemion membrane is composed of two layers.

3
Deposition of Impurities

Mg
Cation Anion
Fe
S-Layer
Ni
Mg
SiO2
Al I/Ba
Ca
Sr I C-Layer
Ba

Deposits in Membranes
→Decrease Membrane Performance!
4
Main Deposit Position and Solubility
Solubility Product Constant
Ksp = [ Mn+ ] [ OH- ]n
Fe(OH)3 Impurity log(Ksp) pH at
[Mn+] = 10-7
Ni(OH)2
Fe -35 4.7
Mg(OH)2 pH: 15 Ni -16 9.5
Mg -12 11.5
pH: 12 Ca(OH)2 Ca -6 14.5

pH: 4

Solubility product of each ion decides the position of

precipitation.

5
Influence of Accumulated Impurities in S-layer

Ni(OH)2
Mg(OH)2 pH: 15

pH: 12

pH: 4

Cell voltage is affected by accumulation of impurities

in the S-layer. Deposition occurs due to sharp pH rise.

6
Accumulate Effect in C-layer

pH: 15

pH: 12 Ca(OH)2

pH: 4 Ba/Iodine

Deposits near the surface of the C-layer decrease C.E.

and increase C.V.

7
Mechanism of High C.E. Performance
Normal State

COO- OH- COO-

H2O
H 2O H 2O
H2O Na+ H 2O H 2O
Na+
H 2O Na+
H 2O H 2O H 2O
COO- H 2O H 2O
COO-

It is hard for anions to pass through the membrane due

to the repulsive force of fixed negative charge.

8
C.E. Decline due to Fine Particle Precipitation
Particle Size < Ion Channel

COO- OH- H 2O COO-

H 2O
H 2O Na+ H 2O
H2 O H 2O
Na+
H2O
COO- H 2O COO-

Decrease in Na ion mobility by dehydrated state

9
C.E. Decline due to Large Particle Precipitation
Particle Size > Ion Channel

COO- OH- COO-

H 2O
H2O H 2O
H2O Na+
H 2O Impurity
Na +

H 2O H 2O H2O
OH-
COO- COO-

OH- can easily pass through the membrane by

ion channel destruction

10
Impurities Matrix
- SiO2 I
OH- Ex.) SiO3 2- Ex.) H2IO6 3-
SiO44-, Si2O76-
Fe
Fe3+
NiFe Fe (+ OH) Fe + SiO2 Fe +I
Ni2+
MgNi Ni (+ OH) Ni + SiO2 Ni +I
SiO
Mg2+2
AlMg Mg (+ OH) Mg + SiO2 Mg + I
Al3+
CaAl Al (+ OH) Al + SiO2 Al +I
SrCa CaI 2+ Ca (+ OH) Ca + SiO2 Ca +I
BaSr Sr2+ Sr (+ OH) Sr + SiO2 Sr +I
Ba Ba2+ Ba (+ OH) Ba + SiO2 Ba +I
- Na+ (Na) (+ OH) (Na) + SiO2 (Na) + I

Combinations of Anion and Cation

11
Deleting Non-existing Combinations
- SiO2 I
OH- Ex.) SiO3 2- Ex.) H2IO6 3-
SiO44-, Si2O76-
Fe Fe3+ Fe (+ OH) Fe + SiO2 Fe +I
Ni Ni2+ Ni (+ OH) Ni + SiO2 Ni +I
Mg Mg2+ Mg (+ OH) Mg + SiO2 Mg + I
Al Al3+ Al (+ OH) Al + SiO2 Al +I
Ca Ca2+ Ca (+ OH) Ca + SiO2 Ca +I
Sr Sr2+ Sr (+ OH) Sr + SiO2 Sr +I
Ba Ba2+ Ba (+ OH) Ba + SiO2 Ba +I
- Na+ (Na) (+ OH) (Na) + SiO2 (Na) + I

12
Impurity Matrix of Harmful Combinations
- SiO2 I
OH- Ex.) SiO3 2- Ex.) H2IO6 3-
SiO44-, Si2O76-
Fe Fe3+ Fe (+ OH)
Ni Ni2+ Ni (+ OH)
Mg Mg2+ Mg (+ OH) Mg + SiO2
Al Al3+ Al (+ OH) Al + SiO2
Ca Ca2+ Ca (+ OH) Ca + SiO2 Ca +I
Sr Sr2+ Sr (+ OH) Sr + SiO2 Sr +I
Ba Ba2+ Ba (+ OH) Ba + SiO2 Ba +I
- Na+ (Na) + SiO2 (Na) + I

13
Structure of Precipitates
- SiO2 I
OH- Ex.) SiO3 2- Ex.) H2IO6 3-
SiO44-, Si2O76-
Fe Fe3+ Fe(OH)3

Ni Ni2+ Ni(OH)2, NixOy

Mg Mg2+ Mg(OH)2 MgSiO3 (Amorphous)

Al3+ Al(OH)3 Na8Al6Si6O24(OH)2・2H2O

Al
Ca2+ Ca(OH)2 Ca5Si6O16(OH)2・8H2O Ca2NaIO6
Ca
Sr2+ Sr(OH)2 SrSiO3 (Amorphous) Sr2NaIO6
Sr
Ba2+ Ba(OH)2 BaSiO3 (Amorphous) Ba2NaIO6
Ba
- Na+ Na2SiO3 (Amorphous) Na5IO6

* Including speculated structure

14
Influence of Impurities to Increase C.V.
- SiO2 I
OH- Ex.) SiO3 2- Ex.) H2IO6 3-
SiO44-, Si2O76-
Fe Fe3+ High
Ni Ni2+ High
Mg Mg2+ High High
Al Al3+ High High
Ca Ca2+ Low Low High
Sr Sr2+ Low Low High
Ba Ba2+ Low Low High
- Na+ Low High

15
Influence of Impurities to Decrease C.E.
- SiO2 I
OH- Ex.) SiO3 2- Ex.) H2IO6 3-
SiO44-, Si2O76-
Fe Fe3+ Low
Ni Ni2+ Low
Mg Mg2+ Low Low
Al Al3+ High High
Ca Ca2+ High High High
Sr Sr2+ High High High
Ba Ba2+ High High High
- Na+ High High

16
Main Position of Precipitation
- SiO2 I
OH- Ex.) SiO3 2- Ex.) 3-
H2IO6 or
S-layer
SiO44-, Si2O76- C-layer ?
Fe Fe3+ S-layer
Ni Ni2+ S-layer
Mg Mg2+ S-layer S-layer
Al Al3+ S & C-layer S & C-layer
Ca Ca2+ C-layer S & C-layer S & C-layer
Sr Sr2+ C-layer S & C-layer S & C-layer
Ba Ba2+ C-layer S & C-layer S & C-layer
- Na+ S & C-layer S & C-layer
*

17
Influence of Impurities on Cell Voltage
Increase of C.V. & Main Comments
Accumulation Position
- SiO2 I S or C
Fe High S Depending on brine acidity

Ni High S Rare cases

Mg High High S C.V. may recover

Al High High S&C C.V. may recover partially

Ca Low Low High S&C Rare cases & C.V. may recover partially

Sr Low Low High S&C Rare cases & C.V. may recover partially

Ba Low Low High S&C C.V. may recover partially

- Low High S&C

18
Influence of Impurities on Current Efficiency
Decrease of C.E. & Main Comments
Accumulation Position
- SiO2 I S or C
Fe minor S

Ni minor S Rare cases

Mg minor minor S

Al high high S&C C.E. may recover partially

Ca high high high S&C C.E. may recover partially

Sr high high high S&C C.E. may recover partially

Ba high high high S&C C.E. may recover partially

- high high S&C

19
Contents

General Information
1) Model of Impurity Deposits
2) Classification of Impurity Influences

Investigated Results; Influential Factor

1) Investigation Method
2) Influential Operation Factors
3) Most Influential Impurities on Cell Voltage
4) Recovery method

Performance of new F-8080 Series

20
Method: Impurities Addition Test
Measurement of C.V. and C.E. Analysis of
1) Effect & 2) Recovery Deposits

Impurities Normal brine Lab. Cell Membrane

addition operation
NaCl
3) Position
4) Quantity
C.V.

Si

C.E.
I
D.O.L. after addition

Fe or Ni or Mg or Al or Ca or Sr or Ba

21
Method: Analysis of Deposits
Analysis of
Deposits
1) Separate
“S-layer” & “C-layer”
3) Position
4) Quantity
2) Measure
Quantity of accumulations
of each layer by ICP

Measure the quantity of deposits by ICP

22
Influence of the Operating Conditions

mild severe
・Impurities Concentration low high
・Current Density low high
・Operating Temperature high low
・NaOH Concentration low high
・Brine Acidity depends on impurities
・Combinations of Impurities depends on impurities

23
Typical case; Impurity upset
（＋） （－） Trouble in purification process
When impurities concentration exceeds
the secondary purification limit….
Brine will contain high conc. of impurities

Cause severe damage to membrane

Ca Upset during Plant Operation
100
C.E.(%)

95
90
Ca Upset
85
80
0 1 2 3 4 5 6
Month
Ca upset : Influence of Ca Concentration

F-8020 6 kA/m2, 90 ℃, 32 % NaOH

5
Ca : 4 Hr addition
Ca = 0.5 ppm
ΔC.E.(%)

0
Ca = 1 ppm
-5
Ca = 2 ppm
Ca = 5 ppm
-10

-15
-5 0 5 10 15

D.O.L after start of addition

C.E. is severely decreased by high Ca concentration

25
Ca upset : Influence of Ca Addition Term

F-8020 6 kA/m2, 90 ℃, 32 % NaOH

5
Ca = 2 ppm
ΔC.E.(%)

0
0.5 Hr addition
1 Hr addition
-5
4 Hr addition

-10
-5 0 5 10 15

D.O.L after start of addition

CE will recover more with shorter time upset

26
Al + SiO2 : Influence of Current Density

F-8020 6 kA/m2, 90 ℃, 32 % NaOH

300
Feed Brine Al / SiO2 = 1 / 30 ppm
250
8 kA/m
ΔC.V.(mV)

2
200
150
100
50
6 kA/m 2

0
-50
0 5 10 15 20 25

D.O.L after start of addition

C.V. increases more in higher C.D.

27
Al + SiO2 : Influence of Current Density

F-8020 90 ℃, 32 % NaOH
2
Feed Brine Al / SiO2 = 1 / 30 ppm
0
ΔC.E.(%)

-2

-4
6 kA/m 2

-6
8 kA/m 2

-8
0 5 10 15 20 25

D.O.L after start of addition

C.E. decreases more in higher C.D.

28
Sr + I : Influence of Operating Temp.

F-8080 8 kA/m2, 32 % NaOH

300
Feed Brine I / Sr = 20 / 1 ppm
80 ℃
ΔC.V.(mV)

200

100
85 ℃
90 ℃
0

-100
0 5 10 15 20 25

D.O.L after start of addition

C.V. increases more in lower temp.

29
Sr + I : Influence of Operating Temp.

F-8080 8 kA/m2, 32 % NaOH

2
Feed Brine I / Sr = 20 / 1 ppm
0
ΔC.E.(%)

90 ℃
-2

-4

-6 80 ℃
-8
85 ℃
0 5 10 15 20 25

D.O.L after start of addition

C.E. decreases more in lower temp.

30
Sr + I : Influence of NaOH Concentration

F-8080 8 kA/m2, 32 % NaOH

100
Feed Brine I / Sr = 20 / 1 ppm
80
ΔC.V.(mV)

34 % NaOH
60
40
32 % NaOH
20
0
-20
0 5 10 15 20 25

D.O.L after start of addition

C.V. increases more in higher

NaOH concentration
31
Sr + I : Influence of NaOH Concentration

F-8080 8 kA/m2, 32 % NaOH

2
Feed Brine I / Sr = 20 / 1 ppm
0
ΔC.E.(%)

-2
32% NaOH
-4
-6
-8
34% NaOH
-10
0 5 10 15 20 25

D.O.L after start of addition

C.E. decreases more in higher

NaOH concentration
32
Fe

F-8020 6 kA/m2, 90 ℃, 32 % NaOH

250
Feed Brine Fe = 5ppm
200
ΔC.V.(mV)

150
100
Depleted Brine
50 Analysis of membrane
pH = 4.5 Fe (μg/cm2)
0
S-layer : 240
-50
C-layer : <1
0 5 10 15 20 25

D.O.L after start of addition

Cell Voltage does not increase with Fe deposition

In spite of high accumulation in S-layer

33
Fe: Influence of Brine Acidity on C.V.

F-8020 6 kA/m2, 90 ℃, 32 % NaOH

250
Feed Brine Fe = 5ppm Depleted Brine
200
ΔC.V.(mV)

pH = 2
150
100
Depleted Brine
50 Analysis of membrane
pH = 4.5 Fe (μg/cm2)
0
S-layer : 240
-50
C-layer : <1
0 5 10 15 20 25

D.O.L after start of addition

At lower pH , C.V. increases more

34
Fe: Effect of Brine Acidity

Outside Inside
pH: 15 pH: 15
Fe(OH)3 Fe(OH)3
Standard Higher
acidity pH: 12 acidity pH: 12

pH: 4
Lower pH

C.V. does not increase C.V. increases

35
Ca, Sr

F-8020 6 kA/m2, 90 ℃, 32 % NaOH

120

90
ΔC.V.(mV)

60

30 Feed Brine
Ca = 0.2 ppm for 22 days
0
Feed Brine
-30 Sr = 5 ppm for 15 days

0 5 10 15 20 25

D.O.L after start of addition

Minor Influence to Cell Voltage

36
Ca, Sr, Ba + SiO2

F-8020 6 kA/m2, 90 ℃, 32 % NaOH

120
All Feed Brine
90
ΔC.V.(mV)

SiO2 = 30 ppm Feed Brine

60
Ca = 0.1 ppm for 15 days
30 Feed Brine
Sr = 5 ppm for 15 days
0
Feed Brine
-30 Ba = 1 ppm for 15 days

0 5 10 15 20 25
D.O.L after start of addition

Also minor Influence to Cell Voltage

37
Ca, Sr, Ba + I
*I/Ba : 80 ℃
F-8020 6 kA/m2, 90 ℃, 32 % NaOH
120 Feed Brine
Ba = 1 ppm for 10 days
90
ΔC.V.(mV)

Feed Brine
60 Ca = 0.2 ppm for 15 days
30 Feed Brine
All Feed Brine Sr = 1 ppm for15 days
0
I = 20 ppm
-30
0 5 10 15 20 25
D.O.L after start of addition

Huge increase in Cell Voltage

38
Quantity of Accumulation
300
+ Iodine : high
Ca, Sr, Ba accumulations

200
(μg/cm2)

C
S
100

+OH :Slight + SiO2 :Slight

0
1
Ca 2
Sr 3
Ca 4
Sr 5
Ba 6
Ca 7
Sr 8
Ba

Quantity of accumulation is changed by the paired anion

Huge increase of Cell Voltage with Iodine

39
Contents

General Information
1) Model of Impurity Deposits
2) Classification of Impurity Influences

Investigated Results; Influential Factor

1) Investigation Method
2) Influential Operation Factors
3) Most Influential Impurities on Cell Voltage
4) Recovery method

Performance of new F-8080 Series

40
Analysis of Used Membranes from Customers

Multivariate Analysis
Q: Which ion is
“The worst impurity 230 data
for voltage increase” ? 230 data
of C.V.

1) C.V. by lab. cell

2) Amount
There of deposits
is no C.V. data

A: “Ba + Iodine” AGC has many used membranes

from Customers

41
Analysis of used Membranes
1 2 3 4 5 6 7 8 9 230

This is just

Increased Voltage.
Amount of deposits
230
1 data
(μg / cm2)
C.V. (mV)

Used New Fe Ni Mg Al Ca Sr Ba I SiO2

Mem.. Mem.
KE are calculated by “Multivariate Analysis”

42
Method of Multivariate Analysis
⊿C.V. 1 : Increased Voltage (Sample No.1)
AE : Amount of Each Deposit (Fe, Ni, Mg, Al, Ca, Sr, Ba, I, SiO2)
KE : Conversion factor of each element (Fe, Ni, Mg, Al, Ca, Sr, Ba, I, SiO2)

⊿C.V.1 ≒ AFe× KFe + ANi× KNi + AMg× KMg + AAl× KAl + ACa× KCa + ASr× KSr + ABa× KBa + AI× KI + ASiO2× KSiO2
⊿C.V.2 ≒ AFe× KFe + ANi× KNi + AMg× KMg + AAl× KAl + ACa× KCa + ASr× KSr + ABa× KBa + AI× KI + ASiO2× KSiO2
⊿C.V.3 ≒ AFe× KFe + ANi× KNi + AMg× KMg + AAl× KAl + ACa× KCa + ASr× KSr + ABa× KBa + AI× KI + ASiO2× KSiO2
⊿C.V.4 ≒ AFe× KFe + ANi× KNi + AMg× KMg + AAl× KAl + ACa× KCa + ASr× KSr + ABa× KBa + AI× KI + ASiO2× KSiO2
………………………………………………………………………………………………………………………………………
⊿C.V.i ≒ AFe× KFe + ANi× KNi + AMg× KMg + AAl× KAl + ACa× KCa + ASr× KSr + ABa× KBa + AI× KI + ASiO2× KSiO2
………………………………………………………………………………………………………………………………………

⊿C.V.227 ≒ AFe× KFe + ANi× KNi + AMg× KMg + AAl× KAl + ACa× KCa + ASr× KSr + ABa× KBa + AI× KI + ASiO2× KSiO2
⊿C.V.228 ≒ AFe× KFe + ANi× KNi + AMg× KMg + AAl× KAl + ACa× KCa + ASr× KSr + ABa× KBa + AI× KI + ASiO2× KSiO2
⊿C.V.229 ≒ AFe× KFe + ANi× KNi + AMg× KMg + AAl× KAl + ACa× KCa + ASr× KSr + ABa× KBa + AI× KI + ASiO2× KSiO2
⊿C.V.230 ≒ AFe× KFe + ANi× KNi + AMg× KMg + AAl× KAl + ACa× KCa + ASr× KSr + ABa× KBa + AI× KI + ASiO2× KSiO2

Each KE are determined by application that leads by least squares method of these 230 formula.

43
Result : Analysis of Used Membranes
Total : 230 data Cause of CV increase

C.V.
Increase Unknown Ba + (I)
> 20 mV 34 %
No C.V.
Increase 92 data
Mg Fe (Al) + SiO2
(≦ 20 mV)

14 % 17 %

Worst impurity : Ba + (Iodine)

44
Contents

General Information
1) Model of Impurity Deposits
2) Classification of Impurity Influences

Investigated Results; Influential Factor

1) Investigation Method
2) Influential Operation Factors
3) Most Influential Impurities on Cell Voltage
4) Recovery method

Performance of new F-8080 Series

45
Recovery Methods

In case of membrane damage by impurities,

AGC recommends three methods.
Recovery method Operation state Condition (example)
Water flushing Shut down R.T. 16 Hrs
Warm water
Shut down 50 oC 16 Hrs
treatment
25 % NaOH
Low NaOH conc. Operating
operating

Recommendation method and recovering effect will depends on

each Customer’s situation.
Please contact AGC for suitable methods and conditions.

46
46
Contents

General Information
1) Model of Impurity Deposits
2) Classification of Impurity Influences

Investigated Results; Influential Factor

1) Investigation Method
2) Influential Operation Factors
3) Most Influential Impurities on Cell Voltage
4) Recovery method

Performance of new F-8080 Series

47
Developments of Flemion

F-8080
3rd Step
F-8020 SP & F-8051
2nd Step
F-8000 Series
New Generation polymer
1st Step

F-890 Series

1990 2001 2008

48
Fe at High Brine Acidity

6 kA/m2, 90 ℃, 32 % NaOH
250
Feed Brine Fe = 5 ppm
200
ΔC.V.(mV)

depleted Brine pH = 2 F-8020

150
100
50
F-8080
0
-50
0 5 10 15 20 25

D.O.L after start of addition

F-8080 has high stability of C.V. against Fe on

C.V. at Low pH ( pH = 2 )
49
Ca + Sr Upset
6 kA/m2, 85 OC, 33 % NaOH, 230 g/l NaCl
Ca / Sr = 0.5 / 1 ppm 4Hr addition
4
2
0 F-8080
⊿CE (%)

-2
F-8020SP
-4
-6
F-8020
-8
-5 0 5 10
DOL after Addition

F-8080 has high stability against Ca/Sr-upset

50
I / Ba = 20 / 1 ppm

6 kA/m2, 80 OC, 32 % NaOH, 190 g/l NaCl

4
I / Ba = 20 / 1 ppm continuous addition
2
0
F-8080
⊿CE (%)

-2
-4
F-8020SP
-6
F-8020
-8
-5 0 5 10 15
DOL after Addition

F-8080 has high stability of C.E. against I/Ba

51
I / Ba = 20 / 1 ppm

6 kA/m2, 80 ℃, 32 % NaOH
120
F-8020
90
ΔC.V.(mV)

60
F-8020SP
30
F-8080
0

-30
0 5 10 15

DOL after Addition

F-8080 has high stability of C.V. against I/Ba

52
I / Sr = 20 / 1 ppm
6 kA/m2, 90 ℃, 32 % NaOH
2
⇒I/ Sr=20/1ppm continuous addition
1
0
⊿C.E.(%)

-1
F-8080
-2
F-8020
-3
-4
-5 0 5 10 15 20 25
D.O.L. after addition

F-8080 has high stability of C.E. against I/Sr

53
I / Sr = 20 / 1 ppm

6 kA/m2, 90 ℃, 32 % NaOH
60
F-8020
⊿CV (mV)

40
F-8020SP
20
F-8080
0

-20
-5 0 5 10 15 20
DOL after Addition

F-8080 has high stability of C.V. against I/Sr

54
I / Ca=20 / 1 ppm

6kA/m2, 90℃, 32% NaOH

120

90
ΔC.V.(mV)

F-8020
60

30

0
F-8080
-30
0 5 10 15 20 25
D.O.L after addition

F-8080 has high stability of C.V. against I/Ca

55
Features of F-808X

1. High Durability against Brine Impurities

• Especially, high resistance against Ca upset
2. Lowest Cell Voltage and high Voltage Stability
• F-8080 is 30 mV lower Voltage at 6 kA/m2 than
present high performance membranes in market
3. Wider Operating Window
4. Suitable for KOH Operation

56
Contents

General Information
1) Model of Impurity Deposits
2) Classification of Impurity Influences

Investigated Results; Influential Factor

1) Investigation Method
2) Influential Operation Factors
3) Most Influential Impurities on Cell Voltage
4) Recovery method

Performance of new F-8080 Series

57
Thank you very much all for listening