Pretreatment: Breakpoint Chlorination Plays Important Role in RO Pretreatment

By James McDonald, PE, CWT Originally Published: Ultrapure Water, January 2003, Volume 20, Number 1

hen chlorination is used in reverse osmosis (RO) pretreatment, breakpoint chlorination can make or break the system. This can be especially critical when treating surface waters, wastewaters, or recycle streams. Too low a chlorination level can lead to microbiological fouling of the RO membranes resulting in reduced RO performance and increased operational costs. Typically, the DPD free chlorine test method is used to monitor free available chlorine levels. Free available chlorine is defined as the amount of chlorine which exists in the treated system as hypochlorous acid and hypochlorite ions after the chlorine demand has been satisfied. The DPD free chlorine test method has several interfering compounds that can affect the test results. One important interference to consider is monochloramine, which is why breakpoint chlorination can be such an important issue. When chlorine gas (Cl2) or bleach (NaOCl) are added to water, they rapidly hydrolyze and dissociate to form hypochlorous acid (HOCl) and hypochlorite ions (OCl-). Hypochlorous acid is the much stronger of the two biocides and can react very quickly with inorganics such as ammonia. Some dissolved organic materials also react rapidly, but the completion of many organochlorine reactions can take hours. (1)

Chloramines
If ammonia exists in the water being pretreated for RO use, the reaction between hypochlorous acid and ammonia is a very important reaction that must be taken into account. Hypchlorous acid and ammonia combine to form inorganic chloramines: monochloramine (NH2Cl), dichloramine (NHCl2) and trichloramines or nitrigen trichloride (NCl3). The relative amounts of the chloramines formed are a function of chlorine fed, the
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chlorine/ammonia ratio, temperature, and pH. In general, monochloramine is formed above pH 7 and dominates at pH 8.3. Monochloramine is a much weaker biocide than hypochlorous acid. The killing power of free residual chlorine (i.e., hypochlorous acid and hypochlorite ion) is as much as 25 times higher than the killing power of combined available chlorines (i.e., monochloramines). (2) Why is all this important? As mentioned, monochloramine is an interference to the DPD free chlorine test. As Table A shows, the interference in the DPD free chlorine test can be rather high considering many control ranges are in the 0.25 to 0.5 parts per million (ppm) free chlorine range. Your free chlorine tests may be showing a free chlorine residual of 0.4 ppm, but if you have ammonia in the source water, this reading may be affected by monochloramine interference. You think you have free chlorine residual as a biocide, but you really only have monochloramine. How do you ensure that monochloramine is not interferring with your free chlorine test? You achieve and exceed breakpoint chlorination. Table A - DPD Free Chlorine Interference (ppm) (3) Monochloramine (NH2Cl) Level (ppm) 1.2 2.5 3.5 5.0 Sample Temperature F (C) 40 (5) +0.15 +0.35 +0.38 +0.68 50 (10) 0.19 0.38 0.56 0.75 68 (20) 0.30 0.55 0.69 0.93 83 (30) 0.29 0.61 0.73 1.05

Breakpoint Chlorination
Breakpoint chlorination is the application of sufficient chlorine to maintain a free available chlorine residual. The principle purpose of breakpoint chlorination is to ensure effective disinfection by satisfying the chlorine demand of the water. In waters that contain ammonia such as wastewater, breakpoint chlorination is a means of eliminating ammonia to achieve a true free chlorine residual. Figure 1 shows the theoretical breakpoint chlorination curve. Adding chlorine to water that contains ammonia or nitrogen-containing organic matter produces an increased combined chlorine residual. Between points A and B on the curve, mono- and dichloramines are formed. Point B represents the point where all ammonia has been oxided to monochloramine and
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dichloramine. Complete monochloramine oxidation to dichloramine, occurring between points B and C, results in a decline in the combined available residuals initially formed. Point C is the breakpoint: the point at which chlorine demand has been satisfied and additional chlorine appears as free residuals. The free available residual chlorine increases in direct proportion to the amount of chlorine applied between points C and D. Many factors affect breakpoint chlorination including the initial ammonia nitrogen concentration, pH, Theortical Breakpoint temperature, and demand Chlorination Curve exerted by other inorganic and 7 organic species. A weight ratio Zero of 8:1 or greater of chlorine 6 Chlorine D applied to initial ammonia Demand 5 nitrogen is required for 4 breakpoint chlorination to be 3 reached. If the weight ratio is B 2 less, there is insufficient chlorine present to oxidize the 1 C A chlorinated nitrogen 0 compounds initially formed. 0 5 10 Cl2 Dosage (ppm) For instantaneous chlorine residual, the weight ratio Figure 1 - Theoretical Breakpoint required may be 20:1 or Chlorination Curve more. Reaction rates are fastest at high temperatures and pH 7-8. (1)

Determining Breakpoint
A field test can lead you in the right direction to finding the chlorination breakpoint. Although the test cannot replicate the exact conditions of the system, it is a starting point. The following procedure has been used with success at several locations.

Test Calculation Data: Household Bleach 5.25% NaOCl NaOCl MW = 74.5 Cl2 MW = 71 71 / 74.5 * 5.25% = 5% as equivalent free Cl2 or 50,000 ppm in household bleach

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Test Procedure:
1. Test the ammonia level in the unchlorinated water to evaluated. Record the result. 2. Add 1 milliliter (mL) of original bleach solution to 99 mL distilled water. This makes approximately a 500 ppm solution. 3. Check strength of 500 ppm solution by adding 0.2 mL with a syringe to 100 mL distilled water. This should give 1 ppm free chlorine. Test using the DPD free chlorine test. Multiply the test result by 5. Record the result. This is the amount of Cl2 per mL that will be add to a 100 mL sample in step 5. 4. In five beakers, add 100 mL each of the water to be evaluated for breakpoint chlorination. Do not filter. 5. Add chlorine solution to each beaker. The amount of chlorine solution added per beaker would be dictated by the dosage (ppm) of Cl2 desired. The amount of chlorine added per mL of prepared solution is: mL added * (ppm Cl2/mL calculated in step 3). To achieve breakpoint chlorination, a minimum ratio of 8:1 of chlorine to ammonia must be achieved. It is recommend that beakers 1 and 2 be at dosages less than the 8:1 ratio, beaker 3 at the 8:1 ratio, and beakers 4 and 5 be greater than the 8:1 ratio. This should give a good breakpoint chlorination curve. If you have to add more than 10 mL of chlorine solution, make a stronger chlorine solution and start at step 2. 6. Wait 30 minutes. 7. Test for free chlorine residual. 8. Graph your results. Another test that can be run on the same five beakers in the above procedure is monochloramine. Hach offers a Monochlor-F test procedure for monochloramine. Monochloramine concentrations will be zero when breakpoint chlorination is achieved (test accuracy is +/-0.1 ppm as Cl2).

Analytical Test Options

As mentioned before, monochloramines interfere with the results of the DPD free chlorine test. This also holds true for the Nessler and Salicylate test methods for ammonia testing. Table A summarizes monochloramines effects on analytical test options available.

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Table B - Analytical Test Options with Monochloramine Analysis Free Chlorine Total Chlorine Monochloramine Ammonia Test Method DPD DPD Monochlor-F Salicylate Nessler Ion Selective Electrode Monochloramine Interference Yes No No Yes Yes No

Testing for ammonia alone using an ion selective electrode (ISE) will not determine when breakpoint chlorinate has been reached since the ammonia concentration will go to zero ppm prior to breakpoint chlorination. Point B in Figure 1 represents the point when ammonia concentrations are zero ppm.

Case Study #1
A large industrial plant recovered wastewater for cooling tower makeup by using RO units. Chlorine was added upstream of the RO with a dechlorination step immediately before the RO. Membrane fouling was becoming a real problem. RO capacity was being reduced and membrane cleaning frequency was increasing. The plant was under pressure to recover more wastewater via the RO system. Membrane biopsies revealed microbiological fouling. One of the first steps to take when approaching a problem is to first determine if the steps currently being taken are being done properly. The plant was feeding chlorine at the proper point. Chlorine was being feed into the Clear Well which was the point of lowest chlorine demand prior to the RO system. The test records showed a consistent free chlorine residual being maintained. So far so good, but was the free chlorine residual they were testing using the DPD free chlorine test method really showing free chlorine or was there monochloramine interference? Water tested prior to chlorine addition showed ammonia levels that ranged from 2.5 ppm to 19 ppm. With water temperatures of 80F and a free chlorine residual control range of 0.25 to 0.5 ppm, you can easily see in Table A that free chlorine residual results could be entirely due to monochloramine interference! The plant thought they were getting proper
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chlorination prior to the RO, but were getting a much weaker biocide (monochloramine) instead. The breakpoint chlorination test procedure described earlier was conducted. Figure 2 shows the results from one round of tests. As you can see, the free chlorine residual curve closely resembles that in Figure 1. Ammonia was also tested using the Salicylate method. Even though monochloramine is an interference for this method, Figure 2 shows that the ammonia level as zero at the breakpoint where all monochloroamine had been oxidized. At the breakpoint and beyond, monochloramine does not exist and is not an interference to chlorine or ammonia testing. The two solutions available to the plant were to increase chlorine feed or supplement with another biocide. Because of variation in ammonia levels and the large chlorine demand required to reach breakpoint chlorination, the plant decided to use DBNPA as a supplemental biocide. With a comparatively minimal DBNPA usage rate, the plant was able to significantly increase membrane life and the time between cleanings.

Breakpoint Chlorination of Clear Well Study 7/24/01

Free Chlorine Residual Test
18 16 14

Ammonia

True Free Chlorine Residual

Test Results (ppm)

12 10 8 6 4 2 0 0 20 40 60 80 100 120 140 160 180

Monochloramine Interferrence Monochloramine Interferrence

Breakpoint

Chlorine Added (ppm)

Figure 2 - Breakpoint Chlorination Example

Case Study #2
A large industrial plant used river water as makeup to a 2,000 gpm RO system for boiler feedwater makeup. Due to fouling problems, each bank of membranes was cleaned twice a week. Cleaning at this frequency is not only bad for the membranes, but requires a lot of manpower commitment. RO pressure differences, permeate quality, and RO feed pressure were
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significantly affected by the fouling. The plant knew this was a problem, but had already had many "experts" review their system over the years with no solution. Nine separate companies had already tried. They were resistant to trying anything else and did not want the RO touched. The advantages of solving this problem were obvious: longer service runs, less damage to membranes, minimized membrane replacement costs, reduced manpower costs, lower water production costs, decreased pumping costs, etc. First, the concepts of breakpoint chlorination were applied. The ammonia concentration in the makeup water was determined. The breakpoint chlorination test procedure previously described was conducted to find the proper chlorine dosage to reach breakpoint chlorination. The plant's current chlorine dosage was no where near that required for breakpoint chlorination. A higher dosage was required for proper disinfection of the raw water prior to being introduced to the RO. Next, to prove the findings, a pilot RO unit was set up parallel with the current RO system. Breakpoint chlorination dosages of chlorine were added to the pilot RO pretreatment train with the water being dechlorinated prior to entering the RO. Once breakpoint chlorination was achieved and a true free chlorine residual was maintained throughout the pretreatment train, the pilot RO performance was greatly improved over that of the current RO system. Much longer service runs between cleanings were observed. Pressure drops across the membranes, feed water pressure, and permeate quality were each greatly improved. With the result of the pilot study as proof, the plant implemented breakpoint chlorination dosages on the current RO and experienced a similar success.

Conclusion
The application of breakpoint chlorination with RO pretreatment has successfully been used to solve baffling microbiological fouling problems of RO membranes. Although the customers thought they were applying sufficient chlorine for disinfection, what they were actually measuring was monochloramine interference to the DPD free chlorine test. Determining the breakpoint chlorination allowed the customers to better disinfect their RO feedwater and resulted in longer service runs between membrane cleanings. RO's are complicated systems with many factors to consider. The application of breakpoint chlorination is just one of those factors that must be considered. When approaching any problem, one of the first steps should be to ensure that the current technology and treatments are being properly applied. Taking into account breakpoint chlorination, as described in this article, is a good method to determine if chlorine chemistry is being properly applied.
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References
1. "Betz Handbook of Industrial Water Conditioning", 9th Edition, Betz Laboratories, Inc., Trevose, PA, pp. 196-199, 1991. 2. George Glifford White, "The Handbook of Chlorination", 2nd Edition, Van Nostrand Reinhold Company, New York, New York, pp. 162-167, 1986. 3. "Water Analysis Handbook", 3rd Edition, Hach Company, Loveland, CO, p. 351, 1992.

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