Control of Ion Exchange in Brine Purification Process using EZ-Brine. Chris Du Bois Exec. VP Systems Integration. presented by Thibaut Bettini
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1 Control of Ion Exchange in Brine Purification Process using EZ-Brine CloroSur Technical Seminar WCC Safety Workshop by Chris Du Bois Exec. VP Systems Integration presented by Thibaut Bettini November th 2018 Quinta Real hotel Monterrey Mexico
2 A brine purity on-line analyzer system that works! Learning from situations Helping tool for production to make the shutdown decision easy in case of brine excursion
3 A brine purity on-line analyzer system that works! Good Analysis Result = Analyzer + Application + Preconditioning AppliTek delivers an analyzer system guaranteeing analysis results
4 A brine purity on-line analyzer system that works! Good Analysis Result HVAC Validation/Calibration Valves = temperature control of sample and EZ-Brine analyzer Sample Cooler / Heater
5 anode cathode MEMBRANE Re-Generation Chemicals ION EXCHANGER A ION EXCHANGER B Re-Generation ION EXCHANGER C BRINE DE- CHLORINATOR Vacuum caustic soda (NaOH) A brine purity on-line analyzer system that works! Where in Process? Water sodium carbonate (Na 2 CO 3 ) hydroxides (NaOH) Return Brine or Depleted Brine Filtration Aid DEPLETED BRINE TANK Further Chlorine Processing HYDROGEN PURIFICATIO N Salt Raw Saturated Brine SETTLING Pre-Purified Brine FILTRATION Chemicals WET chlorine (Cl 2 ) hydrogen (H 2 ) WHY brine Quality Avoid membrane damage EZ-Brine 0 20/50/100 ppb Ca 2+ & Mg 2+ in Ultra-purified brine Sludge Precipitated CaCO 3 ( ) Mg(OH) 2 ( ) Solids hydrogen chloride (HCl) STOP STOP ACIDIFICATION STOP BRINE STORAGE 320 g/l NaCl Ultra-Purified bine Depleted Brine STOP Cl 2 H 2 + _ ELECTROLYZER 33% 30% NaOH Water NaOH caustic soda (NaOH)
6 control of elephant control of mosquito Importance of on-line brine control Challenge! amalgam chlorine plant membrane chlorine plant
7 typical EZ-Brine range: 0 20 ppb Ca ++ & Mg ++ (detection limit < 1 ppb) 1 ppb = 1 part per billion 1 ppb equals finding approx. one ( 1 ) diamond on route ppb of Ca ++ & Mg ++ in brine can already damage your membrane chlorine production 2,448 miles (3,940 km) US Route 66 Will Rogers Highway Main Street of America Mother Road 2,448 miles ( 3,940 km ) 1 ppb equals finding 0.15 (3.9mm) ~ one carat diamond
8 A brine purity on-line analyzer system that works! on-line Ca 2+ & Mg 2+ control has a Direct Financial impact. membrane damage by Ca 2+ & Mg 2+ is non-reversable high costs! Electrical Power Cost Increase Membrane Replacement Cost ( typical life-time > 5 years ) Shut down Cost ( production loss ) Labor Cost
9 A brine purity on-line analyzer system that works! colorimetric measurement using hydroxynaphthol blue color indicator (HNB) in conformance with ASTM 3500-Ca injection of brine sample in EZ-Brine analyzer addition of Sodium hydroxide (NaOH) buffer Alkaline addition of color reagent (HNB) red complex Initial absorbance value is measured at ( ) 610 nm addition of EDTA RED complex is destroyed blue Final Absorbance value is measured at ( ) 610 nm calculation of result: Lambert Beer s Law ABS = Є. b. C Є = molar absorptivity (l. cm-1. mol-1) b = path length (cm) C = concentration (mol/liter) measuring range: ppb Ca ++ & Mg ++ detection limit: analysis frequency: better than 0.6 ppb 1 analysis / 8 minutes
10 A brine purity on-line analyzer system that works! Unique Colorimetric Design: special highly sensitive photometer driven by a unique algorithm LED Detector
11 A brine purity on-line analyzer system that works! EZ-Brine sample temperature Result (ppb Ca 2+ & Mg 2+ ) 10 C C C C C C 67.1 Is the sample temperature controlled before injection into the analyzer prior to analysis? The EZ-Brine analyzer has a Peltier-type sample cooler/heater to control the sample to constant temperature within ± 1 C prior to sample injection and analysis.
12 Purified brine Time Stream ABS0 (mau) ABS1 (mau) A brine purity on-line analyzer system that works! ABS2 (mau) ABS21 (mau) Result (ppb Ca ++ & Mg ++) room temperature ( C) Results EZ-Brine 07:05: :00: :56: :51: :46: Average (ppb Ca ++ & Mg ++ ) Stdev (ppb Ca ++ & Mg ++ ) Purified brine spiked with 20ppb of calcium (Ca ++ ) Time Stream ABS0 (mau) ABS1 (mau) ABS2 (mau) ABS21 (mau) Result (ppb Ca ++ & Mg ++ ) room temperature ( C) 06:41: :36: :31: :27: :22: Average (ppb Ca ++ & Mg ++ ) Stdev (ppb Ca ++ & Mg ++ ) Accuracy (ppb Ca ++ & Mg ++ )
13 A brine purity on-line analyzer system that works! Can you have a False Low Reading due to saturation of the Ion Exchangers Resin Bed Breakthrough? Excess of Ca 2+ & Mg 2+ (ppb --> ppm level) Danger for destroying your membranes! Unnoticed Resin Bed Breakthrough causes Permanent Membrane Damage!
14 Is un-dissolved Ca & Mg being measured? Do we perform an acidification step prior to analysis? A brine purity on-line analyzer system that works! Undisclosed Ca and Mg caused by a filtration or acidification problem in the process will not be measured by the photometric method. But once in the electrolyzer, it may dissolve after brine acidification and damage the membrane The EZ-Brine analyzer system has a built-in acidification step to dissolve any un-dissolved Ca & Mg prior to analysis
15 A brine purity on-line analyzer system that works! Does your analyzer has bi-directional remote control? VNC TM Ethernet software The bi-directional control of the on-line EZ-Brine analyzer touch screen can be remotely be taken over by another PC over a Local Area Network (LAN) using commonly available VNC TM Ethernet software
16 A brine purity on-line analyzer system that works! Does your analyzer has a USB port for quick upload or download of data Data Logging Result & Alarm data export (1.000 results including sample stream, date & time) data curve export (last 30 analysis curves) EZ-Brine program up- & download The results can be recorded on a memory stick and used in a spreadsheet program such as Excel or any other data processing software
17 Production helping tool to make the shutdown decision easy during brine excursion Can you perform manual validation analysis? The EZ-Brine analyzer is equipped with two (2) pcs validation valves allowing manual analysis The validation valves are installed prior to the temperature control. In that way the sample temperature is adjusted before analysis in the same way the on-line analysis are performed
18 Production helping tool to make the shutdown decision easy during brine excursion known sample Validation? EZ-Brine Laboratory
19 Field Example Process Control USA AnaShell single compartment protective walk-in cabinet 2 x multi stream EZ-Brine on-line analyzer systems
20 Field Example USA AnaShell single compartment protective walk-in cabinet 2 x multi stream EZ-Brine on-line analyzer systems
21 Field Example Process Control USA AnaShell single compartment protective shelter 2 x multi stream EZ-Brine on-line analyzer systems
22 Field Example Process Control Germany AnaShell protective shelter including double stream EZ-Brine on-line calcium (Ca 2+ ) and magnesium (Mg 2+ ) in Ultra-purified brine
23 Field Example Process Control USA AnaShell protective cabinet 2 x EZ-Brine on-line analyzer system for Ca ++ & Mg ++ in Ultra-purified brine
24 Field Example Process Control Thailand AnaShell single-compartment protective shelter 1 x EZ-Brine on-line Analyzer system for Ca ++ & Mg ++ in Ultra-purified brine
25 Field Example Process Control Thailand AnaShell single-compartment protective walk-in cabinet 1 x EZ-Brine on-line Analyzer system for Ca ++ & Mg ++ in Ultra-purified brine
26 Field Example Process Control France AnaShell single-compartment protective walk-in cabinet 1 x EZ-Brine on-line Analyzer system for Ca ++ & Mg ++ in Ultra-purified brine
27 Field Example Hungary AnaShell single-compartment protective shelter 2 x EZ-Brine on-line Analyzer system for Ca ++ & Mg ++ in Ultra-purified brine
28 Field Example Hungary AnaShell single-compartment protective shelter 2 x EZ-Brine on-line Analyzer system for Ca ++ & Mg ++ in Ultra-purified brine
29 Field Example Sweden AnaShell single-compartment protective shelter 2 x EZ-Brine on-line Analyzer system for Ca ++ & Mg ++ in Ultra-purified brine
30 up-stream on-line brine control Avoid early membrane damage Raw - Saturated brine Pre - Purified brine Ultra - Purified brine g / L high ppm level of Ca 2+ & Mg 2+ ( > 150 ppm ) EZ-Clarifier Sludge Precipitated CaCO 3 ( ) Mg(OH) 2 ( ) SETTLING high ppm level of Ca 2+ & Mg 2+ ( ~ 5 ppm ) EZ-Brine high FILTRATION Re-Generation Chemicals 2 Low ppb level ph double or triple of Ca 2+ & Mg 2+ CONTROL ION 3 EXCHANGERS hydrogen chloride (HCl) Turbidity EZ-Brine TONI special (Total Ammonia) brine FEED electrolyzers EZ-Brine iodide g/l hydroxides ( NaOH ) g/l carbonates ( Na 2 CO 3 ) by EZ-Settler + acid / base titration ( 2 points ph titration with self-finding inflection points ) ppm Ca 2+ & Mg ppm Mg Mg 2+ by calculation by photometric titration FTU / NTU by Ultrasonic Turbidity ppb Ca 2+ & Mg by colorimetric measurement using hydroxynaphthol blue color indicator (HNB) conf. ASTM 3500-Ca 0 10 ppm TA [ ammonia (NH 3 ) + monochloramine (NH 2 Cl) + dichloramine (NHCl 2 ) ] by colorimetric measurement using adapted Berthelot method conf. ASTM 450-NH3 F ppb iodide ( I - ) by calc ppb iodate ( IO 3- ) ppb iodide ( I - ) + iodate ( IO 3- ) by colorimetric measurement
31 AppliTek your trusted partner in on-line brine control
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