Ultra-pure, electrochemically modified water

Abstract

Ultrapure water with an electrical conductivity of less than 0.1 µS / cm, which is essentially free of organic components and gases, and in which OH is produced by autoprotolytic processes. - -ions and H3O + -ions are formed, characterized by the fact that the ultrapure water has an OH group. - -excess and has a pH value of 7.5 to 9.5.

Description

[0001] The present invention relates to an ultrapure, electrochemically modified water. WATER

[0002] Water is a fundamental requirement for life and is ubiquitous in nature. It exists on the Earth's surface and in the atmosphere in all three states of matter: solid, liquid, and gaseous. Plants and animals consist of 50 to 80% water, while in the human body, water makes up about 70% of total weight. Humans typically consume water daily through fluid intake, but water is also a component of solid human food.

[0003] As a chemical compound, water can be synthesized from the elements hydrogen (H₂) and oxygen (O₂) through an oxidation reaction (oxyhydrogen reaction). This reaction is exothermic. Conversely, water can be broken down into its components, hydrogen and oxygen, for example, through electrolysis by supplying energy using an electric current.

[0004] The water molecule, H₂O, occupies a central position in many fields of application due to its unique chemical and physical properties. These include, above all, its dipole moment, which arises from the differing electronegativities of the constituent elements hydrogen, H, and oxygen, O, as well as from the geometry of the water molecule with a bond angle of approximately 104° and pronounced partial charges, and thus its ability to form hydrogen bonds. This also results in other special properties, such as the high melting and boiling points for a substance with the molecular weight of water, the density anomaly of water, its high specific heat capacity and thermal conductivity compared to other liquids, and its high surface tension.

[0005] Water is not found in nature as a pure substance, but contains dissolved substances such as salt ions and gases. Therefore, water exists in varying qualities depending on its source and has different properties and components. Among other things, water is classified and distinguished as wastewater, brackish water, groundwater, seawater, mineral water, process water, surface water, rainwater, raw water, saltwater, and freshwater.

[0006] The treated or tested water qualities include, among others, drinking water, demineralized water, deionized water, distilled water and ultrapure water. WATER TREATMENT

[0007] Untreated water contains a variety of impurities. Water drawn from natural resources, such as surface water, rainwater, or groundwater, but also seawater or mineral water, contains various impurities, salts, and minerals depending on its origin. These include, among others, magnesium ions (Mg₂). 2+ , sodium Na + Calcium Ca 2+ , Potassium K + , Iron Fe 2+ , Fe 3+ , Chloride Cl - and sulfate SO4 2- present in water. Furthermore, dissolved gases are contained in water, e.g., oxygen, nitrogen, and carbon dioxide, which in aqueous solution exist in equilibrium with the hydrated form as carbonic acid and the associated ions, carbonate, CO3. 2- and hydrogen carbonate, HCO3 -Water can also contain nitrates, nitrites, organic compounds, and other substances that enter the water as "pollution" through direct or indirect sources. Direct sources include, for example, various wastewaters from the sewage systems of residential areas and industry. Indirect sources of unwanted substances into the water include pollutants carried by rain into groundwater or surface water from the soil surface, air, or soils, such as pesticides, particulate matter, oil, sulfur compounds, nitrogen oxides or nitrous gases, fertilizer residues, heavy metals, and components of sewage sludge.

[0008] In contrast, treated water has the aforementioned components removed to a greater or lesser extent, depending on the treatment process and intended use. Water treatment can be achieved, for example, through purification, filtration, softening, desalination, removal of heavy metals such as lead, manganese, cadmium, mercury, and iron, disinfection, and / or sterilization.

[0009] The extraction, treatment, and composition, and thus the quality, of drinking water in Germany are subject to stringent requirements. These are regulated by the Drinking Water Ordinance, the national implementation of the 1998 EU Drinking Water Directive. The Drinking Water Ordinance contains various provisions designed to protect human health from adverse effects resulting from the contamination of water intended for human consumption. To this end, drinking water must not contain waterborne pathogens or chemical substances in concentrations that could harm human health. Furthermore, limit values ​​for specified microbiological and chemical parameters must not be exceeded, and other limit values ​​for indicator parameters must be observed. The specified parameter values ​​for radioactive substances must also not be exceeded.For example, the electrical conductivity of drinking water at 25°C must not exceed 2790 µS / cm. For the parameter total organic carbon (TOC), which measures the organic load of the water, there is currently no limit value specified in the regulation; the measured value must meet the requirement of "no abnormal change." The proportional value for "oxidizability" must not exceed 5.0 mg / l O2. This describes the oxygen requirement for the oxidation of all organic components. The pH value of the drinking water must be between 6.5 and 9.5.

[0010] Only certain substances may be used in the disinfection treatment of drinking water, and minimum concentrations of free chlorine, chlorine dioxide, or other treatment substances must be present for disinfection after completion of the measure.

[0011] For pharmaceutical purposes, demineralized water and distilled water are listed in the European Pharmacopoeia. Accordingly, the monographs for "purified water (Aqua purificata)" and "water for injection (Aqua ad Injectabilia)" are included. Purified water is produced from drinking water, which is treated by ion exchange, reverse osmosis, distillation, or other suitable methods. This treatment corresponds to demineralization, as the anions and cations present in drinking water are largely removed by these processes. Water for injection is distilled water; it may only be produced by distillation due to stringent sterility requirements.

[0012] Ultrapure water (UPW) contains virtually no impurities. It consists primarily of the chemical compound H₂O. This UW is required in many technological fields. For example, it is used in laboratory and medical technology, chemical analysis, biochemistry, research, pharmaceuticals, drug manufacturing, the production of injection fluids and infusion solutions, and in engineering, such as the production of integrated circuits, as well as in the manufacture of cosmetics and for cleaning medical devices and preparations (e.g., endoscopes, implants) and precision parts.

[0013] Ultrapure water (URW) is produced using various methods such as reverse osmosis, electrodeionization, ion exchange, or distillation, sometimes in combination with purification by adsorption onto activated carbon. Often, ultrapure water systems are used that combine different purification processes to produce the purest possible water.

[0014] Electrodeionized water (EDI water) produced by electrodeionization systems already possesses very high water quality. It can be used as a precursor for the production of ultrapure water (URW). EDI water is obtained, for example, in a continuous process by flowing already softened or otherwise treated water through an arrangement of cathode and anode with intermediate chambers, each delimited by an anion exchange membrane or cation exchange membrane. The resulting electric field and the ion-selective membranes between the chambers direct the ions dissolved in the incoming water (permeate) towards the electrodes. In the corresponding chambers, they accumulate in the concentrate remaining as rinse water, while they are removed from the product water, which is extracted as diluate. The diluate consists of highly purified EDI water.

[0015] Furthermore, various specifications exist for water of different purity grades. According to ISO 3696:1987, water for analytical purposes is classified into three different purity grades or quality levels. ASTM D1193-06 (2011), a specification of the American Society for Testing and Materials, describes three grades for pure water and one for ultrapure water.

[0016] Various parameters are used to classify the different described water qualities. Electrical conductivity

[0017] The electrical conductivity of water indicates its ability to conduct electricity. It is expressed as the ratio of current density to electric field strength and is one of the most informative parameters regarding the content of charged or ionic impurities. To determine the electrical conductivity, an anode and a cathode with a defined area and at a defined distance are placed in the water sample. A voltage is applied between them, and the resulting current is measured. The electrical conductivity, particularly of water and solutions, is temperature-dependent and is typically specified for a temperature of 25 °C.Since water molecules themselves, due to their molecular structure, cannot conduct electricity, electrical conductivity indicates the concentration of dissolved ions in the water, which, due to their electrical charge, enable the flow of electricity. With increasing ion concentration, electrical conductivity increases and the electrical resistance of the water decreases. Seawater, with its dissolved salts, exhibits very high conductivity values ​​of 56 mS / cm (corresponding to 56,000 µS / cm). In drinking water, the conductivity value may be up to 2790 µS / cm at 25 °C. On average, German drinking water, due to its dissolved salts, reaches values ​​between 300 and 800 µS / cm, depending on the region, and is thus significantly below the required limit. While rainwater, due to its low dissolved ion content, has an average conductivity of approximately 30 µS / cm, mineral-rich spring water measures approximately 80–130 µS / cm.

[0018] For most applications, such as in technology, industry, and medicine, a low ion concentration in water is crucial. The conductivity of distilled water at 25 °C is between 0.5 and 5 µS / cm due to the removal of most ions, while electrochemically deionized (EDI) water has an electrical conductivity of less than 0.2 µS / cm (down to 0.08 µS / cm). According to DIN ISO 3696:1987, water for analytical purposes of quality grade 1 may have a maximum conductivity of 0.1 µS / cm at 25 °C; the conductivity of grade 2 can be up to 1.0 µS / cm, and that of grade 3 up to 5.0 µS / cm.

[0019] According to ASTM D1193-06 (2011), URW must have a conductivity of no more than 0.056 µS / cm.

[0020] URW, which contains virtually no foreign substances, conducts electricity solely due to the chemical property that the water molecule is an ampholyte, a chemical compound that can both accept and donate protons. This reaction, also known as autoprotolysis, originates from the chemical conversion H2O + H2O ⇌ H3O + + OH - which also occurs in ultrapure water. It should be noted that the free individual ions H3O + and OH - never exist in this form, but always in their hydrated form, surrounded by non-protolyzed water molecules of the form H2O and stabilized via common hydrogen bonds.

[0021] The equilibrium of this reaction lies strongly on the left side. Nevertheless, the charged products on the right side are present in very low concentrations. Therefore, the electrical conductivity of URW has a calculated limit of 0.055 µS / cm at 25 °C, which cannot be undercut in the purest water even in the absence of foreign ions. TOC content

[0022] Another meaningful parameter of water quality is the value representing the total organic carbon (TOC) in a sample volume. TOC includes all organic substances, such as microorganisms, components of biofilms, various sugars, alcohols, and plastic-based derivatives. Inorganic carbon such as carbonate and bicarbonate is not included. The TOC content of a water sample represents a measure of the organic load in the water and is preferably expressed in [mg / l], [ppm], or [ppb]. Here, 1 mg / l = 1 ppm = 1000 ppb. It can be determined by chemical or thermal oxidation of the organic carbon compounds contained in the water to carbon dioxide and subsequent measurement of the resulting CO₂.Reference should be made, for example, to DIN EN 1484, which describes various methods for determining the TOC content in different samples.

[0023] According to regulations, drinking water must have a TOC content "without abnormal changes". This corresponds approximately to a value of less than 1.5 mg / l.

[0024] For URW according to ASTM D1193-06 (2011), a limit value for the TOC content of no more than 0.050 mg / l, corresponding to 0.05 ppm or 50 ppb, is specified.

[0025] Distilled water typically has a TOC content of 0.2 mg / l, while ultrapure water systems can achieve a TOC content in the range of 3 ppb.

[0026] In some cases, instead of determining the TOC content, the chemical oxygen demand (COD) is measured in water samples to quantify organic contaminants. The COD value indicates the amount of oxygen that would be consumed if all oxidizable substances were oxidized using oxygen as the oxidizing agent. The measurement is performed using a wet chemical method in sulfuric acid with an excess of dichromate. Due to the experimental setup, the COD value sometimes also includes inorganic oxidizable compounds in the water. DISINFECTION

[0027] Disinfection involves measures to render dead or living material incapable of infecting individuals with whom it comes into contact. This requires the removal, reduction, or inactivation of infectious agents.

[0028] Infectious germs are pathogenic microorganisms or subcellular structures that, through their penetration and multiplication within humans, animals, or plants, cause infection and, potentially, an infectious disease as a consequence of the infection. These germs primarily include various bacteria, fungi, algae, microalgae, and protozoa. In a broader sense, parasites, viruses, retroviruses, viroids, bacteriophages, prions, and transposons are also included.

[0029] The number of germs or microorganisms present in a sample is expressed as the number of colony-forming units (CFU). To prevent infections, the number of germs present should be reduced, thus decreasing the number of CFU. Germ reduction is expressed in log 10 -levels measured. One log 10A level of 1 corresponds to a reduction in germs by an order of magnitude. For example, washing hands with soap achieves a germ reduction of two log10. 10 -levels, corresponding to a removal of 99% of the CFU present before the measure. Effective disinfection is achieved with a germ reduction of approximately three to seven log 10 -levels reached. In the case of spore-forming germs, e.g. Clostridium species such as Clostridioides difficile or Bacillus species such as Bacillus subtilis, a product is considered sporicidal if, when used as directed, the number of viable spores is reduced by three log 10 -levels are reduced.

[0030] Unlike disinfection, where an object or surface is treated so that it can no longer infect, sterilization in the true sense involves the removal of all viable germs, pathogenic and non-pathogenic, including their dormant forms, e.g. spores, as well as viruses and infectious proteins.

[0031] For sterilization, a germ reduction of eight or more log is required to technically distinguish it from disinfection. 10 -levels. This is done because, in practice, complete sterilization cannot be guaranteed with absolute certainty.

[0032] Disinfection procedures are categorized according to their various applications. These include hygienic and surgical hand disinfection, skin antisepsis, surface, instrument, laundry, and room disinfection, as well as waste disinfection. Water disinfection also plays a crucial role in a wide range of applications, as microorganisms present in water multiply readily at appropriate temperatures due to physiological conditions. Drinking water only needs disinfection if it has a high microbial load. Swimming pool and bathing water, as well as process, cooling, and boiler water used in industry, generally require disinfection.

[0033] In addition to physical methods, chemical disinfectants (and disinfection methods) are used in particular, which can be subdivided according to their spectrum of activity into bactericidal, fungicidal, yeasticidal, sporicidal and virucidal agents (and methods), as well as mycobactericidal and tuberculocidal agents (and methods).

[0034] Additionally, disinfectants, when placed on the market, face the problem that they are subject to various legal regulations. Depending on their area of ​​application, they are classified as medicinal products, medical devices, cosmetics, or biocides. As biocides, they are subject to the EU Biocidal Products Regulation (EU) No. 528 / 2012 of the European Parliament and of the Council of 22 May 2012. This regulation also stipulates that proof of efficacy must be provided for the necessary authorization of a biocidal active substance.

[0035] The effectiveness of a disinfectant against different germs and for different areas of application is examined using test regulations, which can be found, for example, in the European standards.

[0036] The efficacy testing of a disinfectant according to EN 14885 involves a multi-stage process. Phase 1 consists of a qualitative screening test. Phase 2 is divided into Phase 2 Stage 1, in which a quantitative test is performed using suspension in a test tube, and Phase 2 Stage 2, in which the efficacy is investigated in a practical trial. The following European Standards (EN), among others, are applied:

[0037] An overview of European standards whose scope lies in human medicine and the industrial sector:

[0038] Chemical disinfectants exhibit different germ-reducing mechanisms depending on their components, which characterize their different applications. One of these mechanisms is the oxidation effect of various disinfectants. Here, microorganisms are killed or inactivated through electron transfer; for example, SH groups of proteins are oxidized, causing them to lose their functionality.

[0039] Oxidizing disinfectants contain primarily chlorine and chlorine compounds, in addition to hydrogen peroxide, peracids, and ozone. Aqueous solutions of chlorine and chlorine compounds are bactericidal, fungicidal, yeasticidal, virucidal, and sporicidal.

[0040] Chlorine dioxide as a disinfectant is effective over a wide pH range and forms only slightly chlorinated byproducts from the organic impurities in the treated water. A disadvantage is that the production of chlorine dioxide solutions from hydrochloric acid and chlorite requires hazardous chemicals. Furthermore, the solutions exhibit insufficient stability, as chlorine dioxide readily decomposes into chlorite. Toxic gases are released from aqueous chlorite solutions when exposed to acid.

[0041] Hypochlorous acid poses fewer risks in its use. Hypochlorite or chloramine T, in particular, in aqueous solution, is suitable for disinfecting surfaces, instruments, skin, and water. Hypochlorous acid is suitable for a wide range of applications, including in the food industry and drinking water treatment. Its disinfection effect develops within seconds to minutes.

[0042] In disinfectants containing alkali hypochlorite in aqueous solution, dissolved hypochlorite anion, hypochlorous acid, and gaseous chlorine exist in a pH-dependent equilibrium. When gaseous chlorine is introduced into water, the chlorine disproportionates, forming hydrochloric acid and hypochlorous acid. Cl2 + H2O ⇌ HClO + HCl

[0043] Hypochlorous acid is an unstable compound. Even in low concentrations, it tends to disproportionate in aqueous solution to chloric acid and hydrochloric acid. 3 HClO ⇌ HClO3 + 2 HCl

[0044] Therefore, the pH value of solutions containing hypochlorous acid is raised to stabilize them. Upon the addition of, for example, NaOH, the hypochlorous acid dissociates. HClO + NaOH ⇌ ClO - + Na + + H2O

[0045] Similarly, when alkali hypochlorite is dissolved in water at low concentrations, the above equilibrium is initially established, forming a basic solution (pH approximately 9.7). As the pH increases, this equilibrium shifts increasingly towards the hypochlorite anion.

[0046] The Fig. 1 and Fig. 2 illustrate these equilibrium relationships in graphical form.

[0047] According to Fig. In a pH range above 2, only about 35-40% of the available chlorine exists as HClO; approximately 60-65% is chlorine gas (Cl2). This gas can escape from the system, emitting an unpleasant odor and no longer providing the desired disinfecting effect.

[0048] Within a pH range of approximately 3.5 to 7.5, the equilibrium favors undissociated hypochlorous acid, resulting in optimal disinfection. HClO is highly reactive and reacts with a variety of oxidizable biomolecules, for example, at SH groups, C-C double bonds, or various nitrogen groups. By denaturing proteins in microorganisms, it kills or inactivates them.

[0049] If the pH rises above 7.5, the dissociated form of HClO with the hypochlorite anion predominates. The OCl - The -anion exists in hydrated form and can only exert a weak effect against microorganisms, as it can only interact insufficiently with the surfaces of the microorganisms due to the hydration shell and the negative charge.

[0050] Therefore, the problem with disinfectants containing hypochlorite is that, on the one hand, hypochlorous acid is only present in sufficient concentration in undissociated form within a limited pH range of 3.5 to 7.5, in which the best disinfecting effect can be achieved, and on the other hand, it is unstable in this form and tends to decompose.

[0051] Furthermore, in the case of oxidizing disinfectants, the redox voltage, also called redox potential (oxidation-reduction potential, ORP), has a significant influence on the oxidizing ability and thus the effectiveness of the agent.

[0052] In a redox reaction, electrons are transferred from one substance to another. The electron-accepting substance, for example, hypochlorous acid as the active ingredient in the disinfectant, is reduced, while the electron-donating substance, for example, the microorganism to be eliminated, is oxidized. The redox potential is a measure of the active ingredient's propensity to accept electrons and thus exert its disinfecting effect. It depends on pressure, temperature, and pH value and is measured as an electrical voltage in mV. A high positive redox potential of a disinfectant solution indicates a high propensity to accept electrons and destroy microorganisms. The redox potential described here represents the electrical voltage generated by an active ingredient in its oxidized form relative to a reference electrode under standard operating conditions (25 °C; 101.3 kPa; pH = 0; ion activity 1 mol / L).

[0053] The redox potential of a solution can be measured, for example, with a metal sensor immersed in the solution. The voltage across this sensor is measured relative to a reference electrode using a pH / mV meter. A standard hydrogen electrode can serve as the reference electrode, or a system with Ag / AgCl and KCl electrolyte can be used, or other common single-rod redox measuring chains.

[0054] In an aqueous hypochlorite solution produced in situ, the following redox reaction can be carried out immediately after preparation: HClO + H + + 2 e - ⇌ Cl - + H2O At a pH of 0, a potential of +1.48 V is measured. At a pH of 8.5, a potential of +700 mV is still present.

[0055] As the solution ages, the ORP (oxidation-reactive protein) decreases, and consequently, so do its oxidizing power and disinfecting effect. After storage or transport of approximately 7 days, only a fraction of the original potential remains.

[0056] At the same time, hypochlorous acid is also a component of the cellular immune response of vertebrates, including humans. During the oxidative burst, the enzyme myeloperoxidase in neutrophils converts hydrogen peroxide and chloride ions into water and hypochlorous acid, which is then released into the phagosome to deactivate invading microorganisms.

[0057] The desired germ-reducing effects of disinfectants are accompanied by undesirable side effects. For example, alcohol-based disinfectants can damage the skin and are ineffective against bacterial endospores. The use of some disinfectants can lead to the development of resistance in certain microorganisms. As a result, the resistant organisms multiply, rendering disinfection with the respective disinfectant ineffective.

[0058] With hypochlorite-containing solutions, a problem arises because, due to the high reactivity of free HClO (=active chlorine), some of the solution's disinfecting potential is consumed through chlorine depletion. Chlorine depletion represents the consumption of the active chlorine released from the hypochlorite, which occurs through binding to or reaction with all organic and inorganic compounds present in the sample to be disinfected. The higher the initial concentration of impurities in a sample, the more hypochlorite must be used to achieve a sufficient disinfecting effect after chlorine depletion.

[0059] For conventional disinfectants containing hypochlorite in aqueous solution, a disadvantage is that the solution is most effective in a pH range of 4 to 7.5, but at these pH values, hypochlorous acid, as described above, is not very stable even in low concentrations. Both the HClO content and the redox potential of a hypochlorite solution decrease during storage.

[0060] Furthermore, the storage and transport of ready-to-use, aqueous disinfectant solutions incur relatively high costs, as large quantities of water must be transported and stored due to the low concentrations of the disinfecting ingredient. It would therefore be desirable to prepare an aqueous hypochlorite-containing solution only immediately before use. STATE OF THE ART

[0061] Various methods for water treatment or disinfectant production are known from the state of the art.

[0062] For example, systems are offered that electrolytically activate drinking water and prepare it for human consumption. Activation is achieved, for instance, through membrane electrolysis. This treated water is referred to as "alkaline water" or "alkaline activated water." It acts as an antioxidant in the body and neutralizes harmful free radicals. This water contains the usual minerals and dissolved hydrogen. Furthermore, due to the electrochemical treatment, it exhibits a redox potential, which, however, dissipates within 24-36 hours.

[0063] It is also known to treat water without chemical additives by water electrolysis using diamond or metal electrodes. In this so-called "electrical water disinfection," the action of an electric current on the water, without chemical additives, produces ozone, hydrogen peroxide, and hydroxyl radicals with high oxidizing power. The described process is suitable for disinfecting highly purified process water. This is described, for example, on the website www.samro.ch / deutsch / technologien / elektrische-wasserdesinfektion-ewd / of Samro Technik AG.

[0064] The well-known ActiWa® system from Samro Technik AG produces powerful disinfectants from softened water by adding a sodium chloride (NaCl) solution and subsequent electrolysis using a membrane with diamond or metal electrodes. The resulting solution has a pH value of approximately 6–8.5 and a redox potential of approximately 800–1000 mV. The solution's effectiveness is minimal at a pH of 8.5. At a pH of 6, disinfection is still effective, but the solution is highly corrosive. These disinfectants are suitable for water disinfection and for disinfecting surfaces such as machinery in wet areas by rinsing. Disinfection of drying surfaces that should not be flooded with water is not possible. The solutions described have limited storage stability and do not provide long-term disinfection. (www.samro.ch / technologien / Desinfektionsmittel-actiwa / )

[0065] German patent DE 20 2018 102 846 U1 describes a disinfectant containing an aqueous sodium hypochlorite solution with a concentration of ≤ 0.1%, which is additionally stabilized with sodium carbonate at a concentration of 0.4 to 2.5 g / l. Due to the buffering effect of the sodium carbonate, it is very difficult to shift the pH value of this disinfectant into the optimal range of pH 3.5 to 7.5 for hypochlorite.

[0066] DE 10 2006 043 267 A1 describes a process for producing a disinfectant by electrochemical activation (ECA) of water and a process for disinfecting water using such a disinfectant.A method for disinfecting water is proposed in which an electrolyte solution is added to at least a partial stream of the water to be disinfected from drinking water, process water, rainwater, industrial water, or the like by electrochemical activation, and the water exposed to the electrolyte solution is subjected to an electric current in an electrolysis reactor with at least one cathode compartment with a cathode and at least one anode compartment with an anode spatially separated from the cathode compartment, in particular by means of a diaphragm or a membrane, by applying a DC voltage to the electrodes in order to bring the water / electrolyte solution into a state suitable for disinfection, wherein the electrical conductivity of the water to be electrochemically activated is adjusted to a value of no more than 350 µS / cm before the electrolyte solution is added.Due to the spatially separated anode and cathode compartments and a membrane between them, the resulting anolyte has a very low pH, while the catholyte, with its high pH, ​​is completely discarded. The yield is therefore low. The anolyte is highly corrosive to metals. Furthermore, chlorine gas can be produced in the anolyte due to its pH.

[0067] WO 2007 / 093395 A2 describes a similar process for producing a disinfectant by electrochemical activation (ECA) of water. In this process, an electrolyte solution is added to water, and the resulting diluted water / electrolyte solution is subjected to an electric current by applying a DC voltage to the electrodes in an electrolysis reactor. The reactor has at least one cathode compartment with a cathode and at least one anode compartment with an anode, spatially separated from the cathode compartment, in particular by means of a diaphragm or a membrane. This process converts the diluted water / electrolyte solution into a metastable state suitable for disinfection. The pH of the solution in the anode compartment is controlled to a value between 2.5 and 3.5. This process also produces highly acidic anolyte water, which is not suitable for all applications.

[0068] EP 0 470 841 A2 describes a method and apparatus for producing sterilized water, in which water containing sodium chloride and water containing hydrogen chloride are mixed, electrolyzed in an electrolysis cell without a diaphragm, and the resulting electrolyzed water is diluted with water. The pH value is to be adjusted to a range of 3 to 7 and the residual chlorine concentration to a range of 1.0 to 200 ppm. The method is intended to prevent the deposition of calcium carbonate on the cathode. Due to the low pH value, the active chlorine concentration and the redox potential of the water resulting from this process decrease over time. Furthermore, the water has corrosive properties, for example, on the pipe network, in the pH range of 3. Only in a pH range of 6.5 to 9.5 does the water meet drinking water quality standards.

[0069] EP 1 036 037 B1 describes a composition containing electrochemically activated water (ECA water) for the disinfection and sterilization of objects, in which the ECA water contains a corrosion inhibitor or a wetting agent, or a combination of these components. Electrochemical activation, the electrolysis of salt-containing water in cathode and anode chambers separated by a membrane, results in ECA water with a high surface tension, which prevents reliable wetting of the objects to be disinfected and ensures effective disinfection. Furthermore, ECA water is corrosive to metal, which is detrimental to the disinfection of metal objects or pipes. Therefore, in the present mixture, the ECA water is combined with a corrosion inhibitor, a wetting agent, or a combination of both.These additives limit the application range of ECA water for disinfection, as additives are not desirable in all areas.

[0070] The processes known from the prior art produce, on the one hand, highly acidic, anodic solutions which, due to their low pH, are corrosive, difficult to handle, and carry the risk of chlorine outgassing. On the other hand, those processes that electrolyze without a membrane or that recombine anolyte and catholyte after membrane electrolysis produce water that, while disinfecting at the moment of production and providing germ-free water at that time, lacks long-term disinfection due to its composition and is susceptible to recontamination at any time. The disinfecting components react back to sodium chloride and water. TASK

[0071] The present invention is therefore based on the objective of providing a water with which the described disadvantages and problems of the prior art can be overcome. In particular, this water should enable the production of hypochlorite-based disinfection solutions whose hypochlorous acid (HClO) content (active chlorine content) and redox potential (ORP) remain largely constant at the time of use, despite storage and / or transport.

[0072] Furthermore, it is an object of the present invention to provide disinfectant solutions with a low sodium chloride content in order to enable their use on corrosion-sensitive surfaces. INVENTION

[0073] This problem is solved by the ultrapure water according to the invention with the features of claim 1, by the process for producing ultrapure, electrochemically modified water, and by the process for producing a disinfection solution.

[0074] The disinfectant solution produced by the inventive method is universally applicable. It is suitable for skin and hand disinfection by spraying or application and rubbing, as well as for spray disinfection or wipe disinfection of surfaces and instrument disinfection. Furthermore, it can be used for aerosol disinfection of surfaces and rooms or room air, and also for wound disinfection. It can also be used for cold fogging in the sanitization of room air and odor neutralization.

[0075] The disinfectant effect is tested according to European standards. The disinfectant solution according to the invention can reduce the number of germs by at least a factor of 10 compared to bacteria. 5 This can be achieved. A reduction in germs by at least a factor of 10 is possible against mycobacteria, yeasts, fungi, viruses, and also bacteriophages. 2 possible. Spores are detected with a factor of at least 10. 3 decimated.

[0076] Ultrapure water according to the preamble of claim 1 is ultrapure water as defined in various standards, for example, DIN ISO 3696, ASTM D1193-91, DIN EN 13060, Ph. Eur. 10, and DAB 2019. The ultrapure water has an electrical conductivity of less than 0.1 µS / cm and is essentially free of organic components and gases. The electrical conductivity is measured at a temperature of 25 °C. The ultrapure water should be essentially free of inorganic and organic components other than water molecules. A measure of the proportion of organic components is the TOC content. Ultrapure water containing practically no organic components has a TOC content of no more than 0.5 mg / l.

[0077] Since contamination of the ultrapure water by foreign substances from contact surfaces (e.g., containers, stoppers and closures, pipes or filling systems), or from gases and ambient air, cannot be completely ruled out, the water is essentially free of organic components and gases. Ideally, the ultrapure water should contain as few impurities as possible. It has an electrical conductivity of less than 0.1 µS / cm. This conductivity corresponds to water that is essentially free of ions, including ions of heavy metals, alkali metals, and alkaline earth metals.

[0078] Due to autoprotolytic processes, in addition to H2O molecules, oxonium ions (H3O) are also present in stoichiometrically equal proportions in the ultrapure water according to the general term. + -ions) and hydroxide ions (OH - -ions) are present.

[0079] The water according to the invention contains, in addition to the OH produced by autoprotolytic processes, the OH - -ions and H3O + -ions have an excess of OH - -ions. Therefore, the concentration of OH in the water according to the invention is - -ions higher than that at H3O + -ions. The concentration is so increased that a pH value of 7.5 to 9.5 is established.

[0080] It has been shown that it is particularly advantageous if the concentration of excess OH is low. - The concentration of -ions is adjusted so that the pH value is approximately between 8.5 and 9.5. A pH value of 9.2 is particularly preferred.

[0081] The pH value of the water according to the invention can be determined using conventional methods, for example, by means of a glass electrode and a reference electrode, such as a silver-silver chloride half-cell, as a single-rod measuring chain. Other suitable electrodes, such as a standard hydrogen electrode, can also be used as measuring and reference electrodes.

[0082] In the water according to the invention, in addition to the H2O molecules and their autoprotolytically formed oxonium and hydroxide ions, with the exception of the excess OH, there are - -ions contain practically no other components.

[0083] The ultrapure water can also have an electrical conductivity of no more than 0.056 µS / cm and a TOC content of no more than 0.05 mg / l. Due to the excess of OH, the water according to the invention itself then exhibits - -ions no longer detect this low conductivity.

[0084] The water according to the invention receives an excess of OH. - -ions according to a preferred embodiment by electrochemical modification.

[0085] The excess of OH - -ions can be generated, for example, by electrochemically modifying ultrapure water with H + or H3O + -ions are removed. This can be done, for example, by the method according to the invention, or by any other method in which there is an excess of OH. - The process, which generates positively charged hydrogen ions, is also suitable. For example, an electrochemical membrane process would be possible, in which positively charged hydrogen ions are generated. + or H3O + -ions are concentrated on one side of a membrane at a cathode, while simultaneously negatively charged OH groups are present. --ions are concentrated on the other side of the membrane at an anode. The cations are then removed with a rinsing solution. Alternatively, ultrapure water could be enriched with O2 gas, and the O2 molecules then electrochemically converted to OH. - -ions to reduce.

[0086] The electrochemical modification according to claim 3 can be achieved in particular by treating the ultrapure water with electrolysis and removing the hydrogen (H2) produced during electrolysis. The electrolysis comprises passing the water through an electrolysis cell, wherein the electrolysis cell has at least one cathode surface and at least one anode surface, the cathode surface being 10 times larger. 3 up to a factor of 10 7is larger than the anode area. The cathode and anode areas, respectively, are understood here to be the areas available as reaction surfaces for the electrolytic reaction.

[0087] In electrolysis, the ultrapure water is subjected to a voltage from a DC voltage source sufficient for electrochemical modification at the chosen distance via the electrodes, which are arranged at a specific distance from each other.

[0088] The removal of the hydrogen produced during electrolysis takes place either directly in the electrolysis cell or, preferably, after the electrolyzed water has passed through the electrolysis cell using known methods. For example, the resulting gaseous hydrogen can be removed by membrane degassing or vacuum degassing using a water jet pump. The hydrogen can also be removed by thermal or ultrasonic degassing. Ultrasonic degassing usually requires an additional process to achieve the most complete gas removal possible. Advantageously, degassing can be carried out over a large surface area, as this facilitates hydrogen removal.

[0089] Furthermore, cathodes with a significantly larger surface area compared to the anode should be used. The surface area here refers to the interface between the electrode and water where the electrolytic reaction can take place. A rough, granular surface offers more reaction area than a smooth, bare surface. The reaction area of ​​the cathode is approximately 10 times larger. 3 up to a factor of 10 7 The surface area of ​​the cathode is larger than that of the anode. This is achieved, for example, by a larger cathode compared to the anode, but also by a modified geometry, such as a folded surface, a perforated surface, or a grid. In particular, a large surface area can be achieved by increasing the roughness.

[0090] Stainless steel or niobium electrodes can be used. Iron, platinum, or platinized titanium electrodes are also suitable. Diamond electrodes are preferred. These are electrodes made of technical substrates such as niobium, tantalum, silicon, graphite, or conductive ceramics, coated with a conductive diamond layer. The diamond layer may be boron-doped. Diachem® electrodes from CONDIAS GmbH are examples of such electrodes.

[0091] The electrochemical modification of ultrapure water is preferably carried out using an electrolysis cell without a membrane or diaphragm. In electrolysis, a diaphragm or membrane is typically used between the two electrodes in the electrolysis solution when a reaction of the products formed at the two poles must be prevented. According to claim 4 of the invention, the ultrapure water can be electrochemically modified in an electrolysis cell without a membrane or diaphragm. The advantage here is that the membrane-free electrolysis cell does not require high pressures of the water to be electrolyzed in the electrode chambers, resulting in significantly reduced maintenance and wear.

[0092] The electrodes in the electrolysis cell can be arranged without a membrane or diaphragm at a distance of 1 to 4 mm. A voltage of 4.5 to 48 V is applied for the reaction. A higher voltage is required for a greater distance between the electrodes, and vice versa. The electrolysis of the ultrapure water according to the invention is carried out with a low energy input. In conventional processes, voltages of 50 to 100 V are common, for example.

[0093] In contrast to conventional electrochemically modified water, which is also referred to as "basic water", the water according to the invention contains, in addition to H2O molecules, H3O + -ions and OH - The water contains virtually no other ions, molecules, or inorganic components, even in excess concentrations of these ions. Unlike conventional ultrapure water, it is characterized by a higher pH value, ranging from 7.5 to 9.5, preferably 9.2.

[0094] Surprisingly, it has been found that the water according to the invention is exceptionally well suited for producing highly purified solutions of chloride salts. Furthermore, it is very well suited for producing disinfectants based on hypochlorous acid. These disinfectants are superior to those of the prior art. They are characterized, particularly due to their pH value, by high long-term stability and shelf life. Simultaneously and surprisingly, they exhibit a high proportion of undissociated hypochlorous acid in contact with surfaces as well as with human or animal skin. This high proportion of undissociated hypochlorous acid is crucial for the disinfectant effect of the agents. As described above, the hypochlorite anion has only reduced efficacy due to its negative charge and the hydration shell it forms in aqueous solution.In contrast, undissociated hypochlorous acid is able to adhere well to both surfaces to be disinfected and microorganisms to be oxidized due to the lack of an electrical charge.

[0095] Furthermore, the disinfectant produced with the water according to the invention is characterized by a high long-lasting effect; that is, even after several hours, a reduced bacterial count, measured in CFU, can still be observed on a surface treated with this disinfectant. This long-lasting effect has the advantage that surfaces do not need to be re-disinfected as often as would be the case with conventional disinfectants.

[0096] According to the present invention, an ultra-pure, electrochemically modified water according to the invention can be produced by a method as follows.

[0097] For example, ultrapure, electrochemically modified water (URW) can be used as the starting material for the ultrapure, electrochemically modified water. This URW has an electrical conductivity of at most 0.1 µS / cm, preferably 0.06 µS / cm, and a TOC content of at most 0.5 mg / l, preferably at most 0.05 mg / l. URW with this specification can be obtained, for example, from Sigma-Aldrich or Merck. In a first step (1), this URW is degassed. This can be done by any suitable method, for example, by vacuum degassing using a water jet pump, or by membrane degassing, thermal degassing, or ultrasonic degassing. In the case of ultrasonic degassing, a further process usually needs to be added to achieve the most complete removal of the gases possible. Degassing is advantageously carried out on an enlarged surface area. This facilitates the removal of the gases from the URW by increasing the reaction surface area.

[0098] In a further step (2), the degassed URW is treated in a flow-through electrolysis cell without a membrane or diaphragm. Prior art electrolysis involves applying a voltage to at least two electrodes, an anode and a cathode. Between these electrodes, the applied voltage causes direct current to pass through an electrolyte. In the present process, the degassed URW is used instead of an electrolyte.

[0099] In electrolysis, various parameters can be selected, some independently and some interdependently. Overall, however, it is necessary to coordinate these parameters. These include, among others, the volume and geometry of the electrolysis cell, the flow rate of the liquid flowing through the cell, the geometry of the electrodes, the material or coating of the electrodes, the number and polarity of the electrodes, the distance between the electrodes and between the electrodes and the cell, the magnitude of the applied voltage, and the distance between the electrodes and between the electrodes and the cell. Table 2 change Impact on the reaction Increase in current Increased electrolysis rate Increased voltage Increased current intensity and therefore increased electrolysis rate Increase in the concentration of ions in the electrolyte Increased current intensity and therefore increased electrolysis rate Enlargement of the electrode surfaces Increased current intensity and therefore increased electrolysis rate Reduction of the distance between the electrodes Increased current intensity and therefore increased electrolysis rate Replacement of a metal electrode with an inert electrode Electrode material is no longer oxidized / detached

[0100] For example, rod-shaped electrolysis cells can be used, the anode of which comprises a hollow tube connected to the positive terminal of a voltage source, and the cathode of which also comprises a hollow tube, arranged coaxially outside the anode and connected to the negative terminal of a voltage source. Preferably, cylindrical electrolysis cells are used, in whose cavity disc-shaped or nearly disc-shaped electrolysis plates are arranged perpendicular to the axis. These have, for example, a volume of about 2 to 4 liters. However, larger cells can also be used if large quantities of ultrapure, electrochemically modified water are to be produced. For smaller quantities, such as on a laboratory scale, a smaller electrolysis cell with a volume of 0.5 to 2 liters can also be used.

[0101] The flow rate can be selected from approximately 10 l / h to 500 l / h, depending on the size of the cell and the generator. It is particularly dependent on the volume of the electrolysis cell. A cell with a volume of approximately 3 l can be operated with a flow rate of up to 500 l / h.

[0102] Electrolysis is preferably carried out using plate-shaped electrodes. Suitable anodes include, for example, plates made of (coated) titanium, graphite plates made of (high-strength carbon), or diamond-coated electrolysis plates. Titanium can be coated with iridium oxide or rhodium, for instance. The diamond coating must be boron-doped. The coating is applied to a technical substrate, such as fluorinated plastic. Suitable cathodes include plates made of stainless steel, niobium, graphite, or diamond-coated electrolysis plates. The size and shape of the electrolysis plates depend on the dimensions of the electrolysis cell. An electrolysis cell can contain several plates. The number of plates is determined by their size and shape, particularly their thickness, as well as by the size and shape of the electrolysis cell itself.At least three plates must be provided. If coated plates are used, double-sided coated plates can be used in the center, while single-sided coated plates can be used on each of the sides facing the cell, with the coating facing the nearest counter electrode. Electrolysis cells containing five to eleven plates are particularly suitable.

[0103] In the inventive method, it is advantageous if the cathode surface is larger than the anode surface. This can be achieved, on the one hand, by using a larger geometry or larger dimensions of the plates. On the other hand, the roughness of the respective electrode material or electrode coating can also result in a different surface area, even with the same dimensions. Expanded metal can also be applied to increase the surface area. The cathode area is thereby increased by at least a factor of 10.3 up to a factor of 10 7 larger than the anode area.

[0104] Furthermore, the applied voltage must be selected depending on the plate material or coating, the number of plates, the plate size, and the plate shape. The volume flow rate also influences the required voltage. A direct current voltage is required for the method according to the invention. For example, with a volume flow rate of 200 l / h, the degassed URW can be subjected to a voltage of 18 V.

[0105] The following table gives examples of the various possible parameters that can be selected for the electrolysis of ultrapure water in the flow-through electrolysis cell: Table 3 Electrolysis cell volume [ml] 500 1000 3000 - 3500 3500 - 5000 Volume flow rate [l / min] 0,3 0,6 2,5 4,0 Electrode material Diamond, boron-doped; Ir / Rh; Platinum-plated stainless steel, niobium, titanium Diamond, boron-doped; Ir / Rh; Platinum-plated stainless steel, niobium, titanium Diamond, boron-doped; platinum-plated stainless steel, niobium, titanium Diamond, boron-doped: platinum-plated stainless steel, niobium, titanium Electrode geometry 4 x 6 cm, thickness 1.5 mm 4 x 12 cm, thickness 1.5 mm Ø 12 cm, Thickness 2 mm Ø 12 cm, Thickness 2 mm Electrode spacing [mm] 1,5 1,5 2,5 2,5 Applied voltage [V] 7,5 -12 12 - 18 24 24 - 36 Current [Amp] 20 20 40 65 - 80 Technical current type DC DC DC DC

[0106] In a separate step (3), oxygen is added to the degassed and electrolyzed URW. This can be done, for example, by adding pure gaseous O2. A gas mixture containing O2, such as ambient air, can also be used. The electrolyzed water is then reacted with the O2 in the oxygen-enriched product. This is advantageously done on a surface, preferably a large surface, over which the product is passed. A filter, a silicate fiber membrane, or another solid with a porous surface can be used for this purpose.

[0107] It is important that the water obtained in this way is subsequently degassed again in step (4). The aforementioned methods can again be used for degassing. Degassing under vacuum is advantageous. This can also be carried out using a silicate fiber membrane.

[0108] Steps (2) and (3) of this process can now be repeated once or multiple times. For this purpose, the product obtained after step (3) is passed through a flow-through electrolysis cell again. It can be recycled and flow through the first electrolysis cell again, or a second or further electrolysis cell can be used, operated with the same or different parameters compared to the first cell. Step (3) follows each time. Finally, degassing is carried out according to step (4).

[0109] The parameters listed in Table 3 are chosen such that an ultra-pure, electrochemically modified water with a pH value of 7.5 to 9.5 is obtained after just one pass from step (1) to step (4).

[0110] Furthermore, ultrapure, electrochemically modified water can also be produced from drinking water or water of other qualities, such as spring water, groundwater, or surface water, as a starting material by means of the steps preceding the process according to the invention. If water of a quality other than ultrapure water is to be used as a starting material for the production of the water according to the invention, this starting material is pretreated accordingly. This is advantageous, for example, in water-scarce regions or in areas with difficult access to drinking water quality or due to other natural conditions. Surface water, which originates, for example, from reservoirs, lakes, or rivers, or also retained rainwater can be used as the starting material.

[0111] Depending on the TOC content of the starting material, it is first treated in an electrolytic cell. This step (a) is always necessary if the TOC content is greater than 0.5 mg / l. For example, the TOC content in clean spring water is typically around 1-2 mg / l, in slightly polluted rivers a TOC content of approximately 2-5 mg / l can be measured, and in heavily polluted waters, values ​​exceeding 100 mg / l TOC are found.

[0112] Any cell suitable for wastewater treatment or water disinfection can be used as an electrolytic cell. A flow-through electrolysis cell is preferred. For example, electrolysis cells with lead electrodes or boron-doped diamond electrodes can be used. These were developed by the Fraunhofer Institute for Surface Engineering and Thin Films (IST). Electrodes available from Condias GmbH or Samro Technik AG are preferred. It is particularly advantageous if the anode area is larger than the cathode area. For example, an anode area that is 10 times larger is suitable. 3 up to a factor of 10 7 is larger than the cathode area.

[0113] Another suitable method for reducing the TOC content in the starting material is UV treatment with UV-C radiation at a wavelength of approximately 254 to 185 nm. Ultrafiltration is also possible for moderate TOC contents in the starting material.

[0114] The corresponding process reduces the TOC content of the starting material to a value of no more than 0.5 mg / l. If the starting material has a TOC content of 0.5 mg / l or less, this process step can be omitted. Furthermore, it is preferred for the process if the TOC content of the starting material can be reduced to a value of 0.05 mg / l or less.

[0115] In a subsequent optional step (b), the starting material, whose TOC content has been reduced accordingly, is degassed using a suitable method. This can be done by vacuum degassing using a water jet pump, or by membrane degassing, thermal degassing, or ultrasonic degassing. With ultrasonic degassing, a further process is usually necessary to achieve the most complete removal of the gases possible. Degassing is advantageously carried out over an enlarged surface area.

[0116] In step (c), the water obtained after step (a) or (b), or the starting material with a TOC content of no more than 0.5 mg / l, is reduced in the content of inorganic components. This is done if the content of gases and / or heavy metals and / or nitrogen compounds exceeds 0.05 mg / l. Examples of gases include Cl₂, CO₂, and / or N₂. Heavy metals include antimony, arsenic, lead, cadmium, chromium, nickel, mercury, selenium, iron, and / or manganese. The removal of these components is carried out, for example, by filtration through or adsorption onto activated carbon, filtration through graphene oxide, reduced graphene oxide, or graphite, or by another suitable method. This reduces the content of the aforementioned substances to a value of no more than 0.05 mg / l.

[0117] If the water or starting material obtained after step (a), (b), or (c) already has a TOC content of no more than 0.5 mg / l and non-organic components of no more than 0.05 mg / l and a conductivity of more than 30 µS / cm, step (d) is carried out. In this step, the concentrations of alkaline earth metal ions and the anions carbonate, bicarbonate, sulfate, chloride, nitrite, nitrate, and / or phosphate in the water or starting material obtained after step (a), (b), or (c) are reduced using conventional mixed ion exchangers and / or separate cation and anion exchangers so that the conductivity is no more than 30 µS / cm. This corresponds to a hardness of 1° German hardness.

[0118] The conductivity can be measured using a conductivity probe, for example from HANNA Instruments. A strongly acidic cation exchanger is preferably combined with a weakly basic anion exchanger and a strongly basic anion exchanger.

[0119] Subsequently, or if the starting material already has a conductivity of no more than 30 µS / cm, a TOC content of no more than 0.5 mg / l, and non-organic components of no more than 0.05 mg / l, the ion content, especially sodium and chloride ions, is further reduced in step (e) by means of reverse osmosis. Due to the reduction of impurities in the water already achieved in steps (a), (b), (c), and / or (d), or due to the high purity of the starting material, the osmotic pressure is already low, and reverse osmosis can be carried out with low energy consumption.

[0120] In a subsequent step (f) the content of ions or residual ions of alkali, alkaline earth, metal, halide, nitrate, nitrite is further reduced by electrodeionization.

[0121] The water obtained after step (f) has a TOC content of at most 0.5 mg / l and a conductivity of at most 0.1 µS / cm. The process according to the invention can now be carried out with this water, including steps (1), (2), (3) and (4).

[0122] If surface water and / or process water is used as the starting material, it is advantageous to pre-separate coarser and finer particles from the starting material. Coarser particles have an average particle diameter of more than approximately 100 µm. They are separated by coarse filtration or another suitable method. The finer particles, which may be present depending on the starting material, have an average particle diameter of approximately 100 µm to 5 µm. They are preferably removed by fine filtration or another suitable method. Alternatively, separation using a hydrocyclone can be performed instead of coarse and fine filtration.

[0123] The ultrapure, electrochemically modified water according to the invention is used, among other things, in a process for producing a high-purity chloride salt solution. In this process, one or more salts of hydrochloric acid with a purity of at least 99.0% are dissolved in the water according to the invention. Salts of hydrochloric acid with a purity of at least 99.5% are particularly preferably dissolved in the water according to the invention.

[0124] A concentrated solution containing at least 20% by weight of chloride salt is prepared. A brine solution can be produced in which the chloride salt is present until saturation. With multiple chloride salts, the maximum possible saturation concentration may differ and be higher than with a single salt.

[0125] The solubility of a substance can be expressed in different ways. On the one hand, solubility, particularly with regard to saturation, is expressed as the mass of dissolved substance in a given volume of solvent. The resulting solubility in [g / l] is, for example, listed in pharmacopoeias. On the other hand, in a different context, solubility is considered as the mass fraction, which is the ratio of the mass of dissolved substance to the total mass of the resulting solution, composed of the substance and solvent. Here, solubility is expressed as a mass fraction in wt.%, which represents a measure of the mass of dissolved substance in the total mass of solution.

[0126] The salts of hydrochloric acid that can be used include sodium chloride, potassium chloride, magnesium chloride, and / or calcium chloride. A mixture of different chloride salts can also be used. The purity of the chloride salts used is at least 99.0%. This corresponds, for example, to the purity class "purissimum" according to various pharmacopoeias, such as the European Pharmacopoeia (Ph. Eur.), the British Pharmacopoeia (BP), the Japanese Pharmacopoeia (JP), or the United States Pharmacopeia (USP). Particularly suitable examples include NaCl puriss. pa, NaCl optical grade 99.9%, or NaCl Suprapur®, 99.99%.

[0127] At a temperature of 20 °C, the saturation concentration for NaCl is 26.36 wt%. This corresponds to a solubility of 358 g of NaCl in one liter of water. Similarly, the maximum concentration at saturation is 25.76 wt% for KCl, 35.15 wt% for MgCl₂, and 45.53 wt% for CaCl₂.

[0128] The highly purified chloride salt solution can be used, in particular, in a process for producing a disinfectant solution. For this purpose, the chloride salt solution described above is diluted to a concentration of approximately 0.025 to 10 wt%.

[0129] Dilution is achieved with ultrapure water. This water is not electrochemically activated but is URW, as it can be produced using conventional ultrapure water systems. The URW can be produced, for example, by electrodeionization. Softened, demineralized water is used for electrodeionization. Softening and demineralization can be carried out using suitable methods, such as flow through polymeric anion and cation exchangers and reverse osmosis under pressure. The electrical conductivity of the URW used is at most 0.1 µS / cm at 20 °C, and the TOC content is at most 0.5 mg / l.

[0130] It is advantageous if the ultrapure water used to dilute the high-purity chloride salt solution is degassed using a suitable process before being used for dilution.

[0131] Furthermore, the high-purity chloride salt solution can also be diluted with URW to a concentration of approximately 1 wt% to approximately 6 wt%. This is particularly suitable when a disinfectant solution with a concentration of HClO (free chlorine or active chlorine) of approximately 600 mg / l to approximately 2500 mg / l is required. If a disinfectant solution with a concentration of 600 mg / l to 1200 mg / l HClO is needed, the chloride salt solution is preferably diluted to a concentration of 1 wt% to 3 wt%.

[0132] Following the dilution of the high-purity chloride salt solution, which is produced using the water according to the invention, this diluted solution is treated by electrolysis in a cyclic electrolysis cell.

[0133] This electrolysis process produces HClO (active chlorine), which has a disinfecting effect. Furthermore, Cl₂ (chlorine gas) is formed, which reacts with the water present to form HClO and H₂. + and Cl - further reactions. A particular advantage of this electrolysis process is that few interfering byproducts, such as NaOH, Cl, are produced. - , OCl3 - or OCl4 - be formed.

[0134] In the electrolysis process for producing a disinfectant solution, a cyclic electrolysis cell without a membrane or diaphragm is preferably used. Such a cell is characterized by lower maintenance requirements and a longer service life than a cell in which the cathode and anode compartments are separated by a membrane or diaphragm.

[0135] The cyclic electrolysis cell is a closed cell into which a dilute chloride solution is introduced via an inlet line. A voltage is then applied to the electrodes inside the cell—anode and cathode—which are immersed in the dilute solution. After a specific residence time, the electrolyzed dilute solution is discharged from the cyclic cell via an outlet line. It can then be collected in a storage container.

[0136] A cyclic electrolysis cell contains at least one anode and at least one cathode. It is advantageous if the combined anode area of ​​all anodes is larger than the combined cathode area of ​​all cathodes. In particular, an anode area that is 10 times larger is advantageous. 3 up to a factor of 10 7 is larger than the cathode area used.

[0137] During electrolysis, the parameters relating to the volume and geometry of the electrolysis cell, the residence time of the solution in the cell, the geometry of the electrodes, the material or coating of the electrodes, the number and polarity of the electrodes, the magnitude of the applied voltage, the type of current (direct current (DC)), and the distance between the electrodes and from the cell walls are precisely coordinated. The choice of parameters particularly influences the concentration of HClO resulting in the disinfection solution as well as the redox potential for OCl. - / Cl2. For example, the following parameters are suitable: Table 4 Electrolysis cell volume [ml] 500 1000 3000 - 3500 3500 - 5000 > 5000 Time spent [min] 0,45 1,0 1,0 2,0 2,0 Material electrodes Diamond, boron-doped; stainless steel, niobium Diamond, boron-doped; stainless steel, niobium Diamond, boron-doped; stainless steel, niobium Diamond, boron-doped; stainless steel, niobium Diamond, boron-doped; stainless steel, niobium Electrode geometry 4 x 6 cm, rod electrode Rod electrode Ø 12 cm; Thickness 1.5 - 2.0 mm Ø 12 cm; Thickness 1.5 - 2.0 mm 8 x 10 cm Electrode spacing [mm] 1,0 2,5 2,5 - 3,0 2,5 - 4,0 2,5 - 4,0 Applied voltage [V] 5,5 - 7,5 7,5 - 10 10 - 15 20 - 45 > 24 Current [Amp] < 40 < 40 40 - 65 65 -120 > 40 Technical current type DC DC DC DC DC

[0138] The parameters mentioned can be chosen in particular such that the disinfection solution has a redox potential for OCl after the corresponding residence time in the cell. - The ORP of the disinfection solution is typically between +700 and +950 mV. Advantageously, the parameters are chosen so that the disinfection solution exhibits an ORP of +800 to +900 mV, particularly +850 mV, after residence time in the cell.

[0139] Preferably, the aforementioned parameters are chosen such that the disinfection solution has a concentration of 600 to 5000 mg / l ClO₂. - -ions. In particular, disinfectant solutions containing a concentration of ClO are preferred. -The solution contains ions of 600 mg / l, 1200 mg / l, 1800 mg / l, or 2500 mg / l. Furthermore, the parameters can also be selected to produce a highly effective disinfectant solution with 4000 to 5000 mg / l OCl₂. - This is achieved, for example, by electrolysis of a high-purity chloride salt solution diluted to 5 wt% in an electrolysis cell with a volume of 1000 ml. A direct current voltage of 5 V is applied to stainless steel electrodes, increasing the cathode area by a factor of 10. 4 The electrode surface is larger than the anode surface. The electrodes are spaced 2 mm apart. A current of 25 amps flows, and the solution is treated in the electrolysis cell for 0.45 minutes. This yields, for example, a disinfectant solution with a concentration of 1200 mg / l ClO₂. - -ions and an oxidation potential of 800 mV. The present concentration of OCl -The concentration can be determined during the residence time by iodometric titration or iodometric back titration. The redox potential can be measured using known methods, for example, with a standard hydrogen electrode or a silver-silver chloride electrode.

[0140] By diluting the high-purity chloride salt solution to a concentration of 0.025 to 10 wt.% and treating this diluted solution with electrolysis, the solution is converted into a disinfectant solution.

[0141] In a particular embodiment of the method according to the invention, the disinfectant solution obtained after electrolysis in the cyclic electrolysis cell is degassed by a suitable method. Suitable methods include the previously described vacuum degassing using a water jet pump, membrane degassing, thermal degassing, or ultrasonic degassing. For example, degassing can take place over an enlarged surface area.

[0142] The described disinfectant solution is superior to previously known disinfectant solutions, particularly with regard to its long-term stability, but also with regard to its disinfecting oxidation potential and the reproducibility of its disinfection effect. Even after prolonged storage, it still exhibits an oxidation potential of +700 to +950 mV. In any case, after prolonged storage, it still exhibits an oxidation potential of +700 to +850 mV.

[0143] In the inventive process for producing a disinfectant solution, an electrolysis cell without a membrane and / or diaphragm is used. These electrolysis cells do not have an anode compartment and a cathode compartment separated from each other by a membrane or diaphragm. In the inventive process, a single cell is used in which the anode and cathode are in contact with the solution to be electrolyzed in a single chamber. This has the advantage that the process does not require high pressures. Due to these pressures, which were previously required in membrane cell or diaphragm electrolysis, the existing process was expensive and maintenance-intensive. Furthermore, membrane cell or diaphragm electrolysis produces two different solutions in the separate chambers, with a very low pH value on the anode side and a very high pH value on the cathode side.This anodic solution is highly corrosive and loses its ORP and OCl concentration within a short time. - The effectiveness decreases. Due to their corrosiveness and instability, the solutions obtained are only suitable for disinfection to a limited extent, as consistent and reliable disinfecting efficacy is required to achieve verifiable results.

[0144] Surprisingly, despite their high storage and long-term stability, the disinfection solutions obtained using the inventive method are able to exert an optimal disinfecting effect upon contact with the surface to be disinfected, or with the hands or skin. This is achieved through an optimal pH range for microbiological efficacy.

[0145] The disinfectant solution obtained from treatment in the cyclic electrolysis cell can then be further processed by passing it at least once, preferably multiple times, through a flow-through electrolysis cell. Preferably, the disinfectant solution is treated in the cell with the following parameters: Table 5 Electrolysis cell volume [ml] 1000 Volume flow rate [l / min] 5 Electrode material Niobium or Ir / Rh, Niobium / Stainless Steel Electrode geometry around Electrode spacing < 2.5mm Applied voltage [V] from 24 Current [Amp] up to 40 Technical current type DC

[0146] In this process, the chloride salt still dissolved in the disinfectant solution is further converted. During this preparation, the disinfectant solution can be diluted with URW to a desired concentration of 500 mg / l up to 2500 mg / l. For example, a concentration of 600 mg / l, 1200 mg / l, 1800 mg / l, or 2500 mg / l OCl₂ can be achieved. - They should be used in accordance with the specifications from microbiology.

[0147] The disinfectant solution produced according to the described procedure, or the disinfectant solution diluted by the preparation, can advantageously be supplemented with sodium bicarbonate in a concentration of 0.1 g / l to 0.5 g / l.

[0148] Furthermore, the disinfectant solution, or the disinfectant solution diluted by reprocessing, can be additionally mixed with benzalkonium chloride and / or other quaternary ammonium compounds. Benzalkonium chloride includes all those alkylbenzyldimethylammonium chlorides whose alkyl groups are from C8 to C6. 18-chains. Furthermore, other quaternary ammonium compounds can also be used. For example, one or more substances from the group containing cetylalkonium chloride, cetylpyridinium chloride, cetyltrimethylammonium bromide, denatonium benzoate, dimethyldioctadecylammonium chloride, tetrabutylammonium hydroxide (TBAH), paraquat, polyquaternium-7, tetradecyltrimethylammonium oxalate, 3-chloro-2-hydroxypropyl-N,N,N-trimethylammonium chloride, and benzyltrimethylammonium chloride are suitable for addition to the disinfectant solution.

[0149] This additive can further enhance the disinfecting effect of the solution. It also improves the surface-active properties of the disinfectant solution. A disinfectant solution containing benzalkonium chloride and / or other quaternary ammonium compounds exhibits improved wetting of the treated surfaces. This is advantageous for the disinfection effect.

[0150] The benzalkonium chlorides are used here in a concentration of approximately 0.1 g / l to approximately 2.5 g / l. A concentration of 0.5 g / l to 1.5 g / l is preferred. The other quaternary ammonium compounds are preferably used in concentrations of 0.1 g / l to 1 g / l, sometimes up to 10 g / l.

[0151] The disinfectant solution is particularly suitable for disinfection using nebulizers, sprayers, or atomizers. This allows for hand disinfection, surface disinfection, disinfection in veterinary medicine, aerosol-based surface disinfection, odor neutralization, and room air sanitization. For aerosol-based surface disinfection or room air sanitization, the disinfectant solution is sprayed into a fine mist using a nebulizer or spray nozzle. A fan or ventilation system can be used to improve distribution. Due to its non-corrosive properties, the disinfectant solution does not attack nebulization or distribution devices. Because of its low content of HOCl and NaCl, the disinfectant solutions according to the invention are particularly suitable for aerosol disinfection of surfaces, but also for humidification, e.g., for room air sanitization or odor neutralization.

[0152] The disinfectant solution is preferably used for surface disinfection, room air hygiene and odor neutralization.

[0153] The described process for producing ultrapure, electrochemically modified water can be used in combination with the described process for producing a high-purity chloride salt solution and with the described process for producing a disinfection solution in the immediate vicinity of the place of use.

[0154] This process utilizes locally available water and electricity. For example, the setup described below for producing a disinfectant solution can be connected to the locally available water supply, particularly the drinking water supply, and electricity supply.

[0155] The arrangement includes various electrolysis cells as well as devices for ion exchange, reverse osmosis and electrodeionization of the water.

[0156] The water taken on-site first flows through a flow-through electrolysis cell, which reduces the TOC content to a maximum of 0.5 mg / l. The water is then softened using ion exchangers and desalinated in a reverse osmosis process followed by electrodeionization. The resulting ultrapure water (URW) is then degassed using a suitable method. By flowing through a second flow-through electrolysis cell, the degassed URW undergoes further electrolysis. The individual parameters of this flow-through electrolysis cell are selected according to the inventive process. After the addition of ambient air or O2, the resulting water is passed over an enlarged surface area and then degassed again. A reservoir contains a high-purity chloride salt. This is added to the ultrapure, electrochemically modified water, resulting in a high-purity solution.This solution is diluted with URW, which is optionally degassed, to a concentration of approximately 1 to 5 wt% and then treated in a cyclic electrolysis cell for a specific residence time. The individual parameters of this cyclic electrolysis cell are selected according to the inventive method. Subsequently, the disinfection solution is circulated through a flow-through electrolysis cell and diluted with URW to the desired concentration. Once the disinfection solution has reached the desired concentration, it is transferred to a storage chamber. The disinfection solution can then be withdrawn from this storage chamber.

[0157] It is particularly advantageous that the disinfection solution provides a consistent, reproducible, and verifiable disinfection result. In particular, the disinfection solution according to the invention has a low chloride salt content. It is therefore especially suitable for use on surfaces and / or equipment that are susceptible to corrosion.

[0158] Furthermore, the transport of disinfectant solution is avoided, as water and electricity are drawn on-site. Only the chloride salt needs to be transported. Alternatively, the highly purified chloride salt solution could be transported, and the production of the disinfectant solution would begin on-site using the cyclic electrolysis cell.

[0159] Due to the consistent, reproducible, and verifiable disinfection results, a low concentration of 600 to 2500 mg / l HClO or active chlorine can be used in the process according to the invention. The low concentrations of HClO result in skin-friendly disinfection.

[0160] Further features and advantages of the invention will become apparent from the following description of preferred embodiments, which do not represent a limitation of the scope of protection.

[0161] They show: Fig. 3: A piece of clay, overgrown with a conglomerate of fur and red algae; Fig. 4: The clay shard from Fig. 3 after removal from the water, after immersion in a disinfection solution according to the invention for 120 minutes, and after immersion in a disinfection solution according to the invention for 15 hours; Fig.5: A piece of clay, as well as aquarium accessories (air lift filter) immersed in disinfectant solution after 5 minutes, 1 hour, 12 hours, as well as the piece of clay after removal from the disinfectant solution after 12 hours and a rinse with water; Fig. 6: A whirlpool and its hose system, left before and right after a 20-hour treatment with the disinfection solution according to the invention; 1. Preparation of the disinfectant solution:

[0162] To produce the water according to the invention, 50 liters of drinking water are first passed through an electrolytic cell with a volume of 3 liters and five electrodes, wherein the anodes are diamond electrodes and the cathodes are stainless steel electrodes, at an applied voltage of 5 V and a flow rate of 5 liters / min. The water, thus freed from organic impurities, is degassed using a water jet pump. The treated water is then passed through a cylindrical container integrated into the pipe, filled with activated carbon as a fixed-bed absorber (activated carbon filter from Aquaplan). This removes non-organic components. The treated water is then passed through a mixed-bed ion exchanger from Aquaplan to remove any remaining foreign ions before subsequent reverse osmosis. After reverse osmosis, 30 liters of water are obtained, which are then passed through an electrodeionization system.This is followed by degassing using a water jet pump.

[0163] The ultrapure, degassed water is then passed through a flow-through electrolysis cell. In this cell, the electrodes are diamond-doped on the anode side and made of stainless steel on the cathode side. A voltage of 5 V is applied, and the flow rate is maintained at 2 l / min. Oxygen is then introduced via a valve in the piping system. The electrolyzed, oxygen-enriched water is passed over a silicate fiber membrane and subsequently degassed by membrane vacuum degassing.

[0164] 280 g / l of highly purified NaCl (Sigma-Aldrich, CAS 7647-14-5) are dissolved in the resulting water. This chloride salt solution is suitable for storage.

[0165] To prepare a disinfectant solution, 0.5 liters of the chloride salt solution is diluted with approximately 4 liters of ultrapure water. This approximately 3% solution is electrolyzed in a cyclic electrolysis cell with stainless steel niobium cathodes and boron-doped diamond anodes at a voltage of 5 V for at least 1 minute. The surface area of ​​the anodes is increased tenfold by the diamond coating. 4 larger than that of the cathodes. The geometry of the electrodes is adapted to the housing of the electrolysis cell. The distance between the electrodes is 1.5 mm. After 1 minute, enough chloride has been converted that the disinfection solution has a concentration of OCl₂. - -ions of 2000 mg / l and a redox potential of 800 mV. 2. Removal of algae growth on everyday objects:

[0166] To investigate the disinfectant properties and the effect against biofilms, a clay shard covered with algae is prepared according to Fig.3 immersed in this disinfectant solution.

[0167] After 120 minutes and again after 15 hours, the clay shard is removed from the solution and inspected. This reveals... Fig. 4, that the solution according to the invention is able to completely remove the biofilm on consumer goods. 3. Onset of effect:

[0168] To assess the effectiveness of the disinfection, a piece of clay covered in algae and other aquarium equipment (air-lift filter) are immersed in the disinfection solution. The items are then examined after 5 minutes, 1 hour, and 12 hours according to the instructions. Fig. Rated 5.

[0169] It can be seen that the effects begin to take effect after just 5 minutes. 4. Treatment of hose systems:

[0170] 20 liters of disinfectant solution are introduced into the hose system of a whirlpool. After a 12-hour dwell time, the treated hose system is examined.

[0171] This is shown in the illustrations according to Fig. 6. After 12 hours, the biomass in the tubing system can be removed with the disinfectant solution. The removed biomass corresponds to approximately 1.8 kg. The growth is visible on the two horizontal tubing lines running in the center of the image.

[0172] The illustrations in Fig. Figure 6 shows that the removal of algae and biofilms is also possible in closed hose systems. The marked hoses (arrow) are completely free of algae growth and biofilm after 12 hours.

[0173] Overall, experiments 1 to 4 show that the disinfection solution according to the invention exhibits very good efficacy even at a concentration of 2000 mg / l HOCl. The efficacy is approximately 80 times greater than that of a known sodium hypochlorite solution at the same concentration. QUOTES INCLUDED IN THE DESCRIPTION

[0000] This list of documents cited by the applicant was automatically generated and is included solely for the reader's convenience. The list is not part of the German patent or utility model application. The DPMA accepts no liability for any errors or omissions. Cited patent literature

[0000] DE 20 2018 102 846 U1

[0065] DE 10 2006 043 267 A1

[0066] WO 2007 / 093395 A2

[0067] EP 0 470 841 A2

[0068] EP 1 036 037 B1

[0069] Cited non-patent literature

[0000] ISO 3696:1987

[0015] DIN ISO 3696

[0076] DIN EN 13060

[0076]

Claims

[1] Ultrapure water with an electrical conductivity of less than 0.1 µS / cm, which is essentially free of organic components and gases, and in which OH is produced by autoprotolytic processes - -ions and H3O + -ions are formed characterized by that the ultrapure water contains an OH - -excess and has a pH value of 7.5 to 9.

5. [2] Ultrapure water according to claim 1, wherein the OH - -Excess is obtained through electrochemical modification. [3] Ultrapure water according to claim 2, wherein the electrochemical modification comprises electrolysis of the ultrapure water by passing it through an electrolysis cell and removing the hydrogen (H2) produced during electrolysis, wherein the electrolysis cell has at least one cathode surface and at least one anode surface, wherein the cathode surface is increased by a factor of 10 3 up to a factor of 10 7is larger than the anode area. [4] Ultrapure water according to claim 2 or 3, wherein the electrochemical modification is carried out with an electrolysis cell without a membrane or diaphragm and with an electrode spacing of 1 to 4 mm and with a voltage of 4.5 to 48 V.

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