COMPOSITION FOR pH CONTROL

Abstract

A composition for treating swimming pool water comprises sodium bisulphate and aluminium sulphate. The aluminium sulphate in the composition minimizes the precipitation of sodium bisulphate at temperatures lower than about 5 degrees Celsius for a time period to maintain a concentrated form of acid to control the pH level of the water. In some embodiments, the composition includes 30 to 40% sodium bisulphate (NaHSO4) wt/wt %, 0.2% to 5% aluminium sulphate Al2(SO4)3 wt/wt %, 0.1% to 1% copper sulphate/chelating agent wt/wt %, 0.01% to 0.02% sodium hydroxide, and balance water.

Claims

1. A composition for treating swimming pool water, the composition comprising: sodium bisulphate; and aluminium sulphate wherein the aluminium sulphate in the composition minimises the precipitation of sodium bisulphate at temperatures lower than about 5 degrees Celsius for a time period to maintain a concentrated form of acid to control the pH level of the water.

2. A composition according to claim 1 wherein the time period is more than about 8 hours.

3. A composition according to claim 1 wherein the temperature is lower than about 3 degrees Celsius.

4. A composition according to claim 1 wherein the ratio of aluminium sulphate to sodium bisulphate in the composition is between about 1/10 and 1/500 wt/wt %.

5. A composition according to claim 4 wherein the ratio of aluminium sulphate to sodium bisulphate in the composition is between about 1/20 and 1/100 wt/wt %.

6. A composition according to claim 5 wherein the ratio of aluminium sulphate to sodium bisulphate in the composition is between about 1/90 and 1/100 wt/wt %.

7. A composition according to claim 1 wherein the concentration of acid is maintained to control the pH level of the water to between about 7.2 to about 7.6.

8. A composition according to claim 1 further comprising copper sulphate.

9. A composition according to claim 8 wherein the ratio of copper sulphate to sodium bisulphate is between about 1/200 to 1/500 wt/wt %.

10. A composition according to claim 9 further comprising a chelating agent in combination with copper sulphate, wherein the ratio of copper sulphate/chelating agent to sodium bisulphate is between about 1/200 to 1/500 wt/wt %.

11. A composition according to claim 1 further comprising sodium hydroxide as a calcium scale inhibitor, wherein sodium hydroxide is present in the composition in a range of 0.01% to 0.02% by weight.

12. A composition for treating swimming pool water, the composition comprising: 30 to 40% sodium bisulphate (NaHSO.sub.4) wt/wt %; 0.2% to 5% aluminium sulphate Al.sub.2(SO.sub.4).sub.3 wt/wt %; 0.1% to 1% copper sulphate/chelating agent wt/wt %; 0.01% to 0.02% sodium hydroxide and balance water.

13. A composition according to claim 1 for controlling the pH of swimming pool water.

14. A composition according to claim 13 for additionally lowering phosphate levels, improving water clarity or controlling algae in swimming pool water.

15. Use of a composition according to claim 1 for treating water in a swimming pool or spa.

16. Use of a composition according to claim 15 for controlling the pH, lowering phosphate levels, improving water clarity or controlling algae in water in a swimming pool or spa.

Description

DESCRIPTION OF THE INVENTION

[0045] Preferred embodiments of the invention will now be described with reference to the accompanying non-limiting examples.

[0046] A preferred embodiment of the invention is Perox pH Control™ which is a combination of sodium bisulphate, aluminium sulphate, copper sulphate and chelating agent mixed into a solution.

[0047] Sodium bisulphate (NaHSO.sub.4) is a significantly safer option for pool pH control than either sulphuric or hydrochloric (muriatic) acid. Sodium bisulphate is not dangerous to handle, whilst hydrochloric acid in its liquid form requires the use of acid-proof gloves, boots, and facial masks. However, sodium bisulphate is typically available in a solid powder form and this has convenience and handling problems also.

[0048] Sodium bisulphate is safe for the environment and is biodegradable. The US Food & Drug Administration has labelled sodium bisulphate as safe for humans and it is not classified as a hazardous material under DOT/OSHA. It has also been approved for use by the authorities of Mexico, Canada, New Zealand, Australia, and the EU.

[0049] Aluminium sulphate is Al.sub.2(SO.sub.4).sub.3 is soluble in water and is mainly used as a coagulating agent (promoting particle collision by neutralizing charge) and clarifying agent in the purification of drinking water and wastewater treatment plants, and also in paper manufacturing.

[0050] The problem that needed to be overcome when formulating this product was to avoid precipitation of sodium bisulphate at low temperatures (lower than 3 degrees Celsius for more than 8 hours) whilst still maintaining sufficiently concentrated form of acid that would control the pH level in a pool without excessive use.

[0051] While normally used as a coagulating and clarifying agent, the addition of aluminium sulphate to the formula in this case was surprisingly found to enable a higher concentration of sodium bisulphate to be achieved without the formation of precipitation when subjected to low temperatures for an extended period of time.

[0052] The inclusion of copper sulphate and a chelating agent in Perox pH Control™ was surprisingly found to assist with the anti-microbial treatment of the water without the copper precipitating out of solution, and was also found not to interfere with the precipitation of the sodium bisulphate at lower temperatures.

[0053] It was also surprisingly found that a calcium scale inhibitor could be successfully included in the formulation in low concentrations to further increase the advantages of the product. A solution of a low concentration of sodium hydroxide was added to the product and was found to reduce scale formation within the pool structure and also remove existing scale. Further advantages of including the calcium scale inhibitor have been surprisingly found to include prevention of rust discolouration and staining, scum formation and plugging of filters; and prevention of corrosion of metal parts in the pool environment, including filters and recirculating equipment. Further advantageous benefits have been found to include maintaining the integrity of the concrete shells, maintaining the integrity of grout when used between tiles

[0054] Another significant benefit of including a calcium scale inhibitor in the product in low concentrations was modification of the crystal growth of calcium carbonate. Damage to the surface of concrete pools has been known to occur when sulphate levels in the pool water rise above 360 ppm. It is understood that this is because calcium carbonate can form in the microscopic pores of the concrete. Over time, the calcium carbonate crystals increase in size and begin to cause damage to the concrete structure as they expand out and crack the concrete. This action can also cause pool interior surfaces to lift from the concrete shell. It has been surprisingly found that low concentrations of a calcium scale inhibitor can minimise this problem in synergy with the other benefits of the Perox pH Control™ product.

[0055] The general process to formulate the Perox pH Control™ composition is as follows: [0056] 1. Add about 638 grams of water to beaker [0057] 2. Add 450 grams of NaHSO.sub.4 gradually until completely dissolved [0058] 3. Add 60 grams of 8% aluminium solution=4.8 grams of solids [0059] 4. Add 2 grams of combined copper sulphate and chelating agent, preferably monoethanolamine (MEA)/diethanolamine blend at about a 5/95 w/w ratio. [0060] 5. Add about 212 Ml of water to bring to total volume of 1000 Ml

[0061] Calcium scale inhibitor can be added in the form of 5-15% sodium hydroxide solution (Lo˜Chlor Scale and Stain Defense™)(approx. 16 mls of 5-15% solution to 1000 mL of the above composition).

[0062] Final Results:

[0063] Total weight 1310 grams=SG 1.31 g/cm.sup.3

[0064] Actual concentration of NaHSO.sub.4 w/w 34.35%

[0065] pH of the concentrate minus −0.149 at 21° C.

[0066] pH of aluminium sulphate at 8% 2.7 at 20° C.

[0067] Use with Hydroxypure™ Chlorine Free System

[0068] By simplifying technology associated with the advanced treatment of drinking water, Waterco has successfully applied it to the treatment of swimming pool water.

[0069] The end result is a chlorine free swimming pool, fully enriched with oxygen. This is fantastic news for those looking for a healthy alternative to chlorine. With no odours or taste, it's soft and gentle to the skin and no shower is needed after swimming.

[0070] Endorsed by the National Asthma Council of Australia and approved by its Sensitive Choice® program, Hydroxypure™ is an advanced breakthrough in swimming pool and spa sanitisation.

[0071] Hydroxypure™ sanitisation is based on Advanced Oxidation Processes (AOP), which combine Perox, a chlorine free sanitiser (H.sub.2O.sub.2) and hybrid ozone (O.sub.3) to enhance the sanitisation process.

Hydroxypure™=H.sub.2O.sub.2+O.sub.3

[0072] Advances Oxidation Processes (AOPs), in general terms, are a set of chemical treatment procedures designed to remove organic (and sometimes inorganic) materials in water and wastewater by oxidation through reactions with hydroxyl radicals (OH). In Hydroxypure™ applications, Advanced Oxidation Processes refer more specifically to a subset of such chemical processes that employ ozone (O.sub.3) and hydrogen peroxide (H.sub.2O.sub.2) and/or UV light from the sun. The use of ozone and Perox™ in harmony increases active oxygen levels in the water. This synergy ensures the safety of the water environment without creating harmful chemical by-products. The end result is a swimming pool that is free of chlorine treatment and potentially harmful by-products and enriched with oxygen.

[0073] Advanced oxidation processes (AOPs) have been studied for the treatment of different wastewaters. During the AOP treatment of wastewater, hydroxyl radicals (OH.) or sulphate radicals (SO4..sup.−) are generated in sufficient quantity to remove refractory organic matters, traceable organic contaminants, or certain inorganic pollutants, or to increase wastewater biodegradability as a pre-treatment prior to an ensuing biological treatment. Hydroxyl radicals disrupt the composition of those substances-causing them to break down. Hydroxyl radicals oxidize all kinds of organic contaminants in swimming pool water, including sweat, body oils, bacteria, viruses, human waste, and toxins such as pesticides. Further, after hydroxyl radicals oxidize organic and inorganic contaminants in the water, they quickly convert back to oxygen. No noxious by-products are produced or left behind.

[0074] Ozone-Based Advanced Oxidation Processes in the Hydroxypure™ System

[0075] Ozone (O.sub.3) is a strong oxidant itself with an oxidation potential of 2.07 V vs. SCE. However, direct O.sub.3 oxidation is a selective reaction, in which O3 preferentially reacts with the ionized and dissociated form of organic compounds, rather than the neutral form. Under certain conditions, hydroxyl radical OH. is produced from O.sub.3 to initiate indiscriminate oxidation (indirect mechanisms). Different detailed mechanisms have been proposed to explain the complex OH. generation, and the overall reaction involving OH. generation is expressed as below.

3O.sub.3+H.sub.2O.fwdarw.2OH.+4O.sub.2

[0076] In the presence of other oxidants or irradiation, the OH⋅ radical yield can be significantly improved. For example, in the peroxone (O.sub.3/H.sub.2O.sub.2) system, the O.sub.3 decomposition and OH. radical production can be enhanced by hydroperoxide (HO.sub.2.sup.−) produced from H.sub.2O.sub.2 decomposition.

H.sub.2O.sub.2.fwdarw.HO.sub.2.sup.−+H.sup.+

HO.sub.2.sup.−+O.sub.3.fwdarw.OH.+O.sub.2.sup.−+O.sub.2

[0077] In the O.sub.3/ultraviolet (UV) irradiation, H.sub.2O.sub.2 is generated as an additional oxidant primarily through O.sub.3 photolysis.

O.sub.3+H.sub.2O+hv.fwdarw.H.sub.2O.sub.2+O.sub.2

[0078] Advanced oxidation processes (AOPs) can be used to provide swim-ready water without the harsh and dangerous effects of typical chlorine sanitizing treatments. AOPs can be used to safely neutralizes a wide range of contaminants in swimming pool water, including some dangerous pathogens that traditional chlorine treatments cannot tackle.

[0079] Advanced Oxidation Processes can be used to tackle several bugs that can be chlorine resistant including Giardia, and Cryptosporidium parvum (aka “Crypto”). AOP technology destroys the cell walls of the “Crypto” bug to remove it. Sometimes even used in tandem with a small amount of chlorine, AOPs work by oxidizing both organic and inorganic contaminants in the swimming pool environments,

[0080] The efficacy of Advanced Oxidation Processes comes without producing toxic by-products, such as chloramines, that can cause serious irritation for pool users. Chlorinated pools are well known to cause itchy eyes, dry skin, bleach-like odours, sore throats, and faded swimsuits. Some users may even experience nausea or vomiting. Unlike chlorine pool treatments, AOPs destroys chloramines, removing some of the unwanted effects they can cause.

[0081] Within the first 24 to 48 hours of using an Advanced Oxidation Process, hydroxyl radicals clean, sanitize, and micro-flocculate the water. The hydroxyl radicals work in seconds to oxidize contaminants, unlike chlorine which could take several hours.

[0082] Pool systems that use Advanced Oxidation Processes do not eliminate the need for chlorine and other chemicals. However, the requirement for these chemicals is dramatically reduced by the AOP systems. In addition, AOP helps boost the overall effectiveness of the small amount of chemicals that are used.

[0083] In addition, hydroxyl radicals from advanced oxidation processes can be used to prevent the formation of biofilm. Biofilm is an accumulation of bacterial colonies that grow on the tile line and any stone surface in a swimming pool.

[0084] Advanced Oxidation Process technology can also be used to improve water clarity by removing the colloids-tiny particles from dissolved metals, gels, lotions, and other inorganic substances—that make the water look cloudy. Advanced Oxidation Processes can produce “micro-flocculation,” a process of aggregating tiny particles that can then be removed by a pool filter from the water.

[0085] With lower chemical levels in your pool, AOP-treated water causes less irritation to eyes, skin, and lungs, making swimming and pool play safer and more enjoyable for everyone. Further, AOPs are an eco-friendly technology. Swimming pool water is effectively disinfected without any damage to the environment.

[0086] Perox Perfect™ and Perox pH Control™ are two auxiliary chemicals that complement the use of Perox sanitisers in Hydroxypure™ system. These chemicals, when used in harmony in Hydroxypure™ system, guarantee a truly comfortable and chlorine-free swimming experience.

[0087] The Perox Perfect™ has flocculating effects to clump floating microscopic particles such as algae spores and microscopic debris. These clumps known as floc, will then be filtered off by mechanical means in the filter tank. The Perox pH Control™ is the solution to regulate acidity or alkalinity of pool water. Perox pH Control™ contains formulated additives to ensure pH balance of pool water for enhanced clarity. It also works in synergy with H.sub.2O.sub.2 from the Hydroxypure system to maintain sanitary conditions in the swimming pool water. Perox pH Control™ is a multifunction chemical that is new for the swimming pool industry. Perox pH Control™ is specifically designed to work with electronic control equipment, and will not omit corrosive fumes that can lead to corrosion, extend the life of the peristaltic pump squeeze tubes and will enhance the water quality of the pool. It also enhances the ability of hydrogen peroxide to remain extremely active in the swimming pool water ensuring effective oxidation rates. Unlike other forms of acid for swimming pools, pH control will work in harmony with Hydrogen Peroxide and needs no dilution to use with the Hydroxypure™ system.

[0088] Based on a current consumer guide, 150 mls of Perox pH Control™ can reduce the pH by about 0.1 in a 50,000 litre swimming pool. This only applies in the range of pH 1 to 8. If the pH is in the range of 8 to 9, more acid will be required to reduce the pH by 0.1. A maximum dosage rate of 500 mls is recommended to achieve a reduction in pH from 7.8 to 7.4 in a pool containing 50,000 litres. It is not recommended to add any more than 500 mls per dose without checking the pH, to reduce overcorrection. It can take 4 to 6 hours for the chemical to fully react in the water

[0089] In comparison, the following levels of individual product components are generally recommended: [0090] Sodium bisulphate: 680 g in pH is above 8.0 for pools of 40,000 L to 70,000 L [0091] To lower the alkalinity: 240 g per every 10,000 L of pool water [0092] Aluminium sulphate: up to 250 g/10,000 L of pool water at this level will act as flocculant rather than a clarifier [0093] Copper in a solution of 32 g/L of copper present as ethanolamine complex salts at a rate of 415 mL/10,000 L of pool water every 3 months to prevent algal growth.

Field Trial Example

[0094] A commercial example of the composition of the invention, Perox pH Control™ was tested on an Olympic size pool located at Somerset College on the Gold Coast, Brisbane, Australia.

[0095] The pH control method that was used at this site was a combination of hydrochloric acid and CO.sub.2. The reason why both forms of pH control were being used was the constant interruption to the CO.sub.2 supply—with the supplier often not able to supply replacement cylinders in a timely fashion. When CO.sub.2 was not available, hydrochloric acid was used.

[0096] The other challenges noted at this site were as follows: [0097] 1) A high phosphate level was tested in the water (3.2 ppm) [0098] 2) Algae growth on the walls and floor of the pool were a common occurrence resulting in manual brushing of the entire pool at least twice per week. [0099] 3) Water clarity was not always 100% due to the aging filtration system. The filtration system has been installed for almost 20 years without a change of the internal media within the filter so there is a compromise on the filtration capacity of the system.

[0100] From a commercial point of view, the cost to use the Perox pH Control™ must be within a reasonable cost when compared to the alternatives.

[0101] Results after 6 Months: [0102] 1) The phosphate level in the pool was recorded at 0.35 ppm—down from 3.2 ppm [0103] 2) The algae growth on the walls and floor was completely eliminated and thus the need to brush the walls and floors was eliminated. A moderate level of 0.25 ppm of total copper was recorded in the pool when tested. [0104] 3) The water clarity of the pool remained excellent throughout the trial period—a noted improvement overall during the trial [0105] 4) An unexpected result was a reduction in the chlorine consumption—on average a saving of approximately 25% in chlorine consumption was reported by the operator at the site. [0106] 5) The cost to operate this form of pH control was only slightly higher (approximately 6%) than the other forms of pH Control. When the chlorine saving factor and the labour-saving factor was added back into the costs the overall result was a saving. [0107] 6) The operators at the site have continued to use Perox pH Control™ now that the trial has been completed.

[0108] Although the invention has been described with reference to specific examples, it will be appreciated by those skilled in the art that the invention may be embodied in many other forms, in keeping with the broad principles and the spirit of the invention described herein.

[0109] The present invention and the described preferred embodiments specifically include at least one feature that is industrial applicable.