STABLE PERCARBOXYLIC ACID COMPOSITIONS

专利摘要:
stable percarboxylic acid compositions. The present invention relates, in general, to stable percarboxylic acid compositions comprising, inter alia, at least two stabilizing agents, and to various uses for water treatments, including water treatments in connection with oil and gas field operations. The present invention also relates to slick water fluid compositions and gel-based compositions comprising stable percarboxylic acid compositions and the uses thereof in oil and gas field operations.
公开号:BR112015007546B1
申请号:R112015007546-0
申请日:2013-10-04
公开日:2021-08-03
发明作者:Junzhong Li；David McSherry；Allison BREWSTER；Richard Staub；Renato De Paula；John Wilhelm Bolduc；Robert J. Ryther；Victor V. Keasler
申请人:Ecolab Usa Inc.；
IPC主号:

专利说明:

TECHNICAL FIELD
[001] The present invention relates, in general, to stable percarboxylic acid compositions comprising, inter alia, at least two stabilizing agents, and to various uses for water treatments, including water treatments in relation to operations in the oil and gas field. The present invention also relates to slick water fluid compositions and gel-based compositions comprising stable percarboxylic acid compositions and uses thereof in oil and gas field operations. FUNDAMENTALS OF THE INVENTION
[002] Peroxycarboxylic acids are increasingly used as biocides in various fields, due to their broad biocidal efficacy and excellent environmental profiles. The most commonly used peroxycarboxylic acid is peracetic acid. Peracetic acid is a colorless, freely soluble liquid in water that has great biocidal efficacy for various microorganisms, such as bacteria, viruses, yeast, fungi and spores. When decomposed, peracetic acid results in acetic acid (vinegar), water and oxygen. Pure peroxycarboxylic acids, such as peracetic acid, however, are unstable and explosive, and thus commercially available peroxycarboxylic acids are usually sold in an equilibrium solution. In addition to peroxycarboxylic acid, an equilibrium solution also contains the corresponding carboxylic acid, hydrogen peroxide and water. Compared to peroxycarboxylic acid, hydrogen peroxide has only negligible biocidal efficacy, but may pose environmental problems in some applications if it exceeds the specific release limitation. Furthermore, it has been reported that the presence of hydrogen peroxide has negative impacts on the effectiveness of peroxycarboxylic acid for some microorganisms.
[003] In applications such as water treatment for use in oil and gas well fracturing drilling, the hydrogen peroxide that is in the peroxycarboxylic acid compositions can interact with other components used in the applications, such as gelling agents , friction reducers, corrosion inhibitors and scale inhibitors, etc. The presence of hydrogen peroxide in these solutions can cause performance to fail. Thus, there is a need for the development of a peroxycarboxylic acid composition that has as high a peroxycarboxylic acid to hydrogen peroxide ratio as possible for applications as a biocide in general and, in particular, for the treatment of water in drilling. Oil and Gas.
Commercially available peroxycarboxylic acid compositions generally have significantly less or approximately equal weight amounts of peroxycarboxylic acid relative to hydrogen peroxide. It is known that, among other factors, the ratio of hydrogen peroxide to peroxycarboxylic acid plays a significant role in the stability of peroxycarboxylic acid compositions. The greater the ratio of hydrogen peroxide to peroxycarboxylic acid, the more stable the composition. Some commonly available peroxycarboxylic acid compositions have a ratio of about 1.5 to 1 hydrogen peroxide to peroxycarboxylic acid. Although compositions with a higher ratio of peroxycarboxylic acid to hydrogen peroxide are commercially available, these compositions are in small packing sizes limited by the limitations of self-accelerating decomposition temperature (SADT) transport and require temperature-controlled storage due to limited stability of the compositions.
[005] Various stabilizers are used in peroxycarboxylic acid compositions to stabilize the compositions. For example, pyridine-carboxylic acid-based stabilizers such as picolinic acid and salts, pyridine-2,6-dicarboxylic acid and salts, and phosphonate-based stabilizers, such as phosphoric acid and salts, pyrophosphoric acid and salts and, most commonly, 1-hydroxyethylidene-1,1-diphosphonic acid (HEDP) and salts are used. When used individually at the right level, these stabilizers can significantly improve the stability of peroxycarboxylic acid compositions and for conventional peroxycarboxylic acid compositions, the stability profile obtained with these stabilizers allows for commercial use of these compositions. For peroxycarboxylic acid compositions with high ratios of peroxycarboxylic acid to hydrogen peroxide, the additional stability challenge cannot be met by these stabilizers used in traditional matter. BRIEF SUMMARY OF THE INVENTION
[006] The present invention relates to stable percarboxylic acid compositions and their uses. In some embodiments, the present invention relates to a stable peracid composition with a high peracid to hydrogen peroxide ratio. Optionally, the hydrogen peroxide level is further reduced by adding a catalase or peroxidase to the use solution or diluted concentrate prior to use. The disclosed compositions are particularly useful in treating water for use in oil and gas well fracturing drilling.
[007] In one aspect, the present invention is directed to a composition, which comprises: 1) a C1-C22 carboxylic acid; 2) a C1-C22 percarboxylic acid; 3) hydrogen peroxide; 4) a first stabilizing agent, which is a picolinic acid or a compound having the following Formula (IA):
wherein R1 is OH or -NR1aR1b, wherein R1a and R1b are independently hydrogen or (C1-C6) alkyl; R2 is OH or -NR2aR2b, wherein R2a and R2b are independently hydrogen or (C1-C6) alkyl; each R3 is independently (C1-C6) alkyl, (C2-C6) alkenyl or (C2-C6) alkynyl; en is a number from zero to 3; or a salt thereof; or a compound having the following Formula (IB):
wherein R1 is OH or -NR1aR1b, wherein R1a and R1b are independently hydrogen or (C1-C6) alkyl; R2 is OH or -NR2aR2b, wherein R2a and R2b are independently hydrogen or (C1-C6) alkyl; each R3 is independently (C1-C6) alkyl, (C2-C6) alkenyl or (C2-C6) alkynyl; en is a number from zero to 3; or a salt thereof; 5) a second stabilizing agent, which is a compound having the following Formula (IIA):
wherein R1, R2, R3 and R4 are independently hydrogen, (C1-C6) alkyl, (C2-C6) alkenyl or (C2-C6) alkynyl or C6-C20 aryl; R5is (C1-C6) alkyl, (C2-C6) alkenyl or (C2-C6) alkynyl; and R6 is hydrogen, (C1-C6) alkyl, (C2-C6) alkenyl or (C2-C6) alkynyl; or a salt thereof; or a compound having the following Formula (IIB):
wherein R1, R2 and R3 are independently hydrogen, (C1-C6) alkyl, (C2-C6) alkenyl or (C2-C6) alkynyl or C6-C20 aryl; or a salt thereof; and wherein said hydrogen peroxide has a concentration of at least about 0.1% by weight, C1-C22 percarboxylic acid has a concentration of at least about 2 times the concentration of said hydrogen peroxide and said composition has a pH of about 4 or less.
[008] In another aspect, the present invention is directed to a method for storing a composition containing percarboxylic acid, which comprises storing the above composition, wherein said composition retains at least about 80% of the activity of the C1-C22 percarboxylic acid after storage for about 30 days at about 50°C.
[009] In yet another aspect, the present invention is directed to a method for transporting a composition containing percarboxylic acid, which comprises transporting the above composition, preferably, in mass, wherein the SADT of said composition is raised to at least 45°C during transport.
[010] In yet another aspect, the present invention is directed to a method of treating water, which comprises providing the above composition to a water source in need of treatment to form a treated water source, wherein said The treated water source comprises from about 1 ppm to about 1,000 ppm of said C1-C22 percarboxylic acid.
[011] In yet another aspect, the present invention is directed to a method of treating a target, which comprises a step of contacting a target with the above composition at a dilute level to form a treated target composition, wherein the said treated target composition comprises from about 1 ppm to about 10,000 ppm of said C1-C22 percarboxylic acid, and said contacting step lasts sufficient time to stabilize or reduce the microbial population in and/or on said target or said treated target composition.
[012] In yet another aspect, the present invention is directed to a method for reducing the level of hydrogen sulfide (H2S), hydrosulfuric acid or a salt thereof in a water source, which comprises a step of contacting a source of water of the above composition at a diluted level to form a source of treated water, wherein said source of treated water comprises from about 1 ppm to about 10,000 ppm of said C1-C22 percarboxylic acid, and said The contact step lasts long enough to stabilize or reduce the level of H2S, hydrosulfuric acid or a salt thereof in said treated water source.
[013] The present invention also relates to fluid compositions with low rheology (slick water) useful in oil and/or gas drilling that comprise stable percarboxylic acid compositions and uses thereof. In one aspect, the present invention is directed to a composition, which comprises: 6) a C1-C22 carboxylic acid; 7) a C1-C22 percarboxylic acid; 8) hydrogen peroxide; 9) a first stabilizing agent, which is a picolinic acid or a compound having the following Formula (IA):
wherein R1 is OH or -NR1aR1b, wherein R1a and R1b are independently hydrogen or (C1-C6) alkyl; R2 is OH or -NR2aR2b, wherein R2a and R2b are independently hydrogen or (C1-C6) alkyl; each R3 is independently alkyl (C2-C6), alkenyl (C2-C6) or alkynyl (C2-C6); en is a number from zero to 3; or a salt thereof; or a compound having the following Formula (IB):
wherein R1 is OH or -NR1aR1b, wherein R1a and R1b are independently hydrogen or alkyl (CI-C'); R2 is OH or -NR2aR2b, where R2a and R2b are independently hydrogen or alkyl (CI-C'); each R3 is independently alkyl (CI-C'), alkenyl (C2-C') or alkynyl (C2-C6); en is a number from zero to 3; or a salt thereof; 10) a second stabilizing agent, which is a compound having the following Formula (IIA):
wherein R1, R2, R3 and R4 are independently hydrogen, alkyl (CI-C'), alkenyl (C2-C'), alkynyl (C2-C') or C6-C20 aryl; R5 is alkyl (CI-CΘ), alkenyl (C2-CΘ) or alkynyl (C2-CΘ); and R6 is hydrogen, alkyl (CI-CΘ), alkenyl (C2-CΘ) or alkynyl (C2-CΘ); or a salt thereof; or a compound having the following Formula (IIB):
wherein R 1 , R 2 and R 3 are independently hydrogen, alkyl (C 1 -C 6 ), alkenyl (C 2 -C 6 ) or alkynyl (C 2 -C 6 ) or C 6 -C 20 aryl; or a salt thereof; 11) a friction reducer; and wherein said hydrogen peroxide has a concentration of about 1 ppm to about 20 ppm and C1-C22 percarboxylic acid has a concentration of at least about 2 times the concentration of said hydrogen peroxide.
[014] In another aspect, the present invention is directed to a method for fracturing fluid with low rheology (slick water), which comprises directing the above composition in an underground medium.
[015] The present invention further relates to gel-based compositions useful in oil and/or gas drilling that comprise stable percarboxylic acid compositions and the uses thereof. In one aspect, the present invention is directed to a composition, which comprises: 1) a C1-C22 carboxylic acid; [001] a C1-C22 percarboxylic acid; [002] hydrogen peroxide; [003] a first stabilizing agent, which is a picolinic acid or a compound having the following Formula (IA):
wherein: R1 is OH or -NR1aR1b, wherein R1a and R1b are independently hydrogen or (C1-C6) alkyl; R2 is OH or -NR2aR2b, wherein R2a and R2b are independently hydrogen or (C1-C6) alkyl; each R3 is independently alkyl (C2-C6), alkenyl (C2-C6) or alkynyl (C2-C6); en is a number from zero to 3; or a salt thereof; or a compound having the following Formula (IB):
wherein R1 is OH or -NR1aR1b, wherein R1a and R1b are independently hydrogen or (C1-C6) alkyl; R2 is OH or -NR2aR2b, wherein R2a and R2b are independently hydrogen or (C1-C6) alkyl; each R3 is independently alkyl (C2-C6), alkenyl (C2-C6) or alkynyl (C2-C6); en is a number from zero to 3; or a salt thereof; 12) a second stabilizing agent, which is a compound having the following Formula (IIA):
wherein R1, R2, R3 and R4 are independently hydrogen, (C1-C6) alkyl, (C2-C6) alkenyl or (C2-C6) alkynyl or C6-C20 aryl; R5is (C1-C6) alkyl, (C2-C6) alkenyl or (C2-C6) alkynyl; and R6 is hydrogen, (C1-C6) alkyl, (C2-C6) alkenyl or (C2-C6) alkynyl; or a salt thereof; or a compound having the following Formula (IIB):
wherein R1, R2 and R3 are independently hydrogen, (C1-C6) alkyl, (C2-C6) alkenyl or (C2-C6) alkynyl or C6-C20 aryl; or a salt thereof; 13) a viscosity enhancer; and wherein said hydrogen peroxide has a concentration of about 1 ppm to about 15 ppm and said C1-C22 percarboxylic acid has a concentration of at least about 2 times the concentration of said hydrogen peroxide.
[0016] In another aspect, the present invention is directed to a method for high viscosity fracturing, which comprises directing the above composition in an underground medium. BRIEF DESCRIPTION OF THE DRAWINGS
[0017] Figure 1 illustrates the stability of peracetic acid compositions with various stabilizers.
[0018] Figure 2 illustrates the synergistic stabilization performance of HEDP and DPA.
[0019] Figure 3 illustrates the SADT test of peracetic acid compositions with various stabilizers.
[0020] Figure 4 illustrates the kinetic viscosity profile of POAA with various levels of H2O2 in a gel fluid.
[0021] Figures 5A and 5B illustrate an example of H2S reduction using various levels of formulations 13523-37-1 and 13523-37-2.
[0022] Figures 6A and 6B illustrate another example of H2S reduction using various levels of formulations 13523-37-1 and 13523-37-2. DETAILED DESCRIPTION OF THE INVENTION
[0023] For clarification of the disclosure, and not by way of limitation, the detailed description of the invention is divided into the following subsections. DEFINITIONS
[0024] Unless otherwise defined, all technical and scientific terms used in this report have the same meaning as commonly understood by a person of ordinary skill in the art to which this invention belongs. All patents, applications, published applications and other publications referenced in this report are incorporated in their entirety by reference. If a definition presented in this section is contrary to, or otherwise inconsistent with, a definition presented in patents, applications, published applications and other publications which are, in this report, incorporated by reference, the definition presented in this section prevails. on the definition that is incorporated in this report as a reference.
[0025] Embodiments of this invention are not limited to particular peroxycarboxylic acid compositions and methods of using the same, which may vary and are understood by skilled artisans. It should further be understood that all terminology used in this report is for the purpose of describing particular embodiments only, and is not intended to be limiting in any way or scope. For example, all units, prefixes, and symbols can be denoted in their accepted SI form. Numeric ranges cited in the descriptive report are inclusive of the numbers that define the range and include each whole number within the defined range.
[0026] It should be noted that, as used in this descriptive report and the accompanying claims, the singular forms "a", "an", and "o", "a" include plural referents, unless the content indicates clearly otherwise. Thus, for example, reference to a composition containing "a compound" includes a composition having two or more compounds. It should also be noted that the term “or” is generally used in its sense including “and/or”, unless the content clearly indicates otherwise.
[0027] In order that the present invention may be more easily understood, certain terms are first defined. Unless defined otherwise, all technical and scientific terms used in this report have the same meaning as commonly understood by a person of ordinary skill in the art to which the embodiments of the invention belong. Many methods and materials similar, modified or equivalent to those described in this report can be used to practice embodiments of the present invention without undue experimentation, the preferred materials and methods are described in this report. In describing and claiming embodiments of the present invention, the following terminology will be used, in accordance with the definitions set out below.
[0028] As used in this report, the term "about" refers to the variation in numerical quantity that can occur, for example, through typical liquid measurement and handling procedures used to manufacture concentrates or solutions for use worldwide in general; through inadvertent error in these procedures; through differences in the manufacture, source or purity of the ingredients used to make the compositions or carry out the methods; and the like. The term "about" also encompasses amounts that differ due to different equilibrium conditions for a composition resulting from a particular initial blend. Whether or not modified by the term "about", the claims include equivalents to amounts.
[0029] The term “cleaning”, as used in this report, means to carry out or assist in the removal of dirt, bleaching, microbial population reduction or a combination thereof. For the purpose of this patent application, successful microbial reduction is achieved when microbial populations are reduced by at least about 50%, or by significantly more, than is achieved by a water wash. Greater reductions in the microbial population provide greater levels of protection.
[0030] As used in this report, “consisting essentially of” means that the methods and compositions may include additional steps, components, or similar ingredients, but only if the additional steps, components and/or ingredients do not materially change the basic features and new features of the claimed methods and compositions.
[0031] As used in this report, the term “disinfectant” refers to an agent that kills all vegetative cells, including the most recognized pathogenic microorganisms, using the procedure described in A.O.A.C. Use Dilution Methods, Official Methods of Analysis of the Association of Official Analytical Chemists, paragraph 955.14 and applicable sections, 15th Edition, 1990 (EPA Guideline 91-2). As used in this report, the term "high-level disinfection" or "high-level disinfectant" refers to a compound or composition that substantially kills all organisms except high levels of bacterial spores, and is done with a chemical germicide approved for manufacture as a sterilant by the Food and Drug Administration. As used in this report, the term “intermediate level disinfection” or “intermediate level disinfectant” refers to a compound or composition that kills mycobacteria, most viruses and bacteria with a chemical germicide registered as a tuberculocide by Environmental Protection Agency (EPA). As used in this report, the term “low-level disinfection” or “low-level disinfectant” refers to a compound or composition that kills certain viruses and bacteria with a chemical germicide registered as a hospital disinfectant by the EPA.
[0032] As used in this report, the term "free", "none", "substantially none" or "substantially free" refers to a composition, mixture or ingredient that does not contain a particular compound or for which a compound particular compound or a compound containing particular compound was not added. In some embodiments, the reduction and/or elimination of hydrogen peroxide, in accordance with the embodiments, provides compositions free or substantially free of hydrogen peroxide. The particular compound must be present through contamination and/or use in a minimal amount of a composition, mixture or ingredients, the amount of the compound must be less than about 3% by weight. More preferably, the amount of the compound is less than 2% by weight, less than 1% by weight, and more preferably, the amount of the compound is less than 0.5% by weight.
[0033] As used in this report, the term “microorganism” refers to any non-cellular or unicellular (including colonial) organism. Microorganisms include all prokaryotes. Microorganisms include bacteria (including cyanobacteria), spores, lichens, fungi, protozoa, virines, viroids, viruses, phages and some algae. As used in this report, the term “microbe” is synonymous with micro-organism.
[0034] As used in this report, the terms "mixed" or "mixture" when used to refer to "percarboxylic acid composition", "percarboxylic acids", "peroxycarboxylic acid composition" or "peroxycarboxylic acids" refer to a composition or mixture, including more than one percarboxylic acid or peroxycarboxylic acid.
[0035]As used in this report, the term “disinfectant” refers to an agent that reduces the number of bacterial contaminants to safe levels determined by public health requirements. In one embodiment, disinfectants for use in this invention will provide at least a 99.999% reduction (5-log order reduction). These reductions can be assessed using a procedure presented in Germicidal and Detergent Sanitizing Action of Disinfectants, Official Methods of Analysis of the Association of Official Analytical Che mists, para. 960.09 and applicable sections, 15th Edition, 1990 (EPA Guideline 91-2) . According to this reference, a disinfectant should provide a 99.999% reduction (5-log order reduction) within 30 seconds at room temperature, 25±2°C, against various test organisms.
[0036] Differentiating "-cide" or "-static" antimicrobial activity, definitions describing the degree of efficacy and official laboratory protocols for measuring this efficacy are considerations for understanding the relevance of antimicrobial agents and compositions. Antimicrobial compositions can affect two types of microbial cell damage. The first is a lethal and irreversible action resulting in complete microbial cell destruction or incapacitation. The second type of cell damage is reversible, such that if the organism becomes free of the agent, it can multiply again. The first is called microbiocide and the last, microbistatic. A disinfectant is, by definition, an agent that provides antimicrobial or microbiocidal activity. In contrast, a preservative is generally described as an inhibitor or microbistatic composition.
[0037] As used in this report, the term "water" for treatment according to the invention includes a variety of sources, such as fresh water, reservoir water, sea water, salt water or brine source, water brackish, recycled water or the like. It is also understood that waters optionally include fresh and recycled water sources (e.g. "produced water"), as well as any combination of waters for treatment, in accordance with the invention. In some embodiments, produced water (or reuse water) refers to a mixture of water that comprises water recycled from previous or competing oil and gas field operations, e.g., fracturing, and water that has not been used in oil and gas field operations, eg fresh water, reservoir water, sea water, etc.
[0038] As used in this report, "percent by weight", "% by weight", "percent by weight", "% by weight", and variations thereof refer to the concentration of a substance as the weight of such substance divided by the total weight of the composition and multiplied by 100. It should be understood that, as used in this report, “percent”, and the like are synonymous with “percent by weight”, “% by weight”, etc.
[0039] It is to be understood that aspects and embodiments of the invention described in this report include "consisting" and/or "consisting essentially of" aspects and embodiments.
[0040] Throughout this disclosure, various aspects of this invention are presented in a strip format. It is to be understood that the description in strip format is merely for convenience and brevity and is not to be construed as an inflexible limitation on the scope of the invention. Consequently, the description of a range must be considered as it has specifically disclosed all possible sub-ranges, as well as individual numerical values within that range. For example, the description of a range, such as 1 to 6, should be considered as having specifically disclosed sub-ranges, such as 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 such a range, eg 1,2, 3, 4, 5 and 6. This applies regardless of the range's length.
[0041] Other objectives, advantages and characteristics of the present invention will become evident from the following descriptive report taken in combination with the attached drawings. 14) STABLE PERCARBOXYLIC ACID COMPOSITIONS AND USES THEREOF
[0042] The present invention relates to stable percarboxylic acid compositions and their uses. In one aspect, the present invention is directed to a composition, which comprises: a C1-C22 carboxylic acid; a C1-C22 percarboxylic acid; hydrogen peroxide; a first stabilizing agent, which is a picolinic acid or a compound having following Formula (IA):
wherein R1 is OH or -NR1aR1b, wherein R1a and R1b are independently hydrogen or (C1-C6) alkyl; R2 is OH or -NR2aR2b, wherein R2a and R2b are independently hydrogen or (C1-C6) alkyl; each R3 is independently alkyl (C 1 -C 6 ), alkenyl (C 2 -C 6 ) or alkynyl (C 2 -C 6 ); en is a number from zero to 3; or a salt thereof; or a compound having the following Formula (IB):
wherein R1 is OH or -NR1aR1b, wherein R1a and R1b are independently hydrogen or (C1-C6) alkyl; R2 is OH or -NR2aR2b, wherein R2a and R2b are independently hydrogen or (C1-C6) alkyl; each R3 is independently (C1-C6) alkyl, (C2-C6) alkenyl or (C2-C6) alkynyl; en is a number from zero to 3; or a salt thereof; a second stabilizing agent, which is a compound having the following Formula (IIA):
wherein R 1 , R 2 , R 3 and R 4 are independently hydrogen, alkyl (C 1 -C 6 ), alkenyl (C 2 -C 6 ) or alkynyl (C 2 -C 6 ) or aryl C 6 -C 20 ; R5is alkyl (C1-C6), alkenyl (C2-C6) or alkynyl (C2-C6); and R6 is hydrogen, (C1-C6) alkyl, (C2-C6) alkenyl or (C2-C6) alkynyl; or a salt thereof; or a compound having the following Formula (IIB):
wherein R1, R2 and R3 are independently hydrogen, (C1-C6) alkyl, (C2-C6) alkenyl or (C2-C6) alkynyl or C6-C20 aryl; or a salt thereof; and wherein said hydrogen peroxide has a concentration of at least about 0.1% by weight, C1-C22 percarboxylic acid has a concentration of at least about 2 times the concentration of said hydrogen peroxide, and the said composition has a pH of about 4 or less.
[0043] In some embodiments, the present composition is a balanced composition comprising peracid, hydrogen peroxide, carboxylic acid and a solvent, for example, water. In some embodiments, the present composition does not comprise a mineral acid, for example the mineral acids disclosed in WO 91/07375.
[0044]C1-C22 percarboxylic acid can be used at any suitable concentration in relation to the concentration of hydrogen peroxide. In some embodiments, C1-C22 percarboxylic acid has a concentration of at least about 6 times the concentration of hydrogen peroxide. In other embodiments, C1-C22 percarboxylic acid has a concentration of at least about 10 times the concentration of hydrogen peroxide. In yet other embodiments, the C1-C22 percarboxylic acid has a concentration of at least about 6, 7, 8, 9, or 10 times the concentration of hydrogen peroxide. CARBOXYLIC ACID
[0045] The present invention includes a carboxylic acid with the composition of peracid and hydrogen peroxide. A carboxylic acid includes any compound of the formula R-(COOH)n, where R can be hydrogen, alkyl, alkenyl, alkyne, acyl, alicyclic group, aryl, heteroaryl or heterocyclic group, and n is 1, 2 or 3. Preferably , R includes hydrogen, alkyl or alkenyl. The terms "alkyl", "alkenyl", "alkyne", "acyl", "alicyclic group", "aryl", "heteroaryl" and "heterocyclic group" are defined below with respect to peracids.
[0046] Examples of suitable carboxylic acids according to the peracid equilibrium systems according to the invention include a variety of monocarboxylic acids, dicarboxylic acids and tricarboxylic acids. Monocarboxylic acids include, for example, formic acid, acetic acid, propanoic acid, butanoic acid, pentanoic acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, undecanoic acid, dodecanoic acid, glycolic acid, lactic acid, salicylic acid, acetylsalicylic acid, mandelic acid, etc. Dicarboxylic acids include, for example, adipic acid, fumaric acid, glutaric acid, maleic acid, succinic acid, malic acid, tartaric acid, etc. Tricarboxylic acids include, for example, citric acid, trimellitic acid, isocitric acid, agaicic acid, etc.
[0047] In one aspect of the invention, a particularly suitable carboxylic acid is soluble in water, such as formic acid, acetic acid, propionic acid, butanoic acid, lactic acid, glycolic acid, citric acid, mandelic acid, glutaric acid , maleic acid, malic acid, adipic acid, succinic acid, tartaric acid, etc. Preferably, a composition of the invention includes acetic acid, octanoic acid or propionic acid, lactic acid, heptanoic acid, octanoic acid or nonanoic acid.
[0048] Additional examples of suitable carboxylic acids are used in sulfoperoxycarboxylic acid or sulfonated peracid systems, which are disclosed in U.S. Patent Publication Nos. 2010/0021557, 2010/0048730 and 2012/0052134, incorporated in their entirety herein by reference.
[0049] Any suitable C1-C22 carboxylic acid can be used in the present compositions. In some embodiments, the C1-C22 carboxylic acid is a C2-C20 carboxylic acid. In other embodiments, the C1 C22 carboxylic acid is a C1, C2, C3, C4, C5, C6, C7, Cε, C9, C10, C11, C12, C13, C14, C15, C16, C17, C18, carboxylic acid C19, C20, C21 or C22. In yet other embodiments, the C1-C22 carboxylic acid comprises acetic acid, octanoic acid and/or sulfonated oleic acid.
[0050]The C1-C22 carboxylic acid can be used in any suitable concentration. In some embodiments, the C1-C22 carboxylic acid has a concentration of from about 10% by weight to about 90% by weight. In other embodiments, the C1-C22 carboxylic acid has a concentration of from about 20% by weight to about 80% by weight. In yet other embodiments, the C1-C22 carboxylic acid has a concentration of about 10% by weight, 20% by weight, 30% by weight, 40% by weight, 50% by weight, 60% by weight, 70% by weight, 80% by weight or 90% by weight. PERACIDS
[0051] In some aspects, a peracid is included for antimicrobial efficacy in the compositions. As used in this report, the term "peracid" may also be referred to as a "percarboxylic acid" or "peroxyacid". Sulfoperoxycarboxylic acids, sulfonated peracids and sulfonated peroxycarboxylic acids are also included in the term “peracid” as used in this report. The terms "sulfoperoxycarboxylic acid", "sulfonated peracid" or "sulfonated peroxycarboxylic acid" refer to the peroxycarboxylic acid form of a sulfonated carboxylic acid, as disclosed in US Patent Publication Nos. 2010/0021557, 2010/0048730 and 2012/0052134 which are incorporated in this report in their entirety for reference. A peracid refers to an acid having the hydrogen from the hydroxyl group in the carboxylic acid replaced by a hydroxy group. Oxidizing peracids may also be referred to in this report as peroxycarboxylic acids.
[0052] A peracid includes any compound of the formula R-(COOOH)n, where R can be hydrogen, alkyl, alkenyl, alkyne, acyl, alicyclic group, aryl, heteroaryl or heterocyclic group, and n is 1, 2 or 3, and named by prefixing the acid precursor with peroxy. Preferably, R includes hydrogen, alkyl or alkenyl. The terms “alkyl”, “alkenyl”, “alkyne”, “acyl”, “alicyclic group”, “aryl”, “heteroaryl”, and “heterocyclic group” are defined in this report.
[0053] As used in this report, the term "alkyl" includes an aliphatic, saturated, straight or branched hydrocarbon chain having from 1 to 22 carbon atoms, such as, for example, methyl, ethyl, propyl, isopropyl ( 1-methylethyl), butyl, tert-butyl (1,1-dimethylethyl) and the like. The term "alkyl" or "alkyl groups" also refers to saturated hydrocarbons having one or more carbon atoms, including straight chain alkyl groups (eg, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl , nonyl, decyl, etc.), cyclic alkyl groups (or "cycloalkyl" or "alicyclic" or "carbocyclic" groups) (for example, cyclopropyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, etc.) , branched-chain alkyl groups (for example, isopropyl, tert-butyl, sec-butyl, isobutyl, etc.) and alkyl-substituted alkyl groups (for example, alkyl-substituted cycloalkyl groups and cycloalkyl-substituted alkyl groups).
[0054] Unless otherwise specified, the term "alkyl" includes "unsubstituted alkyls" and "substituted alkyls". As used in this report, the term "substituted alkyls" refers to alkyl groups having substituents that replace one or more hydrogens on one or more carbons of the hydrocarbon backbone. Such substituents may include, for example, alkenyl, alkynyl, halogen, hydroxyl, alkylcarbonyloxy, arylcarbonyloxy, alkoxycarbonyloxy, aryloxy, aryloxycarbonyloxy, carboxylate, alkylcarbonyl, arylcarbonyl, alkoxycarbonyl, aminocarbonyl, alkoxycarbonyl, alkylaminocarbonyl, dialkylaminocarbonyl , phosphonate, phosphinate, cyano, amino (including alkylamino, dialkylamino, arylamino, diarylamino and alkylarylamino), acylamino (including alkylcarbonylamino, arylcarbonylamino, carbamoyl and ureido), imino, sulfhydryl, alkylthio, arylthio, thiocarboxylate, sulfates, alkylsulfinyl sulfonates , sulfamoyl, sulfonamido, nitro, trifluoromethyl, cyano, azido, heterocyclic, alkylaryl or aromatic groups (including heteroaromatics).
[0055] The term "alkenyl" includes an unsaturated and aliphatic hydrocarbon chain having from 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 can be terminally substituted with a heteroatom, such as, for example, a nitrogen, sulfur or oxygen atom, forming an aminoalkyl, oxyalkyl or thioalkyl, for example, aminomethyl, thioethyl, oxypropyl and the like. Similarly, the above alkyl or alkenyl can be interrupted in the chain by a heteroatom forming an alkylaminoalkyl, alkylthioalkyl or alkoxyalkyl, for example, methylaminoethyl, ethylthiopropyl, methoxymethyl and the like.
[0056] Also, as used in this report, the term "alicyclic" includes any cyclic hydrocarbyl containing from 3 to 8 carbon atoms. Examples of suitable alicyclic groups include cyclopropanyl, cyclobutanyl, cyclopentanyl, etc. The term "heterocyclic" includes any closed ring structures analogous to carbocyclic groups, in which one or more of the carbon atoms in the ring is an element other than carbon (heteroatom), for example, a nitrogen atom, sulfur or oxygen. Heterocyclic groups can be saturated or unsaturated. Examples of suitable heterocyclic groups include, for example, aziridine, ethylene oxide (epoxides, oxiranes), thiirane (episulfides), dioxirane, azetidine, oxetane, thiethane, dioxetane, dithiethane, dithieth, azolidine, pyrrolidine, pyrroline, oxolane, di- hydrofuran and furan. Additional examples of suitable heterocyclic groups include groups derived from tetrahydrofurans, furans, thiophenes, pyrrolidines, piperidines, pyridines, pyrroles, picoline, coumalin, etc.
[0057] In some embodiments, alkyl, alkenyl, alicyclic groups, and heterocyclic groups may be unsubstituted or substituted, for example, by aryl, heteroaryl, C1-4 alkyl, C1-4 alkenyl, C1-4 alkoxy, amino , carboxy, halo, nitro, cyano, -SO3H, phosphono or hydroxy. When alkyl, alkenyl, alicyclic group or heterocyclic group is substituted, preferably the substitution is C1-4 alkyl, halo, nitro, amido, hydroxy, carboxy, sulfo or phosphono. In one embodiment, R includes hydroxy substituted alkyl. The term "aryl" includes aromatic hydrocarbyl, including fused aromatic rings such as, for example, phenyl and naphthyl. 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, etc. The term "heteroaryl" also includes fused rings, where at least one ring is aromatic, such as, for example, indolyl, purinyl, benzofuryl, etc.
[0058] In some embodiments, aryl and heteroaryl groups may be unsubstituted or ring-substituted, for example, by aryl, heteroaryl, alkyl, alkenyl, alkoxy, amino, carboxy, halo, nitro, cyano, -SO3H, phosphono or hydroxy. When aryl, aralkyl or heteroaryl is substituted, preferably the substitution is C 1-4 alkyl, halo, nitro, amido, hydroxy, carboxy, sulfo or phosphono. In one embodiment, R includes aryl substituted with C1-4 alkyl.
[0059] Suitable peracids for use include any peroxycarboxylic acids, including varying lengths of peroxycarboxylic acids and percarboxylic acids (eg C1-22) which can be prepared from the acid-catalyzed equilibrium reaction between an acid carboxylic described above and hydrogen peroxide. A peroxycarboxylic acid can also be prepared by the autooxidation of aldehydes or by the reaction of hydrogen peroxide with an acid chloride, acid hydride, carboxylic acid anhydride or sodium alcoholate. Alternatively, peracids can be prepared through non-equilibrium reactions that can be generated for use in situ, such as the methods disclosed in US Patent Applications Serial Nos. 13/331,304 and 13/331,486 entitled “In Situ Generation of Peroxycarboxylic Acids at Alkaline pH, and Methods of Use Thereof", which are incorporated herein by reference. Preferably, a composition of the invention includes peroxyacetic acid, peroxyoctanoic acid, peroxypropionic acid, peroxylactic acid, peroxyheptanoic acid, peroxyoctanoic acid and/or peroxynonanoic acid.
[0060] In some embodiments, a peroxycarboxylic acid includes at least one water-soluble peroxycarboxylic acid, where R includes alkyl of 1 to 22 carbon atoms. For example, in one embodiment, a peroxycarboxylic acid includes peroxyacetic acid. In another embodiment, a peroxycarboxylic acid has R which is an alkyl of 1 to 22 carbon atoms substituted with hydroxy. Methods for preparing peroxyacetic acid are known to those of skill in the art, including those disclosed in U.S. Patent No. 2,833,813, which is incorporated herein by reference.
[0061] In another embodiment, a sulfoperoxycarboxylic acid has the following formula:
where R1 is hydrogen or a substituted or unsubstituted alkyl group; R2 is a substituted or unsubstituted alkylene group; X is hydrogen, a cationic group or an ester-forming moiety; or salts or esters thereof. In further embodiments, a sulfoperoxycarboxylic acid is combined with a single or mixed peroxycarboxylic acid composition, such as a sulfoperoxycarboxylic acid with peroxyacetic acid and peroxyoctanoic acid (PSOA/POOA/POAA).
[0062] In other embodiments, a mixed peracid is used, such as a peroxycarboxylic acid, including at least one peroxycarboxylic acid of limited water solubility, wherein R includes alkyl of 5 to 22 carbon atoms and at least one water-soluble peroxycarboxylic acid, where R includes alkyl of 1 to 4 carbon atoms. For example, in one embodiment, a peroxycarboxylic acid includes peroxyacetic acid and at least one other peroxycarboxylic acid such as those named above. Preferably, a composition of the invention includes peroxyacetic acid and peroxyoctanoic acid. Other combinations of mixed peracids are well suited for use in the present invention.
[0063] In another embodiment, a mixture of peracetic acid and peroctanoic acid is used to treat a water source, as disclosed in U.S. Patent No. 5,314,687, which is incorporated herein in its entirety by reference. In one aspect, the peracid mixture is a hydrophilic peracetic acid and a hydrophobic peroctanoic acid, providing antimicrobial synergy. In one aspect, the synergy of a mixed peracid system makes it possible to use lower dosages of peracids.
[0064] In another embodiment, a tertiary peracid blend composition, such as peroxysulfonated oleic acid, peracetic acid and peroctanoic acid, is used to treat a water source, as disclosed in US Patent Publication No. 2010 /00021557 which is incorporated in its entirety in this report by reference. A combination of the three peracids produces significant antimicrobial synergy providing an effective antimicrobial composition for water treatment methods according to the invention. Furthermore, it is considered that the high acidity built into the composition helps to remove chemical contaminants from the water (for example, sulfite and sulfide).
Advantageously, a combination of peroxycarboxylic acids provides a composition with desirable antimicrobial activity in the presence of high loads of organic dirt. Blended peroxycarboxylic acid compositions often provide micro-synergistic efficacy. Accordingly, the compositions of the invention can include a peroxycarboxylic acid, or mixtures thereof.
Several commercial formulations of peracids are available, including, for example, peracetic acid (15%) available as EnviroSan (Ecolablnc, St. Paul MN). Most commercial peracid solutions determine a specific percarboxylic acid concentration without reference to the other chemical components in a use solution. However, it should be understood that commercial products such as peracetic acid will also contain the corresponding carboxylic acid (eg acetic acid), hydrogen peroxide and water.
[0067] Any suitable C1-C22 percarboxylic acid can be used in the present compositions. In some embodiments, the C1-C22 percarboxylic acid is a C2-C20 percarboxylic acid. In other embodiments, the C1-C22 percarboxylic acid is a C1, C2, C3, C4, C5, Cβ, C7, Cs, C9, C10, C11, C12, C13, C14, C15, C18, C17, carboxylic acid Cys, C19, C20, C21 or C22. In yet other embodiments, the C1-C22 percarboxylic acid comprises peroxyacetic acid, peroxyoctanoic acid and/or peroxysulfonated oleic acid.
[0068]C1-C22 percarboxylic acid can be used in any suitable concentration. In some embodiments, the C1-C22 percarboxylic acid has a concentration of from about 1% by weight to about 40% by weight. In other embodiments, the C1-C22 percarboxylic acid has a concentration of from about 1% by weight to about 20% by weight. In yet other embodiments, the C1-C22 percarboxylic acid has a concentration of about 1% by weight, 2% by weight, 3% by weight, 4% by weight, 5% by weight, 6% by weight, % by weight, 8% by weight, 9% by weight, 10% by weight, 11% by weight, 12% by weight, 13% by weight, 14% by weight, 15% by weight, 16% by weight, 17 % by weight, 18% by weight, 19% by weight, 20% by weight, 25% by weight, 30% by weight, 35% by weight or 40% by weight. HYDROGEN PEROXIDE
[0069] The present invention includes the use of hydrogen peroxide. Hydrogen peroxide, H2O2, provides the advantages of having a high ratio of active oxygen because of its low molecular weight (34,014 g/mol) and being compatible with numerous substances that can be treated by the methods of the invention as it is a liquid. faintly acidic, clear and colorless. Another advantage of hydrogen peroxide is that it breaks down into water and oxygen. It is advantageous to have these decomposition products as they are generally compatible with the substances to be treated. For example, decomposition products are generally compatible with metallic substance (eg substantially non-corrosive) and are generally harmless to incidental contact and are environmentally friendly.
[0070] In one aspect of the invention, hydrogen peroxide is initially in an antimicrobial peracid composition in an amount effective to maintain a balance between a carboxylic acid, hydrogen peroxide, a solvent such as water, and a peracid. The amount of hydrogen peroxide should not exceed an amount that would adversely affect the antimicrobial activity of a composition of the invention. In other aspects of the invention, the concentration of hydrogen peroxide is significantly reduced within an antimicrobial peracid composition, preferably containing hydrogen peroxide at a concentration as close to zero as possible. That is, the hydrogen peroxide concentration is minimized through the use of selected catalase or peroxidase enzymes according to the invention. In other aspects, the hydrogen peroxide concentration is reduced and/or eliminated as a result of distilled equilibrium peracid compositions, other catalysts for hydrogen peroxide decomposition (eg, biomimetic complexes) and/or the use of perhydrolysis anionic esters (eg triacetin) to obtain peracids with very low hydrogen peroxide content.
[0071] In some embodiments, an advantage of minimizing the concentration of hydrogen peroxide is that the antimicrobial activity of a composition of the invention is improved compared to conventional equilibrium peracid compositions. Without limiting the invention to a particular theory, significant improvements in antimicrobial efficacy result from the enhanced peracid stability from the reduced hydrogen peroxide concentration in the in-use solution.
[0072]Hydrogen peroxide can be used in any suitable concentration. In some embodiments, the hydrogen peroxide has a concentration of from about 0.5% by weight to about 10% by weight. In other embodiments, the hydrogen peroxide has a concentration of from about 1% by weight to about 2% by weight. In yet other embodiments, the hydrogen peroxide has a concentration of about 0.5% by weight, 1% by weight, 2% by weight, 3% by weight, 4% by weight, 5% by weight, 6 % by weight, 7% by weight, 8% by weight, 9% by weight or 10% by weight. In yet other embodiments, the hydrogen peroxide has a concentration of about 1% by weight, 1.1% by weight, 1.2% by weight, 1.3% by weight, 1.4% by weight, 1.5% by weight, 1.6% by weight, 1.7% by weight, 1.8% by weight, 1.9% by weight or 2% by weight.
[0073] In some embodiments, the C1-C22 carboxylic acid is acetic acid and the C1-C22 percarboxylic acid is peracetic acid. In other embodiments, the C1-C22 carboxylic acid, e.g., acetic acid, has a concentration of about 70% by weight, the C1-C22 percarboxylic acid, e.g., peracetic acid, has a concentration of about 15% by weight and the hydrogen peroxide has a concentration of at least about 1% by weight. STABILIZING AGENTS
[0074] In some aspects, more than one type of stabilizer is used in the compositions. In some embodiments, at least one stabilizer is a phosphonic acid or a derivative thereof. Without limiting the invention to any particular theory, it is considered that, in addition to functioning as a stabilizer through the chelation of transition metal ions, phosphonic acid-based stabilizers, such as HEDP, also act as an acid catalyst and assist in the formation of the peroxycarboxylic acid from the corresponding carboxylic acid and hydrogen peroxide. In some embodiments, a pyridine carboxylic acid based stabilizer is used as a second stabilizer. Pyridine carboxylic acids, such as 2,6-pyridinedicarboxylic acid (DPA), are well known chelators for metal ions. It is considered that through the use of two different types of stabilizers, the transition metals responsible for the catalytic composition of peroxycarboxylic acids are more effectively deactivated through the formation of a more stable complex involving the chelators.
[0075] Any suitable first stabilizing agent can be used in the present compositions. In some embodiments, the first stabilizing agent is a picolinic acid or a salt thereof. In other embodiments, the first stabilizing agent is 2,6-pyridinedicarboxylic acid or a salt thereof. The first stabilizing agent can be used in any suitable concentration. In some embodiments, the first stabilizing agent has a concentration of from about 0.005% by weight to about 5% by weight. In other embodiments, the first stabilizing agent has a concentration of from about 0.05% by weight to about 0.15% by weight. In yet other embodiments, the first stabilizing agent has a concentration of about 0.005% by weight, 0.01% by weight, 0.1% by weight, 1% by weight, 2% by weight, 3% by weight , 4% by weight or 5% by weight. In yet other embodiments, the first stabilizing agent has a concentration of about 0.05% by weight, 0.06% by weight, 0.07% by weight, 0.08% by weight, 0.09% by weight, 0.10% by weight, 0.11% by weight, 0.12% by weight, 0.13% by weight, 0.14% by weight, or 0.15% by weight.
[0076] Any suitable second stabilizing agent can be used in the present compositions. In some embodiments, the second stabilizing agent is 1-hydroxy-ethyllidene-1,1-diphosphonic acid (HEDP) or a salt thereof. The second stabilizing agent can be used in any suitable concentration. In some embodiments, the second stabilizing agent has a concentration of from about 0.1% by weight to about 10% by weight, e.g., 0.1% by weight, 0.5% by weight, 1 % by weight, 2% by weight, 3% by weight, 4% by weight, 5% by weight, 6% by weight, 7% by weight, 8% by weight, 9% by weight or 10% by weight. In other embodiments, the second stabilizing agent has a concentration of from about 0.5% by weight to about 5% by weight, e.g., 0.5% by weight, 1% by weight, 1.5% by weight. weight, 2% by weight, 2.5% by weight, 3% by weight, 3.5% by weight, 4% by weight, 4.5% by weight or 5% by weight. In yet other embodiments, the second stabilizing agent has a concentration of from about 0.6% by weight to about 1.8% by weight, e.g., 0.6% by weight, 0.7% by weight, 0.8% by weight, 0.9% by weight, 1.0% by weight, 1.1% by weight, 1.2% by weight, 1.3% by weight, 1.4% by weight, 1 .5% by weight, 1.6% by weight, 1.7% by weight, 1.8% by weight.
[0077] In some embodiments, the present composition may further comprise a substance that assists in solubilizing the first and/or second stabilizing agents. Exemplary substances that can aid in the solubilization of the first and/or second stabilizing agents include hydrotropes such as sodium xylene sulfonate, sodium cumene sulfonates, and surfactants such as anionic surfactants and nonionic surfactants.
[0078] In some embodiments, the first stabilizing agent is a 2,6-pyridinedicarboxylic acid or a salt thereof and the second stabilizing agent is HEDP or a salt thereof. In other embodiments, the first and second stabilizing agents act synergistically to delay or prevent the composition from meeting its auto-accelerating decomposition temperature (SADT). SADT refers to the lowest temperature at which self-accelerating decomposition can occur with a composition. In some embodiments, SADT refers to the lowest temperature at which self-accelerating decomposition can occur under commercial packaging, storage, transportation and/or conditions of use. SADT can be estimated, calculated, predicted and/or measured by any suitable methods. For example, SADT can be estimated or measured directly by one of 3 methods (H1, H2 and H4) recommended by the UN Committee tee for the Transportation of Dangerous Goods in “Recommendations on the Trans port of Dangerous Goods, Model Regulations” (Rev .17) ST/SG/AC.10/1/Ver.17. For example, the methodology disclosed in Malow and Wehrstedt, J. Hazard Mater., 120(1-3):21-4 (2005) can be used.
The present compositions may retain any suitable level or percentage of C1-C22 percarboxylic acid activity under customary packaging, storage, transportation and/or conditions of use. In some embodiments, the present compositions retain at least about 80% of the C1-C22 percarboxylic acid activity after storage for about 30 days at about 50°C. Preferably, the present compositions retain at least about 85%, 90% or more percent C1-C22 percarboxylic acid activity after storage for about 30 days at about 50°C. ADDITIONAL OPTIONAL MATERIALS
The present compositions may optionally include additional ingredients to enhance the water treatment composition according to the invention, including, for example, friction reducers, viscosity enhancers and the like. Additional optional functional ingredients may include, for example, peracid stabilizers, emulsifiers, corrosion inhibitors and/or scale removing agents (i.e. scale inhibitors), additional surfactants and/or antimicrobial agents for enhanced efficacy (by example, mixed peracids, biocides), defoamers, acidulants (eg, strong mineral acids), additional carboxylic acids, and the like. In one embodiment, no additional functional ingredients are used. FRICTION REDUCERS
[0081] Friction reducers are used in water or other water-based fluids used in hydraulic fracturing treatments for underground well formations, in order to improve the permeability of the desired gas and/or oil that will be recovered from the cracks or fluid-conducting pathways created through the fracturing process. Friction reducers allow water to be pumped faster into formations. Various polymeric additives have been widely used as friction reducers to enhance or modify the characteristics of aqueous fluids used in well drilling, recovery and production applications.
[0082]Examples of commonly used friction reducers include polyacrylamide polymers and copolymers. In one aspect, additional suitable friction reducers may include acrylamide-derived polymers and copolymers, such as polyacrylamide (sometimes abbreviated as PAM), acrylamide-acrylate (acrylic acid) copolymers, acrylic acid-methacrylamide copolymers, copolymer partially hydrolyzed polyacrylamide (PHPA), partially hydrolyzed polymethacrylamide, acrylamide-methyl-propane sulfonate copolymers (AMPS), and the like. Various derivatives of such polymers and copolymers, for example, quaternary amine salts, hydrolyzed versions and the like, are included with the polymers and copolymers described in this report.
[0083] Friction reducers are combined with water and/or other aqueous fluids, which in the combination is often referred to as "slick water fluids". Low rheology fluids (slick water) have drag characteristics of reduced friction and beneficial flow that allow the pumping of aqueous fluids in various areas of gas and/or oil production, including, for example, for fracturing.
[0084] In one aspect of the invention, a friction reducer is present in a use solution in an amount between about 100 ppm to 1000 ppm. In another aspect, a friction reducer is present in a use solution in an amount of at least about 0.01% by weight to about 10% by weight, preferably at least about 0.01% by weight to about 5% by weight, preferably, at least about 0.01% by weight to about 1% by weight, more preferably, at least about 0.01% by weight to about 0.5% by weight, and even more preferably, at least about 0.01% by weight to about 0.1% by weight. Advantageously, the compositions and methods of the invention do not negatively interfere with friction reducers included in an aqueous solution. Without limiting the invention to a particular theory, it is considered that the reduction and/or elimination of oxidizing hydrogen peroxide from the peracid composition promotes the stability and effectiveness of any variation in the amount of friction reducer present in a use solution . VISCOSITY ENHANCER
[0085] Viscosity enhancers are additional polymers used in water or other water-based fluids used in hydraulic fracturing treatments to provide viscosity enhancement. Natural and/or synthetic viscosity-increasing polymers can be used in the compositions and methods according to the invention. Viscosity enhancers may also be referred to as gelling agents and examples include guar, xanthan, cellulose derivatives and polyacrylamide and polyacrylate polymers and copolymers and the like.
[0086] In one aspect of the invention, a viscosity enhancer is present in a use solution in an amount between about 100ppm to 1000ppm. In another aspect, a viscosity enhancer is present in a solution of use in an amount of at least about 0.01% by weight to about 10% by weight, preferably at least about 0.01% by weight. weight to about 5% by weight, preferably, at least about 0.01% by weight to about 1% by weight, at least about 0.01% by weight to about 2% by weight, preferably, at least about 0.01% by weight to about 1% by weight, preferably, at least about 0.01% by weight to about 0.5% by weight. Advantageously, the compositions and methods of the invention do not negatively interfere with the viscosity enhancer included in an aqueous solution. Without limiting the invention to a particular theory, it is believed that the reduction and/or elimination of oxidizing hydrogen peroxide from the peracid composition promotes the stability and effectiveness of any variation in the amount of viscosity enhancer present in a solution of use. CORROSION INHIBITORS
[0087]Corrosion inhibitors are additional molecules used in oil and gas recovery operations. Corrosion inhibitors which may be used in the present disclosure include the exemplary corrosion inhibitors disclosed in US Patent No. 5,965,785, US Patent Application Serial No. 12/263,904, GB Patent No. 1,198,734, WO/03/006581 , WO04/044266 and WO08/005058, fully incorporated herein by reference.
[0088] In one aspect of the invention, a corrosion inhibitor is present in a use solution in an amount between about 100 ppm to 1000 ppm. In another aspect, a corrosion inhibitor is present in a use solution in an amount of at least about 0.0001% by weight to about 10% by weight, preferably at least about 0.0001% by weight to about 5% by weight, preferably, at least about 0.0001% by weight to about 1% by weight, preferably, at least about 0.0001% by weight to about 0.1% by weight, and, even more preferably, at least about 0.000% by weight to about 0.05% by weight. Advantageously, the compositions and methods of the invention do not negatively interfere with the corrosion inhibitor included in an aqueous solution. Without limiting the invention to a particular theory, it is believed that the reduction and/or elimination of oxidizing hydrogen peroxide from the peracid composition promotes the stability and effectiveness of any variation in the amount of corrosion inhibitor present in a wear solution . SCALE INHIBITORS
[0089] Scale inhibitors are additional molecules used in oil and gas recovery operations. Common scale inhibitors that can be used in these types of applications include polymers and copolymers, phosphates, phosphate esters and the like.
[0090] In one aspect of the invention, a scale inhibitor is present in a use solution in an amount between about 100 ppm to 1000 ppm. In another aspect, a scale inhibitor is present in a use solution in an amount of at least about 0.0001% by weight to about 10% by weight, at least about 0.0001% by weight to about 1% by weight, preferably at least about 0.0001% by weight to about 0.1% by weight, preferably at least about 0.0001% by weight to about 0.05% by weight . Advantageously, the compositions and methods of the invention do not negatively interfere with the scale inhibitor included in an aqueous solution. Without limiting the invention to a particular theory, it is considered that the reduction and/or elimination of oxidizing hydrogen peroxide from the peracid composition promotes the stability and effectiveness of any variation in the amount of scale inhibitor present in a solution of use. ADDITIONAL ANTIMICROBIAL AGENTS
[0091] Additional antimicrobial agents may be included in the compositions and/or methods of the invention for enhanced antimicrobial efficacy. In addition to the use of peracid compositions, additional antimicrobial agents and biocides can be used. Additional biocides can include, for example, a quaternary ammonium compound disclosed in U.S. Patent No. 6,627,657, which is incorporated in this report in its entirety by reference. Advantageously, the presence of the quaternary ammonium compound provides synergistic antimicrobial efficacies with peracids, as well as maintaining the long-term biocidal efficacy of the compositions.
[0092] In another embodiment, the additional biocide may include a phosphonium biocide compatible oxidant, such as tributyl tetradecyl phosphonium chloride. The phosphonium biocide provides similar antimicrobial advantages as the quaternary ammonium compound in combination with the peracids. Furthermore, the phosphonium biocide is compatible with the anionic polymeric chemicals commonly used in petroleum field applications, such as the disclosed fracturing methods in accordance with the invention.
[0093] Additional antimicrobial agents and biocides can be used in sufficient amounts to provide antimicrobial efficacy, as they may vary depending on the source of water in need of treatment and the contaminants in it. Such agents may be present in a solution of use in an amount of at least about 0.1% by weight to about 50% by weight, preferably at least about 0.1% by weight to about 20% by weight. weight, more preferably from about 0.1% by weight to about 10% by weight. ACCIDENTS
[0094] Acidulants can be included as additional functional ingredients in a composition, according to the invention. In one aspect, a strong mineral acid, such as nitric acid or sulfuric acid, can be used to treat water sources, as disclosed in U.S. Patent No. 4,587,264, which is fully incorporated herein by reference. The combined use of a strong mineral acid with the peracid composition provides enhanced antimicrobial efficacy as a result of acidity that aids in the removal of chemical contaminants within the water source (eg, sulphite and sulphide). Furthermore, some strong mineral acids, such as nitric acid, provide an additional benefit of reducing the risk of corrosion for metals contacted by the peracid compositions according to the invention. Exemplary products are commercially available from Enviro Tech Chemical Services, Inc. (Reflex brand) and from Solvay Chmicals (Proxitane® NT brand).
[0095] Acidulants can be used in sufficient amounts to provide the intended antimicrobial effectiveness and/or anticorrosion benefits, as may vary depending on the water source in need of treatment and the contaminants in it. Such agents may be present in a solution of use in an amount of at least about 0.1% by weight to about 50% by weight, preferably at least about 0.1% by weight to about 20% by weight. weight, more preferably from about 0.1% by weight to about 10% by weight. CATALASE AND PEROXIDASE ENZYME
[0096] In one aspect of the invention, a catalase or peroxidase enzyme is used to reduce and/or eliminate the concentration of hydrogen peroxide in an antimicrobial peracid composition. Enzymes catalyze the decomposition of hydrogen peroxide into water and oxygen. Advantageously, the reduction and/or elimination of hydrogen peroxide (strong oxidant) results in other additives to a water treatment source (eg water source) not being degraded or made incompatible. Various additives used to enhance or modify the characteristics of aqueous fluids used in well drilling, recovery and production applications are at risk of degradation by the oxidizing effects of hydrogen peroxide. These may include, for example, friction reducers and viscosity enhancers used in commercial well drilling, completion and stimulus, or well production applications.
[0097] Various sources of catalase enzymes can be used in accordance with the invention, including: animal sources such as beef catalase isolated from beef livers; fungal catalases isolated from fungi, including Penicillium chrysogenum, Penicillium notatum and Aspergillus niger; vegetable sources; bacterial sources, such as Staphylcoccus aureus, and genetic variations and modifications thereof. In one aspect of the invention, fungal catalases are used to reduce the hydrogen peroxide content of a peracid composition. Catalases are commercially available in various forms, including liquid and spray-dried forms. Commercially available catalase includes the active enzyme as well as additional ingredients to enhance the stability of the enzyme. Some exemplary commercially available catalase enzymes include Genencor CA-100 and CA-400, as well as Mitsubishi Gas and Chemical (MGC) ASC super G and ASC super 200 and Optimase CA 400L from Genecor International. Further description of suitable catalase enzymes is disclosed and fully incorporated into this report by reference from U.S. Patent Publication No. 2009/0269324.
[0098] In one aspect of the invention, catalase enzymes have a high ability to decompose hydrogen peroxide. Advantageously, the reduction or elimination of hydrogen peroxide from oxidizing compositions removes various detriments caused by oxidizing agents. In particular, the use of catalase with the peracid compositions provides enhanced antimicrobial benefits without causing the harm associated with conventional oxidizing agents (for example, peracetic acid, hypochlorite or hypochlorous acid and/or chlorine dioxide) such as corrosion.
[0099] Peroxidase enzymes can also be used to break down hydrogen peroxide from a peracid composition. Although peroxidase enzymes primarily function to allow the oxidation of substrates via hydrogen peroxide, they are also suitable for effectively reducing hydrogen peroxide to peracid ratios in compositions. Various sources of peroxidase enzymes can be used in accordance with the invention, including, for example, animal sources, fungal peroxidases and genetic variations and modifications thereof. Peroxidases are commercially available in various forms, including liquid and spray-dried forms. Commercially available peroxidases include the active enzyme as well as additional ingredients to enhance enzyme stability.
[00100] In some embodiments, the enzyme catalase or peroxidase is capable of degrading at least about 50% of the initial concentration of hydrogen peroxide in a peracid composition. Preferably, the enzyme is provided in an amount sufficient to reduce the hydrogen peroxide concentration of a peracid composition by at least more than about 50%, more preferably at least about 60%, at least about 70 %, at least about 80%, at least about 90%. In some embodiments, the enzyme reduces the hydrogen peroxide concentration of a peracid composition by greater than 90%.
[00101] In one aspect of the invention, enzymes are suitable for use and have a tolerance over a wide range of temperatures, including temperature ranges in water treatment applications that can range from about 0 to 180°C. A suitable catalase enzyme will maintain at least 50% of its activity under such storage and/or application temperatures for at least about 10 minutes, preferably for at least about 1 hour.
[00102] In another aspect of the invention, catalase or peroxide enzymes if described in this report have a tolerance to pH ranges found in water treatment applications. Acetic acid (or other carboxylic acid) levels in a water treatment application can vary widely in parts per million (ppm) of acetic acid or other carboxylic acid. Solutions may have a corresponding range of pH range from greater than 0 to about 10. A suitable catalase or peroxidase enzyme will maintain at least about 50% of its activity in such acetic acid or other carboxylic acid solutions for a period of time. period of about 10 minutes.
[00103] In one aspect of the invention, a catalase or peroxidase enzyme is present in a solution of use in the water treatment and peracid composition in amounts sufficient to reduce the concentration of hydrogen peroxide from the peracid composition in at least 50% within about 10 minutes, preferably within about 5 minutes, preferably within about 2 to 5 minutes, more preferably within about 1 minute. Enzyme concentration ranges will vary depending on the time within which 50% of the hydrogen peroxide from the peracid composition is removed. In certain aspects of the invention, a catalase or peroxidase enzyme is present in a use solution composition, including the water source to be treated, in amounts between about 1ppm and about 1000ppm, preferably between about 5ppm and 500 ppm, and more preferably between about 10 ppm and about 100 ppm. USES OF THE PRESENT COMPOSITIONS
[00104] In another aspect, the present invention is directed to a method for storing a composition containing percarboxylic acid, which comprises storing the above compositions, wherein said composition retains at least about 80% of the activity of the C1 percarboxylic acid -C22 after storage for any suitable time under any suitable conditions, for example, retaining at least about 80% of the activity of the C1-C22 percarboxylic acid after storage for about 30 days at about 50°C. Preferably, the present compositions retain at least about 85%, 90% or more of the C1-C22 percarboxylic acid activity after storage for about 30 days at about 50°C.
[00105] In yet another aspect, the present invention is directed to a method for transporting a composition containing percarboxylic acid, which comprises transporting the above compositions under ambient conditions, preferably, by mass, for example 1,000 gallons and further, wherein the SADT of said composition is at least 45°C during shipping. Preferably, the SADT of said composition is greater than at least 50°C, 55°C, 60°C, 65°C or 70°C.
[00106] In yet another aspect, the present invention is directed to a method of treating water, which comprises providing the above compositions to a water source in need of treatment to form a treated water source, wherein the said source of treated water comprises from about 1 ppm to about 1000 ppm of said C1-C22 percarboxylic acid.
[00107]The present methods can be used to treat any suitable or desirable water sources. For example, the present methods can be used to treat fresh water, reservoir water, sea water, produced water and a combination thereof. In some embodiments, the water source comprises at least about 1% by weight of produced water. In other embodiments, the water source comprises at least about 1% by weight, 2% by weight, 3% by weight, 4% by weight, 5% by weight, 6% by weight, 7% by weight. are 8% by weight, 9% by weight, or 10% by weight, 15% by weight, 20% by weight, 25% by weight, 30% by weight or more of produced water.
[00108] The treated water source can comprise any suitable concentration of C1-C22 percarboxylic acid. In some embodiments, the treated water source comprises from about 10 ppm to about 200 ppm of the C1-C22 percarboxylic acid. In other embodiments, the treated water source comprises about 1ppm, 10ppm, 100ppm, 200ppm, 300ppm, 400ppm, 500ppm, 600ppm, 700ppm, 800ppm, 900ppm or 1000ppm of C1-C22 percarboxylic acid. The present methods can be used to treat any suitable or desirable water sources. In another example, the present methods can be used to treat fresh water, reservoir water, sea water, produced water and a combination thereof. In some embodiments, the water source comprises at least about 1% by weight of produced water. In other embodiments, the water source comprises at least about 1% by weight, 2% by weight, 3% by weight, 4% by weight, 5% by weight, 6% by weight, 7% by weight, 8% by weight, 9% by weight or 10% by weight, 15% by weight, 20% by weight, 25% by weight, 30% by weight or more produced water.
[00109] Any suitable C1-C22 percarboxylic acid can be used in the present methods. For example, peroxyacetic acid, peroxyoctanoic acid and/or peroxysulfonated oleic acid can be used. In some embodiments, a combination of peroxyacetic acid, peroxyoctanoic acid and peroxysulfonated oleic acid is used.
[00110]The treated water source can comprise any suitable concentration of hydrogen peroxide. In some embodiments, the treated water source comprises from about 1 ppm to about 15 ppm of hydrogen peroxide. In other embodiments, the treated water source comprises about 1ppm, 2ppm, 3ppm, 4ppm, 5ppm, 6ppm, 7ppm, 8ppm, 9ppm, 10ppm, 11ppm, 12ppm , 13 ppm, 14 ppm or 15 ppm of hydrogen peroxide.
[00111] The treated water source can retain any suitable concentration and/or percentage of the initial C1-C22 percarboxylic acid activity in the treated water source for any suitable period of time after the treated water source is formed. In some embodiments, the treated water source retains at least about 60%, 65%, 70%, 75%, 80%, 85% or 90% of the initial C1-C22 percarboxylic acid activity in the water source. treated for a suitable time after the treated water source is formed. In other embodiments, the treated water source retains at least about 60%, 65%, 70%, 75%, 80%, 85% or 90% of the initial C1-C22 percarboxylic acid activity in the water source. treated for at least 15 minutes after the treated water source is formed.
[00112] In some embodiments, the level of a microorganism, if present in the water source, is stabilized or reduced by the present methods. For example, at least 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80% or 90% or more of the micro-organism, if present in the water source, is killed, destroyed, removed and/or inactivated by the present methods.
[00113] In some embodiments, the antimicrobial effectiveness of the composition used in the present methods in the treated water source is comparable to the antimicrobial effect of a water source that does not contain produced water. In other embodiments, the treated water source reduces corrosion caused by hydrogen peroxide and reduces corrosion induced by microbes, and the composition used in the present methods does not substantially interfere with a friction reducer, a viscosity enhancer, other ingredients functional features present in the treated water source or a combination thereof.
[00114] In some embodiments, the present methods may comprise adding a peroxidase or a catalase to further reduce the level of hydrogen peroxide in the treated water source. Peroxidase or catalase can be added in any suitable way. In some embodiments, the peroxidase or catalase can be added to the water source before a composition used in the present methods is supplied to the water source. In other embodiments, the present compositions can be diluted to a suitable intermediate volume, and the peroxidase or catalase can be added to the diluted intermediate volume. Then the diluted intermediate volume, which contains the peroxidase or catalase, can be added to the water source. Any suitable peroxidase or catalase, including those described below, can be used in the present methods.
[00115] In some embodiments, the present methods may further comprise directing the treated water source in an underground environment or discarding the treated water source.
[00116] In some embodiments, the water source treated by the present methods does not comprise reusing water, the treated water source comprises from about 10 ppm to about 20 ppm of the C1-C22 percarboxylic acid and of about 1 ppm to about 2 ppm hydrogen peroxide and the treated water source does not comprise a friction reducer and/or a rheology modifier.
[00117] In some embodiments, the water source treated by the present methods is a mixed water source comprising about 80% by weight of fresh water or reservoir water and about 20% by weight of water from reuse, the treated water source comprises from about 25 ppm to about 35 ppm C1-C22 percarboxylic acid and from about 2 ppm to about 3 ppm hydrogen peroxide and catalase, the treated water source does not comprise a friction reducer and/or a rheology modifier and the treated water source is formed before reaching a mixing barrel.
[00118] In some embodiments, the water source treated by the present methods is a mixed water source comprising about 80% by weight of fresh water or reservoir water and about 20% by weight of water from reuse, the treated water source comprises from about 25 ppm to about 35 ppm C1-C22 percarboxylic acid and from about 2 ppm to about 3 ppm hydrogen peroxide and catalase, the treated water source comprises a friction reducer and/or a rheology modifier and the treated water source is formed in a mixing barrel.
[00119] In some embodiments, the treated water source comprises about 30 ppm or less of C1-C22 percarboxylic acid and about 0.5 ppm or less of hydrogen peroxide, the treated water source comprises a friction reducer and/or a rheology modifier and the treated water source is directed at, or is in, an underground environment.
[00120] In some respects, the disclosed methods for water treatment in oil and gas recovery provide effective antimicrobial efficacy without deleterious interaction with functional agents, including, for example, friction reducers. In another aspect, water treatment methods provide increased antimicrobial efficacy compared to the use of antimicrobial peracids alone. In yet another aspect, the methods of use result in the disposal of cleaner water with low numbers of microorganisms. In yet another aspect of the methods of the invention, the reduction and/or elimination of H2O2 from peracid compositions minimizes the negative effects of the oxidizing H2O2. In addition, the methods of the invention reduce volume expansion within sealed systems used in oil and gas recovery methods, as a result of the reduction and/or elimination of H2O2 from the systems. USE IN WATER TREATMENT
[00121] Treated peracid compositions can be used for a variety of industrial applications, for example, to reduce microbial or viral populations on a surface or object or in a body or stream of water. In some aspects, the invention includes methods of using the treated peracid compositions to prevent biological fouling in various industrial and industrial processes, including oil and gas operations, to control the growth of microorganisms, eliminate microbial contamination, limit or prevent biological dirt in liquid systems, process waters or on equipment surfaces that come in contact with such liquid systems. As noted in this report, microbial contamination can occur in a variety of industrial liquid systems, including, but not limited to, airborne contamination, back-up water, process leaks, and improperly cleaned equipment. In another aspect, peracid and catalase compositions (or other treated peracid compositions having low to substantially no hydrogen peroxide content) are used to control the growth of microorganisms in water used in various operations of oil and gas. In another aspect, the compositions are suitable for incorporating into fracturing fluids to control or eliminate microorganisms.
[00122] As used in this report for the methods of the invention, treated peracid compositions can utilize a variety of peracid compositions having a low to substantially no concentration of hydrogen peroxide. These treated peracid compositions include peracid compositions with a catalase or peroxidase enzyme to reduce hydrogen peroxide to the peracid ratio and/or other reduced peracid-hydrogen peroxide compositions disclosed in this report. In a preferred embodiment, peracid and catalase using solutions having reduced hydrogen peroxide or substantially no hydrogen peroxide are introduced to a water source in need of treatment.
[00123] The methods by which the treated peracid use solutions are introduced into aqueous fluids, according to the invention, are not critical. The introduction of the treated peracid compositions can be carried out in a continuous or intermittent manner and will depend on the type of water to be treated. In some embodiments, the treated peracid compositions are introduced into an aqueous fluid in accordance with the methods disclosed in US Patent Application Serial No. 13/645,671 (Attorney Docket No. 8421), entitled "New Method and Arrangement for Feeding Chemicals into a Hydrofracturing Process and Oil and Gas Applications”, which is hereby incorporated by reference in its entirety.
[00124] In one aspect, the treated peracid use solutions are added to the waters in need of treatment before the drilling and fracturing steps, in order to restrict the introduction of microbes into the reservoir and prevent the microbes from presenting a negative effect on fluid integrity. The treatment of spring water (eg pond, lake, urban water, etc.) and/or produced water is particularly well suited for use in accordance with the invention.
[00125] The treated waters according to the invention can be used for fracturing with fluid with low rheology (slick water) (i.e., using friction reducers) and/or gel fracturing (i.e., using viscosity), depending on the type of formation that will be fractured and the type of hydrocarbon that is expected to be produced. The use of a treated peracid dressing solution, including a catalase treated peracid composition dressing solution having low hydrogen peroxide content to substantially no hydrogen peroxide, is suitable for fracturing with low fluid rheology (slick water) and gel fracturing.
[00126] In one aspect, pretreatment of peracetic acid peracid (including a mixture of acetic acid, hydrogen peroxide and water) with catalase substantially removes hydrogen peroxide with minimal to no impact on fracturing fluids and about the pit by itself. In one aspect, peracetic acid pretreated with catalase allows for gel formation suitable for gel fracturing, unlike untreated peracetic acid/hydrogen peroxide solutions which do not allow a gel to be formed under certain conditions . In another aspect, treated peracid use solutions are added to waters in need of treatment in underground well formations (eg, introduced through a borehole into an underground formation). These methods provide additional control within the well formation suitable to reduce microbial populations already present within the deep well pipe in the well or within the reservoir alone.
[00127] In yet another aspect, the solutions using treated peracid are added to waters in need of treatment before disposal. In such an aspect, return water (eg, post-fracturing) is treated to minimize microbial contamination in the water and remove solids prior to disposal of water in an underground well, reuse in a subsequent fracturing application or return of water in local environmental water sources.
[00128] In one aspect, the source of water in need of treatment can vary significantly. For example, the water source may be a fresh water source (eg, reservoir water), a salt or brine source, a brackish water source, a recycled water source, or the like. In one aspect, where offshore well drilling operations are involved, seawater sources are often used (eg, salt water or non-salt water). Advantageously, the peracid compositions, with or without catalase, of the invention are suitable for use with any type of water and provide antimicrobial efficacy with any such water source.
[00129] Large volumes of water are used, according to the invention, as required in well fluid operations. As a result, in one aspect of the invention, recycled water sources (eg, produced water) are often used to reduce the amount of a fresh water source, reservoir water or seawater required. Recycled or produced water is understood to include non-potable water sources. The use of such produced waters (in combination with fresh water, reservoir water or sea water) reduces certain economic and/or environmental limitations. In one aspect of the invention, thousands to millions of gallons of water can be utilized and the combination of produced water with fresh water sources provides significant economic and environmental advantages. In one aspect of the invention, water produced as a practice is used. In one embodiment at least 1% of produced water is used, preferably at least 5% of produced water is used, preferably at least 10% of produced water is used, preferably at least 20% of produced water are used or, more preferably, more than 20% of produced water is used.
[00130] In one aspect of the invention, the method includes a pre-treatment step, in which the peracid composition is treated with a catalase enzyme to reduce the concentration of hydrogen peroxide in a use solution. The pre-treatment step occurs prior to combining the antimicrobial peracid composition and/or catalase with a water source in need of treatment. In one aspect of the invention, pretreatment can take place within a few minutes to hours prior to addition to a water source. Preferably, a commercial peracid formulation is used (eg peracetic acid). Consequently, the peracid and catalase composition use solution can be diluted to obtain the desired peracetic acid concentrations, with low and/or no hydrogen peroxide concentration.
[00131] According to the embodiments of the invention, a sufficient amount of the use solution of the pretreated peracid composition, with or without catalase, is added to the aqueous water source in need of treatment to provide the concentration of peracid desired for antimicrobial efficacy. For example, a water source is metered amounts of the use solution of the peracid and catalase composition until a concentration of peracid within the water source is detected within the preferred concentration range (eg, about 1 ppm to about 100 ppm peracid). In one aspect, it is preferred to have a microbial count less than about 100,000 microbes/ml, more preferably less than about 10,000 microbes/ml, or more preferably less than about 1000 microbes/ml.
[00132]The methods of use described in this report may vary in temperature and pH conditions associated with the use of aqueous treatment fluids. For example, aqueous treatment fluids may be subjected to ambient temperature variations in accordance with the applications of use disclosed in this report, including variation from about 0°C to about 130°C in the course of treatment operations. Preferably, the temperature range is between about 5°C to about 100°C, more preferably, between about 10°C to about 80°C. However, as most of the antimicrobial activities of the compositions of the invention occur over a short period of time, exposure of the compositions to relatively high temperatures is not a substantial concern. In addition, peracid composition aqueous treatment fluids (i.e., wear solutions) can be subjected to pH range variations, such as from 1 to about 10.5. Preferably, the pH range is less than about 9, less than about 8.2 (representative peracetic acid peracid pKa value) to ensure the antimicrobial effectiveness of the peracid.
[00133] The antimicrobial compositions of the invention are fast acting. However, the present methods require a certain minimum contact time of the compositions with the water in need of treatment for sufficient antimicrobial effect to occur. The contact time may vary with the concentration of the use compositions, method of application of the use compositions, temperature of the use compositions, pH of the use compositions, amount of water that will be treated, amount of dirt or substrates in the water that will be treated or similar. Contact or exposure time can be at least about 15 seconds. In some embodiments, the exposure time is about 1 to 5 minutes. In other embodiments, the exposure time is at least about 10 minutes, 30 minutes, or 60 minutes. In other embodiments, exposure time is from a few minutes to hours. Contact time will still vary based on the concentration of peracid in a use solution. BENEFICIAL EFFECTS OF METHODS OF USE IN WATER TREATMENT
[00134] In one aspect, the methods of use provide an antimicrobial product for use that does not negatively impact the environment. Advantageously, the degradation of the compositions of the invention provides a “green” alternative. In one aspect of the invention, the use of peroxyacetic acid is beneficial as the by-products are non-toxic, non-persistent in the environment, certified as organic and permitted for discharge into surface waters.
[00135] In another aspect, the methods of use provide an antimicrobial product for use that does not negatively interfere with friction reducers, viscosity enhancers and/or other functional ingredients. In another aspect, the methods of use do not negatively interfere with any additional functional agents used in the water treatment methods, including, for example, corrosion inhibitors, scale removal agents and the like. The compositions administered in accordance with the invention provide extremely effective control of microorganisms without adversely affecting the functional properties of any additive polymers of an aqueous system. Furthermore, solutions using the treated peracid composition provide additional benefits to a system, including, for example, reduction of corrosion within the system due to decreased or substantially eliminated hydrogen peroxide from a composition of treated peracid. Advantageously, the non-detrimental effects of the treated peracid compositions (with or without a catalase) on the various functional ingredients used in water treatment methods are obtained irrespective of the constitution of the water source in need of treatment.
[00136] In a further aspect, the methods of use prevent contamination of systems, such as acidification of the well or reservoir. In other respects, the methods of use prevent microbe-influenced corrosion of the systems in which they are used.
[00137] In further aspects of the invention, the reduction and/or elimination of H2O2 from the systems reduces volume expansion within sealed systems (e.g., wells). As a result, there is a significantly reduced or eliminated risk of the well stopping functioning due to the removal of gases in the antimicrobial compositions used to treat the various water sources.
[00138] In other aspects, the methods of use employ the anti-microbial and/or whitening activity of the peracid compositions. For example, the invention includes a method for reducing a microbial population and/or a method for bleaching. These methods can operate on an article, surface, a body or stream of water or a gas or the like, by contacting the article, surface, body or stream with the compositions. Contacting can include any one of numerous methods of applying the compositions, including, but not limited to, providing the antimicrobial peracid compositions in an aqueous use solution and soaking any articles and/or delivering to a water source in need. of treatment.
[00139] The compositions are suitable for antimicrobial effectiveness against a broad spectrum of microorganisms, providing a broad spectrum of bactericide and fungistatic activity. For example, the peracid biocides of this invention provide a broad spectrum of activity against a wide range of different types of microorganisms (including aerobic and anaerobic microorganisms), including bacteria, yeasts, molds, fungi, algae and other microorganisms problems associated with oil and gas field operations.
[00140] Exemplary microorganisms susceptible to the peracid compositions of the invention include, gram positive bacteria (for example, Staphylococcus aureus, Bacillus(sp.) species of the type Bacillus subtilis, Clostridiasp.), gram negative bacteria (for example, Escherichia coli, Pseudomonassp., Klebsiella pneu moniae, Legionellosis pneumophila, Enterobacter sp., Serratia sp., Desulfovibrio sp., and Desulfotomaculum sp.), yeasts (e.g., Saccharomyces cerevisiae and Candida albicans), molds (e.g., Aspergillus , Cephalosporium acremonium, Penicillium notatum and Aureobasidium pullulans), filamentous fungi (eg Aspergillus niger and Cladosporium resine), algae (eg Chlorella vulgaris, Euglena gracilise Selenastrum capricornutum) and other similar micro-organisms by and single-celled organisms example, phytoplankton and protozoa). Other exemplary microorganisms susceptible to the peracid compositions of the invention include the exemplary microorganisms disclosed in US Patent Application 2010/0160449 A1, for example, sulfur or sulphate reducing bacteria such as the Desulfovibrio and Desulfotomaculum. USE IN OTHER TREATMENTS
[00141] Additional embodiments of the invention include water treatments for various industrial processes to treat liquid systems. As used in this report, “liquid system” refers to flood waters or an environment within at least one artificial artifact, containing a substantial amount of liquid that is capable of being biologically fouled. Liquid systems include, but are not limited to, industrial liquid systems, industrial water systems, liquid process streams, industrial liquid process streams, industrial process water systems, process water applications, process water, utility water, water used in manufacturing, water used in industrial services, liquid aqueous streams, liquid streams containing two or more liquid phases, and any combination thereof.
[00142] In another aspect, the compositions can also be used to treat other liquid systems where the antimicrobial function of the compositions and oxidizing properties can be used. In addition to the microbial problems involving wastewater, wastewater is often rich in malodorous sulfur, nitrogen, or reduced phosphorus compounds. A strong oxidizer, such as the compositions disclosed in this report, effectively converts these compounds to their odor-free derivatives, for example, the sulfates, phosphates and amine oxides. These same properties are very useful in the pulp and paper industry where the bleaching property is also very useful. 15) FLUID COMPOSITIONS WITH LOW RHEOLOGY (SLICK WATER) AND USES THEREOF
[00143] The present invention also relates to fluid compositions with low rheology (slick water) useful in oil and/or gas drilling that comprise stable percarboxylic acid compositions and the uses thereof. In one aspect, the present invention is directed to a composition, which comprises: 1) a C1-C22 carboxylic acid; 2) a C1-C22 percarboxylic acid; 3) hydrogen peroxide; 4) a first stabilizing agent, which is a picolinic acid or a compound having the following Formula (IA):
where R1 is OH or -NR1aR1b, where R1a and R1b are independently hydrogen or alkyl (Ci-Cβ); R2 is OH or -NR2aR2b, where R2a and R2b are independently hydrogen or alkyl (CI-C'); each R3 is independently alkyl (CI-C'), alkenyl (C2-C') or alkynyl (C2-C6); en is a number from zero to 3; or a salt thereof; or a compound having the following Formula (IB):
wherein R1 is OH or -NR1aR1b, wherein R1a and R1b are independently hydrogen or (C1-C')alkyl; R2 is OH or -NR2aR2b, wherein R2a and R2b are independently hydrogen or (C1-C')alkyl; each R3 is independently alkyl (C1-C'), alkenyl (C2-C') or alkynyl (C2-C6); en is a number from zero to 3; or a salt thereof; 5) a second stabilizing agent, which is a compound having the following Formula (IIA):
wherein R1, R2, R3 and R4 are independently hydrogen, (C1-C6) alkyl, (C2-C6) alkenyl or (C2-C6) alkynyl or C6-C20 aryl; R5is (C1-C6) alkyl, (C2-C6) alkenyl or (C2-C6) alkynyl; and R6 is hydrogen, (C1-C6) alkyl, (C2-C6) alkenyl or (C2-C6) alkynyl; or a salt thereof; or a compound having the following Formula (IIB):
wherein R1, R2 and R3 are independently hydrogen, (C1-C6) alkyl, (C2-C6) alkenyl or (C2-C6) alkynyl or C6-C20 aryl; or a salt thereof; 6) a friction reducer; and wherein said hydrogen peroxide has a concentration of about 1 ppm to about 20 ppm and C1-C22 percarboxylic acid has a concentration of at least about 2 times the concentration of said hydrogen peroxide.
[00144] In some embodiments, the present composition is a balanced composition comprising peracid, hydrogen peroxide, carboxylic acid and a solvent, for example, water. In some embodiments, the present composition does not comprise a mineral acid, for example the mineral acids disclosed in WO 91/07375.
[00145] The present composition may comprise any level of suitable hydrogen peroxide. In some embodiments, the hydrogen peroxide in the present compositions has a concentration of from about 1ppm to about 10ppm, for example, 1ppm, 2ppm, 3ppm, 4ppm, 5ppm, 6ppm, 7 ppm, 8 ppm, 9 ppm or 10 ppm.
[00146] The present composition may comprise any level of suitable C1-C22 percarboxylic acid relative to the level of hydrogen peroxide. In some embodiments, C1-C22 percarboxylic acid has a concentration of at least about 6 times the concentration of hydrogen peroxide. In other embodiments, the C1-C22 percarboxylic acid has a concentration of at least about 10 times the concentration of hydrogen peroxide. In yet other embodiments, the C1-C22 percarboxylic acid has a concentration of at least about 2, 3, 4, 5, 6, 7, 8, 9, or 10 times the concentration of hydrogen peroxide.
[00147] The present composition may comprise any suitable friction reducer. In some embodiments, the friction reducer is a polyacrylamide polymer and/or copolymer or an acrylamide-derived polymer and/or copolymer. Other exemplary friction reducers include those described in Section B above. The present composition can comprise any suitable friction reducer level. In some embodiments, the friction reducer has a concentration of from about 50 ppm to about 5,000 ppm, preferably from about 100 ppm to about 1,000 ppm. In other embodiments, the friction reducer has a concentration at about 50ppm, 100ppm, 200ppm, 300ppm, 400ppm, 500ppm, 600ppm, 700ppm, 800ppm, 900ppm, 1000ppm, 2000 ppm, 3,000 ppm, 4,000 ppm or 5,000 ppm.
[00148] The present composition may further comprise any substances suitable for oil and/or gas drilling. In some embodiments, the present composition may further comprise a proppant, a surfactant and/or a scale inhibitor. Any suitable proppant can be used. In some embodiments, the proppant is a sand or ceramic bead. Any suitable scale inhibitor can be used. In some embodiments, the scale inhibitor is a polymer, a phosphonate, or a phosphate ester.
[00149] Any suitable C1-C22 percarboxylic acid can be used in the present compositions. In some embodiments, the C1-C22 percarboxylic acid is a C2-C20 percarboxylic acid. In other embodiments, the C1-C22 percarboxylic acid comprises peroxyacetic acid, peroxyoctanoic acid and/or peroxysulfonated oleic acid. Other exemplary C1-C22 percarboxylic acids are described in Section B above. The present composition can comprise any level of the suitable C1-C22 percarboxylic acid and hydrogen peroxide. In some embodiments, C1-C22 percarboxylic acid has a concentration of about 10 ppm to about 30 ppm, for example 10 ppm, 15 ppm, 20 ppm, 25 ppm or 30 ppm and hydrogen peroxide has a concentration of about 1ppm to about 3ppm, for example 1ppm, 1.5ppm, 2ppm, 2.5ppm or 3ppm.
[00150] Any suitable first stabilizing agent can be used in the present compositions. In some embodiments, the first stabilizing agent is a picolinic acid or a salt thereof. In other embodiments, the first stabilizing agent is 2,6-pyridinedicarboxylic acid or a salt thereof. The first stabilizing agent can be used in any suitable concentration. In some embodiments, the first stabilizing agent has a concentration of from about 0.005% by weight to about 5% by weight. In other embodiments, the first stabilizing agent has a concentration of from about 0.05% by weight to about 0.15% by weight. In still other embodiments, the first stabilizing agent has a concentration of about 0.005% by weight, 0.01% by weight, 0.1% by weight, 1% by weight, 2% by weight, 3% by weight. weight, 4% by weight or 5% by weight. In yet other embodiments, the first stabilizing agent has a concentration at about 0.05% by weight, 0.06% by weight, 0.07% by weight, 0.08% by weight, 0.09% by weight. weight, 0.10% by weight, 0.11% by weight, 0.12% by weight, 0.13% by weight, 0.14% by weight, or 0.15% by weight.
[00151] Any suitable second stabilizing agent can be used in the present compositions. In some embodiments, the second stabilizing agent is 1-hydroxy-ethyllidene-1,1-diphosphonic acid (HEDP) or a salt thereof. The second stabilizing agent can be used in any suitable concentration. In some embodiments, the second stabilizing agent has a concentration of from about 0.1% by weight to about 10% by weight, e.g., 0.1% by weight, 0.5% by weight, 1% by weight, 2% by weight, 3% by weight, 4% by weight, 5% by weight, 6% by weight, 7% by weight, 8% by weight, 9% by weight or 10% by weight. In other embodiments, the second stabilizing agent has a concentration of from about 0.5% by weight to about 5% by weight, e.g., 0.5% by weight, 1% by weight, 1.5% by weight. weight, 2% by weight, 2.5% by weight, 3% by weight, 3.5% by weight, 4% by weight, 4.5% by weight or 5% by weight. In yet other embodiments, the second stabilizing agent has a concentration of from about 0.6% by weight to about 1.8% by weight, e.g., 0.6% by weight, 0.7% by weight 0.8% by weight, 0.9% by weight, 1.0% by weight, 1.1% by weight, 1.2% by weight, 1.3% by weight, 1.4% by weight, 1.5% by weight, 1.6% by weight, 1.7% by weight or 1.8% by weight.
[00152] In some embodiments, the first stabilizing agent is a 2,6-pyridinedicarboxylic acid or a salt thereof and the second stabilizing agent is HEDP or a salt thereof.
The present compositions may retain any suitable level or percentage of C1-C22 percarboxylic acid activity for any suitable time after the composition is formed. In some embodiments, the present composition retains at least about 60%, 65%, 70%, 75%, 80%, 85% or 90% of the initial C1-C22 percarboxylic acid activity for any suitable time thereafter. that the composition is formed. In other embodiments, the present composition retains at least about 60% of the initial C1-C22 percarboxylic acid activity for at least 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 20, 25, 30 minutes, 1,2, 5, 10, 15, 20 or 24 hours or more after the composition is formed.
[00154] In some embodiments, the present compositions may comprise a peroxidase or a catalase to further reduce the concentration of hydrogen peroxide. Any suitable peroxidase or catalase can be used in the present compositions. Exemplary peroxidases and catalases are described in Section B above. In other embodiments, the present compositions can further comprise a substance that aids in solubilizing the first and/or second stabilizing agents. Exemplary substances that can aid in the solubilization of the first and/or second stabilizing agents include hydrotropes such as sodium xylene sulfonate, sodium cumene sulfonates, and surfactants such as anionic surfactants and nonionic surfactants.
[00155] In another aspect, the present invention is directed to a method for fracturing fluid with low rheology (slick water), which comprises directing the above composition in an underground environment.
[00156] The present compositions can be directed in an underground environment at any suitable speed. In some embodiments, the present composition is driven in an underground environment at a speed faster than 30 barrels (bbl)/min. In other embodiments, the present composition is driven in an underground environment at a speed of about 50 bbl/min. at about 100 bbl/min., for example, 50, 60, 70, 80, 90 or 100 bbl/min.
[00157] The present compositions may be directed in any suitable underground medium. In some embodiments, the underground environment comprises a well in a shale and/or oil gas reservoir.
[00158] The present compositions may be directed in an underground environment by any suitable methods. In some embodiments, the composition is pumped down a wellbore. 16) GEL-BASED COMPOSITIONS AND USES THEREOF
[00159] The present invention further relates to gel-based compositions useful in oil and/or gas drilling which comprise stable percarboxylic acid compositions and uses thereof. In one aspect, the present invention is directed to a composition, which comprises: 1) a C1-C22 carboxylic acid; 2) a C1-C22 percarboxylic acid; 3) hydrogen peroxide; 4) a first stabilizing agent, which is a picolinic acid or a compound having the following Formula (IA):
wherein R1 is OH or -NR1aR1b, wherein R1a and R1b are independently hydrogen or (C1-C6) alkyl; R2 is OH or -NR2aR2b, wherein R2a and R2b are independently hydrogen or (C1-C6) alkyl; each R3 is independently (C1-C6) alkyl, (C2-C6) alkenyl or (C2-C6) alkynyl; en is a number from zero to 3; or a salt thereof; or a compound having the following Formula (IB):
wherein R1 is OH or -NR1aR1b, wherein R1a and R1b are independently hydrogen or alkyl (CI-C'); R2 is OH or -NR2aR2b, where R2a and R2b are independently hydrogen or alkyl (CI-C'); each R3 is independently alkyl (CI-C'), alkenyl (C2-C') or alkynyl (C2-C6); en is a number from zero to 3; or a salt thereof; 5) a second stabilizing agent, which is a compound having the following Formula (IIA):
wherein R1, R2, R3 and R4 are independently hydrogen, alkyl (CI-C'), alkynyl (C2-C6) or aryl C6-C20; R5is alkyl (C1-Cβ), alkenyl (C2-C6) or alkynyl (C2-C6); and R6 is hydrogen, (C1-C6) alkyl, (C2-C6) alkenyl or (C2-C6) alkynyl; or a salt thereof; or a compound having the following Formula (IIB):
wherein R1, R2 and R3are independently hydrogen, (C1-C6) alkyl, (C2-C6) alkenyl or (C2-C6) alkynyl or C6-C20 aryl; or a salt thereof; 6) a viscosity enhancer; and wherein said hydrogen peroxide has a concentration of about 1 ppm to about 15 ppm and said C1-C22 percarboxylic acid has a concentration of at least about 2 times the concentration of said hydrogen peroxide.
[00160] In some embodiments, the present composition is a balanced composition comprising peracid, hydrogen peroxide, carboxylic acid and a solvent, for example, water. In some embodiments, the present composition does not comprise a mineral acid, for example the mineral acids disclosed in WO 91/07375.
[00161] The present composition may comprise any level of suitable hydrogen peroxide. In some embodiments, the hydrogen peroxide in the present compositions has a concentration of from about 1ppm to about 15ppm, for example, 1ppm, 2ppm, 3ppm, 4ppm, 5ppm, 6ppm, 7 ppm, 8ppm, 9ppm, 10ppm, 11ppm, 12ppm, 13ppm, 14ppm or 15ppm.
[00162] The present composition may comprise any level of suitable C1-C22 percarboxylic acid relative to the level of hydrogen peroxide. In some embodiments, C1-C22 percarboxylic acid has a concentration of at least about 6 times the concentration of hydrogen peroxide. In other embodiments, the C1-C22 percarboxylic acid has a concentration of at least about 10 times the concentration of hydrogen peroxide. In yet other embodiments, the C1-C22 percarboxylic acid has a concentration of at least about 2, 3, 4, 5, 6, 7, 8, 9, or 10 times the concentration of hydrogen peroxide.
[00163] Any suitable viscosity enhancer can be used in the present compositions. In some embodiments, the viscosity enhancer is a conventional linear gel, a borate crosslinked gel, an organometallic crosslinked gel, or an aluminum phosphate-ester oil gel. Other exemplary viscosity enhancers include those described in Section B above. Viscosity enhancer can be used at any suitable levels. In some embodiments, the viscosity enhancer has a concentration of from about 2 to about 100 units pounds per thousand gallons, preferably from about 5 to about 65 units pounds per thousand gallons. In other embodiments, the viscosity enhancer has a concentration of about 2, 3, 4, 5, 6, 7, 8, 9, 10, 20, 30, 40, 50, 60, 70, 80, 90 or 100 units of pounds per thousand gallons.
[00164] The present composition may further comprise any substances suitable for oil and/or gas drilling. In some embodiments, the present composition can further comprise a proppant, a surfactant, a scale inhibitor and/or a breaker. Any suitable proppant can be used. In some embodiments, the proppant is a sand or ceramic bead. Any suitable scale inhibitor can be used. In some embodiments, the scale inhibitor is a polymer, a phosphonate, or a phosphate ester. Any suitable breaker can be used. In some embodiments, the breaker is an oxidizer, an enzyme, or a pH modifier.
[00165] Any suitable C1-C22 percarboxylic acid can be used in the present compositions. In some embodiments, the C1-C22 percarboxylic acid is a C2-C20 percarboxylic acid. In other embodiments, the C1-C22 percarboxylic acid comprises peroxyacetic acid, peroxyoctanoic acid and/or peroxysulfonated oleic acid. Other exemplary C1-C22 percarboxylic acids are described in Section B above.
[00166] The present composition can comprise any level of C1-C22 percarboxylic acid and suitable hydrogen peroxide. In some embodiments, the C1-C22 percarboxylic acid has a concentration that is effective for its antimicrobial function and the hydrogen peroxide has a concentration that will not cause gel failure. In other embodiments, hydrogen peroxide has a concentration that is about 14 ppm or less. In still other embodiments, C1-C22 percarboxylic acid has a concentration of about 10 ppm to about 30 ppm, for example 10 ppm, 15 ppm, 20 ppm, 25 ppm or 30 ppm and hydrogen peroxide it has a concentration of about 1ppm to about 3ppm, for example 1ppm, 1.5ppm, 2ppm, 2.5ppm or 3ppm.
[00167] Any suitable first stabilizing agent can be used in the present compositions. In some embodiments, the first stabilizing agent is a picolinic acid or a salt thereof. In other embodiments, the first stabilizing agent is 2,6-pyridinedicarboxylic acid or a salt thereof. The first stabilizing agent can be used in any suitable concentration. In some embodiments, the first stabilizing agent has a concentration of from about 0.005% by weight to about 5% by weight. In other embodiments, the first stabilizing agent has a concentration of from about 0.05% by weight to about 0.15% by weight. In still other embodiments, the first stabilizing agent has a concentration of about 0.005% by weight, 0.01% by weight, 0.1% by weight, 1% by weight, 2% by weight, 3% by weight. weight, 4% by weight or 5% by weight. In yet other embodiments, the first stabilizing agent has a concentration at about 0.05% by weight, 0.06% by weight, 0.07% by weight, 0.08% by weight, 0.09% by weight. weight, 0.10% by weight, 0.11% by weight, 0.12% by weight, 0.13% by weight, 0.14% by weight, 0.15% by weight.
[00168] Any suitable second stabilizing agent can be used in the present compositions. In some embodiments, the second stabilizing agent is 1-hydroxy-ethyllidene-1,1-diphosphonic acid (HEDP) or a salt thereof. The second stabilizing agent can be used in any suitable concentration. In some embodiments, the second stabilizing agent has a concentration of from about 0.1% by weight to about 10% by weight, e.g., 0.1% by weight, 0.5% by weight, 1% by weight, 2% by weight, 3% by weight, 4% by weight, 5% by weight, 6% by weight, 7% by weight, 8% by weight, 9% by weight or 10% by weight. In other embodiments, the second stabilizing agent has a concentration of from about 0.5% by weight to about 5% by weight, e.g., 0.5% by weight, 1% by weight, 1.5% by weight. weight, 2% by weight, 2.5% by weight, 3% by weight, 3.5% by weight, 4% by weight, 4.5% by weight or 5% by weight. In yet other embodiments, the second stabilizing agent has a concentration of from about 0.6% by weight to about 1.8% by weight, e.g., 0.6% by weight, 0.7% by weight 0.8% by weight, 0.9% by weight, 1.0% by weight, 1.1% by weight, 1.2% by weight, 1.3% by weight, 1.4% by weight, 1.5% by weight, 1.6% by weight, 1.7% by weight or 1.8% by weight.
[00169] In some embodiments, the first stabilizing agent is a 2,6-pyridinedicarboxylic acid or a salt thereof and the second stabilizing agent is HEDP or a salt thereof.
The present compositions may retain any suitable level or percentage of C1-C22 percarboxylic acid activity for any suitable time after the composition is formed. In some embodiments, the present composition retains at least about 60%, 65%, 70%, 75%, 80%, 85% or 90% of the initial C1-C22 percarboxylic acid activity for any suitable time. after the composition is formed. In other embodiments, the present composition retains at least about 60% of the initial C1-C22 percarboxylic acid activity for at least 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 20, 25, 30 minutes, 1,2, 5, 10, 15, 20 or 24 hours or more after the composition is formed.
In some embodiments, the present compositions may comprise a peroxidase or a catalase to further reduce the concentration of hydrogen peroxide. Any suitable peroxidase or catalase can be used in the present compositions. Exemplary peroxidases and catalases are described in Section B above. In other embodiments, the present compositions can further comprise a substance that aids in solubilizing the first and/or second stabilizing agents. Exemplary substances that can aid in the solubilization of the first and/or second stabilizing agents include hydrotropes such as sodium xylene sulfonate, sodium cumene sulfonates, and surfactants such as anionic surfactants and nonionic surfactants.
[00172] In another aspect, the present invention is directed to a method for high viscosity fracturing, which comprises directing the above composition in an underground medium.
[00173] The present methods can be used to direct the above composition into any suitable underground medium. In some embodiments, the present methods can be used to direct the above composition into an underground environment comprising a well in a gas and/or oil field.
[00174] Those skilled in the art will recognize, or be able to verify using no more than routine experimentation, numerous equivalents to the specific procedures, embodiments, claims and examples described in this report. Such equivalents are considered within the scope of this invention and covered by the claims appended hereto. The contents of all references, patents and patent applications cited throughout this application are incorporated by reference to the same degree as if each individual publication or patent application were specifically and individually indicated as incorporated by reference. All publications and patent applications in this descriptive report are indicative of the common level of skill in the art to which this invention belongs. The invention is further illustrated by the following examples, which are not to be construed as limiting. 17) METHODS TO TREAT A TARGET
[00175] In yet another aspect, the present invention is directed to a method of treating a target, which comprises a step of contacting a target with a composition at a dilute level to form a treated target composition, wherein said composition comprises: 1) a C1-C22 carboxylic acid; 2) a C1-C22 percarboxylic acid; 3) hydrogen peroxide; 4) a first stabilizing agent, which is a picolinic acid or a compound having the following Formula (IA):
wherein R1 is OH or -NR1aR1b, wherein R1a and R1b are independently hydrogen or alkyl (Ci-C'); R2 is OH or -NR2aR2b, where R2a and R2b are independently hydrogen or alkyl (Ci-C'); each R3 is independently alkyl (C1 -C'), alkenyl (C2-C') or alkynyl (C2-C'); en is a number from zero to 3; or a salt thereof; or a compound having the following Formula (IB):
wherein R1 is OH or -NR1aR1b, wherein R1a and R1b are independently hydrogen or alkyl (C1-C'); R2 is OH or -NR2aR2b, wherein R2a and R2b are independently hydrogen or (C1-C')alkyl; each R3 is independently alkyl (C1-C'), alkenyl (C2-C') or alkynyl (C2-C'); en is a number from zero to 3; or a salt thereof; 5) a second stabilizing agent, which is a compound having the following Formula (IIA):
6 wherein R 1 , R 2 , R 3 and R 4 are independently hydrogen, alkyl (C 1 -C 6 ), alkenyl (C 2 -C 6 ) or alkynyl (C 2 -C 6 ) or aryl C 6 -C 20 ; R5is alkyl (C1-C6), alkenyl (C2-C6) or alkynyl (C2-C6); and R6 is hydrogen, (C1-C6) alkyl, (C2-C6) alkenyl or (C2-C6) alkynyl; or a salt thereof; or a compound having the following Formula (IIB):
wherein R1, R2 and R3 are independently hydrogen, (C1-C6) alkyl, (C2-C6) alkenyl or (C2-C6) alkynyl or C6-C20 aryl; or a salt thereof; and wherein said hydrogen peroxide has a concentration of at least about 0.1% by weight, C1-C22 percarboxylic acid has a concentration of at least about 2 times the concentration of said hydrogen peroxide, and the said composition has a pH of about 4 or less, and wherein said treated target composition comprises from about 1 ppm to about 10,000 ppm of said C1-C22 percarboxylic acid, and said contacting step lasts for sufficient time to stabilize or reduce the microbial population in and/or on said target or said treated target composition.
[00176] In some embodiments, the composition used in these methods is a balanced composition comprising peracid, hydrogen peroxide, carboxylic acid and a solvent, e.g., water. In some embodiments, the composition used in the present methods does not comprise a mineral acid, for example the mineral acids disclosed in WO 91/07375.
[00177] The composition used in the present methods can comprise any level of the suitable hydrogen peroxide. In some embodiments, the hydrogen peroxide in the balanced composition has a concentration of from about 0.1% to about 15%, e.g., about 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1%, 2%, 3%, 4%, 5%, 6%, 7% , 8%, 9%, 10%, 11%, 12%, 13%, 14% or 15%. Before or during use, exemplary compositions may be diluted to a desired level.
[00178] The composition used in the present methods can comprise any level of suitable C1-C22 percarboxylic acid relative to the level of hydrogen peroxide. In some embodiments, the C1 C22 percarboxylic acid has a concentration of at least about 6 times the concentration of hydrogen peroxide. In other embodiments, the C1-C22 percarboxylic acid has a concentration of at least about 10 times the concentration of hydrogen peroxide. In yet other embodiments, the C1 C22 percarboxylic acid has a concentration of at least about 2, 3, 4, 5, 6, 7, 8, 9, or 10 times the concentration of hydrogen peroxide.
[00179] Any suitable C1-C22 percarboxylic acid can be used in the present methods. In some embodiments, the C1-C22 percarboxylic acid is a C2-C20 percarboxylic acid. In other embodiments, the C1-C22 percarboxylic acid comprises peroxyacetic acid, peroxyoctanoic acid and/or peroxysulfonated oleic acid. Other exemplary C1-C22 percarboxylic acids are described in Section B above. The composition used in the present methods can comprise any level of the suitable C1-C22 percarboxylic acid and hydrogen peroxide. In some embodiments, the C1-C22 percarboxylic acid in the balanced composition has a concentration of from about 0.1% to about 30%, e.g., about 0.1%, 0.2%, 0.3% , 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1%, 2%, 3%, 4%, 5%, 6%, 7 %, 8%, 9%, 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19%, 20%, 21%, 22%, 23%, 24%, 25%, 26%, 27%, 28%, 29% or 30%. Before or during use, exemplary compositions can be diluted to a desired level.
[00180] Any suitable first stabilizing agent can be used in the composition used in the present methods. In some embodiments, the first stabilizing agent is a picolinic acid or a salt thereof. In other embodiments, the first stabilizing agent is 2,6-pyridinedicarboxylic acid or a salt thereof. The first stabilizing agent can be used in any suitable concentration. In some embodiments, the first stabilizing agent has a concentration of from about 0.005% by weight to about 5% by weight. In other embodiments, the first stabilizing agent has a concentration of from about 0.05% by weight to about 0.15% by weight. In yet other embodiments, the first stabilizing agent has a concentration of about 0.005% by weight, 0.01% by weight, 0.1% by weight, 1% by weight, 2% by weight, 3% by weight , 4% by weight or 5% by weight. In yet other embodiments, the first stabilizing agent has a concentration at about 0.05% by weight, 0.06% by weight, 0.07% by weight, 0.08% by weight, 0.09% by weight. weight, 0.10% by weight, 0.11% by weight, 0.12% by weight, 0.13% by weight, 0.14% by weight, or 0.15% by weight.
[00181] Any suitable second stabilizing agent can be used in the present compositions. In some embodiments, the second stabilizing agent is 1-hydroxy-ethyllidene-1,1-diphosphonic acid (HEDP) or a salt thereof. The second stabilizing agent can be used in any suitable concentration. In some embodiments, the second stabilizing agent has a concentration of from about 0.1% by weight to about 10% by weight, e.g., 0.1% by weight, 0.5% by weight, 1% by weight, 2% by weight, 3% by weight, 4% by weight, 5% by weight, 6% by weight, 7% by weight, 8% by weight, 9% by weight or 10% by weight. In other embodiments, the second stabilizing agent has a concentration of from about 0.5% by weight to about 5% by weight, e.g., 0.5% by weight, 1% by weight, 1.5% by weight. weight, 2% by weight, 2.5% by weight, 3% by weight, 3.5% by weight, 4% by weight, 4.5% by weight or 5% by weight. In yet other embodiments, the second stabilizing agent has a concentration of from about 0.6% by weight to about 1.8% by weight, e.g., 0.6% by weight, 0.7% by weight 0.8% by weight, 0.9% by weight, 1.0% by weight, 1.1% by weight, 1.2% by weight, 1.3% by weight, 1.4% by weight, 1.5% by weight, 1.6% by weight, 1.7% by weight or 1.8% by weight.
[00182] In some embodiments, the first stabilizing agent is a 2,6-pyridinedicarboxylic acid or a salt thereof and the second stabilizing agent is HEDP or a salt thereof.
The composition used in the present methods can retain any suitable level or percentage of C1-C22 percarboxylic acid activity for any suitable time after the treated target composition is formed. In some embodiments, the present composition retains at least about 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85% or 90% of the initial C1-C22 percarboxylic acid activity during any suitable time after the treated target composition is formed. In other embodiments, the present composition retains at least about 60% of the initial C1-C22 percarboxylic acid activity for at least 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11 12, 13, 14, 15, 20, 25, 30 minutes, 1,2, 5, 10, 15, 20 or 24 hours or more after the treated target composition is formed.
In some embodiments, the composition used in the present methods may comprise a peroxidase or a catalase to further reduce the concentration of hydrogen peroxide. Any suitable peroxidase or catalase can be used in the present compositions. Exemplary peroxidases and catalases are described in Section B above. In other embodiments, the composition used in the present methods may further comprise a substance that aids in solubilizing the first and/or second stabilizing agents. Exemplary substances that can aid in the solubilization of the first and/or second stabilizing agents include hydrotropes such as sodium xylene sulfonate, sodium cumene sulfonates, and surfactants such as anionic surfactants and nonionic surfactants.
[00185] The present methods can be used to treat any suitable target. For example, the target can be a food item or a vegetable item and/or at least a portion of a medium, a container, an equipment, a system or a facility for growing, maintaining, processing, packaging, storing, transport, preparation, cooking or service of the food item or vegetable item.
[00186]The present methods can be used to treat any suitable plant item. In some embodiments, the vegetable item is a grain, fruit, or flower. In other embodiments, the vegetable item is a live vegetable item or a harvested vegetable item. In still other embodiments, the plant item comprises a seed, a tuber, a growing plant, a cutting or a root stock. In yet other embodiments, the present methods are used to treat living plant tissue comprising treating plant tissue with the above composition at a diluted level to stabilize or reduce the microbial population in and/or on the plant tissue. . In yet other embodiments, the present methods are used for cultivating a plant on a hydroponic substrate in a hydroponic liquid supply medium, comprising: (a) establishing living, growing plant tissue on the hydroponic substrate; (b) contacting the living plant tissue, the hydroponic substrate and the hydroponic liquid with a dilute composition of the present invention to stabilize or reduce the microbial population in and/or on the living plant tissue; and (c) collect a usable plant product with reduced microbial contamination.
[00187] The present methods can be used to treat any suitable food item. For example, the food item can be an animal product, for example an animal carcass or an egg, a fruit, a vegetable or a grain. In some embodiments, the animal carcass can be a beef, pork, veal, buffalo, lamb, pork, seafood or poultry carcass. In other embodiments, the seafood carcass can be scallop, shrimp, crab, octopus, mussel, squid or lobster. In yet other embodiments, the fruit can be a botanical fruit, a culinary fruit, a single fruit, an aggregate fruit, multiple fruits, a berry, an accessory fruit, or a seedless fruit. In still other embodiments, the such vege item may be a flower bud, a seed, a leaf, a leaf sheath, a bud, a stem, a leaf trunk, a stem bud, a tuber, a sprout of total plant, a root or a bulb. In yet other embodiments, the grain may be corn, rice, wheat, barley, sorghum, millet, oats, triticale, rye, buckwheat, fonio or quinoa.
[00188] The present methods can be used to treat a target that is at least a part of a container, an equipment, a system or an installation to contain, process, package, store, transport, prepare, cook or serve the item food or vegetable item. In some embodiments, the target is at least a part of a container, an equipment, a system or an installation for containing, processing, packaging, storing, transporting, preparing, cooking or serving a meat, a fruit, a vegetable or a grain. In other embodiments, the target is at least a part of a container, equipment, system or facility for containing, processing, packaging, storing or transporting an animal carcass. In still other embodiments, the target is at least a part of a container, an equipment, a system or an installation used in the food processing, food service or public health industry. In still other embodiments, the target is at least a portion of a suitable fixed process facility. An exemplary fixed suitable process facility may comprise a milk line dairy establishment, a continuous fermentation system, a pumpable food system or a beverage processing line.
[00189] The present methods can be used to treat a target that is at least a part of a solid surface or liquid medium. In some embodiments, the solid surface is an inanimate solid surface. The inanimate solid surface may be contaminated by a biological fluid, for example, a biological fluid comprising blood, another hazardous bodily fluid, or a mixture thereof. In other embodiments, the solid surface can be a contaminated surface. An exemplary contaminated surface may comprise the surface of goods or food service equipment, or the surface of a fabric.
[00190] The treated target composition can comprise any level of suitable C1-C22 percarboxylic acid. In some embodiments, the treated target composition comprises from about 10ppm to about 200ppm of the C1-C22 percarboxylic acid, for example, about 10ppm, 20ppm, 30ppm, 40ppm, 50ppm, 60 ppm, 70ppm, 80ppm, 90ppm, 100ppm, 110ppm, 120ppm, 130ppm, 140ppm, 150ppm, 160ppm, 170ppm, 180ppm, 190ppm or 200ppm of the C1-C22 percarboxylic acid .
The treated target composition can comprise any suitable C1-C22 percarboxylic acid. In some embodiments, the treated target composition comprises peroxyacetic acid, peroxyoctanoic acid and/or peroxysulfonated oleic acid.
[00192]The treated target composition can comprise any level of the suitable hydrogen peroxide. In some embodiments, the treated target composition comprises from about 1ppm to about 15ppm of the hydrogen peroxide, for example, about 1ppm, 2ppm, 3ppm, 4ppm, 5ppm, 6ppm, 7ppm, 8ppm, 9ppm, 10ppm, 11ppm, 12ppm, 13ppm, 14ppm or 15ppm of hydrogen peroxide.
[00193] The treated target composition can comprise any suitable C1-C22 percarboxylic acid level relative to the hydrogen peroxide level. In some embodiments, the treated target composition comprises C1-C22 percarboxylic acid which has a concentration of at least about 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19 or 20 times the concentration of hydrogen peroxide.
The treated target composition may comprise any suitable first stabilizing agent and second stabilizing agent. In some embodiments, the treated target composition comprises a first stabilizing agent which is a 2,6-pyridinedicarboxylic acid or a salt thereof and a second stabilizing agent which is HEDP or a salt thereof.
The treated target composition can retain any adequate level of initial C1-C22 percarboxylic acid activity for any suitable time. In some embodiments, the treated target composition retains at least about 50%, 60%, 70%, 80%, 90%, 95%, 99%, or 100% of the initial C1-C22 percarboxylic acid activity during any given period. adequate time. In other embodiments, the treated target composition retains an adequate level of initial C1-C22 percarboxylic acid activity for at least 1 minute, 2 minutes, 3 minutes, 4 minutes, 5 minutes, 6 minutes, 7 minutes, 8 minutes, 9 minutes, 10 minutes, 11 minutes, 12 minutes, 13 minutes, 14 minutes or 15 minutes after the treated target composition is formed. In yet other embodiments, the treated target composition retains at least about 60% of the initial C1-C22 percarboxylic acid activity for 15 minutes after the treated target composition is formed.
[00196]The contact step can take any suitable time. In some embodiments, the contact step is at least 10 seconds, 20 seconds, 30 seconds, 40 seconds, 50 seconds, 1 minute, 10 minutes, 30 minutes, 1 hour, 2 hours, 4 hours, 8 hours , 16 hours, 1 day, 3 days, 1 week or more.
[00197]The diluted composition can be applied to the target in any suitable manner. In some embodiments, the diluted composition is applied to the target via a spray, mist or foam. In other embodiments, the diluted composition is applied to the target via application in the form of a thick solution or in the form of a gel. In still other embodiments, all or part of the target is immersed in the diluted composition. The target and/or the diluted composition may be subject to any suitable movement to aid or facilitate contact between the target and the diluted composition. In some embodiments, the diluted composition may be agitated. In other embodiments, the diluted composition can be sprayed onto a target, for example an animal carcass, under suitable pressure and at a suitable temperature. For example, the diluted composition can be sprayed onto an animal carcass at a pressure of at least 50 psi at a temperature of up to about 60 °C, resulting in a contact time of at least 30 seconds.
[00198] The present methods may comprise any suitable additional steps. In some embodiments, the present methods can comprise a vacuum treatment step. In other embodiments, the present methods may comprise a step of applying an activated light source to the target, e.g., an animal carcass.
The present methods can be used to obtain any suitable reduction of the microbial population in and/or on the target or target composition treated. In some embodiments, the present methods can be used to reduce the microbial population in and/or on the treated target or target composition by at least one log™. In other embodiments, the present methods can be used to reduce the microbial population in and/or on the treated target or target composition by at least two log10. In yet other embodiments, the present methods can be used to reduce the microbial population in and/or on the treated target or target composition by at least three log10.
The present methods can be used to stabilize or reduce any suitable microbial population in and/or on the target or target composition treated. In some embodiments, the present methods can be used to stabilize or reduce a prokaryotic microbial population in and/or on the treated target or target composition. Exemplary prokaryotic microbial population may comprise a bacterial population or an Archaea. In other embodiments, the present methods can be used to stabilize or reduce a eukaryotic microbial population in and/or on the treated target or target composition. Exemplary eukaryotic microbial population may comprise a protozoan or fungal population. In yet other embodiments, the present methods can be used to stabilize or reduce a viral population in and/or on the target or target composition treated. Exemplary viral population can comprise a population of a DNA virus, an RNA virus, and a reverse transcription virus.
[00201] The present methods can be used to stabilize or reduce a microbial population in and/or on the treated target or target composition, where the target is a food item or a plant item and the contact step minimizes or does not induces an organoleptic effect in and/or on the food item or a vegetable item. Typical organoleptic properties include aspects of food substances or other substances experienced by the senses, including taste, sight, odor and touch, in cases where dryness, moisture and aging factors must be considered. See, for example, Jasper Womach, the Congressional Research Service document "Report for Congress: Agriculture: A Glossary of Term, Programs, and Laws, 2005 Edition." In some embodiments, organoleptic procedures are performed as part of meat and poultry inspections to detect signs of illness or contamination. In other embodiments, organoleptic tests are conducted to determine whether packaging materials and components can transfer taste and odor to the foods or pharmaceuticals that are packaged. Shelf life studies often use taste, sight, and odor (in addition to food chemistry and toxicology tests) to determine whether a food product is suitable for consumption. In still other embodiments, organoleptic tests are conducted as part of the Hurdle technology. Typically, Hurdlese's technology refers to an intelligent combination of obstacles that ensure microbial safety and stability, as well as organoleptic and nutritional quality and the economic viability of a food product. See generally Leistner L (1995) “In Gould GW (Ed.) New Methods of Food Preservation, Springer, pages 1-21; and Leistner I (2000) “International Journal of Food Microbiology, 55: 181 - 186.
[00202] The present methods can be conducted at any suitable temperature. In some embodiments, the present methods are conducted at a temperature ranging from about 0°C to about 70°C, for example, from about 0°C to about 4°C or 5° C, from about 5°C to about 10°C, from about 11°C to about 20°C, from about 21°C to about 30°C, from about 31°C to about 40°C, including about 37°C, from about 41°C to about 50°C, from about 51°C to about 60°C, or from about 61°C to about 70°C .
The present methods can be used in the methods, processes or procedures described and/or claimed in U.S. Patent Nos. 5,200,189, 5,314,687 and 5,718,910. In some embodiments, the present methods can be used to disinfect facilities or equipment and comprise the steps of contacting the facilities or equipment with the diluted composition (or use) of the present invention at a temperature in the range of about 4°C at about 60°C. The diluted (or used) composition is then circulated or left in contact with the premises or equipment for a time sufficient to disinfect (generally at least 30 seconds) and the treated target composition is consequently drained or removed from the premises or equipment.
[00204] As noted above, the present methods are useful in cleaning or disinfecting processing facilities or equipment in the food service, food processing or public health industries. Examples of process facilities in which the present methods can be used include a milk line dairy establishment, a continuous fermentation system, food processing lines such as pumpable food systems and beverage lines, etc. Food service goods can also be disinfected using the present methods. The present methods are also useful in sanitizing or disinfecting solid surfaces, such as floors, counters, furniture, medical tools and equipment, etc., found in the public health industry. Such surfaces often become contaminated with bodily fluid spills, such as blood, other hazardous color fluids or mixtures thereof.
[00205] In general, actual cleaning of the appropriate system or other surface (i.e., removal of unwanted slack thereon) can be carried out with a different material, such as a formulated detergent that is introduced with warm water. After this cleaning step, the present composition can be applied or introduced into the system at a concentration of use solution in water at room temperature unheated. In some embodiments, the present composition must remain in solution in ice water (eg, 40°F/4°C.) and heated water (eg, 140°F/60°C). Although it is not normally necessary to heat the aqueous use solution of the present composition, under some circumstances heating may be desirable to further enhance its antimicrobial activity.
[00206] In some embodiments, a method of substantially disinfecting fixed suitable process facilities comprises the following steps. The diluted (or in-use) composition of the present invention is introduced into process plants at a temperature in the range of about 4°C to about 60°C. After introduction of the use solution, the solution is circulated throughout the system for a time sufficient to disinfect the process facilities (ie to kill unwanted micro-organisms). After the system has been disinfected by means of the present composition, the composition or use solution is drained from the system. Upon completion of the disinfection step, the system can optionally be rinsed with other materials such as potable water. The present composition is preferably circulated through the process facilities for 10 minutes or less.
[00207] In other embodiments, the present composition can also be used by immersing food processing equipment in the diluted composition or solution (or use) of the present invention, soaking the equipment for a time sufficient to disinfect the equipment and drying or draining excess solution out of the equipment. The composition can further be used by spraying or drying food processing surfaces with the use solution, keeping the surfaces moist for a time sufficient to disinfect the surfaces and removing excess composition or solution by drying, drain vertical, vacuum, etc.
[00208] In still other embodiments, the present composition can also be used in a method for disinfecting hard surfaces, such as institutional type equipment, utensils, tableware, public health equipment or tools, and other hard surfaces. The present composition can also be used to disinfect clothing or fabric items that have been contaminated. The use composition is contacted with any of the above contaminated surfaces or items at or use temperatures in the range of about 4°C to about 60°C for an effective period of time to disinfect, sanitize or sterilize the surface or item. For example, the concentrated composition can be injected into the wash or rinse water of a laundry machine and contacted with the contaminated tissue for a time sufficient to disinfect the fabric. Excess composition or solution can then be removed by rinsing or centrifuging the fabric.
[00209] The present methods can be used in the methods, processes or procedures described and/or claimed in US Patent Nos. 6,165,483 and 6,238,685 B1 to treat plant tissue, seeds, fruits and medium and culture vessels grown in the field or greenhouse. The present composition in diluted (or use) form can reduce natural plant pathogen and human pathogenic microbial load resulting in less residue for mold, decomposition and destruction due to pathogenic poisons.
In some embodiments, the present composition comprising mixed peracids can be used to protect plant tissue growth from the undesirable effects of microbial attack. The mixed peracid materials can be applied to plant tissue culture and can provide residual antimicrobial effects after the plant has completed its growth cycle, fruit or plant material has been harvested and shipped to market. The present composition comprising mixed peracids can be an effective treatment of tissues of living or growing plants, including seeds, roots, tubers, seedlings, cuttings, root stock, crop plants, fruit, fruits and vegetables, etc. Under certain circumstances, a single peroxyacid material can be effective, however, in other circumstances, a mixed peroxyacid has substantially improved and surprising properties.
In some embodiments, the invention involves an antimicrobial peroxyacid concentrate and dilute end use composition, including a microbicidal effective amount of a C2-C4 peroxycarboxylic acid, such as peracetic acid, a microbicidal effective amount of a peroxyacid C5-C12, preferably with a C6-C12 or C8-C12 peroxyacid, or mixtures thereof, and the first and second stabilizing agents described above. The concentrated composition can be diluted with a major proportion of water to form an antimicrobial disinfectant use solution having a pH in the range of about 2 to 8, with a C2-C4 peroxycarboxylic acid concentration of at least about 4 ppm preferably about 10 to 75 ppm, and a concentration of C5-C12, C6-C12 or C8-C12 peroxyacid of at least about 1 ppm, preferably about 1 to 25 ppm. Other components may be added, such as a hydrotrope binding agent to solubilize the fatty peroxy acid in concentrated form and when the concentrated composition is diluted with water.
[00212] In other embodiments, the invention involves a method for controlling fungi and microbial plant pathogens in crop plants by treating said crop plants with a dilute aqueous solution comprising an effective amount of a C2 peroxycarboxylic acid -C4, a C5-C12, C6-C12 or C8-C12 aliphatic peroxycarboxylic acid and the first and second stabilizing agents described above.
[00213] In still other embodiments, the invention further involves a process for controlling fungi and microbial plant pathogens in crop plants by diluting, in an aqueous liquid, a concentrate containing: about 1 to 20% in weight of a C2-C4 peroxycarboxylic acid; about 0.1 to 20% by weight of a C5-C12, C6-C12 or C8-C12 aliphatic peroxycarboxylic acid and the first and second stabilizing agents described above to form a solution; and contacting said crop plants with said solution.
[00214] In still other embodiments, the invention further involves a process for controlling fungi and microbial plant pathogens in crop plants by diluting, in an aqueous liquid, a concentrate containing: about 1 to 20% in weight of a C 2 -C 4 peroxycarboxylic acid; about 0.1 to 20% by weight of a C5-C12, C6-C12 or C8-C12 aliphatic peroxycarboxylic acid; about 5 to 40% by weight of a C 2 -C 4 carboxylic acid; about 1 to 20% by weight of a C8-C12 aliphatic carboxylic acid; about 1 to 30% by weight of hydrogen peroxide, and the first and second stabilizing agents described above, to form a solution; and contacting said crop plants with said solution.
As disclosed in US Patent Nos. 6,165,483 and 6,238,685 B1, low pH C5+ peroxyacids, (eg preferably less than 7), such as fatty peroxyacids, are very potent biocides at low levels when used in combination with a C2-C4 peroxycarboxylic acid, such as peroxyacetic acid, a synergistic effect is obtained, providing a much more potent biocide than can be obtained by using these components separately. This means that substantially lower concentrations of biocide can be used to obtain equal biocidal effects.
[00216] As the term is used in this report, a C5-C12 peroxyacid (or peracid) is intended to mean the product of the oxidation of a C5-C12 acid, such as a fatty acid, or a mixture of acids, to form a peroxyacid having from about 5 to 12 carbon atoms per molecule. The C5-C12 peroxyacids are preferably aliphatic (straight or branched). A C2-C4 peroxycarboxylic acid is intended to mean the oxidation product of a C2-C4 carboxylic acid, or a mixture thereof. This includes straight and branched chain of a C2-C4 carboxylic acid.
[00217] In still other embodiments, the invention is directed to a method for controlling fungi and microbial plant pathogens in crop plants. This treatment uses a combination of two different peroxyacids. This mixture comprises at least 4 parts per million (ppm) of a smaller C2-C4 carboxylic peroxyacid and at least 1 ppm of a larger C5-C12 carboxylic peroxyacid and the first and second stabilizing agents described above. The preferred mixture comprises at least 4 ppm of a C2-C4 minor peroxyacid and at least 1 ppm of a C8-C12 major aliphatic peroxyacid and the first and second stabilizing agents described above.
An especially preferred embodiment of the composition includes a mixture of peroxyacetic acid and peroctanoic acid.
[00219] In some embodiments, the composition used in the present methods may also contain a hydrotrope for the purpose of increasing the aqueous solubility of various slightly soluble organic compounds. The preferred embodiment of the composition uses a hydrotrope chosen from the group of n-octane sulfonate, a xylene sulfonate, a naphthalene sulfonate, ethylhexyl sulfate, lauryl sulfate, an amine oxide or a mixture thereof.
[00220] In some embodiments, the composition used in the present methods may also contain a chelating agent for the purpose of removing ions from solution. The preferred embodiment of the invention uses 1-hydroxyethylidene-1,1-diphosphonic acid.
[00221] In some embodiments, the invention also provides a process for controlling fungi and microbial plant pathogens in crop plants. In this embodiment, the plant is contacted with a solution prepared by diluting, in an aqueous liquid, a concentrate comprising two peroxyacids, and the first and second stabilizing agents described above. This blend includes C2-C4 carboxylic peroxyacid and a larger C8-C12 carboxylic peroxyacid. The preferred blend includes about 1 to 20 percent by weight (% by weight) of a smaller C2-C4 peroxyacid and about 0.1 to 20% by weight of a larger C8-C12 peroxyacid. An especially preferred embodiment of the composition includes a mixture of peroxyacetic acid and peroxyoctanoic acid. The composition may further contain about 1 to 15% by weight of a hydrotrope and about 5% by weight of a chelating agent.
[00222] In other embodiments, the invention also provides a process for controlling fungi and microbial plant pathogens in growing plants. In this embodiment, the plant is contacted with a solution prepared by diluting, in an aqueous liquid, a concentrate containing two peroxyacids and the first and second stabilizing agents described above. This blend includes a C2-C4 minor carboxylic peroxyacid and a C8-C12 major aliphatic carboxylic peroxyacid. An especially preferred embodiment of the composition includes a mixture of peroxyacetic acid and peroctanoic acid. The composition may further contain a hydrotrope and a chelating agent. In addition, the solution contains about 1 to 30% by weight of hydrogen peroxide. The preferred composition includes a mixture of acetic acid and octanoic acid.
[00223] The present methods can be used in the methods, processes or procedures described and/or claimed in U.S. Patent Nos. 6,010,729, 6,103,286, 6,545,047 and 8,030,351 B2 to disinfect animal carcasses.
[00224] In some embodiments, the compositions of the present invention can be used in a method of treating animal carcasses to obtain a reduction of at least one log™ in surface microbial population, which includes the step of treating said carcass with a dilute composition of the present invention comprising an antimicrobially effective amount comprising at least 2 parts per million (ppm, parts by weight per part per million) of one or more peroxycarboxylic acids having up to 12 carbon atoms, an amount an effective antimicrobial agent comprising at least 20 ppm of one or more carboxylic acids having up to 18 carbon atoms and the first and second stabilizing agents described above to reduce the microbial population.
[00225] In other embodiments, the present invention is directed to an antimicrobial composition adapted to clean and disinfect animal carcasses that contains about 0.5 percent by weight (% by weight) to about 20% by weight of a mixture of one or more peroxycarboxylic acids having 2 to 4 carbon atoms and one or more peroxycarboxylic acids having 8 to 12 carbon atoms, from about 0.5% by weight to about 60% by weight of an alpha-hydroxy mono- or dicarboxylic acid having 3 to 6 carbon atoms, an effective amount of a scavenger, an effective amount of a hydrotrope, and the first and second stabilizing agents described above.
[00226] In still other embodiments, the present invention is directed to an antimicrobial composition adapted to treat animal carcasses comprising, essentially consisting of, or consisting of a mixture of peroxyacetic and peroxyoctanoic acid in a ratio of about 10 :1 to about 1:1, from about 0.1 to about 10% by weight acetic acid, from about 4% by weight to about 10% by weight hydrogen peroxide, and about 0. 5% by weight to about 1.5% by weight of a sequestering agent and the first and second stabilizing agents described above.
[00227] In still other embodiments, the present invention is directed to a method of treating an animal carcass to reduce a microbial population in the resulting cut meat, the method comprising the steps of spraying an aqueous antimicrobial treatment composition on said carcass at a pressure of at least 50 psi at a temperature of up to about 60°C resulting in a contact time of at least 30 seconds, the antimicrobial composition comprising an effective antimicrobial amount comprising at least 2 ppm of one or more carboxylic acids, peroxycarboxylic acids or mixtures thereof and the first and second stabilizing agents described above; and obtain at least a logw reduction in the microbial population.
[00228] In still other embodiments, the present invention is directed to a method for treating an animal carcass to reduce a microbial population in the resulting cut meat, the method comprising the steps of placing the animal carcass in a chamber at atmospheric pressure; filling the chamber with condensation vapor comprising an antimicrobial composition, e.g., a dilute composition of the present invention, in a short duration; and quickly ventilate and cool the chamber to prevent browning of the meat carcass; wherein the duration of the steam thermal process can be from about 5 seconds to about 30 seconds and the chamber temperature can range from about 50°C to about 93°C.
[00229] The antimicrobial composition can be applied in a variety of ways to obtain intimate contact with each potential site of microbial contamination. For example, it can be sprayed onto the carcasses or the carcasses can be immersed in the composition. Additional methods include applying a foamed composition and a thick or gel composition. Vacuum and/or light treatments may be included, if desired, with the application of the antimicrobial composition. Heat treatment can also be applied, pre-, concurrent with or post-application of the antimicrobial composition.
[00230] A preferred spraying method for treating carcasses with diluted compositions of the present invention involves spraying the carcass with an aqueous spray at a temperature less than about 60°C at a pressure of about 50 to 500 psi, wherein the spray comprises an antimicrobially effective amount of a carboxylic acid, an antimicrobially effective amount of a peroxycarboxylic acid or mixtures thereof, and the first and second stabilizing agents described above. These sprays may also contain an effective portion of a peroxy compound, such as hydrogen peroxide, and other ingredients, such as sequestering agents, etc. The high pressure spray action of aqueous treatment can remove microbial populations by combining the mechanical action of spraying with the chemical action of antimicrobial materials to result in an improved reduction of such populations on the surface of the carcass.
[00231] All pressures are psig (or measured psi). In some embodiments, differentiating “-cidal” or “-static” antimicrobial activity, definitions describing the degree of efficacy, and official laboratory protocols for measuring this efficacy are important considerations for understanding the relevance of agents antimicrobials in the compositions. Antimicrobial compositions can effect two types of microbial cell damage. The first is a truly lethal and irreversible action resulting in complete microbial cell destruction or incapacitation. The second type of cell damage is reversible, such that if the organism becomes free of the agent, it can multiply again. The former is called bactericide and the latter is bacteriostatic. A disinfectant is, by definition, an agent that provides antibacterial or bactericidal activity and achieves at least a five-fold reduction (ie, a five log 10 reduction) in microbial populations after a contact time of 30 seconds (see AOAC method 960.09).
[00232] The present methods can be used in the methods, processes or procedures described and/or claimed in U.S. Patent Nos. 8,017,409 and 8,236,573. In some embodiments, the present methods can be used for a variety of domestic or industrial applications, for example, to reduce microbial or viral populations on a surface or object or in a body or stream of water. The diluted (or in use) compositions of the present invention can be applied in a variety of areas, including kitchens, bathrooms, factories, hospitals, dental offices and food factories, and can be applied to a variety of hard or soft surfaces having smooth, irregular or porous topography. Suitable hard surfaces include, for example, architectural surfaces (eg, floors, walls, windows, sinks, tables, counters and paintings); kitchen utensils; hard surface medical or surgical instruments and devices; and hard surface package. Such hard surfaces can be made from a variety of materials, including, for example, ceramic, metal, glass, wood or hard plastic. Suitable soft surfaces include, for example, paper; filter media, hospital and surgical bedding and clothing; soft surface medical or surgical instruments and devices; and soft surface package. Such soft surfaces can be made from a variety of materials, including, for example, paper, fiber, woven or non-woven cloth, soft plastics and elastomers. Diluted (or in-use) compositions can also be applied to soft surfaces such as food and skin (eg a hand). The diluted (or in-use) compositions can be used as a foaming or non-foaming environmental disinfectant.
[00233] In other embodiments, the diluted compositions (or use) of the present invention can be included in products such as sterilants, disinfectants, preservatives, deodorants, antiseptics, fungicides, germicides, sporicides, virucides, detergents, bleaches, hard surface cleaners, soaps, waterless hand sanitizers and pre- or post-surgical brushes.
[00234] In still other embodiments, the diluted compositions (or use) of the present invention can also be used in veterinary products such as mammalian skin treatments or in products to disinfect animal enclosures, pens, irrigation stations and veterinary treatment areas such as inspection tables and operating rooms. The diluted (or use) compositions can be used in an antimicrobial foot bath for animals or people.
[00235] In still other embodiments, the present methods can be used to reduce the population of pathogenic microorganisms, such as pathogens from humans, animals and the like. Exemplary pathogenic microorganisms include fungi, molds, bacteria, spores and viruses, for example, S. aureus, E. coli', Streptococci', Legionella, Pseudomonas aeruginosa, mycobacteria, tuberculosis, phages or the like. Such pathogens can cause a variety of diseases and disorders, including mastitis or other milking diseases in mammals, tuberculosis and the like. The present methods can be used to reduce the population of microorganisms on the skin or other external or mucosal surfaces of an animal. In addition, the present methods can be used to kill pathogenic microorganisms that spread through transfer by water, air or a surface substrate. In some applications, the diluted (or in use) compositions of the present invention need only be applied to the skin, other external or mucosal surfaces of an animal's water, air or surface.
[00236] In still other embodiments, the present methods can also be used on food and plant species to reduce surface microbial populations; used in manufacturing or processing sites that handle such food and plant species; or used to treat process water around such sites. For example, the present methods can be used on food transport lines (for example, as belt sprays); boot and glove washing immersion boilers; food storage facilities; anti-deterioration air circulation systems; cooling and refrigerator equipment; beverage coolers and warmers, bleaches, cutting boards, third sink areas and meat coolers or scalding devices. The present methods can be used to treat transport waters, such as those found in artificial channels, tube transports, cutters, bleachers, retort systems, washers and the like. Particular foodstuffs that can be treated with the present methods include eggs, meat, seeds, leaves, fruits and vegetables. Particular plant surfaces include harvested and cultivated leaves, roots, seeds, skins or pods, trunks, stems, tubers, subterranean stems, fruit and the like. The present methods can also be used to treat animal carcasses to reduce pathogenic and non-pathogenic microbial levels.
[00237] In still other embodiments, the present methods may be useful in cleaning or disinfecting containers, processing facilities, or equipment in the food service or food processing industries. The present methods can be used on food packaging materials and equipment, including for aseptic cold or hot packaging. Examples of process facilities in which the present methods can be used include a milk line dairy establishment, a continuous fermentation system, food processing lines such as pumpable food systems and beverage lines, etc. Food service goods can be disinfected with the present methods. For example, the present methods can also be used on or in washing machines for merchandise, dishwashers, container washers, container coolers, heaters, third-sink washers, cutting areas (eg, water knives, cutters and saws) and egg washers. Particular treatable surfaces include packaging such as cardboard boxes, bottles, films and resins; tableware, such as glasses, plates, utensils, pots and pans; merchandise washing machines; exposed food preparation area surfaces such as sinks, counters, tables, floors, and walls; processing equipment such as tanks, kegs, lines, pumps and hoses (for example, dairy processing equipment for processing milk, cheese, ice cream and other dairy plant products); and transport vehicles. Containers include glass bottles, PVC or polyolefin film bags, cans, polyester, multi-volume PEN or PET bottles (100 ml to 2 liters, etc.), one-gallon milk containers, juice or milk containers. cardboard, etc.
[00238] In still other embodiments, the present methods can also be used on or on other industrial equipment and on other industrial process streams, such as heaters, cooling towers, boilers, retort water, rinse water , aseptic packaging wash waters and the like. The present methods can be used to treat microbes and odors in recreational waters, such as in swimming pools, water stations, artificial recreational canals and water slides, fountains and the like.
[00239] In still other embodiments, a filter containing the diluted compositions (or use) of the present invention can be used to reduce the population of microorganisms in air and liquids. Such a filter can be used to remove water and airborne pathogens such as Legionella.
In still other embodiments, the present methods can be used to reduce the population of microbes, fruit flies or other insect larvae on a drain or other surface.
[00241] In still other embodiments, the present methods can also be used by immersing food processing equipment in the composition or diluted solution (or use) of the present invention, soaking the equipment for a sufficient time to disinfect the equipment and dry or drain excess composition or solution out of the equipment. The present methods can further be used by spraying or drying food processing surfaces with the composition or solution of use, keeping the surfaces moist for a time sufficient to disinfect the surfaces, and removing excess composition or solution through drying, vertical drain, vacuum, etc.
[00242] In still other embodiments, the present methods can also be used to disinfect hard surfaces, such as institutional type equipment, utensils, tableware, public health equipment or tools, and other hard surfaces. The present methods can also be used to disinfect items of clothing or fabrics that have been contaminated. The diluted (or in use) compositions of the present invention may be contacted with any contaminated surfaces or items at use temperatures in the range of about 4°C to 60°C, for a period of time effective to disinfect, sanitize or sterilize the surface or item. For example, diluted (or in-use) compositions can be injected into the wash or rinse water of a laundry machine and contacted with the contaminated fabric for a time sufficient to disinfect the fabric. Excess composition can be removed by rinsing or centrifuging the fabric.
[00243] In still other embodiments, the diluted compositions (or use) of the present invention can be applied to microbes or to dirty or cleaned surfaces using a variety of methods. These methods can operate on an object, surface, a body or stream of water or a gas, or the like, through the contact of the object, surface, body or stream with the diluted (or use) composition. Contacting can include any one of a number of methods for applying a composition, such as spraying the composition, dipping the object into the composition, foaming or gel treating the object with the composition, or a combination thereof.
[00244] In still other embodiments, the diluted (or in-use) compositions of the present invention can be used to whiten pulp. Compositions can be used for waste treatment. Such composition may include added bleaching agent.
[00245] In still other embodiments, other hard surface cleaning applications for the diluted (or in-use) compositions of the present invention include clean-in-place (CIP) systems, clean-out-of-place (COP) systems ), washer-decontaminants, sterilizers, fabric laundry machines, ultra and nano-filtration systems and internal air filters. COP systems can include easily accessible systems, including wash tanks, soaking vessels, mop buckets, waste tanks, scrub sinks, vehicle parts washers, non-continuous batch washers and systems, and the like.
[00246] The concentrations of peracid and/or hydrogen peroxide in the diluted (or in-use) compositions of the present invention can be monitored in any suitable way. In some embodiments, peracid and/or hydrogen peroxide concentrations in diluted (or in-use) compositions can be monitored using a kinetic assay procedure, for example, the exemplary procedure disclosed in US Patent Nos. 8,017,409 and 8,236,573. This can be accomplished by exploiting the difference in reaction rates between peracid and hydrogen peroxide when using, for example, a buffered iodide reagent to differentiate peracid and hydrogen peroxide concentrations when these analyte compounds are present in the composition of use. Monitoring the composition of use can also determine peracid and/or hydrogen peroxide concentrations in the presence of other additional ingredients, such as acidulants, one or more stabilizing agents, nonionic surfactants, semi-polar nonionic surfactants, anionic surfactants, amphoteric or ampholytic surfactants, adjuvants, solvents, additional antimicrobial agents or other ingredients that may be present in the composition of use.
[00247] In some embodiments, the exemplary compositions of the present invention comprise the components set forth in the following Tables 1 to 3. Before or during use, the exemplary compositions may be diluted to a desired level. For example, exemplary compositions can be diluted 2, 5, 10, 50, 100, 500, 1,000, 5,000 or 10,000 times. Table 1

Table 2

Table 3

18) METHODS TO REDUCE THE LEVEL OF HYDROGEN SULFIDE
[00248] In yet another aspect, the present invention is directed to a method for reducing the level of hydrogen sulfide (H2S), hydrosulfuric acid or a salt thereof in a water source, which comprises a step of contacting a water source having a composition at a diluted level to form a treated water source, said composition comprising: 1) a C1-C22 carboxylic acid; 2) a C1-C22 percarboxylic acid; 3) hydrogen peroxide; 4) a first stabilizing agent, which is a picolinic acid or a compound having the following Formula (IA):
wherein R1 is OH or -NR1aR1b, wherein R1a and R1b are independently hydrogen or (C1-C6) alkyl; R2 is OH or -NR2aR2b, wherein R2a and R2b are independently hydrogen or (C1-C6) alkyl; each R3 is independently (C1-C6) alkyl, (C2-C6) alkenyl or (C2-C6) alkynyl; en is a number from zero to 3; or a salt thereof; or a compound having the following Formula (IB):
wherein R1 is OH or -NR1aR1b, wherein R1a and R1b are independently hydrogen or alkyl (CI-C'); R2 is OH or -NR2a R2b, wherein R2a and R2b are independently hydrogen or alkyl (CI-C'); each R3 is independently alkyl (CI-C'), alkenyl (C2-C6) or alkynyl (C2-C6); en is a number from zero to 3; or a salt thereof; 6) a second stabilizing agent, which is a compound having the following Formula (IIA):
f OOO R1-OPCPO-R4 1 1c1 o R5O R2 R3(nA) wherein R1, R2, R3 and R4 are independently hydrogen, alkyl (CI-C'), alkenyl (C2-C') or alkynyl (C2- CΘ)or C6-C20 aryl; R5is alkyl (CI-CΘ), alkenyl (C2-CΘ) or alkynyl (C2-CΘ); and R6 is hydrogen, alkyl (CI-CΘ), alkenyl (C2-CΘ) or alkynyl (C2-CΘ); or a salt thereof; or a compound having the following Formula (IIB):
wherein R 1 , R 2 and R 3 are independently hydrogen, alkyl (C 1 -C 6 ), alkenyl (C 2 -C 6 ) or alkynyl (C 2 -C 6 ) or C 6 -C 20 aryl; or a salt thereof; and wherein said hydrogen peroxide has a concentration of at least about 0.1% by weight, C1-C22 percarboxylic acid has a concentration of at least about 2 times the concentration of said hydrogen peroxide and said The composition has a pH of about 4 or less and wherein said treated water source comprises from about 1 ppm to about 10,000 ppm of said C1-C22 percarboxylic acid and said contacting step lasts for sufficient time to stabilize or reduce the level of H2S, hydrosulfuric acid or a salt thereof in said source of treated water.
[00249] In some embodiments, the composition used in these methods is a balanced composition comprising peracid, hydrogen peroxide, carboxylic acid and a solvent, for example, water. In some embodiments, the composition used in the present methods does not comprise a mineral acid, for example the mineral acids disclosed in WO 91/07375.
[00250] The composition used in the present methods can comprise any suitable level of hydrogen peroxide. In some embodiments, the hydrogen peroxide in the balanced composition has a concentration of from about 0.1% to about 15%, for example, about 0.1%, 0.2%, 0.3% , 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1%, 2%, 3%, 4%, 5%, 6%, 7 %, 8%, 9%, 10%, 11%, 12%, 13%, 14% or 15%. Before or during use, exemplary compositions may be diluted to a desired level.
[00251] The composition used in the present methods can comprise any suitable level of C1-C22 percarboxylic acid relative to the level of hydrogen peroxide. In some embodiments, C1-C22 percarboxylic acid has a concentration of at least about 6 times the concentration of hydrogen peroxide. In other embodiments, the C1-C22 percarboxylic acid has a concentration of at least about 10 times the concentration of hydrogen peroxide. In yet other embodiments, the C1 C22 percarboxylic acid has a concentration of at least about 2, 3, 4, 5, 6, 7, 8, 9, or 10 times the concentration of hydrogen peroxide.
[00252] Any suitable C1-C22 percarboxylic acid can be used in the present methods. In some embodiments, the C1-C22 percarboxylic acid is a C2-C20 percarboxylic acid. In other embodiments, the C1-C22 percarboxylic acid comprises peroxyacetic acid, peroxyoctanoic acid and/or peroxysulfonated oleic acid. Other exemplary C1-C22 percarboxylic acids are described in Section B above. The composition used in the present methods can comprise any suitable level of C1-C22 percarboxylic acid and hydrogen peroxide. In some embodiments, the C1-C22 percarboxylic acid in the balanced composition has a concentration of from about 0.1% to about 30%, e.g., about 0.1%, 0.2%, 0.3% , 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1%, 2%, 3%, 4%, 5%, 6%, 7 %, 8%, 9%, 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19%, 20%, 21%, 22%, 23%, 24%, 25%, 26%, 27%, 28%, 29%, or 30%. Before or during use, exemplary compositions can be diluted to a desired level.
[00253] Any suitable first stabilizing agent can be used in the composition used in the present methods. In some embodiments, the first stabilizing agent is a picolinic acid or a salt thereof. In other embodiments, the first stabilizing agent is 2,6-pyridinedicarboxylic acid or a salt thereof. The first stabilizing agent can be used in any suitable concentration. In some embodiments, the first stabilizing agent has a concentration of from about 0.005% by weight to about 5% by weight. In other embodiments, the first stabilizing agent has a concentration of from about 0.05% by weight to about 0.15% by weight. In yet other embodiments, the first stabilizing agent has a concentration of about 0.005% by weight, 0.01% by weight, 0.1% by weight, 1% by weight, 2% by weight, 3% by weight , 4% by weight or 5% by weight. In yet other embodiments, the first stabilizing agent has a concentration at about 0.05% by weight, 0.06% by weight, 0.07% by weight, 0.08% by weight, 0.09% by weight. weight, 0.10% by weight, 0.11% by weight, 0.12% by weight, 0.13% by weight, 0.14% by weight, or 0.15% by weight.
[00254] Any suitable second stabilizing agent can be used in the present compositions. In some embodiments, the second stabilizing agent is 1-hydroxy ethylidene-1,1-diphosphonic acid (HEDP) or a salt thereof. The second stabilizing agent can be used in any suitable concentration. In some embodiments, the second stabilizing agent has a concentration of from about 0.1% by weight to about 10% by weight, e.g., 0.1% by weight, 0.5% by weight, 1 % by weight, 2% by weight, 3% by weight, 4% by weight, 5% by weight, 6% by weight, 7% by weight, 8% by weight, 9% by weight or 10% by weight. In other embodiments, the second stabilizing agent has a concentration of from about 0.5% by weight to about 5% by weight, e.g., 0.5% by weight, 1% by weight, 1.5% by weight, 2% by weight, 2.5% by weight, 3% by weight, 3.5% by weight, 4% by weight, 4.5% by weight or 5% by weight. In yet other embodiments, the second stabilizing agent has a concentration of from about 0.6% by weight to about 1.8% by weight, e.g., 0.6% by weight, 0.7% by weight, 0.8% by weight, 0.9% by weight, 1.0% by weight, 1.1% by weight, 1.2% by weight, 1.3% by weight, 1.4% by weight, 1 .5% by weight, 1.6% by weight, 1.7% by weight or 1.8% by weight.
[00255] In some embodiments, the first stabilizing agent is a 2,6-pyridinedicarboxylic acid or a salt thereof and the second stabilizing agent is HEDP or a salt thereof.
The composition used in the present methods can retain any suitable level or percentage of C1-C22 percarboxylic acid activity for any suitable time after the treated target composition is formed. In some embodiments, the present composition retains at least about 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85% or 90% of the initial C1-C22 percarboxylic acid activity during any suitable time after the treated target composition is formed. In other embodiments, the present composition retains at least about 60% of the initial C1-C22 percarboxylic acid activity for at least 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11 12, 13, 14, 15, 20, 25, 30 minutes, 1,2, 5, 10, 15, 20 or 24 hours or more after the treated target composition is formed.
[00257] In some embodiments, the composition used in the present methods may comprise a peroxidase or a catalase to further reduce the concentration of hydrogen peroxide. Any suitable peroxidase or catalase can be used in the present compositions. Exemplary peroxidases and catalases are described in Section B above. In other embodiments, the composition used in the present methods may further comprise a substance that aids in solubilizing the first and/or second stabilizing agents. Exemplary substances that can aid in the solubilization of the first and/or second stabilizing agents include hydrotropes such as sodium xylene sulfonate, sodium cumene sulfonates, and surfactants such as anionic surfactants and nonionic surfactants.
[00258] The treated water source can comprise any suitable level of C1-C22 percarboxylic acid. In some embodiments, the treated water source comprises from about 10ppm to about 1000ppm of the C1-C22 percarboxylic acid, for example, about 10ppm, 20ppm, 30ppm, 40ppm, 50ppm, 60ppm, 70ppm, 80ppm, 90ppm, 100ppm, 110ppm, 120ppm, 130ppm, 140ppm, 150ppm, 160ppm, 170ppm, 180ppm, 190ppm, 200ppm, 300ppm, 400ppm 500ppm, 600ppm, 700ppm, 800ppm, 900ppm or 1000ppm of the C1-C22 percarboxylic acid.
[00259] The treated water source may comprise any suitable C1-C22 percarboxylic acid. In some embodiments, the treated target composition comprises peroxyacetic acid, peroxyoctanoic acid and/or peroxysulfonated oleic acid.
[00260] The treated water source can comprise any suitable level of hydrogen peroxide. In some embodiments, the treated water source comprises from about 1ppm to about 15ppm of hydrogen peroxide, for example, about 1ppm, 2ppm, 3ppm, 4ppm, 5ppm, 6ppm , 7ppm, 8ppm, 9ppm, 10ppm, 11ppm, 12ppm, 13ppm, 14ppm or 15ppm of the hydrogen peroxide.
[00261] The treated water source can comprise any suitable level of C1-C22 percarboxylic acid in relation to the level of hydrogen peroxide. In some embodiments, the treated water source comprises C1-C22 percarboxylic acid which has a concentration of at least about 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12 , 13, 14, 15, 16, 17, 18, 19 or 20 times the concentration of hydrogen peroxide.
[00262] The treated water source may comprise any suitable first stabilizing agent and second stabilizing agent. In some embodiments, the treated water source comprises a first stabilizing agent which is a 2,6-pyridinedicarboxylic acid or a salt thereof and a second stabilizing agent which is HEDP or a salt thereof.
[00263] The treated water source can retain any suitable level of initial C1-C22 percarboxylic acid activity for any suitable time. In some embodiments, the treated water source retains at least about 50%, 60%, 70%, 80%, 90%, 95%, 99% or 100% of the initial C1-C22 percarboxylic acid activity for any suitable time. In other embodiments, the treated water source maintains an adequate level of initial C1-C22 percarboxylic acid activity for at least 1 minute, 2 minutes, 3 minutes, 4 minutes, 5 minutes, 6 minutes, 7 minutes, 8 minutes, 9 minutes, 10 minutes, 11 minutes, 12 minutes, 13 minutes, 14 minutes or 15 minutes after the treated target composition is formed. In yet other embodiments, the treated water source retains at least about 60% of the initial C1-C22 percarboxylic acid activity for 15 minutes after the treated water source is formed.
[00264]The contact step can take any suitable time. In some embodiments, the contact step lasts at least 10 seconds, 20 seconds, 30 seconds, 40 seconds, 50 seconds, 1 minute, 10 minutes, 30 minutes, 1 hour, 2 hours, 4 hours, 8 hours, 16 hours, 1 day, 3 days, 1 week or more.
[00265] The present methods can be used to reduce the level of hydrogen sulfide (H2S), hydrosulfuric acid or a salt thereof in any suitable water source. Exemplary water source includes fresh water, reservoir water, sea water, produced water and a combination thereof. The water source can comprise any suitable level of produced water, for example, at least about 1% by weight, 2% by weight, 3% by weight, 4% by weight, 5% by weight, 6% by weight, 7% by weight, 8% by weight, 9% by weight, 10% by weight, 20% by weight, 30% by weight, 40% by weight, 50% by weight, 60% by weight, 70% by weight, 80% by weight, 90% by weight or more produced water.
[00266]The present methods can be used to reduce the level of hydrogen sulfide (H2S), hydrosulfuric acid or a salt thereof in a water source to any suitable degree. For example, the level of H2S, hydrosulfuric acid or a salt thereof in the treated water source can be reduced by at least 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80% , 90%, 95%, 99%, or more from the untreated level.
[00267]The present methods can be used to reduce the level of hydrogen sulfide (H2S), hydrosulfuric acid or a salt thereof in a water source from any suitable location. For example, the present methods can be used to reduce the level of hydrogen sulfide (H2S), hydrosulfuric acid or a salt thereof in a water source partially or completely obtained or derived from an underground environment, for example , an oil or gas well.
[00268] In some embodiments, the present methods may further comprise directing the treated water source in an underground environment, for example, an oil or gas well, or discarding the treated water source. 19) EXAMPLES
[00269] The following examples are included for illustrative purposes only and are not intended to limit the scope of the invention. EXAMPLE 1. COMPARISON OF THE STABILITY OF PERACETIC ACID COMPOSITIONS WITH VARIOUS STABILIZERS
[00270] Compositions of peracetic acid (POAA) with various stabilizers described in Table 1 were prepared, and upon reaching equilibrium, the compositions were stored in the oven at 50°C. The level of peracetic acid and hydrogen peroxide was monitored by an iodometric titration method. The results are summarized in Table 4 and Figure 1. Table 4. PERACETIC ACID COMPOSITIONS WITH VARIOUS STABILIZERS


[00271] As can be seen in Table 4, after reaching equilibrium, the level of peracetic acid formed between the compositions is in the order of IC > IB > IA. Without wishing to limit the invention to particular theories, it is considered that this difference in the level of peracetic acid formed is due to the different effectiveness of the stabilizers in the compositions. Once formed, the peracetic acid begins to decompose, and the stabilizer in the composition will have a direct impact on the rate of decomposition of the peracetic acid. Thus, the more effective the stabilizer, the less decomposition will occur in the compositions, and the more peracetic acid will be formed after reaching equilibrium. This is important not only in maintaining the shelf life of a peracetic acid composition, but it is also economically beneficial to be able to form higher levels of peracetic acid in compositions from the same level as the starting materials (eg acid acetic and hydrogen peroxide). Table 5. STABILITY OF PERACETIC ACID COMPOSITIONS WITH VARIOUS STABILIZERS


[00272] As can be seen from Table 5 and Figure 1, a synergistic stabilizing effect was observed when a combination of HEDP and DPA was used in the peracetic acid formulations. Surprisingly, it was found that for the high ratio of tested compositions of peracetic acid to hydrogen peroxide, the most commonly used stabilizer, ie, HEDP, had only marginal effects on the stabilization of peracetic acid. For example, as shown in Table 2, composition I-A lost more than 60% of the peracetic acid formed after just 1 week under the test conditions. Composition I-B, which used only DPA as a stabilizer, showed an improved stabilizing effect compared to composition I-A and lost about 20% peracetic acid in four weeks under the conditions tested. In contrast, the combination of DPA and HEDP was shown to be an excellent stabilizer for the high ratio of peracetic acid to hydrogen peroxide compositions tested. As shown in Table 2, composition I-C, which showed a combination of HEDP and DPA as stabilizers, lost less than 5% peracetic acid in 4 weeks under the same test conditions. The stability effect of the combination of HEDP and DPA is greater than the sum of the individual stability effect of HEDP and DPA. This result demonstrates that the stability effect of the combination of HEDP and DPA is a synergistic stabilizing effect and not merely an additive effect of the individual stability effect of HEDP and DPA. EXAMPLE 2. HIGH RATE SYNERGIC STABILIZATION STUDY OF HEDP AND DPA OF PERACETIC ACID TO HYDROGEN PEROXIDE (POAA/H2O2) COMPOSITIONS
[00273]To systematically study the synergistic stabilization performance of HEDP and DPA, high ratio of POAA/H2O2 peracetic acid compositions with various stabilizers is prepared, as described in Table 6. The compositions, once equilibrium has been reached , were stored in an oven at 50°C, and the level of peracetic acid and hydrogen peroxide was monitored by an iodometric titration method. The results are summarized in Table 7. Table 6. PERACETIC ACID COMPOSITIONS WITH VARIOUS STABILIZERS

Table 7. PERACETIC ACID STABILITY (POAA) AT 50°C


[00274] The results shown in Table 7 clearly indicate that when a single stabilizer is used, simply increasing the levels of stabilizer in the composition will not proportionately increase the stability of peracetic acid. For example, for the series IIA composition, increasing HEDP from 1 to 5% resulted in only a marginal increase in stability. For the series IIB composition, increasing the DPA level beyond 0.06% had virtually no impact on stability. Without limiting the invention to any particular theory, it is believed that stabilizers in peracid compositions stabilize peracids through chelation of trace transition metal ions in the compositions. Thus, the effectiveness of a stabilizer is mainly dependent on its binding constant (Ksp) with the individual ion. Therefore, it is considered that increasing the concentration of a single stabilizer has a very limited effect on the binding capacity of such a stabilizer.
[00275] Without limiting the invention to any particular theory, on the one hand it is considered that the combination of two stabilizers, such as HEDP and DPA, can form ligand complexes mixed with transition metals with an increased binding constant (Ksp) compared to that of the metal complex of the individual binder formed when a single stabilizer is used. It is considered that this mixed binder complex leads to the significant increase in the stabilizing effect observed when using a combination of stabilizers. On the other hand, DPA and related niacin compounds are known hydroxyl radical scavengers (see, for example: Biosci. Biotechnol. Biochem., 2002, 66(3), 641 - 645.), and through extinction of the hydroxyl radicals formed and thus preventing the subsequent chain decomposition reaction involving the peracid, the stability of the corresponding peracid composition will be further improved.
[00276] Figure 2 further illustrates the synergistic stabilization capacity of HEDP and DPA. The percentage of POAA retained at the end of 28 days (compared to 0 day) at 50°C of the series IIC composition, which had a mixture of HEDP and DPA, was compared to the sum of the percentage of POAA retained from the composition. IIA (HEDP as a stabilizer only) and series IIB (DPA as a stabilizer only). For example, composition IIC-2, which contains 1.2% HEDP and 1200 ppm DPA stabilizers, preserved 96% POAA; in contrast, composition IIA-2 which contains 1.2% HEDP as the sole stabilizer, preserved 0.26% POAA; and composition IIB-1 which contains 1,200 ppm DPA as the sole stabilizer, preserved 73.5% POAA. Combined, compositions IIA-2 and IIB-1 have the same stabilizer as IIC-2, but the sum of POAA retained from IIA-2 and IIB-1 is only 73.8%, much less than that of IIC-2. Without wishing to limit the invention to particular theories, the combination of two different types of binders, such as HEDP and DPA, can form mixed ligand complexes with the transition metals that catalytically decompose peracids, and the mixed ligand complexes formed have dramatically increased binding constant (Ksp) compared to that of the metal complex of the individual ligand. The increased transition metal binding efficiency of the mixture of HEDP and DPA thus contributed to the synergistic stabilizing ability of the peracids. EXAMPLE 3. SELF-ACCELERATING DECOMPOSITION TEST OF LOW HYDROGEN PEROXIDE - PEROXYACETIC ACID CHEMICALS
[00277]The following SADT procedure is a standardized United Nations protocol to help determine hazard classes of self-heating substances known as the “H4 method” (sec. 28.4.4, p. 314, UN “ Recommendations on the Transport of Dangerous Goods, Manual of Tests and Criteria”, 5th revised edition (2009).) The method is specific to the type of packaging used, and if the SADT temperature is found to be 45°C or less, the product must be transported, stored and used with strict refrigeration controls. Such demand for controlled temperature makes it impractical to transport and store the products. The self-heating behavior of chemicals at very large package sizes can be simulated in Dewar vials that have been previously tested to determine that they closely reflect the heat transfer properties of the packaging that will be used with the chemicals. Bulk tanks are the largest potential package sizes and to model their heat transfer properties it is recommended to use spherical Dewar flasks. The UN Committee on the Transport of Dangerous Goods still builds a safety margin on the 300 gallon and larger pack sizes by requiring that they have SADT's >50°C. As per UN-H4 guidelines 28.4.1.4.1, if the temperature of the contents inside the vials does not exceed the oven temperature by more than 6°C within 7 days, the SADT, by definition, is greater than the temperature from the oven. The guidelines further define the zero time when the sample temperature is within 2 degrees of the oven temperature and require an 80% filled Dewar set with temperature monitoring and ventilated shutoffs.
[00278]For this experiment, the above test conditions were used and the three spherical Dewar vials were filled to 80% of the total with IA, IB and IC chemistries (See Table 8). Table 8

[00279] As can be seen in Figure 3, the IA and IB chemistries containing, respectively, only HEDP, and only DPA, as stabilizers exceeded the exotherm limit of 6 degrees within 1.5 days and 3 days, respectively . The same concentrations of HEDP and DPA when mixed, however, produced increased stabilization, such that the self-heating effects were not sufficient to reach the oven temperature within the 7-day period. Thus, this combination of stabilizers used with this peracid composition would allow for bulk storage and shipping of the peracid composition without cooling.
[00280] The above examples are included for illustrative purposes only and are not intended to limit the scope of the invention. Many variations described above are possible. Since modifications and variations to the examples described above will be apparent to those of skill in the art, it is intended that this invention be limited only by the scope of the appended claims. EXAMPLE 4. COMPARISON OF THE STABILITY OF THE PERACETIC ACID USE SOLUTION (POAA)
[00281] The stability of the use solution is a very important factor in evaluating the performance of a biocide, especially for the application of water treatment. It is preferred that the biocide is stable over the time period of the treatment, as less biocide will be needed for application and thus is economically and environmentally beneficial. Peroxycarboxylic acids are less susceptible to decomposition than most oxidative biocides, such as halogen-based biocides. However, as strong oxidizing agents, the stability of peroxycarboxylic acids in the use solution is strongly dependent on water conditions, such as contaminants and water pH. This is especially evident in the case of impure groundwater related to oil or gas fracturing operations. In order to conserve water used at fracturing sites, the water is partially recovered and recycled at each site. While it is uncertain which component of the fracturing water used should be responsible for the extinction of the peracetic acid, it is a critical disadvantage to commercial peracetic acid, as it considerably affects the cost and antimicrobial capability of this preferred biocide. This experiment is designed to evaluate the stability of the use solution of various compositions of peracetic acid in water containing reused water from oil and gas fracturing applications.
[00282]The water used in this test contains 20% (volume) of water used from two frac sites of oil and gas wells, respectively, and 80% (volume) of fresh water. Peracetic acid compositions tested include a commercial peracetic acid composition (about 15% POAA, 10% H2O2) currently used as a biocide for treating oil and gas well water; the stable and high ratio of the POAA to H2O2 peracetic acid composition disclosed in this application (composition IC shown in Table 1), and a peracetic acid composition generated by adding a catalase enzyme (100 ppm) to the diluted peracid composition commercial (1% POAA) to eliminate H2O2 at an undetectable level prior to testing. Initial POAA levels are targeted at 30 ppm and the POAA concentration was monitored by the iodometric titration method during the intended application time of 15 minutes. The results are summarized in Table 9 below. Table 9. POAA STABILITY OF VARIOUS PEROXYACETIC ACID COMPOSITIONS IN USE SOLUTION CONTAINING WATER USED FROM OIL AND GAS WELLS

[00283] As shown in Table 9, it was surprisingly found that the presence of H2O2 in the peracetic acid composition has a significantly negative impact on the stability of POAA. For example, the commercial peracid product that contains around 15% POAA and 10% H2O2 lost almost all of its peracid content within 5 minutes, whereas a hydrogen peroxide depleted version of it (pre -treated with catalase enzyme) lost only 3% of its initial activity in 10 minutes and only about 12% in 15 minutes. For composition I-C, which contains around 15% peracetic acid but only 1% hydrogen peroxide, it lost only around 30% POAA in 15 min. This makes composition I-C particularly useful in the application of fracture water treatment compared to commercial peracetic acid compositions, as significantly less amount of POAA was required for treatment. The observed phenomena appear to be universal as two different water combinations from the well sites have similar results as shown in Table 6. Without limiting the invention to any particular theory, the observed results can be explained by the presence of the contaminants related to sulfur commonly found in used well water, which in the presence of H2O2 will generate radical, and this very reactive radical will then react with POAA to decompose it. EXAMPLE 5. GELATION TEST OF PERACETIC ACID (POAA) COMPOSITIONS WITH VARIOUS LEVELS OF HYDROGEN PEROXIDE
[00284]Hydrogen peroxide is a known gel breaker in oil and gas gel fracturing application. H2O2 presented in a peracid composition is expected to negatively impact the gel property. This experiment was designed to evaluate H2O2 levels in peracid compositions and their impacts on gel properties.
[00285]H2O2 free peracetic acid was first prepared by treating a commercial peracetic acid product (15% POAA, 10% H2O2) with catalase and, after treatment, the catalase was confirmed as inactivated. Then, known amount of H2O2 was added to the peracetic acid composition for testing. To ~500 g of water a guar-based gel additive was added, except the crosslinker. The mixture was blended by a blender for ~10 min, then POAA prepared as described, and H2O2 were added to the mixture and the pH of the mixture was then adjusted to 11.5 with KOH/K2CO3 (11.5% wt. so/22.5%), immediately followed by the addition of the crosslinker. The kinetic viscosity of the mixture was then monitored by a viscometer (Kindler) at 275 K for a time period of 2.5 h. The success criterion is that the viscosity of the mixture maintains 200 cp or more at the end of the test. For comparison, a gel mixture with standard glutaraldehyde as the alternative biocide was also tested. The test results are shown in Figure 4.
[00286] Figure 4 clearly shows that under the conditions investigated, at the higher use level of POAA (80 ppm) as a biocide in oil and gas fracturing applications, the presence of 7 ppm of H2O2 had no impact on the gel property compared to the standard control (glutaraldehyde), while the presence of 14 ppm H2O2 caused the gel to fail. EXAMPLE 6. GELATION TEST OF A HIGH RATIO OF POAA TO H2O2 OF THE PERACETIC ACID COMPOSITION
[00287] The gelation experiment described in Example 5 was carried out using different levels of a high ratio of POAA to H2O2 of the peracetic acid (IC) composition as disclosed in this application. The results are summarized in Table 10, along with the results for a commercial peracetic acid product. Table 10. SUMMARY OF POAA KINETIC VISCOSITY TEST RESULTS IN A GEL FLUID

[00288] The results from Table 10 show the significant advantages of the I-C compositions in gel fracturing applications compared to common peracetic acid compositions. For example, at the levels of POAA (30ppm) required for microorganism death, the common peracetic acid composition will fail in the fluid's gel properties due to the high level of co-existing H2O2. In contrast, the high ratio of POAA to H2O2 of the peracetic acid I-C composition does not impact the properties of the gel still used at a much higher level, eg POAA 75 ppm. EXAMPLE 7. ENTHALPY PART I - HIGH AND LOW POTENTIAL ENTHALPY OF HYDROGEN PEROXIDE PRODUCTS - PEROXYACID
[00289] Peroxyacids and hydrogen peroxide are characterized by a relatively weak O-O bond which typically and especially in the case of peroxyacids is prone to homolytic fission which basically produces molecular oxygen, water and the precursor carboxylic acids. The property of labile homolytic fission is essential to the usefulness of peroxyacids in bleaching, polymerization, and antimicrobial applications, but it can also create unwanted hazardous chemical reactions. The eventual release of oxygen is a highly exothermic (heat producing) process and, since oxygen is a potent oxidizing agent, downstream oxidations of organic residues are possible outcomes producing even greater amounts of heat and gas. The worst case is a violent explosion and/or eruption of corrosive materials.
[00290] For these reasons above, peroxyacids fail under the UN category of dangerous goods and as such it is recommended by the UN that they be fully characterized before determining what restrictions should be imposed on the transport, handling and storage of the same. In general, these guidelines are strictly followed by local authorities and therefore a restriction requiring refrigerated handling and storage, for example, would likely limit sales to only a small minority of potential buyers. To avoid such restrictions, most peroxyacid producers first formulate their products, which will be intrinsically stable, and then add stabilizers, such as HEDP, to increase safety against uncontrolled exothermic deterioration, as well as ensuring sufficient shelf life for effectiveness. The inadequate result is that the higher concentrations of hydrogen peroxide required to achieve intrinsic stability increase the potential enthalpy and increase the violence of an uncontrolled chemical reaction.
[00291] As shown in Table 11, formulas III-A, III-B and III-C have approximately twice the potential enthalpy compared to formulas IA, IB and IC and still release 15% of peroxyacetic acid. And while the reduction in hydrogen peroxide improves the enthalpic potential for formula type I, only in the case IC does the product have sufficient shelf stability to allow for manufacture, storage and use before it loses excessive portions of its acid pe -roxyacetic initial. Table 11

[00292] Since the OO bond is intrinsically weak, metallic contaminants such as the ubiquitous ferric and ferrous ions (iron) catalyze the fission of the OO bond and thus require that peroxyacids be formulated to include stabilizers , such as metal chelators. And while the typical chelator is usually sufficient to stabilize formulations prepared with relatively pure chemicals, it cannot be practically high enough to overcome gross contamination events. In fact, accidental contamination of peroxyacid products is not an unknown event and has caused fatal explosions involving peroxides on many occasions. Since metal chelator stabilizers added for transport, handling and storage can be overwhelmed by a gross contamination event, it is desirable to minimize the potential energy relative to the peroxyacid content of the product. This is especially the case when considering mass storage scenarios involving, for example, several thousand gallons of product.
[00293]Currently, there are several provisions made for contamination accidents, one is the formulated metallic chelating agent always present, the other is gas vent arrangements upright in bulk tanks, as well as water cooling means maintained in a state of alert. Again, in the case of formulas IA and IB, while they equally share the potential enthalpy of a typical 15% POAA product, their very low hydrogen peroxide levels severely compromise their self-stability. In fact, stability is also poor for IA and IB, until 100% decomposition occurs within 1 to 2 weeks when stored at 40°C for <1 week. In example I-C, however, the single synergistic stabilizer combination is very successful in providing sufficient shelf life. The combination of synergistic stabilizer found in IC allows the formula of 15% peroxyacetic acid with a very low hydrogen peroxide and thus a reduced potential heat of reaction after a runaway of 230 joules/g (no combustion scenario) or 745 joules/g if combustion scenario predominates. In contrast, the more traditional peroxyacid product represented by III-A to III-C has a potential enthalpy of -515 joules/g (the non-combustion scenario) to -1661 joules/g if the combustion scenario predominates. EXAMPLE 8. ENTHALPY PART II - SELF-ACCELERATING DECOMPOSITION TEST OF LOW HYDROGEN PEROXIDE - PEROXYACETIC ACID CHEMICALS
[00294]The following SADT procedure is a standardized United Nations protocol to help determine the hazardous classes of self-heating substances known as the “H4 method”. The method is packaging specific and if the SADT temperature is 45°C or less, the product must be transported, stored and used with stringent refrigeration controls. Such control requirements would likely make a product impractical for commerce, as well as dangerous and unwanted in most installations.
[00295] In the interests of safety, the self-heating behavior of chemistries at very large package sizes is simulated in De war vials that have been previously tested to determine if they closely reflect the heat transfer properties of the package. Bulk tanks are the largest potential package sizes and to model their heat transfer properties it is recommended to use spherical Dewar flasks. The UN Committee on the Transport of Dangerous Goods still builds a safety margin on sizes of 300 gallons and larger packages by requiring that they have SADT's >50°C. As per UN-H4 guidelines 28.4.1.4.1, if the temperature of the contents does not exceed the oven temperature by more than 6°C within 7 days, the SADT, by definition, is greater than the oven temperature. oven. The guidelines still define zero time when the sample temperature is within 2 degrees of the oven temperature and they require an 80% filled Dewar set with temperature monitoring and ventilated closures. These criteria were performed as 3 spherical Dewar vials 80% filled with IA, IB and IC chemistries (see Table 12 below). Table 12


[00296] As can be seen in Figure 3, formulas I-A and I-B containing, respectively, only HEDP and only DPA, stabilizers exceeded the grade 6 exotherm limit within 1.5 days and 3 days, respectively. The same concentrations of HEDP and DPA when mixed, however, produced such extreme stabilization that the self-heating effects were not sufficient to reach the oven temperature within the 7-day period. On the basis of the H4 protocol, it appears that the synergistic combination of uniquely obtains the concession of uncooled storage and mass transport, at least for this exemplary type of percarboxylic acid and hydrogen peroxide compositions (eg type formula formula IC). EXAMPLE 9. QUANTIFICATION OF DECOMPOSITION PEROXIDE GASES
[00297]The volume of decomposition peroxide gases was measured using a water-filled U-tube fitted with a minimum volume tubing connected to a needle of the coreless syringe. The manometer made of refractory glass was partially filled with deionized water colored with FD&C blue dye #1 and 1000 ppm of nonionic surfactant. The dye allows for increased visibility of the water columns and the surfactant lowers the surface tension considering continuous water columns. The manometer was also adjusted with a metric ruler to allow convenient determination of the difference in column heights. Since 1 atmosphere of pressure corresponds to 1,006 cm of water column height and the resolution limit in the column and ruler combination is about 1 mm, the signal to noise ratio approaches 10:1.
[00298]Procedure. Four-head spaced vials were double rinsed with the sample solution before adding 5 mL of the sample solution (via Repeat Pipettor) and sealing the vials with a silicone-backed PTFE septum with an aluminum cap. Immediately after sealing the vials, the temperature and barometric pressure were recorded. A set of blank water replicas of the same volume was also included. The sealed vials were stored for 24 to 48 hours at ambient temperatures within a dark room to allow for optimal gas pressure generation.
[00299] Calculations. By calibrating the U-tube water column displacement using a precision gas syringe, the ratio of water column height to gas volume was calculated. Using the assumption of decomposition of peroxide to molecular oxygen (ignoring CO2 or CO gases etc.), these values were converted to gas volumes and the loss of available oxygen in the sample was therefore calculated using the formulas below: 2 mols of RCO3H ^ 2 mols of RCO2H + 1 mol of O2 (22.4 L of O2 at standard temperature and pressure) and 2 mols of H2O2 ^ 2 mols of H2O + 1 mol of O2 (22.4 L of O2 at standard temperature and pressure)
[00300] As shown in Table 13 below, the synergistic combination of DPA and HEDP reduced the rate of "Rel Loss." of O2 for IC to 1/9 that of IA and better than 1/3 that of IB, as measured by decomposition gas volumes. Furthermore, it can be seen that the synergistic combination brings essentially equal to the loss rate of the more typical commercial peracids, as well as that of a 50% active hydrogen peroxide raw material. Table 13

EXAMPLE 10. REDUCTION OF HYDROGEN SULFIDE
[00301] Several tests were conducted using exemplary formulations of the present invention to reduce hydrogen sulfide (H 2S) fortified in distilled water. The ingredients of the exemplary formulations (13523-37-1 and 123523-37-2) and a control formulation (Tsunami 100 (EC6734A)) are listed in the following Table 14. Table 14

[00302] The test results are shown in the following Table 15 and in Figures 5A, 5B, 6A and 6B. As shown in Table 15, formulation 13523-37-1 at 1000 ppm reduced H2S by about 95%, while formulation 13523-37-1 at 500 ppm reduced H2S by about 80%. Interestingly, a low dose appears to reduce H2S by close to 50%. When formulation 13523-37-2 was used at 1000 ppm, the level of H2S was reduced to 175 ppm. When formulation 13523-37-2 was used at 500 pm, the level of H2S was reduced to 125 ppm. Figure 5a shows an example of the reaction of hydrogen sulfide (H2S) in deionized water solution with different relative concentrations of peracetic acid and hydrogen peroxide (see Table 15 for concentrations). Increased concentrations are shown to result in increased hydrogen sulfide destruction. Figure 5b shows another example of hydrogen sulfide (H2S) reaction in deionized water solution with different relative concentrations of peracetic acid and hydrogen peroxide (see Table 15 for concentrations). Increased concentrations result in increased hydrogen sulfide destruction. Table 15

1. EXEMPLARY ACHIEVEMENTS
The present invention is further illustrated by the following exemplary embodiments: 2. A composition, which comprises: 1) a C1-C22 carboxylic acid; 2) a C1-C22 percarboxylic acid; 3) hydrogen peroxide; 4) a first stabilizing agent, which is a picolinic acid or a compound having the following Formula (IA):
wherein R1 is OH or -NR1aR1b, wherein R1a and R1b are independently hydrogen or (C1-C6) alkyl; R2 is OH or -NR2aR2b, wherein R2a and R2b are independently hydrogen or (C1-C6) alkyl; each R3 is independently (C1-C6) alkyl, (C2-C6) alkenyl or (C2-C6) alkynyl; en is a number from zero to 3; or a salt thereof; or a compound having the following Formula (IB):
wherein R1a and R1b are independently hydrogen or alkyl (CI-C'); that R2a and R2b are independently hydrogen or alkyl (CI-C'); each R3 is independently alkyl (CI-C'), alkenyl (C2-C') or alkynyl (C2-C'); and n is a number from zero to 3; or a salt thereof; Formula (IIA):
5) a second stabilizing agent, which is a compound having the following R1, R2, R3 and R4 are independently hydrogen, alkyl (CI-C'), alkenyl (C2-C')-C 6)alkynyl or aryl C'-C2O; R5is alkyl (C1-C'), alkenyl (C2-C') or alkynyl (C2-C'); and R6 is hydrogen, alkyl (C1-C'), alkenyl (C2-C') or alkynyl (C2-C'); or a compound having the following Formula (IIB):
wherein R 1 , R 2 and R 3 are independently hydrogen, alkyl (C 1 -C 6 ), alkenyl (C 2 -C 6 ) or alkynyl (C 2 -C 6 ) or C 6 -C 20 aryl; or a salt thereof; and wherein said hydrogen peroxide has a concentration of at least about 0.1% by weight, C1-C22 percarboxylic acid has a concentration of at least about 2 times the concentration of said hydrogen peroxide and said composition has a pH of about 4 or less. 3. The composition according to embodiment 1, wherein the C1-C22 percarboxylic acid has a concentration of at least about 6 times the concentration of hydrogen peroxide. 4. The composition according to embodiment 1, wherein the C1-C22 percarboxylic acid has a concentration of at least about 10 times the concentration of hydrogen peroxide. 5. The composition according to any one of embodiments 1 to 3, wherein the C1-C22 carboxylic acid is a C2-C20 carboxylic acid. 6. The composition according to any one of embodiments 1 to 4, wherein the C1-C22 carboxylic acid comprises acetic acid, octanoic acid and/or sulfonated oleic acid. 7. The composition according to any one of embodiments 1 to 5, wherein the C1-C22 carboxylic acid has a concentration of from about 10% by weight to about 90% by weight. 8. The composition according to any one of embodiments 1 to 5, wherein the C1-C22 carboxylic acid has a concentration of from about 20% by weight to about 80% by weight. 9. The composition according to any one of embodiments 1 to 7, wherein the C1-C22 percarboxylic acid is a C2-C20 percarboxylic acid. 10. The composition according to any one of embodiments 1 to 8, wherein the C1-C22 percarboxylic acid comprises peroxyacetic acid, peroxyoctanoic acid and/or peroxysulfonated oleic acid. 11. The composition according to any one of embodiments 1 to 9, wherein the C1-C22 percarboxylic acid has a concentration of from about 1% by weight to about 40% by weight. 12. The composition according to any one of embodiments 1 to 9, wherein the C1-C22 percarboxylic acid has a concentration of from about 1% by weight to about 20% by weight. 13. The composition according to any one of embodiments 1 to 11, wherein the hydrogen peroxide has a concentration of about 0.5% by weight to about 10% by weight. 14. The composition according to any one of embodiments 1 to 11, wherein the hydrogen peroxide has a concentration of from about 1% by weight to about 2% by weight. 15. The composition according to any one of embodiments 1 to 13, wherein the C1-C22 carboxylic acid is acetic acid and the C1-C22 percarboxylic acid is peracetic acid. 16. The composition according to any one of embodiments 1 to 14, wherein the C1-C22 carboxylic acid has a concentration of about 70% by weight, the C1-C22 percarboxylic acid has a concentration of about 15% by weight and the hydrogen peroxide has a concentration of at least about 1% by weight. 17. The composition according to any one of embodiments 1 to 15, wherein the first stabilizing agent is a picolinic acid or a salt thereof. 18. The composition according to any one of embodiments 1 to 15, wherein the first stabilizing agent is 2,6-pyridinedicarboxylic acid or a salt thereof. 19. The composition according to any one of embodiments 1 to 17, wherein the first stabilizing agent has a concentration of from about 0.005% by weight to about 5% by weight. 20. The composition according to any one of embodiments 1 to 17, wherein the first stabilizing agent has a concentration of from about 0.05% by weight to about 0.15% by weight. 21. The composition according to any one of embodiments 1 to 19, wherein the second stabilizing agent is 1-hydroxy-ethyllidene-1,1-diphosphonic acid (HEDP) or a salt thereof. 22. The composition according to any one of embodiments 1 to 20, wherein the second stabilizing agent has a concentration of from about 0.1% by weight to about 10% by weight. 23. The composition according to any one of embodiments 1 to 20, wherein the second stabilizing agent has a concentration of from about 0.5% by weight to about 5% by weight. 24. The composition according to any one of embodiments 1 to 20, wherein the second stabilizing agent has a concentration of from about 0.6% by weight to about 1.8% by weight. 25. The composition according to any one of embodiments 1 to 23, further comprising a substance that aids in solubilizing the first and/or second stabilizing agents. 26. The composition according to any one of embodiments 1 to 24, wherein the first stabilizing agent is a 2,6-pyridinedicarboxylic acid or a salt thereof and the second stabilizing agent is HEDP or a salt thereof . 27. The composition according to any one of Embodiments 1 to 25, wherein the first and second stabilizing agents delay or prevent the composition from exceeding its self-accelerating decomposition temperature (SADT). 28. The composition according to any one of embodiments 1 to 26, which retains at least about 80% of the activity of the C1-C22 percarboxylic acid after storage for about 30 days at about 50°C . 29. A method for storing a composition containing percarboxylic acid, which comprises storing a composition according to any one of embodiments 1 to 27, wherein said composition retains at least about 80% of the activity of the C1-C22 percarboxylic acid after storage for about 30 days at about 50°C. 30. A method for transporting a composition containing percarboxylic acid, which comprises transporting a composition according to any one of embodiments 1 to 27, wherein the SADT of said composition is raised to at least 45° C during transport. 31. A method of treating water, which comprises providing a composition, according to any one of embodiments 1 to 27, to a water source in need of treatment to form a treated water source, wherein said source of treated water comprises from about 1 ppm to about 1000 ppm of said C1-C22 percarboxylic acid. 32. The method according to embodiment 30, wherein the water source in need of treatment is selected from the group consisting of fresh water, reservoir water, sea water, produced water and a combination. nation of them. 33. The method according to embodiment 31, wherein the water source comprises at least about 1% by weight of produced water. 34. The method according to any one of embodiments 30 to 32, wherein the treated water source comprises from about 10 ppm to about 200 ppm of the C1-C22 percarboxylic acid. 35. The method according to any one of embodiments 30 to 33, wherein the C1-C22 percarboxylic acid comprises peroxyacetic acid, peroxyoctanoic acid and/or peroxysulfonated oleic acid. 36. The method according to any one of embodiments 30 to 34, wherein the treated water source comprises from about 1 ppm to about 15 ppm of the hydrogen peroxide. 37. The method according to any one of embodiments 30 to 35, wherein the treated water source retains at least about 60% of the initial C1-C22 percarboxylic acid activity in the treated water source for 15 minutes after the treated water source is formed. 38. The method according to any one of embodiments 30 to 36, wherein the level of a microorganism, if present in the water source, is stabilized or reduced. 39. The method according to any one of embodiments 30 to 37, wherein the antimicrobial effectiveness of the composition according to any one of embodiments 1 to 27 in the treated water source is comparable to the effect antimicrobial from a water source that does not contain produced water. 40. The method according to any one of embodiments 30 to 38, wherein the treated water source reduces corrosion caused by hydrogen peroxide and reduces corrosion induced by microbes, and the composition, accordingly with any one of embodiments 1 to 27, it does not substantially interfere with a friction reducer, a viscosity enhancer, other functional ingredients present in the treated water source, or a combination thereof. 41. The method according to any one of embodiments 30 to 39, which further comprises adding a peroxidase or a catalase to the water source before a composition according to any one of embodiments 1 to 27, is supplied to the water source, and wherein the peroxidase or a catalase further reduces the level of hydrogen peroxide in the treated water source. 42. The method according to any one of embodiments 30 to 40, which further comprises directing the treated water source into an underground environment or disposing of the treated water source. 43. The method according to any one of embodiments 30 to 41, wherein the water source does not comprise reusing the water, the treated water source comprises from about 10 ppm to about 20 ppm of the CI-C22 percarboxylic acid and from about 1 ppm to about 2 ppm hydrogen peroxide and the treated water source does not comprise a friction reducer and/or a rheology modifier. 44. The method according to any one of embodiments 30 to 42, wherein the water source is a mixed water source comprising about 80% by weight of fresh water or reservoir water and about 20 % by weight of reuse water, the treated water source comprises from about 25 ppm to about 35 ppm of C1-C22 percarboxylic acid and from about 2 ppm to about 3 ppm of hydrogen peroxide and catalase, the source of treated water does not comprise a friction reducer and/or a rheology modifier and the treated water source is formed before reaching a mixing barrel. 45. The method according to any one of embodiments 30 to 43, wherein the water source is a mixed water source comprising about 80% by weight of fresh water or reservoir water and about 20 % by weight of reuse water, the treated water source comprises from about 25 ppm to about 35 ppm of C1-C22 percarboxylic acid and from about 2 ppm to about 3 ppm of hydrogen peroxide and catalase, the source The treated water source comprises a friction reducer and/or a rheology modifier and the treated water source is formed in a mixing barrel. 46. The method according to any one of embodiments 30 to 44, wherein the treated water source comprises from about 30 ppm or less of the C1-C22 percarboxylic acid and about 0.5 ppm or less of the hydrogen peroxide, the treated water source comprises a friction reducer and/or a rheology modifier and the treated water source is directed at or is in an underground environment. 47. A composition, which comprises: 1) a C1-C22 carboxylic acid; 2) a C1-C22 percarboxylic acid; 3) hydrogen peroxide; 4) a first stabilizing agent, which is a picolinic acid or a compound having the following Formula (IA):
wherein R1 is OH or -NR1aR1b, wherein R1a and R1b are independently hydrogen or (C1-C6) alkyl; R2 is OH or -NR2aR2b, wherein R2a and R2b are independently hydrogen or (C1-C6) alkyl; each R3 is independently (C1-C6) alkyl, (C2-C6) alkenyl or (C2-C6) alkynyl; en is a number from zero to 3; or a salt thereof; or a compound having the following Formula (IB):
wherein R1 is OH or -NR1aR1b, wherein R1a and R1b are independently hydrogen or alkyl (CI-C'); R2 is OH or -NR2aR2b, where R2a and R2b are independently hydrogen or alkyl (CI-C'); each R3 is independently alkyl (CI-C'), alkenyl (C2-C') or alkynyl (C2-C6); en is a number from zero to 3; or a salt thereof; 5) a second stabilizing agent, which is a compound having the following 6) Formula (IIA):
R1, R2, R3 and R4 are independently hydrogen, alkyl (CI-C'), alkenyl (C2-C') or alkynyl (C2-C') or C6-C20 aryl; R5 is alkyl (CI-CΘ), alkenyl (C2-CΘ) or alkynyl (C2-CΘ); and R6 is hydrogen, alkyl (CI-CΘ), alkenyl (C2-CΘ) or alkynyl (C2-CΘ); or a salt thereof; or a compound having the following Formula (IIB):
wherein R1, R2 and R3 are independently hydrogen, (C1-C6) alkyl, (C2-C6) alkenyl or (C2-C6) alkynyl or C6-C20 aryl; or a salt thereof; 7) a friction reducer; and wherein said hydrogen peroxide has a concentration of about 1 ppm to about 20 ppm and C1-C22 percarboxylic acid has a concentration of at least about 2 times the concentration of said hydrogen peroxide. 48. The composition according to embodiment 46, wherein the hydrogen peroxide has a concentration of from about 1 ppm to about 10 ppm. 49. The composition according to embodiment 46 or 47, wherein the C1-C22 percarboxylic acid has a concentration of at least about 6 times the concentration of hydrogen peroxide. 50. The composition according to any one of embodiments 46 to 48, wherein the C1-C22 percarboxylic acid has a concentration of at least about 10 times the concentration of the hydrogen peroxide. 51. The composition according to any one of embodiments 46 to 49, wherein the friction reducer is a polyacrylamide polymer and/or copolymer or an acrylamide derived polymer and/or copolymer. 52. The composition according to any one of embodiments 46 to 50, wherein the friction reducer has a concentration of from about 50 ppm to about 5,000 ppm, preferably from about 100 ppm to about 1,000 ppm. 53. The composition according to any one of embodiments 46 to 51, which further comprises a proppant, a surfactant and/or a scale inhibitor. 54. The composition according to embodiment 52, wherein the proppant is a sand or ceramic bead. 55. The composition according to embodiment 52, wherein the scale inhibitor is a polymer, a phosphonate or a phosphate ester. 56. The composition according to any one of embodiments 46 to 54, wherein the C1-C22 percarboxylic acid is a C2-C20 percarboxylic acid. 57. The composition according to any one of embodiments 46 to 55, wherein the C1-C22 percarboxylic acid comprises peroxyacetic acid, peroxyoctanoic acid and/or peroxysulfonated oleic acid. 58. The composition according to any one of embodiments 46 to 56, wherein the C1-C22 percarboxylic acid has a concentration of about 10 ppm to about 30 ppm and the hydrogen peroxide has a concentration of about from 1 ppm to about 3 ppm. 59. The composition according to any one of embodiments 46 to 57, wherein the first stabilizing agent is a picolinic acid or a salt thereof. 60. The composition according to any one of embodiments 46 to 57, wherein the first stabilizing agent is 2,6-pyridinedicarboxylic acid or a salt thereof. 61. The composition according to any one of embodiments 46 to 59, wherein the first stabilizing agent has a concentration of from about 0.005% by weight to about 5% by weight. 62. The composition according to any one of embodiments 46 to 59, wherein the first stabilizing agent has a concentration of from about 0.05% by weight to about 0.15% by weight. 63. The composition according to any one of embodiments 46 to 61, wherein the second stabilizing agent is 1-hydroxy-ethyllidene-1,1-diphosphonic acid (HEDP) or a salt thereof. 64. The composition according to any one of embodiments 46 to 62, wherein the second stabilizing agent has a concentration of from about 0.1% by weight to about 10% by weight. 65. The composition according to any one of embodiments 46 to 62, wherein the second stabilizing agent has a concentration of from about 0.5% by weight to about 5% by weight. 66. The composition according to any one of embodiments 46 to 62, wherein the second stabilizing agent has a concentration of from about 0.6% by weight to about 1.8% by weight. 67. The composition according to any one of embodiments 46 to 65, wherein the first stabilizing agent is a 2,6-pyridinedicarboxylic acid or a salt thereof and the second stabilizing agent is HEDP or a salt thereof . 68. The composition according to any one of embodiments 46 to 66, which retains at least about 60% of the initial C1-C22 percarboxylic acid activity for 15 minutes after the composition is formed. 69. The composition according to any one of embodiments 46 to 67, wherein the hydrogen peroxide concentration is further reduced by a peroxidase or a catalase. 70. The composition according to any one of embodiments 46 to 68, which further comprises a substance which aids in solubilizing the first and/or second stabilizing agents. 71. A method for fracturing fluid with low rheology (slick water) which comprises directing a composition according to any one of embodiments 46 to 69 in an underground medium. 72. The method according to embodiment 70, wherein the composition is directed in an underground medium at a speed faster than 30 barrels (bbl)/min. 73. The method according to embodiment 71, wherein the composition is directed in an underground medium at a speed of about 50 bbl/min to about 100 bbl/min. 74. The method according to any one of embodiments 70 to 72, wherein the underground medium comprises a well in a reservoir of shale and/or oil gas. 75. The method according to any one of embodiments 70 to 73, wherein the composition is pumped down a wellbore. 76. A composition, which comprises: 1) a C1-C22 carboxylic acid; 2) a C1-C22 percarboxylic acid; 3) hydrogen peroxide; 4) a first stabilizing agent, which is a picolinic acid or a compound having the following Formula (IA):
wherein R1 is OH or -NR1aR1b, wherein R1a and R1b are independently hydrogen or (C1-C6) alkyl; R2 is OH or -NR2aR2b, wherein R2a and R2b are independently hydrogen or (C1-C6) alkyl; each R3 is independently alkyl (C 1 -C 6 ), alkenyl (C 2 -C 6 ) or alkynyl (C 2 -C 6 ); en is a number from zero to 3; or a salt thereof; or a compound having the following Formula (IB):
wherein R1 is OH or -NR1aR1b, wherein R1a and R1b are independently hydrogen or (C1-C6) alkyl; R2 is OH or -NR2aR2b, wherein R2a and R2b are independently hydrogen or (C1-C6) alkyl; each R3 is independently alkyl (C1-Ce), alkenyl (C2-C6) or alkynyl (C2-Ce); en is a number from zero to 3; or a salt thereof; 5) a second stabilizing agent, which is a compound having the following Formula (IIA):
wherein R 1 , R 2 , R 3 and R 4 are independently hydrogen, alkyl (C 1 -Cβ), alkenyl (C 2 -C 6 ) or alkynyl (C 2 -C 6 ) or C 6 -C 20 aryl; R5is (C1-C6) alkyl, (C2-C6) alkenyl or (C2-C6) alkynyl; and R6 is hydrogen, (C1-C6) alkyl, (C2-C6) alkenyl or (C2-C6) alkynyl; or a salt thereof; or a compound having the following Formula (IIB):
wherein R1, R2 and R3 are independently hydrogen, (C1-C6) alkyl, (C2-C6) alkenyl or (C2-C6) alkynyl, or C6-C20 aryl; or a salt thereof; 6) a viscosity enhancer; and wherein said hydrogen peroxide has a concentration of about 1 ppm to about 15 ppm and said C1-C22 percarboxylic acid has a concentration of at least about 2 times the concentration of said hydrogen peroxide. 77. The composition according to embodiment 75, wherein the hydrogen peroxide has a concentration of from about 1 ppm to about 10 ppm. 78. The composition according to embodiment 75 or 76, wherein the C1-C22 percarboxylic acid has a concentration of at least about 6 times the concentration of the hydrogen peroxide. 79. The composition according to any one of embodiments 75 to 77, wherein the C1-C22 percarboxylic acid has a concentration of at least about 10 times the concentration of the hydrogen peroxide. 80. The composition according to any one of embodiments 75 to 78, wherein the viscosity enhancer is a conventional linear gel, a borate crosslinked gel, an organometallic crosslinked gel or a phosphate oil gel. aluminum-ester. 81. The composition according to any one of embodiments 75 to 79, wherein the viscosity enhancer has a concentration of from about 2 to about 100 pound units per thousand gallons, preferably from about 5 to about 65 units of pounds per thousand gallons. 82. The composition according to any one of embodiments 75 to 80, which further comprises a proppant, a surfactant, a scale inhibitor and/or a breaker. 83. The composition according to embodiment 81, wherein the proppant is a sand or ceramic bead. 84. The composition according to embodiment 81, wherein the scale inhibitor is a polymer, a phosphonate or a phosphate ester. 85. The composition according to embodiment 81, wherein the cleavage is an oxidizer, an enzyme or a pH modifier. 86. The composition according to any one of embodiments 75 to 84, wherein the C1-C22 percarboxylic acid is a C2-C20 percarboxylic acid. 87. The composition according to any one of embodiments 75 to 85, wherein the C1-C22 percarboxylic acid comprises peroxyacetic acid, peroxyoctanoic acid and/or peroxysulfonated oleic acid. 88. The composition according to any one of embodiments 75 to 86, wherein the C1-C22 percarboxylic acid has a concentration that is effective for its antimicrobial function and the hydrogen peroxide has a concentration that will not cause the gel. 89. The composition according to embodiment 87, wherein the hydrogen peroxide has a concentration that is about 14 ppm or less. 90. The composition according to any one of embodiments 75 to 88, wherein the C1-C22 percarboxylic acid has a concentration of about 10 ppm to about 30 ppm and the hydrogen peroxide has a concentration of about from 1 ppm to about 3 ppm. 91. The composition according to any one of embodiments 75 to 89, wherein the first stabilizing agent is a picolinic acid or a salt thereof. 92. The composition according to any one of embodiments 75 to 90, wherein the first stabilizing agent is 2,6-pyridinedicarboxylic acid or a salt thereof. 93. The composition according to any one of embodiments 75 to 91, wherein the first stabilizing agent has a concentration of from about 0.005% by weight to about 5% by weight. 94. The composition according to any one of embodiments 75 to 92, wherein the first stabilizing agent has a concentration of from about 0.05% by weight to about 0.15% by weight. 95. The composition according to any one of embodiments 75 to 93, wherein the second stabilizing agent is 1-hydroxy-ethyllidene-1,1-diphosphonic acid (HEDP) or a salt thereof. 96. The composition according to any one of embodiments 75 to 94, wherein the second stabilizing agent has a concentration of from about 0.1% by weight to about 10% by weight. 97. The composition according to any one of embodiments 75 to 94, wherein the second stabilizing agent has a concentration of from about 0.5% by weight to about 5% by weight. 98. The composition according to any one of embodiments 75 to 94, wherein the second stabilizing agent has a concentration of from about 0.6% by weight to about 1.8% by weight. 99. The composition according to any one of embodiments 75 to 97, wherein the first stabilizing agent is a 2,6-pyridinedicarboxylic acid or a salt thereof and the second stabilizing agent is HEDP or a salt thereof . 100. The composition according to any one of embodiments 75 to 98, which retains at least about 60% of the initial C1-C22 percarboxylic acid activity for 15 minutes after the composition is formed. 101. The composition according to any one of embodiments 75 to 99, wherein the hydrogen peroxide concentration is further reduced by a peroxidase or a catalase. 102. The composition according to any one of embodiments 75 to 100, which further comprises a substance which aids in solubilizing the first and/or second stabilizing agents. 103. A method for high viscosity fracturing which comprises directing a composition according to any one of embodiments 75 to 101 in an underground medium. 104. The method according to embodiment 102, wherein the underground medium comprises a well in a gas and/or oil. 105. A method of treating a target, which comprises a step of contacting a target with a diluted composition, according to any one of embodiments 1 to 27, to form a treated target composition, wherein said with treated target position comprises from about 1 ppm to about 10,000 ppm of said C1-C22 percarboxylic acid and said contact step lasts long enough to stabilize or reduce the microbial population in, and/or on said target or said target composition treated. 106. The method according to embodiment 104, wherein the target is a food item or a vegetable item and/or at least a portion of a medium, a container, an equipment, a system or an installation for growing , maintenance, processing, packaging, storing, transporting, preparing, cooking or servicing the food item or the vegetable item. 107. The method according to embodiment 105, wherein the vegetable item is a grain, fruit or flower. 108. The method according to embodiment 105, wherein the plant item is a living plant item or a harvested plant item. 109. The method according to embodiment 105, wherein the plant item comprises a seed, a tuber, a crop plant, a cutting or a root stock. 110. The method according to embodiment 105, which is used to treat a living plant tissue comprising treating the plant tissue with a dilute composition, according to any one of embodiments 1 to 27, to stabilize or reduce the microbial population in and/or on plant tissue. 111. The method, according to embodiment 105, which is used for growing a plant in a hydroponic substrate in a hydroponic liquid supply medium, comprising: (a) establishing a culture plant tissue and live in the hydroponic substrate; (b) contacting the living plant tissue, the hydroponic substrate and the hydroponic liquid with a dilute composition, in accordance with any one of embodiments 1 to 27, to stabilize or reduce the microbial population in, and/or on living plant tissue; and (c) collect a usable plant product with reduced microbial contamination. 112. The method according to embodiment 105, wherein the food item is selected from the group consisting of an animal product, for example an animal carcass or an egg, a fruit, a vegetable and a grain. 113. The method according to embodiment 111, wherein the animal carcass is selected from the group consisting of an ox, pork, veal, buffalo, lamb, fish, seafood and chicken carcass . 114. The method according to embodiment 112, wherein the seafood carcass is selected from the group consisting of scallop, shrimp, crab, octopus, mussel, squid and lobster. 115. The method according to embodiment 111, wherein the fruit is selected from the group consisting of a botanical fruit, a culinary fruit, a single fruit, an aggregated fruit, multiple fruits, a berry , an accessory fruit and a seedless fruit. 116. The method according to embodiment 111, wherein the vegetable is selected from the group consisting of a flower bud, a seed, a leaf, a leaf sheath, a bud, a stem, a leaf stem, a stem bud, a tuber, a full-plant bud, a root and a bulb. 117. The method according to embodiment 111, wherein the grain is selected from the group consisting of corn, rice, wheat, barley, sorghum, millet, oats, triticale, rye, buckwheat, fonio and quinoa . 118. The method according to embodiment 105, wherein the target is at least a part of a container, an equipment, a system or an installation for containing, processing, packaging, storing, transporting, preparing, cooking or serving the food item or the vegetable item. 119. The method according to embodiment 105, wherein the target is at least a part of a container, an equipment, a system or an installation for containing, processing, packaging, storing, transporting, preparing, cooking or serving a meat, a fruit, a vegetable or a grain. 120. The method according to embodiment 105, wherein the target is at least a part of a container, an equipment, a system or an installation for containing, processing, packaging, storing or transporting a carcass of animal. 121. The method according to embodiment 104, wherein the target is at least a part of a container, an equipment, a system or an installation used in the food processing, food service or health industry public. 122. The method according to embodiment 104, wherein the target is at least a part of a suitable fixed process installation. 123. The method according to embodiment 121, wherein the fixed suitable process facility comprises a dairy establishment of the milk line, a continuous fermentation system, a pumpable food system or a line of beverage processing. 124. The method according to embodiment 104, wherein the target is at least a portion of a solid surface or liquid medium. 125. The method according to embodiment 123, wherein the solid surface is an inanimate solid surface contaminated by a biological fluid comprising blood, other hazardous bodily fluid or a mixture thereof. 126. The method according to embodiment 123, wherein the solid surface is a contaminated surface. 127. The method according to embodiment 125, wherein the contaminated surface comprises the surface of food service goods or equipment, or the surface of a fabric. 128. The method of any one of embodiments 104 to 126, wherein the treated target composition comprises from about 10 ppm to about 200 ppm of the C1-C22 percarboxylic acid. 129. The method according to any one of embodiments 104 to 127, wherein the C1-C22 percarboxylic acid comprises peroxyacetic acid, peroxyoctanoic acid and/or peroxysulfonated oleic acid. 130. The method according to any one of embodiments 104 to 128, wherein the treated target composition comprises from about 1 ppm to about 15 ppm of the hydrogen peroxide. 131. The method according to any one of embodiments 104 to 129, wherein the C1-C22 percarboxylic acid has a concentration of at least about 3 times the concentration of the hydrogen peroxide. 132. The method according to any one of embodiments 104 to 130, wherein the first stabilizing agent is a 2,6-pyridinedicarboxylic acid or a salt thereof and the second stabilizing agent is HEDP or a salt thereof . 133. The method according to any one of embodiments 104 to 131, wherein the treated target composition retains at least about 60% of the initial C1-C22 percarboxylic acid activity in the treated target composition for 15 minutes thereafter that the treated target composition is formed. 134. The method according to any one of embodiments 104 to 132, wherein the contact step lasts for at least 10 seconds. 135. The method according to any one of embodiments 104 to 133, wherein the diluted composition according to any one of embodiments 1 to 27 is applied to the target by means of a spray, a mist or a foam. 136. The method according to any one of embodiments 104 to 134, wherein the diluted composition according to any one of embodiments 1 to 27 is applied to the target by application in the form of a thick solution or gel. 137. The method according to any one of embodiments 104 to 134, wherein all or part of the target is immersed in the diluted composition, according to any one of embodiments 1 to 27. 138. The method , according to embodiment 136, wherein the diluted composition according to any one of embodiments 1 to 27 is stirred. 139. The method according to any one of embodiments 104 to 134, wherein the diluted composition according to any one of embodiments 1 to 27 is sprayed onto the carcass at a pressure of at least 50 psi at a temperature up to about 60°C, resulting in a contact time of at least 30 seconds. 140. The method according to any one of embodiments 104 to 138, which further comprises a vacuum treatment step. 141. The method according to any one of embodiments 104 to 139, which further comprises a step of applying an activated light source to the target. 142. The method according to any one of embodiments 104 to 140, wherein the microbial population in and/or on the treated target or target composition is reduced by at least one logw. 143. The method according to any one of embodiments 104 to 140, wherein the microbial population in and/or on the treated target or target composition is reduced by at least two logw. 144. The method according to any one of embodiments 104 to 140, wherein the microbial population in and/or on the treated target or target composition is reduced by at least three logw. 145. The method according to any one of embodiments 104 to 143, wherein the microbial population comprises a prokaryotic microbial population. 146. The method of embodiment 144, wherein the prokaryotic microbial population comprises a bacterial population or an Ar chaea. 147. The method according to any one of embodiments 104 to 143, wherein the microbial population comprises a eukaryotic microbial population. 148. The method of embodiment 146, wherein the eukaryotic microbial population comprises a protozoan or fungal population. 149. The method according to any one of embodiments 104 to 143, wherein the microbial population comprises a viral population. 150. The method, according to any one of embodiments 104 to 148, wherein the target is a food item or a vegetable item and the contact step minimizes or does not induce an organoleptic effect on, and/or about the food item or a vegetable item. 151. The method according to any one of embodiments 104 to 149, which is conducted at a temperature ranging from about 0°C to about 70°C. 152. A method of reducing the level of hydrogen sulfide (H2S), hydrosulfuric acid or a salt thereof in a water source, which comprises a step of contacting a water source with a dilute composition, in accordance with any of embodiments 1 to 27, to form a treated water source, wherein said treated water source comprises from about 1 ppm to about 10,000 ppm of said C1-C22 percarboxylic acid and said hard contact step sufficient time to stabilize or reduce the level of H2S, hydrosulfuric acid or a salt thereof in said treated water source. 153. The method according to embodiment 151, wherein the water source is selected from the group consisting of fresh water, reservoir water, sea water, produced water and a combination thereof. 154. The method according to embodiment 152, wherein the water source comprises at least about 1% by weight of produced water. 155. The method according to any one of embodiments 151 to 153, wherein the treated target composition comprises from about 10 ppm to about 1000 ppm of the C1-C22 percarboxylic acid. 156. The method according to any one of embodiments 151 to 154, wherein the C1-C22 percarboxylic acid comprises peroxyacetic acid, peroxyoctanoic acid and/or peroxysulfonated oleic acid. 157. The method according to any one of embodiments 151 to 155, wherein the treated target composition comprises from about 1 ppm to about 15 ppm of the hydrogen peroxide. 158. The method according to any one of embodiments 151 to 156, wherein the C1-C22 percarboxylic acid has a concentration of at least about 3 times the concentration of hydrogen peroxide. 159. The method according to any one of embodiments 151 to 157, wherein the first stabilizing agent is a 2,6-pyridinedicarboxylic acid or a salt thereof and the second stabilizing agent is HEDP, or a salt of the same. 160. The method according to any one of embodiments 151 to 158, wherein the level of H2S, hydrosulfuric acid or a salt thereof in the treated water source is reduced by at least 10% from the untreated level. 161. The method according to any one of embodiments 151 to 159, wherein at least a portion of the water source is obtained or derived from an underground environment. 162. The method according to any one of embodiments 151 to 160, which further comprises directing the treated water source into an underground environment or discarding the treated water source.

权利要求:
Claims (8)
[0001]
1. Composition CHARACTERIZED by the fact that it comprises: 1) a C1-C22 carboxylic acid; 2) a C1-C22 percarboxylic acid; 3) hydrogen peroxide; 4) a first stabilizing agent, which is a picolinic acid or a compound having the following Formula (IA):
[0002]
2. Composition according to claim 1, CHARACTERIZED by the fact that C1-C22 percarboxylic acid has a concentration of at least 6 times the concentration of hydrogen peroxide.
[0003]
3. Composition according to claim 1, CHARACTERIZED by the fact that the C1-C22 carboxylic acid comprises acetic acid, octanoic acid and/or sulfonated oleic acid.
[0004]
4. Composition according to claim 1, CHARACTERIZED by the fact that C1-C22 carboxylic acid has a concentration of 70% by weight, C1-C22 percarboxylic acid has a concentration of 15% by weight and hydrogen peroxide it has a concentration of at least 1% by weight.
[0005]
5. Composition according to claim 1, CHARACTERIZED by the fact that the first stabilizing agent is a 2,6-pyridinedicarboxylic acid or a salt thereof and the second stabilizing agent is HEDP or a salt thereof.
[0006]
6. Composition, according to claim 1, CHARACTERIZED by the fact that the first and second stabilizing agents delay or prevent the composition from exceeding its self-accelerating decomposition temperature (SADT).
[0007]
7. Composition according to any one of claims 1 to 6, CHARACTERIZED by the fact that the first stabilizing agent comprises a concentration of 0.005% by weight to 5% by weight.
[0008]
8. Composition according to any one of claims 1 to 7, CHARACTERIZED by the fact that the second stabilizing agent comprises a concentration of 0.1% by weight to 10% by weight.

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公开号 | 公开日

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BR112015007546A2|2017-07-04|

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法律状态:
2018-03-06| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|

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2018-03-13| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|

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2018-03-20| B06I| Publication of requirement cancelled [chapter 6.9 patent gazette]|Free format text: ANULADA A PUBLICACAO CODIGO 6.6.1 NA RPI NO 2462 DE 13/03/2018 POR TER SIDO INDEVIDA. |

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2019-10-15| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|

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2021-06-08| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|

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2021-08-03| B16A| Patent or certificate of addition of invention granted [chapter 16.1 patent gazette]|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 04/10/2013, OBSERVADAS AS CONDICOES LEGAIS. |

优先权:

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申请号 | 申请日 | 专利标题

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US201261710631P| true| 2012-10-05|2012-10-05|

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US61/710.631|2012-10-05|

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US201361762777P| true| 2013-02-08|2013-02-08|

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US61/762.777|2013-02-08|

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US13/844,515|US9321664B2|2011-12-20|2013-03-15|Stable percarboxylic acid compositions and uses thereof|

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US13/844.515|2013-03-15|

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PCT/US2013/063512|WO2014055900A1|2012-10-05|2013-10-04|Stable percarboxylic acid compositions and uses thereof|

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