Halogen Composition for Water Treatment

Enrico J. Termine, Jonathan N. Howarth, and Alan M. Yeoman


A method for providing aqueous solutions of HOBr or HOCl which includes adding bleach (NaOCl) to a solution of HBr or HCl an identified absorbance or color change in the resulting solution is detected. Dialkylhydantoins are optionally added to the resulting solution to suppress the formation of halate ions. The method provides a simple and reliable method for producing accurately defined solutions of hypohalous acids, which are useful in a variety of ways, including for disinfecting, cleaning, and odor control purposes.


E. J. Termine, J. N. Howarth, A. M. Yeoman, United States Patent No. 5,641,520.
Available at: http://terminegroup.com/archives/333


Halogenated 5,5-dialkylhydantoins (DAH) are common oxidizing biocides used for water sanitization. Examples of halogenated 5,5-alkylhydantoins include: dichlorodimethylhydantoin (DCDMH), dibromodimethylhydantoin (DBDMH), bromochlorodimethylhydantoin (BCDMH) and bromochloromethylethylhydantoin (BCMEH). The dialkylhydantoins are supplied in solid forms such as tablets or granules and are delivered to the system by water flow through a chemical erosion feeder charged with material. A combination of factors hamper the utility of this method. The rate of slug dosing is low because halogenated hydantoins are sparingly soluble in water (0.15-0.21%). The tablets and granules are often supplied as mixtures of chlorinated and brominated material since pure compounds are often difficult to produce. The different solubilities of the different compounds make accurate and reproducible delivery of oxidant difficult to attain. Also with different flow rates, the pressure drop across the chemical feeder varies, and this can produce non-uniform dissolution of the material. This also makes accurate and reproducible delivery difficult to attain.

Hypohalous acids (e.g., HOCl, HOBr) are also well known as oxidizing biocides for water treatment, and generally are generated in the liquid phase. Thus users avoid some of the limitations associated with solid chemicals. However, hypochlorous acid is unstable. Therefore, it is usually formed in-situ by treatment of the water with a precursor such as gaseous chlorine or sodium hypochlorite (bleach). Hypobromous acid is also unstable, and is formed in-situ by a number of methods. One method is the introduction of aqueous NaBr to the water, followed by activation with gaseous chlorine or bleach. Alternatively, stable perbromide (Br.sub.3.sup.-) solutions containing 30-40% Br.sub.2 are added to the water. When injected into the water system, the Br.sub.3.sup.- ion releases Br.sup.- ion and Br.sub.2. The latter immediately hydrolyses to HOBr and HBr according to the equation:

In another method, bromine chloride is introduced which hydrolyses in the water to hypobromous and hydrochloric acids in accordance with the following equation:

All the foregoing methods of generating and delivering hypohalous acids suffer a number of drawbacks. Gaseous chlorine, bromine chloride, and perbromide solutions possess high halogen vapor pressures. These pose serious storage and handling hazards, and are highly corrosive to metering and delivery equipment. In the water system, chlorine, bromine chloride and perbromide solutions release one mole of strong acid (HCl or HBr) per mole of hypohalous acid. Low local pH conditions are corrosive to metals. For perbromide solutions, only one of the three Br moieties of the Br.sub.3.sup.- ion materializes as HOBr, the other two are wasted. Sodium hypochlorite (bleach) is also unstable, and considerable amounts of NaOH are added to suppress deterioration. Therefore, application of bleach inadvertently increases the pH of the water and this can lead to local precipitation of metal hydroxides. The in-situ method of hypobromous acid generation by activation of NaBr with bleach or chlorine occurs under conditions of high dilution, and optimum control of the reaction stoichiometry is difficult. Underdosing of chlorine or bleach results in unreacted NaBr, while overdosing is a waste of material and can result in discharge limits being exceeded. In addition, for certain waters which are rich in ammonia and organic amines, the chlorine or bleach preferentially reacts to form stable chloramines which are unable to react with NaBr to form HOBr. Thus, NaBr is wasted.

Several of these limitations are addressed by an ex-situ system in which accurately defined, higher concentrations of hypobromous acid are prepared and stored for subsequent delivery to the water system. In this method, aqueous NaBr, bleach and HCl are metered to a reaction tank to produce a solution containing 2500 ppm HOBr. The hydrochloric acid neutralizes the hydroxide ions introduced with the bleach. The pH is maintained at 2.5-3.0, since incomplete conversion of Br.sup.- ion to HOBr is claimed under neutral conditions. The weaknesses of this method include the following. Bleach is unstable and must be analyzed routinely. Adjustments to the metering equipment are required to compensate for the varying bleach quality. The metering and control equipment is expensive. The process uses three components: aqueous NaBr, bleach, and HCl.

In a related issue, hypohalite ions are known to disproportionate under alkaline conditions to produce halate ions:

Thus, chlorate can be formed during the manufacture and storage of bleach (to which NaOH is deliberately added to supress deterioration). Bromate can be formed under conditions of high local pH during the activation of NaBr by bleach. Both bromate and chlorate may be present in alkaline water to which the corresponding hypohalous acid (or precursor) has been introduced. Halate ions are undesirable byproducts. They are not biocidally active and are a waste of hypohalous acid. Also, they are contaminants under consideration for regulation by the EPA.


In one aspect of the present invention, there is provided a method for providing an aqueous solution of HOX, in which X is selected from bromine and chlorine, the method comprising the steps of providing an aqueous solution of HX, in which X is selected from the group consisting of bromine and chlorine, adding bleach to the HX solution while monitoring either the color or the absorbance at about 400 nm of the resulting solution, and discontinuing addition of bleach upon detection of a change (by colorimetry or visually) in color from orange to yellow. In certain embodiments, a dialkylhydantoin is added to the resulting solution to suppress the formation of bromate and/or chlorate ions.

It is an object of the present invention to provide a simple and reliable method for producing accurately defined solutions of HOBr and HOCl. These solutions contain up to five times more oxidizing halogen than those prepared from saturated solutions of solid halogenated hydantoins.

A further object of the present invention is to provide for the preparation of aqueous solutions containing hypohalous acids, but without production of halate ions.

Further objects and advantages of the present invention will be apparent from the description which follows.

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Dr. Enrico J. Termine is a senior executive and scientist with thirty years of experience in business leadership, research & development, product engineering, marketing, and manufacturing. He has consulted for a variety of industrial and legal clients on engagements involving valuations, due diligence assignments, market research reports, strategy development reports, science and technology assessments, and root cause investigations. Dr. Termine is a bromine chemistry expert. He specializes in oilfield applications, flame retardant plastics, industrial and recreational water treatment and disinfection, specialty and fine chemicals, polymer additives, plastics, and organic synthesis for life science molecules and advanced materials. Dr. Termine earned both his Bachelor of Science in Chemistry and his Ph.D. in Organic Chemistry from the University of Miami. He has collaborated on more than 38 patents and publications. His technical contributions are useful in consumer electronics; for petroleum and petrochemical processing; in transportation and industrial products; in healthcare; for industrial and household disinfection; and in building and construction materials.

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