Improving Silica Removal By EDI and GTM January 16, 2014 August 27, McIlvaine
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1 Improving Silica Removal By EDI and GTM January 16, 2014 August 27, 2014 McIlvaine Michael J. Snow, Ph.D. President SnowPure Water Technologies (USA)
2 San Clemente, California Headquarters
3 Electropure EDI Operating in 49 Countries
4 The Electropure EDI History 1977 Harry O Hare EDI Prototype 1979 HOH Water Technology founded 1984 HOH EDI Patent Issued 1988 EPM series EDI 1996 HOH becomes Electropure 1999 Excellion IX Membrane Patents 1999 XL series EDI 2004 XLHTS High Temperature Stable 2005 Electropure Management BuyoutSnowPure formed 2006 Electropure China Sales Office Opened 2007 XLR series EDI improvements 2008 SnowPure International (Hong Kong) formed 2009 EXL series EDI introduced in China 2010 EXL series EDI introduced worldwide 2012 EXLHTS high volume, high temperature for sanitization 2013 XLDER EDI for Hemodialysis
5 Agenda 1. Importance of Silica for Power Plants 2. Old EDI Model: Working Bed Polishing Bed 3. New EDI Model: Electropure Specific Ion Model 4. Discussion: Specific ROEDI Cases 5. Rules to Optimize SiO 2 in EDI
6 Silica is Important in Power Plants and Electronics Semiconductor Fabs SiO 2 < 0.1 ppb Combined Cycle High Pressure Boilers SiO 2 < 5 ppb
7 Old EDI Model: Working BedPolishing Bed 18 M Pure Water POLISHING BED 0.5 S WORKING BED Feed from RO 10 S
8 Electropure s New Specific Ion Model SiO 2 & HSiO 3 H 3 BO 3 & H 4 BO 4 Class 4 Transfer Region Extensive Water Splitting Polishing HCO 3 Removal of HCO 3 Na + Cl Ca +2 Mg +2 SO 4 2 All CO 2 to HCO 3 Bulk Conductivity Removed H + OH ph to 7.0 in feed H + and OH in balance I: H + OH II: Na + Cl Ca +2 Mg +2 SO 2 4 III: HCO 3 CO 2 (g) IV: SiO 2 H 3 BO 3
9 Forces on Cations in EDI Force 1: Electrical Attraction to resin K, Selectivity Coefficient Force 2: Electrical attraction to electrodes E, Charge/Mass + Na + R R R K, Selectivity Coefficient Ca +2 > Mg +2 > K + > Na + > H + E, Electrical Force/Mass H + > Mg +2 > Ca +2 > Na + > K + CX resin Slide 9
10 Forces on Anions in EDI Force 1: Electrical Attraction to resin K, Selectivity Coefficient Force 2: Electrical attraction to electrodes E, Charge/Mass + Cl R + R + R + K, Selectivity Coefficient SO 4 2 > Cl > OH > HCO 3 > HSiO 3 E, Electrical Force/Mass OH > Cl > SO 4 2 > HCO 3 > HSiO 3 AX resin Slide 10
11 Electropure s 4 Classes of Ions Electropure Ion Class Class 1 Characteristics Low Selectivity High Mobility Example Ions H + OH Class 2 Conductivity High Selectivity Medium Mobility Ca +2 Mg +2 Na + Cl SO 4 2 Class 3 Bicarbonate Class 4 Weakly Ionized Ions Low Selectivity Low Mobility Moderate Charge, Polar at ph 7 Very Low Selectivity Very Low Mobility Low charge at ph 7 HCO 3 pk = 6.3 HSiO 3 pk = 9.8 H 4 BO 4 pk = 9.3 Slide 11
12 Class1: H+ and OH Na + Cl Ca +2 Mg +2 SO 2 4 HCO 3 SiO 2 H 3 BO 3 H + OH Zone 1 ph adjustment 1: H + OH 2: Na + Cl Ca +2 Mg +2 SO 4 2 3: HCO 3 CO 2 (g) 4: SiO 2 H 3 BO 3 Slide 12
13 Class 2: Easy Ions HCO 3 SiO 2 H 3 BO 3 Na + Cl Ca +2 Mg +2 SO 4 2 Zone 2: Conductivity Removal CO 2 HCO 3 H + OH Zone 1 ph adjustment 1: H + OH 2: Na + Cl Ca +2 Mg +2 SO 4 2 3: HCO 3 CO 2 (g) 4: SiO 2 H 3 BO 3 Slide 13
14 Class 3: Bicarbonate Ion HCO 3 SiO 2 H 3 BO 3 HCO 3 Zone 3: CO 2 Removal Na + Cl Ca +2 Mg +2 SO 4 2 Zone 2: Conductivity Removal CO 2 HCO 3 H + OH Zone 1 ph adjustment 1: H + OH 2: Na + Cl Ca +2 Mg +2 SO 4 2 3: HCO 3 CO 2 (g) 4: SiO 2 H 3 BO 3 Slide 14
15 Class 4: Difficult Ions (SiO 2 ) SiO 2 & HSiO 3 H 3 BO 3 & H 4 BO 4 Zone 4: SiO 2 Removal Water Splitting H 2 O H+ OH HCO 3 Zone 3: CO 2 Removal Na + Cl Ca +2 Mg +2 SO 4 2 Zone 2: Conductivity Removal CO 2 HCO 3 H + OH Zone 1 ph adjustment 1: H + OH 2: Na + Cl Ca +2 Mg +2 SO 2 4 3: HCO 3 CO 2 (g) 4: SiO 2 H 3 BO 3 Slide 15
16 Case of high or low ph in EDI feed SiO 2 & HSiO 3 H 3 BO 3 & H 4 BO 4 HCO 3 Na + Cl Ca +2 Mg +2 SO 4 2 Weakly Ionized Bicarbonate HCO 3 Conductivity ph high or low H + OH 1: H + OH 2: Na + Cl Ca +2 Mg +2 SO 2 4 3: HCO 3 CO 2 (g) 4: SiO 2 H 3 BO 3 Slide 16
17 Case: High conductivity in EDI feed HCO 3 Bicarbonate HCO 3 Na + Cl Ca +2 Mg +2 SO 4 2 High Conductivity RO is bad 1: H + OH 2: Na + Cl Ca +2 Mg +2 SO 2 4 3: HCO 3 CO 2 (g) 4: SiO 2 H 3 BO 3 H + OH ph near 7.0 Slide 17
18 Case: High CO 2 +HCO 3 in EDI feed HCO 3 High CO 2 + HCO 3 1: H + OH 2: Na + Cl Ca +2 Mg +2 SO 2 4 3: HCO 3 CO 2 (g) 4: SiO 2 H 3 BO 3 Na + Cl Ca +2 Mg +2 SO 4 2 H + OH Good RO (1pass or 2pass) Low Conductivity ph near 7.0 Slide 18
19 EDI Optimized for Removal of Silica 1. ph in Control (6.5 to 7.5) 2. High Rejection RO Tall Bed for Polishing Lots of Water Splitting High residence time 3. CO 2 Removal System (GTM) SiO 2 & HSiO 3 H 3 BO 3 & H 4 BO 4 4. Voltage Is Not Too Low HCO 3 Na + Cl Ca +2 Mg +2 SO 4 2 H + OH Low CO 2 + HCO 3 Low Conductivity ph near 7.0 Slide 19
20 EDI How Does It Work Summary Silica < 5 ppb Working BedPolishing Bed EDI Model Electropure Specific Ion EDI Model Electropure s 4 Classes of ions Optimization Rules for SiO 2 ph of Feed (RO permeate) near 7 High rejection RO System Removal of CO 2 Voltage is HighGood Water Splitting Slide 20
21 How does EDI remove CO 2 and SiO 2? EDI removes charged ions CO 2 and SiO 2 are not charged How to optimize EDI Systems to remove CO 2 and SiO 2
22 CO 2 Chemistry (gas) + H 2 O (carbonic acid) H 2 CO 3 H + + (bicarbonate) HCO 3 H + + (carbonate)
23 CO 2 Chemistry and ph CO 2 + H 2 O H 2 CO 3 H 2 CO 3 H + + HCO 3 HCO 3 H + + CO 3 2
24 CO 2 Chemistry and ph
25 CO 2 Chemistry and ph RO EDI
26 CO 2 in ROEDI Systems EDI: ph=7.0 CO 2 +HCO 3 Normal 1pass RO: ph= CO 2 CO 2
27 SiO 2 Chemistry and ph + 2*H 2 O H 4 SiO 4 H + +
28 CO 2 and SiO 2 Conclusions RO: at ph < 6.4 CO 2 is difficult to reject RO: at ph < 9.8 SiO 2 is difficult to reject EDI: at ph = 7.0 HCO 3 is weak EDI: at ph = 7.0 H 4 SiO 4 is weak GTM: at ph < 6.0 GTM is very good for CO 2
29 RO and CO 2 1. Use Corosex to remove CO 2 before the RO 2. ph in 1pass RO above Raise ph in 2pass RO to above 8.3
30 RO Option #1 (Corosex ) ph 5.5 CO 2 high ph 7.0 HCO 3 low ph 6.7 RO Softener ph 7.3 HCO 3 to drain
31 RO Option #2 (ph >6.8) ph 5.5 CO 2 high ph 6.7 Add NaOH RO HCO 3 high ph 7.3
32 RO Option #3 (2pass RO high ph) ph 6.3 CO 2 high ph 7.0 Add NaOH RO #1 RO #2 ph 6.5 ph 8.5
33 GTM (Gas Transfer Membrane) and CO 2 Use GTM (LiquiCel ) to remove CO 2 after the RO ph must be right for GTM GTM removes CO 2 (gas) not HCO 3 ph should be < 6.0
34 ROGTM Option Vacuum CO 2 to drain CO 2 high RO ph CO 2 high LiquiCel
35 EDI Pretreatment Options Corosex removal of CO 2 RO removal of CO 2 ph > 6.6 2pass RO ph > 8.3 ROGTM ph < 6.0
36 EDI Pretreatment Options RO RO
37 Conclusion for CO 2 ph is important ph < 6.4 (for GTM) ph > 6.4 (for RO) Remove CO 2 before EDI Remove CO 2 in EDI (ph = 7.0)
38 Conclusion for SiO 2 ph is important above ph = 9.8 SiO 2 competes with HCO 3 and Cl SiO 2 HCO 3 Cl HCO 3 and Cl are stronger Use EDI pretreatment CO 2 and conductivity removal EDI will remove up to 99% of SiO ppm
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