adjustable biocide generator or formulator system

专利摘要:
These are methods of generating perfromic acid by contacting an aqueous oxidizing agent and a source of aqueous formic acid in liquid phase. A system and apparatus for in situ production of the perforic acid chemicals is further disclosed. In particular, a continuous flow reactor is provided to generate perfromic acid at varying rates. Methods of employing the oxidation biocide for various disinfection applications are also disclosed.
公开号:BR112018003971B1
申请号:R112018003971-3
申请日:2016-09-02
公开日:2021-02-17
发明作者:Paul R. Kraus；Benjamin Crew；Junzhong Li；David D. Mcsherry；Ramakrishnan Balasubramanian；Richard Staub；Ariel Chatman Kleczewski；Minh Tran；Catherine Hanson；Irwan Yunus；Jeffery D. Breshears；Brian Paul Brunner
申请人:Ecolab Usa Inc.；
IPC主号:

专利说明:

[0001] [001] The present invention relates to methods of local generation of perfromic acid using a generator or formulated system. The formation of perfromic acid is obtained on site by contacting an aqueous oxidizing agent and an aqueous formic acid in liquid phase under heated turbulent or laminar flow conditions. In particular, a continuous flow reactor is provided to generate perfromic acid at varying rates, which includes almost instantaneous generation. The composition of perfromic acid and / or mixed peracid generated at the site is suitable for providing an oxidation biocide for various disinfection applications. The perfromic acid compositions generated are useful for treating a target, for example, surface (or surfaces) and / or other items used in papermaking, textiles, food or pharmaceutical industry, target water and / or biofilm treatment . BACKGROUND OF THE INVENTION
[0002] [002] Perforic acid (or peroxyphoric acid) is considered an industrially important percarboxylic acid. Perforic acid has an advantageous degree and range of microbiocidal properties compared to other peroxycarboxylic acids, such as peracetic and perproprionic acids, as revealed by both V. Merka et al in J. Hyg. Epidemic. Microbiol. Immunol, 1965 (IX) 220, as well as in US Patent Application 863,098.96.
[0003] [003] Peroxycarboxylic acid compositions are, in general, produced through an acid catalyzed equilibrium reaction. Most of the time, peroxycarboxylic acids are generated in a chemical plant and then sent to customers for use on site. Due to the limited storage stability of peroxycarboxylic acids, peroxycarboxylic acids must be packaged in special receptacles and shipped under strict guidelines from the Department of Transport (DOT). In addition, excess amounts of reagents (for example, acids, oxidizing agents and stabilizers) are present in the compositions during shipment to prevent decomposition. For peroxyphoric acid, however, the inherent instability of the substance in relation to the higher alkyl peracid and the explosive nature of the substance in the concentrate makes it even more challenging to manufacture, store and transport before dilution before use, in a similar way to upper alkyl peracid. Thus, there are needs for the local generation of peroxycarboxylic acids, especially peroxyphoric acid.
[0004] [004] Permic acid is formed by the original reagents and the reaction products form an equilibrium mixture. However, such a mixture can be quite unstable and / or reactive in handling and storage, typically having a relatively short shelf life. The stability of perfromic acid, in comparison to other peroxycarboxylic acids, such as peracetic acid, presents stability challenges of one to two major orders. For example, the duration of storage of perforic acid is on the order of minutes to hours, compared to the duration of storage of peracetic acid, which is from weeks to months. Due to the characteristics of perfromic acid in having significantly lower shelf life stability, there remains a need to provide in situ generation for local use without requiring storage and / or shipping.
[0005] [005] Permic acid is extremely useful and effective in several fields of technology, such as disinfection, despite its instability. Formed from the reaction of hydrogen peroxide and formic acid, it reacts faster and more powerfully than peracetic acid before separating into water and carbon dioxide. Perforic acid is an environmentally friendly oxidation biocide for various disinfection applications. The application areas involve microbial growth control and surface cleaning on a larger industrial scale, such as urban or industrial wastewater purification, or for process water circulation in the pulp and paper industry. These compositions are more applicable, for example, in hospitals, dental surgeries, kitchens and bathrooms to eliminate infectious organisms.
[0006] [006] Perforic acid solutions are highly reactive. If perfromic acid solutions are brought into contact with impurities, such as zinc dust, lead dioxide or sodium azide, they may react violently and decompose. Peripheral acid typically decomposes to carbon dioxide and water within a few hours at room temperature and pressure.
[0007] [007] Typically, formic acid is formed by reacting aqueous formic acid with aqueous hydrogen peroxide through an exothermic reaction in the presence of a strong mineral acid catalyst, such as sulfuric acid. Due to their instability, perfromic acid solutions should be prepared in situ, preferably at the point of use or directly before use depending on the properties of the reagents and reaction points. However, the presence of strong mineral acid, such as sulfuric acid, in pipes can lead to material corrosion and contamination of the process stream.
[0008] [008] Consequently, it is an object of the invention to provide a method for generating perfromic acid in situ without the presence of an acid catalyst, such as a strong mineral acid catalyst.
[0009] [009] An additional object of the invention includes providing a method for generating perfromic acid in situ that employs heat as the only catalyst, without additional chelating and / or stabilizing agents.
[0010] [0010] Yet an additional objective of the invention is to provide a local generating apparatus for a continuous flow reaction with varying rates for the generation of perfromic acid.
[0011] [0011] Additional objectives of the invention include generating both perfromic acid and mixed peracid compositions that include perfumic acid in situ. Other objects, advantages and resources of the present invention will become evident from the report described below taken in combination with the accompanying drawings. BRIEF SUMMARY OF THE INVENTION
[0012] [0012] In one embodiment, the present invention provides an adjustable biocide generator or formulator system for generating local perforic acid formation composition. The generator or formulator system comprises at least one inlet, one pipe length, one heating device and one outlet for dosing a perfromic acid-forming composition. In one aspect, the inlet (or inlets) is in fluid connection with the pipe length and provides reagents to produce perfromic acid in the pipe length. In a further aspect, the reagents comprise a source of formic acid and an oxidizing agent. In an additional aspect, the pipe length is in fluid connection with the outlet to dispense the performatic acid-forming composition.
[0013] [0013] In one embodiment, the present invention provides a method of composing locally generated formic acid formation comprising: providing a source of formic acid at a pipe length at a desired flow rate; supplying an oxidizing agent to said pipe length at a desired flow rate; bringing said source of formic acid into contact with an effective amount of said oxidizing agent within said length of pipe in the presence of a heating device to form a formic acid; delivering said perfromic acid to a downstream process. In a further aspect, the method includes a heating device that provides sufficient heat to raise the temperature of the solution within the length of a pipe to a temperature that does not exceed 180 ° C and in which said heating device is a cartridge (for example, example) contained with said barrel length and in which the difference between said barrel inner diameter and said cartridge diameter is less than about 12.7 cm (5 inches). In a further aspect, the method includes cooling said perfromic acid to a temperature at or below the freezing point. In yet an additional aspect, the method includes measuring variables that include conductivity, temperature, product levels, concentrations, IR / UV / VIS spectroscopy, pressure, perfromic acid and / or oxidant concentrations, and / or flow rate and controlling the flow rate. method with the use of control software for the operation of said apparatus to generate a composition of performatic acid formation inserted by user or system and said desired flow rate of said composition of performatic acid formation for local generation. In a further aspect, the present invention includes perfromic acid compositions formed using the method of the invention.
[0014] [0014] Although multiple modalities are disclosed, still other modalities of the present invention will become apparent to those skilled in the art from the detailed description below, which shows and describes the illustrative modalities of the invention. Consequently, the drawings and the detailed description should be considered as illustrative in nature and not restrictive. BRIEF DESCRIPTION OF THE DRAWINGS
[0015] [0015] Figure 1 shows a schematic diagram of an adjustable biocide formulating apparatus operated by a user or controller according to an embodiment of the invention.
[0016] [0016] Figures 2 to 4 show diagrams of exemplary modalities of an adjustable biocide formulating apparatus according to the invention.
[0017] [0017] Figure 5 shows the modeling of fluid flow through the reactor according to a modality of the invention, which indicates a correlation between flow rates, pipe diameter and cartridge temperature.
[0018] [0018] Figure 6 shows the relationship between the temperature of the fluid volume cartridge heater film and the flow rate according to an embodiment of the invention.
[0019] [0019] Figure 7 shows the effect of reagent inlet temperature and heater power according to an embodiment of the invention.
[0020] [0020] Figure 8 shows the conductivity measured from two independent experiments designed to generate formic acid by mixing formic acid and hydrogen peroxide according to one embodiment of the invention.
[0021] [0021] Figure 9 shows a diagram of an exemplary embodiment of an adjustable biocide formulating apparatus according to the invention that employs a downward flow of oxidizing agent for the generation of perfromic acid.
[0022] [0022] Figure 10 shows a diagram of an exemplary embodiment of an adjustable biocide formulating apparatus according to the invention that employs a downward flow of mixed reagents for the generation of perfromic acid.
[0023] [0023] Figure 11 shows experimental results that demonstrate iodometric titration of perfromic acid generated by an adjustable biocide formulating apparatus according to an embodiment of the invention.
[0024] [0024] Figure 12 shows a diagram of an exemplary embodiment of an adjustable biocide formulating apparatus according to the invention.
[0025] [0025] Figure 13 shows experimental results that demonstrate microbial efficacy of PFA generated according to an exemplary embodiment of the invention.
[0026] [0026] Figure 14 shows experimental results that demonstrate FeS of oxidation of PFA to iron oxide according to an exemplary embodiment of the invention.
[0027] [0027] Various embodiments of the present invention will be described in detail with reference to the drawings, in which similar reference numerals represent similar parts in the course of the various views. Reference to various modalities does not limit the scope of the invention. The Figures represented in the present document are not limitations to the various modalities according to the invention and are presented for exemplary illustration of the invention. DETAILED DESCRIPTION OF THE INVENTION
[0028] [0028] The present disclosure relates both to forming or generating systems of perforic acid for generating local perforic acid, which includes mixed peracid compositions comprising perforic acid, as well as methods of producing and using such compositions. The compositions and systems for producing the compositions disclosed herein have many advantages over conventional systems and methods for producing perfromic acid compositions. For example, the system allows formulation controlled by user or local system, which eliminates the step of storing unstable perfromic acid compositions. In addition, there are several advantages of the compositions, which include having significantly lower reagent inserts, increased stability, and the ability to be generated in situ or on site.
[0029] [0029] The modalities of this invention are not limited to particular methods and systems for local generation of perfromic acid, which vary and are understood by skilled individuals. It should also be understood that all terminologies used in this document are only for the purpose of describing particular modalities and are not intended to be limiting in any way or in any scope. For example, as used in this specification and the appended claims, the singular forms "one" "one" and "a / o" may include plural references unless the context clearly indicates otherwise. In addition, all units, prefixes and symbols can be denoted in their form accepted by the SI. Numeric ranges declared within the specification are inclusive of the numbers that define the range and include each integer within the defined range.
[0030] [0030] In order that the present invention can be more readily understood, certain terms are defined first. Unless otherwise defined, all technical and scientific terms used in this document have the same meaning as commonly understood by a person of ordinary skill in the technique to which the modalities of the invention belong. Many methods and materials similar, modified or equivalent to those described in this document can be used in the practice of the modalities of the present invention without undue experimentation; preferred materials and methods are described in this document. In describing and claiming the modalities of the present invention, the titles provided are not limitations on the modalities of the invention and the following terminology will be used in accordance with the definitions set out below.
[0031] [0031] The term “about” as used in this document, refers to the variation in numerical quantity that can occur, for example, through typical measurement procedures and liquid handling used for the production of concentrates or solutions in use worldwide real; through inadvertent error in these procedures; through differences in the manufacture, source, or purity of the ingredients used to produce the compositions or to conduct the methods; and the like. The term "about" also encompasses amounts that differ due to different equilibrium conditions for a composition that results from a particular initial blend. Modified or not by the term "about", the claims include equivalents to quantities.
[0032] [0032] The term "cleaning", as used in this document, means to perform or assist in soil removal, bleaching, reduction of microbial population or combinations thereof.
[0033] [0033] As used herein, the term "disinfectant" refers to an agent that eliminates all vegetative cells that include well-recognized pathogenic microorganisms, using the procedure described in A.O.A.C. Use Dilution Methods, Official Methods of Analysis of the Association of Official Analytical Chemists, paragraph 955.14 and applicable sections, 15th edition, 1990 (EPA Guideline 91-2). As used herein, the term "high level disinfection" or "high level disinfectant" refers to a compound or composition that eliminates substantially all organisms, except high levels of bacterial spores, and is carried out with a chemical germicide authorized for marketing as a sterilizer by the Food and Drug Administration (FDA). As used herein, the term “intermediate level disinfection” or “intermediate level disinfectant” refers to a compound or composition that eliminates mycobacteria, most viruses and bacteria with a chemical germicide registered as a tuberculocide by the Environmental Protection (EPA). As used herein, the term "low level disinfection" or "low level disinfectant" refers to a compound or composition that eliminates most viruses and bacteria with a chemical germicide registered as a hospital disinfectant by the EPA .
[0034] [0034] As used in this document, the phrase “food processing surface” refers to a surface of a tool, a machine, equipment, a structure, a building or the like that is employed as part of a processing, preparation activity or food storage. Examples of food processing surfaces include surfaces of food preparation or processing equipment (for example, cutting equipment, canning or conveying, which includes gutters), food processing articles (for example, utensils, tableware, washing articles and bar glasses), and of floors, walls, or installations of structures in which food processing takes place. Food processing surfaces are found and used in air circulation systems against food spoilage, aseptic packaging hygiene, refrigeration and food refrigerant cleaners and sanitizers, article washing sanitizers, bleach cleaning and sanitizer, food packaging materials, cutting board additives, three-compartment sink sanitization, drink coolers and heaters, meat cooling or scorching waters, automatic dish sanitizers, sanitizing gels, cooling towers, food processing antimicrobial mantle sprayers, and lubricants, oils and rinse additives of not so low aqueous concentration of food preparation.
[0035] [0035] As used herein, the phrase “food product” includes any food substance that may require treatment with an antimicrobial agent or composition and that is edible with or without additional preparation. Food products include meat (for example, red meat and pork), seafood, poultry, fruit and vegetables (for example, fruits and vegetables), eggs, live eggs, egg products, ready-to-eat foods, wheat, seeds, roots, tubers, leaves, stems, corn, flowers, buds, condiments or a combination thereof. The term “fruit and vegetables” refers to food products, such as fruits, vegetables, plants or plant-derived materials, which are typically sold uncooked and usually unpackaged, and which can sometimes be eaten raw.
[0036] [0036] As used in this document, it should be understood that the term "fouling" means the undesirable presence of or any deposition of any organic or inorganic material in the applicable chemical composition or substance.
[0037] [0037] As used herein, the term "exempt" or "substantially exempt" refers to a composition, mixture or ingredient that does not contain a particular compound or to which a particular compound or a compound containing the particular compound has not been added. If the particular compound is present through contamination and / or use in a minimum amount of a composition, mixture or ingredients, the amount of the compound must be less than about 3% by weight. More preferably, the amount of the compound is less than 2% by weight, less than 1% by weight and, most preferably, the amount of the compound is less than 0.5% by weight.
[0038] [0038] As used in this document, the term "microorganism" refers to any non-cellular or unicellular organism (including colonial). Microorganisms include all prokaryotes. Microorganisms include bacteria (which include cyanobacteria), spores, lichens, fungi, protozoa, viruses, viroids, viruses, phages and some algae. As used in this document, the term “microbe” is synonymous with microorganism.
[0039] [0039] As used herein, the terms "mixed" or "mixture" when used in relation to "formic acids" or "formic acid composition" refer to a composition or mixture that includes formic acid and at least one other peroxycarboxylic acid.
[0040] [0040] As used in this document, the terms "perfromic acid" or "peroxyphoric acid" refer to an acid that has the formula of CH2O3 and the structure:
[0041] [0041] Generally, formic acid is generated by combining formic acid and hydrogen peroxide under acidic conditions to yield formic acid and water (as shown) and a person skilled in the art will determine that additional carboxylic acids and percarboxylic acids could be additionally included. in the generation steps according to the present invention. HCOOH + H2O2 ⥨ HCO2OH + H2O
[0042] [0042] As used in this document, the term “sanitizer” refers to an agent that reduces the number of bacterial contaminants to safe levels as assessed by public health requirements. In one embodiment, sanitizers for use in this invention will provide at least a 99.999% reduction (5 log reduction). These reductions can be assessed using a procedure established in Germicidal 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 ). According to this reference, a sanitizer must provide a reduction of 99.999% (reduction of order of 5 log) within 30 seconds at room temperature, 25 +/- 2 ° C, in relation to several test organisms.
[0043] [0043] For the purpose of this patent application, the microbial reduction of success is obtained when the microbial populations are reduced by at least about 50%, or by significantly more than when obtained by washing with water. Larger reductions in microbial population provide greater levels of protection.
[0044] [0044] The differentiation of “-cida” or “-static” antimicrobial activity, the definitions that describe the degree of effectiveness and the official laboratory protocols for measuring this effectiveness are considerations for understanding the relevance of antimicrobial agents and compositions. Antimicrobial compositions can affect two types of microbial cell damage. The first is an irreversible and lethal action that results in complete microbial cell destruction or incapacitation. The second type of cell damage is reversible, so that if the organism becomes free of the agent, it can multiply again. The first is called microbiocide and the last, microbiostatic. A sanitizer and disinfectant are, by definition, agents that provide antimicrobial or microbiocidal activity. In contrast, a preservative is, in general, described as an inhibitory or microbiostatic composition.
[0045] [0045] As used in this document, the term "article" refers to items, such as utensils for food and cooking, crockery, and other hard surfaces, such as showers, sinks, toilets, bathtubs, countertops, windows, mirrors, transport vehicles and floors. As used in this document, the term “article washing” refers to the washing, cleaning or rinsing of articles. Articles also refer to items made of plastic. The types of plastics that can be cleaned with the compositions according to the invention include, but are not limited to, those that include polycarbonate (PC) polymers, acrylonitrile-butadiene-styrene (ABS) polymers and polysulfone (PS) polymers. Another exemplary plastic that can be cleaned using the compounds and compositions of the invention includes polyethylene terephthalate (PET).
[0046] [0046] The term "weight percent", "weight percent", "weight percent", "weight percent" and variations thereof, as used in this document, refers to the concentration of a substance such as weight of that substance divided by the total weight of the composition and multiplied by 100. It is understood that, as used here, “percent”, “%” and the like are intended to be synonymous with “weight percent”, “weight% ", etc. MODALITIES OF THE INVENTION - PERFORMIC ACID CHEMICAL SUBSTANCES
[0047] [0047] In accordance with an embodiment of the invention, methods and apparatus for generating local perforic acid chemicals for use as cleaning agents which include, for example, antimicrobial applications, bleaching applications and other cleaning and anti-flaking applications . The methods and apparatus according to the invention have the capacity to generate performatic acid chemicals locally according to user specifications. As noted in this document, it is further understood that performatic acid chemicals include mixed performatic acid chemicals. The invention overcomes the shortages of commercially available perfromic acid by providing user-specific formulations with improved performance efficacy. In addition, the methods and apparatus use heat as the reaction catalyst, which thereby beneficially reduces the costs and risks associated with the transport of active chemicals, provides active chemicals with increased storage durations and reduced waste of substances active chemicals as a result of the production of perfromic acid identified by a local user according to the invention.
[0048] [0048] The methods and apparatus of the present invention overcome the significant limitations of conventional methods of generating perfromic acid, typically catalyzed acid equilibrium reactions. The methods and apparatus of the present invention overcome the many disadvantages to such conventional methods, which include, but are not limited to, eliminating the use of excess amounts of reagents and shipping hazardous conditions.
[0049] [0049] Although an understanding of the mechanism is not necessary to practice the present invention and although the present invention is not limited to any particular mechanism of action, it is contemplated that, in some embodiments, the benefits provided in accordance with the invention result in from the use of heat as the only catalyst in the methods and apparatus of the present invention for generating local perforic acid. Beneficially, the formic acids reacted according to the invention are obtained in greater amounts than in equilibrium chemical substance in which greater amounts of oxidizing agent, for example, hydrogen peroxide, and other reagents, would be present. According to the present invention, an aqueous solution of the formic acid (or formic acids) produced contains a relatively higher concentration of formic acid (or formic acids) when compared to an unreacted oxidizing agent, for example, a peroxide component. hydrogen. Preferably, the average perfromic acid concentration is at least 1% by weight, at least 2% by weight, at least 3% by weight, at least 4% by weight, at least 5% by weight, at least 6% by weight at least 7% by weight, at least 8% by weight, at least 9% by weight, at least 10% by weight, at least 11% by weight, at least 12% by weight, at least 13% by weight, at least 14% by weight or at least 15% by weight. More preferably, the average perfromic acid concentration is at least 2% by weight and, more preferably, the average perfromic acid concentration is at least 5.5% by weight. This is significantly advantageous for the antimicrobial application and other cleaning applications disclosed in the present document as desirable according to the modalities of the invention. However, as a person skilled in the art will observe, the average perfromic acid concentration will vary depending on heating, flow rate, temperatures, pressures, reagent concentration, etc.
[0050] [0050] Instead of providing a perfromic acid composition in an equilibrium mixture, the in situ generation of the perfromic acid composition allows the perfromic acid to be stoichiometrically produced by selecting the composition of the starting materials. The in situ systems of the present invention, therefore, generate higher concentrations of formic acids than are available in equilibrium systems. In particular, according to the invention, the systems generate higher concentrations of perfromic acid and lower concentrations of hydrogen peroxide (e.g., unreacted reagents) than those obtained in equilibrium systems. Preferably, the average perfromic acid concentration is at least 1% by weight. More preferably, the average perfromic acid concentration is at least 5% by weight and, more preferably, the average perfromic acid concentration is at least 5.5% by weight. Preferably, the average hydrogen peroxide concentration is less than 10% by weight. More preferably, the average hydrogen peroxide concentration is less than 5% by weight and, more preferably, the average hydrogen peroxide concentration is less than 1% by weight. However, as a person skilled in the art will observe, the average perfromic acid and / or hydrogen peroxide concentration will vary depending on heating, flow rate, temperatures, pressures, reagent concentration, etc.
[0051] [0051] In some respects, the methods of the present invention generate perfromic acid (or perfomic acids) without the need for additional chelating and / or stabilizing agents, although such agents are compatible with these systems, they are not required components. Instead, chelating and / or stabilizing agents are suitable additional functional ingredients that can be included in the methods of generating perfromic acid and / or added after the completion of the reaction that forms perfromic acid compositions prior to use and / or during the generation of a solution for use of the perfromic acid compositions.
[0052] [0052] In some respects, the present invention requires acidic conditions. Preferably, in some embodiments, the pH of the system does not exceed 7. More preferably, the pH does not exceed 5. Most preferably, the pH does not exceed 3. Even more preferably, the pH does not exceed 2.
[0053] [0053] Beneficially, the generated perfromic acid compositions according to the invention can be combined or additionally produced in combination with additional chemicals, such as, for example, equilibrium chemicals, such as additional peroxycarboxylic acid compositions. FUNCTIONAL INGREDIENTS ELIMINATED
[0054] [0054] Unlike compositional acid compositions based on conventional equilibrium, the compositions disclosed in this document are formed from an unbalanced reaction. In addition, the composition disclosed in this document can be used immediately after generation. Thus, many of the additional ingredients required in balance-based compositions do not need to be included in the present compositions. In some embodiments, stabilizing agents are preferred for certain compositions according to the invention and provide benefits. However, beneficially, the use of unbalanced chemical substance according to the present invention optionally provides that the compositions can be free of, or substantially free of, a stabilizing agent.
[0055] [0055] Stabilizing agents are commonly added to equilibrium perfromic acid compositions to stabilize perfromic acid and hydrogen peroxide and prevent decomposition of these constituents within the compositions. Various embodiments of the invention do not require the use of at least one or more of such stabilizing agents. Examples of stabilizing agents can include, for example, surfactants, couplers, hydrotropes, acid catalysts and the like that are conventionally used in equilibrium perfromic acid compositions to stabilize and improve the shelf life of the composition.
[0056] [0056] Additional examples of stabilizing agents include, for example, chelating or sequestering agents. Such sequestrants include, but are not limited to, organic chelating compounds that sequester metal ions in solution, particularly transition metal ions. Such sequestrants include complexing agents of polyphosphonic acid, organic amino or hydroxy (in both acid and soluble salt forms), carboxylic acids (for example, polymeric polycarboxylate), hydroxycarboxylic acids, aminocarboxylic acids or heterocyclic carboxylic acids, for example, pyridine-2 acid , 6-dicarboxylic (dipicolinic acid). Dipicolinic acid, 1-hydroxy ethylidene-1,1-diphosphonic acid (CH3C (PO3H2) 2OH) (HEDP) are additional examples of stabilizing agents.
[0057] [0057] Additional examples of stabilizing agents commonly used in balancing chemical to stabilize perfromic acid and hydrogen peroxide and / or prevent premature oxidation of the composition include phosphonic acid or phosphonate salt. Phosphonic acids and phosphonate salts include HEDP; ethylenediamine tetrakis methylenephosphonic acid (EDTMP); diethylenetriamine pentaquis methylenophosphonic acid (DTPMP); cyclohexane-1,2-tetramethylene phosphonic acid; amino [tri (methylene phosphonic acid)]; (ethylene diamine acid [tetra methylene phosphonic)]; 2-phosphene butane-1,2,4-tricarboxylic acid; or salts thereof, such as alkali metal salts, ammonium salts, or alkyl amine salts, such as mono-, di- or tetra-ethanolamine salts; picolinic acid, dipicolinic or mixture thereof. In some embodiments, organic phosphonates, for example, HEDP, are well known as used stabilizing agents.
[0058] Exemplary commercially available food additive chelating agents include phosphonates sold under the trade name DEQUEST® which include, for example, 1-hydroxyethylidene1,1-diphosphonic acid, available from Monsanto Industrial Chemicals Co., St. Louis, MO, as DEQUEST® 2010; amino (tri (methylenephosphonic acid)), (N [CH2PO3H2] 3), available from Monsanto as DEQUEST® 2000; ethylenediamine [tetra (methylenephosphonic acid)] available from Monsanto as DEQUEST® 2041; and 2-phosphonobutane-1,2,4-tricarboxylic acid available from Mobay Chemical Corporation, Inorganic Chemicals Division, Pittsburgh, PA, as Bayhibit AM. In addition, the exemplary scavenger can be or include aminocarboxylic acid type scavenger. Suitable aminocarboxylic acid type sequestrants include the alkali metal acids or salts thereof, for example, amino acetates and salts thereof. Suitable aminocarboxylates include Nhydroxyethylaminodiacetic acid; hydroxyethylenediaminetetraacetic acid, nitrilotriacetic acid (NTA); ethylenediaminetetraacetic acid (EDTA); Nhydroxyethyl-ethylenediaminatriacetic acid (HEDTA); diethylenothiaminapentaacetic acid (DTPA); and alanine-N, N-diacetic acid; and the like; and mixtures thereof. Additional sequestrants include polycarboxylates, which include, for example, polyacrylic acid, maleic / olefin copolymer, acrylic / maleic copolymer, polymethacrylic acid, acrylic acid-methacrylic acid copolymers, hydrolyzed polyacrylamide, hydrolyzed polyacrylamide, polysaccharide, hydrolyzed polysaccharide, polymerized hydrolyzed, hydrolyzed polymethacrylonitrile, hydrolyzed acrylonitrile-methacrylonitrile copolymers, polymalleic acid, polyfumaric acid, acrylic and itaconic acid copolymers, phosphine polycarboxylate, acid or salt forms, mixtures thereof and the like.
[0059] [0059] Additionally, unlike conventional equilibrium based perforic acid compositions, the present compositions can also be free of, or substantially free of, surfactants. This is especially advantageous for compositions that incorporate C5-C18 peroxycarboxylic acids. This means that, under perhydrolysis conditions, the peroxycarboxylic acid C5-C18 anions generated are soluble in water. If anions (for example, compositions that form peroxycarboxylic acid) are acidified for end-use applications, the concentrations of peroxycarboxylic acids are below the water solubility limit of peroxycarboxylic acids. Thus, couplers are not necessary to couple peroxycarboxylic acids in solution. ADDITIONAL FUNCTIONAL INGREDIENTS
[0060] [0060] The compositions can also include additional functional ingredients. Additional functional ingredients suitable for use in the present compositions include, but are not limited to, acidulants, hydrotropes, dispersants, antimicrobial agents, optical markers, solidifying agent, aesthetic enhancing agent (i.e., coloring (e.g., pigment), odorous, or perfume), among any number of constituents that can be added to the composition. For example, functional ingredients suitable for various embodiments of the invention are hydrotropes, which may be desired for the production of clear or dispersing compositions that are more effective in producing homogeneous dispersions. Such adjuvants can be pre-formulated with the present compositions or added to the compositions after formation, but before use. In addition, the present invention may include optional use of an acid source both before the reaction and after the completion of the reaction. As a person skilled in the art would observe, the use of an acid source before the reaction would increase the reaction kinetics and / or decrease the heating requirements, while the addition of an acid source after the reaction would boost the pH of the perforic acid below formic acid pKa, which in this way increases the stability of the composition. The compositions can also contain any number of other constituents as required by the application, which are known and which can facilitate the activity of the present compositions.
[0061] [0061] Exemplary additional functional ingredients are disclosed in US Patent Applications Serial No. 14 / 972,308 entitled “Mixture Comprising Formic Acid Hydrogen Peroxide, Methods of Generating the Mixture, and Use of the Mixture for Antimicrobial Control” and 14 / 973,389 entitled “In Situ Generation of Peroxyformic Acid through Polyhydric Alcohol Formate”, which are incorporated in this document as a reference in their entirety.
[0062] [0062] In some embodiments, perfromic acid compositions may include a stabilizing agent, which is not required for formulation of perfromic acid compositions, but can provide benefits for mixed perfromic acid compositions according to the invention. Such stabilizing agents which include, for example, phosphonic acids and phosphonate salts, such as HEDP, may be particularly suitable for use with mixed perfromic acid compositions for use at high temperatures. SYSTEM FOR PRODUCTION OF LOCAL PERFORMIC ACID COMPOSITIONS
[0063] [0063] In some respects, the present invention relates to an adjustable generator apparatus or system for the local generation of perforic acid chemicals. The system produces perfromic acid-forming compositions according to the disclosure presented in this document. The perfromic acid-forming compositions refer to the generation of perfromic acid (which includes mixed peracids that comprise perfromic acid) in situ, in an unbalanced reaction.
[0064] [0064] In some respects, the system for local generation of perfromic acid-forming compositions may comprise, consist of and / or consist essentially of a device that includes one port (or at least two ports, or at least three ports), a pipe length, at least one heating device and an outlet for dosing the chemical substance generated from the pipe length. In some aspects, the system may optionally include a mixer or mixing device within the length of the pipe. In some ways, the system may optionally include a cooling loop or segment. In some respects, the system may optionally include at least one measuring device. In some respects, the system may optionally include a control system. In some respects, the system may optionally include safety devices. INPUT
[0065] [0065] In some respects, the invention consists of at least one inlet through which reagents are supplied at pipe length. In modalities where only one entry is present, the reagents are mixed before entry.
[0066] [0066] In additional embodiments of the invention, at least two inlets are present, in which each reagent enters the length of the barrel through its individual inlet. In such embodiments that have at least two inlets, the inlets can be separated by a pipe length to allow sequential addition of the reagents. In some embodiments, a first entry doses the formic acid (and mixtures of formic acid) to the reactor and a second entry doses the source of hydrogen peroxide to the reactor. In such a mode, one of the inlets can additionally be used to purge the system with water. In embodiments of the invention, the source of formic acid and the oxidizing agent are introduced to the pipe length in a ratio from about 1: 1 to about 5: 1, preferably from about 2: 1 to about 40: 1 and, preferably, about 20: 1.
[0067] [0067] In additional embodiments of the invention, at least three inlets are present, in which each reagent enters the length of the barrel both through its individual inlet and through a third inlet used for purging the system with water and adding an inhibitor of corrosion, biocide or functional component additional to the pipe length. In such embodiments that have at least three inlets, the inlets may be separated by a pipe length to allow for sequential addition of the reagents. In some embodiments, a first entry doses the formic acid to the reactor, a second entry doses the hydrogen peroxide source to the reactor and a third entry allows water to purge through the system and / or provides additional components, such as a corrosion inhibitor or biocide. Alternatively, a third inlet can be placed upstream of the first and / or the second inlet in order to purge the inlets and the rest of the system with water. Still in additional embodiments of the invention, at least four inlets are present, in which each reagent enters the length of the barrel either through its individual inlet or through a third inlet used for an additional peroxycarboxylic acid, and a fourth inlet used for purging the water system, which adds a corrosion inhibitor, biocide or additional functional component to the pipe length. In such embodiments that have at least four inlets, the inlets may be separated by a pipe length to allow for sequential addition of the reagents.
[0068] [0068] In embodiments of the invention, the source of formic acid and the oxidizing agent are introduced to the length of the pipe in a ratio from about 1: 1 to about 5: 1, preferably from about 2 : 1 to about 40: 1 and, preferably, about 20: 1.
[0069] [0069] In a further aspect of the invention, the inlet temperature is approximately that of the ambient temperature. However, as a person skilled in the art would observe, a higher inlet temperature would reduce or eliminate the power required for heating and, therefore, reduce the risk of exceeding the decomposition temperature of perfromic acid. In some ways, the starters may have different temperatures. For example, in modalities in which formic acid and the source of hydrogen peroxide are dosed to the system via separate inputs, the input of formic acid source may have a higher inlet temperature than the input of hydrogen peroxide.
[0070] [0070] According to the modalities of the invention, the direction of flow through the system can be upward, downward or lateral. However, as a person skilled in the art would observe, the flow direction can be dependent on both process and current variables, such as density, temperature and pressure, as well as external mechanical considerations, such as pumping power. In a preferred embodiment of the invention, the second inlet that doses the oxidizing agent to the system has a downward flow.
[0071] [0071] In a further aspect of the invention, inlets may need to undergo degassing in order to remove dissolved gases from liquid streams. As a person skilled in the art would note, degassing may need to occur for a number of reasons and without trying to be limited to a particular theory of invention, gasification can occur in this application to remove dissolved gases from liquids that are possibly sensitive to air or oxygen or to prevent cavitation of pumping systems in a downstream process.
[0072] [0072] In some embodiments of the invention, dilution of the reagents does not occur. PIPE LENGTH
[0073] [0073] In some aspects of the invention, the reaction takes place within a length of pipe that meets the hydraulic requirements of the performatic acid reaction kinetics. As mentioned in this document, the pipe refers, in general, to the length of a body within which the reaction occurs and is contained. It is understood that the pipe includes a length of tubing or other suitable receptacle for containing the reaction flow for the perfromic acid reaction kinetics according to the modalities of the invention. Although not intended to be limited by a particular theory of the invention, the kinetics of the reaction, according to the invention, are dependent on pH, concentration, flow rate and / or temperature, and the reaction begins to produce yield in the order of seconds to minutes. In some aspects of the invention, the reaction can produce at least about 2% perforic acid instantly, at least about 4% perforic acid within 1 minute, at least about 8% perforic acid within 2 minutes and at least minus 15% perfromic acid within 30 minutes. Although not intended to be limited by a particular theory of the invention, the reaction kinetics, according to the invention, are dependent on pH, concentration, flow rate and / or temperature, and the reaction can obtain maximum yield in the order of seconds to minutes. In some aspects, the reaction can achieve maximum perfromic acid yield in about 15 seconds, in about 30 seconds, in about 1 minute or in about 2 to about 5 minutes.
[0074] [0074] The pipe length can be designed in a variety of ways, which includes, for example, shape, size, temperature and material. According to an embodiment of the invention, the pipe length can be of a given internal diameter and is constructed of a material that is not readily corroded and / or damaged by the presence of formic acid, hydrogen peroxide and / or perfromic acid (or formic acids). According to additional modalities, the pipe length is constructed of a material that is not readily corroded and / or damaged by the presence of formic acid, hydrogen peroxide, formic acid (or formic acids), additional peracids and corresponding carboxylic acids, and / or additional functional ingredients, such as optional stabilizers and additional functional ingredients within the formulation for generating perfromic acid.
[0075] [0075] In some modalities, the length of pipes does not include, for example, copper, chromium, brass and / or iron. Certain varieties of stainless steel should also be avoided, for example, SS304. In a preferred embodiment of the invention, the pipe length is constructed from SS316 and / or SS316L. In a preferred embodiment of the invention, the pipe length is constructed from Polytetrafluoroethylene (PTFE) which is a synthetic tetrafluoroethylene fluoropolymer. However, a person skilled in the art will note that other suitable materials are available.
[0076] [0076] Generally, the pipe length is not effectively limited by system pressure due to the open system design of the generators according to the modalities of the invention. However, it is desirable that the pipe can be designed to accommodate the potential occurrence of an uncontrolled reaction based on the pipe material. Preferably, the pipe is designed to accommodate pressures of at least 20 PSI, at least 40 PSI, at least 50 PSI, at least 100 PSI, at least 500 PSI, at least 1,000 PSI, at least 1,000 PSI, at least 2,000 PSI, or greater, which includes all the tracks in them. In one aspect, as a person skilled in the art will determine, the pressure of the system is controlled so as not to exceed the burst pressure of any material employed for the length of the pipe of the generator or apparatus of the invention. Beneficially, additional components of the generator or apparatus may optionally include pressure relief valves, rupture discs or the like to control the pressure of the open system.
[0077] [0077] In some aspects of the invention, flow through the pipe occurs at a rate of about 0.1 ml / min to about 100 ml / min, preferably about 10 ml / min to about 50 ml / min preferably about 20 ml / min to about 40 ml / min. In one aspect of the invention, the highest flow rates can be obtained using the apparatus in parallel. In one aspect of the invention, higher flow rates can be achieved by turbulent flow systems. However, in some aspects, laminar flow systems are provided and can be combined with a mixer or mixing device contained within the pipe length. In one aspect of the invention, it is preferred that the flow through the pipe has a laminar flow pattern, that is, the flow has a Reynolds number of less than about 2,040 in order to allow uniform heating.
[0078] [0078] In some embodiments, the length of pipes can be increased to improve the residence time of the reaction for the generation of peroxyphoric acid in the generator according to the invention. In an exemplary embodiment, the length of the pipes can be at least 0.3 m (1 foot), at least about 3.05 m (10 feet), at least about 15.24 m (50 feet), or at least least about 27.43 m (90 feet). In one embodiment, a spiral length of pipes provides increased length and residence time for the reaction without taking up additional space for the generator pipe length. These and other modifications are included within the scope of the disclosure. HEATING DEVICE
[0079] [0079] In one aspect of the invention, heat is supplied to the system through the use of at least one heating device. In a further aspect of the invention, heat is supplied to the system through the use of at least two heating devices. Suitable heating devices include, for example, cartridge, heat exchanger, heat blanket, steam jacket, solar panels, steam preheating, an electrical source, a heat wrap or combinations thereof, each of which can be referred to in this document as a heating device.
[0080] [0080] In a preferred mode of the system, heat is supplied to the system in an amount sufficient to raise the temperature of the reagents to accelerate the reaction and at a temperature that does not exceed the temperature of decomposition of perfromic acid, or about 200 ° C . Most preferably, the heat is supplied to the system in an amount sufficient to raise the temperature of the reagents to a temperature that does not exceed 180 ° C. In one aspect, the increase in temperature will increase the reaction rate, however, as a person skilled in the art will determine, the stability of perfromic acid should not be compromised by increasing the temperature, which includes at a temperature that does not exceed 200 ° C .
[0081] [0081] In some aspects of the invention, the location of the heating device (or heating devices) is within a pipe section or sections. In some aspects, the location of the heating device (or heating devices) is involved in insulation to eliminate the amount of heat lost to the environment, which can be inside and / or outside the pipe length. In such aspects, the insulation heating device may cover all or a portion of the pipe length.
[0082] [0082] In a preferred aspect, a heating device includes a cartridge located within the barrel length. Such a cartridge has a smaller diameter than the inner diameter of the barrel. According to a preferred embodiment of the invention, it is preferable to maintain the difference between the diameter of the cartridge and the internal diameter of the barrel less than about 12.7 cm (5 inches), more preferable, less than about 7.62 cm ( 3 inches) and, more preferably, less than about 4.45 cm (1.75 inches). In addition, the system has a given cross-sectional area that is available for heat transfer, defined as the internal cross-sectional area of the pipe minus the cross-sectional area of the cartridge heater. However, a person skilled in the art will note that the ideal area available for heat transfer will depend on the temperature of the inlet (or inlets), the flow rate, the length of the heater, etc. Although not intended to be limited by a particular theory of the invention, a larger cross-sectional area is feasible with a lower flow rate due to the fact that the heat transfer rate is lower, which results in a lower temperature on the heater surface cartridge. In a further embodiment of the invention, heaters can be employed in series or in parallel in order to minimize the temperature of the heater. In a further embodiment of the invention, the heat supplied to the system is controlled by means of an electronic control system.
[0083] [0083] In some aspects of the present invention, where the heating device is a cartridge, the available volume of the pipe is affected. The available volume is, therefore, defined as the volume retained inside the pipe at a given time minus the volume occupied by the heating cartridge. In a preferred embodiment, the volume of the system is increased by using systems in parallel instead of increasing the size and / or volume of the pipe.
[0084] [0084] In a further aspect of the invention, uniform heating of the reagents within the length of the pipe is desired, such uniform heating being influenced by the radial distance from the outside of the heater surface to the inside surface of the pipe, in which a greater distance leads to an upper gradient, and the length of the heating zone, where the longer contact with the heater leads to a lower gradient. As a person skilled in the art will observe, these influences have inverse effects on the heat gradient and will thus observe the weight of these influences when determining the dimensions of the heating devices.
[0085] [0085] In a further aspect of the invention, uniform heating of the reagents within the barrel length is not feasible and / or desired. In some embodiments, phased heating can be employed in such a way that, in a first section of the pipe length, the temperature of the reagent (or reagents) is increased by a desired increment (for example, 5 to 10 degrees Celsius), thereafter , in a second section of the barrel length, the temperature of the reagent (or reagents) is increased by a desired increment (for example, 5 to 10 degrees Celsius) and so on.
[0086] [0086] In some aspects of the invention, the power required by the heating device and attached pumps, preferably, does not exceed about 100 watts for flow rates of 50 ml / min. More preferably, the power does not exceed 80 watts and, more preferably, the power does not exceed 50 watts.
[0087] [0087] The heating can also be controlled, regardless of the heater power, through control cycles that involve cycles of time in which the heater is turned on for cycles of time. In one aspect, controlled cycles can include the heater turned on for about 10 to 100% of the generator cycle. In some embodiments, time cycles can be from about 2 seconds to about 100 seconds. In another aspect, the heating can also be controlled by PID loops with a proportionality constant that directly correlates to the flow rate. These and other modifications are included within the scope of the disclosure. EXIT
[0088] [0088] In a preferred aspect of the present invention, an outlet is present. In one aspect of the invention, the outlet supplies the perforic acid chemicals to a downstream process as desired by the controller and / or user. In one aspect, the outlet supplies the perforic acid chemicals to a storage reservoir. In one aspect, the outlet supplies the perforic acid chemicals to a cooling system. In one aspect of the invention, the concentration of perfromic acid at the outlet is at least 1% by weight, more preferably, at least 5% by weight at the outlet. MIXER
[0089] [0089] In a preferred aspect of the present invention, at least one mixer or mixing device is present within the pipe length. The mixing or mixing device can include any shapes suitable for the mixer or mixing device, such as a rotor or any type of static mixer. In some respects, the mixer or mixing device is present at the pipe length at a downstream point from the addition of the hydrogen peroxide source. In such an embodiment, the combined reagents of at least formic acid and the hydrogen peroxide source are combined by mixing. As a person skilled in the art will determine, under laminar flow conditions it is desirable to have a mixer or mixing device. However, a system designed to provide turbulent flow does not require a mixer or mixing device. In some embodiments, both laminar and turbulent flow systems employ a mixer or mixing device. COOLING SYSTEM
[0090] [0090] In another aspect of the invention, the system may include a cooling system or a cooling loop / segment in the reaction vessels. A cooling system can be in combination with a safety mechanism and / or a system measuring device. It may be desirable to have system components under temperature controls. As a person skilled in the art will observe, exothermic reactions can degrade the reagents according to the generation of the perfromic acid compositions of the invention. In one aspect, the cooling system stabilizes the composition of perfromic acid and thereby increases the shelf life by lowering the temperature to a temperature equal to or below the freezing point. In addition, according to an embodiment of the invention, the system has at least one mechanism for cooling the components of the system. Multiple cooling mechanisms can be used both in series and in parallel. Such mechanisms may include, for example, an abrupt cooling mode, increased surface area, cooling jacket, ventilation systems, cold fingers and the like. In a further aspect of the invention, the output of perfromic acid (or performic acids) is cooled using heat exchange, cooling sleeve, fan, cooled container, etc. MEASUREMENT DEVICES
[0091] [0091] In some aspects of the disclosure, the system for local generation of perfromic acid forming compositions may include at least one measuring device or a plurality of measurements. Such measuring devices are those suitable for measuring one or more reaction kinetics or system operations for the generation of perfromic acid-forming compositions, which include, for example, devices for measuring conductivity, weight, flow (for example, switches or flow meters), pH, pressure, temperature and combinations thereof. Such measuring devices can measure system inputs, piping, outputs, etc.
[0092] [0092] Examples of additional suitable measuring devices include, for example, conductivity sensors, thermometers, out-of-product alarms, peroxide monitors, IR / UV / VIS spectroscopy, NMR and pressure switches. For example, in an embodiment of the invention, the temperature is monitored at various points on the apparatus to ensure consistent heating at a temperature that does not exceed the flash point of perfromic acid. Additionally, in an embodiment of the invention, pressure is monitored to ensure that there is no "uncontrolled reaction" occurrence. This pressure monitoring can be performed with the use of a differential pressure sensor within a feedback control loop, in which, in a pressure reading, exceeding a set point causes a safety release valve and / or a rupture disc is used or that ventilation occurs.
[0093] [0093] In another mode of development, the temperature is monitored to indicate an uncontrolled reaction. Temperature probes can be placed upstream and downstream of the reaction. If the downstream temperature is higher than the upstream temperature, then the uncontrolled reaction has occurred.
[0094] [0094] In an additional mode of development, the flow rate is monitored with a pressure sensor or a meter / orifice plate. In addition, conductivity can be monitored to determine the concentration of products in the stream and / or the concentration of perfromic acid at the outlet. In an additional modality, the generation rates, temperatures and concentrations can all be optimized by monitoring systems and / or controllers. In addition, an embodiment of the invention would allow rinsing of the apparatus so that residual chemical substance does not remain in the system.
[0095] [0095] An additional suitable measuring device is an automatic titrator for measuring active PFA and residual peroxide, as disclosed in U.S. Patent No. 8,980,636, which is hereby incorporated by reference. Still further examples of suitable measuring devices are disclosed in this document, in addition to the various modalities of those disclosed in US Patent Application Serial No. 12 / 108,202 and US Patent No. 7,547,421, both entitled Apparatus and Method for Making Peroxycarboxylic Acid , which are incorporated in this document as a reference in their entirety. CONTROL SYSTEM
[0096] [0096] In some respects, the system for producing local formic acid chemical formulation formulations additionally comprises an optional controller or software platform. The software platform provides a user or system to select a generation mode for a desired formic acid formulation for local generation. As a result, the use of the system for generating local perforic acid chemical provides significant user flexibility to generate chemicals for purposes identified by particular users. For example, the controller or control software for operating the system may allow a user or system to select both the formic acid formulation and the desired volume and dosage concentration of the formulation for local generation. In an additional aspect, the control software can determine the timing, sequencing and / or selection of feeding the system with raw materials (eg reagents), mixing time and total reaction time required to produce the formic acid formic acid selected by user or system. In yet a further aspect of the invention, the control system includes the measuring devices described above.
[0097] [0097] According to the invention, the controller can additionally include a mechanism for manually starting / stopping any of the same functions, which includes, for example, a manual switching panel for the same. In addition, for manual controls, such as a manual switching panel, the controller preferably has buttons or other means for selecting particular modes according to the option displayed by the control software platform. A controller mode can additionally include a display screen to assist a user in selecting a generation mode for a desired formic acid formulation and any other options for user selection as a person skilled in the art will determine based on the description of the invention. . The user-friendly instructions displayed are concurrent with the control software for use on the display screen (or similar).
[0098] [0098] In one aspect of the invention, the control software uses a control software algorithm to maximize local active chemical yield and provides safe operating conditions for the reactor vessel (or reactor vessels) of the system. The control software allows the production of chemical substances identified by the user to be carried out in one or multiple reaction vessels and to properly sequence the reactions to obtain active chemical substances.
[0099] [0099] In one aspect of the invention, the control software controls the reaction temperature to form peroxyphoric acid, namely, it controls the heating device of the local generator.
[0100] [00100] Examples of suitable controllers are disclosed in this document, in addition to the various modalities of those disclosed in patent application serial number US 12 / 108,202, and Patent No. US 7,547,421, both entitled Apparatus and Method for Making Peroxycarboxylic Acid, which are incorporated in this document as a reference in their entirety.
[0101] [00101] In another aspect of the invention, the system may include means of data emission for sharing information related to the perfromic acid-forming compositions and / or perfromic acid formulations generated according to the system. For example, a primary information medium can be used to both collect and disseminate data from the process of generating perfromic acid formulations that includes, for example, consumption, dispensing or use of composition and data in relation to the production of additional formulations. . Such data can be generated in real time and / or provided in a historical record of operational data detectable or storable by a user or system. In one embodiment of the invention, a user or system has the ability to monitor usage and performance, which includes, for example, chemical dispensing, managing chemical distribution to various point of use applications, communicating with system operators to control and monitor dispensation, allocation and / or formulation of chemical substance and the like. According to a further embodiment of the invention, a user or system has the ability to control systems, which includes program systems, remotely. Control systems also include safety shutdown of the heater and pumps in the absence of flow and shutdowns when monitoring devices indicate an uncontrolled reaction.
[0102] [00102] According to one aspect of the invention, any system operations suitable for use with the invention can be controlled and / or monitored from a remote location. Control and / or monitoring of remote system operations may additionally include system updates and / or improvements. According to one aspect of the invention, updates and / or improvements to system operations can be downloaded remotely. These and other modalities of means of data emission, information sharing, remote system operations and the like, which can be adapted for use with the present invention, are further described, for example, in US Patent Nos. 7,292,917, 6,895,307, 6,697,706 and 6,377,868 and in US Patent Applications 2005/0102059, 2005/0065644, 2004/0088076, 2003/0195657 and 2003/0195656, which are expressly incorporated herein by way of reference that includes, without limitation, both the descriptive report, claims and summary, as well as any figures, tables or drawings of the same.
[0103] [00103] In another aspect of the invention, the emission of data for sharing information related to the compositions according to the system can coordinate multiple systems in a single site. According to this embodiment of the invention, the sharing of information between multiple systems can happen with the use of any communications network that has the capacity to couple one or more systems according to the present invention, which includes, for example, with the use of a server computer and a database. SECURITY DEVICES
[0104] [00104] In some aspects of the invention, the system may include a variety of security mechanisms. Exemplary local security feedback mechanisms for a system are revealed in further detail in US Patent Application No. 2009/0208365, which is expressly incorporated into this document for reference which includes, without limitation, both the specification, claims and summary, as well as any figures, tables or drawings of the same. Various safety mechanisms can measure pressure, temperature, difference in pressure, difference in temperature or a combination of them and provide a noticeable signal if one or more of these increases above a predetermined level. In one aspect, the level of pressure, temperature, difference in pressure, difference in temperature or a combination of them, in which the safety system provides a perceptible signal, can be selected to allow intervention to avoid undesirable or unsafe conditions. In a further aspect of the invention, the system is designed to accommodate at least 5 times the system pressure (i.e., design pressure), more preferably, at least 3 times the system pressure and, more preferably, at least 1, 5 to 2 times the system pressure. In an additional aspect, the system is designed for explosion safety ratings, such as, for example, according to the American Petroleum Institute (API). In a further aspect of the invention, the system can include pressure relief valves and / or rupture discs to control the pressure of the system. ILLUSTRATED MODALITIES
[0105] [00105] According to an embodiment of the invention, as shown in Figure 1, an admission of controller or process user selects both the formulation and flow rate and such admission information is loaded into the system. The control software, which includes a software algorithm, can be used to calculate the flow rates required for the particular concentration. Raw materials are fed into the system at controlled flow rates and reaction times.
[0106] [00106] As shown in Figure 1 exemplary and non-limiting, an admission of process controller or user (eg, selection of peracid and volume) is provided, and an adjustable biocide formulating system according to the invention is employed to provide raw materials (reagents) to feed a pipe length under heated conditions which are controlled reaction conditions. The represented system can employ a variety of measuring devices that provide feedback to the system. Measuring devices according to the invention may include devices suitable for measuring one or more reaction kinetics or system operations for generating perfromic acid-forming compositions, which include, for example, devices for measuring conductivity, weight , flow, pH, pressure, temperature and combinations thereof. An additional suitable measuring device is an automatic titrator for measuring active PFA and residual peroxide, as disclosed in U.S. Patent No. 8,980,636, which is incorporated herein by reference. Such measuring devices can measure system inputs, pipes, outputs, heating devices, etc. Exemplary measuring devices may include monitoring and reporting the temperature and pressure of the pipe length, the temperature and pressure of the materials at the inlet (or inlets), the temperature and pressure of the materials at the outlet (or outlets) and the rate of flow rate. Additional measuring devices can control: the flow rate; the pH of raw materials and solutions in reaction; and the like. As a person skilled in the art will determine, such regulators, measuring devices, sensors etc. are well known and are not intended to limit the modalities of the present invention.
[0107] [00107] In addition, measurement devices can be used to activate alarms that indicate that the system and / or methods of generating the perfromic acid-forming compositions are outside desirable ranges; for example, measuring devices can be used to generate out-of-product alarms (for example, indicating a starting raw material is ‘low’ or completely out of product). An exemplary measuring device for such an alarm would measure the availability of a particular raw material (pre-combination or the like) from the volume of such raw material in a drum.
[0108] [00108] Optionally, for generating a formic acid formulation (as opposed to anion peroxycarboxylic acid formation compositions), the stability of the reaction intermediates can be improved by adding an acid or an aqueous acidic solution. The system provides the user or process controller with the desired formic acid formulation for use in a cleaning process, which includes, without limitation, antimicrobial, bleaching and sanitizing and / or anti-scaling applications. In addition, various data issues and information sharing methods can optionally be employed according to the methods and systems of the invention.
[0109] [00109] According to an embodiment of the invention shown in Figure 2, the reagents enter the length of pipe 2 through at least three inlets represented 1, 1 ', 10. In one aspect, the reagents include the source of formic acid and the oxidizing agent. In an additional aspect, an inlet is used to purge a system with water as needed. In an exemplary embodiment represented by Figure 2, a source of formic acid is added in 1 or 1 '(and a water purge is suitable for use in 1' or 1) and an oxidizing agent is added in 10. Such reagents they are then placed in contact with at least one heating device 3, 3 ', which catalyzes the reaction of the source of perfromic acid and the oxidizing agent to form the desired product. As shown, the heating device is shown in different shapes, which includes a heating cartridge 3, which penetrates through one end of the pipe length and is disposed through at least a portion of the internal diameter of the pipe 2. A heating device Additional heating is shown 3 'as an insulating heater at least a portion of the pipe length. Without being limited according to the embodiments shown, the insulation heater 3 'could, alternatively I in addition, be wrapped around the outside of the pipe 2 (for example, outside the insulation of the pipe 8). In addition to the represented non-limiting integration, there are several optional measuring devices 5 that can be connected to a control system 6. Any number of measuring devices (or measuring devices) 5 can be included in a system. In addition, the system may include safety devices 7 and / or pipe insulation 8 and / or a mixer 9. The mix as shown shows a rotor, however, in many respects, a static mixer is employed. The 9 representation is a non-limiting representation of a mixer. The perfromic acid forming compositions or perfromic acid compositions of the present invention are then supplied via an outlet 4 to either an optional downstream cooling system, storage reservoir or the desired use.
[0110] [00110] According to an embodiment of the invention shown in Figure 3, the reagents enter the length of pipe 2 through at least two inlets represented 1, 10. In one aspect, the reagents include the source of formic acid and the agent of oxidation. In an exemplary embodiment represented by Figure 3, a source of formic acid is added in 1 and an oxidizing agent is added in 10. Such reagents are then brought into contact with at least one heating device 3, 3 ', shown as a heating cartridge 3 that penetrates through one end of the pipe length 2 and is disposed through at least a portion of the inner diameter of the pipe 2. An additional heating device is shown 3 'as an insulating heater at least a portion of the barrel length. In addition to the represented non-limiting mode, there are several optional measuring devices 5 that can be connected to a control system 6. Any number of measuring devices (or measuring devices) 5 can be included in a system. In addition, the system may include safety devices 7 and / or isolation of the pipe 8 and / or a mixer 9. The perfromic acid forming compositions or perfromic acid compositions of the present invention are then provided via an outlet 4 both to an optional downstream cooling system, storage reservoir and to the intended use.
[0111] [00111] According to an embodiment of the invention shown in Figure 4, a phased heating system is presented for use according to the invention. A pipe length 2 with at least two entries represented 1, 10 and provided to add reagents that include the source of formic acid at entry 1 and the oxidizing agent at entry 10. Such reagents are then brought into contact with at least a heating device 3, 3 ', shown as a heating cartridge 3 that penetrates through one end of the pipe length 2 and is arranged through at least a portion of the inner diameter of the pipe 2. As shown, a series of three pipe length phased heating portions are provided together with a 3 'insulating heating layer at least a portion of the pipe length. In addition to the represented non-limiting mode, there are several optional measuring devices 5 that can be connected to a control system 6. Any number of measuring devices (or measuring devices) 5 can be included in a system. In addition, the system may include safety devices 7 and / or isolation of the pipe 8 and / or a mixer 9. The perfromic acid forming compositions or perfromic acid compositions of the present invention are then provided via an outlet 4 both to an optional downstream cooling system, storage reservoir and to the intended use.
[0112] [00112] According to an embodiment of the invention shown in Figure 9, the reagents enter the length of pipe 2 through at least two inlets represented 1, 10. In one aspect, the reagents include a source of formic acid and oxidizing agent . In an exemplary embodiment represented by Figure 9, a source of formic acid is added in 1 and an oxidizing agent is added in 10. The source of formic acid is then brought into contact with at least one heating device 3, 3 ', shown as a heating cartridge 3 that penetrates through one end of the pipe length 2 and is disposed through at least a portion of the inner diameter of the pipe 2. An additional exemplary heating device is shown 3' as an air heater insulation at least a portion of the pipe length (which may extend further through or along any desired length of the pipe 2, and depicted in this figure as extending only a portion of the pipe 2). Additionally represented in the non-limiting mode shown in the Figure, are the water inlet 1 ', which can be used to rinse inlets 1, 10 and the length of pipe 2 with water. In addition, the system can include several optional measuring devices 5 that can be connected to a control system 6. Any number of measuring devices (or measuring devices) 5 can be included in a system and located at various locations throughout the system . In addition, the system may include safety devices 7 and / or pipe insulation 8 and / or a mixer 9 that can be included in a system and be located at various locations throughout the system. The perfromic acid forming compositions or the perfromic acid compositions of the present invention are then supplied via an outlet 4 to both an optional downstream cooling system, storage reservoir and the desired use. Beneficially, as shown in Figure 9, the generator employs a downward flow direction through the system to more readily come in contact with the reagents for the in-situ reaction and to enable the near instantaneous generation of perfromic acid. The represented modality that employs a downward flow direction of reagents, namely the oxidizing agent 10, adapts to the density of the reagent without requiring (or minimally requiring) external mechanical considerations, such as pumping power. In a preferred embodiment of the invention, as shown in Figure 9, at least the second inlet (which doses the oxidizing agent 10) to the system has a downward flow.
[0113] [00113] According to an embodiment of the invention shown in Figure 10, the reagents enter the length of pipe 2 through at least two inlets represented 1, 10. In one aspect, the reagents include a source of formic acid and oxidizing agent . In an exemplary embodiment represented by Figure 10, a source of formic acid is added in 1 and an oxidizing agent is added in 10. The source of formic acid is then brought into contact with at least one heating device 3, shown as a heating cartridge 3 that penetrates through one end of the pipe length 3 and is disposed through at least a portion of the pipe 2. Additionally shown in the non-limiting embodiment shown in Figure 10 are the water inlet 1 'which can be used to purge inlet 1 and pipe length 2 with water. Degassing can occur at 11 by any suitable method. In addition, the system can include several optional measuring devices 5 that can be connected to a control system 6. Any number of measuring devices (or measuring devices) 5 can be included in a system and located at various locations throughout the system . In addition, the system may include safety devices 7 and / or pipe insulation 8 and / or a mixer 9 that can be included in a system and be located at various locations throughout the system. The perfromic acid forming compositions or the perfromic acid compositions of the present invention are then supplied via an outlet 4 to both an optional downstream cooling system, storage reservoir and the desired use. Beneficially, as shown in Figure 10, the generator employs a downward flow direction through the mixer 9 to more readily come in contact with the reagents for the in-situ reaction and to enable the near instantaneous generation of perforic acid. The represented modality that employs a downward flow direction of reagents, which are mixed in the stream before reaching the mixer 9, adapts to the density of the reagents without requiring (or minimally requiring) external mechanical considerations, such as pumping power.
[0114] [00114] According to an embodiment of the invention shown in Figure 12, the reagents enter the length of pipe 2 through at least two inlets represented 1, 10. In an exemplary embodiment represented by Figure 12, a source of formic acid is added in 1 and an oxidizing agent is added in 10. The source of formic acid is then brought into contact with at least one heating device 3 arranged through at least a portion of the pipe 2. Additionally shown in the non-limiting mode shown in Figure 12 there is an outlet 4 for both an optional downstream cooling system, storage reservoir and for a desired use. Beneficially, as shown in Figure 12, the generator employs a downward flow direction of the oxidizing agent through the mixer 9 to more readily come in contact with the reagents for the in-situ reaction and enable practically instantaneous generation of perfromic acid. The represented modality that employs a downward flow direction of the oxidizing agents reactants, which are mixed in the stream before reaching the mixer 9, adapts to the density of the reagents without requiring (or minimally requiring) external mechanical considerations, such as pumping power .
[0115] [00115] Although not represented in all the modalities of the invention shown in the figures, several additional inlets may be present, such as, for example, water inlets to purge an inlet and / or a length of pipe 2 with water, or inlets for supply of additional components include biocides and / or corrosion inhibitors, or even more additional inputs to supply additional peroxycarboxylic acids (such as those that may contain formic acid). In addition, degassing can occur in 11 by any suitable method within any of the represented modalities. In addition, the systems can include several optional measuring devices 5 that can be connected to a control system 6. Any number of measuring devices (or measuring devices) 5 can be included in a system and located at various locations throughout the system . In addition, the system may include safety devices 7 and / or pipe insulation 8 and / or a mixer 9 that can be included in a system and be located at various locations throughout the system. Each of these components can be included in the generator, according to the invention, which includes configurations represented in each of the figures. In addition, the various inputs and outputs can be configured with an upward or lateral flow and still others configured with a downward flow. PERFORMIC ACID COMPOSITIONS
[0116] [00116] In some embodiments, the system according to the present invention produces perfromic acid forming compositions or perfromic acid compositions for use in a variety of cleaning applications. In some respects, the present disclosure relates to perfromic acid-forming compositions. This means that the compositions have the ability to generate formic acids in situ, in a non-equilibrium reaction. Perforic acid, in general, has the formula CH2O3.
[0117] [00117] In an embodiment of the invention, perfromic acid-forming compositions comprise individual reagents combined according to the invention. Such reagents are described individually in this document and include at least the source of formic acid and an oxidizing agent. Alternatively, as described in this document, there may be benefits in relation to the supply of reagents in various pre-combination formulations to decrease the number of reagents and / or increase the simplicity of the invention. METHODS FOR PRODUCTION OF LOCAL PERFORMIC ACID COMPOSITIONS
[0118] [00118] In some embodiments, the methods according to the present invention for producing perfromic acid forming compositions or perfromic acid compositions comprise, consist of and / or consist essentially of providing a source of formic acid, providing a oxidizing agent, contacting said source of formic acid and the oxidizing agent to form the reaction mixture, heating said reaction mixture at a given flow rate to form perfromic acid and delivering said formic acid to a downstream process. In a further embodiment, the methods according to the present invention for producing perfromic acid-forming compositions or perfromic acid compositions comprise cooling perfromic acid. In an additional embodiment, the methods according to the present invention for producing perfromic acid forming compositions or perfromic acid compositions comprise measuring variables that include conductivity, temperature, product levels, concentration, IR / UV / VIS spectroscopy , pressure, flow rate, etc. In a further embodiment, the methods according to the present invention for producing perfromic acid forming compositions or perfromic acid compositions comprise controlling the system through the use of a control system. In a further embodiment, the methods according to the present invention for producing perfromic acid forming compositions or perfromic acid compositions comprise employing safety devices. FORMIC ACID SOURCE
[0119] [00119] In one aspect of the invention, a source of formic acid is supplied to the system. The source of formic acid used in the present methods can be provided in any suitable manner. In some embodiments, before the contact step, formic acid can be supplied in a composition comprising formic acid, for example, an aqueous solution comprising formic acid and additional optional functional ingredients, such as a corrosion inhibitor. In other embodiments, before the contact step, formic acid can be supplied in a composition that comprises a substance that generates formic acid upon contact with an aqueous composition. Any suitable substance that generates formic acid can be used in the present methods.
[0120] [00120] In one aspect, the source of formic acid is an aqueous solution comprising formic acid. In another aspect, the source of formic acid is a formic acid salt, such as formate, for example, sodium salt or formate ammonium. In one aspect, the source of formic acid is an alcohol ester, such as ethyl formate, propylene formate, glycerol formate, etc.
[0121] [00121] In one aspect, the source of formic acid is a composition comprising formic acid (or a formic acid salt) and additional optional functional ingredients, such as a corrosion inhibitor. Beneficially, formic acid and corrosion inhibitor systems provide a system protected against corrosion. In such an embodiment, the concentration of the corrosion inhibitors will be less than 10% of the formic acid composition, preferably less than% of the formic acid composition. In some embodiments, the corrosion inhibitor may be a phosphate ester, a phosphate ester derivative, a diacid, a diacid derivative, a quaternary amine, a quaternary amine derivative, an imidazoline, an imidazoline derivative, a pyridine of aquila, a derivative of aquila pyridine, a phosphonium salt, a derivative of the phosphonium salt or a combination thereof.
[0122] [00122] In one aspect, the source of formic acid is a composition comprising formic acid (or a formic acid salt) and additional percarboxylic acids and / or carboxylic acids, such as C1-C22 percarboxylic acids and / or carboxylic acids, preferably, C5-C22 percarboxylic acids and / or carboxylic acids, to beneficially provide a mixed formic acid composition to provide synergistic antimicrobial efficacy against microorganisms. In such aspects, a mixture of peroxyphoric acid and percarboxylic acids and / or additional carboxylic acids, such as peracetic acid or peroctanoic acid, as disclosed in US Patent No. 5,314,687 which is incorporated herein by reference in its wholly, are provided. In such an aspect, the peracid mixture provides antimicrobial synergy. In one respect, the synergy of a mixed peracid system allows the use of lower dosages of peracids. OXIDATION AGENT
[0123] [00123] The compositions also include an oxidizing agent. The oxidizing agent can include a source of peroxide. In one aspect, hydrogen peroxide is 1 to 50% w / v of hydrogen peroxide. Oxidizing agents suitable for use with the compositions include the following types of compounds or sources of those compounds, or alkali metal salts that include these types of compounds or that form an adduct with them: hydrogen peroxide, hydrogen peroxide complexes and urea or hydrogen peroxide donors of: group 1 of oxidizing agents (IA), for example, lithium peroxide, sodium peroxide; oxidizing agents group 2 (IIA), for example, magnesium peroxide, calcium peroxide, strontium peroxide, barium peroxide; group 12 of oxidizing agents (IIB), for example, zinc peroxide; group 13 of oxidizing agents (IIIA), for example, boron compound, such as perborates, for example, sodium perborate hexahydrate of the formula Na2 [B2 (O2) 2 (OH) 4] · 6H2O (also called tetrahydrate sodium perborate); sodium peroxyborate tetrahydrate of the formula Na2B2 (O2) 2 [(OH) 4] · 4H2O (also called sodium perborate trihydrate); sodium peroxyborate of the formula Na2 [B2 (O2) 2 (OH) 4] (also called sodium perborate monohydrate); group 14 of oxidizing agents (IVA), for example, perssilicates and peroxycarbonates, which are also called percarbonates, such as alkali metal perssilicates or peroxycarbonates; group 15 of oxidizing agents (VA), for example, peroxynitrous acid and its salts; peroxyphosphoric acids and their salts, for example, phosphates; group 16 of oxidizing agents (VIA), for example, peroxysulfuric acids and their salts, such as peroxymonosulfuric and peroxydisulfuric acids, and their salts, such as persulfates, for example, sodium persulfate; and group of oxidizing agents VIIa, such as sodium periodate, potassium perchlorate. Other active inorganic oxygen compounds can include metal peroxides; and other peroxygen compounds and mixtures thereof.
[0124] [00124] In some embodiments, the compositions of the present invention employ one or more of the inorganic oxidizing agents listed above. Suitable inorganic oxidizing agents include ozone, hydrogen peroxide, hydrogen peroxide adduct, oxidation agent group IIIA, or hydrogen peroxide donors from the oxidation agent group VIA, VA oxidation agent group, oxidation agent group VIIA oxidation or mixtures thereof. Suitable examples of such inorganic oxidizing agents include percarbonate, perborate, persulfate, perphosphate, persulfate or mixtures thereof.
[0125] [00125] In some embodiments, the oxidizing agent includes hydrogen peroxide or a hydrogen peroxide source or donor. In other embodiments, the oxidizing agent includes a peroxide source selected from a percarbonate, perborate urea hydrogen peroxide, PVP peroxides and mixtures thereof. ADDITIONAL OPTIONAL COMPONENTS
[0126] [00126] In one embodiment, the reagents described in this document (for example, formic acid and an oxidizing agent) can be combined with additional optional components. In one aspect, the additional components can include a corrosion inhibitor. Corrosion inhibitors are additional molecules used in oil and gas recovery operations. The corrosion inhibitors that can be employed in the present disclosure are disclosed in US Patent No. 5,965,785, in US Patent Application No. 2010/0108566, in GB Patent No. 1,198,734, and in documents WO / 03 / 006581, WO04 / 044266 and WO08 / 005058, each of which is incorporated in this document as a reference in its entirety.
[0127] [00127] In one aspect, the additional components may include an additional biocide. Additional biocides may include, for example, a quaternary ammonium compound as disclosed in U.S. Patent No. 6,627,657, which is hereby incorporated by reference in its entirety for reference. Beneficially, the presence of the quaternary ammonium compound provides both synergistic antimicrobial efficacy with peracids and maintains long-term biocidal efficacy of the compositions. In another embodiment, the additional biocide may include an oxidizing compatible phosphonium biocide, such as tributyl tetradecyl phosphonium chloride. The phosphonium biocide provides antimicrobial advantages similar to the advantages of the ammonium compound in combination with peracids. In addition, the phosphonium biocide is compatible with non-ionic polymeric chemicals commonly used in oil field applications, such as the drilling methods revealed according to the invention. In a preferred aspect, the additional biocide is Gluteraldehyde, THPS, quaternary amine and / or TTPC.
[0128] [00128] In one aspect, additional components may include a friction reducer. Friction reducers are used in water or other water-based fluids used in hydraulic fracturing treatments for underground well formations to improve the permeability of the desired gas and / or oil recovered from cracks or conductive fluid passages created through the process drilling. Examples of commonly used friction reducers include polyacrylamide polymers and copolymers. In one aspect, additional suitable friction reducers may include polymers and copolymers derived from acrylamide, such as polyacrylamide (sometimes abbreviated PAM), acrylamide acrylate (acrylic acid) copolymers, acrylic acid methacrylamide copolymers, partially polyacrylamide hydrolyzed copolymers. (PHPA), partially hydrolyzed polymethacrylamide, acrylamide-methylpropane sulfonate copolymers (AMPS) and the like. It is understood that various derivatives of such polymers and copolymers, for example, quaternary amine salts, hydrolyzed versions and the like, are included with the polymers and copolymers described herein. PRE-COMBINATION FORMULATIONS
[0129] [00129] In one embodiment, the reagents described in this document (for example, formic acid and an oxidizing agent) can be combined in a pre-combination formulation to reduce the number of starting raw materials required for the methods and compositions and further simplifying the methods of the invention. According to this modality, the supply of pre-combination formulations ensures consistent and stable delivery of reagents.
[0130] [00130] Pre-combination formulations suitable for use according to the invention may comprise, consist of and / or consist essentially of at least the source of formic acid, a combination of formic acid and other C2-C18 carboxylic acids, an oxidizing agent and mixtures thereof.
[0131] [00131] As a person skilled in the art will determine, the use of pre-combinations employs additional functional ingredients for the purpose of stabilizing the pre-combination concentrate for use in the compositions and methods according to the invention. For example, hydrotropes, dispersing agents and / or other solvents may be desirable to maintain the solubility and stability of a particular concentrated pre-combination. The use of any couplers or dispersing agent (such as a surfactant) within a pre-combination formulation is distinct from the use of surfactants in the conventional generation and storage of perfromic acid chemicals, in which the couplers are critical for the establishment and the maintenance of a clear and stable solution of the generated perfromic acid chemical substance.
[0132] [00132] According to the invention, only the use of dispersing agents within a pre-combination formulation does not stabilize the pre-combination composition. Instead, the dispersing agents are supplied in an amount suitable for supplying metastable perfromic acid compositions generated from the pre-combination after acidification, before further dilution for application. It was found that the most efficient dispersing agents were surfactants, and it is known that this type of surfactant has a high foaming profile. For applications involving mechanical actions (eg CIP cleaning), the high foam property of the composition is undesirable. Thus, in addition to the economic reason, it is preferred to use a minimal amount of the dispersing agent to obtain a metastable performatic acid composition to meet the application of usage requirements.
[0133] [00133] According to an embodiment of the invention, less than about 10 ppm, preferably less than about 9 ppm, less than about 8 ppm, less than about 7 ppm, less than about 6 ppm, less than about 5 ppm, less than about 4 ppm, less than about 3 ppm, less than about 2 ppm or less than about 1 ppm of a dispersing agent is included in the perfromic acid chemical generated as a result of use of a surfactant dispersing agent in a concentrated pre-combination formulation according to the invention. This is distinct from the level of surfactants in solutions using a traditional perforic acid chemical, where the amounts of surfactants are usually in excess of about 50 ppm, in excess of about 60 ppm, in excess of about 70 ppm, in excess of about 80 ppm, in excess of about 90 ppm, or in excess of about 100 ppm.
[0134] [00134] According to an embodiment of the invention, the use of a solvent (for example, ethanol) is an efficient way to produce a stable pre-combination composition. Solvents suitable for concentrated pre-combination formulations according to the invention include, for example, organic solvents, such as alcohol, ether or ketone. Preferably, the solvent is a water-soluble alcohol, such as ethanol, methanol, propanol, isopropanol and / or butanol. As one skilled in the art will determine, the various isomers of the solvents, which includes alcohols, are further included within the scope of the solvents suitable for use with the concentrated pre-combination formulations of the invention.
[0135] [00135] Beneficially, the use of concentrated pre-combination formulation does not yet require the use of any chelators and / or stabilizers. As a result, regardless of whether individual reagents or concentrated pre-combination formulations are used in accordance with the invention, both reagents and perfromic acid compositions generated in accordance with the invention provide sustainable chemicals as a result of eliminating use. of various stabilizers and / or additional amounts of chemical substance required to boost the formation of traditional perforic acid chemicals. As a result of reduced reagent intake for the compositions, according to the invention (for example, which results from the use of a non-equilibrium reaction), there is a significantly reduced serviced current (for example, any reagents and / or percentage of composition that does not impact the micro-effectiveness of the compositions). Instead, the present invention provides increased amounts of post-reaction products (e.g., formic acids) with decreased amounts of unreacted reagents.
[0136] [00136] In one aspect of the invention, a pre-combination formulation can deliver the source of formic acid and the oxidizing agent.
[0137] [00137] Dispersing agents suitable for use according to the concentrated pre-combination formulations of the invention include polymers, surface active agents or any compounds that will help to obtain a metastable solution after ester perhydrolysis through interaction with peroxy fatty acids generated through perhydrolysis. These can include, for example, sulfonated oleic acids (SOA), 1-octane sulfonic acid (NAS), sodium lauryl sulfonates (SLS) and the like. In another aspect, a pre-combination formulation includes an ester of a polyhydric alcohol and a carboxylic acid, an oxidizing agent and a solvent. Ethanol and methanol are examples of solvents suitable for use in stabilizing the concentrated pre-combination formulation according to the invention. The use of the solvent in certain modalities prevents the use of a dispersing agent for pre-combination stabilization. However, in alternative embodiments, a pre-combination formulation can include an ester of a polyhydric alcohol and a carboxylic acid, an oxidizing agent, a dispersing agent and a solvent. Without wishing to be limited to a particular theory or mechanism of action of the invention, the combined use of a dispersing agent and a solvent within a concentrated pre-combination formulation reduces the general need for a surfactant dispersing agent in the pre-combination composition. REACTION MIXING FORMATION
[0138] [00138] According to an embodiment of the invention, the source of formic acid and an oxidizing agent are combined to form a reaction mixture. In one embodiment of the invention, the source of formic acid and an oxidizing agent are provided at pipe length. In one embodiment of the invention, the source of formic acid and the oxidizing agent are supplied to a container located upstream of the inlet to the length of the pipe and subsequently supplied to the length of the pipe. According to the modalities of the invention, the flow direction through the system can be upward, downward or lateral. However, as a person skilled in the art would observe, the flow direction can be dependent on both the process and current variable, such as density, temperature and pressure, as well as external mechanical considerations, such as pumping power. In a preferred embodiment of the invention, the second inlet that doses the oxidizing agent to the system has a downward flow. In a further aspect of the invention, the reaction mixture is not formed by mechanical mixing means. In an alternative embodiment of the invention, the reaction mixture is formed by mechanical mixing means, for example, such as a rotor or the like as a person skilled in the art will observe, for circulation inside the reaction vessel, circulation pumps or to be propelled by gravity, they employ additional retention vessels, reagent delivery sensors (for example, proof of perfromic acid chemical delivery sensor and / or reagent) or combinations of these to meet the system keretic reaction kinetics.
[0139] [00139] In one aspect of the invention, the timing of the reaction is dependent on the flow rate and / or the flow direction of the reagents, the amount of heat transfer available and the desired concentration of perfromic acid. Although not intended to be limited by a particular theory of the invention, the kinetics of the reaction, according to the invention, are dependent on pH, concentration, flow rate and / or temperature, and the reaction begins to produce yield in the order of seconds to minutes. In some aspects of the invention, the reaction can produce at least about 2% formic acid instantly, at least about 4% formic acid within about 1 minute and at least about 8% formic acid within about 2 minutes. In a preferred embodiment of the invention, the duration of the reaction is preferably less than about 1 hour, preferably less than about 30 minutes, preferably less than about 15 minutes, and preferably less than about 10 minutes. In a further aspect of the invention, the reaction is carried out until completion, however, as a person skilled in the art can observe, it may be desirable not to carry out the reaction until completion. REACTION MIXTURE HEATING
[0140] [00140] In one aspect of the invention, the reaction mixture is heated within a pipe length in order to perform the conversion of reagents to perfromic acid. In some aspects of the invention, the reaction takes place within a pipe length that meets the hydraulic requirements of the perfromic acid reaction kinetics. Although not intended to be limited by a particular theory of the invention, the reaction kinetics, according to the invention, are dependent on pH, concentration, flow rate and / or temperature, and the reaction can obtain maximum yield in the order of seconds to minutes. Although not intended to be limited by a particular theory of the invention, the kinetics of the reaction, according to the invention, are dependent on pH, concentration, flow rate and / or temperature, and the reaction begins to produce yield in the order of seconds to minutes. In some aspects of the invention, the reaction can produce at least about 2% formic acid instantly, at least about 4% formic acid within about 1 minute and at least about 8% formic acid within about 2 minutes. In some respects, the reaction can achieve maximum yield in about 15 seconds, in about 30 seconds, in about 1 minute or in about 2 to about 5 minutes. The pipe length can be designed in a variety of ways, which includes, for example, shape, size, temperature and material. According to an embodiment of the invention, the pipe length can be of a given internal diameter and is constructed of a material that is not readily corroded and / or damaged by the presence of formic acid, hydrogen peroxide and / or perfromic acid (or formic acids). Such piping materials to be avoided include, for example, copper, chromium, brass and / or iron. Certain varieties of stainless steel should also be avoided, for example, SS304. In a preferred embodiment of the invention, the pipe length is constructed from SS316 and / or SS316L. However, a person skilled in the art will note that other suitable materials are available.
[0141] [00141] In some aspects of the invention, the pipe length is limited by system pressure. For example, the pipe can be designed to accommodate the potential occurrence of an uncontrolled reaction. Preferably the pipe is designed to accommodate pressures of at least 20 PSI, at least 40 PSI, at least 50 PSI, at least 100 PSI, at least 500 PSI, at least 500 PSI, at least 1,000 PSI, or greater, which includes all the tracks in them. In one aspect, as a person skilled in the art will determine, the pressure of the system is controlled so as not to exceed the burst pressure of any material employed for the length of the pipe of the generator or apparatus of the invention. Beneficially, the additional components of the generator or apparatus may optionally include pressure relief valves, rupture discs or the like to control the system pressure.
[0142] [00142] In some aspects of the invention, flow through the pipe occurs at a rate of about 1 ml / minute to about 100 ml / min, preferably about 10 ml / min to about 50 ml / min, preferably , about 20 ml / min to about 40 ml / min. In one aspect of the invention, the highest flow rates can be obtained using the apparatus in parallel. In one aspect of the invention, it is preferred that the flow through the pipe has a laminar flow pattern, that is, the flow has a Reynolds number of less than about 2,040 in order to allow uniform heating.
[0143] [00143] In one aspect of the invention, heat is supplied to the system through the use of a cartridge, heat exchanger, steam jacket, steam preheating, an electrical source, a heat wrap or combinations thereof, which can be referred to in this document as a heating device. In some aspects of the invention, the location of the heating device within the pipe section is additionally involved in insulation to eliminate the amount of heat lost to the environment.
[0144] [00144] In a preferred embodiment of the system, heat is supplied to the system in an amount sufficient to raise the temperature of the reagents to accelerate the reaction and at a temperature that does not exceed the decomposition temperature of perfromic acid, or about 200 ° C . Most preferably, the heat is supplied to the system in an amount sufficient to raise the temperature of the reagents to a temperature that does not exceed 180 ° C. In one aspect, the increase in temperature will increase the reaction rate, however, as a person skilled in the art will determine, the stability of perfromic acid should not be compromised by increasing the temperature, which includes at a temperature that does not exceed 200 ° C .
[0145] [00145] In a further aspect of the invention, uniform heating of the reagents within the length of the pipe is desired, such uniform heating being influenced by the radial distance from the outside of the heater surface to the inside surface of the pipe, in which a greater distance leads to an upper gradient, and the length of the heating zone, where the longer contact with the heater leads to a lower gradient. As a person skilled in the art will observe, these influences have inverse effects on the heat gradient and will thus observe the weight of these influences when determining the dimensions of the heating devices. In an alternative aspect, a phased heating of reagents within the barrel length is desired.
[0146] [00146] In some aspects of the present invention, where the heating device is a cartridge, the available volume of the pipe is affected. The available volume is, therefore, defined as the volume retained inside the pipe at a given time minus the volume occupied by the heating cartridge. In a preferred embodiment, the volume of the system is increased by using systems in parallel instead of increasing the size and / or volume of the pipe.
[0147] [00147] In some aspects of the invention, the power required by the heating device and attached pumps, preferably, does not exceed about 100 watts for flow rates of 50 ml / min. More preferably, the power does not exceed 80 watts and, more preferably, the power does not exceed 50 watts. PERFORMIC ACID DELIVERY
[0148] [00148] In a preferred aspect of the present invention, perfromic acid is delivered to a downstream process via an outlet. In one aspect of the invention, the outlet supplies the perforic acid chemicals to a downstream process as desired by the controller and / or user. In one aspect, the outlet supplies the perforic acid chemicals to a storage reservoir. In one aspect, the outlet supplies the perforic acid chemicals to a cooling system. In one aspect of the invention, the concentration of perfromic acid at the outlet is at least 1% by weight, more preferably, at least 5% by weight at the outlet. PERFORMIC ACID COOLING
[0149] [00149] In a further aspect of the invention, perfromic acid is cooled by means of a cooling loop / segment. Such a cooling system may be in combination with a safety mechanism and / or a system measuring device. It may be desirable to have system components under temperature controls. As a person skilled in the art will observe, exothermic reactions can degrade the reagents according to the generation of the perfromic acid compositions of the invention. In one aspect, the cooling system stabilizes the composition of perfromic acid and thereby increases the shelf life by lowering the temperature to a temperature equal to or below the freezing point. In addition, according to an embodiment of the invention, the system has at least one mechanism for cooling the components of the system. Multiple cooling mechanisms can be used both in series and in parallel. Such mechanisms may include, for example, an abrupt cooling mode, increased surface area, cooling jacket, ventilation systems, cold fingers and the like. In a further aspect of the invention, the output of perfromic acid (or performic acids) is cooled using heat exchange, cooling sleeve, fan, cooled container, etc. MEASUREMENT DEVICES
[0150] [00150] In a further aspect of the invention, methods according to the present invention for producing perfromic acid forming compositions or perfromic acid compositions include measuring at least one value or a plurality of values. Such measurement is performed by the use of measuring devices. Such measuring devices are those suitable for measuring one or more reaction kinetics or system operations for the generation of perfromic acid-forming compositions, which include, for example, devices for measuring conductivity, weight, flow (for example, switches or flow meters), pH, pressure, temperature and combinations thereof. Such measuring devices can measure system inputs, piping, outputs, etc.
[0151] [00151] Examples of additional suitable measuring devices include conductivity sensors, thermometers, out-of-product alarms, peroxide monitors, IR / UV / VIS spectroscopy and pressure switches. For example, in an embodiment of the invention, the temperature is monitored at various points on the apparatus to ensure consistent heating at a temperature that does not exceed the flash point of perfromic acid. Additionally, in an embodiment of the invention, pressure is monitored to ensure that there is no "uncontrolled reaction" occurrence. This pressure monitoring can be performed with the use of a differential pressure sensor within a feedback control loop, in which, in a pressure reading that exceeds a set point, causes a safety release valve to be employed. or that ventilation occurs. In a further embodiment of the invention, the flow rate is monitored with either a pressure sensor or an orifice plate / meter. In addition, conductivity can be monitored to determine the concentration of products in the stream and / or the concentration of perfromic acid at the outlet. In an additional modality, the generation rates, temperatures and concentrations can all be optimized by monitoring systems and / or controllers. In addition, an embodiment of the invention would allow rinsing of the apparatus so that residual chemical substance does not remain in the system. Still further examples of suitable measuring devices are disclosed in this document, in addition to the various modalities of those disclosed in US Patent Application Serial No. 12 / 108,202 and US Patent No. 7,547,421, both entitled Apparatus and Method for Making Peroxycarboxylic Acid , which are incorporated in this document as a reference in their entirety. CONTROL SYSTEM
[0152] [00152] In a further aspect of the invention, the methods according to the present invention for producing perfromic acid forming compositions or perfromic acid compositions includes controlling the method using an optional controller or software platform. The software platform provides a user or system to select a generation mode for a desired formic acid formulation for local generation. As a result, the use of the system for generating local perforic acid chemical provides significant user flexibility to generate chemicals for purposes identified by particular users. For example, the controller or control software for operating the system may allow a user or system to select both the formic acid formulation and the desired volume of the formulation for local generation. In an additional aspect, the control software can determine the timing, sequencing and / or selection of feeding the system with raw materials (eg reagents), mixing time and total reaction time required to produce the formic acid formic acid selected by user or system. In yet a further aspect of the invention, the control system includes the measuring devices described above.
[0153] [00153] According to the invention, the controller can additionally include a mechanism for manually starting / stopping any of the same functions, which includes, for example, a manual switching panel for the same. In addition, for manual controls, such as a manual switching panel, the controller preferably has buttons or other means for selecting particular modes according to the option displayed by the control software platform. A controller mode can additionally include a display screen to assist a user in selecting a generation mode for a desired formic acid formulation and any other options for user selection as a person skilled in the art will determine based on the description of the invention. . The user-friendly instructions displayed are concurrent with the control software for use on the display screen (or similar).
[0154] [00154] In one aspect of the invention, the control software uses a control software algorithm to maximize local active chemical yield and provides safe operating conditions for the reactor vessel (or reactor vessels) of the system. The control software allows the production of chemical substances identified by the user to be carried out in one or multiple reaction vessels and to properly sequence the reactions to obtain active chemical substances.
[0155] [00155] Examples of suitable controllers are disclosed in this document, in addition to the various modalities of those disclosed in patent application serial number US 12 / 108,202, and US Patent No. 7,547,421, both entitled Apparatus and Method for Making Peroxycarboxylic Acid, which are incorporated in this document as a reference in their entirety.
[0156] [00156] In another aspect of the invention, the system may include means of data emission for sharing information related to the perfromic acid-forming compositions and / or perfromic acid formulations generated according to the system. For example, a primary information medium can be used to both collect and disseminate data from the process of generating perfromic acid formulations that includes, for example, consumption, dispensing or use of composition and data in relation to the production of additional formulations. . Such data can be generated in real time and / or provided in a historical record of operational data detectable or storable by a user or system. In one embodiment of the invention, a user or system has the ability to monitor usage and performance, which includes, for example, chemical dispensing, managing chemical distribution to various point of use applications, communicating with system operators to control and monitor dispensation, allocation and / or formulation of chemical substance and the like. According to a further embodiment of the invention, a user or system has the ability to control systems, which includes program systems, remotely.
[0157] [00157] According to one aspect of the invention, any system operations suitable for use with the invention can be controlled and / or monitored from a remote location. Control and / or monitoring of remote system operations may additionally include system updates and / or improvements. According to one aspect of the invention, updates and / or improvements to system operations can be downloaded remotely. These and other modalities of means of data emission, information sharing, remote system operations and the like, which can be adapted for use with the present invention, are further described, for example, in US Patent Nos. 7,292,917, 6,895,307, 6,697,706 and 6,377,868 and in US Patent Applications 2005/0102059, 2005/0065644, 2004/0088076, 2003/0195657 and 2003/0195656, which are expressly incorporated herein by way of reference that includes, without limitation, both the descriptive report, claims and summary, as well as any figures, tables or drawings of the same.
[0158] [00158] In another aspect of the invention, the emission of data to share information related to the compositions according to the system can coordinate multiple systems in a single site. According to this embodiment of the invention, the sharing of information between multiple systems can happen with the use of any communications network that has the capacity to couple one or more systems according to the present invention, which includes, for example, with the use of a server computer and a database. SECURITY DEVICES
[0159] [00159] In a further aspect of the invention, methods according to the present invention for producing perfromic acid forming compositions or perfromic acid composition include employing safety devices. Exemplary local security feedback mechanisms for a system are revealed in further detail in US Patent Application No. 2009/0208365, which is expressly incorporated into this document for reference which includes, without limitation, both the specification, claims and summary, as well as any figures, tables or drawings of the same. Various safety mechanisms can measure pressure, temperature, difference in pressure, difference in temperature or a combination of them and provide a noticeable signal if one or more of these increases above a predetermined level. In one aspect, the level of pressure, temperature, difference in pressure, difference in temperature or a combination of them, in which the safety system provides a perceptible signal, can be selected to allow intervention to avoid undesirable or unsafe conditions. In a further aspect of the invention, the system is designed to accommodate at least 5 times the system pressure (i.e., design pressure), more preferably, at least 3 times the system pressure and, more preferably, at least 1, 5 to 2 times the system pressure. In an additional aspect, the system is designed for explosion safety ratings, such as, for example, according to the American Petroleum Institute (API). In a further aspect of the invention, the system may include pressure relief valves and / or rupture discs. METHODS THAT USE PERFORMIC ACID COMPOSITIONS
[0160] [00160] In some respects, the present disclosure includes methods of using the perfromic acid forming compositions disclosed herein. In some ways, the methods of using the compositions employ a chemical that has a pH of from about 0 to about 5 for various antimicrobial and / or bleaching applications. In other respects, the methods of using the compositions employ a chemical that has a pH of from about 5 to about 9 for various antimicrobial and / or bleaching applications. Still in additional aspects, the methods of using the compositions employ a chemical substance that has a pH of from about 5 to about 14 for various bleaching applications.
[0161] [00161] In some respects, the present disclosure includes methods of using the formic acid and / or formic acid forming compositions disclosed herein. The perfromic acid compositions generated according to the modalities of the invention can be used for a variety of biocidal and / or antimicrobial user identifier purposes. In some respects, the locally generated perfromic acid compositions can be used for use in antimicrobial and / or bleaching methods. In additional aspects, the locally generated perfromic acid compositions can be used for any in-use cleaning methods. For example, the invention includes a method for reducing a microbial population, a method for reducing the population of a microorganism on the skin, a method for treating a skin disease, a method for reducing an odor, or a method for bleaching. These methods can operate on an object, surface, in a body or stream of water or a gas, or the like, by bringing the object, surface, body or stream into contact with a perfromic acid composition of the invention. Contact can include any of the numerous methods for applying a composition, such as spraying the composition, immersing the object in the composition, treating the object's foam or gel with the composition, wiping the composition or a combination thereof
[0162] [00162] In some respects, a composition, obtained according to the methods and apparatus of the present invention, includes an amount of a perfromic acid composition of the present invention effective for eliminating one or more of the associated foodborne pathogenic bacteria to a food product, which includes, but is not limited to, Salmonella typhimurium, Salmonellajaviana, Campylobacterjejuni, Listeria monocytogenes and Escherichia coli O157: H7, yeast and mold. In some embodiments, the compositions, obtained according to the methods and apparatus of the present invention, include an amount of a perfromic acid composition effective for eliminating one or more of the pathogenic bacteria associated with health care surfaces and environments that include, but are not limited to, Salmonella typhimurium, Staphylococcus aureus, Salmonella choleraesurus, Pseudomonas aeruginosa, Escherichia coli, mycobacteria, yeast and mold. The compositions, obtained according to the methods and apparatus of the present invention, have activity against a wide variety of microorganisms, such as Gram positive (for example, Listeria monocytogenes or Staphylococcus aureus) and Gram negative (for example, Escherichia coli or Pseudomonas aeruginosa) bacteria, yeast, molds, bacterial spores, viruses, etc. The compositions, obtained according to the methods and apparatus of the present invention, as described above, have activity against a wide variety of human pathogens. The present compositions, obtained according to the methods and apparatus of the present invention, can eliminate a wide variety of microorganisms on a food processing surface, on the surface of a food product, in water used for washing or processing food product , on a health care surface, in a health care environment or the like.
[0163] [00163] The compositions, obtained according to the methods and apparatus of the invention, can be used for a variety of domestic or industrial applications, for example, to reduce microbial or viral populations on a surface or object or in a body or chain of water. The compositions can be applied in a variety of areas including kitchens, bathrooms, factories, hospitals, dental offices, restaurants, closed-loop cleaning applications, clothing or textile applications and food plants, and can be applied to a variety of surfaces hard or soft that have a smooth, irregular or porous topography. Suitable hard surfaces include, for example, architectural surfaces (for example, floors, walls, windows, sinks, tables, counters and slabs); food utensils; hard-surface medical or surgical instruments and devices; and hard surface packaging. Such hard surfaces can be produced from a variety of materials that include, for example, ceramic, metal, glass, wood or hard plastic.
[0164] [00164] Suitable soft surfaces include, for example, paper; filter media, hospital and surgical garments and clothing; soft-surface medical or surgical instruments and devices; and soft surface packaging. Such soft surfaces can be produced from a variety of materials which include, for example, paper, fiber, woven or non-woven cloth, soft plastics and elastomers. The compositions, obtained according to the methods and apparatus of the invention, can also be applied to soft surfaces, such as food and skin (for example, a hand). The present compositions can be used as a sparkling or non-foaming environmental sanitizer or disinfectant.
[0165] [00165] Perforic acid compositions, obtained according to the methods and system of the present invention, can be included in products such as sterilizers, sanitizers, disinfectants, preservatives, deodorants, antiseptics, fungicides, germicides, sporicides, virucides, detergents , bleaches, hard surface cleaners, hand soap, dry hand sanitizers and pre and post-surgical brushing.
[0166] [00166] The compositions can also be used in veterinary products, such as mammalian skin treatments or in a product for cleaning or disinfecting animal enclosures, pig pens, irrigation stations and veterinary treatment areas, such as inspection tables and rooms of operation. The present compositions can be used in an antimicrobial foot bath for herd or people. The compositions can also be employed as an antimicrobial teat dip.
[0167] [00167] In some aspects, the compositions, obtained according to the methods and apparatus of the present invention, can be used to reduce the population of pathogenic microorganisms, such as pathogens of humans, animals and the like. As a person skilled in the art will determine, the reduction of pathogenic microorganism populations is particularly suitable for institutional and health care applications in use. The compositions exhibit activity against pathogens that include fungi, molds, bacteria, spores and viruses, for example, S. aureus, E. coli, Streptococci, Legionella, Pseudomonas aeruginosa, mycobacteria, tuberculosis, phages or the like. Such pathogens can cause a variety of diseases and disorders, including mastitis or other diseases of mammalian milking, tuberculosis and the like. The compositions of the present invention can reduce the population of microorganisms on the skin or other external or mucous surfaces of an animal. In addition, the present compositions can eliminate pathogenic microorganisms that spread through transfer by water, air or a surface substrate. The composition only needs to be applied to the skin, other external and mucous surfaces of an animal, water, air or surface.
[0168] [00168] Perforic acid compositions, obtained according to the methods and apparatus of the present invention, can also be used in food and plant species to reduce surface microbial populations; used at the manufacturing or processing site that handles such foods and plant species; or used to treat process waters around such sites. For example, the compositions can be used in food conveyor lines (for example, as belt sprayers); immersion pots for washing boots and hands; food storage establishments; air circulation systems against deterioration; refrigeration and refrigerant equipment, coolers and beverage heaters, bleachers, cutting boards, three-compartment sink areas and refrigerating or scorching meat devices. The compositions of the invention can be used to treat freshwater transport waters, such as those found in gutters, transport pipes, cutters, dividers, brighteners, replica systems, cleaners and the like. Particular food products that can be translated with compositions of the invention include, but are not limited to, eggs, meats, seeds, leaves, fruits and vegetables. Particular plant surfaces include leaves, roots, seeds, films or barks, stems, stems, tubers, bulbs, fruit both grown and harvested, and the like. The compositions can also be used to treat animal carcasses to reduce both pathogenic and non-pathogenic microbial levels.
[0169] [00169] The compositions can also be used to treat wastewater in which both its antimicrobial function and its oxidizing properties can be used. In addition to the microbial issues surrounding the wastewater, it is also rich in smelly compounds of reduced sulfur, nitrogen or phosphorus. A strong oxidizer, such as the present invention, effectively converts these compounds to their odor-free derivatives, for example, sulfates, phosphates and amine oxides. These same properties are very useful in the pulp and paper industry where the bleaching property is also very useful.
[0170] [00170] In some respects, the compositions, obtained according to the methods and apparatus of the present invention, are useful in cleaning or sanitizing receptacles, processing establishments, or equipment in the food service or food processing industries. The compositions are of particular value for use in food packaging materials and equipment and especially for cold or hot aseptic packaging. Examples of process establishments in which the composition of the invention can be employed include a dairy line, a continuous preparation system, food processing lines, such as pumpable food systems and beverage lines, etc. Food service items can be treated with an antimicrobial and / or disinfected with the composition of the invention. For example, the compositions can also be used in article washing machines, tableware, bottle washers, bottle coolers, heaters, three-compartment sink washers, cutting areas (for example, knives, dividers, cutters and saw blades). water) egg washers or the like. Particular treatable surfaces include, but are not limited to, packaging such as cardboard, bottles, films and resins; tableware, such as glasses, plates, utensils, pots and pans; washing machines for articles; exposed food preparation area surfaces, such as sinks, counters, tables, floors and walls; processing equipment, such as tanks, vats, lines, pumps and hoses (for example, dairy processing equipment for processing milk, cheese, ice cream and other dairy products); and transportation vehicles. Receptacles include glass bottles, PVC bags or polyolefin film, cans, polyester, multi-volume PEN or PET bottles (100 ml to 2 liters, etc.), 4.4 liter (one gallon) milk receptacles, receptacles of cardboard juice or milk, etc.
[0171] [00171] The compositions can also be used in other industrial equipment and in other industrial process currents, such as heaters, cooling towers, boilers, replica waters, rinse waters, aseptic packaging washing waters and the like. The compositions can be used to treat microbes and odors in recreational waters, such as in swimming pools, spas, recreational gutters and water slides, fountains and the like. The composition can also be used in the treatment of microbes found in aqueous systems associated with oil, LP gas recovery, fermentation processes, pulp and paper processes and the like.
[0172] [00172] A filter containing the perfromic acid compositions of the present invention can reduce the population of microorganisms in air and liquids. Such a filter can remove pathogens transmitted by water and air, such as Legionella.
[0173] [00173] The compositions, obtained according to the methods and apparatus of the present invention, can be used to reduce the population of microbes, fruit flies or other insect larvae in a drain or other surface.
[0174] [00174] The compositions of the present invention can also be used by immersing the food processing equipment in the use solution, soaking the equipment for a time sufficient to sanitize or remove stains from the equipment and drying or draining excess equipment solution. The compositions of the present invention can additionally be employed by spraying or wiping the food processing surfaces with the solution in use, keeping the surfaces moist for a sufficient time to sanitize the surfaces, and removing the excess solution drying, draining vertically, vacuuming, etc.
[0175] [00175] The compositions obtained, according to the methods and system of the present invention, can also be used in a method of cleaning hard surfaces, such as institutional type equipment, utensils, crockery, health care equipment and tools and other hard surfaces.
[0176] [00176] The compositions of the present invention can also be used for clothing or textile applications. The compositions can be used by rinsing clothing or textile surfaces with the use solution, keeping the surfaces moist for a sufficient time to wash, remove stains, sanitize, bleach and / or rinse the surface.
[0177] [00177] Perforic acid compositions can be applied to microbes or to dingy or clean surfaces using a variety of methods. These methods can operate on an object, surface, in a body or stream of water or a gas or the like, by bringing the object, surface, body or stream into contact with a composition of the invention. Contact can include any of the numerous methods for applying a composition, such as spraying the composition, immersing the object in the composition, rinsing the composition, treating the object with the composition, foam or gel treatment, applying it with a mopping system or a combination thereof.
[0178] [00178] A concentrate or concentration of use of a perfromic acid composition, obtained according to the methods and apparatus of the present invention, can be applied to or brought into contact with an object by any conventional method or apparatus for applying a antimicrobial or cleaning composition to an object. For example, the object can be wiped with, sprayed with, foamed in and / or immersed in the composition, or a use solution produced from the composition. The compositions can be sprayed, foamed or wiped on a surface; the composition can be made to flow over the surface, or the surface can be immersed within the composition. The contact can be manual or by machine. Food processing surfaces, food products, food processing or transport waters, and the like can be translated with liquid, foam, gel, aerosol, gas, wax, solid or powdered formic acid compositions according to the invention, or solutions that contain these compositions.
[0179] [00179] Other hard surface cleaning applications for compositions include closed circuit cleaning systems (CIP), open circuit cleaning systems (COP), washer decontaminators, sterilizers, textile laundry machines, ultra and nanofiltration systems and indoor air filters. COP systems can include readily accessible systems that include wash tanks, immersion containers, mop buckets, holding tanks, brush sinks, vehicle part washers, non-continuous washers and batch systems, and the like. CIP systems include the internal components of tanks, lines, pumps and other process equipment used to process streams of typically liquid product, such as beverages, milk, juices.
[0180] [00180] A substantially fixed cleaning method in on-site process establishments includes the following steps. A composition in accordance with various embodiments of the invention is introduced into the process establishments at a temperature in the range of about 4 ° C to 60 ° C. After the introduction of the composition, the solution is retained in a receptacle or circulated through the system for a sufficient time to sanitize the process establishments (for example, to eliminate unwanted microorganisms). After the surfaces have been sanitized using the present compositions, the solution is drained. Upon completion of the hygiene step, the system can optionally be rinsed with other materials, such as drinking water. The compositions can be circulated through the process facilities for 10 minutes or less.
[0181] [00181] The present methods may include delivery of the present composition by air delivery to closed circuit cleaning surfaces or other surfaces, such as those inside pipes and tanks. This air delivery method can reduce the volume of solution required. METHODS FOR CONTACTING A FOOD PRODUCT
[0182] [00182] In some respects, the present invention provides methods for bringing a food product into contact with compositions, according to the invention, which employ any method or apparatus suitable for applying such compositions. For example, in some embodiments, the food product is contacted by the compositions with a spray of the compositions, by immersion in the compositions, treating with foam or gel with the compositions. Contact with a spray, foam, gel or immersion can be accomplished by a variety of methods known to those skilled in the art for applying antimicrobial agents to food. The contact of the food product can occur in any location where the food product can be found, such as field, site or processing plant, vehicle, warehouse, store, restaurant or residence. These same methods can also be adapted to apply the compositions of the present invention to other objects.
[0183] [00183] The present methods require a certain minimum contact time of the compositions with the food product for the occurrence of significant antimicrobial effect. The contact time may vary with the concentration of the compositions for use, method of applying the compositions for use, temperature of the compositions for use, amount of dirt in the food product, number of microorganisms in the food product, type of antimicrobial agent or similar . The exposure time can be at least about 5 to about 15 seconds. In some modalities, the exposure time is about 15 to about 30 seconds. In other modalities, the exposure time is at least about 30 seconds.
[0184] [00184] In some embodiments, the method for washing a food product employs a pressure sprayer that includes the compositions of the present invention. During the application of the spray solution to the food product, the surface of the food product can be moved with mechanical action, for example, agitated, rubbed, brushed, etc. The agitation can be by physical rubbing of the food product, through the action of the spray solution under pressure, through sonication or by other methods. Stirring increases the effectiveness of the spray solution in eliminating microorganisms, perhaps due to the better exposure of the solution in the cracks or small colonies that contain the microorganisms. The spray solution, before application, can also be heated to a temperature of about 15 to 20 ° C, for example, about 20 to 60 ° C to increase efficiency. Spray stabilized compositions can be left in the food product for a sufficient amount of time to adequately reduce the microorganism population and then rinsed, drained or evaporated from the food product.
[0185] [00185] The application of the material by spraying can be carried out with the use of a manual water spray application, an automatic spraying of food product that moves along a production line with the use of multiple spray heads to ensure complete contact, or other spray device. An automatic spray application involves the use of a spray booth. The spray booth substantially confines the sprayed compositions within the booth. The production line moves the food product through the entrance into the spray booth where the food product is sprayed on all its exterior surfaces with sprayers inside the booth. After a complete coverage of the material and draining of the material from the food product inside the cabin, the food product can then leave the cabin. The spray booth may include steam jets that can be used to apply the stabilized compounds of the invention. These steam jets can be used in combination with cooling water to ensure that the treatment that reaches the food product surface is less than 65 ° C, for example, less than 60 ° C. The temperature of the spray on the food product is important to ensure that the food product is not substantially altered (cooked) by the temperature of the spray. The spray pattern can be virtually any useful spray pattern.
[0186] [00186] Immersion of a food product in the liquid compositions of the present invention can be carried out by any one of a variety of methods known to those skilled in the art. For example, the food product can be placed inside a tank or bath that contains the compositions. Alternatively, the food product can be transported or processed in a trough of the compositions. The washing solution can be agitated to increase the efficiency of the solution and the speed at which the solution reduces the microorganisms that accompany the food product. Stirring can be achieved by conventional methods, which include ultrasonic, aeration by bubbling air through the solution, by mechanical methods, such as sieves, shovels, brushes, pump-driven liquid jets or combinations of these methods. The washing solution can be heated to increase the solution's effectiveness in eliminating microorganisms. After the food product has emerged long enough for the desired antimicrobial effect, the food product can be removed from the bath or gutter and the compositions can be rinsed, drained, or evaporated from the food product.
[0187] [00187] In other embodiments, a food product can be translated with a sparkling version of the compositions of the present invention. The foam can be prepared by mixing foaming surfactants with the washing solution at the time of use. Foaming surfactants can be non-ionic, anionic or cationic in nature. Examples of types of useful surfactants include, but are not limited to, the following: alcohol ethoxylates, alcohol ethoxylate carboxylate, amine oxides, alkyl sulphates, aqueous ether sulphate, sulphonates, which include, for example, alkyl aryl sulphonates, compounds of quaternary ammonium, aquyl sarcosines, betaines and aquyl amides. The foaming surfactant is typically mixed at the time of use with the washing solution. The solution levels for the use of the foaming agents are from about 50 ppm to about 2.0% by weight. At the time of use, compressed air can be injected into the mixture, then applied to the surface of the food product through a foam application device, such as a foamer or an aspirator mounted on an aspirated wall.
[0188] [00188] In some embodiments, a food product can be translated with a thickened or gelled version of the compositions of the present invention. In the thickened or gelled state, the washing solution remains in contact with the food product surface for longer periods of time, which in this way increases the antimicrobial effectiveness. The thickened or gelled solution will also adhere to vertical surfaces. The compositions can be thickened or gelled using existing technologies, such as: xanthan gum, polymeric thickeners, cellulose thickeners or the like. Rod-forming micelle systems such as amine oxides and anionic counterions can also be used. The thickening and gel forming agents can be used both in the concentrated product and in mixing with the washing solution, at the time of use. Typical usage levels for thickening agents or gels vary from about 100 ppm to about 10% by weight. METHODS FOR DRINKING, FOOD AND PHARMACEUTICAL PRODUCT PROCESSING
[0189] [00189] The compositions of the present invention can be used in the manufacture of beverage, food and pharmaceutical product materials which include fruit juice, dairy products, malted drinks, soy-based products, yogurts, baby foods, water products bottled, teas, cough medicines, drugs and soft drinks. The compositions of the present invention can be used to sanitize, disinfect, act as a sporicide to, or sterilize bottles, pumps, lines, tanks and mixing equipment used in the manufacture of such drinks. In addition, the compositions of the present invention can be used in cold and aseptic filling operations in which the interior of the food, drink or pharmaceutical product container is sanitized or sterilized before filling. In such operations, a receptacle may be placed in contact with the compositions, typically using a spraying, dipping or filling device to place the inside of the receptacle in deep contact with the compositions, for a sufficient period of time to reduce microorganism populations within the receptacle. The receptacle can then be emptied of the amount of sanitizer or sterilizer used. After emptying, the receptacle can be rinsed with drinking water or sterile water and emptied again. After rinsing, the receptacle can be filled with the beverage, food or pharmaceutical product. The receptacle can then be sealed, capped or closed and then packaged for shipment for final sale. The sealed receptacle can be autoclaved or replicated for additional microorganism elimination.
[0190] [00190] In food, beverage or pharmaceutical products, fungal microorganisms of the genus Chaetomium or Arthrinium, and spores or bacteria of the genus Bacillus spp. can be a significant problem in bottling processes, particularly in cold aseptic bottling processes. The compositions of the present invention can be used for the purpose of controlling or substantially reducing (by more than a reduction of 5 log10) the number of Chabazite or Arthrinium or Bacillus microorganisms in beverage, food or pharmaceutical bottling lines with use of cold aseptic bottling techniques.
[0191] [00191] In such techniques, metal, aluminum or steel cans can be filled, glass bottles or receptacles can be filled, or plastic bottles (PET or PBT or PEN), and the like can be filled using the techniques of cold aseptic filling. In such processes, the compositions of the invention can be used to sanitize the interior of beverage receptacles prior to filling with carbonated (or non-carbonated) drink. Typical carbonated drinks in this application include, but are not limited to, cola drinks, fruit drinks, ginger beer drinks, soda drinks with root extract, iced tea drinks that can be non-carbonated, and other common drinks considered sodas. The compositions of the invention can be used to sanitize both tanks, lines, pumps, and other equipment used for the manufacture and storage of refrigerant material and also used in bottling or receptacles for drinks. In one embodiment, the compositions are useful for eliminating both bacterial and fungal microorganisms that may be present on the surfaces of production equipment and beverage receptacles. METHODS FOR INDUSTRIAL PROCESSING
[0192] [00192] In some respects, the invention includes methods of using perfromic acid and / or formic acid-forming compositions to prevent biological fouling in various industries and industrial processes, which includes oil and gas operations, to control microorganism proliferation, eliminate microbial contamination, limit or avoid biological fouling in liquid systems, process water or on the surfaces of equipment that come into contact with such liquid systems. As noted in this document, microbial contamination can occur in various industrial liquid systems that include, but are not limited to, airborne contamination, water build-up, process leakage and improperly cleaned equipment. In another aspect, perfromic acid and / or formic acid-forming compositions are used to control the proliferation of microorganisms in water used in various oil and gas operations. In a further aspect, the compositions are suitable for incorporation into fracturing fluids to control or eliminate microorganisms.
[0193] [00193] For the various industrial processes disclosed in this document, “liquid system” refers to flood waters or an environment within at least one artificial artifact, which contains a substantial amount of liquid that has the ability to undergo biological encrustation , which includes, but is not limited to, industrial liquid systems, industrial water systems, liquid process currents, industrial liquid process currents, industrial process water systems, process water applications, process waters, utility waters, water used in manufacturing, water used in industrial services, aqueous liquid streams, liquid streams containing two or more liquid phases and any combination thereof.
[0194] [00194] In at least one modality, this technology would be applicable to any process or liquid system of utility in which it is known that microorganisms proliferate and are a problem, and biocides are added. Examples of some industrial process water systems in which the method of this invention can be applied are in process water applications (gutter water, shower water, washers, thermal processing water, infusion, fermentation, CIP (circuit cleaning) hard surface cleaning, etc.), ethanol / biofuel process waters, pre-treatment and utility waters (membrane systems, ion exchange beds), water used in the process / papermaking, roof tiles ceiling, fiber board, microelectronics, E-coat or electrodeposition applications, process cleaning, oil exploration and energy services (completion and working fluids, drilling additive fluids, fracturing fluids, flood waters, etc .; oil fields - line of wells / flow of oil and gas, water systems, gas systems, etc.) and, in particular, water systems in which the installed process equipment exhibits inferior compatibility to halogenated biocides.
[0195] [00195] Those skilled in the art will recognize, or have the ability to determine, using nothing more than routine experimentation, numerous equivalents to the specific procedures, modalities, claims and examples described in this document. Such equivalents are considered to be within the scope of this invention and covered by the claims appended thereto. The contents of all references, patents and patent applications cited in the course of this application are incorporated by reference in this document. The invention is further illustrated by the following examples, which are not to be construed as additionally limiting.
[0196] [00196] All publications and patent applications in this specification are indicative of the level of common skill in the technique to which this invention belongs. All publications and patent applications are incorporated into this document for reference to the same extent as if each individual publication or patent application was special and individually indicated for reference. EXAMPLES
[0197] [00197] The modalities of the present invention are further defined in the following non-limiting Examples. It should be understood that these examples, while indicating certain embodiments of the invention, are given by way of illustration only. From the above discussion and these Examples, a person skilled in the art can determine the essential characteristics of this invention, and without departing from the spirit and scope of it, can make several changes and modifications to the modalities of the invention to adapt it to various uses and conditions. Thus, several modifications to the modalities of the invention, in addition to those shown and described in this document, will be evident to those who are versed in the technique from the above description. Such modifications are also intended to fall within the scope of the appended claims.
[0198] [00198] The configuration and software of the equipment were developed for local generation of perfromic acid compositions, which includes perfromic acid and perfromic acid formation compositions for use as biocides. A reactor module that meets the hydraulic requirements of the reaction kinetics has been developed to obtain precise and repeatable generation of active perfromic acid chemical substance. In addition, a software algorithm has been developed to run one or multiple reactor modules to properly sequence events to maximize active throughput and safely operate the reactor module. EXAMPLE 1
[0199] [00199] A single exemplary reaction module was configured according to Figure 2. In the single reaction module, perfromic acid was generated through the addition of formic acid and hydrogen peroxide. A number of correlations have been developed, for example, Figures 5 and 6 illustrate the relationship between fluid volume temperature, cartridge heater film temperature and flow rate. The Figures were created using the SolidWorks Flow package from SolidWorks Computational Fluid Dynamics (CFD) A simplified model was established to analyze the heat transfer characteristics of the formic acid flow inside the generator until the hydrogen peroxide entry. The model was established using the standard pipe sizes 1.27 cm, 2.54 cm and 5.08 cm (½ ”, 1” and 2 ”(inches)) using stainless steel material properties. A 0.64 cm (¼ ”(inch)) cartridge heater in diameter and 15.24 cm in length (6” (inches)) was inserted through a T-connector and into a 25 mm straight pipe section , 4 cm in length (10 ”(inches)). Formic acid entered the computational domain in a T mounted vertically above the cartridge through a 6.35 cm (2.5 ”(inch) pipe nozzle of the appropriate diameter for each simulation. Using this physical model, two inserts were used to generate the data range, inlet flow rate and heater power. The formic acid that entered the computational domain was defined at a flow rate of both 20 and 40 ml / min. The cartridge heater was adopted to generate a uniform surface flow at various power levels to generate the range of data points. For Figure 5, the cartridge film temperature reported was the maximum temperature found anywhere on the cartridge surface. For both Figures, the average outlet surface temperature was taken as an average area of the fluid temperature along a plane normal to the flow at the end of the pipe section 25.4 cm long (10 ”(inches) ).
[0200] [00200] According to Figure 5, there is an approximately linear relationship between the average outlet surface temperature and the film temperature of the cartridge. Additionally, Figure 6 indicates that the heater power divided by the flow rate is linearly related to the average outlet surface fluid temperature.
[0201] [00201] In addition, Figure 7 illustrates heat flow in a flow rate vs. flow contour plot. Temp. input. The data depicted comes from an equation that defines an outlet temperature of 50 ° C at the end of a heating element, and assumes that all heat from the heating element in the perforic acid generator is transferred into the flowing fluid. in addition to the heating element. This provides a minimum value for the amount of heat required. The Figure shows the effect of reagent inlet temperature and heater power, where the higher heater power is required for higher flow rates and lower reagent temperatures can lead to the thermal decomposition of the reagent. Such a problem can be solved by using stepped heaters and / or by adjusting the size of the heating element. EXAMPLE 2
[0202] [00202] A single exemplary reaction model is configured according to Figure 2. The control software maintained at a set point temperature of 50 ° C at the time of adding the peroxide source to the warm formic acid. A formic acid for a 5.21: 1 peroxide pre-combination formulation was used over a series of titrations. An iodometric titration procedure is used. Approximately 200 g of deionized ice water is added to an Erlenmeyer flask together with about 0.30 to about 0.50 grams of sample. The final sample size is saved for later calculations. Approximately 2 ml of glacial acetic acid, 5 ml of 10% potassium iodine solution and 2 ml of starch are added to the sample, which is then placed on a shaking plate and immediately titrated with 0.1% sodium thiosulfate. No titrating to a colorless end point that persisted for at least 20 seconds. The volume of the titrant used is recorded as titrant 1 for later calculations. In the same flask, approximately 3 ml of 9 N sulfuric acid and 2 ml of ammonium molybdate, which is then allowed to rest in the sample for approximately 2 to 3 minutes. The flask is then placed on a shaking plate and immediately titrated with 0.1 N sodium thiosulfate titrating to a second colorless end point that persists for at least 20 seconds. The volume of the titrant used is recorded as titrant 2 for later calculations. Table 1 indicates the results of the iodometric titration method and the subsequent calculations for measuring perfromic acid and hydrogen peroxide.
[0203] [00203] Table 1 shows the ratio of perfromic acid to hydrogen peroxide generated according to the in situ synthesis of perfromic acid in the apparatus of the invention. EXAMPLE 3
[0204] [00204] A single exemplary reaction model is configured according to Figure 2. A conductivity probe was used to take measurements of the reaction. The use of a conductivity probe provides an electroanalytical method for measuring various parameters of a product. Exemplary conductivity sensors comprise two electrodes and operate by applying a voltage across the two electrodes and measuring a resulting current. The relationship between the magnitudes of the current and the voltage allows the resistance and, therefore, the conductivity of the product to be determined.
[0205] [00205] Figure 8 illustrates the results of the experiments. The conductivity of a reagent and product solution is greater than a reagent solution alone. Table 2 further illustrates the correlation between conductivity and perfromic acid concentration.
[0206] [00206] The system according to one embodiment of the invention has been assembled, which includes a downward flow from the oxidizing agent outlet. The system was operated with an inlet flow of 97% formic acid concentration of 17.6 ml / min and an inlet flow of 35% hydrogen peroxide concentration of 2.4 ml / min. Samples were collected in 2, 5, 10 and 15 minutes and tested according to the iodometric titration procedure according to Example 2 for perfromic acid concentration and hydrogen peroxide concentration. These results are shown in Table 3 and Figure 11.
[0207] [00207] The results shown in Table 3 and Figure 11 indicate that the concentration of perfromic acid reached a stable concentration with a standard deviation of 0.007 within the first 2 minutes of the reaction. EXAMPLE 5
[0208] [00208] The peroxyphoric acid generator, according to the modalities represented in the Figures that have multiple inputs to provide a mixture of both formic acid (formic acid, catalyst and corrosion inhibitor) and hydrogen peroxide, was evaluated under field conditions in an upward-scaling volume. The generator was used in a saline water disposal well.
[0209] [00209] Beneficially, the PFA generated exceeded expectations in laboratory analysis. Approximately 15% PFA was generated at the dosing site. The sampling points were at the sampling ports both higher and lower than the laboratory generation compared to the generation in the field are shown in Table 4.
[0210] [00210] The increase in PFA generation is attributed to the modification of high ambient temperatures coupled with the long residual time of the formic / peroxide mixture supplied by the pipeline from the point of generation to the dosing site (27.43 m (90 feet) )). The flow of peroxide and the flow of formic acid were monitored by means of flow meters. Product formation was monitored both by conductivity and by titration methods. The temperatures were monitored with the use of probes in the generator. Both the peroxide flow was challenged due to excessive heat and the pumps that stopped due to air, which are subjected to modification through both initiator self-application valves and ventilation valves that will remove air from the pipeline, which in this way , allows bubble-free flow. EXAMPLE 6
[0211] [00211] The performance of the chemical substance generated in the field, according to Example 5, was evaluated for micro-efficacy. The PFA dosed at 250 ppm (~ 25 ppm active) indicates at least the reduction in microbial numbers equivalent to 2 to 3 logs, as shown in Figure 13. In the Figures, the GB refers to the treatment measurement site (gun barrel) ), while SWD refers to the measurement of wastewater for micro-efficacy.
[0212] [00212] The reduction in the percentage of microbial numbers compared to water from the source was also evaluated. Microbial numbers were monitored using bottles of traditional serial dilution insects that select populations of SRB or APB. All results showed at least a 2 to 3 log reduction and in some cases a 7 log reduction in microbial population.
[0213] [00213] The oxidation potential of PFA iron has been further evaluated as PFA is an oxidizer and has the ability to oxidize FeS to iron oxide. Samples taken from the water from the treatment site (gun barrel) and waste water (SWD) indicate a reduction in FeS concentration during treatment, as shown in Figure 14. One consequence of this is an increased oil production. Beneficially, the wastewater tested in the initial treatment of PFA and after 15 days of treatment and a reduction in FeS was observed. FeS can be moist oil and retains a lot of oil. Upon oxidation, this oil is released. The BS&W analysis provides a quantitative estimate of the amount of water, solids, emulsion and oil present in the samples. This analysis in the two samples indicates 97% of oil, which is an increase of 92% in the total recoverable oil before and after treatment with PFA.
[0214] [00214] With inventions being thus described, it will be obvious that they can be varied in many ways. Such variations should not be considered as departing from the spirit and scope of the inventions and all such modifications are intended to be included within the scope of the following claims.

权利要求:
Claims (10)
[0001]
Generating system or formulator of adjustable biocide for generating the formation of performatic acid formation in the place characterized by the fact that it comprises: an apparatus comprising at least an inlet, a length of pipe, a heating device and an outlet for dosing a composition of formation of performatic acid from said length of pipe; wherein said inlet (or inlets) is in fluid connection with said pipe length and provides reagents to produce said formic acid formation composition at said pipe length; wherein said reagents comprise a source of formic acid and an oxidizing agent; and wherein said pipe length is in fluid connection with said outlet to dispense said perfromic acid formation composition.
[0002]
System according to claim 1, characterized in that said performatic acid formation composition is an individual or mixed performatic acid formation composition according to a selection entered by user or system.
[0003]
System according to claim 2, characterized in that the mixed perfromic acid-forming composition comprises perfromic acid and an additional C1-C22 percarboxylic acid.
[0004]
System according to any one of claims 1 to 3, characterized in that the reagents are free of a chelating agent, a stabilizing agent and a chemical catalyst.
[0005]
System according to any one of claims 1 to 4, characterized in that it additionally comprises at least one measuring device, wherein said measuring device measures one or more reaction kinetics or system operations for said composition generation formation of perfromic acid.
[0006]
System according to any one of claims 1 to 5, characterized in that said heating device maintains a temperature that does not exceed 200 ° C, preferably 180 ° C for the reagent temperature.
[0007]
System according to claim 1, characterized by the fact that it additionally comprises control software for the operation of said device to generate a performatic acid formation composition inserted by user or system and a desired flow rate of said formation formation perfromic acid for local generation.
[0008]
System according to claim 7, characterized by the fact that said control software determines the flow rate and / or the timing of the feed of said raw materials at said pipe length and the reaction time required for the production of said performatic acid formation composition entered by user or system and the desired flow rate.
[0009]
System according to claim 1, characterized by the fact that it additionally comprises means of data emission for sharing information related to said formulation of performatic acid formation composition, consumption or use of performatic acid formation composition, data related to production of additional formic acid-forming composition or combinations thereof.
[0010]
System according to any one of claims 1 to 9, characterized in that it additionally comprises a safety release valve and / or a rupture disc to ventilate the system.

类似技术:

---

公开号 | 公开日 | 专利标题

---

BR112018003971B1|2021-02-17|adjustable biocide generator or formulator system

---

US10827751B2|2020-11-10|Water temperature as a means of controlling kinetics of onsite generated peracids

---

US8858895B2|2014-10-14|Continuous on-line adjustable disinfectant/sanitizer/bleach generator

---

JP5437806B2|2014-03-12|Apparatus and method for making peroxycarboxylic acid

---

US20120207858A1|2012-08-16|Biocide and bleach compositions and related methods

---

US9675065B2|2017-06-13|Biocide and bleach compositions and related methods

同族专利:

---

公开号 | 公开日

---

AU2019208211A1|2019-08-22|

---

CA2997140A1|2017-03-09|

---

CA2997140C|2022-01-11|

---

AU2016318042A1|2018-03-08|

---

US10729131B2|2020-08-04|

---

WO2017040920A1|2017-03-09|

---

AU2016318042B2|2018-10-04|

---

US10172351B2|2019-01-08|

---

US20190069547A1|2019-03-07|

---

AU2018278935A1|2019-01-17|

---

AU2018278935B2|2019-05-16|

---

US20200323205A1|2020-10-15|

---

EP3344601A4|2019-02-20|

---

US20170064949A1|2017-03-09|

---

AU2019208211B2|2020-05-07|

---

BR112018003971A2|2018-09-25|

---

EP3344601A1|2018-07-11|

引用文献:

---

公开号 | 申请日 | 公开日 | 申请人 | 专利标题

---

---

GB8531384D0|1985-12-20|1986-02-05|Unilever Plc|Sanitizing process|

---

EP0460179B1|1989-12-23|1994-12-07|Solvay Interox Limited|Peroxycarboxylic acids|

---

DE4012769A1|1990-04-21|1991-10-24|Hoechst Ag|STABLE PEROXICARBONIC ACID GRANULES|

---

JPH0798816B2|1990-04-25|1995-10-25|宇部興産株式会社|Process for producing ε-caprolactone|

---

GB9012876D0|1990-06-08|1990-08-01|Interox Chemicals Ltd|Peroxycompounds|

---

GB9027975D0|1990-12-22|1991-02-13|Interox Chemicals Ltd|Peroxycarboxylic acid|

---

TW291496B|1991-02-01|1996-11-21|Hoechst Ag|

---

US5141731A|1991-05-24|1992-08-25|Degussa Aktiengesellschaft|Process for the generation of peroxyacids|

---

US5200189A|1991-07-23|1993-04-06|Ecolab Inc.|Peroxyacid antimicrobial composition|

---

US5616281A|1991-12-13|1997-04-01|The Procter & Gamble Company|Acylated citrate esters as peracid precursors|

---

NL9300445A|1993-03-12|1994-10-03|Kemira Peroxides Bv|Method for disinfecting water, such as "drain water" in horticulture, as well as a device to be used therewith.|

---

GB9305863D0|1993-03-22|1993-05-12|Unilever Plc|Peroxyacids|

---

FR2704726B1|1993-05-05|1995-06-16|Chemoxal Sa|Aqueous composition comprising an organic peroxyacid and its uses as disinfecting agents.|

---

NL9301339A|1993-07-30|1995-02-16|Tno Instituut Voor Reinigingst|Peroxyacids or precursors thereof for use in the cleaning of textiles, and methods and devices for cleaning textiles using such peroxyacids or precursors.|

---

GB9325558D0|1993-12-14|1994-02-16|Solvay Interox Ltd|Percaboxylic acids|

---

US6049002A|1994-03-09|2000-04-11|Kemira Chemicals B.V.|Method for the preparation of aqueous solutions containing performic acid as well as their use|

---

GB9411495D0|1994-06-08|1994-07-27|Unilever Plc|Aqueous bleaching compositions comprising peroxy carboxylic acids|

---

DE19530786A1|1995-08-22|1997-02-27|Hoechst Ag|A bleaching composition containing polyoxometalates as a bleach catalyst|

---

US5576282A|1995-09-11|1996-11-19|The Procter & Gamble Company|Color-safe bleach boosters, compositions and laundry methods employing same|

---

EP0822183A3|1996-07-31|1998-07-29|The Procter & Gamble Company|A process for forming a peracid and a composition comprising said peracid|

---

US5817614A|1996-08-29|1998-10-06|Procter & Gamble Company|Color-safe bleach boosters, compositions and laundry methods employing same|

---

FI103899B1|1996-11-06|1999-10-15|Chempolis Oy|A process for preparing a particularly light pulp|

---

GB9626637D0|1996-12-21|1997-02-12|Solvay Interox Ltd|Percarboxyilic acid solutions|

---

GB9720287D0|1997-09-25|1997-11-26|Simms Robert A|Two pack system for the preparation of peracid compositions for teat-dips|

---

DE19812589A1|1998-03-23|1999-10-07|Degussa|Aqueous disinfectant containing performic acid, process for its preparation and its use|

---

EP0948892A1|1998-04-08|1999-10-13|The Procter & Gamble Company|Disinfecting compositions and processes for disinfecting surfaces|

---

JP2000044509A|1998-07-31|2000-02-15|Sumitomo Chem Co Ltd|Fluorine-including carboxylic acid derivative and its production|

---

GB2341553A|1998-09-15|2000-03-22|Procter & Gamble|Peroxyacid treatment|

---

AU6273899A|1998-10-01|2000-04-17|Minntech Corporation|Reverse flow cleaning and sterilizing device and method|

---

US6537958B1|1999-11-10|2003-03-25|The Procter & Gamble Company|Bleaching compositions|

---

WO2000027977A1|1998-11-10|2000-05-18|The Procter & Gamble Company|Bleaching compositions|

---

FR2785768B1|1998-11-17|2001-02-23|Henkel Ecolab Snc|PROCESS FOR TREATING MAMMALIAN FEET AND ESPECIALLY CATTLE|

---

US6548470B1|1998-12-14|2003-04-15|The Procter & Gamble Company|Bleaching compositions|

---

US6262013B1|1999-01-14|2001-07-17|Ecolab Inc.|Sanitizing laundry sour|

---

EP1025759A1|1999-02-02|2000-08-09|SOLVAY |Aqueous disinfectant compositions, process for preparing them and their use|

---

US6548467B2|1999-09-02|2003-04-15|The Procter & Gamble Company|Sanitizing compositions and methods|

---

DE19962343A1|1999-12-23|2001-07-05|Henkel Ecolab Gmbh & Co Ohg|Disinfectant washing of delicate textiles with peracids|

---

EP1125497B1|2000-02-11|2003-06-18|Kesla Forschung u. Service KG|Product for virucidal disinfection of the hands|

---

US20020161258A1|2000-06-06|2002-10-31|Miracle Gregory Scot|Mid-chain branched peracids and peracid precursors|

---

US6783767B2|2002-02-08|2004-08-31|Healthpoint, Ltd.|Low temperature disinfectant/sterilant for medical devices and topical applications|

---

US7682403B2|2004-01-09|2010-03-23|Ecolab Inc.|Method for treating laundry|

---

US7494963B2|2004-08-11|2009-02-24|Delaval Holding Ab|Non-chlorinated concentrated all-in-one acid detergent and method for using the same|

---

US20060177518A1|2005-02-04|2006-08-10|Stevenson Randal D|Peracetic teat dip|

---

US20070249712A1|2005-02-04|2007-10-25|Dee Alejandro O|Peracetic teat dip|

---

MX2008015347A|2005-02-25|2008-12-16|Solutions Biomed Llc|Aqueous disinfectants and sterilants.|

---

US9034390B2|2006-05-02|2015-05-19|Bioneutral Laboratories Corporation|Anti-microbial composition and method for making and using same|

---

US8110603B2|2005-07-27|2012-02-07|Mitsubishi Gas Chemical Company, Inc.|Organic peracid polymer composition and process for producing the same|

---

EP1760141A1|2005-09-06|2007-03-07|SOLVAY |Coated peroxycarboxylic acid granules, process for their preparation and their use in detergent, bleach or disinfection applications|

---

FI118735B|2005-09-13|2008-02-29|Kemira Oyj|Process for the preparation of peroxy acids|

---

EP1780260A1|2005-10-26|2007-05-02|The Procter & Gamble Company|Process of treating fabrics|

---

US7964378B2|2005-12-13|2011-06-21|E.I. Du Pont De Nemours And Company|Production of peracids using an enzyme having perhydrolysis activity|

---

US8075857B2|2006-10-18|2011-12-13|Ecolab Usa Inc.|Apparatus and method for making a peroxycarboxylic acid|

---

US7547421B2|2006-10-18|2009-06-16|Ecolab Inc.|Apparatus and method for making a peroxycarboxylic acid|

---

US20090175956A1|2008-01-08|2009-07-09|Buschmann Wayne E|Method of preparation and composition of antimicrobial ice|

---

US8809392B2|2008-03-28|2014-08-19|Ecolab Usa Inc.|Sulfoperoxycarboxylic acids, their preparation and methods of use as bleaching and antimicrobial agents|

---

PT2358669E|2008-11-20|2014-08-29|Chd Bioscience Inc|Alpha-keto peracids and methods for producing and using the same|

---

US9044403B2|2008-12-18|2015-06-02|Medivators Inc.|Sporicidal hand sanitizing lotion|

---

JP5523021B2|2009-08-25|2014-06-18|キヤノン株式会社|Heterocyclic compound and organic light emitting device using the same|

---

KR101652559B1|2009-09-07|2016-08-30|라이온 가부시키가이샤|Disinfectant composition and disinfecting method|

---

FI125089B|2010-01-21|2015-05-29|Kemira Oyj|Dispensing device assembly for reactive chemicals|

---

DE102010028483A1|2010-05-03|2011-11-03|Henkel Ag & Co. Kgaa|Dosing system for the release of bleach-containing preparations during a washing program of a washing machine|

---

EP2615932B1|2010-09-14|2021-09-08|Pimi Agro Cleantech Ltd. |Methods of treating edible matter and substrates therefor|

---

EP2625256B1|2010-10-08|2017-11-22|Ecolab USA Inc.|Laundry detergent composition for low temperature washing and disinfection|

---

US9321664B2|2011-12-20|2016-04-26|Ecolab Usa Inc.|Stable percarboxylic acid compositions and uses thereof|

---

WO2012090125A2|2010-12-29|2012-07-05|Ecolab Usa Inc.|Sugar ester peracid on-site generator and formulator|

---

EP2687094B1|2010-12-29|2018-05-02|Ecolab USA Inc.|Generation of peroxcarboxylic acids at alkaline pH, and their use as textile bleaching and antimicrobial agents|

---

DE102011076417A1|2011-05-24|2012-11-29|Henkel Ag & Co. Kgaa|Activator systems for peroxygen compounds|

---

US20150018319A1|2013-01-14|2015-01-15|Solutions International, Llc|Treatment of skin disease|

---

US9752105B2|2012-09-13|2017-09-05|Ecolab Usa Inc.|Two step method of cleaning, sanitizing, and rinsing a surface|

---

US20140120179A1|2012-10-26|2014-05-01|Kim R. Smith|Stabilization of peroxycarboxylic acids using amine acid salts|

---

US20140121272A1|2012-10-26|2014-05-01|Ecolab Usa Inc.|Deodorization of peroxycarboxylic acids using chaotropic agents|

---

US9012504B2|2012-10-26|2015-04-21|Ecolab Usa Inc.|Non-enzymatic removal of hydrogen peroxide from peracids|

---

US8822719B1|2013-03-05|2014-09-02|Ecolab Usa Inc.|Peroxycarboxylic acid compositions suitable for inline optical or conductivity monitoring|

---

US20140256811A1|2013-03-05|2014-09-11|Ecolab Usa Inc.|Efficient stabilizer in controlling self accelerated decomposition temperature of peroxycarboxylic acid compositions with mineral acids|

---

MX350446B|2013-09-30|2017-09-07|Chemlink Laboratories Llc|Environmentally preferred antimicrobial compositions.|

---

GB201402257D0|2014-02-10|2014-03-26|Revolymer Ltd|Novel Peracid - containing particle|

---

CA2971416A1|2014-12-18|2016-06-23|Ecolab Usa Inc.|Methods for forming peroxyformic acid and uses thereof|

---

US9518013B2|2014-12-18|2016-12-13|Ecolab Usa Inc.|Generation of peroxyformic acid through polyhydric alcohol formate|

---

WO2017007416A1|2015-07-07|2017-01-12|Delaval Holding Ab|Acid detergent|

---

US10172351B2|2015-09-04|2019-01-08|Ecolab Usa Inc.|Performic acid on-site generator and formulator|

---

EP3904526A1|2015-09-10|2021-11-03|Ecolab USA Inc.|Self indicating antimicrobial chemistry|

---

US9955698B2|2015-10-28|2018-05-01|Buckman Laboratories International, Inc.|Microbicidal compositions including a monochloramine and a peracid, and methods of using the same|

---

KR101625375B1|2016-02-19|2016-05-30|주식회사 지티물류|Anti-vibration vehicle wheel having an improved rim|

---

MA45743A|2016-02-25|2019-01-02|Ecolab Usa Inc|ETHER AMINES FOR BETTER SPORICIDE PERFORMANCE|

---

CN108697079B|2016-03-22|2021-04-06|斯蒂潘公司|Non-alpha-substituted peroxyacids and uses thereof|US9321664B2|2011-12-20|2016-04-26|Ecolab Usa Inc.|Stable percarboxylic acid compositions and uses thereof|

---

US8835140B2|2012-06-21|2014-09-16|Ecolab Usa Inc.|Methods using peracids for controlling corn ethanol fermentation process infection and yield loss|

---

US20140256811A1|2013-03-05|2014-09-11|Ecolab Usa Inc.|Efficient stabilizer in controlling self accelerated decomposition temperature of peroxycarboxylic acid compositions with mineral acids|

---

US10165774B2|2013-03-05|2019-01-01|Ecolab Usa Inc.|Defoamer useful in a peracid composition with anionic surfactants|

---

CA2971416A1|2014-12-18|2016-06-23|Ecolab Usa Inc.|Methods for forming peroxyformic acid and uses thereof|

---

US9518013B2|2014-12-18|2016-12-13|Ecolab Usa Inc.|Generation of peroxyformic acid through polyhydric alcohol formate|

---

US10172351B2|2015-09-04|2019-01-08|Ecolab Usa Inc.|Performic acid on-site generator and formulator|

---

EP3904526A1|2015-09-10|2021-11-03|Ecolab USA Inc.|Self indicating antimicrobial chemistry|

---

EP3373981A4|2015-11-12|2019-05-22|Ecolab USA Inc.|Identification and characterization of novel corrosion inhibitor molecules|

---

CA3007478C|2015-12-16|2020-11-03|Ecolab Usa Inc.|Peroxyformic acid compositions for membrane filtration cleaning|

---

WO2017181005A1|2016-04-15|2017-10-19|Ecolab Usa Inc.|Performic acid biofilm prevention for industrial co2 scrubbers|

---

PL3601157T3|2017-03-24|2021-11-02|Ecolab USA, Inc.|Low risk chlorine dioxide onsite generation system|

---

CN107091832B|2017-05-09|2019-06-25|山东省城市供排水水质监测中心|UV/H2O2The measuring method of typical organic matter reaction rate constant in degradation water|

---

BR112019025357A2|2017-06-22|2020-06-23|Ecolab Usa Inc.|METHOD OF SANITIZING AND / OR ANTIMICROBIAL DISINFECTANT AND LAUNDERING OF WASHING CLOTHES.|

---

BR112019025085A2|2017-06-22|2020-06-23|Ecolab Usa Inc.|ANTIMICROBIAL HYGIENE METHOD AND / OR DISINFECTION AND LAUNDERING OF WASHING CLOTHES.|

---

US11231360B2|2017-06-29|2022-01-25|Hydrite Chemical Co.|Automatic titration device|

---

UY37638A|2017-08-17|2019-02-28|Ecolab Usa Inc|IN SITU GENERATION SYSTEM FOR LOW RISK CHLORINE DIOXIDE|

---

EP3806637A1|2018-06-15|2021-04-21|Ecolab USA Inc.|On site generated performic acid compositions for teat treatment|

---

WO2020243382A1|2019-05-31|2020-12-03|Ecolab Usa Inc.|Method of monitoring peracid concentrations by conductivity measurements and preacid composition|

---

WO2021183516A1|2020-03-09|2021-09-16|Kemira Oyj|Performic acid production systems and methods|

---

US20210300839A1|2020-03-31|2021-09-30|Ecolab Usa Inc.|Method for quenching peroxycarboxylic acid runaway reactions|

法律状态:
2020-06-09| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|

---

2020-12-01| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|

---

2021-02-17| B16A| Patent or certificate of addition of invention granted [chapter 16.1 patent gazette]|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 02/09/2016, OBSERVADAS AS CONDICOES LEGAIS. |

优先权:

---

申请号 | 申请日 | 专利标题

---

US201562214340P| true| 2015-09-04|2015-09-04|

---

US62/214,340|2015-09-04|

---

US201662303746P| true| 2016-03-04|2016-03-04|

---

US62/303,746|2016-03-04|

---

PCT/US2016/050099|WO2017040920A1|2015-09-04|2016-09-02|Performic acid on-site generator and formulator|

---