on-line analyzer systems for safety and control of chlorine production plants by Chris Du Bois by Thibaut Bettini Buenos Aires Argentina Nov.

Transcription

1 on-line analyzer systems for safety and control of chlorine production plants by Chris Du Bois Exc. VP Systems Integration Div. AppliTek by Thibaut Bettini Project Engineer AppliTek Buenos Aires Argentina Nov. 2016

2 anode cathode MEMBRANE Re-Generation Chemicals ION EXCHANGER A ION EXCHANGER B Re-Generation ION EXCHANGER C BRINE DE- CHLORINATOR 200 AppliTek NV/SA, Vacuum EZ-Brine on-line calcium (Ca 2+ ) and magnesium (Mg 2+ ) in Ultra-Purified brine caustic soda (NaOH) Further Chlorine Processing Water sodium carbonate (Na 2 CO 3 ) hydroxides (NaOH) Return Brine or Depleted Brine Filtration Aid DEPLETED BRINE TANK HYDROGEN PURIFICATIO N Salt Raw Saturated Brine SETTLING Pre-Purified Brine FILTRATION Chemicals WET chlorine (Cl 2 ) hydrogen (H 2 ) WHY brine QUALITY Sludge Solids Precipitated AVOID membrane damage CaCO 3 ( ) range: ppb Mg(OH) 2 ( ) 5 EZ-Brine calcium (Ca 2+ ) & magnesium (Mg 2+ ) in Ultra-Purified Brine hydrogen chloride (HCl) 4 ACIDIFICATION 6 BRINE STORAGE 320 g/l NaCl Ultra-Purified Brine Depleted Brine Saturate d Brine Cl 2 H 2 + _ ELECTROLYZER 33% 30% NaOH Water NaOH caustic soda (NaOH) Where in Process?

3 4 5 6 EZ-Brine on-line calcium (Ca 2+ ) and magnesium (Mg 2+ ) in Ultra-Purified brine AppliTek delivers an analyzer system guaranteeing analysis results other analyzer suppliers selling only an analyzer Field Proven Best Available Technology Analysis Result = Analyzer + Application + Preconditioning WHY on-line EZ-Brine?

4 4 5 6 EZ-Brine on-line calcium (Ca 2+ ) and magnesium (Mg 2+ ) in Ultra-Purified brine AppliTek delivers an analyzer system guaranteeing analysis results HVAC temperature control sample + analyzer Sample Cooler / Heater Field Proven Best Available Technology Why on-line EZ-Brine?

5 4 5 6 EZ-Brine on-line calcium (Ca 2+ ) and magnesium (Mg 2+ ) in Ultra-Purified brine control of elephant control of mosquito Challenge! amalgam chlorine plant membrane chlorine plant

6 4 5 6 EZ-Brine on-line calcium (Ca 2+ ) and magnesium (Mg 2+ ) in Ultra-Purified brine 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 coin in the Andes mountains +20 ppb of Ca ++ & Mg ++ in brine can already damage your membrane chlorine production 7,000,000,000 mm 7,000,000 meter 7,000 km 7 mm Andes mountains length equals to 1 ppb

7 4 5 6 EZ-Brine on-line calcium (Ca 2+ ) and magnesium (Mg 2+ ) in Ultra-Purified brine on-line Ca 2+ & Mg 2+ control has a Direct Financial impact. membrane damage by Ca 2+ & Mg 2+ is nonreturnable high costs! Electrical Power Cost Increase Membrane Replacement Cost (typical life-time > 5 years) Shut down Cost (production loss) Labor Cost Why EZ-Brine?

8 4 5 6 EZ-Brine on-line calcium (Ca 2+ ) and magnesium (Mg 2+ ) in Ultra-Purified brine Analysis Colorimetric method 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: better than 0.6 ppb analysis frequency: 1 analysis / minutes How EZ-Brine?

9 4 5 6 EZ-Brine on-line calcium (Ca 2+ ) and magnesium (Mg 2+ ) in Ultra-Purified brine Unique Colorimetric Design: special highly sensitive photometer driven by a unique algorithm LED Detector How EZ-Brine?

10 4 5 6 EZ-Brine on-line calcium (Ca 2+ ) and magnesium (Mg 2+ ) in Ultra-Purified brine Purified BRINE Time Stream ABS0 (mau) ABS1 (mau) 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 ++ )

11 4 5 6 EZ-Brine on-line calcium (Ca 2+ ) and magnesium (Mg 2+ ) in Ultra-Purified brine Field Example TX USA AnaShell single compartment protective shelter 2 x multi stream EZ-Brine on-line analyzer systems

12 4 5 6 EZ-Brine on-line calcium (Ca 2+ ) and magnesium (Mg 2+ ) in Ultra-Purified brine Field Example TN USA AnaShell single compartment protective shelter 2 x multi stream EZ-Brine on-line analyzer systems

13 4 5 6 EZ-Brine on-line calcium (Ca 2+ ) and magnesium (Mg 2+ ) in Ultra-Purified brine Field Example Frankfurt - Germany AnaShell protective shelter including double stream EZ-Brine on-line calcium (Ca 2+ ) and magnesium (Mg 2+ ) in Ultra-purified brine

14 4 5 6 Field Example EZ-Brine on-line calcium (Ca 2+ ) and magnesium (Mg 2+ ) in Ultra-Purified brine LA - USA AnaShell protective cabinet 2 x EZ-BRINE on-line analyzer system for Ca ++ & Mg ++ in ultra-purified brine

15 4 5 6 Field Example EZ-Brine on-line calcium (Ca 2+ ) and magnesium (Mg 2+ ) in Ultra-Purified brine Samutprakarn - Thailand AnaShell single-compartment protective shelter 1 x EZ-Brine on-line Analyzer system for Ca++ & Mg++ in ultra-purified brine

16 anode cathode MEMBRANE Re-Generation Chemicals ION EXCHANGER A ION EXCHANGER B Re-Generation ION EXCHANGER C BRINE DE- CHLORINATOR 200 AppliTek NV/SA, Vacuum caustic soda (NaOH) Further Chlorine Processing Water sodium carbonate (Na 2 CO 3 ) hydroxides (NaOH) Return Brine or Depleted Brine Filtration Aid DEPLETED BRINE TANK HYDROGEN PURIFICATION Salt Raw Saturated Brine SETTLING Pre-Purified Brine FILTRATION Chemicals WET chlorine (Cl 2 ) hydrogen (H 2 ) Sludge Precipitated CaCO 3 ( ) Mg(OH) 2 ( ) Solids Depleted Brine Cl 2 H 2 + _ EARLY WARNING hydrogen detection PROTECT your Chlorine Plant against hydrogen Explosion FAST hydrogen (H 2 ) in WET chlorine (Cl 2 ) by multi wavelength INFRARED < 30 seconds response time hydrogen chloride (HCl) ACIDIFICATION BRINE STORAGE 320 g/l NaCl Ultra-Purified Brine Saturated Brine ELECTROLYZER 33% 30% NaOH Water NaOH caustic soda (NaOH) FAST oxygen (O 2 ) in WET chlorine (Cl 2 ) by Alternating Pressure Paramagnetic analyzer Where in Process?

17 Vacuum references a study on hydrogen-chlorine low explosibility limits, performed by the laboratory of the safety engineering department of BASF in Ludwigshafen, Germany. The conclusion of the study: maximum allowable value of 3 ± 0.2 % H 2 in Cl 2 at 50 C Lesson learned after Explosion in drying section of a membrane electrolysis unit: the absolute necessity to have a fast detection of hydrogen concentration increase at the outlet of the cells plus an additional monitoring system of the possible membrane damages (voltage / current, quality of products ) Why on-line H 2 in hot-wet Chlorine?

18 Vacuum n 1 Cardinal Rule of safe production of chlorine by WCC Why on-line H 2 in hot-wet Chlorine?

19 Misconceptions! hydrogen is a light gas Why on-line H 2 in hot-wet Chlorine? No Risk hydrogen is not an hydrocarbon No Risk May 6, 1937 Lakehurst, New Jersey USA Hindenburg disaster Plant Safety Critical Equipment

20 High H 2 present High Energy present Defined as: General Purpose Zone ( Non-explosion Proof ) Low voltage High Current = High Energy High Electrical Current NO electrical Ex Proof Technology possible chlorine Electrolysis Process on-line Hydrogen Analyzer system Field Proven Technology Fast Response (T90 = 15 seconds) Good results during start-up Cell Room HAZOP approved Fast on-line analysis of hydrogen (H 2 ) in hot-wet chlorine (Cl 2 ) gas to keep the gas matrix within the flammability limits.

21 hydrogen is not waiting to ignite until you are ready with analysis!!! Every second counts!!! Response time of < 35 seconds T 90 Do not install an analyzer systems that needs minutes to show results T 90 = time needed to detect 90% of Full Scale range when you switch from 0 to 100% at sample point

22 by Gas-Chromatograph (GC) 1 by Thermal Conductivity (TC) 2 by Multi-Wavelength INFRARED (MW-IR) 3 Thermal Conductivity UV light + Multi-Wavelength INFRARED UV light + H 2 + Cl 2 2 HCl H 2 + Cl 2 2 HCl differential measurement Delta TC before - and after oxidation by UV UV reactor H 2 and Cl 2 forms HCl by UV HCl is measured by MW-IR UV reactor % HCl stoechiometrically equal to H 2 Discontinuous measurement Long analysis time (several min.!) Can only be used for Quality Control Cannot be used for Process Control Cannot be used for SAFETY Complex Technology High Maintenance Low Up-time Not Selective measurement for H 2 Calibration Matrix - dependable Does not react first 6 12 min. after Plant Start-up Cannot be used for SAFETY during Plant Start-up Selective measurement for H 2 Calibration Matrix - independable Fast Response (T90 < 20 seconds) Shows Good Plant Start-up Best Available Technology Field Proven High Up-time

23 4 20 ma 200 AppliTek NV/SA, Thermostatically controlled electrically traced thick wall PFA insulated sample bundle % vol HCl stoechiometrically equals to H 2 Process Valve by Customer DIP-tube Sample Take Off Point ( STOP ) # 1 Main Header Salt Washing Water Removal Salt Filtration Pressure Control Flow Control Sample Aspiration Flame Arrestors UV reactor H 2 + Cl 2 2HCl HCl analysis ( corresponds to H 2 ) Multi-wavelength IR analyzer Calibration Preconditioning HMI Human Interface How on-line H 2 in hot-wet Chlorine? Drain FIELD Drain Pump AnaShell corrosion resistant protective cabinet

24 Height = 2 m (6 ft 56) 200 AppliTek NV/SA, Vortex Cooler typical ± 10 m (32 ft) Thermostatically controlled electrically traced thick wall PFA insulated sample bundle Multi-wavelength IR analyzer Logic Control double compartment corrosion resistant insulated protected cabinet IP56 / NEMA 4X Heat Shrink Sample Bundle Entry Salt Washing Water Removal Salt Filtration UV reaction (H 2 + Cl 2 2HCl) Pressure Control Flow Control Sample Aspiration Flame Arrestor Protection Process Valve by Customer DIP-tube STOP Main Chlorine Header Electrical Compartment 1 height = 2 m (6 ft 56) Width = 1 m (3 ft 2) Depth = 0 m 5 (1 ft 64) Analytical Compartment 2 height = 2 m (6 ft 56) Width = 2 m (6 ft 56) Depth = 0 m 5 (1 ft 64) Width = 3 m (9 ft 4) How on-line H 2 in hot-wet Chlorine? Condensate Drain Pump UV - Reactor H 2 + Cl 2 2HCl Water Condensation

25 Start-up Membrane type Chlorine Plant by Gas-Chromatograph (GC) 0.4% H 2 in Cl 2 5 min. 30 s 1 by Multi-Wavelength InfraRed (MW-IR) 3 Air Dilution Multi-Wavelength InfraRed (MW-IR) Hydrogen Start-up Peak ± 5 min. Load (ka) by Thermal Conductivity (TC) 0% H 2 in Cl 2 2 Field Results

26 Field Example Switzerland AnaShell double compartment protective cabinet 1 x single stream on-line Analyzer system for hydrogen in hot-wet chlorine

27 Field Example LA USA AnaShell triple compartment protective cabinet 1 x multi stream on-line Analyzer system for hydrogen in hot-wet chlorine

28 Field Example Brazil AnaShell triple compartment protective cabinet 1 x multi stream on-line Analyzer system for hydrogen in hot-wet chlorine

29 Example Argentina AnaShell double compartment protective cabinet 1 x multi stream on-line Analyzer system for hydrogen in hot-wet chlorine

30 Field Example Belgium AnaShell triple compartment protective cabinet 1 x multi stream on-line Analyzer system for hydrogen in hot-wet chlorine 1 x single stream on-line Analyzer system for oxygen in hot-wet chlorine

31 Field Example Banten - Indonesia AnaShell multi compartment protective cabinet 1 x on-line Analyzer system for hydrogen in hot-wet chlorine

32 Field Example LA, USA AnaShell multi compartment protective cabinet 3 x on-line Analyzer system for hydrogen in hot-wet chlorine ( Multi Wavelength IR )

33 Field Example LA, USA AnaShell multi compartment protective cabinet 3 x on-line Analyzer system for hydrogen in hot-wet chlorine ( Multi Wavelength IR )

34 Field Example Japan AnaShell double compartment protective cabinet 1 x on-line Analyzer system for hydrogen in hot wet chlorine ( Multi Wavelength IR )

35 Field Example Finland 2 x AnaShell double compartment protective cabinet 2 x on-line Analyzer system for hydrogen in hot wet chlorine ( Multi Wavelength IR )

36 Field Example The Netherlands 2 pc AnaShell multi-compartment protective cabinets 1 x on-line Analyzer system for hydrogen in hot wet chlorine ( by multi-wavelength IR ) 1 x on-line Analyzer system for oxygen in hot wet chlorine ( by alternating pressure paramagnetic analyzer )

37 References repeat orders

38 Works Good Looks Good 24 / 7 Worldwide Support Use High Quality - State of the Art BAT Single Source Responsibility International After Sales Service Our goal is to make your plant more safe make your plant more profitable save your plant money Our Mission repeat orders