WO2023105385A1

WO2023105385A1 - Aqueous solution for water treatments

Info

Publication number: WO2023105385A1
Application number: PCT/IB2022/061773
Authority: WO
Inventors: Roberto Benedini
Original assignee: New Tech Solutions S.R.L.
Priority date: 2021-12-06
Filing date: 2022-12-05
Publication date: 2023-06-15
Also published as: IT202100030734A1

Abstract

An aqueous solution for water treatments, comprising a liquid solution comprising water and silver ions in citric acid, the concentration of the silver ions in the liquid solution being comprised between 0.0032 and 0.9 PPM.

Description

AQUEOUS SOLUTION FOR WATER TREATMENTS

The present invention relates to an aqueous solution for water treatments, in particular for use in agriculture, industry or for disinfection treatments.

To date, so-called plant protection products are known and widely used in agriculture.

These are products, generally ready for use after dilution in water (with some exceptions), which can be used to protect and preserve plants (and plant products) or affect their vital processes (growth, etc.).

Plant protection products are used to try to protect plants and fruits from all harmful organisms, also by preventing their effects. Moreover, plant protection products can be used to destroy unwanted plants, or to control or prevent their growth.

Pesticides and fungicides are among the most commonly used plant protection products: the former are mainly insecticides (against plant and animal parasites) while the latter are essentially fungicidal products.

Plant protection products belong to the group of pesticides along with many biocides. Plant protection products are used in agriculture on crops, but also on harvested products; moreover, in the forestry and non- agricultural fields they are used on plants or in the plant world in general.

It is well known that the use of plant protection products, despite the fact that their marketing and use is regulated by specific supranational, national and local regulations, is often dangerous with reference to possible pollution, contamination or accumulation with reference to humans, flora, fauna and, more generally, the environment.

Disinfection of water, for example to render it potable, is usually carried out by means of the so-called chlorination process.

This process can be performed in various ways; in commonly understood chlorination (that of small/medium facilities), a solution of sodium hypochlorite (bleach) is simply added to the water to be rendered potable.

The addition of chlorine to water produces hydrochloric and hypochi orous acid: these compounds are known as free chlorine.

Both when the chlorine is fed directly into the water supply and when it is fed into a reservoir, a "contact time" between water and chlorine of at least 30 minutes should be ensured before use so that the chlorine can carry out its bactericidal action, oxidizing any living form that exists in the water.

In fact, since sodium hypochlorite solutions spontaneously lose (owing to elapsing time, due to light, temperature, due to the action of other substances present in the water) their active chlorine titer, to ensure "at the tap" the required measurement (e.g., 0.2 mg/1), progressively higher dosages (e.g., 0.4 mg/1) are applied in aqueducts.

Chlorine-based treatments are among the most effective and widespread in the common practice of water disinfection and potabilization.

In fact, chlorine, in the various forms in which it is used (sodium hypochlorite, chlorine dioxide, etc.), is a broad- spectrum disinfectant: it destroys most bacterial microorganisms that are harmful to humans, including the bacterium Legionella pneumophila, as well as spores and viruses; moreover, it has excellent persistence, i.e., its effect is maintained over time.

However, introducing chlorine into an aqueous solution leaves various traces and byproducts such as, for example, trihalomethanes. Disinfection byproducts are chlorine-based compounds that are very persistent and capable of reaching the endpoint of the distribution network.

While, on one end, the use of chlorine to ensure potability throughout the distribution network of an aqueduct may seem essential, the presence of chlorine in the water system, on the other hand, causes two main problems that tap water consumers often complain about:

- it alters the smell and taste of the water, making it of lower quality with respect to how it flows from a spring or well; - the limits imposed by law determine the safety conditions within which the concentration of chlorine is not harmful to the human body, but this does not mean that chlorine is not present in the water.

The aim of the present invention is to provide an aqueous solution for water treatment that is capable of improving the background art in one or more of the above aspects.

Within this aim, an object of the invention is to provide an aqueous solution for water treatments which can be used, in agriculture, as a product to increase pH and reduce alkalinity and at the same time to allow to eliminate, or at least reduce drastically, the use of pesticides.

Another object of the invention is to provide an aqueous solution for water treatments which allows to perform disinfection in the integrated water system, both with reference to potabilization processes and with regard to the disinfection of treatment wastewater and its refining for irrigation purposes in agriculture.

Not least object of the invention is to provide an aqueous solution for water treatments that is highly reliable, relatively easy to provide, and at competitive costs.

This aim, as well as these and other objects that will become better apparent hereinafter, are achieved by an aqueous solution for water treatments according to claim 1, optionally having one or more of the characteristics of the dependent claims.

Further characteristics and advantages of the invention will become better apparent from the description of some preferred, but not exclusive, embodiments of the aqueous solution according to the invention.

The aqueous solution for water treatments according to the invention comprises a liquid solution comprising water and silver ions in citric acid.

The concentration of silver ions in the liquid solution is comprised between 0.0032 and 0.9 PPM (parts per million).

Specifically, silver ions in citric acid are constituted by a stabilized complex in which each silver ion is weakly bound to citric acid ions.

The concentration of citric acid in the liquid solution is comprised between 100 and 1000 PPM (parts per million), and more preferably between 400 and 600 PPM (parts per million).

Preferably, the concentration of silver ions in the liquid solution is comprised between 0.0032 and 0.032 PPM (parts per million).

In particular, the silver ions are generated electrolytically.

Transport proteins, traced to more than 500 families, cross the cell membrane and transport different molecules, generally belonging to two categories: nutrients and endogenous substances necessary for cellular function.

Structurally, these transporters are constituted by 12 helices that proceed back and forth in the thickness of the membrane to form a channel through which substances are transported into the cell. In the case of bacteria, transport proteins recognize citric acid as food and therefore transfer it into the microorganism. Once penetrated inside it, the silver cations react rapidly with the negatively charged groups, causing irreversible damage to both the proteins and the DNA and RNA of the bacteria, blocking their metabolic and reproductive functions, ultimately leading to their death.

In practice:

- silver cations inhibit the multiplication of bacteria by irreversibly damaging their DNA and RNA, with production of insoluble silver halides;

- at the level of tissue proteins, silver ions bind to them, causing structural changes to the cellular and intracellular wall, as well as in the nuclear membranes of the bacteria themselves;

- the silver ions in citric acid also bind electrons of sulfur, oxygen and nitrogen of bacteria resulting in precipitation and coagulation of some proteins of the microorganisms.

The aqueous solution according to the invention furthermore comprises, in addition to the liquid solution comprising silver ions in citric acid, ethyl alcohol in a percentage comprised between 6% and 12% of the liquid solution.

It has been found that this aqueous solution can be used in agriculture for various uses.

In particular, this aqueous solution can be used to increase pH and lower alkalinity.

In addition or alternatively, this aqueous solution can be used to replace pesticide products.

In this regard, it has been found that the presence of silver ions in the liquid solution according to the invention allows to achieve an efficacy in disinfection comparable to that of solutions with 70% ethyl alcohol.

Preferably, the aqueous solution according to the invention further comprises a compound chosen from the group comprising:

- fosetyl-aluminum;

- copper oxychloride and/or copper hydroxide;

- sulfur and/or organic sulfur;

- bupiramide;

- azoxystrobin and difenoconazole;

- sweet orange essential oil and/or organic sweet orange essential oil;

- Trichoderma asperellum and/or Trichoderma gamsii.

In particular, it has been found that the addition of fosetyl-aluminum allows to contrast grapevine and melon mildew, apple scab, and pome fruit phytoflora.

It has been found that the addition of copper oxychloride and/or copper hydroxide allows to contrast tomato bacterial speck, cucurbit mildew, anthracnose, mildew, excoriosis, black rot and red fire disease of grapevine, shot hole disease and brown rot of stone fruit.

It has been found that the addition of sulfur and/or organic sulfur allows to contrast powdery mildew of grapevine, pome fruit and stone fruit.

It has been found that the addition of bupiramide allows to contrast powdery mildew of zucchini, melon, tomato and cucumber.

It has been found that the addition of azoxystrobin and difenoconazole allows to counteract powdery mildew of many horticultural crops, downy mildew and root diseases such as Fusarium, Phytium, Sclerotinia, Didymella of melon.

It has been found that the addition of sweet orange essential oil and/or organic sweet orange essential oil is effective for grapevine against excoriosis, powdery mildew, downy mildew, thrips, and leafhoppers; for cucumber against powdery mildew, thrips, and midge; for melon against powdery mildew.

It has been found that the addition of Trichoderma asperellum and/or Trichoderma gamsii is effective against esca disease and brown spot of grapevine, against root diseases of horticultural crops, and Armillaria of fruit trees.

In fact, the presence in the aqueous solution according to the invention of silver ions in citric acid allows to increase exponentially the effectiveness of the additional added components, even if added in extremely small percentages.

Moreover, the present invention relates to the use of an aqueous solution in agriculture.

The aim of the aqueous solution according to the invention is to increase the pH, lower the alkalinity, and carry out or assist the antiparasitic action.

In particular, the concentration of silver ions in the liquid solution is comprised between 0.0032 and 0.32 PPM (parts per million) and has a stabilized complex in which each silver ion is weakly bound to citric acid ions.

In particular, silver ions are generated electrolytically. Advantageously, the aqueous solution according to the invention comprises, in addition to the liquid solution comprising silver ions in citric acid, ethyl alcohol in a percentage comprised between 6% and 12% of the liquid solution.

- fosetyl-aluminum;

- copper oxychloride and/or copper hydroxide;

- sulfur and/or organic sulfur;

- bupiramide;

- azoxystrobin and difenoconazole;

- sweet orange essential oil and/or organic sweet orange essential oil;

- Trichoderma asperellum and/or Trichoderma gamsii.

According to a further aspect, the present invention relates to the use of an aqueous solution for water disinfection.

Specifically, for the potabilization of water or for the treatment of waste water.

In particular, the aqueous solution for water treatments according to the invention comprises a liquid solution comprising silver ions in citric acid and has a stabilized complex in which each silver ion is weakly bound to citric acid ions.

In particular, the concentration of silver ions in the liquid solution is comprised between 0.0032 and 0.9 PPM (parts per million).

In particular, the silver ions are generated electrolytically. It has been found that the aqueous solution according to the invention ensures complete sanitization of water without the addition of chemical additives, eliminating Legionella and molds, among other things, and also sanitizing scale.

It is noted that with reference to collection and for wastewater treatments, the aqueous solution according to the invention is also effective on protozoa, comprising Giarda and Cryptosporidium, allowing simplifications and qualification in the sanitization process.

Disinfection by means of the aqueous solution according to the invention ensures constant control of the microbial load over time with an ever-decreasing presence of bacteria, viruses, fungi and molds in ducts and pipes because it does not create microbial resistance.

The aqueous solution according to the invention has a residual efficacy of at least 18 and at most 24 hours.

Specifically, about 20,000 liters of drinking water can be sanitized with one liter of concentrated aqueous solution.

The ready-to-use diluted product contains 35 PPM of silver ions and about 400/600 PPM of citric acid.

The molecule's mechanism of action (which is seen by bacteria as a metabolic source without generating microbial resistance) ensures a disinfectant efficacy equivalent to about 2000 ppm of chlorine, because of the long-standing certainties about the creation of microbial resistance by all chemicals that nullify over time the variation of the higher concentrations of these products.

Using the aqueous solution according to the invention, the contact time required for microbial load suppression is about 30 seconds for viruses and about 2 minutes for bacteria.

In order to highlight the conservative dilution values, with a 1:35 dilution the WHO parameter is met already at the time of the pouring of the product as it is ready for use, without considering the inevitable effects related to the depletion of the molecule during the process of water potabilization.

It should be noted, moreover, that the optimal dilution for disinfectant efficacy provided for potabilization is about 1: 100 liters, therefore far below the threshold values already met with a dilution that is about three times more concentrated.

Regarding microbiological issues for water intended for human consumption, three areas of possible use within the Integrated Water System have been evaluated:

- Sanitization of storage works (tanks, reservoirs) and other parts of the system with the uses of the aqueous solution according to the invention for shock or scheduled interventions to prevent water pollution situations;

- Validation of the protocol for product use for water disinfection in aqueducts: in this regard, it is possible to promote a shared project between the operator and the control bodies to define a protocol of uses of the aqueous solution according to the invention to enable the evaluation of the effectiveness of the product in the different steps up to the tap, define elements of the monitoring system and specific parameters useful for the action of control of compliance with the quality tables of water intended for human consumption;

- Use of the aqueous solution according to the invention for disinfection of treatment wastewater and its refining for irrigation purposes in agriculture.

The goal is to sanitize water below the parameters of E. coli, Legionella and intestinal nematodes provided by Quality Class A for water refined for irrigation purposes in agriculture. Evaluate and define the protocol for using the aqueous solution according to the invention to comply with the values provided by Class A both for maintaining levels until actual use for irrigation and for overcoming the environmental criticalities of Classes B, C and D. Evaluate the possibility of redesigning sewage treatment plant operation patterns based on the use of the product and its effectiveness on intestinal nematodes, in particular Giardia and Cryptosporidium Parvum.

The use of the aqueous solution as a mouthwash, hand sanitizer or dental canal irrigant can also be considered.

In practice it has been found that the invention achieves the intended aim and objects, providing an extremely effective aqueous solution for use in the agricultural sector and in water disinfection.

With particular reference to use in the agricultural sector, it has been found that the addition of the aqueous solution comprising silver ions in citric acid according to the invention allows to increase exponentially the efficacy of other compounds, such as ethyl alcohol, even added in small percentages.

Likewise, the addition of the aqueous solution of silver ions in citric acid to products already used and certified against specific diseases or against particular pests (e.g., fosetyl-aluminum, copper oxychloride and/or copper hydroxide, sulfur and/or organic sulfur, bupiramide, azoxy strobin and difenoconazole, sweet orange essential oil and/or organic sweet orange essential oil) allows to increase significantly, even exponentially, the efficacy of such products already used and certified against specific diseases or against particular pests.

Therefore, it remains evident that the aqueous solution containing silver ions in citric acid, despite not being "the basic active ingredient" in these specific cases, is nevertheless capable of enhancing, to the point of making them very effective, some disinfectant solutions that currently are "certified" in the various areas related to the resolution of bacterial, viral and any kind of problems.

The invention thus conceived is susceptible of numerous modifications and variations, all of which are within the scope of the accompanying claims; all the details may furthermore be replaced with other technically equivalent elements.

In practice, the materials used, so long as they are compatible with the specific use, as well as the contingent shapes and dimensions, may be any according to the requirements and the state of the art. The disclosures in Italian Patent Application No. 102021000030734, from which this application claims priority, are incorporated herein by reference.

Claims

1. An aqueous solution for water treatments, characterized in that it comprises a liquid solution of silver ions in citric acid, in particular the concentration of the silver ions in the liquid solution being comprised between 0.0032 and 0.9 PPM (parts per million).

2. The aqueous solution according to claim 1, characterized in that the concentration of the citric acid in the liquid solution is comprised between 100 and 1,000 PPM (parts per million) and more preferably between 400 and 600 PPM (parts per million).

3. The aqueous solution according to claim 1 or 2, characterized in that it comprises a stabilized complex in which each silver ion is weakly bonded with citric acid ions, said silver ions being generated electrolytically.

4. The aqueous solution according to one or more of the preceding claims, characterized in that it further comprises ethyl alcohol in a percentage comprised between 6% and 12% of the liquid solution.

5. The aqueous solution according to one or more of the preceding claims, characterized in that it further comprises a compound chosen in the group comprising:

- fosetyl-aluminum;

- copper oxychloride and/or copper hydroxide;

- sulfur and/or organic sulfur;

- bupiramide;

- azoxystrobin and difenoconazole;

- sweet orange essential oil and/or organic sweet orange essential oil;

- Trichoderma asperellum and/or Trichoderma gamsii.

6. Use of an aqueous solution, characterized in that it comprises a liquid solution of silver ions in citric acid in which the concentration of the silver ions in the liquid solution is comprised between 0.0032 and 0.9 PPM (parts per million), in the agricultural field as a pesticide or to increase the pH.

7. Use of an aqueous solution, characterized in that it comprises a liquid solution of silver ions in citric acid, wherein the concentration of the silver ions in the liquid solution is comprised between 0.0032 and 0.9 PPM (parts per million), for water disinfection.

8. Use of an aqueous solution, characterized in that it comprises a liquid solution of silver ions in citric acid, wherein the concentration of the silver ions in the liquid solution is comprised between 0.0032 and 0.9 PPM (parts per million), as a mouthwash.

9. Use of an aqueous solution, characterized in that it comprises a liquid solution of silver ions in citric acid, wherein the concentration of the silver ions in the liquid solution is comprised between 0.0032 and 0.9 PPM (parts per million), as hand sanitizer.

10. Use of an aqueous solution, characterized in that it comprises a liquid solution of silver ions in citric acid, wherein the concentration of the silver ions in the liquid solution is comprised between 0.0032 and 0.9 PPM PPM (parts per million), as a dental canal irrigant.