Introduction to FORBLUE FLEMION F-9060.pptx
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Introduction to FORBLUE FLEMION F-9060.pptx
- 1. Introduction of FORBLUE™ FLEMION™ F-9060 Membrane The World’s Lowest Voltage Membrane
- 2. FLEMION Continuous Development for Lower Voltage F-8080 2005 2010 2020 2025 +90 +60 +30 0 -30 -60 Voltage Reduction Unit : mV at 6 kA/m2 2015 F-8080A F-8020SP F-9010 +120 F-9060 -40mV F-9010A
- 3. Voltage of F-9060 in AGC Commercial Plant 0 100 200 300 400 500 600 700 CV (V) at 6 kA/m 2 DOL BM2.7v5, 5.8 kA/m2, 85ºC, 32 wt% NaOH, 210g/l NaCl -40～50 mV F-9060 holds stable, low voltage in AGC commercial plant for almost 2 years. 50mV F-9010 F-9010A F-9060
- 4. CE of F-9060 in AGC Commercial Plant 0.0 2.0 4.0 6.0 8.0 96.0 96.5 97.0 97.5 98.0 0 100 200 300 400 500 600 700 C.D (kA/m 2 ) CE(%) Anodic Balance DOL BM2.7v5, 5.8 kA/m2, 85ºC, 32 wt% NaOH, 210g/l NaCl F-9010 F-9010A F-9060 F-9060 also shows stable high CE.
- 5. Table of Initial Performance in Laboratory Cell AGC lab cell, 6 kA/m2, 90ºC, NaOH 32 wt%, NaCl 200 g/l CE ⊿CV Features F-8080 ≧96.0 +50mV Previous standard membrane F-8080A ≧96.5 +50mV Higher CE than F-8080 suitable for zero gap technology. F-9010 ≧96.8 0mV Standard Membrane suitable for zero gap technology F-9010A ≧97.0 +20mV Higher CE than F-9010 with CV increase suitable for zero gap technology F-9060 ≧97.0 -40mV the lowest voltage & the highest CE suitable for zero gap technology F-9060 has both the lowest voltage and the highest CE.
- 6. F-9060 Performance Feedback from Customers’ Commercial Plants -100 -80 -60 -40 -20 0 BMv5 plus nx-BiTAC plus e-BiTACv7 (Pilot) NCZ NCZ DCM Other (Zero Gap) Other (Zero Gap) ΔCV vs F-9010 ( at 6kA/m 2 ) Compared with F-9010 Normalized at 6 kA/m2 Target -40mV Voltage Reduction Unit : mV at 6 kA/m2 The voltage of F-9060 in commercial plant is almost as designed.
- 7. Impact of F-9060 on Electricity Cost Saving Voltage Compared with F-9010 at 6 kA/m2 Electricity Cost Saving $2.8 M/y (28 GWh/year) Plant scale: 1 million ton / year electricity price : 0.1 $ / kWh -40 mV *Values are based on AGC’s own calculation and estimation they are NOT intended for performance guarantee
- 8. Contribution of Membrane Performance Improvement Power Consumption Improvement (Electricity Cost Saving) Decarbonization (CO2 Emission Saving) ＋ Membrane Performance Improvement (Voltage Reduction) Further development of membrane would contribute not only economical value but also environmental value.
- 9. Impact of F-9060 on CO2 Emission Saving Voltage Compared with F-9010 at 6 kA/m2 CO2 Emission Saving $1.8 M/Y (17 kton-CO2/y) Plant scale: 1 million ton / year EPA’s non-baseload emission factors (Mar, 2023): 0.00061 t-CO2/kWh (US average) ETS price: € 93.3 /t-CO2, €1=$1.12 (14th Jun, 2023) -40 mV *Values are based on AGC’s own calculation and estimation they are NOT intended for performance guarantee
- 10. Concept of Next Generation Membrane F-9060 High Current Density Operation Zero Gap Electrolyzer Main Required Features High CE Stability in Zero Gap High Durability against Brine Impurities Key Technology New Ion Channel Keyword in Market Rising Electricity Cost & Decarbonization Society Low Voltage New S-Polymer Advanced Cloth (as well F-9010) New Layer Configuration Wider Operational Range F-9060 is the latest membrane based on further evolution and development of the technology of F-9010 series.
- 11. Key Technology of F-9060 New Sulfonic Polymer Low Voltage New Ion Channel Wider Operational Range & High CE Stability in Zero Gap Advanced Cloth as F-9010 Same Mechanical Strength High Durability against Brine Impurities New Layer Configuration
- 12. Concept of Next Generation Membrane F-9060 High Current Density Operation Zero Gap Electrolyzer • Increment of Cell Voltage • Increment of Mass Flow • Fluctuation of Anolyte and Catholyte Concentration • Less Flow of Anolyte/Catholyte at Membrane Surface • High Membrane Temperature • Direct Contact with Cathode Keyword in Market Main Required Feature Low Voltage High Durability against Brine Impurities Wider Operational Range High CE Stability in Zero Gap
- 13. Concept of Next Generation Membrane F-9060 High Current Density Operation Zero Gap Electrolyzer • Increment of Cell Voltage • Increment of Mass Flow • Fluctuation of Anolyte and Catholyte Concentration • Less Flow of Anolyte/Catholyte at Membrane Surface • High Membrane Temperature • Direct Contact with Cathode Keyword in Market Main Required Feature Low Voltage High Durability against Brine Impurities High CE Stability in Zero Gap Wider Operational Range
- 14. Influence of Current Density • Peak CE decreases at high current density. • Peak of CE shifts to high temperature side at high current density. 90 92 94 96 98 100 50 60 70 80 90 100 CE (%) Temperature (°C) 2 kA/m2 4 kA/m2 6 kA/m2 8 kA/m2 F-9010, AGC Lab Cell, 2 - 8 kA/m2, 32 wt% NaOH, 200 g/l NaCl
- 15. Change of Ion Channel Structure with Temp. and C.D. Temperature Low High Ion Channel Size Current Density Low High Low High Capacity Ion Flux CE High Low Low High Proper operating temperature that matches the ion flux leads to high CE.
- 16. Comparison of Operational Range between F-9060 and F-9010 AGC Lab Cell, 2 kA/m2, 32 wt% NaOH, 200 g/l NaCl 92 94 96 98 100 50 60 70 80 90 100 CE (%) Temperature (°C) F-9010 F-9060 manual range
- 17. Comparison of Operational Range between F-9060 and F-9010 AGC Lab Cell, 4 kA/m2, 32 wt% NaOH, 200 g/l NaCl 92 94 96 98 100 50 60 70 80 90 100 CE (%) Temperature (°C) F-9010 F-9060 manual range
- 18. Comparison of Operational Range between F-9060 and F-9010 92 94 96 98 100 50 55 60 65 70 75 80 85 90 95 100 CE (%) Temperature (°C) F-9010 F-9060 AGC Lab Cell, 6 kA/m2, 32 wt% NaOH, 200 g/l NaCl manual range
- 19. Comparison of Operational Range between F-9060 and F-9010 92 94 96 98 100 50 60 70 80 90 100 CE (%) Temperature (°C) F-9010 F-9060 AGC Lab Cell, 8 kA/m2, 32 wt% NaOH, 200 g/l NaCl no manual range (manual max C.D. 7kA/m2)
- 20. F-9060: Operational Temperature Range 92 94 96 98 100 50 60 70 80 90 100 CE (%) Temperature (°C) 2 kA/m2 4 kA/m2 6 kA/m2 8 kA/m2 F-9060 shows wider operational range, especially at higher temperature.
- 21. Concept of Next Generation Membrane F-9060 High Current Density Operation Zero Gap Electrolyzer • Increment of Cell Voltage • Increment of Mass Flow • Fluctuation of Anolyte and Catholyte Concentration • Less Flow of Anolyte/Catholyte at Membrane Surface • High Membrane Temperature • Direct Contact with Cathode Keyword in Market Main Required Feature Low Voltage High Durability against Brine Impurities High CE Stability in Zero Gap Wider Operational Range
- 22. “Zero Gap” Advantages Less Brine Supply High Temperature Weak brine Less Catholyte Flow 2 3 Ni Ni Ni Ni Contacting Cathode parts Ni stain 1 Ni Ni Ni Ni
- 23. F-9060: Resistance to Ni Stain 0 2 4 6 8 10 CE(％) DOL F-8080 F-8080A F-9010 F-9010A F-9060 1% F-9060 shows the highest resistance to Ni stain Precondition；Soaked in a Ni solution AGC Lab Cell, 6 kA/m2, 90ºC, NaOH 32 wt%, NaCl 200 g/l
- 24. F-9060: Temperature Characteristic F-9060 shows higher CE at higher temperature 95.0 95.5 96.0 96.5 97.0 97.5 98.0 65 70 75 80 85 90 95 100 105 CE (%) Temperature (°C) F-9010A F-9060 F-9010 AGC Lab Cell, 6 kA/m2, NaOH 32 wt%, NaCl 200g/l
- 25. F-9060: NaCl Concentration Characteristic 95.5 96.0 96.5 97.0 97.5 98.0 98.5 120 160 200 240 280 CE(%) NaCl(g/l) F-9010A F-9060 F-9010 F-9060 shows higher CE in all brine concentration AGC Lab Cell, 6 kA/m2, 90ºC, NaOH 32 wt%
- 26. Design of Uniform Ion Channel F-9010 COO- COO- COO- COO- H2O H2O Na+ H2O H2O Na+ H2O H2O H2O H2O Na+ H2O H2O H2O H2O COO- COO- COO- COO- H2O H2O Na+ H2O H2O Na+ H2O H2O H2O H2O Na+ H2O H2O H2O H2O COO- COO- COO- COO- H2O H2O Na+ H2O H2O Na+ H2O H2O H2O H2O Na+ H2O H2O H2O H2O COO- COO- COO- COO- H2O H2O Na+ H2O H2O Na+ H2O H2O H2O H2O Na+ H2O H2O H2O H2O Breakthrough ! Proper Proper Proper Proper Uniform Ion Channel
- 27. Further Improvement of Ion Channel F-9060 COO- COO- COO- COO- H2O H2O Na+ H2O H2O Na+ H2O H2O H2O H2O Na+ H2O H2O H2O H2O COO- COO- COO- COO- H2O H2O Na+ H2O H2O Na+ H2O H2O H2O H2O Na+ H2O H2O H2O H2O COO- COO- COO- COO- H2O H2O Na+ H2O H2O Na+ H2O H2O H2O H2O Na+ H2O H2O H2O H2O COO- COO- COO- COO- H2O H2O Na+ H2O H2O Na+ H2O H2O H2O H2O Na+ H2O H2O H2O H2O Breakthrough ! Proper Proper Proper Proper Uniform Ion Channel
- 28. Mechanical Strength Tensile Strength F-8080/F-8080A Approx. 45 N/cm Elongation Approx. 40 % F-9010/F-9010A F-9060 Reinforcement Cloth Type PTFE fiber PET fiber Same Force Direction as Fiber 45 Degree Force Direction for Fiber Tensile Strength Elongation Approx. 15 N/cm Approx. 40 % Conventional Cloth Advanced Cloth
- 29. Concept of Next Generation Membrane F-9060 High Current Density Operation Zero Gap Electrolyzer • Increment of Cell Voltage • Increment of Mass Flow • Fluctuation of Anolyte and Catholyte Concentration • Less Flow of Anolyte/Catholyte at Membrane Surface • High Membrane Temperature • Direct Contact with Cathode Keyword in Market Main Required Feature Low Voltage High Durability against Brine Impurities Wider Operational Range High CE Stability in Zero Gap
- 30. Influence of Brine Impurities on Membrane -8 -6 -4 -2 0 2 0 5 10 15 ⊿CE(%) DOL after Addition 4 kA/m2 6 kA/m2 8 kA/m2 -8 -6 -4 -2 0 2 0 5 10 15 ⊿CE(%) DOL after Addition 4 kA/m2 6 kA/m2 8 kA/m2 (Ca/SiO2 =0.05/30ppm) F-8080, I/Ba = 20/1ppm, 4-8 kA/m2 85ºC, NaOH 32 wt%, 200 g/l NaCl F-8080, Ca/SiO2= 0.05/15 ppm, 4-8 kA/m2 85ºC, NaOH 32 wt%, 200 g/l NaCl High C.D. operation with impurities causes critical damage to membrane.
- 31. High C.D. Operation with Impurities is Critical Damage -8 -6 -4 -2 0 2 2 4 6 8 10 ΔCE(%) C.D. (kA/m2) I/Ba = 20/1ppm Ca/SiO2=0.05/15ppm (4kA/m2 Ca/SiO2=0.05/30ppm) Significant Performance Drop!! F-8080, 85ºC, NaOH 32 wt%, 200 g/l NaCl Durability against brine impurities is even more necessary for long-term performance stability under high current density.
- 32. Higher Durability against SiO2 and Al/SiO2 -8 -6 -4 -2 0 2 0 5 10 15 ⊿CE(％) DOL F-9010 F-9060 -8 -6 -4 -2 0 2 0 5 10 15 ΔCE(％) DOL F-9010 F-9060 SiO2 =50 ppm, 8 kA/m2, 85ºC, NaOH 32 wt% Ca/SiO2 =0.05/15 ppm, 8 kA/m2, 85ºC, NaOH 32 wt%
- 33. Higher Durability against Sr/SiO2 and Ca/SiO2 -8 -6 -4 -2 0 2 0 5 10 15 ΔCE(%) DOL F-9010 F-9060 -12 -10 -8 -6 -4 -2 0 2 0 5 10 ΔCE(%) DOL F-9060 F-9010 Sr/SiO2 =1/30 ppm, 8 kA/m2, 85ºC, NaOH 32 wt% Al/SiO2 =1/30 ppm, 8 kA/m2, 85ºC, NaOH 32 wt%
- 34. Higher Durability against Ca -4 -2 0 2 0 5 10 ΔCE(%) DOL after addition F-9060 F-9010 -4 -2 0 2 0 5 10 ΔCE(％) DOL F-9060 F-9010 Ca = 0.5 ppm * 4 hr, 8 kA/m2, 85ºC, NaOH 32wt% Ca = 0.4 ppm * Continuous Addition, 6 kA/m2, 85ºC, NaOH 32wt%
- 35. Higher Durability against I/Ca -5 -4 -3 -2 -1 0 1 0 5 10 15 ⊿CE(％) DOL F-9010 F-9060 I/Ca =10/0.3 ppm, 8 kA/m2, 85ºC, NaOH 32 wt%
- 36. Why does impurity influence become more severe at High C.D.? F-8080, AGC Lab Cell, 6-8 kA/m2, 80ºC, 32 wt% NaOH, 190 g/l NaCl, I/Ba = 20/1 ppm Durability against brine impurities is even more necessary for long-term performance stability under high current density. Analyze membranes after addition test
- 37. Influence of C.D. on Accumulated Position pH Distribution in C-Layer Accumulated Position in C-Layer Low High C. D. Low C.D. High C.D. pH=15 pH=12 Accumulation (-) 32% NaOH Impurity Low High Concentration of Accumulated Impurity Accumulated impurity becomes more concentrated at high C.D.
- 38. Further Improve Durability against Brine Impurity New Layer Configuration also contributes to ion channel stability during impurity deposition. Breakthrough ! COO- COO- COO- COO- H2O H2O Na+ H2O H2O Na+ H2O H2O H2O H2O Na+ H2O H2O H2O H2O COO- COO- COO- COO- H2O H2O Na+ H2O H2O Na+ H2O H2O H2O H2O Na+ H2O H2O H2O H2O COO- COO- COO- COO- H2O H2O Na+ H2O H2O Na+ H2O H2O H2O H2O Na+ H2O H2O H2O H2O COO- COO- COO- COO- H2O H2O Na+ H2O H2O Na+ H2O H2O H2O H2O Na+ H2O H2O H2O H2O Proper Proper Proper Proper F-9060 New Ion Channel
- 39. Mechanism of High Current Efficiency COO- COO- OH- H2O H2O Na+ H2O H2O Na+ H2O H2O H2O H2O Na+ H2O H2O H2O H2O In the C-layer COO- COO- “Simple ion channel model” is useful for easy understanding! …But it’s not enough for deep understanding & membrane development!
- 40. Ion Channel Models CO O- CO O- COO - COO - H2O H2O Na + H2O H2O Na + H2O H2O H2O H2O Na + H2O H2O H2O H2O CO O- CO O- COO - COO - H2O H2O Na + H2O H2O Na + H2O H2O H2O H2O Na + H2O H2O H2O H2O Simple ion channel model Cluster network model (It’s a little complicated & classic) Simulation model These models can be extended to 2D & 3D Models on the right side are closer to reality We studied many models, many tests, & many analyses
- 41. Further Improve Durability against Brine Impurity Cathode side surface Membrane inside Low water content High water content Sulfonic polymer layer also influences cluster network of carboxylic polymer layer. Optimization of cluster network by new layer configuration achieves further improvement of durability against brine impurities.
- 42. Higher Durability against Fe and Mg 0 50 100 150 200 0 5 10 15 ΔCV(mV) DOL F-9010 F-9060 0 50 100 150 0 5 10 ΔCV (mV) DOL F-9010 F-9060 F-9060 also shows higher durability against Fe and Mg, which deposit in sulfonic layer. Fe = 5 ppm, 8 kA/m2, 85ºC, NaOH 32 wt% Mg=0.2 ppm, 8 kA/m2, 85ºC, NaOH 32wt%
- 43. Further Improve Durability against Brine Impurity New Layer Configuration New Sulfonic Polymer Breakthrough ! COO- COO- COO- COO- H2O H2O Na+ H2O H2O Na + H2O H2O H2O H2O Na+ H2O H2O H2O H2O COO- COO- COO- COO- H2O H2O Na+ H2O H2O Na + H2O H2O H2O H2O Na+ H2O H2O H2O H2O COO- COO- COO- COO- H2O H2O Na+ H2O H2O Na + H2O H2O H2O H2O Na+ H2O H2O H2O H2O COO- COO- COO- COO- H2O H2O Na+ H2O H2O Na + H2O H2O H2O H2O Na+ H2O H2O H2O H2O Proper Proper Proper Proper F-9060
- 44. Next Generation Membrane: F-9060 1. Lowest voltage ・ 40 mV lower voltage than F-9010 at 6 kA/m2 3. Higher CE Stability in Zero Gap and Wider Operational Range 2. Higher Durability against Brine Impurities ・ Contributes to reducing not only electricity cost but also CO2 emissions Based on deeply understanding the correlation between polymer and performance, we achieved further improvement of durability against many species of impurities. ・ Focusing three key influence factor of zero gap, we improved CE stability in zero gap ・ Wider operational range in each current density, especially at higher temperature.
- 45. For More Information: Katie Jarvis katie.jarvis@agc.com
Editor's Notes
- Flemion has been reducing the voltage step by step. In this time, F-9060 has 40mV lower voltage than F-9010
- We already have been operating F-9060 in AGC’s commercial electrolyzers BMv5 It shows from 40mV to 50mV lower voltage than F-9010 for around 2 years.
- F-9060 show not only low voltage but also stable high current efficiency in same electrolyzer
- This is the table of initial performance in laboratory cell In this time, the most notable feature of F-9060 is that it achieves both the lowest voltage and the highest CE by applied to new technologies.
- F-9060 has been operating in customer’s commercial plants as well as AGC plant. It shows almost the same voltage as our design.
- The voltage reduction by F-9060 directly contributes electricity cost saving. Although this is simple calculation, you can see that you can get a big cost saving
- On the background of the trend towards to decarbonization society, further development of membrane would contribute to not only economical value but also environmental value.
- Although here shows agc original calculation, installation of F-9060 contribute to CO2 emission reduction. If the introduction of ETS progress in the future, it will lead to economical value for many customers. ここに示すのは、AGC独自の計算ですが、F-9060の導入により、二酸化炭素の削減にも貢献できます。 今後、ETS(Emission trading scheme)の導入が進むと 、多くのお客様で経済的な価値にもつながります。 Source EPA site:ghg-emission-factors-hub.xlsx (live.com) March 2023 update Total output emission factors 852 lb/MWh ※1lb=0.453592 Non-baseload emission factors 1410lb/MWh ※1lb=0.453592 ETS EU-ETSの排出権（EUA）先物価格 2023年 | Statista
- Well, F-9060 is designed on the back ground of several market demand. As I mentioned, rising electricity cost and decarbonization society leads to further low voltage design. This is the most notable feature of F-9060. In addition, high durability against brine impurities and wider operational range are also big feature for high current density operation. Moreover, it designed to show higher CE stability in zero gap. F-9060 is the latest membrane based on further evolution and development of the technology of F-9010 series. F-9060はいくつかの市場の要求を背景に設計しています。 先に述べた、電気代の高騰や脱炭素社会を背景に低電圧設計しており、最も大きな特徴です。 それに加え、高電密での運転に向けた、不純物耐性の更なる向上、運転領域の拡大、 そしてゼロギャップ槽でより電流効率安定性をより高める膜設計としています。 これらの達成に向け、F-9010に適用した技術を更に進化させて、F-9060を開発しました。
- A brief summary f new technologies applied to F-9060. These new technologies and performance improvements are interrelated in a complex way, but here shows some key correlations. The 1st technology is new S polymer, which achieves lower voltage. 2nd, we have further evolved ion channel to achieve current efficiency in zero gap such as high temperature. 3rd is new layer configuration, which greatly contributes to improved impurity durability. In addition, F-9060 apply the same reinforcement cloth as F-9010, which has almost the same mechanical strength. I’ll explain more details later. F-9060に適用した新技術を簡単にまとめています。これらの新技術と性能向上は複雑に関係していますが、主な相関を示しています。 1つ目の技術は、新しいSポリマーを適用であり、低電圧化を達成しています。 2つ目は、イオンチャネルを更に進化させ、高温環境といったゼロギャップ槽での電流効率安定性、及びを実現しています。 3つ目は、新しい層構造の適用であり、新しイオンチャネルとともに、不純物耐性の向上に大きく貢献しています また、F-9060ではF-9010と同じ補強布を適用しており、従来膜と同レベルの機械強度を有します。後ほどもう少し詳細を説明します。 Noted) Describe the main correlation between technology and performance. Each technology and performance influence each other complexly.
- Now as you know, bipolar electrolyzer with zero gap is the mainstream in the market and membranes must be designed to maximize performance in that environment. Especially, in high current density operation, the voltage increases so the effect of low voltage increases. In addition, since the mass flow of substances increases, when considering long-term operation, the durability against brine impurities and wider operational range are required. As mentioned in the previous section, zero gap requires a stable current efficiency due to its structure. さて、ご存じのようにゼロギャップタイプの複極槽が市場の主流であり、その環境で性能が最大限発現するように膜設計をする必要があります。特に高電密の運転では、電圧が上がるため、低電圧の効果が大きくなり、また物質の移動が増加するため長期運転を考えた場合、不純物耐性や運転領域の拡大が望まれます。ゼロギャップでは前のセクションで述べたように、構造上、電流効率が安定して発現させる必要があります。
- First lets start about wider operational range. まずは運転領域の拡大について述べます。
- This is the relationship between temperature and CE for each current density of F-9010 measured in laboratory cell. As the current density increase, the peak top of CE decreases, and the peak of CE shifts toward higher temperature. Therefore, in the operation manual, the higher the current density, the higher the preferable temperature. こちらはラボ槽で測定した、F-9010の各電流密度の温度と電流効率の関係です。 高電密運転になるほどCEのピークトップは低下、また電流効率のピークが高温側にシフトしていきます。そのため運転マニュアルでは高電密ほど適切な温度が高くなっています。
- Why this peak shift occur? We can understand with ion channels explained yesterday. Ion channel becomes narrower at lower temperature. At low current density, capacity and ion flux match, which result in high CE. On the other hand, if the temperature is low at high current density, there is a gap between the capacity and ion flux, which result in low CE. At high temperature, ion channel become wider and capacity increase, which match ion flux at high current density, therefore CE becomes high. では、このようなピークトップのシフトが起きるのでしょうか。 昨日説明したイオンチャネルで理解することができます。
- Now let’s take a look at the temperature characteristic of F-9010 and F-9060. At 2kA/m2, F-9060 show high CE compared to F-9010 at the manual temperature range. ここからF-9010とF-9060の温度特性を見ていきたいと思います。2kA/m2です。 F-9060はマニュアルの温度領域で高いCEを示します。
- This is 4kA/m2
- 6kA/m2
- Although 8kA/m2 is no stated in the operating manual, laboratory evaluation with short term shows high CE. 8kA/m2でも高いCEを示します。
- This is a graph summarizing the performance of F-9060 at each current density. F-9060 shows wider operational range, especially at higher temperature.
- Next is CE stability in zero gap electrolyzer. 続いてゼロギャップ槽におけるCE安定性です。
- First, the resistance to Ni stain. After FLMION soaked in Ni solution, we check the recovery of membrane performance in AGC laboratory cell. F-9060shows the highest resistance to Ni stain.
- Next is temperature characteristic. F-9060 shows higher CE at higher temperature. こちらは先ほど示したグラフです
- The Last is NaCl characteristic. F-9060 keeps higher CE in weak brine compared to F-9010 更に低塩水環境下でも電流効率が安定しており、運転領域も拡大しています。
- By making the ion channels of polymer more uniform, AGC has reduce the number of channels that cause shrinkage or swelling. Then we improve the operating range and durability against impurity AGCはポリマーのイオンチャネルをより均一にすることで、収縮・膨潤起因となるチャネルを減らし、運転領域の拡大を行い、不純物耐性の改善を行ってきました。
- F-9060 has further more uniform ion channel and optimizes channel to match the environment, which achieved CE stability in zero gap and got wider operational range. This improvement also has impact on durability against brine impurities. F-9060では更に均一化及び環境にあったチャネルに最適化することで更にゼロギャップの安定性および運転領域の拡大を達成しました。 このチャネルの改善は、のちに示す不純物耐性向上にも影響しています。
- Before explain impurities resistance I’d like to explain mechanical strength. F-9060 use the same advanced cloth as F-9010. The tensile strength of the membrane is greatly influenced by cloth. In particular, fiber direction has most influence on PTFE fiber because its diameter is the thicker compared to PET fiber. Although the shape of PTFE fiber cloth has been changed between conventional cloth and advanced cloth, the fiber diameter and density remain the same, so membrane strength is the same. Additionally, if you tensile membrane at 45 degrees to the fiber direction, it will be sighnificantly affected by polymer strenghth and thickness, but the strength is the same before. 不純物耐性を説明する前に、機械強度に関して説明します。 F-9060にはF-9010と同じAdvanced Typeの補強布を適用しています。 膜の引張強度は補強布に大きく影響を受けます。特に糸方向は最も太いPTFE糸の影響が大きいです。ConventionalもAdvancedでもPTFE糸の形状は変えましたが、糸径と密度は変えていないので強度は同じです。 また、糸方向に対し45度に引っ張るとポリマー強度や厚みの影響を大きく受けますが、従来と同等の強度になります。
- Next is CE stability in zero gap electrolyzer. 続いてゼロギャップ槽におけるCE安定性です。
- This is influence of brine impurities on membrane under each current density. High CD operation with impurities causes critical damage to the membrane.
- Durability against brine impurities is even more necessary for long-term performance stability under high current density.
- F-9060 has significantly improved durability against SiO2. Si co precipitates with cation and accelerates performance drop, but we have confirmed that F-9060 has improved durability in each complex. F-9060ではSiO2系の耐性が大幅に上がっています。 Siはアルカリ金属土類と共沈して、性能低下を加速させますが、 F-9060では各コンプレックスで耐性が向上していることを確認しています
- This is complex with Sr and Ca. こちらは、SrとCaとのコンプレックスになります。
- In addition, durability against Ca has been improved. The left graph shows CE recovery after 4 hours Ca addition. On the right side, it shows durability at Ca continuous addition at 6kA/m2.Both has improved durability. また、Ca系の耐性も向上しています。左は8kA/m2で4h添加した後の回復性を見ています。 右は6kA/m2の電密ですが、Caを連続添加した際の耐性になります。いずれも耐性向上しています。
- Moreover, durability against I and Ca is also improved. ヨウ素との組み合わせたでも耐性向上しています。
- By the way, why does impurity influence become more sever at high CD? Left graph is an example of laboratory test results with I/Ba addition at 6 and 8kA/m2. Left graph show correlate between amount of I deposited in the membrane and CE decrease. CE decreases rapidly at high CD, even when the amount of accumulated impurities is the same. ところで高電密になるとなぜ急激に性能低下を引き起こすのでしょうか。 こちらは6kと８kのI/Baのラボ添加試験の結果の1例になります。 試験後の解体膜のヨウ素沈着量を横軸に、縦軸に電流効率低下を取ると、 同じ沈着量でも高電密の方が沈着量が大きいです。
- This may be caused by accumulated position changes depending on CD. At high CD, the amount of transported water increases, which change pH distribution in C-layer. As a result, the amount of accumulated impurity in C-layer surface at high CD increase, which leads to severe CE damage. これは電密によって沈着位置が変化することが影響していると考えられます。 高電密になると水の透過量が増えるため、pH分布が変わり、よりカルボン酸表層でpHが上昇すると考えられます。 これにより、高電密ではカルボン酸表層の沈着量が多くなり、CE低下を招くと考えられます。
- As I mentioned earlier, F-9060 has more uniform and optimized ion channel, which contributes higher durability against brine impurities. However, F-9060 is designed not only to do this, but also by a new layer configuration so that ion channel stable even when impurities are deposited. 先ほど述べたようにF-9060では、F-9010から更に均一化および最適化を行っています。このことが、不純物耐性向上に影響を与えています。 しかし、F-9060はこれだけでなく、新しい層構造を適用したことで不純物沈着した際もイオンチャネルが安定するように設計しています
- Simple ion channel model is useful for easy understanding. But it’s not enough for deep understanding and membrane development. 今まで説明してきたシンプルなイオンチャネルモデルは、膜挙動の理解に非常に有用です。 しかし、当然これだけでは膜開発には不十分であり、別のモデルでも考察していく必要があります
- In addition to the ion channel model, there is also a model called a cluster network. These modes can be extended 2D and 3D. There are also simulation models. The image on right is closer to the actual situation. AGC designed membrane based on various models, tests and analyses. イオンチャネルモデルに加え、クラスターネットワークというモデルもあります。これらのモデルは2次元、3次元にも拡張可能であり、更にシミュレーションモデルもあります。 右側ほどより実際の状態に近く、AGCは様々なモデルおよび評価解析を行い、膜設計を行っています。
- In the development of F-9060, we focused on the fact that Sulfonic polymer layer also influences cluster network of carboxylic polymer layer. By applying a new layer configuration, we are able to control the water content inside membrane, and optimize the cluster network, which achieve further improvement of durability against brine impurities. F-9060の開発では、スルホン酸ポリマー層も、電流効率発現層であるカルボン酸ポリマーのクラスター形成に影響を与えることに着目しました。 新しい層構造を適用することで、層内の含水率分布を制御し、クラスターネットワークを最適化することで、更なる不純物耐性の向上を達成しています。
- Until now, I have been talking about impurities deposited C-layer, but we also improve durability against impurities deposited on S-layer. F-9060 also shows higher durability against Fe and Mg, which deposit in sulfonic layer. 今までカルボン酸ポリマーに沈着する不純物に関して説明してきましたが、スルホン酸に沈着する不純物に対しても改善しています。 ここに示すのはFeとMgですが、F-9010より耐性向上することを確認しています。
- This improvement is due to new S polymer. We deeply understand the correlation between deposited position of each impurities and performance impact and apply as much knowledge as possible to membrane design, which has improved the durability of F-9060 against impurities. この性能向上は新しいスルホン酸ポリマーを適用したことが影響です。 新しい層構造、イオンチャネルを含め、各塩水不純物の沈着挙動および性能影響を深く理解し、 膜設計に落とし込むことで、F-9060では多くの不純物耐性を向上させています
- This is summary my presentation. Thank you.