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FLEMION F-9010 Fluorinated Ion Exchange Membrane

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FLEMION F-9010 is built upon the proven track record performance of FLEMION F-8080 and gives users significant cost-performance benefits. FLEMION-9010 has 50mV lower voltage than F-8080 and F-8080A. It also demonstrates a higher current efficiency in more hydrated and more dehydrated states. In addition, FLEMION F-9010 provides better durability against impurities and improved robustness.

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FLEMION F-9010 Fluorinated Ion Exchange Membrane

  1. 1. 1 © AGC Chemicals All Rights Reserved. 28.39 0 Introduction of New Generation Membrane FLEMIONTM F-9010 March, 2019 Membrane Business Division AGC Chemicals
  2. 2. 2 © AGC Chemicals All Rights Reserved. Key Technologies of New Generation Membrane F-9010 Concept Low Voltage Wider Operational Range Higher Robustness Higher Durability against Brine Impurities Suitability for Zero-Gap Key Technologies New Cloth New Sulfonic Polymer Layer New Ion Channel Others Key Words  High CD Operation • Increment of Cell Voltage • Increment of Mass Flow • Fluctuation of Anolyte / Catholyte Concentration  Zero-Gap Electrolyzer • Increment of NaOH Concentration at Membrane Surface • High Membrane Temperature • Direct Touch to Cathode
  3. 3. 3 © AGC Chemicals All Rights Reserved. 3 Prototypes of new generation membrane keep stable low voltage in AGC commercial electrolyzer more than 3 years. +60 +30 0 -30 -60 -90 VoltageReduction Unit : mV at 6 kA/m2 D.O.L BM2.7v5 (AGC Commercial Plant) BM2.7v6 (AGC Commercial size Pilot) F-8080A F-8020SP F-8020 Note; ・Prototypes;-30~-50 mV ・Latest type after optimizing manufacturing process ; -50 mV -50 mV F-8080 F-9010 Voltage of F-9010 in Commercial Electrolyzer (AGC) 0 200 400 600 800 1000 1200 1400 New Generation 2000 2005 2015 20202010
  4. 4. 4 © AGC Chemicals All Rights Reserved. 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
  5. 5. 5 © AGC Chemicals All Rights Reserved. Ni Ni Ni Ni Contacting Cathode parts Less Brine Supply Ni stain High Temperature Weak brine1 2 3 Less Catholyte Flow 1 2 3 “Zero gap” has Three Key Points Ni Ni Ni Ni
  6. 6. 6 © AGC Chemicals All Rights Reserved. 6 Durability against Ni Stain( for Zero Gap) 91 92 93 94 95 96 0 2 4 6 8 10 CE(%) DOL 6 kA/m2, 90 oC, 32 wt% NaOH, F-9010 shows higher stability of CE against Ni stain. F-8080 F-9010 F-8080A “New Ion Channel” is applied! Acceleration Test
  7. 7. 7 © AGC Chemicals All Rights Reserved. Durability against Ni -40 0 40 80 120 160 0 5 10 15 20 ΔCV(mV) DOL after addition 8 kA/m2, 90 oC, 32 wt% NaOH, Ni=0.1 ppm F-9010 F-8080 F-9010 has higher stability of CV against Ni.
  8. 8. 8 © AGC Chemicals All Rights Reserved. Fx-9010 shows higher CE not only at high temperature but also at low temperature. 8 Higher CE in Wider Temperature Range 95 96 97 98 65 70 75 80 85 90 95 100 105 CE(%) Catholyte outlet temperature (oC) F-8080A F-8080 6 kA/m2, 32 wt% NaOH, 200 g/l NaCl F-9010 shows higher CE not only at high temperature but also at low temperature. 95 96 97 98 65 70 75 80 85 90 95 100 105 CE(%) Catholyte outlet temperature (oC) F-8080A F-8080 6 kA/m2, 32 wt% NaOH, 200 g/l NaCl F-9010
  9. 9. 9 © AGC Chemicals All Rights Reserved. 94 95 96 97 98 25 30 35 40 CE(%) NaOH (wt%) 9 Higher CE in Wider Range of Caustic Strength F-9010 shows higher CE in weak and strong caustic. 6 kA/m2, 90 oC, 200 g/l NaCl F-8080A F-8080 F-9010
  10. 10. 10 © AGC Chemicals All Rights Reserved. Less Brine Supply Weak brine3 3Anode Anode Anode Oval type Circle type F-9010 Previous type F-8080 F-8080A Good Brine Supply Proper Surface Shape Cause Good Brine Supply Note) It also shows good supply of added HCl !
  11. 11. 11 © AGC Chemicals All Rights Reserved. 95 96 97 98 100 150 200 250 CE(%) NaCl (g/l) Fx-9010 shows higher CE in weak brine. It is suitable for electrolyzers which have less inner circulation of brine. 6 kA/m2, 90 oC, 32 wt% NaOH F-8080A F-8080 Higher CE in Weak Brine 95 96 97 98 100 150 200 250 CE(%) NaCl (g/l) F-9010 shows higher CE in weak brine. It is suitable for electrolyzers which have less inner circulation of brine. 6 kA/m2, 90 oC, 32 wt% NaOH F-9010 F-8080A F-8080
  12. 12. 12 © AGC Chemicals All Rights Reserved. Membrane Design for Low Cell Voltage • Reduction of Membrane Thickness • Improvement of Reinforcement • Optimization of Polymer • Improvement of Surface Coating Key point “Shadow influence” How to reduce with “New Cloth”? “Shadow influence”
  13. 13. 13 © AGC Chemicals All Rights Reserved. Standard Cloth Sacrificial Fiber Permanent Fiber Cross Section Plane Figure (PET fiber) Standard Cloth : 1) Plain-woven fabric 2) PTFE and PET fiber. (PTFE fiber) Note; ・F-8080 and F-8080A have standard reinforcing cloth ・PET fiber dissolves under the electrolysis
  14. 14. 14 © AGC Chemicals All Rights Reserved. Influence of Cloth on Cell Voltage PTFE Fiber “Shadow” PTFE fiber interferes the Na+ migration which causes the increase of the cell voltage. Na+ How to reduce the shadow influence? Two kinds of tech. !!
  15. 15. 15 © AGC Chemicals All Rights Reserved. How to Reduce the Shadow Influence (1) Circle type Proper surface shape reduces cell voltage ! Oval type New ClothConventional Cloth Breakthrough ! While maintaining the membrane thickness…
  16. 16. 16 © AGC Chemicals All Rights Reserved. How to Reduce the Shadow Influence (2) PET fiber dissolves under the electrolysis and makes sacrificial fiber holes, Sacrificial Fiber Hole (filled with solution) Circle type PTFE PET New ClothNew Cloth which reduce the shadow influence.
  17. 17. 17 © AGC Chemicals All Rights Reserved. How to Reduce the Shadow Influence (2) PET Fiber PTFE Fiber New ClothConventional Cloth F-8080/F-8080A F-9010 New cloth has 4 PET fibers between PTFE fibers, which reduce the shadow influence more.
  18. 18. 18 © AGC Chemicals All Rights Reserved. How to Reduce the Shadow Influence (2) New ClothConventional 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.
  19. 19. 19 © AGC Chemicals All Rights Reserved. -20 0 20 40 60 80 0 5 10 15 20 ⊿CV(mV) DOL after addition Durability against Mg 8 kA/m2, 90 oC, 32 wt% NaOH, Mg=0.1 ppm F-9010 F-8080 F-9010 has higher stability of CV against Mg.
  20. 20. 20 © AGC Chemicals All Rights Reserved. Durability against Al/SiO2 CE(%) DOL after addition F-9010 F-8080 F-8080 F-9010 6kA/m2 8kA/m2 85 oC, 32wt% NaOH, Al/SiO2=1/30ppmCE(%) DOL after addition
  21. 21. 21 © AGC Chemicals All Rights Reserved. Durability against Ca/SiO2 85 oC, 32wt% NaOH, Ca/SiO2=0.05/15ppmCE(%) CE(%) F-9010 F-8080 F-8080 F-9010 6kA/m2 8kA/m2 DOL after addition DOL after addition
  22. 22. 22 © AGC Chemicals All Rights Reserved. Durability against I/Ba 85 oC, 32wt% NaOH, I/Ba=20/1ppm CE(%) F-9010 F-8080 F-8080 F-9010 6kA/m2 8kA/m2 CE(%) DOL after addition DOL after addition
  23. 23. 23 © AGC Chemicals All Rights Reserved. Durability against Ca Upset 85 oC, 32wt% NaOH, Ca=1.5ppm, 4hrCE(%) CE(%) F-9010 F-8080 F-8080 F-9010 6kA/m2 8kA/m2 DOL after addition DOL after addition
  24. 24. 24 © AGC Chemicals All Rights Reserved. 24 F-8080 F-8080A Fx-XXX F-8080HD RatiotoF-8080 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) F-9010 is more robust than F-8080 and F-8080A. F-9010

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