CN108925556B

CN108925556B - Peroxycarboxylic acid compositions

Info

Publication number: CN108925556B
Application number: CN201810675001.4A
Authority: CN
Inventors: 李俊忠; D·D·麦克谢里; A·布鲁斯特; R·斯特劳布
Original assignee: Ecolab USA Inc
Current assignee: Ecolab USA Inc
Priority date: 2013-03-05
Filing date: 2014-02-20
Publication date: 2022-01-04
Anticipated expiration: 2034-02-20
Also published as: CA2902495C; AU2014226466A1; NZ749649A; MX2015011076A; AU2017251742B2; NZ710927A; CA2902495A1; CN105188775B; CA3223138A1; AU2014226466B2; BR112015021787A2; CN105188775A; AU2017251742A1; BR112015021787B1; CN108925556A; WO2014137605A1

Abstract

Highly acidic, stable and low foaming peroxycarboxylic acid compositions are disclosed having both improved antimicrobial efficacy, and improved shipping and shipping stability, as compared to conventional peroxyoctanoic and peroxyacetic acid compositions for sterilization applications. Peroxycarboxylic acid sterilization compositions containing peroxycarboxylic acid-stabilized fluorescent active compounds are disclosed that are suitable for monitoring by conductivity and/or optical sensors. Advantageously, the sterilized peroxycarboxylic acid compositions are also low odor and low/no VOC dual function acid cleaning and sterilizing compositions.

Description

Peroxycarboxylic acid compositions

This application is a divisional application of application No. 201480011644.9.

Cross reference to related applications

The present application claims priority under 35u.s.c. § 119 of the following applications: U.S. application Ser. No.13/785044(2981US01) entitled "Efficient Stabilizer in Controlling Self accessed compensated Temperature of aerobic Acids composites with minor Acids,"; 13/785047(2982US01), entitled "A Defoamer Usul A Peracid Composition With Anionic Surfactants", and 13/785405(3103US01), entitled "Peroxycarboxylic Acid Compositions capable of being used For insulin Optical Or reduction Monitoring,"; each submitted on 3 months and 5 days 2013. The entire contents of these patent applications, including but not limited to the specification, claims and abstract, and any drawings, tables or figures thereof, are expressly incorporated herein by reference.

Technical Field

The present invention relates to peroxycarboxylic acid compositions according to the invention, which are prone to exothermic decomposition, which are stable under high acidic conditions (e.g. high inorganic acid levels) to provide improved transport and/or storage. The present invention further relates to peroxycarboxylic acid sterilization compositions having advantageous foam profiles under varying water conditions and/or mechanical action during use. The present invention still further relates to peroxycarboxylic acid sterilization compositions containing peroxycarboxylic acid-stabilized fluorescent active compounds suitable for monitoring by conductivity and/or optical sensors. Advantageously, the sterilized peroxycarboxylic acid compositions are also low odor and low/no VOC dual function acid cleaning and sterilizing compositions. Still further, the stable, low foaming composition has improved antimicrobial efficacy for sterilization applications over conventional mixed peroxycarboxylic acid compositions.

Background

Improved stabilization: peroxycarboxylic acids (i.e., peracids, such as peracetic acid) fall into the chemical class of "organic peroxides," which are in turn classified as self-reactive, self-heating substances. Self-reactive materials are strictly regulated by the united states department of transportation (DOT) in accordance with the united states committee guidelines for the transport of hazardous materials (TDG). Similar to DOT in the united states, most regional and national governments strictly comply with the united states TDG guidelines, thus making their "guidelines" essentially a worldwide requirement. These guidelines may be found in the UN document, known as "orange book," entitled communications on the Transport of Dangerous Goods, revision 5, 2009.

The concern with self-heating substances is that most of the decomposition process accelerates with increasing temperature and is usually exponential. A self-heating process that generates heat faster than it cools is defined as a runaway reaction. In the case of organic peroxides, a runaway reaction is accompanied by the generation of large volumes of gas and therefore has the risk of an extreme explosion. An absolute requirement for safety purposes, which has the added benefit of improving both shelf life and quality, is that the rate of heat generation of the organic peroxide-containing product does not exceed the cooling rate of the package. In addition, these self-heating rates limit commercial package size, which in turn limits commercial opportunities, as cooling rates decrease with increasing volume. If, for example, the products fall under UN list 5.2(D), they cannot be sold in packages having a volume of more than 50kg, as do some organic peroxides. Such a limitation may be unacceptable to consumers who consume hundreds of kilograms of product per day.

In summary, there are two aspects (and two sets of tests) that are expected to be addressed by "self-reactive species", the first including characterizing the chemical (5.2A, B, C, D, E, F or G), and the second set of tests evaluating the proposed chemistry of a commercial package. By testing the chemistry of the proposed commercial package, the heat loss characteristics as well as the heat generation characteristics were evaluated at different "ambient" temperatures. The minimum ambient temperature (the temperature at which the chemical self-heats at least 6 degrees celsius above ambient temperature) is defined as the "self-accelerating decomposition temperature" (SADT). The limitations on transportation, storage (i.e. refrigeration requirements) therefore come not only from classification tests but also from SADT. If, for example, the package has a SADT <45 degrees celsius, refrigeration is required. Refrigeration requirements, like classification, severely limit commercial opportunities.

Different factors affect the transportation and/or storage risk and thus require that a particular product be transported below its SADT. For example, the larger the container, the lower its surface-to-volume ratio will be, resulting in less heat being transferred to the surrounding container when undergoing thermal decomposition and a decrease in SADT. This increases the risk of storing and transporting the peroxycarboxylic acid compounds, which are prone to exothermic decomposition, in large containers. This risk can be minimized by storing and transporting such compositions in containers that have been diluted with one or more liquids. The diluted peroxycarboxylic acid may also be formulated as a suspension, emulsion, or solution. Aqueous emulsions or suspensions are generally considered safer formulations because the active peroxide is dispersed in the aqueous phase (e.g., suitable for removing heat that decomposes peroxide molecules, such as by convection and/or evaporation). Commercially available peroxycarboxylic acids are therefore usually sold as equilibrium solutions, which contain the carboxylic acid corresponding to the peroxycarboxylic acid, hydrogen peroxide and water.

The storage and/or transport containers may also be made of substances which are able to withstand the pressure created by the inevitable gaseous decay products, but which must also be made of inert or semi-inert materials. For aqueous organic peroxides, the most common containers are made of high density polyethylene or polypropylene, fitted with a vent cap. No steel is used which is sensitive to corrosion, for example, because it will be treated with transition metal ions such as Fe³⁺Contaminating the product, which is a catalytic decomposition accelerator for most organic peroxides. The package sizes range from a few grams of bottles to bulk storage reservoirs, depending primarily on their category and their package specific SADTs. Still further, the peroxycarboxylic acid compositions can be transported under refrigeration.

In non-refrigerated transport and storage, it becomes almost absolutely necessary to use transition metal chelators or "stabilizers" to raise SADT and maximize the storage life and quality of the organic peroxide. These stabilizers can be used in peroxycarboxylic acid compositions to stabilize the compositions. For example, phosphonate based stabilizers such as phosphoric acid and salts, pyrophosphoric acid and salts, and 1-hydroxyethylidene-1, 1-diphosphonic acid (HEDP) and salts are the most commonly used stabilizers in peroxycarboxylic acid compositions. These stabilizers can significantly improve the stability of the peroxycarboxylic acid compositions when used individually in sufficient concentration, and for conventional (i.e., non-highly acidic) peroxycarboxylic acid compositions, the stability behavior achieved with these stabilizers allows for commercial transport and use of these compositions. However, for peroxycarboxylic acid compositions having highly acidic formulations (including, for example, the use of strong mineral acids), the efficacy of these stabilizers is significantly reduced, and in many cases is substantially absent.

It is therefore an object of the claimed invention to develop stabilized peroxycarboxylic acid compositions having reduced storage and/or transport risks.

In a particular aspect, the stabilized composition overcomes the challenges associated with SADT of conventional peroxycarboxylic acid compositions. In addition these stabilizer compositions can even influence DOT classification, providing in some cases exemption from the typical UN "5.2" class of organic peracids to the reduced risk "5.1" class.

It is another object of the present invention to provide a stabilized peroxycarboxylic acid composition suitable for storage and/or transport at temperatures of at least 50 ℃ without the risk of SADT.

It is still another object of the present invention to provide a stabilized, highly acidic mixed peroxycarboxylic acid composition that employs a unique peracid stabilizer.

Improved foam profile: peroxycarboxylic acids (i.e., peracids) are commercially available as equilibrium solutions containing the carboxylic acid corresponding to the peroxycarboxylic acid, hydrogen peroxide and water. Peroxycarboxylic acids are known to be useful as antimicrobial, disinfectant and/or bleaching agents. However, peroxycarboxylic acid composition formulations (including the selection of peracid-compatible low foaming surfactants) have formulation difficulties, including foam profile, which can interfere with various application applications, including, for example, clean-in-place applications.

It is therefore an object of the claimed invention to develop low foaming, highly acidic peroxycarboxylic acid compositions containing inorganic acids.

It is another object of the present invention to provide a highly acidic mixed peroxycarboxylic acid composition that utilizes a unique combination of low foaming surfactants and defoamers to control foaming under different water conditions, including, for example, deionized water or soft water.

It is still another object of the present invention to provide an antifoaming agent that has a synergistic biocidal efficacy with other peracid components.

Peroxycarboxylic acid monitoring: antimicrobial compositions are used in a variety of automated processing and cleaning applications to reduce the number of microorganisms or viruses on hard or soft surfaces or in bodies of water or streams. Regardless of the application, an antimicrobial or "use" composition is one that contains a specified minimum concentration of one or more active components that exhibit the desired antimicrobial properties. The concentration of the active component in the use composition is selected to achieve the desired level of antimicrobial activity. In use compositions in which one or more peracids are active components, the concentration of hydrogen peroxide tends to increase over time, while the peracid concentration decreases. However, in order to maintain the desired level of antimicrobial activity, the amount of peracid in the use composition must be maintained at a specified minimum concentration. In addition, as the amount of hydrogen peroxide in the use composition increases, the use composition may exceed the prescribed maximum concentration of hydrogen peroxide in solution.

To ensure that the amount of peracid remains at or above some minimum concentration and to determine when the amount of hydrogen peroxide reaches or exceeds the maximum concentration, the concentrations of peracid and hydrogen peroxide in the use composition must be determined. In the past, to determine both peracid concentration and hydrogen peroxide concentration in use compositions, multiple manual titrations were required, several different reagents and a relatively large volume of use composition. Furthermore, the devices and methods used in the past for determining the concentration of both peracid and hydrogen peroxide are only effective over a narrow concentration range.

Accordingly, it is an object of the claimed invention to develop peracid compositions having different beneficial aspects, including compatibility with monitoring of peracid concentration by conductivity and/or optical sensors.

It is another object of the present invention to provide a highly acidic, mixed peroxycarboxylic acid composition having such concentration monitoring compatibility that is also low/no VOC, low odor, low foaming and stable under such highly acidic conditions (e.g., mineral acids in the formulation).

Other objects, advantages and features of the present invention will become apparent from the following specification taken in conjunction with the accompanying drawings.

Disclosure of Invention

The present invention relates to stable, low foaming and/or fluorescent active peroxycarboxylic acid compositions and uses thereof. An advantage of the present invention is that the unusual acidic peroxycarboxylic acid compositions (including mixed peracids) are stabilized without affecting the antimicrobial and/or germicidal efficacy of the composition. Another advantage of the present invention is that the unusual acidic peroxycarboxylic acid compositions (including mixed peracids) are combined with at least one surfactant and an antifoaming agent to provide a wide range of use applications, which are not limited by the foam profile of the composition, and do not affect the antimicrobial and/or germicidal efficacy of the composition. Still another advantage of the present invention is that the peroxycarboxylic acid, inorganic acid and fluorescent active compound provide long term stability of the traceable components of the peroxycarboxylic acid composition concentrate. However, the fluorescent active compounds are also stable in alkaline environments, which provide traceable and/or measurable components. As a result, the composition can be monitored by optical sensors and provided for a wide range of use applications without affecting the antimicrobial and/or sterilization efficacy of the composition.

In one embodiment, the present invention relates to a composition comprising: c₁-C₂₂A carboxylic acid; c₁-C₂₂A percarboxylic acid; hydrogen peroxide; and a stabilizer, wherein the stabilizer is picolinic acid or a compound of formula (IA) below, or a salt thereof:

wherein R is¹Is OH or-NR^1aR^1bWherein R is^1aAnd R^1bIndependently is hydrogen or (C)₁-C₆) An alkyl group; r²Is OH or-NR^2aR^2bWherein R is^2aAnd R^2bIndependently is hydrogen or (C)₁-C₆) An alkyl group; each R³Independently is (C)₁-C₆) Alkyl, (C)₂-C₆) Alkenyl or (C)₂-C₆) An alkynyl group; and n is a number from 0 to 3; or a compound of the following formula (IB):

wherein R is¹Is OH or-NR^1aR^1bWherein R is^1aAnd R^1bIndependently is hydrogen or (C)₁-C₆) An alkyl group; r²Is OH or-NR^2aR^2bWherein R is^2aAnd R^2bIndependently is hydrogen or (C)₁-C₆) An alkyl group; each R³Independently is (C)₁-C₆) Alkyl, (C)₂-C₆) Alkenyl or (C)₂-C₆) An alkynyl group; and n is a number from 0 to 3; and wherein the pH of the composition is about 3 or less.

In another embodiment, the present invention relates to a method of storing and/or transporting a highly acidic, stabilized peroxycarboxylic acid composition comprising: storing the composition, wherein said composition retains at least about 80% of the activity of the C1-C22 percarboxylic acid after storage at about 50 ℃ for about 30 days. In yet another aspect, the present invention relates to a method of transporting a highly acidic, stabilized percarboxylic acid composition, preferably in bulk, wherein the SADT of said composition is increased to at least above 45 ℃ during transportation and/or storage.

In yet another embodiment, the present invention relates to a process for using a highly acidic, stabilized peroxycarboxylic acid composition comprising: providing the peroxycarboxylic acid composition, contacting a surface or substrate with a use solution of the composition for a time sufficient to reduce microbial counts, wherein the use solution has a pH of less than about 4, and wherein the composition retains at least about 80% of the microbial counts after storage at about 50 ℃ for about 30 daysC₁-C₂₂Peroxycarboxylic acid activity.

In another embodiment, the present invention relates to a low foaming balanced peracid composition comprising: c₁-C₂₂A peroxycarboxylic acid; c₁-C₂₂A carboxylic acid; hydrogen peroxide; an inorganic acid; an anionic surfactant; and a metal salt as an antifoaming agent, wherein the use solution pH of the composition is less than about 4. In another aspect, the composition comprises about 1 wt% to about 40 wt% C₁-C₂₂Peroxycarboxylic acid, from about 1% to about 80% by weight of C₁-C₂₂A carboxylic acid, from about 1 wt% to about 80 wt% hydrogen peroxide, from about 1 wt% to about 50 wt% of a mineral acid, from about 0.01 wt% to about 40 wt% of a surfactant, and from about 0.001 wt% to about 10 wt% of a defoamer. In yet another aspect, the composition includes at least one additional agent selected from the group consisting of hydrotropes, solvents, stabilizers, and combinations thereof.

In yet another embodiment, the present invention relates to a method of reducing microbial numbers using a low foaming balanced peroxycarboxylic acid composition comprising: providing the low foaming peroxycarboxylic acid composition described above; and contacting the surface or substrate with a use solution of the composition having a pH of less than about 4 for a time sufficient to reduce the number of microorganisms.

In yet another embodiment, the present invention relates to an equilibrium peracid composition comprising: c₁-C₂₂A peroxycarboxylic acid; c₁-C₂₂A carboxylic acid; hydrogen peroxide; and a fluorescent active compound. In another aspect, the fluorescent active compound is stable in the balanced peracid composition for monitoring peroxycarboxylic acid concentration by an optical sensor. In another aspect, the composition comprises from about 1 wt% to about 40 wt% C₁-C₂₂Peroxycarboxylic acid, from about 1% to about 80% by weight of C₁-C₂₂A carboxylic acid, from about 1 wt% to about 80 wt% hydrogen peroxide, and from about 0.001 wt% to about 10 wt% of a fluorescent active compound.

In yet another embodiment, the present invention relates to a method of monitoring the concentration of peroxycarboxylic acids and/or hydrogen peroxide in a sterilization composition and/or cleaning processA process comprising providing an equilibrium peroxycarboxylic acid composition comprising C₁-C₂₂Peroxycarboxylic acids, C₁-C₂₂Carboxylic acid, hydrogen peroxide and a fluorescent active compound, and wherein the fluorescent active compound is stable in the balanced peracid composition for monitoring peroxycarboxylic acid concentration, including for example by optical sensors. The method further comprises measuring a fluorescence response from the fluorescently active compound in the peroxycarboxylic acid composition with a fluorometer or measuring an optical response from the fluorescently active compound in an optical cell, and determining the concentration of the peroxycarboxylic acid and/or hydrogen peroxide.

While multiple embodiments are disclosed, still other embodiments of the present invention will become apparent to those skilled in the art from the following detailed description, which shows and describes illustrative embodiments of the invention. Accordingly, the drawings and detailed description are to be regarded as illustrative in nature and not as restrictive.

Drawings

Figure 1 shows a graph comparing SADT studies of DPA-stabilized peroxycarboxylic acid compositions and phosphate-based peroxycarboxylic acid compositions according to one embodiment of the present invention.

Figure 2 shows a graph comparing SADT studies of DPA-stable, highly acidic peroxycarboxylic acid compositions with phosphate-based, highly acidic peroxycarboxylic acid compositions according to one embodiment of the present invention.

Fig. 3-4 show graphs comparing SADT studies of highly acidic peracid compositions, where DPA-stabilizers according to embodiments of the present invention provide sufficient stabilization such that the self-heating effect is insufficient to reach the oven temperature within 7 days of time.

Figure 5 shows a graph of foam height comparison formed by different commercially available peracid compositions and low foaming, high acidity peroxycarboxylic acid compositions according to embodiments of the present invention.

Figure 6 shows a graph of the additional biocidal efficacy provided by low foaming, highly acidic peroxycarboxylic acid compositions according to embodiments of the present invention.

Figure 7 shows a graph of the traceability of peroxycarboxylic acid concentration of highly acidic peroxycarboxylic acid compositions according to embodiments of the present invention.

Figure 8 shows a graph of foam height comparisons formed from different commercially available peroxycarboxylic acid compositions and low foaming, highly acidic peroxycarboxylic acid compositions according to embodiments of the invention.

Figure 9 shows a graph of emissions (SU) of highly acidic peroxycarboxylic acid compositions in different types of water according to embodiments of the invention.

Figure 10 shows a graph of the conductivity (us/cm) of highly acidic peroxycarboxylic acid compositions in different types of water according to embodiments of the present invention.

Various embodiments of the present invention will be described in detail with reference to the drawings, wherein like reference numerals represent like parts throughout the several views. Reference to different embodiments does not limit the scope of the invention. The drawings presented herein are not to be limited to the different embodiments of the invention and are presented for illustrative purposes only.

Detailed Description

Embodiments of the present invention are not limited to specific peroxycarboxylic acid compositions and methods of using the same, which can vary and are understood by those skilled in the art. It is further to be understood that all terms used herein are intended to describe specific embodiments only, and are not intended to be limiting in any way or scope. For example, as used in this specification and the appended claims, the singular forms "a," "an," and "the" may include plural referents unless the content clearly dictates otherwise. Further, all units, prefixes, and symbols may be denoted in their SI-recognized form.

The numerical ranges set forth in the specification include the numbers defining the range and include each integer within the defined range. The various aspects of the invention are presented in a range format throughout the present invention. It is to be understood that the description in range format is merely for convenience and brevity and should not be construed as an inflexible limitation on the scope of the invention. Accordingly, the recitation of a range should be considered to disclose explicitly each possible subrange, as well as individual numerical values within that range. For example, recitation of a range such as 1 to 6 should be interpreted to explicitly disclose such sub-ranges as, for example, 1 to 3, 1 to 4, 1 to 5, 2 to 4, 2 to 6, 3 to 6, etc., as well as individual numbers within that range such as, for example, 1, 2, 3, 4, 5, and 6. This applies regardless of the breadth of the range.

Thus, the present invention can be more easily understood when certain terms are first defined. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which embodiments of the present invention belong. Many methods and materials similar, modified or equivalent to those described herein can be used in the practice of embodiments of the present invention without undue experimentation, and the preferred materials and methods are described herein. In describing and claiming embodiments of the present invention, the following terminology will be used in accordance with the definitions set out below.

As used herein, the term "about" refers to a change in quantity that may be typical, for example, through measurement and liquid handling procedures used to make concentrates or use solutions in the real world; inadvertent errors through these procedures; this occurs through the production, source or purity differences, etc. of the ingredients used to produce the composition or perform the method. The term "about" also includes amounts that differ due to different equilibrium conditions for the composition as formed by the particular initial mixture. The claims, whether or not amended with the term "about," include equivalents.

As used herein, the term "cleaning" refers to a process for promoting or assisting in soil removal, bleaching, reduction in microbial numbers, and any combination thereof. As used herein, the term "microorganism" refers to any acellular or unicellular (including cloned) organism. Microorganisms include all prokaryotes. Microorganisms include bacteria (including cyanobacteria), spores, lichens, fungi, protozoa, virosomes, viroids, viruses, bacteriophages and some algae. As used herein, the term "microorganism" is synonymous with microorganism.

As used herein, the term "disinfectant" refers to an agent that kills all viable cells, including most of the recognized pathogenic microorganisms, using the procedures 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 parts, 15 th 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 kills substantially all organisms except for high levels of bacterial spores and is performed by a chemical germicide approved by the food and drug administration for sale as a germicide. As used herein, the term "moderate level disinfection" or "moderate level disinfectant" refers to a compound or composition that kills mycobacteria, most viruses and bacteria with a chemical bactericide registered by the Environmental Protection Agency (EPA) as a tuberculocide. As used herein, the term "low level disinfection" or "low level disinfectant" refers to a compound or composition that kills some viruses and bacteria with a chemical germicide registered by the EPA as a hospital disinfectant.

The term "hard surface" refers to solid, substantially inflexible surfaces such as countertops, tiles, floors, walls, panels, windows, plumbing fixtures, kitchen and bathroom furniture, appliances, engines, circuit boards, and plates. Hard surfaces may include, for example, health care surfaces and food/plant/animal processing surfaces.

As used herein, the term "mixed" or "mixture" when used in reference to a "percarboxylic acid composition," "percarboxylic acid," "peroxycarboxylic acid composition," or "peroxycarboxylic acid" refers to a composition or mixture that includes more than one percarboxylic acid or peroxycarboxylic acid.

In the present patent application, successful microbial reduction is considered to be achieved when the microbial count is reduced by at least about 50%, or to a significantly greater extent than can be achieved by water washing. The greater the reduction in microbial numbers, the greater the level of protection provided. The relevance of antimicrobial agents and compositions is understood in view of the differences in antimicrobial "killing" or "inhibitory" activity (this definition describes the degree of efficacy) and the official laboratory protocols for measuring such efficacy. The antimicrobial composition can affect the destruction of both types of microbial cells. The first is a lethal irreversible effect, which leads to complete microbial cell destruction or incapacitation. The second type of cell damage is reversible so that if the organism is not applied with the agent, it will multiply again. The former are known as microbicidal and the latter are known as microbially inhibited. Sterilizing agents and disinfectants are defined as agents that provide antimicrobial or microbicidal activity. In contrast, preservatives are often described as inhibitors or microbe-inhibiting compositions.

As used herein, the term "sterilant" refers to an agent that reduces the number of bacterial contaminants to a safe level as determined by public health requirements. In one embodiment, the sterilant used in the present invention will provide a reduction (5-log order reduction) of at least 99.999%. These reductions can be performed using the procedures described in Germidic and Detergent Sangiating Action of Disinfectints, Official Methods of Analysis of the Association of Official Analytical Chemists, paragraph 960.09 and applicable parts, 15 th edition, 1990(EPA guidelines 91-2). According to this reference, the sterilant should provide 99.999% reduction (5-log order reduction) at 25 ± 2 ℃ at room temperature in 30 seconds for several test organisms.

As used herein, the terms "sulfoperoxycarboxylic acid," "sulfonated peracid," or "sulfonated peroxycarboxylic acid" refer to the peroxycarboxylic acid form of the sulfonated carboxylic acid. In some embodiments, the sulfonated peracids of the present invention are medium chain sulfonated peracids. As used herein, the term "medium chain sulfonated peracid" refers to a peracid compound comprising a sulfonate group attached to carbon derived from at least one carbon (e.g., three or more) of the carbon of the percarboxylic acid group in the carbon backbone of the percarboxylic acid chain, wherein the at least one carbon is not in a terminal position. As used herein, the term "terminal position" refers to the carbon on the carbon backbone of the percarboxylic acid that is furthest from the percarboxylic group.

As used herein, the terms "weight percent," "wt%", "percent by weight," "wt%", and variations thereof refer to the concentration of a substance that is the weight of that substance divided by the total weight of the composition and multiplied by 100. It is understood that as used herein, "percent," "percent," and the like are intended to be synonymous with "weight percent," "wt%", and the like.

The methods and compositions of the present invention may comprise, consist essentially of, or consist of the components and ingredients of the present invention as well as other ingredients described herein. As used herein, "consisting essentially of" means that the method and composition may include additional steps, components or ingredients, but only that the additional steps, components or ingredients do not materially alter the basic and novel characteristics of the claimed method and composition.

Composition comprising a metal oxide and a metal oxide

Stabilized peroxycarboxylic acids

While understanding the mechanism does not require the practice of the present invention and while the invention is not limited to any particular mechanism of action, it is contemplated that in some embodiments, highly acidic peroxycarboxylic acid compositions are not sufficiently stable when conventional phosphate stabilizers are used. Phosphonates or other metal chelating stabilizers (e.g., HEDP/Dequest 2010) are incompatible and/or ineffective as stabilizers for the highly acidic peracid compositions of the present invention, which results in SADTs that effectively limit the transport and/or storage of these self-accelerating decomposition compounds. The present invention provides peroxycarboxylic acid stabilizing compounds suitable for use in highly acidic, equilibrium compositions. The present invention further provides peroxycarboxylic acid stabilizing compounds suitable for use in compositions having extreme peracid to hydrogen peroxide ratios, wherein the concentration of the peroxyacid significantly exceeds the hydrogen peroxide. In one embodiment, the dipicolinic acid is provided as a peroxycarboxylic acid stabilizer under strongly acidic conditions, instead of a conventional peracid stabilizer, such as Dequest 2010, which is primarily used in commercial peracid products. Advantageously, the peroxycarboxylic acid stabilizer increases the SADT of the composition under strongly acidic conditions, which provides transportation and/or storage benefits.

The stabilized peroxycarboxylic acid compositions according to one embodiment of the invention are suitable for stable storage and/or transport in environments that may sometimes reach about 50 ℃. In one aspect, the stabilized composition retains at least about 80% of the peroxycarboxylic acid activity after storage at about 50 ℃ for about 30 days. Preferably, the peracid composition retains at least about 85%, at least about 90%, or more percent of peracid activity after storage at about 50 ℃ for about 30 days. According to another embodiment, the stabilized composition may be shipped and/or stored, preferably in bulk, wherein the SADT of the composition is raised to at least about 45 ℃ during shipment, or to at least about 50 ℃ or at least about 60 ℃ during shipment (for medium sized packaging).

In one aspect, the composition comprises a concentrated equilibrium composition comprising a stabilizer, a peracid, hydrogen peroxide, a carboxylic acid, a solvent such as water, and optionally additional functional ingredients (e.g., antifoam, fluorescent active compound). In one aspect, the composition includes exemplary ranges of weight percent of the liquid concentrated equilibrium composition shown in table 1.

TABLE 1 stabilized peracid compositions

Low foaming peroxycarboxylic acids

While understanding the mechanism does not require practicing the invention and while the invention is not limited to any particular mechanism of action, it is contemplated that in some embodiments, highly acidic peroxycarboxylic acid compositions are formulated to provide low foaming profiles under different water conditions and/or under mechanical action, which may be present in different use applications, including, for example, clean-in-place applications using high levels of mechanical action/force. The present invention provides peroxycarboxylic acid compositions in highly acidic equilibrium compositions. In one embodiment, a suitable surfactant (e.g., some anionic surfactants) in combination with a defoamer produces critical coupling/wetting that results in improved foam profile compared to known low foaming surfactants, particularly in deionized or soft water. Advantageously, the defoamer is compatible with caustic acidic peroxycarboxylic acid compositions containing mineral acids and unexpectedly produces synergistic biocidal efficacy.

Due to the highly acidic balanced peracid compositions used, and the use of the compositions for high mechanical action/force target applications (e.g., CIP applications), conventional defoamers are incompatible with the compositions or are not effective. For example, such defoamers that are incompatible and/or ineffective for use in highly acidic balanced peracid compositions include silica, silicone or nonionic based defoamers, aliphatic acids or esters; a fatty alcohol; fatty amines or amides; halogenated compounds such as chlorofluorocarbons; vegetable oils, waxes, mineral oils and their sulfonated or sulfated derivatives; a fatty acid; and phosphates such as alkyl and alkaline diphosphates, and tributyl phosphate and the like; and mixtures thereof.

Similarly, the use of different cations (e.g., calcium) to reduce the hydrophilicity of the surfactant may provide antifoaming efficacy, but the cations are incompatible with such peracid compositions and produce precipitation of the surfactant used. Known per-acid compatible different cations (e.g. Mg)²⁺) Fail to provide effective defoaming properties.

In one aspect, the composition comprises a concentrated equilibrium composition comprising a peracid, hydrogen peroxide, a carboxylic acid, a solvent such as water, a surfactant and/or a defoamer, and other optional additional functional ingredients (e.g., stabilizers, fluorescent active compounds). In one aspect, the composition includes exemplary ranges of weight percent of the liquid concentrated equilibrium composition shown in table 2.

TABLE 2

Fluorescent activated peroxycarboxylic acids

While understanding the mechanism does not require the practice of the invention and while the invention is not limited to any particular mechanism of action, it is contemplated that in some embodiments equilibrium peroxycarboxylic acid compositions are formulated to preferably provide highly acidic compositions having stable fluorescently active compounds that allow dose quantification, such as optical measurements. Formulating stable fluorescent active compounds into highly acidic equilibrium peroxycarboxylic acid compositions allows quantification over extended periods of time; for example, over 48 hours of prior art peracid compositions that are combined with the fluorescent component at the point of use. Advantageously, this allows the peroxycarboxylic acid compositions to be formulated to include a fluorescent active compound to replace such points of use with fluorescent compound feeds previously used in certain utility applications. In addition, the present invention is a significant improvement over compositions that form and/or contain peroxycarboxylic acids (which contain only labile fluorescent compounds that are only suitable for visual evaluation of peracids under UV light and in dry conditions to confirm application of the disinfectant). As a result, the concentrated balanced compositions containing stable fluorescent active compounds are suitable for optical measurement of peracid concentrations in various applications, including, for example, clean-in-place, crockery and other sterilization applications, rather than merely visual evaluation of the treated surfaces.

In one aspect, the composition comprises a concentrated equilibrium composition comprising a peracid, hydrogen peroxide, a carboxylic acid, a solvent such as water, a fluorescent active compound, and other optional additional functional ingredients (e.g., stabilizers, surfactants, and/or defoamers). In one aspect, the composition includes exemplary ranges of weight percent of the liquid concentrated equilibrium composition shown in table 3.

TABLE 3

In still other aspects, the compositions of the present invention can comprise non-equilibrium peracid compositions, for example wherein the peroxycarboxylic acid is produced in situ and/or in situ by a process from one or more compositions (e.g., one or more part systems) comprising the respective agents combined according to the present invention. In an exemplary aspect, these agents are described individually herein and include at least one ester of a polyhydric alcohol and a C1-C18 carboxylic acid, an oxidizing agent, an alkalinity source, a solvent, and other functional groups/agents. The acidulant is also described herein as being added to the composition as a reagent after the percarboxylic acid is formed. Alternatively, as described herein, it may be beneficial to provide the reagents in different premix formulations to reduce the number of reagents and/or increase the simplicity of the present invention to produce a peracid composition for a particular use. Premix ingredients suitable for use in the present invention may comprise, consist of and/or consist essentially of at least one ester of a polyhydric alcohol and a C1-C18 carboxylic acid, an oxidizing agent, a solvent, and mixtures thereof. The premix formulation suitable for use in the present invention may also comprise, consist of and/or consist essentially of at least one ester, an oxidizing agent, water, a solvent, a dispersant, a surfactant, a defoamer, and mixtures thereof.

In some aspects of the compositions, whether generated in situ or in situ from one or more premix compositions, or provided as a concentrated equilibrium composition, the pH in the use solution is about 4 or less. Preferably, the pH of the composition in the use solution is at about 3 or less. In one aspect, the use solution of the highly acidic, stable peroxycarboxylic acid composition, when diluted according to EPA sterilant suspension preparation (e.g., 1 ounce of the peracid composition diluted to 8 gallons with 500ppm hard water), has a pH of less than about 3.0, preferably about 2.8-2.9.

Peracid

In accordance with the present invention, peroxycarboxylic acids (i.e., peracids) are included for antimicrobial efficacy in the germicidal compositions disclosed herein. As used herein, the term "peracid" may also be referred to as "percarboxylic acid", "peroxycarboxylic acid" or "peroxyacid". As used herein, sulfoperoxycarboxylic acids, sulfonated peracids, and sulfonated peroxycarboxylic acids are also included in the terms "peroxycarboxylic acid" and "peracid". The terms "sulfoperoxycarboxylic acid," "sulfonated peracid," or "sulfonated peroxycarboxylic acid" refer to a sulfonated carboxylic acid in the peroxycarboxylic acid form, as disclosed in U.S. patent No.8344026 and U.S. patent publication nos. 2010/0048730 and 2012/0052134, each of which is incorporated herein by reference in its entirety. As understood by those skilled in the art, a peracid refers to an acid whose hydrogen in the hydroxyl group of the carboxylic acid is replaced by a hydroxyl group. The oxidizing peracids may also be referred to herein as peroxycarboxylic acids.

The peracid comprises the formula R- - (COOOH)_nWherein R may be hydrogen, alkyl, alkenyl, alkyne, acyclic, alicyclic, aryl, heteroaryl, or heterocyclic, and n is 1, 2, or 3, and is named using peroxy as the prefix for the parent acid. Preferably, R comprises hydrogen, alkyl or alkenyl. The terms "alkyl", "alkenyl", "alkyne", "acyclic radical", "alicyclic radical", "aryl", "heteroaryl" and "heterocyclic radical" are as defined herein.

As used herein, the term "alkyl" refers to saturated hydrocarbons having one or more carbon atoms and includes straight-chain alkyl groups (e.g., methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, etc.), cyclic alkyl groups (or "cycloalkyl" or "alicyclic" or "carbocyclic" groups) (e.g., cyclopropyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, etc.), branched-chain alkyl groups (e.g., isopropyl, tert-butyl, sec-butyl, isobutyl, etc.), and alkyl-substituted alkyl groups (e.g., alkyl-substituted cycloalkyl and cycloalkyl-substituted alkyl groups). Preferably a straight or branched, saturated aliphatic hydrocarbon chain having 1 to 22 carbon atoms, such as, for example, methyl, ethyl, propyl, isopropyl (1-methylethyl), butyl, tert-butyl (1, 1-dimethylethyl) and the like.

Unless otherwise specified, the term "alkyl" includes both "unsubstituted alkyls" and "substituted alkyls". As used herein, the term "substituted alkyl" refers to an alkyl group having a substituent that replaces one or more hydrogens on one or more carbons of the hydrocarbon backbone. Such substituents may include, for example, alkenyl, alkynyl, halogen, hydroxy, alkylcarbonyloxy, arylcarbonyloxy, alkoxycarbonyloxy, aryloxy, aryloxycarbonyloxy, carboxylate, alkylcarbonyl, arylcarbonyl, alkoxycarbonyl, aminocarbonyl, alkylaminocarbonyl, dialkylaminocarbonyl, alkylthiocarbonyl, alkoxy, phosphate, phosphonate, phosphinate, cyano, amino (including alkylamino, dialkylamino, arylamino, diarylamino, and alkylarylamino), acylamino (including alkylcarbonylamino, arylcarbonylamino, carbamoyl and ureido), imino, mercapto, alkylthio, arylthio, thiocarboxylate, sulfate, alkylsulfinyl, sulfonate, sulfamoyl, sulfonamido, nitro, trifluoromethyl, cyano, azido, heterocycle, alkylaryl, or an aromatic (including heteroaromatic) group.

The term "alkenyl" includes unsaturated aliphatic hydrocarbon chains having 2 to 12 carbon atoms, such as, for example, ethenyl, 1-propenyl, 2-propenyl, 1-butenyl, 2-methyl-1-propenyl, and the like. The alkyl or alkenyl groups may be terminally substituted with heteroatoms such as, for example, nitrogen, sulfur or oxygen atoms, which form aminoalkyl, oxyalkyl or thioalkyl groups, e.g., aminomethyl, thioethyl, oxypropyl and the like. Similarly, the above alkyl or alkenyl groups may be interrupted in the chain by heteroatoms to form alkylaminoalkyl, alkylsulfanyl or alkoxyalkyl groups, such as methylaminoethyl, ethylthiopropyl, methoxymethyl and the like.

Furthermore, as used herein, the term "alicyclic" includes any cyclic hydrocarbon group containing from 3 to 8 carbon atoms. Examples of suitable alicyclic groups include cyclopropyl, cyclobutyl, cyclopentyl, and the like. In some embodiments, substituted alkyl groups may include heterocyclic groups. As used herein, the term "heterocyclic group" includes closed ring structures analogous to carbocyclic groups in which one or more carbon atoms in the ring is an element other than carbon, such as nitrogen, sulfur or oxygen. Heterocyclic groups may be saturated or unsaturated. Exemplary heterocyclic groups include, but are not limited to, aziridine, oxirane (epoxide, oxetane), thiirane (episulfide), dioxirane, azetidine, propylene oxide, trimethyleneoxide, diepoxide, ditrimethyleneoxide, dithiocyclobutene, azide (azolidine), pyrrolidine, pyrroline, tetrahydrofuran (oxolane), dihydrofuran, and furan. Further examples of suitable heterocyclic groups include groups derived from tetrahydrofuran, furan, thiophene, pyrrolidine, piperidine, pyridine, pyrrole, picoline, coumalin, and the like.

According to the invention, the alkyl, alkenyl, alicyclic and heterocyclic groups may be unsubstituted or substituted with: for example aryl, heteroaryl, C_1-4Alkyl radical, C_1-4Alkenyl radical, C_1-4Alkoxy, amino, carboxyl, halogen, nitro, cyano, - -SO₃H, phosphino or hydroxy. When the alkyl, alkenyl, alicyclic or heterocyclic group is substituted, the preferred substituent is C_1-4Alkyl, halogen, nitro, amido, hydroxyl, carboxyl, sulfur or phosphino. In one embodiment, R comprises a hydroxy substituted alkyl group. The term "aryl" includes aromatic hydrocarbon groups, including fused aromatic rings, such as phenyl and naphthyl, for example. The term "heteroaryl" includes heterocyclic aromatic derivatives having at least one heteroatom such as, for example, nitrogen, oxygen, phosphorus or sulfur, and includes, for example, furyl, pyrrolyl, thienyl, oxazolyl, pyridyl, imidazolyl, thiazolyl, isoxazolyl, pyrazolyl, isothiazolyl and the like. The term "heteroaryl" also includes fused rings in which at least one of the rings is aromatic, such as, for example, indolyl, purinyl, benzofuranyl, and the like.

According to the invention, aryl and heteroaryl groups may be unsubstituted or substituted on the ring by: for example aryl, heteroaryl, alkyl, alkenyl, alkoxy, amino, carboxyl, halogen, nitro, cyano, - -SO₃H, phosphino or hydroxy. When the aryl, aralkyl or heteroaryl group is substituted, the preferred substituent is C_1-4Alkyl, halogen, nitro, amido, hydroxyl, carboxyl, sulfur or phosphino. In one embodiment, R includes C_1-4Alkyl-substituted aryl.

Suitable peracids include any peroxycarboxylic acid, including peroxycarboxylic acids of varying lengths (e.g., C1-22), which can be prepared by an acid-catalyzed equilibrium reaction between the carboxylic acid and hydrogen peroxide described above. Peroxycarboxylic acids can also be prepared by autoxidation of aldehydes or by reaction of hydrogen peroxide with acid chlorides, anhydrides, carboxylic anhydrides, sodium alcoholates or alkyl and aryl esters. Alternatively, the peracids may be prepared by non-equilibrium reactions, which may be generated In Situ for Use, for example, as disclosed In U.S. patent publication Nos. 2012/0172440 and 2012/0172441, each entitled "In Situ Generation of aerobic Acids at alkali pH, and Methods of Use therof", which are incorporated herein by reference In their entirety. Preferably the composition of the invention comprises peroxyacetic acid, peroxyoctanoic acid, peroxypropionic acid, peroxylactic acid, peroxyheptanoic acid, peroxyoctanoic acid and/or peroxynonanoic acid.

In some embodiments, the peroxycarboxylic acid comprises at least one water-soluble peroxycarboxylic acid in which R comprises an alkyl group of 1 to 22 carbon atoms. For example, in one embodiment, the peroxycarboxylic acid comprises peroxyacetic acid. In another embodiment, R of the peroxycarboxylic acid is an alkyl group of 1 to 22 carbon atoms, which is substituted with a hydroxyl or other polar substituent such that the substituent improves water solubility. Methods for preparing peroxyacetic acid are known to those skilled in the art, including those disclosed in U.S. patent No.2833813, which is incorporated herein by reference in its entirety.

In another embodiment, the sulfoperoxycarboxylic acid has the formula:

wherein R is₁Is hydrogen or substituted or unsubstituted alkyl; r₂Is a substituted or unsubstituted alkylene group; x is hydrogen, a cationic group, or an ester-forming moiety; or a salt or ester thereof. In some embodiments, R₁Is substituted or unsubstituted C_mAn alkyl group; x is a hydrogen cationic group, or an ester-forming moiety; r₂Is substituted or unsubstituted C_nAn alkyl group; m is 1-10; n is 1-10; and m + n is less than 18, or a salt, ester or mixture thereof.

In some embodiments, R₁Is hydrogen. In other embodiments, R₁Is a substituted or unsubstituted alkyl group. In some embodiments, R₁Is a substituted or unsubstituted alkyl group, which excludes cycloalkyl groups.In some embodiments, R₁Is a substituted alkyl group. In some embodiments, R₁Is unsubstituted C₁-C₉An alkyl group. In some embodiments, R₁Is unsubstituted C₇Or C₈An alkyl group. In other embodiments, R₁Is substituted C₈-C₁₀An alkylene group. In some embodiments, R₁Is substituted C₈-C₁₀An alkyl group substituted with at least 1 or at least 2 hydroxyl groups. In yet another embodiment, R₁Is substituted C₁-C₉An alkyl group. In some embodiments, R₁Is substituted C₁-C₉Substituted alkyl with at least 1 SO₃H is substituted. In other embodiments, R₁Is C₉-C₁₀A substituted alkyl group. In some embodiments, R₁Is substituted C₉-C₁₀An alkyl group, wherein at least two carbons of the carbon backbone form a heterocyclic group. In some embodiments, the heterocyclic group is an epoxide group.

In some embodiments, R₂Is substituted C₁-C₁₀An alkylene group. In some embodiments, R₂Is substituted C₈-C₁₀An alkylene group. In some embodiments, R₂Is unsubstituted C₆-C₉An alkylene group. In other embodiments, R₂Is C₈-C₁₀Alkylene which is substituted with at least one hydroxyl group. In some embodiments, R₂Is C₁₀Alkylene which is substituted with at least two hydroxyl groups. In other embodiments, R₂Is C₈Alkylene radical, which is substituted by at least one SO₃H is substituted. In some embodiments, R₂Is substituted C₉A group wherein at least two carbons of the carbon backbone form a heterocyclic group. In some embodiments, the heterocyclic group is an epoxide group. In some embodiments, R₁Is C₈-C₉Substituted or unsubstituted alkyl, and R₂Is C₇-C₈Substituted or unsubstituted alkylene.

These and other suitable sulfoperoxycarboxylic acid compounds for use in the stabilized peroxycarboxylic acid compositions of the present invention are further disclosed in U.S. patent No.8344026 and U.S. patent publication nos. 2010/0048730 and 2012/0052134, which are incorporated herein by reference in their entirety.

In further embodiments, the sulfoperoxycarboxylic acid is combined with a single or mixed peroxycarboxylic acid composition, for example sulfoperoxycarboxylic acid is combined with peroxyacetic acid and peroxyoctanoic acid (PSOA/POOA/POAA). In other embodiments, mixed peracids are used, such as peroxycarboxylic acids comprising at least one limited water solubility peroxycarboxylic acid (in which R comprises an alkyl group of 5 to 22 carbon atoms) and at least one water soluble peroxycarboxylic acid (in which R comprises an alkyl group of 1 to 4 carbon atoms). For example, in one embodiment, the peroxycarboxylic acid comprises peroxyacetic acid and at least one other peroxycarboxylic acid such as those described above. Preferably, the compositions of the present invention include peroxyacetic acid and peroxyoctanoic acid, such as those disclosed in U.S. patent No.5314687, which is incorporated herein by reference in its entirety. In one aspect, the peracid mixture is a hydrophilic peracetic acid and a hydrophobic peroctanoic acid, which provide an antimicrobial synergistic effect. In one aspect, the synergistic effect of the mixed peracid system allows for the use of lower dosages of the peracid.

In another embodiment, ternary peracid mixture compositions such as peroxysulfonated oleic acid, peracetic acid, and peroctanoic acid are used, for example, as disclosed in U.S. patent No.8344026, which is incorporated herein by reference in its entirety. Advantageously, the combination of peroxycarboxylic acids provides compositions having desirable antimicrobial activity in the presence of high organic soil loads. The mixed peroxycarboxylic acid compositions often provide synergistic micro-efficacy. Thus, the compositions of the present invention may comprise peroxycarboxylic acids or mixtures thereof.

Commercially available peracid formulations are commercially available including, for example, peracetic acid (about 15%) sold as EnviroSan (Ecolab, inc., st. paul MN). Most commercial peracid solutions specify specific percarboxylic acid concentrations without mention of using other chemical components in the solution. However, it will be appreciated that commercially available products, such as peracetic acid, will also contain the corresponding carboxylic acid (e.g., acetic acid), hydrogen peroxide and water.

In one aspect, any suitable C₁-C₂₂Percarboxylic acids may be used in the compositions of the present invention. In some embodiments, the C₁-C₂₂The percarboxylic acid being C₂-C₂₀A percarboxylic acid. In other embodiments, the C₁-C₂₂The percarboxylic acid being C₁，C₂，C₃，C₄，C₅，C₆，C₇，C₈，C₉，C₁₀，C₁₁，C₁₂，C₁₃，C₁₄，C₁₅，C₁₆，C₁₇，C₁₈，C₁₉，C₂₀，C₂₁Or C₂₂A carboxylic acid. In still other embodiments, the C₁-C₂₂The percarboxylic acid comprises peroxyacetic acid, peroxyoctanoic acid and/or peroxysulfonated oleic acid.

In one aspect of the invention, the peracid may be selected from concentrated compositions having a hydrogen peroxide to peracid ratio of about 0: 10 to about 10: 0, preferably about 0.5: 10 to about 10: 0.5, preferably about 1: 8-8: 1. the ratio of hydrogen peroxide to peracid is about 0.5: 10 to about 10: 0.5, preferably about 1: 8-8: 1 can be used to produce a use solution for treatment according to the method of the present invention. In another aspect of the invention, the peracid can have a hydrogen peroxide to peracid ratio as low as about 0.01 parts hydrogen peroxide to about 1 part peracid. Without limiting the scope of the invention, this numerical range includes the numbers defining the range and includes each integer within the defined range.

The preferred hydrogen peroxide to peroxycarboxylic acid ratio in the peracid composition can be obtained by a variety of methods suitable for producing very low hydrogen peroxide to peracid ratios. In one aspect, the balanced peracid composition can be distilled to recover a very low hydrogen peroxide peracid mixture. In yet another aspect, the catalyst for hydrogen peroxide decomposition may be combined with a peracid composition, including, for example, a peroxide-reducing agent and/or other biomimetic complex. In yet another aspect, pre-hydrolysis of peracid precursors such as esters (e.g., triacetin) and amides can be used to obtain peracids with very low hydrogen peroxide. These and other methods of Reducing the Hydrogen Peroxide ratio in peracid compositions are disclosed in U.S. patent publication No.2013/0259743, entitled "Use of peracid Acid/Hydrogen Peroxide and catalyst for Treatment of Drilling Fluids, Frac Fluids, Flowback Water and Dispasal Water, and 2013/0264293 and 2013/0264059, entitled" Use of peracid Acid/Hydrogen Peroxide and Peroxide Reducing Agents for Treatment of Drilling Fluids, Frac Fluids, Flowback Water and Dispasal Water ", each of which is incorporated herein by reference in its entirety.

In a preferred aspect, the C₁-C₂₂The percarboxylic acid can be used in any suitable concentration. In some embodiments, the C₁-C₂₂The concentration of percarboxylic acid in the concentrated equilibrium composition is from about 0.1 wt% to about 40 wt%. In other embodiments, the C₁-C₂₂The concentration of percarboxylic acid is from about 1 wt% to about 40 wt%, or from about 1 wt% to about 20 wt%. In still other embodiments, the C₁-C₂₂The concentration of percarboxylic acid is about 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 25, 30, 35, or 40 weight percent. Without limiting the scope of the invention, this numerical range includes the numbers defining the range and includes each integer within the defined range.

Carboxylic acids

The present invention includes carboxylic acid and peracid compositions and hydrogen peroxide. The carboxylic acid comprises the formula R- - (COOH)_nWherein R may be hydrogen, alkyl, alkenyl, alkynyl, acyclic, alicyclic, aryl, heteroaryl, or heterocyclic, and n is 1, 2, or 3. Preferably, R comprises hydrogen, alkyl or alkenyl. The terms "alkyl", "alkenyl", "alkynyl", "acyclic", "cycloaliphatic", "aryl", "or" substituted "alkyl groups,"heteroaryl" and "heterocyclic" groups are defined as above in relation to the peracids.

Examples of suitable carboxylic acids for the peracid balancing system according to the present invention include various monocarboxylic acids, dicarboxylic acids and tricarboxylic acids. Monocarboxylic acids include, for example, formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid, capric acid, undecanoic acid, dodecanoic acid, glycolic acid, lactic acid, salicylic acid, acetylsalicylic acid, mandelic acid, and the like. Dicarboxylic acids include, for example, adipic acid, fumaric acid, glutaric acid, maleic acid, succinic acid, malic acid, tartaric acid, and the like. Tricarboxylic acids include, for example, citric acid, trimellitic acid, isocitric acid, alginic acid, and the like.

In one aspect of the invention, a particularly suitable carboxylic acid is water soluble such as formic, acetic, propionic, butyric, lactic, glycolic, citric, mandelic, glutaric, maleic, malic, adipic, succinic, tartaric acid and the like. Preferably the composition of the invention comprises acetic, caprylic or propionic acid, lactic acid, heptanoic acid, caprylic or pelargonic acid. Additional examples of suitable carboxylic acids are used in sulfoperoxycarboxylic acid or sulfonated peracid systems, as disclosed in U.S. patent No.8344026 and U.S. patent publication nos. 2010/0048730 and 2012/0052134, each of which is incorporated herein by reference in its entirety.

Any suitable C₁-C₂₂Carboxylic acids may be used in the compositions of the present invention. In some embodiments, the C₁-C₂₂The carboxylic acid being C₂-C₂₀A carboxylic acid. In other embodiments, the C₁-C₂₂The carboxylic acid being C₁，C₂，C₃，C₄，C₅，C₆，C₇，C₈，C₉，C₁₀，C₁₁，C₁₂，C₁₃，C₁₄，C₁₅，C₁₆，C₁₇，C₁₈，C₁₉，C₂₀，C₂₁Or C₂₂A carboxylic acid. In still other embodiments, the C₁-C₂₂The carboxylic acid comprises acetic acid, octanoic acid and/or sulfonated oleic acid.

The C is₁-C₂₂The carboxylic acid may be used in any suitable concentration. In some embodiments, the C₁-C₂₂The concentration of carboxylic acid in the equilibrium composition is from about 0.1 wt% to about 90 wt%. In other embodiments, the C₁-C₂₂The concentration of carboxylic acid is from about 1 wt% to about 80 wt%. In still other embodiments, the C₁-C₂₂The concentration of carboxylic acid is from about 1 wt% to about 50 wt%. Without limiting the scope of the invention, this numerical range includes the numbers defining the range and includes each integer within the defined range.

Hydrogen peroxide

The present invention includes hydrogen peroxide. Hydrogen peroxide H₂O₂Provides the advantage of having a high ratio of active oxygen due to its low molecular weight (34.014g/mol) and is compatible with many substances that can be processed by the method of the invention because it is a weakly acidic, transparent and colorless liquid. Another advantage of hydrogen peroxide is that it decomposes into water and oxygen. Having these decomposition products is advantageous because they are generally compatible with the material to be treated. For example, the decomposition products are generally compatible with the metal species (e.g., substantially non-corrosive), and are generally harmless to incidental contact, and are environmentally friendly.

In one aspect of the invention, the hydrogen peroxide is initially present in the antimicrobial peracid composition in an amount effective to maintain a balance between the carboxylic acid, the hydrogen peroxide, and the peracid. The amount of hydrogen peroxide should not exceed an amount that adversely affects the antimicrobial activity of the compositions of the present invention. In another aspect of the invention, the hydrogen peroxide concentration in the antimicrobial peracid composition can be significantly reduced. In some aspects, one advantage of minimizing the concentration of hydrogen peroxide is that the antimicrobial activity of the present compositions is increased compared to conventional balanced peracid compositions.

The hydrogen peroxide may be used in any suitable concentration. In some embodiments, the hydrogen peroxide concentration of the concentrated, equilibrium composition is from about 0.5 wt% to about 90 wt%, or from about 1 wt% to about 90 wt%. In still other embodiments, the concentration of hydrogen peroxide is from about 1 wt% to about 80 wt%, from about 1 wt% to about 50 wt%. Without limiting the scope of the invention, this numerical range includes the numbers defining the range and includes each integer within the defined range.

Advantageously, in providing stabilized balanced peracid compositions, the compositions and methods of the present invention do not rely on and/or are limited to any particular ratio of hydrogen peroxide to peracid for such enhanced stability. Instead, it is surprising that the stabilizer (e.g., DPA) is suitable to provide peracid stability under highly acidic/mineral acid conditions while limiting peracid SADT. This represents a significant improvement over the prior art, where DPA is an optional peracid stabilizer for peracid compositions containing low hydrogen peroxide. See, for example, U.S. publication No.2010/021558, which is incorporated herein by reference in its entirety.

Peracid stabilizers

Peracid stabilizers are included in the compositions of the present invention. Advantageously, the peracid stabilizer prevents the decomposition of the peracid in the balanced peracid composition. In addition, the peracid stabilizers prevent the equilibrium peracid compositions from reaching their self-accelerated decomposition temperature (SADT). The use of peracid stabilizers advantageously stabilizes highly acidic equilibrium peracids (including mixed peracid compositions), as well as extreme chemicals having problematical high peracid to hydrogen peroxide ratios. By increasing the SADT of the composition, the stabilizer contributes a significant safety benefit for the transportation and storage of the composition. In some aspects, the stabilizer delays or prevents the composition from reaching its native SADT.

In one aspect of the invention, the stabilizer is a pyridine carboxylic acid compound. Pyridine carboxylic acids include dipicolinic acid, which includes, for example, 2, 6-pyridinedicarboxylic acid (DPA). In another aspect, the stabilizer is picolinic acid or a salt thereof.

In one aspect of the invention, the stabilizer is picolinic acid or a compound of formula (IA) below, or a salt thereof:

wherein R is¹Is OH or-NR^1aR^1bWherein R is^1aAnd R^1bIndependently is hydrogen or (C)₁-C₆) An alkyl group; r²Is OH or-NR^2aR^2bWherein R is^2aAnd R^2bIndependently is hydrogen or (C)₁-C₆) An alkyl group; each R³Independently is (C)₁-C₆) Alkyl radical (C)₂-C₆) Alkenyl or (C)₂-C₆) An alkynyl group; and n is a number from 0 to 3.

In another aspect of the invention, the peracid stabilizer is a compound of the following formula (IB):

In a preferred aspect, the peracid stabilizer is dipicolinic acid (picolinic acid, 2, 6-pyridinedicarboxylic acid) and provides stability to high inorganic content peracids, wherein the resulting peracid composition has an elevated SADT.

Dipicotinic acid has been used as a stabilizer for peracid compositions, as disclosed, for example, in WO91/07375 and U.S. Pat. No.2609391, which are incorporated herein by reference in their entirety. However, the use of such DPA stabilizers in peracid compositions has not previously been disclosed and/or exploited for its SADT-elevating properties.

In another aspect, the stabilizer may be combined with additional conventional stabilizers, such as phosphonate-based stabilizers, to advantageously provide a further increase in the stability of the composition, and in some aspects, a synergistic increase in the stability of the SADT and peracid of embodiments of the present invention.

The stabilizer may be present in an amount sufficient to provide the targeted stabilization benefit of achieving the desired shelf life and increasing the SADT of the highly acidic peroxycarboxylic acid composition with the pH of the use solution below at least 4, preferably below at least 3. Because the performance of the composition will vary depending on the acidity of the particular peracid composition of the present invention, such peracid stabilizers can be present in the concentrated equilibrium peracid composition in an amount of from about 0.001 wt% to about 25 wt%, from 0.01 wt% to about 10 wt%, and more preferably from about 0.01 wt% to about 1 wt%. Without limiting the scope of the invention, this numerical range includes the numbers defining the range and includes each integer within the defined range.

Inorganic acid

In some embodiments, the compositions of the present invention are strong acid peracids as a result of the inclusion of a strong acid. In some aspects, the pH of the use solution of the peracid composition is 4 or less, and preferably the pH of the use solution is 3 or less. In some embodiments, the compositions of the present invention comprise an inorganic acid. In a preferred embodiment, the composition of the invention comprises an inorganic acid.

Particularly suitable inorganic acids include sulfuric acid (H)₂SO₄) Sodium hydrogen sulphate, nitric acid, sulphamic acid and sulphonic acids of both alkyl and aryl groups, in particular methanesulphonic acid and dodecylbenzenesulphonic acid, toluenesulphonic acid, xylenesulphonic acid, naphthalenesulphonic acid and cumene sulphonic acid, and/or phosphoric acid (H)₃PO₄). Additional phosphonic acids which can be used according to the invention include, for example, aminotrimethylene phosphonic acid, ethylene diamine tetramethylene phosphonic acid, hexamethylene diamine tetramethylene phosphonic acid, diethylene triamine tetramethylene phosphonic acid and 1-hydroxyethylene-1, 1-diphosphonic acid (HEDP).

In another aspect, suitable acids include, but are not limited to, mineral acids. Instead, suitable acids include strong acids, defined as those with a pKa close to or below the lowest pKa of HEDP, which causes significant protonation of HEDP and other phosphate and phosphonate stabilizers and thus reduces their ability to stabilize peracid chemicals. Additional descriptions of mineral acids for use in peracid compositions are disclosed in WO91/07375, which is incorporated herein by reference in its entirety.

In one aspect of the invention, the mineral acid that provides the peracid composition with a strong acidity can be used at any suitable concentration. In some embodiments, the mineral acid concentration of the concentrated equilibrium composition is from about 0.5 wt% to about 50 wt%, or from about 1 wt% to about 50 wt%. In still other embodiments, the concentration of the mineral acid is from about 1 wt% to about 20 wt%, or more preferably from about 5 wt% to about 20 wt%. Without limiting the scope of the invention, this numerical range includes the numbers defining the range and includes each integer within the defined range.

Defoaming agent

The present invention includes an antifoaming agent. Defoamers suitable for use in the peroxycarboxylic acid compositions of the present invention are compatible with the highly acidic peracid composition and the anionic and/or nonionic surfactants useful in the peracid composition. Defoamers suitable for use in the peroxycarboxylic acid compositions of the present invention maintain a low foaming profile under various water conditions, preferably deionized or soft water conditions, and/or under mechanical action. In yet another aspect, the defoamer is compatible with surfactants, preferably anionic surfactants, to achieve key properties such as coupling/wetting, improved material compatibility and enhanced biocidal efficacy. In a preferred aspect, the defoamer provides a synergistic biocidal efficacy.

In one aspect of the invention, the defoaming agent is a metal salt, including, for example, aluminum, magnesium, calcium, zinc and/or other rare earth metal salts. In a preferred aspect, the defoamer is a cation having a high charge density, such as Fe³⁺，Al³⁺And La³⁺. In a preferred aspect, the defoamer is aluminum sulfate.

In one aspect, the defoamer is not a transition metal compound, which is incompatible with the highly acidic balanced peracid compositions of the present invention.

In some embodiments, the compositions of the present invention may include food grade quality anti-foaming agents or anti-foaming agents for a given application of the present methods.

In another embodiment, the compositions of the present invention may include an antifoaming agent that is stable in an acidic environment (e.g., the peracid composition contains an inorganic acid and the use solution has a pH of about 4 or less) and/or is oxidatively stable.

In one aspect of the invention, the defoamer can be used with the surfactants of the invention at any suitable concentration to provide defoaming and to provide synergistic biocidal efficacy. In some embodiments, the defoamer concentration of the concentrated equilibrium composition is from about 0.001 wt% to about 10 wt%, or from about 0.1 wt% to about 5 wt%. In still other embodiments, the concentration of the defoamer is from about 0.1 wt% to about 1 wt%. Without limiting the scope of the invention, this numerical range includes the numbers defining the range and includes each integer within the defined range.

Surface active agent

In some embodiments, the compositions of the present invention comprise a surfactant. Surfactants suitable for use in the compositions of the present invention include, but are not limited to, nonionic surfactants and/or anionic surfactants. Preferably, a low foaming anionic surfactant is included in the peroxycarboxylic acid composition. Advantageously, the use of an antifoaming agent (e.g., aluminum sulfate) in combination with a surfactant, according to embodiments of the present invention, overcomes the foaming problem known to result from the use of conventional low foaming surfactants in peroxycarboxylic acid compositions, particularly deionized water or soft water.

In some embodiments, the compositions of the present invention comprise from about 0 wt% to about 40 wt% of a surfactant. In other embodiments, the compositions of the present invention comprise from about 0.1% to about 40% by weight surfactant, preferably from about 0.1% to about 25% by weight surfactant, and more preferably from about 1% to about 20% by weight surfactant.

Anionic surfactants

Preferably used in the present invention are surface-active substances which are classified as anionic, since the charge on the hydrophobe is electronegative; or surfactants in which the hydrophobic region of the molecule bears no charge until the pH is raised to neutral or higher (e.g., carboxylic acids). Carboxylates, sulfonates, sulfates and phosphates are polar (hydrophilic) solubilizing groups present in anionic surfactants. Among the cations (counter ions) associated with these polar groups, sodium, lithium and potassium impart water solubility; ammonium and substituted ammonium ions provide both water and oil solubility; and calcium, barium and magnesium promote oil solubility. As understood by those skilled in the art, anions are excellent cleaning surfactants and are therefore advantageously added to heavy duty detergent compositions.

Anionic sulfate surfactants suitable for use in the compositions of the present invention include alkyl ether sulfates, alkyl sulfates, linear and branched primary and secondary alkyl sulfates, alkyl ethoxy sulfates, fatty oil-based glycerol sulfates, alkylphenol ethylene oxide ether sulfates, C₅-C₁₇acyl-N- (C)₁-C₄Alkyl) and-N- (C)₁-C₂Hydroxyalkyl) glucosamine sulfates, and sulfates of alkyl polysaccharides such as alkyl polyglycosides, and the like. Also included are alkyl sulfates, alkyl poly (ethyleneoxy) ether sulfates and aromatic poly (ethyleneoxy) sulfates such as the sulfates or condensation products of ethylene oxide and nonylphenol (typically having 1 to 6 oxyethylene groups per molecule).

Anionic sulfonate surfactants suitable for use in the compositions of the present invention also include alkyl sulfonates, linear and branched primary and secondary alkyl sulfonates, and aromatic sulfonates with or without substituents.

Anionic carboxylate surfactants suitable for use in the compositions of the present invention include carboxylic acids (and salts), such as alkanoic acids (and alkanoates), carboxylic acid esters (e.g., alkyl succinates), ether carboxylic acids, sulfonated fatty acids such as sulfonated oleic acid, and the like. Such carboxylates include alkyl ethoxy carboxylates, alkyl aryl ethoxy carboxylates, alkyl polyethoxy polycarboxylate surfactants and soaps (e.g., alkyl carboxylates). Secondary carboxylic acid esters/salts useful in the compositions of the present invention include those comprising a carboxyl unit attached to a secondary carbon. The secondary carbon may be in the ring structure, for example as para-octylbenzoic acid, or as an alkyl-substituted cyclohexyl carboxylate. Secondary carboxylate surfactants typically do not contain ether linkages, ester linkages and hydroxyl groups. In addition, they typically lack a nitrogen atom in the head group (the amphiphilic moiety). Suitable secondary soap surfactants typically contain a total of 11 to 13 carbon atoms, although more carbon atoms (e.g., up to 16) may be present. Suitable carboxylic acid esters/salts also include acyl amino acids (and salts), such as acyl glutamates, acyl peptides, sarcosinates (e.g., N-acyl sarcosinates), taurates (e.g., N-acyl taurates and fatty acid amides of methyl tauric acid), and the like.

Suitable anionic surfactants include alkyl or alkylaryl ethoxy carboxylates of the formula:

R-O-(CH₂CH₂O)_n(CH₂)_m-CO₂X(3)

wherein R is C₈-C₂₂Alkyl or

Wherein R is¹Is C₄-C₁₆An alkyl group; n is an integer from 1 to 20; m is an integer of 1 to 3; and X is a counter ion such as hydrogen, sodium, potassium, lithium, ammonium or an amine salt such as monoethanolamine, diethanolamine or triethanolamine. In some embodiments, n is an integer from 4 to 10 and m is 1. In some embodiments, R is C₈-C₁₆An alkyl group. In some embodiments, R is C₁₂-C₁₄Alkyl, n is 4, and m is 1.

In other embodiments, R is

And R¹Is C₆-C₁₂An alkyl group. In still other embodiments, R¹Is C₉Alkyl, n is 10 and m is 1.

Such alkyl and alkylaryl ethoxy carboxylates are commercially available. These ethoxycarboxylates are typically sold in the acid form, which can be readily converted to the anionic or salt form. Commercially available carboxylic acid esters/salts include Neodox 23-4, C_12-13Alkyl polyethoxy (4) carboxylic acid (Shell Chemical), and Emcol CNP-110, C₉Alkylaryl polyethoxy (10) carboxylic acid (Witco Chemical). Carboxylic acid esters/salts also from Clariant, e.g. products

DTC，C₁₃Alkyl polyethoxy (7) carboxylic acids.

Nonionic surfactant

Useful nonionic surfactants are generally characterized by the presence of both organic hydrophobic and organic hydrophilic groups and are typically produced by condensation of an organic aliphatic, alkylaromatic or polyoxyalkylene hydrophobic compound with a hydrophilic basic oxide moiety which in common practice is ethylene oxide or a polyhydration product thereof, polyethylene glycol. Almost any hydrophobic compound having a hydroxyl, carboxyl, amino or amide group and a reactive hydrogen atom can be condensed with ethylene oxide or its polyhydrated adduct or its mixture with an alkylene oxide such as propylene oxide to form a nonionic surfactant. The length of the hydrophilic polyoxyalkylene moiety (which is condensed with any particular hydrophobic compound) can be readily adjusted to produce a water-dispersible or water-soluble compound having the desired degree of balance of hydrophilicity and hydrophobicity. Useful nonionic surfactants include:

1. block polyoxypropylene-polyoxyethylene polymeric compounds based on propylene glycol, ethylene glycol, glycerol, trimethylolpropane, and ethylene diamine as initiator reactive hydrogen compounds. An example of a polymeric compound produced by sequential propylene and ethylene oxidation of an initiator is under the trade name manufactured by BASF Corp

And

are commercially available.

The compounds are difunctional (two reactive hydrogens) compounds formed by condensation of ethylene oxide with a hydrophobic base formed by the addition of propylene oxide to the two hydroxyl groups of propylene glycol. The molecular weight of such hydrophobic moieties is from about 1000 to about 4000. Ethylene oxide is then added to sandwich this hydrophobe between hydrophilic groups, with the length controlled to between about 10% and about 80% by weight of the final molecule of construction.

The compounds are tetrafunctional block copolymers derived from the sequential addition of propylene oxide and ethylene oxide to ethylene diamine. The molecular weight of the propylene oxide hydrogen form is from about 500 to about 7000; and adding hydrophilic ethylene oxide to make up from about 10% to about 80% by weight of the molecule.

Condensation products of 2.1mol of alkylphenols, where the alkyl chain, in linear or branched configuration, single or two alkyl components, contains from about 8 to about 18 carbon atoms, and from about 3 to about 50mol of ethylene oxide. The alkyl group may be represented, for example, by diisobutylene, dipentyl, polymerized propylene, isooctyl, nonyl, and dinonyl groups. These surfactants may be polyethylene oxide, polypropylene oxide and polybutylene oxide condensates of alkyl phenols. An example of a commercially available compound of this chemical is the trade name manufactured commercially by Rhone-Poulenc

And manufactured by Union Carbide

And (4) selling.

Condensation products of 3.1mol of saturated or unsaturated, linear or branched alcohols having from about 6 to about 24 carbon atoms with from about 3 to about 50mol of ethylene oxide. The alcohol moiety may be derived from a mixture of alcohols in the above carbon rangeOr it may consist of an alcohol having a specific number of carbon atoms within this range. An example of a similar commercially available surfactant is Neodol, trade name manufactured in Shell Chemical Co^TMAlfosic manufactured by Vista Chemical Co^TMAre commercially available.

The condensation product of 4.1 moles of a saturated or unsaturated, straight or branched chain carboxylic acid having from about 8 to about 18 carbon atoms with from about 6 to about 50 moles of ethylene oxide. The acid moiety may consist of a mixture of acids within the above-mentioned carbon atom range or it may consist of an acid having a specific number of carbon atoms within this range. An example of a commercially available compound of this chemical is Nopalcol, a trade name of which is marketed, manufactured by Henkel Corporation^TMLipopeg manufactured by Lipo Chemicals, Inc^TMAre commercially available.

In addition to ethoxylated carboxylic acids (commonly referred to as polyethylene glycol esters), other alkanoic acid esters formed by reaction with glycerides, glycerol, and polyhydric (sugar or sorbitan/sorbitol) alcohols may be used in the present invention for specialized embodiments, particularly indirect food additive applications. All of these ester moieties have one or more reactive hydrogen sites on their molecule which can undergo further acylation or ethylene oxide (alkoxide) addition to control the hydrophilicity of these species. When these fatty esters or acylated carbohydrates are added to the amylase and/or lipase containing compositions of the invention, care must be taken because of potential incompatibility.

Examples of nonionic low foaming surfactants include:

5. a compound from (1) which is modified, substantially reversed, as follows: adding ethylene oxide to ethylene glycol to provide hydrophilicity of a defined molecular weight; propylene oxide is then added to obtain a hydrophobic block at the outside (end) of the molecule. The hydrophobic portion has a molecular weight of about 1000 to about 3100, and the central hydrophilic portion comprises 10% to about 80% by weight of the final molecule. These reversed Pluronics^TMIs sold under the trade name Pluronic by BASF corporation^TMR surfactant. Also, in the same manner as above,Tetronic^TMthe R surfactant is manufactured by BASF corporation by adding ethylene oxide and propylene oxide to ethylene diamine in this order. The hydrophobic portion has a molecular weight of about 2100 to about 6700, and the central hydrophilic portion comprises 10% to 80% by weight of the final molecule.

6. Compounds from groups (1), (2), (3) and (4) which are modified as follows: by reaction with small hydrophobic molecules such as propylene oxide, butylene oxide, benzyl chloride; and short chain fatty acids containing from 1 to about 5 carbon atoms, alcohols or alkyl halides; and mixtures thereof, to "cap" or "end-cap" the terminal hydroxyl or group (polyfunctional moiety) to reduce foaming. Also included are reactants such as thionyl chloride, which converts the terminal hydroxyl groups to chloride groups. Such modification of the terminal hydroxyl groups can result in fully blocked, mixed, heteric or fully mixed non-ions.

Additional examples of effective low foaming nonionic include:

the alkylphenoxypolyethoxyalkanol of U.S. patent No.2903486 to Brown et al, granted on 9/8 1959, and is represented by the formula:

wherein R is an alkyl group of 8 to 9 carbon atoms, A is an alkylene chain of 3 to 4 carbon atoms, n is an integer of 7 to 16, and m is an integer of 1 to 10.

Martin et al, U.S. Pat. No.3048548, issued 8/7/1962, has alternating hydrophilic oxyethylene and hydrophobic oxypropylene chains, where the weight of the terminal hydrophobic chains, the weight of the intermediate hydrophobic units and the weight of the attached hydrophilic units each represent about one third of the condensate.

A defoaming nonionic surfactant disclosed in U.S. Pat. No.3382178 issued 5/7/1968 to Lissant et al having the general formula Z [ (OR)_nOH]_zWherein Z is an oxyalkylatable material, R is a group derived from a basic oxide which may be ethylene and propylene, and n is an integer such as 10 to 2000 orAnd greater, z is an integer determined by the number of reactive oxyalkylatable groups.

Conjugated polyoxyalkylene compounds described in U.S. Pat. No. 2677700 to Jackson et al, granted 5/4/195, which corresponds to formula Y (C)₃H₆O)_n(C₂H₄O)_mH, wherein Y is the residue of an organic compound having from about 1 to 6 carbon atoms and 1 reactive hydrogen atom, n has an average value of at least about 6.4, depending on the hydroxyl number, and m has a value such that the oxyethylene moieties comprise from about 10 to about 90 weight percent of the molecule.

A conjugated polyoxyalkylene compound described in U.S. Pat. No.2674619 issued 4/6 1954 to Lundsted et al, having the formula Y [ (C)₃H₆O_n(C₂H₄O)_mH]_xWherein Y is the residue of an organic compound having from about 2 to 6 carbon atoms and containing x reactive hydrogen atoms, wherein x has a value of at least about 2, n has a value such that the molecular weight of the polyoxypropylene hydrophobe is at least about 900, and m has a value such that the oxyethylene content of the molecule is from about 10 to about 90 weight percent. Compounds falling within the definition of Y include, for example, propylene glycol, glycerol, pentaerythritol, trimethylolpropane, ethylene diamine, and the like. The oxypropylene chain optionally, but advantageously, contains a small amount of ethylene oxide, and the oxyethylene chain also optionally, but advantageously, contains a small amount of propylene oxide.

Further conjugated polyoxyalkylene surfactants which are advantageously used in the compositions of the present invention correspond to the formula: p [ (C)₃H₆O)_n(C₂H₄O)_mH]_xWherein P is the residue of an organic compound having from about 8 to 18 carbon atoms and containing x reactive hydrogen atoms, wherein x has a value of 1 or 2, n has a value such that the molecular weight of the polyoxyethylene moiety is at least about 44, and m has a value such that the oxypropylene content of the molecule is from about 10 to about 90% by weight. In either case, the oxypropylene chain may contain an optional, but advantageously small amount of ethylene oxide, and the oxyethylene chain may also contain an optional, but advantageously small amount of ringsAnd (3) propylene oxide.

8. Suitable polyhydroxy aliphatic amide surfactants for use in the compositions of the present invention include those having the formula R₂CON_R1Those of Z, wherein: r1 is H, C₁-C₄A hydrocarbyl group, 2-hydroxyethyl group, 2-hydroxypropyl group, ethoxy group, propoxy group or a mixture thereof; r₂Is C₅-C₃₁Hydrocarbyl, which may be linear; and Z is a polyhydroxyhydrocarbyl having a linear hydrocarbyl chain with at least 3 hydroxyls directly connected to the chain, or an alkoxylated derivative (preferably ethoxylated or propoxylated) thereof. Z may be derived from a reducing sugar in a reductive amination reaction; such as a glycidyl moiety.

9. Alkyl ethoxylated condensation products of aliphatic alcohols with from about 0 to about 25 moles of ethylene oxide are suitable for use in the compositions of the present invention. The alkyl chain of the aliphatic alcohol may be straight or branched, primary or secondary, and typically contains from 6 to 22 carbon atoms.

10. Ethoxylated C₆-C₁₈Fatty alcohols and C₆-C₁₈Mixed ethoxylated and propoxylated fatty alcohols are suitable surfactants for use in the compositions of the present invention, particularly those that are water soluble. Suitable ethoxylated fatty alcohols include C with a degree of ethoxylation of from 3 to 50₆-C₁₈Ethoxylated fatty alcohols.

11. Suitable nonionic alkyl polysaccharide surfactants, particularly for use in the compositions of the present invention, include those disclosed in U.S. patent No.4565647 to lleado, issued on 21/1 1986. These surfactants include hydrophobic groups containing from about 6 to about 30 carbon atoms and polysaccharides such as polyglycosides and hydrophilic groups containing from about 1.3 to about 10 saccharide units. Any reducing sugar containing 5 or 6 carbon atoms may be used, for example glucose, galactose and galactosyl moieties may be substituted for the glucosyl moieties. (optionally the hydrophobic group is attached at the 2-, 3-, 4-position, etc., thus producing glucose or galactose as opposed to glycoside or galactoside). The intersaccharide linkage may be, for example, between one position of the further saccharide unit and the 2-, 3-, 4-and/or 6-position of the preceding saccharide unit.

12. Fatty acid amide surfactants suitable for use in the compositions of the present invention include those of the formula: r₆CON(R₇)₂Wherein R is₆Is an alkyl group having 7 to 21 carbon atoms, and each R₇Independently of one another is hydrogen, C₁-C₄Alkyl radical, C₁-C₄Hydroxyalkyl radical, or- - (C)₂H₄O)_XH, where x is 1-3.

13. One useful class of nonionic surfactants includes the class of surfactants defined as alkoxylated amines, or most particularly, alcohol alkoxylated/aminated/alkoxylated surfactants. These nonionic surfactants may be represented, at least in part, by the general formula: r²⁰--(PO)_SN--(EO)_tH，R²⁰--(PO)_SN--(EO)_tH(EO)_tH and R²⁰--N(EO)_tH; wherein R is²⁰Is an alkyl, alkenyl or other aliphatic group, or an alkyl-aryl group of 8 to 20, preferably 12 to 14 carbon atoms, EO is oxyethylene, PO is oxypropylene, s is 1 to 20, preferably 2 to 5, t is 1 to 10, preferably 2 to 5, and u is 1 to 10, preferably 2 to 5. Other variations within the scope of these compounds may be represented by alternative formulas: r²⁰--(PO)_V--N[(EO)_wH][(EO)_zH]In which R is²⁰As defined above, v is 1 to 20 (e.g. 1, 2, 3 or 4 (preferably 2)), and w and z are independently 1 to 10, preferably 2 to 5. These compounds are represented commercially by the product line of Huntsman Chemicals as a non-ionic surfactant. Preferred chemicals of this class include Surfonic^TMPEA25 amine alkoxylates. Preferred nonionic surfactants for use in the compositions of the present invention include alcohol alkoxylates, EO/PO block copolymers, alkylphenol alkoxylates, and the like.

The paper Nonionic Surfactants, surface Science Series, volume 1, Marcel Dekker, inc., new york, 1983, edited by Schick, m.j., is an excellent reference for a wide variety of Nonionic compounds commonly used in the practice of the present invention. A typical list of nonionic species and materials for these surfactants is given in U.S. Pat. No.3929678 issued to Laughlin and Heurin at 1975, 12/30. Further examples are given in "Surface Active Agents and detergents" (volumes I and II, Schwartz, Perry and Berch).

Semi-polar nonionic surfactant

Semi-polar types of nonionic surfactants are another class of nonionic surfactants that can be used in the compositions of the present invention. Generally, semi-polar nonionics are high foaming agents and foam stabilizers, which can limit their use in CIP systems. However, in the composition embodiments of the present invention designed for use in high foam cleaning methods, semi-polar nonionic will have immediate utility. The semi-polar nonionic surfactants include amine oxides, phosphine oxides, sulfoxides and alkoxylated derivatives thereof.

14. The amine oxide is a tertiary amine oxide corresponding to the general formula:

wherein the arrow is a conventional representation of a semipolar bond; and R¹，R²And R³May be aliphatic, aromatic, heterocyclic, alicyclic, or a combination thereof. In general, for the purpose of the detergent, R is an amine oxide¹Is an alkyl group of from about 8 to about 24 carbon atoms; r²And R³Is an alkyl or hydroxyalkyl group of 1 to 3 carbon atoms or mixtures thereof; r²And R³May be linked to each other, for example through an oxygen or nitrogen atom, to form a ring structure; r⁴Is a base or a hydroxyalkylene group containing 2 to 3 carbon atoms; and n is 0 to about 20.

Useful water-soluble amine oxide surfactants are selected from coconut or tallow alkyl di (lower alkyl) amine oxides, specific examples of which are dodecyl dimethyl amine oxide, tridecyl dimethyl amine oxide, tetradecyl dimethyl amine oxide, pentadecyl dimethyl amine oxide, hexadecyl dimethyl amine oxide, heptadecyl dimethyl amine oxide, octadecyl dimethyl amine oxide, dodecyl dipropyl amine oxide, tetradecyl dipropyl amine oxide, hexadecyl dipropyl amine oxide, tetradecyl dibutyl amine oxide, octadecyl dibutyl amine oxide, bis (2-hydroxyethyl) dodecyl amine oxide, bis (2-hydroxyethyl) -3-dodecyloxy-1-hydroxypropyl amine oxide, dimethyl- (2-hydroxydodecyl) amine oxide, 3, 6, 9-trioctadecyl) dimethyl amine oxide and 3-dodecyloxy-2-hydroxydodecyl amine oxide Propylbis- (2-hydroxyethyl) amine oxide.

Useful semi-polar nonionic surfactants also include water-soluble phosphine oxides having the following structure:

wherein the arrow is a conventional representation of a semipolar bond; and R¹Is an alkyl, alkenyl or hydroxyalkyl moiety having a chain length of from 10 to about 24 carbon atoms; and R²And R³Each is an alkyl moiety independently selected from alkyl or hydroxyalkyl groups containing from 1 to 3 carbon atoms.

Examples of useful phosphine oxides include dimethyldecylphosphine oxide, dimethyltetradecylphosphine oxide, methylethyltetradecylphosphine oxide, dimethylhexadecylphosphine oxide, diethyl-2-hydroxyoctyldecylphosphine oxide, bis (2-hydroxyethyl) dodecylphosphine oxide and bis (hydroxymethyl) tetradecylphosphine oxide.

Semi-polar nonionic surfactants useful herein also include water-soluble sulfoxide compounds having the following structure:

wherein the arrow is a conventional representation of a semipolar bond; and R¹An alkyl or hydroxyalkyl moiety of from about 8 to about 28 carbon atoms, from 0 to about 5 ether linkages and from 0 to about 2 hydroxyl substituents; and R²Is an alkyl moiety consisting of an alkyl group having 1 to 3 carbon atoms and a hydroxyalkyl group.

Useful examples of such sulfoxides include dodecyl methyl sulfoxide; 3-hydroxytridecyl methyl sulfoxide; 3-methoxytridecylmethyl sulfoxide; and 3-hydroxy-4-dodecyloxybutylmethylsulfoxide.

Semi-polar nonionic surfactants useful in the compositions of the present invention include dimethyl amine oxides, such as lauryl dimethyl amine oxide, myristyl dimethyl amine oxide, cetyl dimethyl amine oxide, combinations thereof, and the like. Useful water-soluble amine oxide surfactants are selected from octyl, decyl, dodecyl, isododecyl, cocoyl or tallowalkyl di (lower alkyl) amine oxides, specific examples of which are octyl dimethyl amine oxide, nonyl dimethyl amine oxide, decyl dimethyl amine oxide, undecyl dimethyl amine oxide, dodecyl dimethyl amine oxide, isododecyl dimethyl amine oxide, tridecyl dimethyl amine oxide, tetradecyl dimethyl amine oxide, pentadecyl dimethyl amine oxide, hexadecyl dimethyl amine oxide, heptadecyl dimethyl amine oxide, octadecyl dimethyl amine oxide, dodecyl dipropyl amine oxide, tetradecyl dipropyl amine oxide, hexadecyl dipropyl amine oxide, tetradecyl dibutyl amine oxide, octadecyl dibutyl amine oxide, bis (2-hydroxyethyl) dodecyl amine oxide, bis (2-hydroxyethyl) -3-dodecyloxy-1-hydroxypropylamine oxide, dimethyl- (2-hydroxydodecyl) amine oxide, 3, 6, 9-trioctadecyldimethylamine oxide and 3-dodecyloxy-2-hydroxypropyldi- (2-hydroxyethyl) amine oxide.

Suitable nonionic surfactants suitable for use in the compositions of the present invention include alkoxylated surfactants. Suitable alkoxylated surfactants include EO/PO copolymers, capped EO/PO copolymers, alcohol alkoxylates, capped alcohol alkoxylates, mixtures thereof, and the like. Suitable alkoxylated surfactants for use as solvents include EO/PO block copolymers, such as Pluronic and reverse Pluronic surfactants; alcohol alkoxylates such as Dehypon LS-54(R- (EO)₅(PO)₄) And Dehypon LS-36(R- (EO)₃(PO)₆) (ii) a And capped alcohol alkoxylates such as Plurafac LF221 and Tegoten EC 11; mixtures thereof and the like.

Additional functional ingredients

In some embodiments, the compositions of the present invention may further comprise additional functional ingredients. In some embodiments, the highly acidic peracid composition includes a defoamer and/or surfactant, a mineral acid, a peroxycarboxylic acid, a carboxylic acid, hydrogen peroxide and water, which make up a substantial or even substantially all of the total weight of the peracid composition. For example, in some embodiments, there are few or no additional functional ingredients present.

In other embodiments, additional functional ingredients may be included in the composition. The functional ingredient provides the desired properties and functionality to the composition. In the present application, the term "functional ingredient" includes materials that, when dispersed or dissolved in a use solution and/or concentrated solution, such as an aqueous solution, provide beneficial properties for a particular use. Some specific examples of functional materials are discussed in more detail below, although the specific materials discussed are given by way of example only, and a wide variety of other functional compositions may also be used. In some aspects, the composition may include stabilizers, additional surfactants, additional antimicrobial agents, anti-redeposition agents, bleaches, solubility modifiers, dispersants, rinse aids, metal protectors, stabilizers, corrosion inhibitors, perfumes and/or dyes, rheology modifiers or thickeners, hydrotropes or coupling agents, buffering agents, solvents and the like.

In a preferred embodiment, the composition further comprises a peracid stabilizer. In another preferred embodiment, the composition does not include a phosphonate based stabilizer (e.g., pyrophosphoric acid and/or salts thereof, HEDP, (H)_n+2PnO_3n+1))。

In a preferred embodiment, the composition further comprises a material that aids in the dissolution of the stabilizer, including, for example, hydrotropes such as Sodium Xylene Sulfonate (SXS), Sodium Cumene Sulfonate (SCS), surfactants such as anionic and nonionic surfactants, and defoamers. In another aspect, the composition may employ an optional hydrotrope to solubilize the stabilizer, including, for example, n-octane sulfonate, xylene sulfonate, naphthalene sulfonate, ethylhexyl sulfate, lauryl sulfate, amine oxide, and the like.

Peracid stabilizers

Peracid stabilizers are preferably included in the compositions of the present invention. Advantageously, the peracid stabilizer prevents the decomposition of the peracid in the balanced peracid composition. In addition, the use of peracid stabilizers also helps to increase the SADT of the composition, which provides a distinct benefit for the transportation and storage of the composition. In some aspects, the stabilizer delays or prevents the composition from reaching its native SADT.

Dipicotinic acid has been used as a stabilizer for peracid compositions, as disclosed in WO91/07375 and U.S. Pat. No.2609391, which are incorporated herein by reference in their entirety. However, the use of such DPA stabilizers in peracid compositions has not previously been disclosed and/or developed for its SADT enhancing performance. In another aspect, the stabilizer may be combined with additional conventional stabilizers, such as phosphonate based stabilizers.

Fluorescent active compounds

In one aspect, the compositions of the present invention are strongly acidic balanced peracids that contain a fluorescent active compound that is stable in the peracid compositions of the present invention. In one aspect, the fluorescent active compound is formulated directly into the balanced peracid composition, instead of being included in a two or more component system (e.g., a peracid precursor or preformed peracid to which the fluorescent active compound is added prior to use and which has short term stability). In additional aspects, the fluorescent active compound is a composition that is further stabilized in and suitable for use in other peracid compositions, including in concentrates and/or use solutions at both acidic and basic pH. For example, in some aspects, the fluorescent active compounds are further stable in highly acidic compositions (e.g., cleaning and disinfecting compositions) and caustic compositions (e.g., laundry compositions). On the other hand, the fluorescent active compound is further stabilized in strong oxidant systems (often used in sterilization compositions) such as chlorine.

In some aspects, the fluorescently active compound can be an inert component of a composition (e.g., a sterile composition). In other aspects, the fluorescent active compound is an active component of a composition (e.g., a cleaning composition).

In one aspect, the fluorescent active compound is an aryl sulfonate. In other aspects, the fluorescent active compound is an alkyl aryl sulfonate. In another aspect, the fluorescent active compound is an aromatic ring having hydrophilic groups (e.g., sulfonate groups, carboxyl groups). Without being bound by a particular theory or mechanism of the present invention, the hydrophilic group comprising an aromatic ring advantageously results in compatibility of the fluorescent active compound with the peracid composition.

Exemplary suitable alkyl aryl sulfonates that can be used in the compositions as the fluorescent active compound can have an alkyl group containing from 0 to 16 carbon atoms and an aryl group that can be at least one of the following: benzene, diphenyl ether and/or naphthalene. Suitable alkyl aryl sulfonates include linear alkyl benzene sulfonates. Suitable linear alkylbenzene sulfonates include linear dodecylbenzyl sulfonate, which may be provided as an acid to neutralize to form the sulfonate. Additional suitable alkyl aryl sulfonates include benzenesulfonate, tosylate, xylenesulfonate, cumene sulfonate, diphenylether disulfonate, naphthalene sulfonate, and naphthalene disulfonate.

Additional exemplary suitable aromatic rings having hydrophilic groups are shown in the following formula:

M＝H⁺or Na⁺

R₁H or alkyl

R₂H or alkyl

M＝H⁺Or Na⁺

R₁H or alkyl

R₂H or alkyl

R₃＝SO₃M, H or alkyl

M＝H⁺Or Na⁺

R₁H or alkyl

R₂H or alkyl

In one aspect, the fluorescent active compound is Sodium Xylene Sulfonate (SXS), such as commercially available from Stepan Company, and/or Sodium Cumene Sulfonate (SCS), such as commercially available from akzo nobel. In one aspect, the fluorescent active compound is sodium alkyldiphenyldisulfonate, such as commercially available from the Dow Company as Dowfax, e.g., Dowfax 2a 1. In one aspect, the fluorescent active compound is sodium naphthalene sulfonate and/or disodium naphthalene disulfonate and/or an alkyl naphthalene sulfonate, such as commercially available as PetroLBA from akzo nobel.

In one aspect, the fluorescently active compound is suitable for indirect food use. In another aspect, the fluorescent active compound is adapted to be greater than mere visual evaluation of peracid concentration (e.g., a UV light source to confirm application of the disinfectant to a dry substrate). Instead, the fluorescently active compound is suitable for dose quantification by optical measurements.

Another fluorescent tracer which may be used in the present application is under the trade name

(Nalco

(Naperville, Ill.)) and/or may be synthesized using techniques known to those skilled in the art of organic chemistry.

In one aspect of the invention, the fluorescent active compound may be used at any suitable concentration. In some embodiments, the concentration of the fluorescent active compound of the concentrated equilibrium composition is from about 0.001 wt% to about 10 wt%, or from about 0.1 wt% to about 10 wt%. In still other embodiments, the concentration of the fluorescently active compound is about 0.5 wt% to about 7.5 wt%, or more preferably about 1 wt% to about 5 wt%. Without limiting the scope of the invention, this numerical range includes the numbers defining the range and includes each integer within the defined range.

Additional functional ingredients

In some embodiments, the compositions of the present invention may further comprise additional functional ingredients. In some embodiments, there is little or no additional functional ingredient present.

In other embodiments, additional functional ingredients may be included in the composition. The functional ingredient provides the desired properties and functionality to the composition. In the present application, the term "functional ingredient" includes materials that, when dispersed or dissolved in a use solution and/or concentrated solution, such as an aqueous solution, provide beneficial properties for a particular use. Some specific examples of functional materials are discussed in more detail below, although the specific materials discussed are given by way of example only, and a wide variety of other functional compositions may also be used. In some aspects, the compositions may include defoamers, surfactants, additional biocides, anti-redeposition agents, bleaches, solubility modifiers, dispersants, rinse aids, metal protectors, stabilizers, corrosion inhibitors, perfumes and/or dyes, rheology modifiers or thickeners, hydrotropes or coupling agents, buffering agents, solvents and the like.

In a preferred embodiment, the composition does not include a phosphonate based stabilizer (e.g., pyrophosphoric acid and/or salts thereof, HEDP, (H)_n+2PnO_3n+1))。

Delivery method and method of use

In one aspect, the invention relates to a method of storing and/or transporting a peroxycarboxylic acid composition, comprising storing the composition, wherein at least about 80% of peroxycarboxylic acid activity is retained after storage for any suitable time under any suitable conditions, for example at least about 80% of peroxycarboxylic acid activity is retained after storage for about 30 days at about 50 ℃. Preferably, the process comprises retaining at least about 85%, at least about 90%, or at least about 95% or more of the peroxycarboxylic acid activity after about 30 days of storage at about 50 ℃.

In another aspect, the invention relates to a method of transporting a composition comprising a peroxycarboxylic acid, the method comprising transporting the composition under ambient conditions, wherein the SADT of the composition is at least about 45 ℃ during transportation. Preferably, the composition has a SADT above at least about 50 ℃, about 55 ℃, about 60 ℃, about 65 ℃ or about 70 ℃. In another aspect, the transportation of the composition containing the peroxycarboxylic acid is conducted in large volumes, e.g., 1000 gallons or more.

In yet another aspect, the present invention includes the use of the composition for sterilizing surfaces and/or products. In another aspect, the compositions of the present invention are particularly suitable for use as hard surface sterilants and/or disinfectants, CIP sterilants, food and/or tissue treatment sterilants (including direct or indirect contact sterilants), environmental sterilants, washing machine bleach and disinfectants, and/or indirect food contact sterilants. The methods of the invention may be used in methods, processes or procedures described and/or claimed in U.S. Pat. nos. 5200189, 5314687, 5718910, 6165483, 6238685, 8017409 and 8236573, each of which is incorporated herein by reference in its entirety.

The method of use is suitable for treating a variety of surfaces, products and/or objects. For example, they may include food or plant items and/or media, containers, devices, systems or facilities for growing, holding, processing, packaging, storing, transporting, preparing, cooking or providing at least a portion of the food or plant items. The method of the invention may be used to treat any suitable plant matter. In some embodiments, the plant item is a grain, fruit, plant or flower plant item, a surviving plant item or a harvested plant item. In addition, the process of the invention may be used to treat any suitable food item such as an animal product, animal carcass or egg, fruit item, plant item or grain item. In still other embodiments, the food item may comprise fruit, grain and/or plant items.

The method of the present invention may be used to treat an object, which is a container, device, system or facility for holding, processing, packaging, storing, transporting, preparing, cooking or providing at least a portion of the food item or plant item. In some embodiments, the target is a container, device, system, or facility for holding, processing, packaging, storing, transporting, preparing, cooking, or providing at least a portion of a meat item, a fruit item, a plant item, or a grain item. In other embodiments, the target is a container, device, system, or facility for holding, processing, packaging, storing, or transporting at least a portion of an animal carcass. In still other embodiments, the target is a container, device, system or facility for use in at least a portion of the food processing, food providing or healthcare industries. In still other embodiments, the target is at least a portion of a processing facility that is fixed in place. An exemplary fixed-in-place processing facility may comprise a milk production line, a continuous brewing system, a pumpable food system or a beverage processing line.

The method of the invention may be used to treat an object, which is at least a portion of a solid surface or a liquid medium. In some embodiments, the solid surface is an inanimate solid surface. The inanimate solid surface may be contaminated with biological fluids such as blood-containing biological fluids, other hazardous bodily fluids, or mixtures thereof. In other embodiments, the solid surface may be a contaminated surface. An exemplary soiled surface may comprise a surface of a food serving vessel or device, or a fabric surface.

Different treatment methods may include using any suitable level of the peroxycarboxylic acid. In some embodiments, the target composition being treated comprises from about 10ppm to about 1000ppm of the peroxycarboxylic acid, including any peroxycarboxylic acid composition of the invention.

In still another aspect, the invention includes water treatment methods and other industrial methods of using the compositions for sterilizing surfaces and/or products. In some aspects, the invention includes methods of using the peroxycarboxylic acid compositions to prevent biofouling in various industrial processes and industries, including oil and gas operations, to control microbial growth, eliminate microbial contamination, limit or prevent biofouling on liquid systems, process waters, or surfaces of equipment in contact with such liquid systems. As referred to herein, microbial contamination can occur in various industrial liquid systems, including but not limited to airborne contamination, water conditioning, process leaks, and improper cleaning of equipment. In another aspect, the peroxycarboxylic acid compositions are used to control the growth of microorganisms in water used in various oil and gas operations. In another aspect, the composition is suitable for incorporation into a fracturing fluid to control or eliminate microorganisms.

For the various industrial processes disclosed herein, a "fluid system" refers to an environment that is filled with water or within at least one manufactured article, which contains a substantial amount of a fluid capable of biofouling, and includes, but is not limited to, industrial fluid systems, industrial water systems, fluid process streams, industrial process water systems, process water applications, process water, utility water, water used in manufacturing, water used in industrial services, aqueous fluid streams, fluid streams containing two or more fluid phases, and any combination thereof.

In at least one embodiment, this technique will be applicable to any such process or utility liquid system where it is known that microorganisms can grow and be problematic, and where biocides are added. Examples of some industrial process water systems in which the process of the invention can be used are process water applications (tank water, shower water, washers, hot process water, brewing, fermentation, CIP (clean in place), hard surface sterilization, etc.), ethanol/biofuel process water, pre-treatment and service water (membrane systems, ion exchange beds) for processing/manufacturing water in: paper, ceiling tile, fiberboard, microelectronics, electrocoating or electrodeposition applications, process cleaning, oil recovery and energy services (completion and service on fluids, drilling additive fluids, fracturing fluids, water flooding, etc.; oil field-oil gas well/flow lines, water systems, gas systems, etc.), and in particular water systems where installed processing equipment exhibits reduced compatibility with halogenated biocides.

The method of introducing the peroxycarboxylic acid composition into an aqueous fluid or liquid system is not critical. The introduction of the peracid composition can be carried out in a continuous or batch manner and will depend on the type of water and/or liquid to be treated. In some embodiments, the peracid composition is incorporated into an aqueous fluid according to the Method disclosed in U.S. patent application Serial No.13/645671, entitled "New Method and Arrangement for Feeding Chemicals in o a hydrorefining Process and Oil and Gas Applications", which is incorporated herein by reference in its entirety.

Those skilled in the art will recognize, or be able to ascertain using no more than routine experimentation, numerous equivalents to the specific procedures, embodiments, claims, and examples described herein. Such equivalents are considered to be within the scope of this invention and are covered by the claims appended hereto. The contents of all references, patents, and patent applications cited throughout this application are hereby incorporated by reference to the same extent as if each individual publication or parent application were specifically and individually indicated to be incorporated by reference. All publications and patent applications in this specification are indicative of the level of skill of those skilled in the art to which this invention pertains. The invention is further illustrated by the following examples, which should not be construed as further limiting.

The various use applications described herein provide the peroxycarboxylic acid compositions to surfaces, liquids, and/or products in need of antimicrobial and/or sterilization treatment. Advantageously, the compositions of the present invention are fast acting. However, the method of the present invention requires a certain minimum contact time of the composition with the surface, liquid and/or product to be treated in order for sufficient antimicrobial effect to occur. The contact time may vary with the concentration of the use composition, the method of applying the use composition, the temperature of the use composition, the pH of the use composition, the surface to be treated, the amount of liquid and/or product, the surface to be treated, the amount of soil or substrate on/in the liquid and/or product, and the like. The contact or exposure time may be at least about 15 seconds. In some embodiments, the exposure time is about 1-5 minutes. In other embodiments, the exposure time is at least about 10 minutes, 30 minutes, or 60 minutes. In other embodiments, the exposure time is from a few minutes to a few hours. In other embodiments, the exposure time is from a few hours to a few days. The contact time will further vary based on the peracid concentration in the use solution.

The process of the invention may be carried out at any suitable temperature. In some embodiments, the process of the invention is carried out at a temperature of from about 0 ℃ to about 70 ℃, for example from about 0 ℃ to about 4 ℃ or 5 ℃, from about 5 ℃ to about 10 ℃, from about 11 ℃ to about 20 ℃, from about 21 ℃ to about 30 ℃, from about 31 ℃ to about 40 ℃, including at a temperature of from about 37 ℃, from about 41 ℃ to about 50 ℃, from about 51 ℃ to about 60 ℃, or from about 61 ℃ to about 70 ℃.

The composition is suitable for broad-spectrum antibacterial effect of microorganism, and can provide broad-spectrum antibacterial and antifungal activity. For example, the peracid biocides of the present invention provide broad spectrum activity against a wide range of different types of microorganisms (including both aerobic and anaerobic microorganisms), including bacteria, yeasts, molds, fungi, algae and other problematic microorganisms.

The methods of the invention may be used to achieve any suitable reduction in the number of microorganisms in and/or on the target or treated target composition. In some embodiments, the methods of the present invention can be used to reduce the number of microorganisms in and/or on a target or treated target composition by at least one log₁₀. In other embodiments, the methods of the present invention can be used to reduce the number of microorganisms in and/or on a target or treated target composition by at least two logs₁₀. In still other embodimentsIn another aspect, the methods of the present invention can be used to reduce the number of microorganisms in and/or on a target or treated target composition by at least three logs₁₀。

The peroxycarboxylic acid composition may comprise a concentrated composition or may be diluted to form a use composition. Generally, a concentrate refers to a composition intended to be diluted with water to provide a use solution in contact with a surface, liquid and/or product to be treated to provide desired cleaning, sterilization, and the like. The peroxycarboxylic acid composition contacted with the surface, liquid and/or product to be treated may be referred to as a concentrate or use composition (or use solution), depending on the formulation used in the process of the invention. It will be appreciated that the concentration of peroxycarboxylic acid in the composition will vary depending on whether the composition is provided as a concentrate or as a use solution.

The use solution may be prepared from a concentrate by diluting the concentrate with water at a dilution ratio to provide the use solution with the desired sterilization and/or other antimicrobial properties. The water used to dilute the concentrate to form the use composition may be referred to as dilution water or diluent, and may vary from location to location. Typical dilution rates are from about 1 to about 10000, but will depend on factors including water hardness, the amount of soil to be removed, and the like. In one embodiment, the concentrate is a concentrate of about 1: 10 to about 1: 10000 concentrate: water ratio. Specifically, the concentrate is a mixture of about 1: 100 to about 1: 5000 of concentrate: water ratio. More specifically, the concentrate is a concentrate of about 1: 250 to about 1: 2000 concentrate: water ratio.

Method for monitoring and/or determining peracid concentration

The method of monitoring and/or detecting the concentration of peracid and/or hydrogen peroxide in use compositions using the peracid compositions of the present invention provides the distinct benefit of tracking, monitoring and/or measuring such concentrations in various peroxycarboxylic acid compositions, including balanced peracid compositions, as well as other strongly oxidizing compositions, such as sterilization compositions. Previously, various inert fluorescent tracers (e.g., 1, 3, 6, 8-pyrenetetrasulfonic acid tetrasodium salt, 2-anthracenesulfonic acid sodium salt, etc.) have been used and are disclosed, for example, in U.S. Pat. No.7910371, which is incorporated herein by reference in its entirety; however, these fluorescent compounds are not approved for non-rinse food contact applications and are unstable in the highly concentrated balanced peracid compositions and/or strong oxidizing compositions of the present invention.

In one aspect, the methods of the invention are suitable for monitoring and/or detecting the concentration of peroxycarboxylic acid compositions delivered to systems and/or cleaning applications. In another aspect, the methods of the present invention are suitable for monitoring and/or detecting the concentration of peroxycarboxylic acid compositions circulating within the system and/or within a cleaning application (e.g., before and/or during application). In yet another aspect, the methods of the present invention are suitable for monitoring and/or detecting the concentration of peroxycarboxylic acid compositions stored and/or contained prior to administration.

In one aspect of the invention, the method of monitoring and/or detecting the concentration of a peroxycarboxylic acid composition is suitable for long-term use due to the stability of the fluorescent active compound within different compositions, including within the equilibrium peroxycarboxylic acid composition. Advantageously, the fluorescently active compound is stable and can be monitored and/or detected for at least about 180 days, preferably at least about 12 months or longer, according to the methods disclosed herein.

The compositions of the present invention are suitable for monitoring the concentration of peroxycarboxylic acid compositions using absorbance or fluorescence. As will be appreciated by those skilled in the art, fluorescence can be measured using a variety of different and suitable techniques. For example, based on substantially continuous fluorescence emission spectroscopy (e.g., fluorometric monitoring) at least for a given time, is one of the preferred analytical techniques according to one embodiment of the present invention. One method for continuous in-process measurement of chemical tracers by fluorescence emission spectroscopy and other analytical methods is described in U.S. patent No.4992380, incorporated herein by reference.

Examples of fluorometers that can be used in practicing the invention include Xe II and Xe

8000 fluorometer (available from Nalco Company); a Hitachi F-4500 fluorometer (available from Hitachi through Hitachi Instruments Inc.); JOBIN YVON FluoroMax-3 "SPEX" fluorometer (available from JOBIN YVON Inc.); and a Gilford Fluoro-IV spectrometer or SFM25 (available from Bio-tech Kontron through Research Instruments International). It should be understood that the foregoing list is not comprehensive and is intended to merely show an example of a representative fluorometer. Other commercially available fluorometers and modifications thereof can also be used in the present invention.

In another aspect, a variety of other suitable assay techniques can be used to measure the amount of the fluorescently active compound. Examples of such techniques include combined HPLC-fluorescence analysis, colorimetric analysis, ion selective electrode analysis, transition metal analysis, chemiluminescence, pulsed fluorescence measurement, and the like.

In one aspect, this allows for precise control of the dosage of the peroxycarboxylic acid composition. For example, the fluorescent signal of the fluorescent active compound can be used to determine the concentration of peroxycarboxylic acid and/or hydrogen peroxide in the cleaning and/or sterilization system. In one aspect, the fluorescent signal of the fluorescently active compound is then used to determine whether a desired amount of peroxycarboxylic acid and/or hydrogen peroxide is present in the concentrate and/or use solution. As a result, the supply of the concentrate and/or use solution of the composition of the invention can thus be regulated.

The fluorescent active compound is used to detect fluorescence at one or more locations within a storage vessel, cleaning system, water system, pipeline, etc., containing/containing the peroxycarboxylic acid composition of the invention (or use solution thereof), as determined by one skilled in the art. In one aspect, the fluorescence is correlated to the concentration of peroxycarboxylic acid and/or hydrogen peroxide in the test solution. Optionally, corrective action may be taken.

In one aspect, the methods of the invention comprise providing one or more fluorometers and placing said fluorometers in situ to sample a use solution of the concentrated peroxycarboxylic acid compositions of the invention. In one aspect, the fluorometer is positioned within or along a feed line that delivers the peroxycarboxylic acid composition to a cleaning application, such as a warewasher and/or CIP application, for example.

The compositions of the present invention are also suitable for monitoring by conductivity and/or optical sensors (which may also be referred to as optical cells and/or optical detectors), such as the methods and/or apparatus disclosed in, for example, U.S. patent publication nos. 2012/014912, 2012/0085931 and 2011/0260079, and U.S. patent nos. 8229204, 8187540, 8143070, 8119412, 8076155, 8076154, 8071390 and 7169236, each of which is incorporated herein by reference in its entirety. The devices, sensors and/or batteries suitable for measuring or monitoring the peroxycarboxylic acid and/or hydrogen peroxide content in the use solution according to the invention are not limiting. Advantageously, any device, sensor and/or battery that is compatible with the highly acidic peroxycarboxylic acid compositions of the present invention can be used.

In one aspect, the method of the present invention comprises providing one or more optical sensors/cells and placing said optical sensors/cells in situ to measure a sample of a use solution of the concentrated peroxycarboxylic acid composition of the present invention. In one aspect, the optical sensor/cell is positioned within or along a feed line that delivers the peroxycarboxylic acid composition to a cleaning application, such as a warewasher and/or CIP application, for example.

In one aspect, the methods of the invention comprise measuring the concentration of peracid and/or hydrogen peroxide using the composition as a result of formulating the composition to include a fluorescent active compound. In one aspect of the invention, the monitoring includes determining whether the concentration of peracid meets at least a minimum threshold concentration. In another aspect of the invention, the monitoring includes determining a time when the hydrogen peroxide concentration exceeds a maximum threshold concentration. Different types of devices and methods for determining the concentration of peracid and/or hydrogen peroxide in a use composition may use the compositions of the present invention.

In one aspect, a detector is used to determine the concentration of peracid and/or hydrogen peroxide in the use composition. In one aspect of the invention, the detector measures at least one characteristic of the sample mixture that is indicative of the concentration of peracid and/or hydrogen peroxide in the use composition, such as a fluorescent active compound. The measurements obtained by the detector may be referred to herein as "response data". In one aspect, the processor determines the concentration of peracid and/or hydrogen peroxide in the use composition based on the response data. In one embodiment, the detector is an optical sensor/cell/detector that measures the light transmittance and/or absorbance of the sample. In such embodiments, the response data may be optical transmittance data or optical absorbance data of the fluorescent active compound as a function of time. In other embodiments, other characteristics indicative of the concentration of peracid and/or hydrogen peroxide in the sample can be measured such as pH, oxidation-reduction potential, conductivity, mass spectrum and/or combinations thereof. In such embodiments, the response data is the corresponding measured characteristic at the appropriate point in time.

Suitable exemplary detectors include photometric detectors, fluorometers and/or optical cells/sensors/detectors. In one aspect, the detector operates in the visible, ultraviolet, or infrared wavelength ranges, although other luminescence detection techniques may be used without departing from the scope of the present invention. Any suitable optical detector may be used without departing from the scope of the invention, and the invention is not limited to this invention.

In one aspect, a detector receives the sample mixture and a processor collects response data from the detector. In the case of an optical detector, the response data is the change in the measured optical response of the detector over time. In some embodiments, the detector measures the response data by measuring a color change (e.g., absorbance or transmittance) of the sample solution within the detector as a function of time. In other words, the voltage response of the detector as a function of time corresponds to the amount of light transmitted through the sample mixture, and thus to the color of the sample mixture as the chemical reaction proceeds. The response data is indicative of the concentrations of peracid and hydrogen peroxide in the use composition.

In one aspect, suitable carriers or solvents for forming the use solution may include different types of water. In one aspect, deionized water, soft water and/or low-grade (e.g., 5-grade) water are preferred for use in certain detection devices, i.e., for measuring conductivity. Advantageously, however, the type of water or solvent used does not affect the optical measurements obtained from the compositions of the present invention. However, it will be appreciated that other suitable reagents and carriers may be used without departing from the scope of the invention and the invention is not limited in this respect.

The concentration of peracid and/or hydrogen peroxide measured according to the method of the present invention can be used, for example, as feedback to a controller to maintain the peracid concentration in the use composition within a predetermined range and/or to cause emptying of the use composition container and the generation of a new use composition when the hydrogen peroxide concentration exceeds a maximum peroxide threshold concentration.

As an exemplary use application, the method for determining the concentration of peracid and/or hydrogen peroxide according to the method of the present invention may be used to ensure that the use composition has a predetermined range of such concentrations. For example, administering specific concentrations may include: sterile bottle rinses typically require about 1000-; or central sterilization typically requires about 100-. For example, if the peracid concentration in the use composition falls below a predetermined level, the use composition may be supplemented by adding the concentrated equilibrium peracid composition of the present invention to the use composition.

As another example, if the hydrogen peroxide concentration in the use composition exceeds a predetermined level, the use composition may be supplemented as follows: emptying the use composition container of the used use composition, and using the concentrated balanced peracid composition of the present invention to produce a new use composition.

The different methods for detecting the peracid and/or hydrogen peroxide concentration of the use solutions of the present invention are based on the relationship of the amount of the fluorescent active compound and the equilibrium peroxycarboxylic acid composition (e.g., the concentration of peroxycarboxylic acid required for the different cleaning and/or sterilization applications for the use of the present invention). In an exemplary embodiment, the amount of the fluorescent active compound added is proportional to the amount of peroxycarboxylic acid. The amount of the fluorescently active compound can be determined by measuring the fluorescent signal of the fluorescently active compound using a fluorometer or other optical device and correlating the amount of the detected fluorescent signal to the amount of inert fluorescently active compound present using a calibration curve. Since the inert fluorescent active compound and peroxycarboxylic acid are formulated in known proportions, by knowing the amount of fluorescent active compound present, the amount of peroxycarboxylic acid present can be calculated.

The frequency of monitoring the peracid and/or hydrogen peroxide concentration of the use solution (e.g., the monitoring frequency) in accordance with the present invention will vary depending on the intended use application. For example, the monitoring device may be programmed to monitor the concentrations of peracid and hydrogen peroxide in the use composition every 15 minutes, every 30 minutes, every 1 hour, every 2 hours, every day, or other suitable time. The monitoring frequency/interval may vary depending on the particular application involved in the use of the composition and the respective threshold concentrations of peracid and hydrogen peroxide, etc. Advantageously, according to the present invention, the fluorescent active compound is stable in the highly acidic, equilibrium peracid composition of the present invention and allows measurement/detection over such extended periods of time.

In one aspect, the methods for determining the concentration of one or more use compositions can be applied to compositions that undergo a dynamic reaction (e.g., to obtain time-response data for the peracid compositions of the present invention). The use solutions of the peracid compositions of the present invention can provide for measuring the concentration of peracid and/or hydrogen peroxide to obtain a desired measurement location (e.g., a location along a mixing curve). In such embodiments, the measurement locations are selected to provide appropriate response data.

All publications and patent applications in this specification are indicative of the level of skill of those skilled in the art to which this invention pertains. All publications and patent applications are herein incorporated by reference to the same extent as if each individual publication or parent application was specifically and individually indicated to be incorporated by reference.

Examples

Embodiments 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, one skilled in the art can ascertain the essential characteristics of this invention without departing from the spirit and scope thereof, and can make various changes and modifications of the embodiment of the invention to adapt it to various usages and conditions. Accordingly, various modifications of the embodiments of the invention in addition to those shown and described herein will become apparent to those skilled in the art from the foregoing description. Such modifications are intended to fall within the scope of the appended claims.

Example 1

Self-accelerated decomposition testing. As used herein, SADT refers to the lowest temperature at which self-accelerated decomposition can occur with peracid compositions. In some embodiments, SADT refers to the lowest temperature at which self-accelerated decomposition can occur under commercial packaging, storage, shipping and/or use conditions. SADT may be estimated, calculated, predicted and/or measured by any suitable method. For example, SADT can be directly estimated or measured by one of the three methods (H1, H2, and H4) recommended by the United nations Commission of transportation of hazardous materials on the Transport of Dangerous Goods, Model Regulations (Rev.17) ST/SG/AC.10/1/Rev.17. For example, the methods disclosed in malonw and Wehrstedt, j. hazard mater, 120 (1-3): 21-4(2005), which is incorporated herein by reference in its entirety.

All test protocols used in this example are described in "Recommendations on the Transport of Dangerous Goods," Manual of Tests and Criteria, revision 5: (United Nations): classification procedures, test methods and criteria relating to self-reactive substructures of Division 4.1and organic peroxides of Division 5.2: test H.4Heat accumulation storage Test (28.4.4).

Because peroxycarboxylic acids fall into the organic peroxide class and are therefore self-reactive, self-heating products, tests were conducted to confirm whether cooling is required for a given package of peroxycarboxylic acid product. One of the four published recommendations of the united nations hazardous materials transport committee allows the use of dewars to simulate large volume packaging. Also, this method is used to simulate large commercial packages, which may have a large hazard if tested directly (i.e., with the H1 method) and inconvenience due to size. In this example, the product is intended to be sold in a 1000L plastic tank called a tote, and it must be determined whether the SADT is greater than or less than 45 ℃. If it is found to be less than 45 ℃, refrigeration is required for transport and storage and use, thus severely limiting the potential of the product for a wide range of applications in the market. Also if the product has a SADT of 50 ℃ or less, the product is not allowed to be transported, stored or used in a container as large as 1000L but must be limited to 200L cylinders or less, which also severely limits the application of the product. The 1L cylindrical dewar was fitted with a lid which allowed it to cool at the same rate as the 1000L polyethylene tank. The dewar was filled to 80% of the total volume with the product, fitted with a special lid and a self-recording thermometer, and placed in an oven set at 45 ℃. Once the inner package temperature rose to a temperature of 43 ℃, a timer was started. If the temperature exceeds the oven temperature by 45 ℃ by an order of 6 ℃ (51 ℃) before the last 7 days, the SADT of the product in a 1000L package is defined as <45 ℃, and the product is considered to require cooling. Again, there may be a need to severely limit the application of the product in many industries, and this SADT is considered an undesirable property. SADT is considered to be >45 ℃ if the temperature does not rise above the oven temperature by 6 ℃, and can be considered for shipping and storage in 1000L packages, without refrigeration.

The H4 test method was used at 50 ℃. The peroxycarboxylic acid compositions tested are shown in table 4.

TABLE 4

Fig. 1 shows the SADT formed from the evaluated formulations. Although the formulations were identical except for their stabilizers, the DPA-stabilized peracid compositions showed a significantly more gradual temperature rise (lower than SADT of peracids), confirming the suitability for stability for transportation and/or storage. In contrast, the phosphate/HEDP-stabilized peracid composition showed an excessive increase in temperature on the first day, which necessitated termination of the test to avoid explosion of the composition/container. The results show the advantage of DPA stabilization in a high acid environment.

Example 2

The method of example 1 was further used to analyze SADT for fatty peracids (a peroxyoctanoic acid composition) with even further increased acidity. Although the formulations were identical except for their stabilizers, the results shown in table 5 again show the advantage of DPA stabilization in a highly acidic environment extended to fatty peracids such as peroxyoctanoic acid.

TABLE 5

Fig. 2 shows the SADT formed from the evaluated formulations. DPA-stabilized peracid compositions exhibit a significantly more gradual temperature rise (below the SADT of the peracid) compared to phosphate/HEDP-stabilized peracid compositions even at increased acidity of the peracid composition. The DPA-stable peracid composition will likely meet DOT standards for transportation, as its temperature will likely not exceed 56 ℃ when reaching 48 ℃ projected to 7 days.

Example 3

Strong acids containing reduced hydrogen peroxide concentrations were evaluated in dewar flasks simulating 300 gallon IBC or plastic tote tanks by the H4-SADT protocol as described in table 6 (and shown in figure 3).

TABLE 6

The stability of the composition was evaluated and the composition containing the DPA stabilizer was stable despite the presence of-17% sulfuric acid. As shown in fig. 3, the stabilization of the composition showed a stabilization of the solution temperature at day 7 only above 50 ℃ ambient temperature to 4.7 ℃. Advantageously, these results allow the highly acidic peracid compositions to be used for transport and storage in 300 gallon totes without refrigeration, demonstrating a significant improvement in instability over equivalent peracid compositions containing HEDP.

Example 4

The method of example 1 was further used to analyze SADT for fatty peracids with HEDP stabilizers (a peroxyoctanoic acid composition) and compared to equivalent peracid compositions with DPA stabilizers, as shown in table 7.

TABLE 7

The stability evaluation of the composition was performed and the composition containing DPA stabilizer according to an embodiment of the invention was stable despite the presence of-14% sulfuric acid, whereas the formulation containing only HEDP stabilizer failed before day 7. As shown in fig. 4, the stabilization of the composition showed a stabilization of the solution temperature at day 7 only above 50 ℃ ambient temperature to 2.8 ℃. Again, these results allow the highly acidic peracid composition stabilized by DPA stabilizer to be used for transport and storage in 300 gallon totes without refrigeration. This demonstrates a significant improvement in instability over an equivalent peracid composition containing HEDP.

Example 5

A study was conducted to determine the foaming performance of selected compositions of the present invention and to compare them to peracid compositions including commercially available surfactants and/or defoamers. The following peracid compositions were prepared:

test solution a: 2262ppm composition A, pH2.9 in soft water, has sulfonated oleic acid and sodium octane sulfonate surfactants.

Test solution a (plus aluminum sulfate): 2262ppm composition A, pH2.9, in soft water, with anionic surfactant, plus aluminum sulfate defoamer.

Test solution B: 2262ppm of composition B in soft water, pH2.9, with anionic surfactant (commercial formulation).

Test solution C: 2262ppm of composition C in soft water, pH2.9 (commercial formulation).

Test solution D: 2262 composition D in soft water, pH2.9 (commercial formulation).

The Glewwe foam meter provides a dynamic foam test, rather than a static test (as is the case in the Ross-Miles foam test). Dynamic foam meters are considered more suitable for simulating industrial conditions such as conditions in a water tank. The apparatus and general procedure for the Glewwe format test is described below in U.S. patent No.3899387, column 12, line 45, which is incorporated herein by reference in its entirety. The foam meter itself consists of a thermostatic vessel and a pump which recirculates the aqueous medium having a tendency to foam. The foam formed by the action of the aqueous stream impinging on the surface of the vessel results in foam formation.

The foam height of the tested compositions was determined using the following method. 3000mL of each batch was first prepared and poured gently into a Glewwe cylinder. The foam height is measured after different time intervals and provides a relative measure of the effectiveness of the anti-foaming agent. The container of this foam meter consisted of a 3000mL capacity stainless steel laboratory beaker. Sealed to this beaker by means of a silicone sealant is a clear plexiglas tube that fits neatly to the inside wall of the beaker. This enables the operator to measure the foam height above the liquid level. The dimensions of the beaker are about 19cm in height and about 17-18cm in diameter, and the plexiglass tube extends about 30-35cm above the edge of this beaker. Further details regarding the Glewwe foam test are shown in U.S. patent No.5447648, which is expressly incorporated herein by reference.

A ruler was attached to the side of the cylinder and the solution was aligned with the bottom of the ruler. The pump is turned on. The foam height was estimated by reading the average level of foam, according to a ruler. Foam height readings are taken with respect to time using a stopwatch or timer. The pump was turned off and the foam height was recorded at different times. The results are shown in fig. 5.

As shown in fig. 5, the aluminum sulfate antifoam incorporated into the highly acidic peracid compositions of the present invention produced a significant improvement in foam profile as evidenced by a significant reduction in foam height at all time points. The graph in fig. 5 measures the effect of aluminum sulfate on the foam height of peracid compositions in soft water, showing that formulations containing aluminum sulfate (test solution of composition a plus aluminum sulfate) produced significantly reduced foam height compared to several other commercially available peracid compositions.

Advantageously, such reduced foam height of the compositions of the present invention is useful when the compositions are used in applications where foam generation is detrimental to the application, such as for in situ cleaning and/or sterilization applications.

Example 6

As a result of the excellent defoaming properties of the aluminum sulfate defoamer described in example 5, a further evaluation of the low foaming peracid composition of example 5 (test solution of composition a (plus aluminum sulfate)) was conducted to determine if there was any effect on biocidal efficacy due to the defoamer-containing composition.

The test solution of composition a was diluted from 1 oz to 7 gal with 500ppm hard water and the solution had a target pH of less than about 3.0. The log reduction of staphylococcus aureus achieved by the compositions evaluated was measured at different concentrations at 15 second and 30 second intervals.

As shown in fig. 6, the aluminum sulfate defoamer incorporated into the highly acidic peracid compositions of the present invention not only further creates compatibility with the peracid composition, it further demonstrates the synergistic biocidal efficacy of the defoamer with anionic surfactants. Advantageously, the combination of the defoamer and surfactant in the highly acidic peracid compositions of the present invention provides improved biocidal activity. Without being bound by a particular theory of the invention, the defoamer may result in an increase in the hydrophobicity of the peracid composition, resulting in such improved biocidal activity.

Example 7

The biocidal efficacy of the different equilibrium peroxycarboxylic acid compositions of the present invention shown in table 8 was evaluated under different conditions described in tables 9-11.

TABLE 8

Compositions for food contact sterilization were tested using AOAC formal method 960.09 (germicidal and decontamination sterilization effect of disinfectants), as shown in table 9.

TABLE 9

The compositions were tested for anti-fouling conditions at 20 ℃ using European Standard EN1276 (11 months 2001) (Chemical semiconductors and antibiotics-Quantitative testing for the Evaluation of bacterial Activity of Chemical semiconductors and antibiotics Used in Food, Industrial, Domestic, and Institutional Areas), as shown in Table 10.

Watch 10

The compositions in the more concentrated use solutions were tested using AOAC formal method 964.02 (test disinfectants-use dilution method) as shown in table 11.

TABLE 11

Example 8

The compound stability of compound 1 of example 7 was evaluated under accelerated conditions (i.e., 4 weeks at 100 ° F). Total peracid and hydrogen peroxide concentrations were measured as shown in figure 7. The results show that the highly acidic equilibrium peroxycarboxylic acid compositions are stable for at least 4 weeks under accelerated conditions, which corresponds to about one year under ambient conditions.

Example 9

A ruler was attached to the side of the cylinder and the solution was aligned with the bottom of the ruler. The pump is turned on. The foam height was estimated by reading the average level of foam, according to a ruler. Foam height readings are taken with respect to time using a stopwatch or timer. The pump was turned off and the foam height was recorded at different times. The results are shown in fig. 8.

As shown in fig. 8, the aluminum sulfate antifoam incorporated into the highly acidic peracid compositions of the present invention produced a significant improvement in foam profile as evidenced by a significant reduction in foam height at all time points. The effect of aluminum sulfate on the foam height of peracid compositions in soft water is measured in the graph in fig. 8, which shows that formulations containing aluminum sulfate (test solution of composition a plus aluminum sulfate) produced significantly reduced foam height compared to several other commercially available peracid compositions.

Example 10

The use solution of the concentrated equilibrium peroxycarboxylic acid composition of the invention was monitored by both conductivity and fluorescence as shown in example 7 (equilibrium composition).

The conductivity is measured by a conductivity meter; and the fluorescence intensity was measured by a hand-held fluorometer (manufactured by Ecolab) with an excitation wavelength of 275 nm. Fluorescence emission was measured in SU and conductivity was measured in us/cm units.

As shown in fig. 9, the increase in peroxycarboxylic acid concentration is proportional to the increase in fluorescence active compound emission in all types of test water, confirming the applicability of using fluorescence active compounds to measure the concentration of peroxycarboxylic acid compositions of the invention.

As shown in fig. 10, the emission intensity of the fluorescent active compound was linearly related to the concentration of peroxycarboxylic acid in deionized water and 5 grain water, but such a linear relationship was not maintained in the well water. This demonstrates the superiority of fluorescence over conductivity protocols according to the invention in measuring peroxycarboxylic acid concentrations.

The invention being thus described, it will be obvious that the same may be varied in many ways. Such variations are not to be regarded as a departure from the spirit and scope of the invention, and all such modifications are intended to be included within the scope of the following claims. The above specification provides instructions for the manufacture and use of the disclosed compositions and methods. Since many embodiments of the invention can be made without departing from the spirit and scope of the invention, the invention resides in the claims hereinafter appended.

Claims

1. A stabilized balanced peracid composition consisting of:

0.1-40 wt% of one or more C₁-C₂₂A peroxycarboxylic acid;

0.1-90 wt% of one or more C₁-C₂₂A carboxylic acid;

1-90 wt% of hydrogen peroxide;

1-50 wt% of an inorganic acid;

1-75 wt% of water;

0.001 wt% to 25 wt% peroxycarboxylic acid stabilizer, wherein the stabilizer is picolinic acid or a compound of formula (IA) below, or a salt thereof:

wherein R is¹Is OH or-NR^1aR^1bWherein R is^1aAnd R^1bIndependently is hydrogen or (C)₁-C₆) An alkyl group; wherein R is²Is OH or-NR^2aR^2bWherein R is^2aAnd R^2bIndependently is hydrogen or (C)₁-C₆) An alkyl group; wherein each R³Independently is (C)₁-C₆) Alkyl, (C)₂-C₆) Alkenyl or (C)₂-C₆) An alkynyl group; and n is a number from 0 to 3;

or a compound of the following formula (IB):

wherein R is¹Is OH or-NR^1aR^1bWherein R is^1aAnd R^1bIndependently is hydrogen or (C)₁-C₆) An alkyl group; wherein R is²Is OH or-NR^2aR^2bWherein R is^2aAnd R^2bIndependently is hydrogen or (C)₁-C₆) An alkyl group; wherein each R³Independently is (C)₁-C₆) Alkyl, (C)₂-C₆) Alkenyl or (C)₂-C₆) An alkynyl group; and n is a number from 0 to 3; and

optionally, one or more additional functional ingredients selected from the group consisting of metal salt defoamers, surfactants, fluorescent active compounds, hydrotropes, perfumes, and dyes;

wherein at least 80% of the one or more C are retained after storage at 50 ℃ for at least 30 days₁-C₂₂Peroxycarboxylic acid activity;

wherein the composition has a use solution pH of less than 4, and wherein the stabilizer delays or prevents the peroxycarboxylic acid from exceeding its self-accelerating decomposition temperature.

2. The composition of claim 1, wherein the inorganic acid comprises sulfuric acid, sodium bisulfate, nitric acid, methanesulfonic acid, phosphoric acid, 1-hydroxyethylidene-1, 1-diphosphonic acid, or a combination thereof.

3. The composition of claim 1, wherein the stabilizer is 2, 6-pyridinedicarboxylic acid or a salt thereof.

4. The composition of claim 1, wherein said composition comprises a hydrotrope that aids in the solubilization of said stabilizing agent.

5. The composition of claim 1, wherein at least 90% of the C is retained after storage at 50 ℃ for at least 30 days₁-C₂₂Peroxycarboxylic acid activity.

6. The composition of claim 1, wherein the composition comprises an anionic surfactant, a metal salt defoamer, or a combination thereof.

7. The composition of claim 6, wherein the metal salt defoamer is an aluminum salt, a magnesium salt, a calcium salt, a zinc salt, and/or a rare earth metal salt.

8. The composition of claim 6, wherein the metal salt defoamer is aluminum sulfate.

9. The composition of claim 1, wherein the pH of the use solution is less than 3.

10. The composition of claim 6, wherein the metal salt defoamer is aluminum sulfate and the anionic surfactant is sodium octane sulfonate, sulfonated oleic acid, or a combination thereof.

11. The composition of claim 1, wherein said C₁-C₂₂The peroxycarboxylic acid comprises at least one C₅-C₂₂Peroxycarboxylic acids and at least one C₁-C₄A peroxycarboxylic acid.

12. The composition of claim 1, wherein the composition comprises an aryl sulfonate fluorescent active compound, wherein the fluorescent active compound is stable in the balanced peracid composition and provides a fluorescent emission for monitoring peroxycarboxylic acid concentration by an optical sensor.

13. The composition of claim 12, wherein the fluorescent active compound is sodium xylene sulfonate, toluene sulfonate, alkylbenzene sulfonate, alkyl diphenyl ether disulfonate, naphthalene sulfonate, alkyl naphthalene sulfonate, naphthalene disulfonate, or sodium cumene sulfonate.

14. The composition of claim 1, wherein said C₁-C₂₂Peroxycarboxylic acids include peroxyacetic acid and peroxyoctanoic acid.

15. The composition of claim 1, wherein said C₁-C₂₂Carboxylic acids include acetic acid and octanoic acid.

16. The composition of claim 1, wherein the one or more C' s₁-C₂₂The peroxycarboxylic acid accounts for 1 to 40 weight percent, and the one or more than one C₁-C₂₂1 to 80 weight percent of carboxylic acid, and the peroxideHydrogen is 1 wt% -80 wt%, the inorganic acid is 5 wt% -50 wt%, and the stabilizer is 0.01 wt% -10 wt%.

17. The composition of claim 1, wherein the one or more C' s₁-C₂₂The peroxycarboxylic acid being one or more C₂-C₂₀Peroxycarboxylic acids and wherein said one or more C₁-C₂₂The carboxylic acid being one or more C₂-C₂₀A carboxylic acid.

18. The composition of claim 1, 6 or 12, wherein the one or more C' s₁-C₂₂The peroxycarboxylic acid is peroxyacetic acid, peroxyoctanoic acid, peroxysulfonated oleic acid, or a combination thereof, and wherein the one or more C₁-C₂₂The carboxylic acid is acetic acid, octanoic acid, sulfonated oleic acid, or a combination thereof.

19. The composition of claim 6, wherein the composition comprises:

1 to 40 wt% of the one or more C₁-C₂₂A peroxycarboxylic acid;

1 to 80 wt% of the one or more C₁-C₂₂A carboxylic acid;

1-80 wt% of the hydrogen peroxide;

1-50 wt% of the inorganic acid;

0.01 wt% to 40 wt% of the anionic surfactant;

0.001 wt% to 10 wt% of the metal salt defoamer; and

0.01 wt% to 10 wt% of the peroxycarboxylic acid stabilizer.

20. The composition of claim 19, wherein the one or more C' s₁-C₂₂The peroxycarboxylic acid accounts for 1 to 20 weight percent, and the one or more than one C₁-C₂₂1 to 50 weight percent of carboxylic acid, 1 to 50 weight percent of hydrogen peroxide, 1 to 20 weight percent of inorganic acid, 0.1 to 25 weight percent of anionic surfactant and 0.1 to 5 weight percent of metal salt defoamert%, and the stabilizer is 0.01 wt% to 1 wt%.

21. The composition of claim 19, further comprising said hydrotrope, wherein said one or more C' s₁-C₂₂The peroxycarboxylic acid is C₂-C₂₀Peroxycarboxylic acids and wherein said one or more C₁-C₂₂The carboxylic acid being C₂-C₂₀A carboxylic acid.

22. The composition of claim 19, wherein the one or more C' s₁-C₂₂The peroxycarboxylic acid is peroxyacetic acid, peroxyoctanoic acid, peroxysulfonated oleic acid, or a combination thereof, wherein the one or more C₁-C₂₂The carboxylic acid is acetic acid, octanoic acid, sulfonated oleic acid, or a combination thereof, and wherein the defoamer is aluminum sulfate.

23. A method of storing and/or transporting a stabilized balanced peroxycarboxylic acid composition comprising storing the peroxycarboxylic acid composition of claim 1.

24. The method of claim 23, wherein the self-accelerating decomposition temperature of the composition is increased to at least 45 ℃ during transportation.

25. The method of claim 23, wherein the one or more C' s₁-C₂₂The peroxycarboxylic acid accounts for 1 to 40 weight percent, and the one or more than one C₁-C₂₂1 to 80 weight percent of carboxylic acid, 1 to 80 weight percent of hydrogen peroxide, 5 to 50 weight percent of inorganic acid and 0.01 to 10 weight percent of stabilizer.

26. The method of claim 23, wherein said composition comprises an anionic surfactant, said hydrotrope, said metal salt defoamer, said fluorescent active, or combinations thereof.

27. The method of claim 23, wherein the one or more C' s₁-C₂₂The peroxycarboxylic acid is peroxyacetic acid, peroxyoctanoic acid, peroxysulfonated oleic acid, or a combination thereof, wherein the one or more C₁-C₂₂The carboxylic acid is acetic acid, octanoic acid, sulfonated oleic acid, or a combination thereof, and wherein the stabilizer is 2, 6-pyridinedicarboxylic acid or a salt thereof.

28. A method of detecting the concentration of peroxycarboxylic acid and/or hydrogen peroxide in a sterilization composition and/or cleaning method, comprising:

providing the balanced peroxycarboxylic acid composition of claim 12;

measuring a fluorescence response with the optical cell, wherein the fluorescence response measures an intensity of a fluorescence emission; and

determining the concentration of the peroxycarboxylic acid and/or the hydrogen peroxide.

29. The method of claim 28 further comprising diluting the balanced peroxycarboxylic acid composition into a use solution.

30. The method of claim 28 wherein the use solution of the balanced peroxycarboxylic acid composition is directed to an optical cell.

31. The method of claim 29 wherein the use solution of the balanced peroxycarboxylic acid composition is measured for a fluorescent response from a fluorescently active compound.

32. The method of claim 31, wherein the fluorescent response is a fluorescent signal detected by an optical cell during the cycling, soaking, cleaning, and/or rinsing steps.

33. The process of claim 28 further comprising placing the optical cell in or along a feed line that delivers the peroxycarboxylic acid composition to a cleaning application.

34. The method of claim 28, further comprising adjusting the concentration of peroxycarboxylic acid and/or hydrogen peroxide of the composition based on the measured fluorescence response.

35. The process of claim 28 further comprising removing at least a portion of the peroxycarboxylic acid composition to provide a new equilibrium peroxycarboxylic acid composition for dilution and use in cleaning and/or sterilization applications.

36. The method of claim 28, wherein the cleaning process is performed on-line or off-line using a clean-in-place system.

37. The method of claim 28, wherein the one or more C' s₁-C₂₂The peroxycarboxylic acid is peroxyacetic acid, peroxyoctanoic acid, peroxysulfonated oleic acid, or a combination thereof, wherein the one or more C₁-C₂₂The carboxylic acid is acetic acid, octanoic acid, sulfonated oleic acid, or a combination thereof, and wherein the fluorescent active compound is sodium xylene sulfonate, toluene sulfonate, alkylbenzene sulfonate, alkyl diphenyl ether disulfonate, naphthalene sulfonate, alkyl naphthalene sulfonate, naphthalene disulfonate, or sodium cumene sulfonate.

38. The method of claim 28, wherein the one or more C' s₁-C₂₂The peroxycarboxylic acid accounts for 1 to 40 weight percent, and the one or more than one C₁-C₂₂1 to 80 weight percent of carboxylic acid, 1 to 80 weight percent of hydrogen peroxide and 0.001 to 10 weight percent of fluorescent active compound.

39. The method of claim 28 wherein the fluorescent active compound is sodium xylene sulfonate, toluene sulfonate, alkylbenzene sulfonate, alkyl diphenyl ether disulfonate, naphthalene sulfonate, alkyl naphthalene sulfonate, naphthalene disulfonate, or sodium cumene sulfonate, and wherein the balanced peroxycarboxylic acid composition comprises a metal salt defoamer, an anionic surfactant, or a combination thereof.

40. A method of reducing microbial numbers using a stabilized balanced peroxycarboxylic acid composition comprising:

providing the peroxycarboxylic acid composition of claim 1; and

the surface or substrate is contacted with the use solution of the composition for a sufficient time to reduce the number of microorganisms.

41. The method of claim 40, wherein the one or more C' s₁-C₂₂The peroxycarboxylic acid is peroxyacetic acid, peroxyoctanoic acid, peroxysulfonated oleic acid, or a combination thereof, wherein the one or more C₁-C₂₂The carboxylic acid is acetic acid, octanoic acid, sulfonated oleic acid, or a combination thereof.

42. The method of claim 40, wherein the stabilizer is 2, 6-pyridinedicarboxylic acid or a salt thereof.

43. The method of claim 40, wherein the composition comprises a metal salt defoamer that is an aluminum salt, a magnesium salt, a calcium salt, a zinc salt, and/or a rare earth metal salt.

44. The method of claim 40, wherein the surface or substrate is a food item, a plant item, an animal item, a container, device, system or facility for growing, holding, processing, packaging, storing, transporting, preparing, cooking, or providing the food item, plant item, or animal item, a hard surface, a fabric surface, or a liquid medium or system.

45. The method of claim 40, wherein the contacting step lasts at least 10 seconds.

46. The method of claim 40, wherein the number of microorganisms in and/or on said surface or substrate is reduced by at least two logs₁₀。