MXPA96005549A - Method and compositions to treat recirculation water systems - Google Patents

Abstract

A new method and compositions for the treatment of water in recirculating water systems is described. The method includes providing a boron level of at least 20 ppm in the water, continuously abrading in the water a disinfectant / algaecide, compressed component including a halogen source material, a boron source material, and glycoluril, and periodically adding to the water an oxidizing clarifier comprising a chlorine source material, a non-halogen chlorine source material and a boron source material. The invention also provides new water treatment chemicals including the disinfectant / algicide, compressed component and the clarifier in the previous system. The system and compositions are safe and reliable, control the growth of algae and fungi and generally provide an improved water quality for recirculating water systems.

Description

"- *. METHOD AND COMPOSITIONS FOR DEALING WITH RECYCLING WATER SYSTEMS FIELD OF THE INVENTION 5 This invention relates to methods and compositions for the treatment of recirculating water systems such as cooling towers, evaporation condensers, air water scrubbers, swimming pools, hot water tubs and springs. The invention relates in particular to the control of microbial growth, in particular to the growth of algae and fungi. BACKGROUND OF THE INVENTION Swimming pools, hot tubs and springs, as well as other water systems, are subject to the contamination of microbes, for example, algae and fungi, causing discoloration or unwanted spots and turbidity in the water system. Typical organisms that will grow in water in these systems include 25 Chlorococcum, Chlorella, Cledaphora, Microcystis, REF: 23528 Oscilratoris, Spirosyra, Olaothrisx, Vanetteria, and Aspergilles flavus. The prevention or inhibition of the growth of these microorganisms in water systems has been a problem. It is usual to treat the water systems with one or more disinfectants and / or combinations of disinfectant / oxidant to control the growth of microorganisms. The disinfectants most commonly used to control the growth of microorganisms are chemical products that generate hypochlorite or hypobromite species when they dissolve in water. There are many chemicals that generate hypochlorite with one of the most common being chlorine gas, alkali metal hypochlorites such as sodium hypochlorites, alkaline earth metal hypochlorites such as calcium hypochlorite and lithium hypochlorite, and halogenated hydantoins and acid derivatives. chlorinated isocyanuric such as potassium dichloro-s-triazinetrione. Although the above halogen species are excellent water treatment agents, it can be difficult to maintain an efficient level of the halogens to control the growth of the microorganisms. This is especially true for bromine systems and unstabilized chlorine systems. In this way, it is necessary with these systems to continuously replace the lost halogens. With this type of treatment program, there are frequently periods of unnecessarily high halogen levels that are uneconomic for the chemicals, and low or no halogen levels, which invite the growth of microorganisms. Hydrogen peroxide and other inorganic peroxide compounds, in particular persulfates and persulphuric acids and their salts, are known to be compounds containing active oxygen, which are also used for the oxidation of water systems. However, hypochlorite compounds and active oxygen compounds are not generally used together to treat water systems. In fact, manufacturers of both chlorine compounds and oxygen compounds, as well as other sources in the literature, have recommended against the mixture of these compounds due to their chemical incompatibilities that can lead to explosions or fire. Also, The Encyclopedia of Chemical Technology (Kirk-Othmer), Volume 17, page 1, reports that hydrolysis to H202 followed by molecular disproportionation of H202 is the main route for the decomposition of inorganic peroxide, for example, K2S208 + 2 H20 > 2 KHS04 + H202 Inorganic peroxides neutralize chlorine in water by acting as dechlorination agents: HOC1 + H202 > 02 (Ag) + H + + Cl "+ H20 Based on the above information, it would seem that a combination of these types of compounds would be impractical. The separate addition of chlorine compounds and a peroxy compound as the oxidizing agents is taught in U.S. Patent No. 3,702,298 issued November, 1972 to F.J. Zsoldos and collaborators. This patent teaches the addition of peroxy compounds to swimming pool water containing multivalent metals such as Ag and Cu to increase the valency of metals to a level at which metals provide an oxidizing action. As well, chlorine can be present as a disinfectant in the water system. However, it has not been suggested that the chlorine source materials are physically combined with the peroxy compounds in the same dry composition. US Patent No. 4,780,216, issued October 25, 1988 to John A. Wojtowicz, discloses calcium hypochlorite disinfectant compositions consisting essentially of a mixture of calcium hypochlorite and a peroxydisulfate compound. The compositions are indicated to be useful in disinfecting water while helping to minimize the increase in pH of the water. In US Patent No. 4,594,091, issued June 10, 1986 to John W. Girvan, a method is described for controlling the growth of algae and fungi using sodium tetraborate or potassium tetraborate in water systems. The Girvan patent teaches a method of adding from 10 to 500 ppm of boron to water systems. Girvan teaches the separate addition of the boron material, particularly sodium tetraborate, to a water system, which may also include a disinfectant. The results achieved with this approach vary greatly from one swimming pool to the other.

The use of calcium hypochlorite mixed with hydrated inorganic salts, soluble in water to provide a composition that is resistant to self-propagating, exothermic decomposition, is described in US Patent No. 3,793,216, issued to Dychdala et al. On February 19, 1974 The inorganic salts are selected from various phosphates of alkali metals and alkaline earth metals, hydrates, silicates, borates, carbonates and sulphates. It has also been known in the prior art to combine boric acid and trichloro-s-triazinetrione. This combination has been described by industry practice for the purpose of increasing solubility and reducing total raw material costs. The present invention is surprising in its divergence from the teachings of the prior art. For example, the prior art has included indications that the boron materials would not be effective at the levels used herein. See, for example, Marshall and Hrenoff, Journal of Infectious Diseases, Vol. 61, p. 42 (1937).

Prior art systems for treating water to control the growth of antimicrobials have generally had difficulties with the provision of consistently reliable results. The theoretical approaches have had deficiencies in practice due to the need for careful attention to chemicals in the water. The best systems are inadequate if they are too difficult to use in practice. The present system and compositions addresses this problem by providing a simple, reliable, and consistent system for the treatment of water systems.

BRIEF DESCRIPTION OF THE INVENTION Briefly describing an aspect of the present invention, a system is provided for the treatment of water systems to control the growth of microbes. The system includes the addition of boron at the level of at least about 20 ppm in water, the use of a component in the form of a solid to continuously add both halogen and boron to the water to help maintain the desired levels of both of these components in water, and the periodic addition of a clarification treatment that combines a chlorine compound, an oxidizing compound, not a halogen, and a boron source material. The system provides an effective, reliable approach to water treatment. In addition, the present invention includes a disinfectant, algicidal, compressed, boron-containing, expendable component, and an oxidizing clarifier. It is an object of the present invention to provide a method and compositions for treating water in recirculating water systems, to more consistently achieve the improved water quality. A further object of the present invention is to provide water treatment in swimming pools, hot-water tubs and springs that allows faster entry of the swimmer in accordance with current regulatory guidelines. It is another object of the present invention to provide chemicals useful for the treatment of water that are safe to transport and use, and that have reduced decomposition and reduced deterioration in packaging.

The additional objects and advantages of the present invention will be apparent from the following descriptions and examples.

DESCRIPTION OF THE PREFERRED MODALITY The present invention provides a broad system for the treatment of recirculating water systems that utilizes specific compositions that provide improved efficacy and reliability for the control of algae and other microorganisms. The composition includes (1) an initial boron contributor, (2) a disinfectant product, halogen / boron algicide, compressed, in the solid form, and (3) an oxidizing clarifier comprising a chlorine compound, an oxidant not halogen, and a boron source. This system has been shown to consistently provide significantly improved results over the above approaches. These results have been achieved in spite of the teachings of the prior art which have suggested the opposite of the present invention. The present invention provides a system and compositions for the treatment of a variety of recirculating water systems. For example, the invention is useful for the treatment of cooling towers, evaporation condensers, air water scrubbers, swimming pools, hot water tubs and springs. The system and compositions are easily adapted for use in these and other environments. The particular mechanisms of action for the compositions and methods of the present invention are not claimed. However, it has been observed that the present invention provides improved water quality in a more consistent base. One explanation for this is a synergistic effect of the boron materials in the water in combination with, for example, enclosed clarifier materials. A second explanation is the operation of the oxidizing clarifier to remove the organic impurities, thus allowing the improved control of the microorganisms by the disinfectant / algicidal component, compressed, containing halogen, primary. The present system includes the use of a boron source material to stabilize the initial boron levels in the treated water. This is complemented by the sustained, subsequent addition of a combination of a halogen source material, and a boron source material. Finally, a third composition, added periodically during the treatment period, improves the operation of the complete system. The new method uses a boron source composition comprising a boron source solubilized for water. In the pH of water systems, for example, neutral pH in the range of 6-8, boron will be present in water mainly in the form of triborate polyions [B303 (OH) 4] -and tetraborate [B405 ( OH)] -2. The boron source composition is initially added to the water system, for example at the beginning of the swimming season, to bring the boron level to at least 20 ppm (by weight). The term "boron level," as used herein, refers to the measurement in terms of elemental boron. The preferred boron level in the treated water ranges from about 20 to about 50 ppm, although larger ranges will be worked. The most preferred range is 20-26 ppm. The boron source material can be any suitable compound or mixture. For example, this material can be selected from the group consisting of boric acid, boric oxide (anhydrous boric acid), and compounds having the formula MnBxOty. ZH20, in which M = any metallic / non-metallic or alkaline earth cation qμe includes but is not limited to sodium, potassium, calcium, magnesium and ammonium, n = 1 to 3, x »any integer from 2 to 10, and - 3x / 2 + 1 yz-0 to 14. The boron compound includes, for example, disodium tetraborate decahydrate, disodium tetraborate pentahydrate, disodium tetraborate tetrahydrate, disodium octaborate tetrahydrate, sodium pentaborate pentahydrate, sodium metaborate tetrahydrate, metaborate of sodium bihydrate, dipotassium tetraborate tetrahydrate, potassium pentaborate tetrahydrate, diammonium tetraborate tetrahydrate, and ammonium pentaborate tetrahydrate. It is generally desirable to maintain a neutral pH in the water systems treated in the present invention. For example, swimming pools are preferably maintained in the range of pH 7-8. At this pH, boron will appear as poly- and polyhydrate tetraborate. The addition of certain boron species, such as tetraborate, will increase the pH of a neutral pH system. For example, the addition of sufficient sodium tetraborate to add 20 ppm of boron to water, approximately .454 Kilograms (1 pound) per 3785 liters (1000 gallons) of water, will typically increase a neutral pH to about 9.0-9.5. If a boron source material is used that increases the pH, then it is required to add a compatible acid, for example sodium bisulfate or muriatic acid, to adjust the pH back to the desired range. In the alternative, a neutral pH composition including the boron source material can be used. In particular, boric acid can be used in combination with any other source of boron, such as the borates that increase the pH previously described. A preferred composition is a combination of boric acid and a tetraborate, particularly, sodium tetraborate. In this embodiment, the composition preferably comprises 50-100 parts of boric acid and 0-50 parts of tetraborate, most preferably 90 parts of boric acid and 10 parts of tetraborate, parts that are by weight. Sodium tetraborate (5 mol) is the preferred compound in this respect.

The second component is a material in the solid form, hereinafter referred to as the "disinfectant / algicidal, compressed component" which includes both a halogen source composition and a boron source composition. These materials are mixed and formed into a tablet, disk, bar or other solid form which is conveniently weathered in the water system in a conventional manner, such as by the use of a swimming basket or float. This compressed disinfectant / algicide component continuously adds both halogen and boron in the water, which helps in maintaining the level of both components at the desired intervals. The halogen source component can be selected from any compatible halogen material useful in the solid form. The halogen is selected from either chlorine or bromine, and can comprise any material in the solid form that provides the halogen in the form of hypohalite ions, ie, hypochlorite or hypobromite ions or as hypohalose acid. For example, the halogen source component may include various chlorine compounds, including calcium hypochlorite, lithium hypochlorite, sodium dichloro-s-triazinetrione, potassium dichloro-s-triazinetrione, and trichloro-s-triazinetrione. Suitable bromine compounds include brominated hydantoins and brominated glycoluril. The boron source composition is included to provide improved characteristics for the tablet and to assist in maintaining the level of boron in the water at a desired level. The boron material has been found to improve the tablet component in several aspects. Tablets formulated with the boron source material have a reduced gas discharge of the chlorine gas. Consequently, the product has less deterioration in packaging and reduced levels of harmful chlorine odor. Also, the boron material is preferably present in an amount to provide a significant supplement to boron in water. The boron material can be selected from any of the boron source compositions previously identified. That is, the boron source material is selected from the group consisting of boric acid, boric oxide and compounds having the formula MnBxOy.ZH20, in which M, n, x, and e z are as previously defined. The respective ranges of the halogen and boron source materials in the second component can vary in this manner considerably. Suitable ranges can be readily determined by those skilled in the art based on the water systems that have been treated, desired erosion rates and / or other physical characteristics of the solid component, and other parameters. In one aspect, the halogen is preferably present in an amount sufficient to maintain the desired level of active halogen in the water, for example 0.5 to 3.0 ppm in hypohalite ion in the swimming pool water. Also, it has been determined that some certain boron materials will adversely affect the ability to compose the entire composition in a solid form having the desirable erosion characteristics. Therefore, there may be a practical limitation in the amount of the boron material that is compounded in the disinfectant / algaecide, compressed component. In view of these considerations, the compressed disinfectant / algicide component preferably comprises from 50.0 to 99.9 parts, more preferably from 80.0 to 95.0 parts, of the halogen source material, and from 0.1 to 50.0 parts, most preferably from 5.0 to 20.0 parts of the boron source material. As used herein, "parts" refers to parts by weight. It has also been discovered that the addition of glycoluril will provide advantages in both the composition of the halogen and boron materials in the solid form having a consistent erosion rate, controlled and in the improvement of the release and availability of halogen in water. This is particularly advantageous since the presence of a boron source material in the tablet will otherwise result in a substantially increased erosion rate. The combination of the boron and halogen source materials will otherwise provide a solid material that wears out too quickly for use in conventional systems. The term glycoluril, unless otherwise indicated, is used in general to refer to compounds that include unsubstituted glycoluril, alkyl substituted glycoluril, phenyl substituted glycoluril, glycoluril substituted with chlorine and glycoluril substituted with bromine. The compressed disinfectant / algicide component obtains desirable erosion characteristics with a surprisingly low amount of glycoluril. The tablet component can be suitably formulated with no more than 5.0 parts of glycoluril. More preferably, the tablet component includes 1 to 3 parts of glycoluril.

/ -. For example, a composition particularly The preferred component of the tablet component consists of 92.5 parts of TCCA, 5 parts of sodium tetraborate, and 2.5 parts of glycoluril. The present invention also contemplates the use of an oxidizing clarifier that provides a greatly improved removal of organic impurities. The clarifying component comprises a unique composition that includes a chlorine source material, an oxygen donor, not a halogen source, and a boron source compound. This combination is useful in itself as a clarifier, apart from the system of the present invention. In addition, when used in the complete system herein, the clarifier provides a supplement for the halogen and boron levels already in the water. When used in the complete system, the oxidation and clarification properties by the clarifying component improve the control of the microorganisms by the compressed disinfectant / algicide component. This third composition also contributes to a surprisingly safe combination of these materials for use. For the clarifying component, the chlorine source material is a hypochlorite donor selected from lithium hypochlorite, sodium or potassium dichloro-s-triazinetrione and trichloro-s-triazinetrione. When used in the previous complete system, however, the clarifying component will not include trichloro-s-triazinetrione. The oxygen, non-halogen donor is selected from peroxydisulfates and salts of persulphuric acid. The peroxydisulfates can include those having the formula NwS208, where N is an alkali metal or an alkaline earth metal or ammonium, and is 1 or 2. The alkali metal can include sodium, potassium or lithium. The alkaline earth metal may include calcium or magnesium. Salts of persulphuric acid include compounds such as KHS04, K2S04 and 2KHS05. An example of a commercial product of salts of persulphuric acid is sold by DuPont under the name 0X0NEMR, which consists essentially of a combination of the compounds KHS04. K2S04 and 2KHS05, The boron source compound is selected from the previously defined group.

Particularly preferred compounds are sodium tetraborate and its derivatives. For the clarifying component, the constituent materials may be present over a wide range. The selection of appropriate ranges can be achieved by those skilled in the art based on the teachings herein and in consideration of the general principles known for water treatment. The hypochlorite donor component is preferably present in an amount of 1 to 99 parts, most preferably 30 to 60 parts by weight. The oxygen donor, non-halogen component in the composition is preferably present in an amount of 1 to 99 parts, more preferably 5 to 50 parts by weight. The boron-containing component is present in an amount of from 1 to 75 parts, most preferably from 5 to 50 parts by weight. In a preferred embodiment, the clarifier consists essentially of the three components, in which case the above amounts constitute percentages by weight in the total composition. The clarifying component may additionally include additives comprising algaecides, clarifying agents such as aluminum sulfate, dispersants, flocculants and other chemicals typically used for the treatment of water systems. By way of example, a preferred clarifier composition includes 60% sodium dichloro-s-triazinetrione, 20% sodium persulfate, 10% sodium tetraborate and 10% aluminum sulfate (an additional clarifying agent). The clarifying component of the present invention can be produced in any suitable dry form. For example, the clarifier could be in the form of granules, pellets, bars or tablets. The product is preferably composed in a form to provide relatively fast dispersion, for example in the space of a few hours. This product is added on a periodic basis, for example anally, to provide the desired additions of the substituent materials, i.e., hypochlorite, oxidant and boron. For example, for the application to swimming pool water, and the material is typically added at the rate of approximately .454 Kg / 37800 liters (1 pound / 10,000 gallons) of pool water. This clarifier product is designed to oxidize organic and inorganic contaminants and to replace boron that is lost through the loss of pool water. In addition to improving the removal of microorganisms by the compressed, disinfectant / algicidal component, the new compositions of the present invention are safe to transport and use. That is, the combination of three components produces a safe composition than for certain individual compounds, such as the chlorine source material. For example, sodium dichloro-s-triazinetrione is classified as an oxidant by DOT regulations. This classification indicates certain levels of safety risks and transport constraints. In contrast, clarifier products formulated based on this disclosed invention have been found to be non-oxidizing by DOT tests, which have low safety risks and transport limitations. The following examples are expressed to more fully illustrate the invention: EXAMPLE 1 The level of boron in the treated water is increased by several compounds containing boron. The addition of each of the following compounds in appropriate amounts provides a boron level in excess of 20 ppm in the water: boric acid, boric oxide, disodium tetraborate decahydrate, disodium tetraborate pentahydrate, disodium tetraborate tetrahydrate, disodium octaborate tetrahydrate, disodium pentaborate, pentrahydrate, sodium metaborate tetrahydrate, disodium metaborate tetrahydrate, disodium metaborate dihydrate, dipotassium tetraborate tetrahydrate, potassium pentaborate tetrahydrate, diammonium tetraborate tetrahydrate, and ammonium pentaborate tetrahydrate. Similarly, the addition of appropriate amounts of the above compounds provides typically desirable amounts of boron levels in the water, for example, 20, 26, 30 and 50 ppm. As indicated previously, a preferred composition is a combination of boric acid, a boron compound which increases the pH, such as tetraborate. The combination of these two components in amounts of 50, 90 and 100 parts of boric acid, and 50, 10 and 0 parts of sodium tetraborate, respectively, provides compositions that adequately add boron to water and allow the control of water pH .

EXAMPLE 2 The compressed algicide / disinfectant is prepared from various combinations of halogen and boron source compounds. The halogen compounds include calcium hypochlorite, lithium hypochlorite, sodium dichloro-s-triazinetrione, potassium dichloro-s-triazinetrione, trichloro-s-triazinetrione, brominated hydantoins and brominated glycoluril. The forum source components include those identified in Example 2. The above compounds are formulated into compressed tablets and the like in conventional manner. The tablets are prepared with various amounts of the components, for example, 50 and 99.9 parts of halogen compound and 0.1 and 50 parts of boron composition, respectively, and in the erosion of the tablets, etc., in the water provide increased levels of halogen and boron in water. In addition, the tablets are compounded with up to 5 parts of glycoluril of the various types previously indicated, and are included at 2 and 3 parts glycoluril levels. These solid forms of the disinfectant / algicidal compositions are easily compounded, wear out at suitable rates, and provide desirable amounts of halogen and boron to water.

EXAMPLE 3 The clarifying compositions are formulated by conventional blending techniques from the previously identified components. Included are the hypochlorite donors selected from lithium hypochlorite, sodium and potassium dichloro-s-triazinetrione, and trichloro-s-triazinetrione. Non-halogen oxidants including peroxydisulfates and salts of persulphuric acid previously identified are also provided. Finally, the boron compounds are included from the previous list. Mixtures of these components in amounts of 1, 30, 60 and 99 parts of the hypochlorite donor, 1, 5, 50 and 99 parts of the non-chlorine oxidant and 1, 5, 50 and 75 parts of the boron-containing compound provide a Oxidizing composition that provides improved clarity to the treated water.

EXAMPLE 4 The Department of Transportation (DOT) (of the United States of America) handles and regulates the transport of hazardous materials. The DOT examines the classification, description, manufacture, labeling, packaging and conditions of hazardous materials transported in the United States of America. The DOT regulations for the transport of hazardous materials are currently set at 49 C.F.R. parts 171-180. The Guides for classification, packing group assignment, and test methods for oxidants (materials of division 1.5) are exposed in the Appendix F to part 173, and provide a test method for measuring the potential for a solid substance to increase the ignition speed or ignition intensity of a combustible substance when the two are thoroughly mixed. In practice, two tests are carried out in triplicate for each substance that is evaluated, one at a ratio of 1 to 1, in mass, from the sample to the sawdust, and one at a ratio of 4 to 1. For the materials classified in the Division 5.1, the ignition characteristics of each mixture are compared to a standard having a ratio of 1 to 1 by mass, of potassium perchlorate and potassium bromate, as appropriate, to sawdust. For materials classified in division 4.1, the packing group is determined using the same method; with the ammonium persulfate substituted by the potassium compound. Potassium perchlorate, potassium bromate and ammonium persulfate are therefore reference substances. For use in the test, these substances must pass through a sieve mesh size less than 0.3 mm and should not be sediment. The reference substances are dried at 65 degrees C for 12 hours and kept in a desiccator until required. The combustible material for this test is soft wood sawdust. It must be passed through a sieve mesh sampler smaller than 1.6 mm and must contain less than 5% water by weight. A mixture of 30.0 ± 0.1 g of the reference substance and sawdust is prepared in a ratio of 1 to 1 by mass. For comparison, two mixtures of 30.0 ± 0.1 g of the material to be tested are prepared in ratios of 1 to 1 by mass, and 4 to 1 by mass, in the particle size in which the material is going to transport, and sawdust. Each mixture is completely mechanically mixed as much as possible without excessive strain. The test is carried out in a ventilated area under the following environmental conditions. Temperature - 20 ° C ± 5 ° C; humidity - 60 percent ± 10 percent. Each of the mixtures is formed in a comic pile with dimensions of approximately 70 mm in diameter of the base and 60 mm in height on a surface of low thermal conduction, impermeable, cold. The stack is ignited by means of an inert metal wire in the form of a circular circuit 40 mm in diameter placed inside the stack 1 mm above the test surface. The wire is electrically heated to 100 degrees C until the first combustion signal is observed, or until it is clear that the pile can not ignite. The electrical energy used to heat the wire is turned off as soon as there is combustion. Time is recorded from the first observable combustion signal at the end of the entire reaction: smoke, flame, incandescence. The test is repeated three times for each of the two mixing ratios. A substance is classified in the Division . 1 if, at any proven concentration, the average sawdust ignition time, established from three tests, is equal to or less than that of the average of the three tests with the ammonium persulfate mixture. Packing group I is assigned to any substance that, in any approved mixing ratio, exhibits a less ignition time than potassium bromate. Packing group II is assigned to any substance that, in any mixture ratio tested, exhibits an ignition time equal to or less than that of potassium perchlorate and the criteria for packing group I are not met. Packing group III is assigned to any substance which, at any mixing ratio tested, exhibits an ignition time equal to or less than that of the ammonium persulfate and the criteria for packing groups I and II are not satisfied. The samples identified in Table 1 are subjected to the oxidant test according to the above test procedures. When the samples were subjected to the oxidant test, it was anticipated that the compositions would remain at least in the oxidizing category of division 5.1, since it is the classification for sodium dichloro-s-triazinetrione. However, surprisingly, the tests indicated that all three samples were classified as non-oxidizing standards by DOT. These results are contrary to what would be expected, particularly in view of the fact that the manufacturers of chlorine oxidants and oxygen-based oxidants frequently recommend that these materials do not mix together due to their incompatibilities.

TABLE 1 Sample No. 150A 147A 150B Dichloro-s-triazinetrione 60% 60% 60% sodium Sodium persulfate 2 0% 3 0% Sodium tetraborate 5 mol 1 0% 1 0% 1 0% Aluminum sulfate 1 0% 1 0% OXONE _ _ _ 2 0% EXAMPLE 5 The three compositions of Example 1 were subjected to the additional hazard test to determine some incompatibilities. The tests performed were DTA, severity of the Explosion in Dust, sensitivity to impact and self-heating test. The results of the test are summarized below, in which DPS refers to sodium persulfate, "dichlor" refers to sodium dichloro-s-triazinetrione, ACL-60 refers to sodium dichloro-s-triazinetrione, borate refers to sodium tetraborate, alum refers to aluminum sulfate, glycoluril refers to unsubstituted glycoluril and all percentages are by weight.

THERMAL STABILITY JANAF 100% sodium dichloride - light exotherm at 140 degrees C; powerful exotherm, sharp at 147 degrees C; catastrophic decomposition (disk rupture), too fast to determine tem / pres .; It will be classified as flammable for transport.

SENSITIVITY TO IMPACT 49. 5% sodium dichlor, 49.5% sodium monopersulfate and 1% glycoluril - 50% probability of initiation at 46.9 centimeters (18.5 inches). 41% sodium dichlor 50% chance of initiation to 46.9 centimeters (18.5 inches).

SEVERITY OF POWDER EXPLOSION 60% ACL-60, 20% OXONE, 10% borate and 10% alum - no test produced a positive result. 60% of ACL-60, 30% of DPS and 10% of borate, no test produced a positive result. 60% of ACL-60, 20% of DPS, 10% of borate and 10% of alum - no test produced a positive result.

SENSITIVITY TO IMPACT 60% of ACL-60, 30% of DPS, and 10% of borate - each material was subjected to a maximum fall height of 99 centimeters (36 inches) with the weight of 2 kg for ten tests per material, using a sample fresh every time No positive results were observed in any trial. 60% of ACL-60, 20% of DPS and 10% of borate - each material was subjected to a maximum height of 99 centimeters (36 inches) with the weight of 2 kg for ten tests per material, using a fresh sample each time . No positive results were observed in any trial. 60% of ACL-60, 20% of OXONE, 10% of borate and 10% of alum - each material was subjected to a maximum height of 99 centimeters (36 inches) with the weight of 2 kg for ten tests per material, using A fresh sample every time. No positive result was obtained in any trial.

THERMAL STABILITY JANAF (DTA) 60% of ACL-60, 20% of DPS, 10% of borate and 10% of alum - in the initial test with this material, an exothermic behavior was observed at approximately 111 degrees C. The temperature of the sample increased during approximately 90 seconds to about 130 degrees C, was maintained for about 30 seconds, and then increased to about 140 degrees C for about 30 seconds, where a catastrophic, acute reaction caused the disk rupture to 210.93 Kg / cm2 (3000 psig). A replication test produced essentially identical results. 60% of ACL-60, 20% of OXONE, 10% of borate and 10% of alum - in the initial test with this material, an exothermic behavior was observed at approximately 111 degrees C. The temperature of the sample increased during approximately 60 seconds to approximately 124 degrees C, stops for approximately 60 seconds, and then increases to approximately 140 degrees C for approximately 30 seconds, where a catastrophic, acute reaction causes identical results, except that the transition points were less sha defined.

THERMAL STABILITY JANAF 60% of ACL-60, 20% of DPS, 10% of borate and 10% of alum - in the initial test with this material, an exothermic behavior was observed at approximately 133 degrees C. Approximately 60 seconds later, at approximately 152 C degrees, a catastrophic, acute reaction caused the rupture of a disk of 210.93 Kg / cm2 (3000 psig). A replica test produced identical results.

OXIDANT TEST 60% of ACL-60, 30% of DPS, 10% of borate and 10% of alum - based on the test results, it is recommended that the material represented by this sample does not need to be classified as an oxidant, as defined by CFR 49, section 173, Appendix F. It is noted that while the average ignition time of the ratio of 1 to 4 was shorter than the reference, the material was not completely consumed. 60% of ACL-60, 20 DPS, 10% of borate and 10% of alum - based on the results of the test, it is recommended that the material represented by this sample does not need to be classified as an oxidant, as it is defined by CFR 49, section 173, Appendix F. It is noted that the average ignition time of the mixture ratio of 1 to 1 was ignited considerably later than the reference. Also, while the average ignition time of the reaction mixture of 4 to 1 was shorter than the reference, the material was not completely consumed. 60% of ACL-60, 20% of OXONE, 10% of borate and 10% of alum - based on the results of the test, it is recommended that the material represented by this sample does not need to be classified as an oxidant, as defined by CFR 49, section 173, Appendix F. It is noted that the average ignition time of the reaction mixture of 1 to 1 was ignited considerably later than the reference, too, while the average ignition time of the mixture of reaction from 4 to 1 was shorter than the reference, the material was not completely consumed.

PROOF OF PRELIMINARY SCREEN DIFFERENT CLASS 4.1 60% ACL-60, 20% OXONE, 10% borate and 10% alum - the sample formed on an unbroken strip of approximately 250 mm long and 20 mm wide by 10 mm high on a plate waterproof base (steel), cold. Ignition of the sample was attempted at one end by a gas burner. The sample did not sustain the ignition after two minutes of exposure to the flame. Based on this result, the ignition speed test different from 4.1 is not required.

PROOF OF PRELIMINARY SIZE DIFFERENT CLASS 4.2 60% of ACL-60, 20% of OXONE, 10% of borate and 10% of alum - 1155.4 grams of the sample were placed in a basket of 10-mesh wire mesh were covered with a basket of larger wire mesh . The sample was maintained at 140 degrees C for 24 hours. Starting at room temperature, the temperature of the sample rose slowly and equaled the oven temperature approximately nine hours after the start. The temperature continued to rise, reaching a maximum temperature of 149 degrees C approximately 12 hours after the start. The temperature then started to fall, falling to 146 degrees C, while it remained for the rest of the 24 hours of the test period. After the test it was allowed to cool, then it was reweighed and examined. The sample experienced a weight loss of 89.6 grams and exhibited no visible change. Results / Discussion: The impact sensitivity test for the three compositions was negative, indicating that the composition does not explode on impact. The key indicator for compatibility is the results of the DTA test. Compositions that did not contain alum exhibited exotherms at 137 degrees C, which is approximately the same for 100% ACL-60 (140 degrees C). The composition containing alum exhibited exotherms around 111 degrees C. Although these exotherms for alum-containing compositions occurred at a lower temperature, these compositions are still considered as safe as calcium hypochlorite having exotherms at 111 degrees C. The results Totals of the combined hazard test indicate that these mixtures will be stable and safe for transport, storage and use.

EXAMPLE 6 Various compositions were tested for storage stability at elevated temperatures. Samples of two hundred grams of the composition were prepared and sealed in one-quarter plastic bottles. The bottles were equipped with two stopcocks that allowed the removal of the collected gases. The bottles were then placed in an oven at 50 degrees C for 72 hours. Within 72 hours, the bottles were removed from the oven and the collected gas was removed from the space between the liquid and the lid by blowing dry air into the bottle that forced the collected air to a gas collection cylinder that contained a potassium iodide / water / ethanol solution. The Kl solution was titrated with sodium thiosulfate and the mg of the chlorine gas was calculated. The results are summarized in Table 2.

Table 2 PROOF SUBSTANCE / RESULTS BOTTLE NO. DICLORO-S- OXONE BORAX Mg.Cl2 SODIUM TRIAZINATRIONA A 60% 30% 10 0.71 B 60% 40% 1.20 C 100% _ _ _ - - _ 1.10 The test results indicate that the compositions are stable and do not produce excessive chlorine gas during storage at elevated temperatures.

EXAMPLE 7 In this example, the oxidation performance of several oxidizing compounds was evaluated. The oxidation performance was determined by measuring the destruction of the crystal violet dye. The following protocol was followed. This protocol was designed to evaluate several oxidizing compounds and combinations of oxidizing compounds as blow products, potentials used in swimming pools and springs. REAGENTS: Crystal Violet Dye Solution. APPARATUS: pH meter: (equipped with palatal electrodes) HACH 3000, Spectrophotometer. PROCEDURE: 1) Prepare the following test solutions: COMPOUND OF COLUMN TO ppm ACTIVE TEST gm / L QUANTITY OF DILUTIONS USE DILUTION Lithium Hypochlorite 2.86 8 ml / 1 8 ppm Cl2 OXONE 1.00 11 ml / 1 0.5 ppm of 02 DPS 1.00 11 ml / 1 0.5 ppm 02 H202 3.70 30 ml / 1 30 ppm 2) In 1000 ml laboratory beakers, 1000 ml of distilled water, 1.64 g of phosphate buffer (pH 7.2-7.6) and 15 drops of the crystal violet dye solution are added. It mixes up evenly. 3) Measure the initial color number in the HACH 3000 spectrophotometer. Follow method No. 16 of HACH. Use distilled water as a white. 4) Add an amount of oxidant dilution from column A to the laboratory glass of 1500 ml. Let mix 5 minutes. 5) Allow the laboratory vessels to stir for 2 hours. Inspect the color number. Calculate the color reduction in percent. The results are summarized in Table 3.

Table 3 COMPOSITE OF Relation Color Color% of TEST Cl 2/02 (ppm) Start No. of 2 Reduction No. Hours of Color LiOCl / OXONE 8.0 / 0.5 244 37 85% LiOCl / DPS 8.0 / 0.5 292 26 91% Li0Cl / H202 8.0 / 30.0 296 268 9. 5 % LiOCl 8.0 / 0 288 120 58% DPS 0 / 0.5 252 252 0% OXONE 0 / 0.5 257 162 37% DP S Sodium persulphate L Í0C 1 Lithium hypochlorite 0X0NEMR Potassium monopersulfate The results of this experiment indicate that the oxidation performance is greatly improved when combining the chlorine oxidant and the oxygen oxidizer. Actually, the DPS used alone does not show color reduction but in combination with the chlorine achieved a color reduction of 85%. The OXONE only reduced the color by only 37%. Chlorine only showed a color reduction of 58%. H202, another popular oxidant, was actually antagonistic to chlorine. This experiment indicates that the DPS or OXONE in combination with the chlorine is not antagonistic, but in fact it seems to improve the oxidation activity.

EXAMPLE 8 During the summer of 1993, a field trial of consumers comprising 48 swimming pools was carried out. As a control group, 27 pools were operated by the consumer only in a traditional chlorine type program using only one disinfectant tablet in a gilder or float for 18 weeks. The disinfectant tablets contained 92.5% trichloro-s-triazinetrione, 5% sodium tetraborate (5 mol) and 2.5% unsubstituted glycoluril that added a very low level of boron, typically less than 0.1 ppm boron for each .454 kg (1 pound) of tablets added to 37,800 liters (10,000 gallons) of pool water. Consumers provided their own stirring treatment and agitated the water at their discretion. The pools were inspected for algae growth during the test period. During the 18 weeks, 81.5% of the pools experienced algae growth. The results are summarized in Table 4.

XX denotes algal growth At the beginning of week 19, pools 1-13 were given a lithium hypochlorite treatment on a weekly basis at a rate of .454 kilograms (1 pound) for up to 113,400 liters (30,000 gallons) ) of water from the swimming pool. Also at the beginning of week 19, pools 14-27 were given the clarifier product which contained 60% sodium dichloro-s-triazinetrione, 20% potassium monopersulfate, 10% sodium tetraborate (5 mol) and 10% aluminum sulfate on a weekly basis at a rate of 0.454 kilograms (1 pound) per up to 113,400 liters (30,000 gallons) of swimming pool water. The test was carried out until the week No. 36. The number of incidences of algae reported was reduced, but still constituted 52% of the pools. The results are summarized in Table 5.

XX denotes algae growth By comparison, 16 pools were initially operated on a commercially available boron system with boron levels maintained at less than 20 ppm. The same chlorine disinfectant tablet used in previous pools was also used to treat these pools. The chlorine tablets were added to the pool by means of a gild or a float. Consumers added their own agitation treatment at their discretion. During the 18-week trial period, 62% of these pools experienced algae growth. The test results are summarized in Table 6.

XX denotes algal growth At the beginning of weeks 17-19, these 16 pools were converted to the method of the present invention. Boron levels increased to 26-30 ppm. The disinfectant tablets that were contained 92.5% trichloro-s-triazinetrione, 5% sodium tetraborate, 5 mol and 2.5% substituted glycoluril were used to provide both chlorine and boron in a continuous base. The pools were treated with the clarifier component mixed on a weekly basis at a rate of 0.454 kilograms (1 pound) per up to 113.400 liters (30,000 gallons) of pool water. During the 19 weeks, only three pools (19.0%) reported algae growth. One pool reported algal growth during week 23 due to mechanical problems that resulted in an interruption of the chlorine feed system and subsequent chlorine readings of 0 ppm. The test results are summarized in Table 7.

XX denotes algal growth The results of the field test of week 36 clearly indicate that the method of the present invention reduces the growth of algae.

EXAMPLE 9 The treatment of various recirculation systems is repeated according to the present invention and the process of Example 8 using various products referred to in Examples 1-3 and suitable results are achieved along the lines of Example 8.

EXAMPLE 10 The loss of the boron component in a water system was demonstrated in a swimming pool of 83,160 liters (22,000 gallons) located in North Atlanta, Georgia. Sodium tetraborate was added to the pool to achieve a concentration of 26 ppm of boron in the pool. The pool continued to operate a chlorine disinfectant with agitation treatment every week. Seven months later, the pool water was checked again. The level of boron had dropped to 20 ppm, indicating that the boron became exhausted over time and should be continuously supplied.

It is noted that in relation to this date, the best method known by the applicant to carry out the present invention is that which is clear from the present description of the invention. Having described the invention as above, the content of the following is claimed as property:

Claims (50)

1. A method for controlling microbial growth in water in recirculating water systems, characterized in that it comprises the steps of: a. provide a boron level in the water of at least about 20 ppm. b. abrading in the water a tablet component comprising a combination of a halogen source material and a boron source material; and c. adding periodically to the water a clarifying composition comprising a combination of chlorine source material, non-halogen oxygen donated material and a boron source material.

2. The method according to claim 1, characterized in that step a. it comprises adding to the water an amount of boron source material sufficient to provide a boron level in the water of about 20 to about 50 ppm.

3. The method according to claim 2, characterized in that the boron source material is selected from the group consisting of boric acid, boric oxide and compounds having the formula MnBxOy. ZH20, where M * sodium, potassium, calcium, magnesium or ammonium, n * 1 to 3, x «any integer from 2 to 10, y = 3x / 2 + 1, and z = 0 to 14.

4. The method according to claim 3, characterized in that the boron source material is a neutral pH material.

5. The method according to claim 4, characterized in that the boron source material comprises a combination of boric acid and a second boron source material selected from the group consisting of compounds having the formula MnBxOy.ZH20, wherein M »sodium, potassium, calcium, magnesium or ammonium, n = 1 to 3, x = any whole number from 2 to 10, and« 3x / 2 + 1, yz - 0 to 14.

6. The method according to claim 1, characterized in that the tablet component comprises a halogen source material selected from the group consisting of calcium hypochlorite, lithium hypochlorite, sodium dichloro-s-triazinetrione, dichloro-s-triazinetrione potassium, trichloro-s-triazinatrion.a, brominated hydantoins and brominated glycoluril, and a boron source material selected from the group consisting of boric acid, boric oxide, and compounds having the formula MnBxOy.ZH20. where M = sodium, potassium, calcium, magnesium or ammonium, n - 1 to 3, x = »any integer from 2 to 10, and» 3x / 2 + 1, and z = 0 to 14.

7. The method according to claim 6, characterized in that the tablet component comprises from 50.0 to 99.9 parts of halogen source material and from 0.1 to 50.0 parts of boron source material.

8. The method of compliance of claim 7, characterized in that the tablet component comprises from 80.0 to 95.0 parts of halogen source material and from 5.0 to 20.0 parts of boron source material.

9. The method according to claim 6, characterized in that the tablet component further comprises glycoluril.

10. The method according to claim 9, characterized in that the glycoluril is selected from the group consisting of unsubstituted glycoluril, glycoluril substituted with alkyl, glycoluril substituted with phenyl, glycoluril substituted with chlorine and glycoluril substituted with bromine.

11. The method according to claim 10, characterized in that the tablet component comprises from 0.1 to 5.0 parts of glycoluril.

12. The method according to claim 11, characterized in that the tablet component comprises from 50.0 to 99.9 parts of halogen source material and from 0.1 to 50.0 parts of boron source material.

13. The method according to claim 11, characterized in that the tablet component comprises 1.0 to 3.0 parts of glycoluril.

14. The method according to claim 13, characterized in that the tablet component comprises from 80.0 to 95.0 parts of halogen source material and 5.0 to 20.0 parts of boron source material.

15. The method according to claim 1, characterized in that the clarifying composition comprises chlorine source material selected from the group consisting of lithium hypochlorite and sodium or potassium dichloro-s-triazinetrione, non-halogen oxygen donor material selected from starting from the group consisting of peroxydisulfates and salts of persulphuric acid, and boron source material selected from the group consisting of boric acid, boric oxide and compounds having the formula MnBxOy.ZH20, wherein M = sodium, potassium, calcium, magnesium or ammonium, n = 1 to 3, x = any whole number from 2 to 10, y = 3x / 2 + 1, and z = 0 to 1.

16. The method according to claim 15, characterized in that the clarifying composition of step c. it comprises from 1 to 99 parts of chlorine source material, from 1 to 99 parts of non-halogen oxygen donor material, and from 1 to 75 parts of boron source material.

17. The method according to claim 16, characterized in that the clarifying composition comprises from 30 to 60 parts of chlorine source material, from 5 to 50 parts of non-halogen oxygen donor material, and from 5 to 50 parts of halogen source material. boron source.

18. The method according to claim 17, characterized in that the clarifying composition consists essentially of chlorine source material, non-halogen oxygen donor material, and boron source material.

19. A tablet composition used to control microbial growth in recirculating water systems, characterized in that it comprises a solid mixture of a halogen source material, a boron source material, and glycoluril.

20. The composition according to claim 19, characterized in that the halogen source material is selected from the group consisting of calcium hypochlorite, lithium hypochlorite, sodium dichloro-s-triazinetrione, potassium dichloro-s-triazinetrione, trichloro-s-triazinatrione, brominated hydantoins and brominated glycoluril.

21. The composition according to claim 19, characterized in that the boron source material is selected from the group consisting of boric acid, boric oxide, and compounds having the formula MnBxOy.ZH20, wherein M = sodium, potassium, calcium, magnesium or ammonium, n * 1 to 3, x * any integer from 2 to 10, and • 3x / 2 + 1, and z = 0 to l4.

22. The composition according to claim 19, characterized in that the glycoluril is selected from the group consisting of unsubstituted glycoluril, glycoluril substituted with alkyl, glycoluril substituted with phenyl, glycoluril substituted with chlorine and glycoluril substituted with bromine.

23. The composition according to claim 22, characterized in that the glycoluril is selected from the group consisting of unsubstituted glycoluril, glycoluril substituted with alkyl, glycoluril substituted with phenyl.

24. The composition according to claim 19, characterized in that it includes from 50.0 to 99.9 parts of halogen source material and from 0.1 to 50.0 parts of boron source material.

25. The composition according to claim 24, characterized in that it includes from 80.0 to 95.0 parts of halogen source material and from 5.0 to 20.0 parts of boron source material.

26. The composition according to claim 19, characterized in that it includes from 0.1 to 5.0 parts of glycoluril.

27. The composition according to claim 26, characterized in that it includes from 50.0 to 99.9 parts of halogen source material and from 0.1 to 50.0 parts of boron source material.

28. The composition according to claim 26, characterized in that it includes from 1.0 to 3.0 parts of glycoluril.

29. The composition according to claim 28, characterized in that it includes from 80.0 to 95.0 parts of halogen source material and from 5.0 to 20.0 parts of boron source material.

30. A method for controlling microbial growth in recirculating water systems, characterized in that it comprises abrading in the water a tablet composition comprising a solid mixture of a halogen source material, a boron source material, and glycoluril.

31. The method according to claim 30, characterized in that the tablet composition is added to the water in an amount sufficient to maintain about 0.5 to about 3.0 ppm of hypohalite ion in the water.

32. The method according to claim 30, characterized in that the tablet composition comprises a halogen source material selected from the group consisting of calcium hypochlorite, lithium hypochlorite, sodium dichloro-s-triazinetrione, dichloro-s- triazinatrione potassium, trichloro-s-triazinatrione, brominated hydantoins and brominated glycoluril, a boron source material selected from the group consisting of boric acid, boric oxide, and compounds having the formula MnBxOy.ZH20, where M = sodium, potassium, calcium, magnesium or ammonium, n = 1 to 3, x * any integer from 2 to 10, and «3x / 2 + 1, yz = 0 to 14, and glycoluril is selected from the group consisting of of unsubstituted glycoluril, glycoluril substituted with alkyl, glycoluril substituted with phenyl, glycoluril substituted with chlorine and glycoluril substituted with bromine.

33. The method according to claim 32, characterized in that the tablet component comprises glycoluril selected from the group consisting of unsubstituted glycoluril, glycoluril substituted with alkyl, and glycoluril substituted with phenyl.

34. The method according to claim 30, characterized in that the tablet composition comprises from 50.0 to 99.9 parts of halogen source material and from 0.1 to 50.0 parts of boron source material.

35. The method according to claim 34, characterized in that the tablet composition comprises from 80.0 to 95.0 parts of halogen source material and from 5.0 to 20.0 parts of boron source material.

36. The method according to claim 30, characterized in that the tablet composition comprises from 0.1 to 5.0 parts of glycoluril.

37. The method according to claim 36, characterized in that the tablet composition comprises 1.0 to 3.0 parts of glycoluril.

38. A clarifying composition for use in the treatment of recirculating water, characterized in that it comprises a combination of a chlorine source material to provide hypochlorite ions to water, a non-halogen oxygen donor material, and a boron source material .

39. The composition according to claim 38, characterized in that the chlorine source material is selected from the group consisting of lithium hypochlorite, sodium or potassium dichloro-s-triazinetrione and trichloro-s-triazinetrione.

40. The composition according to claim 38, characterized in that the non-halogen oxygen source material is selected from the group consisting of peroxydisulfates and salts of the persulphuric acid.

41. The composition according to claim 38, characterized in that the boron source material is selected from the group consisting of boric acid, boric oxide,. and compounds having the formula MnBx0y.ZH20, wherein M - sodium, potassium, calcium, magnesium or ammonium, n = 1 to 3, x = any integer from 2 to 10, y = 3x / 2 + 1, and z = 0 to 14.

42. The composition according to claim 38, characterized in that it comprises from 1 to 99 parts of chlorine source material, from 1 to 99 parts of non-halogen oxygen donor material, and from 1 to 75 parts of boron source material .

43. The composition according to claim 42, characterized in that it comprises from 30 to 60 parts of chlorine source material, from 5 to 50 parts of non-halogen oxygen donor material, and from 5 to 50 parts of boron source material .

44. The composition according to claim 43, characterized in that it consists essentially of chlorine source material, non-halogen oxygen donor material, and boron source material.

45. A method for treating recirculating water, characterized in that it comprises adding to the water a clarifying composition comprising a combination of a chlorine source material to provide hypochlorite ions to the water, non-halogen oxygen donor material, and a source material of boron.

46. The method according to claim 45, characterized in that it comprises adding to the water an amount of the clarifying composition to provide about 1 to about 3 ppm of hypochlorite ion in the water.

47. The method according to claim 45, characterized in that the clarifying composition comprises a chlorine source material selected from the group consisting of lithium hypochlorite, sodium or potassium dichloro-s-triazinetrione and trichloro-s-triazinetrione, a non-halogen oxygen source selected from the group consisting of peroxydisulfates and salts of persulphuric acid, and a boron source material selected from the group consisting of boric acid, boric oxide, and compounds having the formula MnBxOy. ZH20, where M = sodium, potassium, calcium, magnesium or ammonium, n = from 1 to 3, x = * any integer from 2 to 10, and »3x / 2 + 1, yz - 0 to 14.

48. The method according to claim 47, characterized in that the clarifying composition comprises from 1 to 99 parts of chlorine source material, from 1 to 99 parts non-halogen oxygen donor material, and from 1 to 75 parts of source material of boron.

49. The method according to claim 48, characterized in that the clarifying composition comprises from 30 to 60 parts of chlorine source material, from 5 to 50 parts of non-halogen oxygen donor material, and from 5 to 50 parts of halogen source material. boron source.

50. The method according to claim 49, characterized in that the clarifying composition consists essentially of chlorine source material, non-halogen oxygen donor material, and boron source material.