Introduction of New Generation

Membrane FLEMIONTM28.39
F-9010
0

March, 2019
Membrane Business Division
AGC Chemicals

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Key Technologies of New Generation Membrane F-9010

Key Words Concept Key Technologies

 High CD Operation
• Increment of Cell Voltage Low Voltage
• Increment of Mass Flow New Cloth
• Fluctuation of Anolyte / Wider Operational
Catholyte Range
Concentration New Sulfonic
Polymer Layer
Higher Robustness
 Zero-Gap Electrolyzer New Ion Channel
• Increment of NaOH Higher Durability
Concentration against
at Membrane Surface Brine Impurities
Others
• High Membrane Suitability for
Temperature Zero-Gap
• Direct Touch to Cathode

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Voltage of F-9010 in Commercial Electrolyzer (AGC)
Unit : mV 2000 2005 2010 2015 2020
at 6 kA/m2
+60 F-8020 Note;
・Prototypes;-30～-50 mV
・Latest type after optimizing
+30 F-8020SP
manufacturing process ; -50 mV
Voltage Reduction

0 F-8080 F-8080A
New Generation
-30

F-9010
-60
BM2.7v5 (AGC Commercial Plant) -50 mV
BM2.7v6 (AGC Commercial size Pilot)
-90
0 200 400 600 800 1000 1200 1400
D.O.L

Prototypes of new generation membrane keep stable low voltage

in AGC commercial electrolyzer more than 3 years.
3 3
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Voltage of F-9010 in Commercial Electrolyzers
Area Electrolyzer Type MOL Comparison Current
Density
(kA/m2)
A SEA CEC n-BiTAC 20 3 sheets -80 mV vs. F-8080A 5.3 kA/m2
B China AK NCZ 10 4 sheets -20 mV vs. Comp.-1 4 kA/m2

C China CEC n-BiTAC 13 2 sheets -60 mV vs. F-8080A 5.5 kA/m2

D China CEC n-BiTAC 10 4 sheets -40 mV vs. Comp.-2 5.5 kA/m2

E Europe UHDE Gen5 12 10 sheets -60 mV vs. F-8080A 6 kA/m2

F SEA UHDE Gen5 11 6 sheets -40 mV vs. F-8080A 6 kA/m2

G North America UHDE Gen5 12 4 sheets -50 mV vs. F-8080 6 kA/m2

H Japan UHDE Gen5+ 13 186 sheets -70 mV vs. F-8080A 6 kA/m2
I Japan CEC n-BiTAC 11 70 sheets -50 mV vs. F-8080A 6 kA/m2
J Japan CEC BiTAC 12 25 sheets -30 mV vs. Comp-2 5 kA/m2
K North America CEC BiTAC 8 4 sheets -30~40 mV vs. Comp-2 5 kA/m2
L North America CEC BiTAC 6 4 sheets -100 mV vs. Comp-3 5 kA/m2

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“Zero gap” has Three Key Points
1 2 3
Contacting Less Less
Cathode parts Catholyte Flow Brine Supply
Ni
Ni
Ni
Ni
Ni
Ni
Ni
Ni

1 Ni stain 2 High 3 Weak brine

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 Durability against Ni Stain( for Zero Gap)
Soaked in Ni Solution
before installation.
6 kA/m2, 90 oC, 32 wt% NaOH,

96
Ni solution Acceleration Test
FLEMION
95 F-9010
F-8080A
CE(％)
94
Note)
Test conditions are confidential F-8080
93

92

91
0 2 4 6 8 10
DOL

F-9010 shows higher stability of CE against Ni stain.

“New Ion Channel” is applied!
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6
Durability against Ni
8 kA/m2, 90 oC, 32 wt% NaOH, Ni=0.1 ppm
160
F-8080
120
ΔCV(mV)

80
F-9010
40

-40
0 5 10 15 20
DOL after addition

F-9010 has higher stability of CV against Ni.

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Higher CE in Wider Temperature Range
6 kA/m2, 32 wt% NaOH, 200 g/l NaCl
98

F-9010

97
CE (%)

F-8080A
F-8080
96

95
65 70 75 80 85 90 95 100 105
Catholyte outlet temperature (oC)
Fx-9010
F-9010 shows
showshigher
higherCE
CE
not only at high temperature but also at low temperature.
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8
Higher CE in Wider Range of Caustic Strength
6 kA/m2, 90 oC, 200 g/l NaCl
98

F-9010
97
CE (%)

96
F-8080A
95

F-8080
94
25 30 35 40
NaOH (wt%)

F-9010 shows higher CE in weak and strong caustic.

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9
Proper Surface Shape Cause Good Brine Supply
Previous F-8080 3
type F-8080A F-9010 Less
Brine Supply

Anode

Anode
Anode

Oval type Circle type

Good Brine Supply 3 Weak brine

Note) It also shows good supply of added HCl !
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Higher CE in Weak Brine
6 kA/m2, 90 oC, 32 wt% NaOH
98

97
CE (%)

F-9010

96
F-8080A

F-8080
95
100 150 200 250
NaCl (g/l)

Fx-9010
F-9010 shows
showshigher
higherCE
CEin
inweak
weakbrine.
brine.
It is suitable for electrolyzers which have less inner circulation of brine.
11 © AGC Chemicals All Rights Reserved.
Membrane Design for Low Cell Voltage

Key point
“Shadow
influence”
• Reduction of Membrane Thickness

• Improvement of Reinforcement How to reduce

“Shadow
• Optimization of Polymer influence”
with
• Improvement of Surface Coating “New Cloth”?

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Standard Cloth

Cross Section Plane Figure

Permanent Fiber
(PTFE fiber)

Sacrificial Fiber
(PET fiber)
Note;
・F-8080 and F-8080A have standard reinforcing cloth
・PET fiber dissolves under the electrolysis

Standard Cloth : 1) Plain-woven fabric 2) PTFE and PET fiber.

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Influence of Cloth on Cell Voltage

“Shadow”

Na+ PTFE fiber interferes the Na+

migration which causes the
increase of the cell voltage.

PTFE Fiber

How to reduce the shadow influence?

Two kinds of tech. !!
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How to Reduce the Shadow Influence (1)
Conventional Cloth New Cloth
Breakthrough !
While maintaining
the membrane
thickness…

Oval type Circle type

Proper surface shape reduces cell voltage !

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How to Reduce the Shadow Influence (2)
New Cloth New Cloth
PTFE PET

Circle type
Sacrificial Fiber Hole
(filled with solution)

PET fiber dissolves under the electrolysis and makes sacrificial fiber holes,
which reduce the shadow influence.
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How to Reduce the Shadow Influence (2)
Conventional Cloth New Cloth
F-8080/F-8080A F-9010

PTFE Fiber

PET Fiber

New cloth has 4 PET fibers between PTFE fibers,

which reduce the shadow influence more.

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How to Reduce the Shadow Influence (2)
Conventional Cloth New Cloth
F-8080/F-8080A F-9010

New cloth reduces the shadow influence more

and makes F-9010 show lower voltage.
Note; New cloth is a part of voltage reduction technologies.
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Durability against Mg
8 kA/m2, 90 oC, 32 wt% NaOH, Mg=0.1 ppm
80
F-8080
60
⊿CV(mV)

40
F-9010
20

-20
0 5 10 15 20
DOL after addition

F-9010 has higher stability of CV against Mg.

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Durability against Al/SiO2
85 oC, 32wt% NaOH, Al/SiO2=1/30ppm

F-9010

F-9010
F-8080

CE(%)
CE(%)

F-8080

6kA/m2 8kA/m2

DOL after addition DOL after addition

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Durability against Ca/SiO2

85 oC, 32wt% NaOH, Ca/SiO2＝0.05/15ppm

F-9010

F-9010
CE(%)

CE(%)
F-8080

F-8080
6kA/m2 8kA/m2

DOL after addition DOL after addition

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Durability against I/Ba
85 oC, 32wt% NaOH, I/Ba=20/1ppm

F-9010

F-9010
CE(%)

CE(%)
F-8080

F-8080

6kA/m2 8kA/m2

DOL after addition DOL after addition

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Durability against Ca Upset

85 oC, 32wt% NaOH, Ca=1.5ppm, 4hr

F-9010
F-9010

CE(%)
CE(%)

F-8080

F-8080
6kA/m2 8kA/m2

DOL after addition DOL after addition

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Frequent Load Tensile Test
Total number of frequent load tensile test until membrane breaking
(Sum of the value to various direction. Load : 60 % of tensile strength)

Ratio to F-8080

F-8080 F-8080A Fx-XXX

F-9010 F-8080HD

F-9010 is more robust than F-8080 and F-8080A.

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24