NON-INTEGRATED SYSTEM THAT USES AN IONIC EXCHANGE RESIN REGENERATED BY AN ACID AT A POINT OF USE, ME

专利摘要:
acid regeneration of ion exchange resins for industrial applications methods and systems for acid regeneration of ion exchange resins are disclosed. acid resins designed for use in a variety of cleaning applications use an acidified, demineralized water source according to the invention. various methods using acidified demineralized water generated by acid-regenerating ion exchange resins are revealed, in order to beneficially reduce the appearance of stains, film formation and the accumulation of scale on the treated surfaces, reduce and / or eliminate the need as for polymers, threshold reagents and / or washing aids, and use the protons generated in the acidified aqueous effluent to trigger useful events in various cleaning applications.
公开号:BR112014013957B1
申请号:R112014013957-1
申请日:2012-12-12
公开日:2020-09-29
发明作者:Terrence P. Everson；Li Wen；Lylien Tan；Peter Voss；Mark Toetschinger
申请人:Ecolab Usa Inc；
IPC主号:

专利说明:

FIELD OF THE INVENTION
[001] The invention is related to methods and equipment for the acid regeneration of ion exchange resins for use in various industrial cleaning applications at a point of use. In particular, an acid-regenerated resin is designed for use in any cleaning application that uses a water source to provide an acidified demineralized water source that has a relatively lower total dissolved solids (TDS) content. Several methods of using acidified demineralized water generated by ion exchange resins capable of acid regeneration are also disclosed. In addition, the methods and equipment according to the invention are even more beneficial in reducing the appearance of stains and the formation of films on the treated surfaces, avoiding the accumulation of scale on the treated surfaces, reducing polymers and threshold reagents needed in a detergent source. , and uses the protons generated in the acidified aqueous effluent to trigger useful events in various cleaning applications, as disclosed herein. BACKGROUND OF THE INVENTION
[002] Various methods of water treatment to decrease water hardness are known and commercially used. Detergents and other cleaning agents often contain numerous components to improve the cleaning activity of the detergent, including, for example, components to react to the effects of water hardness. Hard water is known to reduce cleaning efficiency, both by forming films on surfaces and by reacting with detergent and other cleaning components, making them less functional in the cleaning process. Various methods for neutralizing and / or eliminating water hardness have been implemented by those usually skilled in the art, including, for example, adding chelating or sequestering agents to detergent compositions in sufficient quantities to treat the ions responsible for the hardness and / or the softening of a water source through ion exchange. Ion exchange can be used to exchange ions responsible for hardness; such as calcium and magnesium, in sodium water or other ions associated with a resin bed in a water softening unit.
[003] Various methods of ion exchange are known to those skilled in the art. In the most usual form, water is run through an ion exchange resin in order to make the resin contained in the demineralizing equipment, the calcium and magnesium ions responsible for the water hardness, adhere to the resin. However, when the resin becomes saturated, it is necessary to regenerate the resin using large amounts of sodium chloride dissolved in water. This regeneration process has numerous known disadvantages; that is, it requires the use of salty and chloride solutions from the addition of added sodium chloride, used for washing the resin. Therefore, when water softeners are regenerated, they produce a tailing stream that contains significant amounts of sodium, creating a load on the system, for example, in the sewer system, into which they are discarded. The generated waste presents a multitude of concerns regarding the reuse of water, including, for example, reuse applications such as use as drinking water and in agriculture. In addition, traditional water softeners add to the salt content in surface discharge water, which becomes an environmental issue in certain locations. These and other limitations of commercially available water softening methods are described in more detail in US Patent Application Serial No. 12/764, 621, entitled “Methods and Apparatus for Controlling Water Hardness”, the entire content of which is here incorporates by reference.
[004] Thus, it is an objective of the invention claimed to develop improved methods and modernized systems for the regeneration of ion exchange resins for use in various industrial and institutional applications.
[005] Another objective of the invention is to develop a system and methods for the use of ion exchange resins capable of acid regeneration for the pre-treatment of water for various institutional and industrial applications, resulting in reduced demand for polymeric reagents and reagents in minimal amounts in cleaning compositions (eg detergents).
[006] Another objective of the invention is to improve the washing of utensils and other cleaning results through the application of acidified demineralized water generated by ion exchange resins capable of acid regeneration at a point of use.
[007] Yet another objective of the invention is to develop methods to apply protons to a source of treated water in order to trigger events, such as the regeneration of resins, dispensing additional detergents and / or other cleaning aids, and the like .
[008] In addition, the invention presents methods and systems to reduce the accumulation of limestone, stains and / or film formation by treating a water source using an ion exchange resin capable of acid regeneration. BRIEF SUMMARY OF THE INVENTION
[009] In one aspect of the invention, a system employing an ion exchange resin regenerated by an acid comprises: an inlet for supplying a water source to a water treatment reservoir; a water treatment component housed in the water treatment reservoir, wherein said water treatment component is at least an ion exchange resin to produce a source of water treated by proton exchange in said dissolved cation resin, including the ions responsible for the hardness of the water and the total dissolved solids in the said water source, where the treated water source is a source of demineralized, acidified water, and of low total dissolved solids (TDS); an outlet fluidly connected to the water treatment reservoir; and a water distribution line in order to supply the source of treated water to a cleaning application and / or a storage tank.
[010] In another aspect of the invention, a method for the treatment of hard water employing an acid-regenerated ion exchange resin comprises: contacting a source of hard water with a water treatment composition in a service cycle, wherein the water treatment composition comprises at least one ion exchange resin, in which the ion exchange resin generates a source of water treated by proton exchange in said dissolved cations resin, including the ions responsible for the water hardness and the total solids dissolved in the said water source, where the treated water source becomes a source of demineralized, acidified water, with a low total dissolved solids (TDS) content, where the treated water source can be used for washing and / or rinse in a variety of cleaning applications; and regeneration of the ion exchange resin upon exhaustion using an acid regenerant.
[011] In yet another aspect of the invention, a method for using an acidified demineralized water source comprises: contacting an article or surface in need of cleaning with a treated water source, wherein said treated water source is a rigid water source water is demineralized, acidified water with a low total dissolved solids (TDS) content, generated by treating a source of hard water with at least one ion exchange resin, where the ion exchange resin generates a source of water treated by proton exchange in said resin of the dissolved cations, including ions responsible for the hardness of the water and total solids dissolved in the said water source, and in which said ion exchange resin is regenerated using an acid.
[012] Although multiple modalities are described, still other modalities of the present invention will be apparent to those skilled in the art from the detailed description presented below, which shows and describes illustrative modalities of the invention. Therefore, drawings and detailed description should be considered as illustrative and not restrictive in nature. BRIEF DESCRIPTION OF THE DRAWINGS
[013] Figures 1A-1B show a modality of equipment that can be adapted to a system for the use of an acid-regenerating ion exchange resin in various cleaning applications.
[014] Figure 2 shows a modality of the equipment that uses an acid regenerator to regenerate an ion exchange resin according to the invention.
[015] Figures 3A-3B show an embodiment of the invention using a layer of layered ion exchange resin (3A) and a layer of layered ion exchange resin (3B) for the treatment of a water source .
[016] Figure 4 shows an embodiment of an improved dishwashing system using acid regenerating ion exchange resin equipment to produce acidified water for use in a cleaning application.
[017] Figure 5 shows a modality of the invention of Figure 4 that still employs additional equipment for additional water treatment with acid-regenerating ion exchange resin.
[018] Figure 6 shows a diagram of the capacity of an acid-regenerating ion exchange resin versus the pH of the treated water according to an embodiment of the invention.
[019] Figure 7 shows a diagram of the capacity of an acid-regenerating ion exchange resin versus the water hardness of the treated water according to one embodiment of the invention.
[020] Figure 8 shows a diagram of the capacity of a layered weak acid ion exchange resin bed (single type of resin) versus a layered weak acid ion exchange resin bed and a resin bed ion exchange of strong acid in the treatment of water hardness.
[021] Figure 9 shows a diagram of the pH versus the capacity (gallons) of a bed of weak acid ion exchange resin (single type of resin) versus a bed of weak acid ion exchange resin and bed of resin ionic exchange of strong acid arranged in layers.
[022] Figures 10A-10B show diagrams of the pH achieved from the acidic resins resulting from regeneration using a strong acidic regenerant for one embodiment of the invention.
[023] Figure 11 shows a diagram of the hardness of the treated water after the regeneration of the resin employing representative acid regenerates, of Figures 10A-10B, according to an embodiment of the invention.
[024] Figure 12 shows a diagram of the pH of the resin employing various suitable acid regenerates, according to the modalities of the invention.
[025] Figure 13 shows a diagram of the hardness of the treated water after the regeneration of the resin using the different suitable acid regenerates of Figure 12, according to the modalities of the invention.
[026] Various modalities of the present invention will be described in detail, with reference to the drawings, where equal numerical references represent similar parts in the course of the different views. The reference to the various modalities does not limit the scope of the invention. The Figures shown here are not limitations on the various modalities according to the invention and are presented for exemplary illustration of the invention. DETAILED DESCRIPTION OF THE INVENTION
[027] The present disclosure refers to methods and systems for the use of ion exchange resins capable of acid regeneration at a point of use (ie, non-integrated systems) of water for pretreatment for various cleaning applications, including applications institutional and industrial. The methods and systems or equipment for obtaining and applying acidified demineralized water here have many advantages over conventional water softening systems and / or equipment designed to reduce water hardness. For example, the invention provides numerous unexpected benefits downstream, including, for example, improving the results of water quality and cleaning, reducing the consumption of detergents, other polymers and / or cleaning components in various cleaning applications, and preventing the accumulation of scale, stains and / or depositing of films on the treated surfaces. In addition, there are several advantages of methods, systems and equipment that use acid-demineralized water, generated at a point of use, according to the invention, in order to initiate downstream events in a cleaning application, including, for example, example, resin regeneration and / or dispensing additional cleaning components in a system.
[028] Modalities of this invention are not limited to particular methods, systems and equipment for obtaining acidified demineralized water at a point of use and application of acidified demineralized water to a particular cleaning application, which can vary and are understood by those usually versed in the technique. It is still to be understood that all the terminology used here is for the purpose of describing only particular modalities, and is not intended to be limiting in any way or scope. For example, as used in this specification and the appended claims, the singular forms "one", "one" and "o" may include plural references, unless the context clearly indicates otherwise. In addition, all units, prefixes and symbols can be denoted in their forms accepted in the International System of Units. The numerical ranges mentioned within the specifications are inclusive of the numbers that define the range and include each integer within the defined range. Definitions
[029] In order that the present invention can be more easily understood, certain terms can be defined first. Unless otherwise stated, all technical and scientific terms used herein have the same meaning as is normally understood by a person skilled in the art to which the modalities of the invention pertain. Many methods and materials similar, modified or equivalent to those described herein can be used in the practice of the modalities of the present invention without undue experimentation, the preferred materials and methods are described herein. In describing and claiming the modalities of the present invention, the terminology presented below will be used in accordance with the definitions presented below.
[030] The term “about”, as used herein, refers to the variation in numerical quantity that can occur, for example, through liquid handling procedures used for the manufacture of concentrates or solutions for use in real world; through involuntary error in these procedures; through differences in the manufacture, source, or purity of the ingredients used to produce the compositions or perform the methods; and the like. The term "about" also covers values that differ due to the different equilibrium conditions for a composition resulting from a particular initial mixture. Whether or not modified by the term "about", the claims include equivalents to quantities.
[031] As used herein, the terms "activator", "chelating agent" and "sequestering" refer to a compound that forms a complex (soluble or not) with the ions responsible for the hardness of the water (from the washing water , dirt and substrates being washed) in a specific molar relationship. Chelating agents that can form a water-soluble complex include sodium tripolyphosphate, EDTA, DTPA, NTA, citrate, and the like. Sequestering agents that can form an insoluble complex include sodium triphosphate, zeolite A, and the like. As used herein, the terms "activator", "chelating agent" and "sequester" are synonymous.
[032] As used herein, the term “an effective amount of a chelating agent (or activator / scavenger) is missing” refers to a composition, mixture or ingredients that contain very little of the chelating agent, activator or scavenger to influence measurable water hardness.
[033] The term “cleaning”, as used here, means to perform or help remove dirt, whiten, reduce the microbial population, or a combination of those mentioned.
[034] As used herein, the term "disinfectant" refers to an agent that kills all vegetative cells, including the most recognized pathogenic microorganisms, using the procedure described in AOAC. Use Dilution Methods, Official Methods of Analysis of the Association of Official Analytical Chemists, paragraph 955.14 and applicable sections, 15th Ed., 1990 (EPA Guideline 91-2). As used herein, the term "high level disinfection" or "high level disinfectant" refers to a compound or composition that kills substantially all organisms, except high levels of bacterial spores being carried out with a chemical germicide marketed as a sterilizing agent by the Food and Drug Administration. As used here, the term “intermediate level disinfection” or “intermediate level disinfectant” refers to a compound or composition that kills mycobacteria, most viruses and bacteria with a chemical germicide registered as tuberculocidal by the Environmental Protection Agency ( EPA). As used herein, the term "low level disinfection" or "low level disinfectant" refers to a compound or composition that kills some viruses and bacteria with a chemical germicide registered as a hospital level disinfectant by the EPA.
[035] As used herein, the phrase “food processing surface” refers to a surface of a tool, a machine, equipment, a building structure, or the like that is used as part of a processing, preparation, or food storage activity. Examples of food processing surfaces include surfaces from food processing or preparation equipment (for example, slicers, canners, or transportation equipment, including channels), from food processing materials (for example, utensils, plates, lava - crockery, and glassware), and of floors, walls or utensils of structures in which food processing takes place. Food processing surfaces are found and used in air circulation systems to prevent food deterioration, aseptic sanitizers for packaging, food cooling and cooling agents and sanitizers, utensil washing sanitizers, bleach and cleaning products. sanitizing, food packaging materials, cutting board additives, third sink sanitizers, beverage coolers and heaters, meat cooling or scald water, dish sanitizers, sanitizing gels, cooling towers, sprays for application in antimicrobial clothing for use in food processing, and lubricants for the preparation of low-water foods, oils, and rinse additives.
[036] As used herein, the phrase “food product” includes any food substance that may need treatment with an antimicrobial agent or composition that is edible and, with or without another preparation. Food products include meat (eg red meat and pork), seafood, poultry, produce (eg fruits and vegetables), eggs, live eggs, egg products, ready-to-eat foods, wheat, seeds , roots, tubers, leaves, stems, grains, flowers, buds, spices, or a combination of these. The term “product” refers to food products, such as fruits and vegetables and plants or materials derived from plants, which are generally sold raw and often unpackaged, and which can sometimes be eaten raw.
[037] As used herein, the phrase “health care surface” refers to the surface of an instrument, device, cart, cage, furniture, structure, building, or the like that is used as part of a health care activity. Examples of health surfaces include surfaces of medical or dental instruments, of medical or dental devices, of electronic equipment used to monitor the health of the patient, and of floors, walls, or accessories of structures where health care occurs. Health care surfaces are found in hospitals, operating theaters, wards, maternity wards, morgues, and clinical diagnostic rooms. These surfaces can be those typified as “hard surfaces” (such as walls, floors, potty, etc.) or textile suspensions, for example, mesh, fabric and non-woven surfaces (such as surgical clothes, curtains, bed sheets) , bandages, etc.) or patient care equipment (such as respirators, diagnostic equipment, shunts, body scopes, wheelchairs, beds, etc.) or equipment for surgical and diagnostic use. Health care surfaces include articles and surfaces used in the field of animal health.
[038] As used herein, the term "equipment" refers to the various medical or dental instruments or devices that can benefit from cleaning with a composition according to the present invention. As used here, the phrases "medical instrument", "dental instrument", "medical device", "dental device", "medical equipment", or "dental equipment" refer to instruments, devices, tools, instruments, equipment and equipment used in medicine or dentistry. Such instruments, devices and equipment can be cold sterilized, soaked or washed and then sterilized by heat or through any other cleaning benefit in a composition of the present invention. These various instruments, devices and equipment include, but are not limited to: diagnostic instruments, trays, pans, holders, shelves, forceps, scissors, pruning machines, saws (for example, bone saws and their blades), hemostats, knives, chisels, rongeurs, files, tweezers, drills, rasp drills, angle grinders, dispersers, circuit breakers, elevators, clamps, needle holders, conveyors, clips, clamps, gouges, curettes, retractors, straighteners, punches, extractors, spoons, keratomas, spatulas , expressors, trocars, dilators, cages, glassware, tubes, catheters, cannulas, plugs, stents, scopes (for example, endoscopes, stethoscopes and artoscopes) and related equipment, and the like, or combinations thereof.
[039] As used herein, the term “washing” refers to woven and non-woven textile articles. For example, washing may include, but is not limited to, clothing, bedding, towels and the like.
[040] As used herein, the term "microorganism" refers to any single-celled or alveolar organism (including colonial). Microorganisms include all prokaryotes. Microorganisms include bacteria (including cyanobacteria), spores, lichens, fungi, protozoa, viruses, viroids, viruses, phages, and some algae. As used here, the term “microbe” is synonymous with microorganism.
[041] As used herein, the term “sanitizer” refers to an agent that reduces the number of contaminating bacteria to safety levels, as assessed by public health requirements. In one embodiment, sanitizers for use in the present invention will provide at least a 99.999% reduction (5-log reduction). These reductions can be assessed using a procedure provided for in the Germicidal and Detergent Sanitizing Action of Disinfectants, Official Methods of Analysis of the Association of Official Analytical Chemists, paragraph 960.09 and applicable sections, Edition 15, 1990 (EPA Guideline 91-2). According to this reference, a sanitizer must provide a 99.999% reduction (reduction of the order of 5-log) within 30 seconds, at room temperature, 25 +/- 2 ° C, against various test organisms.
[042] For the purpose of this patent application, successful microbial reduction is achieved when microbial populations are reduced by at least about 50%, or by significantly more than is achieved by washing with water. Larger reductions in the microbial population provide greater levels of protection.
[043] The differentiation of “acidic” or “static” activity, definitions that describe the degree of effectiveness, and the official laboratory protocols for measuring this effectiveness are considerations for understanding the relevance of antimicrobial agents and compositions. Antimicrobial compositions can affect two types of damage to microbial cells. The first is a lethal and irreversible action, resulting in the destruction or complete incapacitation of microbial cells. The second type of cellular damage is reversible, such that, if the organism becomes free from agent, it can multiply again. The first is called a microbicide and the next is microbiostatic. A sanitizer and disinfectant are, by definition, agents that provide antimicrobial or microbiocidal activity. In contrast, a preservative is generally described as a composition inhibitory or microbiostatic.
[044] As used herein, "the hardness solubilized in water" or "water hardness" refers to the minerals responsible for the hardness dissolved in ionic form in an aqueous system or source; that is, Ca ++ and Mg ++. The hardness solubilized in water does not refer to the ions responsible for the hardness when they are in a precipitated state; that is, when the solubility limit of the various calcium and magnesium compounds in water is exceeded and these compounds precipitate as various salts such as, for example, calcium carbonate and magnesium carbonate.
[045] As used herein, the term “threshold agent” refers to a compound that inhibits in the solution the crystallization of ions responsible for the hardness of water, but which do not need to form a specific complex with the ion responsible for the hardness of the water. Water. This distinguishes a threshold agent from a chelating or sequestering agent. Threshold agents include a polyacrylate, a polymethacrylate, an olefin / maleic acid copolymer, and the like.
[046] As used here, the term “utensil” refers to items such as dishes and utensils used for cooking and eating, and other hard surfaces, such as showers, sinks, toilets, bathtubs, countertops, windows, mirrors, vehicles transport, and floors. Utensils are often composed of several types of plastics, including, but not limited to, polycarbonate (PC) polymers, acrylonitrile-butadiene-styrene (ABS) polymers and polysulfone (PS) polymers. Other representative plastics include polyethylene terephthalate (PET).
[047] As used herein, the term “washing of utensils” refers to the washing, cleaning or rinsing of utensils. Utensils also refer to items made of plastic.
[048] As used herein, the terms "water" or "water source" refer to any water source that can be used with the methods, systems and equipment of the present invention. The embodiments of the invention are particularly suitable for use with sources of hard water (i.e., not softened). Examples of water sources suitable for use in the present invention include, but are not limited to, water from a municipal water source, or a private water system, for example, a public water supply or source. The water can be piped water, water well, water supplied by a municipal water system, water supplied by a private water system, and / or water directly from the system or well. Water may also include water from a used water tank, such as a recycling tank used for the storage of recycled, reused water, a storage tank, or any combination thereof. In some embodiments, the water source is not industrial process water, for example, water produced from a bitumen recovery operation. In other modalities, the water source is not a wastewater stream.
[049] As used herein, the term "water-soluble" refers to a compound or composition that can be dissolved in water at a concentration of more than 1% by weight. As used herein, the term "slightly soluble" or "slightly soluble in water" refers to a compound or composition that can be dissolved in water only to a concentration of 0.1 to 1.0% by weight. As used herein, the term "substantially insoluble in water" or "slightly soluble in water" refers to a compound or composition that can be dissolved in water only to a concentration of less than 0.1% by weight. For example, magnesium oxide is considered insoluble, as it has a water solubility (% by weight) of about 0.00062 in cold water, and about 0.00860 in hot water. Other insoluble compounds for use with the methods of the present invention include, for example: magnesium hydroxide with a water solubility of 0.00090 in cold water and 0.00400 in hot water; aragonite with a water solubility of 0.00153 in cold water and 0.00190 in hot water; and calcite with a water solubility of 0.00140 in cold water and 0.00180 in hot water.
[050] The term "percentage by weight", "% p", "percentage by weight", and its variations, as used herein, refers to the concentration of a substance as the weight of that substance divided by the total weight of the composition and multiplied per 100. It is understood that, as used here, “percent”, “%”, and the like, are intended to be synonymous with “percentage by weight”, “% by weight”, etc. Modalities of the Invention
[051] According to a modality of the methods of the invention, the systems and equipment contribute to the use of ion exchange resins capable of acid regeneration for the pretreatment of water for cleaning applications. Preferably, resins that have a polymeric matrix with carboxylic acid functional groups are used to capture the ions responsible for the hardness of the water and after that the acids are used to regenerate the resin for reuse in the generation of an acidified demineralized water source for use in a cleaning application. Surprisingly, the present invention provides new uses for the various effluent waters of the methods, systems and equipment of the invention. In particular, although the effluent from the regeneration step is placed in a discharge stream and / or the effluent water from the service cycle is acidic demineralized water, it can be used for washing or rinsing in a variety of cleaning applications. Although an understanding of the mechanism is not necessary for the practice of the present invention and although the present invention is not limited to any particular mechanism of action, it is contemplated that in some embodiments the benefits provided under the invention result from the generation of protons from exchange of the ions responsible for the hardness of the water on the resin.
[052] In accordance with another embodiment of the invention, methods, systems and equipment provide new mechanisms for controlling water sources. Unlike monitoring and / or measuring the ions responsible for water hardness in a water source, the use of conventional pH measurements can be used to trigger various events in a cleaning application. For example, a pH measurement (this is caused by an increase in protons / water acidity) can be used to trigger the regeneration step of a water treatment component or equipment, and / or variation in the detergent consumption required to wash or rinse a surface in a specific cleaning application. Alternatively, the pH of the incoming hard water can be compared to acid-treated demineralized water, where the pH differential can be used to monitor a working system.
[053] The present invention overcomes the deficiencies of commercially available water softening methods, providing an improved method for the regeneration of a resin and providing cleaning benefits resulting from the treated effluent of a system, that is, the protons contributing to the effectiveness cleaning in various cleaning applications. In addition, the invention provides the unexpected benefits of requiring the use of reduced amounts of polymers, threshold agents / reagents and / or other components in detergent compositions. In another unexpected application, the invention helps to eliminate the introduction of chemicals in a cleaning application, such as acidic washing aids.
[054] One usually skilled in the art will realize the additional benefits, uses and / or applications based on the disclosure of the methods and systems of the present invention, disclosed herein. Such embodiments are incorporated within the scope of the present invention. Water Treatment Equipment and Systems
[055] In some embodiments of the present invention it relates to equipment and / or systems employing an acid-regenerated ion exchange resin. The equipment and / or systems are suitable for use in controlling the water hardness. In some respects, the equipment and / or systems of the present invention include a resin material substantially insoluble in water. Preferably, the equipment and / or systems of the present invention do not precipitate a substance out of the water (for example, a threshold agent). Without being limited to a particular theory of the invention, the equipment and / or systems result in the release of protons from the resin, in exchange for binding the ions responsible for the hardness of the water over the resin, inducing a change in pH (this ie, water softened by acid), that is, a reduction in pH as a result of the generation of protons by the resin. Most preferably, the equipment and / or systems do not increase the total dissolved solids (TDS) from the treated water source.
[056] In some respects, the equipment and / or systems of the present invention include a water treatment composition or a water preparation system (hereinafter the terms are used interchangeably). The water treatment composition can be in a variety of physical forms. In one embodiment, the water treatment composition comprises an ion exchange resin. Ion Exchange Resins
[057] The ion exchange resin according to the equipment and / or systems of the invention can be in a variety of physical forms, including, for example, a sheet, a granule, a membrane or the like. In some embodiments, the ion exchange resin is a substance substantially insoluble in water. In some embodiments, the ion exchange resin is an acid cation exchange resin. As described herein, a variety of resinous materials can be used with the equipment of the present invention to treat a water source by exchanging protons over ion exchange resins for dissolved cations including ions responsible for water hardness and solids total dissolved in the water source.
[058] In some embodiments, the resinous material includes an acid cation exchange resin. The acid cation exchange resin may include a weak acid cation exchange resin, a strong acid cation exchange resin, and / or their combinations (often referred to as layered resin systems or beds, which may further include systems or beds of mixed resins arranged in layers, as can be seen by those usually skilled in the art).
[059] In an ion exchange resin modality, it is a strong acid exchange resin having a polystyrene matrix and sulfonic acid functional group. In an additional embodiment, the ion exchange resin may have a polystyrene with the sulfonic acid functional group, polystyrene with a sulfonic acid functional group, and mixtures thereof.
[060] Weak acid cation exchange resins suitable for use in the present invention include, but are not limited to, an acrylic acid cross-linked with the carboxylic acid functional group, a methacrylic acid cross-linked with the carboxylic acid functional group, and mixtures thereof. In some embodiments, the resin polymers have additional copolymers added. Copolymers include, but are not limited to, butadiene, ethylene, propylene, acrylonitrile, styrene, vinylidene chloride, vinyl chloride, and derivatives and mixtures thereof.
[061] In a preferred embodiment, the ion exchange resin is a weak acid exchange resin having a polyacrylic copolymer matrix and a carboxylic acid functional group. Preferably, the ion exchange resin has a surface with functional groups comprising carboxylic acids. Alternatively, the ion exchange resin has a surface that comprises functional groups comprising sulfonic acids.
[062] In some embodiments, the resinous material is an acrylic acid polymer that provides a polyacrylate material with a molecular weight of about 150 to about 100,000 relative to the water source. In other embodiments, the resinous material provides a polyacrylate material with a relatively low molecular weight, such as a molecular weight of less than about 20,000, relative to the water source. Without being limited according to the invention, all of the molecular weight ranges cited are inclusive of the numbers that define the range and include each integer within the defined range.
[063] In some embodiments, the resin includes a weak acid cation exchange resin with H + ions attached to the active sites. In additional embodiments, the resin includes a weak acid cation exchange resin that has carboxylic acid functional groups attached to the active sites.
[064] Various weak acid cation exchange resins are commercially available, and include, but are not limited to: Amberlite ® IRC 76 (Dow Chemical Company); Dowex ® MAC-3 (Dow Chemical Company); and a variety of additional resins. Additional descriptions of materials and systems, including additional suitable commercially available resins are revealed in US Patent Application Serial No. 0 12/764, 621, entitled “Methods and Apparatus for Controlling Water Hardness”, the entire content of which is here expressly incorporated by reference.
[065] An alternative embodiment of the invention is the use of an anion exchange resin. Without wishing to be linked to a particular theory of the invention, the use of an anion exchange resin can provide benefits by obtaining an alkaline demineralized water source.
[066] As one skilled in the art will verify, resinous material can be supplied in any shape and size, including granules, sticks, discs or combinations of more than one shape. In some embodiments, the resin material is selected from the group consisting of a gel-like resin structure, a macroporous resin structure, and combinations thereof. Without wishing to be bound by any particular theory, it is believed that the size of the resin particles can affect the ability of the resinous material to control the hardness of the water. For example, in some embodiments, the resinous material can have a particle size of about 0.5 mm to about 1.6 mm. In other embodiments, the resinous material may have a particle size as large as 5.0 mm. The resinous material may also include a mixture of particle sizes, that is, a mixture of large and small particles.
[067] Without being limited according to the invention, all the ranges mentioned are inclusive of the numbers that define the range and include each integer within the defined range.
[068] Additional factors that are considered to have an effect on the ability of the resinous material to control water hardness include, but are not limited to, the particle size distribution, the amount of cross-links, and the polymers used . In some embodiments, the crosslinked polymer; for example, acrylic acid, is cross-linked from about 0.5% to about 25% cross-linked. In other embodiments, the polymer is less than about 8% cross-linked, less than about 4% cross-linked, or less than about 2% cross-linked. Without being limited according to the invention, all the ranges mentioned are inclusive of the numbers that define the range and include each integer contained in the defined range.
[069] In some embodiments, the resinous material's ability to control water hardness is impacted by the existence of a narrow particle size distribution, for example, a uniformity coefficient of 1.2 or less, or a wide one (Gaussian ) particle size distribution, for example, a uniformity coefficient of 1.5 to 1.9. Without being limited according to the invention, all the ranges mentioned are inclusive of the numbers that define the range and include each integer contained in the defined range.
[070] Furthermore, it is considered that the selectivity of the resin can be modified to adapt the resin to have an affinity for an ion over some other. For example, the amount of crosslinking and the types of polymers included in the resin are considered to have an impact on the selectivity of the resin. Selective affinity for specific ions with respect to other ions can be useful in situations where a high affinity for certain ions, for example, copper, can be harmful, for example, obstructing or poisoning the resin itself. The resinous material can bind cations through a variety of mechanisms including, but not limited to, ionic or electrostatic force. Acidic Regenerators
[071] Acid regenerators suitable for use in the regeneration of ion exchange resins according to the equipment and / or systems of the invention are necessary to remove the ions responsible for water hardness from the resins. A variety of acidic regenerants can be employed to provide protons to the resin in order to restore the ability to soften and acidify water in need of treatment, according to the invention. In one aspect, the regenerator is an acid. Examples of acids according to the invention include hydrochloric acid, sulfuric acid, phosphoric acid, nitric acid, citric acid, acetic acid, methanesulfonic acid and methylsulfonic acid. In some ways the acid regenerant is a strong acid. In other respects, the regenerating acid is a weak acid. In an additional aspect, the acid regenerate can be an inorganic and / or organic acid. In an additional aspect, the regenerator is an acid salt. Exemplary acid salts include urea sulfate and monosodium sulfuric acid. In a preferred aspect, the regenerator is urea sulfate.
[072] In one aspect, the acid regenerate is found in a storage reservoir in a concentrated form that is commercially available. Concentrates preferably have a pH less than 5, preferably less than about 2, preferably less than about 1, and more preferably less than about 0. Without being limited according to the invention, all pH ranges mentioned are inclusive of the numbers that define the range and include each integer within the defined range. For example, urea sulfate concentrate having a pH between about -3 and about 1 is used as a concentrated acid regenerate for the ion exchange resins of the invention.
[073] Preferably, the acid regenerate should be diluted before passing over the ion exchange resin. This allows the use of concentrated acid regenerates, which, among other benefits, reduces transport charges and costs. In one aspect, the dilution ratio of acid regenerate to the diluent (e.g., water) is from about 1: 1 to about 1:20, preferably from about 1: 2 to about 1:20. Without being limited according to the invention, all the ranges of dilutions mentioned are inclusive of the numbers that define the range and include each integer contained in the defined range.
[074] In one aspect, the acid regenerate is in contact with the resin for a period of time from a few minutes to about 90 minutes, preferably from about one minute to about 60 minutes, and more preferably about 5 minutes to about 30 minutes.
[075] In one aspect of the invention, the concentration of the acid regenerate used in the regeneration cycle will depend on the type of acid regenerate used. In some embodiments, the concentration of the acid used in a solution to provide the acid regenerant relative to the ion exchange resin is about 1% to about 20%, from about 2% to about 10%, or about from 5% to about 10% of acid access for regeneration. Without being limited according to the invention, all the ranges mentioned are inclusive of the numbers that define the range and include each integer contained in the defined range. In addition, the amount of hardness in the need to remove the ion exchange resin will influence the amount of acid regenerant used for the regeneration step of the invention. Exemplary Water Preparation Systems
[076] The equipment and / or systems of the present invention can be housed within a variety of water preparation systems, to provide the point of generation for the use of acidified water for cleaning applications. Equipment and / or systems can be adapted to a variety of cleaning systems. Cleaning systems may include, for example, dishwashing applications and any other cleaning system suitable for the use of a source of softened water by an acidic route, including those of the invention which have relatively lower levels of total dissolved solids (TDS) ). Such additional cleaning systems may include, for example, washing and / or sanitizing systems, laundry applications, difficult instrument and / or surface cleaning, container washing, on-site cleaning applications, and so on. In addition to the cleaning systems suitable for application of the modernized systems of the invention, any system that uses a source of softened water by acidulated route according to the invention is included in the context of the present invention. These may include, for example, vacuum cleaners, pumps to deliver the source of treated water and / or any other dilution system that is used to supply a chemical and / or a source of water to a system.
[077] An example of a water preparation system or equipment 20 for use in the present invention is shown in Figures 1A-1B; which may comprise, consist of and / or consist essentially of: an inlet 22 for supplying a source of water to a treatment reservoir 26; a treatment reservoir, including a water treatment composition 28 (e.g., ion exchange resin) and the source of water to be treated 29; an outlet 24 for supplying treated acid water 31 from the treatment reservoir 26; and a treated water distribution line 30 for incorporating treated acid water into a cleaning, storage (e.g., reservoir) and / or shipping application 32, 34, 36, respectively.
[078] According to the various methods of the present invention, the water source 29 passes over the ion exchange resin 28, and the cations responsible for the hardness of the water source 29 (for example, calcium and magnesium ions) attach to the ion exchange resin 28, displacing protons in the treated water source creating softened water by acidulated 31.
[079] The equipment and / or systems of the present invention are designed for the regeneration of an acidic regenerant. When the ion exchange resin 28 reaches an exhaustion point (where the multivalent cations responsible for the hardness of the water source have been loaded into the resin such that the ion exchange becomes insufficient or impossible), an acidic regenerant is used to remove it from the resin. multivalent cations responsible for hardness are used for cationic exchange. An exemplary embodiment of such regeneration is shown in Figure 2, in which the water preparation system or equipment 20 further comprises, consists of and / or consists essentially of a storage enclosure or reservoir 42 containing an acid source 44 and a supply line 46 to supply acid source 44 to treatment reservoir 26. supply line 46 connects acid source 44 to a water source 47 to generate a more dilute acid source 48 to regenerate the exchange resin ionic 28. The diluted acid source 48 is then pumped into the treatment reservoir 26 to pass over the ion exchange resin 28 and cause the displacement of cations responsible for the water hardness with the protons from the diluted acid source, thus regenerating the exhausted ion exchange resin and generating a source of water discharge containing ions responsible for hardness 50 to be removed from the water preparation system or equipment 20.
[080] The regeneration of the ion exchange resin can be triggered by a wide variety of events, as set out in the description of the invention. In one embodiment, the concentrated acid source 44 from the storage reservoir 42 is combined with the water source due to the atmospheric pressure within the system triggered by an event. Triggering events, as referred to here for the regeneration of ion exchange resins, may include, for example, regeneration cycles programmed based on any set values (ie, threshold levels) of the following and / or targeted measurements and quantities of the following, including, for example, volume of water treated by an ion exchange resin, TDS levels in the treated water and / or source of water to be treated according to the invention, pH of the treated water, the number of cleaning events / cycles since the previous regeneration of the ion exchange resin, and the like.
[081] As shown in FIG. 2, the regeneration step moves liquids in the opposite direction through the inlets and outlets, 22 and 24, respectively, as described with reference to Figures 1A-1B in which the ion exchange resin 28 is used to remove the hardness of the water from to produce water softened by acidulation. This beneficially reduces the complexity of the water preparation system or equipment 20 in order to minimize the number of inlet / outlet and distribution lines. In an additional embodiment, the residual product from the regeneration step (i.e., water containing ions responsible for hardness 50) can be added to the water source 29 for subsequent treatment according to the methods of the invention.
[082] The equipment and / or systems of the present invention may also employ layered resin beds and / or layered mixed resin beds, as shown in Figures 3A-3B, respectively. In one embodiment of the invention, a layered resin bed includes more than one cation exchange resin in acid. For example, as shown in Figure 3A, the water preparation system or equipment 20 may comprise, consist of and / or consist essentially of: a first inlet 22 to provide a source of water to a first treatment reservoir 26 (which houses a first ion exchange resin 28); a first outlet 24 for providing treated acid water from the first treatment reservoir 26 to a second treatment reservoir 26; a second inlet 22 to supply the source of treated water to the second treatment reservoir 26 (which houses the second ion exchange resin 28); and a second outlet for supplying treated acid water to a treated water supply line 30. It is to be understood from the description of the invention that a plurality of resin beds can be used, for example, more than two treatment reservoirs 26 and more than two ion exchange resins 28. As defined with respect to Figure 1B, various embodiments of the invention can be employed to provide acid-treated treated water for cleaning, storage (eg reservoir) and / or transfer 32, 34, 36.
[083] In another embodiment, as shown in Figure 3B, the water preparation system or equipment 20 may include a layer of mixed resin arranged in layers which may comprise, consist of and / or consist essentially of: a first inlet 22 to provide a water source to a first treatment reservoir 26 (which houses a first ion exchange resin 28); a first outlet 24 for providing treated acidified water from the first treatment reservoir 26 to a second treatment reservoir 26; a second inlet 22 to provide the source of treated water to the second treatment reservoir 26 (housing the second ion exchange resin 28, where the second ion exchange resin is an ion exchange resin different from that housed in the first treatment reservoir or where the second ion exchange resin contains more than one type of ion exchange resin, one of which may be the same as the ion exchange resin housed in the first treatment reservoir); and a second outlet for supplying treated acid water to a treated water distribution line 30.
[084] The layered acidic cation exchange resins shown in Figures 3A-3B may include combinations of weak acid cation exchange resins, strong acid cation exchange resins, and / or combinations of both cation exchange resins in weak acid and cation exchange resins in strong acid.
[085] In some embodiments, the treated water distribution line 30 of a water preparation system or equipment 20 provides treated water 31 for a selected washing and / or cleaning system 32, as shown in Figure 4. As shown in the illustrated embodiment, the treated water supply line is connected to an appliance washing machine as the source of treated water for the described cleaning application. As established in accordance with the invention, the treated water supply line can be connected to a variety of additional cleaning applications, including, for example, dishwashing, including, for example, automatic utensil washing machine, a washing system vehicle washing, an instrument washing machine, an on-site cleaning system, a food processing site cleaning system, a bottle washer, etc., laundry applications, including, for example, automatic washing machines clothing and / or fabrics; industrial and domestic applications; and difficult surface cleaning applications including, for example, on-site cleaning systems (CIP), off-site cleaning systems (COP), automatic bottle washers, decontaminating washing machines, sterilizers, ultrafiltration and nanofiltration systems, filters internal air, etc.
[086] In other embodiments, the treated water supply line 30 provides acidified treated water 31 for additional water treatment equipment 38, as shown in Figure 5. Additional water treatment equipment 38 may include, for example , a carbon filter or a reverse osmosis filter. After that, the treated water can again be supplied as a source for a cleaning application, stored (eg, reservoir) and / or transported to an alternative point of use (eg, 32, 34, 36). The water that has been treated with the additional water treatment equipment 38 can then be connected by a second water supply line 40 to the cleaning application, stored (for example, in the reservoir) and / or transported to an alternative point of use (e.g. 32, 34, 36). One skilled in the art will find that one or more water treatment equipment can be used with the water preparation system or equipment 20 of the invention. In addition, the one or more water treatment equipment may be employed before or after the water source is treated according to the methods of the invention with the water preparation system or equipment 20. As such, the configuration of the system or water preparation equipment 20, as shown in Figure 5 which treats a water source with ion exchange resin 28 prior to the use of additional water treatment equipment 38 is a non-limiting embodiment of the invention. In yet another alternative embodiment, no additional water treatment equipment is used, with the water preparation system or equipment 20 of the invention.
[087] In some modalities, there is no filter between the outlet and the treated water distribution line. In other modalities, there is a filter between the outlet and the treated water distribution line. In addition, a flow control device 40, such as a valve or other mechanism for controlling the flow or pressure of the liquids arranged therein for transportation, can be provided in the treated water supply line 30 to control the flow of treated water 31 for the selected end-use device, for example, a washing system, or in another water treatment device 32, as shown in Figure 1B. In an alternative embodiment, the flow rate of both the water source and / or the treated water can be controlled by flow control devices. In some embodiments, the water treatment reservoir 26 is any reservoir capable of holding the water treatment composition (for example, ion exchange resin) 28. Reservoir 26 can be, for example, a tank, a cartridge, a filter bed of various shapes or sizes, or a column. In other embodiments, the resinous material can be bonded or bonded to a solid substrate. The substrate may include, but is not limited to, a block of the type of pass filter, or paper. The substrate can also be a particulate material that can be fluidized.
[088] The equipment and / or systems of the present invention can include one or more water treatment tanks 26. For example, two, three or four treatment tanks containing the same or different treatment compositions 28 can be used. The one or more treatment reservoirs can be provided in any arrangement, for example, they can be installed in series, or in parallel. In some other embodiments, the entire treatment reservoir can be removable and replaceable. In other embodiments, the treatment reservoir can be configured in such a way that the water treatment composition contained within the treatment reservoir is removable and replaceable.
[089] The treatment reservoir may include an inlet for the supply of water to the treatment reservoir and an outlet for the supply of treated water to a desired end-use location, for example, a washing device or other treatment device of water. In some embodiments, the inlet is located at the top of the reservoir, and the outlet is located at the bottom of the reservoir, as shown in Figure 3. In alternative modalities, the inlet is located at the bottom of the reservoir, and the outlet is located at the top of the reservoir. This allows water to flow through the water treatment composition contained within the treatment reservoir. In still other embodiments, the inlet and outlet can be located at the top of the reservoir, as shown in Figures 1-2. However, as can be seen by one usually skilled in the art, the distribution and / or creation of a treatment reservoir and / or the placement and orientation of the treatment reservoir within the water preparation system or equipment may vary and may be customized for a particular institutional or industrial application for use.
[090] In some embodiments, the treatment reservoir includes an agitated bed of the water treatment composition. Methods for agitating the composition include, for example, the flow of water through a column, by fluidization, mechanical agitation, air spray, educator flow, baffles, flow obstructions, static mixers, high flow backwash, recirculation, and combinations of those mentioned. The treatment reservoir can also include a head space above the composition contained therein, in order to contribute to a more fluidized bed. In some embodiments, the resinous material has a slightly higher density than the water density in order to maximize the fluidization and / or agitation of the resinous material.
[091] In some embodiments, the inlet may also include a pressurized spray nozzle or nozzle. The spray gun can supply water at an increased force to the treatment tank. This increase in pressure force can increase the agitation of the water treatment composition and can circulate the resin through the nozzle. In some embodiments, the spray nozzle delivers water to the treatment reservoir at a speed of about 1.5 m / minute (5 feet / minute) to 61 m / minute (200 feet / minute).
[092] As disclosed herein, the treatment reservoirs where the resins used according to the invention are located may vary in their configuration, orientation, shape and / or size, maintaining the functionality disclosed here for the treatment of water to provide a source of softened acidified water. For example, in one aspect of the invention, a more elongated or narrower housing can be employed for the treatment and / or resin reservoirs to maximize or increase the contact time of the water source with the resin systems. In another aspect of the invention, treatment tanks and / or resins can be shorter in length and / or wider so as to have a relatively shorter contact time between the water source and the resin system and / or to maximize flow and / or pressure drop within the system. According to one aspect of the invention, the shape and size of the housing for the treatment reservoirs and / or resins is adjustable and / or can be modified in order to balance the amount of time that a water source is in contact with cation exchange resin. As a person skilled in the art will appreciate based on the description of the invention, such contact time between the water source and the exchange resin will further impact the characteristics of the water source treated by acidulation, such as the acidity level of the water, the amount of TDS and / or the level of removal of the ions responsible for the hardness. Additional Functional Groups
[093] In some embodiments, an additional functional ingredient may be included in the water preparation systems, together with the water treatment composition (eg, ion exchange resin), housed within a treatment reservoir. The additional functional ingredients can be included in the treatment vessel and / or in the water treatment composition, or they can be supplied to the treatment vessel from an external source, for example, an additional functional ingredient inlet.
[094] Additional functional ingredients can be added directly to the water source to be treated before the water source enters the treatment equipment. Alternatively, the additional ingredient can be added to the treatment vessel before the water source is passed through the ion exchange resin.
[095] Additional functional ingredients suitable for use with the equipment and / or systems of the present invention include any materials that confer beneficial properties to the water treatment methods, the source of water to be treated, or any combination thereof. Examples of suitable additional functional ingredients include surfactants, preferably surfactants that have wetting properties (for example, washing additives in order to increase film formation), sanitizing agents and / or sterilizing agents (for example, providing sanitizing wash), acid detergents, enzymatic detergents, and the like. Methods of Treatment of a Water Source according to the Invention
[096] In some respects, the present invention provides methods for controlling water hardness and the production of an acidified demineralized water source. An acidified demineralized water with a hardness of less than about 2 grains and having a pH of less than about 7, more preferably less than about 6, is produced according to the methods of the invention. After that, acidified demineralized water can be used for a variety of cleaning applications, either at a point of use or stored for such use at a later time and / or point of use.
[097] Methods aimed at controlling water hardness are also understood to include methods for reducing scale, accumulations and / or dirt on treated surfaces where acidified demineralized water according to the invention is applied. In addition, the methods of the present invention are further understood to include protecting equipment, for example, industrial equipment, from the same accumulation of scale and / or dirt and providing increased cleaning efficiency through the application of acidified demineralized water to a surface in need for treatment. Each of the same methods is effective in reducing the use of conventional detergent compositions as a result of acidified demineralized water; and / or reducing the need for specific chemicals, for example, those containing threshold agents, chelating agents, or sequestrants, or phosphorus, in cleaning processes practiced later in the circuit.
[098] The methods, as described herein, may include contacting a water treatment composition (for example, resin material regenerated by acidulation) with a water source, i.e., a hard water source. In some embodiments, the water treatment composition is contained in a treatment reservoir and / or water preparation system. The contact step may include, but is not limited to, running the water source over or through the treatment composition (for example, an ion exchange resin). How an expert in the art will assess the contact time for the water source is dependent on a variety of factors, including, for example, the pH of the water source, the degree of hardness of the water source, and the temperature of the source of water.
[099] A water source can be applied (that is, the water source in contact with the resin) at a variety of flow rates, as the one usually versed in the technique can apply without undue experimentation. For example, in preferred embodiments, the flow through the systems of this invention is from about 0.5 to about 50 gallons per minute. In other embodiments the flow rate is less than about 8 liters per minute, less than about 40 gallons per minute, less than about 100 gallons per minute, less than about 200 gallons per minute, or between about 100 at about 1500 gallons per minute, from about 160 to about 1400 gallons per minute, or about 400 to about 1200 gallons per minute. For another example, in some embodiments, the equipment of the present invention has a flow rate of about less than about 1 cubic feet per minute, less than about 5 to about 200 cubic feet per minute, at about 20 to about 175 cubic feet per minute, or about 50 to about 150 cubic feet per minute. Without being limited according to the invention, all the flow ranges mentioned are inclusive of the numbers that define the range and include each integer within the defined range.
[0100] For example, additional, a conventional ion exchange device, is designed for a flow rate of about 0.3 to about 3.0 feet per minute of water speed. This flow rate is important to allow time for the diffusion of ions to the resin surface from the water for the ion exchange process to occur. Without being limited in accordance with the invention, all flow rate ranges mentioned here are luxury ranges cited are inclusive of the numbers that define the range and include each integer within the defined range.
[0101] Optionally, in some modalities, the method includes heating the water source, before the contact stage of the water treatment composition (for example, resin). Any means of heating the water source can be used with the methods and equipment of the present invention. In some embodiments, the water is heated to a temperature of about 30 ° C to about 100 ° C. All quoted temperature ranges are inclusive of the numbers that define the range and include each integer within the defined range.
[0102] In some aspects, the water treatment according to the invention provides a source of cold hard water to a water preparation system. After contacting the water source with the water treatment (eg resin) and heating composition, a treated water softened by acidulation is obtained and can be applied to the various applications of use disclosed here. Although not intended to be linked to any particular theory of the invention, protons from the resin (for example, H + from the carboxylic acid group in the weak acid ion exchange resin) are exchanged for the ions responsible for the water hardness of the water source, so as to provide acidified treated demineralized water.
[0103] Preferably, the control of the water hardness and the production of an acidified demineralized water source according to the invention results in a source of treated water with a pH below about 7, more preferably below about 6 Without being limited according to the invention, all of the pH ranges mentioned are inclusive of the numbers that define the range and include each integer within the defined range.
[0104] The treated water source preferably has a water hardness of less than about 3 grains, more preferably less than about 2 grains, more preferably less than about 1 grain, and even more preferably about 0 grain. Without being limited according to the invention, all the water hardness ranges mentioned are inclusive of the numbers that define the range and include each integer within the defined range.
[0105] According to the methods of the invention, the resin of the water treatment composition can be brought into contact with the water source to an exhaustion point, that is, loaded with a plurality of multivalent cations responsible for the hardness as a result of having a sufficient amount of the water source running over it. In some embodiments, the plurality of multivalent cations includes, but is not limited to, the calcium and magnesium present in the water source. Without wishing to be bound by any particular theory, it is considered that as water flows over the resin, the calcium and magnesium ions in the water will adhere to the resin, displacing protons into the treated water source, creating water acidified demineralized.
[0106] When the resin is exhausted, for example, it can no longer exchange protons with the ions responsible for the water hardness of the water source, the resin is regenerated according to the methods disclosed here. According to the invention, the ion exchange resin is regenerated with an acid, that is, an acid regenerant. According to the invention, the acid regenerant supplies protons to the resin in order to restore the ability to soften and acidify the water in need of treatment according to the invention. In one aspect, the acid regenerant is a strong mineral acid or an acidic salt. A preferred embodiment for the regeneration of the ion exchange resin uses urea sulfate as an acid regenerator.
[0107] The contact of the spent resin with the acid regenerant can be from a few minutes to about 90 minutes, preferably from about one minute to about 60 minutes, and more preferably from about 5 minutes to about 30 minutes. Without being limited according to the invention, all ranges are inclusive of the numbers that define the range and include each integer within the defined range.
[0108] According to the methods of the invention, the effluent water from the regeneration step can be eliminated from a waste stream. However, afterwards, the effluent water (for example, treated water) in the normal duty cycle is again water softened by acidulated process and can be used according to the various methods described here.
[0109] The regeneration of resins according to the invention can occur based on measurements obtained from the equipment and / or systems of the invention. In an alternative embodiment, the regeneration of the resins according to the invention can occur based on the lapse of a measured amount of time and / or the volume of treated water. Methods to trigger events using acidified demineralized water
[0110] The methods, equipment and / or systems of the present invention can be used for a variety of purposes. For example, the generation of acidified demineralized water according to the invention can be used to trigger different events in a water preparation system or other equipment or system. In particular, the protons generated from the ion exchange of the ions responsible for the hardness in the resin can be monitored or measured in order to trigger different events in the water preparation system, other equipment and / or systems according to the invention.
[0111] The measurements and / or monitoring according to the invention are different from the various commercial sensors for detecting changes and / or measuring the hardness of water in a system. For example, US Patent No. 7,651,663, entitled “Appliance Using a Water Hardness Sensor System and Method of Operating the Same”, hereby incorporated by reference in its entirety, measures the hardness of water according to the present amount of ions responsible for hardness (eg Ca2 +, Mg2 +) in a water source. According to the invention, the methods, equipment and / or systems do not measure the hardness of the water. In contrast to these types of calorimetric or fluorescent tests for measuring ion concentrations such as calcium and magnesium, the present invention measures the output and / or effluents from a water treatment system by measuring the proton released from the ion exchange resin.
[0112] In some aspects, the control or measurement of protons is achieved by measuring the production from the water preparation system or other equipment or systems of the invention. Sensors can be used to measure pH as an example of a suitable measuring device. According to additional modalities, the control or measuring device to measure the pH can be used through the use of electrodes, reference electrodes and / or solid state devices to detect the pH. For example, a pH measurement circuit can be employed, such as a pH sensor, including a measurement electrode, a reference electrode and a sensor, a preamplifier and an analyzer or transmitter. Each of these are examples of suitable measuring devices according to the invention.
[0113] In additional aspects, the pH of an incoming water source (for example, untreated) containing ions responsible for hardness can be compared with treated acidified demineralized water that leaves the water preparation system, other equipment and / or system according to the invention. In such a modality, the pH differential can be used for a variety of purposes, including monitoring a work system. In one embodiment, the pH differential meter can detect a reduction in the pH differential, triggering an applicable event, such as regeneration of the ion exchange resin, addition of detergent and / or washing additives or other cleaning agents to be used with treated water. Measuring the pH differential is generally useful as a result of the variability of water hardness, depending on a water source used, as it is well known that the hardness levels in influential waters are not constant. Therefore, as a result of the methods of the invention that employ the measurement of the pH differential, variations in water hardness will not be detrimental to an application of use as a result of the equipment and / or systems being able to monitor and adjust for that differential. (for example, by triggering various events as disclosed here).
[0114] The regeneration of the ion exchange resins described herein can be triggered through a variety of events and / or measurements, as disclosed herein. In one aspect, the regeneration of the ion exchange resin can be triggered by measuring the TDS in a system, which must be dependent on the specificity of the water entering the system. For example, in one aspect of the invention, ion exchange resins remove about 70% to about 100% of the TDS from the water source. In a preferred aspect, ion exchange resins remove between about 80% to about 100% TDS, or about 90% to about 100% TDS from the water source. Therefore, in the event that the removal of TDS from a treated water source falls below about 70%, or about 80%, or about 90%, such a measurement of the TDS differential between untreated water and the water source treated water can trigger the regeneration of ion exchange resins.
[0115] In an additional aspect, the regeneration of ion exchange resins can be triggered by measuring the pH of the water source and / or the pH of the treated water. For example, increasing the pH of a source of treated water above about 7 can trigger the regeneration of ion exchange resins. Without being limited to a particular theory of the invention, the ion exchange resin can be depleted between a pH of about 4.9 to about 5; therefore, when the pH of the treated water source increases to about 7, or above 7, the ion exchange resin no longer contributes protons from the resin in order to acidify and soften the water source. Therefore, the regeneration of the ion exchange resin is triggered.
[0116] The one usually versed in the technique has knowledge of the various means of monitoring and / or measuring pH according to the methods of triggering events using the acidified demineralized water disclosed here. Therefore, the scope of the invention is not limited to methods for monitoring and / or measurement. Conventional measurement techniques include the use of sensors, preferably a sensor is configured to send a signal to a controller. The sensor can include a substrate and a detection element arranged on the substrate. The detection element is in contact with the water flow, in the equipment and / or system; preferably, the sensing element in contact with both the incoming water flow (eg, untreated) and the effluent water (eg, softened treated water).
[0117] Events triggered according to the use of the equipment and / or systems and / or processes according to the invention include, for example: dispensing detergents, cleaning aids and / or other cleaning compositions; varying the consumption of detergents needed to wash or rinse the surface according to the methods of the invention; the regeneration of ion exchange resins; start and / or stop the generation of treated water disclosed here, etc. The triggering of events is initiated through the measurement step, then communicating with a controller to receive a signal. Then, the controller works to trigger the desired event to an equipment and / or system according to the invention. Methods Using Acidized Demineralized Water
[0118] The methods, equipment and / or systems of the present invention can be used for a variety of cleaning applications that employ acidified demineralized water. Thus, an equipment of the present invention can be used to control water hardness and / or reduce scale formation and / or improve cleaning efficiency, and / or reduce stains and film formation caused by waters with high TDS and / or reduce or eliminate the use of additional chemical streams (for example, for cleaning polymers, threshold agents, etc.). Unexpectedly, according to the invention, protons from acidified demineralized water contribute to the performance of the treated water source.
[0119] The systems and methods of the present invention that use them can be included as part of any system or device that uses a water source and is in need of water treatment, for example, acidification and / or softening using a water treatment system. In particular, the systems and equipment of the present invention can be used with any equipment or device that can provide a source of water that would benefit from treatment using the equipment of the present invention, including one or both of acidification and / or softening.
[0120] In some aspects, the present disclosure includes methods of using acidified demineralized water for washing and sanitizing utensils at low temperature. The treated acidized water can be provided to an automatic washing machine from the treated water supply line of the equipment and / or systems. The equipment can be placed in a variety of locations relative to the washing machine. For example, the equipment may be upstream of the washing machine's power line. Exemplary automatic washing machines suitable for use with the equipment and methods of the present invention include; but not limited to, an automatic dishwasher, a vehicle washing system, an instrument washing machine, an on-site cleaning system, a cleaning system in food processing units, a bottle washer, and an automatic washing machine. Alternatively, the treated water can be used in a manual washing system. Any automatic or manual washing machine of the washing process that can benefit from using treated water according to the methods of the present invention can be used.
[0121] In some respects, the present disclosure includes methods of using acidified demineralized water for dishwashing applications, including those disclosed, for example, in various dishwashing applications using acidulated formulations, including U.S. Patent Nos. 8,114,222, 8,092,613, 7,942,980, and 7,415,983, US Patent Application Serial No. 13 / 474,771 (Attorney docket 2899USU1), 13 / 474,765 (Attorney docket 2897USU1), 13/474, (Attorney docket 2900USU1) 780 and 13 / 112.412 (Attorney docket 2901US01), including all references cited therein, which are incorporated herein by reference in their entirety. A particularly suitable application for the use of acidic water is treated for use in an acidulated wash cycle. For example, treated acidified water can be dispensed with additional acidic compositions by means of a rinse tap, with or without an additional water rinse step, in order to lower the pH of the final rinse. In an additional use application, treated acidulated water can be used in an alternative way with alkaline detergents and steps to improve the removal of dirt.
[0122] In some respects, a non-limiting example of washing machines suitable for using the systems of the present invention for water conditioning and / or a source of cleaning and / or washing water are disclosed, for example, in US Patent Application No. (Attorney Docket number 2973USU1), entitled Dishmachine, all content of which is expressly incorporated herein by reference. Other examples of suitable dishwashing machines for employing the acidified treated water disclosed herein include the US Patents. We. 8,202,373, 8,092,613, 7,942,978, 7,871,521, 5,609,174, 4,826,661, 4,690,305, 4,687,121, 4,426,362 and the reissue of US Patent No. 32,763 and 32,818, the total content of which is expressly incorporated herein by reference. Some non-limiting examples of dishwashers include door or hood machines, conveyor machines, countertop machines, cup washers, on-board machines, pan and tray machines, utensil washers and household dishwashers. The dishwashers can be single-tank or multi-tank machines.
[0123] A door dishwasher, also called a hood washer, refers to a commercial dishwasher in which dirty dishes are placed in a frame and the frame is moved into the dishwasher. Door-type dishwashers clean one or two frames at a time. on such machines, the frame is stationary and the washing and rinsing arms move. A door type machine includes two sets of arms, a set of wash arms and a rinse arm, or a set of rinse arms. Door-type machines can be machines operating at high temperatures or machines operating at low temperatures.
[0124] In high temperature machines the dishes are sanitized by hot water. In a low-temperature machine, mad women are sanitized by a chemical disinfectant. The door machine can be a recirculating machine or a recirculating machine or a filling and emptying machine. In a recirculating machine, the detergent solution is reused, or “recirculated” between washing cycles. The concentration of the detergent solution is adjusted between washing cycles so that an adequate concentration is maintained. In a filling and emptying machine, the washing solution is not reused between washing cycles. New detergent solution is added before the next wash cycle. Some non-limiting examples of door machines include Ecolab Omega HT, Hobart AM-14, Ecolab ES-2000, Hobart LT-1, CMA EVA-200, American Dish Service L-3DW and HT-25, Autochlor A5, Champion D - HB, and Jackson Tempstar star.
[0125] The temperature of cleaning applications in dishwashers according to the invention can also vary depending on the dishwasher, for example, whether the dishwasher is a dishwasher or a consumer dishwasher institutional. The temperature of the cleaning solution in a consumer dishwasher is typically about 43 ° C (110 ° F) to about 66 ° C (150 ° F) with a wash up to about 71 ° C (160 ° F). The temperature of the cleaning solution in a high temperature institutional dishwasher in the US is typically about 66 ° C (150 ° F) to about 74 ° C (165 ° F) with a wash of about 82 ° C (180 ° F) to about 91 ° C (195 ° F). The temperature of a low-temperature institutional dishwasher in the USA is typically about 49 ° C (120 ° F) to about 60 ° C (140 ° F). Low dish temperature machines usually include at least a 30-second rinse with a disinfectant solution. The temperature of a high temperature institutional dishwasher in Asia is typically around 55 ° C (131 ° F) to about 58 ° C (136 ° F) with a final wash at 82 ° C (180 ° F) ).
[0126] The revealed methods of using acidified demineralized water can also be used in a pan and tray type dishwasher, a utensil washer, cup washer and / or a conveyor machine. A conveyor machine refers to a commercial dishwasher in which the dirty dishes are placed on a support that moves through a dishwasher or a conveyor. A conveyor machine continuously cleans the supports with dirty dishes instead of one support at a time. Here the distributors are typically stationary or oscillating and the support structure moves through the machine. A conveyor machine can be a single tank or multiple tank machine. The conveyor machine can be a machine that works at high temperature or that works at low temperature. Finally, conveyor machines primarily recycle the detergent solution. Some non-limiting examples of conveyor machines include Ecolab ES-4400, Jackson AJ-100, stero SCT-44, and Hobart C-44 and C- 66.
[0127] In some embodiments, the dishwasher or utensil washing machine may incorporate an uto plate system or dishwasher may incorporate an ion exchange resin system capable of acid regeneration at a point of use. Beneficially, the use of the ion exchange resin system capable of acid regeneration at the point of use avoids the need for an additional external water conditioning system. Additional benefits result from using the system at a point of use is that the water requirements inside the facility or the operating location are associated with the specific dishwasher or other type of machine, rather than the rest of the water used installation.
[0128] In additional aspects, the present disclosure includes methods of using acidified demineralized water for laundry applications. For example, acid treated water can be used in an automatic textile material washing machine for pretreatment, washing, acidification, demineralization, and / or washing stages. In a particular embodiment, the present invention can be used with a washing machine in a variety of ways. In some embodiments, a treatment reservoir that houses the ion exchange resin can be connected to a detergent dispensing device for use in laundry. The treatment tank can be used to supply treated water to a washing system and / or to a washing machine washing system. In some embodiments, the treatment reservoir can be used to provide a mixture of treated water and detergent to a laundry system.
[0129] Still in additional aspects, the present disclosure includes methods of using acidified demineralized water in a variety of additional industrial and domestic applications. For example, according to embodiments of the invention, acidified demineralized water can be delivered for a variety of cleaning applications, using dilution systems, which may include, for example, a vacuum cleaner or another pump that feeds a cleaning system. .
[0130] Water treatment methods and equipment can be used in a residential environment or a commercial establishment, for example, in a restaurant, hotel, a hospital. In addition to washing utensils (for example, washing dishes and utensils for eating or cooking) and laundry applications, for example, a water treatment method, the system or equipment of the present invention can be used on: difficult surfaces, such as in showers, sinks, toilets, bathtubs, countertops, windows, mirrors and floors; in vehicle care applications, for example, to treat water used for prewash, for example, an alkaline pre-rinse and / or a low pH pre-rinse, washing, polishing and rinsing a vehicle; industrial applications, for example, in cooling towers, boilers, industrial equipment, including heat exchangers; in food service applications, for example, for the treatment of water lines for making coffee, espresso and tea brewing, machine espresso machines, ice machines, water heaters, pasta preparation kitchens, reinforcement heaters, steam tables, production of groceries, vaporizers, and / or fermentation chambers; in health care instrumental applications, for example, immersion, cleaning and / or washing surgical instruments, autoclave sterilizers feed water treatment; and in the feed water for various applications, such as humidifiers, hot tubs and swimming pools. In some embodiments, equipment of the present invention can be used to treat the water provided to an ice maker.
[0131] Additional applications for cleaning difficult surfaces for the source of water treated by acidulation include on-site cleaning systems (CIP), off-site cleaning systems (COP), automatic bottle washers, scrubber washers, sterilizers, washing machines, textiles, ultrafiltration and nanofiltration systems and internal air filters. CIP systems include the internal components of tanks, lines, pumps and other process equipment used for processing typically streams of liquid products, such as beverages, milk, juices. COP systems can include easily accessible systems, including wash tanks, vases, mop dipping buckets, storage tanks, wash sinks, vehicle part washers, washers and batch non-continuous systems, and the like.
[0132] In additional aspects, the use of a source of water treated by acidulation according to the invention reduces or eliminates the use of streams of additional chemicals for cleaning (for example, polymers, threshold agents, etc.). Preferably, the use of a source of acid-treated water according to the invention allows the use of specific environmentally friendly detergent compositions, for example, those substantially free of materials that can form accumulations, chelators, sequestrants, and / or phosphorus.
[0133] The various methods of use that employ the acidified demineralized water according to the invention can be used in combination with any detergent compositions. For example, a cleaning composition, a washing agent composition and / or a drying agent composition can be combined with the treated water to form an in-use solution. The items to be cleaned and / or washed are then contacted with the usage solution. Exemplary detergent compositions include detergent compositions for use in washing utensils, laundry detergent compositions, CIP detergent compositions, environmental cleaning compositions, CIP, environmental cleaning compositions, difficult surface cleaning compositions (such as those for use on counters or floors) ), motor vehicle washing compositions, and glass cleaning compositions. Exemplary washing agent compositions include those compositions used to reduce streak or film formation on a surface, such as on glass. Exemplary compositions of drying agents include dewatering compositions. In the vehicle wash industry, it is often desirable to include a drying step in which a coating film or pearl film forming agent is applied to the exterior of the vehicle.
[0134] However, according to a preferred mode of using acidified treated water, it reduces and / or eliminates the need for additional cleaning compositions (eg polymers, threshold agents, etc.) and / or reduces overall consumption of detergent, due to the increased efficiency of cleaning the treated water. Therefore, in some embodiments, the detergent composition for use with the methods of the present invention includes a detergent that is substantially free of a chelating agent, a builder, sequestrant, and / or threshold agent, for example, an aminocarboxylic acid, a phosphate condensate, a phosphonate, a polyacrylate, or the like. Without wishing to be bound by any particular theory, it is considered that due to the methods and equipment of the present invention they reduce the negative effects of ions responsible for the hardness of the water source, when used with a detergent, there is a substantially reduced or eliminated need to include chelating agents, builders, scavengers, or limit agents in the detergent composition, in order to deal with the ions responsible for the hardness.
[0135] For example, the use of a source of water treated according to the methods of the present invention, increases the effectiveness of conventional detergents. It is known that the ions responsible for hardness combine with soaps and detergents to form an encrustation or slag. In addition, the ions responsible for hardness limit the amount of foam formed with soaps and detergents. Without wishing to be bound by any particular theory, it is considered that by reducing the amount of ions responsible for the hardness the amount of these harmful side effects can be reduced.
[0136] In some modalities of use, there is a substantial reduction in the consumption of detergent as a result of using the acid-treated water source for the cleaning application, including, for example, at least 5% reduction in the consumption of detergent , at least 10% reduction in detergent consumption, at least 20% reduction in detergent consumption or at least 25-30% reduction in detergent consumption. Without being limited, according to the invention, all percentages of the mentioned reduction ranges of detergent consumption are inclusive of the numbers that define the range and include each integer within the defined range.
[0137] As one skilled in the art will verify, in some embodiments, the detergent composition may include other additives, including conventional additives such as bleaching agents, agents responsible for curing or solubility modifiers, anti-foaming agents, anti-replenishing agents, threshold agents , stabilizers, dispersants, enzymes, surfactants, aesthetic enhancing agents (i.e., dyes, perfumes), and the like. Adjuvants and other additive ingredients may vary according to the type of composition to be manufactured. It should be understood that these additives are optional and do not need to be included in the cleaning composition. When included, they can be included in an amount that provides the effectiveness of a particular type of component.
[0138] How the one usually versed in the technique can recognize, or will be able to determine, using no more than routine experimentation, numerous equivalents for the specific procedures, modalities, claims and examples described here. Such equivalents are considered to be within the scope of this invention and are covered by the appended claims. The contents of all references, patents and patent applications cited throughout this application are hereby incorporated by reference. The invention is further illustrated by the following examples, which should also not be construed as limitations.
[0139] All publications and patent applications in this specification are indicative of the level of experience of those usually versed in the technique to which the invention is pertinent. All publications and patent applications are hereby incorporated by reference to the same extent as if each individual publication or patent application was specifically and individually indicated as a reference. EXAMPLES
[0140] Modalities of the present invention are defined in more detail in the following non-limiting examples. It should be understood that these examples, while indicating certain embodiments of the invention, are given by way of illustration only. From the above discussion and those examples, a person skilled in the art can determine the essential characteristics of this invention, and without departing from the spirit and scope of it, can make several changes and modifications to the modalities of the invention to adapt to the various uses and conditions. Thus, various modifications of the modalities of the invention, in addition to those presented and described herein, will be apparent to those skilled in the art from the foregoing description. These modifications are also intended to fall within the scope of the appended claims. EXAMPLE 1
[0141] Previous experience shows that dishwashing results will be improved using water softened by conventional means and acidified by detergents and / or washing additives. When conventional ion exchange resins are depleted, water is no longer softened and brine is typically used to regenerate the resin. Water that is no longer being softened often gives poor washing results unless the additional concentration of detergents containing accumulator elements, chelators or polymer is increased and additional washing additive is used.
[0142] An experiment showing evidence of scale build-up in crockery was conducted using a carbonate at 500 ppm in a 75-cycle test. Table 1 quantifies the results of the utensils treated according to the experiment, in which the 1A glass utensils were treated using only hard water (hard water at 17 grains / gallon), and the 1B glass utensils were treated using softened water. treated according to the invention. The accumulation of scale resulting from the surfaces of the treated utensils is described by photography and measured visually according to a scale scale accumulation (below).
[0143] The 75-cycle test was performed using six 283.5 g (10 oz) Libbey glass cups and 4 plastic cups (SAN = styrene acrylonitrile) in a Hobart AM-14 dishwasher and water at 17 grains (1 grain = 17 ppm). Hobart AM-14 dishwasher specifications include: Water bath volume: 60L; Washing volume: 4.5 L; washing time: 40 seconds; rinsing time: 9 s.
[0144] Initially, the glasses were cleaned according to procedures that ensure the removal of all films and foreign material on the glass surface. The 75-cycle test was started. After the end of each cycle, the machine is properly dosed (automatically) to maintain the initial concentration. Glass cups and plastic cups are then classified for film accumulation using a strong light source. (1- no film formation; 2- film strokes; 3- light film formation; 4- medium film; 5- heavy film). As shown in Table 1, glass cups 1A (hard water - 17 grains) were graded at the level of 5, showing heavy film. The cups treated according to the invention shown in cups 1B (soft acid water) were graded to a level 1, showing no film.
EXAMPLE 2
[0145] An experiment showing the protein removal test in dishes was conducted using the APEXNC 1000 ppm detergent (Ecolab ®) and the seven-cycle protein removal test. Table 2 shows the results of articles treated according to the experiment, in which cups 2A were treated using only hard water (water hardness 5 grains / gallon) and cups 2B were treated using acidified demineralized water according to the invention. . The resulting scale build-up on the surfaces of treated dishes is described by photographs and measured visually according to the scale build-up classification (below).
[0146] The 7-cycle protein test was carried out in order to provide a method of evaluating the formation of film, stains and the removal of dirt on dishes in an institutional dishwasher. Clean test cups are washed in an institutional dishwasher. The performance of the detergent or rinse aid is measured by preventing water stains, or forming films and removing dirt from plastic cups and Libbey glass cups. According to this experience, the performance of using acidified demineralized water (as opposed to hard water with 5 grains) was evaluated.
[0147] Clean Libbey cups were used for each of the test products and new plastic cups were used for each experiment. Food soil was prepared food soil. The dishwasher was filled with the tested water sources (described according to cups 2A-2B) and the heaters were turned on. The final rinse temperature was set to 82.2 ° C (180 ° F) for high temperature machines. The glass and plastic cups were soiled and placed in an oven at 71.1 ° C (160 ° F) for 8 minutes. While the cups were drying, the dishwasher was prepared with 120 g of previously prepared soil (corresponding to 2000 ppm of food soil in the container). Dirty glass / plastic cups are placed in the holder next to the redeposition glass / plastic cups. The washing machine is started and the cups are cycled automatically. When the cycle is over, the tops of the cups are rubbed with a dry towel. The soiling procedure is repeated. At the beginning of each cycle, the appropriate amount of detergent and food dirt are added to the wash tank to reconstitute the rinse dilution. The steps are repeated until seven cycles are complete.
[0148] The results were evaluated using bleaching methods using a Coomassie Blue R dye solution to visually evaluate the glasses against a white background. The cups are first stained with the Coomassie Blue R dye solution and thoroughly washed with the decolorization solution (methanol and acetic acid in distilled water). Each cup is then visually classified in a viewing area against a white background, in which the residual protein remains stained blue. (1- without protein; 2- 20% of the surface of the glass covered with protein; 3- 40% of the surface of the glass covered with protein; and 4 - 60% of the surface of the glass covered with protein; 5 - more than 80% of surface of the cup covered in protein As shown in Table 2 cups 2A (hard water - 5 grains) were classified as level 2, demonstrating 20% of the surface of the cup covered in protein The cups treated according to the invention shown in the cups 2B (acidified demineralized water) were classified at level 1, showing no protein in the glasses.
EXAMPLE 3
[0149] The capacity of a commercially available weak acid resin against the pH of the water has been tested. An Amberlite ® IRC 76 ion exchange resin (commercially available from Rohm and Haas Company) was tested. Amberlite ® IRC 76 ion exchange resin is an example of a commercially available weak acid resin having a polyacrylic copolymer with the carboxylic acid functional group. This particular resin is characterized by a smaller volume variation than conventional weakly acidic resins and can be used in H +, Na + or NH4 + forms and can also be used to remove bicarbonate hardness from water. The resin is known to be sensitive to chlorine in water (which affects the lifetime and performance of the resin). The working capacity of the resin is a function of the analysis of the temperature and the water service flow. The resin is easily regenerated with little more than the stoichiometric amounts of strong acids.
[0150] On average, the use of a conventional weak acid resin used in ion softening water softening applications is designed for bed depths of 2.6 feet for treatment flow rates of about 2 to about 20 gallons per minute. However, one usually skilled in the art can vary water treatment flow rates, including, for example, from about 0.5 to about 50 gallons per minute. The configuration used for testing the capacity of the ion exchange resin used a flow rate of about 5 - 10 liters of water per minute and consumed less than 1 cubic foot of resin for the system. In addition, the various monitoring devices were used within the system to measure flow, water hardness (for example, ions responsible for hardness measured by the titration method), the pressure inside the system (for example, ions responsible for hardness measured by the titration method), pressure within the system (eg measurement of the estimated pressure required for effective washing, preferably a pressure measurement of about 1.4 bar (20 psi)), pH of the effluent (eg , electrode measurement), and TDS (for example, ICP analytical method for TDS).
[0151] Figure 6 shows a diagram of the capacity of an ion exchange resin for acid regeneration v pH of the treated water according to an embodiment of the invention. The best results are obtained from the resin with a pH less than about 6. Preferably the pH is less than about 7. EXAMPLE 4
[0152] The ability of a commercially available weak acid resin against water hardness has been tested. An Amberlite ® IRC 76 ion exchange resin (commercially available from Rohm and Haas Company) was tested. Ion exchange resin Amberlite ® IRC 76 is an example of a commercially available weak acid resin having a polyacrylic copolymer with a carboxylic acid functional group. This particular resin is characterized by less volume variation than conventional weakly acidic resins and can be used in H +, Na + or NH4 + forms and can also be used to remove bicarbonate hardness from water. The resin is known to be sensitive to chlorine in water (which affects the lifetime and performance of the resin). The working capacity of the resin is a function of the analysis of the temperature and the service flow of the water. The resin is easily regenerated with amounts just above the stoichiometric amounts of strong acids.
[0153] The configuration used for testing the capacity of the ion exchange resin used a flow rate of about 5-10 liters of water per minute and consumed less than 1 cubic foot of resin in terms of the system. In addition, the various monitoring devices were used within the system to measure flow, water hardness (for example, ions responsible for hardness measured by the titration method), pressure within the system (for example, measurement of expectation necessary for effective washing, preferably pressure measurement of about 1.4 bar (20 psi), the pH of the effluent (for example, from the measuring electrode), and the TDS (for example, the ICP analytical method for the TDS).
[0154] Figure 7 shows a diagram of the capacity of an ion exchange resin for acid regeneration versus the hardness of water, of water treated according to one embodiment of the invention. The best results are obtained from the resin system, with a water hardness of less than about 2 grains. EXAMPLE 5
[0155] Layered resin bed systems were evaluated to verify the impact on treated water hardness using more than one cation exchange resin in acid. 4710 grams of Dowex® MAC-3 weakly acid cation exchange resins (commercially available from the Dow Chemical Company) were used to form a layered bed employing two of the weakly acid cation exchange resins, as shown in Figure 3A. Dowex® LB MAC-3 resin is an example of a commercially available weak acid resin having a carboxylic acid functional group. The MAC-3 WAC resins were packed in two 48.3 cm (19 inch) long and 12.7 cm (5 inch) diameter connecting tubes. 3575 grams of weak Dowex® MAC-3 cation exchange resin (commercially available from the Dow Chemical Company) and 1,235 grams of Dowex Marathon®-C (form H) strong cation exchange resin (Commercially available from Dow Chemical Company) were used to form a layered mixed bed, as shown in Figure 3B. The cation exchange resins were filled into two 48.3 cm (19 inch) long and 12.7 cm (5 inch) connected diameter tubes.
[0156] Hard water (17 grains) was supplied to the layered resin bed systems shown in Figures 3A-3B, at a controlled rate of about 0.8 gallons per minute. The water from the outlet of the second treatment reservoir was measured for both hardness and pH. Water samples were taken to test pH levels against capacity.
[0157] Figure 8 shows a diagram of the capacity of layered bed systems. As shown, the layered weak acid-regenerated ion exchange resin provided soft water having between about 0.5 to 1 grains, while the layered layer of weak acid-regenerated ion exchange resin and ionic exchange regenerated by strong acid provided soft water having 0 grain of hardness. The use of the layered mixed bed using the strong acid cation exchange resin provided a greater reduction in water hardness, despite its lower total capacity to reduce water hardness if used alone. However, demineralized water using weakly layered acidic ion exchange resins has provided the added benefit of providing demineralized water with reduced pH, which provides additional cleaning benefits.
[0158] As shown in the figure, each of the layered beds has demonstrated sustained efficacy in demineralization for at least 150 gallons of treated water. Then, between about 150 gallons to 200 gallons of resins became depleted and were unable to continue to sufficiently remove the hardness from the water. According to aspects of the invention, for the water treatment equipment evaluated in this Example, the use of acid regeneration may need to be employed after about 150 gallons of treated water.
[0159] Figure 9 shows a diagram of pH versus the capacity of layered bed systems. As shown, the bed of weak acidic ion exchange resin layered (ie, employing a single type of resin) resulted in a less acidified treated water source once the capacity of the system was tested. That is, above about 200 gallons of treated water, the pH of the single resin bed arranged in layers began to rise above about 4, while the mixed resin bed system maintained a constant acidified water having a pH between about 3 to about 3.5. EXAMPLE 6
[0160] The use of an acidic regenerant according to the modalities of the invention was analyzed. A single bed of weak acid resin, as disclosed in Example 4, was regenerated using the various acid regenerants disclosed herein. It was discovered that the regeneration process is initially dominated by thermodynamics. A regenerator with a sufficiently low pH will drive the process over the energy barrier, showing a rapid drop in pH in the first several minutes. Then, the regeneration process is controlled by kinetics. This requires a regenerant to be used for a sufficient period of time (for example, from about 5 to about 90 minutes) to drive the regeneration of the resin to completion.
[0161] As shown in Figures 10A-B, the use of a strong acid regenerant (HCI 0.38M (FIG. 10A), HCL 1.8 M (FIG. 10B)) is necessary to sufficiently lower the pH of the resin in weak acid. According to embodiments of the invention, the concentration of acid regenerant used in the regeneration cycle will depend on the molarity of the acid used. In some embodiments, the concentration of the acid used in a solution to provide the acid regenerant for the ion exchange resin is about 1% to about 20%, from about 2% to about 10%, or about 10% for regeneration.
[0162] After the resin has been regenerated, as shown in Figures 10A-B, the exemplary service cycle (ie, hard water treatment with acid-regenerated resin) can be used to re-supply a source of water treated by acidulation. As shown in Figure 11, the use of the strong acid regenerating agent in Figure 10B provides superior treatment capacity for a longer service cycle. EXAMPLE 7
[0163] The use of additional acidic regenerants was evaluated according to the results of Example 6. The acidic regenerates presented below were used in equivalence of the various acids employed: 1.2 eq of sulfuric acid, 1.2 eq of sulfate urea, 1.2 eq of hydrochloric acid, 1.2 eq of MSA, and 1.4 equivalents of citric acid. Figure 12 shows the drop in the pH of the resin during the regeneration step employing various acid regenerates. Beneficially, the use of equivalence of the various acids used in these examples considers the different fluctuation factors, including the size of the system, the amount of hardness to be removed, etc.
[0164] After the resin has been regenerated, as shown in Figure 12, an exemplary service cycle (ie, hard water treatment with the regenerated acid resin) was used to determine the effectiveness of service cycles, as measured the hardness of the water in the treated water source, based on the use of different acidic regenerants. As shown in Figure 13, the duty cycle of the various acidic regenerants provided acid-treated water having a hardness of about 1 or less than about 1 for at least 100 gallons of treated water.
[0165] Having thus described the invention, it will be evident that it can be varied in several ways. Such variations are not to be considered as departing from the spirit and scope of the invention and all modifications are intended to be covered by the appended claims.

权利要求:
Claims (23)
[0001]
1. Non-integrated system that uses an ion exchange resin regenerated by an acid at a point of use, CHARACTERIZED by the fact that it comprises: an entrance to supply a water source; a water treatment reservoir; a water treatment component housed within the water treatment reservoir, wherein said water treatment component comprises at least one ion exchange resin capable of generating a source of water treated by proton exchange in said resin for dissolved cations, including the ions responsible for the water hardness and total solids dissolved in said water source, and in which said ion exchange resin is in an acid form or in an inert metal form; an outlet; a water distribution line, in fluid communication with a cleaning application and / or storage reservoir to provide the source of treated water to the cleaning application and / or storage reservoir; and a measuring device for obtaining pH and / or proton concentration and / or measurements of total dissolved solids from the water treatment reservoir, water source and / or treated water source, and a controller for receiving measurements and trigger an event; where the triggered event is selected from the group consisting of regenerating the water treatment component resin, varying a detergent or other chemical addition to the treated water source and combinations thereof; where the inlet is in fluid communication with the water treatment reservoir; wherein a first end of the outlet is in fluid communication with the water treatment reservoir and a second end is in fluid communication with the water distribution line; where the source of treated water is softened, acidic water with a low total dissolved solids (TDS) content having a hardness level of less than 2 grains per gallon and a pH of less than 6; and where the non-integrated system is adapted to a cleaning system.
[0002]
2. System, according to claim 1, CHARACTERIZED by the fact that said ion exchange resin is a weak acid cation exchange resin and / or a strong acid cation exchange resin.
[0003]
3. System according to claim 1, CHARACTERIZED by the fact that said ion exchange resin is a weak acid exchange resin having a polyacrylic copolymer matrix and carboxylic acid functional group.
[0004]
4. System, according to claim 1, CHARACTERIZED by the fact that said ion exchange resin is a strong acid exchange resin having a polystyrene matrix and sulfonic acid functional group.
[0005]
5. System, according to claim 1, CHARACTERIZED by the fact that said ion exchange resin is an acid exchange resin selected from the group consisting of a cross-linked acrylic acid with functional group carboxylic acid, a cross-linked methacrylic acid with group functional carboxylic acid, a polystyrene with a sulfonic acid functional group, a polystyrene with a sulfonic acid functional group and mixtures of these.
[0006]
6. System according to claim 1, CHARACTERIZED by the fact that said ion exchange resin has a surface comprising carboxylic acid functional groups and / or sulfonic acid functional groups.
[0007]
7. System, according to claim 1, CHARACTERIZED by the fact that it also includes additional water treatment equipment and water distribution line in fluid connection with the water treatment reservoir.
[0008]
8. System, according to claim 1, CHARACTERIZED by the fact that it also comprises a storage reservoir that houses an acid regenerant and a distribution line connected fluidly with the water treatment reservoir to distribute the acid regenerant to the resin of ion exchange.
[0009]
9. Method for the treatment of hard water using an ion exchange regenerated by acid at a point of use in a non-integrated system CHARACTERIZED by the fact that it comprises: contacting a source of hard water with a water treatment composition in a cycle of service, in which the water treatment composition comprises at least one ion exchange resin, in which the ion exchange resin generates a source of water treated by proton exchange in said resin for dissolved cations, including ions responsible for the hardness of the water and total solids dissolved in said water source, and wherein said ion exchange resin is regenerated using an acid; generate the source of treated water per service cycle comprising softened, acidic water with a low total dissolved solids content (TDS) having a hardness level of less than 2 grains and a pH of less than 6, where the treated water source can be used for washing and / or rinsing in a variety of cleaning applications; measure pH and / or concentration of protons and / or total dissolved solids in the water treatment composition, in the water source and / or in the treated water source, and trigger an event as a result of the measurement obtained, in which the event triggered it is selected from the group consisting of regenerating the water treatment component resin, varying a detergent or other chemical addition to the treated water source and combinations thereof; and in which the regeneration of the ion exchange resin upon exhaustion occurs using an acid regenerant; and where the non-integrated system is adapted (retrofitted) into a cleaning system.
[0010]
10. Method according to claim 9, CHARACTERIZED by the fact that said ion exchange resin is a weak acid cation exchange resin selected from the group consisting of a cross-linked polyacrylic acid with a carboxylic acid functional group, a polymethacrylic acid cross-linked with carboxylic acid functional group and mixtures thereof, and / or a strong acid cation exchange resin selected from the group consisting of a polystyrene with a sulfonic acid functional group, a polystyrene with a sulfonic acid functional group and mixtures thereof.
[0011]
11. Method, according to claim 10, CHARACTERIZED by the fact that said ion exchange resin is a layered bed system that employs at least two of said cation exchange resins.
[0012]
12. Method, according to claim 9, CHARACTERIZED by the fact that a measure of pH and / or concentration of protons is obtained from said source of treated water.
[0013]
13. Method, according to claim 9, CHARACTERIZED by the fact that a pH differential and / or the measurement of the proton concentration is obtained from said source of water and said source of treated water.
[0014]
14. Method, according to claim 9, CHARACTERIZED by the fact that the regeneration of the resin is triggered and comprises providing an acid regenerant to the resin, displacing ions responsible for the hardness of the water in the resin with protons of the acid regenerant and generating an effluent water the regeneration stage.
[0015]
15. Method, according to claim 14, CHARACTERIZED by the fact that the effluent water is placed in a waste stream.
[0016]
16. Method, according to claim 9, CHARACTERIZED by the fact that said treatment composition is placed in front of a dilution system.
[0017]
17. Method, according to claim 16, CHARACTERIZED by the fact that said dilution system is a vacuum cleaner or other pump that feeds a cleaning system.
[0018]
18. Method for using a source of softened acidic water CHARACTERIZED by the fact that it comprises: contacting an article or surface in need of cleaning with a source of treated water, in which said source of treated water is softened acidic water with a low content total dissolved solids (TDS), having a hardness level of less than 2 grains and a pH of less than 6, in which the source of treated water is generated by treating a source of hard water with at least one ion exchange resin , in which the ion exchange resin generates a source of water treated by proton exchange in said resin for dissolved cations, including ions responsible for the hardness of the water and total solids dissolved in said water source, and in which said ion exchange resin it is regenerated using an acid and triggered by measuring pH and / or concentration of protons and / or total dissolved solids in the water treatment composition, in the water source and / or the treated water source.
[0019]
19. Method, according to claim 18, CHARACTERIZED by the fact that it further comprises combining said source of water treated with a detergent or other cleaning composition, in order to form a solution for use in contact with said article or surface .
[0020]
20. Method, according to claim 19, CHARACTERIZED by the fact that the treated water source reduces the total detergent consumption of a cleaning application and / or reduces the use of polymers and threshold agents in said detergent, and in that the use of said source of treated water improves cleaning efficacy as measured by a reduction in the formation of stains and films and / or preventing the accumulation of scale on articles and surfaces compared to cleaning with detergents without the source of potable water.
[0021]
21. Method, according to claim 18, CHARACTERIZED by the fact that said hard water is treated with a resin bed system arranged in layers of at least two ion exchange resins.
[0022]
22. Method, according to claim 18, CHARACTERIZED by the fact that said hard water is treated with said ion exchange resin that is placed in front of a dilution system.
[0023]
23. Method, according to claim 22, CHARACTERIZED by the fact that said dilution system is a vacuum cleaner or other pump that feeds a cleaning system.

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法律状态:
2018-12-04| B06F| Objections, documents and/or translations needed after an examination request according art. 34 industrial property law|

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2019-06-04| B06T| Formal requirements before examination|

---

2019-12-31| B06A| Notification to applicant to reply to the report for non-patentability or inadequacy of the application according art. 36 industrial patent law|

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2020-04-28| B09A| Decision: intention to grant|

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2020-09-29| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 12/12/2012, OBSERVADAS AS CONDICOES LEGAIS. |

优先权:

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申请号 | 申请日 | 专利标题

---

US201161569829P| true| 2011-12-13|2011-12-13|

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US61/569,829|2011-12-13|

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PCT/US2012/069280|WO2013090446A1|2011-12-13|2012-12-12|Acid regeneration of ion exchange resins for industrial applications|

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