Apparatus for making a peroxycarboxylic acid

The present invention relates to devices and methods for making peroxycarboxylic acids. The apparatus of the present invention includes a reaction catalyst and a pretreatment column for pretreating one or more reagents that can increase the life, activity and / or safety of the reaction catalyst. The peroxycarboxylic acid composition produced by the method and apparatus of the present invention can contain one or more peroxycarboxylic acids.

Current methods for making peroxycarboxylic acids include mixing the carboxylic acid or carboxylic acid anhydride with an oxidizing agent (eg, hydrogen peroxide) in water and waiting. Under ambient conditions, this reaction can take a week or more to reach the desired concentration of peroxycarboxylic acid in equilibrium. In addition, due to regulations regarding components such as hydrogen peroxide and acetic acid, and conventions for transporting these components, the concentration, stability, content or purity of these reagents, and thus the concentration of peroxycarboxylic acid obtained. , Stability, content or purity can be limited. For example, acetic acid inevitably contains metals due to common practices in transportation and handling. Conventional peroxycarboxylic acid compositions typically include short-chain peroxycarboxylic acids or mixtures of short-chain peroxycarboxylic acids and medium-chain peroxycarboxylic acids (eg, US Pat. Nos. 5,200,189, 5,314,687). See Nos. 5,409,713, 5,437,868, 5,489,434, 6,674,538, 6,010,729, 6,111,963 and 6,514,556).

Various ongoing research efforts have been sought for improved peroxycarboxylic acid compositions and methods for their preparation. Specifically, these efforts have been sought after for a method that allows the purer and / or more stable peroxycarboxylic acid compositions to be made more quickly, even at the place of use. There is.

<p><patcit num="1"><text>U.S. Pat. No. 5,200,189</text></patcit><patcit num="2"><text>U.S. Pat. No. 5,314,687</text></patcit><patcit num="3"><text>U.S. Pat. No. 5,409,713</text></patcit><patcit num="4"><text>U.S. Pat. No. 5,437,868</text></patcit><patcit num="5"><text>U.S. Pat. No. 5,489,434</text></patcit><patcit num="6"><text>U.S. Pat. No. 6,674,538</text></patcit><patcit num="7"><text>U.S. Pat. No. 6,010,729</text></patcit><patcit num="8"><text>U.S. Pat. No. 6,111,963</text></patcit><patcit num="9"><text>U.S. Pat. No. 6,514,556</text></patcit><patcit num="10"><text>U.S. Pat. No. 5,718,910</text></patcit><patcit num="11"><text>U.S. Pat. No. 6,183,807</text></patcit><patcit num="12"><text>U.S. Patent Application No. 09 / 614,631 (filed July 12, 2000)</text></patcit><patcit num="13"><text>U.S. Patent Application No. 10 / 754,426 (filed January 9, 2004)</text></patcit><patcit num="14"><text>U.S. Patent Application No. 11 / 030,641 (filed January 4, 2005)</text></patcit><patcit num="15"><text>U.S. Pat. No. 3,929,678</text></patcit><patcit num="16"><text>U.S. Pat. No. 4,618,914</text></patcit><patcit num="17"><text>U.S. Pat. No. 4,830,773</text></patcit><patcit num="18"><text>U.S. Pat. No. 5,306,350</text></patcit><patcit num="19"><text>U.S. Pat. No. 5,866,005</text></patcit></p>

<p> The present invention relates to devices and methods for making peroxycarboxylic acids. The apparatus of the present invention includes a reaction catalyst and a pretreatment column for pretreating one or more reagents that can increase the life, activity and / or safety of the reaction catalyst. The peroxycarboxylic acid composition produced by the method and apparatus of the present invention can contain one or more peroxycarboxylic acids.</p><p> The present invention includes an apparatus for producing a peroxycarboxylic acid. In one embodiment, the device of the invention can include a first pretreatment column, a first reaction catalyst column, first and second reagent vessels, a number of conduits, and a safety system. The first and second reagent vessels are in fluid communication with the first pretreatment column. The first pretreatment column is in fluid contact with the first reaction catalyst column. The first reaction catalyst column can be in fluid contact with the storage or use site of the peroxycarboxylic acid composition. The first reagent container may be configured to contain a liquid hydrogen peroxide composition and the second reagent container may be configured to contain a liquid carboxylic acid composition. Can be done. The safety system applies the temperature, pressure, metal content or combination thereof of the hydrogen peroxide composition and the carboxylic acid composition in the pretreatment column, in the pretreatment column, or before entering the pretreatment column. It can be configured to measure.</p><p> The present invention includes methods for making peroxycarboxylic acids. In one embodiment, the methods of the invention include pretreating a liquid composition of carboxylic acid or hydrogen peroxide or both with a pretreatment column. In the method of the present invention, if necessary, the pretreated liquid composition is mixed with the liquid composition of carboxylic acid, hydrogen peroxide, or both in order to obtain a composition containing carboxylic acid and hydrogen peroxide. Can include that. The method of the present invention then comprises reacting the composition containing the carboxylic acid and hydrogen peroxide in the presence of a reaction catalyst to produce the peroxycarboxylic acid composition and recovering the peroxycarboxylic acid composition. Is done. The methods of the invention include monitoring the temperature, pressure or metal content of carboxylic acid or hydrogen peroxide or both before, during or during the pretreatment. If the temperature, temperature difference, pressure, pressure difference, metal content or metal content difference exceeds a predetermined value, the method of the present invention is to activate the pressure release valve, flow one or more reagents. Includes stopping, flushing water through the device, flushing the carboxylic acid composition through the device, terminating the method, or a combination thereof.</p>

<figref num="1">FIG. 1 schematically illustrates an embodiment of an apparatus for making a peroxycarboxylic acid, including a pretreatment column and an embodiment of a reaction catalyst.</figref><figref num="2">FIG. 2 schematically illustrates an embodiment of an apparatus for making a peroxycarboxylic acid, including a pretreatment column and an embodiment of a reaction catalyst.</figref><figref num="3">FIG. 3 schematically illustrates an embodiment of an apparatus for making a peroxycarboxylic acid, including a pretreatment column and an embodiment of a reaction catalyst.</figref><figref num="4">FIG. 4 schematically illustrates an embodiment of an apparatus for making a peroxycarboxylic acid, including a pretreatment column and an embodiment of a reaction catalyst.</figref><figref num="5">FIG. 5 schematically illustrates an embodiment of an apparatus for making a peroxycarboxylic acid, including a pretreatment column and an embodiment of a reaction catalyst.</figref><figref num="6">FIG. 6 schematically illustrates an embodiment of a safety system and a pretreatment column.</figref><figref num="7">FIG. 7 schematically illustrates an embodiment of an apparatus for making a peroxycarboxylic acid, including a pretreatment column, a reaction catalyst and an embodiment of a safety system.</figref><figref num="8">FIG. 8 schematically illustrates an embodiment of an apparatus for making a peroxycarboxylic acid, including a pretreatment column, a reaction catalyst and an embodiment of a safety system.</figref><figref num="9">FIG. 9 schematically illustrates an embodiment of an apparatus for making a peroxycarboxylic acid, including a pretreatment column, a reaction catalyst and an embodiment of a safety system.</figref><figref num="10">FIG. 10 schematically illustrates an embodiment of an apparatus for making a peroxycarboxylic acid, including a pretreatment column, a reaction catalyst and an embodiment of a safety system.</figref><figref num="11">FIG. 11 schematically illustrates an embodiment of an apparatus for producing a peroxycarboxylic acid that is in fluid communication with an embodiment of an aseptic packaging system.</figref><figref num="12">FIG. 12 schematically illustrates an embodiment of an apparatus for making a peroxycarboxylic acid, including a pretreatment column and an embodiment of a reaction catalyst.</figref><figref num="13">FIG. 13 schematically illustrates an embodiment of an apparatus for making a peroxycarboxylic acid, including a pretreatment column and an embodiment of a reaction catalyst.</figref><figref num="14">FIG. 14 schematically illustrates a safety system and a reaction catalyst embodiment.</figref><figref num="15">FIG. 15 schematically illustrates an embodiment of an apparatus for making a peroxycarboxylic acid, including an embodiment of a storage system.</figref><figref num="16">FIG. 16 is a flow diagram illustrating an embodiment of a process in which the controller monitors and / or regulates the concentration of peroxycarboxylic acid and / or the concentration of hydrogen peroxide in the composition used.</figref><figref num="17">FIG. 17 is a flow diagram illustrating an embodiment of a generator monitoring process in which the controller monitors and / or regulates the operation of the peroxycarboxylic acid generator.</figref><figref num="18">FIG. 18 is a schematic view of a beverage factory (including a low temperature aseptic filling factory) that can prepare and bottle either soft or non-soft drinks.</figref>

Various embodiments of the invention are described in detail with reference to the drawings, in which case similar reference numbers represent similar parts throughout some of the figures. References to various embodiments do not limit the scope of the invention, only the claims.

<u style="single">Definition</u> The expression "medium chain carboxylic acid" as used herein is 1) having a reduced odor as compared to the bad, pungent or unpleasant odors associated with small chain carboxylic acids of equal concentration. Alternatively, it is odorless and 2) exhibits a carboxylic acid with a critical micelle concentration greater than 1 mM in an aqueous buffer solution at neutral pH. Medium chain carboxylic acids do not include carboxylic acids that are infinitely soluble in water at 20 ° C or infinitely miscible with water at 20 ° C. Medium chain carboxylic acids include carboxylic acids having a boiling point (at a pressure of 760 mmHg) of 180 ° C to 300 ° C. In one embodiment, the medium chain carboxylic acid comprises a carboxylic acid having a boiling point (at a pressure of 760 mmHg) of 200 ° C to 300 ° C. In one embodiment, medium chain carboxylic acids include carboxylic acids that are less than 1 g / L soluble in water at 25 ° C. Examples of medium chain carboxylic acids include pentanoic acid, caproic acid, heptanic acid, octanoic acid, nonanoic acid, decanoic acid, undecanoic acid and dodecanoic acid.

As used herein, the expression "medium chain peroxycarboxylic acid" refers to the peroxycarboxylic acid form of a medium chain carboxylic acid.

The expression "short chain carboxylic acid" as used herein has 1) a characteristic bad odor, pungent or unpleasant odor, and 2) is infinitely soluble in water at 20 ° C. Or show a carboxylic acid that is infinitely miscible with water at 20 ° C. Examples of short chain carboxylic acids include formic acid, acetic acid, propionic acid and butyric acid.

As used herein, the expression "short-chain peroxycarboxylic acid" refers to the peroxycarboxylic acid form of a short-chain carboxylic acid.

As used herein, the term "inactive metal cation" is substantially unresponsive (eg, undesired level of reaction) to hydrogen peroxide or peroxycarboxylic acids (ie, peroxygene species). Shows such metal cations that are either unresponsive) or unresponsive. For example, sodium and potassium are inert metal cations, whereas iron and copper are not inert metal cations.

The term "insoluble" as used herein is negligible in carriers or solvents used for carboxylic acids, oxidizing agents, peroxycarboxylic acids or combinations thereof to give reasonable concentrations. Used to describe insoluble substances to give concentrations greater than the concentration (eg, less than 0.1 mg / mL).

As used herein, a composition or combination that "becomes essential" from several ingredients comprises such ingredients and is substantially in the basic and novel features of the composition or method. The composition which does not have any influence component is shown. In the expression "becomes essential", a sequestrant, builder, chelating agent or stabilizer is claimed composition unless such a process or ingredient is specifically listed after this expression. Excluded from objects and methods.

As used herein, a composition or combination that "substantially contains" one or more components is a composition that does not contain any of such components, or in trace or contingent amounts. The composition containing such a component of is shown. Trace or accidental amounts can include the amount of components found in other components as impurities or stabilizers, or the amount of components produced by minor side reactions during the formation or decomposition of the peroxycarboxylic acid. For example, commercially available hydrogen peroxide often contains small amounts of stabilizers (eg, tin compounds, etc.) or, optionally, trace amounts of HEDP.

As used herein, the expression "unpleasant odor", the expression "unpleasant odor" or the expression "odor" is, if possible, typical of a person leaving, snorting, or irritating. Indicates an odor or atmospheric environment that is present or unpleasant. The hedonic tone provides a measure of the degree to which the odor is pleasant or unpleasant. An "unpleasant odor", "unpleasant odor" or "bad odor" makes the odor as unpleasant as a solution of 5 wt-% acetic acid, propionic acid, butyric acid or a mixture thereof, or such a solution. Has a hedonic tone that is rated as more unpleasant than.

As used herein, the term "micro-organism" refers to any non-cellular or unicellular organism (including colonial organisms). Micro (small) organisms include all prokaryotes. Micro (small) organisms include bacteria (including cyanobacteria), lichens, fungi, protozoa, virions, viroids, viruses, phages and some algae. The term "microbe" as used herein is synonymous with microorganism.

As used herein, the term "object" refers to something that can be sensed by the five senses, either directly and / or indirectly. Objects include surfaces, which include hard surfaces (eg glass, ceramics, metals, natural and synthetic rocks, wood and polymers, etc.), elastomers or plastics, woven and non-woven substrates, food processing surfaces and healthcare. The surface etc. are included. Objects also include food products (and their surfaces); collections or streams of water or gases (eg, air streams); and surfaces and articles used in the customer service and industrial fields. Objects also include the body or parts of the body of a living organism (eg, the hand).

As used herein, the expression "food product" may require treatment with an antibacterial agent or antibacterial composition, and may be eaten with or without further cooking. Food substances are included. Food products include meat (eg, lean and pork), marine foods, poultry, fruits and vegetables, eggs, raw eggs, egg products, ready-to-eat foods, wheat, seeds, roots, tubers, leaves, stems, bulbs, Includes flowers, buds, seasonings or combinations thereof. The term "agricultural products" is a food product that is typically sold uncooked and often unwrapped and sometimes eaten raw (eg, fruits and vegetables, as well as plants or Plant-derived ones, etc.) are included.

As used herein, the expression "vegetable product" includes any botanical or plant-derived material that may require treatment with an antibacterial agent or antibacterial composition. Plant products include seeds, nuts, nuts, cut flowers, and plants or crops grown or stored in greenhouses and plant factories. Plant products include many animal feeds.

As used herein, processed fruits or vegetables are cut, chopped, sliced, peeled, ground, milled, irradiated, frozen, cooked (eg, boiled, pasteurized) or homogenized. Indicates the fruit or vegetable in which. As used herein, fruits or vegetables that have been washed, colored, waxed, hydrocooled, refrigerated, shelled, or defoliated, stem or husk are unprocessed.

As used herein, the expression "meat product" refers to all forms of animal meat, including the body, muscles, fats, organs, skin, bones and fluids that form an animal and similar components. .. Animal meat includes meat from mammals, birds, fish, reptiles, amphibians, cattle, birch, crustaceans, other edible species (eg, lobsters, crabs, etc.), or other forms of marine food. The form of animal meat includes, for example, whole or part of animal meat, alone or in combination with other ingredients. Typical forms include, for example, processed meat (eg, preserved meat), compartmentalized and formed products, chopped products, chopped products, minced meat and ground meat. Includes products (including minced meat) as well as whole products.

As used herein, the term "poultry" refers to all forms of any bird raised, harvested or domesticated for meat or eggs, including chickens, turkeys, ostriches and hunting birds. Includes chickens, chickens, pheasants, quails, ducks, ostriches or emu, and eggs of these birds. Poultry includes the poultry itself, compartmentalized, processed or cooked poultry, or uncooked poultry, and includes all forms of poultry meat, by-products and by-products. To. Poultry meat contains the muscles, fats, organs, skin, bones and body fluids that make up animals and similar components. The form of animal meat includes, for example, whole or part of animal meat, alone or in combination with other ingredients. Typical forms include, for example, processed poultry meat (eg, preserved poultry meat), compartmentalized and formed products, chopped products, chopped products, and whole. Includes products in.

As used herein, the expression "poultry debris" is any debris, debris, debris, filth, shavings, poultry organs that are removed from the body or part of the poultry during the processing period and enter the stream of waste. , Poultry waste, poultry offal, poultry organs, and fragments or combinations of such things.

Honmyo expressions used in Saisho "food processing surface" indicates food processing activities, tools used as part of the food preparation activity or food storage activities, machinery, equipment, the surfaces of such structure or building. Examples of processed food surfaces include surfaces of food processing equipment or food preparation equipment (eg, slicing equipment, canning equipment or transportation equipment (including transportation channels)), processed food products (eg, kitchen utensils, tableware, etc.). Includes the surface of cleaning products and glass for bars) and the surface of floors, walls or fixtures of structures where food processing takes place. Food processing surface, food anti-corruption air circulation system, sterile packaging disinfection, food refrigeration and food cooler cleaners and sanitizers, product cleaning disinfection, blancher cleaning and disinfection, food packaging materials, cutting board additives, third Third-sink disinfection, beverage coolers and warmers, water for meat cooling or hot water treatment, autodish sanitizers, disinfectant gels, cooling towers, antibacterial clothing for food processing Found and used in sprays and non-aqueous to low aqueous food preparation lubricants, oils and rinse additives.

As used herein, the expression "air flow" includes a food spoilage prevention air circulation system. Airflow also includes airflow typically encountered in hospital rooms, operating rooms, nursing rooms, delivery rooms, morgues and clinical diagnostic rooms.

As used herein, the term "water" includes water for food processes or food transport water. Food process water or food transport water includes product transport water (eg, water found in transport channels, pipe transport, cutters, slicers, blanchers, retort systems and washers, etc.), belt sprays for food transport lines, Includes soaking pans for washing boots and hands, as well as third sink rinse water. Water also includes domestic and recreational water (eg pools, spurs, recreational canals and water slides).

As used herein, the expression "healthcare surface" refers to the surface of an instrument, device, cart, cage, furniture, structure or building used as part of a healthcare activity. Examples of healthcare surfaces are medical or dental device surfaces, medical or dental device surfaces, electronic device surfaces used to monitor the health of a patient, floors of structures where healthcare is performed, etc. Includes the surface of the wall or fixture. Healthcare surfaces are found in hospital rooms, operating rooms, nursing rooms, delivery rooms, morgues and diagnostic rooms. These surfaces may include "hard surfaces" (eg, walls, floors, bed warmers, etc.) or fabric surfaces, such as knit surfaces, woven and non-woven surfaces (eg, surgical gowns, bandages, etc.). Surfaces categorized as sheets and pillowcases, bandages, etc., or as patient care equipment (eg, respiratory equipment, diagnostic equipment, shunts, body scopes, wheelchairs, beds, etc.), or as surgical and diagnostic equipment. Can be mentioned. Healthcare surfaces include articles and surfaces used in animal health care.

As used herein, the term "instrument" refers to a variety of medical or dental instruments or devices that can benefit from cleaning with the stabilized compositions according to the invention.

As used herein, the expression "medical (for) instrument", the expression "dental (for) instrument", the expression "medical (for) device", the expression "dental (for) device", the expression "medical (for)" "Equipment" or the expression "dental (for) equipment" refers to instruments, devices, tools, utensils, devices and equipment used in medicine or dentistry. Such instruments, devices and equipment can be pasteurized, soaked or washed and then pasteurized, or otherwise benefit from cleaning in the compositions of the invention. Can be done. These various instruments, devices and equipment include diagnostic instruments, trays, pans, holders, racks, tweezers, scissors, scissors, trocars (eg, bone trocars and their blades), hemostats, scalpels, chisel, Bone forceps, scissors, nippers, drills, drill bits, stone-grained scissors, bars, spreaders, breakers, raisers, clamps, needle holders, carriers, clips, hooks, osteopaths, curettes, retractors, stray toners, punches, Extractors, spatulas, corneal incisors, spartels, expressors, trocars, dilators, cages, glassware, tubes, catheters, cannulas, tweezers, stents, scopes (eg endoscopy, auditory instruments and arthroscopes) And related equipment, etc., or combinations thereof, but not limited to these.

As used herein, "agricultural" or "veterinary" objects or surfaces include animal feed, animal watering stations and enclosures, zoos, veterinary clinics (eg, surgical or treatment areas). ), As well as animal surgery areas.

As used herein, an object or surface of a "house" or "facility" includes an object or surface found in a human-dwelling structure. Such objects or surfaces include bathroom surfaces, drains, drains and kitchen surfaces, and the like.

As used herein, the expression "dense fluid" refers to a fluid that is in a critical state, a subcritical state, a near critical point state, or a supercritical state. Such fluids are generally gases at 1 atmosphere and 0 ° C standard conditions. As used herein, the expression "supercritical fluid" refers to a dense gas that is maintained above its critical temperature (a temperature above which it cannot be liquefied by pressure). Supercritical fluids are typically less viscous than liquids and diffuse more easily than liquids. In one embodiment, the densifying fluid is at or above that critical point, or just below that critical point. As used herein, the expression "critical point" is a transition point at which the liquid and gaseous states of a substance merge with each other and represent a combination of critical temperature and pressure for a substance. The critical pressure is just enough pressure to cause the appearance of two phases at the critical temperature. Critical temperature and pressure have been reported for numerous organic and inorganic compounds as well as some elements.

As used herein, the term "near critical point" fluid or the term "subcritical" fluid is typically below the critical temperature of a supercritical fluid, but due to the effects of pressure on the fluid. It shows a fluid that is still in a fluid state and maintains a higher density than a typical gas. In one embodiment, the subcritical fluid or fluid near a critical point is at a temperature and / or pressure just below that critical point. For example, a subcritical fluid or a fluid near a critical point is below its critical temperature but above its critical pressure, or below its critical pressure but above its critical temperature. Alternatively, it can be below both its critical temperature and critical pressure. The terms near critical point and subcritical do not refer to substances in their normal gaseous or liquid state.

As used herein, weight percent (wt-%), weight percent percent, weight percent% and similar expressions are the concentration of a substance divided by the weight of the composition and multiplied by 100 for that substance. It is a synonym for weight. Unless otherwise stated, the amount of ingredient indicates the amount of active ingredient.

As used herein, the term "mixed" or the term "mixture", when used in connection with a "peroxycarboxylic acid composition" or "peroxycarboxylic acid", is used in connection with two or more peroxys. The composition or mixture containing carboxylic acid is shown, and for example, the composition or mixture containing peroxyacetic acid and peroxyoctanoic acid is shown.

As used herein, the term "about", which modifies the amount of ingredients in the compositions of the invention or is used in the methods of the invention, refers to, for example, high concentrations or solutions used in practice. Due to the typical measurement and liquid handling techniques used to make in the world, due to inadvertent errors in these methods, and to make the compositions of the present invention, or to make the compositions of the present invention. It shows variations in numerical quantities that may occur due to differences in the manufacture, source or purity of the ingredients used to carry out the method, and others. The term about also includes different amounts due to different equilibrium conditions for the composition resulting from a particular starting mixture. Claims include an equivalent amount, whether or not modified by the term "about".

For the purposes of this patent application, successful microbial reduction is achieved when the microbial population is reduced by at least about 50%, or significantly more than can be achieved by washing with water. To. Greater reductions in microbial populations provide greater levels of protection.

As used herein, the term "sanitizer" refers to an agent that reduces the number of bacterial contaminants to a safe level as determined by public health requirements. In one embodiment, the sanitizer used in the present invention results in a reduction of at least 99.999% (logarithmic reduction of 5 units). These reductions are shown in the Germanicidal and Detergent Sanitizing Action of Disinfectants, Official Methods of Analysis of the Association of Official Analytical Chemists (paragraph 960.09 and applicable sections, 15th edition, 1990 (EPA Guideline 91-2)). It can be evaluated using procedures. According to this reference, the sanitizer must provide a 99.999% reduction (logarithmic reduction of 5 units) within 30 seconds at room temperature (25 ± 2 ° C) for some test organisms.

As used herein, the term "disinfectant" is used in AOAC Use Dilution Methods, Official Methods of Analysis of the Association of Official Analytical Chemists (paragraph 955.14 and applicable sections, 15th edition, 1990 (EPA Guidelines 91-). 2)) Use the procedure described to indicate a drug that kills all vegetative cells, including most recognized pathogenic microorganisms.

The term "spore-killing agent" used in the present invention reduces the number of spores of Bacillus cereus or Bacillus subtilis by more than 90% (a decrease of more than 1 unit in logarithmic value) by 60%. Indicates a physical or chemical agent or process capable of occurring within 10 seconds at ° C. In some embodiments, the spore-killing compositions of the present invention have a reduction of more than 99% (logarithmic reduction of more than 2 units) or a reduction of more than 99.99% (logarithmic 4 units) in such populations. Produces a reduction of more than 99.999% (a reduction of more than 5 units in logarithm) within 10 seconds at 60 ° C.

Definitions of "bactericidal" or "bacteriostatic" activity of antimicrobial agents, definitions of degree of efficacy, and official laboratory protocols for measuring this efficacy provide validity of antimicrobial agents and antibacterial compositions. It is a material for consideration to understand. Antibacterial compositions can result in two types of microbial cell damage. The first is a lethal and irreversible effect that results in the complete destruction or incapacity of microbial cells. The second type of cell damage is reversible so that once the organism is released from the drug, the organism can proliferate again. The former is called bactericidal and the latter is called bacteriostatic. Sanitizers and disinfectants, by definition, are agents that provide antibacterial or bactericidal activity. In contrast, preservatives are commonly described as inhibitors or bacteriostatic compositions.

<u style="single">Equipment for making peroxycarboxylic acid</u> The present invention relates to an apparatus for producing a peroxycarboxylic acid and a method using this apparatus. The apparatus of the present invention includes a reaction catalyst and a pretreatment column. The pretreatment column pretreats one or more of the reagents used in making the peroxycarboxylic acid. For example, acid type or inert metal (eg Na⁺Or K⁺) Type cation exchangers allow positively charged contaminants (eg, metal ions, etc.) to be removed from hydrogen peroxide, carboxylic acids, or mixtures of hydrogen peroxide and carboxylic acids. Reaction of a carboxylic acid (or a suitable precursor) with an oxidizing agent (eg, peroxide, peroxide donor (eg, hydrogen peroxide donor, etc.)) to form a peroxycarboxylic acid with a reaction catalyst. Is catalyzed. For example, a reaction catalyst that is a strong acid (eg, polystyrene sulfonic acid) can catalyze the reaction of hydrogen peroxide with the carboxylic acid to form the peroxycarboxylic acid. The pretreatment column can increase the life, activity and / or safety of the reaction catalyst.

The device of the present invention can also include a safety system. The safety system allows the status of one or more of the pretreatment columns and / or reaction catalysts to be monitored and / or regulated. For example, safety systems can monitor and / or regulate the pressure, temperature, metal content, and / or the presence of gases (eg, oxygen) resulting from the decomposition of peroxides. The safety system puts one or more of these parameters in the pretreatment column, in the pretreatment column, or in the reaction catalyst, or in the reaction catalyst, i.e. before or in the pretreatment column. For one or more of the reagents in or after, or for the reaction mixture before, during or after the pretreatment column, or for the reaction mixture before, during or after the reaction catalyst, or a combination thereof. ) Can be measured for two or more. The safety system can measure the difference in one or more of these parameters between any two points in the device, eg, any two of the listed locations.

In one embodiment, the apparatus of the present invention comprises one or more reagent containers, each of which can contain hydrogen peroxide or a carboxylic acid. These vessels can be in fluid communication with the pretreatment column, and reagent mixing occurs either in front of or within that column. The pretreatment column can be in fluid contact with the reaction catalyst (typically in the column). The resulting peroxycarboxylic acid emerges from the reaction catalyst and the resulting peroxycarboxylic acid can either be used or stored, for example, in a day tank.

When the reaction of the carboxylic acid with the peroxide causes these reagents to come into contact with the reaction catalyst at a controlled and predetermined flow rate (eg, when moving between and / or near the reaction catalysts), the reaction catalyst Occurs in the presence. The size of the pretreatment column, the size of the reaction catalyst bed, and the residence time in each of these so as to provide the desired amount of conversion of carboxylic acid to peroxycarboxylic acid (often as large as possible). Predetermined and controlled. The size of the column, bed or bag of the reaction catalyst, and the residence time therein, are pre-arranged to provide the desired amount of conversion of carboxylic acid to peroxycarboxylic acid (often as large as possible). Determined and controlled. System parameters for the device, such as the amount of reaction catalyst, column of reaction catalyst, size of floor or bag, and reagent flow rate, etc., on the reaction catalyst for conversion to the desired peroxycarboxylic acid composition. It can be selected to provide sufficient residence time for the reaction mixture. The reaction catalyst can produce peroxycarboxylic acids at concentrations as high as, for example, about 35 wt-%, such as about 5 wt-% (eg 5.3 wt-%), about 10 wt-%, about 15 wt-%, It can be produced at concentrations of about 20 wt-% (eg 19 wt-%), about 25 wt-%, about 30 wt-% or about 35 wt-%.

The devices of the present invention also include additional useful or desired systems commonly used for system operation, including catalyst or cation exchanger floors or columns (eg, fittings, valves, pumps, mixing chambers, etc.). Water or additive feed connections, etc.) can be included.

In the apparatus of the present invention, a reagent containing only a volatile component or a reagent containing a very small amount of a non-volatile component can be used. Insignificant amounts of non-volatile components include acceptable amounts for food or beverage containers (eg, sterile packaging) after washing and drying. For example, in the apparatus of the present invention, reagents that do not contain or substantially do not contain stabilizers or chelating agents (eg, HEDP) can be used. As a further example, in the apparatus of the present invention, a reagent having no phosphate can be used.

Therefore, the apparatus of the present invention can produce a peroxycarboxylic acid composition containing only a volatile component or a very small amount of a non-volatile component. For example, the apparatus of the present invention can produce a peroxycarboxylic acid composition that is free or substantially free of stabilizers or chelating agents (eg, HEDP). As a further example, the apparatus of the present invention can produce a peroxycarboxylic acid composition without a phosphate.

Pretreatment column In one embodiment, the apparatus of the present invention comprises one or more pretreatment columns, each of which is in fluid communication with a conduit from only one reagent vessel. The pretreatment column can be directly connected to the reaction catalyst floor, bag or column. Alternatively, the pretreatment column can be in fluid contact with the second pretreatment column, which is also in fluid contact with the source of the second reagent. The pretreatment column may be in fluid communication with the conduit for the second reagent (pretreated or untreated), which mixes the reagents before entering the second pretreatment column. It is possible. The size of the pretreated column and the residence time in the pretreated column are predetermined and controlled to result in the removal of the desired amount of contaminants from the pretreated composition.

In one embodiment, the apparatus of the present invention comprises a large number of reagent containers and a large number (eg, two) pretreatment columns connected in parallel between the reaction catalysts. The flow of reagents through the conduit can be controlled by the valve system. The flow can be guided through the pretreatment column until the pretreatment column is fully used or until it is indicated that the pretreatment column is no longer suitable for use. .. The second pretreatment column can remain available for the duration of use of the first pretreatment column. Then, when the first pretreatment column is no longer available, the valve system can guide the flow through the second pretreatment column. Unused columns can be replaced, serviced or cleaned. For easy replacement, the pretreatment column can be a cartridge that is quickly and easily removed from and installed in the device. The pretreatment column can be washed, for example, with a thin, strong mineral acid (eg, sulfuric acid, etc.).

Alternatively, the pretreatment column or pretreatment system can be configured as a pretreatment floor or pretreatment bag. A pretreatment floor or pretreatment bag can be used in place of the pretreatment column in the embodiments described herein.

Use of the apparatus of the present invention can be continued while one of the pretreatment columns is maintained or replaced. Column replacement can be done according to a predetermined schedule. Alternatively, the condition of the pretreatment column in use can be measured by a safety system that can also control the valve system.

In one embodiment, the pretreatment column is a cartridge or segment that is located in front of the reaction catalyst and can be present in a column, bag or floor containing the reaction catalyst. Such cartridges can be replaced in a reaction catalyst column, bag or floor, and can be replaced in a reaction catalyst column, bag or floor. In one embodiment, the pretreatment column can be part of the cation exchanger at the entrance to the reaction catalyst column, bag or floor, or at the start of the reaction catalyst column, bag or floor. .. This part is configured to be removed and replaced, for example, when the safety system indicates so or after a certain amount of use.

Reaction catalyst The reaction catalyst can be present on one or more floors, bags or columns. These floors, bags or columns can be connected in series, or in parallel, or partly in series and partly in parallel. In one embodiment, the apparatus of the present invention comprises four columns containing a reaction catalyst and connected in series. In other embodiments, the apparatus of the present invention comprises up to about 10 reaction catalyst columns, including, for example, 1 to 10 columns, such as 2, 3, 4 or 5 columns.

The flow of reagents through the bed, bag or column of the reaction catalyst can be controlled by the valve system. The flow should pass through the floor, bag or column until the floor, bag or column is fully used, or until the floor, bag or column is shown to be no longer suitable for use. Can be guided. The second floor, bag or column can be left in a usable state for the duration of use of the first column, bag or floor. Then, when the first floor, bag or column is no longer available, the valve system can guide the flow through the second floor, bag or column. The second set of floors, bags or columns can be left available for the duration of use of the first set of floors, bags or columns. Then, when the first set of floors, bags or columns is no longer available, the valve system can guide the flow through the second set of floors, bags or columns. Unused floors, bags or columns (or sets thereof) can be replaced, serviced or cleaned. Use of the device of the present invention can be continued while one of the floors, bags or columns (sets) is being serviced or replaced. The condition of the floor, bag or column in use can be measured by a safety system that can also control the valve system.

Safety system The apparatus of the present invention can include a safety system capable of measuring one or more properties of the pretreatment column, or one or more properties of the reaction catalyst, or both. For example, a safety system can measure pressure (eg, increased pressure) and / or temperature (eg, increased temperature). An increase in temperature or pressure from the nominal value for the pretreatment column may indicate, for example, an unwanted decomposition of hydrogen peroxide catalyzed by active metal ions. For example, a safety system can measure the temperature difference between two points in or near the pretreatment column (eg, before and after the pretreatment column, or before and inside the pretreatment column). Increases in temperature or pressure differences from nominal values at or near two points in or near the pretreatment column may indicate, for example, unwanted decomposition of hydrogen peroxide catalyzed by active metal ions. The point (s) at which the temperature or pressure is measured can be selected to provide the desired sensitivity to contamination or decomposition. The safety system can include a value or a manometry sensor for measuring changes in the value.

Safety systems can measure pressure, temperature, pressure difference, temperature difference or a combination thereof and provide a perceptible signal if one or more of these increase above a predetermined level. can do. Pressures, temperatures, pressure differences, temperature differences or combinations thereof above a certain level can indicate the hazards arising from the reaction of the peroxide with the metal. The level of pressure, temperature, pressure difference, temperature difference or combination thereof that the safety system provides a perceptible signal can be selected so that intervention can avoid undesired or unsafe conditions. ..

When the safety system detects a pressure, temperature, pressure difference, temperature difference or a combination thereof that exceeds a preselected level, for example, operating the pressure release valve, stopping the flow of one or more reagents. Perceptible to alert the operator to flush the device, flush the carboxylic acid composition through the device, shut down the device, or suspend the operation of the device by a combination of these. It can provide a signal. When the safety system detects a pressure, temperature, pressure difference, temperature difference or a combination thereof that exceeds a preselected level, the operator switches to another pretreatment column or another bed or column of reaction catalyst. Can provide a perceptible signal that alerts the patient.

A safety system can provide a signal to a controller (eg, a controllable logic controller) that activates a pressure release valve, shuts off the flow of one or more reagents, water. Can be flowed through the device, the carboxylic acid composition can be flowed through the device, the device can be shut down, or a combination thereof can be performed. When the safety system detects a pressure, temperature, pressure difference, temperature difference or a combination thereof that exceeds a preselected level, the controller switches to another pretreatment column or another bed or column of reaction catalyst. Can provide a signal to.

The safety system puts the state at the inlet or outlet of the pretreatment column, or inside the column (eg, near the inlet of the column, inside the column, or near the exit from the column), or to the pretreatment column. It can be measured in the incoming conduit or in the outgoing conduit from the pretreatment column. In another embodiment of the safety system, the amount of metal in the pretreatment column or reaction catalyst, or the amount of metal in the pretreatment column or reaction catalyst, can be quantified.

In one embodiment, the safety system is configured to measure temperature at the inlet to the pretreatment column and at the first 25% of the pretreatment column. Not limited to the present invention, because contamination of the pretreatment column can occur with an exponential gradient, and with hydrogen peroxide and contaminants (eg, metal ions, eg Fe) on the column.²⁺Or Cu²⁺Since the reaction with (etc.) is exothermic, it may be desirable to measure this difference.

In one embodiment, the safety system can include a processor and two status sensors (eg, temperature sensor, pressure sensor or metal sensor). The processor can, for example, perform calculations on inputs received from status sensors and also provide signals that can be received and / or perceived by the operator of the device or one or more actuating devices. be able to. In one embodiment, the actuating device is a pressure release valve, stopping the flow of one or more reagents, flowing water through the device, flowing the carboxylic acid composition through the device, shutting down the device. You can signal valves, pumps, switches or other systems to do or combine these, or you can activate valves, pumps, switches or other systems. Alternatively, valves, pumps, switches or other systems can be operated.

The safety system puts the state at the entrance or exit of the reaction catalyst column, floor or bag, or inside the column, floor or bag (eg, near the inlet, inside or near the outlet), or into the reaction catalyst. It can be measured in the conduit or in the conduit exiting the reaction catalyst. In one embodiment, the safety system is configured to measure temperature at the inlet to the reaction catalyst and at the first 25% of the reaction catalyst.

Further system The device of the present invention can also include a system for storing, handling, diluting, and formulating the compositions made by the device. For example, the peroxycarboxylic acid obtained from the reaction catalyst can either be used or stored, for example, in a day tank. The storage system can be a suitable container for containing the peroxycarboxylic acid composition between synthesis and use, such as a day tank or another container. Alternatively, the conduit can be routed directly from the device to the diluter or point of use.

The device of the present invention can include a dilution system and / or a compounding system for diluting and / or formulating a composition from the device or day tank. The device of the present invention can produce a high concentration product that can be diluted before use. The concentration of peroxycarboxylic acid in the solution used can be, for example, about 2 ppm to about 5000 ppm or about 750 ppm to about 3600 ppm. Further suitable dilutions and compositions used are described herein below. The diluting device adds and / or mixes a diluent or carrier (eg, water, etc.) to the peroxycarboxylic acid, for example, to achieve a diluted composition containing the desired concentration of peroxycarboxylic acid. be able to. In one embodiment, the dilution system can include a pump that takes in both the carboxylic acid composition and the diluent and pumps them out to one or more conduits in the desired proportions. The dilution system can provide the diluted composition directly to the site of use, to the day tank, or to the dilution composition storage system. In one embodiment, the dilution system can include an applicator nozzle if the diluted composition is applied directly to the site of use. The applicator nozzle can be configured to heat the composition while applying the composition.

In one embodiment, the apparatus and / or dilution system of the present invention can be configured to add another component to the peroxycarboxylic acid composition. Various such ingredients are described herein below. For example, the dilution system can add a diluent containing the added component. The compounding system can dispense the desired amount of added ingredients into the composition or diluted composition. Such a system is useful for adding components that are incompatible with the synthesis or storage of peroxycarboxylic acids (eg, quaternary ammonium chloride).

The storage system comprises a storage monitor configured to measure the content of peroxycarboxylic acid, the content of carboxylic acid and / or the content of hydrogen peroxide in the composition (eg, the composition used in storage). Can include. In one embodiment, the dilution composition storage system comprises a replenishment system. The replenishment system can monitor the content of the composition used. For example, if the concentration of peroxycarboxylic acid drops below a predetermined level or the concentration of carboxylic acid increases above a predetermined level, the replenishment system uses a higher concentration of peroxycarboxylic acid composition. It can be added to the product or the container of the used used composition can be emptied. The replenishment system can include, for example, a flow meter and a sensor that detects the concentration of peroxycarboxylic acid.

The device of the present invention can also include a reagent flow control system. The reagent flow system can monitor the peroxycarboxylic acid composition after the reaction catalyst, eg, at the outlet from the last reaction catalyst column. This system can determine if the composition contains the desired concentration of peroxycarboxylic acid (eg, equilibrium concentration). If the composition contains a lower concentration than desired, the system can slow the flow rate of the reaction mixture through the reaction catalyst to a flow rate that results in the desired concentration. In this system, changes in flow velocity can be calculated using a variety of factors, including the temperature of the composition and the concentration of peroxycarboxylic acid. The desired concentration of peroxycarboxylic acid can be a lower limit, and the desired concentration can be any achievable concentration above such a lower limit.

In one embodiment, the device of the invention can include an intermediate container configured to receive one or more reagents after the reagents have passed through a pretreatment column. The intermediate vessel can be in fluid contact with the pretreatment column and reaction catalyst. The intermediate vessel can be configured to receive and contain the pretreated reagents. The intermediate vessel can be fluid contacted at the same time as the pretreatment column and reaction catalyst. In one embodiment, the intermediate vessel can be in fluid contact with the pretreatment column and reaction catalyst at different times or at overlapping times. In one embodiment, the intermediate vessel is present in the first position to receive the reagent (s) from the pretreatment column which is transported to the second position to provide the reagent to the reaction catalyst. be able to.

In one embodiment, the apparatus of the present invention can include a purification system that removes non-volatile components from one or more of the reagents, eg, one or more of carboxylic acids and peroxides. In one embodiment, the purification system is configured as a column, bag or floor of anion exchangers that are in fluid contact with the hydrogen peroxide source and pretreatment column.

The device of the present invention can be in fluid communication with the aseptic packaging system and can be configured to provide the peroxycarboxylic acid composition to the aseptic packaging system. The peroxycarboxylic acid composition may be ready for use in an aseptic packaging system or may require dilution prior to use in an aseptic packaging system. In one embodiment, the apparatus of the present invention can provide ready-to-use peroxycarboxylic acid compositions, for example, in bottle wash container tanks and / or cup wash container tanks. In one embodiment, the apparatus of the present invention can supply water or another diluent with a high concentration that can be mixed in or by an aseptic packaging system. Such a packaging system can include a container of water or can be connected to a source of purified water. The aseptic packaging system can include a chamber through which the bottle is rinsed and a chamber in which the cap is contacted with the diluted peroxycarboxylic acid composition or the ready-to-use peroxycarboxylic acid composition. A sterile packaging system is a recirculation system that collects the peroxycarboxylic acid composition applied to the bottle and / or cap and returns it to a suitable container for reuse, or a further bottle and / or cap of the composition. Can include a recirculation system that reapplies to.

Embodiment of the device In one embodiment, the device of the invention can include two or three reagent containers, in which case one contains hydrogen peroxide and one contains a short chain carboxylic acid (eg, acetic acid). If necessary, the third container contains a medium chain carboxylic acid (eg, octanoic acid). A container of short chain carboxylic acid (eg, acetic acid) can be connected to a short chain carboxylic acid (eg, acetic acid) pretreatment column by conduit, and reagent mixing occurs after this column. Short-chain carboxylic acid (eg, acetic acid) pretreatment columns have acid-type or inert metal (eg, Na) cation exchangers.⁺Or K⁺), By this cation exchanger, positively charged contaminants such as metal ions (eg, non-inactive metal ions, eg iron (Fe)).²⁺And / or Fe³⁺) Ion or copper (Cu²⁺) Ions) etc. can be removed from acetic acid. The Inactive metal cation can be selected to bind only weakly by the cation exchanger. Pretreatment columns dedicated to hydrogen peroxide and / or medium chain carboxylic acids are installed as needed.

<u style="single">Embodiment for producing a peroxycarboxylic acid</u> In one embodiment, only short chain carboxylic acids (eg, acetic acid) have a dedicated pretreatment column and no medium chain carboxylic acids are used. In this embodiment, conduits for short chain carboxylic acids (eg, acetic acid) and conduits for hydrogen peroxide merge in front of the main pretreatment column and these reagents mix. The main pretreatment column uses acid-type or inert metals (eg, Na) for the cation exchanger.⁺Or K⁺), With this cation exchanger, positively charged contaminants such as metal ions can be removed from the mixture of hydrogen peroxide and carboxylic acid. A conduit of acetic acid and hydrogen peroxide mixture leads to the main pretreatment column, providing the column with these mixed reagents. This embodiment comprises four columns of reaction catalysts. These four columns are in series and are connected to the main pretreatment column by a conduit. On the opposite side, these four columns supply short-chain peroxycarboxylic acids (eg, peroxyacetic acid) to the conduit to either the storage vessel or the point of use for this composition.

This embodiment can also include a safety system. The safety system monitors the temperature, for example, in the conduit after the mixing of hydrogen peroxide and short chain carboxylic acid (eg, acetic acid) and / or at the inlet to the main pretreatment column. Can include. The safety system can also include sensors that monitor temperature within the main pretreatment column, eg, inside the first 25% of the main pretreatment column. The safety system perceives if the temperature difference between the sensor in front of the main pretreatment column and the sensor in the main pretreatment column increases above a predetermined level (eg, about 10 ° C). It can provide possible signals. In this embodiment, the safety system provides a perceptible signal to the operator and / or a perceptible signal to the controller. Upon receiving the signal, the operator or controller stops the flow of reagents to the main guard column and / or flushes the conduit and main guard column with water or a short chain carboxylic acid (eg, acetic acid).

This embodiment of the device can also include additional useful or desired systems, such as fittings, valves, pumps, mixing chambers, and the supply of water or additives that are useful or convenient in this device. It can include a connection part and the like. This embodiment can also include one or more systems for storing, handling, diluting, and formulating the compositions made by the devices described above.

<u style="single">Embodiment for producing a mixed peroxycarboxylic acid</u> In one embodiment, the apparatus of the present invention can include three reagent containers, one containing hydrogen peroxide, one containing a short chain carboxylic acid (eg, acetic acid), and a third. Container contains a medium chain carboxylic acid (eg, octanoic acid, etc.). A container of short chain carboxylic acid (eg, acetic acid) can be connected to a short chain carboxylic acid (eg, acetic acid) pretreatment column by conduit, and reagent mixing occurs after this column. The short chain carboxylic acid (eg, acetic acid) pretreatment column can be as described for the above embodiments and can operate as described for the above embodiments. Pretreatment columns dedicated to hydrogen peroxide and / or medium chain carboxylic acids (eg, octanoic acid) are installed as needed.

In this embodiment, a conduit for short chain carboxylic acid (eg, acetic acid) and a conduit for hydrogen peroxide merge in front of the first main pretreatment column and these reagents are mixed. This main pretreatment column can be as described for the above embodiments and can operate as described for the above embodiments. A conduit of a mixture of short chain carboxylic acid (eg, acetic acid) and hydrogen peroxide leads to a first main pretreatment column, which provides the mixed reagent to the column. This embodiment comprises a dedicated reaction catalyst (eg, 4) column for producing a short chain peroxycarboxylic acid (eg, peroxyacetic acid). These columns are in series and are connected by a conduit to the first main pretreatment column. On the other side, these columns supply short chain peroxycarboxylic acids (eg, peroxyacetic acid) to the conduit.

This embodiment also includes a conduit for medium chain carboxylic acid and a conduit for hydrogen peroxide, these conduits merging in front of a second main pretreatment column and mixing these reagents. This second main pretreatment column can be as described for the above embodiments and can operate as described for the above embodiments. A conduit of mixed medium chain carboxylic acid and hydrogen peroxide leads to a second main pretreatment column, providing the column with these mixed reagents. This embodiment comprises a dedicated reaction catalyst (eg, 4) column for producing a medium chain peroxycarboxylic acid. These columns are in series and are connected by a conduit to the second main pretreatment column. On the other side, these columns supply medium chain peroxycarboxylic acid to the conduit.

Short-chain peroxycarboxylic acid (eg, peroxyacetic acid) conduits and medium-chain peroxycarboxylic acid (eg, octanoic acid) conduits contain these peracids in storage containers and / to produce mixed peroxycarboxylic acid compositions. Alternatively, it can be sent to a mixing container. Alternatively, these conduits can be merged to produce a mixed peroxycarboxylic acid composition.

This embodiment can also include a safety system. The safety system can include sensors that monitor the temperature in front of and inside each pretreatment column, and the safety system responds to increased temperature differences for either pretreatment column. This embodiment of the device can also include additional useful or desired systems, such as fittings, valves, pumps, mixing chambers, and the supply of water or additives that are useful or convenient in this device. It can include a connection part and the like. This embodiment can also include one or more systems for storing, handling, diluting, and formulating the compositions made by the devices described above.

Device components<u style="single">Pretreatment column</u> The pretreatment column can contain any of a variety of cation exchangers, such as strong cation exchangers. Suitable cation exchangers for pretreatment columns include polystyrene sulfonate resins such as Dowex M31, Dowex DR-2030, Dowex Monosphere M-31, Dowex Monosphere DR-2030, Dowex Marathon 545C, Dowex 50W. X8-H, Dowex 545C, Dowex G26, Amberlyst 15Wet, Amberlyst 15Dry, Amberlyst 31Wet, Amberlyst 131Wet, Amberlyst CH10, Purolite C-100H, Purolite C-150H, Lewatit MonoPlus S100H, and Lewatit MonoPlus Includes cation exchangers sold under trade names such as SP112H. Further cation exchangers suitable for pretreatment columns include sulfonated tetrafluoroethylene copolymers, such as Nafion NR50 (beads), Nafion SAC-13 (granule) and Nafion 117 (film). Includes sulfonated tetrafluoroethylene copolymers and the like sold under trade names such as. Other cation exchangers suitable for pretreatment columns include cation exchangers sold under the trade names Dowex 545C, Dowex G26, which have a large ion capacity. In one embodiment, the pretreatment column comprises an alkali metal (eg, sodium) form of the ion exchanger.

Although not limited to the present invention, polystyrene sulfonate resins with minimal cross-linking (with divinylbenzene) are problematic for initial alkali metal (eg, sodium or potassium) ions, even if all other things are equal. It is believed to exhibit improved selectivity for exchange with transition metal ions or heavy metal (eg, iron and copper) ions.

Suitable pretreatment columns can be sized so that sufficient flow rates and coupling capacities support the required volume of the device. For example, in a pretreatment column in an apparatus in which four columns of reaction catalysts are used, each having a volume of about 10 L, a pretreatment column having a volume of about 5 L can be used. For example, in a pretreatment column in an apparatus for producing a peracid composition of about 11 (eg, 10.7) liters / hour, a pretreatment column containing about 4 (eg, 3.9) liters of resin can be used. For example, in a pretreatment column in an apparatus for producing a peracid composition of about 20 (eg, 21.3) liters / hour, a pretreatment column containing about 8 (eg, 7.8) liters of resin can be used. For example, in a pretreatment column in an apparatus for producing a peracid composition of about 45 (eg, 42.6) liters / hour, a pretreatment column containing about 15 (eg, 15.5) liters of resin can be used.

The pretreatment column can be configured for cleaning the resin or for the convenience and ease of replacing the column. For example, the pretreatment column can be in fluid communication with inlet and outlet conduits with quick connection couplings. Parkers for suitable quick connection couplings Indi-Lok (Stratoflex) couplings or Slide-Lok couplings, or Cole-Parmers, EW-31306-16 couplings are included, in which case the assembly material is preferably polypropylene, polyethylene or polyfluorocarbon. Fast-connect couplings are also used for acid backwashing and for inlets and outlets that can be operated by the controller or manually. The pretreatment column can be a cartridge that can be replaced in and out of the device. Suitable cartridges can be machined from Schedule 40 polyprepylene or high density polyethylene tubing material, which is fitted with a manometry sensor and / or temperature sensor that can be connected to a control device.

The device can be configured to accept only cartridges suitable for use in the device. For example, the device and / or cartridge may be a fitting, radio frequency identification circuit, or other electronic device (eg, a logical chip or barcode or) that indicates to the device that the cartridge is suitable for use in the device. Leader) can be included. For example, the cartridge can include a programmable device that stores the number of times the cartridge has been washed so far. The cartridge and / or the device may indicate after a predetermined number of washes that the cartridge is no longer suitable for use. This instruction can result in the cartridge being removed from the device. Similarly, the device can be configured to remove cartridges that are not suitable for use in the device.

For example, a transponder programmed with an identifier can be placed on the pretreatment column and / or reaction catalyst. This allows the pretreatment column and / or reaction catalyst to be identified as suitable for the apparatus of the present invention. For example, the transponder can be placed in the pretreatment column and / or the reaction catalyst, or it can be molded in the pretreatment column and / or the reaction catalyst. Small injectable transponders (1/16 x1 / 2) work best in pretreatment columns and / or reaction catalysts, in part due to their ease of installation. Also, while transponders can be molded into the rack when the rack is manufactured, it may be desirable to improve existing racks if possible. In alternative embodiments, transponders of other sizes may be acceptable.

The transponder can be placed in any suitable location within the pretreatment column and / or reaction catalyst, or within the pretreatment column and / or reaction catalyst. In one embodiment, the specific orientation of the pretreatment column and / or reaction catalyst is placed with the transponder offset to one side or end of the pretreatment column and / or reaction catalyst, and the transponder's antenna is properly offset. It can be enforced by installing it.

The transponder can be pre-programmed with specific identification information (eg, an identifier value indicating the type of pretreatment column and / or reaction catalyst in use). An example of a transponder that can be used is the Destron / IDI Injectable Transponder Model TX1400L. This Injectable Transponder is a passive radio frequency identification tag designed to work in combination with a compatible radio frequency ID reading system.

In alternative embodiments, image identification can also be used, in which case the respective pretreatment columns and / or reaction catalysts are housed in the apparatus of the present invention. Can be visually identified before. An example of visual identification is when the operator of the device can select several different icons on the computer screen that match the pretreatment column and / or reaction catalyst installed in the device.

Identification of pretreatment columns and / or reaction catalysts, for example, by the use of specially designed pretreatment columns and / or reaction catalysts, or by the use of optical recognition, or by the use of barcodes, or This can be done by the color of the pretreatment column and / or the reaction catalyst, or by the use of a proximity sensor.

One embodiment of the apparatus of the present invention includes a transceiver capable of detecting the type of pretreatment column and / or reaction catalyst from an identifier and transmitting that identification information to a processor. Transceivers generally include a transponder antenna that can be located on the outer edge of the device adjacent to the pretreatment column and / or reaction catalyst, and the transponder thereof. The transponder antenna can also be placed within the device. The transceiver also includes a transponder interface that is connected to the processor for identification information to be received by the processor and subsequently for retrieval in the storage device.

For detectors, barcode scanners similar to the types used in supermarkets can also be used in embodiments. Infrared scanners or proximity sensors can be used. Examples of scanners that can be used are the Pocket Reader Scanner and Pocket Reader EX Scanner from Destron-Fearing Corporation (South St. Paul, Minn.). The corresponding barcode is affixed to the rack for detection by the barcode scanner.

<u style="single">Reaction catalyst</u> The reaction catalyst may include any of a variety of cation exchangers, such as strong cation exchangers. In one embodiment, the reaction catalyst is a protonated form of the proton exchanger. Suitable cation exchangers as reaction catalysts include polystyrene sulfonate resins such as Dowex M31, Dowex DR-2030, Dowex Monosphere M-31, Dowex Monosphere DR-2030, Dowex Marathon 545C, Dowex 50W X8-H, Dowex. 545C, Dowex G26, Amberlyst 15Wet, Amberlyst 15Dry, Amberlyst 31Wet, Amberlyst 131Wet, Amberlyst CH10, Purolite C-100H, Purolite C-150H, Lewatit MonoPlus S100H, and Lewatit MonoPlus Includes cation exchangers sold under trade names such as SP112H. Further cation exchangers suitable as reaction catalysts include sulfonated tetrafluoroethylene copolymers, such as products such as Nafion NR50 (beads), Nafion SAC-13 (granule) and Nafion 117 (film). Includes sulfonated tetrafluoroethylene copolymers and the like sold under the name. Other cation exchangers suitable as reaction catalysts include cation exchangers sold under the trade names Dowex 545C, Dowex G26, which have a large ion capacity.

Further suitable reaction catalysts, in some embodiments, include inorganic compounds that are insoluble strong acids or that contain insoluble strong acids and have a large surface area / weight ratio. Such inorganic catalysts include inorganic catalysts sold under common names such as "sulfated zirconia", "silica-stabilized tetragonal zirconia" and "tungsten oxide zirconia" (these are from Saint-Gobain Norpro). can get). Suitable inorganic catalysts are also collectively referred to as "ZrO".₂Includes zirconia oxides (MEI Chemicals) sold as. Zirconia oxide can be treated with sulfuric acid to make "sulfated zirconia" and then calcined at about 700 ° C. Other suitable inorganic catalysts include sulfated silica or silicon oxide, sulfated or acidified zeolites, sulfated or acidified aluminum oxide, and phosphonic acid derivatized silicon oxide (eg, "Si". -POH₂Includes phosphonic acid derivatized silicon oxide sold under the trade name and alkylphosphonic acid modified silica, which are obtained from Phosphononics Ltd).

Suitable columns, bags or beds of the reaction catalyst can be sized so that sufficient flow rates and binding capacities support the required volume of the device. For example, in a reaction catalyst column, bag or floor in an apparatus for producing a peroxy acid composition of about 40 (eg, 41) liters / hour, each has a volume of about 30 (eg, 31) L and 1 meter. Four columns of reaction catalysts can be used, which are of length and 20 cm in diameter. The reaction catalyst column, bag or floor can be sized in any suitable size to achieve the desired flow rate. Suitable sizes include, for example, from about 0.1 (eg, 0.13) meters to about 15 (eg, 13) meters in length and, for example, from about 10 cm to about 100 cm in diameter. Suitable columns include columns sized to be about 15 (eg, 13) meters in length and about 10 cm in diameter. Suitable columns include columns sized to be about 0.5 (eg, 0.4) meters in length and about 20 cm in diameter. Suitable columns include columns sized to be about 0.15 (eg, 0.13) meters in length and about 100 cm in diameter. The column can take any variety of forms. For example, the column can be a vertical cylindrical tube or a coiled tube. Suitable coiled tubes include tubes that are about 60 (eg, 62) meters in length and about 5 cm in diameter in a coil that is about 1 meter in diameter and has about 20 rotations. The reaction catalyst can be configured to provide a contact time of about 30 minutes to about 300 minutes for the catalyst and the reaction mixture.

The reaction catalyst column, bag or floor can be configured for easy cleaning, regeneration or backwashing of the floor, bag or column. A convenient feature of the reaction catalyst column, bag or floor is not only the discharge of accumulated gas to facilitate pumping and circulation of the cleaning agent or backwashing agent, but also the entire catalyst bed. Includes numerous ports and valves between the catalyst segments that allow selective backwashing of the isolated segments.

reagent Suitable reagents include hydrogen peroxide in water at about 5 wt-% to about 70 wt-%, about 5 wt-% to about 50 wt-%, or about 35 wt-% to about 50 wt-%, eg, It contains hydrogen peroxide at about 35 wt-%, about 45 wt-%, about 50 wt-% or about 70 wt-% in water. Suitable reagents include acetic acid at about 5 wt-% to about 100 wt-% (the rest is water), or about 80 wt-% to about 98 wt-%, eg, about 80 wt-%, about 98 wt. Contains acetic acid at -% or about 100 wt-%. Glacial acetic acid is the preferred form of acetic acid. Suitable reagents include octanoic acid at about 1 wt-% to about 10 wt-% in glacial acetic acid.

Further suitable hydrogen peroxide reagents include urea-hydrogen peroxide, or any other various other nonionic hydrogen peroxide complexes. Further suitable oxidants include caroic acid, acidified sodium persulfate, or other peroxy species that equilibrate to form hydrogen peroxide in water.

Further suitable acetic acid reagents include acetic anhydride, acetyl chloride, polyvinyl acetate, and monoacetyl glycerin, diacetyl glycerin and triacetyl glycerin. Further suitable octanoic acid reagents include about 1 wt-% to about 10 wt-% octanoic acid in propylene glycol; hydrotrope coupling agents (eg, sodium octane sulfonate, or xylene sulfonate, toluene sulfonate, etc. Includes about 1 wt-% to about 10 wt-% octanoic acid in water with dioctyl sulfosuccinate, or other acidic forms of alkyl sulfonates or aryl sulfonates). Other suitable hydrotropes include fatty alcohol ethoxylate phosphate esters such as Ecolab's PE362, Empos PS-236, or Gafac RA-600. For a more suitable carboxylic acid reagent, C₁And C₂₀Alkanic acid; polybasic acid (including glycolic acid, succinic acid, glutaric acid, adipic acid, citric acid, malic acid or lactic acid); α, ω-dicarboxylic acid, such as succinic acid, adipic acid , Pimelic acid, suberic acid, adipic acid or succinic acid and the like. Further suitable peracid precursors include alcohol ethoxylate carboxylate and amide carboxylic acid or imide carboxylic acid.

The reagent composition used in the apparatus of the present invention need not include a stabilizer or chelating agent (eg, HEDP), and in some embodiments, a stabilizer or chelating agent (eg, HEDP). Does not include or has virtually no. The reagent composition used in the apparatus of the present invention can contain only volatile compounds. Reagent compositions containing only volatile compounds can be phosphate-free.

In some embodiments, the composition applied to the reaction catalyst is about 55 (eg, 56.5) wt-% carboxylic acid and about 30 (eg, 30.5) wt-% hydrogen peroxide, or about 45. (Eg, 43.6) wt-% carboxylic acid and about 20 (eg, 20.5) wt-% hydrogen peroxide, or about 20 wt-% carboxylic acid and about 30 (eg, 28) wt-% peroxidation. Hydrogen, or about 80 (eg, 78) wt-% carboxylic acid and about 10 (eg, 7.7) wt-% hydrogen peroxide; or about 5 wt-% carboxylic acid and about 5 wt-% peroxidation. Contains hydrogen.

In some embodiments, the composition applied to the reaction catalyst is about 55 (eg, 56.5) wt-% short chain carboxylic acid and about 30 (eg, 30.5) wt-% hydrogen peroxide, or About 45 (eg, 43.6) wt-% short chain carboxylic acid and about 20 (eg, 20.5) wt-% hydrogen peroxide, or about 20 wt-% short chain carboxylic acid and about 30 (eg, 28). wt-% hydrogen peroxide, or about 80 (eg 78) wt-% short chain carboxylic acid and about 10 (eg 7.7) wt-% hydrogen peroxide; or about 5 wt-% short chain Contains carboxylic acid and about 5 wt-% hydrogen peroxide.

In some embodiments, the composition applied to the reaction catalyst is about 20 wt-% medium chain carboxylic acid and about 30 wt-% hydrogen peroxide, or about 10 wt-% medium chain carboxylic acid and about 20 wt. -% Hydrogen peroxide, or about 5 wt-% medium chain carboxylic acid and about 20 wt-% hydrogen peroxide, or about 3 wt-% medium chain carboxylic acid and about 20 wt-% to about 25 (eg,) 22.5) Contains wt-% hydrogen peroxide.

In some embodiments, the composition applied to the reaction catalyst is about 50 (eg, 48) wt-% short chain carboxylic acid, about 20 wt-% medium chain carboxylic acid and about 10 wt-% peroxidation. Hydrogen, or about 55 (eg, 56) wt-% short-chain carboxylic acid, about 10 (eg, 8) wt-% medium-chain carboxylic acid and about 12 wt-% hydrogen peroxide, or about 60 wt- % Short-chain carboxylic acid, about 2 wt-% medium-chain carboxylic acid and about 15 (eg 13) wt-% hydrogen peroxide, or about 45 (eg 44) wt-% short-chain carboxylic acid, It contains about 1 wt-% medium chain carboxylic acid and about 20 (eg 21) wt-% hydrogen peroxide.

In some embodiments, the compositions of the invention are peroxycarboxylic acid and hydrogen peroxide in a ratio of about 0.3: 1 to about 7: 1, or in a ratio of about 1: 1 to about 3: 1. Alternatively, it is included in a ratio of about 2: 1 to about 3: 1. In some embodiments, the peroxycarboxylic acid and hydrogen peroxide are included in a ratio of about 2: 1 to about 3: 1, for example, in a ratio of 2.4: 1, or the peroxycarboxylic acid and hydrogen peroxide. Is contained in a ratio of about 1: 1 to about 2: 1, for example, a ratio of 1.4: 1, or peroxycarboxylic acid and hydrogen peroxide are contained in a ratio of about 0.3: 1 to about 1: 1. For example, it is contained in a ratio of 0.4: 1, or peroxycarboxylic acid and hydrogen peroxide are contained in a ratio of about 7: 1, for example, in a ratio of 7.1: 1.

In some embodiments, the reagents used in the apparatus of the present invention contain impurities (eg, metal ions, etc.) at levels up to 100 ppm, at levels up to 10 ppm, or at levels up to 1 ppm. Alternatively, it can be included at levels up to 0.1 ppm. Such impurities can include Fe, Cu, Mn, Ni, Ti, Co or any transition metal ion.

Illustrated Embodiment FIG. 1 illustrates an embodiment of the apparatus of the present invention in the form of the peroxycarboxylic acid generating apparatus 20. In FIG. 1, one or more reagent supply containers 21, for example, a first reagent supply container 22 containing hydrogen peroxide and a second reagent supply container 23 containing one or more carboxylic acids. , The guard column 30 is connected by the first line 26 and the second line 28, respectively. Mixing lines 29 where hydrogen peroxide and carboxylic acid are individually reached from the first reagent supply container 22 and the second reagent supply container 24 through the first line 26 and the second line 28, respectively, to the guard column 30. Delivered in. At mixing line 29, these reagents combine to form a reaction mixture. But together can also occur within the guard column 30. The guard column 30 contains a cation exchanger (not shown) that removes metal ions from the reaction mixture. The reaction mixture then proceeds through the third line 32 to one or more reactor columns 34.

The reactor column 34 is packed with a strong acid catalyst (not shown). Inside the reactor column 34, the reaction mixture of hydrogen peroxide and carboxylic acid reacts as it moves through the strong acid catalyst at a predetermined controlled flow rate. The system parameters for the peroxycarboxylic acid generator 20 (eg, column size and reagent flow rate, etc.) provide sufficient residence time of the reaction mixture in the strong acid catalyst for conversion to the desired peroxycarboxylic acid composition. To be selected and / or controlled. Generator design and process control are described in more detail herein below. The peroxycarboxylic acid composition is discharged from the reactor column 34 through the third line 36 into, for example, the storage tank 38.

In one embodiment, the peroxycarboxylic acid generator 20 also includes one or more additional structural components commonly used for the operation of the system, including a packed column (eg, fittings, valves, pumps). , Mixing chambers, water or additive feed connections, etc.). For example, the flow from each reagent supply vessel can be individually controlled by providing valves and pumps close to each reagent supply vessel.

Further representative configurations of the peroxycarboxylic acid generator 20 of the present invention are provided below. The various configuration aspects shown below can be combined or separated to give an even further configuration of the peroxycarboxylic acid generator. As in FIG. 1, the basic components that may exist (eg, control valves, fittings and pumps, etc.) are omitted from the schematic for clarity.

In one embodiment, the peroxycarboxylic acid generator 20 is arranged with one or more guard columns 30 to receive material from either the first reagent supply container 22 or the second reagent supply container 24. Reagent guard column 40 is included. The output from the reagent guard column 40 can proceed directly to the reactor column 34. The reagent guard column 40 can be arranged in the fluid flow between the first reagent supply vessel 22 or the second reagent supply vessel 24 and the reactor column 34.

FIG. 2 illustrates an embodiment of a peroxycarboxylic acid generator 20 comprising two reagent guard columns 40. In the embodiment shown in FIG. 2, the reagent guard column 40 is arranged in the first line 26 connecting the hydrogen peroxide supply container 22 to the guard column 30, and another reagent guard column 40 is a carboxylic acid supply container 24. Is installed on the second line 28, which connects the guard column 30. In other embodiments, only one (or one) of these reagent guard columns 40 can be included and / or the guard column 30 can be omitted. The reagent guard column 40 can be configured as a cartridge that can be easily removed and replaced in the peroxycarboxylic acid generator 20. Other components in FIG. 2 are as described above for FIG.

In another embodiment, the peroxycarboxylic acid generator 20 comprises a large number of guard columns 30. FIG. 3 schematically illustrates an embodiment including two guard columns 30 (the second guard column is the form of the second guard column 130). As exemplified, the guard column 30 and the second guard column 130 are arranged in parallel between the first reagent supply container 22 and the second reagent supply container 24 and the reactor column 34. Reagents flow through the first line 26 and the second line 28 to one or both of the guard column 30 and the second guard column 130 under the control of the valve 54. The column is filled with contaminants by the valve 54 directing the flow through the guard column 30, but the second guard column 130 remains usable. When the guard column 30 is no longer suitable for use, the valve 54 can be configured to guide the flow through the second guard column 130. Columns that are not subject to flow can be cleaned, serviced or replaced. In this mode, the operation of this embodiment of the peroxycarboxylic acid generator 20 may continue while either the first or second guard column (30 or 130) is being serviced or replaced. it can. The state of the first and / or second guard column (30 or 130) can be determined by a measuring device (below) that can also control the setting of the valve 54.

In another embodiment, the peroxycarboxylic acid generator 20 comprises a large number of reactor columns 34. A large number of reactor columns 34 can be connected in series, in parallel, or both. FIG. 4 illustrates an embodiment comprising two reactor columns 34 connected in series. A fifth line 42 connects the two reactor columns. In various embodiments, the peroxycarboxylic acid generator 20 can include up to about 10 reactor columns 34 connected in series, eg, 1 to 10 reactor columns 34 connected in series, eg, It can include two, three, four or five reactor columns 34 connected in series, for example four reactor columns 34 connected in series.

In one embodiment, the apparatus of the present invention comprises a number of reactor columns 34 connected in parallel. Such embodiments can include a large number of reactor columns 34 connected in series, as well as a large number of reactor columns 34 connected in parallel. FIG. 5 schematically illustrates such a system. In this example, the reaction mixture flows from the guard column 30 to the first pair of reactor columns 34 in series connected by a fifth line 42. The guard column 30 is also connected to a second pair of reactor columns 134 in series connected by line 142. The first pair of reactor columns 34 and the second pair of reactor columns 134 are connected in parallel. The reaction mixture flows from the first pair of reactor columns 34 to the storage tank 38 through a third line 36. The reaction mixture flows from the second pair of reactor columns to the storage tank 38 through the sixth line 136. The reactor valve 44 can guide the flow of the reaction mixture through either the first pair of reactor columns 34 or the second pair of reactor columns 134.

Reactor valves 44 configured to guide the flow through the first pair of reactor columns 34 allow those columns to be depleted, consumed or degraded, but the second pair of reactor columns. 134 remains ready for use. When the first pair of reactor columns 34 is no longer suitable for use, the reactor valve 54 can be configured to guide the flow through the second pair of reactor columns 134. Unflowed column pairs can be cleaned, serviced or replaced. In this mode, the operation of this embodiment of the peroxycarboxylic acid generator 20 is performed while either the first pair of reactor columns 34 or the second pair of reactor columns 134 is being serviced or replaced. Can continue. The state of the first and / or second reactor column (34 or 134) can be determined by a measuring device (below) that can also control the configuration of the reactor valve 44.

<u style="single">Monitoring device</u> In one embodiment, the peroxycarboxylic acid generator 20 comprises a cation exchanger, a reagent on the cation exchanger, a cation exchanger column assembly as a whole, a catalyst, a reagent on the catalyst, or a catalyst column assembly as a whole. A device for measuring one or more properties of Lee can be included. For example, such a device can monitor pressure (eg, increased pressure), temperature (eg, increased temperature), or both. Increases in temperature or pressure from nominal values can indicate unwanted decomposition of hydrogen peroxide catalyzed by active metal ions.

For example, the monitoring device 46 can measure the temperature difference between two points in or near the guard column 30 (eg, front and back, or front and middle). Increases in temperature difference or pressure from nominal values at or near two points in or near the guard column 30 may indicate, for example, unwanted decomposition of hydrogen peroxide catalyzed by active metal ions. The point (s) at which the temperature or pressure is measured can be selected to provide the desired sensitivity to contamination or decomposition.

FIG. 6 illustrates an embodiment of the guard column 30 and the monitoring device 46, which is one of the safety system embodiments. The monitoring device 46 includes a control device 48, a first sensor and a second sensor (50 and 52, respectively), and a lead 54. The lead wire 54 connects the first sensor 50 and the second sensor 52 to the control device 48. In an exemplary embodiment, the first sensor 50 monitors the state of the reaction mixture (eg, temperature or pressure) on the mixing line 29 and the second sensor 52 monitors the state inside the guard column 30. In one embodiment, the second sensor can be placed in the guard column 30 at about 10% to about 25% of the distance along the axis of the guard column 30. This same configuration can be used for the reagent guard column 40.

The monitoring device 46 can measure the difference in state (eg, temperature or pressure) between the first sensor 50 and the second sensor 52. The first sensor can be placed in front of the guard column 30 (or reagent guard column 40), for example, on the first line 26, the second line 28 or the mixing line 29. Place the second sensor 52 at the inlet of the guard column 30 (or reagent guard column 40), in the guard column 30 (or reagent guard column 40), or on the guard column 30 (or reagent guard column 40). Can be placed later. For example, a second sensor 52 at the inlet 60 to the guard column 30 or at 62 inside the guard column 30, but in front of the cation exchanger, or inside 64 of the cation exchanger of the guard column 30 ( Near the inlet of the column, inside the column or near the exit from the column), or inside the guard column 30, between the cation exchanger and the outlet 66 from the guard column 30, or from the guard column 30. It can be placed at exit 68. The second sensor can be co-located on the reagent guard column 40. Hydrogen peroxide catalyzed by, for example, active metal ions by a temperature difference or pressure difference from the nominal value between the first sensor 50 and the second sensor 52, or an increase in the temperature difference or pressure difference. Unwanted degradation of can be shown.

The device illustrated in FIG. 6 is a monitored guard column 56. In all of the embodiments illustrated in FIGS. 1-5, the monitored guard column 56 can be used in place of the guard column 30 or reagent guard column 40. For example, FIG. 7 schematically illustrates an embodiment of FIG. 2 modified to include a monitored guard column 56 in place of the guard column 30. In one embodiment, one or more of the reagent guard columns 40 can be the monitored guard column 56. For reagent guard columns that receive carboxylic acids, the sensor can measure metal ions.

When measuring a temperature or pressure difference above a preselected level, the monitoring device 46 can provide a detectable signal that alerts the operator to interrupt operation of the device. For example, the operator activates the pressure release valve 58, shuts off the flow of one or more reagents, flushes water through the guard column 30 and / or reactor column 34, guards the carboxylic acid composition. 30 and / or running through the reactor column 34, shutting down the peroxycarboxylic acid generator 20, or a combination thereof can be performed. In one embodiment, the monitoring device 46 can provide a signal to the control device 48, which can be a controllable logic control device, the control device 48 operating the pressure release valve 58, one. Or stop the flow of multiple reagents, allow water to flow through the guard column 30 and / or the reactor column 34, allow the carboxylic acid composition to flow through the guard column 30 and / or the reactor column 34, peroxycarboxylic acid generator 20. Can be stopped, or a combination of these can be performed.

When measuring a temperature or pressure difference above a preselected level, the monitoring device 46 signals a detectable signal to alert the operator or to the controller 48 to switch to another guard column. A detectable signal can be provided. For example, FIG. 8 is an embodiment of FIG. 3 modified to include first and second monitored guard columns (56 and 156) in place of the first and second guard columns (30 and 130). The morphology is schematically illustrated. In one embodiment, the operator can activate the valve 54 to send a stream of reagents through the second monitored guard column 156. In one embodiment, the monitoring device 46 can provide a signal to a controller 48 (eg, a controllable logical controller), which passes through a second monitored guard column 156. The valve 54 can be activated to feed the flow of reagents.

In another embodiment of the measuring device, the amount of metal in the column, or the amount of metal in the column, can be quantified. For example, the metal monitoring device 68 can be placed at any of the locations described for the monitoring device 46, where the metal monitoring device 68 provides a detectable signal with a predetermined amount of metal in the flow through the system. Can be provided when the level is exceeded. Alternatively, the metal monitoring device 68 can provide a detectable signal when a predetermined amount of metal has passed its position on the device. The detectable signal can be directed to the driver or controller for the purposes and responses described above.

FIG. 9 schematically illustrates an embodiment of a peroxycarboxylic acid generator 20 including a first reagent container 22 and a second reagent container 24. In this embodiment, the first reagent vessel 22 can contain a short chain carboxylic acid, such as acetic acid (eg, 98% acetic acid). The second reagent container 24 can contain an oxidizing agent, for example, hydrogen peroxide (for example, 35% to 45% hydrogen peroxide). This embodiment comprises one reagent guard column 40, a second reagent guard column 140 installed as needed, a monitored guard column 56, four reactor columns 34 connected in series, and five. Includes pressure release valve 58. The guard column 56 being monitored can have the configuration shown in FIG. 6 (eg, the sensor is in front of the guard column 3 and in the cation exchanger). Reagent guard column 40 acid-type or inert metal (eg, Na) cation exchanger⁺Or K⁺) Can be included in the type.

FIG. 10 schematically illustrates an embodiment of a peroxycarboxylic acid generator 20 including a first peroxy acid generator 70 and a second peroxy acid generator 72. The first peroxy acid generator 70 is configured as schematically illustrated in FIG. 9 and as described above.

The second peracid generator 72 in FIG. 10 is generally configured according to FIG. 9 and has components as described above. However, the second peracid generator 72 is configured for the production of medium chain peroxycarboxylic acids. In this embodiment, the third reagent vessel 23 is configured to contain and supply a medium chain carboxylic acid, such as octanoic acid (eg, 5 wt-% octanoic acid in propylene glycol). The second reagent container 124 is configured to contain and supply an oxidant, such as hydrogen peroxide (eg, 35% to 45% hydrogen peroxide). This embodiment comprises one reagent guard column 240, a second reagent guard column 340 installed as needed, a second monitored guard column 156, four reactor columns 134 connected in series, and , Includes 5 pressure release valves 158.

The second monitored guard column 156 can have the configuration shown in FIG. 6 (eg, the sensor is in front of the guard column 30 and in the cation exchanger). Reagent guard column 240 acid-type or inert metal (eg, Na) cation exchanger⁺Or K⁺) Can be included in the type.

Mixing lines of hydrogen peroxide and medium chain carboxylic acid individually from the second reagent supply container 124 and the third reagent supply container 23 to the guard column 30 via the first line 126 and the second line 128, respectively. Delivered to 129. At mixing line 129, the reagents for hydrogen peroxide and medium chain carboxylic acid combine to form a medium chain reaction mixture. But together can also occur in the second monitored guard column 156.

In the embodiment schematically illustrated in FIG. 10, the storage tank 38 and the second storage tank 138 are installed as needed. The storage tank 38 can be used to collect the short chain peroxycarboxylic acid composition. The second storage tank 138 can be used to collect the medium chain peroxycarboxylic acid composition. These peroxycarboxylic acid compositions can then be fed from these tanks to the mixed peracid storage tank 70 in the desired proportions (eg, pumped). Alternatively, storage tanks (38 and 138) can be omitted and these peroxycarboxylic acid compositions can be supplied directly from the reactor columns (34 and 134) in the desired proportions. In another embodiment, the generator comprises one storage tank (38 or 138) and a mixed peracid storage tank 70. In this embodiment, the storage tank (38 or 138) collects one excess peracid composition and then supplies it to the mixed peracid storage tank in the desired proportion. One peracid generator (70 or 72) then feeds the peracid composition directly into the mixed peracid storage tank 70.

Further components and configurations FIG. 11 schematically illustrates a system including a peroxycarboxylic acid generator 20 and an aseptic packaging line 74. The peroxycarboxylic acid generator 20 is configured to provide the peroxycarboxylic acid composition to the sterile packaging line 74. The peroxycarboxylic acid generator 20 can be any of the embodiments exemplified or described herein.

In this embodiment, the peroxycarboxylic acid composition may be ready for use in sterile packaging or may require dilution for use in sterile packaging. The peroxycarboxylic acid generator 20 can provide the ready-to-use peroxycarboxylic acid composition directly to the bottle cleaning tank 78 and / or the cap cleaning tank 80. When the peroxycarboxylic acid composition is supplied as a high concentration, the sterile packaging line 74 provides a water source 76, optionally installed to supply water to dilute the peroxycarboxylic acid composition. Can include. Water and the peroxycarboxylic acid composition can be mixed in the bottle wash tank 78 and the cap wash tank 80. Water can be supplied to these wash tanks via a first water conduit 86 and a second water conduit 88 that are installed as needed. The peroxycarboxylic acid composition can be supplied to these wash tanks via the peracid conduit 90.

Diluted or ready-to-use compositions can be applied to bottles and caps at bottle cleaning station 82 and cap cleaning station 84. A mixing tank is in fluid communication with these wash stations via station conduit 90. The composition used can be recirculated via the first recirculation conduit 92 and the second recirculation conduit 94. Capped bottles can be removed from the system, for example, by a conveyor (not shown).

FIG. 12 schematically illustrates an embodiment of the peroxycarboxylic acid generator 20 of the present invention in which the guard column 30 is a cartridge or segment in the reactor column 34. In FIG. 12, one or more reagent supply containers 21, for example, a first reagent supply container 22 containing hydrogen peroxide and a second reagent supply container 24 containing one or more carboxylic acids. , The first line 26 and the second line 28 and the mixing line 29 are connected to the guard column 30. The guard column 30 contains a cation exchanger (not shown) that removes metal ions from the reaction mixture. The reaction mixture then proceeds to one or more reactor columns 34. The reactor column 34 is packed with a strong acid catalyst (not shown). The peroxycarboxylic acid composition is discharged from the reactor column 34 through the third line 36, for example, into the storage tank 38. In this embodiment, the guard column 30 and / or cation exchanger can be replaced with the reactor column 34, eg, when the safety system indicates so, or after a certain amount of use, or the reactor. It can be replaced from column 34. The guard column can constitute from about the first 1 vol-% to about the first 50 vol-% of the combined guard column 30 and reaction column 34, for example, from about 10 vol-% to about 15 vol-%. can do. Such a guard column 30 can be used in any of the illustrated embodiments.

FIG. 13 schematically illustrates an embodiment of the peroxycarboxylic acid generator 20 of the present invention including the intermediate tank 96. In FIG. 13, one or more reagent supply containers 21, for example, a first reagent supply container 22 containing hydrogen peroxide and a second reagent supply container 24 containing one or more carboxylic acids. , The first line 26 and the second line 28 and the mixing line 29 are connected to the guard column 30. The reaction mixture proceeds through the guard column 30 and the third line 32 to the intermediate tank 96. Reagents or mixed reagents can accumulate in intermediate tank 96. In embodiments that include a reagent guard column (40 or 140), the intermediate tank 96 can be placed after the reagent guard column (40 or 140) and / or after the guard column 30. The intermediate tank 96 is connected to the reactor column 34 by an intermediate line 98. The reactor column 34 is packed with a strong acid catalyst (not shown). The peroxycarboxylic acid composition is discharged from the reactor column 34 through the third line 36, for example, into the storage tank 38.

In one embodiment, the intermediate tank 96 can be configured to receive and contain one or more reagents from the guard column 30 and / or the reagent guard column 40. The generator 20 can be configured such that the intermediate tank 96 is in fluid communication with respect to the guard column 30 and / or the reagent guard column 40 and the reactor column 34 at the same time. In one embodiment, the generator 20 is such that the intermediate tank 96 is in fluid communication with respect to the guard column 30 and / or the reagent guard column 40 and the reactor column 34 at different times or at overlapping times. It is composed of. In one embodiment, the generator 20 is a reagent (one) from the guard column 30 and / or the reagent guard column 40 in which the intermediate tank 96 is transported to a second position for delivering the reagent to the reactor column 34. Or) is configured to be in the first position to receive. That is, in such an embodiment, the generator 20 can be configured in two sets of separate equipment. The first set of equipment can contain all of the upstream components (in the direction of guard column 30 and / or reagent guard column 40) from intermediate tank 96, and the second set of equipment is from intermediate tank 96. All downstream components (in the direction of reactor column 34) can be included.

Any of the embodiments exemplified in FIGS. 1 to 13 can include an intermediate tank 96 and / or can be configured as a first set and a second set of components.

FIG. 14 illustrates an embodiment of the reactor column 34 and the monitoring device 46, which embodiment is an embodiment of a safety system. The monitoring device 46 includes a control device 48, a first sensor and a second sensor (50 and 52, respectively), and a lead 54. The lead wire 54 connects the first sensor 50 and the second sensor 52 to the control device 48. In an exemplary embodiment, the first sensor 50 monitors the state of the reaction mixture (eg, temperature or pressure) in the third line 32 and the second sensor 52 monitors the state inside the reactor column 34. .. In one embodiment, the second sensor can be placed in the reactor column 34 at about 10% to about 25% of the distance along the axis of the reactor column 34. Alternatively, these sensors can be arranged as described above for placing the sensors on the guard column 30.

In one embodiment, for example, in the embodiment illustrated in FIG. 14, the safety system puts the state at the inlet or outlet of the reactor column 34, or inside the reactor column 34 (eg, near the inlet of the column). It can be measured inside the column or near the exit from the column), or in the conduit entering or exiting the reactor column 34. Another embodiment of the safety system can quantify the amount of metal in the reactor column 34, or the amount of metal in the reactor column 34. In one embodiment, the safety system is configured to measure the temperature at the inlet to the reactor column 34 and at the first 25% of the reactor column 34.

<u style="single">Monitoring and control of the composition used</u> FIG. 15 is a schematic diagram illustrating embodiments of a peroxycarboxylic acid generator 20, a control device 48, a POAA storage tank 38, a diluent storage tank 16, and a composition container used 166. The control device 48 can manage some functions with respect to the peroxycarboxylic acid generator 20. For example, controller 48 can control various safety system functions as described above with respect to FIG. The control device 48 can also control the dilution of the high concentration composition produced by the peroxycarboxylic acid generator 20 to form the composition to be used.

In addition, controller 48 receives concentration data regarding the concentrations of peroxycarboxylic acid and hydrogen peroxide in the composition used via line 180. Based on the concentration data, the controller 48 can monitor the concentration of peroxycarboxylic acid and / or hydrogen peroxide in the composition used, and when these concentrations do not meet the predetermined criteria, the composition used. Can be replenished. In addition, the controller 48 sets various operating parameters of the peroxycarboxylic acid generator 20 to influence the concentration of peroxycarboxylic acid in the peroxycarboxylic acid high concentration composition provided by line 36, based on the concentration data. Can be adjusted.

The concentration of peroxycarboxylic acid and / or hydrogen peroxide in the composition used can be determined by many methods. One of the exemplary devices that can be used to determine the concentration of peroxycarboxylic acid and / or hydrogen peroxide in the composition used is the Oxycheck System available from Ecolab Inc. (St. Paul, Minnesota). Concentration data can also be obtained manually. For example, the concentration can be obtained by many prior arts, such as titration, potentiometric titration or amperometry techniques. However, it must be understood that the present invention is not limited in this respect and that concentration data can be obtained in many ways without departing from the scope of the present invention.

To control the dilution of the high-concentration composition, the controller 48 adds a high concentration of peroxycarboxylic acid stored in the POAA storage tank 38 to a diluent (eg, water) stored in the diluent storage tank 164. Can be added and / or mixed. In one embodiment, controller 48 controls one or more valves or pumps that control the flow of the carboxylic acid high concentration composition from the POAA storage tank 38 and the flow of diluent from the diluent storage tank 164. Can be adjusted. The controller 48 pumps the carboxylic acid composition and diluent to flow into the composition vessel 166 in the desired proportion, eg, to achieve the composition in use containing the target concentration of peroxycarboxylic acid. Or more than one) can be adjusted.

The controller 48 can replenish the composition used when the concentration of peroxycarboxylic acid and / or hydrogen peroxide does not meet the predetermined criteria. For example, based on concentration data, the controller 48 may use the peroxycarboxylic acid from the POAA storage tank 38 to ensure that the concentration of peroxycarboxylic acid and / or hydrogen peroxide in the composition used meets certain criteria. The addition of a high concentration or diluent 164 to the composition used 166 can be adjusted. For example, if the concentration of peroxycarboxylic acid in the composition used is too low, controller 48 adds an additional high concentration of peroxycarboxylic acid to the composition used until the target concentration of peroxycarboxylic acid in the composition used is met. You can manage what you do. If the concentration of peroxycarboxylic acid in the composition used is too high, controller 48 controls the addition of additional diluent to the composition used until the target concentration of peroxycarboxylic acid in the composition used is met. Can be done. The target concentration can include a specific concentration or can include a range of acceptable concentrations. As another example, if the concentration of hydrogen peroxide is too high, the controller 48 can empty the composition container used and control the production of new composition used.

FIG. 16 is a flow chart illustrating the process (200) in which the controller 48 monitors and / or regulates the concentrations of peroxycarboxylic acid and hydrogen peroxide in the composition used. When the controller 48 receives the concentration data (202), the controller 48 sets the received hydrogen peroxide concentration to a predetermined H.₂O₂Compare with target criteria (204). The received hydrogen peroxide concentration is H₂O₂If the target criteria are not met, controller 48 can manage to empty the used composition container to the used used composition (206). In other words, the control device 48 can generate a control signal or a sequence of control signals that causes the used composition container to be emptied into the used used composition. The control device 48 can then control the production of the new composition used by controlling the flow of the peroxycarboxylic acid and the diluent into the composition container 166 used (208).

Hydrogen peroxide concentration is predetermined H₂O₂If the target criteria are met (204), controller 48 compares the peroxycarboxylic acid concentration in the composition used with the predetermined POAA target criteria (210). If the peroxycarboxylic acid concentration in the composition used does not meet the POAA target criteria, controller 48 can control the replenishment of the composition used. That is, the controller 48 can adjust the peroxycarboxylic acid concentration in the composition used until the peroxycarboxylic acid concentration in the composition used meets the POAA target criteria (212). To do this, the controller 48 adds a given amount of peroxycarboxylic acid and / or diluent to the composition used in the composition container 166 used, thereby the peroxycarboxylic acid in the composition used. The valve or pump to the POAA high concentration storage tank 38 and / or the diluent storage tank 164 can be controlled so that the resulting increase or decrease in concentration occurs.

In one embodiment, the controller 48 attaches to the composition used, for example, based on a known concentration of peroxycarboxylic acid in the composition used and a known or expected concentration of peroxycarboxylic acid in the high concentration storage tank 38. The amount of peroxycarboxylic acid high concentration or diluent to be added can be calculated by computer. In another embodiment, controller 48 may repeatedly add a constant increment of peroxycarboxylic acid and / or diluent to the composition used until a target concentration of peroxycarboxylic acid in the composition used is achieved. it can.

After the new composition was produced (208) or after the POAA concentration in the composition used was replenished / adjusted (212), the controller 48 received time, concentration data received, the composition used produced. Amount, or composition used, POAA and / or H₂O₂Information on the relative amount of high concentration or diluent required to be in satisfactory agreement with the target criteria of can be recorded. The controller 48 can also analyze the data and issue various alarms, warnings or reports based on the stored information and the results of the analysis. Alerts, warnings or reports are acoustic alerts, such as beep generators, buzzers or recorded scripts, and / or visual indicators, such as LEDs, numerical displays, graphics on the peroxycarboxylic acid generator 20. It can be communicated to the user via a display or a bidirectional display. Alerts, warnings or reports are also sent to remote monitoring rooms via telephone network, wireless network, email, local area network, wide area network or the Internet, either by request or at regular intervals. be able to. In addition, alerts, warnings or reports can be obtained on-site or in the distance via portable devices, such as via laptop computers, tablet PCs, personal digital assistant devices or other handheld or portable devices. it can. The controller 48 then waits for the start of the next monitoring period (214), at which point the controller 48 receives the most recently measured concentration of peroxycarboxylic acid and / or hydrogen peroxide. The next monitoring period can be initiated by the user, either in the field or in the distance, or the controller 48 is used to periodically monitor the concentration of peroxycarboxylic acid and / or hydrogen peroxide in the composition used. / Or can be programmed to adjust.

H₂O₂Target criteria and POAA target criteria can vary depending on the application to which the solution used is directed. For example, H₂O₂Target criteria and POAA target criteria can vary depending on the degree of efficiency required for the specific application to which the solution used is directed. In one embodiment, the POAA target criterion can be the minimum POAA target concentration or the maximum POAA target concentration (eg, does the measured POAA concentration in the solution used have to remain higher than the minimum POAA concentration? , Or must remain below the maximum POAA concentration). In another embodiment, the POAA target criterion can be in the range of acceptable POAA concentrations (eg, the measured POAA concentration in the solution used is higher than the minimum POAA concentration and greater than the maximum POAA concentration. Must remain low). Similarly, in one embodiment, H₂O₂Target standard is minimum H₂O₂Target concentration or maximum H₂O₂Can be a target concentration (eg, measured H in the solution used)₂O₂Concentration is minimum H₂O₂Must remain higher than the concentration or maximum H₂O₂Must remain below the concentration). In another embodiment, H₂O₂Goal criteria are acceptable H₂O₂Can be in the range of concentration (eg, measured H in the solution used)₂O₂Concentration is minimum H₂O₂Higher than the concentration and the highest H₂O₂Must remain below the concentration).

Another function of the controller 48 may be to monitor the overall performance of the peroxycarboxylic acid generator 20. Control 48 can analyze concentration data regarding the concentrations of peroxycarboxylic acid and hydrogen peroxide in the composition used to infer information about the operation of the peroxycarboxylic acid generator 20. For example, the peroxycarboxylic acid generator 20 is designed to make a peroxycarboxylic acid high concentration composition having a known controllable peroxycarboxylic acid concentration. From this known concentration, the high concentration composition in the POAA storage tank 38 is mixed with a known volume of diluent to reach the corresponding expected expected POAA concentration in the used composition stored in the used composition container 166. Will be done. Concentration data showing a lower than expected POAA concentration in the composition used may suggest that the concentration of peroxycarboxylic acid in the high POAA concentration is not at the expected level. As a result, this may suggest that the peroxycarboxylic acid generator 20 does not perform according to the specifications.

When the controller 48 receives concentration data indicating a lower than expected POAA concentration in the composition used and thus a lower than expected POAA concentration in the high concentration composition, it performs one of several series of operations. Can be taken. For example, the controller 48 increases or decreases the lower or higher POAA concentration than expected in the composition used so that the resulting concentration of peroxycarboxylic acid in the POAA high concentration composition provided by line 36 increases or decreases. It can be supplemented by adjusting some operating parameters of the acid generator 20. This can be an iterative process that is repeated until the desired concentration of peroxycarboxylic acid in the high POAA concentration provided by line 36 is achieved. For example, the control device 48 corresponds the amount of reagent flowing out of the reagent supply container (22 and / or 24) and the amount of reagent flowing into the peroxycarboxylic acid generator 20 at the concentration of the produced POAA high concentration. The operation of the pumps (162A and / or 162B) can be controlled to adjust to cause an increase or decrease.

As an alternative, or in addition to compensating for lower / higher concentrations than expected, controller 48 is directed to the user that maintenance of some components of the peroxycarboxylic acid generator 20 may be required. Can issue alarms, warnings or reports. For example, one (22 or 24) or both of the reagent supply vessels may need to be refilled, or pump or valve parameters may require adjustment. Data can also be analyzed and reported. For example, the statistical trend of acetic acid and hydrogen peroxide pump rates relative to the concentration of POAA and hydrogen peroxide in vessel 38 can be used to predict conversion efficiency.

FIG. 17 is a flow chart illustrating an example of a generator inspection process (220) in which the controller 48 monitors and regulates the operation of the peroxycarboxylic acid generator 20. Upon receiving concentration information regarding the concentration of peroxycarboxylic acid and / or hydrogen peroxide in the composition used (222), controller 48 compares the peroxycarboxylic acid concentration with the expected POAA concentration (224). If the concentration of peroxycarboxylic acid does not meet the expected POAA concentration (224), then the controller 48 is the number of peroxycarboxylic acid generators 20 to cause the resulting change in peroxycarboxylic acid concentration at high POAA concentrations. The operating parameters can be adjusted (228).

For example, the control device 48 determines the amount of reagent flowing out of the reagent supply container (22 and / or 24) and the amount of reagent flowing into the peroxycarboxylic acid generator 20 to the concentration of the POAA high concentration composition provided by line 36. The operation of the pumps (162A and / or 162B) can be controlled to adjust to cause the corresponding increase or decrease in. The controller 48 can also increase or decrease the flow rate of the reaction mixture through the reaction catalyst to a flow rate that results in the desired concentration. The controller 48 can calculate the change in flow velocity using various factors including the temperature of the composition and the concentration of peroxycarboxylic acid. Based on the kinetics and thermodynamics of the equilibrium reaction, the contact time with the reactive catalyst determines the final concentration of POAA as exactly the concentration of the reactive species. In this way, the concentration of peroxycarboxylic acid in the composition used can be maintained within the expected range even when the generator 20 is not fully operational to the specification.

After the POAA concentration was confirmed and adjusted (224, 228), if necessary (224, 228), controller 48 made specific adjustments (ie) to the time, the concentration data received, and the various operating parameters of the generator 20. Specific adjustments to the parameters, eg, pump and / or valve speed and / or time, additional POAA or hydrogen peroxide added from the reagent container (22 and / or 24) to bring the system back to specifications. Information about quantity, etc.) can be recorded and stored. This information may be useful to repair inspectors in performing diagnostic and maintenance work on the generator 20 and to monitor the efficiency of the peroxycarboxylic acid generator 20. For example, if the system continuously produces products identified as having a low POAA content, this indicates that the system requires repair by altering the reaction catalyst.

The controller 48 can also analyze the information and issue various alarms, warnings or reports based on this stored information. Alerts, warnings or reports are acoustic alerts, such as beep generators, buzzers or recorded scripts, and / or visual indicators, such as LEDs, numerical displays, graphics on the peroxycarboxylic acid generator 20. It can be communicated to the user via a display or a bidirectional display. Alerts, warnings or reports are also sent to remote monitoring rooms via telephone network, wireless network, email, local area network, wide area network or the Internet, either by request or at regular intervals. be able to. In addition, alerts, warnings or reports can be obtained on-site or in the distance via portable devices, such as via laptop computers, tablet PCs, personal digital assistant devices or other handheld or portable devices. it can.

The controller 48 then waits for the start of the next generator inspection (230), at which point the controller 48 receives the most recent concentration data. The next generator inspection can be initiated by the user, either in the field or in the distance, or the controller 48 can be programmed to perform generator inspections at predetermined periodic intervals. .. For example, controller 48 ensures that the generator 20 performs according to specifications and that the desired level of peroxycarboxylic acid in the composition used is maintained. Therefore, the process shown in FIG. 17 can be repeated on a regular basis. The generator inspection can be performed, for example, daily, weekly or monthly.

<u style="single">How to make peroxycarboxylic acid</u> The present invention includes methods for making peroxycarboxylic acids. The method of the present invention comprises contacting the reagent with a pretreatment column and contacting the reaction mixture with a reaction catalyst. The contacts include one or more reagents used in making the peroxycarboxylic acid, eg, an acid type or an inert metal (eg, Na).⁺Or K⁺) May include contacting with a cation exchanger in type. Reagents can include hydrogen peroxide, or carboxylic acids, or mixtures of hydrogen peroxide and carboxylic acids. To be contacted with the reaction catalyst, to form a peroxycarboxylic acid catalyst a carboxylic acid (or a suitable precursor) and oxidizing agent (e.g., peroxides) contacting the free may rare. The reaction catalyst can be a strong acid (eg, polystyrene sulfonic acid) for catalyzing the reaction of hydrogen peroxide with the carboxylic acid to form the peroxycarboxylic acid. Pretreatment with one or more reagents can increase the life, activity and / or safety of the reaction catalyst.

The methods of the invention can also include monitoring the safety of the method and devices that do so. Monitoring safety may include monitoring and / or adjusting the status of one or more of the pretreatment columns and / or reaction catalysts. Monitoring may include monitoring and / or regulating the pressure, temperature, metal content, and / or the presence of a gas (eg, oxygen) resulting from the decay of the peroxide. Measuring one or more of these parameters in the pretreatment column, in the pretreatment column, or in the reaction catalyst, or in the reaction catalyst, ie, before the pretreatment column, For one or more of the reagents in or after, or for the reaction mixture before, during or after the pretreatment column, or for the reaction mixture before, during or after the reaction catalyst, or a combination thereof. ) Can be done for two or more. The measurement can include finding the difference in one or more of these parameters between any two points, for example, between any two of the listed locations.

The methods of the invention can include providing one or more reagents (eg, hydrogen peroxide or carboxylic acid (s)) in one or more containers. Mixing of reagents can occur before one or more of the reagents come into contact with the pretreatment column, or after one or more of the reagents come into contact with the pretreatment column. The reaction of the pretreated reaction mixture or the mixture of the pretreated reactant with the untreated reactant is then carried out by contacting with a reaction catalyst. The reaction can include contacting the reaction mixture with the reaction catalyst at a controlled flow rate and / or for a period of time. The reaction results in a peroxycarboxylic acid. The methods of the invention can also include the use or storage of peroxycarboxylic acids.

In one embodiment, the method of the invention comprises pretreating one or more reagents independently of the other. Mixing of one or more pretreated reagents with untreated reagents can then occur before pretreating the mixed reagents. Alternatively, each reagent can be independently pretreated and then mixed and contacted with the reaction catalyst. Each pretreatment is carried out over a predetermined time to provide the desired amount of contaminant removal from the pretreated composition.

A large number (eg, two) of pretreatment columns connected in parallel can be used for pretreatment. One column can be put into a wait state while the other column is preprocessing. The method of the present invention can include switching the flow from the used pretreatment column to a pretreatment column that is ready for use. The method of the present invention can include replacing, servicing, or cleaning unused pretreatment columns. Cleaning can include, for example, cleaning with a dilute, strong mineral acid (eg, sulfuric acid). Washing may include backwashing the pretreatment column. The method of the present invention can be continued while one of the pretreatment columns is maintained or replaced. The columns can be replaced according to a predetermined schedule. Alternatively, the methods of the invention can include monitoring the safety of the pretreatment column and, by monitoring, replacing the pretreatment column when a given condition is found.

Contacting the reaction mixture with the reaction catalyst can be performed on one or more beds, backs or columns, in which case these beds, backs or columns are in series, in parallel, or one. The parts can be connected in series and some parts can be connected in parallel. The method of the present invention can be used to contain a reaction catalyst and contact with four columns connected in series. By reacting, the floor, back or column is used until the floor, back or column is fully used, or until the floor, back or column is shown to be no longer suitable for use. Can be done. The second bed, back or column can remain usable for the duration of the reaction on the first bed, back or column. The methods of the invention can also include switching the flow from the first floor, back or column to a second floor, back or column when the first floor, back or column is no longer available. ..

The condition of the floor, back or column in use can be measured by a safety system that can also control the valve system. The reaction catalyst can be replaced according to a predetermined schedule. Alternatively, the methods of the invention can also include monitoring and monitoring the safety of the reaction catalyst, thereby replacing the reaction catalyst when a given condition is found. The method of the present invention can include cleaning the reaction catalyst. Cleaning can include, for example, cleaning with a dilute, strong mineral acid (eg, sulfuric acid). Washing may include backwashing the floor, bag or column of the reaction catalyst.

Monitoring safety can include measuring one or more properties of the pretreatment column, one or more properties of the reaction catalyst, or both. Monitoring safety can include, for example, measuring pressure (eg, increased pressure) and / or temperature (eg, increased temperature). In one embodiment, the measurement is to measure the temperature difference between two points in or near the pretreatment column (eg, before or after the pretreatment column, or before and inside the pretreatment column). May include doing. By measuring the increase in temperature or pressure difference at two points in or near the pretreatment column, the system can provide a perceptible signal if the increase exceeds a given level. Can be brought. Activating a pressure release valve (either manually or by automation) by measuring a level above a predetermined level, stopping the flow of one or more reagents, flowing water through a pretreatment column, The carboxylic acid composition can be run through a pretreatment column, the method can be terminated, or a combination thereof can be initiated. Initiation can also result in switching to another pretreatment column or another bed or column of reaction catalyst.

To monitor safety, the condition can be placed at the inlet or outlet of the pretreatment column, or inside the column (eg, near the inlet of the column, inside the column, or near the exit from the column). , May include measuring in conduits entering the pretreatment column or exiting the pretreatment column. Monitoring may include measuring the temperature at the inlet to the pretreatment column and at the first 25% of the pretreatment column.

The methods of the invention can also include storing, handling, diluting, and formulating the compositions made by this method. For example, the methods of the invention can include the use or storage of peroxycarboxylic acids. The methods of the invention can include diluting and / or formulating compositions from reaction catalysts, or storing. The methods of the invention can include diluting high concentrations for use. By diluting, for example, a diluent or carrier (eg, water) is added and / or mixed with the peroxycarboxylic acid to achieve a diluted composition containing the desired concentration of peroxycarboxylic acid. can do. The desired concentration can be, for example, from about 2 ppm to about 5000 ppm. Dilution may include adding another component to the peroxycarboxylic acid composition. Formulation can include dispensing the desired amount of added ingredients into the composition or diluted composition.

Storage may include monitoring the condition of the composition during the storage period. By monitoring, the content of peroxycarboxylic acid, carboxylic acid and / or hydrogen peroxide can be measured in the composition, eg, in the stored composition used. In one embodiment, the methods of the invention include a replenishment system for stored used compositions. Replenishment may include monitoring the content of the composition used. For example, if the concentration of peroxycarboxylic acid is lower than a given level or the concentration of carboxylic acid is higher than a given level, then supplementation with a higher concentration of peroxycarboxylic acid composition. It involves adding to the composition used or emptying the container of the used composition.

The methods of the invention can also include controlling the flow of reagents. Controlling the flow of reagents can include monitoring the peroxycarboxylic acid composition after the reaction catalyst, for example, at the outlet from the last reaction catalyst column. By monitoring, it can be determined whether the composition contains the desired concentration of peroxycarboxylic acid (eg, equilibrium concentration). If the composition contains a lower concentration than desired, control may include slowing the flow rate of the reaction mixture through the reaction catalyst to a flow rate that results in the desired concentration. Control may include calculating changes in flow velocity using a variety of factors, including the temperature of the composition and the concentration of peroxycarboxylic acid.

The present invention includes a method for making a composition comprising one peroxycarboxylic acid. The method involves contacting the carboxylic acid with a pretreated column, mixing the pretreated carboxylic acid with hydrogen peroxide, and contacting the reaction mixture with a reaction catalyst to produce the peroxycarboxylic acid. including. The peroxycarboxylic acid can be a short-chain peroxycarboxylic acid (eg, peroxyacetic acid) or a medium-chain peroxycarboxylic acid (eg, peroxyoctanoic acid).

The present invention includes methods for making mixed peroxycarboxylic acid compositions. The method involves contacting the short chain carboxylic acid with the first pretreated column, mixing the pretreated short chain carboxylic acid with hydrogen peroxide, and combining the first reaction mixture with the short chain peroxycarboxylic acid. Includes contact with a reaction catalyst to produce an acid. The method involves contacting the medium chain carboxylic acid with a second pretreated column, mixing the pretreated medium chain carboxylic acid with hydrogen peroxide, and mixing the second reaction mixture with the medium chain peroxycarboxylic acid. Includes contact with a reaction catalyst to produce an acid. Mixing the short chain peroxycarboxylic acid and the medium chain peroxycarboxylic acid results in a mixed peroxycarboxylic acid composition.

Method performed at the site of use The present invention also relates to a method of making a peroxycarboxylic acid in the field of its use. For example, the method for producing a peroxycarboxylic acid described above can be carried out in a factory where the peroxycarboxylic acid is used (for example, a beverage factory). The site of use can be any variety of manufacturing facilities where peroxycarboxylic acids may be used. Use sites include beverage factories, food processing factories, demolition factories or meat processing factories. In the field of use, the peroxycarboxylic acid composition can be applied to a variety of objects, including equipment, containers and food products. Food products include, for example, plant products, products, meat, meat products and poultry meat. In one embodiment, the method of the invention can include applying the peroxycarboxylic acid composition of the invention to a beverage container (eg, a plastic bottle or can).

For example, the method for producing a peroxycarboxylic acid described above can be carried out in a wood pulp manufacturing factory or a paper mill in which the peroxycarboxylic acid is used. As a further example, the method for producing a peroxycarboxylic acid described above can be carried out in a waste treatment plant where the peroxycarboxylic acid is used. At the site of use, any various mills where pulp processing, use or handling (eg, bleaching) or papermaking takes place, or waste (eg, industrial waste, food production waste, etc.) This includes any variety of factories that handle waste from beverage factories, waste from food processing factories, waste from dismantling factories, or waste from meat processing factories. In the field of use, the peroxycarboxylic acid composition can be applied to a variety of objects, including equipment, pulp, waste, factory surfaces and buildings, or other objects in factories or facilities. In one embodiment, the method of the invention can include applying the peroxycarboxylic acid composition of the invention to a pulp, waste, waste treatment facility or waste treatment facility.

In this method, carboxylic acids (eg, acetic acid and / or octanoic acid) and / or oxidizing agents (eg, hydrogen peroxide) are provided at the site of use (eg, beverage mill, pulp processing mill or waste treatment mill). , The method of the present invention can include performing on-site with such reagents. In the present method, carboxylic acids (eg, acetic acid and / or octanoic acid) and / or oxidizing agents (eg, hydrogen peroxide) are used to perform the methods of the invention in the field with such reagents. It can include transportation to the site (eg, beverage factory, pulp processing factory or waste treatment factory). In the present method, a factory or factory management staff uses carboxylic acids (eg, acetic acid and / or octanoic acid) and / or oxidizing agents (eg, hydrogen peroxide), the methods of the invention, and such reagents. Can include requesting or ordering for delivery to a site of use (eg, a beverage factory, a pulp processing plant or a waste treatment plant) for on-site use.

Embodiment of this method In one embodiment, the method of the invention comprises contacting the reaction mixture with a reaction catalyst, monitoring the safety of the method, and performing the method. The reaction mixture may include a mixture of hydrogen peroxide and a carboxylic acid. Contacting with the reaction catalyst can include contacting the catalyst with a carboxylic acid (or a suitable precursor) and an oxidizing agent (eg, peroxide) to form the peroxycarboxylic acid. The reaction catalyst can be a strong acid (eg, polystyrene sulfonic acid) for catalyzing the reaction of hydrogen peroxide with the carboxylic acid to form the peroxycarboxylic acid.

Monitoring safety may include monitoring and / or adjusting the status of one or more of the reaction catalysts. Monitoring may include monitoring and / or regulating the pressure, temperature, metal content, and / or the presence of a gas (eg, oxygen) resulting from the decomposition of the peroxide. Measuring one or more of these parameters in or in the reaction catalyst, for example, with respect to the reaction mixture before, during or after the reaction catalyst, or of these (combinations thereof). You can do more than one. The measurement can include finding the difference in one or more of these parameters between any two points, for example, between any two of the listed locations.

Monitoring safety can include measuring the properties of one or more of the reaction catalysts. Monitoring safety can include, for example, measuring pressure (eg, increased pressure) and / or temperature (eg, increased temperature). In one embodiment, the measurement can be to measure the temperature difference between two points in or near the reaction catalyst (eg, before or after the reaction catalyst, or before and inside the reaction catalyst). Can be included. By measuring the increase in temperature or pressure difference at two points in or near the reaction catalyst, the system may also provide a perceptible signal if the increase exceeds a given level. Can be drowned. Activating a pressure release valve (either manually or by automation) by measuring a level above a predetermined level, stopping the flow of one or more reagents, flowing water through a pretreatment column, The carboxylic acid composition can be run through a pretreatment column, the method can be terminated, or a combination thereof can be initiated. Starting can also result in switching to another bed or column of reaction catalyst.

To monitor safety, the condition is placed at the reaction catalyst column, floor or bag inlet or outlet, or inside the reaction catalyst column, floor or bag (eg, near the inlet, inside or near the outlet). Alternatively, measurement may be included in the conduit entering the reaction catalyst or in the conduit exiting the reaction catalyst. Monitoring may include measuring the temperature at the inlet to the reaction catalyst and at the first 25% of the reaction catalyst.

This embodiment does not need to include pretreating reagents with material outside the reaction catalyst column, floor or bag.

<u style="single">Peroxycarboxylic acid composition</u> The methods and devices of the present invention can be used to make any variety of peroxycarboxylic acid compositions. In one embodiment, the methods of the invention include peroxycarboxylic acid compositions made by the methods and / or devices described above herein. The peroxycarboxylic acid compositions according to the invention can have favorable stability, which may be due to low levels of metal ions (eg, metal ions less than about 10 ppm or less than about 10 ppb). Low levels of metal ions can be achieved and maintained in the compositions of the invention without the addition of stabilizers or chelators. Accordingly, the present invention relates to stable peroxycarboxylic acid compositions having no or substantially no stabilizer or chelating agent. The present invention also includes stable peroxycarboxylic acid compositions containing only volatile compounds. The present invention also includes a peroxycarboxylic acid composition containing only volatile compounds.

The term "stable", as applied herein to a peroxycarboxylic acid composition, is a composition that retains about 90% of the peroxycarboxylic acid for at least about 6 months, or about 90% of the peroxycarboxylic acid. Means a composition that retains at least about 7 days, or a composition that retains about 90% of the peroxycarboxylic acid for at least about 1 day. As a stable composition, a composition that retains about 95% peroxycarboxylic acid for at least about 14 days, or a composition that retains about 95% peroxycarboxylic acid for at least about 7 days, or about 95% peroxycarboxylic acid. Compositions that retain the acid for at least about 3 days can be mentioned. The stability threshold of "90%" is generally a function of the equilibrium percarboxylic acid concentration, as trace amounts of metal are removed by the generator. Higher concentrations tend to decompose more quickly.

In some embodiments, the peroxycarboxylic acid compositions of the present invention produce metal ions at levels below about 10 ppm, or at levels less than about 1 ppm, or at levels less than about 100 ppb, or about 10 ppb. Includes at levels less than or at levels less than about 1 ppb. Such metal ions can include Fe, Cu, Mn, Ni, Ti, Co, mixtures thereof, or any transition metal ion.

In some embodiments, the composition in equilibrium is about 35 wt-% peroxycarboxylic acid and about 15 wt-% hydrogen peroxide, or about 15 (eg, 17) wt-% peroxycarboxylic acid and About 15 (eg, 13) wt-% hydrogen peroxide, or about 10 (eg, 9.7) wt-% peroxycarboxylic acid and about 25 (eg, 24) wt-% hydrogen peroxide, or about. 15 (eg 13) wt-% peroxycarboxylic acid and about 2 (eg 1.9) wt-% hydrogen peroxide, or about 0.5 wt-% peroxycarboxylic acid and about 5 (eg 4.8) wt- Contains% hydrogen peroxide.

In some embodiments, the composition in equilibrium is about 35 wt-% short chain peroxycarboxylic acid and about 15 wt-% hydrogen peroxide, or about 15 (eg, 17) wt-% short chains. Peroxycarboxylic acid and about 15 (eg 13) wt-% hydrogen peroxide, or about 10 (eg 9.7) wt-% short chain peroxycarboxylic acid and about 25 (eg 24) wt-% excess Hydrogen oxide, or about 15 (eg, 13) wt-% short-chain peroxycarboxylic acid and about 2 (eg, 1.9) wt-% hydrogen peroxide, or about 0.5 wt-%, short-chain peroxycarboxylic acid. And contains about 5 (eg, 4.8) wt-% hydrogen peroxide.

In some embodiments, the composition in equilibrium is about 20 (eg, 19) wt-% medium chain peroxycarboxylic acid and about 30 (eg, 32) wt-% hydrogen peroxide, or about. 5 (eg, 6.8) wt-% medium chain peroxycarboxylic acid and about 20 wt-% hydrogen peroxide, or about 2 (eg 2.1) wt-% medium chain peroxycarboxylic acid and about 20 (eg, 21) ) Wt-% hydrogen peroxide, or about 1 (eg 1.2) wt-% medium chain peroxycarboxylic acid and about 20 (eg 22) wt-% hydrogen peroxide.

In some embodiments, the composition in equilibrium is about 15 (eg, 14) wt-% short chain peroxycarboxylic acid, about 5 (eg, 5.7) wt-% medium chain peroxycarboxylic acid and about. 3 (eg 2.8) wt-% hydrogen peroxide, or about 20 (eg 19) wt-% short chain peroxycarboxylic acid, about 3 (eg 2.7) wt-% medium chain peroxycarboxylic acid and About 4 wt-% hydrogen peroxide, or about 20 (eg 22) wt-% short chain peroxycarboxylic acid, about 1 (eg 0.7) wt-% medium chain peroxycarboxylic acid and about 5 (eg, eg) 4.6) wt-% hydrogen peroxide, or about 15 (eg 17.4) wt-% short chain peroxycarboxylic acid, about 0.4 wt-% medium chain peroxycarboxylic acid and about 15 (eg 13) wt- Contains% hydrogen peroxide.

In some embodiments, the compositions of the invention are peroxycarboxylic acids and hydrogen peroxide in a ratio of about 2: 1 (eg 2.4: 1), or peroxycarboxylic acids in a ratio of about 1.4: 1. And hydrogen peroxide, or peroxycarboxylic acid and hydrogen peroxide in a ratio of about 0.5: 1 (eg, 0.4: 1), or peroxycarboxylic acid and hydrogen peroxide in a ratio of about 7: 1.

The devices and methods of the present invention can be used to make any variety of peroxycarboxylic acid compositions. Made by the apparatus and method of the present invention, which can include adding various substances (eg, auxiliary agents, stabilizers or chelating agents) after forming the peroxycarboxylic acid. The resulting compositions include US Pat. Nos. 5,200,189, 5,314,687, 5,718,910 and 6,183,807, and pending US Patent Application 09 / 614,631 (filed July 12, 2000). Includes the compositions disclosed in No. 10 / 754,426 (filed January 9, 2004) and No. 11 / 030,641 (filed January 4, 2005) (these disclosures are peroxycarboxylic acid compositions). Incorporated herein for reference).

<u style="single">Embodiment of the present invention</u> Embodiments of the invention include, but are not limited to: In one embodiment, the invention includes an apparatus for making a peroxycarboxylic acid. This embodiment of the apparatus of the present invention can include a first pretreatment column, a first reaction catalyst column, first and second reagent vessels, a safety system, a reaction mixture conduit, and a peracid conduit. .. The first and second reagent vessels can be in fluid communication with the first pretreatment column via the reagent conduit. The first reagent container can be configured to contain a liquid oxidant composition and the second reagent container can be configured to contain a liquid carboxylic acid composition. it can. The reagent conduit defines a mixing chamber for these reagents.

The first pretreatment column can be in fluid communication with the first reaction catalyst column via a reaction mixture conduit. The first pretreatment column can be configured to remove metal ions from the mixture of carboxylic acid composition and oxidant composition. The first reaction catalyst column can be configured to catalyze the reaction of the carboxylic acid and the oxidant to produce the peroxycarboxylic acid. The first reaction catalyst column can be in fluid communication with the storage or use site of the peroxycarboxylic acid composition via a peracid conduit. The safety system includes a processor, a first status sensor and a second status sensor. A first status sensor can be placed in the mixing chamber or on the surface of the mixing chamber and can be configured to measure the condition of the reagents. The second condition sensor may be placed in the first pretreatment column, in the first pretreatment column, or in the reaction mixture conduit near the outlet from the first pretreatment column. It can be configured for measuring the state of the reagent. The processor finds the difference between the state measured by the first state sensor and the state measured by the second state sensor, and can detect if the difference meets or exceeds a predetermined value. Can be configured to provide a signal.

In one embodiment, the first pretreatment column comprises the strong cation exchanger in acid or inert metal form.

The apparatus of the present invention can also include a second pretreatment column. The second pretreatment column can be in fluid communication with the second reagent container and the first pretreatment column via a reagent conduit. The second pretreatment column can be configured to remove metal ions from the carboxylic acid composition. In one embodiment, the second pretreatment column can contain the strong cation exchanger in acid or inert metal form.

The apparatus of the present invention can also include a third pretreatment column. The third pretreatment column can be in fluid communication with the first reagent container and the first pretreatment column via a reagent conduit. The third pretreatment column can be configured to remove metal ions from the oxidant composition. In one embodiment, the third pretreatment column can contain the strong cation exchanger in acid or inert metal form.

The apparatus of the present invention can also include second, third and fourth reaction catalyst columns. The first, second, third and fourth reaction catalyst columns can be connected in series and can be in fluid communication with the storage or use site of the peroxycarboxylic acid composition via a peracid conduit. is there.

In one embodiment, the reaction catalyst comprises a strong acid catalyst that can be physically removed from the reaction mixture. In one embodiment, the reaction catalyst comprises a strong cation exchanger in acid or inert metal form. In one embodiment, the reaction catalyst comprises an inorganic compound containing an insoluble strong acid.

The first and second condition sensors can be configured to measure temperature, pressure, metal content or a combination thereof. For example, the first and second status sensors are configured to measure temperature.

In one embodiment, the safety system is configured to provide a detectable signal if the temperature difference is greater than or equal to 10 ° C or greater than or equal to 10 ° C. Will be done.

This detectable signal can trigger an interruption in the operation of the device. For example, a detectable signal could interrupt the operation of the device and activate the pressure release valve to release the pressure in the first pretreatment column; stop the flow of one or more reagents to the column. To allow water to flow through the reagent conduit, the first pretreatment column and the reaction mixture conduit; to allow the carboxylic acid composition to pass through the reagent conduit, the first pretreatment column and the reaction mixture conduit. The device can be shut down; or activated by a combination of these.

The device of the present invention can also include a peroxy acid vessel, a dilution system, a diluent tank, a refill system and a drainage conduit. The peracid vessel can be in fluid communication with the peracid conduit and can be configured to contain and contain the peroxycarboxylic acid composition. The peroxy acid vessel can be in fluid communication with the dilution system via a drainage conduit. The dilution system can be configured to mix the peroxycarboxylic acid composition and a predetermined amount of carriers to form a diluted composition of a given concentration of peroxycarboxylic acid in the diluent tank. The replenishment system monitors the concentration of peroxycarboxylic acid, the concentration of carboxylic acid, the concentration of oxidant or a combination thereof in a diluted composition, and the concentration of peroxycarboxylic acid, the concentration of carboxylic acid, the oxidant. If the concentration or combination thereof is less than, equal to, or greater than or equal to a predetermined value, the peroxycarboxylic acid composition is configured to be added to the diluted composition. be able to.

In yet another embodiment, the apparatus of the present invention also includes a fourth pretreatment column, a fifth reaction catalyst column, third and fourth reagent vessels, an intermediate reagent conduit, an intermediate reaction mixture conduit, and an intermediate excess. Acid conduits can be included. The third and fourth reagent vessels can be fluidly connected to the fourth pretreatment column via an intermediate reagent conduit. A third reagent container can be configured to contain a liquid oxidant composition and a fourth reagent container can be configured to contain a liquid composition of medium chain carboxylic acid. be able to. Intermediate reagent conduits can define an intermediate mixing chamber for intermediate reagents. The fourth pretreatment column can be in fluid communication with the fifth reaction catalyst column via an intermediate reaction mixture conduit. The fourth pretreatment column can be configured to remove metal ions from the mixture of the liquid composition and the oxidant composition of the medium chain carboxylic acid composition. The fifth reaction catalyst column can be configured to catalyze the reaction of the medium chain carboxylic acid and the oxidant to produce the medium chain peroxycarboxylic acid. The fifth reaction catalyst column is capable of fluid communication with the storage or use site of the medium chain peroxycarboxylic acid composition via an intermediate peracid conduit. The fourth pretreatment column can contain the strong cation exchanger in acid or inert metal form.

In this embodiment or another embodiment, the safety system can also include a third status sensor and a fourth status sensor. The third condition sensor can be placed in the intermediate mixing chamber or on the surface of the intermediate mixing chamber and can be configured to measure the condition of the intermediate reagents. The fourth condition sensor shall be placed in the fourth pretreatment column, in the fourth pretreatment column, or in the intermediate reaction mixture conduit near the outlet from the fourth pretreatment column. Can be configured for measuring the state of intermediate reagents. The processor finds the difference between the state measured by the third state sensor and the state measured by the fourth state sensor, and can detect if this difference meets or exceeds a predetermined value. Can be configured to provide a signal.

In this embodiment or another embodiment, the second reagent vessel is configured to contain a liquid composition of short chain carboxylic acid. The first pretreatment column is configured to remove metal ions from the mixture of short chain carboxylic acid composition and oxidant composition. The first reaction catalyst column is configured to catalyze the reaction of the short chain carboxylic acid and the oxidant to produce the short chain peroxycarboxylic acid.

In this embodiment, the third and fourth condition sensors can be configured to measure temperature, pressure, metal content or a combination thereof. For example, the third and fourth status sensors can be configured to measure temperature.

In this embodiment or another embodiment, a fifth pretreatment column can also be included. The fifth pretreatment column can be in fluid communication with the fourth reagent container and the fourth pretreatment column via an intermediate reagent conduit. The fifth pretreatment column can be configured to remove metal ions from the liquid composition of the medium chain carboxylic acid. The fifth pretreatment column can contain the strong cation exchanger in acid or inert metal form.

In this embodiment or another embodiment, a sixth pretreatment column can also be included. The sixth pretreatment column can be in fluid communication with the third reagent container and the fourth pretreatment column via an intermediate reagent conduit. The sixth pretreatment column can be configured to remove metal ions from the liquid composition of the oxidant. The sixth pretreatment column can contain the strong cation exchanger in acid or inert metal form.

In this embodiment or another embodiment, the reaction catalyst comprises a strong acid catalyst that can be physically removed from the reaction mixture, eg, a strong cation exchanger in acid form, or an inorganic containing an insoluble strong acid. Contains compounds.

This embodiment of the apparatus of the present invention can also include sixth, seventh and eighth reaction catalyst columns. The fifth, sixth, seventh and eighth reaction catalyst columns can be connected in series and have fluid communication with the storage or use site of the medium chain peroxycarboxylic acid composition via an intermediate peracid conduit. Is possible.

In this embodiment, the peroxy acid vessel can be in fluid communication with the intermediate peroxy acid conduit and can be configured to contain and contain a medium chain peroxycarboxylic acid composition.

This embodiment or another embodiment may also include a second processor. The second processor finds the difference between the state measured by the third state sensor and the state measured by the fourth state sensor, and if the difference meets or exceeds a predetermined value. , Can be configured to provide a detectable signal.

In one embodiment, the first reaction catalyst column has a volume of about 9.6 L. In some embodiments, each reaction catalyst column has a volume of about 9.6 L. In one embodiment, the fifth reaction catalyst column has a volume of about 9.6 L.

In one embodiment, the first pretreatment column has a volume of about 4.6 L. In one embodiment, the second pretreatment column has a volume of about 4.6 L. In one embodiment, the third pretreatment column has a volume of about 4.6 L. In one embodiment, the fourth pretreatment column has a volume of about 4.6 L. In one embodiment, the fifth pretreatment column has a volume of about 4.6 L. In one embodiment, the sixth pretreatment column has a volume of about 4.6 L.

In one embodiment, the first reagent container contains from about 35 wt-% to about 45 wt-% hydrogen peroxide. In one embodiment, the second reagent container contains from about 80 wt-% to about 98 wt-% acetic acid. In one embodiment, the third reagent vessel contains from about 35 wt-% to about 45 wt-% hydrogen peroxide. In one embodiment, the second reagent container contains from about 1 wt-% to about 10 wt-% octanoic acid.

The apparatus of the present invention is also configured to contain a liquid medium chain carboxylic acid composition and comprises a third reagent container that is in fluid communication with the first pretreatment column via a reagent conduit. Can be done. Such embodiments can also include a fourth pretreatment column. The fourth pretreatment column can be in fluid communication with the third reagent container and the first pretreatment column via a reagent conduit. The third reagent container can contain from about 1 wt-% to about 10 wt-% octanoic acid.

The present invention also includes methods for making peroxycarboxylic acids. This method provides a liquid composition of carboxylic acid and oxidant; pretreating the liquid composition with a pretreatment column to remove metal ions from the mixed composition; , I) Measure before pretreatment and ii) Measure at the pretreatment site during the pretreatment period; find the difference between i) and ii); if the difference meets or exceeds a predetermined value For example, providing a detectable signal; reacting the pretreated composition in the presence of a reaction catalyst that can be physically removed from the reaction mixture for making the peroxycarboxylic acid composition; , Includes recovering the peroxycarboxylic acid composition.

In one embodiment, pretreatment involves contacting the mixed composition with a strong cation exchanger in acid or inert metal form.

The method also pretreats the carboxylic acid liquid composition to remove metal ions from the carboxylic acid liquid composition; and the carboxylic acid pretreated liquid composition and the oxidizing agent. It can include mixing to form a liquid composition of carboxylic acid and oxidant. In this embodiment, pretreatment can include contacting the liquid composition of the carboxylic acid with a strong cation exchanger in acid or inert metal form.

This method also pretreats the liquid composition of the oxidant to remove metal ions from the liquid composition of the oxidant; and the pretreated liquid composition of the oxidant and the carboxylic acid. It can include mixing to form a liquid composition of carboxylic acid and oxidant. In this embodiment, pretreatment can include contacting the liquid composition of the oxidant with a strong cation exchanger in acid or inert metal form.

The method can include reacting in a column of insoluble reaction catalysts. This embodiment can also include reacting in a second column, a third column and a fourth column of the insoluble reaction catalyst. The first, second, third and fourth reaction catalyst columns can be connected in series.

In this method, the reaction can include contacting the pretreated composition with an insoluble strong acid catalyst. In one embodiment, the reaction can include contacting the pretreated composition with a strong cation exchanger in acid form. In one embodiment, the reaction can include contacting the pretreated composition with an inorganic compound containing an insoluble strong acid.

The method can include measuring the temperature, pressure, metal content or combination thereof of the mixed composition. In one embodiment, the method comprises measuring the temperature of the mixed composition.

The method can include providing a detectable signal if the temperature difference is greater than or equal to 10 ° C or greater than or equal to 10 ° C.

The method also, if the difference meets or exceeds a predetermined value, interrupts the operation of the device and activates a pressure release valve to release the pressure in the device performing the method; one to the device. Or to stop the flow of multiple reagents; to flow water to the pretreatment site; to flow the carboxylic acid composition to the pretreatment site; to shut down the device; or to do with a combination thereof. it can.

The method also mixes the peroxycarboxylic acid composition with a predetermined amount of carriers to form a diluted composition of a given concentration of peroxycarboxylic acid; storing the diluted composition; peroxycarboxylic acid. It can include monitoring the concentration of acid, the concentration of carboxylic acid, the concentration of oxidant or a combination thereof in a diluted composition. If the concentration of peroxycarboxylic acid, the concentration of carboxylic acid, the concentration of oxidant or a combination thereof is less than, equal to, or greater than or equal to a predetermined value, the method is peroxy. It can include adding the carboxylic acid composition to the diluted composition.

The method can also include mixing the liquid composition of the carboxylic acid with the oxidizing agent to form a liquid composition of the carboxylic acid and the oxidizing agent. This makes it possible to form a liquid composition of a carboxylic acid containing about 80 wt-% to 98 wt-% acetic acid. In one embodiment, the oxidant comprises from about 35 wt-% to about 45 wt-% hydrogen peroxide. In one embodiment, the liquid composition of carboxylic acid comprises from about 1 wt-% to about 20 wt-% octanoic acid.

The method can include forming a liquid composition of a large number of carboxylic acids with an oxidizing agent. In one embodiment, the method also comprises a first liquid composition of carboxylic acid, a second liquid composition of carboxylic acid, an oxidant, a large number of carboxylic acids, and a liquid composition of the oxidant. It can include mixing to form an object. In one embodiment, the first liquid composition of carboxylic acid comprises from about 80 wt-% to 98 wt-% acetic acid. In one embodiment, the oxidant comprises from about 35 wt-% to about 45 wt-% hydrogen peroxide. In one embodiment, the second liquid composition of carboxylic acid comprises from about 1 wt-% to about 20 wt-% octanoic acid.

This or another embodiment of the method also pretreats the first liquid composition of the carboxylic acid to remove metal ions from the first liquid composition of the carboxylic acid; and the carboxylic acid. The pretreated first liquid composition of the above can be included in the liquid composition of a large number of carboxylic acids and oxidizing agents.

This or another embodiment of the method also pretreats the liquid composition of the oxidant to remove metal ions from the liquid composition of the oxidant; and the pretreated liquid of the oxidant. The composition can be included in a liquid composition of a large number of carboxylic acids and an oxidizing agent.

This or another embodiment of the method also pretreats the second liquid composition of the carboxylic acid to remove metal ions from the second liquid composition of the carboxylic acid; and the carboxylic acid. The pretreated second liquid composition of the above can be included in the liquid composition of a large number of carboxylic acids and oxidizing agents.

In one embodiment, the liquid composition of the carboxylic acid and oxidant comprises from about 40 wt-% to about 50 wt-% acetic acid and from about 15 wt-% to about 25 wt-% hydrogen peroxide. In one embodiment, the liquid composition of the carboxylic acid and oxidant is about 25 wt-% to about 35 wt-% acetic acid, about 10 wt-% to about 20 wt-% hydrogen peroxide, and about 2 wt-% to. Contains about 4 wt-% octanoic acid.

The method provides, pretreats, measures, seeks, provides, and reacts in the field where the peroxycarboxylic acid composition is used to reduce the population of microorganisms on an object. It can include doing things and recovering. This embodiment of the method can also include delivering carboxylic acids and oxidizing agents to the field. In one embodiment, the method comprises delivering a large number of carboxylic acids to the field. In one embodiment, the method also comprises requesting delivery of the carboxylic acid and oxidant from the field.

In one embodiment, the method also comprises applying the peroxycarboxylic acid composition to a beverage container in a beverage factory.

The present invention also includes methods for making peroxycarboxylic acids. The method delivers the carboxylic acid and oxidant to the site where the peroxycarboxylic acid composition is made and used; to provide a liquid composition of the carboxylic acid and oxidant; to the liquid composition, metal ions. Pretreating with a pretreatment column to remove from the mixed composition; the presence of a reaction catalyst that allows the pretreated composition to be physically removed from the reaction mixture for making the peroxycarboxylic acid composition. Reacting under; recovering the peroxycarboxylic acid composition; and applying the peroxycarboxylic acid composition to the object to reduce the population of microorganisms on the object.

In one embodiment, the method comprises delivering a large number of carboxylic acids to the field. In one embodiment, the method also comprises requesting delivery of the carboxylic acid and oxidant from the field.

In one embodiment, the method also comprises applying the peroxycarboxylic acid composition to a beverage container in a beverage factory.

The present invention also includes methods for making mixed peroxycarboxylic acid compositions. The method provides a liquid composition of short chain carboxylic acid and oxidant; pretreated with a pretreatment column to remove the mixed short chain composition from the mixed composition of short chains. To react; the pretreated short chain composition is reacted in the presence of an insoluble reaction catalyst for producing the short chain peroxycarboxylic acid composition; the liquid composition of the medium chain carboxylic acid and the oxidant is provided. To do; pretreat the mixed medium chain composition with a pretreatment column to remove metal ions from the mixed medium chain composition; the pretreated medium chain composition to have an intermediate peroxycarboxylic acid composition. Reacting in the presence of an insoluble reaction catalyst for the production of the product; the short chain peroxycarboxylic acid composition and the medium chain peroxycarboxylic acid composition are mixed to produce the mixed peroxycarboxylic acid composition. That; measure the state of the short-chain acid composition at the pretreatment site i) before the pretreatment and ii) during the pretreatment period; and determine the difference between i) and ii); If the difference between i) and ii) meets or exceeds a predetermined value, provide a detectable signal; the state of the mixed medium chain composition, iii) before pretreatment, and iv) Measure at the pretreatment site during the pretreatment period; determine the difference between iii) and iv); and the difference between iii) and iv), or the difference between both satisfies the predetermined value. If it exceeds, it involves providing a detectable signal.

The present invention also includes a peroxycarboxylic acid composition prepared by the method according to the present invention. The method of the present invention provides a liquid composition of a carboxylic acid and an oxidizing agent; pretreating the liquid composition with a pretreatment column to remove metal ions from the mixed composition; the liquid composition. Measure the state at i) before pretreatment and at ii) at the pretreatment site during the pretreatment period; find the difference between i) and ii); the difference meets or exceeds a predetermined value. If so, provide a detectable signal; react the pretreated composition in the presence of a reaction catalyst that can be physically removed from the reaction mixture for making the peroxycarboxylic acid composition; And it can include recovering the peroxycarboxylic acid composition.

The present invention includes a peroxycarboxylic acid composition. The composition can include from about 1 wt-% to about 35 wt-% peroxycarboxylic acid, from about 5 wt-% to about 30 wt-% hydrogen peroxide, and metals less than about 10 ppb. In one embodiment, the composition retains 85% peroxycarboxylic acid at 140 ° F for at least 13 days. In one embodiment, the composition retains 95% peroxycarboxylic acid at 140 ° F for at least 7 days. In one embodiment, the composition comprises from about 0.5 wt-% to about 35 wt-% short chain peroxycarboxylic acid. In one embodiment, the composition comprises from about 0.5 wt-% to about 20 wt-% medium chain peroxycarboxylic acid. In one embodiment, the composition comprises from about 0.5 wt-% to about 35 wt-% short chain peroxycarboxylic acid and from about 0.5 wt-% to about 20 wt-% medium chain peroxycarboxylic acid. In one embodiment, the composition comprises a peroxycarboxylic acid and hydrogen peroxide in a ratio of about 0.5: 1 to about 7: 1. In one embodiment, the composition comprises only volatile compounds.

The present invention also includes a system. The system of the present invention is a peroxycarboxylic acid generator that provides a high concentration of peroxycarboxylic acid; a composition container for use that stores a composition of use consisting of a high concentration of peroxycarboxylic acid diluted; and a peroxycarboxylic acid in the composition. Includes a control device that receives concentration data on the concentrations of acids and hydrogen peroxides and manages to replenish the compositions used when these concentrations do not meet predetermined criteria.

In one embodiment, the controller compares the concentration of peroxycarboxylic acid to a predetermined POAA target criterion, and when the concentration data indicates that the concentration of peroxycarboxylic acid in the composition used is too low, the composition used. Control the addition of high concentrations of peroxycarboxylic acid to.

In one embodiment, the controller compares the concentration of peroxycarboxylic acid to a predetermined POAA target criterion, and when the concentration data indicates that the concentration of peroxycarboxylic acid in the composition used is too high, the composition used. Control the addition of diluent to.

In one embodiment, the controller sets the concentration of hydrogen peroxide to a predetermined H.₂O₂When compared to the target criteria and the concentration data indicates that the hydrogen peroxide concentration in the composition used is too high, empty the composition container used and create a new composition used. to manage.

In one embodiment, the controller compares the concentration of peroxycarboxylic acid to the expected POAA target concentration and causes changes in the concentration of peroxycarboxylic acid in the high concentration of peroxycarboxylic acid provided by the peroxycarboxylic acid generator. Adjust the operating parameters of the peroxycarboxylic acid generator.

The present invention also includes methods. The method of the present invention receives concentration data on the concentrations of peroxycarboxylic acid and hydrogen peroxide in the composition used; compares the concentration of peroxycarboxylic acid with a given POAA target criterion; and the concentration of peroxycarboxylic acid is predetermined. When the POAA target criteria of the above are not met, the composition used can be automatically replenished.

In one embodiment of this method, automatic replenishment of the composition used also results in a high concentration of peroxycarboxylic acid when the concentration data indicates that the concentration of peroxycarboxylic acid in the composition used is too low. Includes automatic addition to the composition used.

In one embodiment of this method, automatic replenishment of the composition used also adds a diluent to the composition used when concentration data indicates that the concentration of peroxycarboxylic acid in the composition used is too high. Includes automatic addition.

In one embodiment of this method, automatic replenishment of the composition used also automatically replenishes the composition container used when concentration data indicates that the concentration of hydrogen peroxide in the composition used is too high. Includes emptying and automatically creating new compositions for use.

In one embodiment, the method also compares the concentration of peroxycarboxylic acid to the expected POAA target concentration and changes to the concentration of peroxycarboxylic acid in the high concentration of peroxycarboxylic acid provided by the peroxycarboxylic acid generator. Includes adjusting the operating parameters of the peroxycarboxylic acid generator to exert.

<u style="single">Carboxylic acid, peroxycarboxylic acid and additional ingredients</u> Peroxycarboxylic acids (or percarboxylic acids) are generally represented by the formula R (CO).₃H)_n(In the formula, for example, R is an alkyl group, an arylalkyl group, a cycloalkyl group, an aromatic group or a heterocyclic group, and n is 1, 2 or 3) of the original acid. Named by prefixing with peroxy. The R group can be saturated or unsaturated, as well as substituted or unsaturated. A peroxy form of a carboxylic acid having two or more carboxylate components can have one or more carboxyl components present as peroxycarboxyl components.

In the method of the present invention, for example, a peroxycarboxylic acid containing 2 to 12 carbon atoms can be used. For example, peroxycarboxylic acid (or percarboxylic acid) is expressed in formula R (CO).₃H)_n(In the formula, R is C₁~ C₁₁Alkyl group, C₁~ C₁₁Cycloalkyl group, C₁~ C₁₁Arylalkyl group, C₁~ C₁₁Aryl group or C₁~ C₁₁It is a heterocyclic group, where n is 1, 2 or 3). In the method of the present invention, for example, a medium-chain peroxycarboxylic acid containing 6 to 12 carbon atoms can be used. For example, a medium chain peroxycarboxylic acid (or percarboxylic acid) can be expressed in formula R (CO).₃H)_n(In the formula, R is C₅~ C₁₁Alkyl group, C₅~ C₁₁Cycloalkyl group, C₅~ C₁₁Arylalkyl group, C₅~ C₁₁Aryl group or C₅~ C₁₁It is a heterocyclic group, where n is 1, 2 or 3). In the method of the present invention, for example, a short-chain peroxycarboxylic acid containing 1 to 4 carbon atoms can be used. For example, a short-chain peroxycarboxylic acid (or percarboxylic acid) can be expressed in formula R (CO).₃H)_n(In the formula, R is C₁~ C₃Alkyl group or C₁~ C₃It is a cycloalkyl group, where n is 1 or 2). The mixed peroxycarboxylic acid composition used in the method of the present invention can include one or more short chain peroxycarboxylic acids and one or more medium chain peroxycarboxylic acids.

Peroxycarboxylic acids can be made from acid chlorides and hydrides or anhydrous carboxylic acids by the direct action of oxidants on the carboxylic acids, by the autoxidation of aldehydes, or with hydrogen peroxide or sodium peroxide. it can. In one embodiment, the peroxycarboxylic acid can be made by the direct acid-catalyzed equilibrium action of hydrogen peroxide on the carboxylic acid. Scheme 1 consists of a carboxylic acid and oxidant (Ox) on one side and a peroxycarboxylic acid and reduced oxidant (Ox) on the other side._red) Illustrates the equilibrium with: RCOOH + Ox RCOOOH + Ox_red (1)

Scheme 2 illustrates one embodiment of the equilibrium of Scheme 1, where the oxidant is hydrogen peroxide on one side and peroxycarboxylic acid and water on the other side: RCOOH + H₂O₂ RCOOOH + H₂O (2)

In a conventional mixed peroxycarboxylic acid composition, the equilibrium constant for the reaction exemplified in Scheme 2 is believed to be about 2.7, which may reflect the equilibrium for acetic acid.

Peroxycarboxylic acids useful in the methods of the present invention include peroxygiic acid, peroxyacetic acid, peroxypropionic acid, peroxybutanoic acid, peroxypentanoic acid, peroxyhexanoic acid, peroxyheptanic acid, peroxyoctanoic acid, peroxynonanoic acid, peroxydecanoic acid. , Peroxyundecanoic acid, peroxide decanoic acid, peroxylactic acid, peroxymaleic acid, peroxyascorbic acid, peroxyhydroxyacetic acid, peroxysuccinic acid, peroxymalonic acid, peroxysuccinic acid, peroxyglutaric acid, peroxyadipic acid, peroxypimelic acid, peroxy Includes peroxide or a mixture thereof. Medium-chain peroxycarboxylic acids useful in the compositions and methods of the present invention include peroxypentanoic acid, peroxyhexanoic acid, peroxyheptanic acid, peroxyoctanoic acid, peroxynonanoic acid, peroxydecanoic acid, peroxyundecanoic acid, peroxide decanoic acid, etc. Includes are peroxyascorbic acid, peroxyadipic acid, peroxycitrate, peroxypimelic acid or peroxysveric acid, or mixtures thereof. Short-chain peroxycarboxylic acids useful in the compositions and methods of the invention include peroxyformic acid, peroxyacetic acid, peroxypropionic acid, peroxybutanoic acid, peroxyoxalic acid, peroxymalonic acid, peroxysuccinic acid or mixtures thereof. Is done. The alkyl skeletons of these peroxycarboxylic acids can be linear, branched or a mixture thereof. A peroxy form of a carboxylic acid having two or more carboxylate components can have one or more (eg, at least one) carboxyl components present as peroxycarboxyl components.

In one embodiment, the method of the invention uses peroxyacetic acid. Peroxyacetic acid (or peracetic acid) is expressed in the formula CH₃It is a peroxycarboxylic acid having COOOH. In general, peroxyacetic acid is a liquid with an unpleasant odor at higher concentrations and is freely soluble in water, alcohols, ethers and sulfuric acid. A 50% solution of peroxyacetic acid can be obtained by combining acetic anhydride, hydrogen peroxide and sulfuric acid.

Peroxyoctanoic acid (or peroctanoic acid) is, for example, the formula for n-peroxyoctanoic acid, ie CH.₃(CH₂)₆It is a peroxycarboxylic acid having COOOH. The peroxyoctanoic acid can be an acid having a linear alkyl component, an acid having a branched alkyl component, or a mixture thereof. Peroxycarboxylic acids are surface active and can help wet hydrophobic surfaces (eg, arthropod surfaces).

In one embodiment, the methods of the invention utilize a combination of several different peroxycarboxylic acids. Such combinations include one or more short chain peroxycarboxylic acids (eg, C).₂~ C₄Peroxycarboxylic acid) and one or more medium chain peroxycarboxylic acids (eg C)₇~ C₉Peroxycarboxylic acid) may be included. For example, the short-chain peroxycarboxylic acid can be peroxyacetic acid, and the medium-chain peroxycarboxylic acid can be peroxyoctanoic acid. In one embodiment, the method of the invention uses a composition comprising peroxyoctanoic acid, peroxynonanoic acid or peroxyheptanic acid, for example a composition comprising peroxyoctanoic acid. In one embodiment, the methods of the invention use compositions comprising acetic acid, octanoic acid, peroxyacetic acid and peroxyoctanoic acid. Such compositions can also include a chelating agent.

The compositions and methods of the present invention can include medium chain peroxycarboxylic acids. The medium-chain peroxycarboxylic acid may include C6 to C12 peroxycarboxylic acid, or examples of the medium-chain peroxycarboxylic acid include C6 to C12 peroxycarboxylic acid. C6 ~ C12 peroxycarboxylic acids may include peroxyhexanoic acid, peroxyheptanic acid, peroxyoctanoic acid, peroxynonanoic acid, peroxydecanoic acid, peroxyundecanoic acid, peroxide decanoic acid or mixtures thereof, or C6 ~ Examples of the C12 peroxycarboxylic acid include peroxyhexanoic acid, peroxyheptanic acid, peroxyoctanoic acid, peroxynonanoic acid, peroxydecanoic acid, peroxyundecanoic acid, peroxide decanoic acid or a mixture thereof. The medium-chain peroxycarboxylic acid may include C7 to C12 peroxycarboxylic acid, or examples of the medium-chain peroxycarboxylic acid include C7 to C12 peroxycarboxylic acid. C7 to C12 peroxycarboxylic acids may include peroxyheptanic acid, peroxyoctanoic acid, peroxynonanoic acid, peroxydecanoic acid, peroxyundecanoic acid, peroxide decanoic acid or mixtures thereof, or C7 to C12 peroxycarboxylic acids. Examples thereof include peroxyheptanic acid, peroxyoctanoic acid, peroxynonanoic acid, peroxydecanoic acid, peroxyundecanoic acid, peroxide decanoic acid or a mixture thereof. The medium-chain peroxycarboxylic acid may include C6 to C10 peroxycarboxylic acid, or examples of the medium-chain peroxycarboxylic acid include C6 to C10 peroxycarboxylic acid. C6 to C10 peroxycarboxylic acids may include peroxyhexanoic acid, peroxyheptanic acid, peroxyoctanoic acid, peroxynonanoic acid, peroxydecanoic acid or mixtures thereof, or as C6 to C10 peroxycarboxylic acids, peroxyhexa. Acids, peroxyheptanic acid, peroxyoctanoic acid, peroxynonanoic acid, peroxydecanoic acid or mixtures thereof can be mentioned. The medium-chain peroxycarboxylic acid may include C8 to C10 peroxycarboxylic acid, or examples of the medium-chain peroxycarboxylic acid include C8 to C10 peroxycarboxylic acid. C8 to C10 peroxycarboxylic acids may include peroxyoctanoic acid, peroxynonanoic acid, peroxydecanoic acid or mixtures thereof, or as C8 to C10 peroxycarboxylic acids, oxyoctanoic acid, peroxynonanoic acid, peroxydecane. Acids or mixtures thereof can be mentioned. In some embodiments, the medium chain peroxycarboxylic acid comprises peroxyoctanoic acid, peroxydecanoic acid or a mixture thereof, or, as the medium chain peroxycarboxylic acid, peroxyoctanoic acid, peroxydecanoic acid or a mixture thereof. Examples include mixtures. In one embodiment, the medium chain peroxycarboxylic acid comprises peroxyoctanoic acid, or the medium chain peroxycarboxylic acid includes oxyoctanoic acid. Peroxycarboxylic acids include peroxyoctanoic acid, peroxydecanoic acid or mixtures thereof. In one embodiment, the medium chain peroxycarboxylic acid comprises peroxyoctanoic acid, or the medium chain peroxycarboxylic acid includes oxyoctanoic acid. Peroxycarboxylic acids include peroxyoctanoic acid, peroxydecanoic acid or mixtures thereof. In one embodiment, the medium chain peroxycarboxylic acid comprises peroxyoctanoic acid, or the medium chain peroxycarboxylic acid includes oxyoctanoic acid.

The composition of the present invention can contain a carboxylic acid. In general, carboxylic acids can represent many different groups, including the formula R-COOH (where R is an aliphatic group, an alicyclic group, an aromatic group, a heterocyclic group, but All of these groups can be saturated or unsaturated as well as substituted or unsaturated). Carboxylic acids can have one, two, three or four or more carboxyl groups. Carboxylic acids containing as many as 18 carbon atoms can be used in the compositions and methods of the present invention.

Suitable carboxylic acids have an R group, C₂~ C₁₂Includes carboxylic acids with one or two carboxyl groups, which are primary alkyl chains with a length of. A primary alkyl chain is such a carbon chain of a molecule having a carbon atom of maximum length and a carboxyl functional group attached directly. For example, the carboxylic acid is the formula R-COOH (in the formula, R is C).₁~ C₁₂Alkyl group, C₁~ C₁₁Cycloalkyl group, C₁~ C₁₂Arylalkyl group, C₁~ C₁₁Aryl group or C₁~₁₁It can have a heterocyclic group). In the method of the present invention, for example, a medium-chain carboxylic acid containing 6 to 12 carbon atoms can be used. For example, the medium chain carboxylic acid is of the formula R-COOH (in the formula, R is C).₅~ C₁₁Alkyl group, C₅~ C₁₁Cycloalkyl group, C₅~ C₁₁Arylalkyl group, C₅~ C₁₁Aryl group or C₅~₁₁Heterocyclic groups are possible). For example, short-chain carboxylic acids are represented by the formula R-COOH (where R is H, C in the formula).₁~ C₃Alkyl group or C₃It is a cycloalkyl group, where n is 1 or 2).

Suitable carboxylic acids include formic acid, acetic acid, propionic acid, butanoic acid, pentanoic acid, hexanoic acid, heptic acid, octanoic acid, nonanoic acid, decanoic acid, undecanoic acid, dodecanoic acid, lactic acid, maleic acid, ascorbic acid, citrate Includes acids, hydroxyacetic acids, neopentanoic acids, neoheptanic acids, neodecanoic acids, oxalic acids, malonic acids, succinic acids, glutaric acids, adipic acids, pimeric acids, suberic acids or mixtures thereof. Suitable medium chain carboxylic acids include pentanoic acid, hexanoic acid, heptanic acid, octanoic acid, nonanoic acid, decanoic acid, undecanoic acid, dodecanoic acid, ascorbic acid, citric acid, adipic acid, pimeric acid, suberic acid or these. Contains mixtures and the like. Suitable short-chain carboxylic acids include formic acid, acetic acid, propionic acid, butanoic acid, hydroxyacetic acid, oxalic acid, malonic acid, succinic acid or mixtures thereof. The alkyl backbone of these carboxylic acids can be linear, branched or a mixture thereof. Generally useful carboxylic acids have an R group of C₄~ C₁₁A carboxylic acid having one or two carboxyl groups, which is a primary alkyl chain having a length of. A primary alkyl chain is such a carbon chain of a molecule having a carbon atom of maximum length and a carboxyl functional group attached directly.

In one embodiment, the compositions and methods of the invention comprise a medium chain carboxylic acid. The medium-chain carboxylic acid may include C6 to C12 carboxylic acid, or examples of the medium-chain carboxylic acid include C6 to C12 carboxylic acid. C6 to C12 carboxylic acids may include caproic acid, enanthic acid, octanoic acid, nonanoic acid, decanoic acid, undecanoic acid, dodecanoic acid or mixtures thereof, or as C6 to C12 carboxylic acids, caproic acid, Examples thereof include caproic acid, octanoic acid, nonanoic acid, decanoic acid, undecanoic acid, dodecanoic acid or a mixture thereof. The medium-chain carboxylic acid may include C7 to C12 carboxylic acid, or examples of the medium-chain carboxylic acid include C7 to C12 carboxylic acid. C7 to C12 carboxylic acids can include heptanic acid, octanoic acid, nonanoic acid, decanoic acid, undecanoic acid, dodecanoic acid or mixtures thereof, or as C7 to C12 carboxylic acids, heptanic acid, octanoic acid, Nonanoic acid, decanoic acid, undecanoic acid, dodecanoic acid or a mixture thereof can be mentioned. The medium-chain carboxylic acid may include C6 to C10 carboxylic acid, or examples of the medium-chain carboxylic acid include C6 to C10 carboxylic acid. C6 to C10 carboxylic acids may include caproic acid, enanthic acid, octanoic acid, nonanoic acid, decanoic acid or mixtures thereof, or as C6 to C10 carboxylic acids, caproic acid, heptanoic acid, octanoic acid, Examples include enanthic acid, decanoic acid or mixtures thereof. The medium-chain carboxylic acid may include C8 to C10 carboxylic acid, or examples of the medium-chain carboxylic acid include C8 to C10 carboxylic acid. C8 to C10 carboxylic acids include octanoic acid, nonanoic acid, decanoic acid or mixtures thereof, or C8 to C10 carboxylic acids include octanoic acid, nonanoic acid, decanoic acid or mixtures thereof. it can. In some embodiments, the medium chain carboxylic acid is octanoic acid, decanoic acid or These mixtures are included, or examples of medium chain carboxylic acids include octanoic acid, decanoic acid or mixtures thereof. In one embodiment, the medium chain carboxylic acid comprises octanoic acid, or the medium chain carboxylic acid includes octanoic acid.

In one embodiment, the compositions and methods of the invention comprise a mixed peroxycarboxylic acid and a corresponding mixed carboxylic acid.

In one embodiment, the compositions of the invention, for example, Salmonella typhimurium, are used to kill one or more (eg, at least one) food-borne pathogenic bacteria associated with a food product. Kill one or more (eg, at least one) of Salmonella javiana, Campylobacter jejuni, Listeria monocytogenes and Escherichia coli O157: H7, yeast and mold, etc. Contains an effective amount of mixed peroxycarboxylic acid. In one embodiment, the compositions of the present invention, for example, Salmonella typhimurium, Staphylococcus aureus (eg,) to kill one or more (eg, at least one) pathogenic bacteria associated with health care surfaces and the environment. Staphylococcus aureus), Salmonella choleraesurus, Pseudomonas It contains an amount of mixed peroxycarboxylic acid that is effective in killing one or more (eg, at least one) of aeruginasa), Escherichia coli, Mycobacterium spp., Yeast and mold. The compositions and methods of the invention have activity against a wide variety of microorganisms, such as Gram-positive bacteria (eg, Listeria or Staphylococcus aureus) and Gram-negative bacteria (eg, Escherichia coli or Pseudomonas aeruginosa). ), Yeast, mold, bacterial spores, viruses, etc. The compositions and methods of the present invention have activity against a wide variety of human pathogens, as described above. The compositions and methods of the present invention cover a wide variety of microorganisms in a processed food surface, a surface of a food product, water used for cleaning or processing a food product, a healthcare surface, or a healthcare environment. Can be killed.

Career The compositions of the present invention can also include carriers. The carrier provides a medium for dissolving, suspending or transporting other components of the composition. For example, the carrier can provide a medium for solubilizing, suspending or producing a peroxycarboxylic acid, and a medium for forming an equilibrium mixture. Carriers can also serve to deliver the antibacterial compositions of the invention and moisten them on an object. For this purpose, the carrier can contain any component (s) that can facilitate these functions.

In general, carriers primarily include water, which can promote solubility and also serve as a medium for reaction and equilibrium. Carriers may include predominantly organic solvents such as simple alkyl alcohols such as ethanol, isopropanol and n-propanol, or as carriers predominantly organic solvents such as simple alkyl alcohols. (For example, ethanol, isopropanol and n-propanol, etc.) and the like. Polyols are also useful carriers, including glycerol and sorbitol.

Suitable carriers include glycol ethers. Suitable glycol ethers include diethylene glycol n-butyl ether, diethylene glycol n-propyl ether, diethylene glycol ethyl ether, diethylene glycol methyl ether, diethylene glycol t-butyl ether, dipropylene glycol n-butyl ether, dipropylene glycol methyl ether, dipropylene glycol ethyl ether, Dipropylene glycol propyl ether, dipropylene glycol tert-butyl ether, ethylene glycol butyl ether, ethylene glycol propyl ether, ethylene glycol ethyl ether, ethylene glycol methyl ether, ethylene glycol methyl ether acetate, propylene glycol t-butyl ether, propylene glycol ethyl ether, Propylene glycol methyl ether, propylene glycol n-propyl ether, tripropylene glycol methyl ether and tripropylene glycol n-butyl ether, ethylene glycol phenyl ether (which is Dow as DOWANOL EPH ) Includes (available from Chemical Co.), propylene glycol phenyl ether (which is available from Dow Chemical Co. as DOWANOL PPH ), and mixtures thereof. More suitable commercially available glycol ethers (all of which are available from Union Carbide Corp.) include Butoxyethyl PROPASOL , Butyl CARBITOL Assetate, Butyl CARBITOL , Butyl CELLOSOLVE ( Butyl CELLOSOLVE , Butyl DIPROPASOL , Butyl PROPASOL , CARBITOL PM-600, CARBITOL Low Gravity, CELLOSOLVE Assetate, CELLOSOLVE , Esther EEP , FILMER IBT , Hexyl CARBITOL , Hexyl CELLOSOLVE , Methyl CARBITOL , Methyl CELLOSOLVE Assetate, Methyl CELLOSOLVE , Methyl DIPROPASOL , Methyl PROPASOL Assetate, Methyl PROPASOL , Propyl CARBITOL , Propyl Includes CELLOSOLVE , Propyl DI PROPASOL and Propyl PROPASOL .

In general, carriers make up a large part of the composition of the invention and can be the rest of the composition apart from active antibacterial components, stabilizers, oxidizing agents and auxiliaries and the like. Here again, the concentration and type of carrier depends, among other things, on the properties of the composition as a whole, the environmental storage, and the application method, including the concentration of peroxycarboxylic acid. Obviously, the carrier must be selected and used at a concentration that does not interfere with the antibacterial efficacy of the peroxycarboxylic acid in the compositions of the present invention.

In some embodiments, the compositions of the invention are about 0 wt-% to about 98 wt-% carriers, about 0.001 wt-% to about 99.99 wt-% carriers, about 0.2 wt-% to about 60 wt-%. Carrier, about 1wt-% ~ about 98wt-% carrier, about 5wt-% ~ about 99.99wt-% carrier, about 5wt-% ~ about 97wt-% carrier, about 5wt-% ~ about 90wt-% Carriers, about 5wt-% to about 70wt-% carriers, about 5wt-% to about 20wt-% carriers, about 10wt-% to about 90wt-% carriers, about 10wt-% to about 80wt-% carriers, About 10wt-% to about 50wt-% carrier, about 10wt-% to about 20wt-% carrier, about 15wt-% to about 70wt-% carrier, about 15wt-% to about 80wt-% carrier, about 20wt -% ~ About 70wt-% carrier, about 20wt-% ~ about 50wt-% carrier, about 20wt-% ~ about 40wt-% carrier, about 20wt-% ~ about 30wt-% carrier, about 30wt-% ~ About 75wt-% carrier, about 30wt-% ~ about 70wt-% carrier, about 40wt-% ~ about 99.99wt-% carrier, about 40wt-% ~ about 90wt-% carrier, or about 60wt- Includes% ~ about 70wt-% carriers. The compositions of the present invention can include any of these ranges or amounts that are not modified by about.

Oxidant The compositions and methods of the present invention can include any of a variety of oxidizing agents. Oxidizing agents can be used to maintain or produce peroxycarboxylic acids.

Examples of inorganic oxidants include compounds of the following types or sources of these compounds, or alkali metal salts containing these types of compounds, or alkali metals that form adducts with these types of compounds. Contains salt:

hydrogen peroxide; Group 1 (IA) oxidants, such as lithium peroxide and sodium peroxide; Group 2 (IIA) oxidants, such as magnesium peroxide, calcium peroxide, strontium peroxide and barium peroxide; Group 12 (IIB) oxidants, such as zinc peroxide; Group 13 (IIIA) oxidants, such as boron compounds, such as perborates (eg, formula Na)₂[B₂(O₂)₂(OH)₄] 6H₂Sodium perborate hexahydrate of O (also called sodium perborate tetrahydrate, formerly NaBO₃ 4H₂Written as O); Expression Na₂B₂(O₂)₂[(OH)₄] 4H₂Sodium perborate tetrahydrate of O (also called sodium perborate trihydrate, formerly NaBO₃ 3H₂Written as O); Expression Na₂[B₂(O₂)₂(OH)₄] Sodium perborate (also known as sodium perborate monohydrate, formerly NaBO₃ H₂(Written as O), etc.), etc .; in one embodiment, perborate; Group 14 (IVA) oxidants, such as persilicates and peroxycarbonates (also called peroxycarbonates), such as alkali metal persilicates or peroxycarbonates; others; one embodiment. In, percarbonate; in one embodiment, persilicate; Group 15 (VA) oxidants, eg, peroxynitrite and salts thereof; various peroxyphosphates and salts thereof, eg, perphosphates; others; in one embodiment, perphosphates; Group 16 (VIA) oxidants, such as various peroxysulfates and salts thereof, such as peroxymonosulfate and peroxydisulfate and their salts (eg, persulfates, such as sodium persulfate); etc.; In one embodiment, persulfate; Group VIIa oxidants, such as sodium periodate and potassium perchlorate.

Other active inorganic oxygen compounds may include transition metal peroxides; and other such peroxygen compounds, and mixtures thereof.

In one embodiment, the compositions and methods of the invention use one or more of the inorganic oxidants listed above. Suitable inorganic oxidants include ozone, hydrogen peroxide, hydrogen peroxide adducts, Group IIIA oxidants, Group VIA oxidants, Group VA oxidants, Group VIA oxidants or mixtures thereof. .. Suitable examples of such inorganic oxidants include percarbonates, perborates, persulfates, perphosphates, persilicates or mixtures thereof.

Hydrogen peroxide shows a suitable example of an inorganic oxidant. Hydrogen peroxide can be provided as a mixture of hydrogen peroxide and water, for example as liquid hydrogen peroxide in aqueous solution. Hydrogen peroxide is commercially available in water at concentrations of 35%, 70% and 90%. For safety, 35% is commonly used. The composition of the present invention can contain, for example, about 2 wt-% to about 30 wt-% hydrogen peroxide or about 5 wt-% to about 20 wt-% hydrogen peroxide.

In one embodiment, the inorganic oxidant comprises a hydrogen peroxide adduct. For example, the inorganic oxidant may include hydrogen peroxide, hydrogen peroxide adducts or mixtures thereof. Any variety of hydrogen peroxide adducts are suitable for use in the compositions and methods of the invention. For example, suitable hydrogen peroxide adducts include salts of percarbonates, urea peroxides, peracetylborates, H.₂O₂And an adduct of polyvinylpyrrolidone, sodium percarbonate, potassium percarbonate, or a mixture thereof. Suitable hydrogen peroxide adducts include salts of percarbonates, urea peroxides, peracetylborates, H.₂O₂And an adduct of polyvinylpyrrolidone, or a mixture thereof. Suitable hydrogen peroxide adducts include sodium percarbonate, potassium percarbonate or mixtures thereof, including, for example, sodium percarbonate.

In one embodiment, the compositions and methods of the invention can include hydrogen peroxide as an oxidant. Hydrogen peroxide in combination with peroxycarboxylic acid can provide some antibacterial effect against microorganisms. In addition, hydrogen peroxide can provide a foaming action that can irrigate any surface to which hydrogen peroxide is applied. Hydrogen peroxide, when applied, can work with a mechanical flushing action that further cleans the surface of the object. A further advantage of hydrogen peroxide is the food compatibility of the compositions of the invention during use and decomposition.

In some embodiments, the compositions of the invention are about 0.001 wt-% to about 30 wt-% oxidizer, about 0.001 wt-% to about 10 wt-% oxidizer, about 0.002 wt-% to about 10 wt. -% Oxidizer, about 2wt-% ~ about 30wt-% oxidizer, about 2wt-% ~ about 25% oxidizer, about 2wt-% ~ about 20wt-% oxidizer, about 4wt-% ~ about Contains 20 wt-% oxidant, about 5 wt-% to about 10 wt-% oxidizer, or about 6 wt-% to about 10 wt-% oxidant. The compositions of the present invention can include any of these ranges or amounts that are not modified by about.

<u style="single">Ingredients used as needed</u> Acidulant In one embodiment, the compositions of the invention can include acidulants. The acidity agent can act as a catalyst for converting the carboxylic acid to the peroxycarboxylic acid. Acidic agents can be effective in forming high concentration compositions having a pH of about 1 or less. Acidic agents can be effective in forming used compositions having a pH such as about 5, about 5 or less, about 4, about 4 or less, about 3, about 3 or less, about 2 or about 2 or less. .. In one embodiment, the acidifying agent comprises an inorganic acid. Suitable inorganic acids include sulfuric acid, phosphoric acid, nitric acid, hydrochloric acid, methanesulfonic acid, ethanesulfonic acid, propanesulfonic acid, butanesulfonic acid, xylenesulfonic acid, benzenesulfonic acid or mixtures thereof.

In one embodiment, the acidulant is pK_aIncludes carboxylic acids with a value of less than 4. pK_aSuitable carboxylic acids with a value of less than 4 include hydroxyacetic acid, hydroxypropionic acid, other hydroxycarboxylic acids, or mixtures thereof. Such acidulants are present at concentrations where the acidulants do not act as solubilizers.

In one embodiment, the compositions of the present invention are about 0.001 wt-% to about 50 wt-% acidulant, about 0.001 wt-% to about 30 wt-% acidulant, about 1 wt-% to about 50 wt. -% Acidity agent, about 1wt-% to about 30wt-% acidity agent, about 2wt-% to about 40wt-% acidity agent, about 2wt-% to about 10wt-% acidity agent, about 3wt-% to about 40wt-% acidity agent, about 5wt-% to about 40wt-% acidity agent, about 5wt-% to about 25wt-% acidity agent, about 10wt-% to about 40wt-% Acidity agent, about 10wt-% to about 30wt-% acidity agent, about 15wt-% to about 35wt-% acidity agent, about 15wt-% to about 30wt-% acidity agent, or about Contains 40 wt-% to about 60 wt-% acidulant. The compositions of the present invention can include any of these ranges or amounts that are not modified by about.

Stabilizer The compositions of the invention to stabilize one or more stabilizers, eg, peracids and hydrogen peroxide, and to prevent premature decomposition of this component in the compositions of the invention. Can be added to.

Suitable stabilizers include chelating agents or sequestrants. Suitable sequestrants include organic chelating compounds that block metal ions (specifically, transition metal ions) in solution. Such metal ion sequestering agents include aminopolyphosphonic acid-based or hydroxypolyphosphonic acid-based organic complexing agents (either acid or soluble salt), carboxylic acids (eg, polymeric polycarboxylic acids). , Hydroxycarboxylic acid or aminocarboxylic acid.

Sequestrants can include phosphonic acid or phosphonate salts, or sequestrants can include phosphonic acid or phosphonate salts. Suitable phosphonic acids and phosphonate salts include 1-hydroxyethylidene-1,1-diphosphonic acid (CH).₃C (PO₃H₂)₂OH) (HEDP); ethylenediaminetetraxmethylenephosphonic acid (EDTMP); diethylenetriaminepentaxmethylenephosphonic acid (DTPMP); cyclohexane-1,2-tetramethylenephosphonic acid; amino [tri (methylenephosphonic acid)]; (ethylenediamine [tetra] Methylene-phosphonic acid]); 2-phosphenbutane-1,2,4-tricarboxylic acid; or salts thereof, such as alkali metal salts, ammonium salts, or alkyl oil amine salts (eg, monoethanolamine salts). , Diethanolamine salts or tetraethanolamine salts, etc.); or mixtures thereof.

Suitable organic phosphonates include HEDP.

Commercially available chelating agents for food additives include phosphonates sold under the trade name DEQUEST®, which include, for example, 1-hydroxyethylidene-1,1-diphosphonic acid. Is available as DEQUEST® 2010 from Monsanto Industrial Chemicals Co. (St. Louis, MO)), Amino (Tri (methylenephosphonic acid)) (N [CH₂PO₃H₂]₃) (It is available from Monsanto as DEQUEST® 2000), ethylenediamine [tetra (methylenephosphonic acid)] (it is available from Monsanto as DEQUEST® 2041), and 2- Includes phosphonobustane-1,2,4-tricarboxylic acid, which is available as Bayhibit AM from Mobay Chemical Corporation, Inorganic Chemicals Division (Pittsburg, PA).

Examples of the sequestrant include an aminocarboxylic acid type sequestrant, or the sequestrant may include an aminocarboxylic acid type sequestrant. Suitable aminocarboxylic acid type metal ion sequestering agents include the acid or alkali metal salts thereof, such as aminoacetate and salts thereof. Suitable aminocarboxylates include N-hydroxyethylaminodiacetic acid, hydroxyethylenediaminetetraacetic acid, nitrilotriacetic acid (NTA), ethylenediaminetetraacetic acid (EDTA), N-hydroxyethylethylenediaminetriacetic acid (HEDTA), diethylenetriaminetetraacetic acid (diethylenetriaminetetraacetic acid (EDTA)). DTPA) and alanin-N, N-diacetic acid, etc., as well as mixtures thereof.

Sequestrants can include polycarboxylates, or sequestrants can include polycarboxylates. Suitable polycarboxylates include, for example, polyacrylic acid, maleic acid / olefin copolymer, acrylic acid / maleic acid copolymer, polymethacrylic acid, acrylic acid-methacrylic acid copolymer, hydrolyzed polyacrylamide. , Hydrolyzed polymethacrylicamide, hydrolyzed polyamide-methacrylicamide copolymer, hydrolyzed polyacrylonitrile, hydrolyzed polymethacrylicnitrile, hydrolyzed acrylonitrile-methacrylonitrile copolymer, Includes copolymers of polymaleic acid, polyfumaric acid, acrylic acid and itaconic acid, phosphinopolycarboxylates, acid or salt forms thereof, and mixtures thereof.

In some embodiments, the compositions of the invention are about 0.5 wt-% to about 50 wt-% sequestrant, about 1 wt-% to about 50 wt-% sequestrant, about 1 wt-% ~. About 30 wt-% sequestrant, about 1 wt-% to about 15 wt-% sequestrant, about 1 wt-% to about 5 wt-% sequestrant, about 1 wt-% to about 4 wt-% Sequestrant, sequestrant from about 2wt-% to about 10wt-%, sequestrant from about 2wt-% to about 5wt-%, or sequestrant from about 5wt-% to about 15wt-% Contains agents. The compositions of the present invention can include any of these ranges or amounts that are not modified by about.

In some embodiments, the compositions of the invention are about 0.001 wt-% to about 50 wt-% stabilizers, about 0.001 wt-% to about 5 wt-% stabilizers, about 0.5 wt-% to. About 50 wt-% stabilizer, about 1 wt-% to about 50 wt-% stabilizer, about 1 wt-% to about 30 wt-% stabilizer, about 1 wt-% to about 10 wt-% stabilizer , About 1wt-% ~ about 5wt-% stabilizer, about 1wt-% ~ about 3wt-% stabilizer, about 2wt-% ~ about 10wt-% stabilizer, about 2wt-% ~ about 5wt Includes -% stabilizer or about 5 wt-% to about 15 wt-% stabilizer. The compositions of the present invention can include any of these ranges or amounts that are not modified by about.

Surfactant<u style="single">Nonionic surfactant</u> Suitable nonionic surfactants used as solvents include alkoxylated surfactants. Suitable alkoxylated surfactants include EO / PO copolymers, capped EO / PO copolymers, alcohol alkoxylates, capped alcohol alkoxylates or mixtures thereof and the like. Suitable alkoxylated surfactants used as solvents include EO / PO block copolymers such as Pluronic surfactants and reverse Pluronic surfactants; alcohol alkoxylates such as Dehypon LS-54 (R-). (EO)₅(PO)₄) And Dehypon LS-36 (R- (EO)₃(PO)₆) Etc.; as well as capped alcohol alkoxylates such as Plurafac LF221 and Tegoten EC11; or mixtures thereof. When used as a solvent, the surfactant (eg, nonionic surfactant, etc.) can be present at a higher concentration than conventionally used as a surfactant.

Semi-polar nonionic surfactant The semi-polar type of nonionic surfactant is another class of nonionic surfactants useful in the compositions of the present invention. Semi-polar nonionic surfactants include amine oxides, phosphine oxides, sulfoxides and alkoxylated derivatives thereof.

Amine oxides are quaternary amine oxides that correspond to the following general formula:<chemistry num="1"><img file="JP5437806B2_D0001.tif" /></chemistry>In the above equation, the arrow is the conventional representation of the semi-polar bond, R¹, R²And R³Can be aliphatic, aromatic, heterocyclic, alicyclic or a combination thereof. Generally, for amine oxides, which are attracting attention as a cleaning agent, R¹Is an alkyl group with about 8 to about 24 carbon atoms; R²And R³Is an alkyl or hydroxyalkyl with 1 to 3 carbon atoms, or a mixture of these;²And R³Can bond to each other, for example, via an oxygen or nitrogen atom; R⁴Is an alkylene or hydroxyalkylene group containing 2 to 3 carbon atoms; n ranges from 0 to about 20. Amine oxides can be made from the corresponding amines and oxidizing agents (eg hydrogen peroxide).

Useful water-soluble amine oxide surfactants are octyldi (lower alkyl) amine oxides, decyldi (lower alkyl) amine oxides, dodecyldi (lower alkyl) amine oxides, isododecyldi (lower alkyl) amine oxides, coconut alkyl di (lower alkyl). Select from amine oxides or tallow alkyl di (lower alkyl) amine oxides, specific examples of which are octyldimethylamine oxides, nonyldimethylamine oxides, decyldimethylamine oxides, undecyldimethylamine oxides, dodecyldimethylamine oxides, iso-dodecyldimethylamine oxide, tridecyldimethylamine oxide, tetradecyldimethylamine oxide, pentadecyldimethylamine oxide, hexadecyldimethylamine oxide, heptadecyldimethylamine oxide, octadecyldimethylamine oxide, dodecyldipropylamine oxide, tetradecyl Dipropylamine oxide, hexadecyldipropylamine oxide, tetradecyldibutylamine oxide, octadecyldibutylamine oxide, bis (2-hydroxyethyl) dodecylamine oxide, bis (2-hydroxyethyl) -3-dodecoxy-1-hydroxypropyl Amine oxides, dimethyl- (2-hydroxydodecyl) amine oxides, 3,6,9-trioctadecyldimethylamine oxides and 3-dodecoxy-2-hydroxypropyldi- (2-hydroxyethyl) amine oxides.

<u style="single">Anionic surfactant</u> The composition of the present invention can contain an anionic surfactant as a solubilizer. Suitable anionic surfactants include organic sulfonate surfactants, organic sulfate surfactants, phosphate ester surfactants, carboxylate surfactants or mixtures thereof. In one embodiment, the anionic surfactants include alkyl sulphonates, alkylaryl sulphonates, alkylated diphenyloxide disulphonates, alkylated naphthalene sulphonates, alcohol alkoxylate carboxylates, sarcosinates, taurates, acyl amino acids, Includes alkanoic acid esters, phosphate esters, sulfate esters, salt or acid forms thereof, or mixtures thereof. The specific salt is preferably selected depending on the specific formulation and the needs therein.

Suitable anionic surfactants include sulfonic acids (and salts) (eg, acetylionates (eg, acyl acetyleonates)), alkylaryl sulfonic acids and salts thereof, and alkyl sulfonates and the like. ..

Examples of suitable synthesized water-soluble anionic detergent compounds include alkyl mononuclear aromatic sulfonates (eg, about 5 to about 18 carbon atoms in the alkyl group in a straight or branched chain. Alkylbenzene sulfonate) ammonium and substituted ammonium salts (eg, monoethanolamine, diethanolamine and triethanolamine) and alkali metal salts (eg, sodium, lithium and potassium salts), such as alkylbenzene sulfo. Salts of nat, or salts of alkyltoluene sulfonate, xylene sulfonate, cumene sulfonate and phenol sulfonate, etc .; salts of alkyl naphthalene sulfonate, diamil naphthalene sulfonate, and dinonyl naphthalene sulfonate, and alkoxyls. Includes chemical derivatives or their free acids. Suitable sulphonates include olefin sulphonates (eg, long chain alkene sulphonates, etc.), long chain hydroxyalkane sulphonates, or mixtures of alkene sulphonates and hydroxyalkane sulphonates.

In some embodiments, the compositions of the invention comprising an anionic surfactant (eg, linear C8 sulfonate, etc.) can be non-foaming or low-foaming compositions. Such compositions are convenient for a variety of applications, such as stationary cleaning, mechanical product cleaning, stain removal and disinfection, as well as cleaning, stain removal and disinfection in dry cleaners. obtain.

For applications where foaming is desirable, the foaming agent can be added as part of the composition of the invention or separately. In the two-step provision, the foaming agent can be combined with a non-foaming composition or a dilution of a low foaming composition to form a foaming solution to use. In the one-step provision, the foaming agent can be incorporated into the high concentration composition. One suitable foaming agent is LAS acid. LAS acids can form microemulsions in the compositions of the present invention. LAS acids can form viscoelastic gels or liquids in the compositions of the present invention.

Suitable anionic sulphate surfactants for use in the compositions of the present invention include alkyl ether sulphates, alkyl sulphates, linear and branched primary alkyl sulphates and secondary alkyl sulphates. , Alkylethoxysulfate, Fat Oleyl Glycerol Sulfate, Alkylphenol Ethylene Oxide Ether Sulfate, C₅~ C₁₇Acyl-N- (C₁~ C₄Alkyl) Gurkhamin Sulfate and C₅~ C₁₇Acyl-N- (C₁~ C₂Hydroxyalkyl) glucamine sulfates, as well as alkyl polysaccharide sulfates (eg, alkyl polyglucoside sulfates, etc.) and the like are included. Similarly, alkyl sulphates, alkyl poly (ethyleneoxy) ether sulphates and aromatic poly (ethyleneoxy) sulphates (eg, ethylene oxide and nonylphenol sulphates or condensation products (usually 1 to 6 ethyleneoxy per molecule). It has an ethylene group)) is also included.

Suitable anionic carboxylate surfactants for use in the compositions of the present invention include carboxylic acids (and salts) such as alkanoic acid (and alkanoate), ester carboxylic acids (eg alkyls). Xcinato) and ether carboxylic acids and the like. Such carboxylates include alkylethoxycarboxylates, alkylarylethoxycarboxylates, alkylpolyethoxypolycarboxylate surfactants and soaps (eg, alkylcarboxylates). Secondary carboxylates useful in the compositions of the present invention include secondary carboxylates containing a carboxyl unit that binds to a secondary carbon. Secondary carbons can be present in the ring structure, for example, as in the case of p-octylbenzoic acid or in the case of alkyl-substituted cyclohexylcarboxylates. Secondary carboxylate surfactants typically do not contain ether linkages, ester linkages and hydroxyl groups. In addition, secondary carboxylate surfactants do not have a nitrogen atom in the head group (amphipathic moiety). Suitable secondary soap surfactants typically contain a total of 11 to 13 carbon atoms, but with more carbon atoms (eg, up to 16 carbon atoms). Can be done. Suitable carboxylates also include acyl amino acids (and salts), such as acylgluamate, acyl peptides, sarcosinates (eg, N-acyl sarcosinates), and taurates (eg, N-). Acyltaurat and fatty acid amides of methyltaurid) and the like are included.

Suitable anionic surfactants include alkylethoxycarboxylates or alkylarylethoxycarboxylates of Formula 3 below: RO- (CH₂CH₂O)_n(CH₂)_m-CO₂X (3) In the above equation, R is C₈~ C₂₂Alkyl group or<chemistry num="2"><img file="JP5437806B2_D0002.tif" /></chemistry>(In the formula, R¹Is C₄~ C₁₆Alkyl group) N is an integer from 1 to 20, m is an integer from 1 to 3, and X is a counterion (eg, hydrogen, sodium, potassium, lithium, ammonium or amine salt (eg, monoethanolamine, diethanolamine). Or triethanolamine, etc.). In one embodiment, formula 3 is an integer of 4 to 10 and m is 1. In one embodiment, formula 3 has R of C.₈~ C₁₆It is an alkyl group. In one embodiment, Equation 3 has R as C.₁₂~ C₁₄It is an alkyl group, n is 4 and m is 1.

In one embodiment, Equation 3 has R<chemistry num="3"><img file="JP5437806B2_D0003.tif" /></chemistry>And R¹Is C₆~ C₁₂It is an alkyl group. In one embodiment, Equation 3 is R¹Is C₉It is an alkyl group, n is 10 and m is 1. A variety of such alkyl ethoxycarboxylates and alkyl aryl ethoxycarboxylates are commercially available. These ethoxycarboxylates are typically available in acid form, which can be easily converted to anionic or salt form. Commercially available carboxylates include Neodox23-4, ie C_12~13Includes alkyl polyethoxy (4) carboxylic acid (Shell Chemical) and Emcol CNP-110, ie alkylaryl polyethoxy (10) carboxylic acid (Witco Chemical). Various carboxylates are also available from Clariant (eg, product Sandopan® DTC, ie C.₁₃Alkyl polyethoxy (7) carboxylic acid).

<u style="single">Amphoteric surfactant</u> Amphoteric or ampholytic surfactants contain both basic and acidic hydrophilic groups and organic hydrophobic groups. These ionic components can be either anionic or cationic groups described herein for other types of surfactants. A basic nitrogen group and an acidic carboxylate group are typical functional groups used as a basic hydrophilic group and an acidic hydrophilic group. In a few surfactants, sulfonate, sulfate, phosphonate or phosphate result in a negative charge.

Amphoteric surfactants can be broadly described as derivatives of aliphatic secondary and tertiary amines, where the aliphatic groups may be linear or branched and are fatty. One of the group substituents contains about 8-18 carbon atoms and one contains an anionic water solubilizing group (eg, carboxy, sulfo, sulfato, phosphat or phosphono). Amphoteric surfactants are known to those of skill in the art and can be divided into two major types described in "Surfactant Encyclopedia" (Cosmetics &amp; Toiletries, Vol. 104 (2), 69-71 (1989)). .. The first type includes acyl / dialkylethylenediamine derivatives (eg, 2-alkylhydroxyethylimidazoline derivatives) and salts thereof. The second type includes N-alkyl amino acids and salts thereof. Some amphoteric surfactants can be considered to apply to both types.

Amphoteric surfactants can be synthesized by methods known to those of skill in the art. For example, 2-alkylhydroxyethylimidazoline is synthesized by condensing a long-chain carboxylic acid (or derivative) with dialkylethylenediamine and ring-closing it. Commercially available amphoteric surfactants are derived by subsequent hydrolysis and ring opening of the imidazoline ring by alkylation (eg, alkylation with chloroacetic acid or ethyl acetate). During the alkylation period, one or two carboxy-alkyl groups react to form a tertiary amine and ether linkage, where changing the alkylating agent results in different tertiary amines. Is done.

Long-chain imidazole derivatives for use in the present invention generally have the following general formula:<chemistry num="4"><img file="JP5437806B2_D0004.tif" /></chemistry>In the above formula, R is an acyclic hydrophobic group containing about 8 to 18 carbon atoms, and M is a cation for neutralizing the charge of the anion, generally sodium. .. Outstanding commercially available imidazoline-derived amphoteric surfactants that can be used in the compositions of the present invention include, for example, cocoamphopropionate, cocoamphopropionate-propionate, cocoamphoglycinate, cocoamphocarboxy-. Includes glycinate, cocoamphopropyl-sulfonate and cocoamphocarboxy-propionic acid. Various amphocarboxylic acids can be prepared from fatty imidazoline compounds in which the dicarboxylic acid functionality of the amphodicarboxylic acid is diacetic acid and / or dipropionic acid.

The carboxymethylated compounds (glycinates) described above herein are often referred to as betaines. Betaines are a special type of amphoteric discussed herein in the section entitled Zwitterionic Surfactants.

Various long-chain N-alkyl amino acids are RNH₂(In the formula, R = C₈~ C₁₈(Linear alkyl or branched chain alkyl) is readily prepared by reacting with a halogenated carboxylic acid. Alkylation of the primary amino groups of amino acids results in secondary and tertiary amines. Alkyl substituents can have additional amino groups that provide two or more reactive nitrogen centers. Most commercially available N-alkylamine acids are alkyl derivatives of β-alanine or β-N (2-carboxyethyl) alanine. Examples of commercially available N-alkyl amino acid amphoteric electrolytes for use herein include alkyl β-aminodipropionate, RN (C).₂H₄COOM)₂And RNHC₂H₄COOM is included. In one embodiment, R can be an acyclic hydrophobic group containing about 8 to about 18 carbon atoms and M is a cation for neutralizing the charge of the anion.

Suitable amphoteric surfactants include amphoteric surfactants derived from coconut products (eg, coconut oil or coconut fatty acids). Further suitable coconut-derived surfactants, as part of their structure, include ethylenediamine components, alkanolamide components, amino acid components (eg, glycine), or combinations thereof, and from about 8 to about 18 (eg, glycine). , 12) contains aliphatic substituents on carbon atoms. Such surfactants can also be considered as alkylampodicarboxylic acids. These amphoteric surfactants are C₁₂-Alkyl-C (O) -NH-CH₂-CH₂-N⁺(CH₂-CH₂-CO₂Na)₂-CH₂-CH₂-OH or C₁₂-Alkyl-C (O) -N (H) -CH₂-CH₂-N⁺(CH₂-CO₂Na)₂-CH₂-CH₂Can include chemical structures represented as -OH. Disodium cocoamphonipropionate is one suitable amphoteric surfactant and is commercially available from Rhodia Inc. (Cranbury, NJ) under the trade name of Miranol FBS. Another suitable coconut-derived amphoteric surfactant with the chemical name cocoamphodium disodium acetate is also sold by Rhodia Inc. (Cranbury, NJ) under the trade name Mirataine JCHA.

A typical list of amphoteric species and species of these surfactants is provided in US Pat. No. 3,929,678 (Laughlin and Heuring, December 30, 1975). Further examples are given in "Surface Active Agents and Detergents" (Volumes I and II, by Schwartz, Perry and Berch).

<u style="single">Zwitterionic surfactant</u> Zwitterionic surfactants can be considered as a subset of amphoteric surfactants and can contain anionic charges. In a broad sense, the diionic surfactant is a derivative of a secondary amine and a tertiary amine, a derivative of a heterocyclic secondary amine and a tertiary amine, or a quaternary ammonium compound, a quaternary ammonium compound. It can be described as a derivative of a tertiary phosphonium compound or a tertiary sulfonium compound. Typically, the zwitterionic surfactant comprises a positively charged quaternary ammonium ion, or in some cases a sulfonium ion or a phosphonium ion; a carboxyl group of a loaded electric charge; and an alkyl group. Zwitterionic materials are generally cation groups that can ionize to about the same extent in the isoelectric point region of the molecule and generate a strong "internal salt" attraction between the positively charged center and the charged center. Contains anionic groups. Examples of such diionic synthetic surfactants include derivatives of aliphatic quaternary ammonium compounds, phosphonium compounds and sulfonium compounds, in which the aliphatic groups are linear or branched. It is possible, and one of the aliphatic substituents contains about 8-18 carbon atoms and one contains an anionic water solubilizing group (eg, carboxy, sulfonate, sulfate, phosphate or phosphonate). To do. Betaine-based surfactants and sultine-based surfactants are exemplary zwitterionic surfactants used herein.

The general formula for these compounds is<chemistry num="5"><img file="JP5437806B2_D0005.tif" /></chemistry>And in the formula, R¹Contains an alkyl group, an alkenyl group or a hydroxyalkyl group with 8 to 18 carbon atoms, having 0 to 10 ethylene oxide components and 0 to 1 glyceryl component; Y is a nitrogen atom, Selected from the group consisting of phosphorus and sulfur atoms; R²Is an alkyl or monohydroxyalkyl group containing 1 to 3 carbon atoms; x is 1 when Y is a sulfur atom and 2 when Y is a nitrogen or phosphorus atom. Yes; R³Is an alkylene or hydroxyalkylene or hydroxyalkylene having 1 to 4 carbon atoms; Z is a group selected from the group consisting of a carboxylate group, a sulfonate group, a sulfate group, a phosphonate group and a phosphate group.

Examples of biionic surfactants with the structures shown above include: 4- [N, N-di (2-hydroxyethyl) -N-octadecylammonio] butane-1- Carboxylate; 5- [S-3-hydroxypropyl-S-hexadecylsulfonio] -3-hydroxypentane-1-sulfate; 3- [P, P-diethyl-P-3,6,9-trioxatetra Cosanphosphonio] -2-Hydroxypropan-1-phosphate; 3- [N, N-dipropyl-N-3-dodecoxy-2-hydroxypropylammonio] Propane-1-phosphonate; 3- (N, N-dimethyl) -N-Hexadecyl ammonio) Propane-1-sulfonate; 3- (N, N-Dimethyl-N-Hexadecyl ammonio) -2-Hydroxypropan-1-sulfonate; 4- [N, N-di (2) (2-Hydroxyethyl) -N (2-hydroxydodecyl) ammonio] butane-1-carboxylate; 3- [S-ethyl-S- (3-dodecoxy-2-hydroxypropyl) sulfonio] propan-1-phosphate; 3- [P, P-dimethyl-P-dodecylphosphonio] propan-1-phosphonate; and S [N, N-di (3-hydroxypropyl) -N-hexadecyl ammonio] -2-hydroxypentane-1 -Sulfate. The alkyl group contained in the detergent surfactant can be linear or branched and saturated or unsaturated.

Zwitterionic surfactants suitable for use in the compositions of the present invention include betaines of the following general formula:<chemistry num="6"><img file="JP5437806B2_D0006.tif" /></chemistry>

These surfactant betaines typically do not exhibit strong cationic or anionic features at extreme values of pH and do not exhibit reduced water solubility at their isoelectric points. Unlike "external" quaternary ammonium salts, betaine is compatible with anionic species. Examples of suitable betaines include coconut acylamide propyldimethylbetaine, hexadecyldimethylbetaine, C._12~14Acylamide propyl betaine, C_8~14Acylamide hexyl diethyl betaine, 4-C_14~16Acylmethylamide diethylammonio-1-carboxybutane, C_16~18Acylamide dimethyl betaine, C_12~16Acylamide pentane diethyl betaine and C_12~16Acylmethylamide dimethylbetaine is included.

The sultane useful in the present invention includes the formula (R (R).¹)₂N⁺R²SO₃^-(In the formula, R is C₆~ C₁₈Hydrocarbyl group, each R¹Is typically independent, C₁~ C₃Alkyl (eg, methyl), R²Is C₁~ C₆Hydrocarbyl group (eg C₁~ C₃Such compounds having (which are alkylene or hydroxyalkylene groups) are included.

A typical list of zwitterion types and chemical species of these surfactants is provided in US Pat. No. 3,929,678 (Laughlin and Heuring, issued December 30, 1975). Further examples are given in "Surface Active Agents and Detergents" (Volumes I and II, by Schwartz, Perry and Berch).

In one embodiment, the composition of the invention comprises betaine. For example, the compositions of the present invention can include cocoamide propyl betaine.

Auxiliary agent The antibacterial composition of the present invention can also contain many auxiliaries. Specifically, the composition of the present invention, among many components that can be added to the composition, is an antibacterial solvent, an antibacterial agent, a wetting agent, an antifoaming agent, a thickener, a surfactant, and a starter. Foaming agents, coagulants, aesthetic enhancers (ie, colorants (eg, pigments), odorants or fragrances), stabilizers (eg, HEDP) can be included. Such ancillary agents can be formulated with the antibacterial compositions of the present invention, or can be added to the system at the same time as or even after the addition of the antibacterial composition. it can. The compositions of the invention can also contain many other ingredients known, which can facilitate the activity of the invention, as required by application. Auxiliary agents (s) can be added to the carboxylic acid compositions of the invention in day tanks, in lines or conduits after the reaction catalyst, or in devices or systems that use the peroxycarboxylic acid compositions. ..

<u style="single">Antibacterial solvent</u> Any variety of solvents can be useful as antibacterial solvents in the compositions of the present invention. An antibacterial solvent can be added to the composition used before use. Suitable antibacterial solvents include acetamidophenol; acetoanilide; acetophenone; 2-acetyl-1-methylpyrrole; benzyl acetate; benzyl alcohol; benzyl succinate; benzyloxyethanol; essential oils (eg, benzaldehyde, pinenes, terpeneols, etc.) Terpinenes, carboxylics, cinnamaldehydes, borneols and their esters, citrals, ionenes, jasmine oil, limonene, dipentene, linarool and its esters); diester dicarboxylates (eg, dibasic esters), such as dimethyl adipate, Dimethyl succinate, dimethyl glutarate (for this, Dupon under the trade names DBE, DBE-3, DBE-4, DBE-5, DBE-6, DBE-9, DBE-IB and DBE-ME (Includes products available from Nylon), dimethyl malonate, diethyl adipic acid, diethyl succinate, diethyl glutarate, dibutyl succinate and dibutyl glutarate, dimethyl sebacate, dimethyl pimerate, dimethyl suberate, etc .; dialkyl Carbonates such as dimethylcarbonate, diethylcarbonate, dipropylcarbonate, diisopropylcarbonate and dibutylcarbonate; organic nitriles such as acetonitrile and benzonitrile; and phthalate esters such as dibutyl phthalate, Includes diethyl hexyl phthalate and diethyl phthalate. If desired, a mixture of antibacterial solvents can be used.

The antibacterial solvent is based on the characteristics of the surface and microorganism to which the antibacterial composition is applied, and on the nature of any coating, stain or other substance that is contacted and optionally removed from the surface by the antibacterial composition. Can be selected based on. Polar solvents, and solvents capable of hydrogen bonding, typically work well against a variety of surfaces and microorganisms and can therefore be selected for such applications. In some applications, the antibacterial solvent is applied to a high flash point (eg, a flash point greater than about 30 ° C, or a flash point greater than about 50 ° C, or a flash point greater than about 100 ° C. ), Low odor, and low human and animal toxicity can be selected.

In one embodiment, the antibacterial solvent may be adapted as an indirect or direct food additive or substance (particularly in the Code of Federal Regulations (CFR), Title 21-Food and Drugs, Part 170-186). Can be adapted as a food additive or substance as described). The compositions of the present invention must contain sufficient antibacterial solvent to provide the desired proportion and type of microbial reduction.

The compositions of the present invention can contain an effective amount of antibacterial solvent, eg, about 0.01 wt-% to about 60 wt-% antibacterial solvent, about 0.05 wt-% to about 15 wt-% antibacterial. It can contain a sex solvent or an antibacterial solvent of about 0.08 wt-% to about 5 wt-%.

<u style="single">Additional antibacterial agents</u> The antibacterial composition of the present invention can contain additional antibacterial agents. Additional antibacterial agents can be added to the composition used prior to use. Suitable antibacterial agents include carboxylic acid esters (eg, p-hydroxyalkylbenzoate and alkyl cinnamic acid), sulfonic acids (eg, dodecylbenzenesulfonic acid), iodo compounds or active halogen compounds (eg, elemental halogens, halogens). Oxides (eg NaOCl, HOCl, HOBr, ClO₂), Iodine, interhalogen compounds (eg iodine monochloride, iodine dichloride, iodine trichloride, iodine tetrachloride, bromine chloride, iodine monobromide or iodine dibromide), polyhalide, hypochlorite, hypobromous acid Chloric acid, hypobromite, hypobromous acid, chlorohydridein, bromohydranthin, chlorine dioxide and sodium chlorite, organic peroxides (including benzoyl peroxide, alkylbenzoyl peroxide, ozone, monobromine oxygen). Includes productants and mixtures thereof), phenolic derivatives (eg o-phenylphenol, o-benzyl-p-chlorophenol, tert-amylphenol and hydroxybenzoic acid C)₁~ C₆Alkyl), quaternary ammonium compounds (eg, alkyldimethylbenzylammonium chloride, dialkyldimethylammonium chloride and mixtures thereof), and mixtures of such antibacterial agents provide the desired degree of microbial protection. Included in sufficient quantity for.

In one embodiment, the compositions of the invention can include added peroxycarboxylic acid and / or hydrogen peroxide.

The compositions of the present invention can contain an effective amount of antibacterial agent, eg, about 0.001 wt-% to about 60 wt-% antibacterial agent, about 0.01 wt-% to about 15 wt-% antibacterial agent, or , About 0.08 wt-% to about 2.5 wt-% antibacterial agents can be included.

<u style="single">Hydrotrope</u> The compositions used in the methods of the invention can also include hydrotrope couplers or hydrotrope solubilizers. Such materials can be used to ensure that the composition remains phase stable and remains in a single, highly active aqueous form. Such hydrotrope solubilizers or hydrotrope couplers can be used in compositions that maintain phase stability but do not result in undesired compositional interactions.

Typical types of hydrotrope solubilizers or hydrotrope coupling agents include anionic surfactants, such as alkyl sulphates, alkyl sulphonates or alkan sulphonates, linear alkylbenzene sulphonates or naphthalenes. Sulfonates, secondary alkan sulphonates, alkyl ether sulfates or alkyl ether sulphonates, alkyl phosphates or alkyl phosphonates, dialkyl sulfosuccinates, sugar esters (eg, sorbitan esters), and C._8~10Includes alkyl glucosides and the like.

Preferred coupling agents used in the methods of the invention include n-octane sulfonates and aromatic sulfonates, including, for example, alkylaryl sulfonates (eg, sodium xylene sulfonate or sodium naphthalene sulfonate). .. Many hydrotrope solubilizers independently exhibit some antibacterial activity at low pH. Such action increases the potency of the invention, but is not the primary criterion used in selecting the appropriate solubilizing agent. This coupling agent is effective not only because of its independent antibacterial activity, but also because of its independent antibacterial activity, as the presence of the peroxycarboxylic acid substance in the protonated neutral state provides beneficial bioactive or antibacterial activity. Composition stability must be selected due to its ability to provide the substantially insoluble peroxycarboxylic acid material of the present invention and the more soluble composition. In general, many surfactants can be used consistent with the purpose of this ingredient.

Anionic surfactants useful in the present invention include alkylcarboxylates, linear alkylbenzene sulfonates, paraffin sulfonates and secondary n-alkane sulfonates, sulfosuccinate esters, and sulfated wires. Sulfonic acid is included.

Zwitterionic or amphoteric surfactants useful in the present invention include θ-N-alkylaminopropionic acid, n-alkyl-θ-iminonipropionic acid, imidazolinecarboxylate, n-alkylbetaine, Includes amine oxides, sulfobetaines and sultines.

Nonionic surfactants useful in the context of the present invention are generally polyether compounds, which are also known as polyalkylene oxide compounds, polyoxyalkylene compounds or polyalkylene glycol compounds. More specifically, the polyether compound is generally a polyoxypropylene compound or a polyoxyethylene glycol compound. Typically, a surfactant useful in the context of the present invention is a synthetic organic polyoxypropylene (PO) -polyoxyethylene (EO) block copolymer. These surfactants are diblock polymers containing an EO block and a PO block, a central block of a polyoxypropylene unit (PO), a diblock polymer in which a block of polyoxyethylene is grafted onto a polyoxypropylene unit. Alternatively, it has a diblock polymer grafted to the central block of EO to which the PO block is attached. In addition, the surfactant can have an additional block of either polyoxyethylene or polyoxypropylene in the molecule. The average molecular weight of useful surfactants ranges from about 1000% to about 40,000 and the weight percent content of ethylene oxide ranges from about 10% to 80% by weight.

Also useful in the context of the present invention are surfactants containing alcohol alkoxylates having EO block, PO block and BO block. The straight chain primary aliphatic alcohol alcohol alcocilate can be particularly useful as a sheeting agent. Such alkoxylates are also available from several sources, including BASF Wyandotte, where such alkoxylates are known as "Plurafac" surfactants. A specific group of alcohol alkoxylates found to be useful is the general formula R- (EO)._m-(PO)_n(In the equation, m is an integer of about 2 to 10 and n is an integer of about 2 to 20). R can be any suitable group, such as a linear alkyl group having about 6 to 20 carbon atoms.

Other useful nonionic surfactants of the invention include capped aliphatic alcohol alkoxylates. These end caps include, but are not limited to, methyl, ethyl, propyl, butyl, benzyl and chlorine. Useful alcohol alkoxylates include ethylenediamine ethylene oxide, ethylenediamine propylene oxide, mixtures thereof, and ethylenediamine EO-PO compounds, which include ethylenediamine EO-PO compounds sold under the Tetronic trade name. Is done. Preferably, such surfactants have a molecular weight of about 400-10,000. Capping improves compatibility between nonionic surfactants and oxidizing agents (hydrogen peroxide and peroxycarboxylic acids) when blended into a single composition. Another useful nonionic surfactant is an alkyl polyglycoside.

Another useful nonionic surfactant of the invention is a fatty acid alkoxylate, in which the surfactant is an ester comprising an EO block, a PO block or a mixed block, or a heteric group. Contains fatty acid components with groups. The molecular weight of such surfactants ranges from about 400 to about 10,000, the preferred surfactants have an EO content of about 30 wt-% to 50 wt-%, except that the fatty acid component is from about 8 to about. Contains 18 carbon atoms.

Similarly, alkylphenol alkoxylates have also been found to be useful in the present invention. Such surfactants can be made from alkylphenol components in which the alkyl group has from about 4 to about 18 carbon atoms, such as ethylene oxide blocks, propylene oxide blocks, or mixed ethylene oxide-propylene oxide blocks. Alternatively, it can contain a heteric polymer component. Preferably, such surfactants have a molecular weight of about 400 to about 10,000 and have about 5 to about 20 units of ethylene oxide or propylene oxide or a mixture thereof.

The concentration of hydrotropes useful in the present invention is generally in the range of about 0.1 wt-% to about 20 wt-%, preferably in the range of about 0.5 wt-% to about 10 wt-%, most preferably about 1 wt-. It is in the range of% ~ about 4wt-%.

<u style="single">Wetting or defoaming agent</u> Similarly useful in the compositions of the present invention are wetting and defoaming agents. The wetting agent functions to increase the surface contact activity or surface penetration activity of the antibacterial composition of the present invention. Wetting agents that can be used in the compositions of the present invention include any of such components known in the art to improve the surface activity of the compositions of the present invention.

In general, antifoaming agents that can be used in accordance with the present invention include silica and silicones; fatty acids or esters; alcohols; sulfates or sulphonates; amines or amides; halogenated compounds such as fluorochlorohydrogens; vegetable oils, waxes, etc. Mineral oils, as well as their sulfated derivatives; fatty acid soaps such as alkaline soaps, alkaline earth metal soaps; and phosphates and phosphate esters such as alkyl diphosphonates, alkaline diphosphonates and tributyl phosphates, among others. Etc; as well as mixtures of these.

In one embodiment, the composition of the invention may include an antifoaming agent or antifoaming agent of food standard quality, given the application of the methods of the invention. For this purpose, one of the many effective anti-foaming agents includes silicone. Hydrophobic silica defoaming agents such as various silicones such as dimethyl silicone, glycol polysiloxane, methylphenol polysiloxane, trialkylsilane or tetraalkylsilane, and mixtures thereof, can all be used in defoaming applications. Commercially available commercially available defoamers include a variety of silicones, such as Ardefoam®; silicone esters from the Armor Industrial Chemical Company, which are, among other things, silicones bound to organic emulsions. Similarly, Foam Kill® or Kresseo®, available from the Krusable Chemical Company, which are silicone and non-silicone defoamers; and Dow Corning, both food standard type silicones. Includes Anti-Foam A® and DC-200 from Corporation. These defoamers are in the concentration range of about 0.01wt-% to 5wt-%, or in the concentration range of about 0.01wt-% to 2wt-%, or in the concentration range of about 0.01wt to about 1wt-%. Can be present at.

<u style="single">Thickener or gelling agent</u> The compositions of the present invention can include any of a variety of known thickeners. Suitable thickeners include natural gums derived from plant mucilage, such as xanthan gum, guar gum or other gums; polysaccharide-based thickeners, such as alginates, starches and cellulosic polymers (eg, carboxymethyl cellulose). Etc; polyacrylate thickeners; and hydrocolloid thickeners, such as pectin. In one embodiment, the thickener leaves no contaminating residue on the surface of the object. For example, thickeners or gelling agents can have compatibility with food products or other sensitive products in the contact area. In general, the concentration of thickener used in the compositions or methods of the invention is determined by the desired viscosity of the final composition. However, as a general guideline, the viscosity of the thickener in the compositions of the present invention is about 0.1 wt-% to about 1.5 wt-%, about 0.1 wt-% to about 1.0 wt-%, or about 0.1 wt. It ranges from -% to about 0.5 wt-%.

<u style="single">bleach</u> The compositions of the present invention can include known bleaching agents (eg, active halogen compounds, etc.). Suitable bleaches include any that can remove stains from substrates such as tableware, tableware, pots and pans, fabrics, countertops, instruments, flooring, etc., without significant damage to the substrate. Contains the widely known bleaching agents. An unlimited list of bleaches includes hypochlorites, chlorides, chlorinated phosphates, chloroisocyanates, chloramines, etc .; and peroxide compounds such as hydrogen peroxide, perborates, percarbonates. Contains salt and the like. In general, bleaching agents such as peroxide compounds are generally preferred if the application requires a color sensitive active agent. However, if the application does not require color sensitivity, halogen-based bleach can be used.

Suitable bleaches include active halogen chemicals (eg, chlorine, bromine, hypochlorite ions, hypobromite ions, etc.) under the conditions commonly encountered in typical cleaning processes. Contains bleach that is released with and. The active halogen compound can be, for example, a source of free element halogen or -OX- (where X is Cl or Br) under conditions commonly used in detergent-bleaching cleaning processes. is there. In one embodiment, the active halogen compound releases a chemical species of chlorine or bromine. In one embodiment, the active halogen compound releases chlorine.

Chlorine-releasing compounds include potassium dichloroisocyanurate, sodium dichloroisocyanurate, trisodium chlorinated phosphate, calcium hypochlorite, lithium hypochlorite, monochloroamine, dichloramine, [(monotrichloro) -tetra (monopotassium). Dichloro)] pentaisocyanurate, paratoluenesulfone dichloroamide, trichloromelamine, N-chlorammeline, N-chlorosuccinimide, N, N'-dichloroazodicarboxylicamide, N-chloro-acetylurea, N, N' -Dichlorobiuret, chlorinated dicyandiamide, trichloroisocyanuric acid, dichloroglycolylyl, 1,3-dichloro-5,5-dimethylhydranthin, 1,3-dichloro-5-ethyl-5-methylhydranthin, 1-chloro-3- Includes bromo-5-ethyl-5-methylhydranthin, dichlorohydranthin, trichloromelamine, sulfonedichloroamide, trichloroisocyanuric acid, salts or hydrates thereof, and mixtures thereof. In one embodiment, the chlorine-releasing compound comprises sodium dichloroisocyanurate. In one embodiment, the organochlorine-releasing compound is about 10^-4It may be sufficiently soluble in water to have the above hydrolysis constant (K).

Encapsulated chlorine sources can also be used to enhance the stability of the chlorine source in the composition (see, eg, US Pat. Nos. 4,618,914 and 4,830,773; these disclosures are for reference only. Incorporated herein).

Bleach may also include agents that contain reactive oxygen species, or agents that act as a source of reactive oxygen species. The active oxygen compound acts to provide a source of active oxygen, and for example, active oxygen can be released in an aqueous solution. The active oxygen compound can be inorganic or organic, or a mixture thereof. Some examples of reactive oxygen compounds include peroxygen compounds or adducts of peroxygen compounds. Some examples of active oxygen compounds or sources of active oxygen include hydrogen peroxide, perborates, sodium percarbonates in the presence and absence of activators (eg, tetraacetylethylenediamine). , Phosphate hydrogen peroxide, potassium permonosulfate, and sodium perborate monohydrate and sodium perborate tetrahydrate.

In one embodiment, the bleaching agent is an alkali metal salt of chloroisocyanurate, a hydrate thereof or a mixture thereof. Dichloroisocyanurateni hydrate is a suitable chlorine-releasing compound and is commercially available. This compound can be represented by the following formula: NaCl₂C₃N₃O₃2H₂O.

The compositions of the present invention can also contain effective amounts of known bleach activators, such as tetraacetylethylenediamine or metals (eg, manganese). Can be done.

The compositions of the present invention use bleach at about 0.5 wt-% to 20 wt-% of the composition, or about 1 wt-% to 10 wt-% of the composition, or about 2 wt-% of the composition. Can be included in 8wt-%. The compositions of the present invention can contain up to about 10 wt-% bleach, and in some embodiments can contain from about 0.1 wt-% to about 6 wt-% bleach.

<u style="single">Composition used</u> The compositions of the present invention include high-concentration compositions and compositions used. For example, the high concentration composition can be diluted, for example, with water to form the composition used. In one embodiment, the high concentration composition can be diluted to the composition used prior to application to the object. For economic reasons, high concentrations can be sold and therefore the end user can dilute the high concentrations in the solution used with water or an aqueous diluent.

The level of active ingredient in the high concentration composition depends on the intended dilution factor and desired activity of the peroxycarboxylic acid compound. Dilutions from about 1 fluid ounce to about 20 gallons of water to about 5 fluid ounces to about 1 gallon of water are commonly used for aqueous antibacterial compositions. Higher concentrations of working dilutions can be used if higher working temperatures (working temperatures above 25 ° C) or long exposure times (exposure times greater than 30 seconds) can be used. In a typical place of use, the high concentration is diluted with a large proportion of water using commonly available tap or irrigation water, which allows the substance to be about 3 ounces to about 3 ounces per 100 gallons of water. Mix at a dilution of 20 ounces of high concentration.

For example, the compositions used are a high concentration composition of about 0.01 wt-% to about 4 wt-% and a diluent of about 96 wt-% to about 99.99 wt-%; a high concentration of about 0.5 wt-% to about 4 wt-%. Composition and diluent from about 96 wt-% to about 99.5 wt-%; about 0.5 wt-%, about 1 wt-%, about 1.5 wt-%, about 2 wt-%, about 2.5 wt-%, about 3 wt-%, High concentration composition of about 3.5wt-% or about 4wt-%; High concentration composition of about 0.01wt-% to about 0.1wt-%; Or about 0.01wt-%, about 0.02wt-%, about 0.03wt Includes high concentration compositions of -%, about 0.04wt-%, about 0.05wt-%, about 0.06wt-%, about 0.07wt-%, about 0.08wt-%, 0.09wt-% or about 0.1wt-% be able to. The amount of the component in the composition used can be calculated from the amounts listed above for the high concentration composition and their dilution factors.

The method of the present invention can use peroxycarboxylic acid at an effective concentration to reduce the population of one or more microorganisms. Such effective concentrations include medium-chain peroxycarboxylic acids from about 2 ppm to about 500 ppm, peroxycarboxylic acids from about 2 ppm to about 300 ppm, peroxycarboxylic acids from about 5 ppm to about 100 ppm, and peroxycarboxylic acids from about 5 ppm to about 60 ppm. Acid, about 5ppm to about 45ppm of peroxycarboxylic acid, about 5ppm to about 35ppm of peroxycarboxylic acid, about 5ppm to about 25ppm of peroxycarboxylic acid, about 8ppm to about 50ppm of peroxycarboxylic acid, about 10ppm to about 500ppm of peroxycarboxylic acid Includes acids, from about 10 ppm to about 50 ppm peroxycarboxylic acid, from about 40 ppm to about 140 ppm peroxycarboxylic acid, from about 100 ppm to about 250 ppm peroxycarboxylic acid, or from about 200 ppm to about 300 ppm peroxycarboxylic acid. In one embodiment, the compositions used are about 2 ppm to about 500 ppm of peroxycarboxylic acid, about 5 ppm to about 200 ppm of carboxylic acid, about 95 wt-% to about 99.99 wt-% carriers and / or diluents (eg, eg). Water); and can contain from about 2 ppm to about 23,000 ppm of polyalkylene oxides, capped polyalkylene oxides, alkoxylated surfactants, anionic surfactants or mixtures thereof.

The level of reactive species in the composition used (eg, peroxycarboxylic acid and / or hydrogen peroxide) can be found in the composition used or influenced by the organic matter added to the composition used (eg, peroxycarboxylic acid and / or hydrogen peroxide). Typically can be reduced). For example, when the composition used is a bath or spray used to clean an object, dirt on the object can consume peroxy acids and peroxides. Therefore, it is understood that this amount of ingredients in the composition used indicates the composition before or early in use, and this amount decreases as the organic matter is added to the composition used.

In one embodiment, the compositions used in the present invention can be made more acidic by passing a high concentration product through an acidifying column or by adding an additional acidifying agent to the composition used.

Other fluid compositions The composition of the present invention can include a critical fluid, a fluid near a critical point or a supercritical fluid (high density fluid), and a gaseous composition of an antibacterial agent or an antibacterial agent. The densification fluid can be a near critical point fluid, a critical fluid, a supercritical fluid, or another type of fluid having the properties of a supercritical fluid. Suitable fluids for densification include carbon dioxide, nitrous oxide, ammonia, xenone, krypton, methane, ethane, ethylene, propane and some fluoroalkanes (eg chlorotrifluoromethane and monofluoromethane). , Or a mixture of these. Suitable fluids include carbon dioxide.

In one embodiment, the compositions or methods of the invention include densified carbon dioxide, peroxycarboxylic acids and carboxylic acids. Such a composition can be shown as a densified fluid peroxycarboxylic acid composition. In another embodiment, the antibacterial composition comprises such a fluid, an antibacterial agent, and any optional or added component, but not in the form of a gas.

The densified fluid antibacterial composition can be applied by any of several methods known to those of skill in the art. Such methods include ventilating a container containing a densifying fluid and antibacterial agent towards an object. An aqueous phase containing hydrogen peroxide is conveniently retained in the device. The aerated gas contains an effective amount of antibacterial agent that makes the densified fluid peroxycarboxylic acid composition a suitable antibacterial agent.

Due to the high pressure nature of the densified fluid compositions of the present invention, these compositions typically include pressure release devices designed to facilitate the rapid and efficient coverage of objects. It is applied by aerating the container containing the composition through. Devices that include such pressure release devices include sprayers, atomizers, foam generators, foam pad applicators, brushes that can allow the expansion of fluids from high pressures to ambient pressures while applying the substance to the object. Includes applicator or any other device. The densified fluid peroxycarboxylic acid composition can also be applied to the object by any of the various methods known for applying the gaseous agent to the object.

A densified fluid antibacterial composition can be made by reacting an oxidizing substrate with an oxidant in a medium containing the densified fluid to form the antibacterial composition. This reaction is typically carried out in a vessel suitable for containing the densified fluid. The reaction involves adding an oxidizing substrate and an oxidant to the container and adding a fluid to the container to form an antibacterial composition. In one embodiment, the reaction is between the carboxylic acid and hydrogen peroxide to form the corresponding peroxycarboxylic acid. Hydrogen peroxide is generally supplied in the form of an aqueous solution of hydrogen peroxide.

Supercritical fluids, subcritical fluids, near-supercritical fluids and other high density fluids, and solvents that can be used with such fluids, are described in US Pat. No. 5,306,350 (issued April 26, 1994, Hoy et al.). (This is incorporated herein by reference for such disclosure). Supercritical and other high density forms of carbon dioxide, as well as co-solvents, co-surfactants and other additives that can be used with these forms of carbon dioxide are disclosed in US Pat. No. 5,866,005 (US Pat. No. 5,866,005). Published February 2, 1999, De Simone et al.) (This is incorporated herein by reference for such disclosure).

<u style="single">Method using peroxycarboxylic acid composition</u> The present invention includes various methods using the peroxycarboxylic acid compositions of the present invention. Typically, these methods use the antibacterial or bleaching activity of peroxycarboxylic acids. For example, in the present invention, a method for reducing the population of microorganisms, a method for reducing the population of microorganisms in the skin, a method for treating a skin disease, a method for reducing odor, or a method for reducing odor. Includes methods for bleaching. These methods involve contacting an object, surface, body or stream with the stabilized ester peroxycarboxylic acid composition of the present invention to allow the object, surface, body or stream of water or gas to flow. You can work inside or elsewhere. Contacting can include any of a number of methods for applying the composition, such as spraying the composition, submerging the object in the composition, foaming or gelping the object with the composition. It can be treated with, or a combination thereof and the like can be included.

The compositions of the present invention are used for a variety of household or industrial applications, for example, to reduce microbial or viral populations on surfaces or objects, or in the body or in a stream of water. can do. The compositions of the present invention can be applied in a variety of areas, including kitchens, bathrooms, factories, hospitals, dental offices and food factories, and also have smooth surface shapes, irregular surface shapes or porosity. It can be applied to various hard or soft surfaces with surface shapes. Suitable hard surfaces include, for example, building surfaces (eg floors, walls, windows, sinks, desks, countertops and signs), tableware, hard surface medical or surgical instruments and devices, and hard surfaces. Packaging is included. Such hard surfaces can be made from a variety of materials, including, for example, ceramics, metals, glass, wood or hard plastics. Suitable soft surfaces include, for example, paper, filter media, hospital and surgical linens and garments, soft surface medical or surgical instruments and devices, and soft surface packaging. Such soft surfaces can be made from a variety of materials, including, for example, paper, fibers, woven or non-woven fabrics, soft plastics and elastomers. The compositions of the present invention can also be applied to soft surfaces such as foods and skin (eg, hands). The compositions of the present invention can be used as effervescent or non-effervescent environmental sanitizers or environmental disinfectants.

The antibacterial compositions of the present invention can be included in various products, such as sterilizers, sanitizers, disinfectants, preservatives, deodorants, preservatives, fungicides, fungicides, spore killers, killers. It can be included in viral agents, detergents, bleaches, hard surface cleaners, hand soaps, waterless hand sanitizers, and pre- and post-operative scrubbing agents.

The antibacterial compositions of the present invention may also be used in veterinary products (eg, mammalian skin treatments, etc.) or in animal enclosures, cages, water stations and veterinary treatment areas (eg, examination tables and operating rooms). Etc.) can be used in products for sterilizing or disinfecting. The compositions of the present invention can be used in antibacterial foot wash areas for livestock or people.

The compositions of the present invention can be used to reduce the population of pathogenic microorganisms (eg, pathogens such as humans and animals). The compositions of the present invention include various pathogens including fungi, molds, bacteria, spores and viruses (eg, S. aureus, Escherichia coli, Streptococcus, Legionella, Pseudomonas aeruginosa, Mycobacterium). It can show activity against genus bacteria, tuberculosis or phage, etc.). Such pathogens can cause a variety of diseases and disorders, including mastitis or other mammalian lactation disorders, tuberculosis and other disorders. The compositions of the present invention can reduce the population of microorganisms on the skin or other outer or mucosal surfaces of animals. In addition, the compositions of the present invention can kill pathogenic microorganisms that spread through migration by water, air or surface substrates. The compositions of the present invention only need to be applied to animal skin or other outer or mucosal surfaces, or water, air or surfaces.

The antibacterial compositions of the present invention can also be used against foods and plant species to reduce microbial populations on the surface, or at manufacturing or processing sites where such foods and plant species are handled. It can be used, or it can be used to treat process water around such sites. For example, the composition on a food transport line (eg, as a belt spray); soaking pans for washing boots and hands; food storage facilities; anti-corruption air circulation systems; refrigeration equipment and cooler equipment; beverage cooling equipment and It can be used in warmers, blanchers, cutting boards, third sink areas, as well as meat chillers or hot water treatment devices. The compositions of the present invention can be used to treat product transport water (eg, water found in transport channels, pipe transport, cutters, slicers, blanchers, retort systems and washers, etc.). Specific foods that can be processed by the compositions of the present invention include eggs, meat, seeds, leaves, fruits and vegetables. Specific plant surfaces include both post-harvest and growing leaves, roots, seeds, skins or shells, stems, stems, tubers, corms and fruits. The compositions of the present invention can also be used to treat animal slaughter bodies to reduce both pathogenic and non-pathogenic microbial levels.

The compositions of the present invention are useful in cleaning or sterilizing containers, processing facilities, or equipment in the food delivery or food processing industry. The antibacterial composition of the present invention has specific value for use in food packaging materials and food packaging equipment, especially for low temperature sterile packaging or high temperature sterile packaging. Examples of processing facilities in which the compositions of the present invention may be used may include milking mill milk lines, continuous brewing systems, food processing lines (eg, pumpable food systems and beverage lines, etc.). Food offering products can be disinfected with the compositions of the present invention. For example, the compositions are also product washers, tableware, bottle washers, bottle coolers, warmers, third sink washers, cutting areas (eg water knives, slicers, cutters and saws) and egg washers. Or can be used in them. Specific treatable surfaces include packaging materials such as cartons, bottles, films and resins; tableware such as cups, plates, utensils, pots and breads; product washers; sinks, counter stands, dining tables, floors and walls. Exposed food cooking area surfaces such as; processing equipment such as tanks, jars, lines, pumps and hoses (eg milk processing equipment for processing milk, cheese, ice cream and other dairy products); and transport vehicles Is included. Containers include glass bottles of various volumes (100 ml-2 liters, etc.), PVC or polyolefin film bags, cans, polyester bottles, PEN bottles or PET bottles, 1 gallon milk containers, paperboard juice or milk containers, etc. Is included.

The antibacterial compositions of the present invention are also for other industrial equipment, in other industrial equipment, or for other industrial process streams (eg, heaters, cooling towers, boilers, retort water, rinse water and sterile. It can be used in packaging wash water, etc.). The compositions of the present invention can be used to treat microorganisms and odors in recreational water, such as in pools, spurs, recreational canals and water slides, fountains and the like.

Filters containing the compositions of the present invention can reduce the population of microorganisms in air and liquids. Such filters can remove water-borne and air-borne pathogens (eg, Legionella).

The compositions of the present invention can be used to reduce the population of microorganisms, fruit flies or other insect larvae on drains or other surfaces.

The compositions of the present invention are also provided by submerging the food processing equipment in the solution used, immersing the equipment for a sufficient amount of time to sterilize the equipment, and wiping or flushing excess solution from the equipment. Can be used. The compositions of the present invention further spray or wipe the processed food surface with the composition used, keep the surface moist for a sufficient amount of time to sterilize the surface, and remove excess solution. , Can be used by wiping, flushing vertically, removing by vacuum suction, etc.

The compositions of the present invention can also be used in methods of sterilizing hard surfaces, such as facility-type equipment, utensils, tableware, healthcare equipment or tools, and other hard surfaces. The compositions of the present invention can also be used in sterilizing contaminated clothing or textiles. The solution used is effective for sterilizing, disinfecting or sterilizing any of the above contaminated surfaces or items and at operating temperatures in the range of approximately 4 ° C to 60 ° C. Contacted over a period of time. For example, the high concentration composition can be poured into washing machine water or rinse water and allowed to contact the contaminated fabric for a sufficient amount of time to sterilize the fabric. The excess solution can then be removed by rinsing or dehydrating the fabric.

The antibacterial compositions of the present invention can be applied to microorganisms, or to dirty or cleaned surfaces using a variety of methods. These methods work on an object, on a surface, in a body, in a stream of water or gas, or otherwise by contacting an object, surface, body, or stream with the composition of the invention. be able to. Contacting can include any of a number of methods for applying the composition, such as spraying the composition, submerging the object in a composition or foam or gel, immersing the object in a composition. It can be treated with, or a combination thereof and the like can be included.

The high or used concentrations of the compositions of the present invention can be applied to an object by any conventional method or device for applying an antibacterial or cleaning composition to an object, or an object. Can be contacted with. For example, the object may be wiped with the composition of the invention or a composition of use made from the composition of the invention, and / or by the composition of the invention or the composition of use made from the composition of the invention. Spraying and / or covering with foam from the composition of the invention or the composition of use made from the composition of the invention and / or made from the composition of the invention or the composition of the invention Can be submerged in the composition used. The composition can be sprayed onto the surface, or foamed onto the surface, or smeared onto the surface; the composition can be allowed to flow over the surface, or the surface can be immersed in the composition. The contact can be done by hand or by machine. Food processed surfaces, food products, food processing water or food transport water and the like, liquid compositions, foam compositions, gel compositions, aerosol compositions, gas compositions, wax compositions, solid compositions or others according to the invention. It can be treated with a powdered stabilizing composition or a solution containing these compositions.

The compositions of the present invention can be used to bleach pulp. Such methods include contacting the pulp with the peroxycarboxylic acid composition according to the invention. Such a peroxycarboxylic acid composition can include added bleach.

The compositions of the present invention can be used for waste treatment. Such methods include contacting the waste with the peroxycarboxylic acid composition according to the invention. Such a peroxycarboxylic acid composition can include added bleach.

Cleaning in place Other hard surface cleaning applications for the antibacterial compositions of the present invention include clean-in-place (CIP) systems, decomposition-cleaning (COP) systems, washer-decontamination machines, sterilizers, textile washer, ultrafiltration. Systems and nanofiltration systems, as well as indoor air filters are included. COP systems may include easily operable systems including wash tanks, immersion vessels, mop buckets, storage tanks, scrub wash washers, vehicle parts washers, discontinuous batch washers and systems, and more. it can.

In general, the actual cleaning of the stationary system or other surface (ie, the removal of unwanted waste in it) is achieved by different materials (eg, compound detergents introduced with hot water). After this cleaning step, the composition is applied or introduced into the system at the concentration of solution used in unheated ambient temperature water. CIP typically has a flow rate of about 40 liters / minute to about 600 liters / minute, an ambient temperature to about 70 ° C, and a contact time of at least about 10 seconds (eg, about 30 seconds). ~ Approximately 120 seconds of contact time) is used. The compositions of the present invention can remain in solution in cold water (eg, 40 ° F / 4 ° C) and hot water (eg, 140 ° F / 60 ° C). It is not usually necessary to heat the aqueous solution of the composition of the invention, but under some circumstances it may be desirable to heat it to further enhance its antibacterial activity. These materials are useful at any possible temperature.

A method of sterilizing a substantially fixed in-situ process facility includes the following steps: The solution used in the present invention is introduced into the process facility at a temperature in the range of about 4 ° C to 60 ° C. After introduction of the solution to be used, the solution is retained in a container for sufficient time to sterilize the process facility (ie, to kill unwanted microorganisms) or circulated throughout the system. After the surface is sterilized by the composition of the present invention, the solution used is drained. When the sterilization process is complete, the system can be rinsed with other substances (eg, drinking water, etc.), if desired. The composition can be circulated in the process facility for 10 minutes or less.

The methods of the invention can include delivering the compositions of the invention to a clean-in-place surface or other surface (eg, the inner surface of a pipe and tank) by air delivery. This method of air delivery can reduce the amount of solution required.

Contacting the food product with the peroxycarboxylic acid composition In the methods and systems of the present invention, contacting a food product with a peroxycarboxylic acid composition is provided using any method or apparatus suitable for applying such composition. For example, in the methods and systems of the invention, the food product is either sprayed or submerged in the composition, or foamed or gelled with the composition, or Can be contacted by others. Contact with sprays, foams or gels, or contact by immersion, can be achieved by various methods known to those of skill in the art for applying antibacterial agents to food products. Contacting the food product can be done anywhere the food product can be found, eg, outdoors, at a processing site or processing plant, vehicle, warehouse, store, restaurant or home. it can. These same methods can also be adapted to apply the stabilized compositions of the present invention to other objects.

The method of the present invention requires a certain minimum contact time of the composition with the food product to produce a significant antibacterial effect. The contact time varies depending on the concentration of the composition used, the method of applying the composition used, the temperature of the composition used, the amount of stains in the food product, the amount of microorganisms in the food product, or the type of antibacterial agent. obtain. The exposure time can be at least about 5 seconds to about 15 seconds.

In one embodiment, the method for cleaning food products uses a pressure spray containing the compositions of the present invention. During the period of application of the spray solution to the food product, the surface of the food product can be mechanically moved (eg, agitated, rubbed, brushed, etc.). Stirring is possible by physically scrubbing the food product, by the action of a spray solution under pressure, by sonication, or by other methods. Stirring increases the efficiency of the spray solution in killing microorganisms. This is probably due to better exposure of the solution into crevices or small colonies containing microorganisms. The spray solution can also be heated to a temperature of about 15 ° C to 20 ° C, for example, to a temperature of about 20 ° C to 60 ° C, to increase potency before application. The stabilizing composition for spraying can be left on the surface of the food product for a sufficient period of time to suitably reduce the microbial population, followed by rinsing or draining from the food product. Or it can be evaporated.

Spray substance application, manual spray wand application, or automatic spraying of food products moving along the production line, using multiple spray heads to ensure perfect contact, or This can be achieved using other spray devices. One automatic spray application involves the use of a spray booth. The spray booth substantially limits the sprayed composition within the booth. The production line allows food products to be placed through aisles into a spray booth where the food products are sprayed by the spray material onto all its outer surfaces within the booth. After complete coating of the substance and complete discharge of the substance from the food product can be done in the booth, the food product can then be taken out of the booth. The spray booth can include a steam jet that can be used to apply the stabilized compositions of the present invention. Such steam jets can be used in combination with cooling water to ensure that the treatment reaching the surface of the food product is less than 65 ° C (eg, less than 60 ° C). The temperature of the spray product in the food product is important to ensure that the food product is not substantially altered (cooked) by the temperature of the spray product. The spray pattern can be virtually any useful spray pattern.

Submerging the food product in a liquid stabilized composition can be achieved by any of a variety of methods known to those of skill in the art. For example, the food product can be placed in a tank or bath containing the stabilized composition. Alternatively, the food product can be transported or processed in the transport channel of the stabilized composition. The cleaning solution can be agitated to increase the potency of the solution and the rate at which the solution reduces the microorganisms associated with the food product. Stirring by ultrasound, conventional methods including aeration by bubbling air through a solution, or by mechanical methods (eg, strainers, paddles, brushes, pump-driven liquid jets, etc.) or It can be obtained by a combination of these methods. The wash solution can be heated to increase the potency of the solution in killing microorganisms. After the food product has been submerged for a sufficient period of time for the desired antibacterial effect, the food product can be removed from the bath or transport channel and the stabilized composition rinsed, drained, or food manufactured. It can be evaporated from an object.

In another alternative embodiment of the invention, the food product can be treated by the effervescent form of the composition. Foam can be prepared by mixing the effervescent surfactant with the cleaning solution at the time of use. Effervescent surfactants can be nonionic, anionic or cationic in nature. Examples of useful surfactant types include, but are not limited to: alcohol alkoxylates, alcohol ethoxylate carboxylates, amine oxides, alkyl sulphates, alkyl ether sulphates, sulphonates, quaternary sulphates. Secondary ammonium compounds, alkyl sarcosins, betaines and alkyl amides. The effervescent surfactant is typically mixed with the cleaning solution in use. The solution level of the foaming agent used is about 50 ppm to about 2.0 wt-%. In use, compressed air can be injected into the mixture and then applied to the surface of the food product by a foam application device (eg, a tank foamer or a suction-type wall-fixed foamer).

In another alternative embodiment of the invention, the food product can be treated in a thickened or gelled form of the composition. In the thickened or gelled state, the cleaning solution remains on the surface of the food product for a longer period of time, thus increasing antibacterial drag. Thickening or gelling solutions also adhere to vertical surfaces. The composition or cleaning solution can be thickened or gelled using existing techniques, for example using xanthan gum, polymer thickeners or cellulose thickeners. Rod micelle formation systems (eg amine oxides and anionic counterions) can also be used. Thickeners or gel-forming agents can be used either in high-concentration products or mixed with the cleaning solution at the time of use. Typical levels of use of thickeners or gels range from about 100 ppm to about 10 wt-%.

Aseptic packaging In the methods of the invention, aseptic packaging involves contacting the container with the composition according to the invention. Such contact uses a spray device or immersion tank or container to bring the inside of the container into close contact with the composition for a sufficient period of time to clean or reduce the microbial population in the container. Can be achieved. The container is then dispensed with the amount of the composition of the invention used. After emptying, the container can then be rinsed with drinking water (which can contain rinsing additives) or sterile water and emptied again. After rinsing, the container can be filled with liquid beverages. The container is then sealed or capped or closed and then packed for transport for final sale.

FIG. 18 shows a schematic diagram of an embodiment of a bottle spray / bottling operation using the composition according to the invention. This operation can be a low temperature aseptic operation. FIG. 18 shows a factory 100 where beverage bottles can be contacted with a medium chain peroxycarboxylic acid composition for a sterilization process. In FIG. 18, the bottle 110 is passed through the sterilization tunnel 102. The sterilized bottle 110a then passes through the rinse tunnel 103 and appears as a sterilized rinsed bottle 110b.

In this process, a mass of medium chain peroxycarboxylic acid composition is added to the storage tank 101. Generally, the material is maintained in tank 101 at a temperature of about 22 ° C. In order to obtain an effective working concentration of the medium chain peroxycarboxylic acid composition, make-up water 105 is combined with the high concentration medium chain peroxycarboxylic acid composition in the tank 101. The composition using the medium chain peroxycarboxylic acid is passed through the heater 108 to reach a temperature of about 45 ° C to 50 ° C. The heated medium chain peroxycarboxylic acid use composition is sprayed into the bottle 110 and on all surfaces inside the sterile tunnel 102. Close contact between the medium-chain peroxycarboxylic acid composition and bin 110 is essential to reduce microbial populations to bactericidal levels.

After contact with the medium-chain peroxycarboxylic acid-using composition and after removing any excess composition from the bottle, the sterilized bottle 110 is then sent to the fresh water rinse tunnel 103. Fresh water 108 is provided from the fresh water device into the spray rinse tunnel 103. Fresh water can contain rinsing additives. Excess spray is drained from the rinse tunnel 103 to the drain pipe 106. In the tunnel 103, the sterilized bottle 110a is thoroughly rinsed with fresh water. Complete removal of the medium chain peroxycarboxylic acid composition from bottle 110a is important for maintaining high quality beverage products. The rinsed sterilized bottle 110b is then removed from the rinse tunnel.

The day tank 101, sterilization tunnel 102 and rinse tunnel 103 are all exhausted to a wet scrubber or exhaust port (111a, 111b or 111c) to remove steam or fumes from system components, respectively. The sanitizer material that has been sprayed and discharged from the bin 110a accumulates at the bottom of the spray tunnel 102 and is then recirculated to the day tank 101 through the recirculation line and heater 107.

Contact between the bottle and the medium chain peroxycarboxylic acid antibacterial composition is possible at temperatures above about 0 ° C, above 25 ° C, or above about 40 ° C. Temperatures between about 40 ° C and 90 ° C can be used. In some embodiments, contact over a contact time of at least 5 seconds (eg, at least about 10 seconds) at 40 ° C to 60 ° C is used.

In cold aseptic filling of 16 ounces of polyethylene terephthalate (PET bottles) or other polymeric beverage containers, the process has been employed using a medium chain peroxycarboxylic acid composition. The medium chain peroxycarboxylic acid composition can be diluted to a working concentration of about 0.1 wt% to about 10 wt% and has an effect of about 25 ° C to about 70 ° C (eg, about 40 ° C to about 60 ° C). Can be maintained at a high temperature. Spraying or injecting the bottle with this material ensures contact between the bottle and the sanitizer material for at least 5 seconds (eg, about 10 seconds). After the injection is complete, the bottle can drain all contents for at least 2 seconds, then rinse with sterile water for 5 seconds at 38 ° C (100 ° F), if necessary. Can be continued using about 200 ml of water in. If the bottle is filled with rinse water as needed, the bottle is drained with sterile water rinse for at least 2 seconds and immediately filled with liquid beverage. Rinse water may contain rinse additives. After the rinse is complete, the bottle typically retains less than 10 milliliters (eg, less than 3 milliliters) of rinse water after drainage.

Textile cleaning The present invention includes methods and compositions for removing stains from textiles. The compositions of the present invention can be used with typical commercial textile cleaning or washing processes and machines. The method of the present invention comprises contacting the laundry with the infiltration composition in a washing machine in the form of a soaking step with water, a pre-washing step, a pre-washing step or other steps prior to the cleaning step. Can be done. A washer / dehydrator is used in a suitable washing process. Laundry The cleaning process can include rinsing, detergent washing (sudsing), drainage, bleaching, rinsing, dehydration, repetition of these, or a combination thereof. The bleaching composition can include the composition according to the present invention.

The rinse can include contacting the laundry with the rinse composition. In one embodiment, flushing is the first wetting step on the machine performing the cleaning procedure. Cleaning The washing method can include rinsing once, twice or more. The conventional rinse composition is water (eg, soft water or tap water). In conventional systems, rinsing can separate, but not too much, easy-to-remove stains from the laundry and moisten the laundry. Rinsing can also be referred to as soaking, pre-washing or pre-washing.

Detergent cleaning can include cleaning the laundry with a detergent cleaning cleaning composition. Detergent Cleaning Cleaning compositions typically include surfactants and other cleaning agents, and can also include bleach. Detergent washing can be continued after rinsing.

Ejection involves removing the cleaning composition, rinse composition or other composition from the laundry by, for example, gravity and / or centrifugal force. Emissions can be continued after detergent cleaning. Discharge can be done during repeated rinses. In one embodiment, the fabric is cleaned with a fabric cleaning composition that comprises a builder detergent and chlorine bleach in a detergent cleaner / bleach combination, or in two separate cleaning steps, ie. , Cleaned in a detergent cleaning process with a builder-containing detergent, followed by a bleaching process with chlorine.

Bleaching can include cleaning the laundry with a bleach composition. Bleaching can be continued after draining and / or detergent cleaning. The bleach composition can include the composition according to the present invention.

Rinsing can include contacting the laundry with a suitable rinsing composition to remove residual cleaning composition (detergent cleaning composition and / or bleach composition). The rinsing composition can be, for example, water (eg, soft water or tap water), an acidic (sour) rinsing solution, or a rinsing solution containing a softener. Cleaning Laundry methods can include one, two, three or more rinses. Rinsing can be continued after bleaching and / or detergent cleaning.

Dehydration can include removing the rinse composition from the laundry, typically by centrifugal force. Dehydration can be continued after one or more rinses.

The methods and compositions of the present invention can be used for any variety of textiles. Suitable fabrics include cotton, cotton / polyester blends and polyesters.

The present invention can be better understood by reference to the examples below. These examples are intended to represent specific embodiments of the invention and are not intended to limit the scope of the invention.

<p><u style="single">Example 1-Preparation of Peroxycarboxylic Acid Using Equipment Containing Pretreatment Column and Reaction Catalyst</u> The devices and methods of the present invention were used to make compositions based on Tables 1-4 below. All equilibrium values are 2.70 reported K for peroxyacetic acid compositions._eqIt was a calculated value from. For mixed peracids, K_eqWas assumed to be 2.70.</p><p> Some stability of the test composition was monitored in the presence and absence of added stabilizer (HEDP).</p><p><tables num="1"><img file="JP5437806B2_D0007.tif" /></tables></p><p><tables num="2"><img file="JP5437806B2_D0008.tif" /></tables></p><p><tables num="3"><img file="JP5437806B2_D0009.tif" /></tables></p><p><tables num="4"><img file="JP5437806B2_D0010.tif" /></tables></p><p><tables num="5"><img file="JP5437806B2_D0011.tif" /></tables></p><p><tables num="6"><img file="JP5437806B2_D0012.tif" /></tables></p><p><tables num="7"><img file="JP5437806B2_D0013.tif" /></tables></p><p><tables num="8"><img file="JP5437806B2_D0014.tif" /></tables></p><p> As used herein and in the accompanying claims, the singular forms of "a," "an," and "the" include multiple directive references unless the content explicitly indicates otherwise. You have to keep in mind that you do. Thus, for example, a reference to a composition containing a compound (a compound) includes a mixture of two or more compounds. It should also be noted that the term "or" is commonly used in that sense to include "and (and) / or (or)" unless the content explicitly indicates otherwise.</p><p> All publications and patent applications herein indicate the level of one of ordinary skill in the art in which the invention relates.</p><p> The present invention has been described with reference to various specific and preferred embodiments and techniques. However, it should be understood that many modifications and modifications can be made while still being contained within the spirit and scope of the invention.<u style="single">The embodiments of the invention related to the present invention are listed below.</u><u style="single">[Embodiment 1]</u><u style="single"> Includes first pretreatment column, first reaction catalyst column, first and second reagent vessels, safety system, reagent conduit, reaction mixture conduit, and peroxy acid conduit.</u><u style="single"> The first and second reagent vessels are in fluid communication with the first pretreatment column via reagent conduits, provided that</u><u style="single"> The first reagent container is configured to contain a liquid oxidant composition and the second reagent container is configured to contain a liquid carboxylic acid composition.</u><u style="single"> Reagent conduit defines a mixing chamber for reagents;</u><u style="single"> The first pretreatment column is in fluid communication with the first reaction catalyst column via the reaction mixture conduit, provided that</u><u style="single"> The first pretreatment column is configured to remove metal ions from the mixture of carboxylic acid composition and oxidant composition.</u><u style="single"> The first reaction catalyst column is configured to catalyze the reaction of the carboxylic acid and oxidant to produce the peroxycarboxylic acid;</u><u style="single"> The first reaction catalyst column is in fluid communication with the storage or use site of the peroxycarboxylic acid composition via a peracid conduit;</u><u style="single"> The safety system includes a processor, a first status sensor and a second status sensor, however.</u><u style="single"> The first status sensor is located in the mixing chamber or on the surface of the mixing chamber and is configured to measure the condition of the reagents.</u><u style="single"> The second condition sensor is located in the first pretreatment column, in the first pretreatment column, or in the reaction mixture conduit near the outlet from the first pretreatment column, and the reagent. Configured for measuring the condition of</u><u style="single"> The processor can determine the difference between the state measured by the first state sensor and the state measured by the second state sensor, and can detect if the difference meets or exceeds a predetermined value. Constructed to provide a signal,</u><u style="single">A device for making peroxycarboxylic acids.</u><u style="single">[Embodiment 2]</u><u style="single"> The device according to embodiment 1, wherein the first pretreatment column comprises a strong cation exchanger in acid or inert metal form.</u><u style="single">[Embodiment 3]</u><u style="single"> Including a second pretreatment column,</u><u style="single"> The second pretreatment column is in fluid communication with the second reagent container and the first pretreatment column via a reagent conduit.</u><u style="single"> The device according to embodiment 1, wherein the second pretreatment column is configured to remove metal ions from the carboxylic acid composition.</u><u style="single">[Embodiment 4]</u><u style="single"> The device according to embodiment 3, wherein the second pretreatment column comprises a strong cation exchanger in acid or inert metal form.</u><u style="single">[Embodiment 5]</u><u style="single"> Including a third pretreatment column,</u><u style="single"> The third pretreatment column is in fluid communication with the first reagent container and the first pretreatment column via a reagent conduit.</u><u style="single"> The device according to embodiment 1, wherein the third pretreatment column is configured to remove metal ions from the carboxylic acid composition.</u><u style="single">[Embodiment 6]</u><u style="single"> The device according to embodiment 3, wherein the third pretreatment column comprises a strong cation exchanger in acid or inert metal form.</u><u style="single">[Embodiment 7]</u><u style="single"> The apparatus of embodiment 1, wherein the reaction catalyst comprises a strong acid catalyst that can be physically removed from the reaction mixture.</u><u style="single">[Embodiment 8]</u><u style="single"> The device according to embodiment 7, wherein the reaction catalyst contains a strong cation exchanger in acid form.</u><u style="single">[Embodiment 9]</u><u style="single"> The device according to embodiment 7, wherein the reaction catalyst comprises an inorganic compound containing an insoluble strong acid.</u><u style="single">[Embodiment 10]</u><u style="single"> Further including second, third and fourth reaction catalyst columns,</u><u style="single"> The first, second, third and fourth reaction catalyst columns are connected in series and are in fluid communication with a storage site or a site of use of the peroxycarboxylic acid composition via a peracid conduit, according to the first embodiment. apparatus.</u><u style="single">[Embodiment 11]</u><u style="single"> 10. The apparatus of embodiment 10, wherein the reaction catalyst comprises a strong acid catalyst.</u><u style="single">[Embodiment 12]</u><u style="single"> The device according to embodiment 11, wherein the reaction catalyst contains a strong cation exchanger in acid form.</u><u style="single">[Embodiment 13]</u><u style="single"> The device according to embodiment 11, wherein the reaction catalyst comprises an inorganic compound containing an insoluble strong acid.</u><u style="single">[Embodiment 14]</u><u style="single"> The device according to embodiment 1, wherein the first and second condition sensors are configured to measure temperature, pressure, metal content or a combination thereof.</u><u style="single">[Embodiment 15]</u><u style="single"> The device according to embodiment 14, wherein the first and second status sensors are configured to measure temperature.</u><u style="single">[Embodiment 16]</u><u style="single"> The device of embodiment 15, wherein the safety system provides a detectable signal if the temperature difference is greater than, equal to, equal to, or greater than 10 ° C.</u><u style="single">[Embodiment 17]</u><u style="single"> Detectable signals can cause interruptions in the operation of the device.</u><u style="single"> Actuating the pressure release valve to release the pressure in the first pretreatment column;</u><u style="single"> Stopping the flow of one or more reagents to the column;</u><u style="single"> Flowing water through the reagent conduit, the first pretreatment column and the reaction mixture conduit;</u><u style="single"> Flowing the carboxylic acid composition through the reagent conduit, the first pretreatment column and the reaction mixture conduit;</u><u style="single"> Shut down the device; or</u><u style="single"> A combination of these</u><u style="single">The device according to embodiment 1, which is operated by.</u><u style="single">[Embodiment 18]</u><u style="single"> Further includes a peracid vessel, dilution system, diluent tank, refill system and drainage conduit,</u><u style="single"> The peracid container is fluidly connected to the peracid conduit and is configured to contain and contain the peroxycarboxylic acid composition.</u><u style="single"> The peroxy acid vessel is in fluid communication with the dilution system via a drainage conduit.</u><u style="single"> The dilution system is configured to mix the peroxycarboxylic acid composition and a predetermined amount of carriers to form a diluted composition of a given concentration of peroxycarboxylic acid in the diluent tank.</u><u style="single"> The replenishment system monitors the concentration of peroxycarboxylic acid, the concentration of carboxylic acid, the concentration of oxidant or a combination thereof in a diluted composition, and the concentration of peroxycarboxylic acid, the concentration of carboxylic acid, the concentration of oxidant. Alternatively, if the combination thereof is less than, equal to, or greater than or equal to a predetermined value, the peroxycarboxylic acid composition is configured to be added to the diluted composition. The apparatus according to the first embodiment.</u><u style="single">[Embodiment 19]</u><u style="single"> It further comprises a fourth pretreatment column, a fifth reaction catalyst column, third and fourth reagent vessels, an intermediate reagent conduit, an intermediate reaction mixture conduit, and an intermediate peroxy acid conduit.</u><u style="single"> The third and fourth reagent vessels are in fluid communication with the fourth pretreatment column via an intermediate reagent conduit, provided that</u><u style="single"> The third reagent container is configured to contain the liquid composition of the oxidant, and the fourth reagent container is configured to contain the liquid composition of the medium chain carboxylic acid.</u><u style="single"> Intermediate reagent conduits define an intermediate mixing chamber for intermediate reagents;</u><u style="single"> The fourth pretreatment column is in fluid communication with the fifth reaction catalyst column via an intermediate reaction mixture conduit, provided that</u><u style="single"> The fourth pretreatment column is configured to remove metal ions from the mixture of the liquid composition and the oxidant composition of the medium chain carboxylic acid composition.</u><u style="single"> The fifth reaction catalyst column is configured to catalyze the reaction of the medium chain carboxylic acid and the oxidant to produce the medium chain peroxycarboxylic acid;</u><u style="single"> A fifth reaction catalyst column is in fluid communication with the storage or use site of the medium chain peroxycarboxylic acid composition via an intermediate peracid conduit;</u><u style="single"> The safety system further includes a third status sensor and a fourth status sensor, provided that</u><u style="single"> A third status sensor is located in the intermediate mixing chamber or on the surface of the intermediate mixing chamber and is configured to measure the status of intermediate reagents.</u><u style="single"> The fourth condition sensor is located in the fourth pretreatment column, in the fourth pretreatment column, or in the intermediate reaction mixture conduit near the outlet from the fourth pretreatment column. Constructed for measuring the condition of intermediate reagents,</u><u style="single"> The processor finds the difference between the state measured by the third state sensor and the state measured by the fourth state sensor, and is detectable if the difference meets or exceeds a predetermined value. Constructed to provide a signal;</u><u style="single"> However, in this case</u><u style="single"> A second reagent container is configured to contain a liquid composition of short chain carboxylic acids;</u><u style="single"> The first pretreatment column is configured to remove metal ions from the mixture of short chain carboxylic acid composition and oxidant composition;</u><u style="single"> The apparatus according to embodiment 1, wherein the first reaction catalyst column is configured to catalyze the reaction of the short chain carboxylic acid and the oxidant to produce the short chain peroxycarboxylic acid.</u><u style="single">[Embodiment 20]</u><u style="single"> The device according to embodiment 19, wherein the fourth pretreatment column comprises a strong cation exchanger in acid or inert metal form.</u><u style="single">[Embodiment 21]</u><u style="single"> Including a fifth pretreatment column,</u><u style="single"> The fifth pretreatment column is in fluid communication with the fourth reagent container and the fourth pretreatment column via an intermediate reagent conduit.</u><u style="single"> The apparatus according to embodiment 19, wherein the fifth pretreatment column is configured to remove metal ions from the liquid composition of the medium chain carboxylic acid.</u><u style="single">[Embodiment 22]</u><u style="single"> 21. The apparatus of embodiment 21, wherein the fifth pretreatment column comprises a strong cation exchanger in acid or inert metal form.</u><u style="single">[Embodiment 23]</u><u style="single"> Including a sixth pretreatment column,</u><u style="single"> The sixth pretreatment column is in fluid communication with the third reagent container and the fourth pretreatment column via an intermediate reagent conduit.</u><u style="single"> The device according to embodiment 19, wherein the sixth pretreatment column is configured to remove metal ions from the liquid composition of the oxidant.</u><u style="single">[Embodiment 24]</u><u style="single"> 23. The apparatus of embodiment 23, wherein the sixth pretreatment column comprises a strong cation exchanger in acid or inert metal form.</u><u style="single">[Embodiment 25]</u><u style="single"> 19. The apparatus of embodiment 19, wherein the reaction catalyst comprises a strong acid catalyst.</u><u style="single">[Embodiment 26]</u><u style="single"> 25. The apparatus of embodiment 25, wherein the reaction catalyst comprises a strong cation exchanger in acid form.</u><u style="single">[Embodiment 27]</u><u style="single"> 25. The apparatus of embodiment 25, wherein the reaction catalyst comprises an inorganic compound containing an insoluble strong acid.</u><u style="single">[Embodiment 28]</u><u style="single"> Further including 6th, 7th and 8th reaction catalyst columns,</u><u style="single"> The fifth, sixth, seventh and eighth reaction catalyst columns are connected in series and are in fluid communication with the storage or use site of the medium chain peroxycarboxylic acid composition via an intermediate peracid conduit, embodiment 19. The device described in.</u><u style="single">[Embodiment 29]</u><u style="single"> 28. The apparatus of embodiment 28, wherein the reaction catalyst comprises a strong acid catalyst.</u><u style="single">[Embodiment 30]</u><u style="single"> 29. The apparatus of embodiment 29, wherein the reaction catalyst comprises a strong cation exchanger in acid form.</u><u style="single">[Embodiment 31]</u><u style="single"> 29. The apparatus of embodiment 29, wherein the reaction catalyst comprises an inorganic compound containing an insoluble strong acid.</u><u style="single">[Embodiment 32]</u><u style="single"> The device according to embodiment 19, wherein third and fourth condition sensors are configured to measure temperature, pressure, metal content or a combination thereof.</u><u style="single">[Embodiment 33]</u><u style="single"> 32. The apparatus of embodiment 32, wherein the third and fourth status sensors are configured to measure temperature.</u><u style="single">[Embodiment 34]</u><u style="single"> 33. The apparatus of embodiment 33, wherein the safety system provides a detectable signal if the temperature difference is greater than or equal to 10 ° C, or equal to, or greater than or equal to 10 ° C.</u><u style="single">[Embodiment 35]</u><u style="single"> Detectable signals can cause interruptions in the operation of the device.</u><u style="single"> Actuating the pressure release valve to release the pressure in the fourth pretreatment column;</u><u style="single"> Stopping the flow of one or more reagents to the column;</u><u style="single"> Flowing water through the intermediate reagent conduit, the fourth pretreatment column and the intermediate reaction mixture vessel;</u><u style="single"> The liquid composition of the medium chain carboxylic acid is flowed through the intermediate reagent conduit, the fourth pretreatment column and the intermediate reaction mixture conduit;</u><u style="single"> Shut down the device; or</u><u style="single"> A combination of these</u><u style="single">19. The device of embodiment 19.</u><u style="single">[Embodiment 36]</u><u style="single"> 19. The apparatus of embodiment 19, wherein the peroxy acid vessel is fluidly connected to an intermediate peroxy acid conduit and is configured to contain and contain a medium chain peroxycarboxylic acid composition.</u><u style="single">[Embodiment 37]</u><u style="single"> Including a second processor</u><u style="single"> The second processor finds the difference between the state measured by the third state sensor and the state measured by the fourth state sensor, and if the difference meets or exceeds a predetermined value. 19. The device of embodiment 19, configured for providing a detectable signal.</u><u style="single">[Embodiment 38]</u><u style="single"> The device according to embodiment 1, wherein the first reaction catalyst column has a volume of about 9.6 L.</u><u style="single">[Embodiment 39]</u><u style="single"> The device according to embodiment 10, wherein each reaction catalyst column has a volume of about 9.6 L.</u><u style="single">[Embodiment 40]</u><u style="single"> The device according to embodiment 1, wherein the fifth reaction catalyst column has a volume of about 9.6 L.</u><u style="single">[Embodiment 41]</u><u style="single"> 28. The apparatus of embodiment 28, wherein each reaction catalyst column has a volume of about 9.6 L.</u><u style="single">[Embodiment 42]</u><u style="single"> The apparatus according to embodiment 1, wherein the first pretreatment column has a volume of about 4.6 L.</u><u style="single">[Embodiment 43]</u><u style="single"> The apparatus according to embodiment 3, wherein the second pretreatment column has a volume of about 4.6 L.</u><u style="single">[Embodiment 44]</u><u style="single"> The apparatus according to embodiment 5, wherein the third pretreatment column has a volume of about 4.6 L.</u><u style="single">[Embodiment 45]</u><u style="single"> The apparatus according to embodiment 19, wherein the fourth pretreatment column has a volume of about 4.6 L.</u><u style="single">[Embodiment 46]</u><u style="single"> 21. The apparatus of embodiment 21, wherein the fifth pretreatment column has a volume of about 4.6 L.</u><u style="single">[Embodiment 47]</u><u style="single"> The apparatus according to embodiment 23, wherein the sixth pretreatment column has a volume of about 4.6 L.</u><u style="single">[Embodiment 48]</u><u style="single"> The apparatus according to the first embodiment, wherein the first reagent container contains about 35 wt-% to about 45 wt-% hydrogen peroxide.</u><u style="single">[Embodiment 49]</u><u style="single"> The apparatus according to the first embodiment, wherein the second reagent container contains about 80 wt-% to about 100 wt-% acetic acid.</u><u style="single">[Embodiment 50]</u><u style="single"> The apparatus according to embodiment 19, wherein the third reagent container contains about 35 wt-% to about 45 wt-% hydrogen peroxide.</u><u style="single">[Embodiment 51]</u><u style="single"> The device according to embodiment 19, wherein the second reagent container contains from about 1 wt-% to about 10 wt-% octanoic acid.</u><u style="single">[Embodiment 52]</u><u style="single"> The apparatus of embodiment 1, further comprising a third reagent container that is configured to contain a liquid medium chain carboxylic acid composition and is in fluid communication with the first pretreatment column via a reagent conduit.</u><u style="single">[Embodiment 53]</u><u style="single"> The apparatus according to embodiment 52, further comprising a fourth pretreatment column, wherein the fourth pretreatment column is in fluid communication with the third reagent container and the first pretreatment column via a reagent conduit.</u><u style="single">[Embodiment 54]</u><u style="single"> The device according to embodiment 52, wherein the third reagent container contains from about 1 wt-% to about 10 wt-% octanoic acid.</u><u style="single">[Embodiment 55]</u><u style="single"> To provide a liquid composition of a carboxylic acid and an oxidizing agent;</u><u style="single"> Pretreating the liquid composition with a pretreatment column to remove the metal ions from the mixed composition;</u><u style="single"> The state of the liquid composition is measured at i) before pretreatment and ii) at the pretreatment site during the pretreatment period;</u><u style="single"> Find the difference between i) and ii);</u><u style="single"> If the difference meets or exceeds a given value, provide a detectable signal;</u><u style="single"> The pretreated composition is reacted in the presence of a reaction catalyst that can be physically removed from the reaction mixture for making the peroxycarboxylic acid composition;</u><u style="single"> Recovering the peroxycarboxylic acid composition</u><u style="single">A method for making a peroxycarboxylic acid, which comprises.</u><u style="single">[Embodiment 56]</u><u style="single"> 55. The method of embodiment 55, wherein the pretreatment comprises contacting the mixed composition with a strong cation exchanger in acid or inert metal form.</u><u style="single">[Embodiment 57]</u><u style="single"> Pretreatment of the carboxylic acid liquid composition to remove metal ions from the carboxylic acid liquid composition;</u><u style="single"> Mixing the carboxylic acid pretreated liquid composition and oxidant to form the carboxylic acid and oxidant liquid composition.</u><u style="single">55. The method of embodiment 55.</u><u style="single">[Embodiment 58]</u><u style="single"> 58. The method of embodiment 57, wherein the pretreatment comprises contacting the liquid composition of the carboxylic acid with a strong cation exchanger in acid or inert metal form.</u><u style="single">[Embodiment 59]</u><u style="single"> Pretreatment of the oxidant liquid composition to remove metal ions from the oxidant liquid composition;</u><u style="single"> Mixing the pretreated liquid composition of the oxidant and the carboxylic acid to form the liquid composition of the carboxylic acid and the oxidant.</u><u style="single">55.</u><u style="single">[Embodiment 60]</u><u style="single"> 25. The method of embodiment 59, wherein the pretreatment comprises contacting the liquid composition of the oxidant with a strong cation exchanger in acid or inert metal form.</u><u style="single">[Embodiment 61]</u><u style="single"> 55. The method of embodiment 55, wherein the reaction comprises contacting the pretreated composition with an insoluble strong acid catalyst.</u><u style="single">[Embodiment 62]</u><u style="single"> The method of embodiment 61, wherein the reaction comprises contacting the pretreated composition with a strong cation exchanger in acid form.</u><u style="single">[Embodiment 63]</u><u style="single"> The method of embodiment 61, wherein the reaction comprises contacting the pretreated composition with an inorganic compound containing an insoluble strong acid.</u><u style="single">[Embodiment 64]</u><u style="single"> Including reacting in a column of insoluble reaction catalysts and</u><u style="single"> It involves reacting in the second, third and fourth columns of the insoluble reaction catalyst, provided that</u><u style="single"> The method of embodiment 55, wherein the first, second, third and fourth reaction catalyst columns are connected in series.</u><u style="single">[Embodiment 65]</u><u style="single"> 13. The method of embodiment 64, wherein the reaction comprises contacting the pretreated composition with an insoluble strong acid catalyst.</u><u style="single">[Embodiment 66]</u><u style="single"> 65. The method of embodiment 65, wherein the reaction comprises contacting the pretreated composition with a strong cation exchanger in acid form.</u><u style="single">[Embodiment 67]</u><u style="single"> 65. The method of embodiment 65, wherein the reaction comprises contacting the pretreated composition with an inorganic compound containing an insoluble strong acid.</u><u style="single">[Embodiment 68]</u><u style="single"> 55. The method of embodiment 55, comprising measuring the temperature, pressure, metal content or combination thereof of the mixed composition.</u><u style="single">[Embodiment 69]</u><u style="single"> 55. The method of embodiment 55, comprising measuring the temperature of the mixed composition.</u><u style="single">[Embodiment 70]</u><u style="single"> 29. The method of embodiment 69, comprising providing a detectable signal if the temperature difference is greater than or equal to 10 ° C or greater than or equal to 10 ° C.</u><u style="single">[Embodiment 71]</u><u style="single"> If the difference meets or exceeds the predetermined position, the interruption of operation of the device,</u><u style="single"> Activating a pressure release valve to release pressure in a device performing this method;</u><u style="single"> Stopping the flow of one or more reagents to the device;</u><u style="single"> Flushing water to the pretreatment site;</u><u style="single"> Flowing the carboxylic acid composition to the pretreatment site;</u><u style="single"> Shut down the device; or</u><u style="single"> A combination of these</u><u style="single">55. The method of embodiment 55, further comprising:</u><u style="single">[Embodiment 72]</u><u style="single"> Mixing the peroxycarboxylic acid composition and a predetermined amount of carriers to form a diluted composition of a predetermined concentration of peroxycarboxylic acid;</u><u style="single"> Storage of diluted compositions;</u><u style="single"> Monitor the concentration of peroxycarboxylic acid, the concentration of carboxylic acid, the concentration of oxidant or a combination thereof in a diluted composition;</u><u style="single"> Peroxycarboxylic acid composition if the concentration of peroxycarboxylic acid, the concentration of carboxylic acid, the concentration of oxidant or a combination thereof is less than, equal to, or greater than or equal to a predetermined value. To the diluted composition</u><u style="single">55.</u><u style="single">[Embodiment 73]</u><u style="single"> Mixing the liquid composition of carboxylic acid and the liquid composition of oxidant to form the liquid composition of carboxylic acid and oxidant.</u><u style="single">55.</u><u style="single">[Embodiment 74]</u><u style="single"> 23. The method of embodiment 73, wherein the liquid composition of the carboxylic acid comprises from about 80 wt-% to about 98 wt-% acetic acid.</u><u style="single">[Embodiment 75]</u><u style="single"> 13. The method of embodiment 73, wherein the oxidant comprises from about 35 wt-% to about 45 wt-% hydrogen peroxide.</u><u style="single">[Embodiment 76]</u><u style="single"> 23. The method of embodiment 73, wherein the liquid composition of the carboxylic acid comprises from about 1 wt-% to about 20 wt-% octanoic acid.</u><u style="single">[Embodiment 77]</u><u style="single"> 55. The method of embodiment 55, comprising providing a large number of carboxylic acid and oxidant liquid compositions.</u><u style="single">[Embodiment 78]</u><u style="single"> Mixing the first liquid composition of carboxylic acid, the second liquid composition of carboxylic acid, and the liquid composition of oxidant to form a large number of liquid compositions of carboxylic acid and oxidant.</u><u style="single">The method according to embodiment 77, further comprising.</u><u style="single">[Embodiment 79]</u><u style="single"> The method of embodiment 78, wherein the first liquid composition of the carboxylic acid comprises from about 80 wt-% to about 100 wt-% acetic acid.</u><u style="single">[Embodiment 80]</u><u style="single"> 13. The method of embodiment 73, wherein the oxidant comprises from about 35 wt-% to about 45 wt-% hydrogen peroxide.</u><u style="single">[Embodiment 81]</u><u style="single"> 23. The method of embodiment 73, wherein the second liquid composition of the carboxylic acid comprises from about 1 wt-% to about 20 wt-% octanoic acid.</u><u style="single">[Embodiment 82]</u><u style="single"> Pretreatment of the first liquid composition of carboxylic acid to remove metal ions from the first liquid composition of carboxylic acid;</u><u style="single"> Include a first carboxylic acid pretreated liquid composition in a large number of carboxylic acid and oxidant liquid compositions.</u><u style="single">The method according to embodiment 77, further comprising.</u><u style="single">[Embodiment 83]</u><u style="single"> Pretreatment of the oxidant liquid composition to remove metal ions from the oxidant liquid composition;</u><u style="single"> Including the oxidant pretreated liquid composition in a large number of carboxylic acid and oxidant liquid compositions.</u><u style="single">The method according to embodiment 77, further comprising.</u><u style="single">[Embodiment 84]</u><u style="single"> Pretreatment of the second liquid composition of carboxylic acid to remove metal ions from the second liquid composition of carboxylic acid;</u><u style="single"> Include a second carboxylic acid pretreated liquid composition in a large number of carboxylic acid and oxidant liquid compositions.</u><u style="single">The method according to embodiment 77, further comprising.</u><u style="single">[Embodiment 85]</u><u style="single"> The method of embodiment 55, wherein the liquid composition of the carboxylic acid and oxidant comprises from about 40 wt-% to about 50 wt-% acetic acid and from about 15 wt-% to about 25 wt-% hydrogen peroxide.</u><u style="single">[Embodiment 86]</u><u style="single"> The liquid composition of the carboxylic acid and oxidant contains from about 25 wt-% to about 35 wt-% acetic acid, from about 10 wt-% to about 20 wt-% hydrogen peroxide and from about 2 wt-% to about 4 wt-% octanoic acid. , The method according to embodiment 55.</u><u style="single">[Embodiment 87]</u><u style="single"> Providing, pretreating, measuring, seeking, providing, reacting and recovering, the peroxycarboxylic acid composition is used to reduce the population of microorganisms on an object. What to do in the field</u><u style="single">55. The method of embodiment 55.</u><u style="single">[Embodiment 88]</u><u style="single"> 8. The method of embodiment 87, comprising delivering a large number of carboxylic acids to the field.</u><u style="single">[Embodiment 89]</u><u style="single"> 8. The method of embodiment 87, further comprising requesting delivery of the carboxylic acid and oxidizing agent from the field.</u><u style="single">[Embodiment 90]</u><u style="single"> 8. The method of embodiment 87, further comprising applying the peroxycarboxylic acid to a beverage container in a beverage factory.</u><u style="single">[Embodiment 91]</u><u style="single"> Delivering carboxylic acids and oxidizing agents to the site where the peroxycarboxylic acid composition is made and used;</u><u style="single"> To provide a liquid composition of a carboxylic acid and an oxidizing agent;</u><u style="single"> Pretreating the liquid composition with a pretreatment column to remove the metal ions from the mixed composition;</u><u style="single"> The pretreated composition is reacted in the presence of a reaction catalyst that can be physically removed from the reaction mixture for making the peroxycarboxylic acid composition;</u><u style="single"> Recovering the peroxycarboxylic acid composition; and</u><u style="single"> Applying a peroxycarboxylic acid composition to an object to reduce the population of microorganisms on the object</u><u style="single">A method for making a peroxycarboxylic acid, which comprises.</u><u style="single">[Embodiment 92]</u><u style="single"> The method of embodiment 91, comprising delivering a large number of carboxylic acids to the field.</u><u style="single">[Embodiment 93]</u><u style="single"> 8. The method of embodiment 87, further comprising requesting delivery of the carboxylic acid and oxidizing agent from the field.</u><u style="single">[Embodiment 94]</u><u style="single"> 8. The method of embodiment 87, comprising applying the peroxycarboxylic acid to a beverage container in a beverage factory.</u><u style="single">[Embodiment 95]</u><u style="single"> To provide a liquid composition of short chain carboxylic acid and oxidant;</u><u style="single"> Pretreating the mixed short chain composition with a pretreatment column to remove metal ions from the short chain mixed composition;</u><u style="single"> The pretreated short chain composition is reacted in the presence of an insoluble reaction catalyst to produce a short chain peroxycarboxylic acid composition;</u><u style="single"> To provide a liquid composition of a medium chain carboxylic acid and an oxidizing agent;</u><u style="single"> Pretreating the mixed medium chain composition with a pretreatment column to remove metal ions from the mixed medium chain composition;</u><u style="single"> The pretreated medium chain composition is reacted in the presence of an insoluble reaction catalyst to produce a medium chain peroxycarboxylic acid composition;</u><u style="single"> Mixing short-chain peroxycarboxylic acid compositions and medium-chain peroxycarboxylic acid compositions to produce a mixed peroxycarboxylic acid composition;</u><u style="single"> The state of the short chain composition is measured at i) before pretreatment and ii) at the pretreatment site during the pretreatment period;</u><u style="single"> Find the difference between i) and ii); and</u><u style="single"> If the difference between i) and ii) meets or exceeds a predetermined value, provide a detectable signal;</u><u style="single"> The state of the mixed medium chain composition is measured at iii) before pretreatment and iv) at the pretreatment site during the pretreatment period;</u><u style="single"> Find the difference between iii) and iv); and</u><u style="single"> If the difference between iii) and iv), or the difference between both, meets or exceeds a predetermined value, provide a detectable signal.</u><u style="single">A method for making a mixed peroxycarboxylic acid composition comprising.</u><u style="single">[Embodiment 96]</u><u style="single"> To provide a liquid composition of a carboxylic acid and an oxidizing agent;</u><u style="single"> Pretreating the liquid composition with a pretreatment column to remove the metal ions from the mixed composition;</u><u style="single"> The state of the liquid composition is measured at i) before pretreatment and ii) at the pretreatment site during the pretreatment period;</u><u style="single"> Find the difference between i) and ii);</u><u style="single"> If the difference meets or exceeds a given value, provide a detectable signal;</u><u style="single"> The pretreated composition is reacted in the presence of a reaction catalyst that can be physically removed from the reaction mixture for making the peroxycarboxylic acid composition;</u><u style="single"> Recovering the peroxycarboxylic acid composition</u><u style="single">A peroxycarboxylic acid composition prepared by a method comprising.</u><u style="single">[Embodiment 97]</u><u style="single"> Approximately 1 wt-% to approximately 35 wt-% peroxycarboxylic acid,</u><u style="single"> About 5wt-% to about 30wt-% hydrogen peroxide, and</u><u style="single"> Metals less than about 10ppm</u><u style="single">Peroxycarboxylic acid composition comprising.</u><u style="single">[Embodiment 98]</u><u style="single"> The peroxycarboxylic acid composition according to embodiment 97, wherein 95% of the peroxycarboxylic acid is retained at 70 ° F for at least about 7 days.</u><u style="single">[Embodiment 99]</u><u style="single"> The peroxycarboxylic acid composition according to embodiment 97, which comprises from about 0.5 wt-% to about 35 wt-% short chain peroxycarboxylic acid.</u><u style="single">[Embodiment 100]</u><u style="single"> The peroxycarboxylic acid composition according to embodiment 97, which comprises from about 0.5 wt-% to about 20 wt-% medium chain peroxycarboxylic acid.</u><u style="single">[Embodiment 101]</u><u style="single"> About 0.5 wt-% to about 35 wt-% short-chain peroxycarboxylic acid, and</u><u style="single"> Approximately 0.5 wt-% to approximately 20 wt-% medium-chain peroxycarboxylic acid</u><u style="single">The peroxycarboxylic acid composition according to embodiment 97, which comprises.</u><u style="single">[Embodiment 102]</u><u style="single"> The peroxycarboxylic acid composition according to embodiment 97, which comprises a peroxycarboxylic acid and hydrogen peroxide in a ratio of about 0.5: 1 to about 7: 1.</u><u style="single">[Embodiment 103]</u><u style="single"> The peroxycarboxylic acid composition according to embodiment 97, which comprises only volatile compounds.</u><u style="single">[Embodiment 104]</u><u style="single"> Peroxycarboxylic acid generator that produces high concentrations of peroxycarboxylic acid;</u><u style="single"> Use composition container for storing the use composition consisting of diluted peroxycarboxylic acid high concentration; and</u><u style="single"> A control device that receives concentration data regarding the concentrations of peroxycarboxylic acid and hydrogen peroxide in the composition used, and manages to replenish the composition used when these concentrations do not meet a predetermined standard.</u><u style="single">System including.</u><u style="single">[Embodiment 105]</u><u style="single"> High peroxycarboxylic acid to the composition used when the controller compares the concentration of peroxycarboxylic acid to a given POAA target criterion and the concentration data indicates that the concentration of peroxycarboxylic acid in the composition used is too low. The system according to embodiment 104, which controls the addition of concentrations.</u><u style="single">[Embodiment 106]</u><u style="single"> Addition of diluent to the composition used when the controller compares the concentration of peroxycarboxylic acid to a given POAA target criterion and the concentration data indicates that the concentration of peroxycarboxylic acid in the composition used is too high. The system according to embodiment 104, which manages.</u><u style="single">[Embodiment 107]</u><u style="single"> The control device sets the concentration of hydrogen peroxide to a predetermined H</u>_{<u style="single">2</u>}<u style="single">O</u>_{<u style="single">2</u>}<u style="single">Control the emptying of the used composition container and the preparation of new used compositions when compared to the target criteria and the concentration data indicates that the hydrogen peroxide concentration in the used composition is too high. The system according to embodiment 104.</u><u style="single">[Embodiment 108]</u><u style="single"> The controller compares the concentration of peroxycarboxylic acid with the expected POAA target concentration, and sets the operating parameters of the peroxycarboxylic acid generator to the concentration of peroxycarboxylic acid in the high concentration of peroxycarboxylic acid provided by the peroxycarboxylic acid generator. The system according to embodiment 104, which is adjusted to exert a change.</u><u style="single">[Embodiment 109]</u><u style="single"> Receive concentration data on the concentrations of peroxycarboxylic acid and hydrogen peroxide in the composition used;</u><u style="single"> Comparing the concentration of peroxycarboxylic acid to the prescribed POAA target criteria; and</u><u style="single"> Automatically replenish the composition used when the peroxycarboxylic acid concentration does not meet the prescribed POAA target criteria.</u><u style="single">How to include.</u><u style="single">[Embodiment 110]</u><u style="single"> Automatic replenishment of the composition used Further, when the concentration data indicates that the concentration of peroxycarboxylic acid in the composition used is too high, the concentration of peroxycarboxylic acid is automatically added to the composition used. Included, the method of embodiment 109.</u><u style="single">[Embodiment 111]</u><u style="single"> Automatic replenishment of the composition used further comprises automatically adding a diluent to the composition used when concentration data indicate that the concentration of peroxycarboxylic acid in the composition used is too high. The method according to embodiment 109.</u><u style="single">[Embodiment 112]</u><u style="single"> Automatic replenishment of the composition used In addition, when the concentration data indicates that the concentration of hydrogen peroxide in the composition used is too high, the composition container used is automatically emptied, and The method of embodiment 109, comprising automatically producing a new composition to be used.</u><u style="single">[Embodiment 113]</u><u style="single"> Compare the concentration of peroxycarboxylic acid with the expected POAA target concentration and change the operating parameters of the peroxycarboxylic acid generator to the concentration of peroxycarboxylic acid in the high concentration of peroxycarboxylic acid provided by the peroxycarboxylic acid generator. The method according to embodiment 109, wherein the method is adjusted so as to.</u><u style="single">[Embodiment 114]</u><u style="single"> Includes first pretreatment column, first reaction catalyst column, first and second reagent vessels, safety system, reagent conduit, reaction mixture conduit, and peroxy acid conduit.</u><u style="single"> The first and second reagent vessels are in fluid communication with the first pretreatment column via reagent conduits, provided that</u><u style="single"> The first reagent container is configured to contain a liquid oxidant composition and the second reagent container is configured to contain a liquid source of carboxylic acid.</u><u style="single"> Reagent conduit defines a mixing chamber for reagents;</u><u style="single"> The first pretreatment column is in fluid communication with the first reaction catalyst column via the reaction mixture conduit, provided that</u><u style="single"> The first pretreatment column is configured to remove metal ions from the mixture of liquid source of carboxylic acid and oxidant composition.</u><u style="single"> The first reaction catalyst column is configured to catalyze the reaction of the carboxylic acid and oxidant to produce the peroxycarboxylic acid;</u><u style="single"> The first reaction catalyst column is in fluid communication with the storage or use site of the peroxycarboxylic acid composition via a peracid conduit;</u><u style="single"> The safety system includes a processor, a first status sensor and a second status sensor, however.</u><u style="single"> The first status sensor is located in the mixing chamber or on the surface of the mixing chamber and is configured to measure the condition of the reagents.</u><u style="single"> The second condition sensor is located in the first pretreatment column, in the first pretreatment column, or in the reaction mixture conduit near the outlet from the first pretreatment column, and the reagent. Configured for measuring the condition of</u><u style="single"> The processor can determine the difference between the state measured by the first state sensor and the state measured by the second state sensor, and can detect if the difference meets or exceeds a predetermined value. Constructed to provide a signal,</u><u style="single">A device for making peroxycarboxylic acids.</u><u style="single">[Embodiment 115]</u><u style="single"> The device according to embodiment 114, wherein the liquid source of carboxylic acid comprises a liquid source of acetic acid ester or anhydride.</u><u style="single">[Embodiment 116]</u><u style="single"> To provide a liquid composition containing a source of carboxylic acid and an oxidizing agent;</u><u style="single"> Pretreating the liquid composition with a pretreatment column to remove the metal ions from the mixed composition;</u><u style="single"> The state of the liquid composition is measured at i) before pretreatment and ii) at the pretreatment site during the pretreatment period;</u><u style="single"> Find the difference between i) and ii);</u><u style="single"> If the difference meets or exceeds a given value, provide a detectable signal;</u><u style="single"> The pretreated composition is reacted in the presence of a reaction catalyst that can be physically removed from the reaction mixture for making the peroxycarboxylic acid composition;</u><u style="single"> Recovering the peroxycarboxylic acid composition</u><u style="single">A method for making a peroxycarboxylic acid, which comprises.</u><u style="single">[Embodiment 117]</u><u style="single"> The device according to embodiment 116, wherein the source of the carboxylic acid comprises an ester or anhydride of acetic acid.</u></p>