CN1703148B - System and preparation method for synergistic disinfection and purification of organic compounds and metal ions - Google Patents

Abstract

The present invention discloses a new and useful disinfection and purification system consisting of organic compounds and selected metal ions having a synergistic effect, as well as a method of preparation and use. One of the advantages of this system is that surfaces, fluids or media can be quickly and easily treated to disinfect bacteria, molds, viruses, algae and protozoa using a non-toxic, non-chlorinated mixture that effectively kills all such organisms within minutes or hours. The disinfection and purification system remains effective for long periods of time, maintaining its disinfection capabilities, thereby making it highly effective for storing or transporting media such as potable drinking water. The disinfection and purification system may be used in conjunction with a carbon block or membrane filter to disinfect filtered liquids, such as water, to render them potable. The disinfection and purification system may be infused into a semi-permeable surface or applied to a non-porous surface such that the disinfectant compounds of the system are delivered to the surface of the object for disinfection by leaching, capillary action, pure contact, water activation and/or permeation/diffusion.

Description

System and preparation method for synergistic disinfection and purification of organic compounds and metal ions

invention technical field

The present invention relates to antimicrobial compositions, mainly for disinfecting water, which utilize the synergistic disinfectant properties of selected organic compounds and selected metal ions. The disinfection invention can be used in a variety of applications including, but not limited to: public water systems (PWS); bottled/reserved water; residential point-of-use/point-of-entry (POU/POE) systems, emergency water disinfection in disaster situations, military use , travel, camping, mountaineering, commercial distribution and/or batch processing units, water coolers/dispensers, food surface disinfection, fruit and vegetable disinfection rinses, meat, fish and poultry disinfection, juice and beverage disinfection (including apples) Juice), commercial/domestic ice preparation, medical and dental installations, spas, pools, industrial treatment and wastewater systems, potable and recycled water in ships, aircraft, recreational vehicles and space. Disinfection inventions are also widely used for disinfection of drinking water in third world and developing countries. The present invention can provide highly effective water disinfection within minutes or hours when using government regulated or recommended concentrations of drinking water components, with effective residual disinfectant concentrations. The invention can also be used at substantially reduced concentrations when a sanitizing treatment of minutes or hours is not required, yet still effectively sanitize the water, eg not in the case of stock water intended for direct use. Where such drinking water concentration restrictions or recommendations do not apply, the invention may also be used in concentrations higher than regulated or recommended drinking water, such as food rinsing, industrial process and recreational waters.

The present invention can be used as a sole sanitizer treatment or can be used in conjunction with other purification techniques such as carbon brick filtration or other micromesh filtration techniques. This additional purification technique can be used to remove particulates, organic/inorganic impurities and taste/odor, and provide effective size exclusion removal of macro-organisms such as Cryptosporidium and Giardia. The invention can be used with other disinfection techniques such as ultraviolet light, oxidizing chemicals and heat treatment to inactivate or kill organics such as Cryptosporidium and Giardia.

The present invention utilizes selected metal ions together with natural plant extracts and/or alcohols as disinfectants.

Background technique

Federal and government regulatory agencies, world public health organizations, and the lay public consider microbiologically safe drinking water to be a basic need. The advantages to developed (industrialized) and developing countries alike of more effective, available, widely available and easy-to-use water treatment and disinfection technologies cannot be overemphasized.

The World Health Organization (WHO) estimates that about 20% of the world's population or 1.7 billion people lack improved and safe water supplies, so 3 to 4 million people, especially children, die from unsafe drinking water every year. In the United States, the Centers for Disease Control and Prevention (CDC) estimates that there are 940,000 cases and possibly 900 deaths per year from waterborne microbial transmission, including reported and unreported morbidity. Some people, including infants, older adults, organ transplant patients, cancer treatment patients, AIDS patients, and others with compromised immune systems, are more susceptible to menstrual borne disease.

The U.S. Environmental Protection Agency (EPA) regulates and regulates the drinking water quality of more than 170,000 public water systems (PWS) in the United States. Of these, more than 160,000 PWS were classified as "small" or "very small" and served between 25 and 3,300 individuals. The present invention can be used as a disinfectant for PWS. It is important that the EPA has recognized the many disadvantages of chlorine, the most commonly used disinfectant in PWS. EPA has taken an interest in and invested in research into new alternative water treatment technologies. The most obvious disadvantage of using chlorine as a disinfectant is the formation of disinfection by-products (DBP), some of which are toxic and possibly carcinogenic. This limits the use of chlorine and/or requires additional treatment to reduce DBP formation. Furthermore, the physical and/or chemical properties of the water to be purified limit the effectiveness of chlorine. Limiting factors for chlorine purification efficacy include water temperature, pH, presence of organic carbon, dissolved organic and inorganic matter, and turbidity. The use of chlorine as a disinfectant also has taste and odor issues and problems associated with handling chlorine.

The wide variety of alternative technologies currently endorsed by the EPA in its Alternative Disinfectants and Oxidizers Guidebook limits the widespread use of drinking water disinfection. Furthermore, many alternative technologies still form DBP and/or inorganic by-products. With the exception of chlorine dioxide and monochloramine, none of these alternative sanitizers provide residual disinfection in the distribution system or in the container, thus requiring the supplemental use of some form of chlorine.

To be a truly effective and powerful potable water disinfectant and multiple applications, a disinfectant/disinfectant that is effective against both bacteria and viruses is required.

Other options for chlorine such as ions, permanganate, chloramines, and ozone/peroxide generally do not yield more than 2-log inactivated virus. In some cases, these alternative disinfectants do not provide measurable inactivation of virus, especially in high turbidity, high organic content water. Iodine is recommended by the CDC, but only for short-term emergency use, and has significant adverse taste and aesthetic disadvantages. In conclusion, there is no approved alternative disinfectant that consistently achieves more than 3-log inactivation of bacteria and viruses and also avoids DBP formation and provides effective disinfectant residue for prolonged water storage and/or microbial reinoculation Provide microbiologically safe water later (which usually occurs when the reserve water is actually used).

In addition to PWS, the new effective water disinfection safety method has a variety of additional applications. These include water fountains in offices and public buildings where microbiological quality of water is concerned, drinking water treatment for outdoor activities such as travel, camping, recreational vehicles, seasonal camping and camping, point-of-use (POU) devices such as softeners and carbon filters, benchtop water treatment units, fruit and vegetable rinsing, meat, fish and poultry rinsing, storage and transport of ice for commercial fishing operations, military use such as remote use, military bulk water storage or treatment, and ships, aircraft Applications, NASA (NASA) and so on.

Treating non-potable water to make it microbiologically safe for domestic use typically includes treatment techniques such as submicron filtration, ultraviolet light, ozone, chlorine, iodine, and/or other sanitizing chemicals. Some treatment units utilize resins or media impregnated with biocidal compounds such as iodine, so that a certain level of this biocide is released into the water. While size exclusion and UV light based systems can remove or inactivate certain microorganisms substantially immediately, they do not provide any residual disinfectant to prevent regrowth of the organism. Particulates, high organic content, turbidity, and multiple chemical compositions can have a significant detrimental effect on UV light-based treatments, making them unsuitable for many types of water. They also require some kind of power source, whether (alternating current) AC or (direct current) DC in nature. Size exclusion based methods are generally effective for removing viruses and some smaller bacteria and suffer as filter clogging limits yield.

The present invention provides a new disinfection technique utilizing a mixture of metal ions and natural derivatives. It can be widely used in untreated natural water and/or treated urban water exhibiting various physical/chemical characteristics. As previously mentioned it is also widely used in non-potable water applications including recreational water treatment (hot tubs, swimming pools, therapy pools), dental waterline fixtures, food preparation, water reuse, industrial cooling circuits, cooling towers, etc. It can be used as a stand-alone disinfection treatment or it can be used in conjunction with other water treatment technologies.

Although the use of metal ions alone, in combination with other ions, or in combination with other substances such as free chlorine and Consistently effective in virus inactivation for various test waters over time including hours or days later. Especially when attempting to prepare microbiologically safe drinking water based on the effective goals and standards identified in the EPA's Surface Water Treatment Rule (SWTR) and/or its guidelines and protocols for testing microbial water purifiers, and using shorter contact times in this way. Similarly, despite non-expert claims to the contrary, after expensive testing, when citrus extracts such as the plant extracts used in the most preferred embodiments of the present invention are used alone, even in purified water such as treated city water Or untreated natural water (such as water taken from rivers, streams, creeks, ponds, lakes, springs or wells) was not effective in reducing the virus under the test conditions and without long-term contact time. Laboratory tests confirmed that neither ions alone nor plant extracts alone or a combination of ions and glycerin were effective in reducing the virus. The same tests have consistently demonstrated the ability of the invention to inactivate viruses under the same and more severe test conditions. Laboratory testing of various waters inoculated with bacteria and/or viruses using ions alone, plant extracts alone or a mixture of ions and alcohol (glycerol) yielded the following results:

Copper/silver ions alone - The use of silver ions alone or a specific ratio of mixed copper and silver ions (10:1 to 30:1) reduced Klebsiella by 5 and 6 logs respectively after a 60 minute contact time with the inoculated urban water substrate. Copper ions alone were not effective, with less than 3 log and 5 log reductions after 60 and 240 minute contact times with inoculated city water, respectively. Copper/silver ion treatment was less effective against Pseudomonas aeruginosa in inoculated urban waters compared to a maximum reduction of less than 5 log for Klebsiella after a 90 min contact time.

Untreated natural water inoculated with Klebsiella, such as water taken from rivers, streams, creeks, ponds, lakes, springs, or wells, has a log reduction of less than 3-log after 120 minutes of contact time using silver or copper ions alone. After 120 minutes of contact time, the log reduction was less than 4-log using mixed silver and copper ions.

Within the range tested, copper/silver ions alone, which proved to have a marginal effect on MS2 virus, showed no log reduction within a minimum exposure time, eg, less than 24 hours. No reduction in MS2 virus was observed after 6 hours of exposure time, and a less than 3-log virus reduction was observed at 24 hours. Similar or more pronounced results in reduced inactivation were obtained for inoculated untreated natural water such as water taken from rivers, streams, creeks, ponds, lakes, springs or wells, using copper or copper/silver ions after a 4 hour contact time Less than 1 log inactivation. The use of silver ions alone did not effectively reduce MS2 even after a contact time of 24 hours with inoculated city water or untreated natural water such as water taken from rivers, streams, creeks, ponds, lakes, springs or wells. Therefore, viruses cannot be sterilized satisfactorily using copper and/or silver ions alone.

In conclusion, neither the individual ions alone nor in combination provide acceptable disinfection of bacteria and viruses in urban water or in untreated natural water such as water taken from rivers, streams, creeks, ponds, lakes, springs or wells.

Plant extract, Citiricidal ^™ alone - Inconsistent performance was obtained with Klebsiella inoculated water with Citricidal ^™ alone, whether dissolved in water or glyceryl. The log reduction to the inoculated city water was 4-6 log after 60 minutes. Even after 120 minutes or more of exposure, a log reduction of less than 3 log is observed for inoculated untreated natural water such as water taken from a river, stream, creek, pond, lake, spring or well. Citricidal ^TM is generally completely ineffective against MS2 virus, with no reduction observed even after 24 hours of contact with inoculated urban water or inoculated untreated natural water such as water taken from rivers, streams, creeks, ponds, lakes, springs or wells.

In conclusion, neither plant extracts (ie, Citricidal ^™ alone) are acceptable for disinfection of bacteria and viruses in urban water or untreated natural water such as water taken from rivers, streams, creeks, ponds, lakes, springs or wells.

Mixed Metal Ions and Glycerol (Alcohol) - Mixed use of copper and silver ions and glycerol gave inconsistent performance on water seeded with Klebsiella. The log reduction to the inoculated city water was 5-6 log after 60 minutes. The log reduction of heterotrophic bacteria is less than 1.5 log for uninoculated untreated natural water such as water taken from rivers, streams, creeks, ponds, lakes, springs or wells. No reduction in MS2 virus was observed using mixed ions and glycerol on inoculated city water or untreated natural water such as water taken from rivers, streams, creeks, ponds, lakes, springs or wells.

In summary, neither mixed ions nor glycerin provide acceptable disinfection of bacteria and viruses in urban water or untreated natural water such as water taken from rivers, streams, creeks, ponds, lakes, springs or wells.

As previously stated, the present invention provides a unique blend of metal ions and natural plant extracts and alcohols. Therefore, it is a new method and has not been reported in literature or existing patents. Previously, many researchers attempted to find suitable alternatives to chlorine disinfection, but each had drawbacks. Researchers have attempted to exploit the antimicrobial properties of copper and silver ions by mixing them with various other ingredients to optimize their action, especially against viruses. However, previous efforts have not been able to develop any copper/silver hybrid disinfectants that give acceptable inactivation of bacteria and viruses within a short contact time. Some related studies are briefly described below.

Domek et al., published in Domek, M., M. LeChevallier, S. Cameron and G. McFeters, 1984, Evidence for the Role of Copper in the Injury Process of Coliform Bacteria in Drinking Water, Appui Environ. Microbiol. 48:289-293 The presence of low levels of copper impairs E. coli in drinking water samples, and this effect is dose-related. Subsequent testing revealed decreased cellular oxygen uptake and glucose utilization, as well as changes in metabolic end products due to copper impairment.

Kutz et al., as disclosed in Kutz, S., L. Landeen, M. Yahya and C. Gerba. 1988, Microbiological Evaluation of Copper: Silver Desinfection Units, Proceedings of the Fourth Conference on Progress in Clinical Disinfection, S.U.N.Y., Binghamton, NY, April 11-13, 1988, Detection of electrolytically generated copper (Cu) and silver (Ag) ions alone, free chlorine (FC) alone and Cu/Ag ions plus low levels of FC against seven types of bacteria. Their results showed that all tested bacteria were inactivated faster with the mixed treatment than with the individual treatments.

Landeen et al., as disclosed in Landeen, L., M. Yahya, and C. Gerba 1989, Efficacy of Copper/Silver Ions & Reduced Levels of Free Chlorine in Inactivation of Legionella prreumophila, Appl. Environ. Microbiol. 55: 3045-3050 , also tested copper and silver ions in the presence or absence of FC using Legionella as the target organism, reporting a statistically significant increase in disinfection with the mixed treatment.

Yahya et al., as disclosed in Yahya, M., L. Landeen, M. Mesina, S. Kutz, R. Schultze and C. Gerba, Desinfection of Bacteria in water Systems by Using Electrolytically Generated Copper: Silver & Reduced Levels of FreeChlorine, Can J. Microbiol. 36: 109-116, similar tests were performed using Staphylococcus sp., a previous study showing greater tolerance to treatments compared to coliform bacteria, and the advantages of adding FC to treatments versus copper/silver alone Similar conclusions were obtained for the confinement of ions.

Margolin et al., as disclosed in Margolin, A.B. Control of Microorganisms in Source Water and Drinking Water. Pp. 274-284, In: Manual of Environmental Microbiology, Hurst, C.J., Ed., ASM Press, Washington D.C., 2002, evaluated in FC Copper-impregnated inactivation of MS2 and poliovirus with and without addition. They reported that polioviruses showed greater resistance to copper disinfection than MS2 (1.3 log and 4.0 log inactivation, respectively, within 12 hours), and the addition of FC significantly enhanced the inactivation of both virus types.

Abad et al., as disclosed in Abad, F., R. Pinto, J. Diez and A. Bosch, 1994, Disinfection of Human Enteric Viruses in Water by Copped Silver in Combination with Low levels of Chlorine, Appl. Environ. Microbiol.60 (7): 2377-2383, Testing the efficacy of copper and silver ions mixed with low levels of FC against enteroviruses. They reported that copper plus silver plus 0.5 mg/L FC was not more effective against poliovirus than 1 mg/L FC alone. The authors also observed that under the conditions tested, adenovirus required 120 minutes of disinfectant exposure to obtain a 3 log reduction, hepatitis A virus (HAV) and human rotavirus were more resistant. The authors believe that (when applied) copper and silver in water do not provide reliable alternatives for high levels of FC for disinfection of viral pathogens. However, they also reported the stability of copper and silver levels in the test chamber, with initial inputs of 75% and 44%, respectively, detectable after 60 days.

Lin et al., as disclosed in Lin, Y., R.Vidic, J.Stout and V.Lu, 1996, Individual and Combined Effects of Copper and Silver Ion on Inactivation of Legionella Pneumophila, Wat.Res.30(8):1905- In 1913, the efficacy of copper and silver ions alone and in combination on L. pneumophila serogroup 1 was tested. These authors note that copper is more effective than silver alone, but requires a contact time of 2.5 hours for complete (6 log) inactivation of Legionella (silver requires 24 hours).

Apparently, Lin et al. also noted that copper and silver ions could have additive or synergistic effects depending on the concentrations used, and argued that their combined effect was greater than that observed for either copper or silver alone.

Rohr et al., as disclosed in Rohr, U., S. Weber, F. Selenka and M. Wilhelm, 2000, Impact of Silver and Copper on the Survival of Amoeba and Cilia Protozoa in Vitro, Int. J. Hyg. Environ. Health 203:87-89, Examination of the effect of copper and silver ions on amoebae and ciliated protozoa in vitro. The authors report that within the German drinking water regulatory limits (10 and 100 mg/L for Ag and Cu, respectively), the mixed treatment did not inactivate the test protozoa.

Batterman et al., as disclosed in Batterman, S., K. Mancy, S. Wang, L. Zhang, J. Warila, O., Lev, H. Shuval and B. Fattal, 2001, Evaluation of the efficacy of a New Secondary Disinfectant Formulation Using Hydrogen Peroxide and Silver and the Formulation of Disinfection By-productsResulting From Interactions With Convention Disinfectants, EPA STARGrant No.R825362, working in EPA STAR, evaluating hydrogen peroxide (H ₂ O ₂ ) plus copper and silver ion mixed treatment effect. For bacteria, they report that hydrogen peroxide is less efficient than silver ions _, silver ions are less efficient than _H2O2 mixed with silver ions, and _H2O2 mixed with _silver ions is more efficient than _H2O2 plus _copper ions Low. However, the authors believe that mixing disinfectants would result in unacceptable virus inactivation. A 6-hour contact time was required to inactivate 4 logs of MS2 coliphage and was even less effective against poliovirus, giving only 0.15 logs of inactivation after a 12-hour contact time.

As can be seen from the studies described above, although the use of copper and silver ions alone or in combination with other substances has had some success in inactivating bacteria, no combination has proven effective against viruses in the various waters tested within short contact times.

Similarly, prior art patents disclose various examples of antimicrobial agents that include metal ions alone or in admixture with other substances. However prior art patents generally teach disinfection systems for non-potable water, such as swimming pools and spas. In several instances, prior art patents covered treatment systems for drinking water. None of these prior art patents teach the use of EPA drinking concentrations of plant extracts, alcohols, and metal ions to sanitize water containing bacteria, algae, protozoa, viruses, and mold such that effective kill rates are within minutes or hours Makes previously contaminated water sources potable and provides a disinfectant residue to remain effective in killing or inactivating bacteria and viruses for months or years without formation of disinfection by-products.

invention disclosure

In view of the inherent limitations of known types of disinfection and purification systems and the fact that the prior art does not anticipate or teach that organic compounds act synergistically with selected metal ions, the present invention provides a disinfection and purification system consisting of organic compounds and selected metal ions that act synergistically. Purification system, and method of preparation and use, which are designed to allow the user to quickly and effectively disinfect surfaces, media or fluids such as water from microorganisms (such as bacteria, viruses, protozoa, algae and molds), which are patented or Commercially available similar disinfection systems are significantly different and an improvement. Therefore, the general object of the present invention (described in detail below) is to provide a new and practical disinfection and purification system composed of organic compounds and selected metal ions with synergistic effect, as well as its preparation method and use. The present invention has a number of additional novel features related to solving unsolved problems in the prior art, as follows:

- active ingredient mixtures that produce a synergistically enhanced antimicrobial effect on user-specified surfaces and in user-specified media or fluids such as water; and

- Individual treatment technologies for sanitizing water so that the resulting water is safe to drink from the point of view of bacteria, viricides, moulds, algae and protozoa.

In the most preferred embodiment, the components of the treatment mixture generally consist of:

1. A mixture of active ingredients comprising:

a) one or more water-soluble metal compounds (including but not limited to metal sulfates, metal salts or metal citrates or some other source of metal ions in solution) for use as selected from the periodic table group 1b, 2b, a solution source of one or more metal ions of the metals in 3b, 4b, 5b, 6b, 7b, 8, 3a, 4a and 5a;

b) one or more plant extracts; and

c) one or more alcohols.

The components of the treatment mixture may also consist of:

2. A mixture of active ingredients comprising:

a) one or more water-soluble metal compounds (including but not limited to metal sulfates, metal salts or metal citrates or some other source of metal ions in solution) for use as selected from the periodic table group 1b, 2b, a solution source of one or more metal ions of the metals in 3b, 4b, 5b, 6b, 7b, 8, 3a, 4a, and 5a; and

b) one or more plant extracts.

In another component of the processing mixture, it may also consist of:

3. A mixture of active ingredients comprising:

a) one or more water-soluble metal compounds (including but not limited to metal sulfates, metal salts or metal citrates or some other source of metal ions in solution) for use as selected from the periodic table group 1b, 2b, a solution source of one or more metal ions of the metals in 3b, 4b, 5b, 6b, 7b, 8, 3a, 4a, and 5a; and

b) one or more alcohols.

Although generally the primary objective of the present invention is to avoid the use of disinfectants such as chlorine, radiation, ozone/peroxide, and temperature, the following components of the treatment mixture include these disinfectants at significantly reduced concentrations and/or exposures, thereby reducing Its side effects:

4. A mixture of active ingredients comprising:

a) one or more water-soluble metal compounds (including but not limited to metal sulfates, metal salts or metal citrates or some other source of metal ions in solution) for use as selected from the periodic table group 1b, 2b, a solution source of one or more metal ions of the metals in 3b, 4b, 5b, 6b, 7b, 8, 3a, 4a, and 5a; and

b) one or more plant extracts; and/or

c) one or more alcohols; and/or

d) one or more disinfecting compounds, such as ozone/peroxide or a halogen selected from Group 7a of the Periodic Table of the Elements or its derivatives such as halogenated hydrocarbons, amides, amines, or halogenated dioxides; and/or

e) Once the mixture is applied to or mixed with the sanitizing substance, subject the mixture to antimicrobial physical challenges or treatments such as radiation including ultraviolet and infrared etc., sonic blasting and extreme temperatures of cold or heat.

In order to better understand the following detailed description, and to better understand the present contribution to the prior art, the important features of the present invention are broadly described. Additional features of the invention will be described hereinafter which will form the subject of the claims once a full application is filed.

In this regard, before at least one embodiment of the present invention is described in detail, it is to be understood that the invention, methods and apparatus are not limited in practice to the details of construction and the arrangement of elements set forth in the following specification. The invention, methods and apparatus are capable of other embodiments and of being practiced and carried out in various ways. In addition, it should be understood that the phrases and terminology used herein are for the purpose of description and do not limit the protection scope of the present invention or the claims in any way.

Those skilled in the art will therefore appreciate that the conception upon which the disclosure is based may readily be utilized as a basis for other structural designs, methods and systems for carrying out the several purposes of the present invention. It is therefore important that the claims be construed to cover such equivalent structures and methods as long as they do not depart from the spirit and scope of the invention.

In addition, the purpose of the abstract above is to enable the USPTO and the general public, especially scientists, engineers and practitioners in the field who are not familiar with patent and legal terminology or wording, to quickly understand the nature and nature of the technical content of this application through skimming. characteristic. The abstract is also not intended to limit the invention of the application, which is defined by the claims, nor does it limit the scope of protection of the invention in any way.

Therefore, an object of the present invention is to provide a new and practical disinfection and purification system composed of organic compounds and selected metal ions with a synergistic effect, as well as its preparation method and use, which have various advantages of the above disinfection and purification system. Advantages and has many new features, thus obtain the disinfection and purification system composed of organic compounds and synergistic selected metal ions, and preparation method and use, in any prior art disinfection and purification system alone or in any combination and None of this is intended, evident, suggested or even implied in the method of manufacture.

Another object of the present invention is to provide a sanitizing and decontaminating system composed of organic compounds and synergistically acting selected metal ions which can be easily and efficiently prepared, taught, sold and used by end users.

Another object of the present invention is to provide a sanitizing and decontaminating system composed of organic compounds with synergistically acting selected metal ions, which is of durable and reliable construction.

Another object of the present invention is to provide a disinfection and purification system composed of organic compounds and selected metal ions with synergistic effect, the material and cost of its preparation are all lower, thus it can be sold to users at a lower price, Thereby making this sanitizing and decontaminating system of organic compounds and synergistically acting selected metal ions economical to the purchasing public.

Another object of the present invention is to provide a sanitizing and decontaminating system composed of organic compounds and synergistically acting selected metal ions which maintains effective disinfectant residues over months or years. So far, the present invention has maintained its sanitizing and purifying effects for 21 weeks. City water samples (dechlorinated) at protective concentrations of preferred embodiments of the invention were collected and stored under ambient conditions. After the initial treatment, two aliquots of treated water were periodically removed and inoculated to a ^{concentration} of ^106-107 Kelbsiella/ml sample. During the 21-week data collection period, the log reduction of Klebsiella remained unchanged at 30, 60 and 90 minute exposure times and was completely inactivated at 60 and/or 90 minute exposure times. Such testing is ongoing and it is expected that the present invention should continue to maintain its ability to effectively kill bacteria for stock water samples treated with the present invention. This ability to effectively retain disinfectant residues over extremely long periods of time is a unique feature of the present invention. The results of the residual efficacy study are shown in Figure 5, which was prepared from the data in Figure 6A, Figure 6B and Figure 6C.

Another object of the present invention is to provide a disinfection mechanism that allows the inactivation of microorganisms in repeatedly contaminated/inoculated treated and stored water samples. In practice, this means that the invention is not consumed during the first and subsequent sterilization reactions. The capabilities of the present invention have been demonstrated through a series of experiments. City water samples (dechlorinated) at protective concentrations of preferred embodiments of the invention were collected and stored under ambient conditions. After one month of storage, samples of the treated water were removed and inoculated with 10 ⁶ -10 ⁷ Kelbsiella/ml sample. Then, at periodic intervals, the same samples were re-inoculated with the same concentration of Klebsiella without further addition of disinfectant. This happened at 21 weeks and is still ongoing. After five inoculations, the inactivation efficacy of Klebsiella remained unchanged at 30, 60 and 90 minute contact times, with complete kill (6-7 log) observed at 90 minutes. Beginning with the 6th inoculation, a reduction in killing efficacy was observed at a 30 minute contact time. After 3 additional inoculations, a reduction in killing efficacy was observed at 90 min contact time, although complete (7 log) killing of inoculated Klebsiella was achieved after 120 min contact time. Ongoing experiments are ongoing and include longer contact times beyond 90 minutes to assess the ability of the invention to provide effective disinfection after additional inoculations. The results of the replicated subject study are shown in Figure 7, which was prepared from the data of Figures 8A, 8B and 8C.

Another object of the present invention is to provide a disinfectant solution or material which in its final mixed form exhibits a long shelf life and does not require special storage conditions. Laboratory tests confirmed the present invention that this is definitely the case. Working solutions of the four component concentrations of the most preferred embodiment of the invention were prepared and then stored indoors in sealed containers for 13 months in an uncontrolled temperature environment in South Hero, VT. This preparation goes through temperatures from -20°F to 100+°F, multiple freezes and thaws during storage. It was stored in translucent containers and compared "stored" and fresh disinfectants after 13 months of natural day and night storage. No ^significant difference was observed between fresh and "stocked" disinfectants in the performance of city water inoculated with ^106-107 Kelbsiella/ml samples, with complete kill of inoculated organisms within 60-90 minutes contact time.

Another object of the present invention is to provide a sanitizing and decontaminating system composed of organic compounds and synergistically acting selected metal ions which has some of the advantages of the prior art systems while overcoming the disadvantages of the prior art.

These and other objects of the invention and the various features of the invention will be set forth in the claims. For a better understanding of the invention, its operating advantages and specific purposes of use, reference should be made to the appended description, in which there are illustrated preferred embodiments of the invention.

Best Mode for Carrying Out the Invention

Most Preferred Embodiment - In the most preferred embodiment, the present invention treats drinking water using two selected metal ions, copper and silver, selected from copper sulfate or copper citrate and silver sulfate or silver citrate and placed in a pending solution in treated water. Dissolved metal ions are mixed with plant extracts and alcohol glycerol selected from pomelo seeds. In the most preferred embodiment, the active ingredient concentration in the final water should be:

a) Copper in drinking water is 750ppb at most and does not exceed the allowable concentration of government control selected by the user (such as applicable EPA or WHO standards);

b) Silver in drinking water is 37.5ppb at most and does not exceed the allowable concentration of government control selected by the user (such as applicable EPA or WHO standards);

c) When applicable in drinking water, grapefruit seed extract (i.e. Citricidal ^TM ) reaches 80-110ppm (i.e. 10 drops or 100mg Nutribiotic ^TM Brand grapefruit seed extract) at most not exceeding the allowable concentration of government control selected by the user (if available applicable EPA or WHO standards); and

d) When applicable, glycerol in drinking water up to 160-220ppm does not exceed the user-selected government control allowable concentration (such as applicable EPA or WHO standards).

In potable water treatment, stock solutions can be prepared such that the copper/silver stocks added to 1 liter of water are 1.5 ml and 0.75 ml respectively. By adjusting the strength of the stock solution, this will change the volume fairly easily - so if 5 gallons (20L+/-) of water are being treated, then there is no need to add 30ml copper and 15ml silver, instead the obvious can be used for packaging convenience and other related issues A small volume, but still has disinfection effect. A commercial grapefruit seed extract (GSE) known as Citricidal ^™ is usually commercially packaged as a liquid form of 33% Citricidal ^™ and 67% glycerol. This establishes the Citricidal ^TM and Glycerin ratios described above. However, the use of Citricidal ^™ and glycerin in dry powder form allows for different ratios of these two ingredients. Also, it is not necessary to use the commercially available Citricidal( ^TM) . Other plant extracts, alone or mixed with equivalents, have disinfecting powers.

Effective disinfection was demonstrated with copper/silver ion ratios ranging from 1:1 to 50:1. The best disinfection ability is obtained when the ratio of copper to silver is 20:1. For applications of the invention using long contact times, such as for stock water not intended for immediate use, the ion ratios and concentrations of any or all of the components comprising the composition of the invention have been shown to be significantly lower. The ability to reduce concentration when long contact times are generally consistent with the concept of CT values (concentration x time) established by classical disinfection theory. Therefore, it is clear that if the concentration of these ingredients does not meet the government control level, then higher concentration can be used, thus increasing its antimicrobial effectiveness, or conversely, if longer contact time is applied, then the concentration will be lower, and the present The invention is still valid for drinking water. GSE was measured using "drops" due to its high viscosity (using a commercial Citricidal ^™ /glycerol mixture). Measure 40 drops of 1 ml of Citricidal ^™ /Glycerin using a dropper and add to a commercial GSE bottle. When 10 drops of the Citricidal ^™ /glycerin mixture are used in 1 liter of water to be treated, the concentration corresponds to 0.25 ml Citricidal ^™ /glycerol/liter of water. About 0.125ml Citricidal ^™ /glycerin or less works synergistically with copper and silver ions to effectively sanitize 1 liter of filtered water, whereas about 0.25ml Citricidal ^™ /glycerin is required per liter of cloudy water.

The concentration of the most preferred embodiment does not change substantially over time when dissolved in water, thus achieving effective "instant" disinfection and can provide an effective disinfection residue. This feature of the present invention is particularly useful for maintaining the potability of reserve water due to the potential for reinoculation with unwanted microorganisms.

Initial validation tests were performed using the most preferred embodiment, and tests involving each individual compound were then combined to obtain the most preferred embodiment with the greatest synergistic sanitizing ability. Initial trials were performed on a variety of test waters, including filtered, dechlorinated urban water, natural surface water (untreated natural water such as that obtained from a river, stream, creek, pond, lake, spring, or well) and synthetic water (EPA Test Water #3 - Disclosed in EPA Guidelines). Trials were carried out with various water types inoculated with Klebsiellaterrigena, Pseudomonas aerugiwsa and MS2 antibiotics. Bacteria were typically inoculated to an initial 6-7 log concentration (colony forming units, CFU, per ml sample); virus was inoculated to give a 5 log concentration (plaque forming units (PFU), per ml sample) in each water matrix tested.

Combining copper and silver ions with Citricidal ^TM in a glyceryl base produces a clear synergistic effect, essentially increasing the sanitizing efficacy compared to any of the ingredients alone or in part. Repeat trials/tests conducted over a two-year period demonstrated that the use of the present invention rendered bacteria and viruses less susceptible to both inoculated urban water and inoculated untreated natural water such as water taken from rivers, streams, creeks, ponds, lakes, springs or wells. High log reduction, the prepared samples are microbiologically potable according to EPA and WHO standards.

The most preferred embodiment completely inactivates (6+log) Klebsiella in inoculated urban water within 30 minutes, and within 60 minutes in inoculated untreated natural water such as from rivers, streams, creeks, ponds, lakes, springs or There was a 4+ log reduction in water taken from the well (turbidity >30 NTU, total organic carbon (TOC) >100 mg/L). P. aeruginosa was completely killed (6+log) in inoculated urban water within a 90 minute contact time.

The synergistic effect of the most preferred embodiment is more pronounced for viruses. MS2 was completely inactivated (5+log) in inoculated city water within a contact time of 15-30 minutes. MS2 is completely (5+log ) inactivation. In inoculated synthetic water (turbidity >30 NTU, TDS 1500 mg/L and pH 9.0 - consistent with EPA Test Water #3 published in EPA Guidance Standards), MS2 was reduced by 4+log within 60 minutes and completely (5 +log) inactivation.

The test results of the most preferred embodiments shown in Figures 5, 6A, 6B, 6C, 7, 8A, 8B and 8C clearly demonstrate that the copper Mixing silver ions with pomelo seed extract (ie Citricidal ^™ ) and glycerin in the manner described above substantially enhanced the disinfecting power.

Implementation of the cascade filtering method of the present invention

Mixing copper and silver ions with Citricidal ^™ and glycerin sanitizer in the above preferred test of the present invention can be used in conjunction with any filter device, such as those shown in Figures 1 and 2, carbon block or microporous filters. This combination will filter out unwanted particles or biological matter that may or may not affect the potability of the water but adversely affect its aesthetics and taste.

In the device shown in Figure 1, the water to be sanitized and purified first passes through a standard commercial carbon block filter at which point the water passes through a second chamber where copper and silver ions are optimally mixed with Citricidal ^TM and Glycerin as the sanitizer The concentration is preset and the sanitizing agent (this may be in tablet, liquid or powder form) is present in a predetermined amount sufficient to sanitize a user selected volume of water. As the water passes through the second chamber, its physical action forces the mixed copper and silver ions with Citricidal ^TM and glycerin into solution. The water containing the dissolved compounds then passes through a location selected by the user such as a third chamber or storage vessel of sufficient size to hold the volume of water sanitized and purified according to the quality of the disinfectant used.

In another embodiment shown in Figure 2, the water to be sanitized and purified is first passed through a standard commercial carbon block filter where the water passes through the same chamber as the carbon block filter where copper and silver ions are mixed with Citricidal ^™ and glycerin The best way to mix sanitizer concentrations is preset, said sanitizer (this may be in tablet, liquid or powder form) present in a predetermined amount sufficient to sanitize a volume of water selected by the user. Once out of the carbon block filter, as the water contacts the sanitizing mixture, its physical action forces the mixed copper and silver ions with Citricidal ^™ and glycerin into solution. The water containing the dissolved compounds then passes through a location selected by the user such as a second chamber or storage vessel of sufficient size to hold the volume of water sanitized and decontaminated according to the quality of the disinfectant used.

Embodying the Infused Surface Mode of the Invention

Many industries, such as the food service industry, need to handle food on surfaces that often support the growth of bacteria that can and do cause human illness and even death. In the infused surface approach of the present invention shown in Figure 4, a suitable semipermeable material, polymer or similar material is used to make the desired working surface. The material is then treated with mixed copper and silver ions in the above best mode of the present invention with Citricidal ^™ and glycerin sanitizer (processing can be carried out by injection, dipping, spraying, pressure treatment and/or other mechanical means) so that the sanitizer is as effective as possible Completely absorbed by the materials comprising the product. The mixed copper and silver ions in the above best mode of the present invention with Citricidal ^™ and glycerin sanitizers can be added to the material structure when added as ingredients in the manufacture of the material, composite substances and polymers as shown in FIG. 3 .

When used as a work surface, the sanitizer remains sanitized on the surface by leaching, capillary action, pure contact, water activation, and/or penetration/diffusion. This will prevent the growth of bacteria on the surface, thereby preventing the spread of infectious diseases, and will transfer the disinfectant to substances that come into contact with the work surface.

A further discussion of the modes of use and operation of the invention will be apparent from the foregoing description. Therefore, the use and mode of operation are not discussed further.

With respect to the foregoing description, it should be appreciated that the optimum dimensional relationships and construction of the parts of the invention include variations in size, quality of materials, shape, form, function and manner of operation, assembly and use, and will be clear to those skilled in the art And obviously, the present invention also includes all equivalent relations described in the specification.

Accordingly, the foregoing illustrates by way of example only the principles of the invention. Furthermore, since numerous modifications and changes may occur to those skilled in the art, it is not intended to limit the invention to the precise construction and operation shown and described, and therefore all suitable modifications and equivalents fall within the scope of the invention. within the scope of protection. For example, it will be apparent to those skilled in the art that the concentrations and ratios of the active ingredients disclosed herein can be reduced and the contact time increased to obtain the desired disinfection results, and conversely obtained by increasing the concentrations and ratios of the active ingredients and reducing the contact time required. Desired disinfection result. The novelty of the present invention is evident in the synergistic sanitizing action of said substances or groups of active ingredients, irrespective of their relative concentrations, it being recognized that certain ratios and concentrations of these substances will be better than those described in the most preferred embodiments.

Claims (2)

1. A sanitizing and purifying composition comprising: (a) Copper in drinking water is 750ppb at most and does not exceed the allowable concentration of WHO control standards; (b) Silver in drinking water is 37.5ppb at most and does not exceed the allowable concentration controlled by WHO; (c) The pomelo seed extract in drinking water reaches 80-110ppm and does not exceed the maximum allowable concentration controlled by WHO; and (d) Glycerin in drinking water reaches 160-220ppm and does not exceed the allowable concentration of WHO control selected by the user at most; Wherein the copper and the silver ions are from copper sulfate or copper citrate and silver sulfate or silver citrate, and the ratio of copper ions to silver ions in the disinfection and purification composition is 1:1 to 50:1. 2. The composition of claim 1, wherein the ratio of copper ions to silver ions in the sanitizing and decontaminating composition is 20:1.

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