Conditions for Making Sodium Hypochlorite (Bleach) for Water Treatment in a Developing Country While Avoiding Inorganic Disinfection By-Products

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1 Conditions for Making Sodium Hypochlorite (Bleach) for Water Treatment in a Developing Country While Avoiding Inorganic Disinfection ByProducts Mike Bellamy PhD Northwest Missouri State University House of Hope Haiti bellamy@nwmissouri.edu

2 General Goal: Identify Water Disinfection Technology to Treat Well Water for Schools and Children s Homes in Haiti Treat up to 1,000 gallons at a time. We typically treat well water. Turbidity and concentration of organic molecules are low. Residual disinfectant is desirable since water is used to wash food, bathing etc. Desired equipment cost is less than a few hundred dollars (USD). Easily maintained. Eventually be constructed by the end users. Be used as a laboratory exercise in the high school.

3 Some SmallScale Water Disinfection Options for Developing Countries SODIS Slow Sand Filtration Micro or Ultrafiltration Ultraviolet OxidationReduction Reactions Ozone Mixed Oxidants (HOCl, OCl, O 3, ClO 2 and other oxidants with Cl and O MIOX [1]) Chlorination (HOCl, OCl ) Commercial Bleach OnSite Generation: Divided Cell OnSite Generation: Undivided Cell [1] Bradford ET AL Feb_2011_Parkson.pdf

4 Pros and Cons of Chlorination Pros Villagescale quantities can be made for little cost. Bleach can be made onsite. Some onsite generation (OSG) systems can be made by the end users and can be sustainable. Residual disinfectant. It is fairly easy to test for residual chlorine compared to testing for microorganisms. Cons Inorganic byproducts are likely with commercial bleach [2] and possible with OSG bleach. Organic molecules in surface water will react with chlorine. Taste can be a concern if dosage is not reproducible. Chlorination may not be understood and trusted in some settings. Chlorination is not effective against all microorganisms related to water and sanitation. [2] Stanford ET AL Journal AWWA, Vo. 103, No. 6, June 2011, 113.

5 Some SmallScale OSG Systems: Divided Cells Organization Unit Price Power Source Notes Newlife International $1,050 for basic system that will run off a 12V battery.* Basic system runs off 12V battery. AC pump is extra. Pump could fail. Membrane may foul. Heat exchanger will need cleaning. User training is a concern. Leaking Cl 2 gas is a concern. Free chlorine level in treated water tested multiple times. ByProduct concentrations likely low. Waterstep $1,000 for basic unit. Price is on their website. Basic system runs off 12V battery. AC pump is extra. The M100 is very similar to the system from NewLife. Miox Brine Pump System $7,000* *Denotes information obtained through phone call.

6 *Denotes information obtained through phone call. Some SmallScale OSG Systems: Undivided Cells Organization Unit Price Power Source Notes Safe Water International Ministry (SWIM) Hays Pure Water for all Foundation $50 + battery or power supply 12Volt Batter or Power Supply $227 for CPU. Price is on their website. FlowThrough Design. Fast and inexpensive. Could be made by endusers. Disinfection byproducts are a consideration will all OSG systems. 12V batter. Similar to SWIM unit. CPU connects to plastic beverage bottles. WatAyls (Bulane Product) /divers/brochure%20watalys%20en_2007.p df Could not find price. 12Volt Power Supply Batch (Static) chlorinator similar to the Aqachlor and EnvirOCell2.75. Aquachlor $1,459 for model AC25.* Includes power supply. 12V power supply. Batch (Static) chlorinator. Run times are in hours range. Reproducibly produces 6,000 ppm sodium hypochlorite solutions. SANILEC 6 Severn Trent De Nora $3,900* 110 or 220 V to a DC rectifier. Makes large batches at 5000 ppm NaClO. EnvirOCell hlorite_generator.htm $6,000 at detail/water Treatment_ html Power Supply Seems to be a batch chlorinator similar to the Aquachlor product.

7 Basic Components of FlowThrough OSG Systems Cl Cl 2 HClO ClO ClO 3 ClO 4

8 The same electrodes used to make hypochlorite (bleach) from a salt solution are also used to make chlorate. Industrial Conditions Used for Chlorate Production ph 6 to 7 [5]. Temperature 80ᵒC [5]. Brine concentration 80 to 120 g/l [5]. High current density [6]. [5] ChlorAlkali and Chlorate Technology, Electrochemical Society, Inc. 1999, Edited by Burney et. al. ISBN: [6] Rengarajan, V. et. al. Influence Factors in the Electrolytic Production of Sodium Hypochlorite, Bulletin of Electrochemistry, 12 (56), MayJune 1996, pp

9 Batch Mode Undivided Cell (Hypochlorite Generator) e Flow Na + and Cl 2 Cl (aq) H 2 O Anode = DSA Stainless Steel Cathode 2 Cl (aq) Cl 2 (g) + 2 e Cl 2 H 2 (g) + 2 OH (aq) 2 H 2 O (l) + 2 e H 2 (g) + 2 OH (aq) Cl 2 + OH (aq) HOCl + Cl HOCl + H 2 O OCl + H 3 O + Possible Forms of Cl in Solution: Cl 2 HOCl OCl ClO 2 ClO 3 ClO 4

10 Relative Concentration (M) Electrolytic Production of Bleach (Sodium Hypochlorite) (OnSite Generation or OSG) Desired Reactions Forms of Chlorine vs. ph Anode: 2 Cl Cl 2 (g) + 2 e Cathode: 2 H 2 O H 2 (g) + 2 OH Bulk Solution: Cl 2 (g) + OH HOCl + Cl HOCl + H 2 O OCl + H 3 O [HOCl] [OCl] [Cl] [Cl3] [Cl2] ph

11 Divided Cell (Including Membrane Electrolyser) e Flow Na + and Cl Na + DSA Anode 2 Cl (aq) Cl 2 (g) + 2 e 2 Cl OH H 2 O Stainless Steel Cathode H 2 O (l) + 2 e H 2 (g) + 2 OH (aq) Cl 2 H 2 (g) + 2 OH (aq)

12 Simplified Block Diagram of a Divided Cell Water Chlorination System Cl 2 Gas Water Tank Cl 2 HOCl OCl Water Pump Divided Cell Cl 2 Gas Note that water from the tank passes through a heat exchanger in the reaction chamber.

13 The Importance of Simple, Convenient Technology in the Developing World (Below is an message to the presenter.) (a side note.. Name Removed, the man we are working with in Haiti installed a Name Removed unit before we got there. He paid over $1,000 for it and then had to add additional parts. He build an 8 by 8 block building with roof, cement floor and locked door to house it. The Haitians had to pump from a well into a 5 gallon bucket and dump that into a 125 gallon tank. It was literally steps away. It took 25 buckets to fill the 125 gallon tank. After 2 weeks they decided it was too much work and discontinued its use. They cut the wires off to use elsewhere. Andy went back and removed the equipment. They are now using the Name Removed with a pastor and distributing chlorine in 4 oz bottles to the community. He also has a brand new unit at his house but sees no application for it since he s been using the CPUs)

14 The OSG Equipment from SWIM is an Attractive Option. Observations Equipment costs are low. Sodium hypochlorite (bleach) solutions are made rapidly. The equipment could potentially be made by the endusers creating independence and sustainability. There is no membrane to foul, pump to break, heat exchanger to clean Questions: What are Safe Combinations of current density, brine concentration, and reaction time? Time needed to treat up to 1,000 gallons? Can water be treated to reproducible levels of chlorine? For all OSG systems: What is a viable source of NaCl that is low enough in bromide ion?

15 Free Chlorine (ppm Cl 2 ) Free Chlorine vs. Passes Through SWIM Unit (Two resistors in curcuit; DPD Method) Related to Convenience of the System g/l Power Supply 58 g/l Power Supply g/l Battery 58 g/l Battery g/l Battery Passes Through System

16 Conditions Comparison for Making OCl in with an Undivided Cell Controlled Lab Environment DSA Anode/Stainless Steel Cathode Temperature is kept about room temperature. Current density is constant and low compared to that of chlorate production. Pure salt is used to make brine. Brine concentration is about 29 g/l. Developing Country DSA Anode/Stainless Steel Cathode. Temperature increases fairly linearly with reaction time. Current density varies during the reaction and is higher. Salt Quality Processed salt may contain iodide which will form iodate. Rock salt may contain bromide which will form bromate. Will vary with salt source.

17 Time Needed to Treat 1,000 Gallons It takes about 15 minutes to pass 1 liter of a liter 58 g/l through the system seven times. When added to a 1,000gallon tank the initial concentration of free chlorine would be about 1 ppm. There is enough salt in the container in the photo to treat nearly 13,000 gallons of water to 1 ppm free chlorine.

18 Reproducibility of Chlorine Dose. In field tests we found that we can treat water in Haiti to within about plus or minus 0.2 ppm.

19 Inorganic ByProduct Formation Chemical Reactions [3] Electrochemical ClO 3 formation at Anode: 12OCl + 6H 2 O 4ClO H + +8Cl +3O e Maximum Contaminant Levels in Drinking Water ClO mg/l (Title 40 CFR ) Chemical ClO 3 Formation in Bulk Solution: 2 HOCl + OCl ClO 3 + 2H Cl Chlorite intermediate (ph 1113, AWWA) OCl + OCl ClO 2 + Cl OCl + ClO 2 ClO 3 +Cl Overall: 3 OCl + ClO 2 ClO 3 + Cl ClO mg/l (WHO; unregulated federally) ClO 4 low μg/l (CA = 6 ppb; MA = 2 ppb; NJ proposed 5 ppb [4] ) Chemical ClO 4 Formation in Bulk Solution OCl + ClO 3 Cl + ClO 4 BrO 3 10 μg/l (Title 40 CFR ) Other Possible Electrochemical Conversions Br in salt to BrO 3 I in salt to IO 3 IO 3 (?) [3] AWWA and Water Research Foundation Report: /HypochloriteAssess.pdf [4] Shah, J. et al. MRWA Today, Spring 2012, 3033.

20 Rate Constant (x10 3 M 2 S 1 ) Temperature and Chlorate Formation 2 HOCl + OCl ClO 3 + 2H Cl Rate Chlorate = k HOCl 2 OCl OCl + ClO 3 Cl + ClO 4 Rate Perchlorate = k OCl 1 ClO ExperimentallyMeasured Rate Constants for the Decomposition of Free Chlorine from Gordon et. al. [7] Rate equations are from reference 3. Rate constants increase exponentially according to the Arrhenius equation Temperature (ᵒC) k = Ae E a RT [7] Adam, L.C., Fabian, I. Suzuki, K., Gordon, G., Hypochlorous Acid Decomposition in the ph 58 Region, Inorg. Chem. 1992, 31,

21 Temperature ( C) Rate Constant (x10 3 M 2 S 1 ) 70 Temperature Increases with NaCl Concentration and Reaction Time Temperature vs. Passes thru SWIM OSG PS = 13.8Volt DC Power Supply Battery = 12volt Marine Battery ExperimentallyMeasured Rate Constants for the Decomposition of Free Chlorine [7] g/l NaCl PS g/l NaCl PS 88 g/l NaCl PS g/l NaCl Battery 29 g/l NaCl Battery 58 g/l NaCl Battery Passes Through SWIM OSG System Temperature (ᵒC)

22 Current Efficiency (%) Current Efficiency Current Efficiency for Production of Hypochlorite with Marine Battery Current Efficiency for Production of Hypochlorite with Power Supply g/l Battery 88 g/l Battery 58 g/l Battery g/l PS 58 g/l PS Passes Through System

23 Temperature Can be Controlled in a Flow Through Undivided Cell by: Limiting reaction time. Keeping brine concentration reasonably low. Placing the reaction solution in an ice bath for about 30 seconds between runs. Adding heat exchanger.

24 OnGoing Research Set ph to 7. Let temperature rise. Vary salt concentration. Vary current density by using the two common power sources. Measure concentrations of ClO 3 and ClO 4 versus reaction time. Can we have low concentrations of byproducts without controlling temperature? What is the maximum salt concentration and reaction time that we should use?

25 Bromate Formation is a Concern with OSG Hypochlorite ByProduct Formation Bromide ion in salt is converted to bromate. Bromate is limited to 10 ppb. We can purchase iodized foodgrade salt in Haiti. Is iodate safe? OnGoing Research Bring back rock salt samples from places where OSG hypochlorite is used. Do we need to establish a distribution network of food grade salt that has not been iodized?

26 Conclusions A flowthrough OSG system like that supplied by SWIM is a promising technology to chlorinate water in Haiti and other developing counties. By the summer of 2015 we hope to publish recommended reaction conditions for using the SWIM flowthrough OSG system. We plan to incorporate the chemical principles and use of the unit into the curriculum of our high school in Williamson, Haiti next fall.

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