DuPont de Nemours, Inc. · NYSE:DD
DuPont de Nemours — DuPont — Technical Presentation (September 2012)
38 slides from DuPont de Nemours's technical presentation, Sep 18, 2012
Slide 1: Improving Indoor Air Quality Webinar
Improving Indoor Air Quality Webinar September 18, 2012 Copyright © 2012 DuPont. The DuPont Oval Logo, DuPont™, The miracles of science™, and Oxone® are trademarks or registered trademarks of E.I duPont de Nemours and Company or its affiliates.
Slide 2: Improving Indoor Air Quality Webinar Agenda
Improving Indoor Air Quality Webinar Agenda Chloramines in Swimming Pools Ernest R. Blatchley III, Ph.D., P.E., BCEE Limitation of Breakpoint Chlorination Dr. Thomas Tufano How to Minimize Chloramine Formation Edward Lightcap Q&A 2 Copyright © 2012 DuPont. The DuPont Oval Logo, DuPont™, The miracles
Slide 3: Chloramines in Swimming Pools
Chloramines in Swimming Pools Ernest R. Blatchley III, Ph.D., P.E., BCEE Purdue University School of Civil Engineering Division of Environmental & Ecological Engineering Purdue Water Community [email protected] 3 Copyright © 2012 DuPont. The DuPont Oval Logo, DuPont™, The miracles of science™, and O
Slide 4: Outline
Outline Reactions Between Chlorine and Ammonia Chloramination Breakpoint Chlorination Reactions Between Chlorine and Amines Chloramines in Pools Inorganic Organic Other Disinfection Byproducts (DBPs) in Pools 4 Copyright © 2012 DuPont. The DuPont Oval Logo, DuPont™, The miracles of science™, and Oxo
Slide 5: Chlorine: Ammonia Reactions
Chlorine: Ammonia Reactions + NHCl2 + H2O HOCl + +products +products NH4+ NH3Cl + NH2Cl H+ H+ + OH- + + NH3 + HOCl NH2Cl + H2O +products + NH2Cl acid H+ + NH2Cl NHCl2 + NH3 + OCl- + HOCl NHCl2 + H2O base + 2 HOCl + H2O NO3- + 5 H+ + 4 Cl- base + HOCl H2O + NCl3 + NH2Cl + H2O HOCl + +products + NHCl2
Slide 6: Chlorine:Ammonia Reactions
Chlorine:Ammonia Reactions HOCl + NH3 NH2Cl + H2O HOCl + NH2Cl NHCl2 + H2O HOCl + NHCl2 NCl3 + H2O Fast Substitution; Reversible Slow Oxidation (Moderate Stability) Inorganic Chloramines 6 Copyright © 2012 DuPont. The DuPont Oval Logo, DuPont™, The miracles of science™, and Oxone® are trademarks or
Slide 7: Breakpoint Chlorination Behavior
Breakpoint Chlorination Behavior NH3 = Source of Reduced-N For Cl:N < 1 t = 5 min pH = 7.0 1.0 Slow Oxidation t = 15 min t = 25 min [Residual Chlorine]/[NH3-N]0 Inorganic Chloramines 0.8 Stable 0.6 For Cl:N > 1 Fast Oxidation 0.4 Inorganic Chloramines 0.2 Unstable 0.0 Products: N2, NO3- 0.
Slide 8: Measurement of Chloramines in Pools
Measurement of Chloramines in Pools DPD/KI Method MIMS Colorimetric Endpoint Detection by Mass Spectrometry Widely Used Minimal Interference Simple, Inexpensive Interference! Outlet to Mass Spectrometer Inert Gas Inlet Pervaporation Solution Membrane Solution Inlet Outlet 8 Copyright © 2
Slide 9: Chloramines in Pools: NHCl2
Chloramines in Pools: NHCl2 NHCl2 - MIMS NHCl2 - DPD Concentration (mg/L as Cl 2) 1 0.1 0.01 1 2 3 4 5 6 7 8 9 10 11 Pools 9 Copyright © 2012 DuPont. The DuPont Oval Logo, DuPont™, The miracles of science™, and Oxone® are trademarks or registered trademarks of E.I duPont de Nemours and Company or it
Slide 10: Precursor Structures: Human Urine
Precursor Structures: Human Urine Urea Creatinine* Uric Acid 343 mmol/d 12.9 mmol/d 3.0 mmol/d Glycine Histidine* Arginine* 1790 mol/d 1104 mol/d 25 mol/d Free Amino Acids: 5.7 mmol/d Urine Composition Data from Geigy Scientific Tables (1981) C. Lentner, Ed. 10 Copyright © 2012 DuPont. The DuPont Ov
Slide 11: Chlorination of Urea
Chlorination of Urea Molecular Urea Chlorine Monochloro-urea NH2CONH2 + Cl2 NH2CONCl + Cl- Slow • Rate-Limiting Step! NH2CONCl + HOCl NHClCONHCl + H2O NCl2CONCl2 + HOCl H+ + Cl- + CO2 + NCl3 + NCl Tetrachloro-urea 11 Copyright © 2012 DuPont. The DuPont Oval Logo, DuPont™, The miracles of science™, a
Slide 12: Volatile N-DBPs from Chlorination
Volatile N-DBPs from Chlorination Organic-N Compound Volatile DBP from Chlorination Urea NCl3 Creatinine NCl3, CH3NCl2 Histidine NCl3, CNCHCl2,CNCl Uric acid NCl3, CNCl Glycine NCl3, CNCl Alanine NCl3, CH3CH=NCl 12 Copyright © 2012 DuPont. The DuPont Oval Logo, DuPont™, The miracles of science™, and
Slide 13: Fates of NCl3 in Pools
Fates of NCl3 in Pools NCl3 Chlorine HOCl + NH3 NH2Cl + H2O Reactions are HOCl + NH2Cl NHCl2 + H2O Reversible HOCl + NHCl2 NCl3 + H2O 13 Copyright © 2012 DuPont. The DuPont Oval Logo, DuPont™, The miracles of science™, and Oxone® are trademarks or registered trademarks of E.I duPont de Nemours and C
Slide 14: Limitations of Breakpoint Chlorination
Limitations of Breakpoint Chlorination Tom Tufano DuPont Company 14 Copyright © 2012 DuPont. The DuPont Oval Logo, DuPont™, The miracles of science™, and Oxone® are trademarks or registered trademarks of E.I duPont de Nemours and Company or its affiliates.
Slide 15: What is Breakpoint Chlorination?
What is Breakpoint Chlorination? As first described in the 1930’s in potable water treatment, it is the practice of applying appropriately-high doses of chlorine to eliminate or “break” the ammonia nitrogen content of a target source water As practiced now in the pool industry, it has evolved to the
Slide 16: Chloramines in Recreational Water: Inorganic and Organic
Chloramines in Recreational Water: Inorganic and Organic Ammonia Nitrogen Inorganic Combined Chlorine Free Chlorine + (Chloramines) Organic Nitrogen (mostly from sweat, urine) 16 Copyright © 2012 DuPont. The DuPont Oval Logo, DuPont™, The miracles of science™, and Oxone® are trademarks or registered
Slide 17: Conventional Breakpoint of Ammonia Nitrogen
Conventional Breakpoint of Ammonia Nitrogen Breakpoint Chlorination of Ammonia (Synthetic Pool Water, pH 7.4, TA 110 ppm, Ca.Hd. 250 ppm) 2NH3 + 3Cl2 = N2 + 6HCl 9.00 1ppm ammonia nitrogen dosed at time zero 1.5:1 Cl2/N mole ratio 8.00 7.6:1 Cl2/N weight ratio 7.00 ppm Chlorine (as Cl2) 6.00 NH2Cl 5
Slide 18: Standard Pool Industry Practice for Combined Chlorine Control
Standard Pool Industry Practice for Combined Chlorine Control 1 Determine combined chlorine residual using a standard DPD test kit 2 Use breakpoint chlorination to treat the combined chlorine residual Add a shock dose of chlorine equal to 10x 3 the measured combined chlorine concentration 18 Copyrig
Slide 19: Two Problems with This Approach
Two Problems with This Approach Ineffective at reducing measured combined chlorine residuals Results in over-application of chlorine which leads to unintended consequences that adversely impact indoor air quality 19 Copyright © 2012 DuPont. The DuPont Oval Logo, DuPont™, The miracles of science™, an
Slide 20: Ammonia and Monochloramine
Ammonia (NH3) and Monochloramine (NH2Cl) H N H plus 7.6 -10X FC Breakpoint (N2 is formed) H Cl H plus 7.6 -10X FC Beyond Breakpoint N (NCl3 is formed) H Note: 1ppm of NH2Cl contains only 14/71 X 1 = 0.2 ppm of nitrogen 10 ppm FC : 0.2 ppm N is a 50 : 1 Weight Ratio 20 Copyright © 2012 DuPont. The Du
Slide 21: Relationship of Cl2:N Weight Ratio and Trichloramine Formation
Relationship of Cl2:N Weight Ratio and Trichloramine (NCl3) Formation MIMS DPD/FAS UV-VIS Residual chlorine measurements 30 minutes after chlorination of aqueous ammonia at pH 7 Initial concentration of ammonia 0.5mg/L as N Trichloramine (NCl3) formation starts at mass ration of chlorine-to-ammonia
Slide 22: Chlorination of Ammonia Nitrogen
Chlorination of Ammonia Nitrogen Data from Griffin’s work on potable water treatment: Contact time 2 hours at pH 7 Initial concentration of ammonia 0.5mg/L as N Trichloramine (NCl3) formation starts as the mass ratio of Monochloramine chlorine-to-ammonia N exceeds about 12:1 (6 ppm chlorine X dose o
Slide 23: Over-Application of Chlorine
Over-Application of Chlorine Conventional chlorine pool shock dose is based on a combined chlorine measurement, not an ammonia nitrogen measurement Because of the mass difference between N (=14) and Cl2 (=71), ammonia nitrogen is only a small fraction of the combined chlorine residual A 10:1 shock d
Slide 24: Chloramines in Recreational Water Inorganic and Organic
Chloramines in Recreational Water Inorganic and Organic Ammonia Nitrogen Inorganic Combined Chlorine Free Chlorine + (Chloramines) Organic Nitrogen (mostly from sweat, urine) 24 Copyright © 2012 DuPont. The DuPont Oval Logo, DuPont™, The miracles of science™, and Oxone® are trademarks or registered
Slide 25: Organic Chloramines
Organic Chloramines Form the larger fraction of the total combined chlorine measurement Are NOT effectively reduced by the practice of breakpoint chlorination Are slowly converted to trichloramine gas and other volatile DBPs by over-application of chlorine Many, many other nitrogen-containing organi
Slide 26: Chlorination of Creatinine and Human Sweat
Chlorination of Creatinine and Human Sweat Creatinine Creatinine Human Sweat C h lo rin atio n o f C reatin in e C h lo rin ato n o f H u m an S w eat (S yn th etic P o o l W ater, p H 7.5, T A 110 p p m , C a.H d . 250 p p m ) (S yn th etic P o o l W ater, p H 7.5, T A 110p p m C a.H d . 240 p p m
Slide 27: Chlorination of Water Containing Ammonia and Organic-N
Chlorination of Water Containing Ammonia and Organic-N Study illustrates what would be expected with water containing: 0.3 ppm ammonia nitrogen and 0.3 ppm organic nitrogen Water containing both ammonia and organic nitrogen does not display the classic dip of the breakpoint reaction but rather a pla
Slide 28: Chlorination of Organic Nitrogen
Chlorination of Organic Nitrogen Dose = 23ppm Chlorine per 1ppm Nitrogen at pH 7.5 Chlorination of Creatinine Chlorination of Urea CH3NCl2 formation as a function of time (mg/L as Cl2) NCl3 formation as a function of time (mg/L as Cl2) 35 6 30 5 25 4 20 3 15 2 10 1 5 0 0 1 5 24 48 72 96 1 5 24 48 72
Slide 29: Chlorination of Public Pool Water
Chlorination of Public Pool Water Chlorination of Public Pool Water 7 Total chloramine = 2.1 ppm Free Chlorine "Monochloramine" 1.5 ppm organic chloramine 6 Organic Chloramine Total Chlorine 0.6 ppm “monochloramine” 5 Current practice – apply chlorine Breakpoint shock dose of 10 X 2.1 = 21 ppm p
Slide 30: How to Minimize Chloramine Formation
How to Minimize Chloramine Formation Edward Lightcap Senior Account Executive, DuPont 30 Copyright © 2012 DuPont. The DuPont Oval Logo, DuPont™, The miracles of science™, and Oxone® are trademarks or registered trademarks of E.I duPont de Nemours and Company or its affiliates.
Slide 31: Disinfection By-Products
Disinfection By-Products Volatile DBPs (Trichloramine and many others) OUTPUTS + INPUTS Cl2 Free Chlorine Contaminants Combined Chlorine (sweat, urine, etc.) (Chloramine) 31 Copyright © 2012 DuPont. The DuPont Oval Logo, DuPont™, The miracles of science™, and Oxone® are trademarks or registered trad
Slide 32: How To Improve Indoor Air Quality
How To Improve Indoor Air Quality Use chlorine more effectively – consider the benefits of chlorine sanitation vs. the drawbacks of over-application Move away from traditional shock chlorination Supplement chlorine sanitizers with non-chlorine products and technologies to produce the results we want
Slide 33: Cause and Control of Indoor Air Quality Problems
Cause and Control of Indoor Air Quality Problems CAUSE Indoor Air Quality Problems Ammonia Nitrogen (Inorganic) Combined Volatile Free Chlorine Chlorine + DBPs (Chloramine) (NCl3) Organic Nitrogen (mostly from sweat, urine) CONTROL Stop Breakpoint Improve Bather Reduce Chloramine Chlorination Hygien
Slide 34: Potassium Monopersulfate (KHSO5)
Potassium Monopersulfate (KHSO5) Useful oxidation without raising chlorine concentrations Contaminants are removed by a multi-step process 1. Oxidation 2. Microflocculation 3. Filtration Prevents chloramine formation Reduces/eliminates odors and irritation associated with chloramine Improves indoor
Slide 35: Comparison of Dichlor and Monopersulfate in Residential Pools
Comparison of Dichlor and Monopersulfate in Residential Pools Average Swimmers PPM Free Chlorine PPM Combined Per Day by FAS-DPD Chlorine by FAS- DPD 4.0 0.5 4.0 0.4 3.0 3.0 0.3 2.0 2.0 0.2 1.0 0.1 1.0 0.0 0 0.0 June 15 - June 15 - June 15 - July 31 July 31 July 31 Dichlor Dichlor Dichlor MPS MPS MP
Slide 36: Final Thoughts
Final Thoughts Use chlorine responsibly Supplement chlorine sanitizer with non-chlorine products and technologies Ozone (O3) UV Potassium Monopersulfate (KHSO5) Educate the swimming public Introduce and enforce bather hygiene practices, like showers, etc. Help create a more sustainable futur
Slide 37: Thank You
Thank You Dr. Ernest R. Blatchley III Dr. Thomas Tufano Edward Lightcap School of Civil Engineering Sr. R&D Chemist Sr. Account Manager Purdue University DuPont DuPont [email protected] 610-255-1526 37 Copyright © 2012 DuPont. The DuPont Oval Logo, DuPont™, The miracles of science™, a
Slide 38: DuPont™, The miracles of science™, and Oxone® are
Copyright © 2012 DuPont. The DuPont Oval Logo, DuPont™, The miracles of science™, and Oxone® are trademarks or registered trademarks of E.I duPont de Nemours and Company or its affiliates.